GB2028328A - Fluorine-containing 1,3-dienes, process for their preparation and polymers thereof - Google Patents
Fluorine-containing 1,3-dienes, process for their preparation and polymers thereof Download PDFInfo
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- GB2028328A GB2028328A GB7927945A GB7927945A GB2028328A GB 2028328 A GB2028328 A GB 2028328A GB 7927945 A GB7927945 A GB 7927945A GB 7927945 A GB7927945 A GB 7927945A GB 2028328 A GB2028328 A GB 2028328A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title description 6
- 229910052731 fluorine Inorganic materials 0.000 title description 6
- 239000011737 fluorine Substances 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 5
- 239000011701 zinc Substances 0.000 claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 4
- 150000001983 dialkylethers Chemical class 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 239000005871 repellent Substances 0.000 abstract description 3
- 229910052740 iodine Inorganic materials 0.000 abstract description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- -1 1- fluoro - 1- trifluoromethyl - 1,3butadiene Chemical compound 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000000370 acceptor Substances 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004508 fractional distillation Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- GKIRPKYJQBWNGO-OCEACIFDSA-N clomifene Chemical compound C1=CC(OCCN(CC)CC)=CC=C1C(\C=1C=CC=CC=1)=C(\Cl)C1=CC=CC=C1 GKIRPKYJQBWNGO-OCEACIFDSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- XJGUKDJAOUXADK-UHFFFAOYSA-N [difluoro(naphthalen-2-yl)methyl]phosphonic acid Chemical compound C1=CC=CC2=CC(C(F)(F)P(O)(=O)O)=CC=C21 XJGUKDJAOUXADK-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- AOJDZKCUAATBGE-UHFFFAOYSA-N bromomethane Chemical compound Br[CH2] AOJDZKCUAATBGE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/19—Halogenated dienes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
- C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
- C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
- C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
New 1,3-dienes have the formula <IMAGE> in which Rf is a C1-22 perfluoroalkyl group and each of R<1>, R<2>, R<3> and R<4> is hydrogen, or a C1-10 alkyl, cyclohexyl, benzyl, phenyl, naphthyl, (C1-5 alkyl) phenyl or (C1-5 alkyl) naphthyl group. The compounds are prepared by reacting alkenes of the formula Rf-CF2-CR<1> = CR<2>-CR<3>R<4>X in which X is Cl, Br or I with a metallic halogen- acceptor, preferably zinc/copper, in an inert, aprotic solvent at 40 to 150 DEG C. Polymers of the 1,3-dienes are thermally and chemically stable and oil- and water-repellent, and may be elastomeric or vitreous.
Description
SPECIFICATION
Fluorine - containing 1,3 - dienes, process for their preparation and polymers thereof
This invention relates to fluorine-containing 1,3 dienes, to a process for their preparation and to polymers thereof.
It is known that dienes having conjugated double bonds may be produced by dehalogenation of 1,4 dihalo - 2 - alkenes with suitable metals [cf. "Methoden der Organischen Chemie" (Houben-Weyl) Vol.
V/lc, pages 155 to 160]. The said publication expressly states at page 155 that fluorine is not affected in such 1,4 - dehalogenations. On the contrary, with zinc it is generally possible to achieve even selective elimination of other halogen atoms bonded gemi wally to fluorine.
The present invention is based on the surprising observation that, in the reaction of 1 - perfluoroalkyl 4 - haloalkenes of the formula Rf - CF2 - CR' = CR2
CR3R4X with metallic halogen-acceptors in polar, aprotic solvents, it is possible to split off X and F and to obtain the corresponding 1,3 - dienes in good yields.
The present invention therefore provides 1 - fluoro - 1 - perfluoroalkyl - 1,3 - dienes of the formula
in which Rf is a perfluoroalkyl group having from 1 to 12 carbon atoms and each of R', R2, R3 and R4 is hydrogen, an alkyl group having from 1 to 10 carbon atoms, a cyclohexyl, phenyl, benzyl or napth thyl group, or an alkylphenyl or alkylnaphthyl group in which the alkyl group has from 1 to 5 carbon atoms.
The present invention also provides a process for the preparation of such 1 - fluoro - 1 - perfluoroalkyl 1,3 - dienes which comprises reacting a haloalkene of the formula Rf - CF2 - CR' = CR2 - CR3R4X, in which
Rf, R1, R2, R3 and R4 have the meanings given above and Xis Cl, Br or I, with at least the stoichiometric amount of a metallic halogen-acceptor in the presence of a polar, aprotic solvent at a temperature of from 40 to 150"C.
The 1 - perfluoroalkyl - 4 - haloalkene starting materials can be produced by methods known from the literature. For example, the 4 - chloro - substituted compounds may be obtained by treating the corresponding perfluoroalkyl-substituted, unsaturated alcohols with chlorinating agents [see J. Amer.
Chem. Soc. 83 (1961), pages 3251 to 3258 and Synthesis, 1977, page 297]. From the 4- chloro substituted compounds, it is possible to obtain the corresponding bromine and iodine compounds by substitution of the chlorine with the aid of alkali metal bromides and iodides, respectively.
Preferred haloalkenes of the above formula used in the process according to the present invention are those in which each of R', R2, R3 and R4 is H or a short-chained alkyl group having from 1 to 3 carbon atoms, especially a methyl group, or a benzyl, tolyl, naphthyl or, especially, a phenyl group. The perfluoroalkyl chain in these haloalkenes may be branched, especially terminally methyl-branched; preferably, however, it is straight-chained. Accordingly, the resulting compounds of the formula I having such preferred substituents are themselves preferred.
The reactivity of the haloalkene starting materials decreases in the series X = I > Bur, CI.
The metallic halogen-acceptors used in the process according to the present invention are preferably metallic zinc and magnesium. Calcium, cadmium, iron and lead/sodium alloys are examples of other metallic halogen-acceptors that may be used.
Especially preferred is the use of zinc in the form of an activated metal pair with a second metal.
If magnesium is used asthe metallic halogenacceptor, the process according to the present invention is advantageously carried out by adding the haloalkene starting material, in portions or continuously, to a heated and vigorously stirred suspension of magnesium chips in a dialkyl ether. The minimum temperature required to initiate the reaction is generally from 40 to 60"C for iodides and from 60 to 80"C for bromides. Chlorides react very slowly even at temperatures above 100"C.
The reaction can also be carried out in a similar manner with finely divided metallic zinc.
The conversion of the haloalkene starting materials into the 1 - perfluoroalkyl - substituted 1 - fluoro 1,3 - dienes of the formula I, including chloroalkenes (X = Cl), is best achieved, however, with zinc that is in the form of an activated metal pair. In principle, all metals that are more electropositive than zinc are suitable as the second component of such metal pairs. Preferably, the second component is cadmium, lead, mercury or palladium. The concentration of the second metal is suitably from 0.002 to 0.05 gram atom, preferably from 0.005to 0.015 gram atom per 1 gram atom of zinc. Especially suitable are zinc/copper pairs, the production of which is described, for example, in "Methoden der Organischen Chemie" (Houben-Weyl), Vol. Xlll/2a, pages 570 to 573.
The zinc/metal pair is advantageously used in a finely divided form. In order to achieve optimum yields, an excess of zinc is advantageous. In general, it is advisable to use an excess of from 0.5 to 1 gram atom of zinc per mole of haloalkene starting material.
Suitable aprotic solvents in which the reaction is carried out are, apart from the dialkyl ethers already mentioned, especially dialkylformamides, for example dimethylformamide, and dialkyl sulphoxides, for example dimethyl sulphoxide.
In an especially advantageous process according to the present invention, the haloalkene starting material is added to a heated zinc/copper suspension in anhydrous dimethylformamide while stirring vig orously.
The temperature required to start the reaction depends on the type of haloalkene starting material and lies between 40 and 1200C, preferably between 40 and 100"C. The reaction itself is exothermic, so that heat has to be applied only towards the end of the reaction in order to complete it.
It is important that the reaction is carried out under anhydrous conditions. In orderto ensure the exclusion of moisture, it is expedient to carry out the reaction under an inert gas atmosphere.
Of the resulting 1 - perfluoroalkyl - substituted 1 fluoro - 1,3 - dienes of the formula I, those that have low boiling points can be distilled from the reaction mixture as they are produced. Those dienes having high boiling points, can be isolated by conventional methods, for example by fractional distillation, after the reaction has been completed, optionally after separating the excess metallic halogen-acceptor by filtration or centrifugation.
The 1 - fluoro - 1 - perfluoroalkyl - 1,3 - dienes of the formula I can be polymerised by customary processes, to produce products having good thermostability and high chemical resistance. Polymerisation can be initiated photochemically or thermally or car- ried out in the presence of radical-forming or cationic initiators.
Depending on the polymerisation conditions, elastomeric or vitreous products are obtained which, without exception, have very good oil-repellent and water-repellent properties.
The elastomeric polymers can be vulcanised by customary methods, producing products having the characteristics of synthetic rubber with high thermal resistance and good low-temperature elasticity.
Furthermore, the vitreous poly - [1 - fluoro - 1 perfluoroalkyl - 1,3 - dienes] can be processed thermoplastically. In this manner, it is possible to produce light-resistant and oxidation-resistant protective coatings for metal surfaces. These polymers can also be used especially for obtaining electric cable sleeves having a good insulating effect and high dielectric strength.
The following Examples illustrate the invention. In all the Examples, carefully dried solvents were used, and the reactions were carried out under a nitrogen atmosphere in order to exclude moisture. The products were characterised by elementary analyses, nuclear magnetic resonance spectra and infrared spectra. The proton magnetic resonance spectra were recorded at 60 MHz using tetramethylsilane as the internal standard, and the fluorine NMR spectra were recorded at 56.45 MHz using trifluoroacetic acid as the external standard.
Production of the zinclcopperpair 1 g of copper(ll) acetate (0.005 mole) is dissolved in 100 ml of dimethylformamide (DMF) at 40 to 500C.
35.5 g of zinc dust (0.5 gram atom) and 20 ml of glacial acetic acid are then added, the mixture is stirred for 30 minutes, and the resulting metal pair is filtered off and washed four times, each time with 20
ml of DMF. If further reaction in other solvents (for example, dimethyl sulphoxide, di - n - butyl ether) is
envisaged, these are used as the washing liquor.
The Zn/Cu pair is reacted in the freshly prepared state in order to avoid any loss in activity as a result of ageing.
Production of 1,3- dienes:
Example 1
Preparation of 1- fluoro - 1- trifluoromethyl - 1,3butadiene with zincicopper A four-necked flask of 250 ml capacity is equipped with a stirrer, a dropping funnel, a thermometer and a fractionating column at the inlet of which there is arranged a 5 cm long Vigreux adaptor. 35 g of Zn/Cu and 100 ml of DMF are introduced into the reaction vessel and heated to 850C, and the dropwise addition of 48.6 g of C2F5- CH = CH - CH2CI (0.25 mole) is then started while stirring vigorously.After the addition of approximately 5 ml of chloroalkene, the reaction starts and the temperature of the mixture rises to 100"C. The remaining chloroalkene is added at such a rate that the temperature remains at 100"C, while the product distils off continuously and is collected in a receiver cooled by dry ice. When the dropwise addition has been completed, the reaction is allowed to continue for30 minutes at 100 C.The resulting crude product is purified by fractional distillation under normal pressure. As the main fraction, there is obtained 27.4 g of a colourless, mobile liquid having a boiling point of 37"C (yield: 78.3% of the theoretical amount). Purity according to analysis by gas chromatography (GC) 98.9%.
Analysis of C5H4F4: Calculated: C42.87 H 2.88 F 54.25% Found: 43.0 3.0 53.7 % 'H - NMR 6.88 to 6.30 ppm (multiplet, 1H); 6.12 to 5.25 ppm (multiplet, 2H).
'9F - NMR: indicates 2 isomers A and B in a ratio of 7.5:1
= isomer A
58.0 ppm (doublet of quadruplets, F),3JHF(trans) = 29.4 Hz,3JFF = 11.4 Hz; - 9.0 ppm (doublet, 3F).
= isomer B
53.1 ppm (1 F),3JHF (cis) = 19.2Hz, 3JFF = 9.0 Hz; - 12.5 ppm (3 F).
IR: (C=C) 1689 cm-' (strong), cm-' (medium).
Example 2
A suspension of 35 g of Zn/Cu in 100 ml of di - n butyl ether is reacted in the manner described in Example 1 with 71.5 g of C2Fs - CH=CH - CH2I (0.25 mole). By re-distillation of the crude product, 23.3 g of 1 - fluoro - 1 - trifluoromethyl - 1,3 - butadiene are obtained (66.5% yield).
Isomer ratio of A to B = 8:1
Example 3
Production with magnesium
A suspension of 9.72 g of magnesium chips (0.4 gram atom) in 100 ml ofdi- n - butyl ether is reacted with 71.5 g of C2F5 - CH=CH - CH2L in the manner described in Example 1. Yield of pure 1 - fluoro - 1 trifluoromethyl -1,3 - butadiene: 19.0 g (54.3 /O) Isomer ratio ofAto B = 7.5:1
Example 4 1 - fluoro - 1 perfluoro-n-pentyl- 1,3-butadiene In the apparatus described in Example 1, the fractioning column is replaced by a reflux condenser.A solution of 98.6 g of C6F,3 - CH=CH - CH2CI (0.25 mole) in 50 ml of DMF is added dropwise, while stirring, to a suspension of35 g of Zn/Cu in 100 ml of
DMF at 80 to 1000C and, after addition has been completed, the reaction is allowed to continue for one hour at 1000C. After cooling to room temperature, the mixture is stirred into 300 ml of water, the solid constituents are filtered off, and the lower phase which contains the main amount of the product, is separated off in a separating funnel. The upper phase is extracted twice by shaking with 50 ml of diethyl ether each time. The ether extracts are combined with the lower phase and dried over magnesium sulphate.Evaporation of the ether and fractional distillation produces 58.3 g of colourless, liquid 1 - fluoro - 1 - perfluoro - n - pentyl - 1,3 - butadiene having a boiling point of 65"C at 80 torr (Yield: 68.6%). Purity according to GC: 98.1%
Analysis of C9H4F12:
Calculated: C31.78 H 1.19 F67.03% Found: 32.0 1.3 67.8 %
'H- NMR: 6.98 to 6.39 (multiplet, 1 H); 6.20 to 5.29 (multiplet, 2H).
'9F - NMR: As in the case of the trifluoromethyl compound (Examples 1 to 3) stereoisomers also occur here, and in a ratio of A:B = 10:1.
(A): 52.4 ppm (1 F); 49.0 ppm (2 F); 45.6 ppm (4 F); 40.6 ppm (2 F); 4.5 ppm (3 F).
(B): 47.9 ppm (1 F); 49.0 ppm (2 F); 45.6 ppm (4 F); 37.7 ppm (2 F); 4.5 ppm (3 F).
IR: (C=C) 1683 cm-' (strong), 1615 cm-' (weak).
Example 5
In contrast to Example 4, dimethyl sulphoxide is used instead of DMF. 109.5 g of C6F13 - CH=CH
CH2Br (0.25 mole) are added dropwise at 70 to 80"C and the reaction is allowed to continue for one hour at 90"C. Work-up is as described in Example 4 and produces 36.0 g of 1 - fluoro - 1 - perfluoro - n - pentyl - 1,3 - butadiene (42.4% yield).
Example 6 1- Fluoro - 1- trifluoromethyl - 2 - methyl - 1,3 butadiene
In a reaction of 52.1 g of C2Fs - C(CH3)=CH - CH2CI (0.25 mole) carried out in a manner similar to that described in Example 1,30.3 g of the compound CF3
CF=C (CH3) - CH=CH2 are obtained (78.7% yield)
Boiling point70 C.
Purity (according to GC): 97.3 /O Analysis of C6H,F,: Calculated: C47.76 H 3.92 F49.31% Found: 46.9 4.0 49.1 % 1H - NMR:
6.72 ppm (Ha, 2 doublets of quadruplets), 3J HaHb = 16.7 Hz,3JHaHc = 10.5 Hz,4JHaCH3 = 1.7 Hz; 5.45 ppm (Hb, doublet); 5.31 ppm (Hc, doublet); 1.83 ppm (CH3).
Differs from (A) only in the displacement of Ha (6.80 ppm) and CH3 (1.90 ppm), '9F- NMR: (A): 53.5 ppm (1 F); - 11.75 ppm (3 F),3JFF = 6.5 Hz.
(B): 50.7 ppm (1 F); - 12.2-m (3 F),3JFF = 8.8 Hz, 'JFCH3 = 1.1 Hz.
Ratio of A: B = 1:1.3.
(C=C) 1669cm-1 (strong), 1611 cm-' (medium).
Example 7 1- Fluoro - 1- pe,fluoroheptyl - 2 - methyl - 1,3 butadiene
50.8 g of C8F17 - C(CH3)=CH - CH2CI (0.1 mole) as reacted according to procedure described in Example 4 except that the reaction is allowed to continue for 2 hours at 100"C. 26.0 g of the compound C7F15- CF=C(CH3) - CH=CH2 having a boiling point of 76 to 77"C at 10 torr are obtained (57.2% yield).
Analysis of C,2H6F16: Calculated: C31.74 H 1.33 F66.93% Found: 31.7 1.4 66.7 % The 19F - NMR shows an isomer ratio of A:B = 1:9.
IR: (C=C) 1661 cm-' (medium), 1611 cm-' (weak).
Example 8 1- Fluoro - 1- trifluoromethyl - 4- phenyl - 1,3butadiene
67.6 g (0.25 mole) of C2Fs - CH=CH - CH(C6Hs)CI are reacted with Zn/Cu in a manner similar to that described in Example 4. Work-up is effected by centrifuging off the solid constituents after the reaction has been completed and distilling the liquid phase in vacuo.
41.0 g of the diene having a boiling point of 92"C at 10 torr are obtained (75.9 /O yield).
Analysis of C,1H8F4:
Calculated: C61.12 H3.73 F35.15%
Found: 61.2 3.8 35.0 % 1H - NMR: 7.20 ppm (5 H, aromatic), 6.89 to 5.68 ppm (3H, olefinic).
The main component
= isomer A has the following coupling constants: 3JHaF = 30.7
Hz, 3JHaHb = 10.5 HZt3JHbHC = 15.0 HZt4JHaHC = 0.8 Hz.
19F- NMR: IsomerA: 56.4 ppm (1 F), -6.5 ppm (3
F);
Isomer B: 51.2 ppm (1 F), -11.2 ppm (3 F).
(C=C) 1679 cm-' (very strong), 1624 cm-' (weak).
Example 9 1 -Fluoro - 1 -peffluoro-n -pentyl-4-phenyl- 1,3- butadiene
This diene is obtained by reacting 117.6 g of C8F,3 CH=CH - CH(C6Hs)CI (0.25 mole) with Zn/Cu according to the procedure described in Example 8 except that the reaction is allowed to continue for 2 hours at 100"C.
Yield: 81.0 g (77.9 /O) of a colourless oil having a boiling point of 96"C at 0.2 torr.
Analysis of C15H8F12: Calculated: C43.29 H 1.94 F 54.78% Found: 43.2 2.1 54.5 % '9F - NMR: shows an isomer ratio of A:B = 4:1.
IR: (C=C) 1672 cam~' (strong), cm-' (weak).
Production ofpolymers
Example 10
Poly- [CF3- CF=CH- CH=CH2] A mixture consisting of 5 g of 1 - fluoro - 1 - trifluoro - methyl - 1,3 - butadiene and 0.05 g of azo - bis - isobutyronitrile is maintained at 85"C for 50 hours in a sealed ampoule. As a result, there is obtained a product which melts at 162 C and undergoes thermal decomposition from 250"C and has elastomeric properties.
The'H - NMR spectrum in CD30H shows signals of olefinic protons (6.12 to 5.12 ppm) and saturated protons (2.97 to 2.27 ppm) in a ratio of 1:1.
Example 11
Poly- [CF3 - CF=C(CH - CH=CH2]
An ampoule containing a mixture of the monomer and 1% by weight of azo - bis - isobutyronitrile is heated first at 80"C for 10 hours and then at 90"C for a further 10 hours. A colourless, transparent and glass-hard polymer is obtained. Thermal behaviour:
The polymer becomes vitreous at 80"C, slowly turns brown from 165"C and begins to decompose noticeably at 220"C. Differential thermo-analysis shows decomposition beginning at 1900C and proceeding rapidly above 225"C.
A sample purified by dissolving in benzene and precipitating with methanol has the following proton magnetic resonance spectrum (in C6D6): 5.95 ppm (1 H); 3.28 ppm (1 H); 2.88 ppm (1
H) and 2.00 ppm (CH3).
IR-spectrum: (C=C) 1670 cm-l, (weak).
It can be seen from the spectra that the polymer is produced by head to tail addition of the monomer units and has substantially the following structure:
Example 12
Poly- [C7Frs- CF=C(CH - CH=CH2]
The monomer is polymerised in a manner similar to that described in Example 11. A solid, colourless product which softens from 1200C and decomposes at between 280 and 290 C is obtained. The proton magnetic resonance spectrum of this product is identical to that of the product of Example 11.
Claims (10)
1. Acompound of the formula
in which Rf is a perfluoroalkyl group having from 1 to 12 carbon atoms and each of R', R2, R3 and R4 is hydrogen, an alkyl group having from 1 to 10 carbon atoms, a cyclohexyl, phenyl, benzyl or naphthyl group or an alkylphenyl or alkylnaphthyl group in which the alkyl group has from 1 to 5 carbon atoms.
2. A compound according to claim 1, in which each of R', R2, R3 and R4 is hydrogen, an alkyl group having from 1 to 3 carbon atoms or a benzyl, tolyl, naphthyl or phenyl group.
3. A compound according to claim 1 which is specifically identifed herein.
4. A process for preparing a compound according to claim 1, which comprises reacting a compound of the formula R, - CF2 - CR'=CR2- CR3R4X in which Rf, R', R2, Ra and R4 have the meanings specified in claim 1 and X is chlorine, bromine or iodine, with at least the stiochiometric amount of a metallic halogen-acceptor in a polar, aprotic solvent at a temperature of from 40 to 1 500C.
5. A process'according to claim 4, wherein the metallic halogen-acceptor is an activated metal pair consisting of zinc and a metal which is more elec tropositive than zinc.
6. A process according to claim 5, wherein the activated metal pair consists of zinc and copper.
7. A process according to any one of claims 4 to 6, wherein the polar, aprotic solvent is dimethy.lfor- mamide, dimethyl sulphoxide, a dialkyl ether or a mixture of any two or more thereof.
8. A process according to claim 4, carried out substantially as described in any one of Examples 1 to 9 herein.
9. A compound according to claim 1, whenever prepared by a process according to any one of claims 4 to 8.
10. A polymer produced from a compound according to claim 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782835480 DE2835480A1 (en) | 1978-08-12 | 1978-08-12 | FLUORINE 1.3-DIENES, THEIR PRODUCTION AND THEIR USE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2028328A true GB2028328A (en) | 1980-03-05 |
| GB2028328B GB2028328B (en) | 1982-12-08 |
Family
ID=6046953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7927945A Expired GB2028328B (en) | 1978-08-12 | 1979-08-10 | Fluorine-containing 1,3-dienes process for their preparation and polymers thereof |
Country Status (4)
| Country | Link |
|---|---|
| DE (1) | DE2835480A1 (en) |
| FR (1) | FR2433008A1 (en) |
| GB (1) | GB2028328B (en) |
| IT (1) | IT1122484B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654448A (en) * | 1985-05-29 | 1987-03-31 | Ausimont S.P.A. | Process for the synthesis of hexafluorobutadiene and of higher perfluorinated dienes |
| US5082981A (en) * | 1986-11-27 | 1992-01-21 | Ausimont S.P.A. | Process for the synthesis of perfluoroalkandienes |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4210611A (en) * | 1978-05-25 | 1980-07-01 | Imperial Chemical Industries Limited | Halogenated hydrocarbons, useful as insecticide intermediates, and methods for their preparation |
-
1978
- 1978-08-12 DE DE19782835480 patent/DE2835480A1/en not_active Withdrawn
-
1979
- 1979-08-10 GB GB7927945A patent/GB2028328B/en not_active Expired
- 1979-08-10 IT IT25073/79A patent/IT1122484B/en active
- 1979-08-13 FR FR7920592A patent/FR2433008A1/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654448A (en) * | 1985-05-29 | 1987-03-31 | Ausimont S.P.A. | Process for the synthesis of hexafluorobutadiene and of higher perfluorinated dienes |
| US5082981A (en) * | 1986-11-27 | 1992-01-21 | Ausimont S.P.A. | Process for the synthesis of perfluoroalkandienes |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2028328B (en) | 1982-12-08 |
| FR2433008B1 (en) | 1984-02-10 |
| IT1122484B (en) | 1986-04-23 |
| DE2835480A1 (en) | 1980-02-28 |
| FR2433008A1 (en) | 1980-03-07 |
| IT7925073A0 (en) | 1979-08-10 |
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| PCNP | Patent ceased through non-payment of renewal fee |