Phenoxycarbamoyl chloride compound and method for producing same

Abstract

A phenoxycarbamoyl chloride compound useful as an intermediate for producing a phenoxyurea compound having insecticidal activity, acaricidal activity, and / or nematicidal activity is represented by formula (1) (in the formula, R1 is a substituted or unsubstituted C1-6 alkyl group, Y is a C1-6 haloalkyl group, X is a halogen group, C1-6 alkyl group, or C1-6 haloalkyl group, n is an integer of 0-4, and n is an integer of 0-4. And when n is 2 or more, X may be the same as or different from each other. ). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to phenoxycarbamoyl chloride compounds, phenoxyamine compounds, and methods for producing them. More specifically, the present invention relates to phenoxycarbamoyl chloride compounds useful as production intermediates for phenoxyurea compounds having insecticidal activity, acaricidal activity, and / or nematicidal activity, phenoxyamine compounds useful as production intermediates for phenoxycarbamoyl chloride compounds, and production methods capable of efficiently obtaining these compounds through short processes.

[0002] This application claims priority based on Japanese Patent Application No. 2022-198044 filed on December 12, 2022, and incorporates its content herein. Background Art

[0003] As compounds having insecticidal / acaricidal activity and nematicidal activity, Patent Document 1 discloses compounds represented by the following formula (A) such as 2-{3-[3-bromo-5-(trifluoromethyl)phenoxy]-3-ethylureido}-2-methyl-N-(2,2,2-trifluoroethyl)propanamide (phenoxyurea compounds).

[0004]

[0005] In the above formula (A), R 1 is a hydrogen atom, a substituted or unsubstituted C1-6 alkyl group, etc., R 2 is a hydrogen atom or a C1-6 alkyl group, R 3 and R 4 are each independently a hydrogen atom or a C1-6 alkyl group, R 5 is a substituted or unsubstituted C1-6 alkyl group, etc., Y is a C1-6 haloalkyl group, X is a halogen group, a C1-6 alkyl group, etc., n is any integer from 0 to 4, and when n is 2 or more, X may be the same or different from each other.

[0006] Patent Document 1 discloses a compound represented by the following formula (B1) as a production intermediate for a compound represented by the following formula (A1).

[0007]

[0008] When synthesizing the compound represented by the above formula (B1) using the compound represented by the following formula (C1) as a starting material, since the appropriate solvents used in each reaction stage are different, it is necessary to replace the solvent before each reaction stage.

[0009]

[0010] Prior Art Documents

[0011] Patent Documents

[0012] Patent Document 1: WO 2019 / 198592 A SUMMARY OF THE INVENTION

[0013] An object of the present invention is to provide a phenoxycarbamoyl chloride compound useful as a production intermediate for a phenoxyurea compound having insecticidal activity, acaricidal activity and / or nematicidal activity, a phenoxyamine compound useful as a production intermediate for the phenoxycarbamoyl chloride compound, and a production method capable of efficiently obtaining these compounds through a short process.

[0014] In order to solve the above problems, intensive studies were carried out, and as a result, the present invention including the following aspects was completed.

[0015] [1] A compound represented by formula (1).

[0016]

[0017] (In the above formula (1),

[0018] R 1 is a substituted or unsubstituted C1-6 alkyl group,

[0019] Y is a C1-6 haloalkyl group,

[0020] X is a halogen group, a C1-6 alkyl group or a C1-6 haloalkyl group,

[0021] n represents the number of Xs and is any integer from 0 to 4, and when n is 2 or more, Xs may be the same or different.)

[0022] [2] A method for producing a compound represented by formula (1), comprising: reacting a compound represented by formula (2) with a compound represented by formula (8) in the presence of a base to obtain an N-alkylated compound,

[0023] hydrolyzing the above N-alkylated compound to obtain a compound represented by formula (3),

[0024] and then reacting the compound represented by formula (3) with phosgene or a phosgene equivalent.

[0025]

[0026] (In the above formula (2), R 2 is a C1-8 alkoxy group,

[0027] Y is a C1-6 haloalkyl group,

[0028] X is a halogen group, a C1-6 alkyl group or a C1-6 haloalkyl group,

[0029] n represents the number of Xs, which is any integer from 0 to 4, and when n is 2 or more, the Xs may be the same as or different from each other.)

[0030] R 1 -Za(8)

[0031] (In the above formula (8), R 1 is a substituted or unsubstituted C1-6 alkyl group, and Za is a halogen group or a group represented by the formula: R 1 O-SO3-.

[0032]

[0033] (In the above formula (3),

[0034] R 1 is a substituted or unsubstituted C1-6 alkyl group,

[0035] Y, X, and n are the same as Y, X, and n in the above formula (2).)

[0036]

[0037] (In the above formula (1),

[0038] R 1 , Y, X, and n are the same as R 1 , Y, X, and n in the above formula (3).)

[0039] 〔3〕According to the manufacturing method described in 〔2〕, it further includes: in the presence of a base, reacting a compound represented by formula (4) with a compound represented by formula (5) to obtain the compound represented by the above formula (2).

[0040]

[0041] (In the above formula (4),

[0042] Z is a halogen group,

[0043] X, Y, and n are the same as X, Y, and n in the above formula (2).)

[0044]

[0045] (In the above formula (5),

[0046] R 2 is the same as R 2 in the above formula (2).)

[0047] 〔4〕According to the manufacturing method described in 〔3〕, wherein the above Z is a bromine group.

[0048] [5] A compound represented by formula (3).

[0049]

[0050] (In the above formula (3),

[0051] R 1 is a substituted or unsubstituted C1-6 alkyl group,

[0052] Y is a C1-6 haloalkyl group,

[0053] X is a halogen group, a C1-6 alkyl group or a C1-6 haloalkyl group,

[0054] n represents the number of Xs and is any integer from 0 to 4, and when n is 2 or more, Xs may be the same as or different from each other.)

[0055] [6] The compound according to [5], wherein the above R 1 is a substituted or unsubstituted C2-6 alkyl group.

[0056] [7] A method for producing a compound represented by formula (3), comprising: reacting a compound represented by formula (2) with a compound represented by formula (8) in the presence of a base to obtain an N-alkylated compound,

[0057] and hydrolyzing the above N-alkylated compound.

[0058]

[0059] (In the above formula (2), R 2 is a C1-8 alkoxy group,

[0060] Y is a C1-6 haloalkyl group,

[0061] X is a halogen group, a C1-6 alkyl group or a C1-6 haloalkyl group,

[0062] n represents the number of Xs and is any integer from 0 to 4, and when n is 2 or more, Xs may be the same as or different from each other.)

[0063] R 1 -Za (8)

[0064] (In the above formula (8), R 1 is a substituted or unsubstituted C1-6 alkyl group, and Za is a halogen group or a group represented by the formula: R 1 O-SO3-. )

[0065]

[0066] (In the above formula (3),

[0067] R 1 is a substituted or unsubstituted C1-6 alkyl group,

[0068] Y, X and n are the same as Y, X and n in formula (2) above.)

[0069] [8] The production method according to [7], wherein the above R 1 is a substituted or unsubstituted C2-6 alkyl group.

[0070] [9] A method for producing a compound represented by formula (1), comprising: subjecting a compound represented by formula (3) to a chemical reaction with phosgene or a phosgene equivalent.

[0071]

[0072] (In the above formula (3),

[0073] R 1 is a substituted or unsubstituted C1-6 alkyl group,

[0074] Y is a C1-6 haloalkyl group,

[0075] X is a halogen group, a C1-6 alkyl group or a C1-6 haloalkyl group,

[0076] n represents the number of Xs and is any integer from 0 to 4, and when n is 2 or more, Xs may be the same as or different from each other.)

[0077]

[0078] (In the above formula (1),

[0079] R 1 , Y, X and n are the same as R 1 , Y, X and n in the above formula (3).)

[0080] The phenoxycarbamoyl chloride compound or phenoxyamine compound of the present invention can reduce the frequency of solvent replacement during each stage of the chemical reaction until a phenoxyurea compound having insecticidal activity, acaricidal activity and / or nematicidal activity such as the compound represented by formula (A1) is obtained.

[0081] The production method of the present invention can effectively obtain the phenoxycarbamoyl chloride compound or phenoxyamine compound of the present invention through a short process. Detailed Description

[0082] The phenoxycarbamoyl chloride compound of the present invention is a compound represented by the following formula (1) (hereinafter sometimes referred to as compound (1).).

[0083]

[0084] The phenoxyamine compound of the present invention is a compound represented by the following formula (3) (hereinafter sometimes referred to as compound (3)).

[0085]

[0086] In the above formula, R 1 is a substituted or unsubstituted C1-C6 alkyl group, Y is a C1-C6 haloalkyl group, X is a halogen group, a C1-C6 alkyl group or a C1-C6 haloalkyl group, n represents the number of X, which is any integer from 0 to 4, and when n is 2 or more, X may be the same as or different from each other.

[0087] In the present invention, the term "unsubstituted" means only the group that forms the parent nucleus. When it is described only by the name of the group that forms the parent nucleus without the description of "substituted", it means "unsubstituted" as long as there is no special explanation.

[0088] On the other hand, the term "substituted" means that any hydrogen atom in the group that forms the parent nucleus is replaced by a group (substituent) having the same or different structure from the parent nucleus. Therefore, the "substituent" means another group bonded to the group that forms the parent nucleus. The substituent may be one or two or more. Two or more substituents may be the same or different.

[0089] Terms such as "C1-C6" indicate that the number of carbon atoms in the group that forms the parent nucleus is any one of 1 to 6, etc. The number of carbon atoms does not include the number of carbon atoms present in the substituent. For example, butyl having an ethoxy group as a substituent is classified as C2 alkoxy C4 alkyl.

[0090] The "substituent" is not particularly limited as long as it is chemically acceptable and has the effects of the present invention.

[0091] The following groups that can be "substituents" are exemplified.

[0092] C1-C6 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl;

[0093] C2-C6 alkenyl groups such as vinyl, 1-propenyl, 2-propenyl (allyl), 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl;

[0094] C2-C6 alkynyl groups such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl;

[0095] C3-C6 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;

[0096] phenyl, naphthyl;

[0097] phenyl C1-6 alkyl such as benzyl, phenethyl;

[0098] 3-6 membered heterocyclic group;

[0099] 3-6 membered heterocyclic group C1-6 alkyl;

[0100] hydroxyl;

[0101] C1-6 alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy;

[0102] C2-6 alkenyloxy such as vinyloxy, allyloxy, propenyloxy, butenyloxy;

[0103] C2-6 alkynyloxy such as ethynyloxy, propargyloxy;

[0104] phenoxy, naphthoxy;

[0105] phenyl C1-6 alkoxy such as benzyloxy, phenethyloxy;

[0106] 5-6 membered heteroaryloxy such as thiazolyloxy, pyridyloxy;

[0107] 5-6 membered heteroaryl C1-6 alkoxy such as thiazolylmethoxy, pyridylmethoxy;

[0108] formyl;

[0109] C1-6 alkylcarbonyl such as acetyl, propionyl;

[0110] formyloxy;

[0111] C1-6 alkylcarbonyloxy such as acetoxy, propionyloxy;

[0112] benzoyl;

[0113] C1-6 alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl;

[0114] C1-6 alkoxycarbonyloxy such as methoxycarbonyloxy, ethoxycarbonyloxy, n-propoxycarbonyloxy, isopropoxycarbonyloxy, n-butoxycarbonyloxy, tert-butoxycarbonyloxy;

[0115] carboxyl;

[0116] halogen groups such as fluoro, chloro, bromo, iodo;

[0117] C1-C6 haloalkyl groups such as chloromethyl, chloroethyl, trifluoromethyl, 1,2-dichloropropyl, 1-fluorobutyl, perfluoropentyl, etc.;

[0118] C2-C6 haloalkenyl groups such as 2-chloro-1-propenyl, 2-fluoro-1-butenyl, etc.;

[0119] C2-C6 haloalkynyl groups such as 4,4-dichloro-1-butynyl, 4-fluoro-1-pentynyl, 5-bromo-2-pentynyl, etc.;

[0120] C1-C6 haloalkoxy groups such as trifluoromethoxy, 2-chloropropoxy, 2,3-dichlorobutoxy, etc.;

[0121] C2-C6 haloalkenyloxy groups such as 2-chloropropenyloxy, 3-bromobutenyloxy, etc.;

[0122] C1-C6 haloalkylcarbonyl groups such as chloroacetyl, trifluoroacetyl, trichloroacetyl, etc.;

[0123] Amino;

[0124] C1-C6 alkyl-substituted amino groups such as methylamino, dimethylamino, diethylamino, etc.;

[0125] Anilino, naphthylamino;

[0126] Phenyl C1-C6 alkylamino groups such as benzylamino, phenethylamino, etc.;

[0127] Formylamino;

[0128] C1-C6 alkylcarbonylamino groups such as acetylamino, propionylamino, butyrylamino, isopropylcarbonylamino, etc.;

[0129] C1-C6 alkoxycarbonylamino groups such as methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, isopropoxycarbonylamino, etc.;

[0130] Unsubstituted or substituted aminocarbonyl groups such as aminocarbonyl, dimethylaminocarbonyl, phenylaminocarbonyl, N-phenyl-N-methylaminocarbonyl, etc.;

[0131] Iminomethyl C1-C6 alkyl groups such as (1-imino)ethyl, (1-imino)-n-propyl, etc.;

[0132] Substituted or unsubstituted N-hydroxyiminomethyl C1-C6 alkyl groups such as N-hydroxy-iminomethyl, (1-(N-hydroxy)-imino)ethyl, (1-(N-hydroxy)-imino)propyl, N-methoxy-iminomethyl, (1-(N-methoxy)-imino)ethyl, etc.;

[0133] Aminocarbonyloxy;

[0134] C1-C6 alkyl-substituted aminocarbonyloxy groups such as ethylaminocarbonyloxy, dimethylaminocarbonyloxy;

[0135] Mercapto group;

[0136] C1-C6 alkylthio groups such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio;

[0137] C1-C6 haloalkylthio groups such as trifluoromethylthio, 2,2,2-trifluoroethylthio;

[0138] Phenylthio group, naphthylthio group;

[0139] 5-6 membered heteroarylthio groups such as thiazolylthio, pyridylthio;

[0140] C1-C6 alkylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, tert-butylsulfinyl;

[0141] C1-C6 haloalkylsulfinyl groups such as trifluoromethylsulfinyl, 2,2,2-trifluoroethylsulfinyl;

[0142] Phenylsulfinyl group;

[0143] 5-6 membered heteroarylsulfinyl groups such as thiazolylsulfinyl, pyridylsulfinyl;

[0144] C1-C6 alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, tert-butylsulfonyl;

[0145] C1-C6 haloalkylsulfonyl groups such as trifluoromethylsulfonyl, 2,2,2-trifluoroethylsulfonyl;

[0146] Phenylsulfonyl group;

[0147] 5-6 membered heteroarylsulfonyl groups such as thiazolylsulfonyl, pyridylsulfonyl;

[0148] C1-C6 alkylsulfonyloxy groups such as methylsulfonyloxy, ethylsulfonyloxy, tert-butylsulfonyloxy;

[0149] C1-C6 haloalkylsulfonyloxy groups such as trifluoromethylsulfonyloxy, 2,2,2-trifluoroethylsulfonyloxy;

[0150] Tri-C1-C6 alkyl-substituted silyl groups such as trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl;

[0151] Triphenylsilyl group;

[0152] Cyano group; nitro group.

[0153] In addition, for these "substituents", any hydrogen atom in the substituent can be substituted with a group having a different structure. As the "substituent" in this case, examples include C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, halogen group, cyano group, nitro group, etc.

[0154] In addition, the above-mentioned "3- to 6-membered heterocyclic group" contains 1 to 4 heteroatoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom as ring-constituting atoms. The heterocyclic group can be either a monocyclic or a polycyclic group. As long as at least one ring of the polycyclic heterocyclic group is a heterocyclic ring, the remaining rings can be any one of a saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring. Examples of the "3- to 6-membered heterocyclic group" include a 3- to 6-membered saturated heterocyclic group, a 5- to 6-membered heteroaryl group, a 5- to 6-membered partially unsaturated heterocyclic group, etc.

[0155] Examples of the "3- to 6-membered saturated heterocyclic group" include aziridinyl, epoxy group, pyrrolidinyl, tetrahydrofuryl, thiazolidinyl, piperidinyl, piperazinyl, morpholinyl, dioxolanyl, di alkyl, etc.

[0156] Examples of the "5-membered heteroaryl group" include pyrrolyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, iso oxazolyl, thiazolyl, isothiazolyl, triazolyl, dioxazolyl, thiadiazolyl, tetrazolyl, etc.

[0157] Examples of the "6-membered heteroaryl group" include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, etc.

[0158] Examples of the "5- to 6-membered partially unsaturated heterocyclic group" include pyrrolinyl, dihydrofuryl, dihydrothienyl, imidazolinyl, pyrazolinyl, oxazolinyl, iso oxazolinyl, thiazolinyl, isothiazolinyl, etc., which are 5-membered partially unsaturated heterocyclic groups; and dihydropyranyl, etc., which are 6-membered partially unsaturated heterocyclic groups.

[0159] In the above formula (1), R 1 is a substituted or unsubstituted C1-6 alkyl.

[0160] R 1 The "C1-6 alkyl" in can be linear or branched. Examples of the "C1-6 alkyl" in R 1 include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 2-methylbutyl, isohexyl, etc.

[0161] Examples of R 1The substituents on the "C1-6 alkyl" in [compound name] are preferably a halogen group, a hydroxyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a C3-6 cycloalkyl group, a phenyl group, a 5-membered heteroaryl group, a 6-membered heteroaryl group, or a cyano group; a phenyl group substituted by one or more substituents selected from a C1-6 alkyl group, a C1-6 alkoxy group, a halogen group, a C1-6 haloalkyl group, or a C1-6 haloalkoxy group; a 5-membered heteroaryl group substituted by one or more substituents selected from a C1-6 alkyl group, a C1-6 alkoxy group, a halogen group, a C1-6 haloalkyl group, or a C1-6 haloalkoxy group; or a 6-membered heteroaryl group substituted by one or more substituents selected from a C1-6 alkyl group, a C1-6 alkoxy group, a halogen group, a C1-6 haloalkyl group, or a C1-6 haloalkoxy group.

[0162] In the above formula (1), Y is a C1-6 haloalkyl group (a C1-6 alkyl group substituted by one or more halogen groups).

[0163] Examples of the "C1-6 haloalkyl group" in Y include chloromethyl, chloroethyl, trifluoromethyl, 1,2-dichloropropyl, 1-fluorobutyl, perfluoropentyl, etc., and trifluoromethyl is preferred.

[0164] In the above formula (1), X is a halogen group, a C1-6 alkyl group, or a C1-6 haloalkyl group, and a halogen group is preferred.

[0165] Examples of the "halogen group" in X include a fluorine group, a chlorine group, a bromine group, an iodine group, etc., and a bromine group is preferred. In formula (1), n represents the number of X and is any integer from 0 to 4, and 1 is preferred. When n is 2 or more, Xs can be the same or different from each other.

[0166] Examples of the "C1-6 alkyl group" in X include the same groups as the "C1-6 alkyl group" exemplified in the above R 1 above.

[0167] Examples of the "C1-6 haloalkyl group" in X include the same groups as the "C1-6 haloalkyl group" exemplified in the above Y.

[0168] Compound (1) is not limited by the manufacturing method and can be effectively obtained by the manufacturing method of the present invention.

[0169] The manufacturing method of the present invention includes: in the presence of a base, subjecting a compound represented by the following formula (2) (hereinafter sometimes referred to as compound (2)) to a chemical reaction with a compound represented by the following formula (8) (hereinafter sometimes referred to as compound (8)) to obtain an N-alkylated compound, hydrolyzing the N-alkylated compound to obtain a compound represented by the following formula (3) (hereinafter sometimes referred to as compound (3)), and then subjecting the compound represented by formula (3) to a chemical reaction with phosgene or a phosgene equivalent.

[0170]

[0171] In the above formula (2), R 2 is a C1-8 alkoxy group.

[0172] As the "C1-8 alkoxy group" in R 2 , methoxy, ethoxy, propoxy, butoxy, etc. can be cited. Among these, R 2 is preferably a C1-3 alkoxy group.

[0173] Y, X, and n in the above formula (2) are the same as Y, X, and n in the above formula (1).

[0174] X in formula (2) is preferably a halogen group, more preferably a bromo group.

[0175] n in formula (2) is preferably 1.

[0176] Y in formula (2) is preferably a halomethyl group, more preferably a trifluoromethyl group.

[0177] R 1 -Za(8)

[0178] In the above formula (8), R 1 is a substituted or unsubstituted C1-6 alkyl group, Za is a halogen group or a group represented by the formula: R 1 O-SO3-.

[0179] Specifically, as the compound (8), halogenated alkanes such as methyl bromide, methyl chloride, ethyl bromide, ethyl chloride, etc. can be cited; dialkyl sulfates such as dimethyl sulfate, diethyl sulfate, etc. Among these, the compound (8) is preferably a di-C1-2 alkyl sulfate, more preferably diethyl sulfate.

[0180] As the base used when the above compound (2) reacts with the above compound (8), for example, inorganic bases such as metal hydroxides (KOH, NaOH, Ca(OH)2, etc.), metal hydrides (LiH, NaH, etc.), metal carbonates (Na2CO3, K2CO3, etc.), metal bicarbonates (NaHCO3, K2CO3, etc.); organic bases such as metal alkoxides (NaOMe, t-BuOK, etc.), metal amides (NaNH2, LDA, etc.), organometallic compounds (n-BuLi, Me3Al, etc.), alkylamines (Et3N, TMEDA, piperidine, DABCO, etc.), heterocyclic amines (DBU, pyridine, imidazole, DMAP, etc.). Among these, metal hydroxides are preferably used, and potassium hydroxide is more preferably used.

[0181] When the above-mentioned compound (2) and the above-mentioned compound (8) undergo a chemical reaction, the base used is added dropwise in the form of an aqueous solution under stirring to the mixed solution containing the above-mentioned compound (2) and the above-mentioned compound (8).

[0182] Alternatively, the above-mentioned compound (8) is added dropwise to the mixed solution containing the above-mentioned compound (2) and the base.

[0183] When the above-mentioned compound (2) and the above-mentioned compound (8) undergo a chemical reaction, a solvent can be used. As the solvent, for example, non-polar solvents such as hexane, benzene, toluene, chloroform, carbon tetrachloride, and diethyl ether; protic polar solvents such as water, methanol, and ethanol; and aprotic polar solvents such as dimethyl sulfoxide, dimethylformamide, and hexamethylphosphoric triamide can be cited. Among these, it is preferred to use non-polar solvents and / or aprotic polar solvents, and more preferably toluene and / or dimethyl sulfoxide.

[0184] When the above-mentioned compound (2) and the above-mentioned compound (8) undergo a chemical reaction, a quaternary ammonium salt can be present. The presence of the quaternary ammonium salt sometimes accelerates the chemical reaction. As the quaternary ammonium salt, for example, benzyltributylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetrapropylammonium hydroxide, tetrabutylammonium bromide, trimethylphenylammonium chloride, etc. can be cited, and benzyltributylammonium chloride is preferably used.

[0185] When the above-mentioned compound (2) and the above-mentioned compound (8) undergo a chemical reaction, the temperature is preferably 0 to 150 °C, more preferably 5 to 60 °C, still more preferably 10 to 40 °C. The pressure is not particularly limited, for example, it is normal pressure. The reaction time is about 1 to 8 hours, and it is preferably carried out under stirring.

[0186] The process of making the above-mentioned compound (2) and the above-mentioned compound (8) undergo a chemical reaction preferably includes: step a, adding compound (8) to the mixed solution containing compound (2) and the solvent under stirring; step b; further adding a quaternary ammonium salt to the mixed solution obtained in the above step a; and step c; further dropwise adding an aqueous solution of the base to the mixed solution obtained in the above step b under stirring.

[0187] Alternatively, the process of making the above-mentioned compound (2) and the above-mentioned compound (8) undergo a chemical reaction preferably includes any one of the following steps: step d, dropwise adding compound (8) to the mixed solution containing compound (2), the solvent, the base, and water under stirring; step e, simultaneously dropwise adding compound (8) and an aqueous solution of the base to the reaction solution obtained in the above step d; and step f, dropwise adding an aqueous solution of the base to the reaction solution obtained in the above step d. The above dropwise addition step is preferably carried out over about 5 minutes to 3 hours.

[0188] After the step of subjecting the above compound (2) to a chemical reaction with the above compound (8), an extraction step, a concentration step, and a purification step such as column chromatography can be carried out as needed.

[0189] The amount of the compound (8) relative to 1 mole of the compound (2) is preferably 80 to 320 mol%, more preferably 150 to 250 mol%.

[0190] The amount of the base relative to 1 mole of the compound (2) is preferably 80 to 500 mol%, more preferably 200 to 400 mol%.

[0191] The compound obtained by subjecting the above compound (2) to a chemical reaction with the above compound (8) for N-alkylation is a compound represented by the formula (3p) (hereinafter sometimes referred to as compound (3p)).

[0192]

[0193] In the above formula (3p), R 1 is a substituted or unsubstituted C1-6 alkyl group, and R 2 is a C1-8 alkoxy group, and Y, X, and n are the same as Y, X, and n in the above formula (1).

[0194] In the above formula (3p), R 1 is preferably ethyl.

[0195] In the above formula (3p), R 2 is preferably methoxy.

[0196] In the above formula (3p), X is preferably a halogen group, more preferably a bromo group.

[0197] In the above formula (3p), n is preferably 1.

[0198] In the above formula (3p), Y is preferably a halomethyl group, more preferably a trifluoromethyl group.

[0199] When subjecting the above compound (3p) to a hydrolysis reaction, a solvent can be used. Examples of the solvent include nonpolar solvents such as hexane, benzene, toluene, chloroform, carbon tetrachloride, and diethyl ether; protic polar solvents such as water, methanol, and ethanol; and aprotic polar solvents such as dimethyl sulfoxide, dimethylformamide, and hexamethylphosphoric triamide. Among these, a nonpolar solvent is preferably used, and toluene is more preferably used.

[0200] The presence of a base sometimes promotes the hydrolysis reaction of the compound (3p). Examples of the base include the same substances as those already exemplified as the base used when subjecting the above compound (2) to a chemical reaction with the above compound (8).

[0201] When performing the hydrolysis reaction of the above compound (3p), a quaternary ammonium salt may be present. The presence of the quaternary ammonium salt sometimes accelerates the hydrolysis reaction. As the quaternary ammonium salt, the same quaternary ammonium salts as those already exemplified for the quaternary ammonium salts used when the above compound (2) and the above compound (8) undergo a chemical reaction can be cited.

[0202] When the above compound (3p) is subjected to a hydrolysis reaction, the temperature is preferably 10 to 100 °C, more preferably 40 to 80 °C. The pressure is not particularly limited, for example, it is normal pressure. The reaction time is preferably about 1 to 20 hours, and it is preferably carried out with stirring.

[0203] The step of subjecting the above compound (3p) to a hydrolysis reaction includes: adding an aqueous solution of a base and an aqueous solution of a quaternary ammonium salt to a solution containing the compound (3p) and a solvent, and performing a step of heating and stirring.

[0204] Alternatively, the step of subjecting the above compound (3p) to a hydrolysis reaction includes: adding water and a solvent to the reaction solution obtained in the step of subjecting the above compound (2) and the above compound (8) to a chemical reaction, and performing an extraction step.

[0205] After the step of subjecting the above compound (3p) to a hydrolysis reaction, an extraction step, a concentration step, and a purification step using column chromatography can be carried out.

[0206]

[0207] R in the above formula (3) 1 is a substituted or unsubstituted C1-6 alkyl group, and Y, X, and n are the same as Y, X, and n in formula (1). R in the above formula (3) 1 is preferably a substituted or unsubstituted C2-6 alkyl group.

[0208] R in the above formula (3) 1 is preferably ethyl.

[0209] X in the above formula (3) is preferably a halogen group, more preferably a bromo group.

[0210] n in the above formula (3) is preferably 1.

[0211] Y in the above formula (3) is preferably a halomethyl group, more preferably a trifluoromethyl group.

[0212] Compound (3) is preferably produced by the above method, but it can also be produced by other methods using other starting materials.

[0213] Phosgene (carbonyl chloride) is a compound represented by the molecular formula COCl₂. A phosgene equivalent is a compound that exhibits almost the same function as phosgene. As phosgene equivalents, for example, fluorinated carbonic acid diesters, trichloromethyl chloroformate (diphosgene), bis(trichloromethyl) carbonate (triphosgene), N-substituted imidoyl chlorides, trichloromethyl chloroformate, 1,1'-carbonyldiimidazole, etc. can be cited.

[0214] When a chemical reaction is carried out between compound (3) and phosgene or a phosgene equivalent, a solvent can be used. As the solvent, for example, nonpolar solvents such as hexane, benzene, toluene, chloroform, carbon tetrachloride, diethyl ether, etc. can be cited, and toluene is preferably used.

[0215] When a chemical reaction is carried out between compound (3) and phosgene or a phosgene equivalent, the temperature is preferably 0 to 100 °C, more preferably 30 to 70 °C. The pressure is not particularly limited, for example, it is normal pressure, and the reaction time is, for example, about 30 minutes to 1 hour, and it can be carried out with stirring.

[0216] The step of carrying out a chemical reaction between compound (3) and phosgene or a phosgene equivalent preferably includes, for example: a step of blowing phosgene or a phosgene equivalent into a solvent at a temperature of about 5 to 15 °C for about 10 to 30 minutes; a step of dropping a mixed solution containing compound (3) and a solvent into the solvent into which phosgene or a phosgene equivalent has been previously blown at a temperature of about 40 to 60 °C for about 5 to 30 minutes; a step of stirring at a temperature of about 50 to 60 °C for about 30 minutes to 1 hour; and a step of purging the obtained reaction solution by blowing nitrogen.

[0217] The amount of phosgene or a phosgene equivalent relative to 1 mole of compound (3) is preferably 80 to 320 mol%, more preferably 100 to 200 mol%.

[0218] Compound (1) is useful as a production intermediate of a phenoxyurea compound. For example, a phenoxyurea compound can be obtained by reacting compound (1) with an amino group-containing compound such as 2-amino-2-methyl-N-(2,2,2-trifluoroethyl)propanamide or 2-aminoacetamide (refer to the following formula (6)).

[0219]

[0220] In formula (6), each R independently represents a hydrogen atom or an organic group (for example, 2-methyl-1-oxo-1-[(2,2,2-trifluoroethyl)amino]propan-2-yl, 2-amino-2-oxoethyl, etc.).

[0221] R in formula (6) 1 , Y, X and n are the same as R 1 , Y, X and n in formula (1).

[0222] When reacting compound (1) with an amino group-containing compound, a solvent can be used. As the solvent, for example, non-polar solvents such as hexane, benzene, toluene, chloroform, carbon tetrachloride, diethyl ether, etc. can be cited.

[0223] The compound represented by the above formula (2) is not limited by its production method. For example, it can be effectively obtained by subjecting the compound represented by the following formula (4) (hereinafter sometimes referred to as compound (4)) to a chemical reaction with the compound represented by the following formula (5) (hereinafter sometimes referred to as compound (5)) in the presence of a base.

[0224]

[0225] In formula (4), Z is a halogen group.

[0226] As the "halogen group" in Z, a fluorine group, a chlorine group, a bromine group, an iodine group, etc. can be cited. Z is preferably a bromine group.

[0227] X, Y and n in formula (4) are the same as X, Y and n in formula (2).

[0228] X in formula (4) is preferably a halogen group, more preferably a bromine group.

[0229] n in formula (4) is preferably 1.

[0230] Y in formula (4) is preferably a halomethyl group, more preferably a trifluoromethyl group.

[0231]

[0232] R in formula (5) 2 is the same as 2 R in formula (2).

[0233] That is, compound (5) is a C1-C8 alkyl hydroxycarbamate.

[0234] The compound (5) in formula (5) is preferably a C1-C3 alkyl hydroxycarbamate, preferably methyl hydroxycarbamate or isopropyl hydroxycarbamate.

[0235] As the base used when causing a chemical reaction between compound (4) and compound (5), for example, inorganic bases such as metal hydroxides (KOH, NaOH, Ca(OH)2, etc.), metal hydrides (LiH, NaH, etc.), metal carbonates (Na2CO3, K2CO3, etc.), metal hydrogencarbonates (NaHCO3, KHCO3, etc.) can be cited; organic bases such as metal alkoxides (NaOMe, t-BuOK, etc.), metal amides (NaNH2, LDA, etc.), organometallic compounds (n-BuLi, Me3Al, etc.), alkylamines (Et3N, TMEDA, piperidine, DABCO, etc.), heterocyclic amines (DBU, pyridine, imidazole, DMAP, etc.). Among these, metal hydroxides are preferably used, and potassium hydroxide is more preferably used.

[0236] When causing a chemical reaction between compound (4) and compound (5), a solvent can be used. As the solvent, for example, nonpolar solvents such as toluene; aprotic polar solvents such as ethyl acetate, dichloromethane, acetone, dimethyl sulfoxide, acetonitrile, dimethylformamide, tetrahydrofuran, N-methylpyrrolidone; protic polar solvents such as water, methanol, ethanol can be cited. Among these, nonpolar solvents and / or aprotic polar solvents are preferably used, and toluene and / or dimethyl sulfoxide are more preferably used.

[0237] When causing a chemical reaction between compound (4) and compound (5), the temperature is preferably 0 to 120 °C, more preferably 40 to 70 °C, still more preferably 50 to 65 °C. The pressure is not particularly limited, for example, it is normal pressure. The reaction time is preferably about 3 hours to 10 hours, and it is preferably carried out with stirring.

[0238] The step of causing a chemical reaction between compound (4) and compound (5) may include: a step of stirring a mixed solution containing compound (4), compound (5), a solvent, and a base; or a step of adding dropwise a mixed solution containing compound (5) and a solvent to a mixed solution containing compound (4), a solvent, and a base over about 3 to 5 hours and then stirring.

[0239] After the step of causing a chemical reaction between the above-mentioned compound (4) and compound (5), an extraction step, a concentration step, and a purification step such as silica gel chromatography can be carried out as needed.

[0240] The amount of compound (5) relative to 1 mole of compound (4) is preferably 80 to 320 mol%, more preferably 100 to 200 mol%.

[0241] 〔Examples〕

[0242] Next, examples are shown to explain the present invention more specifically. However, the present invention is not limited by the following examples at all.

[0243] (Example 1-a)

[0244]

[0245] 1,3 - Dibromo - 5 - (trifluoromethyl)benzene (30.4 g) (Compound 4), dimethyl sulfoxide (300 mL), methyl hydroxycarbamate (18.2 g) (Compound 5a), and 85 mass% powdered potassium hydroxide (26.4 g) were mixed and stirred at 52 °C for 8 hours. Water (300 mL), toluene (300 mL), and 35 mass% hydrochloric acid (31.2 g) were added to the resulting liquid and stirred. Thereafter, the toluene layer was separated to obtain a toluene solution of Compound 2a (yield 95%). The concentrate obtained by distilling off toluene was purified by silica gel chromatography to obtain Compound 2a.

[0246] 1 1H - NMR (CDCl3 / TMS, δ (ppm)) 7.85 (s, 1H), 7.47 - 7.48 (m, 1H), 7.44 - 7.46 (m, 1H), 7.30 - 7.32 (m, 1H), 3.86 (s, 3H)

[0247] 13 13C - NMR (CDCl3 / TMS, δ (ppm)) 160.5, 157.7, 133.2, 124.2, 123.2, 121.5, 120.0, 109.6, 53.8

[0248]

[0249] Compound 2a (16.4 g) was dissolved in toluene (50 mL). Diethyl sulfate (8.06 g) was added with stirring to this solution, and 50 mass% aqueous solution of benzyltributylammonium chloride (0.63 g) was further added. A substance obtained by dissolving granular potassium hydroxide (2.61 g) in water (2.61 g) was added dropwise to this liquid. Thereafter, it was heated and stirred at 50 °C for 5 hours. Water (30 g) was added to this liquid to separate the toluene layer, and a toluene solution of Compound 3p (yield 90%) was obtained.

[0250] The toluene solution of Compound 3p was concentrated and then purified by column chromatography for NMR analysis.

[0251] 1 1H - NMR (CDCl3 / TMS, δ (ppm)): 7.43 (s, 1H), 7.39 - 7.41 (m, 1H), 7.24 (s, 1H), 3.81 (s, 3H), 3.71 (q, 2H), 1.23 (t, 3H)

[0252]

[0253] Dissolve compound 3p (10.3 g) in toluene (50 ml). Add 10 mass% aqueous sodium hydroxide solution (60 g) and 50 mass% aqueous benzyltributylammonium chloride solution (0.94 g) to this solution. Heat it and stir for 15 hours at 70 °C. Add water (50 g) to the liquid to separate the toluene layer, and obtain a toluene solution of compound 3 (yield 91%).

[0254] Concentrate the toluene solution of compound 3, then purify it by column chromatography and conduct NMR analysis.

[0255] 1 1H-NMR (CDCl3 / TMS, δ (ppm)): 7.47 - 7.50 (m, 1H), 7.29 - 7.32 (m, 2H), 6.00 (t, 1H), 3.15 (dt, 2H), 1.16 (t, 3H)

[0256] (Example 1-b)

[0257]

[0258] Mix a 69 mass% toluene solution of 1,3-dibromo-5-(trifluoromethyl)benzene (8.79 g), dimethyl sulfoxide (10 mL), and 85 mass% granular potassium hydroxide (5.28 g), and stir at 62 °C for 10 minutes. Dropwise add a dimethyl sulfoxide (4.0 ml) solution of isopropyl hydroxycarbamate (4.81 g) thereto over 4 hours. Thereafter, stir at 62 °C for 3.5 hours. Then, add water (14 mL), toluene (20 mL), and 35 mass% hydrochloric acid (5.77 g), and stir at 45 °C. Separate the toluene layer. Add water (6 mL) to the toluene layer and stir. Separate the toluene layer. Obtain a toluene solution of compound 2b (yield 95%). Distill off toluene therefrom, and purify the residue by silica gel chromatography to obtain compound 2b.

[0259] 1 1H-NMR (CDCl3 / TMS, δ (ppm)): 7.68 (s, 1H), 7.47 (s, 1H), 7.44 (s, 1H), 7.30 - 7.31 (m, 1H), 5.02 - 5.12 (spt, 1H), 1.31 - 1.32 (d, 6H)

[0260]

[0261] To a 50 mL four-necked flask, add a 68 mass% toluene solution of compound 2b (5.07 g), dimethyl sulfoxide (7.84 g), water (2.02 g), and 85 mass% granular potassium hydroxide (2.62 g). Warm it up and add diethyl sulfate (1.55 g) dropwise over 45 minutes at 40 °C. Subsequently, add diethyl sulfate (1.38 g) and 50 mass% aqueous potassium hydroxide solution (2.19 g) dropwise simultaneously over 30 minutes. Then, stir for 1 hour. Cool the liquid, add water (2.02 g) and toluene (6.18 g) at 0 - 5 °C, and separate into an aqueous layer and a toluene layer. The toluene layer contains 0.7 mass% of compound 3. Add toluene (6.23 g) and 35 mass% hydrochloric acid (4.17 g) to the aqueous layer. The pH becomes 4.1. Separate the toluene layer to obtain a toluene solution of compound 3 (yield 87%).

[0262] Concentrate the toluene solution of compound 3, then purify it by column chromatography and perform NMR analysis.

[0263] 1 1H-NMR (CDCl3 / TMS, δ (ppm)): 7.47 - 7.50 (m, 1H), 7.29 - 7.32 (m, 2H), 6.00 (t, 1H), 3.15 (dt, 2H), 1.16 (t, 3H)

[0264] (Example 2)

[0265]

[0266] Bubble phosgene (3 g) into toluene (20 mL) at a temperature of 5 - 10 °C over 15 minutes. Add toluene (17.5 g) to a 58 mass% toluene solution of compound 3 (12 g) and add it dropwise over 10 minutes at 50 - 54 °C. Then stir at 54 - 57 °C for 30 minutes. Bubble nitrogen into the resulting liquid for purging. Subsequently, concentrate the resulting liquid to obtain compound 1 (20 g).

[0267] 1 1H-NMR (CDCl3 / TMS, δ (ppm)): 7.50 (s, 1H), 7.40 (s, 1H), 7.23 (s, 1H), 3.85 - 3.90 (q, 2H), 1.32 - 1.36 (t, 3H)

[0268] 13 13C-NMR (CDCl3 / TMS, δ (ppm)): 158.5, 150.9 (C=O, HMBC correlation), 133.2 - 134.0, 123.9 - 124.0, 123.8, 121.3, 119.9, 109.5 - 109.6, 47.24, 11.82

[0269] IR (cm -1 ): 2983.62, 2110.72, 1743.32 (C=O), 1613.44, 1586.92, 1438.11, 1383.95, 1319.53, 1306.64, 1239.24, 1173.97, 1135.15, 1105.6, 1088.08, 1076.55, 968.26, 931.68, 917.61, 860.57, 806.78, 784.22, 731.36, 713.64, 697.4, 688.99, 660.61, 549.54, 521.62, 506.89, 478.91, 467.14, 443.95, 406.72

[0270] (Example 3)

[0271]

[0272] Dissolve 2-amino-2-methyl-N-(2,2,2-trifluoroethyl)propanamide (23.6 g) in toluene (110 mL). Drop this solution into the toluene solution of Compound 1. Thereafter, stir at 50 - 50 °C for 6 hours. Add water (10 mL) to the resulting liquid. Separate the toluene layer to obtain a toluene solution of Compound 6 (yield 75%).

[0273] Concentrate the toluene solution of Compound 6 and purify it by silica gel chromatography to obtain Compound 6 (2-{3-[3-bromo-5-(trifluoromethyl)phenoxy]-3-ethylureido}-2-methyl-N-(2,2,2-trifluoroethyl)propanamide).

[0274] 1 1H-NMR (CDCl3 / TMS, δ (ppm)): 7.51 (s, 2H), 7.33 (s, 1H), 7.12 (t, 1H), 5.99 (s, 1H), 3.94 (dq, 2H), 3.67 (q, 2H), 1.57 (s, 6H), 1.17 (t, 3H).

[0275] Industrial Applicability

[0276] The phenoxycarbamoyl chloride compound (compound represented by formula (1)) of the present invention is useful as a production intermediate for phenoxyurea compounds having insecticidal activity, acaricidal activity, and / or nematicidal activity. The phenoxyamine compound (compound represented by formula (3)) of the present invention is useful as a production intermediate for the phenoxycarbamoyl chloride compound (compound represented by formula (1)).

Claims

1. A compound represented by formula (1), In the formula (1), R 1 is a substituted or unsubstituted C1-6 alkyl group, Y is a C1-C6 haloalkyl group, X is a halogen group, a C1-C6 alkyl group or a C1-C6 haloalkyl group, n represents the number of X, which is any integer from 0 to 4, and when n is 2 or more, Xs can be the same or different from each other.

2. A method for producing a compound represented by formula (1), comprising: In the presence of a base, a chemical reaction is carried out between the compound represented by formula (2) and the compound represented by formula (8) to obtain an N-alkylated compound, The N-alkylated compound is hydrolyzed to obtain the compound represented by formula (3), and then a chemical reaction is carried out between the compound represented by formula (3) and phosgene or a phosgene equivalent, In the formula (2), R 2 is C1-8 alkoxy, Y is a C1-C6 haloalkyl group, X is a halogen group, a C1-C6 alkyl group or a C1-C6 haloalkyl group, n represents the number of X, which is any integer from 0 to 4, and when n is 2 or more, Xs can be the same or different from each other. R 1 -Za(8) In the formula (8), R 1 is a substituted or unsubstituted C1-6 alkyl group, and Za is a halogen group or a group represented by the formula: R 1 O-SO3- In the formula (3), R 1 is a substituted or unsubstituted C1-6 alkyl group Y, X and n are the same as Y, X and n in the formula (2), In the formula (1), R 1 , Y, X, and n are the same as R in the formula (3). 1 , Y, X, and n.

3. The manufacturing method according to claim 2, further comprising: In the presence of a base, a chemical reaction is carried out between the compound represented by formula (4) and the compound represented by formula (5) to obtain the compound represented by formula (2), In the formula (4), Z is a halogen group, X, Y and n are the same as X, Y and n in the formula (2), In the formula (5), R 2 is the same as R in the formula (2) 2 .

4. The manufacturing method according to claim 3, wherein, The Z is a bromo group.

5. A compound represented by formula (3), In the formula (3), R 1 is a substituted or unsubstituted C1-6 alkyl group, Y is a C1-C6 haloalkyl group, X is a halogen group, a C1-C6 alkyl group or a C1-C6 haloalkyl group, n represents the number of X, which is any integer from 0 to 4, and when n is 2 or more, Xs can be the same or different from each other.

6. The compound according to claim 5, wherein The R 1 is a substituted or unsubstituted C2-6 alkyl group.

7. A method for producing a compound represented by formula (3), comprising: In the presence of a base, a chemical reaction is carried out between the compound represented by formula (2) and the compound represented by formula (8) to obtain an N-alkylated compound, The N-alkylated compound is hydrolyzed, In the formula (2), R 2 is a C1-8 alkoxy group, Y is a C1-C6 haloalkyl group, X is a halogen group, a C1-C6 alkyl group or a C1-C6 haloalkyl group, n represents the number of X, which is any integer from 0 to 4, and when n is 2 or more, Xs can be the same or different from each other. R 1 -Za(8) In the formula (8), R 1 is a substituted or unsubstituted C1-6 alkyl group, Za is a halogen group or a group represented by the formula: R 1 O-SO3- In the formula (3), R 1 is a substituted or unsubstituted C1-6 alkyl group, Y, X and n are the same as Y, X and n in the formula (2).

8. The manufacturing method according to claim 7, wherein, The R 1 is a substituted or unsubstituted C2-6 alkyl group.

9. A method for producing a compound represented by formula (1), comprising: A chemical reaction is carried out between the compound represented by formula (3) and phosgene or a phosgene equivalent, In the formula (3), R 1 is a substituted or unsubstituted C1-6 alkyl group, Y is a C1-C6 haloalkyl group, X is a halogen group, a C1-C6 alkyl group or a C1-C6 haloalkyl group, n represents the number of X, which is any integer from 0 to 4, and when n is 2 or more, Xs can be the same or different from each other. In the formula (1), R 1 、 Y, X, and n are the same as R 1 、 Y, X, and n in the formula (3).

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