Background technology
Trans-4-(trans-4 '-positive alkyl-cyclohexyl) cyclohexyl-3,4, the 5-trifluoro-benzene is the cyclohexane polyfluorobenzene liquid crystal compound.Fluoro liquid crystals is owing to have characteristics such as low-viscosity, moderate dielectric anisotropy, high resistivity, high electric charge conservation rate, and its purposes is increasingly extensive, also is liquid-crystal displays such as STN, TFT with one of staple of mixed liquid crystal.3, the 4-difluoro replaces and 3,4, and the substituted cyclohexane polyfluorobenzene liquid crystal of 5-trifluoro synthetic is one of present important subject.The various liquid crystal material monomers that in liquid-crystal display, use all require very high purity (a lot of liquid crystal monomer purity requirements >=99.9%), and the existence of impurity has bigger negative impact to the liquid-crystal display quality.
Cyclohexane polyfluorobenzene liquid crystal all contains the catalytic hydrogenation reaction step of cyclohexenyl polyfluoro benzene in synthetic.Cyclohexenyl polyfluoro benzene generates the hexanaphthene polyfluoro benzene of cis and trans two kinds of isomer through catalytic hydrogenation reaction; And trans hexanaphthene polyfluoro benzene is only required liquid crystal molecule; Therefore need separate purification to reaction product, above-mentioned these two kinds of isomer obtain required pure trans hexanaphthene polyfluoro benzene liquid crystal material after separating purification.The obvious problem that present this technology exists is that cyclohexenyl polyfluoro benzene exists hydrogenolysis defluorinate problem when catalytic hydrogenation; Some liquid crystal monomer precursor, as: cyclohexenyl-3,4; 5-trifluoro-benzene quasi-molecule is when catalytic hydrogenation reaction; Owing to there are a plurality of fluorine to replace and alkyl substituent group on the phenyl ring, influenced by ortho para orientating group activating effect, the hydrogenation defluorinate is also relatively more serious.Because by product that the hydrogenolysis defluorinate generates and principal product are in the structure of matter and qualitative proximity, defluorinate impurity is difficult to remove from principal product through separation method, has influenced the purity of liquid crystal monomer, thereby causes the decline of synthetic liquid crystal material quality.
The side reaction of hydrogenolysis-dehalogenation is a comparatively general problem in the catalytic hydrogenation, and some patent has proposed some solutions to dehalogenation problem in the shortening.The method of the generation of the hydrogenolysis-dehalogenation side reaction when reducing catalytic hydrogenation has two kinds of approach at present usually: the one, in catalystsystem, add the dehalogenation suppressor factor, and the 2nd, improve catalyst performance, reach the effect that suppresses dehalogenation.For example, in order to suppress hydrogenolysis-dehalogenation on the phenyl ring, U.S. Pat 4070401 discloses and in reaction system, has added polyamine in the halogenated nitrobenzene catalytic hydrogenation process, and reaction is 150 minutes under 60 ℃, hydrogen pressure 5.0MP, makes the dehalogenation rate drop to 0.4%.Though this reaction system has reached the purpose that suppresses the hydrogenation dehalogenation, add the dehalogenation suppressor factor and not only increased production cost, and because separation problem has reduced the quality of product.Another U.S. Pat 5554573 is (in the alloy of Ni/Al=1, to add Mo with improved Raney Ni hydrogenation catalyst; Preparation and obtain Raney Ni/Mo hydrogenation catalyst); 3-chloro-4-fluoronitrobenzene is carried out catalytic hydrogenation reaction; In its hydrogenation reaction of under 60 ℃, 1.8MP hydrogen pressure condition, carrying out, the dehalogenation rate is between 0.4%~3.5%.But catalyst activity is littler than Raney Ni, and hydrogenation activity descends comparatively fast in reaction process, so the catalyzer usage quantity is bigger, increase production cost, and dehalogenation is still comparatively serious comparatively speaking.In Chinese patent 02148509.7 (denomination of invention is the method for halogenated nitrobenzene shortening synthesizing halogen aromatic amines); In order to overcome the shortcoming and raising reaction yield that the halogenated nitrobenzene shortening is easy to generate hydrodehalogenation; This method is raw material with the halogenated nitrobenzene; With nano-carbon tube load Pd or nano-carbon tube load Pt is hydrogenation catalyst; To halogenated nitrobenzene such as o-chloronitrobenzene, parachloronitrobenzene, 3,4-dichloronitrobenzene, 3-chloro-4-fluoronitrobenzene etc. carries out liquid phase catalytic hydrogenation reaction, catalysis synthesizing halogen aromatic amines.This method can suppress the hydrodehalogenation reaction effectively, and has the advantages that catalyst activity is higher, selectivity is good, and the hydrodehalogenation rate is dropped to less than 0.1% from 10%.But used the precious metal of nano-carbon tube load to make catalyzer in this method, price is high a lot, and production cost is increased considerably.
The catalyst system of the dehalogenation side reaction in the time of can effectively suppressing the halogenated aryl hydrocarbon catalytic hydrogenation reports seldom at present how cyclohexenyl polyfluoro benzene suppresses effectively or the document of solution hydrogenolysis defluorinate side reaction does not also appear in the newspapers and relate to when shortening.Current, cyclohexenyl polyfluoro benzene catalytic hydrogenation reaction generally uses active lower neutral Raney Ni or Pd/C makes catalyzer and in neutral solvent, carry out hydrogenation reaction, generates the hexanaphthene polyfluoro benzol mixture of cis, trans two kinds of isomer.Though the use of these catalyzer ratio aspect the defluorinate amount can reduce when using active higher rhodium charcoal, platinum charcoal, alkaline Raney Ni etc. to make catalyzer; But the defluorinate amount still maintains higher level; Still can reach 0.1%~1%, the defluorinate by product causes the quality of Purification and liquid crystal monomer as impurity and seriously influences.Use Pd/C or neutral Raney Ni to make catalyzer when relating to cyclohexenyl polyfluoro benzene hydrogenation; The minimum defluorinate amount that adopts hydrogenation reaction in the neutral solvent is all more than 0.1%; Even up to about 1%; Cause the principal product separation difficulty, the purity of principal product descends, and becomes a big problem that improves liquid crystal monomer purity and performance.
Summary of the invention
The technical issues that need to address of the present invention provide a kind of catalystic converter system that in cyclohexenyl polyfluoro benzene shortening prepares the reaction of hexanaphthene polyfluoro benzene liquid crystal material, can suppress hydrogenolysis defluorinate side reaction effectively, thereby the highly selective of foundation, make the synthesis process of the more easily separated purification of hexanaphthene polyfluoro benzene liquid crystal monomer.
For solving the problems of the technologies described above, the technical scheme that the present invention taked is:
A kind of catalytic hydrogenation method of cyclohexane polyfluorobenzene liquid crystal monomer; Utilize cyclohexenyl polyfluorobenzene compound for catalysis hydrogenation to generate the hexanaphthene polyfluoro benzol mixture of cis and trans two kinds of isomer; Be as reaction substrate, in organic solvent, under normal temperature, the normal pressure with cyclohexenyl polyfluorobenzene compound; With 5%Pd/C is catalyzer, and is the heterogeneous catalytic reaction system of additive with acidic substance.The quality of the catalyzer that in solvent, adds during reaction is 0.01: 1~0.05: 1 with the ratio of the quality of cyclohexenyl polyfluorobenzene compound.
Cyclohexenyl polyfluorobenzene compound of the present invention comprises the material of following structural formula,
Substituent R is methyl-CH in the structural formula
3, ethyl-C
2H
5, propyl group-C
3H
7, butyl-C
4H
9, amyl group-C
5H
11, hexyl-C
6H
13A kind of or its any isomer wherein; Substituting group polyfluoro benzene is selected from 3 in the structural formula, 4-two fluorobenzene or 3,4,5-trifluoro-benzene.
Acidic substance used in the present invention comprise organic acid and mineral acid.Wherein mineral acid is selected from 37% concentrated hydrochloric acid, the vitriol oil; Organic acid is selected from formic acid, acetate, propionic acid, butyric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, boric acid, tosic acid.
Organic solvent of the present invention is one or more the mixing solutions wherein of sherwood oil, ETHYLE ACETATE, toluene, absolute ethyl alcohol, diacetyl oxide, glacial acetic acid, YLENE, methylene dichloride, hexanaphthene, Virahol; The cyclohexenyl polyfluorobenzene compound of every gram need be used 2~8 milliliters dissolution with solvents.It is better that the ratio of using 3: 1~6: 1 is carried out solute effect.
A kind of method of use of organic solvent according to the invention and acidic substance is: when organic solvent is in toluene, sherwood oil, YLENE, the hexanaphthene one or more; Acidic substance are selected a kind of in formic acid, acetate, propionic acid, butyric acid, trifluoroacetic acid, the trifluoromethanesulfonic acid for use; And the milliliter number consumption (volumetric usage of acid; Unit is a milliliter) count consumption (total mass number, unit is gram) more than or equal to the gram of cyclohexenyl polyfluorobenzene compound.
Another method of use of organic solvent according to the invention and acidic substance is: when organic solvent is that one or more and toluene, sherwood oil, YLENE, in the hexanaphthene one or more in absolute ethyl alcohol, diacetyl oxide, ETHYLE ACETATE, the Virahol are when forming mixed solvents; Acidic substance are selected the mixture of a kind of of 37% the concentrated hydrochloric acid or the vitriol oil or two kinds for use; And the milliliter number consumption (volumetric usage of acid; Unit is a milliliter) restrain number consumption (total mass number with cyclohexenyl polyfluorobenzene compound; Unit for the gram) ratio be: 0.1: 1~0.5: 1; The cyclohexenyl polyfluorobenzene compound of promptly every relative 1 gram mass will add 0.1~0.5 milliliter of 37% the concentrated hydrochloric acid or the vitriol oil in organic solvent.
The third method of use of organic solvent according to the invention and acidic substance is: said organic solvent is that one or more and toluene, sherwood oil, YLENE, in the hexanaphthene one or more in absolute ethyl alcohol, diacetyl oxide, ETHYLE ACETATE, the Virahol are when forming mixed solvents; Acidic substance are selected one or more in formic acid, acetate, propionic acid, butyric acid, trifluoroacetic acid, the trifluoromethanesulfonic acid for use; The milliliter number consumption (volumetric usage of acid; Unit is a milliliter) relatively the gram of substrate cyclohexenyl polyfluorobenzene compound count consumption (total mass number; Unit is gram) ratio be 0.02: 1~2: 1, promptly per 1 gram substrate will add 0.02~2 milliliter acidic substance.Use (0.1~1): better effects if during 1 ratio.
The 4th kind of method of use of organic solvent according to the invention and acidic substance is: said organic solvent is that one or more and toluene, sherwood oil, YLENE, in the hexanaphthene one or more in absolute ethyl alcohol, diacetyl oxide, ETHYLE ACETATE, the Virahol are when forming mixed solvents; Acidic substance are selected boric acid and/or tosic acid for use; The gram of acid is counted consumption (total mass number; Unit is gram) relatively the gram of substrate cyclohexenyl polyfluorobenzene compound to count the ratio of consumption be 0.02: 1~2: 1, promptly per 1 gram substrate will add the acidic substance of 0.02~2 gram.Use (0.1~1): better effects if during 1 ratio.
Owing to adopted technique scheme, the technical progress that the present invention obtained is:
Method of the present invention can suppress hydrogenolysis defluorinate side reaction effectively when cyclohexenyl polyfluoro benzene shortening, thereby suppresses the generation of hydrogenolysis defluorinate product, and defluorinate product content is reduced between 0~0.02% from 0.1%~1.0% of original system.Since in the catalytic hydrogenation process defluorinate total impurities effectively reduce to≤0.02%, the separation of liquid crystal monomer is purified becomes easily, purity is easy to reach>=99.9% high purity.Utilize present method catalytic hydrogenation cyclohexenyl polyfluoro benzene synthesizing cyclohexane 1 alkane polyfluorobenzene compound technology simple, solved the high difficult problem of defluorinate product growing amount in the existing catalystsystem; Simultaneously be not less than former catalystsystem, production cost is reduced significantly based on trans product (the being effective liquid crystal molecule) content that this catalystsystem generated.
Embodiment
Below in conjunction with embodiment the present invention is explained further details.
Embodiment 1
In 500 milliliters of single port bottles, add 20 milliliters of toluene, 40 milliliters of diacetyl oxides, 5 milliliters of glacial acetic acids, 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3,4,5-trifluoro-benzene 10 grams, 5%Pd/C 0.5 gram (dry weight.Other embodiment is identical therewith), install the hydrogenation reaction device, after the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 2 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result is: transformation efficiency 100%, defluorinate product content 0.02%, trans product 59%, cis-product 40%.
Embodiment 2
In 500 milliliters of single port bottles, add 20 milliliters in ETHYLE ACETATE, 20 milliliters of glacial acetic acids, 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3; 4; 5-trifluoro-benzene 10 grams, 5%Pd/C 0.5 gram installs the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 1.5 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result is: transformation efficiency 100%, defluorinate product content 0.01%, trans product 55%, cis-product 44%.
Embodiment 3
In 500 milliliters of single port bottles, add 3 milliliters of concentrated hydrochloric acids, 2 milliliters of the vitriol oils, 30 milliliters in ETHYLE ACETATE; 20 milliliters of absolute ethyl alcohols, 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3,4; 5-trifluoro-benzene 10 grams, 5%Pd/C 0.15 gram installs the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 1.5 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result is: transformation efficiency 99.8%, defluorinate product content 0.006%, trans product 54%, cis-product 45%.
Embodiment 4
In 500 milliliters of single port bottles, add 50 milliliters of absolute ethyl alcohols, 5 milliliters of the vitriol oils, 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3; 4; 5-trifluoro-benzene 10 grams, 5%Pd/C 0.4 gram installs the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 1.5 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 99.9%, defluorinate product content 0.01%, trans product 54%, cis-product 45%.
Embodiment 5
In 500 milliliters of single port bottles, add 40 milliliters of diacetyl oxides, boric acid 10 grams, 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3; 4; 5-trifluoro-benzene 10 grams, 5%Pd/C 0.3 gram installs the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 1.5 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 99.98%, defluorinate product content 0.01%, trans product 63%, cis-product 36%.
Embodiment 6
In 500 milliliters of single port bottles, add 25 milliliters of absolute ethyl alcohols, 20 milliliters of toluene, trifluoromethanesulfonic acid 1.0 grams; 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3,4,5-trifluoro-benzene 10 grams; 5%Pd/C 0.2 gram; Install the hydrogenation reaction device, after the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 4 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 99.99%, defluorinate product content 0.006%, trans product 59%, cis-product 40%.
Embodiment 7
In 500 milliliters of single port bottles, add 20 milliliters of hexanaphthenes, 20 milliliters of absolute ethyl alcohols, 2 milliliters of concentrated hydrochloric acids; 4-(trans-the 4-ethyl) cyclohexyl-1-cyclohexenyl-3,4,5-trifluoro-benzene 10 grams; The 5%Pd/C0.4 gram; Install the hydrogenation reaction device, after the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 2.5 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 100%, defluorinate product content 0.01%, trans product 54%, cis-product 45%.
Embodiment 8
In 500 milliliters of single port bottles, add 40 milliliters of absolute ethyl alcohols, 10 milliliters of toluene, boric acid 1.0 grams; 4-(trans-the 4-ethyl) cyclohexyl-1-cyclohexenyl-3,4,5-trifluoro-benzene 10 grams; 5%Pd/C 0.1 gram; Install the hydrogenation reaction device, after the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 4 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 99.98%, defluorinate product content 0.005%, trans product 59%, cis-product 40%.
Embodiment 9
In 500 milliliters of single port bottles, add 40 milliliters of diacetyl oxides, 5 milliliters of trifluoroacetic acids, 4-(trans-the 4-ethyl) cyclohexyl-1-cyclohexenyl-3; 4; 5-trifluoro-benzene 10 grams, 5%Pd/C 0.5 gram installs the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 2 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 99.98%, defluorinate product content 0.01%, trans product 63%, cis-product 36%.
Embodiment 10
In 500 milliliters of single port bottles, add 30 milliliters of absolute ethyl alcohols, 20 milliliters of acetate, 4 milliliters of trifluoromethanesulfonic acids; 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3; 4-two fluorobenzene 20 grams, 5%Pd/C 0.25 gram installs the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 1.5 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 100%, defluorinate product content 0.003%, trans product 53%, cis-product 47%.
Embodiment 11
In 500 milliliters of single port bottles, add 40 milliliters of absolute ethyl alcohols, 10 milliliters of sherwood oils, 5 milliliters of trifluoroacetic acids; 4-(trans-the 4-normal-butyl) cyclohexyl-1-cyclohexenyl-3; 4-two fluorobenzene 10 grams, 5%Pd/C 0.5 gram installs the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 1.5 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 100%, defluorinate product content 0.002%, trans product 53%, cis-product 47%.
Embodiment 12
In 500 milliliters of single port bottles, add 40 milliliters of absolute ethyl alcohols, 10 milliliters of diacetyl oxides, boric acid 8 grams; 4-(trans-the 4-normal-butyl) cyclohexyl-1-cyclohexenyl-3; 4-two fluorobenzene 20 grams, 5%Pd/C 1.0 grams install the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 1 hour under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 100%, defluorinate product content 0.005%, trans product 53%, cis-product 47%.
In the process of the test of the present invention, also be some comparative examples, enumerated eight Comparative Examples below, with comparative illustration effect of the present invention.
Comparative Examples 1
In 500 milliliters of single port bottles, add 50 milliliters of absolute ethyl alcohols, 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3,4; 5-trifluoro-benzene 10 grams, 5%Pd/C 0.5 gram installs the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 1.5 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 100%, defluorinate product content 0.15%, trans product 54%, cis-product 44%.
Comparative Examples 2
In 500 milliliters of single port bottles, add 40 milliliters of sherwood oils (90-105 ℃); 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3,4,5-trifluoro-benzene 10 grams; 5%Pd/C 0.5 gram; Install the hydrogenation reaction device, after the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 2 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 100%, defluorinate product content 0.17%, trans product 54%, cis-product 44%.
Comparative Examples 3
In 500 milliliters of single port bottles, add 20 milliliters of absolute ethyl alcohols, 30 milliliters of toluene, 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3; 4; 5-trifluoro-benzene 10 grams, 5%Pd/C 0.5 gram installs the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 4 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 99.98%, defluorinate product content 0.18%, trans product 58%, cis-product 41%.
Comparative Examples 4
In 500 milliliters of single port bottles, add 20 milliliters of absolute ethyl alcohols, 30 milliliters of sherwood oils, 4-(trans-the 4-ethyl) cyclohexyl-1-cyclohexenyl-3; 4; 5-trifluoro-benzene 10 grams, 5%Pd/C 0.5 gram installs the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 2 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 99.97%, defluorinate product content 0.18%, trans product 58%, cis-product 41%.
Comparative Examples 5
In 500 milliliters of single port bottles, add 20 milliliters of absolute ethyl alcohols; 30 milliliters of toluene, 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3,4-two fluorobenzene 20 grams; 5%Pd/C 0.5 gram; Install the hydrogenation reaction device, after the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 1.5 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 100%, defluorinate product content 0.10%, trans product 53%, cis-product 47%.
Comparative Examples 6
In 500 milliliters of single port bottles, add 20 milliliters of absolute ethyl alcohols; 30 milliliters of toluene, 4-(trans-the 4-normal-butyl) cyclohexyl-1-cyclohexenyl-3,4-two fluorobenzene 20 grams; 5%Pd/C 0.5 gram; Install the hydrogenation reaction device, after the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 1.5 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 100%, defluorinate product content 0.11%, trans product 53%, cis-product 47%.
Comparative Examples 7
In 500 milliliters of single port bottles, add 20 milliliters of absolute ethyl alcohols, 30 milliliters of toluene, 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3; 4; 5-trifluoro-benzene 10 grams, Raney Ni (neutrality) 2.0 grams install the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 6 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 98.88%, defluorinate product content 1.21%, trans product 67%, cis-product 31%.
Comparative Examples 8
In 500 milliliters of single port bottles, add 50 milliliters in ETHYLE ACETATE, 2 milliliters of triethylamines, 4-(trans-the 4-n-propyl) cyclohexyl-1-cyclohexenyl-3; 4; 5-trifluoro-benzene 10 grams, 5%Pd/C 0.5 gram installs the hydrogenation reaction device; After the inflated with nitrogen replacement(metathesis)reaction bottle air, shortening is 3 hours under normal temperature, the normal pressure.Reaction solution gas chromatographic analysis result: transformation efficiency 99.9%, defluorinate product content 0.325%, trans product 58%, cis-product 41%.