CN101367798B - N-(2-pyrimidine oxygen based) benzyl hetercyclic compounds, preparation method and uses thereof - Google Patents
N-(2-pyrimidine oxygen based) benzyl hetercyclic compounds, preparation method and uses thereof Download PDFInfo
- Publication number
- CN101367798B CN101367798B CN2008102010267A CN200810201026A CN101367798B CN 101367798 B CN101367798 B CN 101367798B CN 2008102010267 A CN2008102010267 A CN 2008102010267A CN 200810201026 A CN200810201026 A CN 200810201026A CN 101367798 B CN101367798 B CN 101367798B
- Authority
- CN
- China
- Prior art keywords
- solvent
- midbody
- compound
- heterocyclic compound
- benzyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to an N-(2-pyrimidinyloxy) phenmethyl heterocyclic compound. The compound has a general structural formula as shown below, wherein, D or E is hydrogen, 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 hydrogen, halogen, nitryl, cyano, carboxyl, ester group, sulphonyl, C1-C8 alkoxy amido, C1-C8 alkylogen amino, C1 - C8 halogenating alkylogen amino, C1-C8 halogenating alkyl sulfanilamide, C1-C8 alkyloxyacyl, C1-C8 alkyl, C1-C8 halogenating alkyl, benzyl, bezno or heterocyclic radical, C1-C8 alkoxyl, phenoxy or heterocyclic epoxy radical; and the Figure shows conjugate connected through N-N bonds or non-conjugate five-membered heterocycle or six-membered heterocycle.
Description
Technical field
The present invention relates to one type of new N-(2-2-pyrimidinyl oxy) benzyl heterocyclic compound, preparation method and as the purposes of agrochemicals weedicide.
Background technology
People such as Lv Long have reported one type of new 2-pyrimidinyl oxy-benzyl substituted aryl amino derivative, 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.On this basis, the arylbenzylamines structure is changed into not at N, N lopps structure, its activity is significantly improved, and becomes one type and has higher weeding activity brand new.
Summary of the invention
The problem that the present invention will solve provides a kind of new compound, i.e. N-(2-2-pyrimidinyl oxy) benzyl heterocyclic 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 heterocyclic compound is shown in (I):
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 or C
1-C
8Alkoxyl group can be in any one position in 3,4,5,6 on phenyl ring;
R=hydrogen, halogen, nitro, cyanic acid, carboxyl, ester group, alkylsulfonyl, C
1-C
8Alkyl amido, C
1-C
8Alkane sulfonamido, C
1-C
8Haloalkylamido, C
1-C
8Haloalkane sulfonamido, C
1-C
8Alkyloyl, C
1-C
8Alkyl, C
1-C
8Haloalkyl, phenyl, benzo base, heterocyclic radical, C
1-C
8Alkoxyl group, phenoxy or heterocyclic oxy group;
Expression is with N, conjugation or non-conjugated five yuan or hexa-member heterocycle that the N key links to each other.
structure is following:
R wherein
1Be ester group, alkylsulfonyl, C
1-C
8Alkyloyl, C
1-C
8Alkane alkylsulfonyl, C
1-C
8Haloalkane acyl group, C
1-C
8Haloalkane alkylsulfonyl, C
1-C
8Alkyl, C
1-C
8Haloalkyl or phenyl.
Described R substituting group is recommended as single replacement, two replacements, three replacements or quaternary halogen, nitro, cyanic acid, 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, typical compound involved in the present invention is listed in table one.
Table one
Compound N involved in the present invention-(2-2-pyrimidinyl oxy) benzyl heterocyclic compound can use following reactions step synthetic:
R in the above-mentioned reaction formula, X and D, the substituting group of E representative as previously mentioned.
Midbody (I) is synthetic by salicylic aldehyde or substituted salicylic aldehydes and 2-halo-4-D, and 6-E-substituted pyrimidines or 2-methylsulfonyl-4-D, 6-E-substituted pyrimidines react in the presence of alkali and make.In this step reaction, used alkali can be hydrogenate, alcoxyl metallic compound or its carbonate of monovalence or divalent metal, like 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 YLENE; Halogenated hydrocarbon solvents such as methylene dichloride, ethylene dichloride or chloroform; Ether solvent such as THF or dioxane; Ketones solvent such as acetone or MIBK; Methyl alcohol, alcoholic solvents such as ethanol or Virahol; Also can use the mixture of N, methyl-sulphoxide, acetonitrile and above-mentioned solvent, the optimum solvent of this reaction is N, dinethylformamide.Temperature of reaction be room temperature to solvent boiling point, the reaction times is 0.5 to 20 hour.Salicylic aldehyde or substituted salicylic aldehydes, 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.
The synthetic of midbody (II) can make through reducing compound (I); Reductive agent can be Peng Qinghuana or POTASSIUM BOROHYDRIDE 97MIN; Reactant (I) is 1:0.5-2 with the mol ratio of reductive agent; 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 YLENE; Ether solvent such as THF or dioxane; Methyl alcohol, alcoholic solvents such as ethanol or Virahol; Also can use the mixture of N, methyl-sulphoxide, acetonitrile and above-mentioned solvent, the optimum solvent of this reaction is an alcohols.
The synthetic of midbody (III) can make through compound (II) bromination; Reactant (II) is 1 with the mol ratio of bromide reagent: (1.5-2); Temperature of reaction is extremely 40 ℃ Celsius of room temperatures, reacts 0.5 to 10 hour, and solvent can be varsols such as benzene, toluene or YLENE; Ether solvent such as THF or dioxane; Methyl alcohol, alcoholic solvents such as ethanol or Virahol; Also can use the mixture of N, methyl-sulphoxide, acetonitrile and above-mentioned solvent, the optimum solvent of this reaction is an ethers.
At last; Midbody (III) and compound (IV) reacted in the presence of alkali make title product (V); In this step reaction, used alkali can be hydrogenate, alcoxyl metallic compound or its carbonate of monovalence or divalent metal, like sodium hydride, potassium hydride KH, hydrolith; Sodium methylate or sodium tert-butoxide, potassium methylate or potassium tert.-butoxide; 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 YLENE; Halogenated hydrocarbon solvents such as methylene dichloride, ethylene dichloride or chloroform; Ether solvent such as THF or dioxane; Ketones solvent such as acetone or MIBK; Methyl alcohol, alcoholic solvents such as ethanol or Virahol; Also can use the mixture of N, 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.The mol ratio of midbody (III), reactant (IV) and alkali is (1.0-1.2): 1: (1.2-1.5).Final product can be further purified through silica gel column chromatography or recrystallization.In addition, this title product (V) also can be reacted in the presence of reductive agent by midbody (II) and compound (IV) and make.Reductive agent can be more weak sodium cyanoborohydride of reductibility or cyanic acid POTASSIUM BOROHYDRIDE 97MIN; The mol ratio of midbody (II), reactant (IV) and reductive agent is 1: (1.5-2): (1.2-2); 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 YLENE; Ether solvent such as THF or dioxane; Methyl alcohol, alcoholic solvents such as ethanol or Virahol; Also can use the mixture of N, methyl-sulphoxide, acetonitrile and above-mentioned solvent, the optimum solvent of this reaction is an alcohols.
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 heterocyclic 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 zeyssatite; 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, YLENE, 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, terepthaloyl moietie, USP Kosher and hexalin etc.; And their ether and ester; Also have ketone, for example acetone, pimelinketone and N 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, T 46155 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, X 2073, 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 like tackiness agent, skimmer, 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 is high, 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; Than gramineous weeds, broadleaf weeds and the nutgrass flatsedge of effectively control sensitivity under the low dosage, concrete controlling object comprises float at careless (Echinochloacrusgalli), the lady's-grass (Digitaria sanguinalis) of barnyard grass, Herba Eleusines Indicae (Eleusine indica), Herba Setariae Viridis (Setariaviridis), annual bluegrass (Poa annua), ild avena sativa (Avena fatua), amur foxtail (Alopecurus aequalis), Japanese 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), sunshine careless (Fimbristylis miliacea), 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 10; Embodiment 11 to embodiment 15 provides with compound of the present invention as active constituent; The concrete instance of processing preparation several herbicides formulation; Embodiment 16 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 instance.
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 heterocyclic compound
Synthesize example with 1:
The first step: with 4; 6-dimethoxy-2-methylsulfonyl pyrimidine condensation: with 12.2g (0.1mol) salicylic aldehyde, 21.8g (0.1mol) 4,6-dimethoxy-2-methylsulfonyl pyrimidine; With 41.4g (0.3mol) Anhydrous potassium carbonate 40 ℃ of reactions of oil bath 8-9h in the acetonitrile of 150mL, TLC controls reaction end.Sherwood oil and re-crystallizing in ethyl acetate got the pure article of 22.5g, yield 86.7% after filtration was revolved and done.
Second the step: with the condensation of pyrimidine salicylic aldehyde: 260mg (1mmol) pyrimidine salicylic aldehyde is dissolved in the 20mL anhydrous methanol; Add 326mg (2mmol) compound (IV); The hydrochloric acid of the 5N of 200mg (2mmol) is added drop-wise in the reaction solution, and at room temperature stirring reaction 0.5h joins 76mg (1.2mmol) sodium cyanoborohydride in the reaction solution again; Reaction 2-4h, TLC controls reaction end.The sodium cyanoborohydride that the saturated aqueous ammonium chloride cancellation is excessive; With sodium bicarbonate aqueous solution reaction solution is washed till neutrality again, last dichloromethane extraction twice merges organic phase; Saturated aqueous common salt and water are respectively washed once; Anhydrous sodium sulfate drying, filter revolve do the back column chromatography (sherwood oil: ETHYLE ACETATE=3:1) the pure article of 270mg, yield 66.3%.
Solid
m.p.：113.1±0.5℃
1H?NMR(300MHz，DMSO)：δ2.88(2H，t，CH
2，J＝4.2Hz)，3.63(6H，s，OCH
3)，4.07(2H，s，CH
2)，4.26(2H，t，CH
2，J＝4.2Hz)，5.82(1H，s，CH)，7.09-7.46(4H，m，CH)，7.36(1H，d，CH，J＝1.5Hz)，7.36(1H，d，CH，J＝3Hz)，8.42(1H，d，CH，J＝1.5Hz)，8.42(1H，d，CH，J＝3Hz)
MS(ESI)：408(M+H
+)，430(M+Na
+)，462(M+MeOH+Na
+)
E.A.for?C
21H
21N
5O
4
Embodiment 2
Synthesize example with 5:
The first step: with 4; 6-dimethoxy-2-methylsulfonyl pyrimidine condensation: with 12.2g (0.1mol) salicylic aldehyde, 21.8g (0.1mol) 4,6-dimethoxy-2-methylsulfonyl pyrimidine; With 41.4g (0.3mol) Anhydrous potassium carbonate 40 ℃ of reactions of oil bath 8-9h in the acetonitrile of 150mL, TLC controls reaction end.Sherwood oil and re-crystallizing in ethyl acetate got the pure article of 22.5g, yield 86.7% after filtration was revolved and done.
Second step: salicylic aldehyde reduction: 3g (11.5mmol) pyrimidine salicylic aldehyde is dissolved in the 40mL absolute ethyl alcohol, adds 526mg (13.8mmol) Peng Qinghuana, room temperature reaction 0.5-2h, TLC controls reaction end.Reaction solution is poured in the frozen water, the Peng Qinghuana that the saturated aqueous ammonium chloride cancellation is excessive, ethyl acetate extraction twice merges organic phase, saturated aqueous common salt and water are respectively washed once, anhydrous sodium sulfate drying, filter revolve must 2.84g after doing pure article, yield 94.3%.
The 3rd step: bromination: 2.84g (10.8mmol) compound (II) is dissolved among the anhydrous THF of 40mL, nitrogen protection, slow Dropwise 5 .27g (19.5mmol) phosphorus tribromide under the ice-water bath, room temperature reaction 0.5-2h, TLC controls reaction end.Reaction solution is poured in the frozen water, and ethyl acetate extraction twice merges organic phase, and saturated aqueous common salt and water are respectively washed once, and anhydrous sodium sulfate drying filters to revolve and does the pure article that the back ethyl alcohol recrystallization gets 2.02g, yield 57.7%.
The 4th step: affine replacement: 65mg (1.0mmol) pyrazoles is dissolved among the anhydrous THF of 30mL, adds 112mg (1.0mmol) potassium tert.-butoxide, add 325mg (1.0mmol) compound (III) again behind the reaction 0.5h.Room temperature reaction 8-9h, TLC controls reaction end.Filtration revolve do the back column chromatography (sherwood oil: ETHYLE ACETATE=5:1) the pure article of 191mg, yield 63.1%.
Oil
1H?NMR(300MHz，DMSO)：δ3.72(6H，s，OCH
3)，5.25(2H，s，CH
2)，5.96(1H，s，CH)，6.18(1H，t，CH，J＝2.4Hz)，7.06(1H，dd，CH，J＝0.6Hz)，7.18-7.38(4H，m，CH)，7.63(1H，dd，CH，J＝0.6Hz)
MS(ESI)：341(M+H
+)，363(M+Na
+)，395(M+MeOH+Na
+)
E.A.for?C
18H
20N
4O
3
Embodiment 3
2 synthetic, experimental procedure is with embodiment 1 in detail: (1) and 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: charging capacity 0.1mol6-chloro-salicylic aldehyde, must product 15.4g, yield 69.3%.(2) with the condensation of pyrimidine salicylic aldehyde: charging capacity 2mmol compound (IV) and 1.2mmol sodium cyanoborohydride, reaction 2-4h, TLC controls reaction end.Column chromatography (sherwood oil: ETHYLE ACETATE=3:1) the pure article of 193mg, yield 53.6%.
Solid
m.p.：125.6±0.5℃
1H?NMR(300MHz，DMSO)：δ3.04(2H，t，CH
2，J＝4.2Hz)，3.70(6H，s，OCH
3)，4.26(2H，s，CH
2)，4.43(2H，t，CH
2，J＝4.2Hz)，5.92(1H，s，CH)，7.39-7.55(3H，m，CH)，7.45(1H，d，CH，J＝1.5Hz)，7.45(1H，d，CH，J＝3Hz)，8.48(1H，d，CH，J＝1.5Hz)，8.48(1H，d，CH，J＝3Hz)
MS(ESI)：442(M+H
+)，464(M+Na
+)，496(M+MeOH+Na
+)
E.A.for?C
21H
20ClN
5O
4
Embodiment 4
3 synthetic, experimental procedure is with embodiment 1 in detail: (1) and 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: charging capacity 0.1mol salicylic aldehyde, must product 22.5g, yield 86.7%.(2) with the condensation of pyrimidine salicylic aldehyde: charging capacity 2mmol compound (IV) and 1.2mmol sodium cyanoborohydride, reaction 2-4h, TLC controls reaction end.Column chromatography (sherwood oil: ETHYLE ACETATE=3:1) the pure article of 266mg, yield 65.4%.
Oil
1H?NMR(300MHz，DMSO)：δ2.85(2H，t，CH
2，J＝4.2Hz)，3.63(6H，s，OCH
3)，4.01(2H，s，CH
2)，4.27(2H，t，CH
2，J＝4.2Hz)，5.83(1H，s，CH)，7.09-7.48(4H，m，CH)，7.78(1H，d，CH，J＝1.5Hz)，7.78(1H，d，CH，J＝3Hz)，8.43(1H，d，CH，J＝1.5Hz)，8.43(1H，d，CH，J＝3Hz)MS(ESI)：408(M+H
+)，430(M+Na
+)，462(M+MeOH+Na
+)
E.A.for?C
21H
21N
5O
4
Embodiment 5
4 synthetic, experimental procedure is with embodiment 1 in detail: (1) and 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: charging capacity 0.1mol6-chloro-salicylic aldehyde, must product 15.4g, yield 69.3%.(2) with the condensation of pyrimidine salicylic aldehyde: charging capacity 2mmol compound (IV) and 1.2mmol sodium cyanoborohydride, reaction 2-4h, TLC controls reaction end.Column chromatography (sherwood oil: ETHYLE ACETATE=2:1) the pure article of 265mg, yield 74.1%.
Oil
1H?NMR(300MHz，DMSO)：δ3.01(2H，t，CH
2，J＝4.2Hz)，3.70(6H，s，OCH
3)，4.22(2H，s，CH
2)，4.27(2H，t，CH
2，J＝4.2Hz)，5.92(1H，s，CH)，7.24-7.45(3H，m，CH)，7.83(1H，d，CH，J＝1.5Hz)，7.83(1H，d，CH，J＝3Hz)，8.50(1H，d，CH，J＝1.5Hz)，8.50(1H，d，CH，J＝3Hz)
MS(ESI)：442(M+H
+)，464(M+Na
+)，496(M+MeOH+Na
+)
E.A.for?C
21H
20ClN
5O
4
Embodiment 6
6 synthetic, experimental procedure is with embodiment 2 in detail: (1) and 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: charging capacity 0.1mol6-chloro-salicylic aldehyde, must product 15.4g, yield 69.3%.(2) reduction: charging capacity 23.5mmol pyrimidine salicylic aldehyde and 28.2mmol Peng Qinghuana get product 6.53g, yield 87.1%.(3) bromination: charging capacity 39.6mmol phosphorus tribromide gets product 4.85g, yield 61.3%.(4) affine replacement: charging capacity 1mmol pyrazoles, column chromatography (sherwood oil: ETHYLE ACETATE=3:1) the pure article of 296mg, yield 80.8%.
Solid
m.p.：108.2±0.5℃
1H?NMR(300MHz，DMSO)：δ3.69(6H，s，OCH
3)，5.35(2H，s，CH
2)，5.94(1H，s，CH)，6.07(1H，t，CH，J＝1.8Hz)，7.24-7.49(5H，m，CH)
MS(ESI)：375(M+H
+)，397(M+Na
+)，429(M+MeOH+Na
+)
E.A.for?C
18H
19ClN
4O
3
Embodiment 7
7 synthetic, experimental procedure is with embodiment 2 in detail: (1) and 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: charging capacity 0.1mol salicylic aldehyde, must product 22.5g, yield 86.7%.(2) reduction: charging capacity 21.3mmol pyrimidine salicylic aldehyde and 25.6mmol Peng Qinghuana get product 4.97g, yield 89.7%.(3) bromination: charging capacity 34.4mmol phosphorus tribromide gets product 4.42g, yield 71.4%.(4) affine replacement: charging capacity 1.7mmol3, the 5-dimethyl pyrazole, column chromatography (sherwood oil: ETHYLE ACETATE=3:1) the pure article of 332mg, yield 67.5%.
Oil
1H?NMR(300MHz，DMSO)：δ2.01(3H，s，CH
3)，2.08(3H，s，CH
3)，3.73(6H，s，OCH
3)，5.07(2H，s，CH
2)，5.75(1H，s，CH)，5.96(1H，s，CH)，6.81-7.33(4H，m，CH)
MS(ESI)：313(M+H
+)，335(M+Na
+)，367(M+MeOH+Na
+)
E.A.for?C
16H
16N
4O
3
Embodiment 8
8 synthetic, experimental procedure is with embodiment 2 in detail: (1) and 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: charging capacity 0.1mol6-chloro-salicylic aldehyde, must product 15.4g, yield 69.3%.(2) reduction: charging capacity 23.5mmol pyrimidine salicylic aldehyde and 28.2mmol Peng Qinghuana get product 6.53g, yield 87.1%.(3) bromination: charging capacity 39.6mmol phosphorus tribromide gets product 4.85g, yield 61.3%.(4) affine replacement: charging capacity 1.3mmol3, the 5-dimethyl pyrazole, column chromatography (sherwood oil: ETHYLE ACETATE=3:1) the pure article of 430mg, yield 86.9%.
Solid
m.p.：119.6±0.5℃
1H?NMR(300MHz，DMSO)：δ1.84(3H，s，CH
3)，2.18(3H，s，CH
3)，3.68(6H，s，OCH
3)，5.13(2H，s，CH
2)，5.52(1H，s，CH)，5.89(1H，s，CH)，7.19-7.41(3H，m，CH)
MS(ESI)：347(M+H
+)，369(M+Na
+)，401(M+MeOH+Na
+)
E.A.for?C
16H
15ClN
4O
3
Embodiment 9
9 synthetic, experimental procedure is with embodiment 2 in detail: (1) and 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: charging capacity 0.1mol salicylic aldehyde, must product 22.5g, yield 86.7%.(2) reduction: charging capacity 21.3mmol pyrimidine salicylic aldehyde and 25.6mmol Peng Qinghuana get product 4.97g, yield 89.7%.(3) bromination: charging capacity 34.4mmol phosphorus tribromide gets product 4.42g, yield 71.4%.(4) affine replacement: charging capacity 1.3mmol triazole, column chromatography (sherwood oil: ETHYLE ACETATE=2:1) the pure article of 220mg, yield 50.2%.
Oil
1H?NMR(300MHz，DMSO)：δ3.71(6H，s，OCH
3)，5.34(2H，s，CH
2)，5.96(1H，s，CH)，7.22-7.27(4H，m，CH)
MS(ESI)：314(M+H
+)，336(M+Na
+)，368(M+MeOH+Na
+)
E.A.for?C
15H
15N
5O
3
Embodiment 10
10 synthetic, experimental procedure is with embodiment 2 in detail: (1) and 4,6-dimethoxy-2-methylsulfonyl pyrimidine condensation: charging capacity 0.1mol6-chloro-salicylic aldehyde, must product 15.4g, yield 69.3%.(2) reduction: charging capacity 23.5mmol pyrimidine salicylic aldehyde and 28.2mmol Peng Qinghuana get product 6.53g, yield 87.1%.(3) bromination: charging capacity 39.6mmol phosphorus tribromide gets product 4.85g, yield 61.3%.(4) affine replacement: charging capacity 1.3mmol triazole, column chromatography (sherwood oil: ETHYLE ACETATE=2:1) the pure article of 226mg, yield 49.4%.
Solid
m.p.：150.3±0.5℃
1H?NMR(300MHz，DMSO)：δ3.72(6H，s，OCH
3)，5.47(2H，s，CH
2)，5.99(1H，s，CH)，7.27-7.49(3H，m，CH)
MS(ESI)：348(M+H
+)，370(M+Na
+)，402(M+MeOH+Na
+)
E.A.for?C
15H
14N
5O
3
Embodiment 11-18
11-18's is synthetic, and experimental procedure is with embodiment 1 in detail.
NMR, the MS detailed data is following:
11
1H?NMR(300MHz，DMSO)：δ1.5(2H，t，CH
2)，2.6(2H，t，CH
2)，3.72(6H，s，OCH
3)，4.2(2H，s，CH
2)，5.96(1H，s，CH)，7.18-7.38(4H，m，CH)，7.5(1H，t，CH)
MS(ESI)：315(M+H
+)，337(M+Na
+)，369(M+MeOH+Na
+)
12
1H?NMR(300MHz，DMSO)：δ1.6(2H，t，CH
2)，2.8(2H，t，CH
2)，3.73(6H，s，OCH
3)，4.45(2H，s，CH
2)，5.96(1H，s，CH)，7.22-7.46(3H，m，CH)，7.81(1H，t，CH)
MS(ESI)：349(M+H
+)，371(M+Na
+)，393(M+MeOH+Na
+)
13
1H?NMR(300MHz，DMSO)：δ2.74(2H，t，CH
2)，3.65(2H，t，CH
2)，3.72(6H，s，OCH
3)，3.81(2H，s，CH
2)，5.44(1H，s，CH)，7.18-7.38(4H，m，CH)，7.5(1H，s，CH)
MS(ESI)：331(M+H
+)，353(M+Na
+)，375(M+MeOH+Na
+)
14
1H?NMR(300MHz，DMSO)：δ2.74(2H，t，CH
2)，3.65(2H，t，CH
2)，3.72(6H，s，OCH
3)，4.2(2H，s，CH
2)，5.96(1H，s，CH)，7.22-7.48(3H，m，CH)，7.6(1H，s，CH)
MS(ESI)：365(M+H
+)，387(M+Na
+)，409(M+MeOH+Na
+)
15
1H?NMR(300MHz，DMSO)：δ2.74(3H，s，CH
3)，3.72(6H，s，OCH
3)，4.46(2H，s，CH
2)，4.97(2H，s，CH
2)，5.44(1H，s，CH)，7.18-7.38(4H，m，CH)
MS(ESI)：375(M+H
+)，397(M+Na
+)，419(M+MeOH+Na
+)
16
1H?NMR(300MHz，DMSO)：δ2.76(3H，s，CH
3)，3.73(6H，s，OCH
3)，4.48(2H，s，CH
2)，5.02(2H，s，CH
2)，5.81(1H，s，CH)，7.22-7.56(3H，m，CH)
MS(ESI)：409(M+H
+)，431(M+Na
+)，453(M+MeOH+Na
+)
17
1H?NMR(300MHz，DMSO)：δ3.72(6H，s，OCH
3)，4.42(2H，s，CH
2)，4.46(2H，s，CH
2)，5.44(1H，s，CH)，7.02-7.88(8H，m，CH)
MS(ESI)：489(M+H
+)，511(M+Na
+)，533(M+MeOH+Na
+)
18
1H?NMR(300MHz，DMSO)：δ3.73(6H，s，OCH
3)，4.46(2H，s，CH
2)，4.52(2H，s，CH
2)，5.61(1H，s，CH)，7.22-7.94(7H，m，CH)
MS(ESI)：523(M+H+)，545(M+Na
+)，567(M+MeOH+Na
+)
Embodiment 19 wettable powders
Wettable powder (WP) prescription: the compound with 15% (I-1) (table one), 5% sulfonated lignin (Mq), 1% ethoxylated dodecyl alcohol (JFC), 40% zeyssatite and 44% light calcium carbonate mix equably; Pulverize, promptly get 15% wettable powder.
Embodiment 20 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% YLENE heated and stirred are even, promptly get 10% missible oil.
Embodiment 21 granules
Granule (GR) prescription: the compound with 5% (I-1) (table one), 1% Z 150PH (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; Process 14-32 purpose particles, drying promptly gets 5% granule.
Embodiment 22 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% N, 5% Ucar 35; Surplus is a water; According to each constitutive property, process oil phase and water respectively, then under high-speed stirring; The two is mixed, form 15% aqueous emulsion of good dispersibility.
Embodiment 23 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% terepthaloyl moietie, 1% skimmer, surplus are water, in the adding sand milling still, are ground to certain fineness, process 15% suspension agent.
Embodiment 24 biological activity determinations
Below implement to provide and use compound of the present invention to carry out the instance of biological activity determination, it is to be noted that the present invention not merely is confined in the scope of following instance.
The weeding activity evaluation test is carried out according to following method:
The sandy loam of soil for preparation used in test, and the weeding activity test uses basin alms bowl diameter to be 9.5cm, and safety testing uses basin alms bowl diameter to be 12.0cm.
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 that compound is with 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 be compound with organic solvent dissolutions such as acetone, DMF, and add the laboratory preparation of 0.5% tween-80, thin up is needs dosage again.
The compound treatment concentration of active determination test is 75gai/ha, after the basin alms bowl of processing leaves standstill 1 day, puts into the greenhouse, continues to cultivate, and regularly waters 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 following:
| 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 |
The weeding activity test-results and the crop safety test-results of 75gai/ha dosage processing are for the first time seen table 1.
Living test is tested the result and shown: The compounds of this invention has good weeding activity, than low dosage 75gai/ha gramineous weeds and broadleaf weeds is had the good control effect; And under dosage 75gai/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 following:
| 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 |
Table 1 is the weeding activity test-results for the first time
| Numbering | Dosage (g ai/ha) | The barnyard grass grass | Herba Setariae Viridis | Lady's-grass | Leaf mustard | Amaranthus retroflexus | Eclipta prostrata | Cotton | Paddy rice | Rape | Wheat | Soybean |
| 1 | 75 | 85 | 85 | 85 | 40 | 60 | 10 | |||||
| 2 | 75 | 80 | 80 | 80 | 90 | 90 | 10 | 0 | 0 | 0 | 0 | 0 |
| 3 | 75 | 85 | 90 | 85 | 40 | 70 | 10 | |||||
| 4 | 75 | 90 | 85 | 85 | 95 | 90 | 10 | 0 | 0 | 0 | 0 | 0 |
| 5 | 75 | 60 | 75 | 70 | 60 | 85 | 40 | |||||
| 6 | 75 | 20 | 20 | 10 | 90 | 20 | 10 | |||||
| 7 | 75 | 60 | 60 | 50 | 0 | 10 | 0 | |||||
| 8 | 75 | 20 | 40 | 10 | 100 | 10 | 10 | |||||
| 9 | 75 | 50 | 60 | 50 | 20 | 10 | 10 | |||||
| 10 | 75 | 20 | 10 | 0 | 50 | 0 | 30 | |||||
| 11 | 75 | 30 | 30 | 20 | 80 | 20 | 10 | |||||
| 12 | 75 | 80 | 80 | 80 | 90 | 70 | 20 | 0 | 10 | 0 | 0 | 0 |
| 13 | 75 | 100 | 90 | 0 | 60 | 90 | 50 | 0 | 0 | 0 | 0 | - |
| 14 | 75 | 90 | 85 | 85 | 85 | 80 | 10 | 0 | 0 | 0 | 0 | 0 |
| 15 | 75 | 70 | 75 | 70 | 60 | 85 | 40 | - | - | - | - | - |
| 16 | 75 | 60 | 80 | 20 | 100 | 70 | 80 | 0 | 0 | 0 | 0 | 0 |
| 17 | 75 | 40 | 70 | 50 | 0 | 30 | 0 | - | - | - | - | - |
| 18 | 75 | 20 | 40 | 20 | 90 | 10 | 20 | - | - | - | - | - |
Claims (9)
1. a N-(2-2-pyrimidinyl oxy) benzyl heterocyclic compound, its general structure is following:
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 or C
1-C
8Alkoxyl group;
R=hydrogen, halogen, nitro, cyanic acid, carboxyl, ester group, alkylsulfonyl, C
1-C
8Alkyl amido, C
1-C
8Alkane sulfonamido, C
1-C
8Haloalkylamido, C
1-C
8Haloalkane sulfonamido, C
1-C
8Alkyloyl, C
1-C
8Alkyl, C
1-C
8Haloalkyl, phenyl, heterocyclic radical, C
1-C
8Alkoxyl group, phenoxy or heterocyclic oxy group;
Expression is with N, conjugation or non-conjugated five yuan or hexa-member heterocycle that the N key links to each other.
2. a kind of N-as claimed in claim 1 (2-2-pyrimidinyl oxy) benzyl heterocyclic compound, wherein D and E are methoxyl group.
3. a kind of N-as claimed in claim 1 (2-2-pyrimidinyl oxy) benzyl heterocyclic compound, described heterocyclic radical is pyridyl, thienyl, thiazolyl or pyrimidyl.
4. a kind of N-as claimed in claim 1 (2-2-pyrimidinyl oxy) benzyl heterocyclic compound, described
structure is following:
R wherein
1Be ester group, alkylsulfonyl, C
1-C
8Alkyloyl, C
1-C
8Alkyl, C
1-C
8Haloalkyl or phenyl.
5. the preparation method of a N-as claimed in claim 1 (2-2-pyrimidinyl oxy) benzyl heterocyclic compound, its characteristic makes through following two kinds of methods:
Method one:
(1.1) in organic solvent with room temperature to solvent boiling point, in the presence of alkali, the substituted salicylic aldehyde of X and 2-halo-4-D, 6-E-substituted pyrimidines or 2-methylsulfonyl-4-D, 6-E-substituted pyrimidines react and to make midbody (I) in 0.5 to 20 hour; The substituted salicylic aldehyde of X, 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 hydrogenate, alcoxyl metallic compound or the carbonate of triethylamine, pyridine or monovalence or divalent metal;
(1.2) organic solvent neutralization reaction temperature be room temperature to solvent boiling point, the mol ratio of reactant (I) and reductive agent is 1: (1.2-2), react and made midbody (II) in 0.5 to 10 hour, described reductive agent is Peng Qinghuana or POTASSIUM BOROHYDRIDE 97MIN;
(1.3) be Celsius 0 to spend to solvent boiling point in organic solvent neutralization reaction temperature, reactant (II) is 1 with the mol ratio of bromide reagent: (1.5-2), react and made midbody (III) in 0.5 to 4 hour, described bromide reagent is a phosphorus tribromide;
(1.4) in the presence of the organic solvent neutralization bases, reactant (III) made title product N-(2-2-pyrimidinyl oxy) benzyl heterocyclic compound in 0.5 to 20 hour with reactant (IV) reaction; The mol ratio of midbody (III), midbody (IV) and alkali is (1.0-1.2): 1: (1.2-1.5); Described alkali is hydrogenate, alcoxyl metallic compound or carbonate, triethylamine or the pyridine of monovalence or divalent metal; Temperature of reaction is that room temperature is to solvent boiling point;
Method two
(2.1) in the presence of the organic solvent neutralization bases, X substituted salicylic aldehydes and 2-halo-4-D, 6-E-substituted pyrimidines or 2-methylsulfonyl-4-D, the 6-E-substituted pyrimidines made midbody (I) in 0.5 to 20 hour in reaction; X substituted salicylic aldehydes, 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 hydrogenate, alcoxyl metallic compound or carbonate, triethylamine or the pyridine of monovalence or divalent metal; Temperature of reaction is that room temperature is to solvent boiling point;
(2.2) be room temperature in organic solvent neutralization reaction temperature; The mol ratio of reactant (II), reactant (IV) and reductive agent is 1: (1.5-2): (1.2-2); React and made title product N-(2-2-pyrimidinyl oxy) benzyl heterocyclic compound in 3 to 20 hours, described reductive agent is a sodium cyanoborohydride;
Above-mentioned midbody (I), midbody (II), midbody (III) and midbody (IV) structural formula are as follows:
Wherein, D, E, X, R or
are shown in claim 1.
6. the preparation method of a kind of N-as claimed in claim 5 (2-2-pyrimidinyl oxy) benzyl heterocyclic compound, in described step (1.1) and (2.1), optimum solvent is the amides polar solvent; In step (1.2) and (2.2), optimum solvent is an alcoholic solvent; In described step (1.3) and (1.4), optimum solvent is an ether solvent.
7. the preparation method of a kind of N-as claimed in claim 5 (2-2-pyrimidinyl oxy) benzyl heterocyclic compound is characterized in that final product is through silica gel column chromatography or recrystallization purifying.
8. the purposes of an a kind of N-as claimed in claim 1 (2-2-pyrimidinyl oxy) benzyl heterocyclic compound is characterized in that being used for the pesticide composition of agrochemicals weedicide or chemical herbicide.
9. the purposes of an a kind of N-as claimed in claim 9 (2-2-pyrimidinyl oxy) benzyl heterocyclic compound is characterized in that containing in the described pesticide composition acceptable carrier in compound as claimed in claim 1 and the weeding of herbicidally effective amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102010267A CN101367798B (en) | 2008-10-10 | 2008-10-10 | N-(2-pyrimidine oxygen based) benzyl hetercyclic compounds, preparation method and uses thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102010267A CN101367798B (en) | 2008-10-10 | 2008-10-10 | N-(2-pyrimidine oxygen based) benzyl hetercyclic compounds, preparation method and uses thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101367798A CN101367798A (en) | 2009-02-18 |
| CN101367798B true CN101367798B (en) | 2012-06-27 |
Family
ID=40411824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102010267A Expired - Fee Related CN101367798B (en) | 2008-10-10 | 2008-10-10 | N-(2-pyrimidine oxygen based) benzyl hetercyclic compounds, preparation method and uses thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101367798B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4770691A (en) * | 1985-10-15 | 1988-09-13 | Kumiai Chemical Industry Co., Ltd. | 2-(4',6'-di-substituted pyrimidine-2'-yl)oxy- or thio-benzoic acid |
-
2008
- 2008-10-10 CN CN2008102010267A patent/CN101367798B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4770691A (en) * | 1985-10-15 | 1988-09-13 | Kumiai Chemical Industry Co., Ltd. | 2-(4',6'-di-substituted pyrimidine-2'-yl)oxy- or thio-benzoic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101367798A (en) | 2009-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100203826B1 (en) | Urasil derivatives | |
| CN101935291B (en) | Cyano phthalic diamide compounds, preparation method thereof and use thereof as agricultural chemical pesticide | |
| KR100263409B1 (en) | Sulfonamide herbicides | |
| CN102216294A (en) | Ether compounds with nitrogen-containing 5-member heterocycle and the uses thereof | |
| WO2005068434A1 (en) | 2-pyrimidionxy-n-carbamidophenylbenzylamine compounds and processes of the preparation thereof and the use of the same | |
| CN101967139A (en) | Fluoro methoxylpyrazole-containing o-formylaminobenzamide compound, synthesis method and application thereof | |
| BRPI0616039A2 (en) | use of sulfonanilides as herbicide, sulfonanilides, process for their preparation and for weed control, as well as herbicidal composition and process for their preparation | |
| MX2010014027A (en) | Substituted 1-(diazinyl) pyrazole-4-yl-acetic acids, method for the production thereof, and use thereof as herbicides and plant growth regulators. | |
| KR850000993B1 (en) | Process for preparing n-phenylpyrazole derivatives | |
| CN102143688A (en) | 4-alkyl-substituted diaminopyrimidines | |
| BR102014006229A2 (en) | 4-amino-6- (4-substituted phenyl) picolinates and 6-amino-2- (4-substituted phenyl) pyrimidine-4-carboxylates and their uses as herbicides | |
| Yang et al. | Design, synthesis and herbicidal evaluation of novel uracil derivatives containing an isoxazoline moiety | |
| CN101875639B (en) | Substituted pyrimidinyl ether compound and application thereof | |
| Yoshimura et al. | Synthesis and herbicidal activity of sulfonanilides having a pyrimidinyl-containing group at the 2′-position | |
| TW212793B (en) | ||
| JP2004512326A (en) | 2-Pyrimidinyloxy-N-arylbenzylamine derivatives, their production and use | |
| CN100516052C (en) | Alcohol amide condensed ester compound and its preparation and use | |
| CN101367798B (en) | N-(2-pyrimidine oxygen based) benzyl hetercyclic compounds, preparation method and uses thereof | |
| CN101367766A (en) | (2-pyrimidine oxygen base)benzaldehyde hydrazone compounds, preparation method and uses thereof | |
| BR112020015620A2 (en) | PYRIDAZINOL COMPOUND WITH RING OF FIVE MEMBERS REPLACED AND ITS DERIVATIVES, METHOD OF PREPARATION, HERBICIDE COMPOSITION, AND APPLICATION | |
| CN101367769B (en) | N-(2-pyrimidine oxygen based) benzyl amide compounds, preparation method and uses thereof | |
| CN101381347B (en) | Miazines compounds, preparation method and use thereof | |
| CN100384840C (en) | 2-pyrimidine oxy-benzoic acid [2-(pyrimidine amino methyl)]benester compound, its preparation and use thereof | |
| CN101367768A (en) | N-(2-pyrimidine oxygen based)benzyl sulfonylamines compounds, preparation method and uses thereof | |
| EP0500934A1 (en) | Aralkyloxyamine derivative and herbicide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20090218 Assignee: Qiaochang Chemical Co., Ltd., Shandong Assignor: Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences Contract record no.: 2014370000102 Denomination of invention: N- (2- pyrimidine) benzyl heterocyclic compound, preparation method and use thereof Granted publication date: 20120627 License type: Exclusive License Record date: 20140605 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120627 Termination date: 20171010 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |