CN105152852A - Preparation method of 1-bromo-1-chloro-2,2-difluoroethylene - Google Patents
Preparation method of 1-bromo-1-chloro-2,2-difluoroethylene Download PDFInfo
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Abstract
The invention discloses a method for preparing 1-bromo-1-chloro-2,2-difluoroethylene from waste difluorotrichloroethane (R122) generated in a trifluorodichloroethane production process, which comprises the following step: carrying out reduction dechlorination reaction, bromine addition reaction and hydrogen bromide removal reaction. By using the R123 production waste difluorotrichloroethane to produce the high-added-value fluorine-containing intermediate R111211, the raw material cost is low. Meanwhile, the method implements recovery and reutilization on the solvent and catalyst, and reduces the environmental pollution. The method has the advantages of high operability, mild reaction, high reaction speed, high yield, high selectivity, environment friendliness and the like, and can be used for industrial production.
Description
Technical field
The present invention relates to a kind of preparation of fluorine-containing organic intermediate, specifically the preparation method of chloro-2, the 2-difluoroethylenes of the bromo-1-of a kind of 1-, particularly relate to one and utilize two trifluorotrichloroethanes to produce the preparation method of chloro-2, the 2-difluoroethylenes of the bromo-1-of 1-.
Background technology
Chloro-2, the 2-difluoroethylenes of the bromo-1-of 1-(R111211) is a kind of important fluorine fine chemical material, owing to containing double bond, bromine atoms, chlorine atom in this molecule, and can by the series compound of organic reaction synthesis containing difluoride group.R111211 is a kind of important difluoride group building block molecule, R111211 is mainly used in synthesis some fluorine-containing medicines, pesticide intermediate, the domestic and international application about R111211 is also under development at present, and many product innovations are still in exploitation endlessly, therefore R111211 has very large DEVELOPMENT PROSPECT.At present, R111211 mainly below in two classes reactions synthesis containing the fluoro-containing intermediate of difluoro methylene.
(1) for there is Reformatsky reaction:
The bromo-1-of 1-chloro-2,2-difluoroethylene and zinc react and generate zincon (Reformatsky reagent), it occurs that Reformatsky reacts again with aldehyde, ketone, imines etc. be that organic molecule extends carbochain and introduces the most frequently used method of difluoro methylene building block to organic molecule, and containing chlorine atom and double bond in difluoro methylene building block, a lot of fluoro-containing intermediate (Fujita containing difluoro methylene can be obtained by reacting further, MakotoandHiyama, Tamejiro.
bulletinoftheChemicalSocietyofJapan, 60 (12), 4377-84; 1987.).R111211 zincon also can generate alkene containing difluoro methylene with halogenated aryl hydrocarbon or halogenated alkane generation linked reaction, as reaction formula (1), reaction formula (2) shown in, R in reaction formula
1, R
2, R
3hydrogen, alkyl (saturated hydrocarbyl) can be respectively, comprise methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl.
(2) in R111211 molecule, alkene generation addition reaction generates fluorine-containing intermediate:
In R111211 molecule, alkene and organic molecule generation addition reaction generate the organic intermediate containing chlorine atom, bromine atoms and difluoro methylene, and its advantage is environmental protection, and the refuse of generation is few, and applicable industrialization is produced on a large scale.R111211 and chirality thiol react and generate medicine intermediate, as reaction formula (3) shown (Sachdev, KrishnaG.etal.
journalofChemicalResearch, Synopses,(12), 382-3; 1990.).R111211 passes through the addition reaction of alkene for the production of Fluorine-containing Inhalation Anaesthetics (Kumakura, Manami; Kawai, Toshikazu.
eP530731A1, 10Mar.1993.).
Can find out that chloro-2, the 2-difluoroethylenes of the bromo-1-of 1-are a kind of important fluoro-containing intermediates by above summary, researching and developing its synthetic method has important meaning.
At present, prior art prepares the method key factor of chloro-2, the 2-difluoroethylenes of the bromo-1-of 1-is following two classes:
(1) be that R111211 prepared by raw material with R12311:
Adopt the bromo-2-of 2-chloro-1,1,1-Halothane (R12311) for raw material prepare R111211 time, adopt organo-metallic lithium to react under-80 ~-50 DEG C of low temperature as highly basic and remove a part hydrogen fluoride and obtain R111211.In molecule R12311, C-F key is comparatively strong, and fracture C-F key needs very strong alkali, usually adopts n-BuLi, t-BuLi, LDA, LTMP highly basic, as reaction formula (4) shown (Anilkumar, R.andBurton, DonaldJ.
journalofFluorineChemistry, 126 (5), 835-843; 2005.).Owing to adopting organolithium reagent expensive, react also very high to the requirement of equipment at low temperatures, facility investment is large, energy consumption is also high, raw material R12311 also not easily obtains in addition, adopt this route to synthesize R111211 cost high, be not an economic synthetic route, this preparation method is not suitable for suitability for industrialized production.
(2) be that R111211 prepared by raw material with R11312:
Adopt 1, the bromo-1-of 1-bis-chloro-2,2,2-Halothane (R11312) prepares R111211 by the reduction dehalogenation reaction of zinc powder for raw material, and in raw molecule R12312, C-F key is comparatively strong, and fracture C-F key needs energy high, the yield of product is low, as reaction formula (5) shown (Fujita, MakotoandHiyama, Tamejiro.
bulletinoftheChemicalSocietyofJapan, 60 (12), 4377-84; 1987.).This route raw material R11312 is difficult to obtain and expensive, and reduction dehalogenation reaction yield is low, adopts this route to synthesize R111211 cost high, and be not an economic synthetic route, this preparation method is not suitable for suitability for industrialized production.
Existing employing R12311 or R11312 is the technological line that chloro-2, the 2-difluoroethylenes of the bromo-1-of 1-prepared by raw material, and what mainly there is R12311 or R11312 raw material carrys out source problem, namely how to obtain this raw material in a large number and at an easy rate; Also there is temperature of reaction low simultaneously, high to the requirement of equipment; In zinc powder reduction dehalogenation reaction process, yield is low, also there is the environmental issues such as wastewater flow rate is large in post-reaction treatment process simultaneously.
In sum, the bromo-1-of existing preparation 1-chloro-2,2-difluoroethene compound method there is reaction preference difference or expensive raw material price, cost high, reaction solvent consumption is large, product yield is low, or produce the series of problems such as a large amount of three wastes in reaction process, cause the suitability for industrialized production being difficult to realize chloro-2, the 2-difluoroethylene series compounds of the bromo-1-of 1-.Therefore, find one simple to operate, the synthetic route that environment amenable Suitable commercial amplifies chloro-2, the 2-difluoroethene compounds of the bromo-1-of 1-produced is engaged in task and the challenge of organic fluorine chemistry technician.
Trifluorobichloroethane (CF
3cHCl
2, R123) and as a kind of novel whipping agent, refrigeration agent and clean-out system, can be used as fluoro trichloromethane (CFCl
3, R11) substitute use, its ozone layer destroying power number (ODP) only has 0.02.More significant discovery is: it can be used as high-efficiency fire-extinguishant bromochlorodifluoromethane (CF
2clBr, R12B1) surrogate, so-called illusion is come true.Because it has numerous potential purposes and premium properties, make its progressively substituted freon (Freon) and breathe out dragon (Halon) and well-known.And it also can be used as production pentafluoride ethane (CF
3cHF
2, HCF-125) and fluorine-containing medicines, pesticide intermediate raw material, be with a wide range of applications.
In Chinese patent CN1273426C, describe the production process of trifluorobichloroethane, adopt at present with trieline be starting raw material through fluoridizing synthesis trifluoro-chloroethane, as reaction formula (6) shown in, and then obtain trifluorobichloroethane operational path through thermal chlorination, as reaction formula (7) shown in.
In this operational path, because second step reaction is free radical substitution reaction, cause its poor selectivity, side reaction is many.Except containing except target product trifluorobichloroethane (R123) in mixed gas after thermal chlorination, also containing a large amount of two trifluorotrichloroethane (CF
2clCCl
2h, R122).
Two trifluorotrichloroethane (CF
2clCCl
2h, R122) be produce the difluoro ethylene dichloride intermediate produced in R123 process not transform into trifluoro-chloroethane (R133a) completely; Intermediate difluoro ethylene dichloride is under thermal chlorination reaction conditions, the by product generated after there occurs chlorine substitution reaction, as reaction formula (8) shown in, also be likely that product R123 is under thermal chlorination reaction conditions, first there occurs and eliminate hydrogen fluoride reaction generation dichlorodifluoroethylene, then with the hydrogenchloride addition in reaction system, generate by product two trifluorotrichloroethane, as reaction formula (9) shown in.
At present, the way of industrial main employing separating-purifying, producing the magazins' layout removing produced in trifluorobichloroethane process, obtains qualified trifluorobichloroethane product, but, by product (impurity) after separation, very large to the murder by poisoning of human body and environment, can not directly discharge.The way of current employing is burned, and namely discharges producing after the refuse produced in trifluorobichloroethane process changes into the material of the environmental sound such as carbonic acid gas, water by the way of burning.At present, while producing 10,000 tons of trifluorobichloroethane products year, namely two trifluorotrichloroethanes (R122) (amount of the mixture containing R122) being often only generation reach about 200 tons, and the treatment process of burning causes the significant wastage of resource.Therefore, this area needs to develop a kind of method recycling waste two trifluorotrichloroethane (R122) produced in production trifluorobichloroethane process.
Summary of the invention
The object of this invention is to provide one utilizes two trifluorotrichloroethanes to produce the bromo-1-of 1-chloro-2, the preparation method of 2-difluoroethylene, waste two trifluorotrichloroethane (R122) produced in trifluorobichloroethane production process is particularly utilized to prepare the method for chloro-2, the 2-difluoroethylenes of the bromo-1-of 1-.
The present invention adopts following technical scheme to realize its goal of the invention, the preparation method of chloro-2, the 2-difluoroethylenes of the bromo-1-of a kind of 1-, and it comprises the following steps:
(1), in inert solvent, be obtained by reacting the chloro-vinylidene fluoride of 2-with two trifluorotrichloroethanes for raw material and zinc powder carry out reduction dechlorination;
Inert solvent of the present invention is alcoholic solvent or amide solvent or ether solvent or anhydrides solvent or containing the one in oxygen-nitrogen compound solvent or sulfocompound solvent or combination; The volume ratio of described inert solvent and two trifluorotrichloroethanes is 1 ~ 10:1;
The volume ratio of inert solvent of the present invention and two trifluorotrichloroethanes is preferably 2 ~ 5:1;
The present invention step (1) in, described alcoholic solvent comprises one in methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, glycerine or its combination; Described amide solvent comprises one in DMF, N,N-dimethylacetamide or its combination; Described ether solvent comprises one in ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diglyme, diethyl carbitol, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or its combination; Described anhydrides solvent comprises diacetyl oxide; Describedly comprise one in acetone, acetonitrile, morpholine, N-methylmorpholine or its combination containing oxygen-nitrogen compound solvent; Described sulfocompound solvent comprises one in dimethyl sulfoxide (DMSO), tetramethylene sulfone or its combination.
The mol ratio of zinc powder of the present invention and two trifluorotrichloroethanes is 0.8 ~ 3.0:1;
The mol ratio of zinc powder of the present invention and two trifluorotrichloroethanes is preferably 0.8 ~ 1.5:1;
The present invention step (1) in, described reduction dechlorination reaction is carried out under reaction promoter exists, and described reaction promoter is one in V-Brite B or iodine or glycol dibromide or Diisopropyl azodicarboxylate or dibenzoyl peroxide or combination.
The mol ratio of reaction promoter of the present invention and two trifluorotrichloroethanes is 0.005 ~ 0.2:1;
The mol ratio of reaction promoter of the present invention and two trifluorotrichloroethanes is preferably 0.01 ~ 0.06:1.
The present invention step (1) in, described zinc powder needs in advance through activation treatment, and it comprises following process:
1) zinc powder is stirred together with dilute hydrochloric acid, filter to use distilled water wash three times after disacidify, then use 95 ﹪ washing with alcohol twice, finally wash once with anhydrous diethyl ether, all filter after each washing to remove washings, such zinc powder, just by finish-drying, then grinds if any block in mortar;
2) by process 1) process after zinc powder stir in 10 ﹪ hydrochloric acid, filter, first wash zinc powder with water, then use washing with acetone, the zinc powder after process is for subsequent use.
The present invention step (1) in, the temperature of reaction of described reduction dechlorination reaction is 50 DEG C ~ 200 DEG C.
The chloro-vinylidene fluoride of 2-that (1) obtains of step and bromine in a solvent addition reaction obtain the bromo-2-chlorine-1,1-difluoroethane of 1,2-bis-;
The molar ratio of bromine of the present invention and the chloro-vinylidene fluoride of 2-is 1.0:1.0 ~ 1.2;
The present invention's solvent described in addition reaction is alkane or halohydrocarbon or its combination, comprise the one in normal hexane, hexanaphthene, methylene dichloride, tetracol phenixin, dithiocarbonic anhydride, acetic acid or its combination, the consumption of described solvent is 30 ﹪ ~ 100 ﹪ according to the volume computing of bromine;
At water or/and in organic solvent, in the presence of a catalyst, between temperature-10 DEG C ~ 100 DEG C, (2) step is obtained 1, the bromo-2-chlorine-1,1-difluoroethane of 2-bis-and alkali reaction engaging vibrating bromize hydrogen, carry out reflux condensation mode to product and react 5 hours ~ 30 hours at-10 DEG C ~ 10 DEG C, after reaction terminates, distillation or separation organic phase, obtain chloro-2, the 2-difluoroethylene crude products of the bromo-1-of 1-;
The mol ratio of 1,2-bis-bromo-2-chlorine-1,1-difluoroethane of the present invention and alkali is 1:1.0 ~ 4.0;
Organic solvent of the present invention comprises one in alcoholic solvent, ether solvent, sulfocompound solvent or its combination;
The present invention step (3) in, described organic solvent comprises one in methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, glycerine, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diglyme, diethyl carbitol, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, diacetyl oxide, dimethyl sulfoxide (DMSO), tetramethylene sulfone or its combination.
Alkali of the present invention be mineral alkali or/and organic bases, during use, with water or/and organic solvent dissolution alkali, be mixed with the alkaline solution that percentage composition is 10 ﹪ ~ 60 ﹪; Described mineral alkali comprises one in the phosphoric acid salt of the carbonate of the oxyhydroxide of I A and II A race element, basic metal or alkali earth metal, basic metal or alkali earth metal, metal oxide or its combination; Described organic bases comprises one in amine organic compound, the alkaline metal salt of alcohol, metal alkylide lithium compound, amido lithium compound or its combination;
The present invention step (3) in, described mineral alkali comprises lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, ammoniacal liquor, sodium carbonate, salt of wormwood, sodium phosphate, potassiumphosphate, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, ferric oxide, cupric oxide, the one in zinc oxide, aluminum oxide or its combination; Described organic bases comprises one in primary amine, secondary amine, tertiary amine, ethamine, diisopropylamine, triethylamine, pyridine, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide, potassium tert.-butoxide, butyllithium, phenyl lithium, lithium diisopropyl amido, hexamethyldisilazane lithium or its combination.
The mol ratio of 1,2-bis-bromo-2-chlorine-1,1-difluoroethane of the present invention and catalyzer is 100:0.1 ~ 10;
Catalyzer of the present invention is phase-transfer catalyst;
The present invention step (3) in, described catalyzer is selected from the one in lower group:
1) polyethers: comprise chain polyoxyethylene glycol (H (OCH
2cH
2)
noH), chain dialkylethers (R (OCH
2cH
2)
noR);
2) cyclic crown ether class: comprise 18 hats 6,15 hats 5, cyclodextrin;
3) quaternary ammonium salt phase transfer catalyst: comprise benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride;
4) tertiary amine: R
1r
2r
3n, pyridine, triethylamine, Tributylamine, wherein R
1, R
2, R
3represent C respectively
1-20alkyl;
5) quaternary ammonium hydroxide: R
1r
2r
3r
4n
+oH
-, wherein R
1, R
2, R
3, R
4represent C respectively
1-20alkyl;
6) season phosphonium salt: R
1r
2r
3r
4p
+x
-, wherein R
1, R
2, R
3, R
4represent C respectively
1-20alkyl or C
6-30aryl.
(4) chloro-2, the 2-difluoroethylene crude products of the bromo-1-of 1-step (3) obtained carry out rectification and purification;
Rectifying of the present invention is atmospheric distillation, and the condition of atmospheric distillation is: rectifying still temperature 50 C ~ 80 DEG C, collects the cut between 39 DEG C ~ 41 DEG C by adjustment reflux ratio;
To step (3) in organic solvent and catalyzer reclaim, be recycled and reused for step (3).
The present invention step (5) in, (3) after being separated crude product to step, remaining solution carries out decrease temperature crystalline, separates out organic salt or the inorganic bromide salt of hydrogen bromide, crosses the organic salt or the inorganic bromide salt that filter hydrogen bromide, then, Distillation recovery organic solvent is carried out to filtrate; To the remaining solution of distillation decrease temperature crystalline again, divide the organic salt or the inorganic bromide salt that isolate hydrogen bromide, surplus solution is crystalline mother solution, adopts activated carbon decolorizing 2-3 time to the crystalline mother solution obtained, obtain colourless or lurid clear solution, complete catalyst recovery.
Owing to adopting technique scheme, the present invention achieves goal of the invention preferably, and utilize the fluoro-containing intermediate R111211 of R123 processing waste two trifluorotrichloroethane production high added value, raw materials cost is low; Meanwhile, realize the recycling of solvent, catalyzer, decrease environmental pollution; The present invention has strong operability, reaction temperature and, speed of response is fast, productive rate is high, selectivity is high and advantages of environment protection, can be used for suitability for industrialized production.
Embodiment
The invention provides the preparation method of chloro-2, the 2-difluoroethylenes of the bromo-1-of a kind of 1-, as reaction formula (10) shown in.
The preparation method of chloro-2, the 2-difluoroethylenes of a kind of bromo-1-of 1-, it comprises the following steps:
(1), in inert solvent, be obtained by reacting the chloro-vinylidene fluoride of 2-with two trifluorotrichloroethanes for raw material and zinc powder carry out reduction dechlorination;
Inert solvent of the present invention is alcoholic solvent or amide solvent or ether solvent or anhydrides solvent or containing the one in oxygen-nitrogen compound solvent or sulfocompound solvent or combination; The volume ratio of described inert solvent and two trifluorotrichloroethanes is 1 ~ 10:1;
The volume ratio of inert solvent of the present invention and two trifluorotrichloroethanes is preferably 2 ~ 5:1;
The present invention step (1) in, described alcoholic solvent comprises one in methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, glycerine or its combination; Described amide solvent comprises one in DMF, N,N-dimethylacetamide or its combination; Described ether solvent comprises one in ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diglyme, diethyl carbitol, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or its combination; Described anhydrides solvent comprises diacetyl oxide; Describedly comprise one in acetone, acetonitrile, morpholine, N-methylmorpholine or its combination containing oxygen-nitrogen compound solvent; Described sulfocompound solvent comprises one in dimethyl sulfoxide (DMSO), tetramethylene sulfone or its combination.
The mol ratio of zinc powder of the present invention and two trifluorotrichloroethanes is 0.8 ~ 3.0:1;
The mol ratio of zinc powder of the present invention and two trifluorotrichloroethanes is preferably 0.8 ~ 1.5:1;
The present invention step (1) in, described reduction dechlorination reaction is carried out under reaction promoter exists, and described reaction promoter is one in V-Brite B or iodine or glycol dibromide or Diisopropyl azodicarboxylate or dibenzoyl peroxide or combination.
The mol ratio of reaction promoter of the present invention and two trifluorotrichloroethanes is 0.005 ~ 0.2:1;
The mol ratio of reaction promoter of the present invention and two trifluorotrichloroethanes is preferably 0.01 ~ 0.06:1.
The present invention step (1) in, described zinc powder needs in advance through activation treatment, and it comprises following process:
1) zinc powder is stirred together with dilute hydrochloric acid, filter to use distilled water wash three times after disacidify, then use 95 ﹪ washing with alcohol twice, finally wash once with anhydrous diethyl ether, all filter after each washing to remove washings, such zinc powder, just by finish-drying, then grinds if any block in mortar;
2) by process 1) process after zinc powder stir in 10 ﹪ hydrochloric acid, filter, first wash zinc powder with water, then use washing with acetone, the zinc powder after process is for subsequent use.
The present invention step (1) in, the temperature of reaction of described reduction dechlorination reaction is 50 DEG C ~ 200 DEG C.
The chloro-vinylidene fluoride of 2-that (1) obtains of step and bromine in a solvent addition reaction obtain the bromo-2-chlorine-1,1-difluoroethane of 1,2-bis-;
The molar ratio of bromine of the present invention and the chloro-vinylidene fluoride of 2-is 1.0:1.0 ~ 1.2;
The present invention's solvent described in addition reaction is alkane or halohydrocarbon or its combination, comprise the one in normal hexane, hexanaphthene, methylene dichloride, tetracol phenixin, dithiocarbonic anhydride, acetic acid or its combination, the consumption of described solvent is 30 ﹪ ~ 100 ﹪ according to the volume computing of bromine;
At water or/and in organic solvent, in the presence of a catalyst, between temperature-10 DEG C ~ 100 DEG C, (2) step is obtained 1, the bromo-2-chlorine-1,1-difluoroethane of 2-bis-and alkali reaction engaging vibrating bromize hydrogen, carry out reflux condensation mode to product and react 5 hours ~ 30 hours at-10 DEG C ~ 10 DEG C, after reaction terminates, distillation or separation organic phase, obtain chloro-2, the 2-difluoroethylene crude products of the bromo-1-of 1-;
The mol ratio of 1,2-bis-bromo-2-chlorine-1,1-difluoroethane of the present invention and alkali is 1:1.0 ~ 4.0;
Organic solvent of the present invention comprises one in alcoholic solvent, ether solvent, sulfocompound solvent or its combination;
The present invention step (3) in, described organic solvent comprises one in methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, glycerine, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diglyme, diethyl carbitol, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, diacetyl oxide, dimethyl sulfoxide (DMSO), tetramethylene sulfone or its combination.
Alkali of the present invention be mineral alkali or/and organic bases, during use, with water or/and organic solvent dissolution alkali, be mixed with the alkaline solution that percentage composition is 10 ﹪ ~ 60 ﹪; Described mineral alkali comprises one in the phosphoric acid salt of the carbonate of the oxyhydroxide of I A and II A race element, basic metal or alkali earth metal, basic metal or alkali earth metal, metal oxide or its combination; Described organic bases comprises one in amine organic compound, the alkaline metal salt of alcohol, metal alkylide lithium compound, amido lithium compound or its combination;
The present invention step (3) in, described mineral alkali comprises lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, ammoniacal liquor, sodium carbonate, salt of wormwood, sodium phosphate, potassiumphosphate, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, ferric oxide, cupric oxide, the one in zinc oxide, aluminum oxide or its combination; Described organic bases comprises one in primary amine, secondary amine, tertiary amine, ethamine, diisopropylamine, triethylamine, pyridine, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide, potassium tert.-butoxide, butyllithium, phenyl lithium, lithium diisopropyl amido, hexamethyldisilazane lithium or its combination.
The mol ratio of 1,2-bis-bromo-2-chlorine-1,1-difluoroethane of the present invention and catalyzer is 100:0.1 ~ 10;
Catalyzer of the present invention is phase-transfer catalyst;
The present invention step (3) in, described catalyzer is selected from the one in lower group:
1) polyethers: comprise chain polyoxyethylene glycol (H (OCH
2cH
2)
noH), chain dialkylethers (R (OCH
2cH
2)
noR);
2) cyclic crown ether class: comprise 18 hats 6,15 hats 5, cyclodextrin;
3) quaternary ammonium salt phase transfer catalyst: comprise benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride;
4) tertiary amine: R
1r
2r
3n, pyridine, triethylamine, Tributylamine, wherein R
1, R
2, R
3represent C respectively
1-20alkyl;
5) quaternary ammonium hydroxide: R
1r
2r
3r
4n
+oH
-, wherein R
1, R
2, R
3, R
4represent C respectively
1-20alkyl;
6) season phosphonium salt: R
1r
2r
3r
4p
+x
-, wherein R
1, R
2, R
3, R
4represent C respectively
1-20alkyl or C
6-30aryl.
(4) chloro-2, the 2-difluoroethylene crude products of the bromo-1-of 1-step (3) obtained carry out rectification and purification;
Rectifying of the present invention is atmospheric distillation, and the condition of atmospheric distillation is: rectifying still temperature 50 C ~ 80 DEG C, collects the cut between 39 DEG C ~ 41 DEG C by adjustment reflux ratio;
To step (3) in organic solvent and catalyzer reclaim, be recycled and reused for step (3).
The present invention step (5) in, (3) after being separated crude product to step, remaining solution carries out decrease temperature crystalline, separates out organic salt or the inorganic bromide salt of hydrogen bromide, crosses the organic salt or the inorganic bromide salt that filter hydrogen bromide, then, Distillation recovery organic solvent is carried out to filtrate; To the remaining solution of distillation decrease temperature crystalline again, divide the organic salt or the inorganic bromide salt that isolate hydrogen bromide, surplus solution is crystalline mother solution, adopts activated carbon decolorizing 2-3 time to the crystalline mother solution obtained, obtain colourless or lurid clear solution, complete catalyst recovery.
Below in conjunction with specific embodiment, the invention will be further described.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise per-cent and number calculate by weight.
" R122 " described herein and " two trifluorotrichloroethanes ", " R12212 " and " 1,2-bis-bromo-2-chlorine-1,1-difluoroethane ", " R111211 " and " chloro-2, the 2-difluoroethylenes of the bromo-1-of 1-" are used interchangeably.
Below in an example, the structural formula of compound is determined by nucleus magnetic resonance (NMR) or mass spectrum (MS).NMR displacement (δ) provides with the unit of 1,000,000/(ppm).The mensuration of NMR adopts Varian400MHz nuclear magnetic resonance spectrometer.The mensuration solvent of NMR is deuterochloroform (CDCl
3),
19fNMR calibration is fluoro trichloromethane (CFCl
3), chemical shift is with 10
-6(ppm) provide as unit.
Reacting all liquid starting materials and product adopts gas-chromatography to carry out quantitative analysis, adopts GC-MS to carry out qualitative analysis.Gas chromatographicanalyzer device is: gas chromatograph GC-2010, SHIMADZU.
GC-MS qualitative analysis adopts Voyager mass spectrograph _ Trace2000 gas chromatograph for determination.
Embodiment 1:
Zinc powder pre-treatment:
2 hours are stirred together with 6L2 ﹪ hydrochloric acid with 2.4 ㎏ zinc powders, filter to remove disacidify, zinc powder is placed in 10L plastic beaker, first use 6L2 ﹪ salt acid elution once, then distilled water wash three times (at every turn using 5L) is used, use 95 ﹪ washing with alcohol twice (at every turn using 3L) again, finally wash once with 3L anhydrous diethyl ether.All filter after each washing to remove washings.Zinc powder after process finish-drying under nitrogen protection, has block then to grind in mortar.Zinc powder is after treatment for subsequent use under nitrogen protection.
Preparation R12212:
5 liters of there-necked flasks that mechanical stirrer, constant pressure funnel are housed access two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-20 DEG C ~-10 DEG C, adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Said apparatus is carried out nitrogen replacement, add 1 liter of tetramethylene sulfone (industrial goods under nitrogen protection, Liaoyang Guanghua Chemical Co., Ltd.), the zinc powder activated 113 grams of (analytical pure, Shanghai Shen Xiang chemical reagent company limited) and 3.0 grams of V-Brite Bs, 160 DEG C of reactions, 290g bis-trifluorotrichloroethane (R122 is instilled in 2 hours, GC purity is greater than 95 ﹪, Sinochem Lantian Co., Ltd. produces the by product of R123), and continue reaction 3 hours, the R1122 generated imports in second reaction flask, methylene chloride 40ml is added in second reaction flask, bromine 219 grams, temperature of reaction 40 ± 5 DEG C, and stirring reaction is until the redness (bromine) of reaction solution disappears, then 1 is obtained with the cut that water pump underpressure distillation is collected between 60 DEG C ~ 65 DEG C, the bromo-2-of 2-bis-chloro-1, 2-C2H4F2 C2H4F2 (R12312) product 332g, GC purity is greater than 99 ﹪, productive rate 75 ﹪.The product obtained is the bromo-2-chlorine-1,1-difluoroethane (R12212) of 1,2-bis-through GC-MS, NMR Structural Identification.
MS(Mr=98.1)，m/z(﹪relativeintensity)，EI：50.1(3.6)，63.1(7.7)，70.0(4.1)，79.0(13.9)，81.0(9.8)，90.9(2.8)，98.0(42.1)，100.0(13.9)，126.9(14.9)，128.9(21.4)，130.9(7.9)，141.9(5.1)，143.9(5.1)，159.9(5.1)，176.9(78.4)，178.9(100)，180.9(25.4)，257.8(1.3)。
1H-NMR(400MHz，CDCl
3，TMS)：δ：5.892～5.928(dd，-CHClBr，
3J
HF=5.6Hz，
3J
HF=8.8Hz，1H)ppm。
19F-NMR(376.4MHz，CDCl
3,CFCl
3)：δ：-53.329～-52.886(dd，-C-
1F，
3J
HF=5.6Hz，
2J
FF=161.1Hz，1F)；-56.658～-56.207(dd，-C-
2F，
3J
HF=8.7Hz，
2J
FF=161.1Hz，1F)ppm。
Preparation R111211:
Install with reflux condensing tube, mechanical stirring device, 5 liters of there-necked flasks of constant pressure funnel, temperature of cooling water is controlled in reflux condensing tube at-10 ~ 10 DEG C during reaction, 1 is added in constant pressure funnel, the bromo-2-of 2-bis-chloro-1, 1-C2H4F2 C2H4F2 (R12212 content 99.3 ﹪) 1808 grams, the aqueous sodium hydroxide solution of 1120 gram of 30 ﹪ is added in reaction flask, Tetrabutyl amonium bromide 2.3 grams, adopt oil bath reacting by heating bottle, electronic temperature controller is adopted to control temperature of reaction 70 ± 5 DEG C, under agitation drip R12212, within about 5 hours, drip off, then insulation reaction 1 hour, reaction terminates rear static layering, organic phase 200ml washes and obtains R111211 crude product 1155 grams for 2 times.
The heat-eliminating medium of described reflux condensing tube also can be other conventional media of alcohol, acetone, chilled brine and laboratory, and the circulating temperature of controlled cooling model medium is between-10 ~ 10 DEG C.
The bromo-1-of 1-chloro-2, the rectification and purification of 2-difluoroethylene crude product adopts atmospheric distillation, wherein the condition of atmospheric distillation is: the outer temperature of rectifying still is 50 DEG C ~ 70 DEG C, the cut between 39 DEG C ~ 41 DEG C is collected by adjustment reflux ratio, obtain the bromo-1-of sterling 1-chloro-2,2-difluoroethylene 1055 grams, reaction yield 85 ﹪, gas-chromatography content is 99.5 ﹪.It is consistent with document that the product obtained detects data through GC-MS, NMR, is chloro-2, the 2-difluoroethylenes of the bromo-1-of product 1-.
MS(Mr=98.1)，m/z(﹪relativeintensity)，EI：51.0(8.4)；84.0(15.8)；86.0(9.2)；97.0(35.0)；99.0(10.6)；125.9(10.6)；127.9(14.0)；175.9(75.2)；177.9(100)；179.9(25.2)。
19F-NMR(376.4MHz,CFCl
3)：δ：-83.663(d，=C-
1F，
2J
FF=30.1Hz，1F)；-84.738(d，=C-
2F，
2J
FF=30.1Hz，1F)ppm。
Embodiment 2:
Preparation R12212:
Install with reflux condensing tube, mechanical stirring device, 5 liters of there-necked flasks of constant pressure funnel, add 2 liter 1 under nitrogen protection, 4-dioxane (Chinese 5-linked chemical plant), the zinc powder activated 325 grams of (analytical pure, Shanghai Shen Xiang chemical reagent company limited) and 11 grams of iodines, 100 DEG C of reactions, 580g bis-trifluorotrichloroethane (R122 is instilled in 3 hours, GC purity is greater than 95 ﹪, Sinochem Lantian Co., Ltd. produces the by product of R123), and continue reaction 4 hours, the R1122 generated imports in second reaction flask, solvent acetic acid 60ml is added in second reaction flask, bromine 493 grams, temperature of reaction 40 ± 5 DEG C, and stirring reaction is until the redness (bromine) of reaction solution disappears, first use the washing three times of 300ml respectively, then the cut between organic phase washed with water pump underpressure distillation collection 60 ~ 65 DEG C obtains 1, the bromo-2-of 2-bis-chloro-1, 1-C2H4F2 C2H4F2 (R12312) product 752g, GC purity is greater than 99 ﹪, productive rate 85 ﹪.
Preparation R111211:
Install with reflux condensing tube, mechanical stirring device, 5 liters of there-necked flasks of constant pressure funnel, temperature of cooling water is controlled in reflux condensing tube at-10 ~ 10 DEG C during reaction, 1 is added in constant pressure funnel, the bromo-2-of 2-bis-chloro-1, 1-C2H4F2 C2H4F2 (R12212 content 99.3 ﹪) 1810 grams, 1500 grams of dehydrated alcohols are added in reaction flask, 467 grams of potassium hydroxide, heating for dissolving, be mixed with the potassium hydroxide solution of ethanol, tetrabutylammonium chloride 3.9 grams, ice-water bath cooling is adopted to control temperature of reaction 0 ~ 10 DEG C, under agitation drip R12212, within about 6 hours, drip off, then insulation reaction 2 hours.Reaction terminates rear simple distillation and obtains R111211 crude product 1115 grams.
The bromo-1-of 1-chloro-2, the rectification and purification of 2-difluoroethylene crude product adopts atmospheric distillation, wherein the condition of atmospheric distillation is: the temperature of rectifying still is 50 DEG C ~ 70 DEG C, the cut between 39 DEG C ~ 41 DEG C is collected by adjustment reflux ratio, obtain the bromo-1-of sterling 1-chloro-2,2-difluoroethylene 993 grams, reaction yield 80 ﹪, gas-chromatography content is 99.0 ﹪.It is consistent with document that the product obtained detects data through GC-MS, NMR, is chloro-2, the 2-difluoroethylenes of the bromo-1-of product 1-.
Remaining with embodiment 1.
Embodiment 3:
Preparation R12212:
Install 5 liters of there-necked flasks with reflux condensing tube, mechanical stirring device, constant pressure funnel,
Add 5 liters of N under nitrogen protection, N-N,N-DIMETHYLACETAMIDE (analytical pure, Hangzhou Hui Pu Chemical Co., Ltd.), the zinc powder activated 650 grams of (analytical pure, Shanghai Shen Xiang chemical reagent company limited) and 105 grams of dibenzoyl peroxide (BPO), 80 DEG C of reactions, 1500g bis-trifluorotrichloroethane (R122 is instilled in 12 hours, GC purity is greater than 95 ﹪, Sinochem Lantian Co., Ltd. produces the by product of R123), and continue reaction 4 hours, the R1122 generated imports in second reaction flask, normal hexane solvent 130ml is added in second reaction flask, bromine 1303 grams, temperature of reaction 40 ± 5 DEG C, and stirring reaction is until the redness (bromine) of reaction solution disappears, then the cut between collecting 60 ~ 65 DEG C with water pump underpressure distillation obtains 1, the bromo-2-of 2-bis-chloro-1, 1-C2H4F2 C2H4F2 (R12312) product 2013g, GC purity is greater than 99 ﹪, productive rate 88 ﹪.
Preparation R111211:
Install with reflux condensing tube, mechanical stirring device, 5 liters of there-necked flasks of constant pressure funnel, temperature of cooling water is controlled in reflux condensing tube at-10 ~ 10 DEG C during reaction, 1 is added in constant pressure funnel, the bromo-2-of 2-bis-chloro-1, 1-C2H4F2 C2H4F2 (R12212 content 99.3 ﹪) 1809 grams, 1400 grams of methyl alcohol are added in reaction flask, 315 grams of sodium hydroxide, heating for dissolving, be mixed with the sodium hydroxide solution of methyl alcohol, PEG-400(poly(oxyethylene glycol) 400) phase-transfer catalyst 3.2 grams, adopt water-bath to control interior temperature and be no more than 40 DEG C, at room temperature agitation and dropping R12212, within about 5 hours, drip off, then insulation reaction 2 hours.Reaction terminates rear simple distillation and obtains R111211 crude product 1142 grams.
The bromo-1-of 1-chloro-2, the rectification and purification of 2-difluoroethylene crude product adopts atmospheric distillation, wherein the condition of atmospheric distillation is: the temperature of rectifying still is 50 DEG C ~ 70 DEG C, the cut between 39 DEG C ~ 41 DEG C is collected by adjustment reflux ratio, obtain the bromo-1-of sterling 1-chloro-2,2-difluoroethylene 1018 grams, reaction yield 82 ﹪, gas-chromatography content is 99.2 ﹪.It is consistent with document that the product obtained detects data through GC-MS, NMR, is chloro-2, the 2-difluoroethylenes of the bromo-1-of product 1-.
Remaining with embodiment 1.
Embodiment 4:
Preparation R111211:
Install with reflux condensing tube, mechanical stirring device, 5 liters of there-necked flasks of constant pressure funnel, temperature of cooling water is controlled in reflux condensing tube at-10 ~ 10 DEG C during reaction, 1 is added in reaction flask, the bromo-2-of 2-bis-chloro-1, 1-C2H4F2 C2H4F2 (R12212 content 99.3 ﹪) 1808 grams, add the aqueous sodium hydroxide solution of 1120 gram of 30 ﹪ in constant pressure funnel in batches, phase-transfer catalyst tetrabutylammonium chloride 3.5 grams, adopt oil bath reacting by heating bottle, electronic temperature controller is adopted to control temperature of reaction 70 ± 5 DEG C, under agitation drip R12212, within about 5 hours, drip off, then insulation reaction 1 hour.Reaction terminates rear simple distillation and obtains R111211 crude product 1180 grams.
The bromo-1-of 1-chloro-2, the rectification and purification of 2-difluoroethylene crude product adopts atmospheric distillation, wherein the condition of atmospheric distillation is: the temperature of rectifying still is 50 DEG C ~ 70 DEG C, the cut between 39 DEG C ~ 41 DEG C is collected by adjustment reflux ratio, obtain the bromo-1-of sterling 1-chloro-2,2-difluoroethylene 1080 grams, reaction yield 87 ﹪, gas-chromatography content is 99.2 ﹪.It is consistent with document that the product obtained detects data through GC-MS, NMR, is chloro-2, the 2-difluoroethylenes of the bromo-1-of product 1-.
Get the reaction solution after distilling out crude product R111211, pour 2 liters of there-necked flasks into and be heated to 100 DEG C ~ 120 DEG C, after making dissolution of solid, filtered while hot obtains filtrate 1577 grams, in 2 liters of there-necked flasks, mechanical stirring cools to interior temperature 0 DEG C ~ 5 DEG C, be incubated and carry out recrystallization in 12 hours, filtration obtains wet cake Sodium Bromide 556 grams, filtrate 970 grams; Filtrate is heated to 80 DEG C ~ 90 DEG C, 426 grams of solvents are obtained with water pump underpressure distillation desolventizing, in 2 liters of there-necked flasks, mechanical stirring cools to interior temperature 0 DEG C ~ 5 DEG C again, be incubated and carry out recrystallization in 12 hours, obtain wet cake Sodium Bromide 348 grams in filtration, filtrate 86 grams, merge wet Sodium Bromide, at 100 DEG C ~ 120 DEG C, drying obtains Sodium Bromide solid 669 grams for 3 hours, yield 93 ﹪ of Sodium Bromide.
Crystallization concentrates the secondary filtrate obtained and adds 8 grams of gacs, be heated to 100 DEG C ~ 120 DEG C reactions 3 hours, cool to interior temperature 0 ~ 5 DEG C, be incubated 3 hours, cross and filter gac, three filtrates obtained, add 8 grams of gacs again, be heated to 100 DEG C ~ 120 DEG C reactions 3 hours, cool to interior temperature 0 DEG C ~ 5 DEG C, be incubated 3 hours, cross and filter gac, four filtrates 70 grams obtained, for colourless transparent liquid, main containing phase-transfer catalyst tetrabutylammonium chloride, add the catalyzer tetrabutylammonium chloride of loss, again can prepare the bromo-1-of 1-chloro-2 for dehydrobromination, the reaction of 2-difluoroethylene.
Remaining with embodiment 1.
Embodiment 5:
Through reclaiming the filtrate 70 grams containing phase-transfer catalyst tetrabutylammonium chloride in Example 4, add 0.5 gram of tetrabutylammonium chloride in this filtrate, other experimental implementation with feed intake completely identical with embodiment 4, react and terminate rear simple distillation and obtain R111211 crude product 1185 grams.
The bromo-1-of 1-chloro-2, the rectification and purification of 2-difluoroethylene crude product adopts atmospheric distillation, wherein the condition of atmospheric distillation is: the temperature of rectifying still is 50 DEG C ~ 70 DEG C, the cut between 39 DEG C ~ 41 DEG C is collected by adjustment reflux ratio, obtain the bromo-1-of sterling 1-chloro-2,2-difluoroethylene 1093 grams, reaction yield 88 ﹪, gas-chromatography content is 99.2 ﹪.It is consistent with document that the product obtained detects data through GC-MS, NMR, is chloro-2, the 2-difluoroethylenes of the bromo-1-of product 1-.From result, after supplying the catalyzer of loss, the yield of reaction does not have considerable change, and catalyst recovery way provided by the invention is effective, and solvent also can efficient recovery, decreases environmental pollution.
Remaining with embodiment 1,4.
Embodiment 6:
Preparation R111211:
Install 5 liters of there-necked flasks with reflux condensing tube, mechanical stirring device, constant pressure funnel, temperature of cooling water is controlled in reflux condensing tube at-10 ~ 10 DEG C during reaction, 1 is added in constant pressure funnel, the bromo-2-of 2-bis-chloro-1,1-C2H4F2 C2H4F2 (R12212 content 99.3 ﹪) 1808 grams, in reaction flask, add 1063 grams of triethylamines, add 750 grams, water.Tetrabutyl amonium bromide 2.3 grams, adopts oil bath reacting by heating bottle, adopts electronic temperature controller to control temperature of reaction 90 ± 5 DEG C, under agitation drip R12212, within about 5 hours, drip off, then insulation reaction 1 hour, reaction terminates rear simple distillation and obtains R111211 crude product 1117 grams.
The bromo-1-of 1-chloro-2, the rectification and purification of 2-difluoroethylene crude product adopts atmospheric distillation, wherein the condition of atmospheric distillation is: the temperature of rectifying still is 50 DEG C ~ 70 DEG C, the cut between 39 DEG C ~ 41 DEG C is collected by adjustment reflux ratio, obtain the bromo-1-of sterling 1-chloro-2,2-difluoroethylene 931 grams, reaction yield 75 ﹪, gas-chromatography content is 99.5 ﹪.It is consistent with document that the product obtained detects data through GC-MS, NMR, is chloro-2, the 2-difluoroethylenes of the bromo-1-of product 1-.
Get the reaction solution 2501 grams after distilling out crude product R111211, pour mechanical stirring in 3 liters of there-necked flasks into and cool to interior temperature 0 DEG C ~ 5 DEG C, be incubated and carry out recrystallization in 12 hours, filter and obtain filter cake triethylamine hydrogen bromide salt 901 grams, filtrate 1520 grams; Filtrate is heated to 80 DEG C ~ 90 DEG C, 990 grams of solvents are obtained with water pump underpressure distillation desolventizing, in 2 liters of there-necked flasks, mechanical stirring cools to interior temperature 0 DEG C ~ 5 DEG C again, be incubated and carry out recrystallization in 12 hours, obtain triethylamine hydrogen bromide salt 358 grams in filtration, filtrate 155 grams, merge wet triethylamine hydrogen bromide salt, at 80 DEG C ~ 90 DEG C, vacuum-drying obtains triethylamine hydrogen bromide salt solid 1133 grams for 3 hours, yield 89 ﹪ of triethylamine hydrogen bromide salt.
Crystallization concentrates the secondary filtrate obtained and adds 12 grams of gacs, be heated to 100 DEG C ~ 120 DEG C reactions 3 hours, cool to interior temperature 0 DEG C ~ 5 DEG C, be incubated 3 hours, cross and filter gac, three filtrates obtained, again with adding 12 grams of gacs, be heated to 100 DEG C ~ 120 DEG C reactions 3 hours, cool to interior temperature 0 DEG C ~ 5 DEG C, be incubated 3 hours, cross and filter gac, four filtrates 113 grams obtained, for light yellow clear liquid, main containing phase-transfer catalyst Tetrabutyl amonium bromide, add the catalyzer Tetrabutyl amonium bromide of loss, again can prepare the bromo-1-of 1-chloro-2 for dehydrobromination, 2-difluoroethylene.
Remaining with embodiment 1.
Embodiment 7:
Through reclaiming the filtrate 113 grams containing phase-transfer catalyst Tetrabutyl amonium bromide in Example 6, add 0.5 gram of Tetrabutyl amonium bromide in this filtrate, other experimental implementation with feed intake completely identical with embodiment 6, react and terminate rear simple distillation and obtain R111211 crude product 1115 grams.
The bromo-1-of 1-chloro-2, the rectification and purification of 2-difluoroethylene crude product adopts atmospheric distillation, wherein the condition of atmospheric distillation is: the temperature of rectifying still is 50 DEG C ~ 70 DEG C, the cut between 39 DEG C ~ 41 DEG C is collected by adjustment reflux ratio, obtain the bromo-1-of sterling 1-chloro-2,2-difluoroethylene 969 grams, reaction yield 78 ﹪, gas-chromatography content is 99.5 ﹪.It is consistent with document that the product obtained detects data through GC-MS, NMR, is chloro-2, the 2-difluoroethylenes of the bromo-1-of product 1-.Equally, from result, after supplying the catalyzer of loss, the yield of reaction does not have considerable change, and catalyst recovery way provided by the invention is effective, and solvent also can efficient recovery, decreases environmental pollution.
Remaining with embodiment 1,6.
Embodiment 8:
Preparation R111211:
Install 5 liters of there-necked flasks with reflux condensing tube, mechanical stirring device, constant pressure funnel, temperature of cooling water is controlled in reflux condensing tube at-10 ~ 10 DEG C during reaction, 1 is added in reaction flask, the bromo-2-chlorine-1,1-difluoroethane of 2-bis-(R12212 content 99.3 ﹪) 1811 grams, 470 grams, water, cyclodextrin 8.1 grams, adopt water-bath to control interior temperature and be no more than 40 DEG C, at room temperature stir and add 432 grams, calcium oxide in batches, within about 5 hours, add, then insulation reaction 2 hours.Reaction terminates rear simple distillation and obtains R111211 crude product 1130 grams.
The bromo-1-of 1-chloro-2, the rectification and purification of 2-difluoroethylene crude product adopts atmospheric distillation, wherein the condition of atmospheric distillation is: the temperature of rectifying still is 50 DEG C ~ 70 DEG C, the cut between 39 DEG C ~ 41 DEG C is collected by adjustment reflux ratio, obtain the bromo-1-of sterling 1-chloro-2,2-difluoroethylene 969 grams, reaction yield 78 ﹪, gas-chromatography content is 99.2 ﹪.It is consistent with document that the product obtained detects data through GC-MS, NMR, is chloro-2, the 2-difluoroethylenes of the bromo-1-of product 1-.
Remaining with embodiment 1.
Claims (10)
1. the preparation method of chloro-2, the 2-difluoroethylenes of the bromo-1-of 1-, is characterized in that it comprises the following steps:
(1), in inert solvent, be obtained by reacting the chloro-vinylidene fluoride of 2-with two trifluorotrichloroethanes for raw material and zinc powder carry out reduction dechlorination;
Described inert solvent is alcoholic solvent or amide solvent or ether solvent or anhydrides solvent or containing the one in oxygen-nitrogen compound solvent or sulfocompound solvent or combination; The volume ratio of described inert solvent and two trifluorotrichloroethanes is 1 ~ 10:1; The volume ratio of described inert solvent and two trifluorotrichloroethanes is preferably 2 ~ 5:1;
The mol ratio of described zinc powder and two trifluorotrichloroethanes is 0.8 ~ 3.0:1; The mol ratio of described zinc powder and two trifluorotrichloroethanes is preferably 0.8 ~ 1.5:1;
The chloro-vinylidene fluoride of 2-that (1) obtains of step and bromine in a solvent addition reaction obtain the bromo-2-chlorine-1,1-difluoroethane of 1,2-bis-;
The molar ratio of described bromine and the chloro-vinylidene fluoride of 2-is 1.0:1.0 ~ 1.2;
Solvent described in addition reaction is alkane or halohydrocarbon or its combination, and comprise the one in normal hexane, hexanaphthene, methylene dichloride, tetracol phenixin, dithiocarbonic anhydride, acetic acid or its combination, the consumption of described solvent is 30 ﹪ ~ 100 ﹪ according to the volume computing of bromine;
At water or/and in organic solvent, in the presence of a catalyst, between temperature-10 DEG C ~ 100 DEG C, (2) step is obtained 1, the bromo-2-chlorine-1,1-difluoroethane of 2-bis-and alkali reaction engaging vibrating bromize hydrogen, carry out reflux condensation mode to product and react 5 hours ~ 30 hours at-10 DEG C ~ 10 DEG C, after reaction terminates, distillation or separation organic phase, obtain chloro-2, the 2-difluoroethylene crude products of the bromo-1-of 1-;
The mol ratio of described 1,2-bis-bromo-2-chlorine-1,1-difluoroethane and alkali is 1:1.0 ~ 4.0;
Described organic solvent comprises one in alcoholic solvent, ether solvent, sulfocompound solvent or its combination;
Described alkali be mineral alkali or/and organic bases, during use, with water or/and organic solvent dissolution alkali, be mixed with the alkaline solution that percentage composition is 10 ﹪ ~ 60 ﹪; Described mineral alkali comprises one in the phosphoric acid salt of the carbonate of the oxyhydroxide of I A and II A race element, basic metal or alkali earth metal, basic metal or alkali earth metal, metal oxide or its combination; Described organic bases comprises one in amine organic compound, the alkaline metal salt of alcohol, metal alkylide lithium compound, amido lithium compound or its combination;
The mol ratio of described 1,2-bis-bromo-2-chlorine-1,1-difluoroethane and catalyzer is 100:0.1 ~ 10;
Described catalyzer is phase-transfer catalyst;
(4) chloro-2, the 2-difluoroethylene crude products of the bromo-1-of 1-step (3) obtained carry out rectification and purification;
Described rectifying is atmospheric distillation, and the condition of atmospheric distillation is: rectifying still temperature 50 C ~ 80 DEG C, collects the cut between 39 DEG C ~ 41 DEG C by adjustment reflux ratio;
To step (3) in organic solvent and catalyzer reclaim, be recycled and reused for step (3).
2. the bromo-1-of 1-chloro-2 according to claim 1, the preparation method of 2-difluoroethylene, it is characterized in that step (1) in, described reduction dechlorination reaction is carried out under reaction promoter exists, described reaction promoter is one in V-Brite B or iodine or glycol dibromide or Diisopropyl azodicarboxylate or dibenzoyl peroxide or combination.
3. the preparation method of chloro-2,2-difluoroethylenes of the bromo-1-of 1-according to claim 2, is characterized in that the mol ratio of described reaction promoter and two trifluorotrichloroethanes is 0.005 ~ 0.2:1; The mol ratio of described reaction promoter and two trifluorotrichloroethanes is preferably 0.01 ~ 0.06:1.
4. the preparation method of chloro-2,2-difluoroethylenes of the bromo-1-of 1-according to claim 1, it is characterized in that step (1) in, described zinc powder needs in advance through activation treatment, and it comprises following process:
1) zinc powder is stirred together with dilute hydrochloric acid, filter to use distilled water wash three times after disacidify, then use 95 ﹪ washing with alcohol twice, finally wash once with anhydrous diethyl ether, all filter after each washing to remove washings, such zinc powder, just by finish-drying, then grinds if any block in mortar;
2) by process 1) process after zinc powder stir in 10 ﹪ hydrochloric acid, filter, first wash zinc powder with water, then use washing with acetone, the zinc powder after process is for subsequent use.
5. the preparation method of chloro-2,2-difluoroethylenes of the bromo-1-of 1-according to claim 1, it is characterized in that step (1) in, described alcoholic solvent comprises one in methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, glycerine or its combination; Described amide solvent comprises one in DMF, N,N-dimethylacetamide or its combination; Described ether solvent comprises one in ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diglyme, diethyl carbitol, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or its combination; Described anhydrides solvent comprises diacetyl oxide; Describedly comprise one in acetone, acetonitrile, morpholine, N-methylmorpholine or its combination containing oxygen-nitrogen compound solvent; Described sulfocompound solvent comprises one in dimethyl sulfoxide (DMSO), tetramethylene sulfone or its combination.
6. the preparation method of chloro-2,2-difluoroethylenes of the bromo-1-of 1-according to claim 1, it is characterized in that step (1) in, the temperature of reaction of described reduction dechlorination reaction is 50 DEG C ~ 200 DEG C.
7. the bromo-1-of 1-chloro-2 according to claim 1, the preparation method of 2-difluoroethylene, it is characterized in that step (3) in, described organic solvent comprises one in methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, glycerine, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diglyme, diethyl carbitol, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, diacetyl oxide, dimethyl sulfoxide (DMSO), tetramethylene sulfone or its combination.
8. the bromo-1-of 1-chloro-2 according to claim 1, the preparation method of 2-difluoroethylene, it is characterized in that step (3) in, described mineral alkali comprises lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, ammoniacal liquor, sodium carbonate, salt of wormwood, sodium phosphate, potassiumphosphate, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, ferric oxide, cupric oxide, the one in zinc oxide, aluminum oxide or its combination; Described organic bases comprises one in primary amine, secondary amine, tertiary amine, ethamine, diisopropylamine, triethylamine, pyridine, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide, potassium tert.-butoxide, butyllithium, phenyl lithium, lithium diisopropyl amido, hexamethyldisilazane lithium or its combination.
9. the preparation method of chloro-2,2-difluoroethylenes of the bromo-1-of 1-according to claim 1, it is characterized in that step (3) in, described catalyzer is selected from the one in lower group:
1) polyethers: comprise chain polyoxyethylene glycol (H (OCH
2cH
2)
noH), chain dialkylethers (R (OCH
2cH
2)
noR);
2) cyclic crown ether class: comprise 18 hats 6,15 hats 5, cyclodextrin;
3) quaternary ammonium salt phase transfer catalyst: comprise benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride;
4) tertiary amine: R
1r
2r
3n, pyridine, triethylamine, Tributylamine, wherein R
1, R
2, R
3represent C respectively
1-20alkyl;
5) quaternary ammonium hydroxide: R
1r
2r
3r
4n
+oH
-, wherein R
1, R
2, R
3, R
4represent C respectively
1-20alkyl;
6) season phosphonium salt: R
1r
2r
3r
4p
+x
-, wherein R
1, R
2, R
3, R
4represent C respectively
1-20alkyl or C
6-30aryl.
10. the bromo-1-of 1-chloro-2 according to claim 1, the preparation method of 2-difluoroethylene, it is characterized in that step (5) in, (3) after being separated crude product to step, remaining solution carries out decrease temperature crystalline, separate out organic salt or the inorganic bromide salt of hydrogen bromide, cross the organic salt or inorganic bromide salt that filter hydrogen bromide, then, Distillation recovery organic solvent is carried out to filtrate; To the remaining solution of distillation decrease temperature crystalline again, divide the organic salt or the inorganic bromide salt that isolate hydrogen bromide, surplus solution is crystalline mother solution, adopts activated carbon decolorizing 2-3 time to the crystalline mother solution obtained, obtain colourless or lurid clear solution, complete catalyst recovery.
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