A pyrimidine-biaryl compound, methods of making and use as herbicides

Abstract

The present application relates to herbicide technology, and aims to provide a pyrimidine-biaryl compound, a preparation method and application as a herbicide. The structural formula of the pyrimidine-biaryl compound of the present application is shown in general formula (I); the application method of the compound is to act on the leaves of weeds in the pre-emergence or post-emergence stage with a herbicidal active amount of the compound. Compared with the prior art, the compound of the present application can be used as a post-emergence and pre-emergence herbicide, has a wide weed spectrum and has a wider therapeutic window.

Description

Technical Field

[0001] This invention relates to a novel pyrimidine-biaryl compound, and more particularly to a pyrimidine-biaryl compound, its preparation method, and its application as a herbicide. Background Technology

[0002] In grain cultivation, the use of herbicides increases yield per unit area and crop quality. However, herbicide use also has negative environmental impacts, such as increased weed resistance leading to higher herbicide usage, which poses significant risks to the ecosystem. Therefore, developing efficient, low-toxicity, easily degradable, and environmentally friendly herbicides has become an important direction for innovative research.

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

[0004]

[0005] The widespread use of these herbicides has led to increased weed resistance, threatening their continued application. Existing research indicates that pyrimidine salicylates target acetoacetic acid synthase (AHAS), and the mechanisms of weed resistance to these herbicides mainly manifest in two aspects: target site mutations and metabolic resistance (increased metabolic capacity for herbicides) in non-target resistance. Therefore, designing resistance inhibitors will be a significant challenge.

[0006] To overcome this challenge, researchers discovered a class of pyrimidine-biphenyl compounds that are effective against AHAS inhibitor-resistant Descurania sophia and Ammannia arenaria. These compounds were developed based on the structural optimization of pyrimidine salicylic acid herbicides, retaining the pyrimidine skeleton and carboxylic acid group, and introducing a phenyl or heteroaryl group at the 6-position of the benzene ring. Among them, the 6-phenyl compound is effective against AHAS-resistant weeds.

[0007] Biaryl compounds are the basic skeletons of natural products; they are also common molecular substructures in medicinal chemistry, and due to their internal rotational flexibility, they can adapt to various drug targets. Furthermore, this skeleton is also an important component of pesticide molecules; similarly, it is an important type of skeleton in materials science. Therefore, molecules containing this type of skeleton have broad application prospects. Secondly, these compounds can be rapidly constructed using the Suzuki-Miyaura cross-coupling reaction, effectively expanding new chemical spaces.

[0008] Pyrimidine salicylic acid herbicides all contain a pyrimidine skeleton and a carboxyl group or its ester. Previous studies have consistently suggested that both substructures must be preserved in the design of inhibitors to maintain the herbicidal activity of the compound. Therefore, the research direction of technical personnel in the industry has always revolved around this idea in the development of new herbicides, resulting in the inability to continuously launch products with newer chemical structures and better resistance properties.

[0009] Therefore, the development of this novel pyrimidine-biaryl compound for weed control is urgent and of great significance. Summary of the Invention

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

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

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

[0013]

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

[0015]

[0016]

[0017] in,

[0018] R1 is hydrogen, halogen, amino, hydroxyl, 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 group;

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

[0022] R5 is either hydrogen or fluorine.

[0023] As a preferred embodiment of the present invention, the halogen is fluorine, chlorine, or bromine; the C1-C2 alkyl group is methyl (Me, CH3) or ethyl (Et, C2H5); and the C1-C2 alkoxy group is methoxy (MeO, CH3O) or ethoxy (EtO, C2H5O). The pyrimidine-biaryl compounds of the present invention can be illustrated as specific compounds I-1 to I-78 by combining formula (I) and the specific structures of the 78 Ar compounds listed in Table 1, 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 achieved through either synthetic route one or synthetic route two as follows:

[0029] Synthesis Route 1:

[0030]

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

[0032] Synthesis Route 2:

[0033]

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

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

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

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

[0038] (1) The compound shown in formula (C), the compound shown in formula (D), sodium carbonate and palladium catalyst were added to an appropriate amount of solvent in a molar ratio of 1:1.3:5:0.05 and reacted at 100°C for 1 hour to obtain the compound shown in formula (E).

[0039] (2) Take the compound shown in formula (E), salicylaldehyde and sodium borohydride in a molar ratio of 1:1.5:1.5; first add the compound shown in formula (E) and salicylaldehyde to methanol and react at room temperature for 0.5 hours; then add sodium borohydride and continue to react at room temperature for 0.5 hours to obtain the compound shown in formula (F).

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

[0041] The present invention further provides a herbicidal composition comprising a herbicidal 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 herbicidal active composition, which involves mixing the aforementioned pyrimidine-biaryl compound and at least one formulation adjuvant in an amount that has herbicidal activity.

[0043] The present invention further provides the use of the aforementioned pyrimidine-biaryl compounds as agricultural chemical herbicides.

[0044] The present invention further provides a method for applying the aforementioned pyrimidine-biaryl compound as an agricultural chemical herbicide, which involves applying a herbicidal active amount of the pyrimidine-biaryl compound to the leaves of weeds in the pre-budding or post-budding stage; wherein the weeds are any of the following: barnyard grass, crabgrass, amaranth, velvetleaf, or cassia seed.

[0045] Compared with the prior art, the beneficial effects of the present invention are:

[0046] 1. This invention breaks through the previously commonly used design ideas and adopts a completely new design concept: that is, while retaining the pyrimidine skeleton, the carboxyl group is removed, and a new type of pyrimidine-biaryl compound with a biaryl skeleton is designed. This compound has the following characteristics: (1) In this structure, the aryl group is located in the ortho position of benzylamine. Due to its internal rotational flexibility, it can effectively adapt to the relevant target site. (2) This structure does not contain a carboxyl group and has strong lipophilicity, which is conducive to absorption by plants. (3) The lipophilicity of the compound may enable it to interact with the target enzyme in a hydrophobic-driven manner, which is different from the existing pyrimidine salicylic acid herbicides.

[0047] 2. The pyrimidine-biaryl compound provided by this invention can be used as an agricultural chemical herbicide for the control of various weeds in the agricultural field.

[0048] 3. The pyrimidine-biaryl compounds provided by this invention can be used as post-emergence herbicides, especially effective against barnyard grass, crabgrass, and amaranth; some compounds can effectively control barnyard grass, crabgrass, amaranth, cassia seed, and velvetleaf, with a broad spectrum of herbicidal activity.

[0049] 4. The pyrimidine-biaryl compounds provided by this invention can be used as pre-emergence herbicides, especially effective against barnyard grass, crabgrass, and amaranth; some compounds can effectively control barnyard grass, crabgrass, amaranth, and velvetleaf, with a broad spectrum of herbicidal activity.

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

[0051] 6. The pyrimidine-biaryl compound I-5 provided by this invention can be used as a post-emergence and pre-emergence herbicide; its post-emergence and pre-emergence herbicidal activity is comparable to that of the AHAS inhibitor P, but its post-emergence herbicidal activity is superior to that of the commercial herbicide pretilachlor; in the control of barnyardgrass, a noxious weed, it has a wider application window than pretilachlor. Detailed Implementation

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

[0053] Part 1: Overview of Preparation Methods

[0054] The compounds with the structure shown in general formula (I) of this invention can be prepared via 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 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 synthesized by reacting it with 1.3 moles of the compound having formula (B) (where LG... 1Compounds containing suitable boron substituents, such as borate or 4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl (preferably borate), are optionally converted to compounds of formula (I) by reaction at 100°C for 1 hour in the presence of 6 mol potassium carbonate and 0.05 mol tetra(triphenylphosphine)palladium (0) in a suitable solvent (which may include N,N-dimethylformamide or 1,4-dioxane, preferably N,N-dimethylformamide). The product is purified by silica gel column chromatography.

[0058] Synthesis Route 2:

[0059] Compounds I-23, I-40~I-42, I-46, I-51~I-54, and I-65~I-73 in Table 1 were prepared using synthetic route two.

[0060] In this synthetic route, 1 mole has the formula (C) (where LG 2 A compound having a suitable boron-containing substituent, such as borate or 4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl, preferably 4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl, can be reacted with 1.3 moles of a compound having formula (D) (where X...). 2 The compound having formula (E) is optionally converted in the presence of 5 moles of sodium carbonate and 0.05 moles of a suitable palladium catalyst (which may include tetrakis(triphenylphosphine)palladium(0) or [1,1'-bis(diphenylphosphine)ferrocene]palladium(II), preferably tetrakis(triphenylphosphine)palladium(0)) and in N,N-dimethylformamide, and reacted at 100°C for 1 hour.

[0061] One mole of a compound having formula (E) can be converted into a compound having formula (F) by reacting it with 1.5 moles of salicylaldehyde in methanol at room temperature for 0.5 hours, and further reacting it with 1.5 moles of sodium borohydride at room temperature for 0.5 hours.

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

[0063] In addition, compound I-27 in Table 1 is derived from further modification of compound I-26 and is not classified into the two synthetic routes mentioned above.

[0064]

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

[0066] Part Two: Examples of Compound Preparation

[0067] Example 1: This example illustrates the synthesis of target compound I-1 based on synthetic route one in this 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] Phenylacetic 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). Tetra(triphenylphosphine)palladium (0) (28.9 mg, 0.025 mmol) was added under argon protection, followed by the addition of 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 extraction was performed with ethyl acetate (3 × 10 mL). The combined organic phases were washed with brine, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain crude product I-1. The crude product was separated by silica gel column chromatography [V(petroleum ether) / V(ethyl acetate) = 10 / 1] to give waxy product I-1.

[0074] Example 2: This example illustrates the synthesis of target product I-8 based on synthetic route one in this 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 potassium carbonate aqueous 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 extraction was performed with ethyl acetate (3 × 10 mL). The combined organic phases were washed with brine, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain crude product I-8. The crude product was separated by silica gel column chromatography [V(petroleum ether) / V(ethyl acetate) = 10 / 1] to give waxy product I-8.]

[0077] Example 3: This example illustrates the synthesis of target product I-63 based on synthetic route one in this invention.

[0078]

[0079] 1-H-indazole-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). Tetra(triphenylphosphine)palladium (0) (28.9 mg, 0.025 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. After cooling to room temperature, saturated brine was added to the mixture, and extraction was performed with ethyl acetate (3 × 10 mL). The combined organic phases were washed with brine, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain crude product I-63. The crude product was separated by silica gel column chromatography [V(petroleum ether) / V(ethyl acetate) = 10 / 1] to give waxy product I-63.

[0080] The synthesis of the following compounds can be referred to Examples 1-3, 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; 1¹H NMR (400MHz, CDCl₃) δ 7.45–7.38 (m, 5H), 7.37–7.24 (m, 2H), 7.21–7.06 (m, 4H), 6.78 (t, J = 7.1Hz, 1H), 6.66 (d, J = 8.1Hz, 1H), 5.76 (s, 1H), 4.33 (s, 2H), 3.77 (s, 6H). (No NH₃)

[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℃; 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℃; 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℃; 1¹H NMR (400MHz, CDCl₃) δ 7.39 (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, mp51.7-53.8℃; 1 ¹H NMR (400MHz, CDCl₃) δ 7.43–7.38 (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℃; 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, mp 39.5-42.1℃; 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℃; 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℃; 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℃; 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℃; 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℃; 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: Waxy substance; 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 substance; 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 substance; 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 substance; 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 substance; 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 illustrates the synthesis of target compound I-41 based on synthetic route two in this invention.

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

[0145]

[0146] Pinaryl 2-aminophenylboronic acid (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). Tetra(triphenylphosphine)palladium (0) (34.7 mg, 0.03 mmol) was added under argon protection, followed by 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 the mixture was extracted with ethyl acetate (3 × 10 mL). The combined organic phases were 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 mixture was stirred at room temperature for 0.5 h until the 2'-bromo-5'-methyl-[1,1'-biphenyl]-2-amine was completely eliminated. Subsequently, sodium borohydride (28.4 mg, 0.75 mmol) was slowly added to the reaction mixture, and the mixture was stirred at room temperature for 0.5 h. After the reaction was complete, the solvent was removed under reduced pressure to give 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), followed by the addition of cesium carbonate (244.3 mg, 0.75 mmol) and 2-methylsulfonyl-4,6-dimethoxypyrimidine (131.0 mg, 0.6 mmol). The solution was heated to 110 °C and reacted for 4 hours. After cooling to room temperature, saturated brine was added to the mixture, and the mixture 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 the crude product. The crude product was separated by silica gel column chromatography [V(petroleum ether) / V(ethyl acetate) = 10 / 1] to give a pale yellow waxy product I-41.

[0153] Example 5: This example illustrates the synthesis of target compound I-70 based on synthetic route two in this 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). Under argon protection, [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (22.0 mg, 0.03 mmol) was added, followed by 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. The aqueous layer was extracted with ethyl acetate (3 × 10 mL). The combined organic layers were dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain 2-(benzo[d]thiazole-7-yl)aniline (E-2).

[0157] Step 2: Synthesis of intermediate 2-(((2-(benzo[d]thiazo-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 h until 2-(benzo[d]thiazol-7-yl)aniline was completely eliminated. Subsequently, sodium borohydride (28.4 mg, 0.75 mmol) was slowly added to the reaction mixture, and the mixture was stirred at room temperature for 0.5 h. After the reaction was complete, 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), followed by the addition of cesium carbonate (244.3 mg, 0.75 mmol) and 2-methylsulfonyl-4,6-dimethoxypyrimidine (131.0 mg, 0.6 mmol). The solution was heated to 110 °C and reacted for 4 hours. 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 crude product I-70. The crude product was separated by silica gel column chromatography [V(petroleum ether) / V(ethyl acetate) = 10 / 1] to obtain a pale yellow waxy product I-70.

[0163] The synthesis of the following compounds can be referred to Examples 4 and 5, and 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 [[ID=X]]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 substance; 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 substance; 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 substance; 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 illustrates the preparation method of the target compound I-27.

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

[0185] Synthesis of target compound I-27

[0186]

[0187] Methyl 2'-((2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzyl)amino)-[1,1'-biphenyl]-4-carboxylic acid (I-26) (287.1 mg, 0.6 mmol) was dissolved in a 1:1 methanol-water solution (6 mL), followed by the addition of sodium hydroxide (120.0 mg, 3 mmol). The solution was heated to 80 °C and reacted 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 aqueous phases were combined. After concentration under reduced pressure, 0.5 mol / L dilute hydrochloric acid was slowly added dropwise, precipitating a solid. The solid was filtered and washed with distilled water to obtain the target compound I-27, a pale yellow waxy substance.

[0188] I-27: Waxy substance. 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 Three: Performance Testing and Conclusions of the Compounds

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

[0192] Test reagents: Compounds with structural formula (I) provided by this invention (see Table 3).

[0193] Test targets: barnyard grass, crabgrass, velvetleaf, amaranth, and cassia seed.

[0194] Planting Method: The experimental soil consisted of sandy soil, silty sand, and clay, mixed in a 1:1:1 mass ratio. The mixture was thoroughly stirred and used as the experimental soil. An 8cm diameter flowerpot was filled to 3 / 4 full with the soil, and placed in a large stainless steel basin containing 5cm of water. After the soil was completely moistened, 10-15 of the target weed seeds were sown in the flowerpot. After sowing, the seeds were covered with 0.2-0.5cm of soil and then placed in a greenhouse for cultivation. Watering was provided daily to maintain soil moisture at approximately 80% (relative humidity). The growth temperature was 25±8℃, and the air humidity was above 60%.

[0195] Application method: Using the greenhouse pot method, after the weeds have grown to the 2-leaf stage, post-bud spraying is carried out, with each treatment repeated twice, and a blank control (distilled water as the blank control) is set up. After spraying, the plants are placed indoors to allow the pesticide to be absorbed by the leaves, and then transferred to the greenhouse for cultivation at a growth temperature of 25±8℃.

[0196] Evaluation criteria for herbicidal activity by visual inspection (Table 2).

[0197] Table 2

[0198]

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

[0200] Table 3

[0201]

[0202]

[0203] Table 3 shows that the compounds contained in structural formula (I) generally have strong post-emergence herbicidal activity, especially against barnyard grass, crabgrass, and amaranth, indicating that they can effectively control grass and amaranth weeds after budding. Among them, I-22 has an inhibition rate of ≥95% against the four weed targets tested, and can effectively control not only grass and amaranth weeds, but also 100% against velvetleaf. I-52 is effective against five weed targets, and can control grass and amaranth weeds. At the same time, it has control efficacy of 95% and 85% against cassia seed and velvetleaf, respectively, showing a broad spectrum of herbicides.

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

[0205] Test reagents: Compounds with structural formula (I) provided by this invention (see Table 4).

[0206] Experimental targets: barnyard grass, crabgrass, velvetleaf, amaranth, and cassia seed.

[0207] Planting method: The experimental soil consisted of sandy soil, silty sand, and clay, mixed in a 1:1:1 mass ratio. The mixture was thoroughly stirred and used as the experimental soil. An 8cm diameter flowerpot was filled to 3 / 4 full with the soil, and placed in a large stainless steel basin containing 5cm of water. After the soil was completely moistened, 10-15 seeds of each target weed were sown in the flowerpot, covering them with 0.2-0.5cm of soil. The pots were then placed in a greenhouse for cultivation. The growth temperature was 25±8℃, and the air humidity was above 60%.

[0208] Application method: The greenhouse pot method was adopted. The soil surface was treated with the test agent 24 hours after sowing. Each treatment was repeated twice, and a blank control (distilled water was used as the blank control) was set up. After soil treatment, the plants were moved into the greenhouse for cultivation at a growth temperature of 25±8℃.

[0209] Methods of investigation: The growth and reaction symptoms of weeds were observed regularly after treatment. The herbicidal activity of the compound was evaluated visually 21 days after application. Specific test results are shown in Table 4.

[0210] Table 4

[0211]

[0212]

[0213] As shown in Table 4, the compounds contained in structural formula (I) generally have strong pre-emergence herbicidal activity, especially against barnyard grass, crabgrass, and amaranth, indicating that they can effectively control grass and amaranth weeds before budding. Among them, I-35 has an inhibition rate of ≥90% against the three tested weed targets and can effectively control grass and amaranth weeds. I-52 and I-68 can not only effectively control grass and amaranth weeds with an efficacy of ≥90%, but also have efficacy of 80% and 85% against velvetleaf, respectively, showing a broad spectrum of herbicidal activity.

[0214] As shown in Tables 3 and 4, some of the pyrimidine-biaryl compounds provided by this invention exhibit excellent post-emergence herbicidal activity and can be used as post-emergence herbicides. Some compounds also exhibit excellent pre-emergence herbicidal activity and can be used as pre-emergence herbicides; some compounds exhibit both excellent post-emergence and pre-emergence herbicidal activity and can be used as both pre-emergence and post-emergence herbicides, thus having a wider application window.

[0215] Example 9: This example illustrates the gradient test of the post-emergence and pre-emergence herbicidal activity of the compound with structural formula (I) provided by the present invention.

[0216] Test reagents: Compounds with structural formula (I) provided by this invention (see Table 5).

[0217] Experimental targets: barnyard grass and crabgrass.

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

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

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

[0221] Methods of investigation: The growth and reaction symptoms of weeds were observed regularly after treatment. The herbicidal activity of the compound was evaluated visually 21 days after application. Specific test results are shown in Table 5.

[0222] Table 5

[0223]

[0224]

[0225] Table 5 shows that most of the compounds contained in structural formula (I) still exhibited good post-emergence herbicidal activity at a dose of 375 g ai / ha. When the dose 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 superior to the commercial herbicide pretilachlor. The pre-emergence herbicidal activity of I-5 was tested; I-5 still showed good pre-emergence herbicidal activity, comparable to that of the control AHAS inhibitor P, while its herbicidal activity against barnyard grass was comparable to that of pretilachlor, achieving a 100% inhibition rate. I-5 exhibited good post-emergence and pre-emergence herbicidal activity and can be used as a post-emergence and pre-emergence herbicide. In the control of the noxious weed barnyard grass, it has a wider application window than pretilachlor.

[0226] The pyrimidine-biaryl compounds of the present invention can be used as active components of herbicides. They can be formulated into various emulsions, granules, etc., by adding organic solvents, surfactants, carriers and other adjuvants using pesticide formulation processing methods, and used for weed control of crops.

[0227] Example 10: Emulsion

[0228] The emulsion is obtained by heating and stirring 5% pyrimidine-biaryl compound, 5% agricultural emulsion No. 500 (calcium salt), 5% agricultural emulsion No. 602, 5% N-methyl-2-pyrrolidone and 80% solvent oil No. 330 until homogeneous.

[0229] When applying in the field, spray according to the dosage of pyrimidine-biaryl compound in each example.

[0230] Example 11: Wettable Powder

[0231] A wettable powder is obtained by uniformly mixing 10% pyrimidine-biaryl compound, 5% lignin sulfonate (Mg), 1% lauryl alcohol polyoxyethylene ether (JFC), 40% diatomaceous earth and 44% light calcium carbonate and then pulverizing it.

[0232] When applying in the field, spray according to the dosage of pyrimidine-biaryl compound in each example.

Claims

1. A pyrimidine-biaryl compound, characterized in that, The structural formula of this compound is shown in general formula (I): ； In formula (I), Ar is selected from any one of Ar1 to Ar30 as shown below: ； ； ； ； ； ； ； ； in, R1 is hydrogen, halogen, amino, hydroxyl, 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 methyl ester group; R4 is hydrogen, halogen, methoxy, or C1-C2 alkyl; R5 is either hydrogen or fluorine.

2. The pyrimidine-biaryl compound according to claim 1, characterized in that, The halogen mentioned is fluorine, chlorine, or bromine.

3. The method for preparing the pyrimidine-biaryl compound according to claim 1, characterized in that, The compound was prepared via either synthetic route one or synthetic route two as described below: Synthesis Route 1: ； In formula (B), LG 1 Indicates a boron-containing substituent; Synthesis Route 2: ； In formula (C), LG 2 Indicates a boron-containing substituent; in formula (D), X 2 Indicates a leaving group.

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

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

6. A herbicidal composition, characterized in that, The herbicide contains an amount of the pyrimidine-biaryl compound as described in claim 1 and at least one formulation adjuvant.

7. A method for preparing a herbicidal active composition, characterized in that, It involves mixing a herbicidal active amount of the pyrimidine-biaryl compound as described in claim 1 with at least one formulation adjuvant.

8. The method of applying the pyrimidine-biaryl compound of claim 1 as an agricultural chemical herbicide, characterized in that, It involves applying a herbicidal amount of a pyrimidine-biaryl compound to the leaves of weeds in the pre-bud or post-bud stage; the weeds being any of the following: barnyard grass, crabgrass.

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