CN103193586B - Synthetic method of 1,1,1,4,4,4-hexafluoro-2-butene - Google Patents
Synthetic method of 1,1,1,4,4,4-hexafluoro-2-butene Download PDFInfo
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- CN103193586B CN103193586B CN201310082246.3A CN201310082246A CN103193586B CN 103193586 B CN103193586 B CN 103193586B CN 201310082246 A CN201310082246 A CN 201310082246A CN 103193586 B CN103193586 B CN 103193586B
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Abstract
The invention discloses a synthetic method of 1,1,1,4,4,4-hexafluoro-2-butene, and the synthetic method comprises the steps of carrying out a reaction between hexachlorobutadiene and hydrogen fluoride in the presence of a catalyst to generate 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane, and carrying out a reductive dechlorination reaction on the 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane in a solvent by using zinc powder to generate the 1,1,1,4,4,4-hexafluoro-2-butene. According to the synthetic method, the process is simple, the steps are short, the reaction conditions are mild and the product can be obtained through two steps of reaction; and the raw materials are easy to get, the cost is low, and the byproduct hexachlorobutadiene obtained by reducing tetrachloroethylene by carbon tetrachloride at high temperature can be used as a raw material, so that the cost is further reduced.
Description
Technical field
The present invention relates to the synthetic method of fluoroolefins, be specifically related to a kind of 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene (CF
3cH=CHCF
3) synthetic method.
Background technology
1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene, can be divided into cis and trans two kinds of isomerss, be the gas of colorless and odorless under normal circumstances.Hexafluoro-2-butylene is considered to one of ideal substitute of blowing agent H CFC-141b, can use as novel whipping agent, refrigeration agent and fire-fighting medium.This whipping agent product environmental protection, heat-insulation and heat-preservation characteristic be remarkable, nonflammable, do not consume ozone, low conversion cost can replace other liquid blowing agents, be with a wide range of applications.
1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene mainly contains following several synthetic method.
Honeywell company (patent publication No.: US2011288349A1) adopts R 1216 and trichloromethane to be Material synthesis 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.R 1216 and trichloromethane carry out addition reaction and generate 1,1,1-tri-chloro-2,2,3,4,4,4-hexafluoro butane, 1,1,1-tri-chloro-2,2,3,4,4,4-hexafluoro butane obtains 1 through fluoridizing again, and 1,1,2,2,3,4,4,4-nine fluorine butane, 1,1,1,2,2,3,4,4,4-nine fluorine butane again dehydrofluorination, reductive dehalogenation two step is obtained by reacting 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.
WO2011119388A2 adopts tetracol phenixin and ethene to be Material synthesis 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.Tetracol phenixin and ethene carry out addition reaction and generate 1,1, Isosorbide-5-Nitrae-four chloropropane, 1,1, Isosorbide-5-Nitrae-four chloropropane generates 1,1,1 with tetracol phenixin addition after dehydrochlorination again, 2,4,4,4-heptachlor butane, 1,1,1,2,4,4,4-heptachlor butane through fluoridizing, dehydrochlorination obtains 1,1,1,4,4,4-hexafluoro-2-butylene, yield is 69%.
It is Material synthesis 1,1 that JP2010001244 adopts with the bromo-2-monochloroethane of the fluoro-2-of 1,1,1-tri-, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.The coupling of the fluoro-2-of 1,1,1-tri-bromo-2-monochloroethane zinc powder obtains 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-chlorobutane, 1,1, Isosorbide-5-Nitrae, and 4,4-hexafluoro-2,3-chlorobutane obtains 1,1, Isosorbide-5-Nitrae with zinc powder dechlorination again, 4,4-hexafluoro-2-butylene, and yield is 42 ~ 69%.
All there is certain shortcoming in above-mentioned several route.R 1216 and trichloromethane are raw material method and tetracol phenixin and ethene is that raw material method prepares 1,1, Isosorbide-5-Nitrae, and 4,4-hexafluoro-2-butylene, has the shortcomings such as step length, complex process.The bromo-2-monochloroethane of the fluoro-2-of 1,1,1-tri-is raw material method synthesis 1,1, and Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene has the high and shortcoming be difficult to obtain of cost of material.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, provide that a kind of technique is simple, raw material is easy to get, reaction conditions gentleness 1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of 1,1, Isosorbide-5-Nitrae, and the synthetic method of 4,4-hexafluoro-2-butylene, comprises the following steps:
(1) by after catalyzer, hydrogen fluoride and hexachlorobutadiene 0.02 ~ 0.2:8 in molar ratio ~ 50:1 mixing, first react 0.5 ~ 2 hour at 30 ~ 60 DEG C, be warming up to 60 ~ 150 DEG C again and continue reaction 3 ~ 8 hours, cooling, washing, extraction, layering, alkali cleaning, rectifying obtain 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane;
(2) at 50 ~ 80 DEG C to first time in the mixture of zinc powder and solvent add that step (1) obtains 1, 1, 1, 4, 4, 4-hexafluoro-2, 3-dichlorobutane, after reaction 0.5 ~ 1h, be cooled to 30 ~ 70 DEG C, in reaction mixture, second time adds 1, 1, 1, 4, 4, 4-hexafluoro-2, 3-dichlorobutane, then be warming up to 30 ~ 90 DEG C and continue reaction 2 ~ 6 hours, the mass ratio of described zinc powder and solvent is 1:1.5 ~ 3., zinc powder and add altogether for twice 1, 1, 1, 4, 4, 4-hexafluoro-2, the mol ratio of 3-dichlorobutane is 1 ~ 3:1, reaction terminates rear cooling, filter, namely rectifying obtain 1, 1, 1, 4, 4, 4-hexafluoro-2-butylene.
Further:
Catalyzer described in step (1) is preferably the one in antimony pentachloride, titanium tetrachloride, tin tetrachloride.
The mol ratio of catalyzer, hydrogen fluoride and hexachlorobutadiene described in step (1) is preferably 0.05 ~ 0.1:10 ~ 30:1.
Zinc powder described in step (2) is preferably through zinc powder that dilute hydrochloric acid activated.
Solvent described in step (2) is DMF or dimethyl sulfoxide (DMSO).
Zinc powder described in step (2) and add for the first time 1,1, Isosorbide-5-Nitrae, the mass ratio of 4,4-hexafluoro-2,3-dichlorobutane is 1 ~ 10:1.
Provided by the invention 1,1, Isosorbide-5-Nitrae, 4, the synthetic method of 4-hexafluoro-2-butylene take hexachlorobutadiene as raw material, and hexachlorobutadiene carries out reaction generation 1,1,1 in the presence of a catalyst with hydrogen fluoride, 4,4,4-hexafluoro-2,3-dichlorobutane, 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane carries out reduction dechlorination reaction generation 1,1 with zinc powder more in a solvent, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.The by product hexachlorobutadiene that the present invention can adopt tetracol phenixin high temperature reduction to prepare zellon is main raw material, is obtained by reacting 1,1, Isosorbide-5-Nitrae through two steps, 4,4-hexafluoro-2-butylene, has the advantage that step is short, reaction conditions is gentle, cost is low.
Hexachlorobutadiene and hydrofluoric reaction adopt liquid phase reaction, and catalyzer can select conventional liquid-phase fluorination catalyst, the one in preferred antimony pentachloride, titanium tetrachloride, tin tetrachloride.The consumption of catalyzer is large, and fluoridation speed is fast, but superpolymer increases, and yield is low, and catalyst levels is few, and speed of response is slow, and therefore in the present invention, catalyzer and the suitable mol ratio of hexachlorobutadiene are 0.02 ~ 0.20:1, preferably 0.05 ~ 0.1:1.
The mol ratio of hydrogen fluoride and hexachlorobutadiene has impact to the yield reacted.The mol ratio of hydrogen fluoride and hexachlorobutadiene is large, and fluoridation is complete, and by product is few, but hydrogen fluoride consumption is excessive, and production cost is high, and aftertreatment pressure is large; The mol ratio of hydrogen fluoride and hexachlorobutadiene is little, and fluoridation is incomplete, has the partially fluorinated by product of more amount to generate.Therefore, in the present invention, the mol ratio of hydrogen fluoride and hexachlorobutadiene is 8 ~ 50:1, is preferably 10 ~ 30:1.
Temperature of reaction has impact to hexachlorobutadiene and hydrofluoric reaction.Hexachlorobutadiene and hydrofluoric temperature of reaction high, speed of response is fast, and superpolymer is many, and temperature of reaction is low, and speed of response is slow, and the by product not exclusively fluoridized increases.Therefore the temperature in the present invention when hexachlorobutadiene and hydrogen fluoride reaction is 30 ~ 150 DEG C, preferably 60 ~ 100 DEG C.
In a solvent with zinc powder to 1,1, Isosorbide-5-Nitrae, when 4,4-hexafluoro-2,3-dichlorobutane carries out reduction dechlorination reaction, preferably with the zinc powder activated through dilute hydrochloric acid, zinc powder after dilute hydrochloric acid activation can remove the zone of oxidation on zinc powder surface effectively, reduces kick off temperature, improves speed of reaction.Its preparation method is that zinc powder to be immersed in mass percent concentration be 3 ~ 8h in the dilute hydrochloric acid of 1 ~ 5%, then filters, first washes with water, then use washing with alcohol, finally preserves with sealing after washed with diethylether.
Zinc powder and 1,1, Isosorbide-5-Nitrae, the yield of mol ratio on reaction of 4,4-hexafluoro-2,3-dichlorobutane has impact.Zinc powder and 1,1, Isosorbide-5-Nitrae, the mol ratio of 4,4-hexafluoro-2,3-dichlorobutane is low, and 1,1, Isosorbide-5-Nitrae, not exclusively, yield is low, and the too high then production cost of mol ratio is high for the reaction of 4,4-hexafluoro-2,3-dichlorobutane.Therefore zinc powder and 1,1 in the present invention, Isosorbide-5-Nitrae, the mol ratio of 4,4-hexafluoro-2,3-dichlorobutane is 1.0 ~ 3:1.
Temperature of reaction and time, Isosorbide-5-Nitrae, the reaction of 4,4-hexafluoro-2,3-dichlorobutane also had impact to zinc powder and 1,1.Zinc powder and 1,1, Isosorbide-5-Nitrae, the temperature of reaction of 4,4-hexafluoro-2,3-dichlorobutane is low, and reaction is difficult to cause, long reaction time; Temperature of reaction is high, and reaction is easy to cause, but easily generates more by product, and reaction yield is low, in addition, 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane substep adds the yield being conducive to improving reaction, therefore first adds part 1 in the present invention, 1,1,4,4,4-hexafluoro-2,3-dichlorobutane is cooled to 30 ~ 70 DEG C react 0.5 ~ 1h at 50 ~ 80 DEG C after, in reaction mixture, second time adds 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane, then be warming up to 30 ~ 90 DEG C of reactions 2 ~ 6 hours.The good solvent of zinc powder reduction dechlorination reaction is aprotic polar solvent, is preferably DMF or dimethyl sulfoxide (DMSO).
Compared with prior art, the present invention has the following advantages:
1, technique is simple, and step is short, and reaction conditions is gentle, can obtain product through two-step reaction;
2, raw material is easy to get, and cost is low, and the by product hexachlorobutadiene that tetracol phenixin high temperature reduction can be adopted to prepare zellon is raw material, reduce further cost.
Embodiment
Be specifically described the present invention below by embodiment, following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the scope of the invention.
Embodiment 1
In 1.0L autoclave, add 30g(0.10mol respectively) antimony pentachloride, 400g(20mol) hydrogen fluoride, stir, then add 260.8g(1.0mol with volume pump with the speed of 2.0g/min) chlordene dibutene.After chlordene dibutene adds, at 40 DEG C, react 1h, then be warming up to 80 DEG C of reaction 6h, cooling, joins reaction solution in 1200g frozen water, then adds 300g dichloromethane extraction, layering, organic layer rectifying after the washing of 200g saturated solution of sodium bicarbonate, obtains 202.1g(0.86mol) content is 99.2% 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane, yield 86%.
Be with at 500ml in the four-hole boiling flask of prolong, add 65g(1.0mol) through the zinc powder of dilute hydrochloric acid activation, 180g DMF, passes into the air in nitrogen replacement flask, in prolong, passes into service water, and the tail gas cold-trap of-30 DEG C is collected.Stir, be warming up to 50 DEG C, drip 60g prepare through aforesaid method 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane, after reaction 1h, temperature of reaction is reduced to 40 DEG C, in 2.0h, again drips prepare through aforesaid method 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane, adds 164.5g(0.7mol twice altogether) 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane.1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, after 3-dichlorobutane adds, continue reaction 5h, cooling, filter at 50 DEG C, filtrate mixes rear rectifying and obtains 93.5g(0.57mol with the collection liquid in cold-trap) content is 98.6% 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene cis-trans-isomer mixture, yield 81.4%.
Embodiment 2
In 1.0L autoclave, add 2.6g(0.01mol respectively) tin tetrachloride, 500g(25mol) hydrogen fluoride, stir, then add 130.4g(0.5mol with volume pump with the speed of 1.0g/min) chlordene dibutene.After chlordene dibutene adds, at 50 DEG C, react 0.5h, then be warming up to 150 DEG C of reaction 3h, cooling, joins reaction solution in 2000g frozen water, then adds 400g dichloromethane extraction, layering, organic layer rectifying after the washing of 200g saturated solution of sodium bicarbonate, obtains 62.5g(0.27mol) content is 99.0% 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane, yield 53.2%.
Be with at 250ml in the four-hole boiling flask of prolong, add 48.8g(0.75mol) zinc powder, 100g dimethyl sulfoxide (DMSO), passes into the air in nitrogen replacement flask, in prolong, passes into service water, and the tail gas cold-trap of-30 DEG C is collected.Stir, be warming up to 80 DEG C, drip 10g prepare through aforesaid method 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane, after reaction 0.5h, temperature of reaction is reduced to 70 DEG C, in 1.0h, again drips prepare through aforesaid method 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane, adds 58.8g(0.25mol twice altogether) 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane.1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, after 3-dichlorobutane adds, continue reaction 2h, cooling, filter at 90 DEG C, filtrate mixes rear rectifying and obtains 31.4g(0.19mol with the collection liquid in cold-trap) content is 99.3% 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene cis-trans-isomer mixture, yield 76.5%.
Embodiment 3
In 1.0L autoclave, add 38g(0.20mol respectively) titanium tetrachloride, 160g(8mol) hydrogen fluoride, stir, then add 260.8g(1.0mol with volume pump with the speed of 1.0g/min) chlordene dibutene.After chlordene dibutene adds, at 30 DEG C, react 2h, then be warming up to 60 DEG C of reaction 8h, cooling, joins reaction solution in 1000g frozen water, then adds 200g dichloromethane extraction, layering, organic layer rectifying after the washing of 100g saturated solution of sodium bicarbonate, obtains 155.1g(0.66mol) content is 99.3% 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane, yield 66%.
Be with at 500ml in the four-hole boiling flask of prolong, add 41g(0.63mol) through the zinc powder of dilute hydrochloric acid activation, 80g DMF, passes into the air in nitrogen replacement flask, in prolong, passes into service water, and the tail gas cold-trap of-30 DEG C is collected.Stir, be warming up to 50 DEG C, drip 60g prepare through aforesaid method 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane, after reaction 0.8h, temperature of reaction is reduced to 30 DEG C, in 2.0h, again drips prepare through aforesaid method 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane, adds 141g(0.6mol twice altogether) 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane.1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, after 3-dichlorobutane adds, continue reaction 6h, cooling, filter at 30 DEG C, filtrate mixes rear rectifying and obtains 83.6g(0.51mol with the collection liquid in cold-trap) content is 99.6% 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene cis-trans-isomer mixture, yield 85.0%.
Embodiment 4
In 1.0L autoclave, add 15g(0.05mol respectively) antimony pentachloride, 600g(30mol) hydrogen fluoride, stir, then add 260.8g(1.0mol with volume pump with the speed of 5.0g/min) chlordene dibutene.After chlordene dibutene adds, at 60 DEG C, react 1h, then be warming up to 100 DEG C of reaction 5h, cooling, joins reaction solution in 1800g frozen water, then adds 500g dichloromethane extraction, layering, organic layer rectifying after the washing of 200g saturated solution of sodium bicarbonate, obtains 206.8g(0.88mol) content is 99.5% 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane, yield 88.0%.
Be with at 500ml in the four-hole boiling flask of prolong, add 65g(1.0mol) zinc powder, 100g dimethyl sulfoxide (DMSO), passes into the air in nitrogen replacement flask, in prolong, passes into service water, and the tail gas cold-trap of-30 DEG C is collected.Stir, be warming up to 60 DEG C, drip 30g prepare through aforesaid method 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane, after reaction 0.6h, temperature of reaction is reduced to 50 DEG C, in 2.0h, again drips prepare through aforesaid method 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane, adds 117.5g(0.50mol twice altogether) 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane.1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, after 3-dichlorobutane adds, continue reaction 4h, cooling, filter at 60 DEG C, filtrate mixes rear rectifying and obtains 64.1g(0.391mol with the collection liquid in cold-trap) content is 99.0% 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene cis-trans-isomer mixture, yield 78.2%.
Embodiment 5
In 1.0L autoclave, add 45g(0.15mol respectively) antimony pentachloride, 200g(10mol) hydrogen fluoride, stir, add 260.8g(1.0mol with volume pump with the speed of 2.0g/min) chlordene dibutene.After chlordene dibutene adds, at 50 DEG C, react 2h, then be warming up to 120 DEG C of reaction 4h, cooling, joins reaction solution in 800g frozen water, then adds 200g dichloromethane extraction, layering, organic layer rectifying after the washing of 200g saturated solution of sodium bicarbonate, obtains 197.4g(0.84mol) content is 99.4% 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane, yield 84%.
Be with at 500ml in the four-hole boiling flask of prolong, add 65g(1.0mol) through the zinc powder of dilute hydrochloric acid activation, 160g dimethyl sulfoxide (DMSO), passes into the air in nitrogen replacement flask, in prolong, passes into service water, and the tail gas cold-trap of-30 DEG C is collected.Stir, be warming up to 70 DEG C, drip 40g prepare through aforesaid method 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane, after reaction 0.7h, temperature of reaction is reduced to 60 DEG C, in 2.0h, again drips prepare through aforesaid method 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2,3-dichlorobutane, adds 117.5g(0.50mol twice altogether) 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane.1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, after 3-dichlorobutane adds, continue reaction 3h, cooling, filter at 70 DEG C, filtrate mixes rear rectifying and obtains 68.2g(0.416mol with the collection liquid in cold-trap) content is 98.9% 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene cis-trans-isomer mixture, yield 83.2%.
Be: zinc powder being immersed in mass percent concentration is 3 ~ 8h in the dilute hydrochloric acid of 1 ~ 5%, then filters, first washes with water, then use washing with alcohol finally preserve with sealing after washed with diethylether through the zinc powder preparation method of dilute hydrochloric acid activation in above-described embodiment 1,3,5.
Claims (3)
1. one kind 1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene, is characterized in that comprising the following steps:
(1) by after catalyzer, hydrogen fluoride and hexachlorobutadiene 0.02 ~ 0.2:8 in molar ratio ~ 50:1 mixing, first react 0.5 ~ 2 hour at 30 ~ 60 DEG C, be warming up to 60 ~ 150 DEG C again and continue reaction 3 ~ 8 hours, cooling, washing, extraction, layering, alkali cleaning, rectifying obtain 1,1,1,4,4,4-hexafluoro-2,3-dichlorobutane; Described catalyzer is antimony pentachloride or titanium tetrachloride,
(2) at 50 ~ 80 DEG C to first time in the mixture of zinc powder and solvent add that step (1) obtains 1, 1, 1, 4, 4, 4-hexafluoro-2, 3-dichlorobutane, described zinc powder activated through dilute hydrochloric acid, described solvent is N, dinethylformamide or dimethyl sulfoxide (DMSO), after reaction 0.5 ~ 1h, be cooled to 30 ~ 70 DEG C, in reaction mixture, second time adds 1, 1, 1, 4, 4, 4-hexafluoro-2, 3-dichlorobutane, then be warming up to 30 ~ 90 DEG C and continue reaction 2 ~ 6 hours, the mass ratio of described zinc powder and solvent is 1:1.5 ~ 3., zinc powder and add altogether for twice 1, 1, 1, 4, 4, 4-hexafluoro-2, the mol ratio of 3-dichlorobutane is 1 ~ 3:1, reaction terminates rear cooling, filter, namely rectifying obtain 1, 1, 1, 4, 4, 4-hexafluoro-2-butylene.
2. according to claim 11,1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene, is characterized in that the mol ratio of catalyzer, hydrogen fluoride and the hexachlorobutadiene described in step (1) is 0.05 ~ 0.1:10 ~ 30:1.
3. according to claim 11,1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene, it is characterized in that zinc powder described in step (2) and first time add 1,1, Isosorbide-5-Nitrae, the mass ratio of 4,4-hexafluoro-2,3-dichlorobutane is 1 ~ 10:1.
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