CN100343236C - [N-(2-pyrimidine oxy) benzylamino phenyl] sulfamine compound, and its preparing method and use - Google Patents
[N-(2-pyrimidine oxy) benzylamino phenyl] sulfamine compound, and its preparing method and use Download PDFInfo
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Abstract
The present invention relates to a [N-(2-pyrimidine oxy) benzylamino phenyl] sulfamine compound which has a structural general formula as shown right, wherein D or C equals C1 to C4 alkoxyl group or C1 to C4 halogenating alkoxyl group, X equals hydrogen, halogen, nitro group, C1 to C8 alkyl group, C1 to C8 halogenating alkyl group and C1 to C8 alkoxyl group, and R <1> and R2 equal hydrogen, halogen, nitro group, phenyl group, halogenating, C1 to C4 alkyl substitution phenyl group or heterocyclic group which is pyridyl, thienyl, thiazolyl or pyrimidinyl.
Description
Technical field
The present invention relates to new [N-(2-2-pyrimidinyl oxy) benzyl amino phenyl base] sulfamide compound of a class, preparation method and as the purposes of agrochemicals weedicide.
Background technology
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 (ZL00130735.5, ZL01112689.2, ZL01113199.3, CN1513321A and CN1488626A), they have very high weeding activity, and still different with above-mentioned pyrimidine salicylic acid weedicide is that the new herbicides that they are therefrom developed has good security to rape.Obviously, continually develop new agricultural chemicals initiative kind and be still our research topic.
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 amino phenyl base] sulfamide compound.
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 structural formula that the invention provides a kind of [N-(2-2-pyrimidinyl oxy) benzyl amino phenyl base] sulfamide compound 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.
X is hydrogen, halogen, nitro, C
1-C
8Alkyl, C
1-C
8Haloalkyl, C
1-C
8Alkoxyl group or the like can be in any one position in 3,4,5,6 on phenyl ring.
R
1, R
2Be hydrogen, C
1-C
8Alkyl, C
1-C
8Substituted alkyl (is recommended halogen or C
1-C
8The alkyl that alkoxyl group replaces, for example CH
2OCH
3, CH
2Cl etc.), phenyl, substituted-phenyl or heterocyclic radical such as pyridyl, thienyl, thiazolyl, pyrimidyl etc., perhaps R
1, R
2Be connected to-(CH
2)
mZ (CH
2)
k-, wherein Z is CH
2, NH, O or S, m, k are 1～6 integer.Recommend R
1, R
2Be H,
nBu or
nBu,
nBu, or R
1, R
2Be connected to-(CH
2)
5-.R
1, R
2It is identical or different group.
Substituting group on wherein said substituted-phenyl or the substituted benzoyl is recommended as single replacement, two replacements or polysubstituted halogen, nitro, cyano group, carboxyl, ester group, alkylsulfonyl, C
1-C
8Alkyl, C
1-C
8Haloalkyl, C
1-C
8Alkoxyl group, C
1-C
8Alkyloyl or C
1-C
8Alkyl amido etc.
The compound of recommending of the present invention has following general structure:
R in the formula
1, R
2, D, E, X as previously mentioned
Below, we list in table one with typical compound involved in the present invention.
Table one
Compound involved in the present invention [N-(2-2-pyrimidinyl oxy) benzyl amino phenyl base] sulfamide compound can be synthetic with following reactions steps:
R in the above-mentioned reaction formula
1, R
2, X and D, the substituting group of E representative is as previously mentioned.
Intermediate (I) is synthetic can be by nitrobenzene sulfonyl chloride and replacement amine prepared in reaction, and mol ratio is 1: 1 to 1: 2.Solvent can be varsols such as benzene, toluene or dimethylbenzene; Ether solvent such as tetrahydrofuran (THF) or dioxane; The optimum solvent of this reaction is a tetrahydrofuran (THF).Temperature of reaction be 0 ℃ to room temperature, the reaction times is 0.5 to 12 hour.Intermediate (II) is synthetic by reduction intermediate (I) preparation, can under the effect of catalyzer, make with hydrogen reducing intermediate (I), catalyzer can be Lay Buddhist nun nickel (Raney Ni), palladium carbon or platinum black etc., the mol ratio of intermediate (I), 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 (II) also can make with hydrazine hydrate reduction intermediate (I) under the effect of catalyzer, catalyzer can be a thunder formula nickel (RaneyNi) etc., the mol ratio of intermediate (I), 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, 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.
The synthetic sulfamic substituted 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, used catalyzer can be p-methyl benzenesulfonic acid, methylsulfonic acid, sulfuric acid, hydrochloric acid or acetic acid etc. in the reaction, and catalyzer and mol ratio (II) are 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 ℃ 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 extremely 40 ℃ Celsius of room temperatures, 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 (V), 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 amino phenyl base] sulfamide compound, 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 amino phenyl base] sulfamide compound
Synthesize example with I-4:
The first step: sulfonylation: the there-necked flask at the 100mL dropping funnel adds (5mmol) unsaturated carbonate potassium solution; 221.5mg (1.0mmol) p-nitrophenyl SULPHURYL CHLORIDE and 123mg (1.0mmol) ORTHO ANISIDINE; be heated to 60-70 ℃; add back stir about 2h; cross the leaching filter cake; get 4-oil of mirbane sulphonyl (2 '-methoxyl group) aniline 292mg, yield 95%.
Second step: nitroreduction: 292mg4-oil of mirbane sulphonyl (2 '-methoxyl group) aniline is dissolved in the 20mL anhydrous methanol, add 30mg (quality 10% that is equivalent to 4-oil of mirbane sulphonyl (2 '-methoxyl group) aniline) Raney Ni, 80% the hydrazine hydrate of 100mg (1.5mmol) is added drop-wise in the reaction solution, at room temperature be stirred to and react completely, TLC controls reaction end.After the filtration, filtrate be spin-dried for 285mg4-amino-benzene sulphonyl (2 '-methoxyl group) aniline, yield 98%.
The 3rd step: with the salicylic aldehyde condensation: 285mg4-amino-benzene sulphonyl (2 '-methoxyl group) aniline, and 122mg (1.0mmol) salicylic aldehyde is dissolved in the 15mL methyl alcohol, adds little acetic acid, Anhydrous potassium carbonate catalysis, backflow 4h pours in the frozen water, filter out yellow mercury oxide, directly drop into next step reaction.
The 4th step: Schiff alkali reduction: yellow mercury oxide is joined the 20mL dehydrated alcohol, adds the sodium borohydride of 56mg (1.5mmol) 97% in batches, at room temperature stir 30min after, pour in the frozen water, filter out white precipitate 290mg, two step total recoverys 75%.
The 5th step: with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: with 290mg (0.75mmol) imines reductive product (IV), 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 300mg, yield 80%.
Solid
m.p.：151.5±0.5℃
1H NMR(300MHz，CDCl
3/TMS)：
δ7.50-6.43(12H，m，CH)，7.49(1H，s，NH)，5.76(1H，s，CH)，4.32(2H，s，CH
2，)，3.77(6H，s，OCH
3)，3.64(3H，s，CH
3)
IR(KBr/cm
-1)：3399，3252(γ
N-H)，1600，1571(γ
C＝C)，1195(γ
＝C-O-C)
MS(EI)：335(m/z，100)，245(m/z，95.40)，157(m/z，55.58)，522(M
+.，3.30)
E.A.for C
26H
26N
4O
6S
Calcd：C 59.76，H 5.01，N 10.72
Found：C 59.57，H 5.09，N 10.63
Embodiment 2
I-1's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) sulfonylation: charging capacity 6mmol n-Butyl Amine 99 gets product 1.4g, yield 90%.(2) nitroreduction: charging capacity 6mmol sulfonylation product is spin-dried for the back and directly drops into next step, yield 99%.(3) with the salicylic aldehyde condensation: charging capacity 6mmol amino substance directly enters next step after being spin-dried for, yield 99%.(4) Schiff alkali reduction: charging capacity 6mmol imines thing gets 1.82 gram (5.44mmol) products, yield 90%.(5) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: the employing acetonitrile is a solvent, synthesizes charging capacity 1.82 gram (5.44mmol) imines reductive products, column chromatography (sherwood oil: ethyl acetate=3: 1) get pure product, yield 95% down at 40-50 ℃.
Solid
m.p.：132.2±0.5℃
1H NMR(300MHz，CDCl
3/TMS)：δ7.59-6.57(12H，m，CH)，5.78(1H，s，CH)，4.39(2H，s，CH
2)，3.81(6H，s，OCH
3)，2.89(2H，t，CH
2，J＝7.2Hz)，1.42(2H，m，CH
2)，1.28(2H，m，CH
2)，0.85(3H，t，CH
3，J＝7.5Hz)
IR(KBr/cm
-1)：3405，3318(γ
N-H)，2960，2935(γ
N-H)，1598，1570(γ
C＝C)，1196(γ
＝C-O-C)MS(EI)：157(m/z，72.86)，245(m/z，100)，335(m/z，85.61)，472(M
+.，4.53)
E.A.for C
23H
28N
4O
5S
Calcd：C 58.46，H 5.97，N 11.86
Found：C 58.55，H 5.97，N 11.78
Embodiment 3
I-2's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) sulfonylation: charging capacity 6mmol Di-n-Butyl Amine gets product 1.82g, yield 97%.(2) nitroreduction: charging capacity 6mmol sulfonylation product, when filtering RaneyNi, wash several times yield 99% in this step with trichloromethane.(3) with the salicylic aldehyde condensation: charging capacity 6mmol amino substance directly enters next step after being spin-dried for, yield 99%.(4) Schiff alkali reduction: charging capacity 6mmol imines thing gets 2.214 gram (5.671mmol) products, yield 95%.(5) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: the employing acetonitrile is a solvent, synthesizes charging capacity 2.214 gram (5.671mmol) imines reductive products, column chromatography (sherwood oil: ethyl acetate=2: 1) get pure product, yield 87% down at 40-50 ℃.
Solid
m.p.：106.0±0.5℃
1H NMR(300MHz，CDCl
3/TMS)：δ0.89(6H，t，CH
3，J＝7.2Hz)，1.25-1.35(4H，m，CH
2)，1.44-1.54(4H，m，CH
2)，3.64(4H，t，CH
2，J＝7.5Hz)，3.81(6H，s，OCH
3)，4.38(2H，d，CH
2，J＝5.7Hz)，4.38(1H，t，NH，J＝5.7Hz)，5.78(1H，s，CH)，6.52(2H，d，J＝8.7Hz)，7.15-7.41(4H，m)，7.52(2H，d，J＝8.7Hz)，
IR(KBr/cm
-1)：3383(γ
N-H)，1601，1519，1470(γ
C＝C)，1124，1193，1170，1144(γ
＝C-O-C)
MS(EI)：245(m/z，100)，528(M
+.，6.79)
E.A.for C
27H
36N
4O
5S
Calcd：C 61.34，H 6.86，N 10.60
Found：C 61.49，H 6.95，N 10.78
Embodiment 4
I-3's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) sulfonylation: charging capacity 6mmol 4-monomethylaniline gets product 1.52g, yield 87%.(2) nitroreduction: charging capacity 6mmol sulfonylation product, when filtering Raney Ni, wash several times yield 99% in this step with trichloromethane.(3) with the salicylic aldehyde condensation: charging capacity 6mmol amino substance directly enters next step after being spin-dried for, yield 99%.(4) Schiff alkali reduction: charging capacity 6mmol imines thing gets 2.01 gram (5.46mmol) products, yield 91%.(5) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: the employing acetonitrile is a solvent, synthesizes charging capacity 6mmol imines reductive product, column chromatography (sherwood oil: ethyl acetate=3: 1) get pure product, yield 96% down at 40-50 ℃.
Solid
m.p.：137.2±0.5℃
1H NMR(300MHz，CDCl
3/TMS)：δ7.46-6.41(12H，m，CH)，5.76(1H，s，CH)，4.60(1H，t，NH，J＝5.7Hz)，4.33(2H，d，CH
2，J＝5.1Hz)，3.77(6H，s，OCH
3)，2.27(3H，s，CH
3)
IR(KBr/cm
-1)：3408，3292(γ
N-H)，1599，1568(γ
C＝C)，1197(γ
＝C-O-C)
MS(EI)：335(m/z，73.60)，245(m/z，100)，157(m/z，52.98)，506(M
+.，4.18)
E.A.for C
26H
26N
4O
5S
Calcd：C 61.65，H 5.17，N 11.06
Found：C 61.64，H 5.23，N 10.97
Embodiment 5
I-5's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) sulfonylation: charging capacity 6mmol morphine quinoline gets product 1.51g, yield 92%.(2) nitroreduction: charging capacity 6mmol sulfonylation product, when filtering RaneyNi, wash several times yield 99% in this step with trichloromethane.(3) with the salicylic aldehyde condensation: charging capacity 6mmol amino substance directly enters next step after being spin-dried for, yield 99%.(4) Schiff alkali reduction: charging capacity 6mmol imines thing gets 1.83 gram (5.25mmol) products, yield 88%.(5) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: the employing acetonitrile is a solvent, synthesizes charging capacity 6mmol imines reductive product, column chromatography (sherwood oil: ethyl acetate=2: 1) get pure product, yield 89% down at 40-50 ℃.
Solid
m.p.：146.8±0.5℃
1H NMR(300MHz，CDCl
3/TMS)：δ7.48-6.53(12H，m，CH)，5.78(1H，s，CH)，4.68(1H，t，NH，J＝5.7Hz)，4.38(2H，d，CH
2，J＝5.7Hz)，3.79(6H，s，OCH
3)，3.72(4H，t，CH
2，J＝4.5Hz)，2.94(4H，t，CH
2，J＝4.5Hz)
IR(KBr/cm
-1)：3424(γ
N-H)，2868，2980(γ
C-H)1602，1573，1492(γ
C＝C)，1194(γ
＝C-O-C)
MS(EI)：335(m/z，92.69)，245(m/z，100)，157(m/z，66.98)，486(M
+.，3.72)
E.A.for C
23H
26N
4O
6S
Calcd：C 56.78，H 5.39，N 11.52
Found：C 56.73，H 5.43，N 11.42
Embodiment 6
I-6's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) sulfonylation: charging capacity 6mmol p-Chlorobenzoic acid amide gets product 1.69g, yield 90%.(2) nitroreduction: charging capacity 6mmol sulfonylation product, when filtering RaneyNi, wash several times yield 99% in this step with trichloromethane.(3) with the salicylic aldehyde condensation: charging capacity 6mmol amino substance directly enters next step after being spin-dried for, yield 99%.(4) Schiff alkali reduction: charging capacity 6mmol imines thing gets 2.1 gram (5.4mmol) products, yield 90%.(5) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: the employing acetonitrile is a solvent, synthesizes charging capacity 6mmol imines reductive product, column chromatography (sherwood oil: ethyl acetate=3: 1) get pure product, yield 91% down at 40-50 ℃.
Solid
m.p.：154.2±0.5℃
1H NMR(300MHz，CDCl
3/TMS)：δ8.03(1H，s，NH)，7.50-6.44(12H，m，CH)，5.76(1H，s，CH)，4.34(2H，s，CH
2)，3.77(6H，s，OCH
3)
IR(KBr/cm
-1)：3398，3252(γ
N-H)，1600，1571，1491(γ
C＝C)，1195(γ
＝C-O-C)
MS(EI)：157(m/z，60.00)，245(m/z，100)，335(m/z，38.03)，526(M
+.，2.30)
E.A.for C
25H
23ClN
4O
5S
Calcd：C 56.98，H 4.40，N 10.63
Found：C 57.29，H 4.57，N 10.38
Embodiment 7
I-7's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) sulfonylation: charging capacity 6mmol hexahydropyridine gets product 1.55g, yield 96%.(2) nitroreduction: charging capacity 4.61mmol sulfonylation product, when filtering Raney Ni, wash several times yield 99% in this step with trichloromethane.(3) with the salicylic aldehyde condensation: charging capacity 4.61mmol amino substance directly enters next step after being spin-dried for, yield 99%.(4) Schiff alkali reduction: charging capacity 4.61mmol imines thing gets 1.1 gram (3.16mmol) products, yield 69%.(5) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: the employing acetonitrile is a solvent, synthesizes charging capacity 1.1 gram (3.16mmol) imines reductive products, column chromatography (sherwood oil: ethyl acetate=2: 1) get pure product, yield 92% down at 40-50 ℃.
Solid
m.p.：190.1±0.5℃
1H NMR(300MHz，CDCl
3/TMS)：δ1.38-1.42(2H，m，CH
2)，1.59-1.67(4H，m，CH
2)，2.93(4H，t，CH
2，J＝5.7Hz)，3.81(6H，s，OCH
3)，4.38(2H，s，CH
2)，5.79(1H，s，CH)，6.53-7.49(8H，m，CH)
IR(KBr/cm
-1)：3379(γ
N-H)，1600，1531，1482(γ
C＝C)，1570(γ
C＝N)，1220，1158，1146(γ
＝C-O-C)
MS(EI)：335(m/z，100)，484(M
+.，3.11)
E.A.for C
24H
28N
4O
5S
Calcd：C 59.49，H 5.82，N 11.56
Found：C 59.37，H 5.79，N 11.58
Embodiment 8
I-8's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) sulfonylation: charging capacity 6mmol hexahydropyridine gets product 1.55g, yield 96%.(2) nitroreduction: charging capacity 4.61mmol sulfonylation product, when filtering Raney Ni, wash several times yield 99% in this step with trichloromethane.(3) with 6-chloro-salicylic aldehyde condensation: charging capacity 4.61mmol amino substance directly enters next step after being spin-dried for, yield 93%.(4) Schiff alkali reduction: charging capacity 4.61mmol imines thing gets 1.6 gram (4.3mmol) products, yield 93%.(5) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: the employing acetonitrile is a solvent, synthesizes charging capacity 1.6 gram (4.3mmol) imines reductive products, column chromatography (sherwood oil: ethyl acetate=2: 1) get pure product, yield 94% down at 40-50 ℃.
Solid
MS(ESI)：519
E.A.for C
24H
27ClN
4O
5S
Calcd：C 55.54，H 5.24，N 10.79
Found：C 55.47，H 5.32，N 10.67
Embodiment 9
I-9's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) sulfonylation: charging capacity 6mmol hexahydropyridine gets product 1.55g, yield 96%.(2) nitroreduction: charging capacity 4.61mmol sulfonylation product, when filtering Raney Ni, wash several times yield 99% in this step with trichloromethane.(3) with the salicylic aldehyde condensation: charging capacity 4.61mmol amino substance directly enters next step after being spin-dried for, yield 99%.(4) Schiff alkali reduction: charging capacity 4.61mmol imines thing gets 1.1 gram (3.16mmol) products, yield 69%.(5) with 4,6-dichloro methoxyl group-2-methylsulfonyl pyrimidine condensation: the employing acetonitrile is a solvent, synthesizes charging capacity 1.1 gram (3.16mmol) imines reductive products, column chromatography (sherwood oil: ethyl acetate=2: 1) get pure product, yield 89% down at 40-50 ℃.
Solid
MS(ESI)：552
E.A.for C
24H
26Cl
2N
4O
5S
Calcd：C 52.08，H 4.74，N 10.13
Found：C 52.03，H 4.82，N 10.21
Embodiment 10
I-10's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) sulfonylation: charging capacity 6mmol hexahydropyridine gets product 1.55g, yield 96%.(2) nitroreduction: charging capacity 4.61mmol sulfonylation product, when filtering Raney Ni, wash several times yield 99% in this step with trichloromethane.(3) with the condensation of 6-methoxysalicyl aldehyde: charging capacity 4.61mmol amino substance directly enters next step after being spin-dried for, yield 88%.(4) Schiff alkali reduction: charging capacity 4.61mmol imines thing gets 1.4 gram (3.65mmol) products, yield 79%.(5) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: the employing acetonitrile is a solvent, synthesizes charging capacity 1.4 gram (3.65mmol) imines reductive products, column chromatography (sherwood oil: ethyl acetate=2: 1) get pure product, yield 92% down at 40-50 ℃.
Solid
MS(ESI)：514
E.A.for C
25H
30N
4O
6S
Calcd：C 58.35，H 5.88，N 10.89
Found：C 58.42，H 5.82，N 10.91
Embodiment 11
I-11's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) sulfonylation: charging capacity 6mmol n-Butyl Amine 99 gets product 1.4g, yield 90%.(2) nitroreduction: charging capacity 6mmol sulfonylation product is spin-dried for the back and directly drops into next step, yield 99%.(3) with the condensation of 5-nitrosalicylaldehyde: charging capacity 6mmol amino substance directly enters next step after being spin-dried for, yield 81%.(4) Schiff alkali reduction: charging capacity 6mmol imines thing gets 2.24 gram (5.9mmol) products, yield 97%.(5) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: the employing acetonitrile is a solvent, synthesizes charging capacity 2.27 gram (6mmol) imines reductive products, column chromatography (sherwood oil: ethyl acetate=3: 1) get pure product, yield 95% down at 40-50 ℃.
Solid
MS(ESI)：517
E.A.for C
23H
27N
5O
7S
Calcd：C 53.38，H 5.26，N 13.53
Found：C 53.40，H 5.28，N 13.56
Embodiment 12
I-12's is synthetic, and experimental procedure is with embodiment 1:(1 in detail) sulfonylation: charging capacity 6mmol 4,6-dimethoxy-2-aminopyrimidine gets product 1.92g, yield 94%.(2) nitroreduction: charging capacity 6mmol sulfonylation product is spin-dried for the back and directly drops into next step, yield 98%.(3) with the salicylic aldehyde condensation: charging capacity 6mmol amino substance directly enters next step after being spin-dried for, yield 70%.(4) Schiff alkali reduction: charging capacity 6mmol imines thing gets 2.45 gram (5.88mmol) products, yield 98%.(5) with 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: the employing acetonitrile is a solvent, synthesizes charging capacity 2.45 gram (6mmol) imines reductive products, column chromatography (sherwood oil: ethyl acetate=3: 1) get pure product, yield 97% down at 40-50 ℃.
Solid
MS(ESI)：554
E.A.for C
25H
26N
6O
7S
Calcd：C 54.14，H 4.73，N 15.15
Found：C 54.20，H 4.69，N 15.19
Embodiment 13 wettable powders
Wettable powder (WP) prescription: the 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 15% wettable powder.
Embodiment 14 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 15 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 particle, drying promptly gets 5% granule.
Embodiment 11 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 12 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 13 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 sativa | 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-2 | 150 | 80 | 60 | 30 | 50 | 90 | 30 |
| I-3 | 150 | 80 | 80 | 95 | 60 | 100 | 85 |
| I-4 | 150 | 80 | 80 | 90 | 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 | 98 | 50 | 100 | 60 |
| I-8 | 150 | 80 | 80 | 65 | 50 | 90 | 60 |
| I-9 | 150 | 80 | 80 | 78 | 40 | 100 | 70 |
| I-10 | 150 | 80 | 80 | 90 | 40 | 100 | 80 |
| I-11 | 150 | 80 | 60 | 70 | 50 | 90 | 70 |
| I-12 | 150 | 80 | 80 | 60 | 50 | 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 | / | / | / | / | / | / |
| 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 | 70 | 70 | 75 | 70 | 90 | 80 |
| I-8 | 150 | 60 | 75 | 40 | 50 | 70 | 40 |
| I-9 | 150 | 50 | 60 | 60 | 60 | 65 | 60 |
| I-10 | 150 | 60 | 50 | 50 | 40 | 55 | 50 |
| I-11 | 150 | 70 | 75 | 65 | 50 | 60 | 40 |
| I-12 | 150 | 50 | 50 | 70 | 40 | 70 | 60 |
The weeding activity size evaluation result second time that cauline leaf is handled behind table 3 bud
| Compound number | Dosage (g ai/ha) | The barnyard grass grass | Lady's-grass | Herba Eleusines Indicae | Leaf mustard | Amaranthus retroflexus | Little lamb's-quarters |
| I-3 | 37.5 | 90 | 90 | 85 | 70 | 70 | 80 |
| 75 | 90 | 95 | 90 | 70 | 70 | 90 | |
| 150 | 95 | 98 | 95 | 70 | 70 | 90 |
| I-5 | 37.5 | 50 | 40 | 30 | 70 | 60 | 60 |
| 75 | 50 | 40 | 40 | 70 | 60 | 70 | |
| 150 | 60 | 50 | 40 | 70 | 75 | 75 | |
| I-6 | 37.5 | 85 | 85 | 90 | 60 | 70 | 80 |
| 75 | 85 | 85 | 90 | 60 | 70 | 85 | |
| 150 | 85 | 90 | 80 | 60 | 80 | 85 | |
| I-7 | 37.5 | 80 | 70 | 95 | 60 | 90 | 0 |
| 75 | 85 | 80 | 100 | 60 | 100 | 0 | |
| 150 | 90 | 85 | 100 | 60 | 100 | 0 |
The weeding activity size evaluation result second time of soil treatment before table 4 bud
| Compound number | Dosage (g ai/ha) | The barnyard grass grass | Lady's-grass | Herba Eleusines Indicae | Leaf mustard | Amaranthus retroflexus | Little lamb's-quarters |
| I-3 | 37.5 | 70 | 90 | 85 | 80 | / | 40 |
| 75 | 85 | 90 | 85 | 80 | / | 40 | |
| 150 | 85 | 98 | 90 | 85 | / | 80 | |
| I-5 | 37.5 | 70 | 85 | 80 | 60 | / | 70 |
| 75 | 85 | 90 | 85 | 80 | / | 70 | |
| 150 | 90 | 95 | 90 | 85 | / | 80 | |
| I-6 | 37.5 | 80 | 85 | 80 | 40 | / | 0 |
| 75 | 80 | 90 | 80 | 50 | / | 40 | |
| 150 | 85 | 95 | 85 | 50 | / | 40 | |
| I-7 | 37.5 | 50 | 60 | 50 | 40 | 70 | 0 |
| 75 | 60 | 70 | 60 | 50 | 80 | 30 | |
| 150 | 70 | 80 | 70 | 60 | 90 | 40 |
The crop safety test-results of foliar treatment behind table 5 seedling
| Compound number | Dosage (g ai/ha) | Corn | Wheat | Soybean | Cotton | Rape | Paddy rice |
| I-3 | 75 | 70 | 80 | 60 | 60 | 80 | 60 |
| I-4 | 75 | 0 | 0 | 5 | 0 | 0 | 10 |
| I-6 | 75 | 60 | 60 | 40 | 50 | 80 | 50 |
| I-7 | 37.5 | 10 | 0 | 20 | 20 | 0 | 0 |
| 75 | 10 | 10 | 30 | 30 | 0 | 0 | |
| 150 | 10 | 50 | 30 | 40 | 0 | 10 |
Claims (7)
1, a kind of [N-(2-2-pyrimidinyl oxy) benzyl amino phenyl base] sulfamide compound, its general structure is as follows:
Wherein: D or E=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
1, R
2=hydrogen, halogen, nitro, phenyl, halo or C1-C4 alkyl-substituted phenyl, pyridyl, thienyl, thiazolyl or pyrimidyl.
2, a kind of [N-(2-2-pyrimidinyl oxy) benzyl amino phenyl base] as claimed in claim 1 sulfamide compound is characterized in that in the described structural formula, wherein D and E are methoxyl group.
3, the preparation method of a kind of a kind of [N-(2-2-pyrimidinyl oxy) benzyl amino phenyl base] as claimed in claim 1 sulfamide compound, its feature makes by following method:
(1) be that room temperature is to solvent boiling point in organic solvent neutralization reaction temperature, under catalyst action, amino-benzene sulphonyl substituted aniline (II), substituted salicylic aldehydes and catalyst reaction, mol ratio is followed successively by 1: (0.8-2): (0.1-1), 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) be room temperature to 40 degree Celsius in organic solvent neutralization reaction temperature, reactant (III) is 1 with the mol ratio of reductive agent: 0.5-2, and react and made intermediate (IV) in 0.5 to 10 hour, described reductive agent is sodium borohydride or POTASSIUM BOROHYDRIDE; Described reactant (III) is 1 with the mol ratio of reductive agent: 0.5-2;
Or reactant (III) is under the effect of catalyzer, with hydrogen reducing compound (III), makes intermediate (IV) in 0.5 to 10 hour in room temperature to 40 degree reactions Celsius, and catalyzer is Lay Buddhist nun nickel, palladium carbon or platinum black; The mol ratio of reactant (III), hydrogen and catalyzer is 1: (1-1000): (0.01-0.5);
(3) 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 amino phenyl base] sulfamide compound 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 amino-benzene sulphonyl substituted aniline (II), intermediate (III) and intermediate (IV) structural formula are as follows successively respectively:
Wherein, D, E, X, R
1, R
2Shown in claim 1.
4, the preparation method of a kind of [N-(2-2-pyrimidinyl oxy) benzyl amino phenyl base] as claimed in claim 3 sulfamide compound, in the described method of its feature (1) and (2), described solvent is an alcoholic solvent; In the described method (3), described solvent is an ether solvent.
5, the preparation method of a kind of [N-(2-2-pyrimidinyl oxy) benzyl amino phenyl base] as claimed in claim 3 sulfamide compound is characterized in that final product is through silica gel column chromatography or recrystallization purifying.
6,, wherein contain acceptable carrier in claim 1 compound of herbicidally effective amount and the weeding as the pesticide composition of agrochemicals weedicide.
7, the purposes of a kind of a kind of [N-(2-2-pyrimidinyl oxy) benzyl amino phenyl base] as claimed in claim 1 sulfamide compound is characterized in that being used for the agrochemicals weedicide.
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| US10266488B2 (en) | 2013-10-10 | 2019-04-23 | Eastern Virginia Medical School | 4-((2-hydroxy-3-methoxybenzyl)amino)benzenesulfonamide derivatives as potent and selective inhibitors of 12-lipoxygenase |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347876A (en) * | 2001-04-20 | 2002-05-08 | 中国科学院上海有机化学研究所 | 2-pyrimidyloxybenzyl substituted naphthyl amine derivative and its synthesis and use |
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2005
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| CN1347876A (en) * | 2001-04-20 | 2002-05-08 | 中国科学院上海有机化学研究所 | 2-pyrimidyloxybenzyl substituted naphthyl amine derivative and its synthesis and use |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10266488B2 (en) | 2013-10-10 | 2019-04-23 | Eastern Virginia Medical School | 4-((2-hydroxy-3-methoxybenzyl)amino)benzenesulfonamide derivatives as potent and selective inhibitors of 12-lipoxygenase |
| US10752581B2 (en) | 2013-10-10 | 2020-08-25 | Eastern Virginia Medical School | 4-((2-hydroxy-3-methoxybenzyl)amino)benzenesulfonamide derivatives as potent and selective inhibitors of 12-lipoxygenase |
| US11274077B2 (en) | 2013-10-10 | 2022-03-15 | Eastern Virginia Medical School | 4-((2-hydroxy-3-methoxybenzyl)amino)benzenesulfonamide derivatives as potent and selective inhibitors of 12-lipoxygenase |
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