CN1323788A - 2-pyrimidyloxy-N-amidophynylbenzyl amine, and its prepn. and use - Google Patents
2-pyrimidyloxy-N-amidophynylbenzyl amine, and its prepn. and use Download PDFInfo
- Publication number
- CN1323788A CN1323788A CN 01113199 CN01113199A CN1323788A CN 1323788 A CN1323788 A CN 1323788A CN 01113199 CN01113199 CN 01113199 CN 01113199 A CN01113199 A CN 01113199A CN 1323788 A CN1323788 A CN 1323788A
- Authority
- CN
- China
- Prior art keywords
- amido
- reaction
- compound
- yield
- pyrimidinyl oxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The present invention relates to 2-pyrimidine oxy-N-acylamino phenyl benzylamine compound, its preparation and use as agricultural herbicide, its structural formula (I) is disclosed. Where: D or E=H2, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 halogenated alkyl, C1-C4 alkoxy; R1=H2, halogen, C1-C4 alkyl, C1-C4 alkoxy; R2=H2, C1-C4 alkyl, C1-C4 halogenated alkyl, phenyl, substituted phenyl, heterocyclic compound.
Description
The present invention relates to the new 2-2-pyrimidinyl oxy of a class-N-amido phenyl benzylamine compound, preparation method and as the purposes of agrochemicals weedicide.
Agricultural chemicals is the human grain that obtains, and guarantees agriculture stable yields, the indispensable production means of getting bumper crops, and in the last hundred years, agricultural chemicals such as sterilant, sterilant, weedicide etc. have been made huge contribution for human.In recent years, continuous growth along with world population, human needs to grain are also in continuous increase, but the speed of the growth of ploughing does not catch up with population growth's speed far away, solve this global problem, must rely on the grain yield that improves unit surface and improve crop quality, this just must adopt various means, as breeding, cultivation, fertilising etc., and the application of agricultural chemicals also is one of requisite means wherein.But what should see is, agricultural chemicals is when making huge contribution for human civilization, because the limitation of understanding aspect, the agricultural chemicals of high poison, high residue has also brought negative impact to the environment that the mankind depend on for existence.Along with the raising of the progress of society and civilization, exploitation is efficient, low toxicity, easily degraded, security and the good environment friendly agricultural of Environmental compatibility, has become the direction of current novel pesticide initiative to replace those poor efficiencys, high poison, high residue and the high traditional agricultural chemicals of resistance.
2-pyrimidinyl oxy benzene analog derivative can be used as chemical herbicide early has bibliographical information, as Agr.Biol.Chem., and Vol.30, P896 (1966); Japanese Patent 79-55729; United States Patent (USP) 4,248,619 and 4,427,437.Recently, on the basis of 2-pyrimidinyl oxy benzene analog derivative, a class has the compound of excellent weeding activity--and pyrimidine salicylic acid derivative is found, as European patent 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; English Patent 2,237,570; German Patent 3,942,476 etc.Wherein representative example has: pyrithiobacsodium (Pyrithiobac-sodium, KIH-2031, European patent 315889), two careless ether (Bispyribac-sodium, KIH-2023, European patent 321846), KIH 6127 (Pyriminobac-methyl, KIH-6127, Japanese Patent 04368361), pyribenzoxim (Pyribenzoxim, European patent 658549) and ring grease grass ether (Pyriftalid, European patent 768034), their mechanism of action is identical with sulfonylurea herbicide, is the inhibitor of acetolactate synthestase (ALS), destroys plant vivo acid such as Xie Ansuan, synthesizing of leucine and Isoleucine.Though the pyrimidine salicylic acid compounds has very high weeding activity, be only applicable to the weeding of cotton field and rice terrace at present.
People such as Lv Long have reported the new 2-pyrimidinyl oxy-benzyl substituted aryl amino derivative of a class, preparation method and as agrochemicals herbicide applications (CN00130735.5 and CN01112689.2), they have very high weeding activity, and still different with above-mentioned pyrimidine salicylic acid weedicide is that they have good security to rape.Obviously, the new agricultural chemicals of exploitation is still people's research topic.
The object of the invention provides a kind of 2-2-pyrimidinyl oxy-N-amido phenyl benzylamine compound.
The object of the invention also provides a kind of preparation method of above-claimed cpd.
Another object of the present invention provides a kind of purposes of above-claimed cpd.
The structural formula of a kind of 2-2-pyrimidinyl oxy-N-amido phenyl benzylamine compound provided by the invention is shown in (I):
Wherein:
D and E can be same or different groups, are respectively hydrogen, halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Haloalkyl or C
1-C
4Halogenated alkoxy, especially preferably D and E are methoxyl group.
R
1Be hydrogen, halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, it can be in any one position in 3,4,5,6 on phenyl ring.
R
2Be hydrogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl is trifluoromethyl, phenyl or substituted-phenyl, heterocyclic radical particularly, as heterocyclic radicals such as pyridyl, thienyl, thiazolyl, pyrimidyl, wherein amido (R
2CONH-) can be in phenyl ring the neighbour, or contraposition.
Below, we list in table one with typical compound involved in the present invention.
Table one
Compound 2-2-pyrimidinyl oxy involved in the present invention-N-amido phenyl benzylamine compound can be synthetic with following reactions steps:
R in the above-mentioned reaction formula
1, R
2And D, the substituting group of E representative as previously mentioned, X is halogen or methylsulfonyl.Starting raw material N-amido aniline (II) in the reaction is by following prepared in reaction:
The synthetic N-amido aniline (II) and the salicylic aldehyde prepared in reaction passed through of intermediate (III), mol ratio is 1: 1 to 1: 2.Solvent can be varsols such as benzene, toluene or dimethylbenzene; Halogenated hydrocarbon solvents such as methylene dichloride, ethylene dichloride or chloroform; Ether solvent such as tetrahydrofuran (THF) or dioxane; Ketones solvent such as acetone or methyl iso-butyl ketone (MIBK); Alcoholic solvents such as methyl alcohol, ethanol or Virahol; Also can use the mixture of dimethyl formamide, methyl-sulphoxide, acetonitrile and above-mentioned solvent, the optimum solvent of this reaction is an alcohols.Temperature of reaction be room temperature to solvent boiling point, the reaction times is 0.5 to 12 hour.Reaction can be carried out under the situation of catalyst-free, adding catalyzer sometimes can fast reaction speed and improve reaction yield, catalyzer used in the reaction can be p-methyl benzenesulfonic acid, methylsulfonic acid, sulfuric acid, hydrochloric acid or acetic acid etc., and the mol ratio of catalyzer and N-amido aniline (II) is recommended as 0.01-0.1.
The synthetic of intermediate (IV) can make by reducing compound (III), reductive agent can be sodium borohydride or POTASSIUM BOROHYDRIDE, reactant (III) is 1 with the mol ratio of reductive agent: 0.5-2, temperature of reaction is that room temperature is to 40 degree Celsius, reaction times is 0.5 to 10 hour, and solvent can be varsols such as benzene, toluene or dimethylbenzene; Ether solvent such as tetrahydrofuran (THF) or dioxane; Methyl alcohol, alcoholic solvents such as ethanol or Virahol; Also can use the mixture of dimethyl formamide, methyl-sulphoxide, acetonitrile and above-mentioned solvent, the optimum solvent of this reaction is an alcohols.In addition, this intermediate (IV) also can make with hydrogen reducing compound (III) under the effect of catalyzer, catalyzer can be thunder formula nickel (Raney Ni), palladium carbon or platinum black etc., the mol ratio of reactant (III), hydrogen and catalyzer is 1: 1-1000: 0.01-0.5, use more hydrogen to not influence of reaction.Temperature of reaction is room temperature 40 degree extremely Celsius, and the reaction times is 0.5 to 10 hour, and solvent can be varsols such as benzene, toluene or dimethylbenzene; Ether solvent such as tetrahydrofuran (THF) or dioxane; Methyl alcohol, alcoholic solvents such as ethanol or Virahol; Also can use the mixture of dimethyl formamide, methyl-sulphoxide, acetonitrile and above-mentioned solvent, the optimum solvent of this reaction is an alcohols.
At last, with 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 makes target product (I), in this step reaction, used alkali can be hydride, alcoxyl metallic compound or its carbonate of monovalence or divalent metal, as sodium hydride, potassium hydride KH, hydrolith; Sodium methylate or sodium ethylate, potassium methylate or potassium ethylate; Yellow soda ash, salt of wormwood or lime carbonate etc. also can be organic basess such as triethylamine, pyridine.Reaction solvent can be varsols such as benzene, toluene or dimethylbenzene; Halogenated hydrocarbon solvents such as methylene dichloride, ethylene dichloride or chloroform; Ether solvent such as tetrahydrofuran (THF) or dioxane; Ketones solvent such as acetone or methyl iso-butyl ketone (MIBK); Methyl alcohol, alcoholic solvents such as ethanol or Virahol; Also can use the mixture of dimethyl formamide, methyl-sulphoxide, acetonitrile and above-mentioned solvent, the optimum solvent of this reaction is an ethers.Temperature of reaction be room temperature to solvent boiling point, the reaction times is 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.Final product can be further purified through silica gel column chromatography or recrystallization.
For more effectively actual use, with the active constituent of compound of the present invention as the chemistry of pesticide weedicide, adopt the general method of pesticide industry preparation processing, add various auxiliary agents such as entry, organic solvent, tensio-active agent, carrier, be mixed with various aquas, finish, emulsion, pulvis, granula or capsule etc., can be used for the control of weeds of farm crop such as paddy rice, soybean.
Compound of the present invention and preparation thereof have following characteristics and advantage:
1, the weeding activity that has ultra-high efficiency shows herbicidal effect preferably under low dosage.
2, have efficiently herbicidal effect behind the bud under the low dosage, cauline leaf is handled weedicide.
3, has the preceding weeding activity of bud under the high dosage.
4, the grass spectrum is wider extremely, can not only effectively prevent and kill off gramineous weeds in the farmland, and can prevent and kill off broadleaf weeds and nutgrass flatsedge.
5, crop is had higher security, as safe as a house to soybean, paddy rice especially.
6, above the average age for marriage gramineous weeds (3-7 leaf) also had highly effective weeding activity.
7, residual period, is short in soil, and the growth of crop rotation succession crop is had no adverse effects.
8, Mammals or fish are not had significant toxicity, have higher environmental safety, belong to the environmentally friendly agricultural chemicals of low toxicity.
Structural formula provided by the present invention is the compound of (I), simple synthetic method not only, and weeding activity is arranged, can be used for weedicide.Its preparation can be prevented and treated most of farmland weeds effectively, low dosage is is effectively prevented and treated gramineous weeds down, high dosage is is effectively prevented and treated broadleaf weeds and nutgrass flatsedge down, and concrete controlling object comprises barnyard grass grass (Echinochloa crusgalli), lady's-grass (Digitaria sanguinalis), Herba Eleusines Indicae (Eleusine indica), Herba Setariae Viridis (Setaria viridis), annual bluegrass (Poa annua), wild avena sativa (Avena fatua), amur foxtail (Alopecurus aequalis), Japan amur foxtail (Alopecurus japonicus), Amaranthus retroflexus (Amaranthus retroflexus), thorn amaranth (Amaranthus spinosus), lamb's-quarters (Chenopodium album), leaf mustard (Brassica juncea), purslane (Portulaca oleracea), Herba Acalyphae (Acalypha australis), Herba Cyperi Difformis (Cyperus difformis), Semen Euphorbiae (Leptochloachinensis), Rhizoma Cyperi (Cyperus rotundus), grass (Fimbristylis miliacea) floats sunshine, chickweed (Stallaria media), Stellaria alsine Grim. (Stellaria alsine), Herba Erigerontis Annui (Erigeron annuus), short arrowhead (Sagittariasagittifolia), Herba seu Flos Convolvuli arvensis (Convolvulus arvensis) etc.
Put up with the part example below and provide the required analytical data of detailed reaction conditions, purification process, physical constant and structural confirmation, it is to be noted that the present invention not merely is confined in the scope of following embodiment.
Embodiment one: (compound number I-1 in the table one)
27.6 gram (0.2mol) p-Nitroaniline are dissolved in the 200mL tetrahydrofuran (THF), add 55.2 gram (0.4mol) Anhydrous potassium carbonates and 42.6 gram (0.4mol) isobutyryl chlorides, at room temperature stirred 5 hours, reaction solution is poured in the 100mL10% hydrochloric acid, use the extracted with diethyl ether organic phase, obtain yellow solid to different propionamido oil of mirbane, yield 83.2%.
31.2 grams (0.15mol) to different propionamido oil of mirbane, are dissolved in the 200mL anhydrous methanol, add an amount of Raney-Ni and 40mL hydrazine hydrate, reaction is 6 hours under the room temperature, and suction filtration gets filtrate, concentrates filtrate to different propionamido aniline, yield 96%.
17.8 grams (0.1mol) are dissolved in the 200mL anhydrous methanol different propionamido aniline, drip 14.6 gram (0.12mol) salicylic aldehydes, at room temperature stirring reaction is after 50 minutes, filter, solid washs with anhydrous methanol, gets 26.4 gram yellow solids (III-1), yield 93.6%.
Get the above-mentioned compound that makes (III-1) 14.1 grams (0.05mol), be dissolved in the 250mL anhydrous methanol, at room temperature add 1.89 gram (0.05mol) sodium borohydrides in batches, stirring reaction is 20 minutes under the room temperature, concentrates to remove methyl alcohol, adds chloroform 200mL then in residue, water 150mL, stir, leave standstill, tell organic layer, wash with water, anhydrous sodium sulfate drying, concentrate 13.8 gram white solids (IV-1), yield 97.6%.
Get compound (IV-1) 2.84 grams (0.01mol) that make above, 2-methylsulfonyl-4,6-dimethoxypyridin 2.18 grams (0.01mol), be dissolved in the 100mL dioxane, add 2.76 gram (0.02mol) salt of wormwood under the room temperature, back flow reaction 11 hours, suction filtration, filter cake washs with the 20mL dioxane, mother liquor concentrates, and bottom product adds 10mL ethanol and stirs, and suction filtration gets 3.7 gram white solid product 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-and N-(the different propionamido phenyl of 4-) benzylamine (I-1), yield 90.1%.m.p.:134.1-134.7℃；m/z:422(M
+)；
1HNMR:δ6.96-7.49(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。Ultimate analysis: calculated value: C, 65.39; H, 6.20; N, 13.26;
Measured value: C, 65.39; H, 6.06; N, 13.40;
Embodiment two: (compound number I-2 in the table one)
27.6 gram (0.2mol) p-Nitroaniline are dissolved in the 200mL tetrahydrofuran (THF), add 55.2 gram (0.4mol) Anhydrous potassium carbonates and 56.2 gram (0.4mol) Benzoyl chlorides, at room temperature stirred 5 hours, reaction solution is poured in the 100mL10% hydrochloric acid, use the extracted with diethyl ether organic phase, obtain yellow solid benzoyl amino aniline, yield 78.2%.
29 grams (0.12mol) to the amino oil of mirbane of benzoyl, are dissolved in the 200mL anhydrous methanol, add an amount of Raney-Ni and 38mL hydrazine hydrate, reaction is 6 hours under the room temperature, and suction filtration gets filtrate, concentrates filtrate to the benzoyl amino aniline, yield 93.2%.
24.2 grams (0.1mol) are dissolved in the 200mL anhydrous methanol the benzoyl amino aniline, drip 14.6 gram (0.12mol) salicylic aldehydes, at room temperature stirring reaction is after 50 minutes, filter, solid washs with anhydrous methanol, gets 28.4 gram yellow solids (III-2), yield 90%.
Get the above-mentioned compound that makes (III-2) 15.8 grams (0.05 mole), be dissolved in the 250mL anhydrous methanol, at room temperature add 1.89 gram (0.05mol) sodium borohydrides in batches, stirring reaction is 20 minutes under the room temperature, concentrates to remove methyl alcohol, adds chloroform 200mL then in residue, water 150mL, stir, leave standstill, tell organic layer, wash with water, anhydrous sodium sulfate drying, concentrate 15.2 gram white solids (IV-2), yield 96%.
Get compound (IV-2) 3.18 grams (0.01mol) that make above, 2-methylsulfonyl-4,6-dimethoxypyridin 2.18 grams (0.01mol), be dissolved in the 100mL dioxane, add 2.76 gram (0.02mol) salt of wormwood under the room temperature, back flow reaction 11 hours, suction filtration, filter cake washs with the 20mL dioxane, mother liquor concentrates, and bottom product adds 10mL ethanol and stirs, and suction filtration gets 4.06 gram white solid product 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-and N-(4-benzamido phenyl) benzylamine (I-2), yield 89%.m.p.:152.8-153.4℃；m/z:456(M
+)；
1HNMR: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。Ultimate analysis: calculated value: C, 68.41; H, 5.30; N, 12.27;
Measured value: C, 67.70; H, 5.34; N, 12.12;
Embodiment three: (compound number I-3 in the table one)
27.6 gram (0.2mol) p-Nitroaniline are dissolved in the 200mL trifluoracetic acid, add 84 gram (0.4mol) trifluoroacetic anhydride (TFAA)s, reflux 3 hours, reaction solution is poured in the 500mL frozen water, have precipitation to generate, filter, solid washs with normal hexane, get 39.8 gram solids to fluoroform amido oil of mirbane, yield 85.2%.
35.1 grams (0.15mol) to fluoroform amido oil of mirbane, are dissolved in the 200mL anhydrous methanol, add an amount of Raney-Ni and 40mL hydrazine hydrate, reaction is 6 hours under the room temperature, and suction filtration gets filtrate, concentrates filtrate to fluoroform amido aniline, yield 94%.
20.4 grams (0.1mol) are dissolved in the 200mL anhydrous methanol fluoroform amido aniline, drip 14.6 gram (0.12mol) salicylic aldehydes, at room temperature stirring reaction is after 50 minutes, filter, solid washs with anhydrous methanol, gets 28.3 gram yellow solids (III-3), yield 92%.
Get the above-mentioned compound that makes (III-3) 15.4 grams (0.05 mole), be dissolved in the 250mL anhydrous methanol, at room temperature add 1.89 gram (0.05mol) sodium borohydrides in batches, stirring reaction is 20 minutes under the room temperature, concentrates to remove methyl alcohol, adds chloroform 200mL then in residue, water 150mL, stir, leave standstill, tell organic layer, wash with water, anhydrous sodium sulfate drying, concentrate 14.8 gram white solids (IV-3), yield 96%.
Get compound (IV-3) 3.1 grams (0.01mol) that make above, 2-methylsulfonyl-4,6-dimethoxypyridin 2.18 grams (0.01mol), be dissolved in the 100mL dioxane, add 2.76 gram (0.02mol) salt of wormwood under the room temperature, back flow reaction 11 hours, suction filtration, filter cake washs with 20 milliliters of dioxane, mother liquor concentrates, and bottom product adds 10 milliliters of ethanol and stirs, and suction filtration gets 3.94 gram white solid product 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-and N-(4-fluoroform amido phenyl) benzylamine (I-3), yield 88%.m.p.:159.0-159.6℃?m/z:448(M
+)；
1HNMR：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。Ultimate analysis: calculated value: C, 56.25; H, 4.27; N, 12.49;
Measured value: C, 56.37; H, 4.27; N, 12.54;
Embodiment four: (compound number I-4 in the table one)
27.6 gram (0.2mol) p-Nitroaniline are dissolved in the 200mL acetic acid, add 40.8 gram (0.4mol) aceticanhydrides, reflux 3 hours, reaction solution is poured in the 500mL frozen water, had precipitation to generate, filter, solid washs with normal hexane, gets 30.9 gram solids to formamido group oil of mirbane, yield 86%.
27 grams (0.15mol) to formamido group oil of mirbane, are dissolved in the 200mL anhydrous methanol, add an amount of Raney-Ni and 40mL hydrazine hydrate, reaction is 6 hours under the room temperature, and suction filtration gets filtrate, concentrates filtrate to formamido group aniline, yield 94%.
15 grams (0.1mol) are dissolved in the 200mL anhydrous methanol formamido group aniline, drip 14.6 gram (0.12mol) salicylic aldehydes, at room temperature stirring reaction filtered after 50 minutes, and solid washs with anhydrous methanol, got 23.3 gram yellow solids (III-4), yield 92%.
Get the above-mentioned compound that makes (III-4) 12.7 grams (0.05mol), be dissolved in the 250mL anhydrous methanol, at room temperature add 1.89 gram (0.05mol) sodium borohydrides in batches, stirring reaction is 20 minutes under the room temperature, concentrates to remove methyl alcohol, adds chloroform 200mL then in residue, water 150mL, stir, leave standstill, tell organic layer, wash with water, anhydrous sodium sulfate drying, concentrate 12.5 gram white solids (IV-4), yield 98%.
Get compound (IV-4) 2.56 grams (0.01mol) that make above, 2-methylsulfonyl-4,6-dimethoxypyridin 2.18 grams (0.01mol), be dissolved in the 100mL dioxane, add 2.76 gram (0.02mol) salt of wormwood under the room temperature, back flow reaction 11 hours, suction filtration, filter cake washs with the 20mL dioxane, mother liquor concentrates, and bottom product adds 10mL ethanol and stirs, and suction filtration gets 3.35 gram white solid product 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-and N-(4-formamido group phenyl) benzylamine (I-4), yield 85%.m.p.:162.0-162.8℃；m/z:394(M
+)；
1HNMR: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。Ultimate analysis: calculated value: C, 63.95; H, 5.62; N, 14.20;
Measured value: C, 64.49; H, 5.78; N, 13.80;
Embodiment five: (compound number I-5 in the table one)
27.6 gram (0.2mol) p-Nitroaniline are dissolved in the 200ml tetrahydrofuran (THF), add 55.2 gram (0.4mol) Anhydrous potassium carbonates and 58.6 gram (0.4mol) 2-thiophene chlorides, at room temperature stirred 5 hours, reaction solution is poured in the 100mL10% hydrochloric acid, use the extracted with diethyl ether organic phase, obtain yellow solid to (2-thiophene) amido oil of mirbane, yield 83.2%.
37.2 grams (0.15mol) to (2-thiophene) amido oil of mirbane, are dissolved in the 200mL anhydrous methanol, add an amount of Raney-Ni and 40mL hydrazine hydrate, reaction is 6 hours under the room temperature, and suction filtration gets filtrate, it is to (2-thiophene) amido aniline that filtrate concentrating obtained product, yield 96%.
21.8 grams (0.1mol) are dissolved in the 200mL anhydrous methanol (2-thiophene) amido aniline, drip 14.6 gram (0.12mol) salicylic aldehydes, at room temperature stirring reaction is after 50 minutes, filter, solid washs with anhydrous methanol, gets 29.3 gram yellow solids (III-5), yield 91%.
Get above-mentioned (III-5) that makes 16.1 grams (0.05mol), be dissolved in the 250mL anhydrous methanol, at room temperature add 1.89 gram (0.05mol) sodium borohydrides in batches, stirring reaction is 20 minutes under the room temperature, concentrates to remove methyl alcohol, adds chloroform 200mL then in residue, water 150mL, stir, leave standstill, tell organic layer, wash with water, anhydrous sodium sulfate drying, concentrate 15.7 gram white solids (IV-5), yield 97.6%.
Get compound (IV-5) 3.24 grams (0.01mol) that make above, 2-methylsulfonyl-4,6-dimethoxypyridin 2.18 grams (0.01mol), be dissolved in the 100mL dioxane, add 2.76 gram (0.02mol) salt of wormwood under the room temperature, back flow reaction 11 hours, suction filtration, filter cake washs with the 20mL dioxane, mother liquor concentrates, and bottom product adds 10mL ethanol and stirs, and suction filtration gets 3.88 gram white solid product 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-and N-[4-(2-thiophene amido) phenyl] benzylamine (I-5), yield 85%.m.p.:147.3-147.9℃；m/z:464(M
+)；
1HNMR: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。Ultimate analysis: calculated value: C, 62.05; H, 5.21; N, 12.06;
Measured value: C, 62.21; H, 4.73; N, 12.13;
Embodiment six: (table-middle compound number I-6)
27.6 gram (0.2mol) p-Nitroaniline are dissolved in the 200mL tetrahydrofuran (THF), add 55.2 gram (0.4mol) Anhydrous potassium carbonates and 83.4 gram (0.4mol) m-trifluoromethyl benzoyl chlorides, at room temperature stirred 5 hours, reaction solution is poured in the 100mL10% hydrochloric acid, use the extracted with diethyl ether organic phase, obtain yellow solid to (3-trifluoromethyl) amido oil of mirbane, yield 83.2%.
Restrain (0.15mol) to (3-trifluoromethyl amido oil of mirbane is dissolved in the 200mL anhydrous methanol, adds an amount of Raney-Ni and 40mL hydrazine hydrate with 46.5, reaction is 6 hours under the room temperature, and suction filtration gets filtrate, concentrate filtrate to (3-trifluoromethyl) amido aniline, yield 96%.
28 grams (0.1mol) are dissolved in the 200mL anhydrous methanol (3-trifluoromethyl) amido aniline, drip 14.6 gram (0.12mol) salicylic aldehydes, at room temperature stirring reaction is after 50 minutes, filter, solid washs with anhydrous methanol, gets 30.7 gram yellow solids (III-6), yield 80%.
Get the above-mentioned compound that makes (III-6) 19.2 grams (0.05mol), be dissolved in the 250mL anhydrous methanol, at room temperature add 1.89 gram (0.05mol) sodium borohydrides in batches, stirring reaction is 20 minutes under the room temperature, concentrates to remove methyl alcohol, adds chloroform 200mL then in residue, water 150mL, stir, leave standstill, tell organic layer, wash with water, anhydrous sodium sulfate drying, concentrate 18.5 gram white solids (IV-6), yield 96%.
Get compound (IV-6) 3.86 grams (0.01mol) that make above, 2-methylsulfonyl-4,6-dimethoxypyridin 2.18 grams (0.01mol), be dissolved in the 100mL dioxane, add 2.76 gram (0.02mol) salt of wormwood under the room temperature, back flow reaction 11 hours, suction filtration, filter cake washs with the 20mL dioxane, mother liquor concentrates, and bottom product adds 10mL ethanol and stirs, and suction filtration gets 4.29 gram white solid product 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-and N-[4-(3-trifluoromethyl benzamido) phenyl] benzylamine (I-6), yield 82%.m.p.:150.1-150.7℃；m/z:524(M
+)；
1HNMR: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。Ultimate analysis: calculated value: C, 61.83; H, 4.42; N, 10.68;
Measured value: C, 61.85; H, 4.46; N, 10.67;
Embodiment seven: (compound number I-7 in the table one)
27.6 gram (0.2mol) p-Nitroaniline are dissolved in the 200mL tetrahydrofuran (THF), add 55.2 gram (0.4mol) Anhydrous potassium carbonates and 42.6 gram (0.4mol) isobutyryl chlorides, at room temperature stirred 5 hours, reaction solution is poured in the 100mL10% hydrochloric acid, use the extracted with diethyl ether organic phase, obtain the amino oil of mirbane of yellow solid isobutyryl, yield 83.2%.
2.6 grams (12.5mmol) to the amino oil of mirbane of isobutyryl, are dissolved in the 10mL anhydrous methanol, add an amount of 0.2 gram Raney-Ni and 1.1 gram (18.8mmol, 85%) hydrazine hydrate, reaction is 6 hours under the room temperature, suction filtration, get filtrate, filtrate concentrating obtained to the isobutyryl amino aniline yield 96%.
2.14 grams (12mmol) are dissolved in the 200mL dehydrated alcohol the isobutyryl amino aniline, add 2.19 gram (14.4mmol) O-VANILLINs, at room temperature stirring reaction is complete, TLC controls reaction end, filter, the solid absolute ethanol washing gets 3.70 gram yellow solids (III-7), yield 98.8%.
Get the above-mentioned compound that makes (III-7) 3.7 grams (11.86mmol), be dissolved in the 20mL dehydrated alcohol, at room temperature add 0.7 gram (17.8mmol) sodium borohydride in batches, stirring reaction is 30 minutes under the room temperature, reactant is poured in the frozen water, filtered drying, get 3.3 and digest compound (IV-7), yield 88.7%.
Get compound (IV-7) 3.14 grams (10mmol) that make above, 2-methylsulfonyl-4,6-dimethoxypyridin 2.18 grams (10mmol), be dissolved in the 30mL dioxane, add 2.76 gram (20mmol) salt of wormwood under the room temperature, back flow reaction 11 hours, suction filtration, filter cake washs with the 20mL dioxane, and mother liquor concentrates, and bottom product adds 10mL ethanol and stirs, suction filtration gets 4.0 gram white solid product 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-and 3-methoxyl group-N-(4-isobutyryl aminophenyl) benzylamine (I-7), yield 89.0%, re-crystallizing in ethyl acetate gets pure product.m.p.:171.5-172.5℃；m/z:108(M
+,100)；
1HNMR:δ0.87-0.90(6H,d,CH
3,
3J
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,
3J
HH=5.4Hz),4.91-5.0(1H,s,NH),5.59(1H,s,CH),6.21-6.35(2H,d,
3J
HH=6.7Hz),6.71-6.84(2H,m),6.86-6.99(1H,t,
3J
HH=7.8Hz),7.05-7.1(2H,d),8.35-8.45(1H,s,NH)ppm。IR:3381(V
NHCO),3327(V
NHCH2),1664(V
CO)cm
-1。Ultimate analysis: calculated value: C, 63.70; H, 6.24; N, 12.38;
Measured value: C, 63.79; H, 6.55; N, 12.41;
Embodiment eight: (compound number I-8 in the table one)
1.38 gram (10mmol) p-Nitroaniline are dissolved in the 10mL Glacial acetic acid, at room temperature drip 1.88mL (20mmol) diacetyl oxide lentamente, reflux 30 minutes, be cooled to room temperature, join in the frozen water, filter, frozen water is washed till neutrality, dry 1.69 gram products, the yield 93.8% of getting.
With 1.69 gram (9.38mmol) acetparaminosalol oil of mirbane, be dissolved in the 10mL anhydrous methanol, add an amount of 0.13 gram Raney-Ni and 0.83 gram (14.1mmol, 85%) hydrazine hydrate, reaction is 6 hours under the room temperature, and suction filtration gets filtrate, it is acetparaminosalol aniline that filtrate concentrating obtained product, yield 100%.
1.41 gram (9.37mmol) acetparaminosalol aniline are dissolved in the 15mL dehydrated alcohol, add 1.71 gram (11.4mmol) O-VANILLINs, at room temperature stirring reaction is complete, TLC controls reaction end, filters the solid absolute ethanol washing, get 2.18 gram yellow solids (III-8), yield 81.8%.
Get the above-mentioned compound that makes (III-8) 2.18 grams (7.665mmol), be dissolved in the 20mL dehydrated alcohol, at room temperature add 0.445 gram (11.5mmol in batches, 96%) sodium borohydride, stirring reaction is 30 minutes under the room temperature, and reactant is poured in the frozen water, filter, drying gets 2.19 and digests compound (IV-8), yield 100%.
Get compound (IV-8) 2.19 grams (7.66mmol) that make above, 2-methylsulfonyl-4,6-dimethoxypyridin 1.67 grams (7.66mmol), be dissolved in the 30mL dioxane, add 2.12 gram (15.3mmol) salt of wormwood under the room temperature, back flow reaction 11 hours, suction filtration, filter cake washs with the 20mL dioxane, and mother liquor concentrates, and bottom product adds 10mL ethanol and stirs, suction filtration gets 2.83 gram white solid product 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-and 3-methoxyl group-N-(4-acetylamino phenyl) benzylamine (I-8), yield 87.0% gets pure product with re-crystallizing in ethyl acetate.m.p.:169.8-170.8℃；m/z:150(M
+,100)；
1HNMR: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,
3J
HH=5.64Hz),4.95-5.0(1H,s,NH),5.09(1H,s,CH),6.2-6.3(2H,d,
3J
HH=6.75Hz),6.71-6.83(2H,m),6.85-6.95(1H,t,
3J
HH=7.2Hz),7.0-7.08(2H,d,
3J
HH=2.1Hz),8.5(1H,s,NH)ppm。IR:3368(V
NH),1670(V
CO)cm
-1。Ultimate analysis: calculated value: C, 62.25; H, 5.70; N, 13.20;
Measured value: C, 61.86; H, 5.71; N, 13.10;
Embodiment nine: (compound number I-9 in the table one)
Adopt m-nitraniline as starting raw material, experimental procedure is with embodiment four in detail: 3-formamido group oil of mirbane, yield 82%; 3-formamido group aniline (II-9), yield 95%; 2-hydroxy-n-(3-formamido group phenyl) benzyl imines (III-9), yield 88%; 2-hydroxy-n-(3-formamido group phenyl) benzylamine (IV-9), yield 98%; 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-N-(3-formamido group phenyl) benzylamine (I-4), yield 85%; M.p.141-142 ℃; M/z=394 (M
+);
1H NMR: δ 6.70-7.54 (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; Ultimate analysis: calculated value, C:63.95; H:5.62; N:14.20;
Measured value: C:63.97; H:5.63; N:14.06.
Embodiment ten: (compound number I-10 in the table one)
Adopt m-nitraniline as starting raw material, in detail experimental procedure with the embodiment example-: the different propionamido oil of mirbane of 3-, yield 88%; The different propionamido aniline of 3-(II-10), yield 95%; 2-hydroxy-n-(the different propionamido phenyl of 3-) benzyl imines (III-10), yield 89.5%; 2-hydroxy-n-(the different propionamido phenyl of 3-) benzylamine (IV-10), yield 95%; 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-N-(the different propionamido phenyl of 3-) benzylamine (I-10), yield 80%.M/z:422 (M
+);
1HNMR: δ 6.90-7.68 (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; Ultimate analysis: calculated value: C, 65.39; H, 6.20; N, 13.26;
Measured value: C, 65.28; H, 6.10; N, 13.44;
Embodiment 11: (table-middle compound number I-11)
Adopt m-nitraniline as starting raw material, experimental procedure is same as embodiment two in detail: 3-benzoyl amino aniline, yield 78.2%; 3-benzoyl amino aniline (II-11), yield 93.2%; 2-hydroxy-n-(3-benzamido phenyl) benzyl imines (III-11), yield 86%; 2-hydroxy-n-(3-benzamido phenyl) benzylamine (IV-11), yield 98%; 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-N-(3-benzamido phenyl) benzylamine (I-11), yield 84%; M/z:456 (M
+);
1HNMR: δ 7.00-8.05 (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; Ultimate analysis: calculated value: C, 68.41; H, 5.30; N, 12.27;
Measured value: C, 68.16; H, 5.35; N, 12.29;
Embodiment 12: (compound number I-12 in the table one)
Adopt m-nitraniline as starting raw material, experimental procedure is with embodiment three in detail: 3-fluoroform amido oil of mirbane, yield 90%; 3-fluoroform amido aniline (II-12), yield 93%; 2-hydroxy-n-(3-fluoroform amido phenyl) benzyl imines (III-12), yield 90%; 2-hydroxy-n-(3-fluoroform amido phenyl) benzylamine (IV-12), yield 94%; 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-N-(3-fluoroform amido phenyl) benzylamine (I-12), yield 85%.m/z:448(M
+)；
1HNMR: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。Ultimate analysis: calculated value: C, 56.25; H, 4.27; N, 12.49;
Measured value: C, 56.40; H, 4.22; N, 12.58;
Embodiment 13: (table-middle compound number I-13)
Adopt o-Nitraniline as starting raw material, experimental procedure is with embodiment four in detail: 2-formamido group oil of mirbane, yield 89%; 2-formamido group aniline (II-13), yield 94%; 2-hydroxy-n-(2-formamido group phenyl) benzyl imines (III-13), yield 84%; 2-hydroxy-n-(2-formamido group phenyl) benzylamine (IV-13), yield 97%; 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-N-(2-formamido group phenyl) benzylamine (I-13), yield 80%; M/z=394 (M
+);
1HNMR: δ 6.67-7.52 (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; Ultimate analysis: calculated value, C:63.95; H:5.62; N:14.20;
Measured value: C:63.88; H:5.60; N:14.24.
Embodiment 14: (compound number I-14 in the table one)
Adopt o-Nitraniline as starting raw material, experimental procedure is with the different propionamido oil of mirbane of embodiment one: 2-, yield 92% in detail; The different propionamido aniline of 2-(II-14), yield 97%; 2-hydroxy-n-(the different propionamido phenyl of 2-) benzyl imines (III-14), yield 86%; 2-hydroxy-n-(the different propionamido phenyl of 2-) benzylamine (IV-14), yield 99%; 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-N-(the different propionamido phenyl of 2-) benzylamine (I-14), yield 79%.M/z:422 (M
+);
1HNMR: δ 6.84-7.65 (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; Ultimate analysis: calculated value: C, 65.39; H, 6.20; N, 13.26;
Measured value: C, 65.30; H, 6.15; N, 13.40;
Embodiment 15: (compound number I-15 in the table one)
Adopt o-Nitraniline as starting raw material, experimental procedure is with embodiment two in detail: 2-benzoyl amino aniline, yield 86%; 2-benzoyl amino aniline (II-15), yield 96%; 2-hydroxy-n-(2-benzamido phenyl) benzyl imines (III-15), yield 83%; 2-hydroxy-n-(2-benzamido phenyl) benzylamine (IV-15), yield 96%; 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-N-(4-benzamido phenyl) benzylamine (I-15), yield 82%; M/z:456 (M
+);
1HNMR: δ 7.10-8.09 (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; Ultimate analysis: calculated value: C, 68.41; H, 5.30; N, 12.27;
Measured value: C, 68.36; H, 5.34; N, 12.20;
Embodiment 16: (compound number I-16 in the table one)
Adopt o-Nitraniline as starting raw material, experimental procedure is with embodiment three in detail: 2-fluoroform amido oil of mirbane, yield 88%; 2-fluoroform amido aniline (II-16), yield 91%; 2-hydroxy-n-(2-fluoroform amido phenyl) benzyl imines (III-16), yield 84%; 2-hydroxy-n-(2-fluoroform amido phenyl) benzylamine (IV-16), yield 90%; 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy)-N-(2-fluoroform amido phenyl) benzylamine (I-12), yield 82%.m/z:448(M
+)；
1HNMR: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。Ultimate analysis: calculated value: C, 56.25; H, 4.27; N, 12.49;
Measured value: C, 56.30; H, 4.42; N, 12.68;
Embodiment 17 (wettable powder agent prescription)
Following examples 17 to embodiment 23 provide with compound of the present invention as the active substance component, and the concrete instance of processing preparation several herbicides formulation it is to be noted that the present invention not merely is confined in the scope of following example.In these prescription examples, all " % " all refer to weight percent, and " g ai/ha " all refers to every gram actives/hectare.
Compound with 15% (I-1) (table one), 5% sulfonated lignin (M
q), 1% ethoxylated dodecyl alcohol (JFC), 40% diatomite and 44% light calcium carbonate mix equably, pulverizes, and promptly gets wettable powder.
Embodiment 18 (emulsifiable concentrate formulation)
No. 602, the compound with 10% (I-1) (table one), 5% farming breast No. 500 (calcium salts), 5% farming breast, 5% N-N-methyl-2-2-pyrrolidone N-and 75% dimethylbenzene heated and stirred are even, promptly get missible oil.
Embodiment 19 (granula prescription)
Compound with 5% (I-1) (table 1), 1% polyvinyl alcohol (PVA), 4% naphthalenesulfonic acid-formaldehyde condensate (NMO) and 90% clay mix equably; pulverize; add 20 parts of water to these 100 parts of mixtures then; mediate; with the extruding granulator; make 14-32 purpose particle, drying promptly gets granule.
Provide below and use compound of the present invention to carry out the example of biological activity determination, it is to be noted that the present invention not merely is confined in the scope of following example.
5 grades of appearance method judgement criterias of weeding activity and crop safety (being phytotoxicity) are listed in table two.
Table two, weeding activity and phytotoxicity evaluating standard
| Grading index | Phytotoxicity (%) | Weeding activity comment (inhibition, deformity, albefaction etc.) | Crop safety comment (inhibition, deformity, albefaction etc.) |
| ????0 | ?????0 | With contrast, anti-, eliminate | With contrast, anti-, normal |
| ????1 | ????10-20 | Gently, influential slightly, eliminate | Gently, influential slightly, can consider |
| ????2 | ????30-40 | Gently, influential, eliminate | Sensitivity, influential, eliminate |
| ????3 | ????50-60 | Sensitivity, influential, can consider further transformation | Responsive, poisoning is heavy, eliminates |
| ????4 | ????70-80 | Responsive, can consider | Extremely responsive, poisoning is heavy, eliminates |
| ????5 | ????90-100 | Extremely responsive, good | Extremely responsive, poisoning is heavy, eliminates |
Embodiment 20 weedicide wares are surveyed the weeding activity test
With wheat, barnyard grass grass, jowar, rape, radish, cucumber is model animals, the seed of each target is put into culture dish, adding concentration is the medicament 9mL of 100mg/L, put into 25 ℃, cultivate in the growth chamber of RH75%, the extent of injury of range estimation target plant after 7 days, concrete test-results sees Table three.Table three, weedicide ware are surveyed the weeding activity test
| Zhejiang institute compound number | Concentration ppm | Wheat | The barnyard grass grass | Jowar | 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 |
The weeding activity test that cauline leaf is handled behind embodiment 21 seedlings
Be equipped with test with the basin alms bowl of soil in (diameter 9.5cm) sow the seed of barnyard grass, lady's-grass, Cowhells, leaf mustard, Amaranthus retroflexus and purslane respectively equably, overburden soil 0.5cm is thick, the basin alms bowl is placed 20～25 ℃ greenhouse cultivation 10 days.During the plant strain growth two leaf stage, will be according to the preparation dilute with water of formulation examples two preparation, carry out the cauline leaf spraying and handle cultivating the examination material with the dosage of 750g ai/ha.Routine observation is respectively handled the plant strain growth state, the symptom of being injured.The weeding activity of 5 grades of appearance method assessing compounds, concrete test-results sees Table four.
The weeding activity evaluation that cauline leaf is handled behind table four, the seedling
| Compound number | Dosage (g ai/ha) | The weeding activity index | |||||
| The barnyard grass grass | Lady's-grass | Herba Eleusines Indicae | Leaf 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 |
The weeding activity of soil treatment test before embodiment 22 seedlings
Be equipped with test with native basin alms bowl in (diameter 9.5cm) sow the seed of barnyard grass, lady's-grass, Cowhells, leaf mustard, Amaranthus retroflexus and purslane respectively equably, overburden soil 0.5cm is thick, will be after 12 hours according to the preparation dilute with water of formulation examples two preparation, carry out soil surface and handle cultivating the examination material with the dosage of 750gai/ha.Routine observation is respectively handled the plant strain growth state, the symptom of being injured.The weeding activity of 5 grades of appearance method assessing compounds, concrete test-results sees Table five.
Table five: the weeding activity evaluation of soil treatment before the seedling
| Compound number | Dosage (gai/ha) | The weeding activity index | |||||
| The barnyard grass grass | Lady's-grass | Herba Eleusines Indicae | Leaf 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 |
The weeding activity dosage gradient test that cauline leaf is handled behind embodiment 23 seedlings
With barnyard grass grass, lady's-grass, Cowhells, leaf mustard, Amaranthus retroflexus and purslane is the weeds target, carries out the test of various dose gradient.Test is provided with 3 grades of dosage.When gramineous weeds growth two leaf stage, 2 leaf periods of broadleaf weeds growth, will be diluted with water to 3 concentration according to the preparation of formulation examples two preparations, with 300,150, the dosage of 75gai/ha carries out the cauline leaf spraying to the examination material of cultivating and handle.Handle the back routine observation, the weeding activity of 5 grades of appearance method assessing compounds, concrete test-results sees Table six.
Table six: the weeding activity of seedling aftertreatment size is estimated before the seedling
| Compound number | Dosage (gai/ha) | The barnyard grass grass | Lady's-grass | Herba Eleusines Indicae | Leaf mustard | Amaranthus retroflexus | Purslane | ||||||
| Before the bud | Behind the bud | Before the bud | Behind the bud | Before the bud | Behind the bud | Before the bud | Behind the bud | Before the bud | Behind the bud | Before the bud | Behind the 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 | |
| ????Ⅰ-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 | |
The crop safety test that cauline leaf is handled behind embodiment 24 seedlings
In the basin alms bowl (diameter 12cm) that test soil is housed, routine or the Hybrid of difference sowing cotton, rape, soybean, corn, wheat, paddy rice, place 20～25 ℃ of greenhouses to grow, after waiting to grow into the certain period, to be finite concentration according to the preparation dilute with water of formulation examples two preparation, with 300,150, three dosage of 75gai/ha carry out the cauline leaf spraying to the examination material of cultivating and handle.Handle the back routine observation plant strain growth state and the symptom of being injured, with the crop safety of 5 grades of appearance method assessing compounds, test-results sees Table seven, and the result shows that this compounds is to soybean, rice safety.
Table seven: the crop safety of the back foliar treatment of emerging
| Compound number | Dosage (gai/ha) | Corn | Wheat | Soybean | Cotton | Rape | Paddy rice |
| ??Ⅰ-1 | ????375 | ????4 | ????2 | ????1 | ????3 | ????2 | ????1 |
| ????150 | ????3 | ????3 | ????0 | ????2 | ????1 | ????0 | |
| ????75 | ????2 | ????1 | ????0 | ????2 | ????1 | ????0 | |
| ??Ⅰ-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 |
The transplanting rice safety testing that embodiment 25 cauline leafs are handled
In the basin alms bowl (diameter 12cm) that test soil is housed, transplant the rice seedling of 2-3 leaf phase, place 20～30 ℃ of greenhouses to grow, wait to grow into 4-5 leaf after date, to be finite concentration according to the preparation dilute with water of formulation examples two preparations, and with 150gai/ha dosage rice seedling be carried out the cauline leaf spraying and handle.Handle the back routine observation plant strain growth state and the symptom of being injured, with the security of 5 grades of appearance method assessing compounds to the paddy rice seedling, test-results sees Table eight, and the result shows that this compounds is safer to paddy rice.
Table eight, chemical compounds I-1, I-2 and I-3 pair 4-5 leaf phase transplanting rice seedling safety evaluation
| Compound number | Dosage (gai/ha) | To the influence of tillering | Downgrade | The leaf look |
| ????Ⅰ-1 | ????150 | Do not have | ＜10％ | Recover normal |
| ????Ⅰ-2 | ????150 | Do not have | 10-15％ | Yellow slightly |
| ????Ⅰ-3 | ????150 | Do not have | 20-25％ | Yellow slightly |
Claims (9)
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.
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, 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 that described heterocyclic radical is pyridyl, thienyl, thiazolyl or pyrimidyl.
5, 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, mol ratio is followed successively by 1: 0.8-2, react and made intermediate (III) in 0.5 to 12 hour, described catalyzer is p-methyl benzenesulfonic acid, methylsulfonic acid, sulfuric acid, hydrochloric acid or acetic acid;
(2) reactant (III) is 1 with the mol ratio of reductive agent: 0.5-2: 0-0.5, 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 respectively:
, wherein, D, E, R
1, R
2Or described 2-2-pyrimidinyl oxy-N-amido phenyl benzylamine compound is shown in claim 1.
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 alcoholic solvent.
7, 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.
8, 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.
9, 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.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011131993A CN1166642C (en) | 2001-06-29 | 2001-06-29 | 2-pyrimidyloxy-N-amidophynylbenzyl amine, and its prepn. and use |
| US10/380,865 US6800590B2 (en) | 2000-10-16 | 2001-09-13 | 2-Pyrimidinyloxy-n-aryl-benzylamine derivatives,their processes and uses |
| MXPA03001972A MXPA03001972A (en) | 2000-10-16 | 2001-09-13 | New 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their processes and uses. |
| PCT/CN2001/001395 WO2002034724A1 (en) | 2000-10-16 | 2001-09-13 | New 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their processes and uses |
| BR0114812-5A BR0114812A (en) | 2000-10-16 | 2001-09-13 | 2-Pyrimidinyloxy-n-aryl benzylamine derivatives, their preparation and use processes |
| AT01988710T ATE378320T1 (en) | 2000-10-16 | 2001-09-13 | NEW 2-PYRIMIDINYLOXY-N-ARYLBENZYLAMINE DERIVATIVES, METHODS AND USES THEREOF |
| EP01988710A EP1327629B1 (en) | 2000-10-16 | 2001-09-13 | New 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their processes and uses |
| AU2002220458A AU2002220458A1 (en) | 2000-10-16 | 2001-09-13 | New 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their processes and uses |
| KR10-2003-7005070A KR100511489B1 (en) | 2000-10-16 | 2001-09-13 | New 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their processes and uses |
| PL361309A PL216218B1 (en) | 2000-10-16 | 2001-09-13 | New 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their processes and uses |
| JP2002537715A JP4052942B2 (en) | 2000-10-16 | 2001-09-13 | 2-Pyrimidinyloxy-N-arylbenzylamine derivatives, their production and use |
| CA002425984A CA2425984C (en) | 2000-10-16 | 2001-09-13 | 2-pyrimidinyloxy-n-aryl-benzylamine derivatives, their preparation processes and uses |
| DE60131437T DE60131437T2 (en) | 2000-10-16 | 2001-09-13 | NEW 2-PYRIMIDINYLOXY-N-ARYLBENZYLAMINE DERIVATIVES, THEIR METHOD AND USES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011131993A CN1166642C (en) | 2001-06-29 | 2001-06-29 | 2-pyrimidyloxy-N-amidophynylbenzyl amine, and its prepn. and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1323788A true CN1323788A (en) | 2001-11-28 |
| CN1166642C CN1166642C (en) | 2004-09-15 |
Family
ID=4659941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011131993A Expired - Fee Related CN1166642C (en) | 2000-10-16 | 2001-06-29 | 2-pyrimidyloxy-N-amidophynylbenzyl amine, and its prepn. and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1166642C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100361978C (en) * | 2005-09-02 | 2008-01-16 | 中国科学院上海有机化学研究所 | 2-pyrimidine oxy-N-aryl 7-nitrile or organic phosphate benzylamine compound, its production and use thereof |
| CN100402524C (en) * | 2006-07-28 | 2008-07-16 | 华中师范大学 | Synthesis of 8-(4,6-dimethoxy pyrimidine oxy)-2-substituted phentriazine-1-one derivative and its herbicide activity |
| CN103156844A (en) * | 2011-12-15 | 2013-06-19 | 天津市国际生物医药联合研究院 | Application of Schiff base compound in inhibition of activity of NDM-1 |
| CN106689141A (en) * | 2017-03-10 | 2017-05-24 | 合肥星宇化学有限责任公司 | Pyribambenz-propyl and quizalofop-P-tefuryl compound weeding composition as well as preparation and application thereof |
-
2001
- 2001-06-29 CN CNB011131993A patent/CN1166642C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100361978C (en) * | 2005-09-02 | 2008-01-16 | 中国科学院上海有机化学研究所 | 2-pyrimidine oxy-N-aryl 7-nitrile or organic phosphate benzylamine compound, its production and use thereof |
| CN100402524C (en) * | 2006-07-28 | 2008-07-16 | 华中师范大学 | Synthesis of 8-(4,6-dimethoxy pyrimidine oxy)-2-substituted phentriazine-1-one derivative and its herbicide activity |
| CN103156844A (en) * | 2011-12-15 | 2013-06-19 | 天津市国际生物医药联合研究院 | Application of Schiff base compound in inhibition of activity of NDM-1 |
| CN103156844B (en) * | 2011-12-15 | 2016-11-16 | 天津市国际生物医药联合研究院 | The application in the medicine of preparation suppression NDM-1 activity of the Schiff base compounds |
| CN106689141A (en) * | 2017-03-10 | 2017-05-24 | 合肥星宇化学有限责任公司 | Pyribambenz-propyl and quizalofop-P-tefuryl compound weeding composition as well as preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1166642C (en) | 2004-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1138763C (en) | Di- or tri-fluoromethanesulfonyl anilide derivs., process for preparation of them and herbicides contg. them as active ingredient | |
| CN1033201C (en) | Herbicidal composition | |
| CN101935291B (en) | Cyano phthalic diamide compounds, preparation method thereof and use thereof as agricultural chemical pesticide | |
| CN1044427C (en) | 2-Alkoxy phenoxy sulfonylurea with heterocycle and their uses as herbicides or plant-grown regulator | |
| CN1488626A (en) | 2-pyrimidine oxy-N-ureido phenyl-benzyl amide compound, preparing method and use thereof | |
| CN1069268A (en) | New herbicides | |
| CN1927860A (en) | Pyrazolecarboxamide compounds, intermediate thereof and pest control chemicals with the same as active component | |
| CN1127293C (en) | 2-pyrimioxybenzyl substituted phenyl amine derivatives | |
| RU2670439C2 (en) | Substituted pyrazolyl pyrazole derivative and use thereof as herbicide | |
| KR0155560B1 (en) | Uracil derivatives, their production and use | |
| CN1036571A (en) | Benzoxazinone compound and the herbicidal composition that contains this compound | |
| JP4052942B2 (en) | 2-Pyrimidinyloxy-N-arylbenzylamine derivatives, their production and use | |
| CN1060385A (en) | Weed killer herbicide | |
| CN1147479C (en) | 2-pyrimidyloxybenzyl substituted naphthyl amine derivative and its synthesis and use | |
| CN1166642C (en) | 2-pyrimidyloxy-N-amidophynylbenzyl amine, and its prepn. and use | |
| CN1039417A (en) | Replace the sulfonic acid diamine class, their preparation method and as the application of weedicide and plant-growth regulator | |
| CN100516052C (en) | Alcohol amide condensed ester compound and its preparation and use | |
| CN1048725C (en) | Nicotinic acid derivatives and herbicide | |
| CN1122800A (en) | Pyrimidinyl acrylic acid derivatives | |
| CN100343236C (en) | [N-(2-pyrimidine oxy) benzylamino phenyl] sulfamine compound, and its preparing method and use | |
| CN1142150C (en) | Pyrimidinoxy salicylic acid derivative | |
| CN1120836C (en) | 2-pirimioxybenzyl substituted pyridyl amine derivative | |
| CN100384840C (en) | 2-pyrimidine oxy-benzoic acid [2-(pyrimidine amino methyl)]benester compound, its preparation and use thereof | |
| CN101367769B (en) | N-(2-pyrimidine oxygen based) benzyl amide compounds, preparation method and uses thereof | |
| CN1032006A (en) | Thionamic acid phenyl ester, its preparation method of heterocyclic substituted and make weedicide and the purposes of plant-growth regulator |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 200032 Shanghai Fenglin Road No. 354 Co-patentee after: Zhejiang Research Institute of Chemical Industry, Ltd. Patentee after: Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences Address before: 200032 Shanghai Fenglin Road No. 354 Co-patentee before: Chemical Industry Inst. of Zhejiang Prov. Patentee before: Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040915 Termination date: 20120629 |