CN102746150A - Method for preparing ethyl difluorobromoacetate with high-boiling-point substances from difluoromonochlorethane process - Google Patents
Method for preparing ethyl difluorobromoacetate with high-boiling-point substances from difluoromonochlorethane process Download PDFInfo
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- CN102746150A CN102746150A CN2012102682218A CN201210268221A CN102746150A CN 102746150 A CN102746150 A CN 102746150A CN 2012102682218 A CN2012102682218 A CN 2012102682218A CN 201210268221 A CN201210268221 A CN 201210268221A CN 102746150 A CN102746150 A CN 102746150A
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Abstract
The invention relates to a method for preparing ethyl difluorobromoacetate with high-boiling-point substances from a difluoromonochlorethane process. The method comprises the steps of reacting high-boiling-point substances from the difluoromonochlorethane process with chlorine in a liquid-phase reactor under the action of catalytic medium ultraviolet light to synthesize difluorotrichloroethane, then directly brominating difluorotrichloroethane to prepare difluorobromotrichloroethane, and directly oxidizing difluorobromotrichloroethane with oxygen in ethanol solvent to prepare ethyl difluorobromoacetate. The preparation method thoroughly solves the difficulty troubling 142b process and has positive contribution to environmental protection aspect; and prepared ethyl difluorobromoacetate is high in purity, low in cost and is suitable for commercial manufacture.
Description
Technical field
The present invention relates to a kind of preparation method of medicine intermediate ethyl bromide difluoride, particularly a kind of high boiling material that adopts difluoro monochlorethane technology prepares the method for ethyl bromide difluoride.
Background technology
Along with the application of pvdf in sun power backboard film and lithium cell sticker, the demand of pvdf has obtained growth at full speed, and the demand of monomer whose vinylidene also increases day by day.Difluoro monochlorethane (142b) is the basic material of vinylidene, so the output of domestic difluoro monochlorethane (142b) also improves rapidly.
But prepare in the 142b technology in the C2H4F2 C2H4F2 chlorination; 3 ~ 5% high boiling material is arranged approximately, and (high boiling material of indication of the present invention promptly is difluoro ethylene dichloride and two trifluorotrichloroethanes; Wherein 90% (wt%) difluoro ethylene dichloride, 10% (wt%), two trifluorotrichloroethanes) produce, at present this high boiling material at home 142b manufacturing firm all do not obtain utilizing, mostly be to adopt the method for hoarding or burning to dispose this high boiling material; So not only cause environmental pollution, and cause the wasting of resources.
Ethyl bromide difluoride is the midbody of anticarcinogen gemcitabine (Gemcitabine); Domestic commerce is made commonplace employing trifluorochloroethylene and bromine addition reaction generation difluoro bromo-chloro-bromothane at present; Adopt the oleum oxidation to prepare the difluoro bromoacetyl chloride again, difluoro bromoacetyl chloride and ethanol synthesis prepare ethyl bromide difluoride then.For example U.S. Pat 6906219, and Korean Patent KR20020096912, Russ P SU568631A1 etc. are this operational paths of describing.
Summary of the invention
The purpose of this invention is to provide the method that a kind of high boiling material that adopts difluoro monochlorethane technology prepares ethyl bromide difluoride; Adopt high boiling material (difluoro ethylene dichloride and two trifluorotrichloroethanes) the preparation ethyl bromide difluoride of difluoro monochlorethane (142b) technology; Not only thoroughly solve the difficult problem of puzzlement 142b technology, and aspect environment protection, also made positive contribution.
To achieve these goals; Technical scheme of the present invention is: the high boiling material of difluoro monochlorethane technology is under the catalytic media action of ultraviolet light; In Liquid-phase reactor, synthesize two trifluorotrichloroethanes with chlorine; The direct bromination of two trifluorotrichloroethanes prepares difluoro bromine trichloroethane then, and difluoro bromine trichloroethane directly adopts dioxygen oxidation to prepare ethyl bromide difluoride in alcohol solvent.
The high boiling material of difluoro monochlorethane (142b) (90% (wt%) difluoro ethylene dichloride, 10% (wt%), two trifluorotrichloroethanes), with synthetic two trifluorotrichloroethanes of chlorine, directly bromination prepares difluoro bromine trichloroethane then in Liquid-phase reactor.
CF
2HCCl
2H?+Cl
2------?CF
2HCCl
3+HCl
CF
2HCCl
3+Br
2------CF
2BrCCl
3+HBr
Difluoro bromine trichloroethane is direct dioxygen oxidation prepared in reaction ethyl bromide difluoride in alcohol solvent.
2CF
2BrCCl
3+O
2+2C
2H
5OH------?2CF
2Br-COOC
2H
5+2HCl+Cl
2
The temperature of reaction of said chlorine and above-mentioned high boiling material is 20～50 ℃, and reaction pressure is 0.01 ~ 0.2Mpag, and the reaction times is 3 ~ 5 hours.
The temperature of reaction of bromine and two trifluorotrichloroethanes is 50～70 ℃ in the said bromination, and reaction pressure is 0. 1 ~ 0.2Mpag, and the reaction times is 4 ~ 6 hours.
Said difluoro bromine trichloroethane 120～150 ℃ of direct oxidation temperature of reaction in alcohol solvent.Reaction pressure is 0. 3 ~ 1.1Mpag, and the reaction times is 6 ~ 8 hours.
Said catalytic media ultraviolet light wavelength 100 ~ 300nm.
The weight ratio of said chlorine and high boiling material is 0.5 ~ 1:1.
The weight ratio of said bromine and two trifluorotrichloroethanes is 0.4 ~ 1:1.
In alcohol solvent in the oxidizing reaction, the weight ratio of difluoro bromine trichloroethane and oxygen is 14 ~ 20:1 at said difluoro bromine trichloroethane.
Preparing method of the present invention has thoroughly solved the difficult problem of puzzlement 142b technology, and aspect environment protection, has also made positive contribution; The purity of the ethyl bromide difluoride of the present invention's preparation is high, and cost is low, is suitable for commercial the manufacturing.
Embodiment
Through following examples the present invention is further specified.Embodiment adopts GC-MASS6890N to detect.
Embodiment 1
, drops into 50L carbon steel lining 30 kilograms of the high boiling material of 142b technology in moulding the autoclave of jacketed, 100nm light source and stirring and device for absorbing tail gas; Wherein the difluoro ethylene dichloride is 27 kilograms; 3 kilograms of two trifluorotrichloroethanes start light source and whipping appts then, in chuck, feed recirculated water; Temperature in the control reaction kettle is 25 ℃, and the pressure of reaction kettle is 0.015Mpag.Drop into chlorine continuously, the rate of feeding of chlorine is 5 kilograms/hour, and charging time is 3 hours.Be incubated after 0.5 hour, reacting kettle jacketing is changed feed 60 ℃ of hot water, when controlling warm reaction kettle system temperature and being 60 ℃, drop into bromine continuously, the rate of feeding of bromine is 4 kilograms/hour, and charging time is 4 hours, is incubated 1 hour.Stopped reaction, obtaining purity through rectifying is 40 kilograms of 99.5% difluoro bromine trichloroethane.
Serve as a contrast 30 kilograms of ethanol of input in the autoclave of moulding jacketed and stirring and device for absorbing tail gas at the 100L carbon steel, start then and stir, drop into 40 kilograms of difluoro bromine trichloroethane; Chuck feeds steam; The temperature of control reaction kettle system is 120 ℃, continuous aerating oxygen, and the rate of feeding of oxygen is 600 Grams Per Hours; Charging time is 6 hours, and the pressure-controlling of reaction kettle is at 0.5Mpa.Feed intake after the end, be incubated 1 hour, then cooling discharging.Thick product is purified through rectifying tower, and to obtain purity be 30 kilograms of 99.6% ethyl bromide difluorides.
Embodiment 2
, drops into 50L carbon steel lining 30 kilograms of the high boiling material of 142b technology in moulding the autoclave of jacketed, 300nm light source and stirring and device for absorbing tail gas; Wherein the difluoro ethylene dichloride is 27 kilograms; 3 kilograms of two trifluorotrichloroethanes start light source and whipping appts then, in chuck, feed recirculated water; Temperature in the control reaction kettle is 30 ℃, and the pressure of reaction kettle is 0.015Mpag.Drop into chlorine continuously, the rate of feeding of chlorine is 5 kilograms/hour, and charging time is 4 hours.Stir after 1 hour, reacting kettle jacketing is changed feed 70 ℃ of hot water, when controlling warm reaction kettle system temperature and being 70 ℃, drop into bromine continuously, the rate of feeding of bromine is 5 kilograms/hour, and charging time is 5 hours, is incubated 1 hour.Stopped reaction, obtaining purity through rectifying is 38 kilograms of 99.5% difluoro bromine trichloroethane.
Serve as a contrast 30 kilograms of ethanol of input in the autoclave of moulding jacketed and stirring and device for absorbing tail gas at the 100L carbon steel, start then and stir, drop into 38 kilograms of difluoro bromine trichloroethane; Chuck feeds steam; The temperature of control reaction kettle system is 150 ℃, continuous aerating oxygen, and the rate of feeding of oxygen is 800 Grams Per Hours; Charging time is 6 hours, and the pressure-controlling of reaction kettle is 0.9Mpa.Feed intake and finish insulation 1 hour, cooling discharging then.Thick product is purified through rectifying tower, and to obtain purity be 29 kilograms of 99.7% ethyl bromide difluorides.
Embodiment 3
, drops into 50L carbon steel lining 30 kilograms of the high boiling material of 142b technology in moulding the autoclave of jacketed, 300nm light source and stirring and device for absorbing tail gas; Wherein the difluoro ethylene dichloride is 27 kilograms; 3 kilograms of two trifluorotrichloroethanes start light source and whipping appts then, in chuck, feed recirculated water; Temperature in the control reaction kettle is 50 ℃, and the pressure of reaction kettle is 0.1Mpag.Drop into chlorine continuously, the rate of feeding of chlorine is 5 kilograms/hour, and charging time is 5 hours.Stir after 1 hour, reacting kettle jacketing is changed feed 50 ℃ of hot water, when controlling warm reaction kettle system temperature and being 50 ℃, drop into bromine continuously, the rate of feeding of bromine is 5 kilograms/hour, and charging time is 6 hours, is incubated 1 hour.Stopped reaction, obtaining purity through rectifying is 38 kilograms of 99.5% difluoro bromine trichloroethane.
Serve as a contrast 30 kilograms of ethanol of input in the autoclave of moulding jacketed and stirring and device for absorbing tail gas at the 100L carbon steel, start then and stir, drop into 38 kilograms of difluoro bromine trichloroethane; Chuck feeds steam; The temperature of control reaction kettle system is 130 ℃, continuous aerating oxygen, and the rate of feeding of oxygen is 600 Grams Per Hours; Charging time is 8 hours, and the pressure-controlling of reaction kettle is 1.1Mpa.Feed intake and finish insulation 1 hour, cooling discharging then.Thick product is purified through rectifying tower, and to obtain purity be 29 kilograms of 99.8% ethyl bromide difluorides.
The foregoing description does not limit the present invention in any way, and every employing is equal to the technical scheme that replacement or the mode of equivalent transformation obtain and all drops in protection scope of the present invention.
Claims (5)
1. a high boiling material that adopts difluoro monochlorethane technology prepares the method for ethyl bromide difluoride; It is characterized in that: the high boiling material of difluoro monochlorethane technology is under the catalytic media action of ultraviolet light; With synthetic two trifluorotrichloroethanes of chlorine, the direct bromination of two trifluorotrichloroethanes prepares difluoro bromine trichloroethane then in Liquid-phase reactor, and difluoro bromine trichloroethane directly adopts dioxygen oxidation to prepare ethyl bromide difluoride in alcohol solvent; Wherein, The temperature of reaction of said chlorine and above-mentioned high boiling material is 20～50 ℃, and reaction pressure is 0.01 ~ 0.2Mpag, and the reaction times is 3 ~ 5 hours; The temperature of reaction of bromine and two trifluorotrichloroethanes is 50～70 ℃ in the said bromination, and reaction pressure is 0. 1 ~ 0.2Mpag, and the reaction times is 4 ~ 6 hours; Said difluoro bromine trichloroethane 120～150 ℃ of direct oxidation temperature of reaction in alcohol solvent.Reaction pressure is 0. 3 ~ 1.1Mpag, and the reaction times is 6 ~ 8 hours.
2. the high boiling material of employing difluoro monochlorethane technology according to claim 1 prepares the method for ethyl bromide difluoride, it is characterized in that: said catalytic media ultraviolet light wavelength 100 ~ 300nm.
3. the high boiling material of employing difluoro monochlorethane technology according to claim 1 prepares the method for ethyl bromide difluoride, it is characterized in that: the weight ratio of said chlorine and high boiling material is 0.5 ~ 1:1.
4. the high boiling material of employing difluoro monochlorethane technology according to claim 1 prepares the method for ethyl bromide difluoride, it is characterized in that: the weight ratio of said bromine and two trifluorotrichloroethanes is 0.4 ~ 1:1.
5. the high boiling material of employing difluoro monochlorethane technology according to claim 1 prepares the method for ethyl bromide difluoride; It is characterized in that: in alcohol solvent in the oxidizing reaction, the weight ratio of difluoro bromine trichloroethane and oxygen is 14 ~ 20:1 at said difluoro bromine trichloroethane.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628559A (en) * | 2013-11-06 | 2015-05-20 | 连云港金康医药科技有限公司 | Ozone oxidation method used for preparing halogenated acetic acid and esters of halogenated acetic acid |
| WO2015156245A1 (en) * | 2014-04-09 | 2015-10-15 | 国立大学法人神戸大学 | Method for producing halogenated carboxylic acid ester |
| CN105461509A (en) * | 2015-12-01 | 2016-04-06 | 仇颖超 | Liquid-phase production method for difluorotrichloroethane |
| 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 |
| CN109180479A (en) * | 2018-09-30 | 2019-01-11 | 禾信天成科技（天津）有限公司 | A kind of preparation method of difluoro bromacetate |
| CN117263774A (en) * | 2023-09-22 | 2023-12-22 | 丰镇市汇杰环保科技发展有限公司 | Treatment method of 1, 1-difluoro chloroethane high-boiling-point substance |
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| CN1131659A (en) * | 1994-12-05 | 1996-09-25 | 埃尔夫阿托化学有限公司 | Process for preparation of alkyl halodifluoroacetates |
| CN1392133A (en) * | 2001-06-18 | 2003-01-22 | 阿托菲纳公司 | Process for preparing bromodifluoacetic acid compounds |
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2012
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Patent Citations (2)
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| CN1131659A (en) * | 1994-12-05 | 1996-09-25 | 埃尔夫阿托化学有限公司 | Process for preparation of alkyl halodifluoroacetates |
| CN1392133A (en) * | 2001-06-18 | 2003-01-22 | 阿托菲纳公司 | Process for preparing bromodifluoacetic acid compounds |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628559A (en) * | 2013-11-06 | 2015-05-20 | 连云港金康医药科技有限公司 | Ozone oxidation method used for preparing halogenated acetic acid and esters of halogenated acetic acid |
| WO2015156245A1 (en) * | 2014-04-09 | 2015-10-15 | 国立大学法人神戸大学 | Method for producing halogenated carboxylic acid ester |
| JP6057449B2 (en) * | 2014-04-09 | 2017-01-11 | 国立大学法人神戸大学 | Method for producing halogenated formate |
| CN105461509A (en) * | 2015-12-01 | 2016-04-06 | 仇颖超 | Liquid-phase production method for difluorotrichloroethane |
| 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 |
| CN107400053B (en) * | 2017-07-21 | 2020-12-15 | 山东飞源新材料有限公司 | Green synthesis method of ethyl difluorobromoacetate |
| CN109180479A (en) * | 2018-09-30 | 2019-01-11 | 禾信天成科技（天津）有限公司 | A kind of preparation method of difluoro bromacetate |
| CN117263774A (en) * | 2023-09-22 | 2023-12-22 | 丰镇市汇杰环保科技发展有限公司 | Treatment method of 1, 1-difluoro chloroethane high-boiling-point substance |
| CN117263774B (en) * | 2023-09-22 | 2024-07-19 | 丰镇市汇杰环保科技发展有限公司 | Treatment method of1, 1-difluoro chloroethane high-boiling-point substance |
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Application publication date: 20121024 |