Nitrogen-containing heterocyclic compound having an oxime group, agricultural and horticultural herbicide containing said compound, and method of using the same

Abstract

The present invention addresses the problem of providing a new herbicide which has both a high safety for crops and an excellent herbicidal activity on weeds. The herbicide is for overcoming a food crisis accompanying the expected increase in the global human population in the near future. The problem is solved by: a compound represented by general formula (1) or salts thereof; an agricultural / horticultural herbicide having said compound or salts thereof as an active ingredient; and a method of using the agricultural / horticultural herbicide.

Description

[Technical Field]

[0001] The present invention relates to a nitrogen-containing heterocyclic compound having an oxime group and a salt thereof, an agricultural and horticultural herbicide containing the compound or a salt thereof as an active ingredient, and a method of using them. [Background technology]

[0002] Patent Document 1 describes that certain nitrogen-containing fused heterocyclic compounds having an oxime group have insecticidal activity. However, this document does not describe the specific structure of the compound of the present invention, nor does it disclose or suggest compounds useful as herbicides. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2017 / 065183 Brochure Summary of the Invention [Problem to be solved by the invention]

[0004] A stable supply of food is essential to alleviating the food crisis that is expected to accompany the expected increase in global population in the near future. A stable food supply requires economical and efficient methods of killing or controlling weeds that interfere with crop cultivation and harvesting, and the development of new herbicides and plant growth regulators that can solve this problem is becoming increasingly important. The present invention addresses this social need by providing a novel herbicide that is both highly safe for crops and has excellent herbicidal activity against weeds. Furthermore, the aging of farmers has led to a demand for various labor-saving application methods, and there is a need for the creation of methods for using agricultural and horticultural herbicides that are suitable for these application methods. [Means for solving the problem]

[0005] The present inventors have conducted extensive research to develop novel agricultural and horticultural herbicides, and as a result have found that the nitrogen-containing heterocyclic compounds having an oxime group represented by general formula (1) of the present invention or salts thereof are useful as agricultural and horticultural herbicides, thereby completing the present invention.

[0006] That is, the present invention is [1] General formula (1): [ka] {In the formula, Q represents Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, Q10, Q11, Q12, Q13, Q14, Q15, Q16, Q17 or Q18. [ka] (In the formula, R 1 teeth, (a1) halogen atoms; (a2) (C1-C6) alkyl group; (a3) (C2-C6) alkenyl group; (a4) (C2-C6)alkynyl group; (a5) (C3-C6) cycloalkyl group; (a6) halo(C1-C6)alkyl group; (a7) halo(C2-C6)alkenyl group; (a8) halo(C2-C6)alkynyl group; (a9) halo(C3-C6)cycloalkyl group; (a10) dioxolanyl group; (a11) a dioxanyl group; (a12) Dioxepanyl group; (a13) dihydropyranyl group; (a14) tetrahydropyranyl group; (a15) tetrahydrothiopyranyl group; (a16) piperidinyl group; (a17) a substituted piperidinyl group having, on the ring, 1 to 3 substituents independently selected from the group consisting of a (C1-C6) alkyl group, a (C1-C6) alkylcarbonyl group, and a (C1-C6) alkoxycarbonyl group; (a18) thienyl group; (a19) a substituted thienyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a20) a thiazolyl group; (a21) a substituted thiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a22) Thiadiazolyl group; (a23) a substituted thiadiazolyl group having, on the ring, one substituent independently selected from the substituent group Y; (a24) Pyrazolyl group; (a25) a substituted pyrazolyl group having, on the ring, 1 to 3 substituents independently selected from a substituent group Y; (a26) Phenyl group; (a27) a substituted phenyl group having, on the ring, 1 to 5 substituents independently selected from a substituent group Y; (a28) pyridyl group; (a29) a substituted pyridyl group having, on the ring, 1 to 4 substituents independently selected from a substituent group Y; (a30) a pyridazinyl group; (a31) a substituted pyridazinyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a32) a pyrimidinyl group; (a33) a substituted pyrimidinyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a34) pyrazinyl group; (a35) a substituted pyrazinyl group having, on the ring, 1 to 3 substituents independently selected from a substituent group Y; (a36) amino group; (a37) carboxyl group; (a38) (C1-C6)alkoxy group; (a39) a halo(C1-C6)alkoxy group; (a40) (C1-C6) alkylsulfanyl group; (a41) (C1-C6) alkylsulfinyl group; (a42) (C1-C6) alkylsulfonyl group; (a43) (C3-C6)cycloalkenyl group; (a44) (C1-C6)alkoxy(C1-C6)alkyl group; (a45) (C1-C6) alkylsulfanyl(C1-C6) alkyl group; (a46) (C1-C6) alkylsulfinyl(C1-C6) alkyl group; (a47) (C1-C6) alkylsulfonyl(C1-C6) alkyl group; (a48) (C1-C6) alkylcarbonyl group; (a49) (C1-C6)alkoxycarbonyl group; (a50) halo(C1-C6)alkylcarbonyl group; (a51) a halo(C1-C6)alkoxycarbonyl group; (a52) Phenylcarbonyl group; (a53) a substituted phenylcarbonyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a54) phenylaminocarbonyl group; (a55) a substituted phenylaminocarbonyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a56) benzhydrylideneamino group; (a57) oxopyrrolidinyl group; (a58) oxopyridyl group; (a59) a substituted dioxolanyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (a60) a substituted dioxanyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (a61) furanyl group; (a62) a substituted furanyl group having, on the ring, 1 to 3 substituents independently selected from a substituent group Y; (a63) isothiazolyl group; (a64) a substituted isothiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a65) an oxazolyl group; (a66) a substituted oxazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a67) Isoxazolyl group; (a68) a substituted isoxazolyl group having, on the ring, 1 to 2 substituents independently selected from a substituent group Y; (a69) quinolinyl group; (a70) a substituted quinolinyl group having, on the ring, 1 to 6 substituents each independently selected from a substituent group Y; (a71) Benzothienyl group; (a72) a substituted benzothienyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a73) Phenoxy group; (a74) a substituted phenoxy group having, on the ring, 1 to 5 substituents independently selected from a substituent group Y; (a75) phenyl(C1-C6) alkyl group; (a76) a substituted phenyl(C1-C6)alkyl group having, on the ring, 1 to 5 substituents each independently selected from the substituent group Y; (a77) Phenyl(C1-C6)alkoxy group; (a78) a substituted phenyl(C1-C6)alkoxy group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a79) (C1-C6) alkylamino group; (a80) halo(C1-C6)alkoxycarbonylamino group; (a81) oxazolidinonyl group; (a82) (C1-C6)alkoxy(C1-C6)alkoxy group; (a83) tetrahydrofuranyl(C1-C6)alkoxy group; or (a84) represents a (C3-C6)cycloalkyl(C1-C6)alkoxy group. R 2 teeth, (b1) hydrogen atom; (b2) a halogen atom; or (b3) (C1-C6) alkyl group. R 2a teeth, (b1') a hydrogen atom; or (b2') represents a (C1-C6) alkyl group. R 3 teeth, (c1) hydrogen atom; (c2) halogen atoms; (c3) hydroxyl group; (c4) (C1-C6) alkyl group; (c5) a (C2-C6) alkenyl group; (c6) (C2-C6) alkynyl group; (c7) (C3-C6) cycloalkyl group; (c8) halo(C1-C6)alkyl group; (c9) a halo(C2-C6)alkenyl group; (c10) halo(C2-C6)alkynyl group; (c11) halo(C3-C6)cycloalkyl group; (c12) (C1-C6)alkoxy group; (c13) (C1-C6) alkylsulfanyl group; (c14) (C1-C6) alkylsulfinyl group; (c15) (C1-C6) alkylsulfonyl group; (c16) halo(C1-C6)alkoxy group; (c17) a halo(C1-C6)alkylsulfanyl group; (c18) halo(C1-C6)alkylsulfinyl group; (c19) halo(C1-C6)alkylsulfonyl group; (c20) a (C1-C6) alkoxycarbonyl group; or (c21) a (C1-C6) alkylamino group, R 2 and R 3 may be bonded to each other to form a 5- or 6-membered ring. R 3a teeth, (c1') a hydrogen atom; or (c2') represents a (C1-C6) alkyl group. The substituent group Y is (d1) halogen atoms; (d2) cyano group; (d3) nitro group; (d4) amino group; (d5) (C1-C6) alkyl group; (d6) (C2-C6) alkenyl group; (d7) (C2-C6)alkynyl group; (d8) (C3-C6) cycloalkyl group; (d9) halo(C1-C6)alkyl group; (d10) halo(C2-C6)alkenyl group; (d11) halo(C2-C6)alkynyl group; (d12) halo(C3-C6)cycloalkyl group; (d13) (C1-C6)alkoxy group; (d14) (C1-C6) alkylsulfanyl group; (d15) (C1-C6) alkylsulfinyl group; (d16) (C1-C6) alkylsulfonyl group; (d17) halo(C1-C6)alkoxy group; (d18) halo(C1-C6)alkylsulfanyl group; (d19) halo(C1-C6)alkylsulfinyl group; (d20) halo(C1-C6)alkylsulfonyl group; (d21) N‐((C1-C6) alkylcarbonyl)amino group; (d22) N,N-di((C1-C6)alkylcarbonyl)amino group (the (C1-C6)alkylcarbonyl may be the same or different); (d23) di(C1-C6)alkoxyphosphanyl group (the (C1-C6)alkoxy may be the same or different); (d24) imidazolyl group; (d25) an imidazolyl group having, on the ring, 1 to 3 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (d26) Phenyl group; (d27) a phenyl group having on the ring 1 to 5 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (d28) pyridyl group; (d29) a pyridyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (d30) di(C1-C6) alkylamino group; (d31) (C1-C6)alkoxycarbonyl group; and (d32) Two adjacent substituents Y taken together form a methylenedioxy group which may be substituted with 1 to 2 substituents selected from the group consisting of a halogen atom, a phenyl group, and a (C1-C6) alkyl group. ● represents the binding site with D. ); R 4 teeth, (e1) hydrogen atom; (e2) amino group; (e3) (C1-C6) alkyl group; (e4) N-(C1-C6) alkylamino group; (e5) N,N-di(C1-C6)alkylamino group (the (C1-C6)alkyl may be the same or different); (e6) N‐((C1-C6) alkylcarbonyl)amino group; (e7) N,N-di((C1-C6)alkylcarbonyl)amino group (the (C1-C6)alkylcarbonyl may be the same or different); (e8) N-(halo(C1-C6)alkylcarbonyl)amino group; (e9) N-((C1-C6)alkoxycarbonyl)amino group; or (e10) An N-(C1-C6) alkyl-N-((C1-C6) alkylcarbonyl) amino group. R 5 teeth, (f1) (C1-C6) alkyl group; (f2) (C2-C6) alkenyl group; (f3) (C2-C6)alkynyl group; (f4) (C3-C6) cycloalkyl group; (f5) halo(C1-C6)alkyl groups; (f6) halo(C2-C6)alkenyl group; (f7) halo(C2-C6)alkynyl group; (f8) halo(C3-C6)cycloalkyl group; (f9) (C3-C6)cycloalkyl(C1-C6)alkyl group; (f10) (C1-C6)alkoxy(C1-C6)alkyl group; (f11) (C1-C6) alkylsulfanyl(C1-C6) alkyl group; (f12) (C1-C6) alkylsulfinyl(C1-C6) alkyl group; (f13) (C1-C6) alkylsulfonyl(C1-C6) alkyl group; or (f14) represents a phenyl (C1-C6) alkyl group. A is, (g1) (C1-C6)alkoxy group; (g2) a halo(C1-C6)alkoxy group; (g3) N‐(C1-C6) alkylaminocarbonyl group; (g4) N,N-di(C1-C6)alkylaminocarbonyl group (the (C1-C6)alkylcarbonyl may be the same or different); (g5) CO2R 7 (In the formula, R 7 teeth, (h1) hydrogen atom, (h2) (C1-C6) alkyl group, (h3) a (C2-C6) alkenyl group, (h4) a (C2-C6)alkynyl group, (h5) (C3-C6) cycloalkyl group, (h6) halo(C1-C6)alkyl group, (h7) a halo(C2-C6)alkenyl group, (h8) a halo(C2-C6)alkynyl group, (h9) a halo(C3-C6)cycloalkyl group, or (h10) represents a phenyl (C1-C6) alkyl group; (g6) SO n R 8 (In the formula, R 8 teeth, (i1) (C1-C6) alkyl group, (i2) a (C2-C6) alkenyl group, (i3) a (C2-C6)alkynyl group, (i4) (C3-C6) cycloalkyl groups, (i5) halo(C1-C6)alkyl group, (i6) a halo(C2-C6)alkenyl group, (i7) a halo(C2-C6)alkynyl group, (i8) a halo(C3-C6)cycloalkyl group, or (i9) (C1-C6) alkylcarbonyl (C1-C6) alkyl group. n represents 0, 1, or 2; or (g7) SO2N(R 9 )R 10 (In the formula, R 9 and R 10 teeth, (j1) hydrogen atom, (j2) (C1-C6) alkyl group, (j3) a (C2-C6) alkenyl group, (j4) a (C2-C6)alkynyl group, (j5) (C3-C6) cycloalkyl group, (j6) halo(C1-C6)alkyl group, (j7) a halo(C2-C6)alkenyl group, (j8) a halo(C2-C6)alkynyl group, (j9) halo(C3-C6)cycloalkyl group, (j10) Phenyl(C1-C6) alkyl group (j11) (C1-C6) alkylcarbonyl group, (j12) (C1-C6)alkoxycarbonyl group, (j13) a halo(C1-C6)alkylcarbonyl group, or (j14) a halo(C1-C6)alkoxycarbonyl group; R 9 and R 10 may be the same or different. A, Q, and C(R 4 )=N~OR 5 D substituted with represents a ring D1, D2, D3, or D4. [ka] (In the formula, R 6a and R 6b teeth, (k1) hydrogen atom; (k2) a halogen atom; or (k3) represents a (C1-C6) alkyl group, R 6a and R 6b may be the same or different.)} or a salt thereof.

[0007] [2] Q and D are the same as in [1] above, R 1 but, (a1) halogen atoms; (a2) (C1-C6) alkyl group; (a3) (C2-C6) alkenyl group; (a5) (C3-C6) cycloalkyl group; (a9) halo(C3-C6)cycloalkyl group; (a10) dioxolanyl group; (a11) a dioxanyl group; (a12) Dioxepanyl group; (a13) dihydropyranyl group; (a14) tetrahydropyranyl group; (a15) tetrahydrothiopyranyl group; (a16) piperidinyl group; (a17) a substituted piperidinyl group having, on the ring, 1 to 3 substituents independently selected from the group consisting of a (C1-C6) alkyl group, a (C1-C6) alkylcarbonyl group, and a (C1-C6) alkoxycarbonyl group; (a18) thienyl group; (a19) a substituted thienyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a20) a thiazolyl group; (a21) a substituted thiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a22) Thiadiazolyl group; (a23) a substituted thiadiazolyl group having, on the ring, one substituent independently selected from the substituent group Y; (a24) Pyrazolyl group; (a25) a substituted pyrazolyl group having, on the ring, 1 to 3 substituents independently selected from a substituent group Y; (a26) Phenyl group; (a27) a substituted phenyl group having, on the ring, 1 to 5 substituents independently selected from a substituent group Y; (a28) pyridyl group; (a29) a substituted pyridyl group having, on the ring, 1 to 4 substituents independently selected from a substituent group Y; (a30) a pyridazinyl group; (a31) a substituted pyridazinyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a32) a pyrimidinyl group; (a33) a substituted pyrimidinyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a34) pyrazinyl group; (a35) a substituted pyrazinyl group having, on the ring, 1 to 3 substituents independently selected from a substituent group Y; (a36) amino group; (a37) carboxyl group; (a38) (C1-C6)alkoxy group; (a39) a halo(C1-C6)alkoxy group; (a40) (C1-C6) alkylsulfanyl group; (a41) (C1-C6) alkylsulfinyl group; (a42) (C1-C6) alkylsulfonyl group; (a43) (C3-C6)cycloalkenyl group; (a44) (C1-C6)alkoxy(C1-C6)alkyl group; (a45) (C1-C6) alkylsulfanyl(C1-C6) alkyl group; (a46) (C1-C6) alkylsulfinyl(C1-C6) alkyl group; (a47) (C1-C6) alkylsulfonyl(C1-C6) alkyl group; (a48) (C1-C6) alkylcarbonyl group; (a49) (C1-C6)alkoxycarbonyl group; (a50) halo(C1-C6)alkylcarbonyl group; (a51) a halo(C1-C6)alkoxycarbonyl group; (a52) Phenylcarbonyl group; (a53) a substituted phenylcarbonyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a54) phenylaminocarbonyl group; (a55) a substituted phenylaminocarbonyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a56) benzhydrylideneamino group; (a57) oxopyrrolidinyl group; (a58) oxopyridyl group; (a59) a substituted dioxolanyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (a60) a substituted dioxanyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (a61) furanyl group; (a62) a substituted furanyl group having, on the ring, 1 to 3 substituents independently selected from a substituent group Y; (a63) isothiazolyl group; (a64) a substituted isothiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a69) quinolinyl group; (a70) a substituted quinolinyl group having, on the ring, 1 to 6 substituents each independently selected from a substituent group Y; (a71) Benzothienyl group; (a72) a substituted benzothienyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a73) Phenoxy group; (a74) a substituted phenoxy group having, on the ring, 1 to 5 substituents independently selected from a substituent group Y; (a75) phenyl(C1-C6) alkyl group; (a76) a substituted phenyl(C1-C6)alkyl group having, on the ring, 1 to 5 substituents each independently selected from the substituent group Y; (a77) Phenyl(C1-C6)alkoxy group; (a78) a substituted phenyl(C1-C6)alkoxy group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a79) (C1-C6) alkylamino group; (a80) halo(C1-C6)alkoxycarbonylamino group; (a81) oxazolidinonyl group; (a82) (C1-C6)alkoxy(C1-C6)alkoxy group; (a83) tetrahydrofuranyl(C1-C6)alkoxy group; or (a84) a (C3-C6)cycloalkyl(C1-C6)alkoxy group, R 2 but, (b1) hydrogen atom; (b2) a halogen atom; or (b3) a (C1-C6) alkyl group; R 2a but, (b1') a hydrogen atom; or (b2') a (C1-C6) alkyl group; R 3 but, (c1) hydrogen atom; (c2) halogen atoms; (c3) hydroxyl group; (c4) (C1-C6) alkyl group; (c5) a (C2-C6) alkenyl group; (c6) (C2-C6) alkynyl group; (c7) (C3-C6) cycloalkyl group; (c8) halo(C1-C6)alkyl group; (c12) (C1-C6)alkoxy group; (c13) (C1-C6) alkylsulfanyl group; (c14) (C1-C6) alkylsulfinyl group; (c15) (C1-C6) alkylsulfonyl group; (c16) halo(C1-C6)alkoxy group; (c17) a halo(C1-C6)alkylsulfanyl group; (c18) halo(C1-C6)alkylsulfinyl group; (c19) halo(C1-C6)alkylsulfonyl group; (c20) a (C1-C6) alkoxycarbonyl group; or (c21) a (C1-C6) alkylamino group, R 2 and R 3 may be bonded to each other to form a 5- or 6-membered ring, R 3a but, (c1') a hydrogen atom; or (c2') a (C1-C6) alkyl group; The substituent group Y is (d1) halogen atoms; (d2) cyano group; (d3) nitro group; (d4) amino group; (d5) (C1-C6) alkyl group; (d8) (C3-C6) cycloalkyl group; (d9) halo(C1-C6)alkyl group; (d13) (C1-C6)alkoxy group; (d14) (C1-C6) alkylsulfanyl group; (d15) (C1-C6) alkylsulfinyl group; (d16) (C1-C6) alkylsulfonyl group; (d17) halo(C1-C6)alkoxy group; (d18) halo(C1-C6)alkylsulfanyl group; (d19) halo(C1-C6)alkylsulfinyl group; (d20) halo(C1-C6)alkylsulfonyl group; (d21) N‐((C1-C6) alkylcarbonyl)amino group; (d22) N,N-di((C1-C6)alkylcarbonyl)amino group (the (C1-C6)alkylcarbonyl may be the same or different); (d23) di(C1-C6)alkoxyphosphanyl group (the (C1-C6)alkoxy may be the same or different); (d24) imidazolyl group; (d25) an imidazolyl group having, on the ring, 1 to 3 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (d26) Phenyl group; (d27) a phenyl group having on the ring 1 to 5 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (d28) pyridyl group; (d29) a pyridyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (d30) di(C1-C6) alkylamino group; (d31) (C1-C6)alkoxycarbonyl group; and (d32) Two adjacent substituents Y taken together form a methylenedioxy group which may be substituted with 1 to 2 substituents selected from the group consisting of a halogen atom, a phenyl group, and a (C1-C6) alkyl group; R 4 but, (e1) hydrogen atom; (e2) amino group; (e3) (C1-C6) alkyl group; (e4) N-(C1-C6) alkylamino group; (e5) N,N-di(C1-C6)alkylamino group (the (C1-C6)alkyl may be the same or different); (e6) N‐((C1-C6) alkylcarbonyl)amino group; (e7) N,N-di((C1-C6)alkylcarbonyl)amino group (the (C1-C6)alkylcarbonyl may be the same or different); or (e8) N-(halo(C1-C6)alkylcarbonyl)amino group, R 5 but, (f1) (C1-C6) alkyl group; (f2) (C2-C6) alkenyl group; (f3) (C2-C6)alkynyl group; (f4) (C3-C6) cycloalkyl group; (f5) halo(C1-C6)alkyl groups; (f9) (C3-C6)cycloalkyl(C1-C6)alkyl group; (f10) (C1-C6)alkoxy(C1-C6)alkyl group; (f11) (C1-C6) alkylsulfanyl(C1-C6) alkyl group; (f12) (C1-C6) alkylsulfinyl(C1-C6) alkyl group; or (f13) (C1-C6) alkylsulfonyl(C1-C6) alkyl group, A, (g1) (C1-C6)alkoxy group; (g3) N‐(C1-C6) alkylaminocarbonyl group; (g4) N,N-di(C1-C6)alkylaminocarbonyl group (the (C1-C6)alkylcarbonyl may be the same or different); (g5') CO2R 7 (In the formula, R 7 teeth, (h1) hydrogen atom, (h2) (C1-C6) alkyl group, (h3) a (C2-C6) alkenyl group, (h4) a (C2-C6)alkynyl group, (h5) (C3-C6) cycloalkyl group, (h6) a halo(C1-C6)alkyl group, or (h10) represents a phenyl (C1-C6) alkyl group; (g6') SO n R 8 (In the formula, R 8 teeth, (i1) (C1-C6) alkyl group, (i2) a (C2-C6) alkenyl group, (i3) a (C2-C6)alkynyl group, (i4) (C3-C6) cycloalkyl groups, (i5) a halo(C1-C6)alkyl group, or (i9) (C1-C6) alkylcarbonyl (C1-C6) alkyl group. n represents 0, 1, or 2; or (g7') SO2N(R9 )R 10 (In the formula, R 9 and R 10 teeth, (j1) hydrogen atom, (j2) (C1-C6) alkyl group, (j3) a (C2-C6) alkenyl group, (j4) a (C2-C6)alkynyl group, (j5) (C3-C6) cycloalkyl group, (j11) (C1-C6) alkylcarbonyl group, (j12) (C1-C6)alkoxycarbonyl group, (j13) a halo(C1-C6)alkylcarbonyl group, or (j14) a halo(C1-C6)alkoxycarbonyl group; R 9 and R 10 may be the same or different. R 6a and R 6b but, (k1) hydrogen atom; (k2) a halogen atom; or (k3) a (C1-C6) alkyl group, R 6a and R 6b may be the same or different, the compound or salt thereof according to [1] above.

[0008] [3] Q and D are the same as [1] above, R 1 but, (a1) halogen atoms; (a2) (C1-C6) alkyl group; (a3) (C2-C6) alkenyl group; (a5) (C3-C6) cycloalkyl group; (a13) dihydropyranyl group; (a14) tetrahydropyranyl group; (a16) piperidinyl group; (a18) thienyl group; (a19) a substituted thienyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a20) a thiazolyl group; (a21) a substituted thiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a22) Thiadiazolyl group; (a23) a substituted thiadiazolyl group having, on the ring, one substituent independently selected from the substituent group Y; (a24) Pyrazolyl group; (a25) a substituted pyrazolyl group having, on the ring, 1 to 3 substituents independently selected from a substituent group Y; (a26) Phenyl group; (a27) a substituted phenyl group having, on the ring, 1 to 5 substituents independently selected from a substituent group Y; (a28) pyridyl group; (a29) a substituted pyridyl group having, on the ring, 1 to 4 substituents independently selected from a substituent group Y; (a32) a pyrimidinyl group; (a34) pyrazinyl group; (a36) amino group; (a37) carboxyl group; (a38) (C1-C6)alkoxy group; (a39) a halo(C1-C6)alkoxy group; (a40) (C1-C6) alkylsulfanyl group; (a42) (C1-C6) alkylsulfonyl group; (a43) (C3-C6)cycloalkenyl group; (a44) (C1-C6)alkoxy(C1-C6)alkyl group; (a45) (C1-C6) alkylsulfanyl(C1-C6) alkyl group; (a46) (C1-C6) alkylsulfinyl(C1-C6) alkyl group; (a47) (C1-C6) alkylsulfonyl(C1-C6) alkyl group; (a48) (C1-C6) alkylcarbonyl group; (a49) (C1-C6)alkoxycarbonyl group; (a52) Phenylcarbonyl group; (a54) phenylaminocarbonyl group; (a56) benzhydrylideneamino group; (a57) oxopyrrolidinyl group; (a58) oxopyridyl group; (a59) a substituted dioxolanyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (a60) a substituted dioxanyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (a61) furanyl group; (a63) isothiazolyl group; (a64) a substituted isothiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a69) quinolinyl group; (a71) Benzothienyl group; (a74) a substituted phenoxy group having, on the ring, 1 to 5 substituents independently selected from a substituent group Y; (a75) phenyl(C1-C6) alkyl group; (a82) (C1-C6)alkoxy(C1-C6)alkoxy group; (a83) tetrahydrofuranyl(C1-C6)alkoxy group; or (a84) a (C3-C6)cycloalkyl(C1-C6)alkoxy group, R 2 but, (b1) hydrogen atom; (b2) a halogen atom; or (b3) a (C1-C6) alkyl group; R 2a but, (b1') a hydrogen atom, R 3 but, (c1) hydrogen atom; (c2) halogen atoms; (c3) hydroxyl group; (c4) (C1-C6) alkyl group; (c5) a (C2-C6) alkenyl group; (c8) halo(C1-C6)alkyl group; (c12) (C1-C6)alkoxy group; (c13) (C1-C6) alkylsulfanyl group; (c14) (C1-C6) alkylsulfinyl group; (c15) a (C1-C6) alkylsulfonyl group; or (c20) a (C1-C6) alkoxycarbonyl group, R 2 and R 3 may be bonded to each other to form a 5- or 6-membered ring, R 3a but, (c1') a hydrogen atom, The substituent group Y is (d1) halogen atoms; (d2) cyano group; (d3) nitro group; (d4) amino group; (d5) (C1-C6) alkyl group; (d8) (C3-C6) cycloalkyl group; (d9) halo(C1-C6)alkyl group; (d13) (C1-C6)alkoxy group; (d14) (C1-C6) alkylsulfanyl group; (d17) halo(C1-C6)alkoxy group; (d21) N‐((C1-C6) alkylcarbonyl)amino group; (d24) imidazolyl group; (d26) Phenyl group; (d28) pyridyl group; (d30) di(C1-C6) alkylamino group; (d31) (C1-C6)alkoxycarbonyl group; and (d32) Two adjacent substituents Y taken together form a methylenedioxy group which may be substituted with 1 to 2 substituents selected from the group consisting of a halogen atom, a phenyl group, and a (C1-C6) alkyl group; R 4 but, (e2) amino group; (e3) (C1-C6) alkyl group; (e6) N‐((C1-C6) alkylcarbonyl)amino group; (e7) N,N-di((C1-C6)alkylcarbonyl)amino group (the (C1-C6)alkylcarbonyl may be the same or different); or (e8) N-(halo(C1-C6)alkylcarbonyl)amino group, R 5 but, (f1) (C1-C6) alkyl group; (f5) halo(C1-C6)alkyl group; or (f10) (C1-C6)alkoxy(C1-C6)alkyl group, A, (g1) (C1-C6)alkoxy group; (g4) N,N-di(C1-C6)alkylaminocarbonyl group (the (C1-C6)alkylcarbonyl may be the same or different); (g5'') CO2R 7 (In the formula, R 7 teeth, (h1) a hydrogen atom, or (h2) (C1-C6) alkyl group; (g6'') SO n R 8 (In the formula, R 8 teeth, (i1) a (C1-C6) alkyl group, or (i9) (C1-C6) alkylcarbonyl (C1-C6) alkyl group. n represents 2; or (g7'') SO2N(R 9 )R 10 (In the formula, R 9 and R 10 teeth, (j1) hydrogen atom, (j2) (C1-C6) alkyl group, (j11) a (C1-C6) alkylcarbonyl group, or (j12) (C1-C6) alkoxycarbonyl group. R 9 and R 10 may be the same or different. R 6a and R 6b but, (k1) The compound or salt thereof according to the above [1], wherein R is a hydrogen atom.

[0009] [4] R 1 , R 2 , R 3 , R 4 , R 5 , R 6a , R 6b , A, and the substituent group Y are the same as those in [1] above, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, or Q10; The compound or salt thereof according to [1] above, wherein D is D1 or D2. [5] R 1 , R 2 , R 3 , R 4 , R 5 , R 6a , R 6b , A, and the substituent group Y are the same as those in [1] above, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, or Q10; The compound or salt thereof according to [1] above, wherein D is D1. [6] R 1 , R 2 , R 3 , R 4 , R 5 , R 6a , R 6b , A, and the substituent group Y are the same as those in [2] above, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, or Q10; The compound or salt thereof according to [2] above, wherein D is D1 or D2. [7] R 1 , R 2 , R 3 , R 4 , R 5 , R 6a , R 6b , A, and the substituent group Y are the same as those in [2] above, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, or Q10; The compound or salt thereof according to [2] above, wherein D is D1. [8] R 1 , R 2 , R 3 , R 4 , R 5 , R 6a , R 6b , A, and the substituent group Y are the same as those in [3] above, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, or Q10; The compound or salt thereof according to [3] above, wherein D is D1 or D2. [9] R 1 , R 2 , R 3 , R 4 , R 5 , R 6a , R 6b , A, and the substituent group Y are the same as those in [3] above, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, or Q10; The compound or salt thereof according to [3] above, wherein D is D1.

[0010]

[10] An agricultural and horticultural herbicide comprising the compound or salt thereof according to any one of the above [1] to [9] as an active ingredient.

[11] A method for using the agricultural and horticultural herbicide according to

[10] above, which comprises applying an effective amount of the agricultural and horticultural herbicide to weeds, soil, paddy fields, or cultivation carriers.

[12] A method for controlling weeds, comprising applying an effective amount of the agricultural and horticultural herbicide according to

[10] above to weeds, soil, paddy fields, or cultivation carriers. [Effects of the Invention]

[0011] The nitrogen-containing heterocyclic compound having an oxime group or a salt thereof of the present invention has excellent effects as an agricultural and horticultural herbicide. DETAILED DESCRIPTION OF THE INVENTION

[0012] In the definition of the general formula (1) of the compound of the present invention, "halo" means a "halogen atom", and is usually exemplified by a chlorine atom, a bromine atom, an iodine atom, or a fluorine atom.

[0013] The term "(C1-C6) alkyl group" refers to a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, secondary butyl group, tertiary butyl group, normal pentyl group, isopentyl group, tertiary pentyl group, neopentyl group, 2,3-dimethylpropyl group, 1-ethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, normal hexyl group, isohexyl group, 2-hexyl group, 3-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1,2-trimethylpropyl group, or 3,3-dimethylbutyl group.

[0014] The term "(C2-C6) alkenyl group" refers to a linear or branched alkenyl group having 2 to 6 carbon atoms, such as a vinyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 2-methyl-2-propenyl group, a 1-methyl-2-propenyl group, a 2-methyl-1-propenyl group, a pentenyl group, a 1-hexenyl group, or a 3,3-dimethyl-1-butenyl group. The term "C6) alkynyl group" refers to a straight-chain or branched-chain alkynyl group having 2 to 6 carbon atoms, such as an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 3-methyl-1-propynyl group, a 2-methyl-3-propynyl group, a pentynyl group, a 1-hexynyl group, a 3-methyl-1-butynyl group, or a 3,3-dimethyl-1-butynyl group.

[0015] The "(C3-C6) cycloalkyl group" refers to a cyclic alkyl group having 3 to 6 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group. Examples of the "(C1-C6) alkoxy group" include a methoxy group, an ethoxy group, a normal propoxy group, an isopropoxy group, a normal butoxy group, a secondary butoxy group, a tertiary butoxy group, a normal pentyloxy group, an isopentyloxy group, a tertiary pentyloxy group, a neopentyloxy group, a 2,3-dimethylpropyloxy group, a 1-ethylpropyloxy group, a 1-methylbutyloxy group, a normal alkoxy group, a 2,3-dimethylpropyloxy group, a 1-ethylpropyloxy group, a 1-methylbutyloxy group, a 2,3-dimethyl ... It refers to a linear or branched alkoxy group having 1 to 6 carbon atoms, such as a hexyloxy group, an isohexyloxy group, or a 1,1,2-trimethylpropyloxy group. An example of a "(C2-C6) alkenyloxy group" is a linear or branched alkenyloxy group having 2 to 6 carbon atoms, such as a propenyloxy group, a butenyloxy group, a pentenyloxy group, or a hexenyloxy group. An example of a "(C2-C6) alkynyloxy group" is a linear or branched alkynyloxy group having 2 to 6 carbon atoms, such as a propynyloxy group, a butynyloxy group, a pentynyloxy group, or a hexynyloxy group.

[0016] The term "(C1-C6) alkylsulfanyl group" refers to a linear or branched alkylsulfanyl group having 1 to 6 carbon atoms, such as a methylthio group, an ethylthio group, a normal propylthio group, an isopropylthio group, a normal butylthio group, a secondary butylthio group, a tertiary butylthio group, a normal pentylthio group, an isopentylthio group, a tertiary pentylthio group, a neopentylthio group, a 2,3-dimethylpropylthio group, a 1-ethylpropylthio group, a 1-methylbutylthio group, a normal hexylthio group, an isohexylthio group, or a 1,1,2-trimethylpropylthio group.

[0017] The term "(C1-C6) alkylsulfinyl group" refers to a linear or branched alkylsulfinyl group having 1 to 6 carbon atoms, such as a methylsulfinyl group, ethylsulfinyl group, normal propylsulfinyl group, isopropylsulfinyl group, normal butylsulfinyl group, secondary butylsulfinyl group, tertiary butylsulfinyl group, normal pentylsulfinyl group, isopentylsulfinyl group, tertiary pentylsulfinyl group, neopentylsulfinyl group, 2,3-dimethylpropylsulfinyl group, 1-ethylpropylsulfinyl group, 1-methylbutylsulfinyl group, normal hexylsulfinyl group, isohexylsulfinyl group, or 1,1,2-trimethylpropylsulfinyl group.

[0018] The term "(C1-C6) alkylsulfonyl group" refers to a linear or branched alkylsulfonyl group having 1 to 6 carbon atoms, such as a methylsulfonyl group, ethylsulfonyl group, normal propylsulfonyl group, isopropylsulfonyl group, normal butylsulfonyl group, secondary butylsulfonyl group, tertiary butylsulfonyl group, normal pentylsulfonyl group, isopentylsulfonyl group, tertiary pentylsulfonyl group, neopentylsulfonyl group, 2,3-dimethylpropylsulfonyl group, 1-ethylpropylsulfonyl group, 1-methylbutylsulfonyl group, normal hexylsulfonyl group, isohexylsulfonyl group, or 1,1,2-trimethylpropylsulfonyl group.

[0019] The term "(C1-C6) alkylcarbonyl group" refers to an alkylcarbonyl group having 2 to 7 carbon atoms, such as an alkylcarbonyl group having the above-mentioned (C1-C6) alkyl group, such as an acetyl group, a propanoyl group, a butanoyl group, a 2-methylpropanoyl group, a pentanoyl group, a 2-methylbutanoyl group, a 3-methylbutanoyl group, a pivaloyl group, or a hexanoyl group.

[0020] The term "(C1-C6) alkylcarbonyloxy group" refers to an alkylcarbonyloxy group having 2 to 7 carbon atoms, such as an alkylcarbonyloxy group having the above-mentioned (C1-C6) alkyl group, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a 2-methylpropanoyloxy group, a pentanoyloxy group, a 2-methylbutanoyloxy group, a 3-methylbutanoyloxy group, a pivaloyloxy group, or a hexanoyloxy group.

[0021] The term "N-(C1-C6) alkylaminocarbonyl group" refers to an alkylaminocarbonyl group having 2 to 7 carbon atoms and having a linear or branched alkyl group having 1 to 6 carbon atoms, such as an N-methylaminocarbonyl group, N-ethylaminocarbonyl group, N-normal propylaminocarbonyl group, N-isopropylaminocarbonyl group, N-normal butylaminocarbonyl group, N-isobutylaminocarbonyl group, N-secondary butylaminocarbonyl group, N-tertiary butylaminocarbonyl group, N-normal pentylaminocarbonyl group, N-isopentylaminocarbonyl group, N-tertiary pentylaminocarbonyl group, N-neopenthylaminocarbonyl group, N-normal hexylaminocarbonyl group, or N-isohexylaminocarbonyl group.

[0022] Examples of the "N,N-di(C1-C6)alkylaminocarbonyl group" include an N,N-dimethylaminocarbonyl group, an N,N-diethylaminocarbonyl group, an N,N-di-normal propylaminocarbonyl group, an N,N-diisopropylaminocarbonyl group, an N,N-di-normal butylaminocarbonyl group, an N,N-di-secondary butylaminocarbonyl group, an N,N-di-tertiary butylaminocarbonyl group, an N-methyl-N-ethylaminocarbonyl group, an N-methyl-N-normal propylaminocarbonyl group, an N-methyl-N-isopropylaminocarbonyl group, an N-methyl-N-normal butylaminocarbonyl group, an N-methyl-N-secondary butylaminocarbonyl group, and an N-methyl-N-tertiary butylaminocarbonyl group. and dialkylaminocarbonyl groups having 3 to 13 carbon atoms and having a linear or branched alkyl group having 1 to 6 carbon atoms, such as an N-methyl-N-normal pentylaminocarbonyl group, an N-methyl-N-isopentylaminocarbonyl group, an N-methyl-N-tertiary pentylaminocarbonyl group, an N-methyl-N-neopentylaminocarbonyl group, an N-methyl-N-(2,3-dimethylpropyl)aminocarbonyl group, an N-methyl-N-(1-ethylpropyl)aminocarbonyl group, an N-methyl-N-(1-methylbutyl)aminocarbonyl group, an N-methyl-N-normal hexylaminocarbonyl group, an N-methyl-N-isohexylaminocarbonyl group, or an N-methyl-N-(1,1,2-trimethylpropyl)aminocarbonyl group.

[0023] The term "(C1-C6)alkoxycarbonyl group" refers to an alkoxycarbonyl group having 2 to 7 carbon atoms, such as an alkoxycarbonyl group having the (C1-C6)alkoxy group, such as a methoxycarbonyl group, an ethoxycarbonyl group, a normal propoxycarbonyl group, an isopropoxycarbonyl group, a normal butoxycarbonyl group, an isobutoxycarbonyl group, a secondary butoxycarbonyl group, a tertiary butoxycarbonyl group, or a pentyloxycarbonyl group.

[0024] The above-mentioned "(C1-C6) alkyl group," "(C2-C6) alkenyl group," "(C2-C6) alkynyl group," "(C1-C6) alkoxy group," "(C1-C6) alkylsulfanyl group," "(C1-C6) alkylsulfinyl group," "(C1-C6) alkylsulfonyl group," "(C3-C6) cycloalkyl group," "(C1-C6) alkylcarbonyl group," "(C1-C6) alkoxycarbonyl group," "(C1-C6) alkylcarbonyloxy group," etc. may be substituted with one or more halogen atoms at substitutable positions, and when there are two or more halogen atoms substituted, the halogen atoms may be the same or different.

[0025] When substituted with a halogen atom, it is represented by the following: "halo(C1-C6)alkyl group," "halo(C2-C6)alkenyl group," "halo(C2-C6)alkynyl group," "halo(C1-C6)alkoxy group," "halo(C1-C6)alkylsulfanyl group," "halo(C1-C6)alkylsulfinyl group," "halo(C1-C6)alkylsulfonyl group," "halo(C3-C6)cycloalkyl group," "halo(C1-C6)alkylcarbonyl group," "halo(C1-C6)alkoxycarbonyl group," "halo(C1-C6)alkylcarbonyloxy group," etc.

[0026] In the present invention, expressions such as "(C1-C6)", "(C2-C6)", "(C3-C6)" and the like indicate the range of the number of carbon atoms of various substituents. Furthermore, the above definitions can also be applied to groups to which the above substituents are linked. For example, "(C1-C6)alkoxy(C1-C6)alkyl group" indicates that a linear or branched alkoxy group having 1 to 6 carbon atoms is linked to a linear or branched alkyl group having 1 to 6 carbon atoms.

[0027] Examples of salts of the compound represented by general formula (1) of the present invention include inorganic acid salts such as hydrochloride, sulfate, nitrate, and phosphate; organic acid salts such as acetate, fumarate, maleate, oxalate, methanesulfonate, benzenesulfonate, and paratoluenesulfonate; and salts with inorganic or organic bases such as sodium ion, potassium ion, calcium ion, and trimethylammonium.

[0028] The compound represented by general formula (1) of the present invention and its salts may have one or more asymmetric centers in their structural formula, and may exist as two or more optical isomers and diastereomers. The present invention encompasses all of the optical isomers and mixtures containing them in any ratio. Furthermore, the compound represented by general formula (1) of the present invention and its salts may exist as two or more geometric isomers derived from a carbon-carbon double bond and a carbon-nitrogen double bond in their structural formula, and the present invention encompasses all of the geometric isomers and mixtures containing them in any ratio. That is, the oxime group in the compound represented by general formula (1) of the present invention may be an E (entgegen) isomer, a Z (zusammen) isomer, or a mixture thereof.

[0029] In the compound of the present invention represented by general formula (1), preferred embodiments are shown below. Q is preferably Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, or Q10; More preferably, Examples include Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, and Q10.

[0030] R 1 Preferably, (a1) halogen atoms; (a2) (C1-C6) alkyl group; (a3) (C2-C6) alkenyl group; (a5) (C3-C6) cycloalkyl group; (a9) halo(C3-C6)cycloalkyl group; (a10) dioxolanyl group; (a11) a dioxanyl group; (a12) Dioxepanyl group; (a13) dihydropyranyl group; (a14) tetrahydropyranyl group; (a15) tetrahydrothiopyranyl group; (a16) piperidinyl group; (a17) a substituted piperidinyl group having, on the ring, 1 to 3 substituents independently selected from the group consisting of a (C1-C6) alkyl group, a (C1-C6) alkylcarbonyl group, and a (C1-C6) alkoxycarbonyl group; (a18) thienyl group; (a19) a substituted thienyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a20) a thiazolyl group; (a21) a substituted thiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a22) Thiadiazolyl group; (a23) a substituted thiadiazolyl group having, on the ring, one substituent independently selected from the substituent group Y; (a24) Pyrazolyl group; (a25) a substituted pyrazolyl group having, on the ring, 1 to 3 substituents independently selected from a substituent group Y; (a26) Phenyl group; (a27) a substituted phenyl group having, on the ring, 1 to 5 substituents independently selected from a substituent group Y; (a28) pyridyl group; (a29) a substituted pyridyl group having, on the ring, 1 to 4 substituents independently selected from a substituent group Y; (a30) a pyridazinyl group; (a31) a substituted pyridazinyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a32) a pyrimidinyl group; (a33) a substituted pyrimidinyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a34) pyrazinyl group; (a35) a substituted pyrazinyl group having, on the ring, 1 to 3 substituents independently selected from a substituent group Y; (a36) amino group; (a37) carboxyl group; (a38) (C1-C6)alkoxy group; (a39) a halo(C1-C6)alkoxy group; (a40) (C1-C6) alkylsulfanyl group; (a41) (C1-C6) alkylsulfinyl group; (a42) (C1-C6) alkylsulfonyl group; (a43) (C3-C6)cycloalkenyl group; (a44) (C1-C6)alkoxy(C1-C6)alkyl group; (a45) (C1-C6) alkylsulfanyl(C1-C6) alkyl group; (a46) (C1-C6) alkylsulfinyl(C1-C6) alkyl group; (a47) (C1-C6) alkylsulfonyl(C1-C6) alkyl group; (a48) (C1-C6) alkylcarbonyl group; (a49) (C1-C6)alkoxycarbonyl group; (a50) halo(C1-C6)alkylcarbonyl group; (a51) a halo(C1-C6)alkoxycarbonyl group; (a52) Phenylcarbonyl group; (a53) a substituted phenylcarbonyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a54) phenylaminocarbonyl group; (a55) a substituted phenylaminocarbonyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a56) benzhydrylideneamino group; (a57) oxopyrrolidinyl group; (a58) oxopyridyl group; (a59) a substituted dioxolanyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (a60) a substituted dioxanyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (a61) furanyl group; (a62) a substituted furanyl group having, on the ring, 1 to 3 substituents independently selected from a substituent group Y; (a63) isothiazolyl group; (a64) a substituted isothiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a69) quinolinyl group; (a70) a substituted quinolinyl group having, on the ring, 1 to 6 substituents each independently selected from a substituent group Y; (a71) Benzothienyl group; (a72) a substituted benzothienyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a73) Phenoxy group; (a74) a substituted phenoxy group having, on the ring, 1 to 5 substituents independently selected from a substituent group Y; (a75) phenyl(C1-C6) alkyl group; (a76) a substituted phenyl(C1-C6)alkyl group having, on the ring, 1 to 5 substituents each independently selected from the substituent group Y; (a77) Phenyl(C1-C6)alkoxy group; (a78) a substituted phenyl(C1-C6)alkoxy group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a79) (C1-C6) alkylamino group; (a80) halo(C1-C6)alkoxycarbonylamino group; (a81) oxazolidinonyl group; (a82) (C1-C6)alkoxy(C1-C6)alkoxy group; (a83) tetrahydrofuranyl(C1-C6)alkoxy group; or (a84) a (C3-C6)cycloalkyl(C1-C6)alkoxy group, More preferably, (a1) halogen atoms; (a2) (C1-C6) alkyl group; (a3) (C2-C6) alkenyl group; (a5) (C3-C6) cycloalkyl group; (a13) dihydropyranyl group; (a14) tetrahydropyranyl group; (a16) piperidinyl group; (a18) thienyl group; (a19) a substituted thienyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a20) a thiazolyl group; (a21) a substituted thiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a22) Thiadiazolyl group; (a23) a substituted thiadiazolyl group having, on the ring, one substituent independently selected from the substituent group Y; (a24) Pyrazolyl group; (a25) a substituted pyrazolyl group having, on the ring, 1 to 3 substituents independently selected from a substituent group Y; (a26) Phenyl group; (a27) a substituted phenyl group having, on the ring, 1 to 5 substituents independently selected from a substituent group Y; (a28) pyridyl group; (a29) a substituted pyridyl group having, on the ring, 1 to 4 substituents independently selected from a substituent group Y; (a32) a pyrimidinyl group; (a34) pyrazinyl group; (a36) amino group; (a37) carboxyl group; (a38) (C1-C6)alkoxy group; (a39) a halo(C1-C6)alkoxy group; (a40) (C1-C6) alkylsulfanyl group; (a42) (C1-C6) alkylsulfonyl group; (a43) (C3-C6)cycloalkenyl group; (a44) (C1-C6)alkoxy(C1-C6)alkyl group; (a45) (C1-C6) alkylsulfanyl(C1-C6) alkyl group; (a46) (C1-C6) alkylsulfinyl(C1-C6) alkyl group; (a47) (C1-C6) alkylsulfonyl(C1-C6) alkyl group; (a48) (C1-C6) alkylcarbonyl group; (a49) (C1-C6)alkoxycarbonyl group; (a52) Phenylcarbonyl group; (a54) phenylaminocarbonyl group; (a56) benzhydrylideneamino group; (a57) oxopyrrolidinyl group; (a58) oxopyridyl group; (a59) a substituted dioxolanyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (a60) a substituted dioxanyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (a61) furanyl group; (a63) isothiazolyl group; (a64) a substituted isothiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a69) quinolinyl group; (a71) Benzothienyl group; (a74) a substituted phenoxy group having, on the ring, 1 to 5 substituents independently selected from a substituent group Y; (a75) phenyl(C1-C6) alkyl group; (a82) (C1-C6)alkoxy(C1-C6)alkoxy group; (a83) tetrahydrofuranyl(C1-C6)alkoxy group; or (a84) (C3-C6)cycloalkyl(C1-C6)alkoxy groups can be mentioned.

[0031] R 2 Preferably, (b1) hydrogen atom; (b2) a halogen atom; or (b3) a (C1-C6) alkyl group; More preferably, (b1) a hydrogen atom; or (b2) Halogen atoms can be mentioned.

[0032] R 2a Preferably, (b1') a hydrogen atom; or (b2') a (C1-C6) alkyl group; More preferably, (b1') Hydrogen atoms can be mentioned.

[0033] R 3 Preferably, (c1) hydrogen atom; (c2) halogen atoms; (c3) hydroxyl group; (c4) (C1-C6) alkyl group; (c5) a (C2-C6) alkenyl group; (c6) (C2-C6) alkynyl group; (c7) (C3-C6) cycloalkyl group; (c8) halo(C1-C6)alkyl group; (c12) (C1-C6)alkoxy group; (c13) (C1-C6) alkylsulfanyl group; (c14) (C1-C6) alkylsulfinyl group; (c15) (C1-C6) alkylsulfonyl group; (c16) halo(C1-C6)alkoxy group; (c17) a halo(C1-C6)alkylsulfanyl group; (c18) halo(C1-C6)alkylsulfinyl group; (c19) halo(C1-C6)alkylsulfonyl group; (c20) a (C1-C6) alkoxycarbonyl group; or (c21) a (C1-C6) alkylamino group, Also, R 2 and R 3 may be bonded to each other to form a 5- or 6-membered ring, More preferably, (c1) hydrogen atom; (c2) halogen atoms; (c3) hydroxyl group; (c4) (C1-C6) alkyl group; (c5) a (C2-C6) alkenyl group; (c8) halo(C1-C6)alkyl group; (c12) (C1-C6)alkoxy group; (c13) (C1-C6) alkylsulfanyl group; (c14) (C1-C6) alkylsulfinyl group; (c15) a (C1-C6) alkylsulfonyl group; or (c20) (C1-C6) alkoxycarbonyl group; Also, R 2 and R 3 However, they may be bonded to each other to form a 5- or 6-membered ring.

[0034] R 3a Preferably, (c1') a hydrogen atom; or (c2') a (C1-C6) alkyl group; More preferably, (c1') Hydrogen atoms can be named.

[0035] The substituent group Y is preferably (d1) halogen atoms; (d2) cyano group; (d3) nitro group; (d4) amino group; (d5) (C1-C6) alkyl group; (d8) (C3-C6) cycloalkyl group; (d9) halo(C1-C6)alkyl group; (d13) (C1-C6)alkoxy group; (d14) (C1-C6) alkylsulfanyl group; (d15) (C1-C6) alkylsulfinyl group; (d16) (C1-C6) alkylsulfonyl group; (d17) halo(C1-C6)alkoxy group; (d18) halo(C1-C6)alkylsulfanyl group; (d19) halo(C1-C6)alkylsulfinyl group; (d20) halo(C1-C6)alkylsulfonyl group; (d21) N‐((C1-C6) alkylcarbonyl)amino group; (d22) N,N-di((C1-C6)alkylcarbonyl)amino group (the (C1-C6)alkylcarbonyl may be the same or different); (d23) di(C1-C6)alkoxyphosphanyl group (the (C1-C6)alkoxy may be the same or different); (d24) imidazolyl group; (d25) an imidazolyl group having, on the ring, 1 to 3 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (d26) Phenyl group; (d27) a phenyl group having on the ring 1 to 5 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (d28) pyridyl group; (d29) a pyridyl group having on the ring 1 to 4 substituents independently selected from the group consisting of halogen atoms and (C1-C6) alkyl groups; (d30) di(C1-C6) alkylamino group; (d31) (C1-C6)alkoxycarbonyl group; and (d32) Two adjacent substituents Y taken together form a methylenedioxy group which may be substituted with 1 to 2 substituents selected from the group consisting of a halogen atom, a phenyl group, and a (C1-C6) alkyl group; More preferably, (d1) halogen atoms; (d2) cyano group; (d3) nitro group; (d4) amino group; (d5) (C1-C6) alkyl group; (d8) (C3-C6) cycloalkyl group; (d9) halo(C1-C6)alkyl group; (d13) (C1-C6)alkoxy group; (d14) (C1-C6) alkylsulfanyl group; (d17) halo(C1-C6)alkoxy group; (d21) N‐((C1-C6) alkylcarbonyl)amino group; (d24) imidazolyl group; (d26) Phenyl group; (d28) pyridyl group; (d30) di(C1-C6) alkylamino group; (d31) (C1-C6)alkoxycarbonyl group; and (d32) Two adjacent substituents Y taken together form a methylenedioxy group which may be substituted with 1 or 2 substituents selected from the group consisting of a halogen atom, a phenyl group, and a (C1-C6) alkyl group.

[0036] R 4 Preferably, (e1) hydrogen atom; (e2) amino group; (e3) (C1-C6) alkyl group; (e4) N-(C1-C6) alkylamino group; (e5) N,N-di(C1-C6)alkylamino group (the (C1-C6)alkyl may be the same or different); (e6) N‐((C1-C6) alkylcarbonyl)amino group; (e7) N,N-di((C1-C6)alkylcarbonyl)amino group (the (C1-C6)alkylcarbonyl may be the same or different); or (e8) N-(halo(C1-C6)alkylcarbonyl)amino group, More preferably, (e2) amino group; (e3) (C1-C6) alkyl group; (e6) N‐((C1-C6) alkylcarbonyl)amino group; (e7) N,N-di((C1-C6)alkylcarbonyl)amino group (the (C1-C6)alkylcarbonyl may be the same or different); or (e8) N-(halo(C1-C6)alkylcarbonyl)amino group.

[0037] R 5 Preferably, (f1) (C1-C6) alkyl group; (f2) (C2-C6) alkenyl group; (f3) (C2-C6)alkynyl group; (f4) (C3-C6) cycloalkyl group; (f5) halo(C1-C6)alkyl groups; (f9) (C3-C6)cycloalkyl(C1-C6)alkyl group; (f10) (C1-C6)alkoxy(C1-C6)alkyl group; (f11) (C1-C6) alkylsulfanyl(C1-C6) alkyl group; (f12) (C1-C6) alkylsulfinyl(C1-C6) alkyl group; or (f13) (C1-C6) alkylsulfonyl(C1-C6) alkyl group, More preferably, (f1) (C1-C6) alkyl group; (f5) halo(C1-C6)alkyl group; or (f10) (C1-C6)alkoxy(C1-C6)alkyl groups can be mentioned.

[0038] A is preferably (g1) (C1-C6)alkoxy group; (g3) N‐(C1-C6) alkylaminocarbonyl group; (g4) N,N-di(C1-C6)alkylaminocarbonyl group (the (C1-C6)alkylcarbonyl may be the same or different); (g5') CO2R 7 (In the formula, R 7 represents (h1) a hydrogen atom, (h2) a (C1-C6) alkyl group, (h3) a (C2-C6) alkenyl group, (h4) a (C2-C6) alkynyl group, (h5) a (C3-C6) cycloalkyl group, (h6) a halo(C1-C6) alkyl group, or (h10) a phenyl(C1-C6) alkyl group; (g6') SO n R 8 (In the formula, R 8 represents (i1) a (C1-C6) alkyl group, (i2) a (C2-C6) alkenyl group, (i3) a (C2-C6) alkynyl group, (i4) a (C3-C6) cycloalkyl group, (i5) a halo(C1-C6) alkyl group, or (i9) a (C1-C6) alkylcarbonyl(C1-C6) alkyl group; and n represents 0, 1, or 2; or (g7') SO2N(R 9 )R 10 (In the formula, R 9 and R 10represents (j1) a hydrogen atom, (j2) a (C1-C6) alkyl group, (j3) a (C2-C6) alkenyl group, (j4) a (C2-C6) alkynyl group, (j5) a (C3-C6) cycloalkyl group, (j11) a (C1-C6) alkylcarbonyl group, (j12) a (C1-C6) alkoxycarbonyl group, (j13) a halo(C1-C6) alkylcarbonyl group, or (j14) a halo(C1-C6) alkoxycarbonyl group; R 9 and R 10 may be the same or different. More preferably, (g1) (C1-C6)alkoxy group; (g4) N,N-di(C1-C6)alkylaminocarbonyl group (the (C1-C6)alkylcarbonyl may be the same or different); (g5'') CO2R 7 (In the formula, R 7 represents (h1) a hydrogen atom or (h2) a (C1-C6) alkyl group; (g6'') SO n R 8 (In the formula, R 8 represents (i1) a (C1-C6) alkyl group, or (i9) a (C1-C6) alkylcarbonyl(C1-C6) alkyl group; n represents 2; or (g7'') SO2N(R 9 )R 10 (In the formula, R 9 and R 10 is (j1) a hydrogen atom, (j2) a (C1-C6) alkyl group, (j11) a (C1-C6) alkylcarbonyl group, or (j12) (C1-C6) alkoxycarbonyl group, R 9 and R 10 may be the same or different.

[0039] D is preferably D1 or D2, More preferably, I can give you D1.

[0040] R 6a and R 6b Preferably, (k1) hydrogen atom; (k2) a halogen atom; or (k3) a (C1-C6) alkyl group, More preferably, (k1) I can name a hydrogen atom.

[0041] R 6a and R 6b may be the same or different.

[0042] The various compounds of the present invention can be produced, for example, by the following production methods, but the present invention is not limited to these.

[0043] Manufacturing method 1 The compounds of the present invention represented by general formula (1a) and (1a-1) can be produced from the compound of general formula (2a) by the following steps [a], [b] and [c]. [ka]

[0044] wherein A, D, Q and R 5 is the same as above. L represents a leaving group such as chlorine, bromine, iodine, or a (C1-C6) alkylcarbonyloxy group. R 4’ and R 4’’ represents a (C1-C6) alkyl group, a (C1-C6) alkylcarbonyl group, a halo(C1-C6) alkylcarbonyl group, or a (C1-C6) alkoxycarbonyl group. 4’ and R 4’’ may be the same or different).

[0045] Manufacturing method of step [a] A compound represented by general formula (2a') can be produced by reacting a compound represented by general formula (2a) with a compound represented by formula (3) or a salt thereof in the presence of a base and an inert solvent.

[0046] Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; acetates such as sodium acetate and potassium acetate; alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; tertiary amines such as triethylamine, N,N-diisopropylethylamine, and DBU (1,8-diazabicyclo[5.4.0]undec-7-ene); and organic bases such as nitrogen-containing aromatic compounds such as pyridine and N,N-dimethyl-4-aminopyridine. The amount of base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (2a).

[0047] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include inert solvents such as linear or cyclic saturated hydrocarbons such as pentane, hexane, cyclohexane, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc.; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, etc.; linear or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane, tetrahydrofuran, etc.; nitriles such as acetonitrile, propionitrile, etc.; esters such as methyl acetate, etc.; ketones such as acetone, methyl ethyl ketone, etc.; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, etc.; and alcohols such as methanol, ethanol, propanol, butanol, 2-propanol, etc. These inert solvents can be used alone or in combination. The amount used may be appropriately selected usually from the range of 0.1 L to 100 L per mole of the compound represented by the general formula (2a).

[0048] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any compound may also be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but is typically selected appropriately within the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like. Alternatively, the target product may be subjected to the next step without isolation.

[0049] Manufacturing method of step [b] The compound represented by general formula (1a) of the present invention can be produced by reacting the compound represented by general formula (2a') with the compound represented by general formula (4) in the presence of an inert solvent and a base.

[0050] Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, and sodium hydride; acetates such as sodium acetate and potassium acetate; alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; tertiary amines such as triethylamine, N,N-diisopropylethylamine, and DBU; and nitrogen-containing aromatic compounds such as pyridine and N,N-dimethyl-4-aminopyridine. The amount of the base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (2a').

[0051] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, such as aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ketones such as acetone and methyl ethyl ketone; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (2a').

[0052] Since this reaction is an equimolar reaction, each compound may be used in equimolar amounts, although any compound may be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but may typically be selected appropriately within the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and the target product can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like.

[0053] Manufacturing method of step [c] The compound represented by general formula (1a-1) of the present invention can be produced by reacting the compound represented by general formula (1a) with the compound represented by general formula (5) and / or (5') in the presence of an inert solvent and a base.

[0054] Examples of the base that can be used in this reaction include alkyllithiums such as methyllithium, normal butyllithium, secondary butyllithium, and tertiary butyllithium; organometallic compounds such as lithium hexamethyldisilazane and sodium hexamethyldisilazane; hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; carbonates such as lithium carbonate, lithium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, cesium carbonate, potassium hydrogencarbonate, calcium carbonate, and magnesium carbonate; acetates such as lithium acetate, sodium acetate, and potassium acetate; alkoxides such as sodium methoxide, sodium ethoxide, sodium tertiary butoxide, and potassium tertiary butoxide; metal hydrides such as sodium hydride and potassium hydride; and organic bases such as pyridine, picoline, lutidine, triethylamine, tributylamine, and N,N-diisopropylethylamine. The amount of base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (1a).

[0055] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, such as aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ketones such as acetone and methyl ethyl ketone; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (1a).

[0056] Since this reaction is an equimolar reaction, each compound may be used in equimolar amounts, although any compound may be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but may typically be selected appropriately within the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and the target product can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like.

[0057] Manufacturing method 2 The compound of the present invention represented by general formula (1a) can be produced from the compound of general formula (2a) by the following step [a']. [ka]

[0058] wherein A, D, Q and R 5 is the same as above.

[0059] Manufacturing method of step [a'] The compound represented by general formula (1a) of the present invention can be produced by reacting the compound represented by general formula (2a) with the compound represented by general formula (3') or a salt thereof in the presence of a base and an inert solvent.

[0060] Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate; acetates such as sodium acetate and potassium acetate; alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; tertiary amines such as triethylamine, N,N-diisopropylethylamine, and DBU; and nitrogen-containing aromatic compounds such as pyridine and N,N-dimethyl-4-aminopyridine. The amount of the base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (2a).

[0061] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include inert solvents such as linear or cyclic saturated hydrocarbons such as pentane, hexane, cyclohexane, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc.; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, etc.; linear or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane, tetrahydrofuran, etc.; nitriles such as acetonitrile, propionitrile, etc.; esters such as methyl acetate, etc.; ketones such as acetone, methyl ethyl ketone, etc.; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, etc.; and alcohols such as methanol, ethanol, propanol, butanol, 2-propanol, etc. These inert solvents can be used alone or in combination. The amount used may be appropriately selected usually from the range of 0.1 L to 100 L per mole of the compound represented by the general formula (2a).

[0062] Since this reaction is an equimolar reaction, each compound may be used in equimolar amounts, although any compound may be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but may typically be selected appropriately within the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and the target product can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like.

[0063] Manufacturing method 3 The compound of the present invention represented by general formula (1a) can be produced from the compound of general formula (2b) by the following step [d] or [e]. [ka]

[0064] {where A, D, Q, R 4 and R 5 is the same as above. X represents a leaving group such as chlorine, bromine, or iodine.}

[0065] Manufacturing method of step [d] The compound represented by general formula (1a) of the present invention can be produced by reacting the compound represented by general formula (2b) with the compound represented by general formula (6) in the presence of a base and an inert solvent.

[0066] Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, and sodium hydride; acetates such as sodium acetate and potassium acetate; alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; tertiary amines such as triethylamine, N,N-diisopropylethylamine, and DBU; organic bases such as nitrogen-containing aromatic compounds such as pyridine and N,N-dimethyl-4-aminopyridine; alkyllithiums such as methyllithium, normal butyllithium, secondary butyllithium, and tert-butyllithium; and organometallic compounds such as lithium hexamethyldisilazane and sodium hexamethyldisilazane. The amount of base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (2b).

[0067] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include inert solvents such as linear or cyclic saturated hydrocarbons such as pentane, hexane, cyclohexane, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc.; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, etc.; linear or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane, tetrahydrofuran, etc.; nitriles such as acetonitrile, propionitrile, etc.; esters such as methyl acetate, etc.; ketones such as acetone, methyl ethyl ketone, etc.; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, etc.; and alcohols such as methanol, ethanol, propanol, butanol, 2-propanol, etc. These inert solvents can be used alone or in combination. The amount used may be appropriately selected usually from the range of 0.1 L to 100 L per mole of the compound represented by general formula (2b).

[0068] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although an excess of one compound may also be used. The reaction temperature in this reaction is typically between 0°C and the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but is typically selected appropriately from a few minutes to 48 hours. After completion of the reaction, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like.

[0069] Manufacturing method of step [e] The compound represented by general formula (1a) of the present invention can be produced by reacting the compound represented by general formula (2b) with the compound represented by general formula (6) in the presence of a metal catalyst and an inert solvent.

[0070] Examples of metal catalysts that can be used in this reaction include palladium catalysts, nickel catalysts, iron catalysts, ruthenium catalysts, platinum catalysts, rhodium catalysts, and iridium catalysts. Examples of these metal catalysts that can be used include metals, supported metals, metal salts such as metal chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, and oxides, and complex compounds such as olefin complexes, phosphine complexes, amine complexes, ammine complexes, and acetylacetonate complexes.

[0071] Among metal catalysts, palladium catalysts are particularly preferred, and examples of the palladium catalyst include palladium metal such as palladium black and palladium sponge; supported palladium metal such as palladium / alumina, palladium / carbon, palladium / silica, and palladium / Y-type zeolite; metal salts such as palladium chloride, palladium bromide, palladium iodide, and palladium acetate; π-allylpalladium chloride dimer, palladium acetylacetonate, dichlorobis(acetonitrile)palladium, dichlorobis(benzonitrile)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tris(dibenzylideneacetone)dipalladium (chloroform adduct), and dichlorodiaminepalladium. Examples of the metal catalyst include dichlorobis(triphenylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, tetrakis(triphenylphosphine)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, and diphenylphosphinoferrocene dichloropalladium-dichloromethane complex. The amount of these metal catalysts used may be selected appropriately from a range of 0.001 to 0.5 times the molar amount of the compound represented by general formula (2b).

[0072] These palladium catalysts may be used alone or in combination with a tertiary phosphine. Examples of the tertiary phosphines that can be used include triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri(tertiarybutyl)phosphine, tricyclohexylphosphine, tri-o-tolylphosphine, trioctylphosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(ditertiarybutylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, 1,2-bis(diphenylphosphino)ethane, 1,3 ... Examples of the tertiary phosphine include bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl. The amount of these tertiary phosphines used may be appropriately selected usually from a range of 0.5 to 10 times the molar amount of the metal catalyst.

[0073] Inert solvents that do not significantly inhibit the reaction include, for example, alcohols such as methanol, ethanol, propanol, butanol, and 2-propanol; linear or cyclic ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane (DME); aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitriles such as acetonitrile; esters such as ethyl acetate; polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone; and water. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, but is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (2b).

[0074] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any compound may also be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., but may be appropriately selected from the range of several minutes to 48 hours. This reaction can also be carried out under an inert gas atmosphere, such as nitrogen gas or argon gas. After completion of the reaction, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like.

[0075] Manufacturing method 4 The compound represented by general formula (1b) of the present invention can be produced from the compound represented by general formula (1a-2) of the present invention by the following steps [l] and [f]. [ka]

[0076] {where D, Q, R 4 , R 5 , R 9 and R 10 is the same as above. R represents, for example, a (C1-C4) alkyl group such as a tertiary butyl group, or a hydrogen atom.

[0077] Manufacturing method of step [l] The compound represented by general formula (2c) can be produced by reacting the compound represented by general formula (1a-2) with a thiol compound represented by general formula (15) in the presence of a base and an inert solvent.

[0078] Examples of bases that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, and potassium bicarbonate; acetates such as sodium acetate and potassium acetate; alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; tertiary amines such as triethylamine, N,N-diisopropylethylamine, and DBU; and nitrogen-containing aromatic compounds such as pyridine and N,N-dimethyl-4-aminopyridine. The amount of base used is usually 1 to 10 times the molar amount of the compound represented by formula (1a-2). When an alkali salt of the compound represented by formula (15) is used, a base need not be used.

[0079] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, such as aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ketones such as acetone and methyl ethyl ketone; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (1a-2).

[0080] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any of the reactants may be used in excess. The reaction temperature in this reaction is typically within the range of -20°C to the boiling point of the solvent used. The reaction time varies depending on the reaction scale and reaction temperature, but may be within the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and can be produced by purification, as needed, by recrystallization, column chromatography, or the like. Alternatively, the target product may be subjected to the next step without isolation.

[0081] Manufacturing method of step [f] The compound represented by general formula (1b) of the present invention can be produced by reacting the compound represented by general formula (2c) with a halogenating agent in the presence of an inert solvent to cause chlorosulfonylation, and then aminating the compound represented by general formula (7) in the presence of an inert solvent in the presence or absence of a base.

[0082] Examples of halogenating agents that can be used in this chlorosulfonylation reaction include thionyl chloride, chlorine, sulfuryl chloride, 1,3-dichloro-5,5-dimethylhydantoin, and N-chlorosuccinimide. These halogenating agents can be appropriately selected in an amount generally in the range of 0.5 to 5 times the molar amount of the compound represented by general formula (2c).

[0083] The inert solvent that can be used in this chlorosulfonylation reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, nitriles such as acetonitrile and propionitrile, organic acids such as acetic acid and propionic acid, and water. These inert solvents can be used alone or in combination of two or more. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is usually selected appropriately from the range of 0.5 L to 100 L per mole of the compound represented by general formula (2c).

[0084] Since this chlorosulfonylation reaction is an equimolar reaction, each reactant may be used in equimolar amounts, but any one of the reactants may be used in excess. The reaction temperature in this reaction is usually in the range from room temperature to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale and reaction temperature, but may be in the range of several minutes to 48 hours. After completion of the reaction, if the chlorosulfonylated product is stable, it can be isolated from the reaction system containing the target product by a conventional method, and if necessary, it can be purified by recrystallization, column chromatography, etc. On the other hand, if the chlorosulfonylated product is unstable, the reaction system can be used directly in the next reaction without purification.

[0085] Examples of the base that can be used in this amination reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, and potassium bicarbonate; acetates such as sodium acetate and potassium acetate; alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; tertiary amines such as triethylamine, N,N-diisopropylethylamine, and DBU; and nitrogen-containing aromatic compounds such as pyridine and N,N-dimethyl-4-aminopyridine. The amount of the base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (2c).

[0086] Inert solvents that can be used in this amination reaction are not particularly limited as long as they do not significantly inhibit the progress of this reaction. Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; alcohols such as methanol, ethanol, propanol, and isopropyl alcohol; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (2c).

[0087] Since this amination reaction is an equimolar reaction, each compound may be used in equimolar amounts, although any compound may be used in excess. The reaction temperature in this reaction is typically between 0°C and the boiling point of the solvent used. The reaction time varies depending on the reaction scale and reaction temperature, but may be within the range of several minutes to 48 hours. After completion of the reaction, the target product can be isolated from the reaction system containing it by conventional methods, and can be purified by recrystallization, column chromatography, or the like, as needed, to produce the target product.

[0088] Manufacturing method 5 Among the compounds represented by general formula (1) of the present invention, the compounds represented by general formulas (1c) and (1c-1) in which Q is the above-mentioned Q7 can be produced from the compound represented by general formula (2b) by the following steps [g], [h] and [i]. [ka]

[0089] {where A, D, R 1 , R 4 and R 5 is the same as above. R 3’ represents a halogen atom. X represents a leaving group such as chlorine, bromine, or iodine. X 1 represents a halogen atom such as chlorine, bromine, or iodine.}

[0090] Manufacturing method of step [g] The compound represented by general formula (8) can be produced by reacting the compound represented by general formula (2b) with tributyl(1-ethoxyvinyl)tin in the presence of a palladium catalyst and an inert solvent, followed by acid treatment.

[0091] Examples of palladium catalysts that can be used in this reaction include bis(triphenylphosphine)palladium(II) chloride, palladium(II) acetate, palladium(II) chloride, tetrakistriphenylphosphinepalladium(0), and bis(tri-tertiarybutylphosphine)palladium(0). The amount of the catalyst used is in the range of 0.001 to 0.5 times the molar amount of the compound represented by general formula (2b).

[0092] The inert solvent used in this reaction may be any solvent that does not significantly inhibit the reaction, such as aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.); halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, etc.); halogenated aromatic hydrocarbons (e.g., chlorobenzene, dichlorobenzene, etc.); linear or cyclic ethers (e.g., diethyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran, etc.); esters (e.g., ethyl acetate, etc.); amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, etc.); ketones (e.g., acetone, methyl ethyl ketone, etc.); alcohols (e.g., methanol, ethanol, propanol, butanol, 2-propanol, etc.); and polar solvents (e.g., dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, etc.). These inert solvents may be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is sufficient to dissolve the reaction reagents, and may be appropriately selected from the range of 0.5 L to 100 L per mole of the compound represented by general formula (2b).

[0093] Examples of acids that can be used in this reaction include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, and benzoic acid; and sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid. The amount of the acid used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (2b).

[0094] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any compound may also be used in excess. The reaction temperature in this reaction is typically between 0°C and the boiling point of the solvent used, and the reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but may typically be selected appropriately from a few minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and the target product can be produced by purifying it, if necessary, by recrystallization, column chromatography, etc.

[0095] Manufacturing method of step [h] A compound represented by general formula (9) can be produced by halogenating a compound represented by general formula (8) with a halogenating agent in the presence of an inert solvent. Also, a compound represented by general formula (1c) can be produced by halogenating a compound represented by general formula (1c-1) with a halogenating agent in the presence of an inert solvent.

[0096] Examples of halogenating agents include halogen molecules such as chlorine, bromine, and iodine, halogenated ammonium salts of halogen molecules, halogenated succinimides such as N-chlorosuccinimide and N-bromosuccinimide, halogenated hydantoins such as diiodohydantoin, and sulfuryl chloride. The amount of the halogenating agent used is usually in the range of 0.5 to 10 times the molar amount of the compound represented by general formula (8) or general formula (1c-1).

[0097] The inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit the reaction, and examples thereof include alcohols such as methanol, ethanol, propanol, butanol, and 2-propanol; linear or cyclic ethers such as diethyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as ethyl acetate; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, water, and acetic acid. These inert solvents can be used alone or in combination. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is usually selected appropriately from the range of 0.5 L to 100 L per mole of the compound represented by general formula (8) or general formula (1c-1).

[0098] The reaction temperature in this reaction is usually in the range of -30°C to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but can usually be selected appropriately from the range of several minutes to 48 hours. After the reaction is completed, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purification, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be subjected to the next step without isolation.

[0099] Manufacturing method of step [i] The compound represented by general formula (1c) of the present invention can be produced by reacting the compound represented by general formula (9) with the compound represented by general formula (10) in the presence or absence of a base and in the presence of an inert solvent.

[0100] The base used in this reaction may be an inorganic base or an organic base. Examples of the inorganic base include hydroxides of alkali metal atoms such as sodium hydroxide and potassium hydroxide, hydrides of alkali metals such as sodium hydride and potassium hydride, alkali metal salts of alcohols such as sodium ethoxide and potassium tert-butoxide, and carbonates such as sodium carbonate, potassium carbonate, cesium carbonate and sodium hydrogencarbonate. Examples of the organic base include triethylamine, pyridine, DBU, etc., and the amount used is usually within a range of 0.01 to 10 times the molar amount of the compound represented by general formula (9).

[0101] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include alcohols such as methanol, ethanol, propanol, butanol, and 2-propanol; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is usually selected appropriately from a range of 0.5 L to 100 L per mole of the compound represented by general formula (9).

[0102] Since this reaction is an equimolar reaction, each compound may be used in equimolar amounts, although any compound may be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale and reaction temperature, but is typically selected appropriately from a range of several minutes to 48 hours. After completion of the reaction, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like.

[0103] Manufacturing method 6 Among the compounds represented by general formula (1) of the present invention, compounds represented by general formulas (1c') and (1c'-1), in which Q is the above-mentioned Q12, can be produced from a compound represented by general formula (9) by the following steps [i] and [h]. The reaction conditions for steps [i] and [h] are the same as those described above. [ka]

[0104] {where A, D, R 1 , R 4 and R 5 is the same as above. R 3’ represents a halogen atom. X 1 represents a halogen atom such as chlorine, bromine, or iodine.}

[0105] Manufacturing method 7 Among the compounds represented by general formula (1) of the present invention, a compound represented by general formula (1d) in which Q is the above-mentioned Q8 can be produced from a compound represented by general formula (2d) by the following steps [j], [k] and [i]. The reaction conditions for step [i] are the same as those described above. [ka]

[0106] {where A, D, R 1 , R 2 , R 4 and R 5 is the same as above. R' represents a (C1-C6) alkyl group such as a methyl group or an ethyl group. L represents a leaving group such as chlorine, bromine, iodine, or a (C1-C6) alkylcarbonyloxy group.}

[0107] Manufacturing method of step [j] A compound represented by general formula (11) can be produced by reacting a compound represented by general formula (2d) with ammonia in the presence or absence of a base and in the presence of an inert solvent.

[0108] The amount of ammonia used in this reaction is usually in the range of 1 to 10 times by mole relative to the compound represented by general formula (2d).

[0109] The base used in this reaction may be an inorganic base or an organic base. Examples of the inorganic base include hydroxides of alkali metal atoms such as sodium hydroxide and potassium hydroxide, hydrides of alkali metals such as sodium hydride and potassium hydride, alkali metal salts of alcohols such as sodium ethoxide and potassium tert-butoxide, and carbonates such as sodium carbonate, potassium carbonate, cesium carbonate and sodium hydrogencarbonate. Examples of the organic base include triethylamine, pyridine, DBU, etc., and the amount used is usually within a range of 0.01 to 10 times the molar amount of the compound represented by general formula (2d).

[0110] The inert solvent used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, acetone, methyl ethyl ketone, and water. These inert solvents may be used alone or in combination. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected appropriately from a range of 0.5 L to 100 L per mole of the compound represented by general formula (2d).

[0111] The reaction temperature in this reaction is usually in the range of 0°C to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but can usually be selected appropriately from the range of several minutes to 48 hours. After the reaction is completed, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be used in the next step without purification.

[0112] Manufacturing method of step [k] A compound represented by general formula (12) can be produced by reacting a compound represented by general formula (11) with a sulfurizing agent in the presence of an inert solvent.

[0113] Examples of sulfurizing agents that can be used in this reaction include Lawesson's Reagent and diphosphorus pentasulfide, and the amount used is usually in the range of 1.0 to 10 times the molar amount of the compound represented by general formula (11).

[0114] This reaction can be performed with or without a solvent. Solvents that do not significantly inhibit the reaction are suitable, including inert solvents such as linear or cyclic saturated hydrocarbons (e.g., pentane, hexane, cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, xylene), halogenated aromatic hydrocarbons (e.g., chlorobenzene, dichlorobenzene), linear or cyclic ethers (e.g., diethyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran), nitriles (e.g., acetonitrile, propionitrile), aprotic polar solvents (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone), and alcohols (e.g., methanol, ethanol, propanol, butanol, 2-propanol). These inert solvents can be used alone or in combination. The amount of solvent used is typically selected from the range of 0.1 to 100 L per mole of the compound represented by formula (11).

[0115] The reaction temperature in this reaction may generally be in the range of about 0°C to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but may generally be selected appropriately in the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by a conventional method, and the target product can be produced by purifying it by recrystallization, column chromatography, etc. as necessary.

[0116] Manufacturing method 8 Among the compounds represented by general formula (1) of the present invention, the compound represented by general formula (1e) of the present invention, in which Q is the above-mentioned Q10, can be produced from the compound represented by general formula (2e) by the following step [c']: [ka]

[0117] {where A, D, R 1 , R 3 , R 4 and R 5 is the same as above. L represents a leaving group such as chlorine, bromine, iodine, or a (C1-C6) alkylcarbonyloxy group.

[0118] Manufacturing method of step [c'] The compound represented by general formula (1e) of the present invention can be produced by reacting the compound represented by general formula (2e) with the compound represented by general formula (66) in the presence or absence of copper acetate, in an inert solvent, and in the presence of a base.

[0119] The copper acetate used in this reaction may be a hydrate, and is usually used in an amount of 0.1 to 1 mole per mole of the compound represented by general formula (2e).

[0120] Examples of the base that can be used in this reaction include alkyllithiums such as methyllithium, normal butyllithium, secondary butyllithium, and tertiary butyllithium; organometallic compounds such as lithium hexamethyldisilazane and sodium hexamethyldisilazane; hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; carbonates such as lithium carbonate, lithium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, cesium carbonate, potassium hydrogencarbonate, calcium carbonate, and magnesium carbonate; acetates such as lithium acetate, sodium acetate, and potassium acetate; alkoxides such as sodium methoxide, sodium ethoxide, sodium tertiary butoxide, and potassium tertiary butoxide; metal hydrides such as sodium hydride and potassium hydride; and organic bases such as pyridine, picoline, lutidine, triethylamine, tributylamine, and N,N-diisopropylethylamine. The amount of base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (2e).

[0121] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, such as aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ketones such as acetone and methyl ethyl ketone; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (2e).

[0122] Since this reaction is an equimolar reaction, each compound may be used in equimolar amounts, although any compound may be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but may typically be selected appropriately within the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and the target product can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like.

[0123] Manufacturing method 9 Among the compounds represented by general formula (1) of the present invention, a compound represented by general formula (1f) in which Q is the above-mentioned Q18 can be produced from a compound represented by general formula (11) by the following step [i]. The reaction conditions for step [i] are the same as those described above. [ka]

[0124] {where A, D, R 1 , R 2 , R 4 and R 5 is the same as above. L represents a leaving group such as chlorine, bromine, iodine, or a (C1-C6) alkylcarbonyloxy group.

[0125] Manufacturing method 10 Among the compounds represented by general formula (1) of the present invention, a compound represented by general formula (1g) in which Q is the above-mentioned Q11 can be produced from a compound represented by general formula (2f) by the following step [c']. The reaction conditions for step [c'] are the same as those described above. [ka]

[0126] {where A, D, R 1 , R 3 , R 4 and R 5is the same as above. L represents a leaving group such as chlorine, bromine, iodine, or a (C1-C6) alkylcarbonyloxy group.

[0127] Starting material manufacturing method 1 Among the compounds represented by general formula (2a) which are starting materials in Production Methods 1 and 2, Q is the above Q1, and A is the above SO2N(R 9 )R 10 The compound represented by general formula (2a-1), which is represented by general formula (14), can be produced from the compound represented by general formula (14) by the following steps [l], [m], [n], [o], [f] and [p]. The reaction conditions for steps [l] and [f] are the same as those described above. [ka]

[0128] {where, D, R 1 , R 3 , R 9 and R 10 is the same as above. R represents, for example, a (C1-C4) alkyl group such as a tertiary butyl group, or a hydrogen atom. R' and R'' represent, for example, a (C1-C6) alkyl group such as a methyl group or an ethyl group. X represents, for example, a leaving group such as chlorine, bromine, or iodine.}

[0129] Manufacturing method of step [m] A compound represented by general formula (17) can be produced by hydrolyzing a compound represented by general formula (16) in the presence of a base, water and an inert solvent.

[0130] Examples of the base that can be used in this reaction include organic bases such as hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide, and the amount used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (16).

[0131] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit this reaction, and examples thereof include non-polar solvents such as linear or cyclic saturated hydrocarbons such as pentane, hexane, and cyclohexane, linear or cyclic ethers such as diethyl ether, tetrahydrofuran (THF), and dioxane, and aromatic hydrocarbons such as benzene, toluene, and xylene. These inert solvents can be used alone or in combination of two or more. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is usually selected appropriately from the range of 0.5 L to 100 L per mole of the compound represented by general formula (16).

[0132] The reaction temperature in this reaction is usually in the range of 0°C to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but can be appropriately selected from the range of several minutes to 48 hours. After completion of the reaction, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purification, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be subjected to the next step without isolation.

[0133] Manufacturing method of step [n] A compound represented by general formula (19) can be produced by reacting a compound represented by general formula (17) with a compound represented by general formula (18) using a condensing agent in the presence of a base, a condensing agent, and an inert solvent.

[0134] Condensing agents that can be used in this condensation reaction include, for example, acid-activating reagents such as phosgene, phosphorus trichloride, phosphorus oxychloride, oxalyl chloride, and thionyl chloride; carbodiimides such as N,N'-dicyclohexylcarbodiimide (DCC) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDCI); and others such as phosphorus pentoxide, polyphosphoric acid, N,N'-carbonyldiimidazole, 2-chloropyridine 1-methiodide (Mukaiyama reagent), 2-ethoxy-N- Ethoxycarbonyl-1,2-dihydroquinoline (EEDQ), triphenylphosphine / carbon tetrachloride, bromotripyrrolidinophosphonium hexafluorophosphate (BROP), O-(1H-benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate (BOP), N,N,N',N'-bis(tetramethylene)chlorouronium tetrafluoroborate, O-(1H-benzotriazol-1-yl)-N,N ,N',N'-tetramethyluronium hexafluorophosphate (HBTU), O-(1H-benzotriazol-1-yl)-N,N,N',N'-bis(tetramethylene)uronium hexafluorophosphate, O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate (TBTU), O-(1H-benzotriazol-1-yl)-N,N,N',N'-bis(tetramethylene)uronium tetra Examples of suitable condensing agents include tetrafluoroborate, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU), 1-hydroxybenzotriazole (HOBt), propylphosphonic anhydride (T3P), and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium salt (DMT-MM). These reagents can be used alone or in combination. The amount of the condensing agent used can be selected appropriately from a range of 0.5 to 5 times the molar amount of the compound represented by general formula (17).

[0135] Examples of bases that can be used in this condensation reaction include carbonates such as lithium carbonate, lithium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, cesium carbonate, potassium hydrogen carbonate, calcium carbonate, and magnesium carbonate, acetates such as lithium acetate, sodium acetate, and potassium acetate, and organic bases such as pyridine, picoline, lutidine, triethylamine, tributylamine, and N,N-diisopropylethylamine. The amount of the base used can be appropriately selected usually from a range of 0.5 to 5 times the molar amount of the compound represented by general formula (17), and the base can also be used as a solvent.

[0136] Inert solvents that can be used in this condensation reaction are not particularly limited as long as they do not significantly inhibit the reaction. Examples include linear or cyclic saturated hydrocarbons such as pentane, hexane, and cyclohexane; linear or cyclic ethers such as diethyl ether, THF, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; nitriles such as acetonitrile and isopropylnitrile; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from the range of 0.5 L to 100 L per mole of the compound represented by general formula (17). Furthermore, when the base is used as a solvent, no solvent is required.

[0137] Since this condensation reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any compound may also be used in excess. The reaction temperature in this reaction is typically between 0°C and the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but is typically selected appropriately from a range of several minutes to 48 hours. After completion of the reaction, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like. Alternatively, the target product can be used in the next step without isolation.

[0138] Manufacturing method of step [o] A compound represented by general formula (21) can be produced by reacting a compound represented by general formula (19) with a compound represented by general formula (20) or a salt thereof in the presence of an inert solvent and in the presence or absence of a base.

[0139] Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate; acetates such as sodium acetate and potassium acetate; alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; tertiary amines such as triethylamine, N,N-diisopropylethylamine, and DBU; and nitrogen-containing aromatic compounds such as pyridine and N,N-dimethyl-4-aminopyridine. The amount of the base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (19).

[0140] Inert solvents that can be used in this reaction are not particularly limited as long as they do not significantly inhibit the progress of this reaction. Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; alcohols such as methanol, ethanol, propanol, and isopropyl alcohol; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ketones such as acetone and methyl ethyl ketone; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (19).

[0141] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any of the reactants may be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale and reaction temperature, but may be within the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like. Alternatively, the target product may be subjected to the next step without isolation.

[0142] Manufacturing method of step [p] The compound represented by general formula (2a-1) can be produced by reacting the compound represented by general formula (22) with a cyanating agent in the presence of a base and an inert solvent, in the presence or absence of a metal catalyst.

[0143] Examples of the cyanating agent that can be used in this reaction include sodium cyanide, potassium cyanide, trimethylsilyl cyanide, and zinc cyanide, and the amount used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (22).

[0144] Examples of the base that can be used in this reaction include carbonates such as lithium carbonate, lithium hydrogencarbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium hydrogencarbonate, calcium carbonate, and magnesium carbonate; acetates such as lithium acetate, sodium acetate, and potassium acetate; and organic bases such as pyridine, picoline, lutidine, triethylamine, tributylamine, N,N-diisopropylethylamine, and 1,4-diazabicyclo[2.2.2]octane. The amount of the base that can be used is usually in the range of 1 to 5 times the molar amount of the compound represented by general formula (22).

[0145] Examples of metal catalysts that can be used in this reaction include palladium catalysts, nickel catalysts, iron catalysts, ruthenium catalysts, platinum catalysts, rhodium catalysts, iridium catalysts, etc. Examples of these metal catalysts that can be used include metals, supported metals, metal salts such as metal chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, and oxides, and complex compounds such as olefin complexes, phosphine complexes, amine complexes, ammine complexes, and acetylacetonate complexes.

[0146] Among metal catalysts, palladium catalysts are particularly preferred, and examples of palladium catalysts include palladium metal such as palladium black and palladium sponge, as well as supported palladium metal such as palladium / alumina, palladium / carbon, palladium / silica, and palladium / Y-type zeolite. Further examples include metal salts such as palladium chloride, palladium bromide, palladium iodide, and palladium acetate. Further examples include complex compounds such as π-allylpalladium chloride dimer, palladium acetylacetonate, dichlorobis(acetonitrile)palladium, dichlorobis(benzonitrile)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tris(dibenzylideneacetone)dipalladium (chloroform adduct), dichlorodiaminepalladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, tetrakis(triphenylphosphine)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, and diphenylphosphinoferrocene dichloropalladium-dichloromethane complex. The amount of the metal catalyst used may be appropriately selected from the range of usually 0.001 to 0.5 times by mole relative to the compound represented by general formula (22).

[0147] These palladium catalysts may be used alone or in combination with a tertiary phosphine. Examples of the tertiary phosphine that can be used include triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, tri-o-tolylphosphine, trioctylphosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(ditertiarybutylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, 1,2- Examples include bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, etc. The amount of these tertiary phosphines used may be appropriately selected from the range of usually 0.5 to 10 times the molar amount of the metal catalyst.

[0148] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit this reaction, and examples thereof include alcohols such as methanol, ethanol, propanol, butanol, and 2-propanol; linear or cyclic saturated hydrocarbons such as pentane, hexane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran, and cyclopentyl methyl ether; esters such as ethyl acetate; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ketones such as acetone and methyl ethyl ketone; polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone; and water. These inert solvents can be used alone or in combination. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagent, and is usually selected appropriately from the range of 0.5 L to 100 L per mole of the compound represented by general formula (22).

[0149] The reaction temperature in this reaction is usually in the range of 0°C to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but can be appropriately selected from the range of several minutes to 48 hours. After completion of the reaction, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purification, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be used in the next reaction without isolation.

[0150] Starting material manufacturing method 2 Among the compounds represented by general formula (2a) which are starting materials in Production Methods 1 and 2, Q is the above Q2, and A is the above SO2N(R 9 )R 10The compound represented by general formula (2a-2), which is represented by general formula (17), can be produced from the compound represented by general formula (17) by the following steps [q], [r], [s], [f] and [p]. The reaction conditions for steps [f] and [p] are the same as those described above. [ka]

[0151] {where, D, R 1 , R 2 , R 3 , R 9 and R 10 is the same as above. R represents, for example, a (C1-C4) alkyl group such as a tertiary butyl group, or a hydrogen atom. X represents, for example, a leaving group such as chlorine, bromine, or iodine. L represents, for example, a leaving group such as chlorine, bromine, iodine, or a (C1-C6) alkylcarbonyloxy group.}

[0152] Manufacturing method of step [q] A compound represented by general formula (23) can be produced by reacting a compound represented by general formula (17) with a compound represented by general formula (13) in the presence of a base and an inert solvent.

[0153] Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate; acetates such as sodium acetate and potassium acetate; alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; tertiary amines such as triethylamine, N,N-diisopropylethylamine, and DBU; and nitrogen-containing aromatic compounds such as pyridine and N,N-dimethyl-4-aminopyridine. The amount of the base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (17).

[0154] The inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction. Examples of inert solvents that can be used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ketones such as acetone and methyl ethyl ketone; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (17).

[0155] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any of the reactants may be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale and reaction temperature, but may be within the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like. Alternatively, the target product may be subjected to the next step without isolation.

[0156] Manufacturing method of step [r] A compound represented by general formula (24) can be produced by reacting a compound represented by general formula (23) with a nitrogen source in the presence of an acid and an inert solvent.

[0157] Examples of the nitrogen source that can be used in this reaction include ammonia, ammonium carbamate, ammonium acetate, and ammonium carbonate. The amount of the nitrogen source used can be appropriately selected from the range of usually 1 to 20 times the molar amount of the compound represented by general formula (23).

[0158] Examples of acids that can be used in this reaction include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, and benzoic acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and paratoluenesulfonic acid; and phosphoric acid. The amount of the acid used can be appropriately selected usually from a range of 0.01 to 10 times the molar amount of the compound represented by general formula (23), and the acid can also be used as a solvent.

[0159] Inert solvents that can be used in this dehydration reaction are not particularly limited as long as they do not significantly inhibit the progress of this reaction. Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ketones such as acetone and methyl ethyl ketone; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from the range of 0.5 L to 100 L per mole of the compound represented by general formula (23) obtained in the condensation reaction. Furthermore, when the acid is used as the solvent, no solvent is required.

[0160] The reaction temperature in this dehydration reaction may generally be in the range of room temperature to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale and reaction temperature, but may be appropriately selected from the range of several minutes to 48 hours. After the reaction is complete, the target product can be isolated from the reaction system containing the target product by a conventional method, and can be produced by purifying the product, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be subjected to the next step without isolation.

[0161] Manufacturing method of step [s] A compound represented by general formula (26) can be produced by reacting a compound represented by general formula (24) with a compound represented by general formula (25) in the presence of an inert solvent and a base.

[0162] Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, and sodium hydride; acetates such as sodium acetate and potassium acetate; alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; tertiary amines such as triethylamine, N,N-diisopropylethylamine, and DBU; and nitrogen-containing aromatic compounds such as pyridine and N,N-dimethyl-4-aminopyridine. The amount of the base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (24).

[0163] The inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction. Examples of inert solvents that can be used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ketones such as acetone and methyl ethyl ketone; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (24).

[0164] Since this reaction is an equimolar reaction, each compound may be used in equimolar amounts, although any compound may be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but may typically be selected appropriately within the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and the target product can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like.

[0165] Starting material manufacturing method 3 Among the compounds represented by general formula (2a) which are starting materials in Production Methods 1 and 2, Q is the above-mentioned Q5, and A is the above-mentioned CO2R 7 The compound represented by general formula (2a-3), which is represented by general formula (28), can be produced from the compound represented by general formula (28) by the following steps [t], [u], [v], [w], [x], [j] and [y]. The reaction conditions for step [j] are the same as those described above. [ka]

[0166] {where, D, R 1 , R 3 and R 7 is the same as above. X represents a leaving group such as chlorine, bromine, or iodine. X 1 represents a halogen atom such as chlorine, bromine, or iodine. L' represents a leaving group such as chlorine, bromine, iodine, a halo(C1-C6)alkoxy group, or an imidazolyl group.

[0167] Manufacturing method of step [t] A compound represented by general formula (30) can be produced by reacting a compound represented by general formula (28) with a compound represented by general formula (29) in the presence or absence of an acid and in the presence of an inert solvent.

[0168] Examples of acids that can be used in this reaction include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, and benzoic acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and paratoluenesulfonic acid; and phosphoric acid. The amount of the acid used is usually in the range of 0.01 to 10 times the molar amount of the compound represented by general formula (28).

[0169] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include alcohols such as methanol, ethanol, propanol, butanol, and 2-propanol; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (28) obtained by the condensation reaction.

[0170] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any compound may also be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale and reaction temperature, but may be appropriately selected from the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like. Alternatively, the target product may be subjected to the next step without isolation.

[0171] Manufacturing method of step [u] A compound represented by general formula (31) can be produced by reacting a compound represented by general formula (30) with a halogenating agent in the presence or absence of a base and in the presence of an inert solvent.

[0172] Examples of halogenating agents that can be used in this reaction include N-halosuccinimides such as N-chlorosuccinimide and N-bromosuccinimide, alkali metal hypohalites such as sodium hypochlorite, hypohalite esters such as tert-butyl hypochlorite, elemental halogens such as chlorine gas, phosphorus pentachloride, sulfuryl chloride, etc., and the amount used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (30).

[0173] Examples of the base that can be used in this reaction include alkali metal hydrides such as sodium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate, inorganic salts, and organic bases such as pyridine, DBU and triethylamine. The amount of the base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (30).

[0174] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; esters such as ethyl acetate and methyl acetate; linear or cyclic ethers such as tetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1,2-dimethoxyethane, and dioxane; nitriles such as acetonitrile; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and water. These inert solvents can be used alone or in combination. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from the range of 0.5 L to 100 L per mole of the compound represented by general formula (30).

[0175] The reaction temperature in this reaction may be selected appropriately from the range of -50°C to the boiling point of the inert solvent used, and the reaction time varies depending on the scale of the reaction and the reaction temperature, but ranges from a few minutes to 48 hours. After the reaction is complete, if the compound represented by general formula (31) is stable, it can be isolated from the reaction system containing the target product by conventional methods, and if necessary, the target product can be produced by purification by recrystallization, column chromatography, etc., but it can also be used directly in the next reaction without isolation. If the compound represented by general formula (31) is unstable, the reaction solution can be used directly in the next step without purification.

[0176] Manufacturing method of step [v] A compound represented by general formula (33) can be produced by aminating a compound represented by general formula (31) with a compound represented by general formula (32) in the presence of an inert solvent and in the presence or absence of a base.

[0177] Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate; acetates such as sodium acetate and potassium acetate; alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; tertiary amines such as triethylamine, N,N-diisopropylethylamine, and DBU; and nitrogen-containing aromatic compounds such as pyridine and N,N-dimethyl-4-aminopyridine. The amount of the base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (31).

[0178] The inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction. Examples of inert solvents that can be used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; alcohols such as methanol, ethanol, propanol, and isopropyl alcohol; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (31).

[0179] Since this reaction is an equimolar reaction, each compound may be used in equimolar amounts, although any compound may be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale and reaction temperature, but may be within the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like. Alternatively, the target product may be subjected to the next step without isolation.

[0180] Manufacturing method of step [w] A compound represented by general formula (35) can be produced by reacting a compound represented by general formula (33) with a compound represented by general formula (34) in the presence of a base and an inert solvent.

[0181] Examples of the base that can be used in this reaction include inorganic bases such as hydroxides of alkali metal atoms, such as sodium hydroxide and potassium hydroxide; hydrides of alkali metals, such as sodium hydride and potassium hydride; alkali metal salts of alcohols, such as sodium ethoxide and potassium tert-butoxide; carbonates, such as sodium carbonate, potassium carbonate, cesium carbonate and sodium hydrogencarbonate; and organic bases, such as triethylamine, pyridine, N,N-dimethyl-4-aminopyridine and DBU. The amount of the base used can be appropriately selected usually from a range of 1 to 10 times the molar amount of the compound represented by general formula (33), and the base can also be used as a solvent.

[0182] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include inert solvents such as linear or cyclic saturated hydrocarbons such as pentane, hexane, cyclohexane, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc.; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, etc.; linear or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane, tetrahydrofuran, etc.; nitriles such as acetonitrile, propionitrile, etc.; esters such as methyl acetate, etc.; ketones such as acetone, methyl ethyl ketone, etc.; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, etc.; and alcohols such as methanol, ethanol, propanol, butanol, 2-propanol, etc. These inert solvents can be used alone or in combination. The amount used may be appropriately selected usually within the range of 0.1 L to 100 L per mole of the compound represented by the general formula (33). When the base is used as the solvent, no solvent may be used.

[0183] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any compound may also be used in excess. The reaction temperature in this reaction is typically between 0°C and the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but is typically selected appropriately from a few minutes to 48 hours. After completion of the reaction, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purification, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be used in the next step without isolation.

[0184] Manufacturing method of step [x] A compound represented by general formula (35) can be synthesized according to the method (Heck reaction) described in JP-A-2005-272338, in which an ester group is introduced at the 3- and 6-positions, as represented by general formula (36). After the reaction is complete, the target product can be isolated from the reaction system containing the target product by a conventional method, and can be purified by recrystallization, column chromatography, or the like, as needed, to produce the target product. Alternatively, the target product can be used in the next step without isolation.

[0185] Manufacturing method of step [y] A compound represented by general formula (2a-3) can be produced by reacting a compound represented by general formula (37) with a dehydrating agent in the presence or absence of a base and in the presence of an inert solvent.

[0186] Examples of the dehydrating agent used in this reaction include trifluoroacetic anhydride, phosphorus oxychloride, diphosphorus pentoxide, etc., and the amount used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (37).

[0187] Examples of the base used in this reaction include inorganic bases and organic bases. Examples of the inorganic base include hydroxides of alkali metal atoms such as sodium hydroxide and potassium hydroxide, hydrides of alkali metals such as sodium hydride and potassium hydride, alkali metal salts of alcohols such as sodium ethoxide and potassium tert-butoxide, and carbonates such as sodium carbonate, potassium carbonate, cesium carbonate and sodium hydrogencarbonate. Examples of the organic base include triethylamine, pyridine, DBU, and the like. The amount of the base used may be appropriately selected usually from a range of 0.01 to 10 times the moles of the compound represented by general formula (37).

[0188] The inert solvent used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, acetone, and methyl ethyl ketone. These inert solvents may be used alone or in combination. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (37).

[0189] The reaction temperature in this reaction is usually in the range of 0°C to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but can usually be selected appropriately from the range of several minutes to 48 hours. After the reaction is completed, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be used in the next step without purification.

[0190] Method for producing starting materials 4 Among the compounds represented by general formula (2a) which are starting materials in Production Methods 1 and 2, Q is the above Q7 or Q12, and A is the above CO2R 7 The compound represented by general formula (2a-4), which is represented by general formula (38), can be produced from the compound represented by general formula (38) by the following steps [z], [aa], [h], [i], [x], [j] and [y]. The reaction conditions for steps [h], [i], [x], [j] and [y] are the same as those described above. [ka]

[0191] {where, D, R 1 , R 3 and R 7 is the same as above. Z represents an oxygen atom or a sulfur atom. X represents a leaving group such as chlorine, bromine, or iodine. X 1 and X 2 represents a halogen atom such as chlorine, bromine, or iodine.}

[0192] Manufacturing method of step [z] The compound represented by general formula (40) can be produced by reacting the compound represented by general formula (38) with a halogenating agent in the presence of an inert solvent to form an acid halide, and then reacting the acid halide with the compound represented by formula (39) in the presence of an inert solvent in the presence or absence of a base.

[0193] Examples of halogenating agents that can be used in this halogenation reaction include oxalyl chloride, thionyl chloride, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, and phosphorus oxychloride. The amount of the halogenating agent used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (38).

[0194] Inert solvents that can be used in this halogenation reaction may be any solvent that does not significantly inhibit the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; esters such as ethyl acetate and methyl acetate; linear or cyclic ethers such as tetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1,2-dimethoxyethane, and dioxane; nitriles such as acetonitrile; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from the range of 0.5 L to 100 L per mole of the compound represented by general formula (38).

[0195] The reaction temperature for this halogenation reaction may generally be in the range of room temperature to the boiling point of the solvent used, and the reaction time varies depending on the scale and reaction temperature, but is in the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by a conventional method, and can be used in the next step without purification.

[0196] Examples of the base that can be used in this amidation reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, and potassium bicarbonate; acetates such as sodium acetate and potassium acetate; alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; tertiary amines such as triethylamine, N,N-diisopropylethylamine, and DBU; and nitrogen-containing aromatic compounds such as pyridine and N,N-dimethyl-4-aminopyridine. The amount of the base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (38).

[0197] Inert solvents that do not significantly inhibit the progress of this reaction include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; alcohols such as methanol, ethanol, propanol, and isopropyl alcohol; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from the range of 0.5 L to 100 L per mole of the compound represented by general formula (38).

[0198] Since this amidation reaction is an equimolar reaction, each compound may be used in equimolar amounts, although any compound may be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale and reaction temperature, but may be within the range of several minutes to 48 hours. After completion of the reaction, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be purified by recrystallization, column chromatography, or the like, as needed, to produce the target product. Alternatively, the target product can be used in the next step without purification.

[0199] Manufacturing method of step [aa] A compound represented by general formula (42) can be produced by reacting a compound represented by general formula (40) with an organomagnesium compound represented by general formula (41) in the presence of an inert solvent.

[0200] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; and polar solvents such as linear or cyclic ethers as tetrahydrofuran, diethyl ether, methyl tertiary butyl ether, 1,2-dimethoxyethane, and dioxane. These inert solvents can be used alone or in combination. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is usually selected appropriately from the range of 0.5 L to 100 L per mole of the compound represented by general formula (40).

[0201] Since this reaction is equimolar, equimolar amounts of each compound may be used; however, one compound may also be used in excess. The reaction temperature in this reaction is typically within the range of -78°C to the boiling point of the solvent used. The reaction time varies depending on the reaction scale and reaction temperature, but may be within the range of several minutes to 48 hours. After completion of the reaction, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be purified by recrystallization, column chromatography, or the like, as needed, to produce the target product. Alternatively, the product can be used in the next step without purification.

[0202] Method for producing starting materials 5 Among the compounds represented by general formula (2b) which are starting materials in Production Method 3, A is the SO2N(R 9 )R 10 The compound represented by general formula (2b-1), which is represented by general formula (48), can be produced by the following steps [ab], [ac], [p] and [a']. The reaction conditions for steps [p] and [a'] are the same as those described above. [ka]

[0203] {where, D, R 5 , R 9 and R 10is the same as above. X represents a leaving group such as chlorine, bromine, or iodine.}

[0204] Manufacturing method of step [ab] The compound represented by general formula (48) is chlorosulfonylated according to the method described in Organic Process Research & Development, 2009, 13, 875-879 or International Publication No. 2020 / 041169. A compound represented by general formula (49) can be produced.

[0205] After completion of the reaction, the target product can be isolated from the reaction system containing the target product by a conventional method, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be subjected to the next step without isolation.

[0206] Manufacturing method of step [ac] A compound represented by general formula (50) can be produced by reacting a compound represented by general formula (49) with a compound represented by general formula (7) in the presence of an inert solvent and in the presence or absence of a base.

[0207] Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate; acetates such as sodium acetate and potassium acetate; alkali metal alkoxides such as potassium tert-butoxide, sodium methoxide, and sodium ethoxide; tertiary amines such as triethylamine, N,N-diisopropylethylamine, and DBU; and nitrogen-containing aromatic compounds such as pyridine and N,N-dimethyl-4-aminopyridine. The amount of the base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (49).

[0208] The inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction. Examples of inert solvents that can be used include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; alcohols such as methanol, ethanol, propanol, and isopropyl alcohol; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from the range of 0.5 L to 100 L per mole of the compound represented by general formula (49).

[0209] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any compound may be used in excess. The reaction temperature in this reaction is typically between 0°C and the boiling point of the solvent used. The reaction time varies depending on the reaction scale and reaction temperature, but may be within the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and can be produced by purification, as needed, by recrystallization, column chromatography, or the like. Alternatively, the target product may be used in the next step without isolation.

[0210] Method for producing starting materials6 Among the compounds represented by general formula (2d) which are starting materials in Production Method 7, A is the above-mentioned SO2R 8 The compound represented by general formula (2d-1), wherein A is the same as SOR, can be produced from the compound represented by general formula (14) by the following steps [l], [ad], [p], and [a']. In the compound represented by general formula (2b), which is the starting material of Production Method 3, A is the same as SOR. 8The compound represented by general formula (2b-2) can be produced from the compound represented by general formula (2d-1) by the following steps [m], [ae], and [af]. The reaction conditions for steps [l], [p], [a'], and [m] are the same as those described above. [ka]

[0211] {where, D, R 5 and R 8 is the same as above. X represents a leaving group such as chlorine, bromine, or iodine. R' represents a (C1-C6) alkyl group such as methyl or ethyl.

[0212] Manufacturing method of step [ad] A compound represented by general formula (54) can be produced by reacting a compound represented by general formula (53) with an oxidizing agent in the presence of an inert solvent.

[0213] Examples of the oxidizing agent that can be used in this reaction include peroxides such as hydrogen peroxide, perbenzoic acid, and metachloroperbenzoic acid, and the amount used is usually in the range of 1 to 5 times the molar amount of the compound represented by general formula (53).

[0214] The inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit the reaction, and examples thereof include linear or cyclic ethers such as diethyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitriles such as acetonitrile; esters such as ethyl acetate; organic acids such as formic acid and acetic acid; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and water. These inert solvents can be used alone or in combination. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected appropriately from a range of 0.5 L to 100 L per mole of the compound represented by general formula (53).

[0215] The reaction temperature in this reaction is usually in the range of -10°C to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but can usually be selected appropriately from the range of several minutes to 48 hours. After the reaction is completed, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purification, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be subjected to the next step without isolation.

[0216] Manufacturing method of step [ae] The compound represented by general formula (57) can be produced by reacting the compound represented by general formula (56) with diphenylphosphoryl azide in the presence of tertiary butyl alcohol according to the Curtius rearrangement reaction, i.e., the method described in JAChem.Soc.1972, 94, 6203-6205, and then reacting the resulting mixture in the presence of an acid and an inert solvent.

[0217] Examples of acids that can be used in this reaction include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, and benzoic acid; and sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid. The amount of the acid used can be appropriately selected usually from a range of 1 to 10 times the molar amount of the compound represented by general formula (56), and the acid can also be used as a solvent.

[0218] The inert solvent used in this reaction may be any solvent that does not significantly inhibit the reaction, such as aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.); halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, etc.); halogenated aromatic hydrocarbons (e.g., chlorobenzene, dichlorobenzene, etc.); linear or cyclic ethers (e.g., diethyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran, etc.); esters (e.g., ethyl acetate, etc.); amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, etc.); ketones (e.g., acetone, methyl ethyl ketone, etc.); polar solvents (e.g., dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, etc.). These inert solvents may be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from the range of 0.5 L to 100 L per mole of the compound represented by general formula (56).

[0219] The reaction temperature in this reaction is usually in the range of -10°C to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale and reaction temperature, but is usually in the range of several minutes to 48 hours. After the reaction is completed, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purification, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be used in the next step without isolation.

[0220] Manufacturing method of step [af] The amino group of the compound represented by general formula (57) can be converted to a halogen atom by the Sandmeyer reaction, i.e., the method described in Chem. Rev. 1988, 88, 765, to produce the compound represented by general formula (2b-2).

[0221] After the reaction is complete, the target product can be isolated from the reaction system containing the target product by a conventional method, and if necessary, purified by recrystallization, column chromatography, etc. to produce the target product.

[0222] Method for producing starting materials 7 Among the compounds represented by general formula (2c), which are the starting materials for Production Method 4, compounds represented by general formula (2c-1), in which Q is the above-mentioned Q1, can be produced from compounds represented by general formula (38) by the following steps [ag], [p], [l], [a], and [b]. The reaction conditions for steps [p], [l], [a], and [b] are the same as those described above. Furthermore, compounds represented by general formula (58) can be produced by the methods described in Chem. Ber., 1982, 115, 2807-2818 and WO 2018 / 160845 pamphlet, or by appropriately modifying these methods. [ka]

[0223] {where, D, R 1 , R 3 and R 5 is the same as above. L represents a leaving group such as chlorine, bromine, iodine, or a (C1-C6) alkylcarbonyloxy group. R represents a (C1-C4) alkyl group such as a tertiary butyl group or a hydrogen atom. X represents a leaving group such as chlorine, bromine, or iodine.}

[0224] Manufacturing method of process [ag] The compound represented by general formula (38) and the compound represented by general formula (58) are subjected to a condensation reaction in the presence of a base, a condensing agent, and an inert solvent to form an amide compound, and then the amide compound is subjected to a dehydration reaction in the presence of an acid and an inert solvent to produce the compound represented by general formula (59).

[0225] Condensing agents that can be used in this condensation reaction include, for example, acid-activating reagents such as phosgene, phosphorus trichloride, phosphorus oxychloride, oxalyl chloride, and thionyl chloride; carbodiimides such as N,N'-dicyclohexylcarbodiimide (DCC) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDCI); and others such as phosphorus pentoxide, polyphosphoric acid, N,N'-carbonyldiimidazole, 2-chloropyridine 1-methiodide (Mukaiyama reagent), 2-ethoxy-N- Ethoxycarbonyl-1,2-dihydroquinoline (EEDQ), triphenylphosphine / carbon tetrachloride, bromotripyrrolidinophosphonium hexafluorophosphate (BROP), O-(1H-benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate (BOP), N,N,N',N'-bis(tetramethylene)chlorouronium tetrafluoroborate, O-(1H-benzotriazol-1-yl)-N,N ,N',N'-tetramethyluronium hexafluorophosphate (HBTU), O-(1H-benzotriazol-1-yl)-N,N,N',N'-bis(tetramethylene)uronium hexafluorophosphate, O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate (TBTU), O-(1H-benzotriazol-1-yl)-N,N,N',N'-bis(tetramethylene)uronium tetra Examples of suitable condensing agents include tetrafluoroborate, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU), 1-hydroxybenzotriazole (HOBt), propylphosphonic anhydride (T3P), and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium salt (DMT-MM). These reagents can be used alone or in combination. The amount of the condensing agent used is usually in the range of 0.5 to 5 times the molar amount of the compound represented by general formula (38).

[0226] Examples of bases that can be used in this condensation reaction include carbonates such as lithium carbonate, lithium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, cesium carbonate, potassium hydrogen carbonate, calcium carbonate, and magnesium carbonate, acetates such as lithium acetate, sodium acetate, and potassium acetate, and organic bases such as pyridine, picoline, lutidine, triethylamine, tributylamine, and N,N-diisopropylethylamine. The amount of the base used can be appropriately selected usually from a range of 0.5 to 5 times the molar amount of the compound represented by general formula (38), but the base can also be used as a solvent.

[0227] Inert solvents that can be used in this condensation reaction are not particularly limited as long as they do not significantly inhibit the reaction. Examples include linear or cyclic saturated hydrocarbons such as pentane, hexane, and cyclohexane; linear or cyclic ethers such as diethyl ether, THF, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; nitriles such as acetonitrile and isopropylnitrile; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, but it can usually be selected appropriately from a range of 0.5 L to 100 L per mole of the compound represented by general formula (38). Furthermore, when the base is used as a solvent, no solvent is required.

[0228] Since this condensation reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any compound may also be used in excess. The reaction temperature in this condensation reaction is typically within the range of 0°C to the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but is typically selected appropriately from a range of several minutes to 48 hours. After completion of the reaction, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like. Alternatively, the target product can be subjected to the subsequent dehydration reaction without isolation.

[0229] Examples of acids that can be used in this dehydration reaction include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, and benzoic acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and paratoluenesulfonic acid; and phosphoric acid. The amount of the acid used can be appropriately selected usually from a range of 0.01 to 10 times the molar amount of the amide compound, and the acid can also be used as a solvent.

[0230] Inert solvents that can be used in this dehydration reaction are not particularly limited as long as they do not significantly inhibit the progress of this reaction. Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, methyl tert-butyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ketones such as acetone and methyl ethyl ketone; and polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, but it can usually be selected appropriately from the range of 0.5 L to 100 L per mole of the amide compound obtained in the condensation reaction. Furthermore, when the acid is used as a solvent, no solvent is required.

[0231] The reaction temperature in this dehydration reaction is usually in the range of room temperature to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale and reaction temperature, but can usually be selected appropriately from the range of several minutes to 48 hours. After the reaction is completed, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purification, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be used in the next step without isolation.

[0232] Method for producing starting materials 8 Among the compounds represented by general formula (2a) which are starting materials in Production Methods 1 and 2, Q is the above Q5, and A is the above SO2N(R 9 )R 10 The compound represented by general formula (2a-5), which is represented by general formula (16), can be produced from the compound represented by general formula (16) by the following steps [ah], [ai], [c'], [f], and [p]. The reaction conditions for steps [c'], [f], and [p] are the same as those described above. [ka]

[0233] {where, D, R 1 , R 3 , R 9 and R 10 is the same as above. R' represents a (C1-C6) alkyl group such as a methyl group or an ethyl group. X represents a leaving group such as chlorine, bromine, or iodine. L represents a leaving group such as chlorine, bromine, iodine, or a (C1-C6) alkylcarbonyloxy group.}

[0234] Manufacturing method of step [ah] A compound represented by general formula (63) can be produced by reacting a compound represented by general formula (16) with hydrazine in the presence or absence of a base and in the presence of an inert solvent.

[0235] The hydrazine used in this reaction may be a salt such as hydrochloride or a hydrate, and is usually used in an amount of 1 to 10 times the moles of the compound represented by general formula (16).

[0236] The base used in this reaction may be an inorganic base or an organic base. Examples of the inorganic base include hydroxides of alkali metal atoms such as sodium hydroxide and potassium hydroxide, hydrides of alkali metals such as sodium hydride and potassium hydride, alkali metal salts of alcohols such as sodium ethoxide and potassium tert-butoxide, and carbonates such as sodium carbonate, potassium carbonate, cesium carbonate and sodium hydrogencarbonate. Examples of the organic base include triethylamine, pyridine, DBU, etc., and the amount used is usually within a range of 0.01 to 10 times the molar amount of the compound represented by general formula (16).

[0237] The inert solvent used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, acetone, methyl ethyl ketone, and water. These inert solvents may be used alone or in combination. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (16).

[0238] The reaction temperature in this reaction is usually in the range of 0°C to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but can usually be selected appropriately from the range of several minutes to 48 hours. After the reaction is completed, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be used in the next step without purification.

[0239] Manufacturing method of process [ai] A compound represented by general formula (65) can be produced by reacting a compound represented by general formula (63) with a compound represented by general formula (64) in the presence of a base and an inert solvent.

[0240] Examples of the base that can be used in this reaction include inorganic bases such as hydroxides of alkali metal atoms, such as sodium hydroxide and potassium hydroxide; hydrides of alkali metals, such as sodium hydride and potassium hydride; alkali metal salts of alcohols, such as sodium ethoxide and potassium tert-butoxide; carbonates, such as sodium carbonate, potassium carbonate, cesium carbonate and sodium hydrogencarbonate; and organic bases, such as triethylamine, pyridine, N,N-dimethyl-4-aminopyridine and DBU. The amount of the base used can be appropriately selected usually from a range of 1 to 10 times the molar amount of the compound represented by general formula (63), and the base can also be used as a solvent.

[0241] The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include inert solvents such as linear or cyclic saturated hydrocarbons such as pentane, hexane, cyclohexane, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc.; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, etc.; linear or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane, tetrahydrofuran, etc.; nitriles such as acetonitrile, propionitrile, etc.; esters such as methyl acetate, etc.; ketones such as acetone, methyl ethyl ketone, etc.; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, etc.; and alcohols such as methanol, ethanol, propanol, butanol, 2-propanol, etc. These inert solvents can be used alone or in combination. The amount used may be appropriately selected usually within the range of 0.1 L to 100 L per mole of the compound represented by general formula (63). When the base is used as a solvent, no solvent may be used.

[0242] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any compound may also be used in excess. The reaction temperature in this reaction is typically between 0°C and the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but is typically selected appropriately from a few minutes to 48 hours. After completion of the reaction, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purification, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be used in the next step without isolation.

[0243] Method for producing starting materials9 Among the compounds represented by general formula (2c) which are starting materials in Production Method 4, the compound represented by general formula (2c-2) in which Q is the above-mentioned Q8 is a compound represented by general formula (1d) of the present invention in which A is the above-mentioned SO2R 8It can be produced from the compound of the present invention represented by general formula (1d-1), which is represented by the following step [l]. The reaction conditions for step [l] are the same as those described above. [ka]

[0244] {where, D, R 1 , R 2 , R 5 and R 8 is the same as above. R represents, for example, a (C1-C4) alkyl group such as a tertiary butyl group, or a hydrogen atom.

[0245] Method for producing starting materials10 Among the compounds represented by general formula (2e) which are starting materials in Production Method 8, A is the above-mentioned SO2R 8 The compound represented by general formula (2e-1), which is represented by general formula (69), can be produced from the compound represented by general formula (69) by the following steps [z], [aa], [aj], [ad], [p] and [a']. The reaction conditions for steps [z], [aa], [ad], [p] and [a'] are the same as those described above. [ka]

[0246] {where, D, R 3 , R 5 and R 8 is the same as above. X represents a leaving group such as chlorine, bromine, or iodine. X 2 represents a halogen atom such as chlorine, bromine, or iodine.}

[0247] Manufacturing method of step [aj] A compound represented by general formula (72) can be produced by reacting a compound represented by general formula (71) with a carbon-increasing agent and hydrazine in the presence or absence of a base and in the presence of an inert solvent.

[0248] Examples of the carbon-increasing agent used in this reaction include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide di-tert-butyl acetal, tert-butoxybis(dimethylamino)methane, trimethyl orthoformate, methyl formate, and ethyl formate. The amount of the carbon-increasing agent used is usually in the range of 1 to 20 times the molar amount of the compound represented by general formula (71).

[0249] The hydrazine used in this reaction may be a salt such as hydrochloride or a hydrate, and is usually used in an amount of 1 to 10 times the moles of the compound represented by general formula (71).

[0250] Examples of the base that can be used in this reaction include inorganic bases such as hydroxides of alkali metal atoms, such as sodium hydroxide and potassium hydroxide; hydrides of alkali metals, such as sodium hydride and potassium hydride; alkali metal salts of alcohols, such as sodium ethoxide and potassium tert-butoxide; carbonates, such as sodium carbonate, potassium carbonate, cesium carbonate and sodium hydrogencarbonate; and organic bases, such as triethylamine, pyridine, N,N-dimethyl-4-aminopyridine and DBU. The amount of base used is usually in the range of 1 to 10 times the molar amount of the compound represented by general formula (71).

[0251] The inert solvent used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; linear or cyclic ethers such as diethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, acetone, methyl ethyl ketone, and water. These inert solvents may be used alone or in combination. The amount of the inert solvent used is not particularly limited as long as it is an amount that can dissolve the reaction reagents, and is typically selected from a range of 0.5 L to 100 L per mole of the compound represented by general formula (71).

[0252] The reaction temperature in this reaction is usually in the range of 0°C to the boiling point of the solvent used, and the reaction time varies depending on the reaction scale, reaction temperature, etc., and is not constant, but can usually be selected appropriately from the range of several minutes to 48 hours. After the reaction is completed, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, etc. Alternatively, the target product can be used in the next step without purification.

[0253] Method for producing starting materials11 Among the compounds represented by general formula (2c) which are starting materials in Production Method 4, the compound represented by general formula (2c-3) in which Q is the above-mentioned Q10 is a compound represented by general formula (1e) of the present invention in which A is the above-mentioned SO2R 8 It can be produced from the compound of the present invention represented by general formula (1e-1) by the following step [l]. The reaction conditions for step [l] are the same as those described above. [ka]

[0254] {where, D, R1 , R 3 , R 4 , R 5 , and R 8 is the same as above. R represents, for example, a (C1-C4) alkyl group such as a tertiary butyl group, or a hydrogen atom.

[0255] Method for producing starting materials12 Among the compounds represented by general formula (2b) which are starting materials in Production Method 4, A is the above-mentioned SO2R 8 The compound represented by general formula (2b-3), which is represented by general formula (54), can be produced from the compound represented by general formula (54) by the following steps [g], [a'], [m], [ae] and [af]. The reaction conditions for steps [g], [a'], [m], [ae] and [af] are the same as those described above. [ka]

[0256] {where, D, R 5 and R 8 is the same as above. R' represents a (C1-C6) alkyl group such as a methyl group or an ethyl group. X represents a leaving group such as chlorine, bromine, or iodine.}

[0257] Method for producing starting materials13 Among the compounds represented by general formula (f) which are starting materials in Production Method 10, A is the above-mentioned SO2R 8 The compound represented by general formula (2f-1), which is: can be produced from the compound represented by general formula (2b-2) by the following steps [ak] and [al]. [ka]

[0258] {where, D, R 3 , R 5 and R 8 is the same as above. X represents a leaving group such as chlorine, bromine, or iodine.}

[0259] Manufacturing method of process [ak] The compound represented by general formula (80) can be produced by reacting the compound represented by general formula (2b-2) with the compound represented by general formula (79) in the presence of a palladium catalyst, copper iodide, a base, and an inert solvent.

[0260] Examples of the palladium catalyst used in this reaction include metal salts such as palladium chloride, palladium bromide, palladium iodide, and palladium acetate, π-allylpalladium chloride dimer, palladium acetylacetonate, dichlorobis(acetonitrile)palladium, dichlorobis(benzonitrile)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tris(dibenzylideneacetone)dipalladium (chloroform adduct), dichlorodiaminepalladium, dichlorobis(triphenylphosphine)palladium, and dichlorobis(tricyclohexylphosphine)palladium. Examples of the metal catalyst include complex compounds such as radium, tetrakis(triphenylphosphine)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, and diphenylphosphinoferrocene dichloropalladium-dichloromethane complex. The amount of these metal catalysts used may be selected appropriately from a range of 0.001 to 0.5 times the molar amount of the compound represented by general formula (2b-2).

[0261] These palladium catalysts may be used alone or in combination with a tertiary phosphine. Examples of the tertiary phosphine that can be used include triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, tri-o-tolylphosphine, trioctylphosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(ditertiarybutylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, 1,2- Examples include bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, etc. The amount of these tertiary phosphines used may be appropriately selected usually from a range of 0.5 to 10 times the molar amount of the palladium catalyst.

[0262] The amount of copper iodide used in this reaction is usually within a range of 0.01 to 0.5 times by mole relative to the compound represented by general formula (2b-2).

[0263] Examples of the base that can be used in this reaction include inorganic bases such as carbonates, e.g., sodium carbonate, potassium carbonate, cesium carbonate, and sodium hydrogencarbonate; and organic bases such as triethylamine, pyridine, N,N-dimethyl-4-aminopyridine, and DBU. The amount of the base used can be appropriately selected usually from a range of 1 to 10 times the molar amount of the compound represented by general formula (2b-2), and the base can also be used as a solvent.

[0264] Inert solvents that do not significantly inhibit the reaction include alcohols such as methanol, ethanol, propanol, butanol, and 2-propanol; linear or cyclic ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane (DME); aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitriles such as acetonitrile; esters such as ethyl acetate; polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone; and water. These inert solvents can be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is sufficient to dissolve the reaction reagents; it is typically selected from the range of 0.5 L to 100 L per mole of the compound represented by general formula (2b-2). Furthermore, when the base is used as a solvent, no solvent is required.

[0265] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any compound may also be used in excess. The reaction temperature in this reaction is typically within the range from room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., but may be appropriately selected from the range of several minutes to 48 hours. This reaction can also be carried out under an inert gas atmosphere, such as nitrogen gas or argon gas. After completion of the reaction, the target product can be isolated from the reaction system containing the target product by conventional methods, and can be produced by purification, as needed, by recrystallization, column chromatography, or the like. Alternatively, the target product can be used in the next reaction without isolation.

[0266] Manufacturing method of step [al] The compound represented by the general formula (2f-1) can be produced by reacting the compound represented by the general formula (80) with sodium azide (81) in the presence of diazetoxyiodobenzene and an inert solvent.

[0267] The amount of diacetoxyiodobenzene used in this reaction is usually within a range of 1 to 10 times by mole relative to the compound represented by general formula (80).

[0268] Any inert solvent that does not significantly inhibit the reaction may be used. Examples include alcohols such as methanol, ethanol, propanol, butanol, and 2-propanol; linear or cyclic ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane (DME); aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitriles such as acetonitrile; esters such as ethyl acetate; polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone; and water. These inert solvents may be used alone or in combination. The amount of inert solvent used is not particularly limited as long as it is sufficient to dissolve the reaction reagents; however, it is generally selected from the range of 0.5 L to 100 L per mole of the compound represented by general formula (80). Furthermore, when the base is used as the solvent, no solvent is required.

[0269] Since this reaction is an equimolar reaction, equimolar amounts of each compound may be used, although any compound may also be used in excess. The reaction temperature in this reaction is typically within the range of room temperature to the boiling point of the solvent used. The reaction time varies depending on the reaction scale, reaction temperature, etc., but may be appropriately selected from the range of several minutes to 48 hours. After completion of the reaction, the target product may be isolated from the reaction system containing the target product by conventional methods, and can be produced by purifying it, if necessary, by recrystallization, column chromatography, or the like. Alternatively, the target product may be subjected to the next reaction without isolation.

[0270] Method for producing starting materials14 QH represented by general formula (6) in Production Method 3 can be produced by the methods described in the following documents or by appropriately modifying the methods. Q1-H is, for example, the method described in Organic Letters, 2015, 17, 2894-2897. Q2-H is, for example, the method described in Bioorganic & Medicinal Chemistry Letters, 2012, 22, 7036-7040. Q3-H is, for example, the method of Heterocycles, 1983, 20, 1243-1246. Q4-H is, for example, the method described in Organic Process Research & Development, 2004, 8, 28-32. Q5-H is, for example, the method described in Bioorganic & Medicinal Chemistry Letters, 2021, 41, 127984. Q6-H is, for example, the method of U.S. Patent Publication No. 5,449,784. Q7-H is, for example, the method described in Journal of the American Chemical Society, 2015, 137, 2738-2747. Q8-H is, for example, the method of U.S. Patent Publication No. 4,282,364. Q9-H is, for example, the method described in Organic Letters, 2007, 9, 4009-4012. Q10-H is, for example, the method of Chem. Ber., 1960, 93, 1208-11. Q11-H is, for example, the method in Organic Letters, 2020, 22, 1396-1401. Q12-H is, for example, the method of Synlett, (1999), (10), 1642-1644. Q13-H is, for example, the method described in Journal of the American Chemical Society, 1937, 59, 2262-2264. Q14-H can be prepared, for example, by the method described in Tetrahedron Letters, 1994, 35, 1585-1586. Q15-H is, for example, the method described in Journal of Chemical and Pharmaceutical Research, 2012, 4, 1772-1781. Q16-H is, for example, the method described in Journal of Medicinal Chemistry, 2016, 59, 8398-8411. Q17-H is, for example, the method of Chemistry-A European Journal, 2016, 22(3), 911-915. Q18-H is, for example, the method described in Journal of Organic Chemistry, 1990, 55(3), 929-35.

[0271] Representative examples of the compound represented by general formula (1) of the present invention are shown below in Tables 1 to 21, but the present invention is not limited to these. 1 The contents described as R 1 and R 1 The content of the substituent group Y and the content of the substituent group Y may both be included. Next, specific examples of the compound of the present invention are shown below. In the table below, Me is a methyl group, Et is an ethyl group, i-Pr is an isopropyl group, n-Pr is a normal propyl group, c-Pr is a cyclopropyl group, i-Bu is an isobutyl group, n-Br is a normal butyl group, c-Bu is a cyclobutyl group, t-Bu is a tertiary butyl group, c-Pen is a cyclopentyl group, i-pen is an isopentyl group, c-Hex is a cyclohexyl group, Ac is an acetyl group, Ph is a phenyl group, Bn is a benzyl group, Bz is a benzoyl group, and i-allyl is an isoallyl group. Physical properties include melting point (°C), refractive index (n D ) or 1 H-NMR is shown. The brackets next to the refractive index indicate the measurement temperature (°C). 1 The 1 H-NMR data is shown in Table 22.

[0272] [ka]

[0273] Table 1 (In Table 1, R 6a and R 6b indicates a hydrogen atom.) [Table 1-1]

[0274] [Table 1-2]

[0275] [Table 1-3]

[0276] [Table 1-4]

[0277] [Table 1-5]

[0278] [Table 1-6]

[0279] [Table 1-7]

[0280] [Table 1-8]

[0281] [Table 1-9]

[0282] [Table 1-10]

[0283] [Table 1-11]

[0284] [Table 1-12]

[0285] [ka]

[0286] Table 2 (In Table 2, R 6a and R 6b indicates a hydrogen atom.) [Table 2-1]

[0287] [Table 2-2]

[0288] [Table 2-3]

[0289] [Table 2-4]

[0290] [Table 2-5]

[0291] [Table 2-6]

[0292] [Table 2-7]

[0293] [ka]

[0294] Table 3 (In Table 3, R 6a and R 6b indicates a hydrogen atom.) [Table 3-1]

[0295] [Table 3-2]

[0296] [Table 3-3]

[0297] [Table 3-4]

[0298] [Table 3-5]

[0299] [Table 3-6]

[0300] [Table 3-7]

[0301] [Table 3-8]

[0302] [Table 3-9]

[0303] [Table 3-10]

[0304] [Table 3-11]

[0305] [Table 3-12]

[0306] [Table 3-13]

[0307] [ka]

[0308] Table 4 (In Table 4, R 6a and R 6b indicates a hydrogen atom.) [Table 4-1]

[0309] [Table 4-2]

[0310] [Table 4-3]

[0311] [Table 4-4]

[0312] [Table 4-5]

[0313] [Table 4-6]

[0314] [Table 4-7]

[0315] [Table 4-8]

[0316] [Table 4-9]

[0317] [Table 4-10]

[0318] [Table 4-11]

[0319] [ka]

[0320] Table 5 (In Table 5, R 6a and R 6b indicates a hydrogen atom.) [Table 5-1]

[0321] [Table 5-2]

[0322] [Table 5-3]

[0323] [Table 5-4]

[0324] [Table 5-5]

[0325] [Table 5-6]

[0326] [ka]

[0327] Table 6 (In Table 6, R 6a and R 6b indicates a hydrogen atom.) [Table 6-1]

[0328] [Table 6-2]

[0329] [Table 6-3]

[0330] [Table 6-4]

[0331] [Table 6-5]

[0332] [ka]

[0333] Table 7 (In Table 7, R 6a and R 6b indicates a hydrogen atom.) [Table 7-1]

[0334] [Table 7-2]

[0335] [Table 7-3]

[0336] [Table 7-4]

[0337] [Table 7-5]

[0338] [Table 7-6]

[0339] [ka]

[0340] Table 8 (In Table 8, R 6a and R 6bindicates a hydrogen atom. In Table 8-1, R 2 indicates a hydrogen atom.) [Table 8-1]

[0341] [Table 8-2]

[0342] [Table 8-3]

[0343] [Table 8-4]

[0344] [ka]

[0345] Table 9 (In Table 9, R 6a and R 6b indicates a hydrogen atom.) [Table 9-1]

[0346] [Table 9-2]

[0347] [Table 9-3]

[0348] [Table 9-4]

[0349] [Table 9-5]

[0350] [ka]

[0351] Table 10 (In Table 10, R 6a and R 6b indicates a hydrogen atom.) [Table 10-1]

[0352] [Table 10-2]

[0353] [Table 10-3]

[0354] [Table 10-4]

[0355] [Table 10-5]

[0356] [Table 10-6]

[0357] [ka]

[0358] Table 11 (In Table 11, R 6a and R 6b indicates a hydrogen atom.) [Table 11-1]

[0359] [Table 11-2]

[0360] [Table 11-3]

[0361] [Table 11-4]

[0362] [Table 11-5]

[0363] [Table 11-6]

[0364] [Table 11-7]

[0365] [Table 11-8]

[0366] [ka]

[0367] Table 12 (In Table 12, R 6a and R 6b indicates a hydrogen atom.) [Table 12-1]

[0368] [Table 12-2]

[0369] [Table 12-3]

[0370] [Table 12-4]

[0371] [Table 12-5]

[0372] [ka]

[0373] Table 13 (In Table 13, R 6a and R 6b indicates a hydrogen atom.) [Table 13-1]

[0374] [Table 13-2]

[0375] [Table 13-3]

[0376] [Table 13-4]

[0377] [Table 13-5]

[0378] [ka]

[0379] Table 14 (In Table 14, R 2 , R 6a and R 6b indicates a hydrogen atom.) [Table 14-1]

[0380] [Table 14-2]

[0381] [Table 14-3]

[0382] [Table 14-4]

[0383] [Table 14-5]

[0384] [ka]

[0385] Table 15 (In Table 15, R 2 , R 6a and R 6b indicates a hydrogen atom.) [Table 15-1]

[0386] [Table 15-2]

[0387] [Table 15-3]

[0388] [Table 15-4]

[0389] [Table 15-5]

[0390] [ka]

[0391] Table 16 (In Table 16, R 2 , R 2a , R 6a and R 6b indicates a hydrogen atom.) [Table 16-1]

[0392] [Table 16-2]

[0393] [Table 16-3]

[0394] [Table 16-4]

[0395] [Table 16-5]

[0396] [Table 16-6]

[0397] [ka]

[0398] Table 17 (R in Table 17 6a and R 6b indicates a hydrogen atom, and ● indicates a bond position.) [Table 17-1]

[0399] [Table 17-2]

[0400] [Table 17-3]

[0401] [Table 17-4]

[0402] [Table 17-5]

[0403] [Table 17-6]

[0404] [ka]

[0405] Table 18 (In Table 18, R 6a indicates a hydrogen atom, and ● indicates a bond position.) [Table 18-1]

[0406] [Table 18-2]

[0407] [Table 18-3]

[0408] [Table 18-4]

[0409] [Table 18-5]

[0410] [ka]

[0411] Table 19 (In Table 19, R 6b indicates a hydrogen atom, and ● indicates a bond position.) [Table 19-1]

[0412] [Table 19-2]

[0413] [Table 19-3]

[0414] [Table 19-4]

[0415] [Table 19-5]

[0416] [Table 19-6]

[0417] [ka]

[0418] Table 20 (In Table 20, R 6a and R 6b indicates a hydrogen atom.) [Table 20-1]

[0419] [Table 20-2]

[0420] [Table 20-3]

[0421] [ka]

[0422] Table 21 (In Table 21, R 6a and R 6b indicates a hydrogen atom.) [Table 21-1]

[0423] [Table 21-2]

[0424] [Table 21-3]

[0425] Table 22 (In Table 22, * indicates the concentration in DMSO-d6) 1 H-NMR data.) [Table 22-1]

[0426] [Table 22-2]

[0427] [Table 22-3]

[0428] [Table 22-4]

[0429] [Table 22-5]

[0430] [Table 22-6]

[0431] [Table 22-7]

[0432] [Table 22-8]

[0433]

Table 22-9

[0434]

Table 22-10

[0435]

Table 22-11

[0436]

Table 22-12

[0437]

Table 22-13

[0438]

Table 22-14

[0439]

Table 22-15

[0440]

Table 22-16

[0441] The useful plants for which the nitrogen-containing heterocyclic compound or salts thereof of the present invention can be used are not particularly limited, and examples thereof include cereals (rice, barley, wheat, rye, oats, corn, etc.), beans (soybeans, adzuki beans, broad beans, peas, kidney beans, peanuts, etc.), fruit trees and fruits (apples, citrus fruits, pears, grapes, peaches, plums, cherries, walnuts, chestnuts, almonds, bananas, etc.), leafy vegetables (cabbage, tomato, spinach, broccoli, lettuce, onion, leeks (chives, scallions), bell peppers, eggplant, strawberries, peppers, okra, chives, etc.), root vegetables (carrots, potatoes, sweet potatoes, taro, daikon radish, turnips, lotus root, burdock, garlic, etc.), and the like. , shallots, etc.), processing crops (cotton, hemp, beets, hops, sugarcane, sugar beets, olives, rubber, coffee, tobacco, tea, etc.), gourds (pumpkin, cucumber, watermelon, Sakhalin gourd, melon, etc.), pasture grasses (orchard grass, sorghum, timothy, clover, alfalfa, etc.), turfgrass (Korean grass, bentgrass, etc.), ornamental crops for perfumes and the like (lavender, rosemary, thyme, parsley, pepper, ginger, etc.), flowers (chrysanthemums, roses, carnations, orchids, tulips, lilies, etc.), garden trees (ginkgo, cherry trees, Japanese laurels, etc.), forest trees (abies firs, spruces, pines, hiba, cedar, cypress, eucalyptus, etc.).

[0442] The above-mentioned "plant" also includes plants to which tolerance has been imparted, by classical breeding methods or by genetic engineering techniques, to HPPD inhibitors such as isoxaflutole, ALS inhibitors such as imazethapyr and thifensulfuron methyl, EPSP synthase inhibitors such as glyphosate, glutamine synthase inhibitors such as glufosinate, acetyl-CoA carboxylase inhibitors such as sethoxydim, and herbicides such as bromoxynil, dicamba, and 2,4-D.

[0443] Examples of "plants" that have been conferred resistance through classical breeding methods include rapeseed, wheat, sunflower, and rice that are resistant to imidazolinone ALS-inhibiting herbicides such as imazethapyr. Rice is already sold under the trade name Clearfield®. Similarly, soybeans that have been conferred resistance to sulfonylurea ALS-inhibiting herbicides such as thifensulfuron methyl through classical breeding methods are already sold under the trade name STS soybeans. Similarly, examples of plants that have been conferred resistance to acetyl-CoA carboxylase inhibitors such as trione oxime and aryloxyphenoxypropionic acid herbicides through classical breeding methods include SR corn. Plants that have been conferred resistance to acetyl-CoA carboxylase inhibitors are described in Proceedings of the National Academy of Sciences of the United States of America (Proc. Natl. Acad. Sci. USA), Vol. 87, pp. 7175-7179 (1990), etc. Mutant acetyl-CoA carboxylases resistant to acetyl-CoA carboxylase inhibitors have been reported in Weed Science, Vol. 53, pp. 728-746 (2005), among others. By introducing such mutant acetyl-CoA carboxylase genes into plants using genetic engineering or by introducing resistance-conferring mutations into plant acetyl-CoA carboxylase, plants resistant to acetyl-CoA carboxylase inhibitors can be produced. Furthermore, by introducing nucleic acids with base substitution mutations, such as those typified by chimeraplasty technology (Gura T. 1999. Repairing the Genome's Spelling Mistakes. Science 285: 316-318.), into plant cells to introduce site-specific amino acid substitution mutations into the plant acetyl-CoA carboxylase gene or ALS gene, plants resistant to acetyl-CoA carboxylase inhibitors or ALS inhibitors can be produced. The nitrogen-containing heterocyclic compounds or salts thereof of the present invention can also be used on these plants. The compounds of the present invention do not harm these useful plants.

[0444] Weeds that can be controlled by the nitrogen-containing heterocyclic compound or salt thereof of the present invention include dicotyledonous weeds, such as morning glory (Ipomoea), Lindernia (Lindernia), Sesbania (Sesbania), Abutilon (Abutilon), Chamomile (Matricaria), Rorippa (Rorippa), Nettle (Urtica), Dead nettle (Lamium), Cocklebur (Xanthium), Mustard (Sinapis), Rotala, Speedwell (Veronica), Poppy (Papaver), Chenopodium (Chenopodium), White clover (Trifolium), Purslane (Portulaca), and Viola. , common morning glory (Pharbitis), Galeopsis, Datura, eggplant (Solanum), shepherd's purse (Capsella), thistle (Cirsium), sonchus (Sonchus), Galinsoga, chickweed (Stellaria), Senecio, Amaranthus, ragweed (Ambrosia), Kochia, Lamium, shepherd's purse (Leipidium), willow (Polygonum), cleaver (Galium), cornflower (Centaurea), mugwort (Artemisia), etc.

[0445] Monocotyledonous weed genera include Leptochloa, Phleum, Poa, Bolboschoenus, Festuca, Setaria, Eleusine, Sagittaria, Agropyron, Ischaemum, Cyperus, and Avena. , Bromus, Panicum, Cynodon, Monochoria, Alopecurus, Paspalum, Commelina, Fimbris, Lolium, Brachiaria, Agrostis, Eleocharis, Echinochloa esculenta, Scirpus, Schoenoplectus, Digitaria, Sorghum, etc.

[0446] Specific examples of other weeds include Spirogyra, Amaranthus retroflexus, Amaranthus viridis, Setaria faberi, Leersia japonica, Leptochloa chinensis, Lindernia angustifolia, Lindernia procumbens, Dopatrium junceum, Ipomoea hederacea, Lindernia dubia, Sida spinosa, Polygonum pensylvanicum, Sesbania exaltata, Geranium carolinense, and Chenopodium ambrosioides, ragweed (Conyza bonariensis), foxtail (Setaria italica), burlap ragweed (Amaranthus powellii), knotweed (Polygonum cuspidatum), velvetleaf (Abutilon theophrasti), chamomile (Matricaria perforata), Japanese knotweed (Polygonum longisetum), persimmon (Veronica polita), barnyard grass (Echinochloa crus-galli), black-eyed jasmine (Amaranthus lividus), nightshade (Solanum nigrum), night burdock (Schoenoplectus juncoides (Roxb.) Palla), barnyard grass (Bromus catharticus), warbler (Murdannia keisak), and float clubweed (Bolboschoenus fluviatilis), Floating Crab (Scirpus maritimus), Bromus tectorum, Sagittaria pygmaea Miq, Rumex obtusifolius, Leersia oryzoides(L.) Sw.), green foxtail (Setaria viridis), sickleweed (Cassia obtusifolia), giant ragweed (Conyza sumatrensis), common persian violet (Veronica persica), duckweed (Spirodela polyrhiza), cocklebur (Xanthium canadens), goldenrod (Coreopsis lanceolata), common morning glory (Panicum dichotomiflorum), giant milkweed (Asclepias syriaca), celery (Euphorbia maculata), plantain (Plantago asiatica), common red snapper (Rudbeckia laciniata), common amaranthus (Amaranthus palmeri), oats (Avena sativa), cocklebur (Xanthium strumarium, wild oat (Avena sterilis), goosegrass (Eleusine indica), arrowhead (Sagittaria trifolia), Dutch buttercup (Erodium cicutarium), Dutch earwort (Cerastium glomeratum), orchard daisy (Matricaria matricarioides), chamomile (Matricaria chamomilla), vetch (Vicia angustifolia), bromegrass (Bromus secalinus), wild oat (Avena fatua), oat grass (Rotala indica Koehne), Rumex japonicus, knotweed (Paspalum distichum), foxglove (Bromus remotiflorus), yellow nutsedge (Cyperus esculentus), and burdock (Galium kinuta), Setaria glauca, Pueraria lobata, Eleocharis kuroguwai Ohwi, Sagittaria trifolia Caerulea, Ambrosia trifida, Hydrillaverticillata), Siberian clubweed (Bolboschoenus maritimus (L.) Palla), Corn marigold (Chrysanthemum segetum), Japanese sedge (Cyperus iria), Monochoria vaginalis, Echinochloa colona, ​​Japanese sedge (Alisma plantago-aquatica), Weedy rice (Oryza sativa), Polygonum lapathifolium, Finger millet (Eleusine coracana), Siberian sedge (Schoenoplectus nipponicus), Siberian sedge (Cyperus malaccensis), Quackgrass (Agropyron repens), Shattercane (Sorghum vulgare), Silky bentgrass (Apera spica-venti), Chenopodium album), white clover (Trifolium repens), white morning glory (Datura stramonium), horsetail (Equisetum arvense), annual bluegrass (Poa annua), annual bromegrass (Bromus japonicus), annual foxtail (Alopecurus aequalis), purslane (Portulaca oleracea), goldenrod (Solidago altissima), common sorghum (Sorghum halepense), common mustard (Brassica juncea), common dandelion (Taraxacum officinale), common bindweed (Convolvulus arvensis), water parsley (Oenanthe javanica), bindweed (Polygonum convolvulus), barnyardgrass (Echinochloa oryzicola Vasing, Taiwan ivy (Ischaemum rugosum), Veronica arvensis, Cyperus difformis L., Amaranthus rudis, Timothy (Phleumpratense, Clove Polygonum (Ludwigia prostrata Roxburgh), Dayflower (Commelina communis), Texas Panicum (Panicum texanum), Spurge (Euphorbia helioscopia), Spotted Tit (Festuca parvigluma), Long-legged Dock (Rumex crispus), Shepherd's Purse (Capsella bursa-pastoris), Calendula (Euphorbia pseudochamaesyce), Heart Millet (Brachiaria plantaginea), Lolium multiflorum, Field Thistle (Cirsium japonicum), Black-legged Foxtail (Alopecurus myosuroides), Field Mustard (Sinapis arvensis), Groundnut (Senecio vulgaris), and Galinsoga ciliata, Amaranthus tricolor, Chickweed (Stellaria media), Papyrus (Cyperus papyrus), Cyperus rotundus, Amaranthus spinosus, Polygonum persicaria, Senecio cannabifolius, Cyperus flaccidus, Corn poppy (Papaver rhoeas), Sunflower (Helianthus annuus), Lamium purpureum, Kyllinga gracillima, Lythrum salicaria (Ammannia multiflora), Artemisia canadensis (Erigeron canadensis), Pondweed (Potamogeton distinctus A. Benn), Water hyacinth (Amaranthus tuberculatus), field pansy (Viola arvensis), Japanese thistle (Cirsium purpuratum), ragweed (Ambrosia artemisiifolia), Japanese ragweed (Schoenoplectus tabernaemontani), Japanese ragweed (Veronicahederaefolia, blackgrass (Alopecurus myosuroides), Florida beggarweed (Desmodium tortuosum), plantain (Plantago lanceolata), kochia (Kochia scoparia), burdock (Lolium rigidum), loose-leaved ryegrass (Ammannia coccinea), loose-leaved ryegrass (Lolium perenne), bulrush (Scirpus juncoides Roxburgh), henbit (Lamium amplexicaule), ash grass (Najas graminea), red amaranthus (Amaranthus hybridus), pine needles (Eleocharis acicularis L.), portulaca grandiflora, morning glory (Ipomoea lacunosa), round morning glory (Ipomoea purpurea, common morning glory (Ipomoea hederacea var integriuscula), common dayflower (Commelina bengharensis), water laurel (Monochoria korsakowii), water sorghum (Cyperus serotinus Rottboel), water chickweed (Elatine triandra Schk), crabgrass (Digitaria ciliaris), crabgrass (Digitaria sanguinalis), sorghum (Sorghum bicolor), cleaver (Galium aparine), mugwort (Artemisia princeps), wild pansy (Viola tricolor), wild radish (Raphanus raphanistrum), forget-me-not (Myosotis arvensis), and arrowhead (Alisma canaliculatum). The nitrogen-containing heterocyclic compound or a salt thereof of the present invention inhibits the growth of these weeds.

[0447] The nitrogen-containing heterocyclic compound or salt thereof of the present invention is generally formulated into a convenient form for use according to the conventional method for formulating agricultural chemicals. That is, the compound represented by the general formula (1) of the present invention or a salt thereof may be blended in an appropriate ratio with an appropriate inert carrier, or if necessary, an adjuvant, and then dissolved, separated, suspended, mixed, impregnated, adsorbed or attached to the carrier, and then formulated into an appropriate dosage form, such as a suspension, emulsion, solution, wettable powder, water dispersible granule, granule, dust, tablet, pack, etc., for use.

[0448] In addition to the active ingredient, the composition (agricultural and horticultural herbicide) of the present invention may contain additives commonly used in pesticide formulations or agricultural and horticultural herbicides, as needed. Examples of such additives include carriers such as solid carriers and liquid carriers, surfactants, dispersants, wetting agents, binders, tackifiers, thickeners, colorants, spreaders, adhesives, antifreeze agents, anticaking agents, disintegrants, and antidecomposition agents. Other additives, such as preservatives and plant fragments, may also be used as needed. These additives may be used alone or in combination of two or more.

[0449] Examples of solid carriers include natural minerals such as quartz, clay, kaolinite, pyrophyllite, sericite, talc, bentonite, acid clay, attapulgite, zeolite, and diatomaceous earth; inorganic salts such as calcium carbonate, ammonium sulfate, sodium sulfate, and potassium chloride; organic solid carriers such as synthetic silicic acid, synthetic silicates, starch, cellulose, and plant powders (e.g., sawdust, coconut shells, corn cobs, and tobacco stalks); plastic carriers such as polyethylene, polypropylene, and polyvinylidene chloride; urea; inorganic hollow bodies; plastic hollow bodies; and fumed silica (fumed silica, white carbon). These may be used alone or in combination of two or more.

[0450] Examples of liquid carriers include monohydric alcohols such as methanol, ethanol, propanol, isopropanol, and butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and glycerin; polyhydric alcohol compounds such as propylene glycol ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; ethers such as ethyl ether, dioxane, ethylene glycol monoethyl ether, dipropyl ether, and THF; normal paraffin, naphthene, isoparaffin, and the like. Examples of suitable solvents include aliphatic hydrocarbons such as ethanol, kerosene, and mineral oil, aromatic hydrocarbons such as benzene, toluene, xylene, solvent naphtha, and alkylnaphthalene, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, esters such as ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, and dimethyl adipate, lactones such as γ-butyrolactone, amides such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-alkylpyrrolidinone, nitriles such as acetonitrile, sulfur compounds such as dimethyl sulfoxide, vegetable oils such as soybean oil, rapeseed oil, cottonseed oil, and castor oil, and water. These may be used alone or in combination of two or more.

[0451] Examples of surfactants used as dispersants, wetting agents, spreading agents and spreaders include sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene resin acid esters, polyoxyethylene fatty acid diesters, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene dialkylphenyl ethers, polyoxyethylene alkylphenyl ether formalin condensates, polyoxyethylene polyoxypropylene block copolymers, polystyrene polyoxyethylene block polymers, alkyl polyoxyethylene polypropylene block copolymer ethers, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene fatty acid bisphenyl ethers, polyalkylene benzyl phenyl ethers, polyoxyalkylene styryl phenyl ethers, acetylenic diols, polyoxyalkylene-added acetylenic diols, polyoxyethylene ether-type silicones, and ester-type silicones. nonionic surfactants such as fluorine-based surfactants, polyoxyethylene castor oil, and polyoxyethylene hydrogenated castor oil; anionic surfactants such as alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkylbenzenesulfonates, alkylarylsulfonates, ligninsulfonates, alkylsulfosuccinates, naphthalenesulfonates, alkylnaphthalenesulfonates, salts of formalin condensates of naphthalenesulfonic acid, salts of formalin condensates of alkylnaphthalenesulfonic acid, fatty acid salts, polycarboxylates, polyacrylates, N-methyl-fatty acid sarcosinates, resinates, polyoxyethylene alkyl ether phosphates, and polyoxyethylene alkyl phenyl ether phosphates; cationic surfactants such as alkylamine salts such as laurylamine hydrochloride, stearylamine hydrochloride, oleylamine hydrochloride, stearylamine acetate, stearylaminopropylamine acetate, alkyltrimethylammonium chloride, and alkyldimethylbenzalkonium chloride;Examples of such surfactants include amphoteric surfactants such as amino acid surfactants and betaine surfactants. These surfactants may be used alone or in combination of two or more.

[0452] Examples of binders and tackifiers include carboxymethyl cellulose and its salts, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinylpyrrolidone, gum arabic, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, polyethylene glycol having an average molecular weight of 6,000 to 20,000, polyethylene oxide having an average molecular weight of 100,000 to 5,000,000, phospholipids (for example, cephalin, lecithin, etc.), cellulose powder, dextrin, modified starch, polyaminocarboxylic acid chelate compounds, crosslinked polyvinylpyrrolidone, copolymers of maleic acid and styrenes, (meth)acrylic acid copolymers, half esters of polymers composed of polyhydric alcohols and dicarboxylic acid anhydrides, water-soluble salts of polystyrene sulfonic acid, paraffin, terpene, polyamide resins, polyacrylates, polyoxyethylene, wax, polyvinyl alkyl ethers, alkylphenol-formalin condensates, and synthetic resin emulsions.

[0453] Examples of thickeners include water-soluble polymers such as xanthan gum, guar gum, diutan gum, carboxymethyl cellulose, polyvinylpyrrolidone, carboxyvinyl polymers, acrylic polymers, starch compounds, and polysaccharides, and inorganic fine powders such as high-purity bentonite and fumed silica (white carbon).

[0454] Examples of colorants include inorganic pigments such as iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes.

[0455] Examples of antifreezing agents include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin.

[0456] Examples of adjuvants for preventing caking or promoting disintegration include starch, alginic acid, polysaccharides such as mannose and galactose, polyvinylpyrrolidone, fumed silica (white carbon), ester gum, petroleum resin, sodium tripolyphosphate, sodium hexametaphosphate, metal stearates, cellulose powder, dextrin, methacrylic acid ester copolymers, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compounds, sulfonated styrene-isobutylene-maleic anhydride copolymers, and starch-polyacrylonitrile graft copolymers.

[0457] Examples of anti-decomposition agents include desiccants such as zeolite, quicklime, and magnesium oxide; antioxidants such as phenol compounds, amine compounds, sulfur compounds, and phosphoric acid compounds; and ultraviolet absorbers such as salicylic acid compounds and benzophenone compounds.

[0458] Examples of preservatives include potassium sorbate and 1,2-benzothiazolin-3-one. Furthermore, other adjuvants such as functional spreading agents, activity enhancers such as metabolic decomposition inhibitors such as piperonyl butoxide, antifreeze agents such as propylene glycol, antioxidants such as BHT, and ultraviolet absorbers may also be used as needed.

[0459] The blending ratio of the active ingredient compound can be adjusted as needed and may be appropriately selected from the range of 0.01 to 90 parts by weight per 100 parts by weight of the agricultural and horticultural herbicide of the present invention. For example, when the agricultural and horticultural herbicide is formulated as a dust, granule, emulsifiable concentrate or wettable powder, the blending ratio is appropriately 0.01 to 50% by weight based on the total weight of the agricultural and horticultural herbicide.

[0460] The amount of the nitrogen-containing heterocyclic compound or salt thereof of the present invention to be used varies depending on various factors, such as the purpose, target weeds, crop growth conditions, weed infestation tendency, weather, environmental conditions, formulation, application method, application location, application time, etc., but may be appropriately selected depending on the purpose from a range of 0.001 g to 10 kg, preferably 0.01 g to 1 kg, of the active ingredient compound per 10 ares.

[0461] The agricultural and horticultural herbicides containing the nitrogen-containing heterocyclic compound or salts thereof of the present invention as an active ingredient can be directly sprayed onto the foliage of weeds in an amount effective for weed control, either as is or after being appropriately diluted or suspended in water or the like, to control various weeds. In addition, they can also be used by treating the soil or a cultivation carrier, for example, by immersing seeds in the herbicide, seed dressing, seed treatment of useful plants such as calper treatment, incorporation into the entire soil layer, row application, incorporation into bed soil, treatment with cell seedlings, treatment in planting holes, treatment at the base of plants, top dressing, treatment in rice boxes, application on the water surface, etc.

[0462] Examples of methods for treating seeds of useful plants include a method in which seeds are immersed in a liquid or solid formulation, diluted or undiluted, to allow the agent to penetrate the seeds; a method in which a solid or liquid formulation is mixed with seeds and coated onto the seed surface; a method in which the formulation is mixed with an adhesive carrier such as a resin or polymer and then coated onto the seeds; and a method in which the formulation is sprayed around the seeds at the same time as planting. The "seeds" to be subjected to the seed treatment refer to plant bodies in the early stages of cultivation used for propagating useful plants, and examples thereof include seeds, as well as bulbs, tubers, seed potatoes, sprouts, corms, bulbils, or plant bodies for vegetative propagation used for cultivation by cuttings.

[0463] When carrying out the method of use of the present invention, the term "soil" or "cultivation carrier" for plants refers to a support for cultivating crops, particularly a support for growing roots. The material is not particularly limited, and any material capable of growing useful plants may be used, such as soil, a seedling mat, or water. Specific examples of the material include sand, pumice, vermiculite, diatomaceous earth, agar, a gel-like substance, a polymeric substance, rock wool, glass wool, wood chips, and bark.

[0464] For application to rice seedling boxes, the formulation may vary depending on the application time, such as application at the time of sowing, application during the greening period, or application at the time of transplanting, but may be in the form of a dust, water dispersible granule, granule, or the like. Application can also be by mixing with the culture soil, and the culture soil can be mixed with a dust, water dispersible granule, or granule, for example, by mixing with the bed soil, mixing with the covering soil, or mixing with the entire culture soil. Application can also be simply by layering the culture soil and various formulations alternately.

[0465] For application to paddy fields, solid formulations such as jumbo formulations, pack formulations, granules, and water dispersible granules, or liquid formulations such as flowable and emulsifiable concentrates, are usually sprayed onto flooded paddy fields. Alternatively, at the time of rice planting, appropriate formulations can be sprayed or injected directly into the soil, or mixed with fertilizer. Furthermore, by using emulsions, flowables, and other chemical solutions at the source of water flow into paddy fields, such as water inlets and irrigation systems, they can be applied in a labor-saving manner in conjunction with the water supply. When using spraying equipment, any commonly used equipment can be used, such as a punkul sprayer, manned helicopter, radio-controlled helicopter, radio-controlled boat, drone, one-shot sprayer, powered (manual or automatic) sprayer, carry-type power sprayer, backpack-type power sprayer, manual sprayer, etc.

[0466] The nitrogen-containing heterocyclic compound or salt thereof of the present invention can be used in combination with other herbicides, plant growth regulators, phytotoxicity reducers (safeners), soil conditioners, fertilizers, etc., in order to extend the range of weeds to be controlled or the optimum control period, or for the purpose of reducing the dosage, and can also be used in combination with agricultural and horticultural insecticides, miticides, nematicides, fungicides, biological pesticides, etc., depending on the application scene. Representative compounds are exemplified below, but the present invention is not limited to these.

[0467] Other herbicides used for this purpose include, for example, 1-naphthylacetamide, 2,4-PA, 2,3,6-TBA, 2,4,5-T, 2,4,5-TB, 2,4-D, 2,4-DB, 2,4-DEB, 2,4-DEP, 3,4-DA, 3,4-DB, 3,4-DP, 4-CPA, 4-CPB, 4-CPP, MCP, MCPA, MCPA thioethyl, MCPB, ioxynil, icafolin, aclonifen, azafenidin, Acifluorfen, Aziprotryne, Azimsulfuron, Asulam, Acetochlor, Atrazine, Atraton, Anisuron, Anilofos, Aviglycine, Abscisic Acid acid, amicarbazone, amidosulfuron, amitrole, aminocyclopyrachlor, aminopyralid, amivudine, amiprophos-methyl, ametridione, ametryn, alachlor, allidochlor, alloxydim, and alora c), iofensulfuron, isouron, isocarbamide, isoxachlortole, isoxapyrifop, isoxaflutole, isoxaben, isocil, isonoruron, isoproturon, isopropalin, isopolinate, isomethiozin,Inabenfide, ipazine, iptriazopyrid, ipfencarbazone, iprimidam, imazaquin, imazapic, imazapyr, imazamethapyr, imazamethabenz, imazamethabenz-methyl, imazamox, imazethapyr, imazosulfuron, indaziflam, indanofan, indolauxipyr, indolauxipyr-cyanomethyl, indolebutyric acid acid), uniconazole-P, eglinazine, esprocarb, ethametsulfuron, ethametsulfuron-methyl, ethalfluralin, ethiolate, ethychlozate-ethyl ethyl), etidimuron, ethinofen, ethephon, ethoxysulfuron, ethoxyfen, etonipromide, etofumesate, etobenzanid, epirifenacil, epronaz, erbon, endothal, oxadiazon, oxadiargyl, oxaziclomefone, oxasulfuron, oxapyrazon, oxyfluorfen,Oryzalin, orthosulfamuron, orbencarb, cafenstrole, cambendichlor, carbasulam, carfentrazone, carfentrazone-ethyl, karbutilate, carbetamide, carboxazole azole), quizalofop, quizalofop-P, quizalofop-ethyl, xylachlor, quinoclamine, quinonamid, quinclorac, quinmerac, cumyluron, clacyfos, cliodinate, glyphosate, glyphosate glufosinate, glufosinate-P, credazine, clethodim, cloxyfonac, clodinafop, clodinafop-propargyl, chlortoluron, clopyralid, cloproxydim, cloprop, clobromuron chlorbromuron, clofop, clomazone, chlomethoxynil, chlomethoxyfen, clomeprop, chlorazifop, chlorazine, chlorasulam, chloranocryl, chloramben, chloransulam-methyl,Chloridazon, chlorimuron, chlorimuron-ethyl, chlorsulfuron, chlorthal, chlorthiamid, chlornitrofen, chlorfenac, chlorfenprop, chlorbufam, chlorflurazol e), chlorflurenol, chlorprocarb, chlorpropham, chlormequat, chloreturon, chloroxynil, chloroxuron, chloropon, saflufenacil, cyanazine, cyanatrin, di-allate , diuron, diethamquat, dioxopyritrione, dicamba, cycluron, cycloate, cycloxydim, diclosulam, cyclosulfamuron, cyclopyranil, cyclopyrimorate, dichlorprop, di Dichlorprop-P, dichlobenil, diclofop, diclofop-methyl, dichromate, dichloralurea, diquat, cisanilide, disul, siduron, dithiopyr, dinitramine, cinidon-ethyl,Dinosam, cinosulfuron, dinoseb, dinoterb, dinofenate, dinoprop, cyhalofop-butyl, cypyrafluone, diphenamid, difenoxuron, difenopenten, difenzoquat, sibutrin tryne), cyprazine, cyprazole, diflufenican, diflufenzopyr, dipropetryn, cypromid, cyperquat, gibberellin, simazine, dimexano, dimesulfazet, dimethachlor, dimedazone midazon, dimethametryn, dimethenamid, simetryn, simeton, dimepiperate, dimefuron, cinmethylin, swep, sulglycapin, sulcotrione, sulfalate, sulfentrazone, sulfosulfuron sulfosulfuron, sulfometuron, sulfometuron-methyl, secbumeton, sethoxydim, sebuthylazine, terbacil, daimuron, dazomet, dalapon, thiazafluron, thiazopyr, thiafenacil,Thiencarbazone, thiencarbazone-methyl, thiocarbazil, thioclorim, thiobencarb, thidiazimine, thidiazuron, thifensulfuron, thifensulfuron-methyl, desmedipham, desme Desmetryn, tetflupyrolimet, tetrafluron, thenylchlor, tebutam, tebuthiuron, terbumeton, tepraloxydim, tefuryltrione, tembotrione, delachlor, terbacil, terbucarb erbucarb, terbuchlor, terbuthylazine, terbutryn, topramezone, tralkoxydim, triaziflam, triasulfuron, triafamone, triallate, trietazine, tricamba, triclopyr ), tridiphane, tritac, tritosulfuron, tripyrasulfone, trifludimoxazin, triflusulfuron, triflusulfuron-methyl, trifluralin, trifloxysulfuron, tripropindan,Tribenuron-methyl, tribenuron, triphop, trifopsime, trimeturon, tolpyralate, naptalam, naproanilide, naproxen, nicosulfuron, nitralin, nitrofen, nitrofluorfen nitrofluorfen, nipyraclofen, neburon, norflurazon, noruron, barban, paclobutrazol, paraquat, parafluron, haloxydine, haloxifen, haloxyfop, haloxyfop-P, haloxyfop haloxyfop-methyl, halosafen, halosulfuron, halosulfuron-methyl, bixlozone, picloram, picolinafen, bicyclopyrone, bispyribac, bispyribac-sodium, pydanon, pinoxaden (pinoxaden), bipyrazone, bifenox, piperophos, hymexazol, pyraquinate, pyraclonil, pyrasulfotole, pyrazoxyfen, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazolate,Bilanafos, pyraflufen-ethyl, pyri, Chlor (pyriclor), pyridafol, pyrithiobac, pyrithiobac-sodium, pyridate, pyriftalid, pyributicarb, pyriflubenzoxim, pyribenzoxim, pyrimisulfan, pyrimisulfuron, pyriminobac pyriminobac-methyl, flusulfinam, broclozone, pyroxasulfone, pyroxsulam, fenasulam, phenisopham, fenuron, fenoxasulfone, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl (fenoxaprop-ethyl), fenothiol, fenoprop, fenobenzuron, fenquinotrione, fentiaprop, fenteracol, fentrazamide, fenpyrazone, phenmedipham, phenmedipham-ethyl yl), butachlor, butafenacil, butamifos, buthiuron, buthidazole, butyrate, buturon, butenachlor, butroxydim, butralin, flazasulfuron, flamprop, furyloxyfen,Prinachlor, primisulfuron-methyl, fluazifop, fluazifop-P, fluazifop-butyl, fluazolate, fluchloraminopyr, fluchloraminopyr-tefuryl, fluroxypyr, fluothiuron ron), fluometuron, fluoroglycofen, flurochloridone, fluorodifen, fluoronitrofen, fluoromidine, flucarbazone, flucarbazone sodium, fluchloralin, flucetosulfuron ron), fluthiacet, fluthiacet-methyl, flupyrsulfuron, flufenacet, flufenoximacil, flufenican, flufenpyr, flupropacil, flupropanate, flupoxam, flumioxazin , flumiclorac, flumiclorac pentyl, flumipropyn, flumezin, fluometuron, flumetsulam, fluridone, flurtamone, fluroxypyr, pretilachlor, proxan, proglinadin,Procyazine, prodiamine, prosulfalin, prosulfuron, prosulfocarb, propaquizafop, propachlor, propazine, propanil, propyzamide, propisochlor, prohydrojasmone smon), propyrisulfuron, propham, profluazol, profluralin, prohexadione calcium, propoxycarbazone, propoxycarbazone sodium, profoxydim, bromacil, brompyrazone yrazon, prometryn, prometon, bromoxynil, bromofenoxim, bromobutide, bromobonil, florasulam, florpyrauxifen, hexachloroacetone, hexazinone, pethoxamid, benazolin (benazolin), penoxsulam, pebulate, beflubutamid, beflubutamid-M, vernolate, perfluidone, bencarbazone, benquitrione, benzadox, benzipram, benzylaminopurine,Benzthiazuron, benzfendizone, bensulide, bensulfuron-methyl, benzoylprop, benzobicyclon, benzofenap, benzofluor, bentazone, pentanochlor, benthiocarb, pendimethalin, pentoxazone, benfluralin, benfuresate, fosamine, fomesafen, foramsulfuron, forchlorfenuron, maleic hydrazide hydrazide), mecoprop, mecoprop-P, medinoterb, mesosulfuron, mesosulfuron-methyl, mesotrione, mesoprazine, mesoprothrin, metazachlor, methazole, metazosulfuron, methabenzthiazuron, methamite metamitron, metamifop, metam, methalpropalin, methiuron, methiozolin, methiobencarb, methyldymron, metoxuron, metoslam, metsulfuron, metsulfuron-methyl, metflurazon, metobromuron,Methobenzuron, methometon, metolachlor, metribuzin, mepiquat chloride, mefenacet, mefluidide, monalide, monisouron, monunuron, monochloroacetic acid Examples of suitable herbicides include iodosulfuron, monolinuron, molinate, morphamquat, iodosulfuron, iodosulfuron-methyl-sodium, iodobonil, iodomethane, lactofen, lancotrione, linuron, rimisoxafen, rimsulfuron, lenacil, rhodetanil, calcium peroxide, and methyl bromide. They can also be used in combination with biological pesticides used as herbicides against Xanthomonas campestris, etc.

[0468] In addition, it is also possible to use in combination with a safener such as 1,8-naphthalic anhydride, isoxadifen-ethyl, furilazole, cyprosulfamide, cyometrinil, dichlormid, dimepiperate, thiencarbazone-methyl, fenchlorazole-ethyl, fenclorim, fluxofenim, flurazole, benoxacor, metcamifen, or mefenpyr-diethyl.

[0469] Furthermore, as biological pesticides, for example, natural enemies of Encarsia formosa, Aphidius colemani, Aphidoletes aphidimyza, Diglyphus isaea, Dacnusa sibirica, Phytoseiulus persimilis, Amblyseius cucumeris, Orius sauteri, and the like, and Beauveria brongniartii, It can also be used in combination with microbial pesticides such as Pseudomonas brongniartii, and pheromone agents such as (Z)-10-tetradecenyl acetate, (E,Z)-4,10-tetradecadinyl acetate, (Z)-8-dodecenyl acetate, (Z)-11-tetradecenyl acetate, (Z)-13-icosen-10-one, and 14-methyl-1-octadecene. [Example]

[0470] Representative examples of the present invention will be given below, but the present invention is not limited to these.

[0471] Manufacturing Example 1 Preparation of (Z)-ethyl 6-(N'-ethoxycarbamimidoyl)-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate (Compound No. 5-3) Manufacturing Example 1-1 Preparation of (Z)-ethyl 6-(N'-hydroxycarbamimidoyl)-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate [ka] To a solution of ethyl 6-cyano-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate (0.73 g, 2.1 mmol) in ethanol (21 mL), hydroxylamine hydrochloride (0.22 g, 3.2 mmol) and sodium acetate (0.26 g, 3.2 mmol) were added and the mixture was stirred under reflux for 2 hours. The reaction mixture was concentrated under reduced pressure, and saturated aqueous sodium bicarbonate was added, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-ethyl 6-(N'-hydroxycarbamimidoyl)-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate (0.72 g, 1.6 mmol). Yield: 89% Physical properties: Melting point: 127-128℃

[0472] Manufacturing Example 1-2 Preparation of (Z)-ethyl 6-(N'-ethoxycarbamimidoyl)-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate (Compound No. 5-3) [ka] To a solution of (Z)-ethyl 6-(N'-hydroxycarbamimidoyl)-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate (0.30 g, 0.78 mmol) in N,N-dimethylformamide (8.0 mL) was added cesium carbonate (0.51 g, 1.6 mmol) and ethyl iodide (0.13 mL, 1.6 mmol) at room temperature, and the mixture was stirred at room temperature. Saturated aqueous ammonium chloride solution was added to the reaction mixture, which was then extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give (Z)-ethyl 6-(N'-ethoxycarbamimidoyl)-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate (0.35 mg, 0.78 mmol). Yield: 100% Physical properties: Refractive index: 1.4692 (20.1°C)

[0473] Manufacturing Example 2 Preparation of (Z)-ethyl 6-(N'-ethoxycarbamimidoyl)-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate (Compound No. 7-1) Manufacturing Example 2-1 Preparation of (Z)-ethyl 6-(N'-hydroxycarbamimidoyl)-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate [ka] Hydroxylamine hydrochloride (20 mg, 0.27 mmol) and sodium acetate (23 mg, 0.27 mmol) were added to a solution of ethyl 6-cyano-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate (63 mg, 0.18 mmol) in ethanol (1.0 mL) at room temperature, and the mixture was stirred under reflux for 3 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and saturated aqueous sodium bicarbonate was added to the residue, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give (Z)-ethyl 6-(N'-hydroxycarbamimidoyl)-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate (51 mg, 0.13 mmol). Yield: 74%

[0474] Manufacturing Example 2-2 Preparation of (Z)-ethyl 6-(N'-ethoxycarbamimidoyl)-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate (Compound No. 7-1) [ka] To a solution of (Z)-ethyl 6-(N'-hydroxycarbamimidoyl)-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate (40 mg, 0.11 mmol) in N,N-dimethylformamide (8.0 mL) was added cesium carbonate (70 mg, 0.21 mmol) and ethyl iodide (20 μL, 0.21 mmol) at room temperature, followed by stirring at room temperature for 2 hours. After completion of the reaction, saturated aqueous ammonium chloride solution was added to the reaction solution, which was then extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give (Z)-ethyl 6-(N'-ethoxycarbamimidoyl)-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate (36 mg, 0.088 mmol). Yield: 83% Physical properties: 1H-NMR(CDCl3):δ 8.06(d,1H),8.01(d,1H),7.91-7.81(m,2H),7.44-7.38(m,3H),5.53( s,2H),4.21(q,2H),4.18(q,2H),2.73(s,3H),1.35(t,3H),1.08(t,3H)

[0475] Manufacturing Example 3 Preparation of (Z)-N'-ethoxy-6-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)-5-(N-methylsulfamoyl)picoline imidamide (Compound No. 1-4) [ka] To a solution of 6-cyano-N-methyl-2-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)pyridine-3-sulfonamide (0.16 g, 0.45 mmol) in methanol (2.0 mL) was added a solution of sodium methoxide in methanol (28 wt%, 0.10 mL, 0.45 mmol) and stirred at room temperature for 30 minutes. After confirming the disappearance of the starting materials, O-ethylhydroxylamine hydrochloride (67 mg, 0.69 mmol) was added to the reaction mixture and stirred at room temperature for 30 minutes. Saturated aqueous ammonium chloride was added, and the mixture was extracted with ethyl acetate. The organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give (Z)-N'-ethoxy-6-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)-5-(N-methylsulfamoyl)picoline imidamide (89.1 mg, 0.21 mmol). Yield: 47% Physical properties: 1 H-NMR(CDCl3):δ 8.46(d,1H),8.26(d,1H),8.03-7.99(m,2H),7.79-7.73(m,1H),7.51-7.4 3(m,3H),5.44(s,2H),4.24(q,2H),4.10(s,1H),2.79(d,3H),1.37(t,3H)

[0476] Manufacturing Example 4 Preparation of (Z)-N'-ethoxy-6-(1-methyl-4-phenyl-1H-imidazol-2-yl)-5-(N-methylsulfamoyl)picoline imidamide (Compound No. 2-33) [ka] To a solution of 6-cyano-N-methyl-2-(1-methyl-4-phenyl-1H-imidazol-2-yl)pyridine-3-sulfonamide (0.10 g, 0.28 mmol) in methanol (1.0 mL), sodium methoxide-methanol solution (28 wt%, 0.050 mL, 0.77 mmol) was added and stirred at room temperature for 30 minutes. After confirming the disappearance of the raw materials, O-ethylhydroxylamine hydrochloride (42 mg, 0.42 mmol) was added and stirred at room temperature for 30 minutes. Saturated aqueous ammonium chloride was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was concentrated. The residue was purified by silica gel column chromatography to obtain the desired product (83 mg, 0.20 mmol). Yield: 72% Physical properties: Melting point: 237-238℃

[0477] Manufacturing Example 5 Preparation of (Z)-N'-ethoxy-6-(5-methyl-3-phenyl-1H-1,2,4-triazol-1-yl)-5-(N-methylsulfamoyl)picoline imidamide (compound number: 3-3) [ka] To a solution of (Z)-6-chloro-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (80 mg, 0.27 mmol) in N,N-dimethylacetamide (1.5 mL), potassium carbonate (0.13 g, 0.96 mmol) and 5-methyl-3-phenyl-1H-1,2,4-triazole (53 mg, 0.27 mmol) were added and stirred at 130 °C for 4 hours. After the reaction was completed, water and ethyl acetate were added for extraction. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-N'-ethoxy-6-(5-methyl-3-phenyl-1H-1,2,4-triazol-1-yl)-5-(N-methylsulfamoyl)picoline imidamide (84 mg, 0.19 mmol). Yield: 68% Physical properties: 1 H-NMR(CDCl3):δ 8.48(d,1H),8.28(d,1H),8.04-8.01(m,2H),7.49-7.45(m,3H),6.34(q ,1H),5.39(brs,2H),4.24(q,2H),2.79(d,3H),2.61(s,3H),1.37(t,3H)

[0478] Production Example 6 Preparation of (Z)-N'-ethoxy-6-(5-methyl-3-phenyl-1H-pyrazol-1-yl)-5-(N-methylsulfamoyl)picoline imidamide (Compound Number: 4-6) [ka] To a solution of (Z)-6-chloro-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (70 mg, 0.25 mmol) in N,N-dimethylacetamide (1.4 mL), potassium carbonate (0.12 g, 0.87 mmol) and 5-methyl-3-phenyl-1H-pyrazole (40 mg, 0.25 mmol) were added and the mixture was stirred at 130°C for 5 hours. After completion of the reaction, the reaction mixture was extracted with water and ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-N'-ethoxy-6-(5-methyl-3-phenyl-1H-pyrazol-1-yl)-5-(N-methylsulfamoyl)picoline imidamide (28 mg, 0.070 mmol). Yield: 28% Physical properties: 1 H-NMR(CDCl3):δ 8.46(d,1H),8.20(d,1H),7.72-7.69(m,1H),7.45-7.40(m,2H),7.38-7.34(m,1H),6.79 (q,1H),6.60(s,1H),5.41(brs,2H),4.23(q,2H),2.77(d,3H),2.43(s,3H),1.37(t,3H)

[0479] Manufacturing Example 7 Preparation of (E)-4-(6-(1-(ethoxyimino)ethyl)-3-(methylsulfonyl)pyridin-2-yl)-3-methyl-1-phenyl-1H-1,2,4-triazol-5(4H)-one (Compound No. 6-1) [ka] To a solution of (E)-1-(6-chloro-5-(methylsulfonyl)pyridin-2-yl)ethanone O-ethyl oxime (60 mg, 0.22 mmol) in N,N-dimethylformamide (1.0 mL), 3-methyl-1-phenyl-1H-1,2,4-triazol-5(4H)-one (76 mg, 0.43 mmol), 4,5'-bis(diphenylphosphino)-9,9'-dimethylxanthene (25 mg, 0.043 mmol), and tris(dibenzylideneacetone)dipalladium(0) (20 mg, 0.022 mmol) were added and stirred at 120°C for 3 hours. Saturated aqueous ammonium chloride was added to the reaction mixture, which was then extracted with ethyl acetate and washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (E)-4-(6-(1-(ethoxyimino)ethyl)-3-(methylsulfonyl)pyridin-2-yl)-3-methyl-1-phenyl-1H-1,2,4-triazol-5(4H)-one (4.0 mg, 0.0084 mmol). Yield: 4% Physical properties: 1 H-NMR(CDCl3):δ 8.44(d,1H),8.24(d,1H),8.02-7.95(m,2H),7.49-7.40(m,2H),7.26-7. 21(m,1H),4.36q,2H),3.40(s,3H),2.29(s,3H),2.21(s,3H),1.38(t,3H)

[0480] Production Example 8 Preparation of (Z)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-N'-ethoxy-4-(N-methylsulfamoyl)benzimidamide (Compound No. 17-2) [ka] To a solution of (Z)-4-((4-(tert-butyl)benzyl)thio)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-N'-ethoxybenzimidamide (0.23 g, 0.42 mmol) in chloroform (4.2 mL), 1,3-dichloro-5,5-dimethylhydantoin (0.25 g, 1.3 mmol), acetic acid (75 μL, 1.3 mmol), and water (45 μL, 2.5 mmol) were added at 0°C and stirred at the same temperature for 10 minutes. A solution of methylamine in methanol (9.8 M, 0.43 mL, 4.2 mmol) was added and stirred for 10 minutes. After stirring, the reaction mixture was diluted with water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-N'-ethoxy-4-(N-methylsulfamoyl)benzimidamide (72 mg, 0.16 mmol). Yield: 37% Physical properties: Melting point: 167-168℃

[0481] Manufacturing Example 9 Preparation of (Z)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-N'-ethoxy-4-(N-methylsulfamoyl)benzimidamide (Compound No. 1-12) [ka] To a solution of (Z)-6-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-N'-ethoxy-5-(N-methylsulfanyl)picoline imidamide (0.10 g, 0.22 mmol) in N,N-dimethylacetamide (2 mL) were added acetic anhydride (0.067 g, 0.33 mmol) and cesium carbonate (0.22 g, 0.33 mmol) at room temperature and stirred at 50°C for 10 minutes. A solution of methylamine in methanol (9.8 M, 0.43 mL, 4.2 mmol) was added and stirred for 10 minutes. Water was then added to the reaction mixture, which was then extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-N-acetyl-N-((5-(N-acetyl-N-methylsulfamoyl)-6-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)pyridin-2-yl)(ethoxyimino)methyl)acetamide (62 mg, 0.11 mmol). Yield: 50% Physical properties: 1 H-NMR(CDCl3):δ 8.79(d,1H),8.34(d,1H),7.93-7.90(m,1H),7.53-7.50(m,1H),7.38-7.35(m,2 H),4.44(q,2H),3.85(s,3H),3.05(s,3H),2.32(s,9H),2.16(s,3H),1.40(t,3H)

[0482] Manufacturing Example 10 Preparation of (Z)-N'-ethoxy-6-(4-methyl-1-(2-nitrophenyl)-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)-5-(N-methylsulfamoyl)picoline imidamide (Compound No. 5-19) [ka] To a solution of 6-cyano-N-methyl-2-(4-methyl-1-(2-nitrophenyl)-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)pyridine-3-sulfonamide (1.0 g, 2.4 mmol) in methanol (10 mL) was added a solution of sodium methoxide in methanol (28 wt%, 0.55 mL, 2.4 mmol) and stirred at room temperature for 30 minutes. After confirming the disappearance of the raw materials, O-ethylhydroxylamine hydrochloride (0.36 g, 3.7 mmol) was added to the reaction solution and stirred at room temperature for 30 minutes. A saturated aqueous solution of ammonium chloride was added to the reaction solution, which was extracted with ethyl acetate, and the organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give (Z)-N'-ethoxy-6-(4-methyl-1-(2-nitrophenyl)-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)-5-(N-methylsulfamoyl)picoline imidamide (0.92 g, 1.9 mmol). Yield: 79% Physical properties: 1 H-NMR(CDCl3):δ 8.43(d,1H),8.29(d,1H),7.96-7.90(m,2H),7.78-7.72(m,1H),7.56-7.50(m,1 H),5.84(q,1H),5.45(s,2H),4.24(q,2H),3.42(s,3H),2.71(d,3H),1.37(t,3H)

[0483] Manufacturing Example 11 Preparation of (Z)-N'-ethoxy-5-(N-methylsulfamoyl)-6-(2-phenylthiazol-4-yl)picoline imidamide (Compound No. 7-18) and (Z)-6-(5-bromo-2-phenylthiazol-4-yl)-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (Compound No. 7-19) Manufacturing Example 11-1 Preparation of (Z)-6-acetyl-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide [ka] To a solution of (Z)-6-chloro-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (1.0 g, 3.4 mmol) in dimethoxyethane (20 mL), tetrakis(triphenylphosphine)palladium(0) (0.40 g, 0.34 mmol) and tributyl(1-ethoxyvinyl)tin (1.7 mL, 5.1 mmol) were added and stirred at 110 °C for 5 hours under an argon atmosphere. After completion of the reaction, tetrahydrofuran (10 mL) and 1N hydrochloric acid (10 mL) were added to the reaction mixture, which was stirred overnight at room temperature. Water and ethyl acetate were then added for extraction. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-6-acetyl-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (0.55 g, 1.8 mmol). Yield: 54% Physical properties: Melting point: 100-101℃

[0484] Manufacturing Example 11-2 Preparation of (Z)-6-(2-bromoacetyl)-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide [ka] Phenyltrimethylammonium tribromide (0.62 g, 1.7 mmol) was added to a solution of (Z)-6-acetyl-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (0.50 g, 1.7 mmol) in tetrahydrofuran (10 mL) and stirred at room temperature for 2 hours. After the reaction was completed, the reaction solution was extracted with water and ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give (Z)-6-(2-bromoacetyl)-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (0.71 g, 1.8 mmol). Yield: 100% Physical properties: 1 H-NMR(CDCl3):δ 8.31-8.27(m,1H),8.11-8.09(m,1H),5.51(brs,2H),4.23(q,2H),3.00(s,2H),1.36(t,3H)

[0485] Manufacturing Example 11-3 Preparation of (Z)-N'-ethoxy-5-(N-methylsulfamoyl)-6-(2-phenylthiazol-4-yl)picoline imidamide (compound number 7-18) [ka] Thiobenzamide (0.21 g, 1.5 mmol) was added to a solution of (Z)-6-(2-bromoacetyl)-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (0.71 g, 1.8 mmol) in ethanol (10 mL) and stirred under reflux for 2 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and the resulting residue was extracted with saturated aqueous sodium bicarbonate and ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-N'-ethoxy-5-(N-methylsulfamoyl)-6-(2-phenylthiazol-4-yl)picoline imidamide (0.28 g, 0.68 mmol). Yield: 36% Physical properties: Melting point: 189-190℃

[0486] Manufacturing Example 11-4 Preparation of (Z)-6-(5-bromo-2-phenylthiazol-4-yl)-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (Compound No. 7-19) [ka] N-Bromosuccinimide (0.13 g, 0.70 mmol) was added to a solution of (Z)-N'-ethoxy-5-(N-methylsulfamoyl)-6-(2-phenylthiazol-4-yl)picoline imidamide (0.24 g, 0.58 mmol) in chloroform (5.0 mL). The mixture was stirred at 50°C for 7 hours and then at room temperature overnight. After the reaction was complete, water was added to the reaction mixture and the mixture was extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-6-(5-bromo-2-phenylthiazol-4-yl)-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (0.23 g, 0.46 mmol). Yield: 79% Physical properties: Melting point: 159-160℃

[0487] Manufacturing Example 12 Preparation of (Z)-N'-ethoxy-5-(methylsulfonyl)-6-(4-phenylthiazol-2-yl)picoline imidamide (Compound No. 8-17) and (Z)-N'-ethoxy-5-(N-methylsulfofamoyl)-6-(4-phenylthiazol-2-yl)picoline imidamide (Compound No. 8-2) Manufacturing Example 12-1 Preparation of (Z)-6-(N'-ethoxycarbamimidoyl)-3-(methylsulfonyl)picolinamide [ka] (Z)-Methyl 6-(N'-ethoxycarbamimidoyl)-3-(methylsulfonyl)picolinate (1.4 g, 4.5 mmol) was added to a solution of ammonia in methanol (2 mol / L, 10 mL) and stirred overnight at room temperature. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and the resulting residue was extracted with water and ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-6-(N'-ethoxycarbamimidoyl)-3-(methylsulfonyl)picolinamide (0.32 g, 1.1 mmol). Yield: 24% Physical properties: 1 H-NMR(CDCl3):δ 8.49(d,1H),8.28(d,1H),6.79(brs,1H),5.81(brs,1H),5.43(brs,2H),4.23(q,2H),3.56(s,3H),1.36(t,3H)

[0488] Manufacturing Example 12-2 Preparation of (Z)-6-(N'-ethoxycarbamimidoyl)-3-(methylsulfonyl)pyridine-2-carbothioamide [ka] To a solution of (Z)-6-(N'-ethoxycarbamimidoyl)-3-(methylsulfonyl)picolinamide (0.32 g, 1.1 mmol) in toluene (5.0 mL), Lawesson's reagent (0.45 g, 1.1 mmol) was added and the mixture was stirred at 90°C for 3 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to give (Z)-6-(N'-ethoxycarbamimidoyl)-3-(methylsulfonyl)pyridine-2-carbothioamide (0.27 g, 0.90 mmol). Yield: 82% Physical properties: Melting point: 243-245℃

[0489] Manufacturing Example 12-3 Preparation of (Z)-N'-ethoxy-5-(methylsulfonyl)-6-(4-phenylthiazol-2-yl)picoline imidamide (Compound No. 8-17) [ka] Phenacyl bromide (0.17 g, 0.84 mmol) was added to a solution of (Z)-6-(N'-ethoxycarbamimidoyl)-3-(methylsulfonyl)pyridine-2-carbothioamide (0.23 g, 0.77 mmol) in ethanol (2.5 mL) and stirred under reflux for 2 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and the resulting residue was extracted with saturated aqueous sodium bicarbonate and ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-N'-ethoxy-5-(methylsulfonyl)-6-(4-phenylthiazol-2-yl)picoline imidamide (0.27 g, 0.67 mmol). Yield: 87% Physical properties: Melting point: 177-179℃

[0490] Manufacturing Example 12-4 Preparation of (Z)-5-((4-(tert-butyl)benzyl)thio)-N'-ethoxy-6-(4-phenylthiazol-2-yl)picoline imidamide [ka] Cesium carbonate (0.38 g, 1.2 mmol) and (4-(tert-butyl)phenyl)methanethiol (0.16 mL, 0.87 mmol) were added to a solution of (Z)-N'-ethoxy-5-(methylsulfonyl)-6-(4-phenylthiazol-2-yl)picoline imidamide (0.23 g, 0.58 mmol) in N,N-dimethylacetamide (3.0 mL), and the mixture was stirred at 60°C for 1 hour. After completion of the reaction, the reaction mixture was extracted with water and ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-5-((4-(tert-butyl)benzyl)thio)-N'-ethoxy-6-(4-phenylthiazol-2-yl)picoline imidamide (0.23 g, 0.46 mmol). Yield: 80% Physical properties: Melting point: 204-206℃

[0491] Manufacturing Example 12-5 Preparation of (Z)-N'-ethoxy-5-(N-methylsulfofamoyl)-6-(4-phenylthiazol-2-yl)picoline imidamide (Compound No. 8-2) [ka] To a solution of (Z)-5-((4-(tert-butyl)benzyl)thio)-N'-ethoxy-6-(4-phenylthiazol-2-yl)picoline imidamide (0.11 g, 0.22 mmol) in chloroform (5.0 mL), acetic acid (0.038 mL, 0.66 mmol) and water (0.024 mL, 1.3 mmol) were added, and 1,3-dichloro-5,5-dimethylhydantoin (0.13 g, 0.66 mmol) was added in an ice bath. After stirring for 5 minutes, the reaction mixture was added dropwise to a solution of methylamine in methanol (9.8 mol / L, 5.0 mL) and stirred for 5 minutes. After completion of the reaction, water was added to the reaction mixture, which was then extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-N'-ethoxy-5-(N-methylsulfofamoyl)-6-(4-phenylthiazol-2-yl)picoline imidamide (44 mg, 0.11 mmol). Yield: 48% Physical properties: Melting point: 157-158℃

[0492] Manufacturing Example 13 Preparation of (Z)-N'-ethoxy-6-(4-methyl-1-phenyl-1H-pyrazol-3-yl)-5-(methylsulfonyl)picoline imidamide (Compound No. 10-16) and (Z)-N'-ethoxy-6-(4-methyl-1-phenyl-1H-pyrazol-3-yl)-5-(N-methylsulfamoyl)picoline imidamide (Compound No. 10-2) Manufacturing Example 13-1 Preparation of (Z)-N'-ethoxy-6-(4-methyl-1-phenyl-1H-pyrazol-3-yl)-5-(methylsulfonyl)picoline imidamide (compound number: 10-16) [ka] To a solution of (Z)-N'-ethoxy-6-(4-methyl-1H-pyrazol-3-yl)-5-(methylsulfonyl)picoline imidamide (0.58 g, 1.8 mmol) in N,N-dimethylacetamide (10 mL), iodobenzene (0.20 mL, 1.8 mmol), cesium carbonate (1.2 g, 3.7 mmol), and copper(II) acetate monohydrate (38 mg, 0.19 mmol) were added and stirred at 140 °C for 3 hours. After completion of the reaction, saturated aqueous ammonium chloride solution was added to the reaction solution, which was then extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give (Z)-N'-ethoxy-6-(4-methyl-1-phenyl-1H-pyrazol-3-yl)-5-(methylsulfonyl)picoline imidamide (0.15 g, 0.37 mmol). Yield: 21% Physical properties: Melting point: 150-151℃

[0493] Manufacturing Example 13-2 Preparation of (Z)-5-((4-(tert-butyl)benzyl)thio)-N'-ethoxy-6-(4-methyl-1-phenyl-1H-pyrazol-3-yl)picoline imidamide [ka] To a solution of (Z)-N'-ethoxy-6-(4-methyl-1-phenyl-1H-pyrazol-3-yl)-5-(methylsulfonyl)picoline imidamide (0.15 g, 0.42 mmol) in N,N-dimethylacetamide (2.0 mL), cesium carbonate (0.41 g, 1.3 mmol) and (4-(tert-butyl)phenyl)methanethiol (0.15 mL, 0.82 mmol) were added at room temperature, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, saturated aqueous ammonium chloride solution was added to the reaction mixture, which was then extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to give (Z)-5-((4-(tert-butyl)benzyl)thio)-N'-ethoxy-6-(4-methyl-1-phenyl-1H-pyrazol-3-yl)picoline imidamide (0.10 g, 0.21 mmol). Yield: 50%

[0494] Manufacturing Example 13-3 Preparation of (Z)-N'-ethoxy-6-(4-methyl-1-phenyl-1H-pyrazol-3-yl)-5-(N-methylsulfamoyl)picoline imidamide (Compound No. 10-2) [ka] To a solution of (Z)-5-((4-(tert-butyl)benzyl)thio)-N'-ethoxy-6-(4-methyl-1-phenyl-1H-pyrazol-3-yl)picoline imidamide (0.10 g, 0.21 mmol) in chloroform (2.0 mL), 1,3-dichloro-5,5-dimethylhydantoin (0.12 g, 0.62 mmol), acetic acid (40 μL, 0.63 mmol), and water (25 μL, 1.2 mmol) were added at 0°C and stirred at the same temperature for 10 minutes. After completion of the reaction, methylamine (40% methanol solution, 0.21 mL, 2.1 mmol) was added to the reaction solution and stirred for an additional 10 minutes. After completion of the reaction, water was added to the reaction solution, which was then extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to give (Z)-N'-ethoxy-6-(4-methyl-1-phenyl-1H-pyrazol-3-yl)-5-(N-methylsulfamoyl)picoline imidamide (67 mg, 0.16 mmol). Yield: 76% Physical properties: Melting point: 130-131℃

[0495] Manufacturing Example 14 Preparation of (Z)-N'-ethoxy-6-(4-methyl-5-phenyl-2H-1,2,3-triazol-2-yl)-5-(N-methylsulfamoyl)picoline imidamide (compound number: 20-17) [ka] To a solution of (Z)-6-chloro-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (0.12 g, 0.41 mmol) in N,N-dimethylacetamide (2.0 mL), potassium carbonate (87 mg, 0.87 mmol) and 4-methyl-5-phenyl-2H-1,2,3-triazole (66 mg, 0.41 mmol) were added and stirred at 130°C for 17 hours. After completion of the reaction, the reaction mixture was extracted with water and ethyl acetate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (Z)-N'-ethoxy-6-(4-methyl-5-phenyl-2H-1,2,3-triazol-2-yl)-5-(N-methylsulfamoyl)picoline imidamide (28 mg, 0.067 mmol). Yield: 16% Physical properties: Melting point: 72-77℃

[0496] Manufacturing Example 15 Preparation of (Z)-N'-ethoxy-6-(5-methyl-2-(2-nitrophenyl)-2H-1,2,3-triazol-4-yl)-5-(methylsulfonyl)picoline imidamide (0.21 g, 0.47 mmol) (Compound No. 11-95) [ka] To a solution of (Z)-N'-ethoxy-6-(5-methyl-2H-1,2,3-triazol-4-yl)-5-(methylsulfonyl)picoline imidamide (0.18 g, 0.56 mmol) in N,N-dimethylacetamide (3 mL), potassium carbonate (0.17 g, 0.85 mmol) and 2-fluoronitrobenzene (0.059 mL, 0.56 mmol) were added and stirred at 130 °C for 7 hours. The reaction mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was concentrated under reduced pressure, and the residue was purified by silica gel chromatography to give (Z)-N'-ethoxy-6-(5-methyl-2-(2-nitrophenyl)-2H-1,2,3-triazol-4-yl)-5-(methylsulfonyl)picoline imidamide (0.21 g, 0.47 mmol). Yield: 83% Physical properties: Melting point: 179-184℃

[0497] Reference Example 1 Preparation of ethyl 6-cyano-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate (starting material for Preparation Example 1-1)

[0498] Reference manufacturing example 1-1 Preparation of (E)-3,6-dichloro-2-((2-phenylhydrazono)methyl)pyridine [ka] Phenylhydrazine (1.7 mL, 31 mmol) was added to a solution (60 mL) of 3,6-dichloropicolinaldehyde (3.0 g, 17 mmol) in ethanol, and the mixture was stirred for 3 hours. The resulting solid was collected by filtration, washed with ethanol, and then dried to obtain the target product (4.3 g, 16 mmol). Yield: 96%

[0499] Reference manufacturing example 1-2 Preparation of 3-(3,6-dichloropyridin-2-yl)-4-methyl-1-phenyl-1H-1,2,4-triazol-5(4H)-one [ka] Phosphorus pentachloride (4.1 g, 20 mmol) was added to a solution of (E)-3,6-dichloro-2-((2-phenylhydrazono)methyl)pyridine (3.5 g, 13 mmol) in chloroform (65 mL) at room temperature, and the mixture was stirred at 80°C for 3 hours. Water was added to the reaction mixture, which was then extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran (65 mL), and 40% methylamine solution (6.6 mL, 65 mmol) was added. The mixture was stirred for 1 hour. Further water was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was dissolved in chloroform (130 mL), and pyridine (2.6 mL, 33 mol) and triphosgene (5.8 g, 20 mmol) were added. The mixture was stirred for 1 hour. Water was added, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give 3-(3,6-dichloropyridin-2-yl)-4-methyl-1-phenyl-1H-1,2,4-triazol-5(4H)-one (1.5 g, 4.7 mmol). Yield: 36%

[0500] Reference manufacturing example 1-3 Preparation of ethyl 6-carbamoyl-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate [ka] To a solution of 3-(3,6-dichloropyridin-2-yl)-4-methyl-1-phenyl-1H-1,2,4-triazol-5(4H)-one (1.5 g, 4.8 mmol) in ethanol (47 mL), 1,4-bis(diphenylphosphino)butanetetramethylenebis(diphenylphosphine) (72 mg, 0.0020 mmol), bis(triphenylphosphine)palladium(II) dichloride (67 mg, 0.0010 mmol), and triethylamine (2.0 mL, 1.4 mmol) were added and stirred at 130°C under a 4 MPa carbon monoxide atmosphere for 3 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography. A 4% ammonia-ethanol solution (50 mL) was added to the resulting solid and stirred overnight at room temperature. Water was added, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain ethyl 6-carbamoyl-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate (0.78 g, 2.1 mmol). Yield: 45% Physical properties: Melting point: 137-138℃

[0501] Reference manufacturing example 1-4 Preparation of ethyl 6-cyano-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate [ka] To a solution of ethyl 6-carbamoyl-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate (0.78 g, 2.1 mmol) in N,N-dimethylformamide (21 mL) was added phosphoryl chloride (0.79 mL, 8.5 mmol) at room temperature and stirred for 1 hour. Saturated aqueous sodium bicarbonate was added to the reaction mixture, which was then extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give ethyl 6-cyano-2-(4-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)nicotinate (0.73 g, 2.1 mmol). Yield: 100% Physical properties: Melting point: 138-139℃

[0502] Reference Example 2 Preparation of ethyl 6-cyano-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate (starting material for Preparation 2) Reference production example 2-1 Preparation of 3,6-dichloro-N-methoxy-N-methylpicolinamide [ka] To a solution of 3,6-dichloropicolinic acid (10 g, 52 mmol) in tetrahydrofuran (0.10 L), N,N-dimethylformamide (0.4 mL, 5.3 mmol) and oxalyl chloride (5.0 mL, 57 mmol) were added at room temperature and stirred for 0.5 hours. The reaction mixture was concentrated under reduced pressure, and then chloroform (0.10 L), triethylamine (28 mL, 0.21 mol), and N-methoxy-N-methylamine hydrochloride (6.1 g, 62 mmol) were added to the residue and stirred overnight at room temperature. After completion of the reaction, water was added to the reaction mixture, which was then extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give 3,6-dichloro-N-methoxy-N-methylpicolinamide (12 g, 52 mmol). Yield: 100% Physical properties: 1H-NMR(CDCl3):δ 7.70(d,1H),7.33(d,1H),3.61(s,3H),3.39(s,3H)

[0503] Reference manufacturing example 2-2 Preparation of 1-(3,6-dichloropyridin-2-yl)propan-1-one [ka] A solution of 3,6-dichloro-N-methoxy-N-methylpicolinamide (5.0 g, 21 mmol) in tetrahydrofuran (0.10 L) was added with a diethyl ether solution of ethylmagnesium bromide (27 mL, 81 mmol) at 0°C and stirred at room temperature for 2 hours. After completion of the reaction, saturated aqueous ammonium chloride solution was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give 1-(3,6-dichloropyridin-2-yl)propan-1-one (1.8 g, 8.7 mmol). Yield: 41% Physical properties: 1 H-NMR(CDCl3):δ 7.74(d,1H),7.39(d,1H),3.10(q,2H),1.20(t,3H)

[0504] Reference production example 2-3 Preparation of 2-bromo-1-(3,6-dichloropyridin-2-yl)propan-1-one [ka] Bromine (0.30 mL, 5.6 mmol) was added to a solution of 1-(3,6-dichloropyridin-2-yl)propan-1-one (1.1 g, 5.2 mmol) in acetic acid (17 mL) and the mixture was stirred at 120°C for 2 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and water was added to the resulting residue, which was then extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was then purified by silica gel column chromatography to give 2-bromo-1-(3,6-dichloropyridin-2-yl)propan-1-one (1.2 g, 4.3 mmol). Yield: 85%

[0505] Reference production example 2-4 Preparation of 4-(3,6-dichloropyridin-2-yl)-5-methyl-2-phenylthiazole [ka] Benzothioamide (1.1 g, 3.6 mmol) was added to a solution of 2-bromo-1-(3,6-dichloropyridin-2-yl)propan-1-one (0.51 g, 3.6 mmol) in ethanol (7.0 mL), and the mixture was stirred at 80°C for 2.5 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, followed by the addition of saturated aqueous sodium bicarbonate and extraction with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give 4-(3,6-dichloropyridin-2-yl)-5-methyl-2-phenylthiazole (0.95 g, 3.0 mmol). Yield: 75%

[0506] Reference manufacturing example 2-5 Preparation of diethyl 6-(5-methyl-2-phenylthiazol-4-yl)pyridine-2,5-dicarboxylate [ka] 4-(3,6-Dichloropyridin-2-yl)-5-methyl-2-phenylthiazole (0.95 g, 3.0 mmol), dichlorobis(triphenylphosphine)palladium (42 mg, 0.060 mmol), bis(diphenylphosphino)butane (51 mg, 0.12 mmol), triethylamine (1.0 mL, 7.4 mmol), and ethanol (10 mL) were added to an autoclave reaction vessel and stirred at 130 °C under a carbon monoxide atmosphere (4.0 MPa) for 3 hours. The reaction mixture was concentrated under reduced pressure, and then aqueous sodium bicarbonate was added to the resulting residue, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give diethyl 6-(5-methyl-2-phenylthiazol-4-yl)pyridine-2,5-dicarboxylate (0.82 g, 2.1 mmol). Yield: 70% Physical properties: Melting point: 69-70℃

[0507] Reference production example 2-6 Preparation of ethyl 6-carbamoyl-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate [ka] Ammonia (28% aqueous solution, 10 mL) was added to a solution of diethyl 6-(5-methyl-2-phenylthiazol-4-yl)pyridine-2,5-dicarboxylate (0.80 g, 2.0 mmol) in ethanol (10 mL) at room temperature, and the mixture was stirred overnight at room temperature. The reaction mixture was filtered, and the residue was washed with ethanol to give ethyl 6-carbamoyl-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate (0.74 g, 2.0 mmol). Yield: 100% (3 steps) Physical properties: Melting point: 147-148℃

[0508] Reference production example 2-7 Preparation of ethyl 6-cyano-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate [ka] Phosphoryl chloride (0.5 mL, 5.4 mmol) was added to a solution of ethyl 6-carbamoyl-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate (0.50 g, 1.4 mmol) in N,N-dimethylformamide (6.8 mL) at 0°C, and the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, saturated aqueous sodium bicarbonate was added to the reaction solution at 0°C, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and evaporated under reduced pressure to give ethyl 6-cyano-2-(5-methyl-2-phenylthiazol-4-yl)nicotinate (0.48 g, 1.4 mmol). Yield: 100%

[0509] Reference Example 3 Preparation of 6-cyano-N-methyl-2-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)pyridine-3-sulfonamide (starting material for Preparation 3) Reference manufacturing example 3-1 Preparation of methyl 3-((4-(tert-butyl)benzyl)thio)-6-chloropicolinate [ka] To a solution of methyl 3,6-dichloropyrrolinate (20 g, 97 mmol) in tetrahydrofuran (0.50 L), sodium hydride (60 wt%, 4.70 g, 0.12 mol) was added in an ice bath and stirred for 15 minutes. After stirring for 15 minutes, (4-(tert-butyl)phenyl)methanethiol (18 mL, 0.10 mol) was added dropwise and the mixture was stirred at room temperature for 3 hours. A saturated aqueous solution of ammonium chloride was added to the reaction solution in an ice bath, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, concentrated, and the residue was washed with hexane to give methyl 3-((4-(tert-butyl)benzyl)thio)-6-chloropicolinate (30 g, 86 mmol). Yield: 88% Physical properties: 1 H-NMR(CDCl3):δ 7.66-7.63(m,1H),7.37-7.28(m,5H),4.12(s,2H),3.98(s,3H),1.31(s,9H)

[0510] Reference production example 3-2 Preparation of 3-((4-(tertiarybutyl)benzyl)thio)-6-chloropicolinic acid. [ka] To a solution of methyl 3-((4-(tert-butyl)benzyl)thio)-6-chloropicolinate (30 g, 86 mmol) in methanol (200 mL) and tetrahydrofuran (50 mL) was added lithium hydroxide (4.3 g, 0.10 mol) at room temperature, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was concentrated under reduced pressure, and 2 M hydrochloric acid was added. The resulting solid was collected by filtration and washed with hexane to give 3-((4-(tert-butyl)benzyl)thio)-6-chloropicolinic acid (30 g, 85 mmol). Yield: 100%

[0511] Reference production example 3-3 Preparation of 3-((4-(tertiarybutyl)benzyl)thio)-6-chloro-2-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)pyridine [ka] To a solution of 3-((4-(tert-butyl)benzyl)thio)-6-chloropicolinic acid (10 g, 30 mmol) and ethyl benzimidate hydrochloride (5.6 g, 30 mmol) in N,N-dimethylformamide (60 mL) was added N,N-diisopropylethylamine (15 mL, 90 mmol) and 1-[bis(dimethylamino)methylene]-1H-benzotriazolium 3-oxide hexafluorophosphate (17 g, 45 mmol), and the mixture was stirred at room temperature overnight. Water was added to the reaction solution, which was then extracted with chloroform. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was dissolved in ethanol (60 mL), and methylhydrazine (2.4 mL, 45 mmol) was added. The mixture was heated to reflux for 2 hours. The residue was concentrated under reduced pressure and purified by silica gel column chromatography to give 3-((4-(tert-butyl)benzyl)thio)-6-chloro-2-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)pyridine (2.1 g, 4.6 mmol). Yield: 5%

[0512] Reference production example 3-4 Preparation of 6-chloro-N-methyl-2-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)pyridine-3-sulfonamide [ka] To a solution of 3-((4-(tert-butyl)benzyl)thio)-6-chloro-2-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)pyridine (2.1 g, 4.6 mmol) in chloroform (50 mL), water (0.50 mL, 27 mmol) and acetic acid (0.80 mL, 14 mmol) were added, and 1,3-dichloro-5,5-dimethylhydantoin (2.7 g, 14 mmol) was added in an ice bath. After confirming the disappearance of the raw materials, the reaction mixture was added dropwise to a methylamine-methanol solution (9.8 mol / L, 20 mL) in an ice bath and stirred for 30 minutes. Saturated aqueous ammonium chloride was then added, and the mixture was extracted with ethyl acetate, followed by concentration of the organic layer. The residue was purified by silica gel column chromatography to give 6-chloro-N-methyl-2-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)pyridine-3-sulfonamide (0.70 g, 1.9 mmol). Yield: 42% Physical properties: 1 H-NMR(CDCl3):δ 8.46(d,1H),8.14(q,1H),8.00-7.95(m,2H),7.59(d,1H),7.50-7.41(m,3H),4.18(s,3H),2.80(s,3H)

[0513] Reference production example 3-5 Preparation of 6-cyano-N-methyl-2-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)pyridine-3-sulfonamide [ka] To a solution of 6-chloro-N-methyl-2-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)pyridine-3-sulfonamide (0.30 g, 0.83 mmol) in dimethyl sulfoxide (2.0 mL), sodium cyanide (61 mg, 1.2 mmol) and 1,4-diazabicyclo[2.2.2]octane (47 mg, 0.4 mmol) were added and stirred at 40 °C for 2 hours. Saturated brine was added, and the mixture was extracted with ethyl acetate. The organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give 6-cyano-N-methyl-2-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)pyridine-3-sulfonamide (0.16 g, 0.45 mmol). Yield: 55%

[0514] Reference Example 4 Preparation of 6-cyano-N-methyl-2-(1-methyl-4-phenyl-1H-imidazol-2-yl)pyridine-3-sulfonamide (starting material for Preparation 4) Reference production example 4-1 Preparation of 2-oxo-2-phenylethyl 3-((4-(tert-butyl)benzyl)thio)-6-chloropicolinate [ka] Phenacyl chloride (3.0 g, 20 mmol) and N,N-diisopropylethylamine (8.3 mL, 49 mmol) were added to a solution of 3-((4-(tert-butyl)benzyl)thio)-6-chloropicolinic acid (6.6 g, 20 mmol) in N,N-dimethylformamide (28 mL) under ice cooling, and the mixture was stirred overnight at room temperature. After the reaction was complete, water and ethyl acetate were added for extraction, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give crude 2-oxo-2-phenylethyl 3-((4-(tert-butyl)benzyl)thio)-6-chloropicolinate (7.8 g, 17 mmol). Yield: 88%

[0515] Reference production example 4-2 Preparation of 3-((4-(tertiarybutyl)benzyl)thio)-6-chloro-2-(4-phenyl-1H-imidazol-2-yl)pyridine. [ka] To a solution of 2-oxo-2-phenylethyl 3-((4-(tert-butyl)benzyl)thio)-6-chloropicolinate (7.8 g, 17 mmol) in acetic acid (86 mL), ammonium acetate (27 g, 0.34 mol) was added and the mixture was stirred under reflux. The reaction mixture was concentrated under reduced pressure and extracted with saturated aqueous sodium bicarbonate and ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give 3-((4-(tert-butyl)benzyl)thio)-6-chloro-2-(4-phenyl-1H-imidazol-2-yl)pyridine (7.4 g, 17 mmol). Yield: 99%

[0516] Reference production example 4-3 Preparation of 3-((4-(tertiarybutyl)benzyl)thio)-6-chloro-2-(1-methyl-4-phenyl-1H-imidazol-2-yl)pyridine [ka] To a solution of 3-((4-(tert-butyl)benzyl)thio)-6-chloro-2-(4-phenyl-1H-imidazol-2-yl)pyridine (7.4 g, 17 mmol) in tetrahydrofuran (90 mL), potassium tert-butoxide (2.1 g, 18.8 mmol) and iodomethane (1.2 mL, 19 mmol) were added under ice cooling and stirred at room temperature for 2 hours. Saturated aqueous ammonium chloride and ethyl acetate were added for extraction, and the organic layer was dried over sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to give 3-((4-(tert-butyl)benzyl)thio)-6-chloro-2-(1-methyl-4-phenyl-1H-imidazol-2-yl)pyridine (4.6 g, 10 mmol). Yield: 59%

[0517] Reference production example 4-4 Preparation of 6-chloro-N-methyl-2-(1-methyl-4-phenyl-1H-imidazol-2-yl)pyridine-3-sulfonamide [ka] To a solution of 3-((4-(tert-butyl)benzyl)thio)-6-chloro-2-(1-methyl-4-phenyl-1H-imidazol-2-yl)pyridine (2.0 g, 4.5 mmol) in chloroform (50 mL), water (0.50 mL, 27 mmol) and acetic acid (0.77 mL, 13 mmol) were added, and 1,3-dichloro-5,5-dimethylhydantoin (2.6 g, 13 mmol) was added in an ice bath. After confirming the disappearance of the raw materials, the reaction solution was added dropwise to a methylamine-methanol solution (30 mL) in an ice bath and stirred for 30 minutes. Saturated aqueous ammonium chloride was added, and the mixture was extracted with ethyl acetate. The organic layer was concentrated. The residue was purified by silica gel column chromatography to give 6-chloro-N-methyl-2-(1-methyl-4-phenyl-1H-imidazol-2-yl)pyridine-3-sulfonamide (0.51 mg, 1.4 mmol). Yield: 31% Physical properties: 1 H-NMR(CDCl3):δ 8.95(q,1H),8.42(d,1H),7.67-7.63(m,2H),7.48-7.38(m,3H),7.33-7.29(m,2H),3.97(s,3H),2.78(d,3H)

[0518] Reference production example 4-5 Preparation of 6-cyano-N-methyl-2-(1-methyl-4-phenyl-1H-imidazol-2-yl)pyridine-3-sulfonamide [ka] To a solution of 6-chloro-N-methyl-2-(1-methyl-4-phenyl-1H-imidazol-2-yl)pyridine-3-sulfonamide (0.43 g, 1.2 mmol) in dimethyl sulfoxide (10 mL), sodium cyanide (70 mg, 1.4 mmol) and 1,4-diazabicyclo[2.2.2]octane (67 mg, 0.60 mmol) were added and stirred at 40 °C for 2 hours. Saturated brine was added, and the mixture was extracted with ethyl acetate. The organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give 6-cyano-N-methyl-2-(1-methyl-4-phenyl-1H-imidazol-2-yl)pyridine-3-sulfonamide (0.10 g, 0.28 mmol). Yield: 24%

[0519] Reference Example 5 Preparation of (Z)-6-chloro-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (starting material for Preparations 5 and 6) Reference production example 5-1 Preparation of 2,6-dichloro-N-methylpyridine-3-sulfonamide [ka] To a solution of 2,6-dichloropyridine-3-sulfonyl chloride in tetrahydrofuran (0.20 L), a 7.0% solution of methylamine in tetrahydrofuran (31 mL, 61 mmol) was added under ice cooling and stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture was extracted with saturated aqueous ammonium chloride and ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give 2,6-dichloro-N-methylpyridine-3-sulfonamide (6.4 g, 27 mmol). Yield: 44% Physical properties: 1 H-NMR(CDCl3):δ 8.35(d,1H),7.46(d,1H),5.10(br.s,1H),2.71(d,3H)

[0520] Reference production example 5-2 Preparation of 2-chloro-6-cyano-N-methylpyridine-3-sulfonamide [ka] To a solution of 2,6-dichloro-N-methylpyridine-3-sulfonamide (9.8 g, 40 mmol) and 1,4-diazabicyclo[2.2.2]octane (0.81 g, 7.2 mmol) in dimethyl sulfoxide (0.10 L), a solution of sodium cyanide (2.3 g, 47 mmol) in water (10 mL) was added dropwise and stirred at room temperature. After completion of the reaction, the reaction mixture was extracted with water and ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give 2-chloro-6-cyano-N-methylpyridine-3-sulfonamide (7.7 g, 33 mmol). Yield: 82% Physical properties: 1 H-NMR(CDCl3):δ 8.56(d,1H),7.82(d,1H),5.07(q,1H),2.74(d,3H)

[0521] Reference production example 5-3 Preparation of (Z)-6-chloro-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide [ka] To a solution of 2-chloro-6-cyano-N-methylpyridine-3-sulfonamide (1.1 g, 2.9 mmol) in methanol (20 mL), a 28 wt% solution of sodium methoxide in methanol (0.59 mL, 2.9 mmol) was added and stirred at room temperature. After the raw materials disappeared, O-ethylhydroxylamine hydrochloride (0.37 g, 3.8 mmol) was added and stirred at room temperature. After the reaction was completed, water and ethyl acetate were added for extraction. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give (Z)-6-chloro-N'-ethoxy-5-(N-methylsulfamoyl)picoline imidamide (1.2 g, 2.9 mmol). Yield: 100% Physical properties: 1H-NMR(CDCl3):δ 8.35(d,1H),8.07(d,1H),5.45(br.s,2H),5.05(q,1H),4.20(q,2H),2.68(d,3H),1.34(t,3H)

[0522] Reference Example 6 Preparation of (E)-1-(6-chloro-5-(methylsulfonyl)pyridin-2-yl)ethanone O-ethyl oxime (starting material for Preparation Example 7) Reference production example 6-1 Preparation of methyl 6-chloro-3-(methylsulfanyl)picolinate [ka] To a solution of methyl 3,6-dichloropicolinate (21 g, 0.10 mol) in N,N-dimethylformamide (0.20 L) was slowly added methanethiol sodium salt (8.2 g, 0.11 mol) at 0°C, and the mixture was stirred for 2 hours at 0°C. After completion of the reaction, water was added to the reaction solution, and the precipitated solid was collected by filtration, washed with ethanol, and dried to obtain methyl 6-chloro-3-(methylsulfanyl)picolinate (18 g, 80 mmol). Yield: 80%

[0523] Reference production example 6-2 Preparation of methyl 6-chloro-3-(methylsulfonyl)picolinate [ka] Metachloroperbenzoic acid (22 g, 82 mmol) was added to a chloroform solution (160 mL) of methyl 6-chloro-3-(methylsulfanyl)picolinate (7.2 g, 33 mmol), and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, saturated aqueous sodium bicarbonate and saturated aqueous sodium thiosulfate were added to the reaction mixture, which was then extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give methyl 6-chloro-3-(methylsulfonyl)picolinate (8.1 g, 33 mmol). Yield: 99%

[0524] Reference production example 6-3 Preparation of (E)-methyl 6-(1-(ethoxyimino)ethyl)-3-(methylsulfonyl)picolinate [ka] To a solution of methyl 6-chloro-3-(methylsulfonyl)picolinate (11 g, 41 mmol) in 1,2-dimethoxyethane (0.20 L) was added tributyl(1-ethoxyvinyl)tin (17 mL, 49 mmol) and tetrakis(triphenylphosphine)palladium(0) (2.5 g, 2.2 mmol) under an argon atmosphere at room temperature, followed by stirring at 110 °C for 3 hours. After returning to room temperature, tetrahydrofuran (0.10 L) and 2N hydrochloric acid (0.10 L) were added and the mixture was stirred at 50 °C for 3 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain methyl 6-acetyl-3-(methylsulfonyl)picolinate. The resulting methyl 6-acetyl-3-(methylsulfonyl)picolinate was dissolved in chloroform (0.20 L), pyridine (60 mL) and O-ethylhydroxylamine hydrochloride (5.94 g, 60.9 mmol) were added, and the mixture was stirred overnight at room temperature. 1N hydrochloric acid was added to the reaction mixture, followed by extraction with chloroform. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give crude (E)-methyl 6-(1-(ethoxyimino)ethyl)-3-(methylsulfonyl)picolinate, which was used in the next step without further purification.

[0525] Reference production example 6-4 Preparation of (E)-6-(1-(ethoxyimino)ethyl)-3-(methylsulfonyl)picolinic acid [ka] A 4M aqueous solution of lithium hydroxide (16 mL) was added to a methanol solution (0.15 L) of (E)-methyl 6-(1-(ethoxyimino)ethyl)-3-(methylsulfonyl)picolinate at room temperature, and the mixture was stirred for 1 hour. The reaction mixture was extracted with 2N hydrochloric acid and chloroform, and the aqueous layer was extracted with 2N aqueous sodium hydroxide. 2N aqueous hydrochloric acid was added to the aqueous layer, and the mixture was extracted with ethyl acetate under acidic conditions. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Methyl tert-butyl ether and hexane were added to the residue, and the precipitated solid was filtered to give (E)-6-(1-(ethoxyimino)ethyl)-3-(methylsulfonyl)picolinic acid (8.4 g, 32 mmol). Yield: 80% (3 steps)

[0526] Reference production example 6-5 Preparation of (E)-1-(6-amino-5-(methylsulfonyl)pyridin-2-yl)ethanone O-ethyl oxime [ka] Triethylamine (0.73 mL, 5.2 mmol) and diphenylphosphoryl azide (1.2 mL, 5.2 mmol) were added to a tertiary butyl alcohol solution (20 mL) of (E)-6-(1-(ethoxyimino)ethyl)-3-(methylsulfonyl)picolinic acid (1.0 g, 3.5 mmol), and the mixture was stirred at 100°C for 2 hours. The reaction mixture was concentrated under reduced pressure, and water was added to the resulting residue, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. Trifluoroacetic acid (10 mL) was added to the residue, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the mixture was concentrated under reduced pressure, and saturated aqueous sodium bicarbonate solution was added to the resulting residue, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (E)-1-(6-amino-5-(methylsulfonyl)pyridin-2-yl)ethanone O-ethyl oxime (0.68 g, 2.6 mmol). Yield: 75%

[0527] Reference production example 6-6 Preparation of (E)-1-(6-chloro-5-(methylsulfonyl)pyridin-2-yl)ethanone O-ethyl oxime [ka] To a solution (4.0 mL) of (E)-1-(6-amino-5-(methylsulfonyl)pyridin-2-yl)ethanone O-ethyl oxime (0.22 g, 0.84 mmol) in tetrahydrofuran, copper(II) chloride (0.17 g, 1.3 mmol) and tert-butyl nitrite (0.20 mL, 1.7 mmol) were added at room temperature, and the mixture was stirred at 60°C for 1 hour. A saturated aqueous solution of ammonium chloride was added, and the mixture was extracted with ethyl acetate and washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give (E)-1-(6-chloro-5-(methylsulfonyl)pyridin-2-yl)ethanone O-ethyl oxime (0.14 g, 0.51 mmol). Yield: 60% Physical properties: 1 H-NMR (CDCl3): δ8.37(d,1H),8.08(d,1H),4.33(q,2H),3.32(s,3H),2.31(s,3H),1.36(t,3H)

[0528] Reference Example 7 Preparation of (Z)-4-((4-(tert-butyl)benzyl)thio)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-N'-ethoxybenzimidamide (starting material for Preparation 8) Reference production example 7-1 Preparation of 3-(2-chlorophenyl)-5-(2-fluoro-5-iodophenyl)-1-methyl-1H-1,2,4-triazole [ka] To a solution of 2-chloro-N'-methylbenzimide hydrazide dihydrochloride (3.5 g, 19 mmol) and 2-fluoro-5-iodobenzoic acid (5.1 g, 19 mmol) in pyridine (50 mL), N,N-dimethyl-4-aminopyridine (2.4 g, 19 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (4.1 g, 21 mmol) were added and stirred at room temperature overnight. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and 0.5 N hydrochloric acid was added to the residue. The mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Acetic acid (50 mL) was added to the residue, and the mixture was stirred under reflux for 1 hour. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. Saturated aqueous sodium bicarbonate was added to the resulting residue, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was then purified by silica gel column chromatography to give 3-(2-chlorophenyl)-5-(2-fluoro-5-iodophenyl)-1-methyl-1H-1,2,4-triazole (1.8 g, 4.4 mmol). Yield: 23% Physical properties: 1 H-NMR(CDCl3):δ 8.03(dd,1H),7.91(dd,1H),7.83(ddd,1H),7.51(dd,1H),7.38-7.33(m,2H),7.03(dd,1H),3.96(s,3H)

[0529] Reference production example 7-2 Preparation of 3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-4-fluorobenzonitrile [ka] To a solution of 3-(2-chlorophenyl)-5-(2-fluoro-5-iodophenyl)-1-methyl-1H-1,2,4-triazole (1.6 g, 3.9 mmol) in N,N-dimethylacetamide (45 mL), triethylamine (0.81 mL, 5.9 mmol), tetrakis(triphenylphosphine)palladium(0) (0.45 g, 0.39 mmol), and zinc cyanide (0.70 g, 5.9 mmol) were added at room temperature and stirred at 110 °C for 2 hours. After completion of the reaction, the reaction solution was filtered through Celite and washed with ethyl acetate. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to give 3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-4-fluorobenzonitrile (1.1 g, 3.5 mmol). Yield: 90% Physical properties: 1 H-NMR(CDCl3):δ 8.09(dd,1H),7.92(dd,1H),7.87(ddd,1H),7.52(dd,1H),7.41(dd,1H),7.39-7.34(m,2H),3.97(s,3H)

[0530] Reference production example 7-3 Preparation of 4-((4-(tertiarybutyl)benzyl)thio)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)benzonitrile [ka] To a solution of 3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-4-fluorobenzonitrile (0.50 g, 1.6 mmol) in N,N-dimethylacetamide (5.5 mL), cesium carbonate (0.78 g, 2.4 mmol) and (4-(tert-butyl)phenyl)methanethiol (0.35 mL, 1.9 mmol) were added at room temperature and stirred at the same temperature for 2 hours. After completion of the reaction, saturated aqueous ammonium chloride solution was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give 4-((4-(tert-butyl)benzyl)thio)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)benzonitrile (0.78 g, 1.6 mmol). Yield: 100% Physical properties: 1 H-NMR(CDCl3):δ 7.95(dd,1H),7.71-7.67(m,2H),7.52-7.48(m,2H),7.36-7.31(m,4H),7.24(d,2H),4.15(s,2H),3.80(s,3H),1.29(s,9H)

[0531] Reference production example 7-4 Preparation of (Z)-4-((4-(tert-butyl)benzyl)thio)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-N'-hydroxybenzimidamide [ka] To a solution of 4-((4-(tert-butyl)benzyl)thio)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)benzonitrile (0.78 g, 1.6 mmol) in ethanol (8.2 mL), sodium acetate (0.21 g, 2.5 mmol) and hydroxylamine hydrochloride (0.17 g, 2.5 mmol) were added at room temperature and stirred at 80°C for 2 hours. After completion of the reaction, water was added to the reaction solution, which was then extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give (Z)-4-((4-(tert-butyl)benzyl)thio)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-N'-hydroxybenzimidamide (0.72 g, 1.4 mmol). Yield: 86%

[0532] Reference production example 7-5 Preparation of (Z)-4-((4-(tert-butyl)benzyl)thio)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-N'-ethoxybenzimidamide [ka] Cesium carbonate (0.27 g, 0.82 mmol) and ethyl iodide (55 μL, 0.66 mmol) were added to a solution of (Z)-4-((4-(tert-butyl)benzyl)thio)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-N'-hydroxybenzimidamide (0.28 g, 0.54 mmol) in N,N-dimethylformamide (3.0 mL) at room temperature, and the mixture was stirred at the same temperature for 2 hours. After completion of the reaction, saturated aqueous ammonium chloride solution was added to the reaction mixture, which was then extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was then purified by silica gel column chromatography to give (Z)-4-((4-(tert-butyl)benzyl)thio)-3-(3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl)-N'-ethoxybenzimidamide (0.23 g, 0.43 mmol). Yield: 78%

[0533] Reference Example 8 Preparation of 6-cyano-N-methyl-2-(4-methyl-1-(2-nitrophenyl)-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)pyridine-3-sulfonamide (starting material for Preparation Example 10-1) Reference production example 8-1 Preparation of 3-((4-(tertiarybutyl)benzyl)thio)-6-chloropicolinohydrazide. [ka] To a solution of methyl 3-((4-(tert-butyl))thio)-6-chloropicolinate (11 g, 30 mmol) in methanol (30 mL) and tetrahydrofuran (86 mL) was added hydrazine monohydrate (2.2 mL, 45 mmol) at room temperature and stirred overnight. The reaction mixture was concentrated under reduced pressure, and the resulting solid was collected by filtration and washed with hexane to give 3-((4-(tert-butyl)benzyl)thio)-6-chloropicolinohydrazide (11 g, 30 mmol). Yield: 100%

[0534] Reference production example 8-2 Pr...

Claims

1. General formula (1): 【Chemical 1】 {In the formula, Q represents Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, Q10, Q11, Q12, Q13, Q14, Q15, Q16, Q17 or Q18. 【Chemistry 2】 (In the formula, R １ teeth, (a1) a halogen atom; (a2) (C １ -C ６ ) alkyl group; (a3) (C ２ -C ６ ) alkenyl groups; (a4) (C ２ -C ６ ) an alkynyl group; (a5) (C ３ -C ６ ) a cycloalkyl group; (a6) Halo (C １ -C ６ ) alkyl group; (a7) Halo (C ２ -C ６ ) alkenyl groups; (a8) Halo (C ２ -C ６ ) an alkynyl group; (a9) Halo (C ３ -C ６ ) a cycloalkyl group; (a10) a dioxolanyl group; (a11) a dioxanyl group; (a12) a dioxepanyl group; (a13) a dihydropyranyl group; (a14) a tetrahydropyranyl group; (a15) a tetrahydrothiopyranyl group; (a16) a piperidinyl group; (a17) (C １ -C ６ ) alkyl group, (C １ -C ６ ) alkylcarbonyl group and (C １ -C ６ ) a substituted piperidinyl group having 1 to 3 substituents independently selected from the group consisting of alkoxycarbonyl groups on the ring; (a18) a thienyl group; (a19) a substituted thienyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a20) a thiazolyl group; (a21) a substituted thiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a22) a thiadiazolyl group; (a23) a substituted thiadiazolyl group having, on the ring, one substituent independently selected from the substituent group Y; (a24) a pyrazolyl group; (a25) a substituted pyrazolyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a26) a phenyl group; (a27) a substituted phenyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a28) a pyridyl group; (a29) a substituted pyridyl group having, on the ring, 1 to 4 substituents independently selected from the substituent group Y; (a30) a pyridazinyl group; (a31) a substituted pyridazinyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a32) a pyrimidinyl group; (a33) a substituted pyrimidinyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a34) a pyrazinyl group; (a35) a substituted pyrazinyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a36) amino group; (a37) carboxyl group; (a38) (C １ -C ６ ) an alkoxy group; (a39) Halo (C １ -C ６ ) an alkoxy group; (a40) (C １ -C ６ ) an alkylsulfanyl group; (a41) (C １ -C ６ ) an alkylsulfinyl group; (a42) (C １ -C ６ ) an alkylsulfonyl group; (a43) (C ３ -C ６ ) a cycloalkenyl group; (a44) (C １ -C ６ ) alkoxy(C １ -C ６ ) alkyl group; (a45) (C １ -C ６ ) alkylsulfanyl (C １ -C ６ ) alkyl group; (a46) (C １ -C ６ ) alkylsulfinyl (C １ -C ６ ) alkyl group; (a47) (C １ -C ６ ) alkylsulfonyl (C １ -C ６ ) alkyl group; (a48) (C １ -C ６ ) an alkylcarbonyl group; (a49) (C １ -C ６ ) an alkoxycarbonyl group; (a50) Halo (C １ -C ６ ) an alkylcarbonyl group; (a51) Halo (C １ -C ６ ) an alkoxycarbonyl group; (a52) a phenylcarbonyl group; (a53) a substituted phenylcarbonyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a54) a phenylaminocarbonyl group; (a55) a substituted phenylaminocarbonyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a56) benzhydrylideneamino group; (a57) an oxopyrrolidinyl group; (a58) an oxopyridyl group; (a59) Halogen atoms and (C １ -C ６ ) a substituted dioxolanyl group having 1 to 4 substituents on the ring, each independently selected from the group consisting of alkyl groups; (a60) Halogen atoms and (C １ -C ６ ) a substituted dioxanyl group having 1 to 4 substituents on the ring, each independently selected from the group consisting of alkyl groups; (a61) a furanyl group; (a62) a substituted furanyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a63) an isothiazolyl group; (a64) a substituted isothiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a65) an oxazolyl group; (a66) a substituted oxazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a67) an isoxazolyl group; (a68) a substituted isoxazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a69) a quinolinyl group; (a70) a substituted quinolinyl group having, on the ring, 1 to 6 substituents each independently selected from the substituent group Y; (a71) a benzothienyl group; (a72) a substituted benzothienyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a73) a phenoxy group; (a74) a substituted phenoxy group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a75) Phenyl (C １ -C ６ ) alkyl group; (a76) Substituted phenyl (C １ -C ６ ) alkyl group; (a77) Phenyl (C １ -C ６ ) an alkoxy group; (a78) Substituted phenyl (C １ -C ６ ) an alkoxy group; (a79) (C １ -C ６ ) alkylamino group; (a80) Halo (C １ -C ６ ) an alkoxycarbonylamino group; (a81) an oxazolidinonyl group; (a82) (C １ -C ６ ) alkoxy(C １ -C ６ ) an alkoxy group; (a83) tetrahydrofuranyl (C １ -C ６ ) an alkoxy group; or (a84) (C ３ -C ６ ) cycloalkyl (C １ -C ６ ) represents an alkoxy group. R ２ teeth, (b1) hydrogen atom; (b2) a halogen atom; or (b3) (C １ -C ６ ) represents an alkyl group. R ２ａ teeth, (b1') a hydrogen atom; or (b2') (C １ -C ６ ) represents an alkyl group. R ３ teeth, (c1) hydrogen atom; (c2) a halogen atom; (c3) a hydroxyl group; (c4) (C １ -C ６ ) alkyl group; (c5) (C ２ -C ６ ) alkenyl groups; (c6) (C ２ -C ６ ) an alkynyl group; (c7) (C ３ -C ６ ) a cycloalkyl group; (c8) Halo (C １ -C ６ ) alkyl group; (c9) Halo (C ２ -C ６ ) alkenyl groups; (c10) Halo (C ２ -C ６ ) an alkynyl group; (c11) Halo (C ３ -C ６ ) a cycloalkyl group; (c12) (C １ -C ６ ) an alkoxy group; (c13) (C １ -C ６ ) an alkylsulfanyl group; (c14) (C １ -C ６ ) an alkylsulfinyl group; (c15) (C １ -C ６ ) an alkylsulfonyl group; (c16) Halo (C １ -C ６ ) an alkoxy group; (c17) Halo (C １ -C ６ ) an alkylsulfanyl group; (c18) Halo (C １ -C ６ ) an alkylsulfinyl group; (c19) Halo (C １ -C ６ ) an alkylsulfonyl group; (c20) (C １ -C ６ ) an alkoxycarbonyl group; or (c21) (C １ -C ６ ) an alkylamino group, R ２ and R ３ may be bonded to each other to form a 5- or 6-membered ring. R ３ａ teeth, (c1') a hydrogen atom; or (c2') (C １ -C ６ ) represents an alkyl group. The substituent group Y is (d1) a halogen atom; (d2) a cyano group; (d3) a nitro group; (d4) amino group; (d5) (C １ -C ６ ) alkyl group; (d6) (C ２ -C ６ ) alkenyl groups; (d7) (C ２ -C ６ ) an alkynyl group; (d8) (C ３ -C ６ ) a cycloalkyl group; (d9) Halo (C １ -C ６ ) alkyl group; (d10) Halo (C ２ -C ６ ) alkenyl groups; (d11) Halo (C ２ -C ６ ) an alkynyl group; (d12) Halo (C ３ -C ６ ) a cycloalkyl group; (d13) (C １ -C ６ ) an alkoxy group; (d14) (C １ -C ６ ) an alkylsulfanyl group; (d15) (C １ -C ６ ) an alkylsulfinyl group; (d16) (C １ -C ６ ) an alkylsulfonyl group; (d17) Halo (C １ -C ６ ) an alkoxy group; (d18) Halo (C １ -C ６ ) an alkylsulfanyl group; (d19) Halo (C １ -C ６ ) an alkylsulfinyl group; (d20) Halo (C １ -C ６ ) an alkylsulfonyl group; (d21) N-((C １ -C ６ ) alkylcarbonyl) amino group; (d22) N,N-di((C １ -C ６ ) alkylcarbonyl) amino group (the (C １ -C ６ ) alkylcarbonyl may be the same or different); (d23) Ji (C １ -C ６ ) alkoxyphosphanyl group (the (C １ -C ６ ) the alkoxy may be the same or different); (d24) an imidazolyl group; (d25) Halogen atoms and (C １ -C ６ ) an imidazolyl group having on the ring 1 to 3 substituents independently selected from the group consisting of alkyl groups; (d26) phenyl group; (d27) Halogen atoms and (C １ -C ６ ) a phenyl group having 1 to 5 substituents on the ring, each independently selected from the group consisting of alkyl groups; (d28) a pyridyl group; (d29) Halogen atoms and (C １ -C ６ ) a pyridyl group having 1 to 4 substituents on the ring, each independently selected from the group consisting of alkyl groups; (d30) Ji (C １ -C ６ ) alkylamino group; (d31) (C １ -C ６ ) alkoxycarbonyl groups; and (d32) A halogen atom, a phenyl group, and (C) formed by two adjacent substituents Y together １ -C ６ ) a methylenedioxy group which may be substituted with 1 to 2 substituents selected from the group consisting of alkyl groups. ● represents the binding site with D); R ４ teeth, (e2) an amino group; (e3) (C １ -C ６ ) alkyl group; (e6) N-((C １ -C ６ ) alkylcarbonyl) amino group; or (e8) N-(halo(C １ -C ６ ) alkylcarbonyl) amino group. R ５ teeth, (f1) (C １ -C ６ ) alkyl group; or (f5) Halo (C １ -C ６ ) represents an alkyl group. A is, (g4) N,N-di(C １ -C ６ ) alkylaminocarbonyl group (the (C １ -C ６ ) alkylcarbonyl may be the same or different); (g5) CO ２ R ７ (In the formula, R ７ teeth, (h2) (C １ -C ６ ) denotes an alkyl group; (g6) SO ｎ R ８ (In the formula, R ８ teeth, (i1) (C １ -C ６ ) an alkyl group, or (i9) (C １ -C ６ ) alkylcarbonyl (C １ -C ６ ) represents an alkyl group. n represents 2; SO 2 NH(C 1 -C 6 ) alkyl groups; SO 2 N((C 1 -C 6 )alkyl)(C 1 -C 6 )alkyl groups, wherein the (C 1 -C 6 )alkyl groups may be the same or different; or SO 2 N((C 1 -C 6 )alkoxycarbonyl)(C 1 -C 6 )alkyl group. A, Q, and C(R ４ ) = N to OR ５ D substituted with represents a ring of D1, D2, D3, or D4. 【Chemistry 3】 (In the formula, R ６ａ and R ６ｂ teeth, (k1) hydrogen atom; (k2) a halogen atom; or (k3) (C １ -C ６ ) represents an alkyl group, R ６ａ and R ６ｂ may be the same or different.)} or a salt thereof.

2. R 4 , R 5 , A, Q and D are the same as in claim 1, R １ but, (a1) a halogen atom; (a2) (C １ -C ６ ) alkyl group; (a3) (C ２ -C ６ ) alkenyl groups; (a5) (C ３ -C ６ ) a cycloalkyl group; (a9) Halo (C ３ -C ６ ) a cycloalkyl group; (a10) a dioxolanyl group; (a11) a dioxanyl group; (a12) a dioxepanyl group; (a13) a dihydropyranyl group; (a14) a tetrahydropyranyl group; (a15) a tetrahydrothiopyranyl group; (a16) a piperidinyl group; (a17) (C １ -C ６ ) alkyl group, (C １ -C ６ ) alkylcarbonyl group and (C １ -C ６ ) a substituted piperidinyl group having 1 to 3 substituents independently selected from the group consisting of alkoxycarbonyl groups on the ring; (a18) a thienyl group; (a19) a substituted thienyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a20) a thiazolyl group; (a21) a substituted thiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a22) a thiadiazolyl group; (a23) a substituted thiadiazolyl group having, on the ring, one substituent independently selected from the substituent group Y; (a24) a pyrazolyl group; (a25) a substituted pyrazolyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a26) a phenyl group; (a27) a substituted phenyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a28) a pyridyl group; (a29) a substituted pyridyl group having, on the ring, 1 to 4 substituents independently selected from the substituent group Y; (a30) a pyridazinyl group; (a31) a substituted pyridazinyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a32) a pyrimidinyl group; (a33) a substituted pyrimidinyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a34) a pyrazinyl group; (a35) a substituted pyrazinyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a36) amino group; (a37) carboxyl group; (a38) (C １ -C ６ ) an alkoxy group; (a39) Halo (C １ -C ６ ) an alkoxy group; (a40) (C １ -C ６ ) an alkylsulfanyl group; (a41) (C １ -C ６ ) an alkylsulfinyl group; (a42) (C １ -C ６ ) an alkylsulfonyl group; (a43) (C ３ -C ６ ) a cycloalkenyl group; (a44) (C １ -C ６ ) alkoxy(C １ -C ６ ) alkyl group; (a45) (C １ -C ６ ) alkylsulfanyl (C １ -C ６ ) alkyl group; (a46) (C １ -C ６ ) alkylsulfinyl (C １ -C ６ ) alkyl group; (a47) (C １ -C ６ ) alkylsulfonyl (C １ -C ６ ) alkyl group; (a48) (C １ -C ６ ) an alkylcarbonyl group; (a49) (C １ -C ６ ) an alkoxycarbonyl group; (a50) Halo (C １ -C ６ ) an alkylcarbonyl group; (a51) Halo (C １ -C ６ ) an alkoxycarbonyl group; (a52) a phenylcarbonyl group; (a53) a substituted phenylcarbonyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a54) a phenylaminocarbonyl group; (a55) a substituted phenylaminocarbonyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a56) benzhydrylideneamino group; (a57) an oxopyrrolidinyl group; (a58) an oxopyridyl group; (a59) Halogen atoms and (C １ -C ６ ) a substituted dioxolanyl group having 1 to 4 substituents on the ring, each independently selected from the group consisting of alkyl groups; (a60) Halogen atoms and (C １ -C ６ ) a substituted dioxanyl group having 1 to 4 substituents on the ring, each independently selected from the group consisting of alkyl groups; (a61) a furanyl group; (a62) a substituted furanyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a63) an isothiazolyl group; (a64) a substituted isothiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a69) a quinolinyl group; (a70) a substituted quinolinyl group having, on the ring, 1 to 6 substituents each independently selected from the substituent group Y; (a71) a benzothienyl group; (a72) a substituted benzothienyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a73) a phenoxy group; (a74) a substituted phenoxy group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a75) Phenyl (C １ -C ６ ) alkyl group; (a76) Substituted phenyl (C １ -C ６ ) alkyl group; (a77) Phenyl (C １ -C ６ ) an alkoxy group; (a78) Substituted phenyl (C １ -C ６ ) an alkoxy group; (a79) (C １ -C ６ ) alkylamino group; (a80) Halo (C １ -C ６ ) an alkoxycarbonylamino group; (a81) an oxazolidinonyl group; (a82) (C １ -C ６ ) alkoxy(C １ -C ６ ) an alkoxy group; (a83) tetrahydrofuranyl (C １ -C ６ ) an alkoxy group; or (a84) (C ３ -C ６ ) cycloalkyl (C １ -C ６ ) an alkoxy group, R ２ but, (b1) hydrogen atom; (b2) a halogen atom; or (b3) (C １ -C ６ ) alkyl group, R ２ａ but, (b1') a hydrogen atom; or (b2') (C １ -C ６ ) alkyl group, R ３ but, (c1) hydrogen atom; (c2) a halogen atom; (c3) hydroxyl group; (c4) (C １ -C ６ ) alkyl group; (c5) (C ２ -C ６ ) alkenyl groups; (c6) (C ２ -C ６ ) an alkynyl group; (c7) (C ３ -C ６ ) a cycloalkyl group; (c8) Halo (C １ -C ６ ) alkyl group; (c12) (C １ -C ６ ) an alkoxy group; (c13) (C １ -C ６ ) an alkylsulfanyl group; (c14) (C １ -C ６ ) an alkylsulfinyl group; (c15) (C １ -C ６ ) an alkylsulfonyl group; (c16) Halo (C １ -C ６ ) an alkoxy group; (c17) Halo (C １ -C ６ ) an alkylsulfanyl group; (c18) Halo (C １ -C ６ ) an alkylsulfinyl group; (c19) Halo (C １ -C ６ ) an alkylsulfonyl group; (c20) (C １ -C ６ ) an alkoxycarbonyl group; or (c21) (C １ -C ６ ) an alkylamino group, R ２ and R ３ may be bonded to each other to form a 5- or 6-membered ring, R ３ａ but, (c1') a hydrogen atom; or (c2') (C １ -C ６ ) alkyl group, The substituent group Y is (d1) a halogen atom; (d2) a cyano group; (d3) a nitro group; (d4) amino group; (d5) (C １ -C ６ ) alkyl group; (d8) (C ３ -C ６ ) a cycloalkyl group; (d9) Halo (C １ -C ６ ) alkyl group; (d13) (C １ -C ６ ) an alkoxy group; (d14) (C １ -C ６ ) an alkylsulfanyl group; (d15) (C １ -C ６ ) an alkylsulfinyl group; (d16) (C １ -C ６ ) an alkylsulfonyl group; (d17) Halo (C １ -C ６ ) an alkoxy group; (d18) Halo (C １ -C ６ ) an alkylsulfanyl group; (d19) Halo (C １ -C ６ ) an alkylsulfinyl group; (d20) Halo (C １ -C ６ ) an alkylsulfonyl group; (d21) N-((C １ -C ６ ) alkylcarbonyl) amino group; (d22) N,N-di((C １ -C ６ ) alkylcarbonyl) amino group (the (C １ -C ６ ) alkylcarbonyl may be the same or different); (d23) Ji (C １ -C ６ ) alkoxyphosphanyl group (the (C １ -C ６ ) the alkoxy may be the same or different); (d24) an imidazolyl group; (d25) Halogen atoms and (C １ -C ６ ) an imidazolyl group having on the ring 1 to 3 substituents independently selected from the group consisting of alkyl groups; (d26) phenyl group; (d27) Halogen atoms and (C １ -C ６ ) a phenyl group having 1 to 5 substituents on the ring, each independently selected from the group consisting of alkyl groups; (d28) a pyridyl group; (d29) Halogen atoms and (C １ -C ６ ) a pyridyl group having 1 to 4 substituents on the ring, each independently selected from the group consisting of alkyl groups; (d30) Ji (C １ -C ６ ) alkylamino group; (d31) (C １ -C ６ ) alkoxycarbonyl groups; and (d32) A halogen atom, a phenyl group, and (C) formed by two adjacent substituents Y together １ -C ６ ) a methylenedioxy group optionally substituted with 1 to 2 substituents selected from the group consisting of alkyl groups; R ６ａ and R ６ｂ but, (k1) hydrogen atom; (k2) a halogen atom; or (k3) (C １ -C ６ ) alkyl group, R ６ａ and R ６ｂ and may be the same or different, or a salt thereof, of the compound according to claim 1 .

3. R 4 , R 5 , A, Q and D are the same as in claim 1, R １ but, (a1) a halogen atom; (a2) (C １ -C ６ ) alkyl group; (a3) (C ２ -C ６ ) alkenyl groups; (a5) (C ３ -C ６ ) a cycloalkyl group; (a13) a dihydropyranyl group; (a14) a tetrahydropyranyl group; (a16) a piperidinyl group; (a18) a thienyl group; (a19) a substituted thienyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a20) a thiazolyl group; (a21) a substituted thiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a22) a thiadiazolyl group; (a23) a substituted thiadiazolyl group having, on the ring, one substituent independently selected from the substituent group Y; (a24) a pyrazolyl group; (a25) a substituted pyrazolyl group having, on the ring, 1 to 3 substituents independently selected from the substituent group Y; (a26) a phenyl group; (a27) a substituted phenyl group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a28) a pyridyl group; (a29) a substituted pyridyl group having, on the ring, 1 to 4 substituents independently selected from the substituent group Y; (a32) a pyrimidinyl group; (a34) a pyrazinyl group; (a36) amino group; (a37) carboxyl group; (a38) (C １ -C ６ ) an alkoxy group; (a39) Halo (C １ -C ６ ) an alkoxy group; (a40) (C １ -C ６ ) an alkylsulfanyl group; (a42) (C １ -C ６ ) an alkylsulfonyl group; (a43) (C ３ -C ６ ) a cycloalkenyl group; (a44) (C １ -C ６ ) alkoxy(C １ -C ６ ) alkyl group; (a45) (C １ -C ６ ) alkylsulfanyl (C １ -C ６ ) alkyl group; (a46) (C １ -C ６ ) alkylsulfinyl (C １ -C ６ ) alkyl group; (a47) (C １ -C ６ ) alkylsulfonyl (C １ -C ６ ) alkyl group; (a48) (C １ -C ６ ) an alkylcarbonyl group; (a49) (C １ -C ６ ) an alkoxycarbonyl group; (a52) a phenylcarbonyl group; (a54) a phenylaminocarbonyl group; (a56) benzhydrylideneamino group; (a57) an oxopyrrolidinyl group; (a58) an oxopyridyl group; (a59) Halogen atoms and (C １ -C ６ ) a substituted dioxolanyl group having 1 to 4 substituents on the ring, each independently selected from the group consisting of alkyl groups; (a60) Halogen atoms and (C １ -C ６ ) a substituted dioxanyl group having 1 to 4 substituents on the ring, each independently selected from the group consisting of alkyl groups; (a61) a furanyl group; (a63) an isothiazolyl group; (a64) a substituted isothiazolyl group having, on the ring, 1 to 2 substituents independently selected from the substituent group Y; (a69) a quinolinyl group; (a71) a benzothienyl group; (a74) a substituted phenoxy group having, on the ring, 1 to 5 substituents independently selected from the substituent group Y; (a75) Phenyl (C １ -C ６ ) alkyl group; (a82) (C １ -C ６ ) alkoxy(C １ -C ６ ) an alkoxy group; (a83) tetrahydrofuranyl (C １ -C ６ ) an alkoxy group; or (a84) (C ３ -C ６ ) cycloalkyl (C １ -C ６ ) an alkoxy group, R ２ but, (b1) hydrogen atom; (b2) a halogen atom; or (b3) (C １ -C ６ ) alkyl group, R ２ａ but, (b1') a hydrogen atom, R ３ but, (c1) hydrogen atom; (c2) a halogen atom; (c3) hydroxyl group; (c4) (C １ -C ６ ) alkyl group; (c5) (C ２ -C ６ ) alkenyl groups; (c8) Halo (C １ -C ６ ) alkyl group; (c12) (C １ -C ６ ) an alkoxy group; (c13) (C １ -C ６ ) an alkylsulfanyl group; (c14) (C １ -C ６ ) an alkylsulfinyl group; (c15) (C １ -C ６ ) an alkylsulfonyl group; or (c20) (C １ -C ６ ) an alkoxycarbonyl group, R ２ and R ３ may be bonded to each other to form a 5- or 6-membered ring, R ３ａ but, (c1') a hydrogen atom, The substituent group Y is (d1) a halogen atom; (d2) a cyano group; (d3) a nitro group; (d4) amino group; (d5) (C １ -C ６ ) alkyl group; (d8) (C ３ -C ６ ) a cycloalkyl group; (d9) Halo (C １ -C ６ ) alkyl group; (d13) (C １ -C ６ ) an alkoxy group; (d14) (C １ -C ６ ) an alkylsulfanyl group; (d17) Halo (C １ -C ６ ) an alkoxy group; (d21) N-((C １ -C ６ ) alkylcarbonyl) amino group; (d24) an imidazolyl group; (d26) phenyl group; (d28) a pyridyl group; (d30) Ji (C １ -C ６ ) alkylamino group; (d31) (C １ -C ６ ) alkoxycarbonyl groups; and (d32) A halogen atom, a phenyl group, and (C) formed by two adjacent substituents Y together １ -C ６ ) a methylenedioxy group optionally substituted with 1 to 2 substituents selected from the group consisting of alkyl groups; R ６ａ and R ６ｂ but, The compound or salt thereof according to claim 1, wherein (k1) is a hydrogen atom.

4. R １ , R ２ , R ３ , R ４ , R ５ , R ６ａ , R ６ｂ , A, and the substituent group Y are the same as in claim 1, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, or Q10; The compound or salt thereof according to claim 1, wherein D is D1 or D2.

5. R １ , R ２ , R ３ , R ４ , R ５ , R ６ａ , R ６ｂ , A, and the substituent group Y are the same as in claim 1, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, or Q10; The compound or salt thereof according to claim 1, wherein D is D1.

6. R １ , R ２ , R ３ , R ６ａ , R ６ｂ and the substituent group Y is the same as in claim 2, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, or Q10; The compound or salt thereof according to claim 2, wherein D is D1 or D2.

7. R １ , R ２ , R ３ , R ６ａ , R ６ｂ and the substituent group Y is the same as in claim 2, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, or Q10; The compound or salt thereof according to claim 2, wherein D is D1.

8. R １ , R ２ , R ３ , R ６ａ , R ６ｂ and the substituent group Y is the same as in claim 3, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, or Q10; The compound or salt thereof according to claim 3, wherein D is D1 or D2.

9. R １ , R ２ , R ３ , R ６ａ , R ６ｂ and the substituent group Y is the same as in claim 3, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, or Q10; The compound or salt thereof according to claim 3, wherein D is D1.

10. 10. An agricultural and horticultural herbicide comprising the compound or salt thereof according to any one of claims 1 to 9 as an active ingredient.

11. A method for using the agricultural and horticultural herbicide according to claim 10, which comprises applying an effective amount of the agricultural and horticultural herbicide to weeds, soil, paddy fields or cultivation carriers.

12. A method for controlling weeds, which comprises applying an effective amount of the agricultural and horticultural herbicide according to claim 10 to weeds, soil, paddy fields or cultivation carriers.

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