Pyrimidine-biaryl compounds, preparation method therefor and use thereof as herbicides

Abstract

The present invention relates to herbicide technology, and aims to provide pyrimidine-biaryl compounds, a preparation method therefor and the use thereof as herbicides. The structural formula of the pyrimidine-biaryl compounds is shown as general formula (I). An application method of the compounds comprises applying a herbicidally active amount the compounds to leaves of pre-emergence or post-emergence weeds. Compared with the prior art, the compounds provided by the present invention can be used as pre-emergence and post-emergence herbicides, have wide weed control spectrums, and have wider herbicide application windows.

Description

A pyrimidine-biaryl compound, preparation method and use as a herbicide Technical Field

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

[0002] In grain cultivation, the use of herbicides is essential for increasing yields per unit area and crop quality, ensuring food production meets the needs of a growing population. However, this use also has certain negative impacts on the environment. For example, increased weed resistance leads to increased herbicide usage, posing significant risks to ecosystems. Therefore, the development of highly effective, low-toxic, biodegradable, and environmentally friendly herbicides has become a key area of ​​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:

[0004] The widespread use of these herbicides has led to an increase in weed resistance, threatening their continued use. Previous studies have shown that pyrimidine salicylate herbicides target acetoacetate synthase (AHAS), and that weed resistance to these herbicides manifests primarily through two mechanisms: target site mutations and non-target metabolic resistance (increased herbicide metabolism). Therefore, designing resistance inhibitors will be a major challenge.

[0005] To overcome this problem, people have discovered that a class of pyrimidine-biphenyl compounds is effective against Descurania Sophia and Ammannia arenaria, which 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 resistant to AHAS.

[0006] Biaryl compounds are the basic skeletons of natural products and 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 an important component of pesticide molecular structures and is also an important skeleton in materials science. Therefore, molecules containing this skeleton have broad application prospects. Secondly, the Suzuki-Miyaura Cross-Coupling reaction can be used to rapidly construct this type of compound, effectively expanding new chemical space.

[0007] Pyrimidine salicylate herbicides all contain a pyrimidine backbone and a carboxyl group or its ester. Previous research has consistently assumed that inhibitor design requires the retention of both substructures in order for the compound to maintain herbicidal activity. Consequently, industry researchers have consistently focused on developing new herbicides based on this approach, resulting in the inability to continuously release products with novel chemical structures and improved resistance properties.

[0008] 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

[0009] The present invention aims to overcome the deficiencies of the prior art by providing a pyrimidine-biaryl compound, a preparation method, and its use as a herbicide. The compound can be used as an agrochemical herbicide for weed control in agricultural fields, exhibiting excellent post-emergence and pre-emergence herbicidal activity.

[0010] To solve the technical problem, the solution of the present invention is:

[0011] Provided is a pyrimidine-biaryl compound, the structural formula of which is shown in general formula (I):

[0012] In formula (I), Ar is selected from any one of Ar1 to Ar30 shown below:

[0013] in,

[0014] R1 is hydrogen, halogen, amino, hydroxy, cyano, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl or C1-C2 alkyl;

[0015] R2 is hydrogen, halogen, amino, methoxy or C1-C2 alkyl;

[0016] R3 is hydrogen, halogen, C1-C2 alkyl, C1-C2 alkoxy, acetyl, benzoyl, carboxyl or carbomethoxy;

[0017] R4 is hydrogen, halogen, methoxy or C1-C2 alkyl;

[0018] R5 is hydrogen or fluorine.

[0019] 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); and the C1-C2 alkoxy is methoxy (MeO, CH3O) or ethoxy (EtO, C2H5O). The pyrimidine-biaryl compounds of the present invention can be combined with formula (I) and the 78 specific structures of Ar listed in Table 1 to present specific compounds I-1 to I-78, but the present invention is not limited to these compounds.

[0020] Table 1

[0021] 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:

[0022] Synthesis route 1:

[0023] In formula (B), LG 1 represents a boron-containing substituent;

[0024] Synthesis route 2:

[0025] In formula (C), LG 2 represents a boron-containing substituent; in formula (D), X 2 represents a leaving group.

[0026] As a preferred embodiment of the present invention, the preparation method based on synthetic route 1 specifically includes:

[0027] The intermediate represented by formula (A), the compound represented by formula (B), potassium carbonate and a palladium catalyst are added to an appropriate amount of solvent in a molar ratio of 1:1.3:6:0.05, and the reaction is carried out 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).

[0028] As a preferred embodiment of the present invention, the preparation method based on the second synthetic route specifically includes:

[0029] (1) Adding the compound represented by formula (C), the compound represented by formula (D), sodium carbonate, and a 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 the compound represented by formula (E);

[0030] (2) The compound represented by formula (E), salicylaldehyde, and sodium borohydride are prepared in a molar ratio of 1:1.5:1.5; the compound represented by formula (E) and salicylaldehyde are first added to methanol and reacted at room temperature for 0.5 hours; then sodium borohydride is added and the reaction is continued at room temperature for 0.5 hours to obtain the compound represented by formula (F);

[0031] (3) The compound represented by formula (F), an equivalent amount of 2-methylsulfonyl-4,6-dimethoxypyrimidine and cesium carbonate were added to an appropriate amount of 1,4-dioxane in a molar ratio of 1:1.2:1.5, and the mixture was reacted at 110°C for 4 hours; the reaction product was separated and purified by silica gel column chromatography to finally obtain a pyrimidine-biaryl compound represented by formula (I).

[0032] 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.

[0033] 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.

[0034] The present invention further provides use of the aforementioned pyrimidine-biaryl compound as an agricultural chemical herbicide.

[0035] The present invention further provides a method for using the aforementioned pyrimidine-biaryl compound as an agricultural chemical herbicide, comprising applying a herbicidally active amount of the pyrimidine-biaryl compound to the leaves of weeds in the early or late sprout stages; the weeds are any one of the following: barnyard grass, crabgrass, Amaranthus retroflexus, velvetleaf, or Cassia seed.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] 1. This invention breaks through the previously commonly used design ideas and adopts a new design concept: that is, retaining the pyrimidine skeleton while 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) The aromatic group in this structure is located in the ortho position of the benzylamine. Due to its internal rotation flexibility, it can effectively adapt to the relevant target. (2) This structure does not contain a carboxyl group and has a strong lipophilicity, which is conducive to plant absorption; (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.

[0038] 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.

[0039] 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 spectrum of weed control.

[0040] 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 spectrum of weed control.

[0041] 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 efficacy.

[0042] 6. The pyrimidine-biaryl compound I-5 provided by the present invention can be used as a post-emergence and pre-emergence herbicide; its post-emergence and pre-emergence herbicidal activities are comparable to those of the AHAS inhibitor P, but its post-emergence herbicidal activity is superior to that of the commercial herbicide pretilachlor; and it has a wider window of efficacy than pretilachlor for the prevention and control of the malignant weed barnyardgrass. DETAILED DESCRIPTION

[0043] The following provides specific implementation schemes and examples to illustrate the implementation process of the present invention.

[0044] Part I Overview of Preparation Methods

[0045] The compound of the structure represented by general formula (I) of the present invention can be prepared through two main synthetic routes.

[0046] Synthesis route 1:

[0047] 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 1.

[0048] In this synthetic route, the compound of 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 of formula (A) can be synthesized by reacting with 1.3 moles of the compound of 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 in the presence of 6 moles of potassium carbonate and 0.05 moles of tetrakis(triphenylphosphine)palladium(0) at 100° C. for 1 hour 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.

[0049] Synthesis route 2:

[0050] Compounds I-23, I-40 to I-42, I-46, I-51 to I-54, and I-65 to I-73 in Table 1 were prepared using the method of synthetic route 2.

[0051] In this synthetic route, 1 mol of the compound having the 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)) in N,N-dimethylformamide and reacted at 100°C for 1 hour.

[0052] One mole of the compound of formula (E) can be converted into the compound of formula (F) by reacting with 1.5 moles of salicylaldehyde in methanol at room temperature for 0.5 hours, and further reacting with 1.5 moles of sodium borohydride at room temperature for 0.5 hours.

[0053] 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 in 1,4-dioxane at 110° C. for 4 hours. The product is separated and purified using silica gel column chromatography.

[0054] In addition, compound I-27 in Table 1 was further modified from compound I-26 and is not classified into the two aforementioned synthetic routes.

[0055] In this 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).

[0056] Part II Preparation Examples of Compounds

[0057] Example 1: This example is used to illustrate the synthesis of target compound I-1 based on synthesis route 1 in the present invention.

[0058] Synthesis of intermediate N-(2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzyl)-2-iodoaniline (A).

[0059] Intermediate (A) can be synthesized according to the method reported by Meng et al. in Org. Chem. Front. 2020, 7, 267-272.

[0060] Synthesis of target product I-1.

[0061] 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). Tetrakis(triphenylphosphine)palladium(0) (28.9 mg, 0.025 mmol) was added under argon protection, followed by a 1.5 mol / L aqueous potassium carbonate 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 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 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 of I-1.

[0062] Example 2: This example is used to illustrate the synthesis of the target product I-8 based on the first synthetic route in the present invention.

[0063] [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). 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 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 the crude product I-8. The crude product was separated by silica gel column chromatography [V (petroleum ether) / V (ethyl acetate) = 10 / 1] to obtain the waxy product I-8.

[0064] 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.

[0065] 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). Tetrakis(triphenylphosphine)palladium(0) (28.9 mg, 0.025 mmol) was added under argon protection, followed by a 1.5 mol / L aqueous potassium carbonate 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 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 crude I-63. The crude product was separated by silica gel column chromatography [V(petroleum ether) / V(ethyl acetate)=10 / 1] to obtain the waxy product I-63.

[0066] The synthesis of the following compounds can refer to Examples 1 to 3 and will not be described in detail here.

[0067] 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:

[0068] I-1: waxy substance; 1H NMR (400 MHz, CDCl3) δ 7.45–7.38 (m, 5H), 7.37–7.24 (m, 2H), 7.21–7.06 (m, 4H), 6.78 (t, J = 7.1 Hz, 1H), 6.66 (d, J = 8.1 Hz, 1H), 5.76 (s, 1H), 4.33 (s, 2H), 3.77 (s, 6H). (no NH)

[0069] I-2: waxy substance; 1 H NMR(400MHz, CDCl3) δ7.35(d,J=7.6Hz,1H),7.30–7.21(m,4H),7.20–7.08(m,4H),6.98(dd,J=7.4,1.5Hz,1 H),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)

[0070] I-3: waxy substance; 1 H NMR(400MHz, CDCl3) δ7.44(d,J=7.5Hz,1H),7.37–7.21(m,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)

[0071] 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)

[0072] 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)

[0073] 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)

[0074] 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)

[0075] I-8: solid, mp 84.8-87.0℃; 1H NMR (400 MHz, 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)

[0076] I-9: solid, mp 51.7-53.8 °C; 1 H NMR (400 MHz, 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))

[0077] 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).

[0078] 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).

[0079] 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).

[0080] 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).

[0081] 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).

[0082] 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).

[0083] 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).

[0084] 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).

[0085] 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).

[0086] 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).

[0087] 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).

[0088] 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).

[0089] 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).

[0090] 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).

[0091] 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).

[0092] 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).

[0093] 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).

[0094] 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).

[0095] 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).

[0096] 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).

[0097] 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).

[0098] 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).

[0099] 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).

[0100] 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).

[0101] 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).

[0102] 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).

[0103] 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).

[0104] 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).

[0105] 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).

[0106] 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).

[0107] I-45: waxy; 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).

[0108] 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).

[0109] 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).

[0110] 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).

[0111] 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).

[0112] 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).

[0113] 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).

[0114] 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, z1H), 5.76 (s, 1H), 4.35 (s, 2H), 3.78 (s, 6H).

[0115] 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).

[0116] 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).

[0117] 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).

[0118] 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).

[0119] 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).

[0120] 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).

[0121] 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).

[0122] 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).

[0123] 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).

[0124] 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).

[0125] 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).

[0126] 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).

[0127] Example 4: This example is used to illustrate the synthesis of target compound I-41 based on synthesis route 2 in the present invention.

[0128] Step 1: Synthesis of intermediate 2'-bromo-5'-methyl-[1,1'-biphenyl]-2-amine (E-1).

[0129] 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). Tetrakis(triphenylphosphine)palladium(0) (34.7 mg, 0.03 mmol) was added under argon protection, followed by a 1.5 mol / L aqueous potassium carbonate 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 removed under reduced pressure to provide 2'-bromo-5'-methyl-[1,1'-biphenyl]-2-amine (E-1).

[0130] Step 2: Synthesis of intermediate 2-(((2'-bromo-5'-methyl-[1,1'-biphenyl]-2-yl)amino)methyl)phenol (F-1).

[0131] 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 the complete disappearance of 2'-bromo-5'-methyl-[1,1'-biphenyl]-2-amine. 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 completion of the reaction, the solvent was removed under reduced pressure to yield 2-(((2'-bromo-5'-methyl-[1,1'-biphenyl]-2-yl)amino)methyl)phenol (F-1).

[0132] Step 3: Synthesis of target product I-41

[0133] 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 removed under reduced pressure to obtain a crude product. The crude product was separated by silica gel column chromatography [V (petroleum ether) / V (ethyl acetate) = 10 / 1] to afford the product I-41 as a light yellow wax.

[0134] Example 5: This example is used to illustrate the synthesis of target compound I-70 based on synthesis route 2 in the present invention.

[0135] Step 1: Synthesis of intermediate 2-(benzo[d]thiazol-7-yl)aniline (E-2).

[0136] 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, [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (22.0 mg, 0.03 mmol) was added, followed by a 1.5 mol / L aqueous potassium carbonate 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 the aqueous layer was extracted with ethyl acetate (3 × 10 mL). The organic layers were combined, dried over sodium sulfate, filtered, and the solvent removed under reduced pressure to provide 2-(benzo[d]thiazol-7-yl)aniline (E-2).

[0137] Step 2: Synthesis of intermediate 2-(((2-(benzo[d]thiazol-7-yl)phenyl)amino)methyl)phenol (F-2).

[0138] 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 the 2-(benzo[d]thiazol-7-yl)aniline disappeared. 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 completion of the reaction, the solvent was removed under reduced pressure to yield 2-(((2-(benzo[d]thiazol-7-yl)phenyl)amino)methyl)phenol (F-2).

[0139] Step 3: Synthesis of target compound I-70.

[0140] 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 the crude product I-70. The crude product was separated by silica gel column chromatography [V (petroleum ether) / V (ethyl acetate) = 10 / 1] to obtain the product I-70 as a light yellow wax.

[0141] The synthesis of the following compounds can refer to Examples 4 and 5 and will not be described in detail here.

[0142] The confirmation numbers of compounds I-23, I-40~I-42, I-46, I-51~I-54, I-65~I-73 are as follows:

[0143] 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).

[0144] 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).

[0145] I-41: waxy substance; 1 H NMR (400MHz, CDCl3) δ7.55(d,J=8.1Hz,1H),7.46(d,J=7.6Hz,1H),7.27(td,J=7.7,1.5Hz,1H),7.21–7.09(m,4H),7.04(dd,J=8.1,1.8Hz,1 H),6.98(dd,J=7.4,1.5Hz,1H),6.75(t,J=7.4Hz,1H),6.60(d,J=8.1Hz,1H),5.77(s,1H),4.35(d,J=1.9Hz,2H),3.79(s,6H),2.34(s,3H).

[0146] I-42: waxy substance; 1 H NMR(400MHz, CDCl3) δ7.38(dd,J=8.1,2.1Hz,1H),7.36–7.32(m,2H),7.27(td,J=7.7,1.5Hz,1H),7.21–7.08(m,4H),6.93 (dd,J=7.4,1.5Hz,1H),6.74(t,J=7.4Hz,1H),6.61(d,J=8.1Hz,1H),5.78(s,1H),4.32(s,2H),3.78(s,6H),2.08(s,3H).

[0147] I-46: solid, mp, 113.5-115.2°C; 1 H NMR (600MHz, CDCl3) δ7.43(t,J=7.7Hz,1H),7.39(d,J=7.5Hz,1H),7.31(d,J =7.6Hz,1H),7.27(td,J=7.7,1.7Hz,1H),7.18(td,J=7.6,1.3Hz,1H),7.15–7 .11(m,3H),6.94(dd,J=7.4,1.6Hz,1H),6.72(td,J=7.4,1.1Hz,1H),6.58(d ,J=8.1Hz,1H),5.79(s,1H),4.34(s,2H),3.79(s,6H),2.59(d,J=2.5Hz,3H).

[0148] I-51: waxy substance; 1 H NMR (400MHz, CDCl3) δ8.55(d,J=4.8Hz,1H),7.75(td,J=7.9,1.8Hz,1H),7.67(d,J=8.2Hz,1H),7.54(d,J=7.8Hz,1H), 7.47(d,J=7.5Hz,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).

[0149] I-52: waxy substance; 11H 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).

[0150] 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).

[0151] I-54: Wax; 1 1H 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).

[0152] I-65: Wax; 11H 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).

[0153] 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).

[0154] 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).

[0155] I-68: Wax; 1 1H NMR (500 MHz, CDCl3) δ 7.56 (dd, J = 7.7, 1.6 Hz, 1H), 7.46 (dd, J = 7.5, 1.7 Hz, 1H), 7.39–7.31 (m, 2H), 7.28–7.21 (m, 2H), 7.19–7.13 (m, 2H), 7.10 (d, J = 7.9 Hz, 1H), 6.79 (t, J = 7.4 Hz, 1H), 6.66 (d, J = 7.7 Hz, 1H), 5.74 (s, 1H), 4.35 (s, 2H), 3.77 (s, 6H), 2.64 (s, 3H).

[0156] 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).

[0157] 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).

[0158] 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).

[0159] I-72: waxy; 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).

[0160] I-73: waxy; 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).

[0161] Example 6: This example is used to illustrate the preparation method of the target compound I-27

[0162] 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.

[0163] Synthesis of target compound I-27

[0164] 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, after cooling to room temperature, saturated brine was added to the mixture, 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 wax.

[0165] I-27: Wax. 1 H NMR (400MHz, DMSO-d6) δ8.00(d,J=8.3Hz,2H),7.54(d,J=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).

[0166] Part III Performance Test and Conclusion of Compounds

[0167] 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.

[0168] Test agent: the compound of structural formula (I) provided by the present invention (see Table 3).

[0169] Test targets: Echinochloa crusgalli, Digitaria sanguinalis, Ramulus flavosum, Amaranthus retroflexus, and Cassia seed.

[0170] Planting method: The soil used in the experiment 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 experiment. 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 basin filled with 5 cm deep water. After the soil is completely moistened, sow 10-15 target weed seeds mentioned above 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 around 80% (relative humidity), the growth temperature at 25±8°C, and the air humidity above 60%.

[0171] Application method: Use the greenhouse potting method. When weeds reach the 2-leaf stage, spray them post-emergence. Repeat each treatment twice, and set a blank control (distilled water as a blank control). After spraying, let the weeds stand still indoors. After the weed leaves absorb the solution, move them to the greenhouse for cultivation. The growth temperature is 25±8℃.

[0172] Visual evaluation criteria for herbicidal activity (Table 2).

[0173] Table 2

[0174] Investigation method: The growth and reaction symptoms of the treated weeds were regularly observed. 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.

[0175] Table 3

[0176] 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, suggesting that they can effectively control grass and Amaranth weeds after emergence. Among them, I-22 has an inhibition rate of ≥95% against the four weed targets tested, not only effectively controlling grass and Amaranth weeds, but also achieving 100% control efficacy against velvet. I-52 is effective against five weed targets, controlling grass and Amaranth weeds, and achieving control efficacy of 95% and 85% against Cassia seed and velvet, respectively, showing a broad weed control spectrum.

[0177] 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.

[0178] Test agent: the compound of structural formula (I) provided by the present invention (see Table 4).

[0179] Test targets: barnyard grass, crabgrass, velvetleaf, amaranthus retroflexus, and cassia seed.

[0180] Planting Method: The test soil is a mixture of sand, silt, and clay in a 1:1:1 mass ratio. Mix thoroughly and use as the test soil. Fill an 8cm-diameter flower pot three-quarters full with soil. Place the pot in a larger stainless steel basin filled with 5cm of water. Once the soil is thoroughly moistened, sow 10-15 seeds of each target weed species in the pot, covering the pot with 0.2-0.5cm of soil. Cultivate the pot in a greenhouse. Maintain a growth temperature of 25±8°C and an air humidity of at least 60%.

[0181] Application method: Use the greenhouse potting method. 24 hours after sowing, treat the soil surface with the test agent. Repeat twice for each treatment, and set a blank control (distilled water as a blank control). After soil treatment, move the soil into the greenhouse for cultivation at a growth temperature of 25±8℃.

[0182] Investigation Method: The growth and symptoms of treated weeds were regularly observed. Twenty-one days after application, the herbicidal activity of the compound was evaluated visually. Detailed test results are shown in Table 4.

[0183] Table 4

[0184] 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, suggesting that they can effectively control grass and Amaranth weeds before emergence. Among them, I-35 has an inhibition rate of ≥90% against the three weed targets tested, and can effectively control grass and Amaranth weeds. I-52 and I-68 are not only effective in controlling grass and Amaranth weeds, with a control efficiency of ≥90%, but also have a control efficiency of 80% and 85% against velvetleaf, respectively, showing a broad spectrum of weed control.

[0185] As shown in Tables 3 and 4, some of the pyrimidine-biaryl compounds provided herein 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 herbicidal activity and excellent pre-emergence herbicidal activity, making them suitable for use as both pre-emergence and post-emergence herbicides, with a wider window of efficacy.

[0186] 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.

[0187] Test agent: the compound of structural formula (I) provided by the present invention (see Table 5).

[0188] Test targets: barnyard grass and crabgrass.

[0189] Control agent: pretilachlor; AHAS inhibitor P: 2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzoic acid.

[0190] Planting method: Post-emergence test is the same as in Example 8; pre-emergence test is the same as in Example 9.

[0191] Application method: Post-emergence test is the same as in Example 8; pre-emergence test is the same as in Example 9.

[0192] Investigation Method: The growth and symptoms of treated weeds were regularly observed. Twenty-one days after application, the herbicidal activity of the compound was evaluated visually. Detailed test results are shown in Table 5.

[0193] Table 5

[0194] As shown in Table 5, most of the compounds contained in 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. I-5 was tested for its pre-emergence herbicidal activity, and I-5 still exhibited good pre-emergence herbicidal activity, comparable to that of the control AHAS inhibitor P. Its herbicidal activity against barnyardgrass was comparable to that of pretilachlor, achieving 100% inhibition. I-5 exhibited good post-emergence and pre-emergence herbicidal activity, and can be used as a post-emergence and pre-emergence herbicide. It has a wider window of efficacy than pretilachlor for the control of the malignant weed barnyardgrass.

[0195] The pyrimidine-biaryl compound of the present invention can be used as an active ingredient of a herbicide, and can be prepared into various emulsions, granules, etc. by adding various adjuvants such as organic solvents, surfactants, and carriers using a pesticide preparation processing method for weed control on crops.

[0196] Example 10: Emulsion

[0197] 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 330# to obtain an emulsion.

[0198] When applied in the field, spraying operation is performed with reference to the amount of pyrimidine-biaryl compound used in each example.

[0199] Example 11: Wettable powder

[0200] 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.

[0201] When applied in the field, spraying operation is performed with reference to the amount of 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 compound is prepared 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: The intermediate represented by formula (A), the compound represented by formula (B), potassium carbonate and a palladium catalyst are added to an appropriate amount of solvent in a molar ratio of 1:1.3:6:0.05, and the reaction is carried out 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 a 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 the compound represented by formula (E); (2) The compound represented by formula (E), salicylaldehyde, and sodium borohydride are prepared in a molar ratio of 1:1.5:1.5; the compound represented by formula (E) and salicylaldehyde are first added to methanol and reacted at room temperature for 0.5 hours; then sodium borohydride is added and the reaction is continued at room temperature for 0.5 hours to obtain the compound represented by formula (F); (3) The compound represented by formula (F), an equivalent amount of 2-methylsulfonyl-4,6-dimethoxypyrimidine and cesium carbonate were added to an appropriate amount of 1,4-dioxane in a molar ratio of 1:1.2:1.5, and the mixture was reacted at 110°C for 4 hours; the reaction product was 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 according to 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 leaves of weeds in the early or late sprout stage; the weeds are any one of the following: barnyard grass, crabgrass, amaranth, velvetleaf or cassia seed.