CN104829450B - A kind of preparation method containing bromo-ester - Google Patents

A kind of preparation method containing bromo-ester Download PDF

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Publication number
CN104829450B
CN104829450B CN201510181866.1A CN201510181866A CN104829450B CN 104829450 B CN104829450 B CN 104829450B CN 201510181866 A CN201510181866 A CN 201510181866A CN 104829450 B CN104829450 B CN 104829450B
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ester
chxcoor
bromine
binding agent
containing bromo
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CN104829450A (en
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叶立峰
王树华
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Juhua Group Technology Centre
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Juhua Group Technology Centre
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    • 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
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/63—Halogen-containing esters of saturated acids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Containing bromo-ester be by general formula it is CH the invention discloses a kind of preparation method containing bromo-ester3For the ester of CHXCOOR in the presence of initiator, acid binding agent, ultraviolet light and solvent, it is CH to generate general formula with bromine reaction3The target product containing bromo-ester of CXBrCOOR, wherein X represent halogen, including fluorine, chlorine, bromine, R represent alkyl.The method of the present invention has high selectivity, advantage at low cost.

Description

A kind of preparation method containing bromo-ester
Technical field
The present invention relates to a kind of preparation methods containing bromo-ester.
Background technology
General formula is CH3CXBrCOOR's contains bromo-ester, can slough a molecular halides hydrogen under suitable condition and generate 2- Haloacrylic acid esters.2- haloacrylic acid esters can be used as polymerized monomer to be used in plastic optical fiber, such as with 2- fluoroacrylic methyl esters Plastic optical fiber made of polymer for monomer, maximum operation (service) temperature are higher than common plastics optical fiber, suitable for temperature compared with In high working environment.
A kind of preparation method (the application number for 2- propylene halides acid alkyl ester that China State Intellectual Property Office is announced： 201210396238.1 publication No.：CN102875380A, date of publication：2013.01.16), with 2,3- dihalo alkyl propionates To react starting material, DMSO is heated to 30 DEG C~189 DEG C, 2,3- dihalos third are then continuously pumped into reactive distillation kettle Acid alkyl ester and polymerization inhibitor, side border ring rectifying makes 2- haloacrylic acid esters and unclassified stores detach, and since temperature is higher, is easy Generate more side reactions.
A kind of preparation method (the application number for 2- propylene halides acid alkyl ester that China State Intellectual Property Office is announced： 201210255161.6 publication No.：CN102757347A, date of publication：2012.10.31), this method is with corresponding halogenated acetic acids Arrcostab and dimethyl oxalate are reaction starting material, are once carried out according to the following steps：(1) by base catalyst and dimethyl oxalate It is dissolved in high boiling solvent of the boiling point more than 100 DEG C, is heated to 30 DEG C~80 DEG C；(2) 0 DEG C~20 DEG C are cooled to, is directly added Enter paraformaldehyde, be to slowly warm up to 30 DEG C~60 DEG C, the reaction was continued 0.5~5 hour；(3) it filters, polymerization inhibitor is added in filtrate, It carries out being evaporated under reduced pressure to crude product, crude product carries out rectifying again.Although high-purity 2- propylene halide dialkylaminobenzoic acids can be obtained Ester is reduced " three wastes ", reduces cost of material, but intermediate product is unstable, and raw material is difficult to remove totally, reduces receipts Rate.
A kind of manufacturing method (the application number for 2- fluorinated monomers that China State Intellectual Property Office is announced： 201080022012.4 notification number：CN102428067A, the day for announcing：2012.04.25).It has been directed to the fluoro- 2- of 2- containing bromo-ester The preparation method of bromo-propionic acid ester.But the patent has used " bromating agent with nitrogen-bromine key ", such as N-bromosuccinimide (NBS).And it is well known that " bromating agent with nitrogen-bromine key " is expensive, usage amount is big, therefore causes product cost high, no Conducive to industrialized production.
Invention content
The present invention in view of the deficiencies of the prior art, provides a kind of using cheap bromine as CH3The bromination of CHXCOOR is tried Agent come prepare general formula be CH3CXBrCOOR's contains bromo-ester, with the advantage that reaction condition is mild, at low cost.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：
A kind of preparation method containing bromo-ester, it is characterised in that：Containing bromo-ester be by general formula be CH3The ester of CHXCOOR is causing In the presence of agent, acid binding agent, ultraviolet light and solvent, it is CH to generate general formula with bromine reaction3The target product containing bromo-ester of CXBrCOOR, Wherein X represents halogen, including fluorine, chlorine, bromine, R represent alkyl.
Preferably, alkyl includes methyl, ethyl and trifluoroethyl.
Further, bromine and CH3The ratio of the amount of the substance of CHXCOOR is 0.9~1.5:1, bromine and CH3The proportioning shadow of CHXCOOR Ring raw material CH3The conversion ratio of CHXCOOR, bromine dosage is few, CH3CHXCOOR conversions are incomplete, bromine dosage be more than to a certain degree after, it is right CH3The raising of CHXCOOR conversion ratios influences less, but causes the waste of bromine.
Further, initiator is azo isobutyronitrile (AIBN), benzoyl peroxide, tert-butyl peroxide.
Preferably, the dosage of initiator is CH3The 1~10% of CHXCOOR mass.
Further, acid binding agent is the mixture of sodium dihydrogen phosphate, disodium hydrogen phosphate or the two.
Preferably, acid binding agent and CH3The ratio of the amount of the substance of CHXCOOR is 0.9~1.5:1, acid binding agent and CH3CHXCOOR Proportioning influence CH3The selectivity of CXBrCOOR, acid binding agent dosage is few, product CH3CXBrCOOR is selectively low, acid binding agent dosage It is smaller more than then being influenced on selectivity of product after certain proportion.
Further, solvent is carbon tetrachloride, 1,2- difluoro tetrachloroethanes.
Preferably, the dosage of solvent is CH33~20 times of CHXCOOR mass.
Further, the temperature of reaction is 60~90 DEG C, and reaction temperature has large effect, reaction temperature to reaction speed Low, reaction speed is slow, and required time is grown, and reaction temperature is high, and reaction speed is fast, but side reaction increases.
The present invention is by adopting the above-described technical solution, have the advantages that：
Bromide reagent is cheap used in the preparation method of the present invention, so that production cost is substantially reduced, is conducive to work Industry metaplasia is produced, and under the conditions of existing for initiator, acid binding agent, ultraviolet light and solvent, improves CH3The selectivity of CXBrCOOR, By controlling bromine and CH3CHXCOOR, acid binding agent and CH3The proportioning of CHXCOOR, improves CH3The conversion ratio of CHXCOOR, and The dosage of bromine is saved.
Specific implementation mode
It is CH that a kind of preparation method containing bromo-ester of the present invention, which containing bromo-ester is by general formula,3The ester of CHXCOOR in initiator, tie up In the presence of sour agent, ultraviolet light and solvent, wherein initiator can be azo-initiator, can also peroxide initiator, The dosage of preferably azo isobutyronitrile (AIBN), benzoyl peroxide, tert-butyl peroxide, initiator is CH3CHXCOOR mass 1~10%, acid binding agent is the mixture of sodium dihydrogen phosphate, disodium hydrogen phosphate or the two, acid binding agent and CH3The object of CHXCOOR The ratio of the amount of matter is 0.9~1.5:1, acid binding agent and CH3The proportioning of CHXCOOR influences CH3The selectivity of CXBrCOOR, acid binding agent Dosage is few, product CH3CXBrCOOR is selectively low, acid binding agent dosage be more than certain proportion after then on selectivity of product influence compared with Small, solvent is low polarity or nonpolar solvent, and preferably carbon tetrachloride, 1,2- difluoro tetrachloroethanes, the dosage of solvent is CH33~20 times of CHXCOOR mass, the temperature preferably reacted are 60~90 DEG C, and reaction temperature has reaction speed larger shadow It rings, reaction temperature is low, and reaction speed is slow, and required time is grown, and reaction temperature is high, and reaction speed is fast, but side reaction increases, anti-with bromine It is CH that general formula, which should be generated,3The target product containing bromo-ester of CXBrCOOR, bromine and CH3The ratio of the amount of the substance of CHXCOOR be 0.9~ 1.5:1, bromine and CH3The proportioning of CHXCOOR influences raw material CH3The conversion ratio of CHXCOOR, bromine dosage is few, CH3CHXCOOR is converted not Completely, after bromine dosage is more than to a certain degree, to CH3The raising of CHXCOOR conversion ratios influences less, but causes the waste of bromine, Wherein X represents halogen, including fluorine, chlorine, bromine, R represent alkyl, can be free from the alkyl of halogen, can also be halogen-containing alkane Base, it is preferred that alkyl includes methyl, ethyl and trifluoroethyl.
Embodiment 1
10.6g (0.1mol) 2- fluorine methyl propionate, tetra- chlorinations of 100g are added in the 250ml conical flasks with condenser pipe Carbon, 19.2g (0.12mol) bromine, 18.2g (0.12mol) disodium hydrogen phosphate, 0.2g azo isobutyronitriles, stirring are with wavelength The ultra violet lamp of 254nm.Oil bath heating is reacted to 70 DEG C.After 10h, add 0.1g azo isobutyronitriles, later every 10h adds 0.1g azo isobutyronitriles.After 40h, 0.3g azo isobutyronitriles have been added altogether, and the conversion ratio of 2- fluorine methyl propionates is The selectivity of the fluoro- 2 bromopropionic acid methyl esters of 94.6%, 2- is 85.6%.
Embodiment 2
Be added in the 250ml conical flasks with condenser pipe 13.5g (0.1mol) 2- chloropropionates, 80g carbon tetrachloride, 17.6g (0.11mol) bromine, 13.2g (0.11mol) sodium dihydrogen phosphate, 0.3g benzoyl peroxides, stirring, is 254nm with wavelength Ultra violet lamp.Oil bath heating is reacted to 60 DEG C.After 10h, 0.25g benzoyl peroxides are added, later every 10h Add 0.25g benzoyl peroxides.After 50h, 1.0g benzoyl peroxides have been added altogether, and the conversion ratio of 2- chloropropionates is The selectivity of the chloro- 2 bromopropionic acid ethyl ester of 92.4%, 2- is 87.2%.
Embodiment 3
16.7g (0.1mol) 2 bromopropionic acids methyl esters, 50g1,2- difluoros are added in the 250ml conical flasks with condenser pipe Tetrachloroethanes, 15.4g (0.09mol) bromine, 13.7g (0.09mol) disodium hydrogen phosphate, 0.2g benzoyl peroxides, stirring, use wave The ultra violet lamp of a length of 365nm.Oil bath heating is reacted to 80 DEG C.After 8h, 0.1g benzoyl peroxides are added, after 0.1g benzoyl peroxides are added every 8h.After 32h, 0.3g benzoyl peroxides, the conversion of 2 bromopropionic acid methyl esters have been added altogether Rate is 85.4%, and the selectivity of 2,2- dibromo-propionic acid methyl esters is 89.5%.
Embodiment 4
Be added in the 250ml conical flasks with condenser pipe 15.6g (0.1mol) 2- fluorine propionic acid -2,2,2- trifluoro ethyl esters, 230g1,2- difluoros tetrachloroethanes, 22.4g (0.14mol) bromine, 10.6g (0.07mol) sodium dihydrogen phosphate, 8.4g (0.07mol) Disodium hydrogen phosphate, 0.1g tert-butyl peroxides, stirring, the ultra violet lamp for being 254nm with wavelength.Oil bath heating to 90 DEG C, into Row reaction.After 12h, 0.1g tert-butyl peroxides are added, are reacted for 24 hours, 2- fluorine propionic acid -2,2, the conversion ratio of 2- trifluoro ethyl esters is The selectivity of the fluoro- 2 bromopropionic acid -2,2 of 78.5%, 2-, 2- trifluoro ethyl esters is 84.7%.
Embodiment 5
12.0g (0.1mol) 2- fluorine ethyl propionate, 180g1,2- difluoros are added in the 250ml conical flasks with condenser pipe Tetrachloroethanes, 24.0g (0.15mol) bromine, 22.5g (0.15mol) sodium dihydrogen phosphate, 0.2g tert-butyl peroxides, stirring, use wave The ultra violet lamp of a length of 254nm.Oil bath heating is reacted to 90 DEG C.After 12h, 0.2g tert-butyl peroxides are added, are reacted For 24 hours, it is 87.2% that the conversion ratio of 2- fluorine ethyl propionate, which is the selectivity of the fluoro- 2 bromopropionic acid ethyl esters of 88.3%, 2-,.
It these are only specific embodiments of the present invention, but the technical characteristic of the present invention is not limited thereto.It is any with this hair Based on bright, for the technique effect for realizing essentially identical, made ground simple change, equivalent replacement or modification etc. are all covered Among protection scope of the present invention.

Claims (1)

1. a kind of preparation method containing bromo-ester, it is characterised in that：It is described containing bromo-ester be by general formula be CH3The ester of CHXCOOR is causing In the presence of agent, acid binding agent, ultraviolet light and solvent, the dosage of the initiator is the CH3The 1~10% of CHXCOOR mass, The initiator be azo isobutyronitrile (AIBN), benzoyl peroxide, tert-butyl peroxide, the acid binding agent with it is described CH3The ratio of the amount of the substance of CHXCOOR is 0.9~1.5:1, the acid binding agent is sodium dihydrogen phosphate, disodium hydrogen phosphate or the two Mixture, the dosage of the solvent is the CH33~20 times of CHXCOOR mass, the solvent are carbon tetrachloride, 1,2- Difluoro tetrachloroethanes, reaction temperature are 60~90 DEG C, and it is CH to generate general formula with bromine reaction3The target containing bromo-ester of CXBrCOOR is produced Object, the bromine and the CH3The ratio of the amount of the substance of CHXCOOR is 0.9~1.5:1, wherein X represent halogen, including fluorine, chlorine, Bromine, R represent alkyl, and the alkyl includes methyl, ethyl and trifluoroethyl.
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JP6678986B2 (en) * 2015-09-15 2020-04-15 国立大学法人島根大学 Method for producing α-bromo-α-fluorocarboxylic acid esters
CN110937999B (en) * 2019-11-19 2022-08-02 苏州斐然医药科技有限公司 Synthetic method of artificial cell membrane raw material 2, 3-dibromo-2-methyl hydroxyethyl propionate

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CN1944388A (en) * 2005-10-09 2007-04-11 巨化集团公司 Process for preparing 2-flaoro methyl isobutyrate
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