CN101367769B - N-(2-pyrimidine oxygen based) benzyl amide compounds, preparation method and uses thereof - Google Patents
N-(2-pyrimidine oxygen based) benzyl amide compounds, preparation method and uses thereof Download PDFInfo
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Abstract
The present invention relates to an N-(2-pyrimidinyloxy) benzyl amide compound, a preparation method thereof and an application thereof as a chemical weed killer in the agriculture. The compound has a structural formula as shown on the right, wherein, D or E is halogen, hydroxyl, C1-C4 alkoxyl or C1-C4 halogenating alkoxyl; X is hydrogen, halogen, nitryl, C1-C8 alkyl, C1-C8 halogenating alkyl or C1-C8 alkoxyl; R is C1-C8 alkyl, R1 substituted benzyl or R1 substituted heterocyclic group, C1-C8 alkoxyl, R1 substituted benzyl or R1 substituted heterocyclic oxyl, R2 substituted amidogen and R3 substituted amidogen, R1 substituted benzyl or R1 substituted heterocyclic sulfonic acid amido; wherein, the R1 is hydrogen, halogen, nitryl, cyano, carboxyl, ester group, sulphonyl, C1-C8 alkoxy amido,C1-C8 halogenating alkoxy amido, C1-C8 alkyloxyacyl, C1-C8 alkyl, C1-C8 halogenating alkyl, C1-C8 alkoxyl, benzoyl, benzo, phenyl or heterocyclic group; R2 is hydrogen, C1-C8 alkyloxyacyl, C1-C8 halogenating alkyloxyacyl, benzoyl, benzoyl or C1-C8 alkyl; and R3 is ester group, sulphonyl, C1-C8 alkyl, C1-C8 halogenating alkyl, C1-C8 alkoxyl, C1-C8 alkyloxyacyl, phenyl or heterocyclic group.
Description
Technical field
The present invention relates to the new N-of a class (2-2-pyrimidinyl oxy) benzyl amide compounds compounds, preparation method and as the purposes of agrochemicals weedicide.
Background technology
2-pyrimidinyl oxy benzene analog derivative can be used as chemical herbicide early bibliographical information, 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)
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 (ZL00130735.5, ZL01112689.2, ZL01113199.3, CN1513321A and CN1488626A), they have very high weeding activity.Their mechanism of action is the inhibitor of acetolactate synthestase (ALS), destroys the synthetic of plant vivo acid such as Xie Ansuan, leucine and Isoleucine.
2-pyrimidinyl oxy benzene analog derivative can be used as chemical herbicide early bibliographical information, 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).The pyrimidine salicylic acid compounds has very high weeding activity, is only applicable to the weeding of cotton field and rice terrace at present.
Different with above-mentioned pyrimidine salicylic acid weedicide is that the new herbicides that they are therefrom developed has good security to rape.The present invention introduces amide group in new 2-pyrimidinyl oxy-benzyl substituted aryl amino derivative, obtain good active structure.
Summary of the invention
The problem to be solved in the present invention provides a kind of new compound, i.e. N-(2-2-pyrimidinyl oxy) benzyl amide compounds.
The problem that the present invention also will solve provides the preparation method of above-claimed cpd.
Another problem that the present invention will solve provides a kind of purposes of above-claimed cpd.
The invention provides a kind of [structural formula of N-(2-2-pyrimidinyl oxy) benzyl aminoamide compound is shown in (I):
Wherein:
D and E can be same or different groups, are respectively hydrogen, halogen, hydroxyl, 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.
X=hydrogen, halogen, nitro, C
1-C
8Alkyl, C
1-C
8Haloalkyl or C
1-C
8Alkoxyl group or the like can be in any one position in 3,4,5,6 on phenyl ring.
R=C
1-C
8Alkyl, R
1Substituted-phenyl or R
1Substituted heterocyclic radical, C
1-C
8Alkoxyl group, R
1Substituted-phenyl or R
1Substituted heterocyclic radical oxygen base, R
2And R
3Substituted amido, R
1Substituted-phenyl or R
1The substituted heterocyclic radical sulfoamido; R wherein
1=hydrogen, halogen, nitro, cyano group, carboxyl, ester group, alkylsulfonyl, C
1-C
8Alkyl amido, C
1-C
8Haloalkylamido, C
1-C
8Alkyloyl, C
1-C
8Alkyl, C
1-C
8Haloalkyl, C
1-C
8Alkoxyl group, phenyl, benzo base, phenyl or heterocyclic radical; R
2=hydrogen, C
1-C
8Alkyloyl, C
1-C
8Haloalkane acyl group, benzoyl, benzoyl, C
1-C
8Alkyl; R
3=ester group, alkylsulfonyl, C
1-C
8Alkyl, C
1-C
8Haloalkyl, C
1-C
8Alkoxyl group, C
1-C
8Alkyloyl, phenyl or heterocyclic radical.
Described heterocyclic radical is pyridyl, thienyl, thiazolyl or pyrimidyl.
Wherein said R
1Substituting group on substituted-phenyl or the substituted benzoyl is recommended as single replacement, two replacements, three polysubstituted or quaternary halogens, nitro, cyano group, carboxyl, ester group, alkylsulfonyl, 2-pyrimidinyl oxy, C
1-C
8Alkyl, C
1-C
8Haloalkyl, C
1-C
8Alkoxyl group, C
1-C
8Alkyloyl or C
1-C
8Alkyl amido etc.
Below, we list in table one with typical compound involved in the present invention.
Table one
Compound N involved in the present invention-(2-2-pyrimidinyl oxy) benzyl amide compounds can be synthetic with following reactions steps:
R, X and D, the substituting group of E representative is as previously mentioned.
Intermediate (II) is synthetic can be by replacing aldehyde and oxammonium hydrochloride prepared in reaction, and mol ratio is 1: 1 to 1: 2.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; Best alkali is selected sodium bicarbonate for use, mol ratio 1.05 to 1.5.Solvent can be varsols such as benzene, toluene or dimethylbenzene; Ether solvent such as tetrahydrofuran (THF) or dioxane; Alcoholic solvent such as methyl alcohol, ethanol; The optimum solvent of this reaction is an ethyl acetate.Temperature of reaction be 0 ℃ to room temperature, the reaction times is 0.5 to 12 hour.
Intermediate (III) is synthetic by reduction intermediate (II) preparation, can under the effect of catalyzer, make with hydrogen reducing intermediate (II), catalyzer can be Raney Ni (RaneyNi), palladium carbon or platinum black etc., the mol ratio of intermediate (II), 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.This intermediate (III) also can make with hydrazine hydrate reduction intermediate (II) under the effect of catalyzer, catalyzer can be a Raney Ni (RaneyNi) etc., the mol ratio of intermediate (II), hydrazine hydrate and catalyzer is 1: (1-1.5): (0.01-0.5), use more hydrazine hydrate to not influence of reaction.Temperature of reaction is extremely 40 ℃ Celsius of room temperatures, and the reaction times is 0.5 to 10 hour, ether solvents such as solvents tetrahydrofurane 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.
The synthetic adjacent hydroxy benzylamine (III) and the preparation of replacement acyl chloride reaction by replacing of intermediate (IV), 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 ethers.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, used alkali can be hydride, alcoxyl metallic compound or its carbonate of monovalence or divalent metal in the reaction, 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, and alkali and mol ratio (III) are recommended as 1.1-1.2.
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.
Unless otherwise indicated, alkyl of the present invention, substituted alkyl, alkoxyl group, haloalkyl, halogenated alkoxy all refer to the group of straight or branched, be recommended as 1 to 8 carbon number, further are recommended as 1 to 4 carbon number.
The invention provides the purposes of above-mentioned N-(2-2-pyrimidinyl oxy) benzyl amide compounds, promptly can be used for weedicide.
With the active constituent of compound of the present invention as the chemistry of pesticide weedicide, be mixed with various liquors, missible oil, suspension agent, aqueous suspension, microemulsion, (water) emulsion, pulvis, wettable powder, soluble powder, (water dispersible) granule or capsule etc., can be used for the control of weeds of farm crop such as paddy rice, soybean, wheat, cotton, corn and rape.
The weight percentage of active constituent is recommended as 5～90% in the preparation, and all the other are carrier, and carrier comprises two kinds at least, and wherein at least a is tensio-active agent.Carrier can be solid or liquid.Suitable solid carrier comprises natural or synthetic clay and silicate, for example natural silica and diatomite; Magnesium Silicate q-agent is talcum for example; Magnesium aluminum silicate is kaolinite, kaolin, polynite and mica for example; White carbon black, lime carbonate, light calcium carbonate; Calcium sulfate; Wingdale; Sodium sulfate; Amine salt such as ammonium sulfate, hexamethylene diamine.Liquid vehicle comprises water and organic solvent, and when water was cooked solvent or thinner, organic solvent also can be used as auxiliary or antifreeze additive.Appropriate organic solvent comprises aromatic hydrocarbons for example benzene, dimethylbenzene, toluene etc.; Hydrochloric ether, for example chlorinated benzene, vinylchlorid, trichloromethane, methylene dichloride etc.; Aliphatic hydrocarbon, for example petroleum fractions, hexanaphthene, light mineral oil; Alcohols, for example Virahol, butanols, ethylene glycol, glycerol and hexalin etc.; And their ether and ester; Also have ketone, for example acetone, pimelinketone and dimethyl formamide and N-methyl-pyrrolidone.
Tensio-active agent can be emulsifying agent, dispersion agent or wetting agent; Can be ionic or non-ionic type.Nonionic emulsifier is polyoxyethylene fatty acid fat, polyoxyethylene aliphatic alcohol ether, polyoxyethylene fatty amine for example, and commercially available emulsifying agent: agricultural newborn 2201B, agricultural newborn 0203B, farming breast 100
#, farming breast 500
#, farming breast 600
#, agricultural newborn 600-2
#, farming breast 1601, farming breast 2201, agricultural newborn NP-10, agricultural newborn NP-15, farming breast 507
#, agricultural newborn OX-635, agricultural newborn OX-622, agricultural newborn OX-653, agricultural newborn OX-667, peaceful breast 36
#Dispersion agent comprises sodium lignosulfonate, draws back powder, calcium lignin sulphonate, condensation compound of methyl naphthalene sulfonic acid and formaldehyde etc.Wetting agent is: sodium laurylsulfate, Sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate etc.
These preparations can be prepared by method in common.For example, active substance is mixed with liquid solvent and/or solid carrier, add tensio-active agent such as emulsifying agent, dispersion agent, stablizer, wetting agent simultaneously, can also add other auxiliary agent as tackiness agent, defoamer, oxygenant etc.
Weeding active compound of the present invention can with sterilant, sterilant, nematocides, plant-growth regulator, fertilizer, and other weedicide or other agrochemicals use that is mixed.
Compound of the present invention and preparation thereof have following characteristics and advantage:
1, have weeding activity efficiently, weeding activity after not only showing preferably bud under 37.5～75g ai/ha low dosage, and show preferably weeding activity before the bud.
2, the grass spectrum is wider extremely, can effectively prevent and kill off farmland gramineous weedss such as barnyard grass grass, lady's-grass, Herba Eleusines Indicae, and leaf mustard, Amaranthus retroflexus, little lamb's-quarters are also had the good control effect.
3, crop safety height, under 75～150g ai/ha high dosage to crop safeties such as corn, wheat, rape, paddy rice.
4, dispenser phase broad also has highly effective weeding activity to above the average age for marriage 3～6 leaf phase susceptible weeds.
5, residual period, is short in soil, and leaching, residual quantity are low in soil, and the succession crop growth is had no adverse effects.
6, have rational toxicity, eco-toxicity and Environmental compatibility, 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 have good weeding activity and crop-selective, can be used for weedicide.Its preparation can be prevented and treated most of farmland weeds effectively, effectively prevent and treat responsive gramineous weeds down than low dosage, broadleaf weeds and nutgrass flatsedge, concrete controlling object comprises barnyard grass grass (Echinochloacrusgalli), lady's-grass (Digitaria sanguinalis), Herba Eleusines Indicae (Eleusine indica), Herba Setariae Viridis (Setariaviridis), annual bluegrass (Poa annua), wild avena sativa (Avena fatua), amur foxtail (Alopecurus aequalis), Japan amur foxtail (Alopecurus japonicus), Amaranthus retroflexus (Amaranthus retroflexus), thorn amaranth (Amaranthusspinosus), lamb's-quarters (Chenopodium album), leaf mustard (Brassica juncea), purslane (Portulaca oleracea), Herba Acalyphae (Acalypha australis), Herba Cyperi Difformis (Cyperus difformis), Semen Euphorbiae (Leptochloa chinensis), Rhizoma Cyperi (Cyperus rotundus), grass (Fimbristylis miliacea) floats sunshine, chickweed (Stallaria media), Stellaria alsine Grim. (Stellaria alsine), Herba Erigerontis Annui (Erigeron annuus), short arrowhead (Sagittaria sagittifolia), Herba seu Flos Convolvuli arvensis (Convolvulus arvensis) etc.
Embodiment
Below enforcement 1 provides the synthetic example of The compounds of this invention to enforcement 7, embodiment 8 to embodiment 12 provides with compound of the present invention as active constituent, the concrete instance of processing preparation several herbicides formulation, embodiment 13 provides with The compounds of this invention and carries out the biological activity determination method concrete instance as active constituent, it is to be noted that following examples helps to understand the present invention, but the present invention is confined to not merely in the scope of following example.
Wherein with compound of the present invention as active constituent, among the embodiment of processing preparation several herbicides formulation, all " % " all refer to weight percent, " g ai/ha " all refers to restrain active constituent/hectare.
Embodiment
Following examples help to understand the present invention, but the present invention not merely is confined in the scope of following embodiment.
Embodiment 1
Synthesizing of N-(2-2-pyrimidinyl oxy) benzyl amide compounds
Synthesize example with I-5: (o-chlorobenzoyl chloride)
There-necked flask at 250mL adds 9.92g (81.3mmol) salicylic aldehyde, 5.93g (85.3mmol) oxammonium hydrochloride and 7.51g (89.4mmol) sodium bicarbonate, and ethyl acetate 100ml and about 8ml water, room temperature, stir about spends the night.Filter, washing, ethyl acetate extraction, anhydrous sodium sulfate drying filters, be spin-dried for 10g, yield 89.7%.
Be reduced into benzylamine: product 13.7g (0.1mol) is dissolved in the 20mL anhydrous methanol, pours in the 250ml there-necked flask, add zinc powder 40.8g (0.624mol) in the stirring, add 28.9g (0.458mol) formic acid methanolic ammonia solution at last.Room temperature reaction spends the night.Transfer PH to 3, filter, filtrate transfers to neutrality with ammoniacal liquor, faint yellow solid occurs.Filter oven dry.Get 7.96g, yield 64.7%.
Replace acyl chloride reaction and become amide structure: 1.23g (10mmol) product joins in the 40ml tetrahydrofuran (THF), inserts the there-necked flask of 100ml, adds 1.656g (12mmol) salt of wormwood again.Under the ice-water bath, slowly be added dropwise to the o-chlorobenzoyl chloride of 1.837g (10.5mmol).Reaction is 3 hours under the room temperature.Filter, the filter cake ethyl acetate is washed, and is spin-dried for filtrate, ethyl alcohol recrystallization.Get the 2.48g product, yield 95%
With 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: will go up step product 195mg (0.75mmol), 164mg (0.75mmol) 4,6-dimethoxy-2-methylsulfonyl pyrimidine, with 155mg (1.5mmol) Anhydrous potassium carbonate room temperature reaction 8-9h in the DMF of 20mL, TLC controls reaction end.Reaction solution is poured in the 200mL water, and ethyl acetate extraction three times merges organic phase, and saturated aqueous common salt and water are respectively washed once, anhydrous sodium sulfate drying, filter be spin-dried for the back column chromatography (sherwood oil: ethyl acetate=2:1) the pure product of 240mg, yield 80%.
Solid
m.p.：128±1℃
1H?NMR(300MHz，DMSO/TMS)：δ8.09-8.12(1H，m，CH)，7.37-6.96(8H，m，CH，NH)，5.96(1H，s，CH)，4.237(2H，s，CH
2)，3.749(6H，s，OCH
3)
MS(ESI)：425(M
+，100)，437(M+Na
+，10)
E.A.for?C
20H
19ClN
4O
4
Calcd：C57.91，H4.62，N13.51
Found：C57.64，H4.44，N13.41
Embodiment 2
I-1's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) 2-hydroxy benzylamine and isobutyryl chloride reaction: the isobutyryl chloride 6mmol that feeds intake, must product 1.065g, yield 92%.(2) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation, the employing acetonitrile is a solvent, and is synthetic down at 40-50 ℃.Column chromatography (sherwood oil: ethyl acetate=3:1) pure product, yield 90%.
Solid
m.p.：118-120℃
1H?NMR(300MHz，CDCl
3/TMS)：δ7.37-6.85(4H，m，CH)，6.634(1H，s，NH)，5.768(1H，s，CH)，4.61-4.63(2H，d，J＝5.1Hz)，4.20(1H，m，CH)，3.81(6H，s，OCH
3)，2.52(6H，s，CH
3，J＝7.2Hz)
MS(EI)：332(M
+，100)，354(M+Na
+，20)
E.A.for?C
17H
21N
3O
4
Calcd：C61.62，H6.39，N12.68
Found：C61.76，H6.54，N12.76
Embodiment 3
I-2's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) 2-hydroxyl-6-chlorobenzylamine and isobutyryl chloride reaction: the isobutyryl chloride 6mmol that feeds intake, must product 1.294g, yield 95%.(2) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation, the employing acetonitrile is a solvent, and is synthetic down at 40-50 ℃.Column chromatography (sherwood oil: ethyl acetate=3:1) pure product, yield 85%.
Solid
m.p.：140-142℃
1H?NMR(300MHz，CDCl
3/TMS)：δ7.43-7.05(3H，m，CH)，6.63(1H，s，NH)，5.87(1H，s，CH)，4.61-4.63(2H，d，J＝5.1Hz)，4.20(1H，m，CH)，3.81(6H，s，OCH
3)，2.52(6H，s，CH
3，J＝7.2Hz)
MS(EI)：366(M
+，100)，388(M+Na
+，20)
E.A.for?C
17H
20ClN
3O
4
Calcd：C55.82，H5.51，N11.49
Found：C55.90，H5.65，N11.65
Embodiment 4
I-3's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) 2-hydroxy benzylamine and methyl-chloroformate reaction: the methyl-chloroformate 6mmol that feeds intake, low temperature is reaction down, gets product 0.956g, yield 88%.(2) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation, the employing acetonitrile is a solvent, and is synthetic down at 40-50 ℃.Column chromatography (sherwood oil: ethyl acetate=3:1) pure product, yield 90%.
Solid
m.p.：110-121℃
1H?NMR(300MHz，CDCl
3/TMS)：δ7.45-7.12(4H，m，CH)，5.79(1H，s，CH)，5.15(1H，br，NH，)，4.35(2H，d，CH
2，J＝5.1Hz)，3.80(6H，s，OCH
3)，3.65(3H，s，CH
3)
MS(EI)：319(M
+，100)，319(M+Na
+，20)
E.A.for?C
15H
17N
3O
5
Calcd：C56.42，H5.37，N13.16
Found：C56.65，H5.54，N13.37
Embodiment 5
I-4's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) 2-hydroxy benzylamine and isobutyl chlorocarbonate reaction: the isobutyl chlorocarbonate 6mmol that feeds intake, low temperature is reaction down, gets product 1.244g, yield 93%.(2) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation, the employing acetonitrile is a solvent, and is synthetic down at 40-50 ℃.Column chromatography (sherwood oil: ethyl acetate=3:1) pure product, yield 90%.
Solid
m.p.：73±0.5℃
1H?NMR(300MHz，DMSO/TMS)：δ7.40-7.10(4H，m，CH)，5.97(1H，s，CH)，4.10(2H，s，CH
2)，3.745(6H，s，OCH
3，2H，CH
2)，1.81(1H，br，CH)，0.75-0.90(6H，m，CH
3)
MS(EI)：362(M
+，100)，361(M+Na
+，20)
E.A.for?C
18H
23N
3O
5
Calcd：C59.82，H6.41，N11.63
Found：C59.70，H6.23，N11.42
Embodiment 6
I-6's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) 2-hydroxy benzylamine and parachlorobenzoyl chloride reaction: the parachlorobenzoyl chloride 6mmol that feeds intake, must product 1.244g, yield 93%.(2) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation, the employing acetonitrile is a solvent, and is synthetic down at 40-50 ℃.Column chromatography (sherwood oil: ethyl acetate=3:1) pure product, yield 90%.
Solid
m.p.：158-159℃
1H?NMR(300MHz，CDCl
3/TMS)：δ7.59-7.62(2H，d，CH，J＝7.5Hz)，7.36-7.11(5H，m，CH)，6.51(1H，br，NH)，5.74(1H，s，CH)，4.65(2H，d，，J＝4.5)，3.78(6H，s，OCH
3)
MS(EI)：(M
+，100)，(M+Na
+，15)
E.A.for?C
20H
17Cl
2N
3O
4
Calcd：C55.31，H3.95，N9.68
Found：C55.45，H4.12，N9.88
Embodiment 7
I-7's is synthetic, experimental procedure is with embodiment 1:(1 in detail) to react with the 2-hydroxy benzylamine: the triphosgene of 3mmol is dissolved in the 30ml tetrahydrofuran (THF) and pours in the 250ml there-necked flask, the triethylamine of 9mmol p-Nitroaniline and 9mmol is dissolved in the 30ml tetrahydrofuran (THF), is added dropwise to reaction flask; After 1 hour, add the 2-hydroxy benzylamine of 9mmol and the triethylamine mixing tetrahydrofuran (THF) 30ml of 9mmol.Reaction is spent the night.Filter, and column chromatography (sherwood oil: ethyl acetate=3:1), yield 31.1%.(2) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation, the employing acetonitrile is a solvent, and is synthetic down at 40-50 ℃.Column chromatography (sherwood oil: ethyl acetate=3:1) pure product, yield 90%.
Solid
m.p.：174-177℃
1H?NMR(300MHz，DMSO/TMS):δ8.21-8.12(2H，d，CH，J＝7.5Hz)，7.85-7.86(2H，d，CH，J＝7.5Hz)，7.37-6.96(4H，m，CH)，5.96(1H，s，CH)，5.53(1H，br，NH)，4.237(2H，s，CH
2)，3.749(6H，s，OCH
3)
MS(ESI)：426(M
+，100)，438(M+Na
+，10)
E.A.for?C
20H
19N
5O
6
Calcd：C56.47，H4.50，N16.46
Found：C56.35，H4.44，N16.36
Embodiment 8
I-8's is synthetic, experimental procedure is with embodiment 1:(1 in detail) to react with the 2-hydroxy benzylamine: the triphosgene of 3mmol is dissolved in the 30ml tetrahydrofuran (THF) and pours in the 250ml there-necked flask, the triethylamine of 9mmol m-chloro aniline and 9mmol is dissolved in the 30ml tetrahydrofuran (THF), is added dropwise to reaction flask; After 1 hour, add the 2-hydroxy benzylamine of 9mmol and the triethylamine mixed solvent tetrahydrofuran (THF) 30ml of 9mmol.Reaction is spent the night.Filter, and column chromatography (sherwood oil: ethyl acetate=3:1), yield 37.6%.(2) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation, the employing acetonitrile is a solvent, and is synthetic down at 40-50 ℃.Column chromatography (sherwood oil: ethyl acetate=3:1) pure product, yield 90%.
Solid
m.p.：189-190℃
1H?NMR(300MHz，DMSO/TMS)：δ8.09-8.12(1H，m，CH)，7.37-6.96(8H，m，CH)，5.96(1H，s，CH)，5.65(1H，br，NH)，4.237(2H，s，CH
2)，3.749(6H，s，OCH
3)
MS(ESI)：425(M
+，100)，437(M+Na
+，10)
E.A.for?C
20H
19ClN
4O
4
Calcd：C57.91，H4.62，N13.51
Found：C57.78，H4.46，N13.44
Embodiment 9
I-9's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) with the reaction of 2-hydroxy benzylamine: the triphosgene of 3mmol is dissolved in the 30ml tetrahydrofuran (THF) to be poured in the 250ml there-necked flask, and the triethylamine of 9mmol Isopropylamine and 9mmol is dissolved in 30mlTHF, is added dropwise to reaction flask; After 1 hour, add the 2-hydroxy benzylamine of 9mmol and the triethylamine mixing tetrahydrofuran (THF) 30ml of 9mmol.Reaction is spent the night.Filter, and column chromatography (sherwood oil: ethyl acetate=3:1), yield 26.3%.(2) with 4,6-dichloro methoxyl group-2-methylsulfonyl pyrimidine condensation: employings acetonitrile is a solvent, 40-50 ℃ synthetic down, (sherwood oil: ethyl acetate=4:1) gets pure product, yield 89% to column chromatography.
Oil
MS(ESI)：415(M
+，100)，437(M+Na
+，45)
E.A.for?C
17H
20Cl
2N
4O
4
Calcd：C49.17，H4.85，N13.49
Found：C49.31，H4.99，N13.53
Embodiment 10
I-10's is synthetic, experimental procedure is with embodiment 1:(1 in detail) to react with 2-hydroxyl-6 methoxybenzylamine: the triphosgene of 3mmol is dissolved in the 30ml tetrahydrofuran (THF) and pours in the 250ml there-necked flask, with 4 of 9mmol, the triethylamine of 6-dimethoxy-2-aminopyrimidine and 9mmol is dissolved in 30mlTHF, is added dropwise to reaction flask; After 1 hour, add the 2-hydroxy benzylamine of 9mmol and the triethylamine mixing tetrahydrofuran (THF) 30ml of 9mmol.Reaction is spent the night.Filter, and column chromatography (sherwood oil: ethyl acetate=3:1), yield 40%.(2) with 4,6-dichloro methoxyl group-2-methylsulfonyl pyrimidine condensation: employings acetonitrile is a solvent, 40-50 ℃ synthetic down, (sherwood oil: ethyl acetate=4:1) gets pure product, yield 89% to column chromatography.
Solid
m.p.：171-172℃
MS(ESI)：472(M
+，100)
E.A.for?C
21H
24N
6O
7
Calcd：C53.39，H5.12，N17.79
Found：C53.51，H5.02，N17.90
Embodiment 11
I-11's is synthetic, experimental procedure is with embodiment 1:(1 in detail) react with the 2-hydroxy benzylamine: 2-hydroxy benzylamine of 8mmol adds in the 100ml single port bottle, the 30ml tetrahydrofuran (THF) is a solvent, the triethylamine that adds 8mmol is an alkali, react after 1 hour, add the tetrahydrofuran solution of 4mmol ethylsulfonic acid carbimide.Reaction is spent the night.Column chromatography (sherwood oil: ethyl acetate=2:1), yield 70%.(2) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation, the employing acetonitrile is a solvent, and is synthetic down at 40-50 ℃.Get pure product with sherwood oil and re-crystallizing in ethyl acetate, yield 90%
Solid
m.p.：151-153℃
1H?NMR(300MHz，DMSO/TMS)：δ9.00(1H，br，NH)，7.48-7.19(4H，m，CH)，6.73(1H，br，NH)，5.85(1H，s，CH)，4.39(2H，d，CH
2，J＝5.7Hz)，3.80(6H，s，OCH
3)，3.40(2H，t，CH
2，J＝7.5Hz)，1.32(3H，t，CH
3，J＝7.5Hz)
MS(ESI)：397(M
+，65)，419(M+Na
+，100)
E.A.for?C
16H
20N4
5O
6S
Calcd：C48.48，H5.09，N14.13
Found：C48.56，H.5.29，N14.21
Embodiment 12
I-12's is synthetic, experimental procedure is with embodiment 1:(1 in detail) react with the 2-hydroxy benzylamine: 2-hydroxy benzylamine of 8mmol adds in the 100ml single port bottle, the 30ml tetrahydrofuran (THF) is a solvent, the triethylamine that adds 8mmol is an alkali, react after 1 hour, add the tetrahydrofuran solution of 4mmol rubigan sulfonic acid carbimide.Reaction is spent the night.Column chromatography (sherwood oil: ethyl acetate=2:1), yield 85%.(2) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation, the employing acetonitrile is a solvent, and is synthetic down at 40-50 ℃.Column chromatography (sherwood oil: ethyl acetate=3:1) pure product, yield 88%.
Oil
1H?NMR(300MHz，DMSO/TMS)：δ8.00(1H，s，NH)，7.925(2H，d，CH，J＝8.1Hz)，7.72(2H，d，CH，J＝8.1Hz)，7.27-7.14(4H，m，CH)，6.87(1H，br，NH)，6.026(1H，s，CH)，4.11(2H，d，CH
2，J＝3.9Hz)，3.78(6H，s，OCH
3)
MS(ESI)：479(M
+，100)
E.A.for?C
20H
19ClN
4O
6S
Calcd：C50.16，H4.00，N11.70
Found：C50.24，H4.22，N11.86
Embodiment 13
I-14's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) 2-hydroxyl-6 methoxybenzylamine and o-fluoro-benzoyl chloride reaction: the adjacent fluorobenzoyl 6mmol that feeds intake, must product 1.567g, yield 95%.(2) with 4,6-dichloro methoxyl group-2-methylsulfonyl pyrimidine condensation, the employing acetonitrile is a solvent, and is synthetic down at 40-50 ℃.Column chromatography (sherwood oil: ethyl acetate=3:1) pure product, yield 83%.
MS(ESI)：482(M
+，100)
E.A.for?C
21H
18Cl
2FN
3O
5
Calcd：C52.3，H3.76，N8.71
Found：C52.06，H3.54，N8.52
Embodiment 14
I-17's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) 2-hydroxyl-6 methoxybenzylamine and parachlorobenzoyl chloride reaction: the parachlorobenzoyl chloride 6mmol that feeds intake, must product 1.664g, yield 94%.(2) with 4,6-two chloro-2-methylsulfonyl pyrimidine condensations, the employing acetonitrile is a solvent, salt of wormwood is alkali, and is synthetic down at 40-50 ℃.Get pure product with sherwood oil and re-crystallizing in ethyl acetate, yield 88%.
MS(ESI)：434(M
+，100)
E.A.for?C
21H
18F
3N
3O
4
Calcd：C58.20，H4.19，N9.70
Found：C58.36，H4.02，N9.78
Embodiment 15
I-20's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) 2-hydroxy benzylamine and m-trifluoromethyl benzoyl chloride reaction: the m-trifluoromethyl benzoyl chloride 6mmol that feeds intake, must product 1.60g, yield 90%.(2) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation, the employing acetonitrile is a solvent, salt of wormwood is alkali, and is synthetic down at 40-50 ℃.Column chromatography (sherwood oil: ethyl acetate=3:1) pure product 1.887g, yield 80%.
MS(ESI)：438(M
+，100)
E.A.for?C
19H
14Cl
3N
3O
3
Calcd：C52.03，H3.22，N9.58
Found：C52.06，H3.44，N9.73
Embodiment 16
I-22's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) 2-hydroxyl-6 methoxybenzylamine with to the methoxy methyl acyl chloride reaction: to the methoxyl group 6mmol that feeds intake, product 1.388g, yield 90%.(2) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation, the employing acetonitrile is a solvent, salt of wormwood is alkali, and is synthetic down at 40-50 ℃.Get pure product with sherwood oil and re-crystallizing in ethyl acetate, yield 90%.
MS(ESI)：396(M
+，100)
E.A.for?C
21H
21N
3O
5
Calcd：C63.79，H5.35，N10.63
Found：C63.58，H5.24，N10.70
Embodiment 17 wettable powders
Wettable powder (WP) prescription: the compound with 15% (I-1) (table one), 5% sulfonated lignin (Mq), 1% ethoxylated dodecyl alcohol (JFC), 40% diatomite and 44% light calcium carbonate mix equably, pulverize, promptly get 15% wettable powder.
Embodiment 18 missible oil
Missible oil (EC) prescription: 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 10% missible oil.
Embodiment 19 granules
Granule (GR) prescription: the compound with 5% (I-1) (table one), 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 particles, drying promptly gets 5% granule.
Embodiment 20 aqueous emulsions
Aqueous emulsion (EW) prescription: the compound with 15% (I-1) (table one), 8% alkylaryl formaldehyde resin Soxylat A 25-7,10% calcium dodecylbenzene sulphonate, 3% tetradecanol, 10% dimethyl formamide, 5% propylene glycol, surplus is a water, according to each constitutive property, make oil phase and water respectively, then under high-speed stirring, the two is mixed, form 15% aqueous emulsion of favorable dispersity.
Embodiment 21 water suspending agents
Water suspending agent (SC) prescription: the compound with 15% (I-1) (table one), 5% calcium lignin sulphonate, 0.5% white carbon black, 4% ethylene glycol, 1% defoamer, surplus are water, in the adding sand milling still, are ground to certain fineness, make 15% suspension agent.
Embodiment 22 biological activity determinations
Below implement to provide 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.
The weeding activity evaluation test is carried out according to following method:
Test is the sandy loam of preparation with soil, and the weeding activity test is 9.5cm with basin alms bowl diameter, and safety testing is 12.0cm with basin alms bowl diameter.
The basin alms bowl that test is handled before the bud carries out the soil surface spraying one day after in sowing to be handled, the soup of handling is compound acetone, N, dinethylformamide organic solvent dissolutions such as (DMF), and add the laboratory preparation of 0.5% tween-80, thin up is needs dosage again.
The basin alms bowl that test is handled behind the bud was after planting put into hot-house culture after 7～9 days, carrying out the cauline leaf spraying handles, the soup of handling is organic solvent dissolutions such as compound acetone, DMF, and adds the laboratory preparation of 0.5% tween-80, and thin up is needs dosage again.
For the first time the compound treatment concentration of active determination test is 150gai/ha, for the second time the compound treatment concentration of active determination test be 75,150,300gai/ha or 37.5,75,150gai/ha.After the basin alms bowl of handling leaves standstill 1 day, put into the greenhouse, continue to cultivate, regularly water the weeding activity of appearance method observed and recorded compound after 14～21 days.
With the weeding activity of hazard of plant symptom (inhibition, deformity, yellow, albefaction) performance degree range estimation compound, 0 expression does not have herbicidal effect or to crop safety, weeds or crop are killed in 100% expression fully.
Weeding activity and crop safety appearance method judgement criteria are as follows:
| Phytotoxicity (%) | Weeding activity comment (inhibition, deformity, albefaction etc.) | Crop safety comment (inhibition, deformity, albefaction etc.) |
| 0 | With contrast, anti-, eliminate | With contrast, anti-, normal |
| 10-20 | Gently, influential slightly, eliminate | Gently, influential slightly, can consider |
| 30-40 | Gently, influential, eliminate | Sensitivity, influential, eliminate |
| 50-60 | Sensitivity, influential, can consider further transformation | Responsive, poisoning is heavy, eliminates |
| 70-80 | Responsive, can consider | Extremely responsive, poisoning is heavy, eliminates |
| 90-100 | Extremely responsive, good | Extremely responsive, poisoning is heavy, eliminates |
For the first time the weeding activity test-results handled of high dosage sees Table 1 and table 2; The weeding activity test-results that reduces for the second time dosage sees Table 3 and table 4; The crop safety test-results sees Table 5
Living test is tested the result and shown: The compounds of this invention has good weeding activity, than low dosage 37.5～75gai/ha gramineous weeds and broadleaf weeds is had the good control effect; And under dosage 75～150gai/ha, target crop such as corn, paddy rice, rape are showed safety.
The weeds and the crop species of the biological activity determination test usefulness of selecting are as follows:
| Chinese name | English name | The science title | Abbreviation |
| The barnyard grass grass | Barnyardgrass | Echinochloa?crusgalli | ECHCG |
| Lady's-grass | Crabgrass | Digitaria?sanguinalis | DIGSA |
| Herba Eleusines Indicae | Bullgrass | Eleusine?indica | ELEIN |
| Herba Setariae Viridis | Giant?foxtail | Setaria?faberii | SETEFA |
| Leaf mustard | Leaf?mustard | Brassica?juncea | BRAJU |
| Amaranthus retroflexus | Amaranth?pigweed | Amaranthus?retroflexus | AMARE |
| Purslane | Common?purslane | Portulaca?oleracea | POROL |
| Little lamb's-quarters | Lambsquarters | Chenopodium?album | CHEAL |
| Corn | Corn | Zea?mays | ZEAMX |
| Soybean | Soybean | Glycine?max | GLXMA |
| Cotton | Cotton | Gossypium?hispitum | GOSHI |
| Wheat | Wheat | Triticum?aestivum | TRZAW |
| Paddy rice | Rice | Oryza?sativs | ORYSD |
| Rape | Rape | Brassica?napus | BRSNW |
The weeding activity test-results first time that cauline leaf is handled behind table 1 bud
| Compound number | Dosage (g ai/ha) | The barnyard grass grass | Lady's-grass | Herba Setariae Viridis | Leaf mustard | Amaranthus retroflexus | Little lamb's-quarters |
| I—1 | 150 | 80 | 75 | 30 | 60 | 90 | 35 |
| I—2 | 150 | 80 | 60 | 30 | 50 | 90 | 30 |
| I—3 | 150 | 80 | 80 | 45 | 90 | 90 | 50 |
| I—4 | 150 | 80 | 80 | 75 | 40 | 100 | 80 |
| I—5 | 150 | 80 | 90 | 100 | 40 | 100 | 75 |
| I—6 | 150 | 85 | 80 | 85 | 60 | 100 | 80 |
| I—7 | 150 | 85 | 80 | 65 | 50 | 100 | 60 |
| I—8 | 150 | 80 | 80 | 98 | 50 | 90 | 60 |
| I—9 | 150 | 80 | 80 | 78 | 40 | 100 | 70 |
| I—10 | 150 | 80 | 80 | 70 | 40 | 100 | 80 |
| I—11 | 150 | 70 | 70 | 80 | 60 | 90 | 80 |
| I—12 | 150 | 80 | 70 | 80 | 50 | 90 | 70 |
| I—10 | 150 | 60 | 60 | 50 | 40 | 55 | 70 |
| I—11 | 150 | 70 | 75 | 80 | 80 | 80 | 80 |
| I—12 | 150 | 50 | 50 | 70 | 90 | 70 | 60 |
| I—13 | 150 | 60 | 60 | 30 | 50 | 90 | 30 |
| I—14 | 150 | 80 | 80 | 45 | 80 | 90 | 50 |
| I—15 | 150 | 80 | 80 | 75 | 40 | 100 | 80 |
| I—17 | 150 | 70 | 80 | 78 | 40 | 100 | 80 |
| I—19 | 150 | 80 | 80 | 70 | 40 | 100 | 80 |
| I—20 | 150 | 80 | 70 | 80 | 50 | 90 | 70 |
| I—21 | 150 | 80 | 70 | 80 | 60 | 90 | 70 |
The weeding activity test-results first time of soil treatment before table 2 bud
| Compound number | Dosage (g ai/ha) | The barnyard grass grass | Lady's-grass | Herba Setariae Viridis | Leaf mustard | Amaranthus retroflexus | Little lamb's-quarters |
| I—1 | 150 | 50 | 40 | 40 | 50 | 50 | 40 |
| I—2 | 150 | 50 | 40 | 30 | 50 | 70 | 60 |
| I—3 | 150 | 65 | 75 | 60 | 40 | 80 | 60 |
| I—4 | 150 | 60 | 75 | 60 | 60 | 80 | 40 |
| I—5 | 150 | 60 | 75 | 70 | 60 | 85 | 40 |
| I—6 | 150 | 70 | 80 | 60 | 60 | 80 | 40 |
| I—7 | 150 | 80 | 70 | 60 | 50 | 50 | 40 |
| I—8 | 150 | 70 | 75 | 75 | 70 | 90 | 80 |
| I—9 | 150 | 50 | 60 | 60 | 60 | 65 | 60 |
| I—10 | 150 | 60 | 50 | 65 | 40 | 55 | 50 |
| I—11 | 150 | 80 | 75 | 80 | 60 | 70 | 80 |
| I—12 | 150 | 50 | 50 | 70 | 40 | 70 | 60 |
| I—13 | 150 | 80 | 60 | 30 | 55 | 90 | 30 |
| I—14 | 150 | 80 | 70 | 45 | 90 | 80 | 50 |
| I—15 | 150 | 80 | 65 | 75 | 50 | 100 | 75 |
| I—17 | 150 | 70 | 80 | 78 | 40 | 100 | 70 |
| I—19 | 150 | 80 | 80 | 70 | 40 | 100 | 80 |
| I—20 | 150 | 80 | 80 | 90 | 60 | 90 | 70 |
| I—21 | 150 | 80 | 80 | 80 | 50 | 100 | 70 |
The weeding activity size evaluation result second time that cauline leaf is handled behind table 3 bud
The weeding activity size evaluation result second time of soil treatment before table 4 bud
The crop safety test-results of foliar treatment behind table 5 seedling
Claims (7)
1. a N-(2-2-pyrimidinyl oxy) benzyl amide compounds, its general structure is as follows:
Wherein: D or E=halogen, hydroxyl, C
1-C
4Alkoxyl group or C
1-C
4Halogenated alkoxy;
X=hydrogen, halogen, nitro, C
1-C
8Alkyl, C
1-C
8Haloalkyl, C
1-C
8Alkoxyl group; R=C
1-C
8Alkyl, R
1Substituted-phenyl, R
1Substituted heterocyclic radical, C
1-C
8Alkoxyl group or R
1Substituted heterocyclic radical oxygen base, R
2And R
3Substituted amido or R
1The substituted heterocyclic radical sulfoamido; R wherein
1=hydrogen, halogen, nitro, cyano group, carboxyl, ester group, alkylsulfonyl, C
1-C
8Alkyl amido, C
1-C
8Haloalkylamido, C
1-C
8Alkyloyl, C
1-C
8Alkyl, C
1-C
8Haloalkyl, C
1-C
8Alkoxyl group, phenyl or heterocyclic radical; R
2=hydrogen, C
1-C
8Alkyloyl, C
1-C
8Haloalkane acyl group, benzoyl, benzoyl or C
1-C
8Alkyl; R
3=ester group, alkylsulfonyl, C
1-C
8Alkyl, C
1-C
8Haloalkyl, C
1-C
8Alkoxyl group, C
1-C
8Alkyloyl, phenyl or heterocyclic radical;
Described heterocyclic radical is pyridyl, thienyl, thiazolyl or pyrimidyl.
2. a kind of N-as claimed in claim 1 (2-2-pyrimidinyl oxy) benzyl amide compounds is characterized in that in the described structural formula, wherein D and E are methoxyl group.
3. the preparation method of an a kind of N-as claimed in claim 1 (2-2-pyrimidinyl oxy) benzyl amide compounds, its feature makes by following method:
(1) be that room temperature is to solvent boiling point in organic solvent neutralization reaction temperature, oxammonium hydrochloride, substituted salicylic aldehydes reaction response under the alkali effect made intermediate (II) in 0.5 to 12 hour, and the mol ratio of described oxammonium hydrochloride, substituted salicylic aldehydes and alkali is followed successively by 1: (0.8-2): (0.1-1); Described alkali is hydride, alcoxyl metallic compound or the carbonate of sodium methylate or sodium ethylate, potassium methylate or potassium ethylate, triethylamine or pyridine or monovalence or divalent metal;
(2) be room temperature 40 degree extremely Celsius in organic solvent neutralization reaction temperature, intermediate (II) made intermediate (III) in 0.5 to 10 hour with the reductive agent reaction, and described intermediate (II) is 1 with the mol ratio of reductive agent: 3-6, and described reductive agent is a zinc powder;
Or reactant (II) is under the effect of catalyzer, with hydrogen reducing compound (II), makes intermediate (III) in 0.5 to 10 hour in room temperature to 40 degree reactions Celsius, and described catalyzer is Raney Ni, palladium carbon or platinum black; The mol ratio of described reactant (II), hydrogen and catalyzer is 1: (1-1000): (0.01-0.5);
(3) intermediate (IV), amide structure can make with replacing acyl chlorides, chloro-formic ester and intermediate (III) during carbamate; Ureas is with replacing amine, and under the triphosgene condition, (III) becomes urea with intermediate; During the sulfonylurea structure, adopt the reaction of substituted sulfonic acid carbimide method and intermediate (III) to constitute;
(4) in the presence of the organic solvent neutralization bases, intermediate (IV) and 2-halo-4-D, 6-E-substituted pyrimidines or 2-methylsulfonyl-4-D, the 6-E-substituted pyrimidines made target product N-(2-2-pyrimidinyl oxy) benzyl amide compounds in 0.5 to 20 hour in reaction, 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 or pyridine, temperature of reaction are that room temperature is to solvent boiling point;
Above-mentioned intermediate (II), intermediate (III) and intermediate (IV) structural formula are as follows successively respectively:
Wherein, D, E, X, R are shown in claim 1.
4. the preparation method of a kind of N-as claimed in claim 3 (2-2-pyrimidinyl oxy) benzyl amide compounds, in the described step of its feature (1) and (2), optimum solvent is an alcoholic solvent; In the described step (3), optimum solvent is an ether solvent.
5. the preparation method of a kind of N-as claimed in claim 3 (2-2-pyrimidinyl oxy) benzyl amide compounds, the final product that it is characterized in that step (4) is through silica gel column chromatography or recrystallization purifying.
6. the purposes of an a kind of N-as claimed in claim 1 (2-2-pyrimidinyl oxy) benzyl amide compounds is characterized in that being used for the pesticide composition of agrochemicals weedicide or chemical herbicide.
7. the purposes of an a kind of N-as claimed in claim 6 (2-2-pyrimidinyl oxy) benzyl amide compounds is characterized in that containing in the described pesticide composition acceptable carrier in claim 1 compound of herbicidally effective amount and the weeding.
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