CN104693164A - Preparation method of 2,2-difluoro methyl piperate - Google Patents
Preparation method of 2,2-difluoro methyl piperate Download PDFInfo
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- CN104693164A CN104693164A CN201510149045.XA CN201510149045A CN104693164A CN 104693164 A CN104693164 A CN 104693164A CN 201510149045 A CN201510149045 A CN 201510149045A CN 104693164 A CN104693164 A CN 104693164A
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- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring 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 atoms of the carbocyclic ring
- C07D317/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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Abstract
The invention relates to the field of organic synthesis, in particular to a preparation method of 2,2-difluoro methyl piperate. The preparation method of the 2,2-difluoro methyl piperate includes the following steps that 2,2- difluoro piperyl fluorine (II) and methanol are reacted, 2,2- difluoro methyl piperate (III) is obtained through esterification reaction, and please see the reaction formula in the specifications. The preparation method of 2,2-difluoro methyl piperate has the advantages that the synthesis route is short, the process is easy to control, reaction is complete, the yield is high, and prepared target products are high in purity, are stable in quality and completely meet the use requirements as a pesticide or medical intermediate; in addition, raw materials and reagents used in the method are cheap, the amount of solvents used in each step of reaction is small, a little waste liquid is generated, the cost is reduced, environmental pollution is reduced, and the 2,2-difluoro methyl piperate is quite convenient to produce in a large scale in a commercialization mode.
Description
Technical field
The present invention relates to organic synthesis field, particularly relate to a kind of preparation method of 2,2-difluoro methyl piperate.
Background technology
2,2-difluoro methyl piperate is the increasingly extensive intermediate of a kind of purposes, is the intermediate of conventional synthesis pharmaceutical compound, agricultural chemical compound and electronic chemical product.Be use bromo-2, the 2-difluoro piperonyl cyclonenes of 5-and carbon monoxide under four triphenyl phosphorus palladium chtalyst in prior art, carry out reaction under high pressure, prepare corresponding 2,2-difluoro methyl piperates (WO2005075435).The method cost is higher, its raw material used need through superchlorination, fluoridize, bromination obtain, step is long, and total reaction yield is lower.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of preparation method of 2,2-difluoro methyl piperate, for solving the problems of the prior art.
For achieving the above object and other relevant objects, the invention provides a kind of 2, the preparation method of 2-difluoro methyl piperate, comprise the steps: 2,2-difluoro pepper acyl fluorides (II) and methyl alcohol effect, prepare 2,2-difluoro methyl piperate (III) by esterification, its reaction equation is as follows:
Preferably, the concrete grammar of described esterification is: be added drop-wise to by methyl alcohol in 2,2-difluoro pepper acyl fluorides, after having reacted, reaction solution is joined in alkaline aqueous solution, with organic solvent extraction, be separated and obtain organic phase, namely 2,2-difluoro methyl piperate is prepared after precipitation, purifying.
Preferred, described alkaline aqueous solution is selected from one or more the combination in sodium bicarbonate aqueous solution, wet chemical, aqueous sodium carbonate, aqueous sodium hydroxide solution etc., described organic solvent is selected from one or more the combination in chloroform, methylene dichloride, ethylene dichloride, ethyl acetate etc., and the method for described purifying is distillation.
Preferred, the temperature of described esterification is preferably in the scope of-10-240 DEG C, and be more preferably 20-70 DEG C, the reaction times of esterification is in 0.1-100 hour, is more preferably in 2-20 hour.
Preferred, the consumption of methyl alcohol is 1.0-50 times of molar weight of 2,2-difluoro pepper acyl fluorides, is more preferably 1.0-5 times of molar weight, more preferably 2-4 times of molar weight.
Preferably, the preparation method of described 2,2-difluoro pepper acyl fluorides is: 2,2-dichloro pepper acyl chlorides (I) and hydrogen fluoride are carried out fluoridation, and obtain 2,2-difluoro pepper acyl fluorides (II), reaction equation is as follows:
Preferred, the concrete grammar of described fluoridation is: 2,2-dichloro pepper acyl chlorides is placed in reaction vessel, then passes into hydrogen fluoride and react, and hydrogen fluoride adopts and passes into or the disposable form passed in batches.
Preferred, hydrofluoric usage quantity is 2-20 times of molar weight of 2,2-dichloro pepper acyl chlorides, is more preferably 3.0-5.0 times of molar weight.
Preferred, the temperature of fluoridation, preferably in the scope of 30-120 DEG C, is more preferably 50-70 DEG C, and the preferred reaction times is 0.1-100 hour, is more preferably 2-20 hour.
Preferably, the preparation method of described 2,2-dichloro pepper acyl chlorides is: take piperonylaldehyde as raw material, and react with chlorinated with chlorine under initiator or light-initiated effect and prepare 2,2-dichloro pepper acyl chlorides (I), reaction equation is as follows:
Preferably, the concrete grammar of described chlorination reaction is: when use initiator causes chlorination reaction, by chlorine and be dissolved in the piperonylaldehyde of reaction solvent, initiator adds in reaction vessel simultaneously; When using light-initiated chlorination reaction, chlorine and the piperonylaldehyde being dissolved in reaction solvent being added in reaction vessel simultaneously, and illumination is carried out to reaction system; After chlorination reaction terminates, degassed, distillation, collects target fraction.
Preferred, the ratio adding speed of piperonylaldehyde in speed and reaction solvent that adds of chlorine is preferably 2-10 times of molar weight, is more preferably 2-5:1, most preferably is 2-4:1.The mol ratio of chlorine and piperonylaldehyde is preferably 2-10:1, is more preferably 2-5:1, more preferably 2-4:1.
Preferred, when causing chlorination reaction with initiator, described initiator is selected from one or more the combination in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo two cyclohexanenitrile, benzoyl peroxide etc., and the weight ratio of described initiator and piperonylaldehyde is 0.01%-5.0%:1.When using light-initiated chlorination reaction, described light is preferably UV-light.
Preferred, the temperature of described chlorination reaction is 60-240 DEG C, is more preferably 80-150 DEG C, most preferably is 120-140 DEG C.Faster reaction speed can be obtained at this temperature and produce tar little.
The present invention further provides a kind of preparation method of 2,2-difluoro methyl piperate, comprise the steps:
1) chlorination reaction: take piperonylaldehyde as raw material, under initiator or light-initiated effect, prepare 2,2-dichloro pepper acyl chlorides with chlorine reaction, reaction equation is as follows:
2) fluoridation: 2,2-dichloro pepper acyl chlorides (intermediate compound I) and hydrogen fluoride are carried out fluoridation, and obtain 2,2-difluoro pepper acyl fluorides (intermediate II), reaction equation is as follows:
3) esterification: by 2,2-difluoro pepper acyl fluorides and methyl alcohol effect, prepare 2,2-difluoro methyl piperate, its reaction equation is as follows:
Major advantage of the present invention is as follows:
(1) synthetic route of the preparation method of 2,2-difluoro methyl piperates provided by the present invention is short, and technical process is easy to control, react completely, yield is high, and the target product purity prepared is high, steady quality, meets the service requirements as agricultural chemicals or medicine intermediate completely.
(2) cheaply, specifically, raw material piperonylaldehyde low price, chlorine and hydrogen fluoride are all low-cost basic chemical raw materials for the raw material that the preparation method of 2,2-difluoro methyl piperates provided by the present invention is used and reagent.
(3) in each step reaction of the preparation method of 2,2-difluoro methyl piperates provided by the present invention, solvent for use amount is few, produces waste liquid few, not only reduces costs minimizing environmental pollution, be also very convenient to large-scale commercial production.
Embodiment
Inventor with a piperonylaldehyde for raw material, acquisition 2 is obtained successively through chlorination reaction, fluoridation, esterification three-step reaction, 2-difluoro methyl piperate, thus provide that a kind of technique is simple, reaction conditions is gentle, intermediate without the need to purifying, applicable industrial scale operation that quality product is high 2, the preparation method of 2-difluoro methyl piperate, completes the present invention on this basis.
The invention provides a kind of preparation method of 2,2-difluoro methyl piperate, comprise the steps:
1) chlorination reaction: take piperonylaldehyde as raw material, under initiator or light-initiated effect, prepare 2,2-dichloro pepper acyl chlorides with chlorine reaction, reaction equation is as follows:
Preferably, the concrete grammar of described chlorination reaction is: when use initiator causes chlorination reaction, by chlorine and be dissolved in the piperonylaldehyde of reaction solvent, initiator adds in reaction vessel simultaneously; When using light-initiated chlorination reaction, chlorine and the piperonylaldehyde being dissolved in reaction solvent being added in reaction vessel simultaneously, and illumination is carried out to reaction system; The ratio adding speed of piperonylaldehyde in speed and reaction solvent that adds of chlorine is preferably 2-10 times of molar weight, be more preferably 2-5:1, most preferably be 2-4:1, what those skilled in the art can control chlorine and the reaction solvent containing piperonylaldehyde according to the reaction process conversion situation of chlorine and piperonylaldehyde (in the reaction system) monitoring result adds speed.
In described step 1, spendable reaction solvent includes but not limited to benzene, chlorobenzene, dichlorobenzene, fluorobenzene, phenylfluoroform, p-chloro benzo trifluoride-99, methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin, fluoro trichloromethane, 1, 1, 2-trichloroethane, 1, 1-difluoro tetrachloroethane, 1, 2-difluoro tetrachloroethane, seven fluoro-2, 3, 3-tri-chlorobutane, 1, 1, 1, 3,-tetrachloro tetrafluoropropane, 1, 1, 1-trichloropentafluoropropane, 1, 1, one or more combination in 1-Refrigerant R 113, consumption for reaction solvent is not particularly limited, only otherwise to goal of the invention of the present invention produce and limit, preferably, the usage quantity of reaction solvent is piperonylaldehyde 0-20 times weight, be more preferably 1-5 times of weight, in a preferred embodiment, described reaction solvent is p-chloro benzo trifluoride-99.Those skilled in the art can control the reaction times of fluoridation according to reaction process (Expenditure Levels of reaction system Raw), after chlorination reaction terminates, degassed, distillation, collects target fraction.In a preferred embodiment, target fraction is 134-136 DEG C/1.4KPa (document: 145 DEG C/15mmHg, Yagupol'skii, L.M.; ZhurnalObshchei Khimii 1960, V30, P3129-32).After chlorination reaction terminates, also can not do any process, under directly dropping into, walk fluoridation.
In the chlorination reaction of described step (1), the mol ratio of chlorine and piperonylaldehyde is preferably 2-10:1, is more preferably 2-5:1, more preferably 2-4:1, and in a preferred embodiment, the mol ratio of chlorine and piperonylaldehyde is 3:1.The mol ratio of chlorine and piperonylaldehyde is general corresponding with the ratio adding speed of chlorine and piperonylaldehyde, namely after the mol ratio of chlorine and piperonylaldehyde is determined, and its velocity ratio added also ratio for this reason.
In described step (1), available initiator causes chlorination reaction, and also available light causes chlorination reaction.When causing chlorination reaction with initiator, described initiator can select the various chlorination reaction in this area initiator applicatory, concrete available initiator includes but not limited to: one or more the combination in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo two cyclohexanenitrile, benzoyl peroxide etc., in a preferred embodiment, described initiator is selected from Diisopropyl azodicarboxylate.When using light-initiated chlorination reaction, preferably cause chlorination reaction by UV-light.The weight ratio of described initiator and piperonylaldehyde is 0.01%-5.0%:1, and in a preferred embodiment, the mol ratio of initiator and piperonylaldehyde is 0.1:1.
In described step (1).The temperature of chlorination reaction is 60-240 DEG C, is more preferably 80-150 DEG C, most preferably is 120-140 DEG C.Faster reaction speed can be obtained at this temperature and produce tar little.
2) fluoridation: 2,2-dichloro pepper acyl chlorides (intermediate compound I) and hydrogen fluoride are carried out fluoridation, and obtain 2,2-difluoro pepper acyl fluorides (intermediate II), reaction equation is as follows:
Use in described step (2) 2,2-dichloro pepper acyl chlorides can be step (1) products therefrom, described product can be gained 2 after distillation purifying, 2-dichloro pepper acyl chlorides, also can be the product not making any process gained after piperonylaldehyde and chlorine carry out chlorination reaction, can directly drop in the fluoridation of step (2).
In described step (2), the concrete grammar of fluoridation is: 2,2-dichloro pepper acyl chlorides is placed in reaction vessel, and then pass into hydrogen fluoride and react, hydrogen fluoride can pass in batches, also can disposablely pass into.
In described step (2), hydrofluoric usage quantity is preferably 2-20 times of molar weight of 2,2-dichloro pepper acyl chlorides, is more preferably 3.0-5.0 times of molar weight.
In described step (2), the temperature of fluoridation, preferably in the scope of 30-120 DEG C, is more preferably 50-70 DEG C, and those skilled in the art can control the reaction times of fluoridation according to reaction process, the preferred reaction times is 0.1-100 hour, is more preferably 2-20 hour.
After fluoridation terminates, any process can not be done, under directly dropping into, walk esterification.
3) esterification: by 2,2-difluoro pepper acyl fluorides and methyl alcohol effect, prepare 2,2-difluoro methyl piperate, its reaction equation is as follows:
Use in described step (3) 2,2-difluoro pepper acyl fluorides can be step (2) products therefrom, described product is 2, do not make the product of any process gained after 2-dichloro pepper acyl chlorides and hydrogen fluoride carry out fluoridation, can directly drop in the esterification of step (3).
In described step (3), the concrete grammar of esterification is: methyl alcohol is added drop-wise to 2, in 2-difluoro pepper acyl fluorides, after having reacted, reaction solution is joined in alkaline aqueous solution, with organic solvent extraction, be separated and obtain organic phase, after precipitation, purifying, namely prepare 2,2-difluoro methyl piperate.Described alkaline aqueous solution is preferably one or more the combination in sodium bicarbonate aqueous solution, wet chemical, aqueous sodium carbonate, aqueous sodium hydroxide solution etc., be more preferably saturated sodium bicarbonate aqueous solution, in a preferred embodiment, described alkaline aqueous solution is 5wt% sodium bicarbonate aqueous solution.Those skilled in the art can select suitable organic solvent to extract according to practical situation, and available organic solvent includes but not limited to: one or more the combination in chloroform, methylene dichloride, ethylene dichloride, ethyl acetate etc.Described purifying can select the various purification process in this area, and be preferably distillation, those skilled in the art can judge the cut of target product, in a preferred embodiment, collects the cut that boiling point is 118-120 DEG C/6KPa during distillation.
In described step (3), the temperature of esterification is preferably in the scope of-10-240 DEG C, and be more preferably 20-100 DEG C, described esterification at room temperature also can be carried out, and in a preferred embodiment, temperature of reaction is 70 DEG C.
In described step (3), those skilled in the art can control the reaction times of esterification according to reaction process, and the reaction times of esterification is in 0.1-100 hour, preferred, and the reaction times is in 2-20 hour.
In described step (3), the consumption of methyl alcohol is 1.0-50 times of molar weight of 2,2-difluoro pepper acyl fluorides, is more preferably 1.0-5 times of molar weight, more preferably 2-4 times of molar weight.Described step (3) can not add solvent, also can react in reaction solvent.Described reaction solvent is selected from the aliphatic solvents such as pentane, hexane, heptane, cyclohexane, sherwood oil, one or more the combination in methylene dichloride, ethylene dichloride, chloroform, ethyl acetate, isopropyl acetate, acetonitrile, propionitrile, benzene, toluene, ethylbenzene, dimethylbenzene, chlorobenzene, dichlorobenzene, fluorobenzene, phenylfluoroform, oil of mirbane, ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, glycol dimethyl ether, diethylene glycol dimethyl ether etc.Consumption for reaction solvent in described step (3) is not particularly limited, and only otherwise to goal of the invention of the present invention produce and limit, preferably, the usage quantity of reaction solvent is 0-20 times of weight of piperonylaldehyde, is more preferably 0-2 times of weight.
In addition, due to 2,2-dichloro pepper acyl chlorides (intermediate compound I, CAS:72769-07-4) and 2,2-difluoro pepper acyl fluorides (intermediate II, CAS:656-44-0) be known compound, therefore, also can start preparation respectively using these two kinds of intermediates as raw material, obtain 2,2-difluoro methyl piperate product.
The present invention also provides the purposes of preparation method in the preparation field of 2,2-difluoro methyl piperate of described 2,2-difluoro methyl piperates.
Preparation method's synthetic route of 2,2-difluoro methyl piperates provided by the present invention is short, with low cost, and technical process is easy to control, react completely, yield is high, and the target product purity prepared is high, steady quality, and low in the pollution of the environment, be very applicable to large-scale industrial production.
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification sheets can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Notice, in the following example, the concrete processing unit that indicates or device all adopt conventional equipment in this area or device; All force value and scope all refer to absolute pressure.Unless otherwise indicated, otherwise all numbers are molar part, and all per-cent is weight percentage.
In addition should be understood that the one or more method stepss mentioned in the present invention do not repel and can also to there is additive method step or can also insert additive method step before and after described combination step between these steps clearly mentioned, except as otherwise noted; Will also be understood that, the relation that is connected between the one or more equipment/devices mentioned in the present invention is not repelled and can also to be there are other equipment/devices or can also insert other equipment/devices before and after described clustered aggregates/device between these two equipment/devices clearly mentioned, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Embodiment 1
The preparation of 2,2-dichloro pepper acyl chlorides
By after 300g piperonylaldehyde, the mixing of 0.3g Diisopropyl azodicarboxylate and after 600g p-chloro benzo trifluoride-99 mixed dissolution, be added dropwise in reactor, pass into chlorine (total amount 426g) with the speed of 71g/ hour simultaneously, and warm 120-140 DEG C in keeping.Piperonylaldehyde solution dropwises for about 6 hours, and reaction terminates.Reduce pressure degassed, then removed under reduced pressure p-chloro benzo trifluoride-99, then carry out underpressure distillation, collect the cut of 134-136 DEG C/1.4kPa, obtain 2,2-dichloro pepper acyl chlorides 479g, the productive rate of chlorination reaction is 94.4%.
Embodiment 2
The preparation of 2,2-difluoro pepper acyl fluorides
479g 2,2-dichloro pepper acyl chlorides is put into polytetrafluoro reactor, by temperature rise to 40 DEG C in reactor, passes into 120g hydrogen fluoride under stirring, stir half an hour after having led at 50-70 DEG C, reaction terminates.Recorded by GC-MS method, reaction product is 2,2-difluoro pepper acyl fluorides.This reaction solution is directly used as the next step.
Embodiment 3
The preparation of 2,2-difluoro methyl piperate
Above-mentioned reaction solution is risen to 70 DEG C, then drips 128g methyl alcohol, drip rear continuation back flow reaction 1 hour, reaction terminates.After being cooled to room temperature, reaction solution is transferred in the sodium hydrogen carbonate solution containing 500g 5% weight, stirs separatory after half an hour, be transferred in rectifying still after filtering after organic phase anhydrous magnesium sulfate drying.Collect the cut of 118-120 DEG C/6KPa, obtain 2,2-difluoro methyl piperate 337g, the productive rate fluoridizing esterification two-step reaction is the purity of 82.7%, 2,2-difluoro methyl piperate is 99.8%.
1H-NMR(CDCl3)δ7.86(d,1H,J＝8.3Hz)；7.70(m,1H)；7.10(d,1H,J＝8.3Hz)；3.93(s,3H)。
19F-NMR(CDCl3)δ-49.7。
m/z：216(M
+)，185，157，119，91，63。
In sum, the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (9)
1. the preparation method of a difluoro methyl piperate, comprises the steps: 2,2-difluoro pepper acyl fluorides (II) and methyl alcohol effect, prepare 2,2-difluoro methyl piperate (III) by esterification, its reaction equation is as follows:
2. one 2 as claimed in claim 1, the preparation method of 2-difluoro methyl piperate, it is characterized in that, the concrete grammar of described esterification is: be added drop-wise to by methyl alcohol in 2,2-difluoro pepper acyl fluorides, join in alkaline aqueous solution after having reacted by reaction solution, with organic solvent extraction, be separated and obtain organic phase, after precipitation, purifying, namely prepare 2,2-difluoro methyl piperate.
3. one 2 as claimed in claim 2, the preparation method of 2-difluoro methyl piperate, it is characterized in that, described alkaline aqueous solution is selected from one or more the combination in sodium bicarbonate aqueous solution, wet chemical, aqueous sodium carbonate, aqueous sodium hydroxide solution etc.;
And/or described organic solvent is selected from one or more the combination in chloroform, methylene dichloride, ethylene dichloride, ethyl acetate etc., the method for described purifying is distillation;
And/or the temperature of described esterification is in the scope of-10-240 DEG C;
And/or the reaction times of esterification is in 0.1-100 hour;
And/or the consumption of methyl alcohol is 1.0-50 times of molar weight of 2,2-difluoro pepper acyl fluorides.
4. one 2 as claimed in claim 1, the preparation method of 2-difluoro methyl piperate, it is characterized in that, described 2, the preparation method of 2-difluoro pepper acyl fluorides is: 2,2-dichloro pepper acyl chlorides (I) and hydrogen fluoride are carried out fluoridation, obtains 2,2-difluoro pepper acyl fluorides (II), reaction equation is as follows:
5. the preparation method of a kind of 2,2-difluoro methyl piperate as claimed in claim 6, it is characterized in that, the concrete grammar of described fluoridation is: 2,2-dichloro pepper acyl chlorides is placed in reaction vessel, then passes into hydrogen fluoride and react.
6. the preparation method of a kind of 2,2-difluoro methyl piperate as claimed in claim 7, it is characterized in that, hydrofluoric usage quantity is 2-20 times of molar weight of 2,2-dichloro pepper acyl chlorides;
And/or hydrogen fluoride adopts and passes into or the disposable form passed in batches;
And/or the temperature of fluoridation is preferably in the scope of 30-120 DEG C;
And/or the reaction times is 0.1-100 hour.
7. one 2 as claimed in claim 4, the preparation method of 2-difluoro methyl piperate, it is characterized in that, described 2, the preparation method of 2-dichloro pepper acyl chlorides is: take piperonylaldehyde as raw material, react with chlorinated with chlorine under initiator or light-initiated effect and prepare 2,2-dichloro pepper acyl chlorides, reaction equation is as follows:
8. one 2 as claimed in claim 7, the preparation method of 2-difluoro methyl piperate, it is characterized in that, the concrete grammar of described chlorination reaction is: when use initiator causes chlorination reaction, by chlorine and be dissolved in the piperonylaldehyde of reaction solvent, initiator adds in reaction vessel simultaneously; When using light-initiated chlorination reaction, chlorine and the piperonylaldehyde being dissolved in reaction solvent being added in reaction vessel simultaneously, and illumination is carried out to reaction system; After chlorination reaction terminates, degassed, distillation, collects target fraction.
9. the preparation method of a kind of 2,2-difluoro methyl piperate as claimed in claim 8, it is characterized in that, the ratio adding speed of piperonylaldehyde in speed and reaction solvent that adds of chlorine is preferably 2-10 times of molar weight;
And/or the mol ratio of chlorine and piperonylaldehyde is preferably 2-10:1;
And/or when causing chlorination reaction with initiator, described initiator is selected from one or more the combination in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo two cyclohexanenitrile, benzoyl peroxide etc.; When using light-initiated chlorination reaction, described light is UV-light;
And/or the temperature of described chlorination reaction is 60-240 DEG C.
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| CN1653029A (en) * | 2002-04-30 | 2005-08-10 | 三菱瓦斯化学株式会社 | High-purity (fluoroalkyl)benzene derivative and process for producing the same |
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| CN101066926A (en) * | 2007-06-01 | 2007-11-07 | 上海康鹏化学有限公司 | Prepn process of 3-trifluoro methyl benzoate |
| CN102351704A (en) * | 2011-08-25 | 2012-02-15 | 浙江巍华化工有限公司 | Method for synthesizing methyl 3-(trifluoromethyl)benzoate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061389A (en) * | 2015-08-20 | 2015-11-18 | 黄冬焱 | Preparation method for 2,2-difluoro-methyl piperate |
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