CN109180479A - A kind of preparation method of difluoro bromacetate - Google Patents

A kind of preparation method of difluoro bromacetate Download PDF

Info

Publication number
CN109180479A
CN109180479A CN201811160110.9A CN201811160110A CN109180479A CN 109180479 A CN109180479 A CN 109180479A CN 201811160110 A CN201811160110 A CN 201811160110A CN 109180479 A CN109180479 A CN 109180479A
Authority
CN
China
Prior art keywords
reaction
bromacetate
difluoro
preparation
bis
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
Application number
CN201811160110.9A
Other languages
Chinese (zh)
Inventor
韩红旗
周欣悦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wo Letter Tiancheng Technology (tianjin) Co Ltd
Original Assignee
Wo Letter Tiancheng Technology (tianjin) Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wo Letter Tiancheng Technology (tianjin) Co Ltd filed Critical Wo Letter Tiancheng Technology (tianjin) Co Ltd
Priority to CN201811160110.9A priority Critical patent/CN109180479A/en
Publication of CN109180479A publication Critical patent/CN109180479A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/14Preparation of carboxylic acid esters from carboxylic acid halides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/013Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/04Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58Preparation of carboxylic acid halides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention provides a kind of preparation methods of difluoro bromacetate, comprising the following steps: (1) with CF2X‑CHCl2For raw material, CF is obtained by dehydrochlorination elimination reaction, bromine addition reaction2Br-CClXBr, wherein X is H or Cl;(2) CF in step (1)2Br-CClXBr carry out photooxidation or with sulfur trioxide oxidation reaction, reaction obtain CF2Br-COCl;(3) by the CF in step (2)2Br-COCl and alcohol carry out esterification, arrive product 2, the fluoro- 2- bromacetate of 2- bis- by separating, distilling.The preparation method of difluoro bromacetate of the present invention, so that 1,1- bis- fluoro- 2,2- dichloroethanes or 1,1- bis- fluoro- 1,2, both by-products of 2- trichloroethanes are utilized, mitigate the pollution that they generate environment, and the process for producing difluoro bromacetate is environmentally protective, the yield of difluoro bromacetate and safety are higher.

Description

A kind of preparation method of difluoro bromacetate
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of preparation method of difluoro bromacetate.
Background technique
Difluoro bromoacetic acid ester type compound is as the important building block in organic synthesis, in recent years in medicine, pesticide It is had been more and more widely used in synthesis.Wherein ethyl bromide difluoride is a kind of important fluorochemical, in cyclisation, oxygen Change, the industrial circles such as the catalyst of halogenation have been widely used and development prospect, be especially used for agriculture chemistry and drug Chemical field.In medical industry, it is to prepare fluorinated pyrimidine class antineoplastic that ethyl fluoroacetate, which is a kind of important medicine intermediate, The starting material of object and fluorine quino Mek-Tol Unit antibacterials.
1,1- bis- fluoro- 2,2- dichloroethanes is that Difluoroethane chlorination prepares by-product in R142b technique, and 1,1- bis- is fluoro- 1,2,2- trichloroethanes is the by-product prepared in R113 technique, these by-products mostly use greatly the method for burning to locate at present Reason, not only pollutes environment, but also waste of resource in this way.
Summary of the invention
In view of this, the present invention is directed to propose a kind of preparation method of difluoro bromacetate, the preparation method use 1,1- Two fluoro- 2,2- dichloroethanes or 1,1- bis- fluoro- 1, both by-products of 2,2- trichloroethanes are that raw material prepares difluoro bromoacetic acid Ester utilizes both by-products, mitigates the pollution that they generate environment, and produce difluoro bromoacetic acid The process of ester is environmentally protective, and the yield of difluoro bromacetate and safety are higher.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of preparation method of difluoro bromacetate, comprising the following steps:
(1) with CF2X-CHCl2For raw material, CF is obtained by dehydrochlorination elimination reaction, bromine addition reaction2Br- CClXBr, wherein X is H or Cl;
(2) CF in step (1)2Br-CClXBr carry out photooxidation or with sulfur trioxide oxidation reaction, reaction obtains CF2Br-COCl;
(3) by the CF in step (2)2Br-COCl and alcohol carry out esterification, arrive product 2 by separating, distilling, The fluoro- 2- bromacetate of 2- bis-.
Further, the photooxidation in step (2) turns to ultraviolet oxidation.
Further, the step of ultraviolet oxidation are as follows: molar ratio is the CF of 1:1.3-1.5:0.3-0.52Br-CClXBr、 Enter photooxidation reaction device after oxygen, chlorine are preheated, carry out photooxidation reaction with ultraviolet light, wherein X is H or Cl.
Further, the effective wavelength of ultraviolet light is 300-400nm, the unit volume of ultraviolet source in photooxidation reaction device Light source power is 5-195W/L, and reaction pressure is 0-0.5MPa in terms of gauge pressure, and reaction temperature is 60-120 DEG C, and the residence time is 0.2-25min。
Further, ultraviolet source unit volume light source power is 50-100W/L in photooxidation reaction device, anti-in terms of gauge pressure Answering pressure is 0-0.2MPa, residence time 3-10min.
Further, the CF in step (1)2When Br-CClXBr is with sulfur trioxide oxidation reaction, sulfur trioxide and CF2Br- The molar ratio of CClXBr is 1.2-2.5:1, and the rate of addition of sulfur trioxide is 0.1-0.6g/min, reaction temperature 30-45 DEG C, it is warming up to 70-120 DEG C after being added dropwise, reacts 1-3 hours, tail gas is absorbed with 10%-30%wt sodium hydrate aqueous solution, Wherein X is H or Cl.
Further, the reaction temperature of esterification is -10-30 DEG C in step (3), is separated into step (3) using full It is washed with sodium bicarbonate aqueous solution, distillation is air-distillation to collect target product fraction in step (3).
Further, the alcohol in step (3) is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, trifluoroethanol, trifluoro Any one in propyl alcohol, five fluorine propyl alcohol and hexafluoroisopropanol.
Compared with the existing technology, the preparation method of difluoro bromacetate of the present invention has the advantage that
The preparation method of difluoro bromacetate of the present invention, using fluoro- 2, the 2- dichloroethanes of 1,1- bis- or 1,1- Two fluoro- 1, both by-products of 2,2- trichloroethanes are that raw material prepares difluoro bromacetate, obtain both by-products Utilization has been arrived, has mitigated the pollution that they generate environment, and the process for producing difluoro bromacetate is environmentally protective, difluoro bromine second The yield of acid esters and safety are higher.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase Mutually combination.
Below in conjunction with embodiment, the present invention will be described in detail.
Embodiment 1
A kind of preparation method of difluoro bromacetate, comprising the following steps:
(1) 40g 1 is added in the reactor, the potassium hydroxide of fluoro- 2, the 2- dichloroethanes of 1- bis- and 150g 20%wt are water-soluble Liquid, using 0.8g tetrabutylammonium bromide as catalyst, 60 DEG C of reactions obtain difluoro vinyl chloride;By obtained difluoro vinyl chloride with The rate of 0.12g/min is added in 45g bromine, reacts 5h, and reaction temperature is not higher than 10 DEG C, then with the rate of 0.05g/min Being added to reaction terminates, and distillation obtains 1,1-, the bis- bromo- 2- chloroethanes of fluoro- 1,2- bis-, purity 99%.
(2) by obtained 1,1-, the bis- bromo- 2- chloroethanes of fluoro- 1,2- bis- and oxygen, chlorine according to 1:1.5:0.3 mole Than being passed into the photooxidation reaction device of 2L, it is passed through 1,1-, the bis- bromo- 2- chloroethanes of fluoro- 1,2- bis- of 0.22mol in 1h, uses The high-pressure sodium lamp of single 100W/L provides ultraviolet source, in terms of gauge pressure reaction pressure be 0MPa, 110 DEG C of conditions of reaction temperature Under, the gas phase photo-oxidation product of illumination reaction 4min is continuously discharged from reactor head, obtains CF2Br-COCl, conversion ratio 99.3%.
(3) dehydrated alcohol is added in the reactor, then passes to CF2Br-COCl, reaction carry out under the conditions of ice-water bath, After completion of the reaction, it is washed with saturated sodium bicarbonate aqueous solution, is then distilled, collected 110-112 DEG C of fraction, obtain 2,2- bis- Fluoro- 2- bromoacetate sterling.
Embodiment 2
A kind of preparation method of difluoro bromacetate, comprising the following steps:
(1) 40g 1,1- bis- fluoro- 1, the sodium hydroxide of 2,2- trichloroethanes and 130g 20%wt are added in the reactor Aqueous solution, using 1.0g dodecyl trimethyl ammonium bromide as catalyst, 50 DEG C of reactions obtain dichlorodifluoroethylene;By what is obtained Dichlorodifluoroethylene is passed into 40g bromine with the rate of 0.10g/min, reacts 4h, then be passed through with the rate of 0.04g/min Terminate to reaction, distillation obtains 1,1-, bis- bromo- 2, the 2- dichloroethanes of fluoro- 1,2- bis-.
(2) by obtained 1,1-, bis- bromo- 2, the 2- dichloroethanes of fluoro- 1,2- bis- and oxygen, chlorine according to 1:1.3:0.3's Molar ratio is passed into the photooxidation reaction device of 2L, and 1,1-, bis- bromo- 2, the 2- bis- of fluoro- 1,2- bis- of 0.2mol is passed through in 50min Chloroethanes provides ultraviolet source with the high-pressure sodium lamp of single 200W, in terms of gauge pressure reaction pressure be 0MPa, reaction temperature 100 Under the conditions of DEG C, the gas phase photo-oxidation product of illumination reaction 5min is continuously discharged from reactor head, obtains CF2Br-COCl turns Rate 99.3%.
(3) anhydrous isopropyl alcohol is added in the reactor, then passes to CF2Br-COCl, reaction under the conditions of ice-water bath into Row, after completion of the reaction, is washed with saturated sodium bicarbonate aqueous solution, is then distilled, and is collected 125-130 DEG C of fraction, is obtained 2,2- Two fluoro- 2- isopropyl acetate bromide sterlings.
Embodiment 3
A kind of preparation method of difluoro bromacetate, comprising the following steps:
(1) 40g 1,1- bis- fluoro- 1, the sodium hydroxide of 2,2- trichloroethanes and 130g 20%wt are added in the reactor Aqueous solution, using 1.0g dodecyl trimethyl ammonium bromide as catalyst, 50 DEG C of reactions obtain dichlorodifluoroethylene;By what is obtained Dichlorodifluoroethylene is passed into 40g bromine with the rate of 0.10g/min, reacts 4h, then be passed through with the rate of 0.04g/min Terminate to reaction, distillation obtains 1,1-, bis- bromo- 2, the 2- dichloroethanes of fluoro- 1,2- bis-.
(2) by obtained 1,1-, bis- bromo- 2, the 2- dichloroethanes of fluoro- 1,2- bis- and oxygen, chlorine according to 1:1.3:0.3's Molar ratio is passed into the photooxidation reaction device of 2L, and 1,1-, bis- bromo- 2, the 2- bis- of fluoro- 1,2- bis- of 0.2mol is passed through in 50min Chloroethanes provides ultraviolet source with the high-pressure sodium lamp of single 100W, in terms of gauge pressure reaction pressure be 0.1MPa, reaction temperature 80 Under the conditions of DEG C, the gas phase photo-oxidation product of illumination reaction 5min is continuously discharged from reactor head, obtains CF2Br-COCl turns Rate 99.5%.
(3) dehydrated alcohol is added in the reactor, then passes to CF2Br-COCl, reaction carry out under the conditions of ice-water bath, After completion of the reaction, it is washed with saturated sodium bicarbonate aqueous solution, is then distilled, collected 110-112 DEG C of fraction, obtain 2,2- bis- Fluoro- 2- bromoacetate sterling.
Embodiment 4
A kind of preparation method of difluoro bromacetate, comprising the following steps:
(1) 40g 1,1- bis- fluoro- 1, the sodium hydroxide of 2,2- trichloroethanes and 130g 20%wt are added in the reactor Aqueous solution, using 1.0g dodecyl trimethyl ammonium bromide as catalyst, 50 DEG C of reactions obtain dichlorodifluoroethylene;By what is obtained Dichlorodifluoroethylene is passed into 40g bromine with the rate of 0.10g/min, reacts 4h, then be passed through with the rate of 0.04g/min Terminate to reaction, distillation obtains 1,1-, bis- bromo- 2, the 2- dichloroethanes of fluoro- 1,2- bis-.
(2) by obtained 1,1-, bis- bromo- 2, the 2- dichloroethanes of fluoro- 1,2- bis- and oxygen, chlorine according to 1:1.3:0.3's Molar ratio is passed into the photooxidation reaction device of 2L, and 1,1-, bis- bromo- 2, the 2- bis- of fluoro- 1,2- bis- of 0.2mol is passed through in 50min Chloroethanes provides ultraviolet source with the high-pressure sodium lamp of single 200W, in terms of gauge pressure reaction pressure be 0MPa, 80 DEG C of reaction temperature Under the conditions of, the gas phase photo-oxidation product of illumination reaction 1min is continuously discharged from reactor head, obtains CF2Br-COCl, conversion Rate 55.6%.
(3) dehydrated alcohol is added in the reactor, then passes to CF2Br-COCl, reaction carry out under the conditions of ice-water bath, After completion of the reaction, it is washed with saturated sodium bicarbonate aqueous solution, is then distilled, collected 110-112 DEG C of fraction, obtain 2,2- bis- Fluoro- 2- bromoacetate sterling.
Embodiment 5
A kind of preparation method of difluoro bromacetate, comprising the following steps:
(1) 80g 1,1- bis- fluoro- 1, the sodium hydroxide of 2,2- trichloroethanes and 230g 25%wt are added in the reactor Aqueous solution, using 0.8g dodecyl trimethyl ammonium bromide and 0.5g benzyltriethylammoinium chloride as catalyst, 70 DEG C of reactions are obtained Dichlorodifluoroethylene;Obtained dichlorodifluoroethylene is passed into 40g bromine with the rate of 0.10g/min, reacts 4h, then Being passed through with the rate of 0.04g/min to reaction terminates, and distillation obtains 1,1-, bis- bromo- 2, the 2- dichloroethanes of fluoro- 1,2- bis-.
(2) obtained 1,1-, bis- bromo- 2, the 2- dichloroethanes of fluoro- 1,2- bis- is added in reactor, is then slowly added dropwise Sulfur trioxide, rate of addition 0.3g/min control sulfur trioxide and 1, and bis- bromo- 2, the 2- dichloroethanes of fluoro- 1,2- bis- of 1- rubs Your ratio is 1.5:1, and dropping temperature is controlled at 30-45 DEG C, and 80 DEG C are warming up to after being added dropwise to complete, and keeps the temperature 2hr, the CF that will be obtained2Br- COCl is passed into esterifier, and tail gas is absorbed with 30% sodium hydrate aqueous solution.
(3) anhydrous trifluoroethanol is added in esterifier, then passes to CF2Br-COCl is reacted in ice-water bath condition Lower progress is washed with saturated sodium bicarbonate aqueous solution after completion of the reaction, is then distilled, and is collected 98-100 DEG C of fraction, is obtained 2, The fluoro- 2- bromoacetic acid trifluoro ethyl ester sterling of 2- bis-.
Embodiment 6
A kind of preparation method of difluoro bromacetate, comprising the following steps:
(1) 80g 1,1- bis- fluoro- 1, the sodium hydroxide of 2,2- trichloroethanes and 230g 25%wt are added in the reactor Aqueous solution, is catalyst with 0.8g tetrabutylammonium chloride and 0.5g18- crown ether -6, and 40 DEG C of reactions obtain dichlorodifluoroethylene;It will Obtained dichlorodifluoroethylene is passed into 40g bromine with the rate of 0.10g/min, reacts 4h, then with the rate of 0.04g/min Being passed through to reaction terminates, and distillation obtains 1,1-, bis- bromo- 2, the 2- dichloroethanes of fluoro- 1,2- bis-.
(2) obtained 1,1-, bis- bromo- 2, the 2- dichloroethanes of fluoro- 1,2- bis- is added in reactor, is then slowly added dropwise Sulfur trioxide, rate of addition 0.6g/min control sulfur trioxide and 1, and bis- bromo- 2, the 2- dichloroethanes of fluoro- 1,2- bis- of 1- rubs Your ratio is 2.5:1, and dropping temperature is controlled at 30-45 DEG C, and 100 DEG C are warming up to after being added dropwise to complete, and keeps the temperature 3hr.By what is obtained CF2Br-COCl is passed into esterifier, and tail gas is absorbed with 10% sodium hydrate aqueous solution.
(3) anhydrous hexafluoroisopropanol is added in esterifier, then passes to CF2Br-COCl is reacted in ice-water bath item It is carried out under part, after completion of the reaction, is washed with saturated sodium bicarbonate aqueous solution, then distilled, collected 105-110 DEG C of fraction, obtain To the fluoro- 2- bromoacetic acid hexafluoro isopropyl ester sterling of 2,2- bis-.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (8)

1. a kind of preparation method of difluoro bromacetate, it is characterised in that: the following steps are included:
(1) with CF2X-CHCl2For raw material, CF is obtained by dehydrochlorination elimination reaction, bromine addition reaction2Br-CClXBr, Middle X is H or Cl;
(2) CF in step (1)2Br-CClXBr carry out photooxidation or with sulfur trioxide oxidation reaction, reaction obtain CF2Br- COCl;
(3) by the CF in step (2)2Br-COCl and alcohol carry out esterification, arrive product 2,2- bis- by separating, distilling Fluoro- 2- bromacetate.
2. the preparation method of difluoro bromacetate according to claim 1, it is characterised in that: the photooxidation in step (2) For ultraviolet oxidation.
3. the preparation method of difluoro bromacetate according to claim 2, it is characterised in that: the step of ultraviolet oxidation Are as follows: molar ratio is the CF of 1:1.3-1.5:0.3-0.52Enter photooxidation reaction device after Br-CClXBr, oxygen, chlorine are preheated, Photooxidation reaction is carried out with ultraviolet light, wherein X is H or Cl.
4. the preparation method of difluoro bromacetate according to claim 3, it is characterised in that: the effective wavelength of ultraviolet light is 300-400nm, the unit volume light source power of ultraviolet source is 5-195W/L, the reaction pressure in terms of gauge pressure in photooxidation reaction device For 0-0.5MPa, reaction temperature is 60-120 DEG C, residence time 0.2-25min.
5. the preparation method of difluoro bromacetate according to claim 4, it is characterised in that: ultraviolet in photooxidation reaction device Light source unit volume light source power is 50-100W/L, and reaction pressure is 0-0.2MPa, residence time 3-10min in terms of gauge pressure.
6. the preparation method of difluoro bromacetate according to claim 1, it is characterised in that: the CF in step (1)2Br- When CClXBr is with sulfur trioxide oxidation reaction, sulfur trioxide and CF2The molar ratio of Br-CClXBr is 1.2-2.5:1, sulfur trioxide Rate of addition be 0.1-0.6g/min, reaction temperature is 30-45 DEG C, is warming up to 70-120 DEG C after being added dropwise, reaction 1-3 is small When, tail gas is with the absorption of 10%-30%wt sodium hydrate aqueous solution, and wherein X is H or Cl.
7. the preparation method of difluoro bromacetate according to claim 1, it is characterised in that: esterification in step (3) Reaction temperature be -10-30 DEG C, be separated into step (3) and washed using saturated sodium bicarbonate aqueous solution, distillation in step (3) It is air-distillation to collect target product fraction.
8. the preparation method of difluoro bromacetate according to claim 1, it is characterised in that: the alcohol in step (3) is first It is any one in alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, trifluoroethanol, trifluoropropanol, five fluorine propyl alcohol and hexafluoroisopropanol Kind.
CN201811160110.9A 2018-09-30 2018-09-30 A kind of preparation method of difluoro bromacetate Pending CN109180479A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811160110.9A CN109180479A (en) 2018-09-30 2018-09-30 A kind of preparation method of difluoro bromacetate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811160110.9A CN109180479A (en) 2018-09-30 2018-09-30 A kind of preparation method of difluoro bromacetate

Publications (1)

Publication Number Publication Date
CN109180479A true CN109180479A (en) 2019-01-11

Family

ID=64946456

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811160110.9A Pending CN109180479A (en) 2018-09-30 2018-09-30 A kind of preparation method of difluoro bromacetate

Country Status (1)

Country Link
CN (1) CN109180479A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020138434A1 (en) * 2018-12-28 2020-07-02 Agc株式会社 Production method for haloalkyl acid halide, production method for haloalkyl acid ester, and production method for haloalkyl acid amide
CN112079721A (en) * 2020-09-16 2020-12-15 南通宝凯药业有限公司 Production process of ethyl difluorobromoacetate
CN112979465A (en) * 2019-12-02 2021-06-18 浙江省化工研究院有限公司 Method for preparing ethyl difluorobromoacetate

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747176A (en) * 2009-12-24 2010-06-23 杭州原正化学工程技术装备有限公司 Method for preparation of trifluoro acetyl chloride with trifluoroethane chlorinated mixture
CN102746150A (en) * 2012-07-30 2012-10-24 内蒙古奥特普氟化学新材料开发有限公司 Method for preparing ethyl difluorobromoacetate with high-boiling-point substances from difluoromonochlorethane process
CN104761446A (en) * 2015-04-15 2015-07-08 江西盛伟实业有限公司 Preparation method of 2-bromo-2,2-difluoroacetyl chloride and 2-bromo-2,2-difluoro acetate and recycling method of waste difluoro trichloroethane
CN106397186A (en) * 2016-08-31 2017-02-15 河北正朗制药有限公司 Preparation method of ethyl bromodifluoroacetate
CN106892813A (en) * 2015-12-17 2017-06-27 浙江蓝天环保高科技股份有限公司 A kind of method that difluoro chloracetyl chloride is prepared by gas phase photooxidation reaction
CN107400053A (en) * 2017-07-21 2017-11-28 山东飞源新材料有限公司 A kind of green synthesis method of ethyl bromide difluoride
CN108558650A (en) * 2018-05-29 2018-09-21 江苏蓝色星球环保科技股份有限公司 The method that tetrachloro-ethylene prepares trifluoro-acetyl chloride

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747176A (en) * 2009-12-24 2010-06-23 杭州原正化学工程技术装备有限公司 Method for preparation of trifluoro acetyl chloride with trifluoroethane chlorinated mixture
CN102746150A (en) * 2012-07-30 2012-10-24 内蒙古奥特普氟化学新材料开发有限公司 Method for preparing ethyl difluorobromoacetate with high-boiling-point substances from difluoromonochlorethane process
CN104761446A (en) * 2015-04-15 2015-07-08 江西盛伟实业有限公司 Preparation method of 2-bromo-2,2-difluoroacetyl chloride and 2-bromo-2,2-difluoro acetate and recycling method of waste difluoro trichloroethane
CN106892813A (en) * 2015-12-17 2017-06-27 浙江蓝天环保高科技股份有限公司 A kind of method that difluoro chloracetyl chloride is prepared by gas phase photooxidation reaction
CN106397186A (en) * 2016-08-31 2017-02-15 河北正朗制药有限公司 Preparation method of ethyl bromodifluoroacetate
CN107400053A (en) * 2017-07-21 2017-11-28 山东飞源新材料有限公司 A kind of green synthesis method of ethyl bromide difluoride
CN108558650A (en) * 2018-05-29 2018-09-21 江苏蓝色星球环保科技股份有限公司 The method that tetrachloro-ethylene prepares trifluoro-acetyl chloride

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020138434A1 (en) * 2018-12-28 2020-07-02 Agc株式会社 Production method for haloalkyl acid halide, production method for haloalkyl acid ester, and production method for haloalkyl acid amide
CN112979465A (en) * 2019-12-02 2021-06-18 浙江省化工研究院有限公司 Method for preparing ethyl difluorobromoacetate
CN112979465B (en) * 2019-12-02 2022-06-28 浙江省化工研究院有限公司 Method for preparing ethyl difluorobromoacetate
CN112079721A (en) * 2020-09-16 2020-12-15 南通宝凯药业有限公司 Production process of ethyl difluorobromoacetate

Similar Documents

Publication Publication Date Title
EP2814796B1 (en) Process for making tetrafluoropropene
CN109180479A (en) A kind of preparation method of difluoro bromacetate
CN108503531B (en) Preparation method of 3, 3-dimethyl-2-oxobutyric acid
CN107400053B (en) Green synthesis method of ethyl difluorobromoacetate
CN102311343A (en) Processing technique of ethyl difluoroacetate
CN109809959B (en) Preparation method of 1,1,1,2, 3-pentachloropropane
CN107118090B (en) Method for preparing 1-chloro-1' -chloroacetyl cyclopropane by taking trichloroisocyanuric acid as chlorinating agent
EP2343269B1 (en) Method of producing fluoromethyl 1,1,1,3,3,3-hexafluoroisopropyl ether
CN105016966A (en) Preparation method of (E)-1-chloro-6,6-dimethyl-2-heptene-4-alkyne
JP2009167120A (en) Method for producing perfluoroallyl bromide
CN108069817B (en) Method for preparing 1,1,1,2, 3-pentachloropropane with high selectivity and high yield by one-pot method
ES2952272T3 (en) Processes for the preparation of halo-substituted benzoic acid compounds
CN106749108B (en) A method of preparing perfluor -2,3- epoxy -2- methylpentane
CN104628559B (en) Ozone oxidation method used for preparing halogenated acetic acid and esters of halogenated acetic acid
CN110950735B (en) Method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by gas phase method
EP1094053B1 (en) Method of preparing fluoroaromatic compounds
CN113512004B (en) Synthetic method of 2-fluoro-5-trifluoromethylpyrimidine
CN110003165B (en) Synthesis method of chloro-2, 2-di (perfluorinated substituent) -1, 3-dioxolane compound
CN110713442A (en) Preparation method of o-nitrobenzaldehyde
CN106467463B (en) A kind of synthesis technology of ethyl difluoro
CN113045380B (en) Method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefin
EP2789603B1 (en) Method for producing pentafluorosulfanyl benzoic acid
CN112374966B (en) Preparation method of chloral hydrate
CN114805010B (en) Preparation method of 4-halogenated-1, 2-trifluoro-1-butene
CN111333501B (en) Preparation method of fluorine-containing carboxylic 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: 20190111