CN105601468B - The method for preparing dichloro hexafluoro cyclopentene isomer simultaneously - Google Patents
The method for preparing dichloro hexafluoro cyclopentene isomer simultaneously Download PDFInfo
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Abstract
The present invention relates to a kind of while preparing the method for dichloro hexafluoro cyclopentene isomer, the first step is reacted using perhalogenated cyclopentene or/and perhalogeno cyclopentadiene as raw material, under conditions of fluorination reagent and solvent exist, stirred, occur liquid phase exchange chloride for fluoride and obtain four kinds of isomers of the fluorine cyclopentene of trichlorine five, again using any one or more isomers of fluorine cyclopentene of trichlorine five as raw material, under conditions of fluorination reagent and solvent are present, occur liquid phase exchange chloride for fluoride and obtain dichloro hexafluoro cyclopentene isomer.Raw material of the present invention is easy to get, fluorination reagent cheap, and the yield of isomer is higher, prepare the isomer of perhalogenated cyclopentene simultaneously suitable for extensive liquid phase reactor.
Description
Technical field
The present invention relates to a kind of while prepare the method for dichloro hexafluoro cyclopentene isomer, more particularly to one kind passes through
Hexacholorocyclopentadiene (or octachlorocyclopentene) first obtains four kinds of isomers of the fluorine cyclopentene of trichlorine five with fluorination nak response,
Any isomer of the fluorine cyclopentene of trichlorine five obtains three kinds of isomerisms of dichloro hexafluoro cyclopentene with fluorination nak response again
The preparation method of body.
Background technology
Perhalogenated cyclopentene is the particularly important industrial chemicals or intermediate of a class, can synthesize etching agent octafluoro ring penta
Alkene, fluorine cyclopentene of intermediate 1- chlorine seven of the fluorine pentamethylene of cleaning agent 1,1,2,2,3,3,4- seven etc..According to Gaussian Computation, perhalogeno ring
The isomer of amylene causes its compound capacity volume variance very big, in some exchange chloride for fluoride due to the difference in structure
In, using the relatively low isomer of the of a relatively high isomer alternative compounds energy of compound energy, often
Structure identical target product can be obtained under the reaction condition of milder, and its yield is higher.Therefore, perhalogenated cyclopentene
The research of isomer has important theory significance and application value.
Document [ChemischeBerichte；vol.117；nb.3；(1984)；P.1153-1160] report by chlordene ring
Pentadiene is raw material, and chloroform is solvent, is reacted with xenon difluoride and fluorine gas, obtains (3R, 4R/S) -1,2,3,4,5,
5- chlordene -3,4- difluoros cyclopentene, (4S, 5R/S) -1,2,3,3,4,5- chlordene -4,5- difluoros cyclopentene totally four kinds of isomerisms
Body.Japan Patent JP2001247493A reports the in the mixed solvent in dimethylformamide dimethyl acid amides and toluene, 1,2- dichloro hexafluoro
Liquid phase exchange chloride for fluoride occurs for cyclopentene, the mixture of the fluorine cyclopentene of trichlorine five and tetrachloro tetrafluoro cyclopentene and potassium fluoride, obtains
While to principal product 1- seven fluorine cyclopentene of chlorine, accessory substance 1,3- dichloro hexafluoro cyclopentene and Isosorbide-5-Nitrae-dichloro hexafluoro cyclopentene are obtained
The mixture of two kinds of isomers, both yield sums are up to 17.2%.There is following defect in the above method：Fluorination reagent
Xenon difluoride is expensive, and the similar manufacturing process being fluorinated using xenon difluoride as fluorination reagent is rarely seen extensive in fluoride process
Prepare the manufacturing process of fluoride；By the mixed of 1,2- dichloro hexafluoros cyclopentene, the fluorine cyclopentene of trichlorine five and tetrachloro tetrafluoro cyclopentene
Compound mixed material is difficult to obtain, and the reappearance of experiment is poor, product 1,3- dichloro hexafluoro cyclopentene and Isosorbide-5-Nitrae-dichloro hexafluoro
The yield sum of two kinds of isomers of cyclopentene is relatively low.
The content of the invention
The technical problems to be solved by the invention be to solve in background technology not enough there is provided a kind of not only raw material is easy
, fluorination reagent it is cheap, and the yield of isomer is higher, prepare perhalogeno ring penta simultaneously suitable for extensive liquid phase reactor
The method of alkene isomer.
It is a kind of while prepare the method for dichloro hexafluoro cyclopentene isomer, the dichloro hexafluoro cyclopentene isomerism
Body is 1,2- dichloro hexafluoros cyclopentene, 1,3- dichloro hexafluoro cyclopentene and Isosorbide-5-Nitrae-dichloro hexafluoro cyclopentene, and this method includes as follows
Step：
The first step is reacted using perhalogenated cyclopentene or/and perhalogeno cyclopentadiene as raw material, in fluorination reagent and solvent presence, is stirred
Under conditions of mixing, occur liquid phase exchange chloride for fluoride and obtain isomer 1, the fluorine cyclopentene of 2,4- trichlorine five, 1,2,3- tri-
The fluorine cyclopentene of chlorine five, the fluorine cyclopentene of 1,3,3- trichlorines five and the fluorine cyclopentene of 1,4,4- trichlorines five；The perhalogenated cyclopentene, perhalogeno ring
Pentadiene is hexacholorocyclopentadiene, octachlorocyclopentene, the fluorine cyclopentene of 1,2,3,3,4,4,5- heptachlors one, 1,2,3,4,4,5- chlordenes
Difluoro cyclopentene, 1,2,3,4,4- pentachloro- trifluoros cyclopentene, 1,2,4,4- tetrachloro tetrafluoros cyclopentene, 1,2,3,3- tetrachloro ptfe rings
The mol ratio of one or more in amylene, wherein fluorination reagent, solvent and raw material is 4~6：10~20：1, reaction temperature is
70~150 DEG C, the reaction time is 2~30 hours；
Second step is reacted with the fluorine cyclopentene of 1,2,4- trichlorines five, the fluorine cyclopentene of 1,2,3- trichlorines five, the fluorine of 1,3,3- trichlorines five
One or more in cyclopentene or Isosorbide-5-Nitrae, the fluorine cyclopentene of 4- trichlorines five is raw material, in the presence of fluorination reagent and solvent, occurs liquid
Phase exchange chloride for fluoride and obtain dichloro hexafluoro cyclopentene isomer；The wherein mol ratio of fluorination reagent, solvent and raw material
For 0.5~3：5~20：1, reaction temperature is 50~150 DEG C, and the reaction time is 1~10 hour.
The fluorination reagent is potassium fluoride, sodium fluoride, cesium fluoride, antimony trifluoride, antimony pentafluoride or tetrafluoride germanium.
Solvent is dimethylformamide, dimethyl sulfoxide (DMSO) or sulfolane in the reaction.
The raw material of the first step reaction is octachlorocyclopentene and/or hexacholorocyclopentadiene.
In the first step reaction, wherein raw material is hexacholorocyclopentadiene, and fluorization agent is potassium fluoride, and solvent is dimethyl methyl
Acid amides.
The condition of first step reaction is：Potassium fluoride, dimethylformamide and octachlorocyclopentene or chlordene ring penta 2
The mol ratio of alkene is 4~6：10~20：1, reaction temperature is 70~150 DEG C, and the reaction time is 2~30 hours.
The condition of first step reaction is：Potassium fluoride, dimethylformamide and octachlorocyclopentene or chlordene ring penta 2
The mol ratio of alkene is 4.5~5.5：12~16：1, reaction temperature is 100~130 DEG C, and the reaction time is 7~20 hours.
In the second step reaction, wherein raw material is the fluorine cyclopentene of 1,2,4- trichlorine five or 1, the fluorine ring penta of 2,3- trichlorine five
Alkene, fluorization agent is potassium fluoride, and solvent is dimethylformamide.
The condition of second step reaction is：Potassium fluoride, dimethylformamide and the fluorine cyclopentene of 1,2,4- trichlorines five, 1,2,
The mol ratio of the fluorine cyclopentene of 3- trichlorines five, the fluorine cyclopentene of 1,3,3- trichlorines five or the fluorine cyclopentene of 1,4,4- trichlorines five is 0.5~3：5
~20：1, reaction temperature is 50~150 DEG C, and the reaction time is 1~10 hour.
The condition of second step reaction is：Potassium fluoride, dimethylformamide and the fluorine cyclopentene of 1,2,4- trichlorines five, 1,2,
The mol ratio of the fluorine cyclopentene of 3- trichlorines five, the fluorine cyclopentene of 1,3,3- trichlorines five or the fluorine cyclopentene of 1,4,4- trichlorines five is 1~2：10
~15：1, reaction temperature is 80~130 DEG C, and the reaction time is 3~7 hours.
The first step of the present invention is reacted with octachlorocyclopentene (or hexacholorocyclopentadiene) for raw material, is handed over by liquid phase fluorine chlorine
Reaction is changed, while obtaining the fluorine cyclopentene of 1,2,4- trichlorine five, the fluorine cyclopentene of 1,2,3- trichlorine five, the fluorine cyclopentene of 1,3,3- trichlorine five
Or the fluorine cyclopentene of 1,4,4- trichlorines five.Its key reaction is as follows：
Second step reaction of the present invention is with the fluorine cyclopentene of 1,2,4- trichlorines five, the fluorine cyclopentene of 1,2,3- trichlorines five, 1,3,3- tri-
The fluorine cyclopentene of chlorine five or Isosorbide-5-Nitrae, the fluorine cyclopentene of 4- trichlorines five are raw material, by liquid phase exchange chloride for fluoride, while obtaining 1,2- bis-
Chlorine hexafluoro cyclopentene, 1,3- dichloro hexafluoro cyclopentene and 1,4- dichloro hexafluoro cyclopentene.Wherein, 1, the fluorine cyclopentene of 2,4- trichlorine five
Or 1, when the fluorine cyclopentene of 2,3- trichlorine five is raw material, 1,2- dichloro hexafluoros cyclopentene, 1,3- dichloro hexafluoros ring penta can be obtained simultaneously
Alkene and 1,4- dichloro hexafluoro cyclopentene；And the fluorine cyclopentene of 1,3,3- trichlorine five or Isosorbide-5-Nitrae, when the fluorine cyclopentene of 4- trichlorines five is raw material,
1,3- dichloro hexafluoro cyclopentene and Isosorbide-5-Nitrae-dichloro hexafluoro cyclopentene can be obtained simultaneously, without 1,2- dichloro hexafluoro cyclopentene.It is led
React as follows：
The present invention can be carried out at ambient pressure, can also be carried out under high pressure.Due to being liquid phase reactor, be not related to phase feed or
Product, therefore, pressurization are little on reaction influence of the present invention, therefore, the present invention preferably normal pressure.
The present invention can be carried out in the reactor of glass material, stainless steel or polytetrafluoro material vinyl material.
The invention provides it is a kind of can be with the isomer of the fluorine cyclopentene of coproduction trichlorine five and dichloro hexafluoro cyclopentene
The preparation method of isomer, wherein the fluorine cyclopentene isomer of trichlorine five include the fluorine cyclopentene of 1,2,4- trichlorine five, 1,
The fluorine cyclopentene of 2,3- trichlorine five, the fluorine cyclopentene of 1,3,3- trichlorine five and Isosorbide-5-Nitrae, the fluorine cyclopentene of 4- trichlorines five, dichloro hexafluoro cyclopentene
Isomer includes 1,2- dichloro hexafluoros cyclopentene, 1,3- dichloro hexafluoro cyclopentene and 1,4- dichloro hexafluoro cyclopentene.Only need
Respectively to the fluorine cyclopentene of 1,2,4- trichlorines five, the fluorine cyclopentene of 1,2,3- trichlorines five, the fluorine cyclopentene of 1,3,3- trichlorines five, 1,4,4- tri-
The products such as the fluorine cyclopentene of chlorine five, 1,2- dichloro hexafluoros cyclopentene, 1,3- dichloro hexafluoro cyclopentene and 1,4- dichloro hexafluoro cyclopentene
Carry out except the post processing such as solvent, water removal, refined, you can obtain corresponding product：The fluorine cyclopentene boiling point of 1,4,4- trichlorines five is 109-
113 DEG C (760mmHg), the fluorine cyclopentene boiling point of 1,3,3- trichlorine five is 115-117 DEG C (760mmHg), the fluorine ring of 1,2,4- trichlorine five
Amylene boiling point be 123-124 DEG C (760mmHg), the fluorine cyclopentene boiling point of 1,2,3- trichlorine five be 129-130 DEG C (760mmHg), 1,
4- dichloro hexafluoro cyclopentene boiling point is 80-84 DEG C (760mmHg), and 1,3- dichloro hexafluoro cyclopentene boiling point is 86-88 DEG C
(760mmHg), 1,2- dichloro hexafluoro cyclopentene boiling point is 90-91 DEG C (760mmHg).
Advantages of the present invention：The technical method that the present invention is provided not only can the fluorine cyclopentene isomer of coproduction trichlorine five
(including the fluorine cyclopentene of 1,2,4- trichlorines five, the fluorine cyclopentene of 1,2,3- trichlorines five, the fluorine cyclopentene of 1,3,3- trichlorines five and 1,4,4- tri-
The fluorine cyclopentene of chlorine five) and dichloro hexafluoro cyclopentene isomer (including 1,2- dichloro hexafluoros cyclopentene, 1,3- dichloro hexafluoro rings
Amylene and Isosorbide-5-Nitrae-dichloro hexafluoro cyclopentene), wherein, 1,3- dichloro hexafluoro cyclopentene and Isosorbide-5-Nitrae-dichloro hexafluoro cyclopentene yield compared with
Height, both yield sums are up to 56.78% (see embodiment 24), and raw material is easy to get, fluorination reagent cheap, suitable for big rule
Mould liquid phase prepares the fluorine cyclopentene isomer of trichlorine five and dichloro hexafluoro cyclopentene isomer simultaneously.
Embodiment
Analytical instrument：The glad chromatogram GC-930 in Shanghai sea, hydrogen flame detector, chromatographic column is capillary column Al2O3/S“50m×
0.320mm × 0.25 μm " (manufacture of chromatographic technique research and development centre of Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences).
Gas chromatography analysis method：Reaction product takes gaseous sample to carry out gas-chromatography point after washing, alkali cleaning and drying
Analysis.High Purity Nitrogen and hydrogen are used as carrier gas.Testing conditions are 250 DEG C of temperature of vaporization chamber, 250 DEG C of 2 temperature of auxiliary furnace, detector temperature
250 DEG C, 40 DEG C of post stove initial temperature is kept for 10 minutes, 15 DEG C/min of heating rate, 230 DEG C of final temperature, is kept for 3 minutes.
It is following that the present invention is described in further detail in conjunction with the embodiments, but do not limit the scope of the invention.
Embodiment 1
Under normal pressure, stirring condition, burnt in 250 milliliters of glass equipped with condenser pipe and bubbler (making reaction be in normal pressure)
In bottle, potassium fluoride, dimethylformamide and hexacholorocyclopentadiene, its molar ratio potassium fluoride/dimethylformamide/chlordene are added
Cyclopentadiene is 5/14/1,120 DEG C of reaction temperature, 10 hours reaction time.After reaction terminates, removed through washing 100ml × 3 time
Solvent, anhydrous magnesium sulfate 2.0g is dried, and is filtrated to get organic phase, takes organic phase to carry out the composition of gas chromatographic analysis organic matter,
It the results are shown in Table 1.
Above-mentioned organic phase is subjected to rectifying, the isomer Isosorbide-5-Nitrae of the fluorine cyclopentene of trichlorine five, the fluorine ring penta of 4- trichlorines five is obtained
Alkene, the fluorine cyclopentene of 1,3,3- trichlorines five, the fluorine cyclopentene of 1,2,3- trichlorines five and the fluorine cyclopentene of 1,2,4- trichlorines five.Wherein, Isosorbide-5-Nitrae,
The fluorine cyclopentene boiling point of 4- trichlorines five is 109-113 DEG C (760mmHg), and the fluorine cyclopentene boiling point of 1,3,3- trichlorine five is 115-117 DEG C
(760mmHg), the fluorine cyclopentene boiling point of 1,2,3- trichlorine five is 129-130 DEG C (760mmHg), the boiling of the fluorine cyclopentene of 1,2,4- trichlorine five
Point is 123-124 DEG C (760mmHg).
Embodiment 2
Operation same as Example 1, except that mole of potassium fluoride/dimethylformamide/hexacholorocyclopentadiene
Ratio is 4/20/1, the results are shown in Table 1.
Embodiment 3
Operation same as Example 1, except that mole of potassium fluoride/dimethylformamide/hexacholorocyclopentadiene
Ratio is 4.5/16/1, the results are shown in Table 1.
Embodiment 4
Operation same as Example 1, except that mole of potassium fluoride/dimethylformamide/hexacholorocyclopentadiene
Ratio is 5.5/12/1, the results are shown in Table 1.
Embodiment 5
Operation same as Example 1, except that mole of potassium fluoride/dimethylformamide/hexacholorocyclopentadiene
Ratio is 6/10/1, the results are shown in Table 1.
Embodiment 6
Operation same as Example 1, except that 70 DEG C of reaction temperature, in 30 hours reaction time, the results are shown in Table 1.
Embodiment 7
Operation same as Example 1, except that 90 DEG C of reaction temperature, in 20 hours reaction time, the results are shown in Table 1.
Embodiment 8
Operation same as Example 1, except that 100 DEG C of reaction temperature, in 17 hours reaction time, the results are shown in Table 1.
Embodiment 9
Operation same as Example 1, except that 110 DEG C of reaction temperature, in 13 hours reaction time, the results are shown in Table 1.
Embodiment 10
Operation same as Example 1, except that 130 DEG C of reaction temperature, in 7 hours reaction time, the results are shown in Table 1.
Embodiment 11
Operation same as Example 1, except that 140 DEG C of reaction temperature, in 4 hours reaction time, the results are shown in Table 1.
Embodiment 12
Operation same as Example 1, except that 150 DEG C of reaction temperature, in 2 hours reaction time, the results are shown in Table 1.
Embodiment 13
Operation same as Example 1, except that hexacholorocyclopentadiene such as is changed at the octachlorocyclopentene of the amount of material,
It the results are shown in Table 1.
Embodiment 14
Operation same as Example 1, except that hexacholorocyclopentadiene such as is changed at the 1,2,3,3,4 of the amount of material,
The fluorine cyclopentene of 4,5- heptachlor one, the results are shown in Table 1.
Embodiment 15
Operation same as Example 1, except that hexacholorocyclopentadiene such as is changed at the 1,2,3,4,4 of the amount of material,
5- chlordene difluoro cyclopentene, the results are shown in Table 1.
Embodiment 16
Operation same as Example 1, except that hexacholorocyclopentadiene such as is changed at the 1,2,3,4,4- of the amount of material
Pentachloro- trifluoro cyclopentene, the results are shown in Table 1.
Embodiment 17
Operation same as Example 1, except that hexacholorocyclopentadiene such as is changed at the 1,2,3,3,4- of the amount of material
Pentachloro- trifluoro cyclopentene, the results are shown in Table 1.
Embodiment 18
Operation same as Example 1, except that hexacholorocyclopentadiene such as is changed at 1, the 2,4,4- tetra- of the amount of material
Chlorine tetrafluoro cyclopentene, the results are shown in Table 1.
Embodiment 19
Operation same as Example 1, except that hexacholorocyclopentadiene such as is changed at 1, the 2,3,3- tetra- of the amount of material
Chlorine tetrafluoro cyclopentene, the results are shown in Table 1.
Embodiment 20
Operation same as Example 1, except that potassium fluoride such as changes at the cesium fluoride of the amount of material, the results are shown in Table 1.
Embodiment 21
Operation same as Example 1, except that potassium fluoride such as changes at the antimony trifluoride of the amount of material, the results are shown in Table
1。
Embodiment 22
Operation same as Example 1, except that potassium fluoride such as changes at the antimony pentafluoride of the amount of material, the results are shown in Table
1。
Embodiment 23
Operation same as Example 1, except that potassium fluoride such as changes at the tetrafluoride germanium of the amount of material, the results are shown in Table
1。
Embodiment 24
Operation same as Example 1, except that dimethylformamide such as changes at the dimethyl sulfoxide (DMSO) of the amount of material,
It the results are shown in Table 1.
Embodiment 25
Operation same as Example 1, except that dimethylformamide such as changes at the sulfolane of the amount of material, as a result
It is shown in Table 1.
Embodiment 26
Under normal pressure, stirring condition, burnt in 250 milliliters of glass equipped with condenser pipe and bubbler (making reaction be in normal pressure)
In bottle, potassium fluoride, dimethylformamide and 1, the fluorine cyclopentene of 2,3- trichlorine five, its molar ratio potassium fluoride/dimethyl methyl are added
Acid amides/1,2, the molar ratio of the fluorine cyclopentene of 4- trichlorines five is 1.5/13/1,130 DEG C of reaction temperature, 3 hours reaction time.Instead
After should terminating, through washing 100ml × 3 time, anhydrous magnesium sulfate 2.0g is dried, and is filtrated to get organic phase, takes organic phase to carry out gas phase
The composition of chromatography organic matter, the results are shown in Table 2.
Above-mentioned organic phase is subjected to rectifying, isomer Isosorbide-5-Nitrae-dichloro hexafluoro ring penta of dichloro hexafluoro cyclopentene is obtained
Alkene, 1,3- dichloro hexafluoros cyclopentene, 1,2- dichloro hexafluoro cyclopentene.Wherein, Isosorbide-5-Nitrae-dichloro hexafluoro cyclopentene boiling point is 80-84 DEG C
(760mmHg), 1,3- dichloro hexafluoro cyclopentene boiling point is 86-88 DEG C (760mmHg), and 1,2- dichloro hexafluoro cyclopentene boiling point is
90-91℃(760mmHg)。
Embodiment 27
Operated with the identical of embodiment 26, except that reaction mass potassium fluoride/dimethylformamide/1,2,4- trichlorines
The molar ratio of five fluorine cyclopentene is 0.5/20/1, the results are shown in Table 2.
Embodiment 28
Operated with the identical of embodiment 26, except that reaction mass potassium fluoride/dimethylformamide/1,2,4- trichlorines
The molar ratio of five fluorine cyclopentene is 1/15/1, the results are shown in Table 2.
Embodiment 29
Operated with the identical of embodiment 26, except that reaction mass potassium fluoride/dimethylformamide/1,2,4- trichlorines
The molar ratio of five fluorine cyclopentene is 2/10/1, the results are shown in Table 2.
Embodiment 30
Operated with the identical of embodiment 26, except that reaction mass potassium fluoride/dimethylformamide/1,2,4- trichlorines
The molar ratio of five fluorine cyclopentene is 3/5/1, the results are shown in Table 2.
Embodiment 31
Operated with the identical of embodiment 26, except that 50 DEG C of reaction temperature, in 10 hours reaction time, the results are shown in Table 2.
Embodiment 32
Operated with the identical of embodiment 26, except that 80 DEG C of reaction temperature, in 7 hours reaction time, the results are shown in Table 2.
Embodiment 33
Operated with the identical of embodiment 26, except that 90 DEG C of reaction temperature, in 6 hours reaction time, the results are shown in Table 2.
Embodiment 34
Operated with the identical of embodiment 26, except that 100 DEG C of reaction temperature, in 5.5 hours reaction time, the results are shown in Table
2。
Embodiment 35
Operated with the identical of embodiment 26, except that 110 DEG C of reaction temperature, in 5 hours reaction time, the results are shown in Table 2.
Embodiment 36
Operated with the identical of embodiment 26, except that 120 DEG C of reaction temperature, in 4 hours reaction time, the results are shown in Table 2.
Embodiment 37
Operated with the identical of embodiment 26, except that 140 DEG C of reaction temperature, in 1.5 hours reaction time, the results are shown in Table
2。
Embodiment 38
Operated with the identical of embodiment 26, except that 150 DEG C of reaction temperature, in 1 hour reaction time, the results are shown in Table 2.
Embodiment 39
Operated with the identical of embodiment 26, except that the fluorine cyclopentene of 1,2,4- trichlorine five such as changes at the 1 of the amount of material,
The fluorine cyclopentene of 2,3- trichlorine five, the results are shown in Table 2.
Embodiment 40
Operated with the identical of embodiment 26, except that the fluorine cyclopentene of 1,2,4- trichlorine five such as changes at the 1 of the amount of material,
The fluorine cyclopentene of 3,3- trichlorine five, the results are shown in Table 2.
Embodiment 41
Operated with the identical of embodiment 26, except that the fluorine cyclopentene of 1,2,4- trichlorine five such as changes at the 1 of the amount of material,
The fluorine cyclopentene of 4,4- trichlorine five, the results are shown in Table 2.
Embodiment 42
Operate, except that potassium fluoride such as changes at the cesium fluoride of the amount of material, the results are shown in Table with the identical of embodiment 26
2。
Embodiment 43
Operate, except that potassium fluoride such as changes at the antimony trifluoride of the amount of material, as a result see with the identical of embodiment 26
Table 2.
Embodiment 44
Operate, except that potassium fluoride such as changes at the antimony pentafluoride of the amount of material, as a result see with the identical of embodiment 26
Table 2.
Embodiment 45
Operate, except that potassium fluoride such as changes at the tetrafluoride germanium of the amount of material, as a result see with the identical of embodiment 26
Table 2.
Embodiment 46
With the identical of embodiment 26 operate, except that dimethylformamide change into wait the amount of material dimethyl Asia
Sulfone, the results are shown in Table 2.
Embodiment 47
With the identical of embodiment 26 operate, except that dimethylformamide change into wait the amount of material sulfolane, tie
Fruit is shown in Table 2.
Table 1
Note：(1) " raw material " that embodiment " 1-12 " and embodiment " 18-23 " are used is hexacholorocyclopentadiene.
(2) " raw material " that embodiment " 13 " is used is octachlorocyclopentene.
(3) " raw material " that embodiment " 14 " is used is the fluorine cyclopentene of 1,2,3,3,4,4,5- heptachlors one.
(4) " raw material " that embodiment " 15 " is used is 1,2,3,4,4,5- chlordene difluoro cyclopentene.
(5) " raw material " that embodiment " 16 " is used is 1,2,3,4,4- pentachloro- trifluoro cyclopentene.
(6) " raw material " that embodiment " 17 " is used is 1,2,3,3,4- pentachloro- trifluoro cyclopentene.
(7) " raw material " that embodiment " 18 " is used is 1,2,4,4- tetrachloro tetrafluoro cyclopentene.
(8) " raw material " that embodiment " 19 " is used is 1,2,3,3- tetrachloro tetrafluoro cyclopentene.
Table 2
Note：(1) raw material used in embodiment " 26-38 " and embodiment " 42-47 " is the fluorine cyclopentene of 1,2,4- trichlorines five.
(2) raw material used in embodiment " 39 " is the fluorine cyclopentene of 1,2,3- trichlorines five.
(3) raw material used in embodiment " 40 " is the fluorine cyclopentene of 1,3,3- trichlorines five.
(4) raw material used in embodiment " 41 " is the fluorine cyclopentene of 1,4,4 trichlorine five.
Claims (8)
1. a kind of while prepare the method for dichloro hexafluoro cyclopentene isomer, the dichloro hexafluoro cyclopentene isomer
For 1,2- dichloro hexafluoros cyclopentene, 1,3- dichloro hexafluoro cyclopentene and Isosorbide-5-Nitrae-dichloro hexafluoro cyclopentene, this method includes following step
Suddenly：
The first step is reacted using perhalogenated cyclopentene or/and perhalogeno cyclopentadiene as raw material, is existed in fluorination reagent and solvent, stirring
Under the conditions of, occur liquid phase exchange chloride for fluoride and obtain isomer 1, the fluorine cyclopentene of 2,4- trichlorine five, 1,2,3- trichlorines five
Fluorine cyclopentene, the fluorine cyclopentene of 1,3,3- trichlorines five and the fluorine cyclopentene of 1,4,4- trichlorines five；The perhalogenated cyclopentene, perhalogeno ring penta 2
Alkene is hexacholorocyclopentadiene, octachlorocyclopentene, the fluorine cyclopentene of 1,2,3,3,4,4,5- heptachlors one, 1,2,3,4,4,5- chlordene difluoros
Cyclopentene, 1,2,3,4,4- pentachloro- trifluoros cyclopentene, 1,2,3,3,4- pentachloro- trifluoros cyclopentene, 1,2,4,4- tetrachloros ptfe ring penta
One or more in the tetrachloro tetrafluoro cyclopentene of alkene 1,2,3,3-, the wherein mol ratio of fluorination reagent, solvent and raw material are 4~6：
10~20：1, reaction temperature is 70~150 DEG C, and the reaction time is 2~30 hours；
Second step is reacted with the fluorine cyclopentene of 1,2,4- trichlorines five, the fluorine cyclopentene of 1,2,3- trichlorines five, the fluorine ring penta of 1,3,3- trichlorines five
One or more in alkene or Isosorbide-5-Nitrae, the fluorine cyclopentene of 4- trichlorines five is raw material, under conditions of fluorination reagent and solvent are present, is occurred
Liquid phase exchange chloride for fluoride and the isomer for obtaining dichloro hexafluoro cyclopentene；Wherein fluorination reagent, solvent and raw material rubs
You are than being 0.5~3：5~20：1, reaction temperature is 50~150 DEG C, and the reaction time is 1~10 hour；
The fluorination reagent is potassium fluoride, sodium fluoride, cesium fluoride, antimony trifluoride, antimony pentafluoride or tetrafluoride germanium；
Solvent is dimethylformamide, dimethyl sulfoxide (DMSO) or sulfolane in the reaction.
2. according to the method described in claim 1, the raw material of the first step reaction is octachlorocyclopentene and/or chlordene ring penta 2
Alkene.
3. method according to claim 2, in the first step reaction, wherein raw material is hexacholorocyclopentadiene, fluorization agent
For potassium fluoride, solvent is dimethylformamide.
4. method according to claim 2, the condition of first step reaction is：Potassium fluoride, dimethylformamide and eight
The mol ratio of chlorine cyclopentene or hexacholorocyclopentadiene is 4~6：10~20：1, reaction temperature is 70~150 DEG C, reaction time
For 2~30 hours.
5. method according to claim 4, the condition of the first step reaction is：Potassium fluoride, dimethylformamide and eight
The mol ratio of chlorine cyclopentene or hexacholorocyclopentadiene is 4.5~5.5：12~16：1, reaction temperature is 100~130 DEG C, reaction
Time is 7~20 hours.
6. according to the method described in claim 1, in the second step reaction, wherein raw material is the fluorine cyclopentene of 1,2,4- trichlorine five
Or 1, the fluorine cyclopentene of 2,3- trichlorine five, fluorization agent is potassium fluoride, and solvent is dimethylformamide.
7. according to the method described in claim 1, the condition of the second step reaction is：Potassium fluoride, dimethylformamide and 1,
The fluorine cyclopentene of 2,4- trichlorines five, the fluorine cyclopentene of 1,2,3- trichlorines five, the fluorine cyclopentene of 1,3,3- trichlorines five or the fluorine of 1,4,4- trichlorines five
The mol ratio of cyclopentene is 0.5~3：5~20：1, reaction temperature is 50~150 DEG C, and the reaction time is 1~10 hour.
8. method according to claim 7, the condition of second step reaction is：Potassium fluoride, dimethylformamide and 1,
The fluorine cyclopentene of 2,4- trichlorines five, the fluorine cyclopentene of 1,2,3- trichlorines five, the fluorine cyclopentene of 1,3,3- trichlorines five or the fluorine of 1,4,4- trichlorines five
The mol ratio of cyclopentene is 1~2：10~15：1, reaction temperature is 80~130 DEG C, and the reaction time is 3~7 hours.
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