US3843735A - 3-perfluoroalkyl-1 propenes and process for producing - Google Patents
3-perfluoroalkyl-1 propenes and process for producing Download PDFInfo
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- US3843735A US3843735A US00177091A US17709171A US3843735A US 3843735 A US3843735 A US 3843735A US 00177091 A US00177091 A US 00177091A US 17709171 A US17709171 A US 17709171A US 3843735 A US3843735 A US 3843735A
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- Prior art keywords
- percent
- perfluoroalkyl
- zinc
- allyl
- ether
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- 238000000034 method Methods 0.000 title claims description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 11
- 125000005010 perfluoroalkyl group Chemical group 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 14
- 239000011701 zinc Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 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 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 6
- -1 fluoroalkyl fumarates Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- LWJHSQQHGRQCKO-UHFFFAOYSA-N 1-prop-2-enoxypropane Chemical compound CCCOCC=C LWJHSQQHGRQCKO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001351 alkyl iodides Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- 238000007342 radical addition reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- AHUMDLIBMIYQMU-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-7-iodoheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I AHUMDLIBMIYQMU-UHFFFAOYSA-N 0.000 description 1
- BBZVTTKMXRPMHZ-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoro-2-iodopropane Chemical compound FC(F)(F)C(F)(I)C(F)(F)F BBZVTTKMXRPMHZ-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- NUPSHWCALHZGOV-UHFFFAOYSA-N acetic acid n-decyl ester Natural products CCCCCCCCCCOC(C)=O NUPSHWCALHZGOV-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- JDNTWHVOXJZDSN-UHFFFAOYSA-N iodoacetic acid Chemical compound OC(=O)CI JDNTWHVOXJZDSN-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
- C07C43/137—Saturated ethers containing hydroxy or O-metal groups containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
- C07C17/367—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms by depolymerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/12—Saturated ethers containing halogen
Definitions
- R is a long chain straight or branched perfluoroalkyl group of the formula C,,F where n is an integer from 3 to 14 and more preferably 6 to 12.
- the present compounds are useful intermediates for application in textile finishes.
- the 3-perfluoroalkyl-l-propenes of the present disclosure may be converted to fluoroalkyl fumarates which may be employed as textile finishes.
- the 3-perfluoroalkyl-l-propenes are formed by treatment of specific 3- perfluoroalkyl-Z-iodo-I-alkyl ethers or 3- point of economic consideration, R; desirably contains six to 12 carbon atoms.
- R groups-containing less than six carbon atoms do provide soil repellency in textile finishes. Nevertheless, due to industry standards of high repellency levels, an additional fluorine content is dea suitable R group contains seven carbon atoms.
- the present process is directed to the treatment of the disclosed 3-perfluoroalkyl-2-iodo-l alkyl ethers or esters with zinc to obtain terminal unsaturation rendering novelty to the present technique.
- a hydroxylic solvent may be employed in conjunction with the disclosed process.
- the present process employs the utilization of starting materials comprising fluorinated iodoalkyl ethers and esters with zinc.
- the fluorinated iodoalkyl compounds utilized in this technique are known in the art and may be prepared in accordance with Brace US. Pat. No. 3,145,222 and Brace, J. Org Chem. 27, 3033, (l962), namely: g
- R is a straight or branch chain perfluoroalkyl group containing three to 14 carbon atoms, and more desirably six to 12 carbon atoms.
- v The reaction to produce the 3-perfluoroalkyl-l propene is carried out in the presence of zinc. A hydroxylic solvent may be employed. Additionally a proton donor
- the Brace disclosure illustrates the principle that in reacting fluorinated iodoalkyl esters in the presence of zinc, reduction of the fluorinated alkyl iodide takes place, namely the replacement by iodine by hydrogen.
- the present invention employs starting compounds which are closely re- 7 lated to prior art starting compounds but forms a reactant product which is totally unexpected.
- R cH cH a cn cz ca omzn whereih Rji aiong chain perfluoroalkyl group either straight or branched chain of the formula C,,F where n is an integer from 3 to 14; R represents lower .alkyl containing one to four carbon atoms, lower acyl may be used in analogous fashion as prior art disclosures but a different result is obtained in the present use with the present selection of starting compounds. Suit- .239132 sa slaqsgssissss@QH.
- able solvents include methanol, isopropanol, cellosolves and ethylene glycol, etc.
- Proton donor systems if employed, can include hydrogen chloride, formic acid etc. and systems disclosed in the Haszeldine and Steele disclosures, supra.
- the addition of the acetate takes approximately 45 minutes.
- the reaction mixture is continuously stirred for an additional 2% hours and the temperature maintained at 60C. Thereafter the reaction mixture is cooled to room temperature, the unreacted zinc is filtered off and the product washed with 1500 ml. of water.
- the oily layer is dried over molecular sieve and then distilled through an 18 inch spinning band column; 19.6 grams of product boiling at 142l44C/760 mm. is obtained.
- EXAMPLE 8 Preparation of 4-'l"rifluoromethyl-4,5 ,5 ,S-tetrafluorol -pentene (CF11 from (CF CFCH CHlCH O CCH (30.0g, 0.0756 mole) was added slowly from a Varibor dropping funnel to a slurrly of zinc (10.0g, 0.153g-atom) in oxydiethanol (diethylene glycol, ml), while stirring by a magnet in a total reflux, partial take-off distilling apparatus connected to a Dry-Ice trap. The iodo acetate was.
- a Fischer Porter aerosol tube was charged with allyl benzoate (16.2 g, 0.100 mol), l-iodoperfluoroheptane (49.6 g, 0.100 mol, and azobisisobutyronitrile (0.328 g, 2.00 mmol). After the usual procedure the tube was heated at 70 for 12 hr, the reaction product (two layers) filtered through a sintered disc and distilled without a column, using a variable take-off head. C F, l (15.1 g, percent recovery) and allyl benzoate (1.7 g) were removed.
- the colorless clear mixture became cloudy. It was filtered through a sintered glass disc and distilled in column A. A mixture of C F, l and allyl propyl ether (657g, n D 1.3905), and C F, l (9.27g, n D 1.3300) were recovered; C F, CH Cl-llC1-l -OCl-l Cl-l Cl-l distilled, bp 81-83/0.85 mm, n D 1.3767, 42.65g (71.5 percent conversion). A residue of 1.0g remained. The trap contained 2.50g of starting materials (n D 1.3500).
- a process for the preparation of 3-perfluoroalkyl l-propene which comprises treating R CH CIIHCH OR I where Rf is CnF n is an integer from 3 to .14 and R is lower alkyl, lower carboxylac'yl, benzoyl or aryl, with zinc in the presence of an alkanol of one to three carbon atoms, a glycol of up to three carbon atoms, ethylene glycol or diethylene glycol.
- n is an integer from 6 to 12.
Abstract
This invention discloses the preparation of 3-perfluoroalkyl-1propenes with the perfluoroalkyl group containing three to fourteen carbon atoms. These compounds are formed by treatment of
D R A W I N G
D R A W I N G
Description
United States Patent 1191 Knell et al.
3-PERFLUOROALKYL-l PROPENES AND PROCESS FOR PRODUCING Inventors: Martin Knell, 4 Possum Rd.,
Ossining, NY. 10562; Neal 0. Brace, 1202 Howard Cle., Wheaton, 111. 60187 Filed: Sept. 1, 1971 Appl. No.: 177,091
U.S. Cl. 260/6533 Int. Cl. C07c 17/00, C070 21/18 Field of Search 260/6533 References Cited UNITED STATES PATENTS 3/1959 Miller 260/6533 1 51 Oct. 22, 1974 5 7 ABSTRACT This invention discloses the preparation of 3-perfluoroalkyl-l-propenes with the perfluoroalkyl group containing three to fourteen carbon atoms. These compounds are formed by treatment of with zinc wherein R, is perfluoroalkyl, and R is lower alkyl, acyl, benzoyl or aryl.
5 Claims, No Drawings g the formula:
4 wherein R; is a long chain straight or branched perfluoroalkyl group of the formula C,,F where n is an integer from 3 to 14 and more preferably 6 to 12. There compounds are disclosed in Anello et al U.S. Pat. No. 3,576,858 issued Apr. 27, 1 971.
The present compounds are useful intermediates for application in textile finishes. lllustratively, the 3-perfluoroalkyl-l-propenes of the present disclosure may be converted to fluoroalkyl fumarates which may be employed as textile finishes. Reference is made to E. K. Kleiner and M. Knell, US. Pat. application Ser. No. 720,370 filed Apr. 10, 1968 for employment of the fluoroalkyl fumarates as soil repellents.
In the technique of this disclosure, the 3-perfluoroalkyl-l-propenes are formed by treatment of specific 3- perfluoroalkyl-Z-iodo-I-alkyl ethers or 3- point of economic consideration, R; desirably contains six to 12 carbon atoms. R, groups-containing less than six carbon atoms do provide soil repellency in textile finishes. Nevertheless, due to industry standards of high repellency levels, an additional fluorine content is dea suitable R group contains seven carbon atoms.
Pstflyorqsllsx ii dq-llallsy rs .W FPll QW 7 sults in terminal unsaturation. In contrast, the prior art teaches the treatment of closely related fluorinated iodoalkanes with zinc-results in a different reaction,
namely replacement of the iodine atom by hydrogen (Haszeldine and Steele, J. Chem, Inc. 1953, I 199; Haszeldine and Steele, J. Chem, lnc. I953, 1592.)
CHCH OR The present process is directed to the treatment of the disclosed 3-perfluoroalkyl-2-iodo-l alkyl ethers or esters with zinc to obtain terminal unsaturation rendering novelty to the present technique. A hydroxylic solvent may be employed in conjunction with the disclosed process.
DESCRIPTION OF THE INVENTION The present process employs the utilization of starting materials comprising fluorinated iodoalkyl ethers and esters with zinc. The fluorinated iodoalkyl compounds utilized in this technique are known in the art and may be prepared in accordance with Brace US. Pat. No. 3,145,222 and Brace, J. Org Chem. 27, 3033, (l962), namely: g
peroxide I t catalyst R Cf t -lCi-i OR In the present disclosure R; is a straight or branch chain perfluoroalkyl group containing three to 14 carbon atoms, and more desirably six to 12 carbon atoms. v The reaction to produce the 3-perfluoroalkyl-l propene is carried out in the presence of zinc. A hydroxylic solvent may be employed. Additionally a proton donor The Brace disclosure illustrates the principle that in reacting fluorinated iodoalkyl esters in the presence of zinc, reduction of the fluorinated alkyl iodide takes place, namely the replacement by iodine by hydrogen.
In contrast to known teachings utilizing fluorinated alkyl iodide constituents and zinc, the present invention employs starting compounds which are closely re- 7 lated to prior art starting compounds but forms a reactant product which is totally unexpected.
SUMMARY OF THE INVENTION The present process may be summarized by the following equation:
R cH cH a cn cz ca omzn whereih Rji aiong chain perfluoroalkyl group either straight or branched chain of the formula C,,F where n is an integer from 3 to 14; R represents lower .alkyl containing one to four carbon atoms, lower acyl may be used in analogous fashion as prior art disclosures but a different result is obtained in the present use with the present selection of starting compounds. Suit- .239132 sa slaqsgssissss@QH.
able solvents include methanol, isopropanol, cellosolves and ethylene glycol, etc. Proton donor systems, if employed, can include hydrogen chloride, formic acid etc. and systems disclosed in the Haszeldine and Steele disclosures, supra.
In the reaction to form the 3-perfluoroalkyl-lpropenes utilizing the starting compounds defined herein, namely and zinc, it is not directly understood why replacement of the iodine with hydrogen does not take place under CH +Zn 05 r similar reaction conditions as the prior art employing closely related fluorinated iodoalkanes. Nevertheless, in spite of the prior art indication and illustration of the replacement of iodine by hydrogen in the presence of present invention the following examples are provided:
- EXAMPLE 1 i l ,1 ,2,3,3-pentahydro-Z-iodoperfluorol -decyl acetate 19.0 Grams of zinc dust and 20 ml. of anhydrous ethanol are added to a 500 ml. flask and stirred rapidly while ml. of 36 percent hydrochloric acid are added. The reaction mixture is heated to 60C and 50.0 grams of 1 ,1 ,2,3 ,3pentahydro-Z-iodoperfluoro- 1 decyl acetate (prepared according to method of Brace, J. Org Chem. 27, 3033 (1962)) is added with 100 ml. of anhydrous ethanol. The addition of the acetate takes approximately 45 minutes. The reaction mixture is continuously stirred for an additional 2% hours and the temperature maintained at 60C. Thereafter the reaction mixture is cooled to room temperature, the unreacted zinc is filtered off and the product washed with 1500 ml. of water. The oily layer is dried over molecular sieve and then distilled through an 18 inch spinning band column; 19.6 grams of product boiling at 142l44C/760 mm. is obtained.
Preparation of ,3,3-pentahydroperfluoro-l-decene from ,3,3-pentahydro-2-iodoperfluoro-1decyl hydroxyethyl ether A slurry of 8.0 grams (.122 mole) of zinc dust in 80 ml. of acetic acid and 55 ml. of ether is heated to reflux with stirring and a solution of 50.0 grams (0.083 mole) of 1,1,2,3,3pentahydro-2iodoperfluoro-l-decyl hydroxyethyl ether (prepared from perfluoroheptyl iodide and allyl hydroxyethyl ether according to the method of Brace. J. Org Chem. 27,3033 (1962)) in 25 ml. of ether is added dropwise. Reflux with stirring is continued for about 12 hours. The clear colorless solution is then separated from the unreacted zinc; water and sodium bicarbonate is added to neutralize the acetic acid. The ether solution is dried over anhydrous magnesium sulfate and the ether removed with the aid of a water pump. The residue is then fractionally distilled through a short Vigreux column. The first fraction, boiling at 4647.5 at 16 mm. pressure, weighs 22.3 grams and is shown to be 1,l,2,3,3- pentahydroperfluoro- 1 decene.
EXAMPLE 3 Preparation of Bis( 1,1,2,2,3,3-hexahydroperfluoro-l-decyl) F umarate a) 1,1,2,2,3.3-Hexahydroperfluoro-l-Bromodecane 15.6 Grams of 1,1,2,3,3-pentahydroperfluoro-ldecene are added to a quartz glass Fischer Porter tube and brought to boiling to remove any possible trapped air. It is then closed off, cooled to the temperature of liquid nitrogen and 7.0 grams of dry hydrogen bromide added. The reaction mixture is allowed to warm to room temperature and it is then placed centimeters from a 250 watt UV light source for 4% hours. The excess hydrogen bromide is permitted to escape and the product is then washed with 50 ml. of water to remove any trapped hydrogen bromide. It is then washed with 25 ml. of a 10 percent solution of sodium thiosulfate and dried over molecular sieve. Distillation yields 16.8 grams of product boiling mainly at 9596C./24 mm.
Analysis for C H BrF C H Br F Calc.: 24.46; 1.23; 16.27; 58.04 Found: 24.31; 1.27; 17.50; 511.10
, EXAMPLE 4'" b) Bis( l ,1 ,2,2,3,3-l-1exahydroperfluorol decyl) Fumarate Analysis for C H F O H F Calc.: 30.78; 1.51; 60.87 Found: 31.08; 1.62; 60.83
EXAMPLE 5 Preparation of l,1,2,3,3 pentahydro-2-iodo-perfluoro- 1 decylphenyl ether (C 11 OCH CH1CH C F Allyl phenyl ether (Aldrich, 13.4g, 0.100 mol), liodoperfluoroheptane (redistilled, bp /70 mm, r1 D 1.3286; 49.6g, 0.100 mol) and azobisisobutyronitrile (0.456g, 0.00278 mol) were charged to a Fischer Porter aerosol tube, cooled to 78, evacuated and filled three times with nitrogen, sealed and heated at 700 for 21 hr. An orange, cloudy mixture formed, which was cooled to 20, filtered through a sintered disc into a distillation flask (62.5g) and distilled in a two-foot platinum spinning band column (Column A). liodoperfluoroheptane (bp 36/l0 mm, n D 1.3308, 21.5g), allyl phenyl ether (bp 3910.20 mm, n D 1.5184, 4.72g) and the adduct (C H OCH CHICH C F bp 96-99/0.14 mm, n D 1.4245, 29.55g), a residual brown oil (4.0g) and trap liquid (2.0g, n 1.3794, mostly C F 1) were obtained. The yield of the adduct was 89 percent, and conversion was 47 percent based on recovered starting materials.
Analysis for C..,H,,,F,,10;
Ca1c.: C. 30.4);
EXAMPLE 6 Preparation of l .1 .2,3 .3-pentahydro-perfluorol -decene from Zinc powder (9.2g, 0.14 mol, 60-200 mesh size), was added to a solution of 50 ml of ethanol and ml of 36 percent hydrochloric acid in a 500 ml r.b. flask. fitted with a paddle stirrer, refluxcondenser and dropping funnel, and heated to 60. A solution of C H OCH CHICH C F, (28.5g, 0.0470 mol) in ethanol (50 ml) was added during l hr at 60-70 while stirring. A gray cloudy slurry formed with an exothermic reaction. Stirring was continued for 2.0 hr at 70 ;.5 ml of 36 percent HCl was added, and stirred for 2.5 hr at 70. The reaction mixture had separated into 2 layers. To the cooled reaction mixture, decanted from zinc, was added 200 ml of water, and the lower layer removed (17.1g, 88
percent crude yield). The aqueous layer was extracted Analysis for C H Fm Cale: c, 29.35; H, 1.12; F, 60.49 Found: c, 29.52; H, 1.32; F 67.93
EXAMPLE 7 Preparation of t mcthikfisiitetteflustt kpe y acetate (cFabcFCl-lzCl-llCH O Ccl-w 2-Iodoperfluoropropane (29.6g, 0.100 mol), allyl acetate (10.0g, 0.100 mol) and azobisisobutyronitrile (0.328g, 2.00 mmol) were charged to a Fischer Porter aerosol tube; after the usual procedure, the tube was heated at 700 for hr. Distillation in Column A gave (CF CFCH -CHlCH O CClbp 70/4.3 mm, n D 1.4069, 34.60g (in 3 cuts); an impure higher boiling mixture, bp 72-69/0.15 mm, n D 1.4292, 1.05g, and a residue, 0.5g. The 78 trap contained two layers (5.0g), recovered (CF CFl and allyl acetate. The conversion to product was 87.5 percent.
Analysis 1111 C,H,F,10, Cale; C. 24.26: Found: C, 24.09;
EXAMPLE 8 Preparation of 4-'l"rifluoromethyl-4,5 ,5 ,S-tetrafluorol -pentene (CF11 from (CF CFCH CHlCH O CCH (30.0g, 0.0756 mole) was added slowly from a Varibor dropping funnel to a slurrly of zinc (10.0g, 0.153g-atom) in oxydiethanol (diethylene glycol, ml), while stirring by a magnet in a total reflux, partial take-off distilling apparatus connected to a Dry-Ice trap. The iodo acetate was.
v p.p.m. from tetramethyl silane as a doublet of doublets;
and for CH=CH at 5.05 to 6.25 p.p.m., as a multiplet. These data were consistent for (C .3)2CFCH CH=CH Analysis for C,,H,,F,:
Culc.: C, 34.30;
H, 2.40 Found: C, 30.76; H, 2.20
The volatility of the sample caused elemental analysis to be inaccurate.
EXAMPLE 9 Free Radical Addition of R,l (R C C C to Allyl Acetate; Preparation of 2-iodo-3-perfluoroalkyll-propyl acetate (R,CH CHICH O CCH Perfluoroalkyl iodide mixture was fractionally distilled and a solid residue was obtained having the composition by glpc analysis: R11, R C F I, 11.5 percent; C, F l, 83.8 percent and C F I, 2.3 percent. There were several unknown substances present 7 in small amount. This material was used in the following preparation. R,l (64.6g, ca. 0.100 mol) and benzoyl peroxide (0.484g, 2.00 mmol)were placed in a ml r.b. flask fitted with a nitrogen inlet, reflux condenser, Varibor dropping funnel, and stirred by a magnet while heated in an oil bath. Allyl acetate (100g, 0.100 mol) was added dropwise during 35 min at 97-102 (inside), cooling as necessary to maintain reaction temperature at 100 fl. Heating in the bath at 100 was continued for 3 hr, and allowed to stand overnight. A solid mass of crystals formed, which would not distill 'at 100 (12 mm pressure); m.p. (sinter 54) 56-59; ir showed 7C=O 1750 cm, heavy 'yCF and other bands antici pated for the adduct R,CH CHlCl-l O CCH A 5.0g portion of the product was recrystallized from ca. 50 ml of ligroine (6090 bp). Fractions collected were: (1 1.8g, mp 63-64; (2) 2.5g (after chilling, and evaporation), mp 63-64; (3) 0.9g, mp 55"-58; (4) 0.8g, soft solid. VPC analysis of the mixture showed R CHgCHlCHzOzCCHgRFCgFm, percent; CgFn, 12.6 percent and C F- 76.6 percent. After recrystallization R C,, F 4.8 percent; C F 83.0 percent. An nmr spectrum agreed with structure.
EXAMPLE Preparation of l,1,2,3,3-pentahydro-perfluoro-l-tridecene (C F CH CH=CH from 2-iodo-3-(pe'rfluorodecyl)- l-propyl acetate The crude adduct (R,CH CHICH O CCH mp 5659, 37.3g, 0.0500 mol) was dissolved in 80 ml of hot ethanol, and added during 25 min at 76-78 to a slurry of zinc dust (9.8g, 0.15 g-atom), ethanol ml) and 36 percent hydrochloric acid (5m1). There was some exothermic reaction. After 1 hr further at 78 the two layers which had formed were poured into water (100 ml) and extracted with dichloromethane (100 ml). Three layers now formed. The lowest layer was removed (14.6g), which solidified at room temperature; mp ca. 30. It was distilled under reduced pressure in a variable take off still without a column; bp 8599/9.0 mm, n D 1.3100, 8.5g. Solid formed in the still head (1.0g recovered), and remained in the pot flask (235g). The dichloromethane extract was washed further with dilute sodium sulfite solution, dried over MgSO, and distilled. Product, bp 8893/9.0 mm, n D 1.3135, 5.2g was again obtained. (Total yield of distilled product 55 percent),A residue of 3.2g solid remained. An NMR spectrum agreed with structure, R,CH CH==H Addition of C F 1 to Allyl Benzoate; 1,1 ,2,3,3-penta-hydro-2-iodo-perfluorol -decyl benzoate (C7F15CH2CHICH202CC6H5) Allyl benzoate was prepared from allyl alcohol and benzoyl chloride, bp 102104/13 mm, n 'D 1.5165 lit.*, bp 106/l2 mm, n D 1.5174. A Fischer Porter aerosol tube was charged with allyl benzoate (16.2 g, 0.100 mol), l-iodoperfluoroheptane (49.6 g, 0.100 mol, and azobisisobutyronitrile (0.328 g, 2.00 mmol). After the usual procedure the tube was heated at 70 for 12 hr, the reaction product (two layers) filtered through a sintered disc and distilled without a column, using a variable take-off head. C F, l (15.1 g, percent recovery) and allyl benzoate (1.7 g) were removed. The residue was placed on column A and more allyl benzoate (1.7 g, total 21 percent recovery), C,F, CH CH1CH O C H bp 104-107/0.30 mm, n D 1.4290, and bp 11 l-1 12/0.25 mm, n -"D 1.4286, 49.96 g (76 percent conversion, 96 percent yield, based on recovered allyl benzoate), and a residual oil (6.8 g) were obtained, The product turned solid when cooled to 10.
Hurd and Filuchionc. J. Am. Chem. 500.. 61, 1156 (1939); Tommilu. Ann. Acad. Sui.. Fcnn., [A], 59, No. 3, 7 (1942); Bcilstein, Vol 1X, Elll. p. 402.
EXAMPLE 12 Preparation of 1,1,2,3,3-pentahydroperfluorol -decene from C7F15CH2CHICH2O2CC6H5 Using a procedure similar to that for (CF C FCH CH'-=CH a slurry of zinc dust (9.2 g, 0.14 g-atom) and 2,2-oxydiethanol (20 ml) washeat d to 1 15" -122 (inside) while C F, CH CHICH O CC H (35.0 g, 0.053 mol) was added during a half hr. After the first 15 min, a water pump was attached to reduce the pressure; C F CH CH=CH distilled, bp 86-88/1 10 mm, n D 1.3076, 18.5 g. After all the olefin was obtained the pressure was reduced further during 20 min to strip any remaining product from the pot liquid. The final pot temperature was 138 at 10 mm pressure. The cold trap contained 1.4 g; total 19.9 g (91.5 percent yield). The product was dried over a little Drierite. A check by glpc (6 ft Carbowax 20M, 10 percent on Chromosorb W, at 68 and 15 psi helium pressure) showed one peak at 1.2 minutes. An infrared spectrum was identical to that of C F, Cl-l Cl-l=Cl-l previously prepared.
EXAMPLE 13 Free Radical Addition of l-lodoperfluoroheptane to Allyl Propyl Ether; Propyl 2-1odo-l,1,2,3,3-pentahydro-perfluoro-l-decyl Ether (C F, CH CHICH OCH CH CH l-Iodoperfluoroheptane (49.6g, 0.100 mole), allyl propyl ether (15.0g, 0.l50 mole, Chem Samples Co., 97 percent) and azobisisobutyronitrile (0.328g, 2.00 mmole) were charged to a Fischer-Porter aerosol tube. After the usual procedure the tube was heated for 12 hrs. at 70. The colorless clear mixture became cloudy. It was filtered through a sintered glass disc and distilled in column A. A mixture of C F, l and allyl propyl ether (657g, n D 1.3905), and C F, l (9.27g, n D 1.3300) were recovered; C F, CH Cl-llC1-l -OCl-l Cl-l Cl-l distilled, bp 81-83/0.85 mm, n D 1.3767, 42.65g (71.5 percent conversion). A residue of 1.0g remained. The trap contained 2.50g of starting materials (n D 1.3500).
Analysis for C H F OI: V
Calc.: C. 26.19; H, 2.03; F, 47.81; 1, 21.29 Found: C, 26.50; H. 2.10; F, 47.08; 1, 21.31
EXAMPLE 14 hour under 60 mm pressure. The distillate consisted of two layers (19.4g); the -78 trap liquid (2.86g) also formed two layers. After drying over MgSO distillation in column A gave the following: l, bp 44/6O mm, (n 'D not taken), 1.40, 2 layers; 11, bp 68-73 /60 mm, n D 1.3143, 0.40 g; 111, bp 73-74/60 mm, n 'D 1.3084, 4.20g,C F, CH C1-1=CH 1V,bp 74/60 mm to 56/21 mm, n D 1.3070, 4.24g, C F,,,CH CH=CH V,
bp 94/21 mm, n D 1.3155; 080g; V1, bp 94/21 mm.
to 87/6 mm, n D 1.3361, 0.95 g; and VII, bp 85/l.1 mm, n D 1.3694, 3.75g, recovered C F CH CHlCH- O(Cl-l CH There was no residue. The infrared spectrum of fraction V11 was identical to that of the starting material. The retention time of the peak in glpc analyses of fractions 111 and IV was identical to that of C F CH CH=CH previously prepared. The conversion to C F, CH CH=CH was 34 percent; the recovery of starting material was 12 percent. Undoubtedly more starting material remained in the reaction mixture which could have been recovered. Nevertheless, reaction of this ether appeared, to be more sluggish than that of the benzoate or acetate esters.
What is claimed is: 1. A process for the preparation of 3-perfluoroalkyl l-propene which comprises treating R CH CIIHCH OR I where Rf is CnF n is an integer from 3 to .14 and R is lower alkyl, lower carboxylac'yl, benzoyl or aryl, with zinc in the presence of an alkanol of one to three carbon atoms, a glycol of up to three carbon atoms, ethylene glycol or diethylene glycol.
2. The process of claim 1 wherein n is an integer from 6 to 12.
3. The process of claim 1 wherein R is lower alkyl.
4. The process of claim 1 wherein R is lower carboxylacyl.
5. The process of claim 1 wherein the reaction is effec'ted in the presence of an acid.
I A'IRS lA'lIJNl OFFICE cma l u lcATls 01 CORRECTION Patent: No. 3,8 8,735 Dated October" 2, 97
Inventor) MARTIN KN'ELL ET AL It: is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
In column 10, 1, lines 12 and 13, after the phrase "three cerbon atoms, delete "a glycol of up to three carbon atoms, ethylene glycol or diethylene glycol" and insert therefor ethylerle glycol or diethylene glycol at a temperature of 60C to the reflux temperature of th e system Signed and sealed this 31st da y-of December 1974.
(SEAL) Attest:v
I IcCOY M. GIBSON JR. c. :mesmu mm? Attesting Officer Commissioner of Patents
Claims (5)
1. A PROCESS FOR THE PREPARATION OF 3-PERFLUOROALKYL-1PROPENE WHICH COMPRISES TREATING
2. The process of claim 1 wherein n is an integer from 6 to 12.
3. The process of claim 1 wherein R is lower alkyl.
4. The process of claim 1 wherein R is lower carboxylacyl.
5. The process of claim 1 wherein the reaction is effected in the presence of an acid.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE788214D BE788214A (en) | 1971-09-01 | PROCESS FOR THE PRODUCTION OF 3-PERFLUOROALKYL-1-PROPENES | |
US00177091A US3843735A (en) | 1971-09-01 | 1971-09-01 | 3-perfluoroalkyl-1 propenes and process for producing |
GB3547772A GB1377235A (en) | 1971-09-01 | 1972-07-28 | Process for producing 3-perfluoroalkyl-1-propenes |
JP47083384A JPS4834805A (en) | 1971-09-01 | 1972-08-22 | |
DE2241252A DE2241252A1 (en) | 1971-09-01 | 1972-08-22 | PROCESS FOR THE PRODUCTION OF 3-PERFLUORALKYL-1-PROPENENE |
CH1268672A CH570949A5 (en) | 1971-09-01 | 1972-08-28 | |
FR7230560A FR2150915A1 (en) | 1971-09-01 | 1972-08-28 | |
IT52426/72A IT962277B (en) | 1971-09-01 | 1972-08-30 | PROCEDURE FOR THE PRODUCTION OF 3 PERFLUORO ALCYL I PROPENI |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00177091A US3843735A (en) | 1971-09-01 | 1971-09-01 | 3-perfluoroalkyl-1 propenes and process for producing |
Publications (1)
Publication Number | Publication Date |
---|---|
US3843735A true US3843735A (en) | 1974-10-22 |
Family
ID=22647155
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00177091A Expired - Lifetime US3843735A (en) | 1971-09-01 | 1971-09-01 | 3-perfluoroalkyl-1 propenes and process for producing |
Country Status (8)
Country | Link |
---|---|
US (1) | US3843735A (en) |
JP (1) | JPS4834805A (en) |
BE (1) | BE788214A (en) |
CH (1) | CH570949A5 (en) |
DE (1) | DE2241252A1 (en) |
FR (1) | FR2150915A1 (en) |
GB (1) | GB1377235A (en) |
IT (1) | IT962277B (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4900874A (en) * | 1988-02-12 | 1990-02-13 | Daikin Industries, Ltd. | Method for producing fluorine-containing olefin |
WO2005074639A3 (en) * | 2004-01-30 | 2005-12-08 | Pcbu Services Inc | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
WO2005074593A3 (en) * | 2004-01-30 | 2006-03-16 | Pcbu Services Inc | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
WO2005074594A3 (en) * | 2004-01-30 | 2006-03-30 | Pcbu Services Inc | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
KR100945557B1 (en) | 2008-04-28 | 2010-03-08 | 나노크리스탈주식회사 | Method of preparing Perfluoro-alkyl modified alkylalkoxysilane |
WO2011085058A1 (en) | 2010-01-06 | 2011-07-14 | Nature Works Llc | Polylactide molding compositions and molding process |
US8318656B2 (en) | 2007-07-03 | 2012-11-27 | E. I. Du Pont De Nemours And Company | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
WO2017189452A1 (en) | 2016-04-28 | 2017-11-02 | Natureworks Llc | Polymer foam insulation structures having a facing layer of a polylactide resin |
WO2017189453A1 (en) | 2016-04-28 | 2017-11-02 | Natureworks Llc | Polymer foam insulation structure having a facing of a multi-layer sheet that contains a heat resistant polymer layer and a polylactide resin layer |
-
0
- BE BE788214D patent/BE788214A/en unknown
-
1971
- 1971-09-01 US US00177091A patent/US3843735A/en not_active Expired - Lifetime
-
1972
- 1972-07-28 GB GB3547772A patent/GB1377235A/en not_active Expired
- 1972-08-22 JP JP47083384A patent/JPS4834805A/ja active Pending
- 1972-08-22 DE DE2241252A patent/DE2241252A1/en active Pending
- 1972-08-28 CH CH1268672A patent/CH570949A5/xx not_active IP Right Cessation
- 1972-08-28 FR FR7230560A patent/FR2150915A1/fr not_active Withdrawn
- 1972-08-30 IT IT52426/72A patent/IT962277B/en active
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4900874A (en) * | 1988-02-12 | 1990-02-13 | Daikin Industries, Ltd. | Method for producing fluorine-containing olefin |
WO2005074639A3 (en) * | 2004-01-30 | 2005-12-08 | Pcbu Services Inc | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
WO2005074593A3 (en) * | 2004-01-30 | 2006-03-16 | Pcbu Services Inc | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
WO2005074594A3 (en) * | 2004-01-30 | 2006-03-30 | Pcbu Services Inc | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
US20080009655A1 (en) * | 2004-01-30 | 2008-01-10 | Janet Boggs | Production Processes and Systems, Compositions, Surfactants, Monomer Units, Metal Complexes, Phosphate Esters, Glycols, Aqueous Film Forming Foams, and Foam Stabilizers |
US7943567B2 (en) | 2004-01-30 | 2011-05-17 | E.I. Du Pont De Nemours And Company | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
US8318656B2 (en) | 2007-07-03 | 2012-11-27 | E. I. Du Pont De Nemours And Company | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
KR100945557B1 (en) | 2008-04-28 | 2010-03-08 | 나노크리스탈주식회사 | Method of preparing Perfluoro-alkyl modified alkylalkoxysilane |
WO2011085058A1 (en) | 2010-01-06 | 2011-07-14 | Nature Works Llc | Polylactide molding compositions and molding process |
WO2017189452A1 (en) | 2016-04-28 | 2017-11-02 | Natureworks Llc | Polymer foam insulation structures having a facing layer of a polylactide resin |
WO2017189453A1 (en) | 2016-04-28 | 2017-11-02 | Natureworks Llc | Polymer foam insulation structure having a facing of a multi-layer sheet that contains a heat resistant polymer layer and a polylactide resin layer |
Also Published As
Publication number | Publication date |
---|---|
IT962277B (en) | 1973-12-20 |
FR2150915A1 (en) | 1973-04-13 |
BE788214A (en) | 1973-02-28 |
JPS4834805A (en) | 1973-05-22 |
GB1377235A (en) | 1974-12-11 |
DE2241252A1 (en) | 1973-03-08 |
CH570949A5 (en) | 1975-12-31 |
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