CN1166642C - 2-Pyrimidinyloxy-N-amidophenylbenzylamine compounds, preparation method and use thereof - Google Patents

Abstract

The present invention relates to a 2-pyrimidine oxy-N-acylamino phenyl benzylamine compound, a preparation method and applications of the compound serving as an agricultural chemical herbicide. The structural formula of the compound is given below, wherein D or E represents hydrogen, halogen and C1 to C4 alkyl group or C1 to C4 alkoxyl group or C1 to C4 halogenating alkyl group or C1 to C4 halogenating alkoxyl group; R1 represents hydrogen, halogen and C1 to C4 alkyl group or C1 to C4 alkoxyl group; R2 represents hydrogen and C1 to C4 alkyl group or C1 to C4 halogenating alkyl group or phenyl group or substituted phenyl group or a heterocyclic ring.

Description

2-pyrimidinyloxy-N-amidophenylbenzylamine compounds, preparation method and use thereof

The present invention relates to a new class of 2-pyrimidinyloxy-N-acylaminophenylbenzylamine compounds, a preparation method and its use as an agricultural chemical herbicide.

Pesticides are an indispensable means of production for human beings to obtain food and ensure stable and high yields in agriculture. In the past century, pesticides such as insecticides, fungicides, and herbicides have made great contributions to human beings. In recent years, with the continuous growth of the world population, human beings' demand for food is also increasing, but the growth rate of cultivated land is far behind the speed of population growth. To solve this worldwide problem, we must rely on increasing the food production per unit area. To increase yield and improve crop quality, various means must be adopted, such as breeding, cultivation, fertilization, etc., and the application of pesticides is also one of the indispensable means. However, it should be noted that while pesticides have made great contributions to human civilization, due to limitations in understanding, highly toxic and high-residue pesticides have also brought negative impacts on the environment on which human beings depend. With the progress of society and the improvement of civilization, it is necessary to develop green pesticides with high efficiency, low toxicity, easy degradation, safety and environmental compatibility to replace those traditional pesticides with low efficiency, high toxicity, high residue and high resistance. Become the direction of the creation of new pesticides today.

Pyrimidinyloxybenzene derivatives have long been reported as chemical herbicides, such as Agr. Biol. Chem., Vol. Recently, on the basis of pyrimidine oxybenzene derivatives, a class of compounds with excellent herbicidal activity - pyrimidine salicylic acid derivatives were found, such as European patents 223,406, 249,708, 287,072, 287,079, 315,889, 321,846, 330,990, 335,409, 346,789, 363,040, 402,751, 435,170, 435,186, 457,505, 459,243, 468,690, 658,549 and 768034; Japanese patent 04368361; British patent 2,237,570; German patent 43,9642, etc. Representative examples include: pyrithiobac-sodium (KIH-2031, European patent 315889), bispyribac-sodium (Bispyribac-sodium, KIH-2023, European patent 321846), pyriminobac-methyl , KIH-6127, Japanese patent 04368361), pyrimidine saflufenacil (Pyribenzoxim, European patent 658549) and cyclolipid (Pyriftalid, European patent 768034), their mechanism of action is the same as that of sulfonylurea herbicides, all of which are acetyl Inhibitor of lactate synthase (ALS), which disrupts the synthesis of amino acids such as valine, leucine and isoleucine in plants. Although pyrimidine salicylates have high herbicidal activity, they are currently only suitable for weeding in cotton and paddy fields.

Lv Long and others have reported a new class of pyrimidinyloxybenzyl substituted arylamine derivatives, preparation methods and their application as agrochemical herbicides (CN 00130735.5 and CN01112689.2), which have very high herbicidal activity , but unlike the above-mentioned pyrimidine salicylate herbicides, they have a good safety profile on rapeseed. Obviously, the development of new pesticides is still a research topic.

The object of the present invention is to provide a 2-pyrimidinyloxy-N-amidophenylbenzylamine compound.

The object of the present invention is also to provide a preparation method of the above-mentioned compound.

Another object of the present invention is to provide a use of the above compound.

The structural formula of a kind of 2-pyrimidinyloxy-N-amidophenylbenzylamine compound provided by the invention is as shown in (I):

in:

D and E can be the same or different groups, respectively hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ haloalkane Oxygen, it is especially preferred that both D and E are methoxy.

R ₁ is hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, and it can be in any one of the 3, 4, 5, and 6 positions on the benzene ring.

R ₂ is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl especially trifluoromethyl, phenyl or substituted phenyl, heterocyclic group such as pyridyl, thienyl, thiazolyl, pyrimidinyl and other heterocyclic groups, wherein the amido group (R ₂ CONH-) can be in the ortho, meta or para position of the benzene ring.

Below, we list the typical compounds involved in the present invention in Table 1.

Table I

The compound 2-pyrimidinyloxy-N-acylaminophenylbenzylamine compound involved in the present invention can be synthesized with the following reaction steps:

The substituents represented by R ₁ , R ₂ and D, E in the above reaction formula are as mentioned above, and X is halogen or sulfonyl.

The starting material N-amidoaniline (II) in the reaction is prepared by the following reaction:

The synthesis of intermediate (III) is prepared by reacting N-amidoaniline (II) with salicylaldehyde in a molar ratio of 1:1 to 1:2. Solvents can be hydrocarbon solvents such as benzene, toluene or xylene; halogenated hydrocarbon solvents such as dichloromethane, dichloroethane or chloroform; ether solvents such as tetrahydrofuran or dioxane; acetone or methyl isobutyl ketone, etc. Ketone solvents; alcohol solvents such as methanol, ethanol or isopropanol; dimethylformamide, dimethyl sulfoxide, acetonitrile and mixtures of the above solvents can also be used, and the best solvent for this reaction is alcohols. The reaction temperature is from room temperature to the boiling point of the solvent, and the reaction time is from 0.5 to 12 hours. The reaction can be carried out without a catalyzer, and adding a catalyzer can speed up the reaction speed and improve the reaction yield sometimes. The catalyzer used in the reaction can be p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid or acetic acid, etc. The catalyst and The molar ratio of N-acylaminoanilide (II) is recommended to be 0.01-0.1.

The synthesis of intermediate (IV) can be obtained by reducing compound (III), and the reducing agent can be sodium borohydride or potassium borohydride, the molar ratio of reactant (III) and reducing agent is 1: 0.5-2, and the reaction temperature is From room temperature to 40 degrees Celsius, the reaction time is 0.5 to 10 hours, the solvent can be hydrocarbon solvents such as benzene, toluene or xylene; ether solvents such as tetrahydrofuran or dioxane; alcohol solvents such as methanol, ethanol or isopropanol ; Dimethylformamide, dimethyl sulfoxide, acetonitrile and a mixture of the above-mentioned solvents can also be used, and the best solvent for this reaction is alcohols. In addition, the intermediate (IV) can also be prepared by reducing the compound (III) with hydrogen under the action of a catalyst, the catalyst can be Raney Ni (RaneyNi), palladium carbon or platinum black, etc., the reactant (III), hydrogen and The molar ratio of the catalyst is 1:1-1000:0.01-0.5, and the use of more hydrogen has no effect on the reaction. The reaction temperature is from room temperature to 40 degrees Celsius, and the reaction time is 0.5 to 10 hours. The solvent can be hydrocarbon solvents such as benzene, toluene or xylene; ether solvents such as tetrahydrofuran or dioxane; methanol, ethanol or isopropanol, etc. Alcohol solvents; dimethylformamide, dimethyl sulfoxide, acetonitrile and mixtures of the above solvents can also be used, and the best solvent for this reaction is alcohol.

Finally, the intermediate (IV) is reacted with 2-halo-4-D, 6-E-substituted pyrimidine or 2-thiamphenyl-4-D, 6-E-substituted pyrimidine in the presence of a base to obtain the target Product (I), in this step reaction, used alkali can be the hydride of monovalent or divalent metal, metal alkoxide compound or its carbonate, as sodium hydride, potassium hydride, calcium hydride; Sodium methylate or sodium ethylate , potassium methylate or potassium ethylate; sodium carbonate, potassium carbonate or calcium carbonate, etc., or organic bases such as triethylamine and pyridine. The reaction solvent can be hydrocarbon solvents such as benzene, toluene or xylene; halogenated hydrocarbon solvents such as dichloromethane, dichloroethane or chloroform; ether solvents such as tetrahydrofuran or dioxane; acetone or methyl isobutyl ketone Ketone solvents such as methanol, ethanol or isopropanol and other alcohol solvents; dimethylformamide, dimethyl sulfoxide, acetonitrile and the mixture of the above solvents can also be used, and the best solvent for this reaction is ethers. The reaction temperature is from room temperature to the boiling point of the solvent, and the reaction time is from 0.5 to 20 hours. The molar ratio of intermediate (IV), 2-halo-4-D, 6-E-substituted pyrimidine or 2-thiamphenyl-4-D, 6-E-substituted pyrimidine and base is 1:1.0-1.2: 1-5. The final product can be further purified by silica gel column chromatography or recrystallization.

For more effective practical use, use the compound of the present invention as the active component of pesticide chemical herbicide, adopt the general method of pesticide industrial preparation processing, add various auxiliary agents such as water, organic solvent, surfactant, carrier, be formulated into Various water preparations, oil preparations, emulsions, powders, granules or capsules, etc., can be used for the control of weeds in rice, soybeans and other crops.

The compounds of the present invention and preparations thereof have the following characteristics and advantages:

1. It has super-efficient herbicidal activity and shows better herbicidal effect at low dosage.

2. It has a high-efficiency post-emergence herbicide effect at low doses, and is a herbicide for stem and leaf treatment.

3. It has pre-emergent herbicidal activity at high doses.

4. The herbicidal spectrum is wide, not only can effectively control grass weeds in farmland, but also can control broad-leaved weeds and sedges.

5. High safety for crops, especially for soybeans and rice.

6. It also has very effective herbicidal activity on older grass weeds (3-7 leaves).

7. It has a short residual period in the soil and has no adverse effects on the growth of crops after crop rotation.

8. It has no significant toxicity to mammals or fish, has high environmental safety, and is a low-toxic and environment-friendly pesticide.

The compound with the structural formula (I) provided by the invention not only has a simple synthesis method, but also has herbicidal activity and can be used as a herbicide. Its preparations can effectively control most of the weeds in farmland, such as grass weeds at low doses, broad-leaved weeds and sedges at high doses, and the specific control targets include barnyardgrass (Echinochloa crusgalli), crabgrass (Digitaria sanguinalis), goosegrass (Eleusine indica), foxtail (Setaria viridis), bluegrass (Poa annua), wild oats (Avena fatua), alopecurus aequalis, Japanese alopecurus japonicus, Alopecurus japonicus Amaranthus retroflexus, Amaranthus spinosus, Chenopodium album, Brassica juncea, Portulaca oleracea, Acalypha australis, Cyperus diffformis Leptochloachinensis), Cyperus rotundus, Fimbristylis miliacea, Chickweed (Stallaria media), Stellaria alsine, Erigeron annuus, Sagittarias agittifolia, Field spin Flower (Convolvulus arvensis) etc.

The following will give detailed reaction conditions, purification methods, physical constants and analytical data required for structure confirmation with respect to some examples. It should be pointed out that the present invention is not limited to the scope of the following examples.

Example 1: (Compound No. I-1 in Table 1)

Dissolve 27.6 grams (0.2mol) of p-nitroaniline in 200mL of tetrahydrofuran, add 55.2 grams (0.4mol) of anhydrous potassium carbonate and 42.6 grams (0.4mol) of isobutyryl chloride, stir at room temperature for 5 hours, and dissolve the reaction solution Pour into 100 mL of 10% hydrochloric acid, and extract the organic phase with ether to obtain a yellow solid p-isopropionamidonitrobenzene with a yield of 83.2%.

Dissolve 31.2 g (0.15 mol) of p-isopropionamidonitrobenzene in 200 mL of anhydrous methanol, add an appropriate amount of Raney-Ni and 40 mL of hydrazine hydrate, react at room temperature for 6 hours, and filter with suction to obtain a filtrate, which is concentrated to obtain p-Isopropanil, yield 96%.

Dissolve 17.8 grams (0.1mol) of p-isopropionamidoaniline in 200mL of anhydrous methanol, dropwise add 14.6 grams (0.12mol) of salicylaldehyde, stir and react at room temperature for 50 minutes, filter, and wash the solid with anhydrous methanol , to obtain 26.4 g of yellow solid (III-1), with a yield of 93.6%.

Take 14.1 g (0.05 mol) of compound (III-1) prepared above, dissolve it in 250 mL of anhydrous methanol, add 1.89 g (0.05 mol) sodium borohydride in batches at room temperature, stir the reaction at room temperature for 20 minutes, concentrate Remove methanol, then add 200 mL of chloroform and 150 mL of water to the residue, stir well, let stand, separate the organic layer, wash with water, dry over anhydrous sodium sulfate, and concentrate to obtain 13.8 g of white solid (IV-1). 97.6%.

Take 2.84 grams (0.01mol) of compound (IV-1) prepared above, 2.18 grams (0.01mol) of 2-thiamphenyl-4,6-dimethoxypyrimidine, dissolve in 100mL dioxane, and Next, add 2.76 grams (0.02mol) of potassium carbonate, reflux reaction for 11 hours, suction filtration, the filter cake is washed with 20mL dioxane, the mother liquor is concentrated, the residual product is added with 10mL ethanol and stirred, and 3.7 grams of white solid product 2-( 4,6-Dimethoxy-2-pyrimidinyloxy)-N-(4-isopropionamidophenyl)benzylamine (I-1), yield 90.1%.

mp: 134.1-134.7°C; m/z: 422 (M ⁺ );

¹ HNMR: 66.96-7.49 (8H, m, Ar-H), 6.45-6.57 (2H, m, CH ₂ ), 5.75 (1H, m, CH), 4.35 (1H, m, NH), 3.80 (6H, s, OCH ₃ ), 2.45 (1H, m, CH), 1.76 (1H, m, NH), 1.24 (6H, d, CH ₃ ) ppm.

Elemental Analysis: Calculated: C, 65.39; H, 6.20; N, 13.26;

  Measured values: C, 65.39; H, 6.06; N, 13.40;

Example 2: (Compound No. I-2 in Table 1)

Dissolve 27.6 grams (0.2mol) of p-nitroaniline in 200mL of tetrahydrofuran, add 55.2 grams (0.4mol) of anhydrous potassium carbonate and 56.2 grams (0.4mol) of benzoyl chloride, stir at room temperature for 5 hours, and dissolve the reaction solution Pour into 100 mL of 10% hydrochloric acid, and extract the organic phase with ether to obtain benzamidoaniline as a yellow solid with a yield of 78.2%.

Dissolve 29 grams (0.12 mol) of p-benzamidonitrobenzene in 200 mL of anhydrous methanol, add an appropriate amount of Raney-Ni and 38 mL of hydrazine hydrate, react at room temperature for 6 hours, and filter with suction to obtain the filtrate, which is concentrated to the right Benzylaminoaniline, the yield is 93.2%.

Dissolve 24.2 g (0.1 mol) of p-benzamidoaniline in 200 mL of anhydrous methanol, dropwise add 14.6 g (0.12 mol) of salicylaldehyde, stir and react at room temperature for 50 minutes, filter, and wash the solid with anhydrous methanol. 28.4 g of yellow solid (III-2) was obtained, with a yield of 90%.

Take 15.8 g (0.05 mol) of the compound (III-2) prepared above, dissolve it in 250 mL of anhydrous methanol, add 1.89 g (0.05 mol) sodium borohydride in batches at room temperature, stir the reaction at room temperature for 20 minutes, concentrate Remove methanol, then add 200 mL of chloroform and 150 mL of water to the residue, stir well, let stand, separate the organic layer, wash with water, dry over anhydrous sodium sulfate, and concentrate to obtain 15.2 g of white solid (IV-2). 96%.

Take 3.18 grams (0.01mol) of compound (IV-2) prepared above, 2.18 grams (0.01mol) of 2-thiamphenyl-4,6-dimethoxypyrimidine, dissolve in 100mL dioxane, and Add 2.76 grams (0.02mol) of potassium carbonate, reflux reaction for 11 hours, suction filtration, the filter cake is washed with 20mL dioxane, the mother liquor is concentrated, the residual product is stirred with 10mL ethanol, and 4.06 grams of white solid product 2-( 4,6-Dimethoxy-2-pyrimidinyloxy)-N-(4-benzamidophenyl)benzylamine (I-2), yield 89%.

mp: 152.8-153.4°C; m/z: 456 (M ⁺ );

¹ H NMR: δ7.1-7.9 (13H, m, Ar-H), 6.55 (2H, m, CH ₂ ), 5.75 (1H, m, CH), 4.4 (1H, m, NH), 3.82 (6H, s, OCH ₃ ), 1.69 (1H, m, NH) ppm.

Elemental Analysis: Calculated: C, 68.41; H, 5.30; N, 12.27;

  Measured values: C, 67.70; H, 5.34; N, 12.12;

Example 3: (Compound No. I-3 in Table 1)

Dissolve 27.6 grams (0.2 mol) of p-nitroaniline in 200 mL of trifluoroacetic acid, add 84 grams (0.4 mol) of trifluoroacetic anhydride, heat and reflux for 3 hours, pour the reaction solution into 500 mL of ice water, and a precipitate forms. After filtering, the solid was washed with n-hexane to obtain 39.8 g of solid p-trifluoroformamidonitrobenzene, with a yield of 85.2%.

Dissolve 35.1 g (0.15 mol) of p-trifluoroformamidonitrobenzene in 200 mL of anhydrous methanol, add an appropriate amount of Raney-Ni and 40 mL of hydrazine hydrate, react at room temperature for 6 hours, and filter with suction to obtain the filtrate, which is concentrated To obtain p-trifluoroformamidoaniline in a yield of 94%.

Dissolve 20.4 grams (0.1mol) of p-trifluoroformamidoaniline in 200mL of anhydrous methanol, dropwise add 14.6 grams (0.12mol) of salicylaldehyde, stir and react at room temperature for 50 minutes, filter, and wash the solid with anhydrous methanol After washing, 28.3 g of yellow solid (III-3) was obtained, with a yield of 92%.

Take 15.4 g (0.05 mol) of the compound (III-3) prepared above, dissolve it in 250 mL of anhydrous methanol, add 1.89 g (0.05 mol) sodium borohydride in batches at room temperature, stir the reaction at room temperature for 20 minutes, concentrate Remove methanol, then add 200 mL of chloroform and 150 mL of water to the residue, stir well, let stand, separate the organic layer, wash with water, dry over anhydrous sodium sulfate, and concentrate to obtain 14.8 g of white solid (IV-3). 96%.

Take 3.1 grams (0.01mol) of compound (IV-3) prepared above, 2.18 grams (0.01mol) of 2-thiamphenicol-4,6-dimethoxypyrimidine, dissolve in 100mL dioxane, and Next, add 2.76 grams (0.02mol) of potassium carbonate, reflux reaction for 11 hours, suction filtration, the filter cake is washed with 20 milliliters of dioxane, the mother liquor is concentrated, and the residual product is stirred with 10 milliliters of ethanol, and 3.94 grams of white solid product 2 is obtained by suction filtration. -(4,6-Dimethoxy-2-pyrimidinyloxy)-N-(4-trifluoroformylaminophenyl)benzylamine (I-3), yield 88%.

mp: 159.0-159.6°C; m/z: 448 (M ⁺ );

¹ H NMR: δ7.10-7.78 (8H, m, Ar-H), 6.56 (2H, m, CH ₂ ), 5.78 (1H, m, CH), 4.36 (1H, m, NH), 3.84 (6H, s, OCH ₃ ), 1.6 (1H, m, NH) ppm.

Elemental Analysis: Calculated: C, 56.25; H, 4.27; N, 12.49;

  Measured values: C, 56.37; H, 4.27; N, 12.54;

Example 4: (Compound No. I-4 in Table 1)

Dissolve 27.6 g (0.2 mol) of p-nitroaniline in 200 mL of acetic acid, add 40.8 g (0.4 mol) of acetic anhydride, heat and reflux for 3 hours, pour the reaction solution into 500 mL of ice water, a precipitate is formed, filter, and use the solid After washing with n-hexane, 30.9 g of solid p-formamidonitrobenzene was obtained, with a yield of 86%.

Dissolve 27 grams (0.15 mol) of p-formamidonitrobenzene in 200 mL of anhydrous methanol, add an appropriate amount of Raney-Ni and 40 mL of hydrazine hydrate, react at room temperature for 6 hours, and filter with suction to obtain the filtrate, which is concentrated to the right Formamidoaniline, yield 94%.

Dissolve 15 grams (0.1mol) of p-carboxamidoaniline in 200mL of anhydrous methanol, dropwise add 14.6 grams (0.12mol) of salicylaldehyde, stir and react at room temperature for 50 minutes, filter, and wash the solid with anhydrous methanol. 23.3 g of yellow solid (III-4) was obtained, with a yield of 92%.

Take 12.7 g (0.05 mol) of compound (III-4) prepared above, dissolve it in 250 mL of anhydrous methanol, add 1.89 g (0.05 mol) sodium borohydride in batches at room temperature, stir the reaction at room temperature for 20 minutes, concentrate Remove methanol, then add 200 mL of chloroform and 150 mL of water to the residue, stir well, let stand, separate the organic layer, wash with water, dry over anhydrous sodium sulfate, and concentrate to obtain 12.5 g of white solid (IV-4). 98%.

Take 2.56 grams (0.01mol) of compound (IV-4) prepared above, 2.18 grams (0.01mol) of 2-thiamphenyl-4,6-dimethoxypyrimidine, dissolve in 100mL of dioxane, room temperature Add 2.76 grams (0.02mol) of potassium carbonate, reflux reaction for 11 hours, suction filtration, the filter cake is washed with 20mL dioxane, the mother liquor is concentrated, the residual product is added with 10mL ethanol and stirred, and 3.35 grams of white solid product 2-( 4,6-Dimethoxy-2-pyrimidinyloxy)-N-(4-formamidophenyl)benzylamine (I-4), yield 85%.

mp: 162.0-162.8°C; m/z: 394 (M ⁺ );

¹ H NMR: δ7.10-7.5 (8H, m, Ar-H), 6.5 (2H, m, CH ₂ ), 5.80 (1H, m, CH), 4.25 (1H, s, NH), 3.80 (6H, s, OCH ₃ ), 2.12 (3H, s, CH ₃ ), 1.70 (1H, m, NH) ppm.

Elemental Analysis: Calculated: C, 63.95; H, 5.62; N, 14.20;

  Measured values: C, 64.49; H, 5.78; N, 13.80;

Example 5: (Compound No. I-5 in Table 1)

27.6 grams (0.2mol) of p-nitroaniline were dissolved in 200ml of tetrahydrofuran, 55.2 grams (0.4mol) of anhydrous potassium carbonate and 58.6 grams (0.4mol) of 2-thiophenoyl chloride were added, stirred at room temperature for 5 hours, and The reaction solution was poured into 100 mL of 10% hydrochloric acid, and the organic phase was extracted with ether to obtain p-(2-thiophene)amidonitrobenzene as a yellow solid with a yield of 83.2%.

Dissolve 37.2 grams (0.15 mol) of p-(2-thiophene)amidonitrobenzene in 200 mL of anhydrous methanol, add an appropriate amount of Raney-Ni and 40 mL of hydrazine hydrate, react at room temperature for 6 hours, and filter with suction to obtain the filtrate. The filtrate was concentrated to obtain the product p-(2-thiophene)amidoanilide with a yield of 96%.

Dissolve 21.8 grams (0.1mol) of p-(2-thiophene)amidoanilide in 200mL of anhydrous methanol, add dropwise 14.6 grams (0.12mol) of salicylaldehyde, stir and react at room temperature for 50 minutes, filter, and use the solid with After washing with water and methanol, 29.3 g of yellow solid (III-5) was obtained with a yield of 91%.

Take 16.1 g (0.05 mol) of (III-5) prepared above, dissolve it in 250 mL of anhydrous methanol, add 1.89 g (0.05 mol) sodium borohydride in batches at room temperature, stir and react at room temperature for 20 minutes, and concentrate to remove Methanol, then add 200mL of chloroform and 150mL of water to the residue, stir well, let stand, separate the organic layer, wash with water, dry over anhydrous sodium sulfate, concentrate to give 15.7 g of white solid (IV-5), yield 97.6 %.

Take 3.24 grams (0.01mol) of compound (IV-5) prepared above, 2.18 grams (0.01mol) of 2-thiamphenyl-4,6-dimethoxypyrimidine, dissolve in 100mL dioxane, and Add 2.76 grams (0.02mol) of potassium carbonate, reflux reaction for 11 hours, suction filtration, the filter cake is washed with 20mL dioxane, the mother liquor is concentrated, the residual product is stirred with 10mL ethanol, and 3.88 grams of white solid product 2-( 4,6-Dimethoxy-2-pyrimidinyloxy)-N-[4-(2-thienamido)phenyl]benzylamine (I-5), yield 85%.

mp: 147.3-147.9°C; m/z: 464 (M ⁺ );

¹ H NMR: δ7.0-7.78 (8H, m, Ar-H), 6.52 (2H, m, CH ₂ ), 5.76 (1H, m, CH), 4.35 (2H, m, CH), 4.16 (1H, m, NH), 3.84 (6H, s, OCH ₃ ), 1.76 (1H, m, NH) ppm.

Elemental Analysis: Calculated: C, 62.05; H, 5.21; N, 12.06;

  Measured values: C, 62.21; H, 4.73; N, 12.13;

Example 6: (Compound No. I-6 in Table 1)

Dissolve 27.6 grams (0.2mol) of p-nitroaniline in 200mL of tetrahydrofuran, add 55.2 grams (0.4mol) of anhydrous potassium carbonate and 83.4 grams (0.4mol) of m-trifluoromethylbenzoyl chloride, and stir at room temperature for 5 After hours, the reaction solution was poured into 100 mL of 10% hydrochloric acid, and the organic phase was extracted with ether to obtain a yellow solid p-(3-trifluoromethylphenyl)amidonitrobenzene with a yield of 83.2%.

Dissolve 46.5 g (0.15 mol) of p-(3-trifluoromethylphenylamidonitrobenzene) in 200 mL of anhydrous methanol, add an appropriate amount of Raney-Ni and 40 mL of hydrazine hydrate, react at room temperature for 6 hours, and filter with suction. The filtrate was obtained, and the filtrate was concentrated to obtain p-(3-trifluoromethylphenyl)amidoanilide with a yield of 96%.

28 grams (0.1mol) of p-(3-trifluoromethylphenyl)amidoanilide was dissolved in 200mL of anhydrous methanol, 14.6 grams (0.12mol) of salicylaldehyde was added dropwise, and after stirring and reacting at room temperature for 50 minutes, After filtration, the solid was washed with anhydrous methanol to obtain 30.7 g of yellow solid (III-6), with a yield of 80%.

Take 19.2 g (0.05 mol) of compound (III-6) prepared above, dissolve it in 250 mL of anhydrous methanol, add 1.89 g (0.05 mol) sodium borohydride in batches at room temperature, stir the reaction at room temperature for 20 minutes, concentrate Remove methanol, then add 200 mL of chloroform and 150 mL of water to the residue, stir well, let stand, separate the organic layer, wash with water, dry over anhydrous sodium sulfate, and concentrate to obtain 18.5 g of white solid (IV-6). 96%.

Take 3.86 grams (0.01mol) of compound (IV-6) prepared above, 2.18 grams (0.01mol) of 2-thiamphenyl-4,6-dimethoxypyrimidine, dissolve in 100mL dioxane, and Add 2.76 grams (0.02mol) of potassium carbonate, reflux reaction for 11 hours, suction filtration, the filter cake is washed with 20mL dioxane, the mother liquor is concentrated, the residual product is stirred with 10mL ethanol, and 4.29 grams of white solid product 2-( 4,6-Dimethoxy-2-pyrimidinyloxy)-N-[4-(3-trifluoromethylbenzamido)phenyl]benzylamine (I-6), yield 82%.

mp: 150.1-150.7°C; m/z: 524 (M ⁺ );

¹ H NMR: δ7.1-8.15 (12H, m, Ar-H), 6.55 (2H, m, CH ₂ ), 5.8 (1H, m, CH), 4.30 (1H, m, NH), 3.82 (6H, s, OCH ₃ ), 1.65 (1H, m, NH) ppm.

Elemental Analysis: Calculated: C, 61.83; H, 4.42; N, 10.68;

  Measured values: C, 61.85; H, 4.46: N, 10.67;

Example 7: (Compound No. I-7 in Table-)

Dissolve 27.6 grams (0.2mol) of p-nitroaniline in 200mL of tetrahydrofuran, add 55.2 grams (0.4mol) of anhydrous potassium carbonate and 42.6 grams (0.4mol) of isobutyryl chloride, stir at room temperature for 5 hours, and dissolve the reaction solution Pour into 100 mL of 10% hydrochloric acid, and extract the organic phase with ether to obtain isobutyrylaminonitrobenzene as a yellow solid with a yield of 83.2%.

Dissolve 2.6 grams (12.5 mmol) of p-isobutyrylaminonitrobenzene in 10 mL of anhydrous methanol, add an appropriate amount of 0.2 grams of Raney-Ni and 1.1 grams (18.8 mmol, 85%) of hydrazine hydrate, and react at room temperature for 6 hours. Filtrate with suction to obtain a filtrate, and concentrate the filtrate to obtain p-isobutyrylaminoanilide with a yield of 96%.

Dissolve 2.14 grams (12 mmol) of p-isobutyraminoaniline in 200 mL of absolute ethanol, add 2.19 grams (14.4 mmol) of o-vanillin, and stir at room temperature to complete the reaction. After washing with ethanol, 3.70 g of yellow solid (III-7) was obtained with a yield of 98.8%.

Take 3.7 g (11.86 mmol) of the compound (III-7) prepared above, dissolve it in 20 mL of absolute ethanol, add 0.7 g (17.8 mmol) sodium borohydride in batches at room temperature, stir and react at room temperature for 30 minutes, and The reactant was poured into ice water, filtered, and dried to obtain 3.3 g of compound (IV-7), with a yield of 88.7%.

Take 3.14 grams (10 mmol) of compound (IV-7) prepared above, 2.18 grams (10 mmol) of 2-thiamphenyl-4,6-dimethoxypyrimidine, dissolve in 30 mL of dioxane, and add 2.76 grams (20mmol) of potassium carbonate, reflux reaction for 11 hours, suction filtration, the filter cake was washed with 20mL dioxane, the mother liquor was concentrated, the residual product was stirred with 10mL ethanol, and 4.0 grams of white solid product 2-(4,6 -Dimethoxy-2-pyrimidinyloxy)-3-methoxy-N-(4-isobutyrylaminophenyl)benzylamine (I-7), yield 89.0%, recrystallized from ethyl acetate to obtain Pure.

mp: 171.5-172.5°C; m/z: 108 (M ⁺ , 100);

¹ HNMR: δ0.87-0.90 (6H, d, CH ₃ , ³ J _HH = 6.7Hz), 2.2-2.32 (1H, m, CH), 2.6 (3H, s, OCH ₃ ), 3.55 (6H, s , OCH ₃ ), 4.0-4.1 (2H, d, CH ₂ , ³ J _HH = 5.4Hz), 4.91-5.0 (1H, s, NH), 5.59 (1H, s, CH), 6.21-6.35 (2H, d, ³ J _HH = 6.7Hz), 6.71-6.84 (2H, m), 6.86-6.99 (1H, t, ³ J _HH = 7.8Hz), 7.05-7.1 (2H, d), 8.35-8.45 (1H, s, NH) ppm.

IR: 3381 (ν _NHCO ), 3327 (ν _NHCH2 ), 1664 (ν _CO ) cm ^-1 .

Elemental Analysis: Calculated: C, 63.70; H, 6.24; N, 12.38;

  Measured values: C, 63.79; H, 6.55; N, 12.41;

Example 8: (Compound No. I-8 in Table 1)

Dissolve 1.38 g (10 mmol) of p-nitroaniline in 10 mL of glacial acetic acid, slowly add 1.88 mL (20 mmol) of acetic anhydride dropwise at room temperature, heat to reflux for 30 minutes, cool to room temperature, add to ice water, filter, and wash with ice water To neutrality, 1.69 g of product was obtained by drying, yield 93.8%.

Dissolve 1.69 g (9.38 mmol) of p-acetamidonitrobenzene in 10 mL of anhydrous methanol, add an appropriate amount of 0.13 g of Raney-Ni and 0.83 g (14.1 mmol, 85%) of hydrazine hydrate, react at room temperature for 6 hours, and filter with suction , the filtrate was obtained, and the filtrate was concentrated to obtain the product p-acetamidoaniline, with a yield of 100%.

Dissolve 1.41 g (9.37 mmol) of para-acetamidoaniline in 15 mL of absolute ethanol, add 1.71 g (11.4 mmol) of o-vanillin, and stir at room temperature to complete the reaction. TLC controls the reaction end point, filters, and the solid is dehydrated with absolute ethanol After washing, 2.18 g of yellow solid (III-8) was obtained with a yield of 81.8%.

Take 2.18 g (7.665 mmol) of the compound (III-8) prepared above, dissolve it in 20 mL of absolute ethanol, add 0.445 g (11.5 mmol, 96%) sodium borohydride in batches at room temperature, and stir the reaction at room temperature for 30 minutes, the reactant was poured into ice water, filtered, and dried to obtain 2.19 g of compound (IV-8), with a yield of 100%.

Take 2.19 grams (7.66mmol) of compound (IV-8) prepared above, 1.67 grams (7.66mmol) of 2-thiamphenyl-4,6-dimethoxypyrimidine, dissolve in 30mL dioxane, room temperature Add 2.12 grams (15.3 mmol) of potassium carbonate, reflux reaction for 11 hours, suction filtration, the filter cake is washed with 20 mL of dioxane, the mother liquor is concentrated, the residual product is stirred with 10 mL of ethanol, and 2.83 grams of white solid product 2-( 4,6-dimethoxy-2-pyrimidinyloxy)-3-methoxy-N-(4-acetamidophenyl)benzylamine (I-8), yield 87.0%, and weighed with ethyl acetate Crystallization was pure.

mp: 169.8-170.8°C; m/z: 150 (M ⁺ , 100);

¹ H NMR: δ1.7 (1H, s, CH ₃ ), 2.1 (3H, s, OCH ₃ ), 3.55 (6H, s, OCH ₃ ), 4.0-4.05 (2H, d, CH ₂ , ³ J _HH = 5.64Hz), 4.95-5.0(1H, s, NH), 5.09(1H, s, CH), 6.2-6.3(2H, d, ³ J _HH = 6.75Hz), 6.71-6.83(2H, m), 6.85 -6.95(1H, t, ³ J _HH ＝7.2Hz), 7.0-7.08(2H, d, ³ J _HH ＝2.1Hz), 8.5(1H, s, NH)ppm.IR: 3368(ν _NH ), 1670 (ν _CO )cm ^-1 .

Elemental Analysis: Calculated: C, 62.25; H, 5.70; N, 13.20;

  Measured values: C, 61.86; H, 5.71; N, 13.10;

Example 9: (Compound No. I-9 in Table 1)

Adopt m-nitroaniline as starting raw material, detailed experimental procedure is with embodiment four:

3-Formylaminonitrobenzene, yield 82%;

3-formamidoaniline (II-9), yield 95%;

2-Hydroxy-N-(3-formylaminophenyl) benzyl imine (III-9), yield 88%;

2-Hydroxy-N-(3-formamidophenyl)benzylamine (IV-9), yield 98%;

2-(4,6-dimethoxy-2-pyrimidinyloxy)-N-(3-formamidophenyl)benzylamine (I-4), yield 85%; mp141-142°C; m/ z=394 (M ⁺ ); ¹ HNMR: δ6.70-7.54 (8H, m, Ar-H), 5.80 (1H, m, CH), 4.36 (2H, s, CH ₂ ), 3.82 (6H, s , OCH ₃ ), 1.76 (3H, s, CH ₃ ) ppm;

Elemental analysis: Calculated, C: 63.95; H: 5.62; N: 14.20;

  Measured values: C: 63.97; H: 5.63; N: 14.06.

Example 10: (Compound No. I-10 in Table 1)

Adopt m-nitroaniline as starting raw material, detailed experimental procedure is the same as embodiment example one:

3-isopropionamidonitrobenzene, yield 88%;

3-isopropionamidoaniline (II-10), yield 95%;

2-Hydroxy-N-(3-isopropionylaminophenyl) benzyl imine (III-10), yield 89.5%;

2-Hydroxy-N-(3-isopropionamidophenyl)benzylamine (IV-10), yield 95%;

2-(4,6-Dimethoxy-2-pyrimidinyloxy)-N-(3-isopropionamidophenyl)benzylamine (I-10), yield 80%. m/z: 422 (M ⁺ ); ¹ H NMR: δ6.90-7.68 (8H, m, Ar-H), 6.48 (2H, m, CH ₂ ), 5.70 (1H, m, CH), 4.30 (1H , m, NH), 3.80 (6H, s, OCH ₃ ), 2.40 (1H, m, CH), 1.75 (1H, m, NH), 1.25 (6H, s, CH ₃ ) ppm;

Elemental Analysis: Calculated: C, 65.39; H, 6.20; N, 13.26;

  Measured values: C, 65.28; H, 6.10; N, 13.44;

Example 11: (Compound No. I-11 in Table-)

Adopt m-nitroaniline as starting raw material, detailed experimental procedure is the same as embodiment two:

3-benzamidoaniline, yield 78.2%;

3-benzamidoaniline (II-11), yield 93.2%;

2-Hydroxy-N-(3-benzamidophenyl) benzyl imine (III-11), yield 86%:

2-Hydroxy-N-(3-benzamidophenyl)benzylamine (IV-11), yield 98%;

2-(4,6-dimethoxy-2-pyrimidinyloxy)-N-(3-benzamidophenyl)benzylamine (I-11), yield 84%; m/z: 456 ( M ⁺ ); ¹ HNMR: δ7.00-8.05 (13H, m, Ar-H), 6.50 (2H, m, CH ₂ ), 5.78 (1H, m, CH), 4.43 (1H, m, NH), 3.82 (6H, s, OCH ₃ ), 1.70 (1H, m, NH) ppm;

Elemental Analysis: Calculated: C, 68.41; H, 5.30; N, 12.27;

  Measured values: C, 68.16; H, 5.35; N, 12.29;

Example 12: (Compound No. I-12 in Table 1)

Adopt m-nitroaniline as starting raw material, detailed experimental procedure is with embodiment three:

3-trifluoroformylaminonitrobenzene, yield 90%;

3-trifluoroformamidoaniline (II-12), yield 93%;

2-Hydroxy-N-(3-trifluoroformylaminophenyl) benzyl imine (III-12), yield 90%;

2-Hydroxy-N-(3-trifluoroformylaminophenyl)benzylamine (IV-12), yield 94%;

2-(4,6-Dimethoxy-2-pyrimidinyloxy)-N-(3-trifluoroformylaminophenyl)benzylamine (I-12), yield 85%. m/z: 448 (M ⁺ ); ¹ H NMR: δ7.10-7.80 (8H, m, Ar-H), 6.55 (2H, m, CH ₂ ), 5.80 (1H, m, CH), 4.35 (1H , m, NH), 3.82 (6H, s, OCH ₃ ), 1.63 (1H, m, NH) ppm.

Elemental Analysis: Calculated: C, 56.25; H, 4.27; N, 12.49;

  Measured values: C, 56.40; H, 4.22; N, 12.58;

Example 13: (Compound No. I-13 in Table 1)

Adopt o-nitroaniline as starting raw material, detailed experimental procedure is with embodiment four:

2-Formylaminonitrobenzene, yield 89%;

2-formamidoaniline (II-13), yield 94%;

2-Hydroxy-N-(2-formylaminophenyl) benzyl imine (III-13), yield 84%;

2-Hydroxy-N-(2-formamidophenyl)benzylamine (IV-13), yield 97%;

2-(4,6-dimethoxy-2-pyrimidinyloxy)-N-(2-formamidophenyl)benzylamine (I-13), yield 80%; m/z=394 (M ⁺ ); ¹ HNMR: δ6.67-7.52 (8H, m, Ar-H), 5.80 (1H, m, CH), 4.34 (2H, s, CH ₂ ), 3.80 (6H, s, OCH ₃ ), 1.78 (3H, s, CH ₃ )ppm

Elemental analysis: Calculated, C: 63.95; H: 5.62; N: 14.20;

  Measured values: C: 63.88; H: 5.60; N: 14.24.

Example 14: (Compound No. I-14 in Table 1)

Adopt o-nitroaniline as starting raw material, detailed experimental procedure is with embodiment one:

2-isopropionamidonitrobenzene, yield 92%;

2-isopropionamidoaniline (II-14), yield 97%;

2-Hydroxy-N-(2-isopropionylaminophenyl) benzyl imine (III-14), yield 86%;

2-Hydroxy-N-(2-isopropionamidophenyl)benzylamine (IV-14), yield 99%:

2-(4,6-Dimethoxy-2-pyrimidinyloxy)-N-(2-isopropionamidophenyl)benzylamine (I-14), yield 79%. m/z: 422 (M ⁺ ); ¹ H NMR: δ6.84-7.65 (8H, m, Ar-H), 6.48 (2H, m, CH ₂ ), 5.73 (1H, m, CH), 4.30 (1H , m, NH), 3.83 (6H, s, OCH ₃ ), 2.41 (1H, m, CH), 1.74 (1H, m, NH), 1.25 (6H, d, CH ₃ ) ppm;

Elemental Analysis: Calculated: C, 65.39; H, 6.20; N, 13.26;

  Measured values: C, 65.30; H, 6.15; N, 13.40;

Example 15: (Compound No. I-15 in Table-)

Adopt o-nitroaniline as starting raw material, detailed experimental procedure is with embodiment two:

2-benzamidoaniline, yield 86%;

2-benzamidoaniline (II-15), yield 96%;

2-Hydroxy-N-(2-benzamidophenyl) benzyl imine (III-15), yield 83%;

2-Hydroxy-N-(2-benzamidophenyl)benzylamine (IV-15), yield 96%;

2-(4,6-dimethoxy-2-pyrimidinyloxy)-N-(4-benzamidophenyl)benzylamine (I-15), yield 82%; m/z: 456 ( M ⁺ ); ¹ HNMR: δ7.10-8.09 (13H, m, Ar-H), 6.55 (2H, m, CH ₂ ), 5.80 (1H, m, CH), 4.45 (1H, m, NH), 3.80 (6H, s, OCH ₃ ), 1.70 (1H, m, NH) ppm;

Elemental Analysis: Calculated: C, 68.41; H, 5.30; N, 12.27;

  Measured values: C, 68.36; H, 5.34; N, 12.20;

Example 16: (Compound No. I-16 in Table 1)

Adopt o-nitroaniline as starting raw material, detailed experimental procedure is with embodiment three:

2-trifluoroformylaminonitrobenzene, yield 88%;

2-trifluoroformamidoaniline (II-16), yield 91%;

2-Hydroxy-N-(2-trifluoroformylaminophenyl) benzyl imine (III-16), yield 84%;

2-Hydroxy-N-(2-trifluoroformylaminophenyl)benzylamine (IV-16), yield 90%;

2-(4,6-Dimethoxy-2-pyrimidinyloxy)-N-(2-trifluoroformylaminophenyl)benzylamine (I-12), yield 82%. m/z: 448 (M ⁺ ); ¹ H NMR: δ7.11-7.88 (8H, m, Ar-H), 6.55 (2H, m, CH ₂ ), 5.85 (1H, m, CH), 4.30 (1H , m, NH), 3.84 (6H, s, OCH ₃ ), 1.60 (1H, m, NH) ppm.

Elemental Analysis: Calculated: C, 56.25; H, 4.27; N, 12.49;

  Measured values: C, 56.30; H, 4.42; N, 12.68;

Example 17 (wettable powder formulation)

The following examples 17 to 23 provide the actual examples of processing and preparing several herbicide formulations using the compound of the present invention as an active substance component. It should be pointed out that the present invention is not limited to the scope of the following examples Inside. In these formulation examples, all "%" refer to percent by weight, and "ga ai/ha" refers to per gram of active matter per hectare.

15% compound (I-1) (Table 1), 5% lignosulfonate (M _q ), 1% lauryl polyoxyethylene ether (JFC), 40% diatomaceous earth and 44% The light calcium carbonate is evenly mixed and pulverized to obtain a wettable powder.

Example 18 (cream formula)

10% of compound (I-1) (Table 1), 5% of Nongru No. 500 (calcium salt), 5% of Nongru No. 602, 5% of N-methyl-2-pyrrolidone and 75% of Xylene is heated and stirred evenly to obtain emulsifiable oil.

Example 19 (granule formulation)

5% of compound (I-1) (Table 1), 1% of polyvinyl alcohol (PVA), 4% of sodium naphthalenesulfonate formaldehyde condensate (NMO) and 90% of clay were uniformly mixed, pulverized, and then added to Add 20 parts of water to 100 parts of the mixture, knead, and use an extrusion granulator to make 14-32 mesh granules, and dry to obtain granules.

Examples of bioactivity assays using the compounds of the present invention are given below, and it should be noted that the present invention is not limited to the scope of the following examples.

Herbicidal activity and crop safety (ie, phytotoxicity) 5-level visual method evaluation criteria are listed in Table II.

Table 2. Herbicidal activity and phytotoxicity evaluation criteria Grading Index Phytotoxicity (%) Herbicidal activity evaluation (inhibition, malformation, albinism, etc.) Crop safety comments (inhibition, malformation, albinism, etc.) 0 0 Same comparison, resistance, elimination Same as control, resistant, normal 1 10-20 light, slightly affected, eliminated Light, slightly affected, can be considered 2 30-40 light, impactful, eliminated Sensitive, influential, eliminated 3 50-60 Sensitive and influential, further modification may be considered More sensitive, serious drug damage, eliminated 4 70-80 more sensitive, consider Extremely sensitive, serious drug damage, eliminated 5 90-100 very sensitive, ok Extremely sensitive, serious drug damage, eliminated

Example 20 Herbicide dish test for herbicidal activity

Using wheat, barnyardgrass, sorghum, rape, radish, and cucumber as model organisms, put the seeds of each target into a petri dish, add 9mL of medicament with a concentration of 100mg/L, and put them in a plant growth chamber at 25°C and RH75%. After 7 days, the damage degree of the target plant was visually inspected, and the specific test results are shown in Table 3.

Table 3. Herbicide dish test for herbicidal activity Compound No. of Zhejiang Institute Concentration ppm wheat barnyard grass sorghum rape radish cucumber stem root stem root stem root stem root stem root stem root I-1 100 90.0 85.0 50.0 50.0 90.0 95.0 70.0 40.0 0.0 50.0 0.0 0.0 I-2 100 70.0 70.0 50.0 50.0 85.0 85.0 0.0 40.0 0.0 0.0 0.0 0.0 I-3 100 70.0 70.0 50.0 50.0 85.0 85.0 0.0 40.0 0.0 0.0 0.0 0.0 I-4 100 85 60 80 60 80 60 0 40 0 40 40 60 I-5 100 70 40 80 60 80 60 0 40 0 40 40 60 I-6 100 70 40 60 40 80 60 0 40 0 0 0 60

Example 21 Herbicidal Activity Test of Postemergence Stem and Leaf Treatment

Sow the seeds of barnyardgrass, crabgrass crabgrass, beef tendon, mustard, retroflexus and purslane evenly respectively in pots and pots (9.5 cm in diameter) that are equipped with test soil, cover soil 0.5 cm thick, put the pots and pots at 20 Cultivate in a greenhouse at ~25°C for 10 days. During the two-leaf stage of plant growth, the preparation prepared according to formula example two will be diluted with water, and the cultivation test material will be sprayed with stems and leaves at a dose of 750g ai/ha. Regularly observe the growth status and damage symptoms of each treatment plant. The herbicidal activity of the compound was evaluated by a 5-level visual method, and the specific test results are shown in Table 4.

Table 4. Herbicidal activity evaluation of post-emergence stem and leaf treatments Compound number Dose (g ai/ha) Herbicidal activity index barnyard grass crabgrass goosegrass mustard Amaranthus retroflexus purslane I-1 750 5 5 4 5 5 4 I-2 750 5 5 4 4 5 4 I-3 750 4 5 4 4 5 4

Example 22 Herbicidal activity test of pre-emergence soil treatment

Sow the seeds of barnyardgrass, crabgrass crabgrass, beef tendon, mustard, retroflexus and purslane evenly respectively in pots and pots (diameter 9.5cm) that are equipped with test soil, cover soil 0.5cm thick, after 12 hours, the seeds will be planted according to the formula The preparation prepared by example two is diluted with water, and the soil surface treatment is carried out to the culture test material with the dosage of 750g ai/ha. Regularly observe the growth status and damage symptoms of each treatment plant. The herbicidal activity of the compound was evaluated by a 5-level visual inspection method, and the specific test results are shown in Table 5.

Table 5: Evaluation of herbicidal activity of pre-emergence soil treatments Compound number Dose (g ai/ha) Herbicidal activity index barnyard grass crabgrass goosegrass mustard Amaranthus retroflexus purslane I-1 750 4 4 4 5 5 5 I-2 750 4 4 4 4 4 4 I-3 750 4 4 4 5 5 5

Example 23 Herbicidal activity dose gradient test of post-emergence stem and leaf treatment

Using barnyardgrass, crabgrass, tendon, mustard, amaranthus and purslane as weed targets, different dose gradient experiments were carried out. The test set 3 doses. When grass weeds grow two leaves stage and broad-leaved weeds grow two true leaf stages, the preparation prepared according to formula example two is diluted with water into 3 concentrations, and cultivated at the dosage of 300, 150, 75g ai/ha The test materials were sprayed with stems and leaves. Periodic observation was performed after treatment, and the herbicidal activity of the compound was evaluated by a 5-level visual inspection method. The specific test results are shown in Table 6.

Table 6: Evaluation of the herbicidal activity of pre-emergence and post-emergence treatments Compound number Dose (g ai/ha) barnyard grass crabgrass goosegrass mustard Amaranthus retroflexus purslane before bud after bud before bud after bud before bud after bud before bud after bud before bud after bud before bud after bud I-1 75 1 5 1 4 1 4 1 5 3 5 3 5 150 1 5 1 4 1 5 1 5 3 5 3 5 300 2 5 2 4 2 5 1 5 3 5 1 5 I-2 75 1 5 1 4 1 4 1 5 3 5 3 5 150 2 5 2 5 2 5 1 5 4 5 4 5 300 3 5 3 5 3 5 2 5 4 5 4 5 1-3 75 1 4 1 4 1 4 1 4 4 5 4 4 150 1 5 1 4 1 4 1 4 4 4 4 4 300 2 5 2 5 2 5 2 5 4 5 4 5

Example 24 Crop Safety Test of Postemergence Stem and Leaf Treatment

In pots (diameter 12cm) equipped with test soil, sow conventional or hybrid varieties of cotton, rapeseed, soybean, corn, wheat, and rice, and place them in a greenhouse at 20-25°C for growth. After a certain period of growth, The preparation prepared according to formula example two is diluted with water to a certain concentration, and the test materials cultivated are sprayed with stems and leaves with three dosages of 300, 150, and 75g ai/ha. After the treatment, the growth status and damage symptoms of the plants were regularly observed, and the crop safety of the compound was evaluated by a 5-level visual inspection method. The test results are shown in Table 7, and the results showed that the compound was safe for soybeans and rice.

Table 7: Crop safety of post-emergence foliar treatments Compound number Dose (g ai/ha) corn wheat soybean cotton rape rice I-1 375 4 2 1 3 2 1 150 3 3 0 2 1 0 75 2 1 0 2 1 0 1-2 375 3 2 1 3 1 1 150 2 2 0 2 1 1 75 2 1 0 2 1 0 I-3 375 4 3 3 2 3 1 150 3 2 2 2 2 1 75 2 1 1 1 1 0

      Example 25 Safety Test of Transplanted Rice with Stem and Leaf Treatment

In the pot (diameter 12cm) that test soil is housed, transplant the paddy rice seedling of 2-3 leaf stage, be placed in 20～30 ℃ of greenhouses and grow, treat to grow to 4-5 leaf stage after, will follow formula example two The prepared preparation is diluted with water to a certain concentration, and the rice seedlings are sprayed with stems and leaves at a dose of 150g ai/ha. After the treatment, the growth status and damage symptoms of the plants were regularly observed, and the safety of the compound on rice seedlings was evaluated by a 5-level visual inspection method. The test results are shown in Table 8, and the results show that this type of compound is relatively safe to rice.

Table 8. Compounds I-1, I-2 and I-3 evaluate the safety of transplanted rice seedlings at the 4-5 leaf stage Compound number Dose (g ai/ha) Effects on Tillers dwarf leaf color I-1 150 none <10% Back to normal I-2 150 none 10-15% slightly yellow I-3 150 none 20-25% slightly yellow

Claims (8)

1, a kind of 2-2-pyrimidinyl oxy-N-amido phenyl benzylamine compound, its structural formula is as follows:

Wherein:

D or E=hydrogen, halogen, C ₁-C ₄Alkyl, C ₁-C ₄Alkoxyl group, C ₁-C ₄Haloalkyl or C ₁-C ₄Halogenated alkoxy; R ₁=hydrogen, halogen, C ₁-C ₄Alkyl or C ₁-C ₄Alkoxyl group; R ₂=H, C ₁-C ₄Alkyl, C ₁-C ₄Haloalkyl, phenyl, substituted-phenyl or heterocyclic radical, the substituting group on the described substituted-phenyl are CF ₃, described heterocyclic radical is pyridyl, thienyl, thiazolyl or pyrimidyl.

2, a kind of 2-2-pyrimidinyl oxy as claimed in claim 1-N-amido phenyl benzylamine compound is characterized in that in the described structural formula, wherein D and E are methoxyl group.

3, a kind of 2-2-pyrimidinyl oxy as claimed in claim 1-N-amido phenyl benzylamine compound is characterized in that in the described structural formula, wherein R ₂It is trifluoromethyl.

4, the preparation method of a kind of a kind of 2-2-pyrimidinyl oxy as claimed in claim 1-N-amido phenyl benzylamine compound, its feature makes by following method:

(1) be that room temperature is to solvent boiling point in solvent neutralization reaction temperature, N-amido aniline (II), salicylic aldehyde and catalyst reaction, described N-amide group aniline (II) is 1: 1 to 1: 2 with the mol ratio of salicylic aldehyde, carry out under the described situation that is reflected at catalyst-free or the mol ratio of catalyzer and N-amide group aniline (II) is 0.01-0.1, react and made intermediate (III) in 0.5～12 hour, described catalyzer is a tosic acid, methylsulfonic acid, sulfuric acid, hydrochloric acid or acetic acid, described solvent are varsol, halogenated hydrocarbon solvent, ether solvent, ketones solvent, alcoholic solvent or dimethyl formamide, methyl-sulphoxide, the mixture of acetonitrile and above-mentioned solvent.

(2) reactant (III) is 1 with the mol ratio of reductive agent: 0.5-2, and temperature of reaction is room temperature 40 degree extremely Celsius, reacts to make intermediate (IV) in 0.5 to 10 hour, described reductive agent is sodium borohydride or POTASSIUM BOROHYDRIDE;

Or reactant (III) is under the effect of catalyzer, with hydrogen reducing compound (III), made intermediate (IV) in 0.5 to 10 hour in room temperature to 40 degree reactions Celsius, catalyzer is thunder formula nickel (RaNey Ni), palladium carbon or platinum black, and the mol ratio of reactant (III), hydrogen and catalyzer is 1: 1-1000: 0.01-0.5;

(3) in organic solvent, intermediate (IV) and 2-halo .-4-D, 6-E-substituted pyrimidines or 2-methylsulfonyl-4-D, the 6-E-substituted pyrimidines reacts in the presence of alkali and made target product 2-2-pyrimidinyl oxy-N-amido phenyl benzylamine compound in 0.5 to 20 hour, intermediate (IV), 2-halo-4-D, 6-E-substituted pyrimidines or 2-methylsulfonyl-4-D, the mol ratio of 6-E-substituted pyrimidines and alkali is 1: 1.0-1.2: 1-5, described alkali is the hydride of monovalence or divalent metal, alcoxyl metallic compound or its carbonate, triethylamine, pyridine, temperature of reaction be room temperature to solvent boiling point, above-mentioned N-amido aniline (II), intermediate (III) and intermediate (IV) structural formula are as follows successively:

With

, wherein, D, E, R ₁, R ₂Or described 2-2-pyrimidinyl oxy-N-amido phenyl benzylamine compound is shown in claim 1.

5, the preparation method of a kind of 2-2-pyrimidinyl oxy as claimed in claim 5-N-amido phenyl benzylamine compound, in the described reaction of its feature (1) and (2), described solvent is an alcoholic solvent.

6, the preparation method of a kind of 2-2-pyrimidinyl oxy as claimed in claim 5-N-amido phenyl benzylamine compound, in the described reaction of its feature (1) and (2), described solvent is an ether solvent.

7, the preparation method of a kind of 2-2-pyrimidinyl oxy as claimed in claim 5-N-amido phenyl benzylamine compound, its feature final product is through silica gel column chromatography or recrystallization purifying.

8, the purposes of a kind of a kind of 2-2-pyrimidinyl oxy as claimed in claim 1-N-amido phenyl benzylamine compound is characterized in that being used for the agrochemicals weedicide.