JPH01216946A - Production of alpha,omega-diiodoopolyfluoroalkane - Google Patents
Production of alpha,omega-diiodoopolyfluoroalkaneInfo
- Publication number
- JPH01216946A JPH01216946A JP3952488A JP3952488A JPH01216946A JP H01216946 A JPH01216946 A JP H01216946A JP 3952488 A JP3952488 A JP 3952488A JP 3952488 A JP3952488 A JP 3952488A JP H01216946 A JPH01216946 A JP H01216946A
- Authority
- JP
- Japan
- Prior art keywords
- group
- omega
- alpha
- formula
- short
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- IGGDHHHKQANRAY-UHFFFAOYSA-N 3,3,4,4,5,5,6,6-octafluoro-1,8-diiodooctane Chemical compound ICCC(F)(F)C(F)(F)C(F)(F)C(F)(F)CCI IGGDHHHKQANRAY-UHFFFAOYSA-N 0.000 abstract 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- -1 pentafluorobenzyl group Chemical group 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- KAVGMUDTWQVPDF-UHFFFAOYSA-N perflubutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)F KAVGMUDTWQVPDF-UHFFFAOYSA-N 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 229950003332 perflubutane Drugs 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 108700041286 delta Proteins 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Chemical class 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical class [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Chemical class 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- UBKCMQCDHVYUAF-UHFFFAOYSA-N (2,2-dichloro-3-diphenylphosphanylpropyl)-diphenylphosphane Chemical compound ClC(CP(C1=CC=CC=C1)C1=CC=CC=C1)(CP(C1=CC=CC=C1)C1=CC=CC=C1)Cl UBKCMQCDHVYUAF-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- LSMWOQFDLBIYPM-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-2h-imidazol-1-ium-2-ide Chemical compound CC1=CC(C)=CC(C)=C1N1[C-]=[N+](C=2C(=CC(C)=CC=2C)C)CC1 LSMWOQFDLBIYPM-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZMYDAPJHGNEFGQ-UHFFFAOYSA-N 6-(2-fluorophenyl)-5h-[1,3]dioxolo[4,5-g]quinolin-8-one Chemical compound FC1=CC=CC=C1C(NC1=C2)=CC(=O)C1=CC1=C2OCO1 ZMYDAPJHGNEFGQ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YWHYLYDGWQNMND-UHFFFAOYSA-N [Rh].C=1C=CC=CC=1P(C=1C=CC=CC=1)(Cl)(C=1C=CC=CC=1)C(=O)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [Rh].C=1C=CC=CC=1P(C=1C=CC=CC=1)(Cl)(C=1C=CC=CC=1)C(=O)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 YWHYLYDGWQNMND-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- VSPLSJCNZPDHCN-UHFFFAOYSA-M carbon monoxide;iridium;triphenylphosphane;chloride Chemical compound [Cl-].[Ir].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VSPLSJCNZPDHCN-UHFFFAOYSA-M 0.000 description 1
- VUBLMKVEIPBYME-UHFFFAOYSA-N carbon monoxide;osmium Chemical group [Os].[Os].[Os].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] VUBLMKVEIPBYME-UHFFFAOYSA-N 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- USVZFSNDGFNNJT-UHFFFAOYSA-N cyclopenta-1,4-dien-1-yl(diphenyl)phosphane (2,3-dichlorocyclopenta-1,4-dien-1-yl)-diphenylphosphane iron(2+) Chemical compound [Fe++].c1cc[c-](c1)P(c1ccccc1)c1ccccc1.Clc1c(cc[c-]1Cl)P(c1ccccc1)c1ccccc1 USVZFSNDGFNNJT-UHFFFAOYSA-N 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
- 150000001993 dienes Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- JEWCZPTVOYXPGG-UHFFFAOYSA-N ethenyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)C=C JEWCZPTVOYXPGG-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940087654 iron carbonyl Drugs 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical class [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- XAFJSPPHVXDRIE-UHFFFAOYSA-L platinum(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Pt+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XAFJSPPHVXDRIE-UHFFFAOYSA-L 0.000 description 1
- SYKXNRFLNZUGAJ-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SYKXNRFLNZUGAJ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical class [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は含フツ素ポリマー原料として有用な下記−数式
（ＩＩ）で表わされるα、ω−ジョートポリフルオロア
ルカンの製造方法に関する。α、ω−ジョードポリフル
オロアルカンを塩基と作用させて得られるジオレフィン
は耐熱性、耐酸化性にすぐれた含フツ素シリコーンポリ
マー原料となることが報告されている＊ （０，Ｒ，
Ｒｌｅｒｃｅａｎｄ Ｙ、に、Ｋｉｍ、Ａｐｐｌ ｉ
ｓｄＰｏｌｙｍｅｒ Ｓｙｍｐｏｓｉｕｍ Ｎｏ２
２゜１０３ （１９７３）、）。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an α,ω-jotopolyfluoroalkane represented by the following formula (II), which is useful as a raw material for a fluorine-containing polymer. It has been reported that diolefin obtained by reacting α,ω-jodo polyfluoroalkane with a base can be used as a raw material for fluorine-containing silicone polymers with excellent heat resistance and oxidation resistance* (0, R,
Rlerceand Y, Kim, Appli
sdPolymer Symposium No2
2゜103 (1973), ).
Ｃ従来の技術〕
従来、このよなα、ω−ジョートポリフルオロアルカン
を合成するには、α、ω−ジョートポリフルオロアルカ
ンとエチレンを２００℃以上で加熱する方法（１，Ｌ、
Ｋｎｕｎｙａｎｔｓら、Ｉｚｙ、Ａｋａｄ、Ｎａｎｋ
υＳＳＲ，Ｓｅｒ。C. Prior Art] Conventionally, in order to synthesize such α,ω-jotopolyfluoroalkane, a method (1,L,
Knunyants et al., Izy, Akad, Nank
υSSR, Ser.
Ｋｈｌｍ、３８４ （１９６４）及び Ｎ、Ｏ，Ｂｒａｃｅ、Ｕ、Ｓ、Ｐａｔｅｎｔ。Khlm, 384 (1964) and N, O, Brace, U, S, Patent.
３．０１６，４０７ （１９６２））のみが公知である
。この方法は１５０℃では全く反応が進行しないと明記
されており極めて高温を必要とし、従って極高圧の反応
装置を必要とするなど反応操作の観点から工業的に採用
し難い。3.016, 407 (1962)) is known. This method specifies that the reaction does not proceed at all at 150° C., and therefore requires extremely high temperatures and therefore requires an extremely high pressure reactor, making it difficult to adopt industrially from the viewpoint of reaction operation.
一方、”？−Ｆペルフルオロアルカンとオレフィンの反
応においては同様な付加反応が上記のような熱的な方法
だけでなく、先約条件やラジカル開始剤で進行すること
が公知であるＣＭ。On the other hand, in the reaction of "?-F perfluoroalkane and olefin, it is known that a similar addition reaction proceeds not only by the above-mentioned thermal method but also by prior conditions or a radical initiator.
Ｈｕｄｌｉｃｋｙ、Ｃｈａｍｌｓｔｒｙ ｏｆＯｒｇ
ａｎｉｃ Ｆｌｕｏｒｉｎ。Hudlicky, Chamlstry of Org
Anic Fluorin.
Ｃｏｍｐｏｕｎｄｓ Ｔｈｅ Ｍａｃｍｉｌｌ
ａｎＣｏｍｐａｎｙ）。Compounds The Macmill
anCompany).
しかしながら、Ｏ，Ｒ，Ｐｉｅｒｃｅらによればα、ω
−ジコードベルフルオロアルカンの場合には、ラジカル
開始剤では反応が全く進行しないと記載され°ζいる。However, according to O. R. Pierce et al., α, ω
- In the case of dicode perfluoroalkane, it is stated that the reaction does not proceed at all with a radical initiator.
（Ａｐｐｌｉｅｄ
Ｐｏｌｙｍｅｒ Ｓｙｍｐｏｓｉｕｍ、Ｎｏ２２゜１
０３ （１９７３）、）。(Applied Polymer Symposium, No. 22゜1
03 (1973), ).
本発明はα、ω−ジョートポリフルオロアルカンを簡便
、安全かつ有利に製造する方法を提供するものである。The present invention provides a simple, safe and advantageous method for producing α,ω-jotopolyfluoroalkane.
以下、本発明を更に詳しく説明する。The present invention will be explained in more detail below.
本発明は、第■族遷移金属触媒下、−ａ式％式％（１）
〔式中、ｎは２以上の整数を表わす〕で示されるα、ω
−ジロートポリフルオロアルカンと一般弐ＣＨ富−ＣＨ
Ｒ−（ＩＩ）
〔式中、Ｒは水素原子、アルキル基、アラルキル基また
はシリル基を表わす〕で示されるオレフィンとを反応さ
せて一般式
〔式中、Ｒ及びｎは上記と同じ意味を表わす、〕で示さ
れるα、ω−ジョートポリフルオロアルカンを製造する
方法である。The present invention provides α, ω represented by -a formula % formula % (1) [wherein n represents an integer of 2 or more] under a Group Ⅰ transition metal catalyst.
- Dirothopolyfluoroalkane and general 2CH-rich -CH
R-(II) [wherein R represents a hydrogen atom, an alkyl group, an aralkyl group or a silyl group] is reacted with an olefin represented by the general formula [wherein R and n represent the same meanings as above] , ] is a method for producing an α,ω-jotopolyfluoroalkane.
本発明において出発物質として用いる前記−数式（１）
で示されるα、ω−ショートペルフルオロアルカンは工
業的に入手可能である。The above formula (1) used as a starting material in the present invention
The α,ω-short perfluoroalkane represented by is commercially available.
本発明のもう一つの原料である前記−数式（ｎ）で示さ
れるオレフィンも工業的に入手可能であり、−数式（Ｉ
Ｉ）中、アルキル基としては置換基を有していてもよい
炭素数１〜１０個のアルキルが好ましく、メチル基、エ
チル基、プロピル基、３゜３．３−トリフルオロプロピ
ル基、ブチル基、ヘキシル基、シクロヘキシル基、３．
３．４，４゜５．５．６．６．６−ノナフルオロヘキシ
ル基、オクチル基、デシル基等を例示することができる
。The olefin represented by the formula (n), which is another raw material of the present invention, is also industrially available, and the olefin represented by the formula (I
In I), the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, such as a methyl group, an ethyl group, a propyl group, a 3゜3.3-trifluoropropyl group, a butyl group. , hexyl group, cyclohexyl group, 3.
Examples include 3.4,4°5.5.6.6.6-nonafluorohexyl group, octyl group, and decyl group.
アラルキル基としては置換基を有していてもよい炭素数
７〜１０個のアラルキル基たとえばベンジル基、ペンタ
フルオロベンジル基、フェネチル基等を例示することが
できる。シリル基とは一般式％式％
〔式中、ＲＩＲｘおよびＲ５はそれぞれ互いに異なって
もよいアルキル基、フェニル基、ハロゲン原子又はアル
コキシ基を表わす、〕で示されるものであり、たとえば
トリメチルシリル基、クロロ（ジメチル）シリル基、ジ
クロロ（メチル）シリル基、メトキシ（ジメチル）シリ
ル基、エトキシ（ジメチル）シリル基、ジメトキシ（メ
チル）シリル基、ジェトキシ（ジメチル）シリル基、メ
トメトキシ（メチル）（３，３，３−）リフルオロプロ
ピル）シリル基、エトキシ（メチル）（３゜３．３−）
リフルオロプロピル）シリル基、クロロ（メチル） （
３，３，３−トリフルオロプロピル）シリル基、クロロ
ビス（３，３，３−トリフルオロプロピル）トリフェニ
ルシリル基、クロロ（メチル）（フェニル）シリル基、
メトキシ（メチル）（フェニル）シリル基、エトキシ（
ジフェニル）シリル基、クロロ（メチル）（ペンタフル
オロフェニル）シリル基等を例示することができる。オ
レフィンの使用量は前記一般式（１）で表わされるα、
ω−ショートペルフルオロアルカンに対して２等量ない
し過剰用いる。Examples of the aralkyl group include an aralkyl group having 7 to 10 carbon atoms which may have a substituent, such as a benzyl group, a pentafluorobenzyl group, and a phenethyl group. A silyl group is represented by the general formula % [wherein RIRx and R5 each represent an alkyl group, a phenyl group, a halogen atom, or an alkoxy group which may be different from each other], such as a trimethylsilyl group, a chloro (dimethyl)silyl group, dichloro(methyl)silyl group, methoxy(dimethyl)silyl group, ethoxy(dimethyl)silyl group, dimethoxy(methyl)silyl group, jetoxy(dimethyl)silyl group, metomethoxy(methyl)(3,3, 3-)lifluoropropyl)silyl group, ethoxy(methyl)(3°3.3-)
(lifluoropropyl)silyl group, chloro(methyl) (
3,3,3-trifluoropropyl)silyl group, chlorobis(3,3,3-trifluoropropyl)triphenylsilyl group, chloro(methyl)(phenyl)silyl group,
Methoxy(methyl)(phenyl)silyl group, ethoxy(
Examples include diphenyl)silyl group, chloro(methyl)(pentafluorophenyl)silyl group, and the like. The amount of olefin used is α represented by the above general formula (1),
It is used in an amount of 2 equivalents to an excess of ω-short perfluoroalkane.
本発明は、第■族遷移金属触媒の存在下に行なうことを
必須の条件とする。用いることのできる第■族遷移金属
触媒としては、鉄、ルテニウム、オスミウム、コバルト
、ロジウム、イリジウム、ニッケル、パラジウム、白金
の金属、金属塩、金ｍ諸化合物、−酸化炭素を配位子と
する有機金属錯体、ハロゲン原子を配位子とする有機金
属錯体、３級ホスフィンを配位子とする有機金属錯体、
オレフィン類あるいはアセチレン類を配位子とする有機
金ｘｓｉ体およびこれらの第■属遷移金属化合物をシリ
カゲルあるいはアルミナの担体に担持したものを使用す
ることができる。適当な触媒としては、鉄カルボニル、
ルテニウムカルボニル、オスミウムカルボニル、コバル
トカルボニル、ロジウムカルボニル、ニッケルカルボニ
ル、塩化鉄、塩化コバルト、塩化ルテニウム、塩化ロジ
ウム、塩化ニッケル、塩化パラジウム、塩化白金、ジク
ロロビス（トリフェニルホスフィン）ニッケル、ジクロ
ロビス（トリフェニルホスフィン）パラジウム、ジクロ
ロ（１，２−ビスジフェニルホスフィノエタン）パラジ
ウム、ジクロロ〔１，３−ビス（ジフェニルホスフィノ
）プロパン〕パラジウム、ジクロロ〔ｌ、４−ビス（ジ
フェニルホスフィノ）ブタン〕パラジウム、ジクロロ（
１，１’−ビス（ジフェニルホスフィノ）フェロセン〕
パラジウム、ジクロロビス（ジフェニルメチルホスフィ
ン）パラジウム、ジクロロビス（トリフェニルホスフィ
ン）白金、ビス（シクロオクタジエン）ニッケル、ジク
ロロ（シクロオクタジエン）パラジウム、クロロトリス
（トリフェニルホスフィン）イリジウム、クロロカルボ
ニルビス（トリフェニルホスフィン）ロジウム、クロロ
カルボニルビス（トリフェニルホスフィン）イリジウム
、テトラキス（トリフェニルホスフィン）パラジウム、
テトラキス（トリフェニルホスフィン）白金等を例示す
ることができる。第■属遷移金属触媒の使用量は、前記
一般式（りで表わされるα、ω−ジ３−ドペルフルオロ
アルカンに対してｌ／１００００ないし１／２当量の範
囲を適宜選択できるが、１）５００ないし１／３の範囲
が好ましい。The present invention requires that the reaction be carried out in the presence of a Group Ⅰ transition metal catalyst. Group (IV) transition metal catalysts that can be used include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum metals, metal salts, gold compounds, and carbon oxide as ligands. Organometallic complexes, organometallic complexes having a halogen atom as a ligand, organometallic complexes having a tertiary phosphine as a ligand,
It is possible to use organic gold xsi forms having olefins or acetylenes as ligands and their Group Ⅰ transition metal compounds supported on silica gel or alumina carriers. Suitable catalysts include iron carbonyl,
Ruthenium carbonyl, osmium carbonyl, cobalt carbonyl, rhodium carbonyl, nickel carbonyl, iron chloride, cobalt chloride, ruthenium chloride, rhodium chloride, nickel chloride, palladium chloride, platinum chloride, dichlorobis(triphenylphosphine)nickel, dichlorobis(triphenylphosphine) Palladium, dichloro(1,2-bisdiphenylphosphinoethane)palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[l,4-bis(diphenylphosphino)butane]palladium, dichloro(
1,1'-bis(diphenylphosphino)ferrocene]
Palladium, dichlorobis(diphenylmethylphosphine)palladium, dichlorobis(triphenylphosphine)platinum, bis(cyclooctadiene)nickel, dichloro(cyclooctadiene)palladium, chlorotris(triphenylphosphine)iridium, chlorocarbonylbis(triphenylphosphine) Rhodium, chlorocarbonylbis(triphenylphosphine)iridium, tetrakis(triphenylphosphine)palladium,
Examples include tetrakis(triphenylphosphine)platinum. The amount of the Group IV transition metal catalyst to be used can be appropriately selected from the range of l/10,000 to 1/2 equivalent relative to the α,ω-di3-doperfluoroalkane represented by the general formula (1). A range of 500 to 1/3 is preferred.
また所望なら助触媒として、ピリジン、トリエチルアミ
ン、ジエチルアミン、エタノールアミンのようなアミン
弗を添加することもできる。If desired, amine fluorides such as pyridine, triethylamine, diethylamine, and ethanolamine can also be added as cocatalysts.
反応は０℃〜１５０℃で円滑に進行する。The reaction proceeds smoothly at 0°C to 150°C.
本発明を実施するに際しては無溶媒下で反応を行なうこ
とができるが、所望なら反応に関与しない溶媒を用いて
もさしつかえない。When carrying out the present invention, the reaction can be carried out without a solvent, but if desired, a solvent that does not participate in the reaction may be used.
以下、実施例により本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例１
１ （ＣＦ富）４１ ＋ ＣＨ＊−ＣＨ＊ −−→Ｉ
ＣＨｓ ＣＨ＊ （ＣＦ ｔ）ａ ＣＨ雪ＣＨＭ
１）０ｍｌステンレス製オートクレーブに、１．４−シ
ョートペルフルオロブタン（１８０μｚ、１．０ｍｍｏ
１） 、鉄ペンタカルボニル（１４，ｕｎ！。Example 1 1 (CF rich) 41 + CH*-CH* −-→I
CHs CH* (CF t)a CH Snow CHM
1) In a 0ml stainless steel autoclave, add 1.4-short perfluorobutane (180 μz, 1.0 mmo
1), iron pentacarbonyl (14, un!.
Ｑ、１ｍｍｏ ｌ） 、エタノールアミン（１２μｌ。Q, 1 mmol), ethanolamine (12 μl).
０．２ｍｍｏｌ）を入れ、エチレン（１０ａｔｍ）を封
入し、１００℃で３時間攪拌した０反応混合物にエーテ
ルを加え、標準物質としてオクタンを入れ、ＧＬＣを測
定したところ、１，８−ショート−３，３，４，４，５
，５，６，６−オクタフルオロオクタンが７８％の収率
で生成していた０反応混合物に塩酸を加えエーテル層を
分液し、エーテルを留去した後、メタノールで再結晶す
ることにより１，８−ジロードー３．３．４．４．５，
５゜６．６−オクタフルオロオクタンを単離精製した。1,8-short-3 ,3,4,4,5
, 5,6,6-octafluorooctane was produced in a yield of 78%. Hydrochloric acid was added to the reaction mixture to separate the ether layer, the ether was distilled off, and recrystallization was performed with methanol to obtain 1. ,8-Giraudeau 3.3.4.4.5,
5°6.6-octafluorooctane was isolated and purified.
１．８−ショート−３，３，４，４，５，５，６゜６−
オクタフルオロオクタン
ＩＲ１）９５，１）？１．１）１２゜
１０６４．７２２．５１２ｃｍ−’。1.8-Short-3,3,4,4,5,5,6゜6-
Octafluorooctane IR1)95,1)? 1.1) 12°1064.722.512 cm-'.
’ ＨＮ Ｍ Ｒ（ＣＤ Ｃｌ ｓ −Ｔ Ｍ Ｓ ）
δ２．１〜３．０ （ｂｍ、４Ｈ）、３．０〜３．６
（ｂｍ。'HNMR(CDCls-TMS)
δ2.1~3.0 (bm, 4H), 3.0~3.6
(bm.
４Ｈ）。4H).
ＩＩＦ ＮＭＲ（ＣＤＣＩｓ−ＣＦＣＩｓ）δ−１）
４，４（ｍ、 ４Ｆ） 、 −１２３，０（ｍ、４Ｆ
）。IIF NMR (CDCIs-CFCIs) δ-1)
4,4(m, 4F), -123,0(m, 4F
).
Ｍａｓｓ ｍ／ａ （ｒｅｌ、Ｉｎｔ、）５１０ （
Ｍ’、８５）、３８３ （５５）。Mass m/a (rel, Int,)510 (
M', 85), 383 (55).
１４１ （６７）、７７ （１００）、６５（７２）、
５１ （２５）、４７ （２１）。141 (67), 77 (100), 65 (72),
51 (25), 47 (21).
２８ （２５）、２７ （３５）。28 (25), 27 (35).
ｅ、 ａ、 Ｃａ １ ｃ ｄ、 ｆ ｏ ｒ Ｃ
＊ＨｓＦ會１ｔ。e, a, Ca 1 c d, f o r C
*HsF meeting 1t.
ＣＩ Ｂ、８４． Ｈ１，５８゜
ｏｕｎｄ
Ｃ１８，７６、Ｈ１，４２゜
実施例２〜１６
実施例１と同様にして行った０反応に用しまた１、４−
ショートペルフルオロブタンおよびエチレンの量、用い
た触媒およびアミンの種類と量、反応温度、反応時間並
びに収率を表１に示す。CI B, 84. H1,58゜ound C18,76,H1,42゜Examples 2 to 16
Table 1 shows the amounts of short perfluorobutane and ethylene, the types and amounts of the catalyst and amine used, the reaction temperature, reaction time, and yield.
実施例１７
ｒ （ＣＦｔ）ａｌ ＋／７＼ＳＩＭｅｓ −〉キ
ャンプ付試験管に、１．４−ショートペルフルオロブタ
ン（９０ｔｔ １． ０．５ｒｒｚｎｏ Ｉ ） 、ビ
ニ／Ｌ／トリメチルシラン（２３０μｌ、ｌ、５ｍｍｏ
＋）、鉄ペンタカルボニル（”１）１）．０．０５ｍ
ｍｏ ｌ）、エタノールアミン（６１）４！、０．１ｍ
ｍｏ Ｉ）を入れ、室温で５分攪拌した０反応混合物に
塩酸およびエーテルを加え、エーテル層を分液しエーテ
ルを留去した後、カラムクロマトグラフィー〈展開溶媒
：ヘキサン）で単離精製することにより、１．８−ショ
ート−１，８−ビス（トリメチルシリル）−３，３，４
，４，５，５，６，６−オクタフルオロオクタンを７６
％の収率で得た。Example 17 r (CFt)al +/7\SIMes -> In a test tube with camp, 1.4-short perfluorobutane (90tt 1.0.5rrzno I), vinyl/L/trimethylsilane (230 μl, 1, 5 mmo
+), iron pentacarbonyl (”1)1).0.05m
mol), ethanolamine (61) 4! ,0.1m
Add hydrochloric acid and ether to the reaction mixture containing mo I) and stirring at room temperature for 5 minutes, separate the ether layer, distill off the ether, and then isolate and purify by column chromatography (developing solvent: hexane). 1,8-short-1,8-bis(trimethylsilyl)-3,3,4
, 4,5,5,6,6-octafluorooctane 76
% yield.
１．８−ショート−１，８−ビス（トリメチルシリル）
−３，３，４，４，５，５，６，６−オクタフルオロオ
クタン
ＩＲ２９７０，１２５３，１２０９，１）８Ｂ。1.8-short-1,8-bis(trimethylsilyl)
-3,3,4,4,5,5,6,6-octafluorooctane IR2970, 1253, 1209, 1) 8B.
１）６４．１）００．８４２ｃｍ−’。1) 64.1) 00.842 cm-'.
’ ＨＮ Ｍ Ｒ（ＣＤ ＣＩ ２ Ｔ Ｍ Ｓ ）
δ ０．１５（ｓ、 １８Ｈ）、２．３−２．９
（ｍ、４Ｈ）。'HNMR(CDCI2TMS)
δ 0.15 (s, 18H), 2.3-2.9
(m, 4H).
３．１〜３．３ （ｍ、２Ｈ）。3.1-3.3 (m, 2H).
”Ｆ ＮＭＲ（ＣＤＣＩり一〇 Ｆ Ｃｌ ｓ）δ−
１）４，４（ｍ、４Ｆ）、−１２３，０（ｍ、４Ｆ）。”F NMR (CDCI 10 F Cl s) δ-
1) 4,4 (m, 4F), -123,0 (m, 4F).
Ｍａｓｓ ｍ／ｓ （ｒｅｌ、ｉｎｔ、）６５４（Ｍ
”、 ＜１）、 ２１６ （８） 、 １９６（５）、
１８５ （１））、７７ （４９）。Mass m/s (rel, int,)654 (M
”, <1), 216 (8), 196 (5),
185 (1)), 77 (49).
７３ （１００）、４５ （６）。73 (100), 45 (6).
ｅ、ａ、Ｃａ Ｉ Ｃｄ ｆ Ｏｒ Ｃ＋ａＨ＊ｎ
ＦｓｌｘＳ ｌｘ。e, a, Ca I Cd f Or C+aH*n
FslxS lx.
Ｃ２５，７０，Ｈ３，７０゜
ｆ ｏａｎｄ
Ｃ２５，８８，Ｈ３，６８゜
実施例１７と同様にして行った０反応に用し）た１、４
−ショートペルフルオロブタン（１）およびビニルトリ
メチルシラン（２）の置、用し）た触媒およびアミンの
種類と量、反応温度、反応時間並びに収率を表２に示す
。C25,70,H3,70°f oand C25,88,H3,68°1,4
Table 2 shows the types and amounts of catalysts and amines, reaction temperatures, reaction times, and yields used for -short perfluorobutane (1) and vinyltrimethylsilane (2).
実施例２６
１（ＣＦ ｔ）ａｌ ＋ ／’＼ＳＩＭｅｔ（Ｏｕｔ）
−キキャップ付試験管に、ｌ、４−ショートペルフル
オロブタン＜９０ｔｔ１．０．５ｍｍｏ ｌ） 、ビニ
ルエトキシジメチルシラン（２５０μｚ、２．５ｍｍｏ
Ｉ） 、鉄ペンタカルボニル（１４ｕＬＯ，Ｉｍｍｏ
Ｊ）を入れ、１００℃で３時間攪拌した０反応混合物に
ヘキサンを加え、触媒を除去した後、ｍ縮することによ
り１．８−ショート−１，８−ビス（エトキシジメチル
シリル）−３，３，４゜４．５．５．６．６−オクタフ
ルオロオクタンを１，８−ショート−１，８−とス ジ
メチルエトキンシリル−３，３，４，４，５，５，６，
６−オクタフルオロオクタン
ＩＲ２９８０，１２５７，１２・０９゜１）６５．１）
０Ｂ、１０９３，９５０゜８３２０１）−’。Example 26 1(CF t)al + /'\SIMet(Out)
- In a test tube with a cap, add l,4-short perfluorobutane <90tt1.0.5mmol), vinyl ethoxydimethylsilane (250μz, 2.5mmol
I), iron pentacarbonyl (14uLO, Immo
J) and stirred at 100°C for 3 hours, hexane was added to the reaction mixture, the catalyst was removed, and condensation was performed to obtain 1,8-short-1,8-bis(ethoxydimethylsilyl)-3, 3,4゜4.5.5.6.6-octafluorooctane with 1,8-short-1,8-dimethylethquinsilyl-3,3,4,4,5,5,6,
6-octafluorooctane IR2980,1257,12.09゜1)65.1)
0B, 1093,950°83201)-'.
’ ＨＮ Ｍ Ｒ（ＣＤ Ｃｌ ｓ Ｔ Ｍ Ｓ ）
δ０．３５←ａ、１２Ｈ）、１．２０ （ｔ、Ｊ−７
Ｈｚ、６Ｈ）２．２〜３．３ （ｍ、６Ｈ）。'HNMR(CDClsTMS)
δ0.35←a, 12H), 1.20 (t, J-7
Hz, 6H) 2.2-3.3 (m, 6H).
３．７３ （ｑ、Ｊ＝７Ｈｚ、４Ｈ）。3.73 (q, J=7Hz, 4H).
”Ｆ ＮＭＲ（ＣＤＣ１ａ−ＣＦＣｌ、）δ−１）４
，１（ｒｎ、４Ｆ）、−１２２，７（ｒｎ、４Ｆ）。"F NMR (CDC1a-CFCl,) δ-1) 4
, 1(rn, 4F), -122,7(rn, 4F).
Ｍａｓｓ ｍ／ｅ （ｒｅｌ、１ｎｔ、）１５４（４
）、ＬＯＴ （９）、１０５ （４）。Mass m/e (rel, 1nt,) 154 (4
), LOT (9), 105 (4).
１Ｇ４ （１０）、 １０３ （１００）。1G4 (10), 103 (100).
７９ （１４）、 ７７ （１７）、７５ （
２７）。79 (14), 77 (17), 75 (
27).
５９（１２）。59(12).
ｅ、 ａ、 Ｃａ １ ｃ ｄ、 Ｃ＋蟲Ｈ
＊ｓＦ＊１ｇＯ＊Ｓ ｌｘ。e, a, Ca 1 c d, C + insect H
*sF*1gO*S lx.
Ｃ２６，９０，Ｈ３，９５゜
ｏａｎｄ
Ｃ２６，９０，Ｈ４，１４゜
実施例２７
１（Ｃｈ）ｉｆ ＋ ＣＨｔ −ＣＨｇＩＣ
１ｂＣＨｔ（Ｃｈ）ａｃＨｔｃ１）ｍ１５０ｍｌオート
クレーブに１．６−ショートペルフルオロヘキサン（２
，５８ｇ、４．４６ｍｍｏ １）鉄ドデカカルボニル（
１６３ｍ、０．３２ｍｍｏ １）を入れエチレン（１０
ａｔｍ）を封入し、８０℃で一ドー３．３．４．４．５
．５，６．６．７．７゜８．８−ドデカフルオロデカン
（２，６５ｇ）を９３％の収率で得た。C26,90,H3,95°oand C26,90,H4,14°Example 27 1(Ch)if + CHt -CHgIC
1bCHt(Ch)acHtc1)m1.6-Short perfluorohexane (2
, 58g, 4.46mmo 1) Iron dodecacarbonyl (
163m, 0.32mmo 1) was added and ethylene (10
3.3.4.4.5
．． 5,6.6.7.7°8.8-dodecafluorodecane (2.65 g) was obtained with a yield of 93%.
’ＨＮＭＲ（ＣＤＣＩ！−ＴＭＳ）６２．３〜３．１
（ｍ、４Ｈ）、３．１〜３．４ （ｍ。'HNMR (CDCI!-TMS) 62.3~3.1
(m, 4H), 3.1-3.4 (m.
４Ｈ）。4H).
”Ｆ ＮＭＲ（ＣＤＣＩｓ ＣＦＣＩｓ）δ−１）
４，２（ｒｎ、 ４Ｆ） 、 −１２２，１（ｒｎ
、 ４Ｆ） 、 −１２３，０（ｒｎ、 ４Ｆ）
。"F NMR (CDCIs CFCIs) δ-1)
4,2(rn, 4F), -122,1(rn
, 4F) , -123,0(rn, 4F)
.
ＪＲ（ＫＢｒ） １２１５．１）７０゜１）３４．１
０６２．６８８．５１２ｃｍ−’。JR (KBr) 1215.1) 70°1) 34.1
062.688.512 cm-'.
Ｍａｓｓ ｍ／ｅ （ｒａｌ、ｉｎｔ、）６１０（Ｍ
”、１００）、４６３ （２４）。Mass m/e (ral, int,)610 (M
”, 100), 463 (24).
１４１ （４６）、？？ （６５）、６５（４３）
、５１ （２０）、２７ （１９）。141 (46),? ? (65), 65(43)
, 51 (20), 27 (19).
Claims (1)
ω−ジョードペルフルオロアルカンと一般式 ＣＨ＿２＝ＣＨＲ 〔式中、Ｒは水素原子、アルキル基、アラルキル基又は
シリル基を表わす。〕で示されるオレフィンを反応され
ることからなる一般式 ▲数式、化学式、表等があります▼ 〔式中、Ｒ及びｎは上記と同じ意味を表わす。〕で示さ
れるα，ω−ジョードポリフルオロアルカンの製造方法(1) In the presence of a Group VIII transition metal catalyst, the general formula I(CF_2)_nI [wherein n represents an integer of 2 or more]. ] denoted by α,
ω-Jodoperfluoroalkane and general formula CH_2=CHR [wherein R represents a hydrogen atom, an alkyl group, an aralkyl group or a silyl group]. [In the formula, R and n have the same meanings as above. ] Method for producing α,ω-jodopolyfluoroalkane
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3952488A JPH01216946A (en) | 1988-02-24 | 1988-02-24 | Production of alpha,omega-diiodoopolyfluoroalkane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3952488A JPH01216946A (en) | 1988-02-24 | 1988-02-24 | Production of alpha,omega-diiodoopolyfluoroalkane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01216946A true JPH01216946A (en) | 1989-08-30 |
Family
ID=12555432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3952488A Pending JPH01216946A (en) | 1988-02-24 | 1988-02-24 | Production of alpha,omega-diiodoopolyfluoroalkane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01216946A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153803A (en) * | 1997-06-02 | 2000-11-28 | Solvay Societe Anonyme | Process for the preparation of halohydrocarbons |
| JP2002145811A (en) * | 2000-11-08 | 2002-05-22 | F-Tech Inc | Method for producing highly pure perfluoroalkyl- di(ethyl iodide) and method for producing colorless perfluoroalkyldiethylene. |
| JP2013510150A (en) * | 2009-11-04 | 2013-03-21 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Catalytic olefin insertion |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60104023A (en) * | 1983-10-21 | 1985-06-08 | ヘキスト・アクチエンゲゼルシヤフト | Manufacture of fluoroalkyl substituted alkane or alkene |
| JPS60106533A (en) * | 1983-10-21 | 1985-06-12 | ヘキスト・アクチエンゲゼルシヤフト | Manufacture of fluoralkyl replaced iodine alkane |
-
1988
- 1988-02-24 JP JP3952488A patent/JPH01216946A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60104023A (en) * | 1983-10-21 | 1985-06-08 | ヘキスト・アクチエンゲゼルシヤフト | Manufacture of fluoroalkyl substituted alkane or alkene |
| JPS60106533A (en) * | 1983-10-21 | 1985-06-12 | ヘキスト・アクチエンゲゼルシヤフト | Manufacture of fluoralkyl replaced iodine alkane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153803A (en) * | 1997-06-02 | 2000-11-28 | Solvay Societe Anonyme | Process for the preparation of halohydrocarbons |
| JP2002145811A (en) * | 2000-11-08 | 2002-05-22 | F-Tech Inc | Method for producing highly pure perfluoroalkyl- di(ethyl iodide) and method for producing colorless perfluoroalkyldiethylene. |
| JP4707819B2 (en) * | 2000-11-08 | 2011-06-22 | 東ソ−・エフテック株式会社 | Method for producing uncolored perfluoroalkyldiethylene |
| JP2013510150A (en) * | 2009-11-04 | 2013-03-21 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Catalytic olefin insertion |
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