CN1056370C - 4-aryloxy (arylthio or arylamino) pyrimidine derivative with herbicide active, and method for prepn. of same - Google Patents
4-aryloxy (arylthio or arylamino) pyrimidine derivative with herbicide active, and method for prepn. of same Download PDFInfo
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- CN1056370C CN1056370C CN95112057A CN95112057A CN1056370C CN 1056370 C CN1056370 C CN 1056370C CN 95112057 A CN95112057 A CN 95112057A CN 95112057 A CN95112057 A CN 95112057A CN 1056370 C CN1056370 C CN 1056370C
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- sulphur
- oxygen
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Abstract
The present invention relates to 4-aryloxy (arylthio or arylamino) pyrimidine derivative which has herbicide activity and is disclosed in a general formula (I), and a preparation method thereof. The inventive compound of general formula (I) is a broad-spectrum herbicide which can be used for removing unwanted plants in orchards, forests, agriculture and pastures.
Description
The title compound general formula:
The past people have noticed the research of exploitation novel herbicide.The compound that EP346789 discloses following general formula is as weedicide:
Wherein: R
1, R
2, R
3, R
4, R
5Be substituting group: X=O, S; Y, Z=N, CH.
But this patent does not disclose the synthetic and weeding activity of any 4-benzene oxygen (sulphur or ammonia) yl pyrimidines derivative.
The compound that EP593252 discloses following general formula is as weedicide:
Wherein, X
1, X
2, X
3, R
1, R
2, R
3Be substituting group, X=O, S.
But this patent has only disclosed a class joint compound that closes substituted-phenyl on phenyl ring.
The present invention proposes and relate to new 4-virtue oxygen (sulphur or ammonia) yl pyrimidines derivative as weedicide with following general formula (I);
Wherein, A is the fragrant heterocycle that contains 1-3 oxygen, sulphur, nitrogen-atoms of (not) substituted benzene ring or (not) replacement, and for example A can be the substituting group shown in the A1-A4:
X is O, S (O) n (n=0,1,2), NR
5Y, Z, W=O, S, N, CH, NR
6R
1, R
2Be halogen, the alkyl that (not) replaces, the alkoxyl group that (not) replaces, the alkylamino that (not) replaces, the alkylthio that (not) replaces, the aryloxy that (not) replaces etc.; R
3, R
4Be hydrogen, halogen, nitro; (not) amino of Qu Daiing, the alkyl that (not) replaces, the aryl that (not) replaces; (not) alkoxyl group of Qu Daiing; (not) alkylthio of Qu Daiing, the alkylsulfonyl that (not) replaces, the sulfonic group that (not) replaces; (not) aldehyde radical of Qu Daiing; (not) the benzene oxygen of Qu Daiing (sulphur or ammonia) base, fragrant heterocycle oxygen (sulphur or the ammonia) base that contains 1-3 oxygen, sulphur, nitrogen-atoms that (not) replaces ,-C (R
7)=NOR
8,-(CH
2) mCO
2R
9(m=0-10) etc.; R
5, R
6=hydrogen, the alkyl that (not) replaces, the aryl that (not) replaces, the acyl group that (not) replaces, the alkylsulfonyl that (not) replaces etc.; R
7=hydrogen, the alkyl that (not) replaces etc.; R
8, R
9The alkyl that=hydrogen, (not) replace, the aryl that (not) replaces, the amino that (not) replaces, the salt that forms with basic metal, alkaline-earth metal, transition metal etc. etc.
4-virtue oxygen (sulphur or ammonia) yl pyrimidines derivative of the present invention can prepare by following reaction formula:
L is leavings groups such as halogen, alkyl or benzyl alkylsulfonyl.
Reaction is at inert solvent, as: the ether of ethers, THF and ethylene glycol bis methyl ether; The toluene of hydro carbons and acetonitrile, N, N-dialkyl amide such as DMF; The methylene dichloride of halohydrocarbon carries out in the solvent that chloroform and ketone etc. does not participate in reacting.Also can use mixed solvent.This reaction is generally carried out under 20 ℃-160 ℃ temperature under 1 normal atmosphere.
Alkali used in the reaction can be basic metal, alkali-metal hydride, the oxyhydroxide of alkali metal alkaline earth metal, carbonate etc.
In the intermediate II, A can be A1-A4, can make by ordinary method.For example 2, the 6-methyl dihydroxy benzoate can prepare by the method among the BP916548.
Intermediate III is worked as L=CL, R
1, R
2=OCH
3The time, can make by trichloropyrimidine and the reaction of nucleophilic reagent sodium methylate.
The preparation of trichloropyrimidine, J.CHEM.SOC.1944, reported method is that barbituric acid and phosphorus oxychloride are reacted in the presence of xylidene(s) in 678.Because reaction is violent, wayward, yield only is 46%.
The present invention proposes to adopt triethylamine to make alkali when the preparation trichloropyrimidine, adds solvent, and this reaction is more easily carried out.
The consumption of alkali and phosphorus oxychloride is generally 1-5 times (mole ratio) of barbituric acid, the ethers of solvent for not participating in reacting, (halo) hydro carbons, nitrile; Temperature of reaction is 20-150 ℃, yield 95%.
Following examples will further specify the present invention, but absolutely not in order to restriction the present invention.Table 1 has exemplified example and the fusing point and the 1 HNMR data of 4-virtue oxygen (sulphur or ammonia) the yl pyrimidines derivative that makes.
Embodiment 1:2,4, the preparation of 6-trichloropyrimidine
In the there-necked flask, add exsiccant barbituric acid 12.8 grams, 20 milliliter 1, the 2-ethylene dichloride, 37 milliliters of phosphorus oxychloride stir and drip 25 milliliters of triethylamines down, reflux 5 hours is poured reactant in the 200 gram ice into, tells organic phase, 1, the 2-ethylene dichloride extracts inorganic phase secondary, 2 * 20 milliliters, merge organic phase, be washed to nearly neutrality, underpressure distillation removes to desolvate and promptly gets title compound 17.4 grams behind the anhydrous sodium sulfate drying, productive rate 95%, at 15-18mm Hg, 80-90 ℃ can steam pure product.
Embodiment 2:4-chloro-2, the preparation of 6-dimethoxypyridin
18.4 gram trichloropyrimidines are joined in 20 ml methanol, drip 38.6 milliliters of methanol solutions containing 28% sodium methylate under the room temperature, 40 ℃ were stirred 3 hours down, and the pressure reducing and steaming solvent adds 40 milliliters in water, solid collected by filtration, and dry back weighs 17.3 grams, yield 96%.(wherein, contain 2-chloro-4 approximately, 6-dimethoxypyridin 10%, available recrystallization method is removed).57-62 ℃ of product fusing point.
The preparation of embodiment 3:2-(2,6-dimethoxypyridin-4-oxygen) methyl benzoate
In the there-necked flask, drop into Methyl salicylate 2.3 grams, 40 milliliters of DMF add sodium hydride 0.4 gram, the cooling of water-bath simultaneously in batches, stir and add 1.6 gram 4-chloro-2 after 20 minutes, the 6-dimethoxypyridin, is poured resistates in 40 ml waters into after 15 hours 70-120 ℃ of reaction, with the inorganic phase secondary of ethyl acetate extraction, 2 * 10 milliliters, merge organic phase, be washed to nearly neutrality, behind the anhydrous sodium sulfate drying, decompression is distilling off solvent down, with resistates with column chromatography purify raw material 4-chloro-2,6-dimethoxypyridin 0.5 gram, title compound 1.0 gram elutriant (ethyl acetate: sherwood oil=1: 5), be oily matter.Productive rate 56% (in Chloropyrimide).
The preparation of embodiment 4:2-6-two (2,6-dimethoxypyridin-4-oxygen) methyl benzoate
In the there-necked flask, drop into 1.7 grams 2, the 6-methyl dihydroxy benzoate, 40 milliliters of DMF add sodium hydride 0.6 gram, the cooling of water-bath simultaneously in batches, stir and add 4.2 gram 4-chloro-2 after 20 minutes, the 6-dimethoxypyridin, is poured resistates in 40 ml waters into after 15 hours 70-120 ℃ of reaction, with the inorganic phase of ethyl acetate extraction three times, 3 * 20 milliliters, merge organic phase, be washed to nearly neutrality, behind the anhydrous sodium sulfate drying, decompression is distilling off solvent down, purifies to such an extent that title compound 0.4 restrain elutriant (ethyl acetate: sherwood oil=1: 5), be oily matter with column chromatography resistates.Productive rate 9%.
Embodiment 5
The benzoic preparation of 2-(2,6-dimethoxypyridin-4-oxygen):
Product 1.8 grams of embodiment 3 join in 30 ml methanol and 30 ml waters that contain 0.25 gram sodium hydroxide, stir 3 hours pressure reducing and steaming methyl alcohol under the room temperature, add dilute hydrochloric acid and be transferred to PH=3, the oily matter that comes out is placed after fixing, solid collected by filtration, heavy 1.4 grams behind the washing and drying, productive rate 82%.Fusing point 122-123 ℃.
Embodiment 6
The preparation of 2-(2,6-dimethoxypyridin-4-oxygen) Sodium Benzoate:
Product 2.8 grams of embodiment 3 join in 40 ml methanol and 40 ml waters that contain 0.4 gram sodium hydroxide, stir 3 hours under the room temperature, remove by filter a little insolubles, and pressure reducing and steaming methyl alcohol and water get white solid, and dry back weighs 2.4 grams, productive rate 84%.220 ℃ of decomposition of fusing point.
Embodiment 7
The preparation of 2-(2,6-dimethoxypyridin-4-oxygen) peruscabin:
Product 0.6 gram of embodiment 6 joins among 15 milliliters of DMF, stir and add 2 milliliters of benzyl chlorides down, reacted 5 hours down at 50-60 ℃, this mixture is poured in 60 ml waters into ethyl acetate extraction three times, 3 * 20 milliliters, after the washing organic phase, underpressure distillation removes and desolvates, and resistates is purified to such an extent that title compound 0.5 restrains elutriant (ethyl acetate: sherwood oil=1: 5), be oily matter through column chromatography.Productive rate 68%.
The structure of table 1 compound and fusing point thereof,
1The HNMR data
Code name R
3R
4Fusing point ℃
1HNMR (ppm)
1 H H oil 7.20(5H，m)5.70(1H，S)
3.90(6H，d)d
2 Cl H 55-7 7.30(4H，m)5.90(1H，S)
3.95(3H，S)3.80(3H，S)
3 H 4-cl 71-3 7.30(4H，m)5.80(1H，S)
3.90(3H，S)3.80(3H，S)4 Ph H oil 7.30(9H，m)5.70(1H，S)
3.90(3H，S)3.80(3H，S)5 H 4-CO2Et 44-7 8.00(2H，m)7.30(2H，m)
5.90(1H，S)4.30(2H，q)
3.90(3H，s)3.80(3H，s)
1.30(3H，t)6 OCH3 H oil 7.00(4H，m)5.70(1H，S)
3.90(3H，S)3.80(3H，S)7 H 4-CH3 oil 7.10(4H，m)5.70(1H，S)
3.90(6H，d)2.30(3H，S)8 CO2Me H oil 7.30-8.00(4H，m)5.85(1H，S)
3.95(3H，S)3.80(3H，S)
3.78(3H，S)9 CO2H H 122-3 9.56(1H，S)8.07(1H，m)
7.66(1H，m)7.36(1H，m)
7.20(1H，m)5.81(1H，S)
3.95 (3H, S) 3.80 (3H, S) 10 CO2Na H 220d11 CO2Me 3-(pho-), 12 CO2Me
Fusing point oil 7.00-7.80 (3H, m)
5.82(2H，S)
3.93(3H，S)3.85(6H，S)
3.79(6H，S)13 CO2Me
14 CO2Me
15 CHO H 63-5 10.21(1H，S)7.25-7.95?(4H，m?)
5.89(1H，S)3.96(3H，S)3.86(3H，S)16 CO2CH2- H oil 7.27-3.05(4H，m)?5.84(1H，S)
C≡CH 4.75(2H，d)3.92(3H，S)3.78(3H，S)
2.40(1H，t)17 CO2CH2- H oil
ph18 CO2H HNMe2 H?oil19
151-3 7.20(15H，m)6.0(1H，S)
101-3 7.30(12H，m)6.2(1H，S)21
178?80 12.77(1H，S) 6.14(1H，S)
3.89(6H，S)22
Compound of the present invention is a broad-spectrum herbicide, can be used for removing in forest, orchard, agricultural, the grassland unwanted plant.
4-virtue oxygen (sulphur or ammonia) yl pyrimidines derivative of the present invention can mix use separately or with other known weedicide, can blended known weedicide have 2,4-D, bentazone, chlorine sulphur are grand, glyphosate, 2 first, 4 chlorine, trifluralin, Butachlor technical 92, chlorotoluron, nitrofen, simazine, desmetryn, TCE-styrene, Imazethapyr etc.
In preparation, the content of compound of the present invention is 0.1-99% (weight percentage).
Compound of the present invention, energy and carrier, emulsifying agent, diffusant, developping agent etc. are made into pulvis, wettable powder, emulsion, water dispersant, granule, suspension concentrate.
Adopt the activity of greenhouse testing method (soil treatment, cauline leaf are handled) assessment 4-virtue of the present invention oxygen (sulphur or ammonia) yl pyrimidines derivative to several conventional weeds.Dosage is per hectare 2250 grams, respectively organizes plant with the level evaluation of A, B, C, D, and wherein, A represents mortality ratio more than 90%, and B represents mortality ratio at 70-89%, and C represents mortality ratio at 50-69%, and D represents mortality ratio below 50%.Table 2 has been listed the result that test compound obtained under the described dosage.Table 2 weeding activity
| The dog tail oil dish radish piemarker thing grass 1 B C C D D D 2 D D D D D D 3 D D D D D D 4 D D D D D D 5 D D D D D D 6 D D D D D D 7 B A B A C B 8 A A A A A A 9 A A A A A A 10 A A A A A A 11 A A A A A A 12 A A A A A A 13 A A A A A A 14 A A A A A A 19 D D D D D D 20 D D D D D D of soil treatment chemical combination barnyard grass mare Tang | Cauline leaf is processed the dog tail oil dish radish piemarker grass D D D D D D D D D D D D D D D D D D D D D D D D D D D D D D D D D D D D B D D B C C A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A D D D D D D D D D D D D of barnyard grass mare Tang |
Claims (6)
1, a kind of 4-virtue oxygen, sulphur or aminopyridine derivative with weeding activity, general formula is:
In the formula, A is phenyl ring or the fragrant heterocycle that contains 1-3 oxygen, sulphur, nitrogen-atoms, and this virtue heterocycle is selected from the substituting group shown in the A1-A4:
X is O, S (O) n, n=0,1,2 wherein, NR
5
Y、Z、W＝O、S、N、CH、NR
6；
R
1, R
2Be halogen, alkyl, alkoxyl group, alkylamino, alkylthio, aryloxy;
R
3, R
4Be hydrogen, halogen, nitro, amino, alkyl, aryl, alkoxyl group, alkylthio, alkylsulfonyl, sulfonic group, aldehyde radical, benzene oxygen (sulphur or ammonia) base contains fragrant heterocycle oxygen, sulphur or the amino of 1-3 oxygen, sulphur, nitrogen-atoms ,-C (R
7)=NOR
8,-(CH
2) mCO
2R
9M=0-10 wherein; R
5, R
6Be hydrogen, alkyl, aryl, acyl group, alkylsulfonyl; R
7Be hydrogen, alkyl; R
8, R
9Be hydrogen, alkyl, aryl, amino.
2, according to the described 4-virtue of claim 1 oxygen, sulphur or aminopyridine derivative, it is characterized in that the A in the general formula (I) can be respectively following substituting group:
R in the formula
3, R
4, R
6According to claim 1.
According to claim 1 or 2 described compounds, it is characterized in that 3, general formula (I) can be respectively following three kinds of structures:
X, R in the formula
1, R
2, R
3, R
4, R
9According to claim 1.
According to the synthetic method of the described compound of claim 1, it is characterized in that 4, product is generated by following reaction:
In the formula, A, X, R
1, R
2According to claim 1; L is halogen, alkyl or benzyl alkylsulfonyl.
5, a kind of weedicide that contains the described compound of claim 1 is characterized in that, this weedicide can be pulvis, wettable powder, water dispersant, granule, suspension concentrate; The content of the described compound of claim 1 in this weedicide is 0.1-99% (weight percentage).
6, the described compound of claim 1 can be used for removing in orchard, forest, agricultural, the grassland unwanted plants such as barnyard grass grass, lady's-grass, Herba Setariae Viridis, rape, radish, piemarker.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112057A CN1056370C (en) | 1995-10-17 | 1995-10-17 | 4-aryloxy (arylthio or arylamino) pyrimidine derivative with herbicide active, and method for prepn. of same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112057A CN1056370C (en) | 1995-10-17 | 1995-10-17 | 4-aryloxy (arylthio or arylamino) pyrimidine derivative with herbicide active, and method for prepn. of same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1148043A CN1148043A (en) | 1997-04-23 |
| CN1056370C true CN1056370C (en) | 2000-09-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95112057A Expired - Fee Related CN1056370C (en) | 1995-10-17 | 1995-10-17 | 4-aryloxy (arylthio or arylamino) pyrimidine derivative with herbicide active, and method for prepn. of same |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR081331A1 (en) | 2010-04-23 | 2012-08-08 | Cytokinetics Inc | AMINO- PYRIMIDINES COMPOSITIONS OF THE SAME AND METHODS FOR THE USE OF THE SAME |
| US9133123B2 (en) | 2010-04-23 | 2015-09-15 | Cytokinetics, Inc. | Certain amino-pyridines and amino-triazines, compositions thereof, and methods for their use |
| AR081626A1 (en) | 2010-04-23 | 2012-10-10 | Cytokinetics Inc | AMINO-PYRIDAZINIC COMPOUNDS, PHARMACEUTICAL COMPOSITIONS THAT CONTAIN THEM AND USE OF THE SAME TO TREAT CARDIAC AND SKELETIC MUSCULAR DISORDERS |
| US8759380B2 (en) | 2011-04-22 | 2014-06-24 | Cytokinetics, Inc. | Certain heterocycles, compositions thereof, and methods for their use |
| CN104387328A (en) * | 2014-11-27 | 2015-03-04 | 太仓运通生物化工有限公司 | Method of preparing 2-chloropyrimidine |
| WO2021226261A1 (en) | 2020-05-06 | 2021-11-11 | Ajax Therapeutics, Inc. | 6-heteroaryloxy benzimidazoles and azabenzimidazoles as jak2 inhibitors |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0346789A2 (en) * | 1988-06-16 | 1989-12-20 | BASF Aktiengesellschaft | Salicylic-acid derivatives and their sulfur analogues |
| EP0593252A1 (en) * | 1992-10-16 | 1994-04-20 | Sumitomo Chemical Company, Limited | 2-substituted 6-phenyl-benzoic acid derivatives, their preparation and their use as herbicides |
-
1995
- 1995-10-17 CN CN95112057A patent/CN1056370C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0346789A2 (en) * | 1988-06-16 | 1989-12-20 | BASF Aktiengesellschaft | Salicylic-acid derivatives and their sulfur analogues |
| EP0593252A1 (en) * | 1992-10-16 | 1994-04-20 | Sumitomo Chemical Company, Limited | 2-substituted 6-phenyl-benzoic acid derivatives, their preparation and their use as herbicides |
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| Publication number | Publication date |
|---|---|
| CN1148043A (en) | 1997-04-23 |
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