CN106083722A - A kind of Six Steps prepares the synthesis technique of pyrazoles Fluoxastrobin - Google Patents
A kind of Six Steps prepares the synthesis technique of pyrazoles Fluoxastrobin Download PDFInfo
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- CN106083722A CN106083722A CN201610384285.2A CN201610384285A CN106083722A CN 106083722 A CN106083722 A CN 106083722A CN 201610384285 A CN201610384285 A CN 201610384285A CN 106083722 A CN106083722 A CN 106083722A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
- C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
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Abstract
The present invention provides a kind of Six Steps to prepare the synthesis technique of pyrazoles Fluoxastrobin, and synthesis technique step is as follows: the reduction reaction of (1) ortho-methylnitrobenzene；(2) acylation reaction of azanol；(3) methylation reaction；(4) N methoxyl group N 2 2-bromomethylphenyl methyl carbamate is obtained by bromination reaction；The synthesis of synthesis (6) pyraclostrobin of (5) 1 (4 chlorphenyl) pyrazolidine 3 ketone.Compared with prior art, the preparation method of the present invention is simple, and raw material is cheap and easy to get, and reaction condition is gentle, and the target product purity obtained and yield are high.
Description
Technical field
The present invention relates to the synthesis of pyrazoles Fluoxastrobin, be specifically related to a kind of Six Steps and prepare the synthesis work of pyrazoles Fluoxastrobin
Skill.
Background technology
Pyrazoles Fluoxastrobin is a kind of methoxy acrylic acid having pyrrazole structure concurrently that BASF Aktiengesellschaft found with 1993
Methyl ester class wide-spectrum bactericide.It can prevent and treat by ascus guiding principle, Basidiomycetes, deuteromycetes and Oomycete etc. almost all kinds of very
The plant disease that bacterium pathogen causes, it is again a kind of hormone-type antibacterial simultaneously, can make the more nitrogen of Crop, promotes to make
The growth of thing.This kind not only toxicity is low, to non-target organism safety, and also friendly to user and environment all safety.Pyrazoles
Fluoxastrobin can be processed into the multiple dosage forms such as liquor, aqueous suspension, wettable powder, powder, unguentum.Also can compound with various sterilization agent
The mixed effect played potentiation and expand antibacterial.Since within 2002, promoting listing, being the user's favorite, sales volume is fast
Speed rises, and according to China's pesticide the 6th phase in 2007, ranks the 3rd in most important 15 the antibacterial kinds in the whole world.Pyrazoles
The preparation of Fluoxastrobin respectively triumphant to wash in a pan, Kai Ze, the trade name of hundred Thailands are registered in China and enter domestic market sales.
Sum up to get up to be divided into two to the synthetic route of pyrazoles Fluoxastrobin the most both at home and abroad:
1) by ortho-methylnitrobenzene, first obtaining o-nitrobenzyl bromide through Benzylphosphonium Bromide, o-nitrobenzyl bromide is with 1-(4-chlorine
Phenyl)-3-hydroxypyrazoles is condensed to yield 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] Nitrobenzol, then obtains through reduction
N-hydroxy-n-2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl]-aniline, then with methylchloroformate reaction obtain N-hydroxy-n-
2-[(N-rubigan)-3-pyrazoles epoxide methyl] carbanilate, it is phonetic that last and dimethyl sulfate reaction obtains pyrazoles
Bacterium ester.
2) by ortho-methylnitrobenzene, o-methyl-phenyl-azanol is obtained through reduction, then with methylchloroformate reaction obtains
N-hydroxy-n-toluidino methyl formate, then obtain N-methoxy-. N-methyl phenylcarbamic acid first with dimethyl sulfate reaction
Ester.N-methoxy-. N-methyl phenylcarbamate obtains pyrazoles Fluoxastrobin with 1-(4-chlorphenyl)-3-hydroxypyrazoles again.
Article 1, the advantage of route is that method of purification is simple, the beneficially lifting of final products purity, but shortcoming is adjacent nitre
Base toluene bromo is that productivity is relatively low；The advantage of Article 2 route is the disappearance of strong electron-withdrawing group nitro so that the productivity of bromo
Higher, but due to ortho-methylnitrobenzene, to be reduced into the productivity of azanol relatively low, and the condensation productivity of final step is relatively low and final products
Purification difficult.
Summary of the invention
The present invention provides a kind of five-step approach to prepare the synthesis technique of pyrazoles Fluoxastrobin, it is characterised in that synthesis technique step
As follows:
(1) in reactor, add the ortho-methylnitrobenzene of 10 weight portions, the zinc powder of 3-5 weight portion, the acetic acid of 12 weight portions
Ammonium, the acetone of 30-50 weight portion, at 35-55 DEG C stir 20h, reaction terminate after filter, filtering residue with a small amount of 1,2-dichloroethanes
After rinsing standby, filtrate concentrate after obtain orange solids, after ethanol rinse orange solids, heavily tie with acetone/petroleum ether
Crystalline substance obtains orange crystal, the most i.e. can get N-(2-aminomethyl phenyl) azanol standby；
(2) N-(2-aminomethyl phenyl) azanol 7 weight portion, sodium bicarbonate 10 weight portion and the dichloromethane that will obtain in step 1
Stir after the mixing of alkane solvents 15-20 weight portion, after N-(2-aminomethyl phenyl) azanol fully dissolves, be slowly added dropwise when 5-10 DEG C
Methylchloroformate, is incubated after being added dropwise to complete, and filters, washes, distillation of reducing pressure, carries out recrystallization, the white solid obtained after drying
Being N-hydroxy-n-2-toluidino methyl formate standby, the dichloromethane obtained after decompression distillation is for follow-up reaction；
(3) by N-hydroxy-n-2-toluidino methyl formate 7 weight portion obtained in step 2, potassium carbonate 11 weight portion and
Stir, after N-hydroxy-n-2-toluidino methyl formate fully dissolves, at 40-50 after the mixing of dichloromethane 10-15 weight portion
It is slowly added dropwise dimethyl sulfate at DEG C, is incubated after being added dropwise to complete, then carry out decompression distillation, washing, obtain brown oil after drying
Thing, obtains N-methoxyl group-N-2-methYlphenvlcarbamate；
(4) by N-methoxyl group-N-2-methYlphenvlcarbamate 5 weight portion obtained in step 3, N-bromo fourth two
Acid imide 4-7 weight portion and solvent carbon dichloride 10-15 weight portion, after solid fully dissolves, be slowly added dropwise 3-8 weight portion
Azodiisobutyronitrile, reaction terminate after wash, be dried, reduce pressure distill after obtain yellow oil, be N-methoxyl group-N-2-bromine
MethYlphenvlcarbamate；
(5) in reactor, add dehydrated alcohol 100 weight portion, open jacket steam and heat up, system temperature is controlled
40-60 DEG C, add metallic sodium 20 weight portion, be sufficiently stirred for reaction, turn off jacket steam, after naturally cooling to 20-35 DEG C,
It is slowly added to p-hydrochloride 70 weight portion, continues stirring 20min, add acrylamide 30 weight portion, slowly heat up
To 70-80 DEG C of backflow, continuing stirring 5-7h, reaction generates milky material after terminating, decompression distills out ethanol, reclaims after being evaporated
Ethanol；Milky material is cooled to 10-20 DEG C, then drips the hydrochloric acid conditioning solution pH to 6 that concentration is 10%, after stirring 0.5h
Sucking filtration obtains white solid；
(6) by the N-methoxyl group-N-2-2-bromomethylphenyl methyl carbamate of 5 weight portions, in the step 5 of 7 weight portions
White solid, the dichloromethane of 20 weight portions, the potassium carbonate of 8 weight portions, stirs 40min, is slowly added dropwise 5 weight after mix homogeneously
The dimethyl sulfate of part, after reaction terminates, respectively extracts 2 times with the ammonia that concentration is 10% and clear water, and the organic layer after extraction is used
Anhydrous sodium sulfate is dried, and obtains yellow oil, then with recrystallisation from isopropanol, obtain end product pyrrole after drying after decompression distillation
Azoles Fluoxastrobin.
The invention have the benefit that 1) by selecting ammonium acetate to react with zinc powder, it is possible not only to effectively reduce cost, with
Time can reduce pollution；2) by improving the synthesis technique of 1-(4-chlorphenyl) pyrazolidine-3-ketone, productivity and product can be improved
Purity, and productivity is about 89%, and purity can reach about 95%；3) in the post processing of Fluoxastrobin synthesis, ammonia is used
Water and clear water extraction, not only low cost, it is ensured that the quality of product, the yield of the Fluoxastrobin after recrystallization is 87%, purity
It is 92%.
Detailed description of the invention:
By embodiment, the detailed description of the invention of the present invention is made an explanation below.
Embodiment
The invention provides a kind of Six Steps and prepare the synthesis technique of pyrazoles Fluoxastrobin, step is as follows: (1) is in reactor
Adding the ortho-methylnitrobenzene of 10 weight portions, the zinc powder of 5 weight portions, the ammonium acetate of 12 weight portions, the acetone of 30 weight portions, at 40 DEG C
Stirring 20h, reacts and filters after terminating, and filtering residue is with 1, and standby after the rinsing of 2-dichloroethanes, filtrate obtains orange solids after concentrating, and uses
After ethanol rinse orange solids, carry out being recrystallized to give orange crystal with acetone/petroleum ether, the most i.e. can get N-(2-first
Base phenyl) azanol is standby；(2) by N-(2-aminomethyl phenyl) azanol 7 weight portion obtained in step 1, sodium bicarbonate 10 weight portion
Stir after mixing with dichloromethane solvent 15 weight portion, after N-(2-aminomethyl phenyl) azanol fully dissolves, slowly drip when 5 DEG C
Add 3 weight portion methylchloroformates, be incubated after being added dropwise to complete, filter, wash, distillation of reducing pressure, carry out recrystallization after drying, obtain
It is standby that white solid is N-hydroxy-n-2-toluidino methyl formate, and the dichloromethane obtained after decompression distillation is for follow-up
Reaction；(3) by N-hydroxy-n-2-toluidino methyl formate 7 weight portion obtained in step 2, potassium carbonate 11 weight portion and
Stir after the mixing of dichloromethane 12 weight portion, after N-hydroxy-n-2-toluidino methyl formate fully dissolves, slow at 45 DEG C
Slow dropping 5 parts sulfuric acid dimethyl esters, are incubated after being added dropwise to complete, then carry out decompression distillation, washing, obtain brown oil after drying
Thing, obtains N-methoxyl group-N-2-methYlphenvlcarbamate；(4) the N-methoxyl group-N-2-methyl that will obtain in step 3
Phenylcarbamate 5 weight portion, N-bromo-succinimide 5 weight portion and solvent carbon dichloride 12 weight portion, treat solid
After fully dissolving, be slowly added dropwise the azodiisobutyronitrile of 5 weight portions, reaction washes after terminating, be dried, reduce pressure distill after obtain Huang
Color grease, is N-methoxyl group-N-2-2-bromomethylphenyl methyl carbamate；(5) in reactor, dehydrated alcohol 100 is added
Weight portion, opens jacket steam and heats up, control system temperature, at 50 DEG C, to add metallic sodium 20 weight portion, is sufficiently stirred for anti-
Should, turn off jacket steam, after naturally cooling to 30 DEG C, be slowly added to p-hydrochloride 70 weight portion, continue stirring
20min, adds acrylamide 30 weight portion, is to slowly warm up to 75 DEG C of backflows, continues stirring 6h, and reaction generates milky white after terminating
Color substance, decompression distills out ethanol, reclaims ethanol after being evaporated；Milky material is cooled to 20 DEG C, then to drip concentration be 10%
Hydrochloric acid conditioning solution pH to 6, stirring 0.5h after sucking filtration obtain white solid；(6) by the N-methoxyl group-N-2-bromine of 5 weight portions
MethYlphenvlcarbamate, the white solid in the step 5 of 7 weight portions, the dichloromethane of 20 weight portions, 8 weight portions
Potassium carbonate, stirs 40min after mix homogeneously, be slowly added dropwise the dimethyl sulfate of 5 weight portions, after reaction terminates, by concentration be
The ammonia of 10% and clear water respectively extract 2 times, and the organic layer anhydrous sodium sulfate after extraction is dried, and obtain yellow oil after decompression distillation
Shape thing, then with recrystallisation from isopropanol, obtain end product pyrazoles Fluoxastrobin after drying.
The pyrazoles Fluoxastrobin productivity that the preparation method that the present invention provides obtains is 90%, and product purity is 92%.
Claims (1)
1. the present invention provides a kind of Six Steps to prepare the synthesis technique of pyrazoles Fluoxastrobin, it is characterised in that synthesis technique step is such as
Under:
(1) in reactor, add the ortho-methylnitrobenzene of 10 weight portions, the zinc powder of 3-5 weight portion, the ammonium acetate of 12 weight portions,
The acetone of 30-50 weight portion, stirs 20h at 35-55 DEG C, reaction is filtered after terminating, and filtering residue is with 1, and 2-dichloroethanes rinses standby
With, filtrate obtains orange solids after concentrating, and after ethanol rinse orange solids, carries out being recrystallized to give orange with acetone/petroleum ether
Color crystal, the most i.e. can get N-(2-aminomethyl phenyl) azanol standby；
(2) by molten to N-(2-aminomethyl phenyl) azanol 7 weight portion, sodium bicarbonate 10 weight portion and the dichloromethane that obtain in step 1
Stir after the mixing of agent 15-20 weight portion, after N-(2-aminomethyl phenyl) azanol fully dissolves, be slowly added dropwise 3 weights when 5-10 DEG C
Amount part methylchloroformate, is incubated after being added dropwise to complete, and filters, washes, distillation of reducing pressure, carries out recrystallization, the white obtained after drying
It is standby that solid is N-hydroxy-n-2-toluidino methyl formate, and after decompression distillation, the dichloromethane that obtains is for follow-up anti-
Should；
(3) N-hydroxy-n-2-toluidino methyl formate 7 weight portion, potassium carbonate 11 weight portion and the dichloro that will obtain in step 2
Stir, after N-hydroxy-n-2-toluidino methyl formate fully dissolves, at 40-50 DEG C after the mixing of methane 10-15 weight portion
It is slowly added dropwise 5 parts sulfuric acid dimethyl esters, is incubated after being added dropwise to complete, then carry out decompression distillation, washing, obtain brown oil after drying
Shape thing, obtains N-methoxyl group-N-2-methYlphenvlcarbamate；
(4) by N-methoxyl group-N-2-methYlphenvlcarbamate 5 weight portion obtained in step 3, N-bromo succinyl Asia
Amine 4-7 weight portion and solvent carbon dichloride 10-15 weight portion, after solid fully dissolves, be slowly added dropwise the azo of 3-8 weight portion
Bis-isobutyronitrile, reaction terminate after wash, be dried, reduce pressure distill after obtain yellow oil, be N-methoxyl group-N-2-bromomethyl
Phenylcarbamate；
(5) in reactor, add dehydrated alcohol 100 weight portion, open jacket steam and heat up, system temperature is controlled at 40-60
DEG C, add metallic sodium 20 weight portion, be sufficiently stirred for reaction, turn off jacket steam, after naturally cooling to 20-35 DEG C, slowly
Add p-hydrochloride 70 weight portion, continue stirring 20min, add acrylamide 30 weight portion, be to slowly warm up to 70-
80 DEG C of backflows, continue stirring 5-7h, and reaction generates milky material after terminating, decompression distills out ethanol, reclaims ethanol after being evaporated；
Milky material is cooled to 10-20 DEG C, then drips the hydrochloric acid conditioning solution pH to 6 that concentration is 10%, sucking filtration after stirring 0.5h
Obtain white solid；
(6) by the N-methoxyl group-N-2-2-bromomethylphenyl methyl carbamate of 5 weight portions, the white in the step 5 of 7 weight portions
Solid, the dichloromethane of 20 weight portions, the potassium carbonate of 8 weight portions, stirs 40min, is slowly added dropwise 5 weight portions after mix homogeneously
Dimethyl sulfate, after reaction terminates, respectively extracts 2 times with the ammonia that concentration is 10% and clear water, and the organic layer after extraction is with anhydrous
Sodium sulfate is dried, and obtains yellow oil, then with recrystallisation from isopropanol, obtain end product pyrazoles after drying phonetic after decompression distillation
Bacterium ester.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106543066A (en) * | 2016-11-11 | 2017-03-29 | 深圳市新阳唯康科技有限公司 | A kind of pyraclostrobin novel crystal forms and preparation method thereof |
| CN106631965A (en) * | 2016-12-21 | 2017-05-10 | 深圳市新阳唯康科技有限公司 | Novel pyraclostrobin crystal form and preparation method thereof |
| CN106749025A (en) * | 2016-11-14 | 2017-05-31 | 四川福思达生物技术开发有限责任公司 | A kind of method of succinct synthesizing pyrazole kresoxim-methyl |
| CN110590672A (en) * | 2019-09-09 | 2019-12-20 | 海利尔药业集团股份有限公司 | Preparation method of pyraclostrobin II crystal form |
| CN110845370A (en) * | 2019-11-29 | 2020-02-28 | 江苏宝灵化工股份有限公司 | Method for synthesizing nitrapyrin intermediate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543066A (en) * | 2016-11-11 | 2017-03-29 | 深圳市新阳唯康科技有限公司 | A kind of pyraclostrobin novel crystal forms and preparation method thereof |
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| CN106749025A (en) * | 2016-11-14 | 2017-05-31 | 四川福思达生物技术开发有限责任公司 | A kind of method of succinct synthesizing pyrazole kresoxim-methyl |
| CN106749025B (en) * | 2016-11-14 | 2019-10-08 | 四川福思达生物技术开发有限责任公司 | A kind of method of succinct synthesizing pyrazole kresoxim-methyl |
| CN106631965A (en) * | 2016-12-21 | 2017-05-10 | 深圳市新阳唯康科技有限公司 | Novel pyraclostrobin crystal form and preparation method thereof |
| CN110590672A (en) * | 2019-09-09 | 2019-12-20 | 海利尔药业集团股份有限公司 | Preparation method of pyraclostrobin II crystal form |
| CN110845370A (en) * | 2019-11-29 | 2020-02-28 | 江苏宝灵化工股份有限公司 | Method for synthesizing nitrapyrin intermediate |
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Application publication date: 20161109 |