CN107365252A - The synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids - Google Patents
The synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids Download PDFInfo
- Publication number
- CN107365252A CN107365252A CN201610312992.0A CN201610312992A CN107365252A CN 107365252 A CN107365252 A CN 107365252A CN 201610312992 A CN201610312992 A CN 201610312992A CN 107365252 A CN107365252 A CN 107365252A
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- saponification
- vinyl
- chloro
- chlorphenyls
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Abstract
The invention discloses a kind of synthetic method of 3 (2 chlorine 2 (4 chlorphenyl) vinyl) 2,2 dimethyl cyclopropane carboxylic acids, comprise the following steps：4 chlorobenzyl diethyl phosphates, the aldehyde radical ethyl cyclopropane dicarboxylate of 2,2 dimethyl 3 are dissolved in solvent, aqueous slkali is added dropwise into reaction system at 20~60 DEG C, after 2~20h is added dropwise, 1~3h is incubated at 20~60 DEG C；React and saponification agent distilled water progress saponification is added in the reaction solution after terminating, extracted after saponification resultant heating precipitation with hydrochloric acid acid adjustment, toluene, obtain product 3 (2 chlorine 2 (4 chlorphenyl) vinyl) 2,2 dimethyl cyclopropane carboxylic acids after recrystallization.This method is " one kettle way ", and relative to traditional handicraft, this method process costs are cheap, few, the easy industrial operation smaller to environmental hazard of high income, waste water；And high income, the purity of product are high.
Description
Technical field
The present invention relates to a kind of synthetic method of pesticide intermediate, and in particular to a kind of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2-
The synthetic method of dimethyl cyclopropane carboxylic acid, this method are " one kettle ways ".
Background technology
3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids are a kind of important pesticide intermediates, are mainly used to
Synthesize flumethrin etc..
At present, 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acid's synthetic methods are：Put into synthesis reactor
Dichloromethane, sodium hydrate aqueous solution, phase transfer catalyst agitation and dropping 4- chlorobenzyls diethyl phosphate, 2,2- dimethyl -3-
Aldehyde radical-ethyl cyclopropane dicarboxylate, reaction terminate rear oil reservoir and 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) are obtained after washing desolventizing
- 2,2- dimethyl cyclopropane carboxylic acid's ethyl ester, then by 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethylcyclopropane carboxylics
Acetoacetic ester saponification, acidifying, extraction, washing, precipitation, crystallization.The Waste water is big, cumbersome, yield more only 55%
Left and right.
The content of the invention
The technical problems to be solved by the invention are to be directed to the deficiencies in the prior art, and provide a kind of 3- (2- chloro- 2- (4- chlorobenzenes
Base) vinyl) -2,2- dimethyl cyclopropane carboxylic acids synthetic method, using " one kettle way " synthesize 3- (the chloro- 2- of 2- (4- chlorphenyls) ethene
Base) -2,2- dimethyl cyclopropane carboxylic acids, relative to traditional handicraft, this method process costs are cheap, and high income, waste water are slightly to environment
Endanger smaller, easy industrial operation；And high income, the purity of product are high.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids, comprises the following steps：2,
2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate, 4- chlorobenzyl diethyl phosphates are reacted with aqueous slkali in a solvent, reaction solution
3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids are obtained after saponification is acidified.
In above-mentioned technical proposal, synthetic method specifically includes following steps：
(1) 4- chlorobenzyls diethyl phosphate, 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate are dissolved in solvent, at 20~60 DEG C
Under the conditions of aqueous slkali is added dropwise into reaction system, after 2~20h is added dropwise, insulation is to 2,2- dimethyl -3- at 20~60 DEG C
Aldehyde radical-ethyl cyclopropane dicarboxylate conversion ratio is more than 99%, generates 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethylcyclopropane carboxylics
Acetoacetic ester；
Described solvent is mixed for any one in ethanol, methanol, triethylamine etc., two kinds and the above with arbitrary proportion
The mass ratio of mixture, described 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate and solvent is 1:0.1~4；
The mol ratio of described 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate and 4- chlorobenzyl diethyl phosphates is 1:1~1.2；
The mol ratio of described 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate and alkali in aqueous slkali is 1:3.5~5.5；
Described aqueous slkali be caustic alcohol or the ethanol solution of potassium ethoxide, the methanol solution of potassium methoxide or sodium methoxide, sodium hydroxide or
Any one in aqueous solution of potassium hydroxide etc.；
(2) saponification agent is added in the reaction solution after terminating to step (1) reaction, 70~82 DEG C is warming up to and protects at this temperature
Warm 2h carries out saponification, and saponification resultant is warming up to 102 DEG C of precipitations；Product after precipitation add the acid adjustment of water hydrochloric acid, toluene extraction,
Product 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids are obtained after recrystallization；
Described saponification agent is the mass ratio 1~3 of distilled water, saponification agent and 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate:1.
In above-mentioned technical proposal, in step (1), described 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate, 4- chlorobenzyls
The mol ratio of diethyl phosphate is preferably 1:1.08~1.12.
In above-mentioned technical proposal, in step (1), in described 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate and aqueous slkali
The mol ratio of alkali is preferably 1:4~5.
In above-mentioned technical proposal, in step (1), the matter of described 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate and solvent
Measure ratio preferably 1:0.1~2.
In above-mentioned technical proposal, in step (1), described aqueous slkali is preferably the ethanol solution of caustic alcohol or potassium ethoxide, enters one
Step is preferably the ethanol solution of caustic alcohol.
In above-mentioned technical proposal, in step (1), the dropping temperature of described aqueous slkali is preferably 35~45 DEG C, and time for adding is excellent
Elect 4~8h as；Described holding temperature is preferably 35~45 DEG C.
In above-mentioned technical proposal, in step (2), the temperature of described saponification is preferably 80~82 DEG C.
In above-mentioned technical proposal, in step (2), described saponification agent and 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate
Mass ratio is preferably 1.5~2:1.
The advantages of technical solution of the present invention, is：Present invention synthesis 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethylcyclopropanes
The method of carboxylic acid is " one kettle way ", and relative to traditional handicraft, this method process costs are cheap, and high income, waste water are few to environment
Endanger smaller, easy industrial operation；And high income, the purity of product are high.
Embodiment
The embodiment of technical solution of the present invention is described in detail below, but the present invention is not limited to description below：
Embodiment 1：
A kind of synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids, comprises the following steps：
(1) in 1000ml four-hole boiling flask, ethanol 120g, 2,2- dimethyl -3- aldehyde radicals-cyclopropane-carboxylic acid second are sequentially added
Ester 60g, 4- chlorobenzyl diethyl phosphate 85g, it is warming up to after 35~45 DEG C and the ethanol solution (ethanol that 486g contains caustic alcohol is added dropwise
Sodium mass fraction 20%), the ethanol solution of caustic alcohol is incubated after 1h through liquid chromatogram after 6h is added dropwise at 35~45 DEG C
Middle controlled Analysis measures 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate conversion ratio 99.13%；
(2) to step (1) reaction terminate after reaction solution in add saponification agent distilled water 120g, be warming up to 80~82 DEG C and
2h is incubated at a temperature of this and carries out saponification, saponification resultant is warming up to 102 DEG C of de- ethanol；Product after de- ethanol is dissolved in 200g
In solvent distilled water, the salt acid for adjusting pH extremely≤1 that mass fraction is 30% is added, the progress of 200g toluene is continuously added after acid adjustment
Final product 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acid's butts are obtained after extraction, recrystallization
81.8g, content 98.3%, yield 75.55%.
Embodiment 2：
A kind of synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids, comprises the following steps：
(1) in 1000ml four-hole boiling flask, triethylamine 6.0g, 2,2- dimethyl -3- aldehyde radicals-cyclopropane-carboxylic acid are sequentially added
Ethyl ester 60g, 4- chlorobenzyl diethyl phosphate 85g, it is warming up to the sodium hydroxide that 214.2g mass fractions 30% are added dropwise after 35~45 DEG C
The aqueous solution, sodium hydrate aqueous solution are incubated after 1h through liquid chromatogram Middle controlled Analysis after 8h is added dropwise at 35~45 DEG C
Measure 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate conversion ratio 99.08%；
(2) to step (1) reaction terminate after reaction solution in add saponification agent distilled water 120g, be warming up to 80~82 DEG C and
2h is incubated at a temperature of this and carries out saponification, saponification resultant is warming up to 102 DEG C of precipitations；Product after precipitation is dissolved in 200g solvents
In distilled water, add salt acid for adjusting pH that mass fraction is 30% to≤1, continuously added after acid adjustment 200g toluene extracted,
Final product 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids butt 78.5 is obtained after recrystallization,
Content is 98.1%g, yield 72.36%.
Embodiment 3：
A kind of synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids, comprises the following steps：
(1) in 1000ml four-hole boiling flask, methanol 60g, 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate are sequentially added
60g, 4- chlorobenzyl diethyl phosphate 85g, it is warming up to after 35~45 DEG C and the ethanol solution (caustic alcohol that 486g contains caustic alcohol is added dropwise
Mass fraction 20%), the ethanol solution of caustic alcohol is incubated after 1h through in liquid chromatogram after 6h is added dropwise at 35~45 DEG C
Control analytic approach measures 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate conversion ratio 99.17%；
(2) to step (1) reaction terminate after reaction solution in add saponification agent distilled water 120g, be warming up to 80~82 DEG C and
2h is incubated at a temperature of this and carries out saponification, saponification resultant is warming up to 102 DEG C of desolventizings；Product after desolventizing is dissolved in 200g
In solvent distilled water, reenter salt acid for adjusting pH that mass fraction is 30% to≤1, continuously added after acid adjustment the extraction of 200g toluene,
Final product 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acid butt 81.67g are obtained after recrystallization,
Content is 98.4%, yield 75.51%.
Embodiment 4：
A kind of synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids, comprises the following steps：
(1) in 1000ml four-hole boiling flask, ethanol 60g, 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate are sequentially added
60g, 4- chlorobenzyl diethyl phosphate 93.5g, it is warming up to after 35~45 DEG C and the ethanol solution (ethanol that 486g contains caustic alcohol is added dropwise
Sodium mass fraction 20%), the ethanol solution of caustic alcohol is incubated after 1h through liquid chromatogram after 6h is added dropwise at 35~45 DEG C
Middle controlled Analysis measures 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate conversion ratio 99.49%；
(2) saponification agent distilled water 80g is added in the reaction solution after terminating to step (1) reaction, is warming up to 80~82 DEG C and herein
At a temperature of be incubated 2h and carry out saponification, saponification resultant is warming up to 102 DEG C of de- ethanol；It is molten that product after de- ethanol is dissolved in 200g
In agent distilled water, add salt acid for adjusting pH that mass fraction is 30% to≤1, continuously added after acid adjustment the extraction of 200g toluene,
Final product 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acid butt 82.2g are obtained after recrystallization,
Yield is 75.91%, content 98.3%.
Embodiment 5：
A kind of synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids, comprises the following steps：
(1) in 1000ml four-hole boiling flask, ethanol 120g, 2,2- dimethyl -3- aldehyde radicals-cyclopropane-carboxylic acid second are sequentially added
Ester 60g, 4- chlorobenzyl diethyl phosphate 85g, it is warming up to after 20~30 DEG C and the ethanol solution (ethanol that 486g contains caustic alcohol is added dropwise
Sodium mass fraction 20%), the ethanol solution of caustic alcohol is incubated after 3h through liquid chromatogram after 8h is added dropwise at 20~30 DEG C
Middle controlled Analysis measures 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate conversion ratio 99.04%；
(2) to step (1) reaction terminate after reaction solution in add saponification agent distilled water 120g, be warming up to 80~82 DEG C and
2h is incubated at a temperature of this and carries out saponification, saponification resultant is warming up to 102 DEG C of de- ethanol；Product after de- ethanol is dissolved in 200g
In solvent distilled water, the salt acid for adjusting pH extremely≤1 that mass fraction is 30% is added, 200g toluene extraction is continuously added after acid adjustment
Take, recrystallize after obtain final product 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acid butt 81.8g,
Yield is 75.76%, content 98.6%.
Examples detailed above is technical concept and technical characterstic to illustrate the invention, and the protection model of the present invention can not be limited with this
Enclose.The equivalent transformation or modification that all essence according to the present invention is done, should all be included within the scope of the present invention.
Claims (10)
1. a kind of synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids, its feature exist
In comprising the following steps：2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate, 4- chlorobenzyls diethyl phosphate in a solvent with
Aqueous slkali is reacted, and reaction solution obtains 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- after saponification is acidified, recrystallized
Dimethyl cyclopropane carboxylic acid.
2. according to the method for claim 1, it is characterised in that synthetic method specifically includes following steps：
(1) 4- chlorobenzyls diethyl phosphate, 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate are dissolved in solvent, at 20~60 DEG C
Under the conditions of aqueous slkali is added dropwise into reaction system, after 2~20h is added dropwise, insulation is to 2,2- dimethyl -3- at 20~60 DEG C
Aldehyde radical-ethyl cyclopropane dicarboxylate conversion ratio is more than 99%, generates 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- diformazan basic rings
Propanecarboxylic acid's ethyl ester；
The mol ratio of described 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate and 4- chlorobenzyl diethyl phosphates is 1:1~1.2；
The mol ratio of described 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate and alkali in aqueous slkali is 1:3.5~5.5；
Described 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate and the mass ratio of solvent are 1:0.1~4；
(2) saponification agent is added in the reaction solution after terminating to step (1) reaction, 70~82 DEG C is warming up to and protects at this temperature
Warm 2h carries out saponification, and saponification resultant is warming up to 102 DEG C of precipitations；Product after precipitation is extracted after adding water with hydrochloric acid acid adjustment, toluene
Take, recrystallize after obtain product 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids；
Described saponification agent is the mass ratio 1~3 of distilled water, saponification agent and 2,2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate:1.
3. described method according to claim 2, it is characterised in that in step (1), described solvent be ethanol,
In methanol, triethylamine any one, the mixture that is mixed with arbitrary proportion of two kinds and the above.
4. described method according to claim 2, it is characterised in that in step (1), described aqueous slkali is second
The ethanol solution of sodium alkoxide or potassium ethoxide, the methanol solution of potassium methoxide or sodium methoxide, sodium hydroxide or potassium hydroxide the aqueous solution in
Any one.
5. described method according to claim 4, it is characterised in that described aqueous slkali is caustic alcohol or potassium ethoxide
Ethanol solution.
6. described method according to claim 2, it is characterised in that in step (1), described 2,2- dimethyl
- 3- aldehyde radicals-ethyl cyclopropane dicarboxylate, the mol ratio of 4- chlorobenzyl diethyl phosphates are 1:1.08~1.12.
7. described method according to claim 2, it is characterised in that in step (1), described 2,2- dimethyl
The mol ratio of -3- aldehyde radicals-ethyl cyclopropane dicarboxylate and alkali in aqueous slkali is 1:4~5.
8. described method according to claim 2, it is characterised in that in step (1), the drop of described aqueous slkali
Heating degree is preferably 35~45 DEG C, and time for adding is preferably 4~8h；Described holding temperature is preferably 35~45 DEG C.
9. described method according to claim 2, it is characterised in that in step (2), described saponification
Temperature is 80~82 DEG C.
10. described method according to claim 2, it is characterised in that in step (2), described saponification agent and 2,
The mass ratio of 2- dimethyl -3- aldehyde radicals-ethyl cyclopropane dicarboxylate is 1.5~2:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610312992.0A CN107365252A (en) | 2016-05-11 | 2016-05-11 | The synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610312992.0A CN107365252A (en) | 2016-05-11 | 2016-05-11 | The synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107365252A true CN107365252A (en) | 2017-11-21 |
Family
ID=60303996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610312992.0A Pending CN107365252A (en) | 2016-05-11 | 2016-05-11 | The synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107365252A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4276306A (en) * | 1977-07-06 | 1981-06-30 | Bayer Aktiengesellschaft | Combating arthropods with 3-phenoxybenzyl 2,2-dimethyl-3-vinyl-cyclopropane carboxylates |
| US4316913A (en) * | 1979-04-23 | 1982-02-23 | Bayer Aktiengesellschaft | Arthropodicidally active styrylcyclopropanecarboxylic acid esters |
| DE3211036A1 (en) * | 1982-03-25 | 1983-09-29 | Bayer Ag, 5090 Leverkusen | Process for the preparation of alkenes |
-
2016
- 2016-05-11 CN CN201610312992.0A patent/CN107365252A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4276306A (en) * | 1977-07-06 | 1981-06-30 | Bayer Aktiengesellschaft | Combating arthropods with 3-phenoxybenzyl 2,2-dimethyl-3-vinyl-cyclopropane carboxylates |
| US4316913A (en) * | 1979-04-23 | 1982-02-23 | Bayer Aktiengesellschaft | Arthropodicidally active styrylcyclopropanecarboxylic acid esters |
| DE3211036A1 (en) * | 1982-03-25 | 1983-09-29 | Bayer Ag, 5090 Leverkusen | Process for the preparation of alkenes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103772324B (en) | A kind of Improved synthesis method of acryloyl morpholine | |
| CN101945861A (en) | A kind of preparation method of benzamide compound | |
| JP5628427B2 (en) | Method for preparing rosuvastatin calcium intermediate | |
| US4127604A (en) | Process for the preparation of acetic acid derivatives | |
| CN103102307A (en) | Method for synthesizing tolfenpyrad | |
| CN109970580B (en) | Extraction and preparation method of R-3-aminobutanol | |
| CN103896855A (en) | Method for synthesizing 4-(1-bromoethyl) -5-fluoro-6-chloropyrimidine | |
| CN107365252A (en) | The synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids | |
| EP2247572A1 (en) | A one-pot process for preparing 3-(2,2,2-trimethylhydrazinium)propionate dihydrate | |
| WO2019178947A1 (en) | Preparation method for azoxystrobin and intermediate thereof | |
| CN109467532B (en) | Preparation method of 4-trifluoromethyl nicotinic acid | |
| CN103450092B (en) | Synthesis method of metronidazole-sulfanilamide derivatives | |
| CN105461630B (en) | Luso replaces Buddhist nun's intermediate (R) 3（The base of 4 bromine 1H pyrazoles 1）The synthetic method of 3 cyclopenta propionitrile | |
| CN105420338B (en) | A kind of method that lipase fractionation DL- Valsartan ester prepares L- Valsartan | |
| CN102675092B (en) | Method for preparing 2-aryl-2,2-dimethyl methyl acetate | |
| KR20100052230A (en) | The preparation of pitavastatine intermediate and the preparation of pitavastatine hemi-calcium salt using the preparation method | |
| CN111348996B (en) | 2-benzoyl malonate compound, and preparation method and application thereof | |
| CN107417516A (en) | One kind recycles the method that one kettle way prepares the vinasse of the chlorpromazine chlorides of D (+) 2 | |
| CN103396304B (en) | Nervonic acid chemosynthesis method | |
| JPH0466859B2 (en) | ||
| SU504489A3 (en) | Method for preparing 4n-benzo (4,5) cyclohepta- (1,2-b) -thiophene derivatives | |
| CN112876377A (en) | Preparation method of hydroxypropyl acrylamide | |
| CN108727187A (en) | It is a kind of（R）-（+）The preparation method of -2- para hydroxybenzene oxygroup propionic acid | |
| CN106866384B (en) | Preparation method of hydroxytyrosol | |
| EP3013786B1 (en) | Improved process for the preparation of derivatives of 1-(2-fluoro[1,1'-biphenyl]-4-yl)-cyclopropanecarboxylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171121 |