Pyrimidine-biaryl compound, preparation method and application of pyrimidine-biaryl compound as herbicide

Abstract

The invention relates to a herbicide technology, and aims to provide a pyrimidine-biaryl compound, a preparation method and application of the pyrimidine-biaryl compound as a herbicide. The structural formula of the pyrimidine-biaryl compound is shown as a general formula (I). According to the application method of the compound, the compound with the herbicidal activity amount acts on leaves of weeds in the early bud stage or the later bud stage. Compared with the prior art, the compound disclosed by the invention can be used as a post-emergence and pre-emergence herbicide, is wide in herbicide controlling spectrum and has a wider drug window period.

Description

Technical Field

[0001] The present invention relates to a novel pyrimidine-biaryl compound, in particular to a pyrimidine-biaryl compound, a preparation method and application thereof as a herbicide. Background Art

[0002] In the process of grain cultivation, the use of herbicides is to increase the yield per unit area and the quality of crops. However, on the other hand, the use of herbicides also has certain negative impacts on the environment. For example, the increase in weed resistance leads to an increase in the amount of herbicides used, which brings huge risks to the ecosystem. Therefore, the development of high-efficiency, low-toxic, easily degradable and environmentally friendly herbicides has become an important development direction for innovative research.

[0003] Pyrimidine salicylic acid herbicides are widely used for weed control in rice fields and cotton fields. So far, five herbicides have been registered in relevant countries and used for the control of important weeds in farmland. Their structural formulas are:

[0004]

[0005] The widespread use of these herbicides has led to an increase in weed resistance and threatens the continued use of these herbicides. Existing studies have shown that the target of pyrimidine salicylic acid herbicides is acetoacetate synthase (AHAS), and the resistance mechanism of weeds to these herbicides is mainly manifested in two aspects: target site mutation and metabolic resistance in non-target resistance (increased metabolic capacity to herbicides). Therefore, designing resistance inhibitors will become a major challenge.

[0006] In order to overcome this problem, people have found that a class of pyrimidine-biphenyl compounds are effective against Descurania Sophia and Ammannia arenaria that are resistant to AHAS inhibitors. This class of pyrimidine-biphenyl compounds was discovered based on the structural optimization of pyrimidine salicylic acid herbicides. It retains the pyrimidine skeleton and carboxylic acid group, and introduces a phenyl or heteroaryl group at the 6-position of the benzene ring. Among them, the 6-position phenyl compound is effective against weeds that are resistant to AHAS.

[0007] Biaryl compounds are the basic skeletons of natural products. They are also common molecular substructures in medicinal chemistry. Due to their internal rotational flexibility, they can adapt to various drug targets. In addition, this skeleton is also an important component of the molecular structure of pesticides. It is also an important skeleton in materials science. Therefore, molecules containing this type of skeleton have broad application prospects. Secondly, the Suzuki-Miyaura Cross-Coupling reaction can be used to quickly construct this type of compound, which can effectively expand new chemical space.

[0008] Pyrimidine salicylic acid herbicides all contain a pyrimidine skeleton and a carboxyl group or its ester. Previous studies have always believed that these two substructures must be retained in the design of inhibitors in order for the compounds to maintain their herbicidal activity. Therefore, the research direction of technical personnel in the industry has always been based on this idea to develop new herbicides, resulting in the inability to continuously launch products with newer chemical structures and better resistance properties.

[0009] Therefore, it is urgent and of great significance to develop this new type of pyrimidine-biaryl compound and use it for weed control. Summary of the invention

[0010] The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide a pyrimidine-biaryl compound, a preparation method and an application as a herbicide. The compound can be used as an agricultural chemical herbicide for weed control in the agricultural field and exhibits excellent post-emergence and pre-emergence herbicidal activity.

[0011] To solve the technical problem, the solution of the present invention is:

[0012] Provided is a pyrimidine-biaryl compound, the structural formula of the compound is shown in general formula (I):

[0013]

[0014] In formula (I), Ar is selected from any one of Ar1 to Ar30 shown below:

[0015]

[0016]

[0017] in,

[0018] R1 is hydrogen, halogen, amino, hydroxy, cyano, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl or C1-C2 alkyl;

[0019] R2 is hydrogen, halogen, amino, methoxy or C1-C2 alkyl;

[0020] R3 is hydrogen, halogen, C1-C2 alkyl, C1-C2 alkoxy, acetyl, benzoyl, carboxyl or methyl ester;

[0021] R4 is hydrogen, halogen, methoxy or C1-C2 alkyl;

[0022] R5 is hydrogen or fluorine.

[0023] As a preferred embodiment of the present invention, the halogen is fluorine, chlorine or bromine; the C1-C2 alkyl is methyl (Me, CH3) or ethyl (Et, C2H5); the C1-C2 alkoxy is methoxy (MeO, CH3O) or ethoxy (EtO, C2H5O). The pyrimidine-biaryl compound of the present invention can be combined with the specific structures of the 78 kinds of Ar listed in formula (I) and Table 1 to show specific compounds I-1 to I-78, but the present invention is not limited to these compounds.

[0024] Table 1

[0025]

[0026]

[0027]

[0028] The present invention further provides a method for preparing the aforementioned pyrimidine-biaryl compound, which is prepared by the following synthetic route 1 or synthetic route 2:

[0029] Synthesis route 1:

[0030]

[0031] In formula (B), LG 1 represents a boron-containing substituent;

[0032] Synthesis route 2:

[0033]

[0034] In formula (C), LG 2 represents a boron-containing substituent; in formula (D), X 2 represents a leaving group.

[0035] As a preferred embodiment of the present invention, the preparation method based on synthetic route 1 specifically includes:

[0036] According to the molar ratio of 1:1.3:6:0.05, the intermediate represented by formula (A), the compound represented by formula (B), potassium carbonate and palladium catalyst are added to an appropriate amount of solvent and reacted at 100°C for 1 hour; the reaction product is separated and purified by silica gel column chromatography to finally obtain a pyrimidine-biaryl compound represented by formula (I).

[0037] As a preferred embodiment of the present invention, the preparation method based on the second synthetic route specifically comprises:

[0038] (1) adding the compound represented by formula (C), the compound represented by formula (D), sodium carbonate and palladium catalyst to an appropriate amount of solvent at a molar ratio of 1:1.3:5:0.05, and reacting at 100° C. for 1 hour to obtain a compound represented by formula (E);

[0039] (2) taking a compound represented by formula (E), salicylaldehyde and sodium borohydride at a molar ratio of 1:1.5:1.5; firstly adding the compound represented by formula (E) and salicylaldehyde into methanol, and reacting them at room temperature for 0.5 hour; then adding sodium borohydride, and continuing to react at room temperature for 0.5 hour, to obtain a compound represented by formula (F);

[0040] (3) The compound represented by formula (F), an equivalent amount of 2-methylsulfonyl-4,6-dimethoxypyrimidine and cesium carbonate are added to an appropriate amount of 1,4-dioxane in a molar ratio of 1:1.2:1.5, and the mixture is reacted at 110° C. for 4 hours; the reaction product is separated and purified by silica gel column chromatography to finally obtain a pyrimidine-biaryl compound represented by formula (I).

[0041] The present invention further provides a herbicidal composition comprising a herbicidally active amount of the aforementioned pyrimidine-biaryl compound and at least one formulation adjuvant.

[0042] The present invention further provides a method for preparing a herbicidally active composition, which comprises mixing a herbicidally active amount of the aforementioned pyrimidine-biaryl compound and at least one formulation adjuvant.

[0043] The present invention further provides the use of the aforementioned pyrimidine-biaryl compound as an agricultural chemical herbicide.

[0044] The present invention further provides a method for using the aforementioned pyrimidine-biaryl compound as an agricultural chemical herbicide, which comprises applying a herbicidally active amount of the pyrimidine-biaryl compound to the leaves of weeds in the pre-germination or post-germination stage; the weeds are any one of the following: barnyard grass, crabgrass, Amaranthus retroflexus, Ramie or Cassia seed.

[0045] Compared with the prior art, the present invention has the following beneficial effects:

[0046] 1. The present invention breaks through the previously commonly used design ideas and adopts a new design concept: that is, while retaining the pyrimidine skeleton, removing the carboxyl group, and using the biaryl skeleton to design a new type of pyrimidine-biaryl compound. This compound has the following characteristics: (1) In this structure, the aromatic group is located in the ortho position of the benzylamine. Due to its internal rotation flexibility, it can effectively adapt to related targets. (2) This structure does not contain a carboxyl group and has a strong lipophilicity, which is conducive to being absorbed by plants; (3) The lipophilicity of the compound may realize its interaction with the target enzyme in a hydrophobic-driven manner, which is different from the existing pyrimidine salicylic acid herbicides.

[0047] 2. The pyrimidine-biaryl compounds provided by the present invention can be used as agricultural chemical herbicides for the prevention and control of various weeds in the agricultural field.

[0048] 3. The pyrimidine-biaryl compounds provided by the present invention can be used as post-emergence herbicides, especially for barnyard grass, crabgrass and Amaranthus retroflexus. Some of the compounds can effectively control barnyard grass, crabgrass, Amaranthus retroflexus, Cassia seed and Abutilon, with a broad weed control spectrum.

[0049] 4. The pyrimidine-biaryl compounds provided by the present invention can be used as pre-emergence herbicides, especially for barnyard grass, crabgrass and Amaranthus retroflexus. Some of the compounds can effectively control barnyard grass, crabgrass, Amaranthus retroflexus and velvetleaf, with a broad weed control spectrum.

[0050] 5. The pyrimidine-biaryl compound provided by the present invention can be used as a post-emergence and pre-emergence herbicide and has a wider window of application.

[0051] 6. The pyrimidine-biaryl compound I-5 provided by the present invention can be used as a post-emergence and pre-emergence herbicide; the post-emergence and pre-emergence herbicidal activities are equivalent to those of the AHAS inhibitor P, but the post-emergence herbicidal activity is better than that of the commercial herbicide pretilachlor; in the prevention and control of the malignant weed barnyard grass, it has a wider drug window period than pretilachlor. DETAILED DESCRIPTION

[0052] The following specific implementation schemes and examples are provided to illustrate the implementation process of the present invention.

[0053] Part I Overview of Preparation Methods

[0054] The compound of the structure represented by the general formula (I) of the present invention can be prepared by two main synthetic routes.

[0055] Synthesis route 1:

[0056] Compounds I-1 to I-22, I-24 to I-26, I-28 to I-39, I-43 to I-45, I-47 to I-50, I-55 to I-64, and I-74 to I-78 in Table 1 were prepared using the method of synthetic route one.

[0057] In this synthetic route, the compound having formula (A) can be synthesized according to the method reported by Meng et al. in Org. Chem. Front. 2020, 7, 267-272. 1 mole of the compound having formula (A) can be prepared by reacting with 1.3 moles of the compound having formula (B) (wherein LG 1A compound representing a suitable boron-containing substituent, such as a boronic acid group or a 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl group, preferably a boronic acid group) is optionally reacted at 100° C. for 1 hour in the presence of 6 moles of potassium carbonate and 0.05 moles of tetrakis(triphenylphosphine)palladium(0) and in a suitable solvent (which may include N,N-dimethylformamide or 1,4-dioxane, preferably N,N-dimethylformamide) to form a compound having formula (I). The product is separated and purified using silica gel column chromatography.

[0058] Synthesis route 2:

[0059] Compounds I-23, I-40 to I-42, I-46, I-51 to I-54, I-65 to I-73 in Table 1 were prepared using the method of synthetic route 2.

[0060] In this synthetic route, 1 mol of formula (C) (wherein LG 2 A compound representing a suitable boron-containing substituent, such as a boronic acid group or a 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl group, preferably a 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl group) can be prepared by reacting with 1.3 moles of a compound having formula (D) (wherein X 2 represents a suitable leaving group, such as bromine or iodine, preferably iodine) is optionally converted into a compound having formula (E) in the presence of 5 mol of sodium carbonate and 0.05 mol of a suitable palladium catalyst (which may include tetrakis(triphenylphosphine)palladium(0) or [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), preferably tetrakis(triphenylphosphine)palladium(0)) and in N,N-dimethylformamide at 100°C for 1 hour.

[0061] 1 mol of the compound having formula (E) can be converted into the compound having formula (F) by reacting with 1.5 mol of salicylaldehyde in methanol at room temperature for 0.5 hour, and further reacting with 1.5 mol of sodium borohydride at room temperature for 0.5 hour.

[0062] 1 mol of the compound of formula (F) can be converted into the compound of formula (I) by reacting with 1.2 mol of 2-methylsulfonyl-4,6-dimethoxypyrimidine in the presence of 1.5 mol of cesium carbonate and in 1,4-dioxane at 110° C. for 4 hours. The product is separated and purified using silica gel column chromatography.

[0063] In addition, compound I-27 in Table 1 is further modified from compound I-26 and is not classified into the aforementioned two synthetic routes.

[0064]

[0065] In the preparation method, 1 mole of a compound having formula (I-26) can be reacted in the presence of 5 moles of sodium hydroxide in a methanol aqueous solution with a volume ratio of 1:1 at 80°C for 1 hour, and then acidified with 0.5 mol / L dilute hydrochloric acid to obtain a compound having formula (I-27).

[0066] Part II Preparation Examples of Compounds

[0067] Example 1: This example is used to illustrate the synthesis of target compound I-1 based on synthesis route 1 in the present invention.

[0068] Synthesis of intermediate N-(2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzyl)-2-iodoaniline (A).

[0069]

[0070] Intermediate (A) can be synthesized according to the method reported by Meng et al. in Org. Chem. Front. 2020, 7, 267-272.

[0071] Synthesis of target product I-1.

[0072]

[0073] Phenylboronic acid (B-1) (79.2 mg, 0.65 mmol) and N-(2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzyl)-2-iodoaniline (A) (231.6 mg, 0.5 mmol) were dissolved in N,N-dimethylformamide (4 mL), and tetrakis(triphenylphosphine)palladium(0) (28.9 mg, 0.025 mmol) was added under argon protection, followed by a 1.5 mol / L potassium carbonate aqueous solution (2 mL), and the resulting mixture was heated at 100°C for 1 hour. After cooling to room temperature, saturated brine was added to the mixed solution, and extracted with ethyl acetate (3×10 mL), and the combined organic phase was washed with brine, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain a crude product of I-1. The crude product was separated by silica gel column chromatography [V (petroleum ether) / V (ethyl acetate)=10 / 1] to obtain a waxy product I-1.

[0074] Example 2: This example is used to illustrate the synthesis of the target product I-8 based on synthetic route 1 in the present invention.

[0075]

[0076] [2-Aminophenylboronic acid pinacol ester (C-1) (142.4 mg, 0.65 mmol) and N-(2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzyl)-2-iodoaniline (A) (231.6 mg, 0.5 mmol) were dissolved in N, N-dimethylformamide (4 mL), and tetrakis(triphenylphosphine)palladium(0) (28.9 mg, 0.025 mmol) was added under argon protection, followed by an aqueous potassium carbonate solution (2 mL, 1.5 mol / L). The resulting mixture was heated at 100°C for 1 hour. After cooling to room temperature, saturated brine was added to the mixture, and extracted with ethyl acetate (3×10 mL). The combined organic phase was washed with brine, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain a crude product of I-8. The crude product was separated by silica gel column chromatography [V (petroleum ether) / V (ethyl acetate)=10 / 1] to obtain a waxy product I-8.

[0077] Example 3: This example is used to illustrate the synthesis of the target product I-63 based on synthetic route 1 in the present invention.

[0078]

[0079] 1-Hydrogen-indazol-4-ylboronic acid (B-2) (105.3 mg, 0.65 mmol) and N-(2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzyl)-2-iodoaniline (A) (231.6 mg, 0.5 mmol) were dissolved in 1,4-dioxane (4 mL), and tetrakis(triphenylphosphine)palladium(0) (28.9 mg, 0.025 mmol) was added under argon protection, followed by a 1.5 mol / L potassium carbonate aqueous solution (2 mL). The resulting mixture was heated at 100°C for 1 hour. After cooling to room temperature, saturated brine was added to the mixture, and extracted with ethyl acetate (3×10 mL), and the combined organic phase was washed with brine, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain a crude product of I-63. The crude product was separated by silica gel column chromatography [V (petroleum ether) / V (ethyl acetate)=10 / 1] to obtain a waxy product I-63.

[0080] The synthesis of the following compounds can refer to Examples 1 to 3 and will not be described in detail here.

[0081] The confirmatory data of compounds I-1~I-22, I-24~I-26, I-28~I-39, I-43~I-45, I-47~I-50, I-55~I-64, I-74~I-78 are as follows:

[0082] I-1: waxy substance; 1H NMR (400 MHz, CDCl3) δ7.45–7.38 (m, 5H), 7.37–7.24 (m, 2H), 7.21–7.06 (m, 4H), 6.78 (t, J = 7.1 Hz, 1H), 6.66 (d, J = 8.1 Hz, 1H), 5.76 (s, 1H), 4.33 (s, 2H), 3.77 (s, 6H). (without NH)

[0083] I-2: waxy substance; 1 H NMR (400MHz, CDCl3) δ7.35 (d, J=7.6Hz, 1H), 7.30–7.21 (m,

[0084] 4H),7.20–7.08(m,4H),6.98(dd,J=7.4,1.5Hz,1H),6.75(t,J=7.3Hz,1H),6. 62(d,J=8.1Hz,1H),5.77(s,1H),4.31(s,2H),3.78(s,6H),2.15(s,3H).(No NH)

[0085] I-3: waxy substance; 1 H NMR (400MHz, CDCl3) δ7.44 (d, J=7.5Hz, 1H), 7.37–7.21 (m,

[0086] 4H),7.23–7.07(m,5H),6.75(td,J=7.4,1.1Hz,1H),6.61(d,J=8.1Hz,1H),5.78(s,1H),4.35(s,2H),3.78(s,6H),2.41(s,3H).(No NH)

[0087] I-4: solid, mp 82.6-83.9℃; 1 H NMR (400MHz, CDCl3) δ7.44–7.37(m,1H),7.32–7.24(m,3H),7.22(d,J=7.9Hz,2H),7.20–7.15(m,1H),7.14–7.08(m,2H),7.06(dd ,J=7.4,1.5Hz,1H),6.74(td,J=7.4,1.0Hz,1H),6.62(d,J=8.1Hz,1H),5.76(s,1H),4.32(s,2H),3.76(s,6H),2.39(s,3H).(No NH)

[0088] I-5: waxy substance; 1H NMR(400MHz, CDCl3)δ7.45(d,J=7.5Hz,1H),7.36(td,J=8.2,1.7Hz,1H),7.30–7.22(m,2H),7.20–6.96(m,6H),6 .76(t,J=7.2Hz,1H),6.61(d,J=7.8Hz,1H),5.78(s,1H),4.35(d,J=4.1Hz,2H),3.82(s,3H),3.80(s,6H).(No NH)

[0089] I-6: solid, mp 118.5-120.1 °C; 1 H NMR (400MHz, CDCl3) δ7.43–7.39(m,1H),7.33(t,J=7.9Hz,1H),7.27(td,J=7.7,1.7Hz,1H),7.18(td,J=7.5,1.1Hz,1H),7.15–7.06(m,3H),7.0 3–6.95(m,2H),6.90–6.86(m,1H),6.74(td,J=7.4,0.9Hz,1H),6.60(d, J=8.0Hz,1H),5.76(s,1H),4.33(s,2H),3.83(s,3H),3.77(s,6H).(No NH)

[0090] I-7: solid, mp 104.8-105.3°C; 1 H NMR (400MHz, CDCl3) δ7.40 (dd, J=7.6, 1.1Hz, 1H), 7.31 (d, J=8.6Hz, 2H), 7. 27(td,J=7.9,1.6Hz,1H),7.17(td,J=7.5,1.0Hz,1H),7.14–7.08(m,2H),7. 05(dd,J=7.4,1.5Hz,1H),6.95(d,J=8.7Hz,2H),6.75(t,J=7.4Hz,1H),6.64 (d,J=8.1Hz,1H),5.76(s,1H),4.32(s,2H),3.84(s,3H),3.76(s,6H).(No NH)

[0091] I-8: solid, mp 84.8-87.0℃; 1H NMR (400 MHz, CDCl3) δ7.39 (d, J = 7.6 Hz, 1H), 7.26 (dd, J = 7.7, 1.6 Hz, 1H), 7.21–7.06 (m, 6H), 6.82 (td, J = 7.4, 1.0 Hz, 1H), 6.80–6.72 (m, 2H), 6.62 (d, J = 8.1 Hz, 1H), 5.78 (s, 1H), 4.33 (d, J = 1.8 Hz, 2H), 3.78 (s, 6H). (no NH, no NH2)

[0092] I-9: solid, mp 51.7-53.8 °C; 1 H NMR (400 MHz, CDCl3) δ7.43–7.38 (m, 1H), 7.27 (td, J = 7.7, 1.6 Hz, 1H), 7.23–7.15 (m, 2H), 7.13–7.06 (m, 3H), 6.80 (d, J = 7.5 Hz, 2H), 6.74–6.65 (m, 2H), 6.57 (d, J = 8.0 Hz, 1H), 5.76 (s, 1H), 4.31 (s, 2H), 3.78 (s, 6H). ((no NH, no NH2))

[0093] I-10: waxy substance; 1 H NMR (400MHz, CDCl3) δ7.41(dd,J=7.5,1.3Hz,1H),7.27(td,J=7.8,1.7Hz,1H),7.23(d,J=8.4Hz,2H),7.18(td,J=7.5,1.1Hz,1H),7 .14–7.02(m,3H),6.80(d,J=8.3Hz,2H),6.72(td,J=7.4,1.0Hz,1H),6.57(d,J=8.1Hz,1H),5.77(s,1H),4.31(s,2H),3.78(s,6H).

[0094] I-11: waxy substance; 1 H NMR(400MHz, CDCl3)δ7.34–7.13(m,7H),7.12(d,J=8.0Hz,1H),7.05–6.95(m,2H),6.9 0(td,J=7.5,0.9Hz,1H),6.77(d,J=9.1Hz,1H),5.77(s,1H),4.26(s,2H),3.75(s,6H).

[0095] I-12: solid, mp 52.4-54.2℃; 11H NMR (400 MHz, CDCl3) δ 7.42–7.36 (m, 1H), 7.30–7.22 (m, 3H), 7.17 (td, J = 7.5, 1.1 Hz, 1H), 7.13–7.07 (m, 2H), 7.04 (dd, J = 7.4, 1.5 Hz, 1H), 6.87 (d, J = 8.5 Hz, 2H), 6.74 (t, J = 7.4 Hz, 1H), 6.62 (d, J = 8.1 Hz, 1H), 5.76 (s, 1H), 4.31 (s, 2H), 3.77 (s, 6H).

[0096] I-13: Solid, m.p. 101.2 - 102.4 °C; 1 1H NMR (400 MHz, CDCl3) δ 7.43 (dd, J = 7.5, 1.0 Hz, 1H), 7.40–7.31 (m, 2H), 7.27 (td, J = 7.7, 1.5 Hz, 1H), 7.24–7.05 (m, 6H), 6.76 (dd, J = 7.4, 0.7 Hz, 1H), 6.62 (d, J = 8.1 Hz, 1H), 5.77 (s, 1H), 4.36 (s, 2H), 3.78 (s, 6H).

[0097] I-14: Solid, m.p. 89.9 - 91.9 °C; 1 1H NMR (400 MHz, CDCl3) δ 7.45–7.34 (m, 3H), 7.29 (td, J = 7.8, 1.5 Hz, 1H), 7.23–7.08 (m, 5H), 7.05 (dd, J = 7.4, 1.5 Hz, 1H), 6.75 (dd, J = 7.4, 0.7 Hz, 1H), 6.65 (d, J = 8.1 Hz, 1H), 5.78 (s, 1H), 4.34 (s, 2H), 3.77 (s, 6H).

[0098] I-15: Solid, m.p. 126.2 - 127.2 °C; 1 1H NMR (400 MHz, CDCl3) δ 7.53–7.47 (m, 1H), 7.44 (d, J = 7.5 Hz, 1H), 7.35–7.23 (m, 4H), 7.17 (t, J = 7.7 Hz, 2H), 7.11 (d, J = 8.0 Hz, 1H), 7.02 (dd, J = 7.4, 1.3 Hz, 1H), 6.76 (td, J = 7.4, 0.6 Hz, 1H), 6.62 (d, J = 8.2 Hz, 1H), 5.78 (s, 1H), 4.35 (s, 2H), 3.78 (s, 6H).

[0099] I-16: solid, mp 105.1-106.2°C; 1 H NMR (400MHz, CDCl3) δ7.41–7.27(m,6H),7.22–7.08(m,3H),7.03(dd,J=7.5,1.5Hz,1H ),6.75(t,J=7.4Hz,1H),6.66(d,J=8.1Hz,1H),5.76(s,1H),4.32(s,2H),3.75(s,6H).

[0100] I-17: solid, mp39.5-42.1℃; 1 H NMR (400MHz, CDCl3) δ7.69(d,J=7.7Hz,1H),7.45(d,J=6.9Hz,1H),7.38(t,J=7.2Hz,1H),7.33–7.20(m,3H),7.17(t,J=7.6Hz,2H),7. 11(d,J=7.9Hz,1H),7.00(dd,J=7.4,1.4Hz,1H),6.76(t,J=7.3Hz,1H),6.62(d,J=8.1Hz,1H),5.78(s,1H),4.35(s,2H),3.78(s,6H).

[0101] I-18: solid, mp 150.6-151.7 °C; 1 H NMR (400MHz, CDCl3) δ7.79(d,J=7.8Hz,1H),7.58(t,J=7.4Hz,1H),7.48(t,J=7.6Hz,1H),7.34(d,J=7.5Hz,2H),7.26(td,J=7.7,1.5Hz,1H),7.20–7 .12(m,2H),7.09(d,J=8.0Hz,1H),6.99(d,J=7.4Hz,1H),6.73(td,J=7.4, 0.7Hz,1H),6.59(d,J=8.1Hz,1H),5.77(s,1H),4.31(s,2H),3.77(s,6H).

[0102] I-19: solid, mp 112.2-114.2 °C; 11H NMR (400 MHz, CDCl3) δ 7.68 (d, J = 8.0 Hz, 2H), 7.54 (d, J = 8.0 Hz, 2H), 7.42 (d, J = 7.5 Hz, 1H), 7.30 (t, J = 7.6 Hz, 1H), 7.24–7.10 (m, 3H), 7.05 (dd, J = 7.4, 1.1 Hz, 1H), 6.77 (t, J = 7.4 Hz, 1H), 6.68 (d, J = 8.2 Hz, 1H), 5.77 (s, 1H), 4.35 (s, 2H), 3.75 (s, 6H).

[0103] I-20: Wax; 1 1H NMR (400 MHz, CDCl3) δ 8.60 (d, J = 8.0 Hz, 1H), 8.30 (d, J = 8.2 Hz, 1H), 8.27 (dd, J = 7.9, 0.9 Hz, 1H), 7.83–7.76 (m, 1H), 7.62 (t, J = 7.5 Hz, 1H), 7.39–7.32 (m, 1H), 7.30–7.23 (m, 3H), 7.20 (d, J = 7.3 Hz, 1H), 7.06 (t, J = 7.4 Hz, 1H), 6.98 (d, J = 7.2 Hz, 1H), 5.79 (s, 1H), 5.64 (s, 2H), 3.85 (s, 6H).

[0104] I-21: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.46 (d, J = 6.9 Hz, 1H), 7.40–7.33 (m, 1H), 7.30–7.12 (m, 6H), 7.10 (dd, J = 7.9, 0.8 Hz, 1H), 7.03 (dd, J = 7.4, 1.4 Hz, 1H), 6.76 (td, J = 7.3, 0.7 Hz, 1H), 6.60 (d, J = 8.1 Hz, 1H), 5.77 (s, 1H), 4.34 (s, 2H), 3.79 (s, 6H), 2.38 (s, 3H).

[0105] I-22: Wax; 1 1H NMR (400 MHz, CDCl3) δ 8.13 (t, J = 8.0 Hz, 1H), 7.69–7.54 (m, 2H), 7.40 (d, J = 7.4 Hz, 1H), 7.33–7.06 (m, 6H), 6.72–6.65 (m, 1H), 6.57 (d, J = 8.2 Hz, 1H), 5.75 (s, 1H), 4.29 (q, J = 12.3 Hz, 2H), 3.76 (s, 6H), 2.41 (s, 3H).

[0106] I-24: waxy substance; 1 H NMR (400MHz, CDCl3) δ7.99(d,J=8.2Hz,2H),7.52(d,J=8.3Hz,2H),7.40(dd,J=7.5,1.3Hz,1H),7.29(td,J=7.6,1.3Hz,1H),7.23–7.09 (m,3H),7.06(dd,J=7.5,1.4Hz,1H),6.76(t,J=7.4Hz,1H),6.66(d,J=8.2Hz,1H),5.75(s,1H),4.33(s,2H),3.74(s,6H),2.62(s,3H).

[0107] I-25: waxy substance; 1 H NMR (400MHz, CDCl3) δ7.92–7.79(m,4H),7.65–7.57(m,1H),7.56–7.47(m,4H),7.39(dd,J=7.5,1.1Hz,1H),7.29(td,J= 7.7,1.4Hz,1H),7.22–7.08(m,4H),6.80(t,J=7.1Hz,1H),6.70(d,J=8.2Hz,1H),5.74(s,1H),4.35(s,2H),3.75(s,6H).

[0108] I-26: waxy substance; 1 H NMR (400MHz, CDCl3) δ8.07(d,J=8.3Hz,2H),7.48(d,J=8.3Hz,2H),7.39(dd,J=7.5,1.3Hz,1H),7.29(td,J=7.7,1.5Hz,1H),7.21–7.09(m ,3H),7.06(dd,J=7.5,1.5Hz,1H),6.76(td,J=7.4,0.7Hz,1H),6.67(d,J=8.1Hz,1H),5.75(s,1H),4.32(s,2H),3.94(s,3H),3.74(s,6H).

[0109] I-28: waxy substance; 11H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 7.2 Hz, 1H), 7.28 (t, J = 7.6 Hz, 1H), 7.22–7.04 (m, 6H), 7.00 (d, J = 7.2 Hz, 1H), 6.75 (t, J = 7.2 Hz, 1H), 6.59 (d, J = 8.0 Hz, 1H), 5.79 (s, 1H), 4.33 (s, 2H), 3.80 (s, 6H), 2.36 (s, 3H), 2.09 (s, 3H).

[0110] I-29: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.37 (d, J = 7.6 Hz, 1H), 7.27 (td, J = 7.8, 1.6 Hz, 1H), 7.21–7.07 (m, 5H), 7.02 (s, 1H), 6.98 (dd, J = 7.4, 1.5 Hz, 1H), 6.75 (td, J = 7.3, 0.7 Hz, 1H), 6.60 (d, J = 8.1 Hz, 1H), 5.78 (s, 1H), 4.33 (s, 2H), 3.79 (s, 6H), 2.35 (s, 3H), 2.12 (s, 3H).

[0111] I-30: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.39 (d, J = 6.6 Hz, 1H), 7.27 (td, J = 7.7, 1.7 Hz, 1H), 7.18 (td, J = 7.5, 1.0 Hz, 1H), 7.13–7.08 (m, 2H), 7.06 (dd, J = 7.5, 1.5 Hz, 1H), 7.01 (s, 2H), 6.97 (s, 1H), 6.76 (t, J = 7.3 Hz, 1H), 6.65 (d, J = 7.7 Hz, 1H), 5.75 (s, 1H), 4.34 (s, 2H), 3.77 (s, 6H), 2.35 (s, 6H).

[0112] I-31: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 7.4 Hz, 1H), 7.25 (d, J = 7.2 Hz, 1H), 7.18–7.07 (m, 5H), 6.94 (d, J = 8.1 Hz, 1H), 6.86 (d, J = 7.5 Hz, 1H), 6.73 (t, J = 7.3 Hz, 1H), 6.57 (d, J = 7.9 Hz, 1H), 5.77 (s, 1H), 4.35 (s, 2H), 3.91 (s, 3H), 3.80 (s, 6H), 3.61 (s, 3H).

[0113] I-32: waxy substance; 1 H NMR(400MHz, CDCl3)δ7.45(d,J=7.1Hz,1H),7.26(td,J=7.7,1.6Hz,1H),7.20–7.06(m,4H),6.96–6.81(m,3H),6.75 (t,J=7.3Hz,1H),6.59(d,J=7.0Hz,1H),5.77(s,1H),4.35(d,J=3.9Hz,2H),3.80(s,6H),3.79(s,3H),3.75(s,3H).

[0114] I-33: solid, mp 95.3-97.2 °C; 1 H NMR (400MHz, CDCl3) δ7.36(dd,J=7.6,1.3Hz,1H),7.26(td,J=7.7,1.6Hz,1H),7.21–7.11(m,3H),7.11(dd,J=8.1,1.1Hz,1H),6.99(dd,J=7.4,1. 6Hz,1H),6.83(dd,J=8.4,2.8Hz,1H),6.78–6.72(m,2H),6.61(d,J=8.1H z,1H),5.77(s,1H),4.32(s,2H),3.79(s,3H),3.78(s,6H),2.07(s,3H).

[0115] I-34: waxy substance; 1 H NMR(600MHz, CDCl3)δ7.45(d,J=7.3Hz,1H),7.26(td,J=7.6,1.2Hz,1H),7.19–7.13(m,2H),7.11(t,J=7.6Hz,2H),7.07(dd,J=7.5,1.4Hz, 2H), 6.89 (d, J = 8.3Hz, 1H), 6.75 (t, J = 6.8Hz, 1H), 6.57 (s, 1H), 5.77 (s, 1H), 4.34 (q, J = 16.3Hz, 2H), 3.80 (s, 6H), 3.78 (s, 3H), 2.33 (s, 3H).

[0116] I-35: solid, mp 103.6-105.3 °C; 11H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 7.6 Hz, 1H), 7.27 (td, J = 7.8, 1.7 Hz, 1H), 7.18 (td, J = 7.5, 1.1 Hz, 1H), 7.14–7.05 (m, 3H), 6.84–6.67 (m, 4H), 6.63 (d, J = 8.0 Hz, 1H), 5.75 (s, 1H), 4.34 (s, 2H), 3.81 (s, 3H), 3.77 (s, 6H), 2.37 (s, 3H).

[0117] I-36: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.47–7.40 (m, 1H), 7.26 (td, J = 7.6, 1.5 Hz, 1H), 7.22–7.01 (m, 7H), 6.75 (t, J = 7.3 Hz, 1H), 6.60 (d, J = 7.4 Hz, 1H), 5.77 (s, 1H), 4.36 (s, 2H), 3.80 (s, 6H), 3.45 (s, 3H), 2.35 (s, 3H).

[0118] I-37: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 8.8 Hz, 1H), 7.46 (d, J = 7.5 Hz, 1H), 7.26 (td, J = 7.7, 1.5 Hz, 1H), 7.16 (t, J = 7.7 Hz, 2H), 7.10 (d, J = 7.9 Hz, 1H), 7.00 (dd, J = 7.4, 1.5 Hz, 1H), 6.86 (d, J = 3.0 Hz, 1H), 6.82–6.71 (m, 2H), 6.61 (d, J = 8.1 Hz, 1H), 5.76 (s, 1H), 4.34 (s, 2H), 3.79 (s, 3H), 3.78 (s, 6H).

[0119] I-38: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.47–7.34 (m, 3H), 7.27 (td, J = 7.7, 1.6 Hz, 1H), 7.21–7.08 (m, 3H), 7.03 (dd, J = 7.5, 1.5 Hz, 1H), 6.86 (d, J = 8.8 Hz, 1H), 6.75 (t, J = 7.3 Hz, 1H), 6.60 (d, J = 6.6 Hz, 1H), 5.78 (s, 1H), 4.34 (d, J = 5.6 Hz, 2H), 3.80 (s, 6H), 3.79 (s, 3H).

[0120] I-39: solid, mp 51.2-53.4 °C; 1 H NMR (400MHz, CDCl3) δ7.45(d,J=7.5Hz,1H),7.33(t,J=7.9Hz,1H),7.25(td,J=7.7,1.5Hz,1H),7.19–7.12(m,2H),7.10(dd,J=8.0,0.9Hz,1H),6. 99(dd,J=7.4,1.5Hz,1H),6.91(d,J=7.9Hz,2H),6.75(t,J=7.4Hz,1H),6 .59(d,J=8.1Hz,1H),5.77(s,1H),4.33(s,2H),3.94(s,3H),3.78(s,6H).

[0121] I-43: waxy substance; 1 H NMR(400MHz, CDCl3)δ7.40(dd,J=7.5,1.2Hz,1H),7.36(d,J=2.0Hz,1H),7.28(td,J=7.6,1.5Hz,1H),7.24–7.16(m,2H),7.14–7.08(m,2H),7 .04(d,J=8.3Hz,1H),7.01(dd,J=7.5,1.5Hz,1H),6.72(dd,J=7.4,0.8Hz,1H),6.61(d,J=8.1Hz,1H),5.77(s,1H),4.33(s,2H),3.76(s,6H).

[0122] I-44: waxy substance; 1 H NMR (400MHz, CDCl3) δ7.41–7.36(m,2H),7.33–7.22(m,2H),7.18(td,J=7.5,1.0Hz,1H),7.12(td,J=8.2,1.2Hz,2H),7.02(dd,J=7.5 ,1.5Hz,1H),6.96(d,J=8.4Hz,1H),6.74(t,J=7.4Hz,1H),6.65(d,J=8.1Hz,1H),5.76(s,1H),4.33(s,2H),3.94(s,3H),3.76(s,6H).

[0123] I-45: wax; 11H NMR (400 MHz, CDCl3) δ 7.43–7.36 (m, 2H), 7.28 (td, J = 7.6, 1.6 Hz, 1H), 7.23 (dd, J = 8.4, 2.1 Hz, 1H), 7.18 (td, J = 7.5, 1.1 Hz, 1H), 7.14–7.08 (m, 2H), 7.02 (dd, J = 7.5, 1.5 Hz, 1H), 6.95 (d, J = 8.4 Hz, 1H), 6.73 (t, J = 7.4 Hz, 1H), 6.61 (d, J = 8.1 Hz, 1H), 5.76 (s, 1H), 4.33 (s, 2H), 4.14 (q, J = 7.0 Hz, 2H), 3.76 (s, 6H), 1.50 (t, J = 7.0 Hz, 3H).

[0124] I-47: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.33 (d, J = 7.6 Hz, 1H), 7.29 (td, J = 7.7, 1.7 Hz, 1H), 7.21–7.16 (m, 3H), 7.13 (d, J = 8.0 Hz, 1H), 7.09 (dd, J = 8.2, 2.2 Hz, 1H), 7.06 (d, J = 2.2 Hz, 1H), 6.92 (d, J = 8.2 Hz, 1H), 6.89 (td, J = 7.4, 1.2 Hz, 1H), 6.76 (d, J = 7.9 Hz, 1H), 5.77 (s, 1H), 4.27 (s, 2H), 3.75 (s, 6H), 2.32 (s, 3H).

[0125] I-48: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 6.7 Hz, 1H), 7.28 (td, J = 7.6, 1.1 Hz, 1H), 7.23–7.14 (m, 3H), 7.12 (d, J = 8.0 Hz, 1H), 7.05 (d, J = 7.4 Hz, 1H), 7.01–6.94 (m, 1H), 6.75 (t, J = 7.4 Hz, 1H), 6.64 (d, J = 8.2 Hz, 1H), 5.77 (s, 1H), 4.34 (s, 2H), 3.99 (d, J = 1.0 Hz, 3H), 3.77 (s, 6H).

[0126] I-49: Wax; 11H NMR (400 MHz, CDCl3) δ 7.90 (t, J = 9.3 Hz, 2H), 7.67 (d, J = 8.4 Hz, 1H), 7.58–7.48 (m, 2H), 7.46–7.39 (m, 2H), 7.29 (d, J = 7.6 Hz, 1H), 7.25–7.19 (m, 2H), 7.15–7.10 (m, 2H), 7.07 (dd, J = 8.0, 1.0 Hz, 1H), 6.82 (td, J = 7.4, 0.9 Hz, 1H), 6.68 (d, J = 8.1 Hz, 1H), 5.74 (s, 1H), 4.27 (s, 2H), 3.75 (s, 6H).

[0127] I-50: Wax; 1 1H NMR (400 MHz, CDCl3) δ 8.17 (d, J = 8.3 Hz, 1H), 7.64 (d, J = 8.4 Hz, 1H), 7.57 (t, J = 7.2 Hz, 1H), 7.52–7.43 (m, 1H), 7.35 (dd, J = 7.7, 5.5 Hz, 1H), 7.31–7.17 (m, 4H), 7.16–7.04 (m, 3H), 6.80 (dd, J = 7.4, 0.6 Hz, 1H), 6.70 (d, J = 8.1 Hz, 1H), 5.74 (s, 1H), 4.27 (s, 2H), 3.75 (s, 6H).

[0128] I-55: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.61–7.57 (m, 1H), 7.49 (t, J = 1.6 Hz, 1H), 7.43 (dd, J = 7.5, 1.3 Hz, 1H), 7.29 (td, J = 7.8, 1.6 Hz, 1H), 7.19 (td, J = 7.5, 1.1 Hz, 1H), 7.17–7.07 (m, 3H), 6.71 (td, J = 7.4, 1.0 Hz, 1H), 6.62 (d, J = 8.1 Hz, 1H), 6.58 (dd, J = 1.7, 0.7 Hz, 1H), 5.75 (s, 1H), 4.35 (s, 2H), 3.77 (s, 6H).

[0129] I-56: Wax; 11H NMR (400 MHz, CDCl3) δ 7.49–7.44 (m, 2H), 7.41 (dd, J = 7.7, 1.5 Hz, 1H), 7.29 (td, J = 7.8, 1.6 Hz, 1H), 7.19 (td, J = 7.5, 1.2 Hz, 1H), 7.13 (dd, J = 8.0, 1.1 Hz, 1H), 7.10–7.04 (m, 1H), 6.73–6.66 (m, 1H), 6.62 (d, J = 8.2 Hz, 1H), 6.55–6.51 (m, 1H), 6.50–6.44 (m, 1H), 5.73 (s, 1H), 4.44 (s, 2H), 3.76 (s, 6H).

[0130] I-57: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 7.6 Hz, 1H), 7.40 (dd, J = 4.9, 3.0 Hz, 1H), 7.34 (dd, J = 2.9, 1.3 Hz, 1H), 7.29 (td, J = 7.8, 1.6 Hz, 1H), 7.23–7.08 (m, 5H), 6.72 (td, J = 7.4, 1.0 Hz, 1H), 6.61 (d, J = 8.2 Hz, 1H), 5.76 (s, 1H), 4.35 (s, 2H), 3.78 (s, 6H).

[0131] I-58: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 7.5 Hz, 1H), 7.33 (dd, J = 5.1, 1.1 Hz, 1H), 7.29 (td, J = 7.8, 1.6 Hz, 1H), 7.25–7.17 (m, 2H), 7.16–7.06 (m, 4H), 6.71 (td, J = 7.4, 0.9 Hz, 1H), 6.61 (d, J = 8.2 Hz, 1H), 5.76 (s, 1H), 4.36 (s, 2H), 3.78 (s, 6H).

[0132] I-59: Wax; 1H NMR(400MHz, CDCl3)δ7.44(dd,J=7.7,1.7Hz,1H),7.29(td,J=7.8,1.7Hz,1H),7.26–7.19(m,3H),7.18(dd,J=3.6,1.1Hz,1H),7 .16–7.10(m,3H),7.06–7.01(m,2H),6.73(td,J=7.5,1.1Hz,1H),6.67(d,J=8.2Hz,1H),5.74(s,1H),4.39(s,2H),3.75(s,6H).

[0133] I-60: waxy; 1 H NMR(400MHz, CDCl3)δ8.32(s,1H),7.39(d,J=8.0Hz,2H),7.30–7.07(m,8H),6.79(t,J= 7.3Hz,1H),6.65(d,J=8.0Hz,1H),6.43(s,1H),5.76(s,1H),4.31(s,2H),3.77(s,6H).

[0134] I-61: waxy substance; 1 H NMR(400MHz, CDCl3)δ8.61(s,1H),7.67(dd,J=7.1,1.9Hz,1H),7.32–7.08(m,9H),6.78(td,J=7.4,1.2Hz,1H),6.7 0(d,J=8.2Hz,1H),6.58(dd,J=3.2,2.0Hz,1H),5.76(d,J=0.9Hz,1H),4.30(dd,J=47.3,13.3Hz,2H),3.75(s,6H).

[0135] I-62: waxy substance; 1 H NMR (400MHz, CDCl3) δ11.13(s,1H),8.36(d,J=4.7Hz,1H),7.47–7.30(m,2H),7.31–7.13(m,5H),7.10(d,J=7.9Hz ,1H),6.80(t,J=7.1Hz,1H),6.69(d,J=8.1Hz,1H),6.46(d,J=3.5Hz,1H),5.73(s,1H),4.34(s,2H),3.74(s,6H).

[0136] I-63: waxy substance; 11H NMR (600 MHz, CDCl3) δ 8.00 (s, 1H), 7.48 (d, J = 8.3 Hz, 1H), 7.45–7.39 (m, 1H), 7.38 (d, J = 7.4 Hz, 1H), 7.31–7.12 (m, 5H), 7.10 (d, J = 8.0 Hz, 1H), 6.80 (t, J = 7.4 Hz, 1H), 6.68 (d, J = 8.2 Hz, 1H), 5.73 (s, 1H), 4.33 (s, 2H), 3.75 (s, 6H).

[0137] I-64: Wax; 1 1H NMR (500 MHz, CDCl3) δ 8.03 (s, 1H), 7.73 (dd, J = 8.1, 1.0 Hz, 1H), 7.34 (dd, J = 7.0, 1.0 Hz, 1H), 7.25–7.13 (m, 5H), 7.11–7.04 (m, 2H), 6.77 (td, J = 7.4, 1.1 Hz, 1H), 6.68 (dd, J = 8.3, 1.1 Hz, 1H), 5.72 (s, 1H), 4.27 (s, 2H), 3.70 (s, 6H).

[0138] I-74: Wax; 1 1H NMR (400 MHz, CDCl3) δ 8.92 (dd, J = 4.2, 1.7 Hz, 1H), 8.15 (d, J = 8.5 Hz, 1H), 8.00 (dd, J = 8.5, 0.7 Hz, 1H), 7.78 (dd, J = 8.5, 7.1 Hz, 1H), 7.51 (dd, J = 7.0, 1.0 Hz, 1H), 7.35 (dd, J = 8.5, 4.2 Hz, 1H), 7.25–7.20 (m, 3H), 7.14–7.09 (m, 1H), 7.08–7.05 (m, 2H), 6.80 (td, J = 7.4, 0.9 Hz, 1H), 6.68 (d, J = 8.2 Hz, 1H), 5.72 (s, 1H), 4.25 (s, 2H), 3.72 (s, 6H).

[0139] I-75: Wax; 1H NMR (400MHz, CDCl3) δ9.29(s,1H),8.45(d,J=5.9Hz,1H),7.99(t,J=4.7Hz,1H),7.66(d,J=5.0Hz,2H),7.47(d,J=5.9Hz,1H),7.30–7.17(m,3 H),7.12(td,J=7.5,1.0Hz,1H),7.09–7.01(m,2H),6.80(td,J=7.4,0.8Hz,1H),6.69(d,J=8.1Hz,1H),5.72(s,1H),4.26(s,2H),3.72(s,6H).

[0140] I-76: waxy; 1 H NMR(400MHz, CDCl3) δ7.46(d,J=7.6Hz,1H),7.28(td,J=7.6,1.5Hz,1H),7.20–7.08(m,4H),6.94–6.87(m,2H),6. 87–6.81(m,1H),6.76(t,J=7.2Hz,1H),6.61(d,J=8.0Hz,1H),5.78(s,1H),4.35(s,2H),4.27(s,4H),3.80(s,6H).

[0141] I-77: waxy; 1 H NMR (400MHz, CDCl3) δ7.45–7.39(m,1H),7.27(td,J=7.7,1.6Hz,1H),7.18(td,J=7.5,1.1Hz,1H),7.13–7.01(m,3H), 6.94–6.85(m,3H),6.72(t,J=7.4Hz,1H),6.58(d,J=8.1Hz,1H),5.76(s,1H),4.33(s,2H),4.29(s,4H),3.77(s,6H).

[0142] I-78: waxy; 1H NMR(600MHz, CDCl3)δ7.59(d,J=7.5Hz,1H),7.38–7.28(m,3H),7.25(td,J=7.8,1.7Hz,1 H),7.20(dd,J=7.5,1.6Hz,1H),7.17–7.09(m,3H),6.97(dd,J=7.3,1.6Hz,1H),6.72(td, J=7.3,1.2Hz,1H),6.58(d,J=8.1Hz,1H),5.77(s,1H),4.29(qd,J=16.2,4.3Hz,2H),3.9 1(s,1H),3.78(s,6H),3.61(q,J=4.7Hz,4H),3.33(dd,J=63.5,13.7Hz,2H),2.32(s,4H).

[0143] Example 4: This example is used to illustrate the synthesis of target compound I-41 based on synthesis route 2 in the present invention.

[0144] Step 1: Synthesis of intermediate 2'-bromo-5'-methyl-[1,1'-biphenyl]-2-amine (E-1).

[0145]

[0146] 2-Aminophenylboronic acid pinacol ester (C-1) (131.5 mg, 0.6 mmol) and 4-bromo-3-iodotoluene (D-1) (231.6 mg, 0.78 mmol) were dissolved in N, N-dimethylformamide (4 mL), and tetrakis(triphenylphosphine)palladium (0) (34.7 mg, 0.03 mmol) was added under argon protection, followed by a 1.5 mol / L potassium carbonate aqueous solution (2 mL). The mixture was heated at 100 ° C for 1 hour. After cooling to room temperature, saturated brine was added to the mixture, and extracted with ethyl acetate (3×10 mL). The combined organic phase was washed with brine, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain 2'-bromo-5'-methyl-[1,1'-biphenyl]-2-amine (E-1).

[0147] Step 2: Synthesis of intermediate 2-(((2'-bromo-5'-methyl-[1,1'-biphenyl]-2-yl)amino)methyl)phenol (F-1).

[0148]

[0149] 2'-Bromo-5'-methyl-[1,1'-biphenyl]-2-amine (E-1) (131.1 mg, 0.5 mmol) was dissolved in methanol (6 mL), followed by the addition of salicylaldehyde (91.6 mg, 0.75 mmol). The reaction was stirred at room temperature for 0.5 hours until 2'-bromo-5'-methyl-[1,1'-biphenyl]-2-amine completely disappeared. Subsequently, sodium borohydride (28.4 mg, 0.75 mmol) was slowly added to the reaction mixture, and the reaction was stirred at room temperature for 0.5 hours. After the reaction was completed, the solvent was removed under reduced pressure to obtain 2-(((2'-bromo-5'-methyl-[1,1'-biphenyl]-2-yl)amino)methyl)phenol (F-1).

[0150] Step 3: Synthesis of target product I-41

[0151]

[0152] 2-(((2'-bromo-5'-methyl-[1,1'-biphenyl]-2-yl)amino)methyl)phenol (F-1) (184.2 mg, 0.5 mmol) was dissolved in 1,4-dioxane (6 mL), and then cesium carbonate (244.3 mg, 0.75 mmol) and 2-methylsulfonyl-4,6-dimethoxypyrimidine (131.0 mg, 0.6 mmol) were added. The solution was heated to 110°C and reacted for 4 hours. After cooling to room temperature, saturated brine was added to the mixed solution, and extracted with ethyl acetate (3×10 mL), the organic layers were combined, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain a crude product, which was separated by silica gel column chromatography [V (petroleum ether) / V (ethyl acetate)=10 / 1] to obtain a light yellow waxy product I-41.

[0153] Example 5: This example is used to illustrate the synthesis of target compound I-70 based on synthesis route 2 in the present invention.

[0154] Step 1: Synthesis of intermediate 2-(benzo[d]thiazol-7-yl)aniline (E-2).

[0155]

[0156] 2-Aminophenylboronic acid (C-2) (82.8 mg, 0.6 mmol) and 7-bromobenzo[d]thiazole (D-2) (167.0 mg, 0.78 mmol) were dissolved in N,N-dimethylformamide (4 mL), and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (22.0 mg, 0.03 mmol) was added under argon protection, followed by 1.5 mol / L potassium carbonate aqueous solution (2 mL). The resulting mixture was heated at 100°C for 1 hour. Subsequently, after cooling to room temperature, saturated brine was added to the mixture, and the aqueous layer was extracted with ethyl acetate (3×10 mL). The organic layers were combined, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain 2-(benzo[d]thiazol-7-yl)aniline (E-2).

[0157] Step 2: Synthesis of intermediate 2-(((2-(benzo[d]thiazol-7-yl)phenyl)amino)methyl)phenol (F-2).

[0158]

[0159] 2-(Benzo[d]thiazol-7-yl)aniline (E-2) (113.2 mg, 0.5 mmol) was dissolved in methanol (6 mL), followed by the addition of salicylaldehyde (91.6 mg, 0.75 mmol). The mixture was stirred at room temperature for 0.5 hours until 2-(benzo[d]thiazol-7-yl)aniline disappeared completely. Subsequently, sodium borohydride (28.4 mg, 0.75 mmol) was slowly added to the reaction mixture, and the reaction was stirred at room temperature for 0.5 hours. After the reaction was completed, the solvent was removed under reduced pressure to give 2-(((2-(benzo[d]thiazol-7-yl)phenyl)amino)methyl)phenol (F-2).

[0160] Step 3: Synthesis of target compound I-70.

[0161]

[0162] 2-(((2-(Benzo[d]thiazol-7-yl)phenyl)amino)methyl)phenol (F-2) (166.2 mg, 0.5 mmol) was dissolved in 1,4-dioxane (6 mL), and then cesium carbonate (244.3 mg, 0.75 mmol) and 2-methylsulfonyl-4,6-dimethoxypyrimidine (131.0 mg, 0.6 mmol) were added. The solution was heated to 110°C and reacted for 4 hours. Subsequently, saturated brine was added to the mixed solution after cooling to room temperature, and the aqueous layer was extracted with ethyl acetate (3×10 mL). The organic layers were combined, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain a crude product of I-70. The crude product was separated by silica gel column chromatography [V (petroleum ether) / V (ethyl acetate) = 10 / 1] to obtain a light yellow waxy product I-70.

[0163] The synthesis of the following compounds can refer to Examples 4 and 5, which will not be described in detail here.

[0164] The confirmation numbers of compounds I-23, I-40~I-42, I-46, I-51~I-54, I-65~I-73 are as follows:

[0165] I-23: waxy substance; 1 H NMR (500MHz, CDCl3) δ8.24 (dd, J=8.0, 1.3Hz, 1H), 7.65 (td, J=7.5, 1.4Hz, 1H), 7.56 (td, J=7.7, 1.4Hz, 1H),7.39(dd,J=7.6,1.6Hz,1H),7.34(dd,J=7.5,1.3Hz,1H),7.25(td,J=7.7,1.7Hz,1H),7.24–7.17(m ,1H),7.15(td,J=7.5,1.2Hz,1H),7.08(dd,J=8.0,1.2Hz,1H),7.06(dd,J=7.5,1.6Hz,1H),6.76(t,J= 7.4Hz,1H),6.66(dd,J=8.3,1.0Hz,1H),5.76(s,1H),4.30(q,J=15.6Hz,2H),3.76(s,6H),2.78(s,3H).

[0166] I-40: waxy substance; 1 H NMR(400MHz, CDCl3)δ7.45(dd,J=7.6,1.2Hz,1H),7.31–7.23(m,3H),7.21–7.07(m,4H),6.99(dd,J=7.4,1.5H z,1H),6.77(td,J=7.4,0.9Hz,1H),6.61(d,J=8.1Hz,1H),5.78(s,1H),4.35(s,2H),3.80(s,6H),2.50(s,3H).

[0167] I-41: waxy substance; 11H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 8.1 Hz, 1H), 7.46 (d, J = 7.6 Hz, 1H), 7.27 (td, J = 7.7, 1.5 Hz, 1H), 7.21–7.09 (m, 4H), 7.04 (dd, J = 8.1, 1.8 Hz, 1H), 6.98 (dd, J = 7.4, 1.5 Hz, 1H), 6.75 (t, J = 7.4 Hz, 1H), 6.60 (d, J = 8.1 Hz, 1H), 5.77 (s, 1H), 4.35 (d, J = 1.9 Hz, 2H), 3.79 (s, 6H), 2.34 (s, 3H).

[0168] I-42: Wax; 1 1H NMR (400 MHz, CDCl3) δ 7.38 (dd, J = 8.1, 2.1 Hz, 1H), 7.36–7.32 (m, 2H), 7.27 (td, J = 7.7, 1.5 Hz, 1H), 7.21–7.08 (m, 4H), 6.93 (dd, J = 7.4, 1.5 Hz, 1H), 6.74 (t, J = 7.4 Hz, 1H), 6.61 (d, J = 8.1 Hz, 1H), 5.78 (s, 1H), 4.32 (s, 2H), 3.78 (s, 6H), 2.08 (s, 3H).

[0169] I-46: Solid, m.p, 113.5 - 115.2 °C; 1 1H NMR (600 MHz, CDCl3) δ 7.43 (t, J = 7.7 Hz, 1H), 7.39 (d, J = 7.5 Hz, 1H), 7.31 (d, J = 7.6 Hz, 1H), 7.27 (td, J = 7.7, 1.7 Hz, 1H), 7.18 (td, J = 7.6, 1.3 Hz, 1H), 7.15–7.11 (m, 3H), 6.94 (dd, J = 7.4, 1.6 Hz, 1H), 6.72 (td, J = 7.4, 1.1 Hz, 1H), 6.58 (d, J = 8.1 Hz, 1H), 5.79 (s, 1H), 4.34 (s, 2H), 3.79 (s, 6H), 2.59 (d, J = 2.5 Hz, 3H).

[0170] I-51: Wax; 11H NMR (400 MHz, CDCl3) δ 8.55 (d, J = 4.8 Hz, 1H), 7.75 (td, J = 7.9, 1.8 Hz, 1H), 7.67 (d, J = 8.2 Hz, 1H), 7.54 (d, J = 7.8 Hz, 1H), 7.47 (d, J = 7.5 Hz, 1H), 7.27–7.22 (m, 1H), 7.19–7.04 (m, 4H), 6.78–6.67 (m, 2H), 5.69 (s, 1H), 4.49 (s, 2H), 3.75 (s, 6H).

[0171] I-52: Wax; 1 1H NMR (500 MHz, CDCl3) δ 8.68 (d, J = 1.7 Hz, 1H), 8.57 (d, J = 4.7 Hz, 1H), 7.75 (dt, J = 7.8, 2.0 Hz, 1H), 7.39 (dd, J = 7.7, 1.6 Hz, 1H), 7.34 (dd, J = 7.8, 4.9 Hz, 1H), 7.28 (dd, J = 7.7, 1.7 Hz, 1H), 7.20–7.14 (m, 2H), 7.11 (dd, J = 8.0, 1.0 Hz, 1H), 7.04 (dd, J = 7.4, 1.7 Hz, 1H), 6.76 (t, J = 7.4 Hz, 1H), 6.64 (dd, J = 8.2, 1.1 Hz, 1H), 5.75 (s, 1H), 4.32 (s, 2H), 3.75 (s, 6H).

[0172] I-53: Wax; 1 1H NMR (400 MHz, CDCl3) δ 8.64 (d, J = 5.1 Hz, 2H), 7.44 (d, J = 5.4 Hz, 2H), 7.39 (dd, J = 7.5, 1.5 Hz, 1H), 7.29 (td, J = 7.8, 1.6 Hz, 1H), 7.23–7.16 (m, 2H), 7.12 (dd, J = 8.0, 1.1 Hz, 1H), 7.06 (dd, J = 7.5, 1.5 Hz, 1H), 6.77 (td, J = 7.4, 0.9 Hz, 1H), 6.67 (d, J = 8.2 Hz, 1H), 5.75 (s, 1H), 4.33 (s, 2H), 3.75 (s, 6H).

[0173] I-54: Wax; 11H NMR (400 MHz, CDCl3) δ 9.03 (dd, J = 4.8, 1.4 Hz, 1H), 7.88 (dd, J = 8.9, 1.3 Hz, 1H), 7.55–7.50 (m, 2H), 7.47 (d, J = 7.5 Hz, 1H), 7.25 (td, J = 7.7, 1.5 Hz, 1H), 7.20–7.09 (m, 3H), 6.74–6.66 (m, 2H), 5.67 (s, 1H), 4.53 (s, 2H), 3.76 (s, 6H).

[0174] I-65: Wax; 1 1H NMR (500 MHz, CDCl3) δ 7.78 (dd, J = 8.1, 1.1 Hz, 1H), 7.76 (s, 1H), 7.29 (dd, J = 8.2, 7.2 Hz, 1H), 7.25–7.21 (m, 2H), 7.21–7.16 (m, 1H), 7.14–7.05 (m, 4H), 6.74 (td, J = 7.4, 1.1 Hz, 1H), 6.64 (d, J = 8.1 Hz, 1H), 5.74 (s, 1H), 4.28 (s, 2H), 3.72 (s, 6H), 3.34 (s, 3H).

[0175] I-66: Wax; 1 1H NMR (600 MHz, CDCl3) δ 8.11 (s, 1H), 7.57 (dd, J = 7.9, 1.1 Hz, 1H), 7.50 (d, J = 7.4 Hz, 1H), 7.45 (t, J = 7.7 Hz, 1H), 7.42 (dd, J = 7.4, 0.9 Hz, 1H), 7.24 (d, J = 7.6 Hz, 2H), 7.20–7.14 (m, 2H), 7.09 (d, J = 7.8 Hz, 1H), 6.81 (t, J = 7.3 Hz, 1H), 6.69 (d, J = 7.3 Hz, 1H), 5.74 (s, 1H), 4.36 (s, 2H), 3.76 (s, 6H).

[0176] I-67: Wax; 1 1H NMR (500 MHz, CDCl3) δ 8.11 (s, 1H), 7.79–7.74 (m, 1H), 7.46–7.40 (m, 3H), 7.29–7.24 (m, 1H), 7.23–7.14 (m, 3H), 7.13–7.06 (m, 1H), 6.80 (t, J = 7.5 Hz, 1H), 6.69 (d, J = 8.4 Hz, 1H), 5.73 (s, 1H), 4.34 (s, 2H), 3.74 (s, 6H).

[0177] I-68: waxy; 1 H NMR(500MHz, CDCl3)δ7.56(dd,J=7.7,1.6Hz,1H),7.46(dd,J=7.5,1.7Hz,1H),7.39–7.31(m,2H),7.28–7.21(m,2H),7.19–7.13 (m,2H),7.10(d,J=7.9Hz,1H),6.79(t,J=7.4Hz,1H),6.66(d,J=7.7Hz,1H),5.74(s,1H),4.35(s,2H),3.77(s,6H),2.64(s,3H).

[0178] I-69: waxy; 1 H NMR(400MHz, CDCl3)δ9.02(s,1H),8.03–7.91(m,1H),7.62–7.41(m,3H),7.25–7.12(m,4H),7.08(d,J= 7.9Hz,1H),6.82(td,J=7.4,0.7Hz,1H),6.69(d,J=8.1Hz,1H),5.75(s,1H),4.33(s,2H),3.77(s,6H).

[0179] I-70: waxy; 1 H NMR (400MHz, CDCl3) δ9.01(s,1H),8.12(d,J=8.1Hz,1H),7.59(t,J=7.7Hz,1H),7.43(d,J=7.2Hz,1H),7.36(d,J=7.5Hz,1H),7.30–7.16(m,3H) ,7.16(dd,J=7.5,1.0Hz,1H),7.08(dd,J=8.0,1.0Hz,1H),6.79(t,J=7.4Hz,1H),6.70(d,J=8.1Hz,1H),5.73(s,1H),4.31(s,2H),3.74(s,6H).

[0180] I-71: waxy substance; 1 H NMR (400MHz, CDCl3) δ7.62(d,J=2.1Hz,1H),7.50(d,J=8.2Hz,1H),7.36(dt,J=10.6,5.3Hz,2H),7.31–7.22(m,2H),7.2 1–7.13(m,3H),7.09(d,J=8.0Hz,1H),6.79(t,J=7.3Hz,1H),6.73–6.63(m,2H),5.74(s,1H),4.32(s,2H),3.75(s,6H).

[0181] I-72: waxy substance; 1 H NMR(400MHz, CDCl3) δ7.89(d,J=8.0Hz,1H),7.46–7.38(m,2H),7.37–7.32(m,2H),7.28–7.23(m,1H),7.21–7.13( m,4H),7.10(d,J=8.0Hz,1H),6.79(t,J=7.4Hz,1H),6.66(d,J=8.1Hz,1H),5.76(s,1H),4.31(s,2H),3.77(s,6H).

[0182] I-73: waxy substance; 1 H NMR (400MHz, CDCl3) δ7.67(d,J=7.9Hz,1H),7.34–6.98(m,9H),6.94(d,J=7.9Hz,1H) ,6.63(t,J=7.4Hz,1H),6.50(d,J=8.2Hz,1H),5.59(s,1H),4.16(s,2H),3.61(s,6H).

[0183] Example 6: This example is used to illustrate the preparation method of the target compound I-27

[0184] The synthesis of the raw material 2'-((2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzyl)amino)-[1,1'-biphenyl]-4-carboxylic acid methyl ester (I-26) was prepared according to the method disclosed in Example 1.

[0185] Synthesis of target compound I-27

[0186]

[0187] 2'-((2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzyl)amino)-[1,1'-biphenyl]-4-carboxylic acid methyl ester (I-26) (287.1 mg, 0.6 mmol) was dissolved in a methanol aqueous solution (6 mL) with a volume ratio of 1:1, and then sodium hydroxide (120.0 mg, 3 mmol) was added. The solution was heated to 80°C and reacted for 1 hour. Subsequently, saturated brine was added to the mixed solution after cooling to room temperature, and the aqueous layer was extracted with ethyl acetate (3×10 mL), and the aqueous phases were combined. After concentration under reduced pressure, 0.5 mol / L dilute hydrochloric acid was slowly added dropwise to precipitate a solid, which was filtered and washed with distilled water to obtain the target compound I-27 as a light yellow waxy substance.

[0188] I-27: Wax. 1H NMR (400MHz, DMSO-d6) δ8.00 (d, J=8.3Hz, 2H), 7.54 (d, J=

[0189] 8.3Hz,2H),7.41(dd,J=7.4,1.0Hz,1H),7.30(td,J=7.7,1.5Hz,1H),7.22(dd,J=7.4,0.7Hz,1H),7.16(dd,J=7.9,1.0Hz,1H),7.00 (dd,J=7.5,1.4Hz,1H),6.65(t,J=7.4Hz,1H),6.46(d,J=8.2Hz,1H),5.99(s,1H),5.34(s,1H),4.18(d,J=3.2Hz,2H),3.74(s,6H).

[0190] Part III Performance Test and Conclusion of Compounds

[0191] Example 7: This example is used to illustrate the post-emergence herbicidal activity of the compound of structural formula (I) provided by the present invention.

[0192] Test agent: the compound of structural formula (I) provided by the present invention (see Table 3).

[0193] Test targets: Echinochloa crusgalli, Digitaria sanguinalis, Ramie flax, Amaranthus retroflexus, Cassia seed.

[0194] Planting method: The test soil is sandy soil, silt soil and clay, which are prepared in a mass ratio of 1:1:1. After mixing and stirring evenly, they are used as special soil for the test. Take a flower pot with a diameter of 8 cm, fill the soil to 3 / 4 of the flower pot, and place the flower pot in a large stainless steel pot with 5 cm deep water. After the soil is completely moistened, sow 10-15 target weed seeds in the flower pot. After sowing, cover with 0.2-0.5 cm of soil, and then place it in a greenhouse for cultivation. Replenish water every day to keep the soil moisture at about 80% (relative humidity), the growth temperature at 25±8℃, and the air humidity above 60%.

[0195] Application method: Use the greenhouse potting method, wait for the weeds to grow to the 2-leaf stage, and spray after budding. Repeat twice for each treatment, and set a blank control (distilled water as a blank control). After spraying, let it stand in the room, and after the weed leaves absorb the liquid, move it into the greenhouse for cultivation, and the growth temperature is 25±8℃.

[0196] Visual evaluation criteria for herbicidal activity (Table 2).

[0197] Table 2

[0198]

[0199] Investigation method: The growth and reaction symptoms of the weeds after treatment were observed regularly, and the herbicidal activity of the compound was evaluated by visual inspection 21 days after the application. The specific test results are shown in Table 3.

[0200] Table 3

[0201]

[0202]

[0203] As can be seen from Table 3, the compounds contained in structural formula (I) generally have strong post-emergence herbicidal activity, especially against barnyard grass, crabgrass and Amaranthus retroflexus, indicating that they can effectively control grass weeds and Amaranthaceae weeds after emergence; among them, I-22 has an inhibition rate of ≥95% on the four weed targets tested, which can not only effectively control grass weeds and Amaranthaceae weeds, but also has a control effect of 100% on velvet; I-52 is effective on five weed targets, can control grass weeds and Amaranthaceae weeds, and has a control effect of 95% and 85% on Cassia seed and velvet, respectively, with a broad weed control spectrum.

[0204] Example 8: This example is used to illustrate the pre-emergence herbicidal activity of the compound of structural formula (I) provided by the present invention.

[0205] Test agent: the compound of structural formula (I) provided by the present invention (see Table 4).

[0206] Test targets: Echinochloa crusgalli, Digitaria sanguinalis, Ramie fructus, Amaranthus retroflexus, Cassia seed.

[0207] Planting method: The test soil is sandy soil, silt soil and clay, which are prepared in a mass ratio of 1:1:1, mixed and stirred evenly as special soil for the test. Take a flower pot with a diameter of 8 cm, fill the soil to 3 / 4 of the flower pot, and place the flower pot in a large stainless steel pot with 5 cm deep water. After the soil is completely moistened, sow the above target weed seeds in the flower pot, ensuring that there are 10-15 seeds of each weed, covered with 0.2-0.5 cm of soil, and then placed in a greenhouse for cultivation. The growth temperature is 25±8℃, and the air humidity is above 60%.

[0208] Application method: Use greenhouse potting method, treat soil surface with test agent 24 hours after sowing, repeat twice for each treatment, set blank control (distilled water as blank control). After soil treatment, move to greenhouse for cultivation, growth temperature is 25±8℃.

[0209] Investigation method: Regularly observe the growth and reaction symptoms of the treated weeds, and evaluate the herbicidal activity of the compound by visual inspection 21 days after the application. The specific test results are shown in Table 4.

[0210] Table 4

[0211]

[0212]

[0213] As can be seen from Table 4, the compounds contained in structural formula (I) generally have strong pre-emergence herbicidal activity, especially against barnyard grass, crabgrass and Amaranthus retroflexus, indicating that they can effectively control grass weeds and Amaranthaceae weeds before emergence; among them, I-35 has an inhibition rate of ≥90% on the three weed targets tested, and can effectively control grass weeds and Amaranthaceae weeds; I-52 and I-68 can not only effectively control grass weeds and Amaranthaceae weeds, with a control effect of ≥90%, but also have a control effect on velvetleaf of 80% and 85% respectively, with a wide spectrum of weed control.

[0214] As can be seen from Tables 3 and 4, among the various pyrimidine-biaryl compounds provided by the present invention, some have excellent post-emergence herbicidal activity and can be used as post-emergence herbicides. Some compounds also have excellent pre-emergence herbicidal activity and can be used as pre-emergence herbicides; some compounds exhibit excellent post-emergence herbicidal activity and also excellent pre-emergence herbicidal activity, and can be used as pre-emergence and post-emergence herbicides, with a wider drug use window.

[0215] Example 9: This example is used to illustrate the gradient test of the post-emergence and pre-emergence herbicidal activities of the compound of structural formula (I) provided by the present invention.

[0216] Test agent: the compound of structural formula (I) provided by the present invention (see Table 5).

[0217] Test targets: barnyard grass, crabgrass.

[0218] Control drug: pretilachlor; AHAS inhibitor P: 2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzoic acid.

[0219] Planting method: post-emergence test is the same as in Example 8; pre-emergence test is the same as in Example 9.

[0220] Application method: post-emergence test is the same as in Example 8; pre-emergence test is the same as in Example 9.

[0221] Investigation method: Regularly observe the growth and reaction symptoms of the treated weeds, and evaluate the herbicidal activity of the compound by visual inspection 21 days after the application. The specific test results are shown in Table 5.

[0222] Table 5

[0223]

[0224]

[0225] As can be seen from Table 5, most of the compounds contained in the structural formula (I) still exhibited good post-emergence herbicidal activity at a dosage of 375 g ai / ha; when the dosage was reduced to 187.5 g ai / ha, the post-emergence herbicidal activity of compounds I-2 and I-5 was comparable to that of the control AHAS inhibitor P, and was superior to the commercial herbicide pretilachlor. The pre-emergence herbicidal activity of I-5 was tested, and I-5 still exhibited good pre-emergence herbicidal activity, which was comparable to that of the control AHAS inhibitor P, and the herbicidal activity against barnyardgrass was comparable to that of pretilachlor, reaching an inhibition rate of 100%; I-5 exhibited good post-emergence and pre-emergence herbicidal activity, and could be used as a post-emergence and pre-emergence herbicide, and had a wider window of application than pretilachlor in the control of the malignant weed barnyardgrass.

[0226] The pyrimidine-biaryl compound of the present invention can be used as an active ingredient of a herbicide, and various adjuvants such as organic solvents, surfactants, carriers, etc. are added by a pesticide preparation processing method to prepare various emulsions, granules, etc. for weed control of crops.

[0227] Example 10: Emulsion

[0228] Heat and stir 5% of pyrimidine-biaryl compound, 5% of Nongru No. 500 (calcium salt), 5% of Nongru No. 602, 5% of N-methyl-2-pyrrolidone and 80% of solvent oil No. 330 to obtain an emulsion.

[0229] When applied in the field, spraying is performed with reference to the amount of the pyrimidine-biaryl compound used in each example.

[0230] Example 11: Wettable powder

[0231] 10% of pyrimidine-biaryl compound, 5% of lignin sulfonate (Mg), 1% of lauryl alcohol polyoxyethylene ether (JFC), 40% of diatomaceous earth and 44% of light calcium carbonate are uniformly mixed and crushed to obtain a wettable powder.

[0232] When applied in the field, spraying is performed with reference to the amount of the pyrimidine-biaryl compound used in each example.

Claims

1. A pyrimidine-biaryl compound, characterized in that The structural formula of the compound is shown in general formula (I): In formula (I), Ar is selected from any one of Ar1 to Ar30 shown below: in, R1 is hydrogen, halogen, amino, hydroxy, cyano, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl or C1-C2 alkyl; R2 is hydrogen, halogen, amino, methoxy or C1-C2 alkyl; R3 is hydrogen, halogen, C1-C2 alkyl, C1-C2 alkoxy, acetyl, benzoyl, carboxyl or carbomethoxy; R4 is hydrogen, halogen, methoxy or C1-C2 alkyl; R5 is hydrogen or fluorine.

2. The pyrimidine-biaryl compound according to claim 1, characterized in that The halogen is fluorine, chlorine or bromine; the C1-C2 alkyl is methyl (Me, CH3) or ethyl (Et, C2H5); the C1-C2 alkoxy is methoxy (MeO, CH3O) or ethoxy (EtO, C2H5O).

3. The method for preparing the pyrimidine-biaryl compound according to claim 1, characterized in that: The preparation of the compound is achieved by the following synthetic route 1 or synthetic route 2: Synthesis route 1: In formula (B), LG 1 represents a boron-containing substituent; Synthesis route 2: In formula (C), LG 2 represents a boron-containing substituent; in formula (D), X 2 represents a leaving group.

4. The method according to claim 3, characterized in that The preparation method based on synthetic route 1 specifically includes: According to the molar ratio of 1:1.3:6:0.05, the intermediate represented by formula (A), the compound represented by formula (B), potassium carbonate and palladium catalyst are added to an appropriate amount of solvent and reacted at 100°C for 1 hour; the reaction product is separated and purified by silica gel column chromatography to finally obtain a pyrimidine-biaryl compound represented by formula (I).

5. The method according to claim 3, characterized in that: The preparation method based on synthetic route 2 specifically includes: (1) adding the compound represented by formula (C), the compound represented by formula (D), sodium carbonate and palladium catalyst to an appropriate amount of solvent at a molar ratio of 1:1.3:5:0.05, and reacting at 100° C. for 1 hour to obtain a compound represented by formula (E); (2) taking a compound represented by formula (E), salicylaldehyde and sodium borohydride at a molar ratio of 1:1.5:1.5; firstly adding the compound represented by formula (E) and salicylaldehyde into methanol, and reacting them at room temperature for 0.5 hour; then adding sodium borohydride, and continuing to react at room temperature for 0.5 hour, to obtain a compound represented by formula (F); (3) The compound represented by formula (F), an equivalent amount of 2-methylsulfonyl-4,6-dimethoxypyrimidine and cesium carbonate are added to an appropriate amount of 1,4-dioxane in a molar ratio of 1:1.2:1.5, and the mixture is reacted at 110° C. for 4 hours; the reaction product is separated and purified by silica gel column chromatography to finally obtain a pyrimidine-biaryl compound represented by formula (I).

6. A herbicidal composition, characterized in that: The method comprises a herbicidally active amount of the pyrimidine-biaryl compound according to claim 1 and at least one formulation adjuvant.

7. A method for preparing a herbicidally active composition, characterized in that: The method comprises mixing a herbicidally active amount of the pyrimidine-biaryl compound as claimed in claim 1 and at least one formulation auxiliary.

8. Use of the pyrimidine-biaryl compound of claim 1 as an agricultural chemical herbicide.

9. The method for using the pyrimidine-biaryl compound as an agricultural chemical herbicide according to claim 1, characterized in that: The method comprises the following steps: applying a herbicidal amount of a pyrimidine-biaryl compound to the leaves of weeds in the pre-germination stage or the post-germination stage; the weeds are any one of the following: barnyard grass, crabgrass, Amaranthus retroflexus, Abutilon venetum or Cassia seed.

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