JP2684296B2 - Method for producing fluorine-containing organosilicon compound - Google Patents
Method for producing fluorine-containing organosilicon compoundInfo
- Publication number
- JP2684296B2 JP2684296B2 JP4227986A JP22798692A JP2684296B2 JP 2684296 B2 JP2684296 B2 JP 2684296B2 JP 4227986 A JP4227986 A JP 4227986A JP 22798692 A JP22798692 A JP 22798692A JP 2684296 B2 JP2684296 B2 JP 2684296B2
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- general formula
- fluorine
- reaction
- formula
- Prior art date
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- 229910052731 fluorine Inorganic materials 0.000 title claims description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 29
- 239000011737 fluorine Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 150000003961 organosilicon compounds Chemical class 0.000 title description 2
- -1 silane compound Chemical class 0.000 claims description 23
- 229910000077 silane Inorganic materials 0.000 claims description 21
- 150000003752 zinc compounds Chemical class 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 15
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 6
- 239000010702 perfluoropolyether Chemical group 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 150000002497 iodine compounds Chemical class 0.000 claims description 4
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- KWXGJTSJUKTDQU-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-8-iodooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I KWXGJTSJUKTDQU-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- PGRFXXCKHGIFSV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-iodobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)I PGRFXXCKHGIFSV-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 2
- NUFVQEIPPHHQCK-UHFFFAOYSA-N ethenyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)C=C NUFVQEIPPHHQCK-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- IDYHGSXNTVTKAC-UHFFFAOYSA-N 2-methoxyethenyl(dimethyl)silane Chemical compound COC=C[SiH](C)C IDYHGSXNTVTKAC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- SLFKPACCQUVAPG-UHFFFAOYSA-N carbon monoxide;nickel;triphenylphosphane Chemical compound O=C=[Ni]=C=O.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 SLFKPACCQUVAPG-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 230000009849 deactivation Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- IDIOJRGTRFRIJL-UHFFFAOYSA-N iodosilane Chemical compound I[SiH3] IDIOJRGTRFRIJL-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、取扱いが容易で且つ経
済的にも有利な亜鉛触媒を用いて、含フッ素有機ケイ素
化合物を製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a fluorine-containing organosilicon compound using a zinc catalyst which is easy to handle and economically advantageous.
【０００２】[0002]
【従来の技術】従来、含フッ素有機基を炭化水素に導入
する反応としては、下記式(6):Conventionally, as a reaction for introducing a fluorine-containing organic group into a hydrocarbon, the following formula (6):
【化５】 〔式中、Rfは含フッ素有機基である〕で表される反応が
代表的であり、この反応を利用して、含フッ素シラン等
も製造されている。Embedded image A reaction represented by [wherein Rf is a fluorine-containing organic group] is typical, and fluorine-containing silane and the like are also produced by utilizing this reaction.
【０００３】ところで、上記反応の触媒としては、 (イ) Et3 B [Katsukiyo Miura, Masahiko Taniguchi, Ky
oko Nozaki, KoichiroOshima, Kiitiro Utimoto, Tetra
hedron Letters 31, 6391(1991); YoshiheroTakeyama,
Yoshifumi Ichinose, Koichiro Oshima, Kiitiro Utimo
to, Ibid, 30, 3159(1989)等参照] (ロ) Me3 Al [Keiji Maruoka, Hiromi Sano, Yoshimi Fu
kutani, HisashiYamamoto, Chemistry Letters 1689(19
85)参照] (ハ) Pd(PPh3 ) 4 [Takashi Ishihara, Manabu Kurobosh
i, Yoshiji Okada,Chemistry Letters 1895(1986)参照] (ニ) PPh3 , P(OEt)3 , NH3 OH [Wei-Yuan Huang, Han-
Zhong Zhang,J. Fluorine Chem, 50, 133(1990) 参照] (ホ) Ru3 (CO)12, Fe3 (CO)12, Fe2 (CO)9 , Fe(CO)5 ,
Co2 (CO)8 , Ni(CO)2(PPh3 ) 2 , W(CO) 5 〔P(OE
t)3 〕, Mo(CO)5 (PPh3 ), [Takamasa Fuchikami,Iwao
Ojima, Tetrahedron Letters, 25, 303(1984), 同Tet
rahedron Letters,25, 307(1984);米国特許第 5,017,71
8号参照] (ヘ) ClRh(PPh3 ) 3 [Qing-Yun Chen, Zhen-Yu Yang, J.
Fluorine Chem, 39,217(1988) 参照] (ト) Ru／carbon, Pt／carbon, Ag／Al2 O 3 [Konard Vo
n Werner, J.FluorineChem, 28, 229(1985) 参照] が知られている。上記において、Meはメチル基、Etはエ
チル基、Phはフェニル基をそれぞれ示す。By the way, as the catalyst for the above reaction, (a) Et 3 B [Katsukiyo Miura, Masahiko Taniguchi, Ky
oko Nozaki, KoichiroOshima, Kiitiro Utimoto, Tetra
hedron Letters 31 , 6391 (1991); Yoshihero Takeyama,
Yoshifumi Ichinose, Koichiro Oshima, Kiitiro Utimo
to, Ibid, 30 , 3159 (1989) etc.] (b) Me 3 Al [Keiji Maruoka, Hiromi Sano, Yoshimi Fu
kutani, HisashiYamamoto, Chemistry Letters 1689 (19
(See 85)] (C) Pd (PPh 3 ) 4 [Takashi Ishihara, Manabu Kurobosh
i, Yoshiji Okada, Chemistry Letters 1895 (1986)] (D) PPh 3 , P (OEt) 3 , NH 3 OH [Wei-Yuan Huang, Han-
See Zhong Zhang, J. Fluorine Chem, 50 , 133 (1990)] (e) Ru 3 (CO) 12 , Fe 3 (CO) 12 , Fe 2 (CO) 9 , Fe (CO) 5 ,
Co 2 (CO) 8 , Ni (CO) 2 (PPh 3 ) 2 , W (CO) 5 〔P (OE
t) 3 ), Mo (CO) 5 (PPh 3 ), (Takamasa Fuchikami, Iwao
Ojima, Tetrahedron Letters, 25 , 303 (1984), Tet
rahedron Letters, 25 , 307 (1984); U.S. Pat.No. 5,017,71
No. 8] (f) ClRh (PPh 3 ) 3 [Qing-Yun Chen, Zhen-Yu Yang , J.
Fluorine Chem, 39 , 217 (1988)] [G] Ru / carbon, Pt / carbon, Ag / Al 2 O 3 [Konard Vo
n Werner , J. Fluorine Chem, 28 , 229 (1985)] is known. In the above, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.
【０００４】[0004]
【発明が解決しようとする課題】然しながら、上記の触
媒中、Pd(PPh3 ) 4 , ClRh(PPh3 ) 3 , Ru／carbon, Pt
／carbon, Ag／Al2 O 3 等は、高価な貴金属を使ってい
るため経済的に不利であり、またこれらの触媒を用いて
の反応は、75℃以上の比較的高温の反応条件を必要とす
るという問題がある。また、上記の触媒中、Fe3 （CO）
12等の金属カルボニル醋体は、一酸化炭素の発生という
危険性をはらんでおり、量産には不適当である。更に P
Ph3 , P(OEt)3 , NH3 OHは塩基であるから、前記反応に
おける反応生成物であるアイオダイドと塩を生成するた
め、触媒失活という問題を生じる。比較的低温で行い得
る触媒としては、Et3 B , Me3 Alがあるが、これらは空
気に触れると発火するという問題がある。However, in the above catalyst, Pd (PPh 3 ) 4 , ClRh (PPh 3 ) 3 , Ru / carbon, Pt
/ Carbon, Ag / Al 2 O 3, etc. are economically disadvantageous because they use expensive noble metals, and the reaction using these catalysts requires relatively high temperature reaction conditions of 75 ° C or higher. There is a problem that In addition, in the above catalyst, Fe 3 (CO)
Metal carbonyl compounds such as 12 have the risk of carbon monoxide generation and are not suitable for mass production. Further P
Since Ph 3 , P (OEt) 3 and NH 3 OH are bases, iodide and a salt, which are reaction products in the above reaction, are formed, which causes a problem of catalyst deactivation. Et 3 B and Me 3 Al are catalysts that can be used at relatively low temperatures, but they have a problem that they ignite when they come into contact with air.
【０００５】また本発明者等は、上述した反応に適した
触媒としてＡＩＢＮを先に提案した（特願平４−173864
号）。この触媒は安価であり、取扱いが容易であるとい
う利点を有しているが、これを含フッ素シラン化合物の
合成に適用した場合、得られるヨードシランのヨード部
分が、さらにもう一分子のビニルシランと反応するとい
う問題がある。The present inventors have previously proposed AIBN as a catalyst suitable for the above reaction (Japanese Patent Application No. 4-173864).
issue). This catalyst has the advantage of being inexpensive and easy to handle, but when it is applied to the synthesis of a fluorine-containing silane compound, the iodo moiety of the obtained iodosilane reacts with another molecule of vinylsilane. There is a problem of doing.
【０００６】従って本発明の目的は、上述した種々の問
題が解消し、安価で且つ取扱いが容易な触媒を用いて、
低温での反応により含フッ素シラン化合物を製造する方
法を提供することにある。Therefore, an object of the present invention is to solve the above-mentioned various problems and to use a catalyst which is inexpensive and easy to handle,
It is to provide a method for producing a fluorinated silane compound by a reaction at a low temperature.
【０００７】[0007]
【課題を解決するための手段】本発明によれば、下記一
般式（1a）： Rf1 Ｉ （1a） 〔式中、Rf1 は炭素数１〜15のパーフルオロアルキル基
またはパーフルオロポリエーテル基を示す〕で示される
ヨウ素化合物と、下記一般式(2):According to the present invention, the following general formula (1a): Rf 1 I (1a) [In the formula, Rf 1 is a perfluoroalkyl group having 1 to 15 carbon atoms or perfluoropolyether. And an iodine compound represented by the following general formula (2):
【化６】 〔式中、Ｘは炭素数１〜５のアルコキシ基、Ｒ1 は炭素
数１〜10の非置換もしくは置換炭化水素基、ａは０〜３
の整数である〕で表されるビニルシランとを、下記一般
式(3): Ｒ2 Zn (3) 〔式中、Ｒは炭素数１〜５の非置換の一価炭化水素基で
ある〕で表される亜鉛化合物の存在下に反応させる工程
を有する、下記一般式(4):Embedded image [In the formula, X is an alkoxy group having 1 to 5 carbon atoms, R 1 is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and a is 0 to 3
A vinyl silane represented by the following general formula (3): R 2 Zn (3) [wherein, R is an unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms] Having a step of reacting in the presence of a zinc compound represented by the following general formula (4):
【化７】 〔式中、Rf1 , Ｒ1 及びａは前述の通りである〕で表さ
れる含フッ素シラン化合物の製造方法が提供される。Embedded image A method for producing a fluorine-containing silane compound represented by the formula: wherein Rf 1 , R 1 and a are as described above is provided.
【０００８】また本発明によれば、下記一般式（1b）： Ｉ−Rf2 −Ｉ （1b） 〔式中、Rf2 は炭素数１〜15のパーフルオロアルキレン
基もしくは二価のパーフルオロポリエーテル基である〕
で示されるヨウ素化合物と、一般式(2):[0008] According to the present invention, the following general formula (1b): I-Rf 2 -I (1b) wherein, Rf 2 is perfluoro perfluoroalkylene group or a divalent 1-15 carbon atoms It is an ether group]
With an iodine compound represented by the general formula (2):
【化８】 〔式中、Ｘ及びａは前述の通りである〕で表されるビニ
ルシランとを、一般式(3): Ｒ2 Zn (3) 〔式中、Ｒは前述の通りである〕で表される亜鉛化合物
の存在下に反応させる工程を有する、一般式(5):Embedded image [Wherein X and a are as described above] and a vinylsilane represented by the general formula (3): R 2 Zn (3) [wherein R is as described above] Having a step of reacting in the presence of a zinc compound, the general formula (5):
【化９】 〔式中、Rf2 , Ｘ, Ｒ1 及びａは前述の通りである〕で
表される含フッ素シラン化合物の製造方法が提供され
る。Embedded image There is provided a method for producing a fluorine-containing silane compound represented by the formula: wherein Rf 2 , X, R 1 and a are as described above.
【０００９】含フッ素アイオダイド；本発明において、
出発化合物としては、前記一般式（1a）で表される含フ
ッ素モノアイオダイド或いは前記一般式（1b）で表され
る含フッ素ジアイオダイドが使用される。即ち、一般式
（1a）の含フッ素モノアイオダイドを使用した場合に
は、前記一般式(4) で表されるシラン化合物が得られ、
一般式（1b）の含フッ素ジアイオダイドを使用した場合
には、前記一般式(5) で表されるシラン化合物が得られ
る。 Fluorine-containing iodide ; in the present invention,
As the starting compound, the fluorine-containing monoiodide represented by the general formula (1a) or the fluorine-containing diiodide represented by the general formula (1b) is used. That is, when the fluorine-containing monoiodide of the general formula (1a) is used, a silane compound represented by the general formula (4) is obtained,
When the fluorine-containing diiodide of the general formula (1b) is used, the silane compound represented by the general formula (5) is obtained.
【００１０】一般式（1a）において、基Rf1 は、炭素数
１〜15の含フッ素基であり、パーフルオロアルキル基ま
たはパーフルオロアルキルポリエーテル基である。ここ
でパーフルオロアルキル基としては、Ｃ4 Ｆ9 , Ｃ6 Ｆ
13, Ｃ8 Ｆ17, Ｃ10Ｆ21等を例示することができる。ま
たパーフルオロアルキルポリエーテル基としては、下記
式：In the general formula (1a), the group Rf 1 is a fluorine-containing group having 1 to 15 carbon atoms and is a perfluoroalkyl group or a perfluoroalkylpolyether group. Here, the perfluoroalkyl group includes C 4 F 9 and C 6 F
Examples thereof include 13 , C 8 F 17 , C 10 F 21 and the like. Further, the perfluoroalkyl polyether group has the following formula:
【化１０】 〔式中、Ｙは、ＦまたはCF3 を示し、ｎは、１〜５の整
数、ｍは、０または１である〕で表される基を例示する
ことができ、その中でも代表的なものとして、以下のも
のを挙げることができる。Embedded image [In the formula, Y represents F or CF 3 , n is an integer of 1 to 5, and m is 0 or 1]. The following can be cited as examples.
【化１１】 Embedded image
【００１１】また一般式（1b）において、炭素数が１〜
15の二価の含フッ素基Rf2 は、パーフルオロアルキレン
基またはパーフルオロポリエーテル基である。このパー
フルオロアルキレン基としては、例えば−Ｃ4 Ｆ8 −,
−Ｃ6 Ｆ12−, −Ｃ8 Ｆ16−等を例示することができ
る。また二価のパーフルオロポリエーテル基としては、
下記式：In the general formula (1b), the number of carbon atoms is 1 to
The divalent fluorine-containing group Rf 2 of 15 is a perfluoroalkylene group or a perfluoropolyether group. As the perfluoroalkylene group, for example, -C 4 F 8 -,
-C 6 F 12 -, -C 8 F 16 - , etc. can be exemplified. Further, as the divalent perfluoropolyether group,
The following formula:
【化１２】 〔式中、ｘ, ｙは１〜５の整数である〕で表されるも
の、例えば、Embedded image [Wherein x and y are integers of 1 to 5], for example,
【化１３】 等を例示することができる。Embedded image And the like.
【００１２】ビニルシラン；本発明において、前記含フ
ッ素アイオダイドと反応させるべきビニルシランとして
は、前記一般式(2) で表されるものが使用される。この
一般式(2) において、炭素数１〜10の炭化水素基Ｒ1 と
しては、例えばメチル基、エチル基、プロピル基等のア
ルキル基、シクロヘキシル基等のシクロアルキル基、フ
ェニル基等のアリール基、及びCF3 CH2 CH2 −, Ｃ4 Ｆ
9 CH2 CH2−, Ｃ6 Ｆ13CH2 CH2 −, Ｃ8 Ｆ17CH2 CH2
−等のフッ素置換アルキル基等を例示することができ
る。また炭素数１〜５のアルコキシ基Ｘとしては、メト
キシ基、エトキシ基、プロポキシ基、ブトキシ基等を例
示することができる。 Vinylsilane : In the present invention, as the vinylsilane to be reacted with the fluorine-containing iodide, the one represented by the general formula (2) is used. In the general formula (2), examples of the hydrocarbon group R 1 having 1 to 10 carbon atoms include an alkyl group such as a methyl group, an ethyl group and a propyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group. , And CF 3 CH 2 CH 2 −, C 4 F
9 CH 2 CH 2 −, C 6 F 13 CH 2 CH 2 −, C 8 F 17 CH 2 CH 2
Examples thereof include fluorine-substituted alkyl groups such as-. Examples of the alkoxy group X having 1 to 5 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group and the like.
【００１３】前記含フッ素アイオダイドとビニルシラン
との反応は、前記反応式(6) のビニル化合物を上記ビニ
ルシランに置き換えた形で進行する。ここでビニルシラ
ンは過剰に使用することが有利であり、一般に、含フッ
素モノアイオダイドを用いた場合には、アイオダイド／
ビニルシラン＝ 1.0〜1.5 （モル比）の割合で使用さ
れ、また含フッ素ジアイオダイドを用いた場合には、ア
イオダイド／ビニルシラン＝ 2.0〜3.0 （モル比）の割
合で使用される。The reaction between the fluorine-containing iodide and vinylsilane proceeds in a form in which the vinyl compound represented by the reaction formula (6) is replaced with the vinylsilane. Here, it is advantageous to use vinylsilane in excess, and in general, when a fluorine-containing monoiodide is used, iodide /
The vinylsilane is used at a ratio of 1.0 to 1.5 (molar ratio), and when the fluorine-containing diiodide is used, it is used at a ratio of iodide / vinylsilane = 2.0 to 3.0 (molar ratio).
【００１４】亜鉛化合物；本発明においては、上記の含
フッ素アイオダイドとビニルシランとの反応を、前記一
般式(3) で表される亜鉛化合物の存在下で行なうことが
顕著な特徴である。即ち、この亜鉛化合物は安価であっ
て経済的に有利であるとともに、比較的取り扱いやす
く、且つ上記反応を低温で進行させることができる。 Zinc compound : In the present invention, it is a remarkable feature that the reaction between the above-mentioned fluorine-containing iodide and vinylsilane is carried out in the presence of the zinc compound represented by the general formula (3). That is, this zinc compound is inexpensive and economically advantageous, and is relatively easy to handle, and the above reaction can proceed at a low temperature.
【００１５】一般式(3) において、炭素数１〜５の非置
換炭化水素基としては、例えばメチル基、エチル基、プ
ロピル基、ブチル基等のアルキル基を例示することがで
きるが、工業的にはエチル基が有利である。In the general formula (3), examples of the unsubstituted hydrocarbon group having 1 to 5 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group and butyl group. Is preferably an ethyl group.
【００１６】この亜鉛化合物は、一般に 0.1モル／リッ
トル程度の濃度のヘキサン溶液として得られ、これをそ
のまま使用することができる。またビニルシランのケイ
素原子に結合しているアルコキシ基等によって、この亜
鉛化合物あるいはこの亜鉛化合物から生じた活性種が失
活する場合があるので、ガスクロマトグラフィーで反応
の状況を見ながら、亜鉛化合物のヘキサン溶液を滴下し
て反応系に供給することが好ましい。また、このために
亜鉛化合物の使用量を一義的には決定することはできな
いが、一般的には、ヨウ素１モルに対して１／1000モル
〜１／50モルの範囲が好適である。尚、亜鉛化合物のヘ
キサン溶液の滴下は、反応の進行状況によって異なって
くるが、実用的には、４〜８時間で滴下を完了させるこ
とが望ましい。This zinc compound is generally obtained as a hexane solution having a concentration of about 0.1 mol / liter, which can be used as it is. In addition, since the zinc compound or the active species generated from the zinc compound may be deactivated by the alkoxy group or the like bonded to the silicon atom of the vinylsilane, the zinc compound It is preferable to add a hexane solution dropwise to the reaction system. For this reason, the amount of the zinc compound used cannot be uniquely determined, but in general, a range of 1/1000 mol to 1/50 mol is suitable for 1 mol of iodine. The dropping of the hexane solution of the zinc compound depends on the progress of the reaction, but practically it is desirable to complete the dropping in 4 to 8 hours.
【００１７】反応 上記亜鉛化合物を触媒としての反応は、一般に、０〜70
℃、特に15〜30℃が好適である。さらに、亜鉛化合物添
加後、２〜５時間の反応熟成時間をとることが好まし
い。また反応は、反応に対して不活性である限り任意の
溶媒を使用することができるが、特に溶媒を使う必要は
ない。反応終了後、減圧蒸留等のそれ自体公知の精製処
理を行なうことにより、目的とする含フッ素シラン化合
物が得られる。 Reaction The reaction using the above zinc compound as a catalyst is generally from 0 to 70.
C., especially 15 to 30.degree. C. are preferred. Furthermore, it is preferable to take a reaction aging time of 2 to 5 hours after the addition of the zinc compound. Further, the reaction may use any solvent as long as it is inert to the reaction, but it is not particularly necessary to use a solvent. After the completion of the reaction, the desired fluorine-containing silane compound is obtained by performing a known purification treatment such as vacuum distillation.
【００１８】含フッ素シラン化合物；かくして得られる
含フッ素シラン化合物は、一般式(4) または(5) で表さ
れるものであり、この化合物は、フッ素化合物に特有な
耐溶剤性、耐薬品性、低表面エネルギーを有しており、
これらの特性が要求される材料として使用に供される。
具体的には、繊維処理剤、離型剤、ゴム内添剤、架橋剤
等の原料として有用である。 Fluorine-containing silane compound : The fluorine-containing silane compound thus obtained is represented by the general formula (4) or (5), and this compound has solvent resistance and chemical resistance peculiar to the fluorine compound. Has a low surface energy,
It is used as a material that requires these properties.
Specifically, it is useful as a raw material for a fiber treating agent, a release agent, a rubber internal additive, a crosslinking agent, and the like.
【００１９】[0019]
【実施例】実施例１ 攪拌子、温度計、ジムロート、三方コックを付した 500
ml四つ口フラスコに、 パーフルオロオクチルアイオダイド（Ｃ8 Ｆ17Ｉ） 273
ｇ(0.5モル) トリメチルビニルシラン 55ｇ（0.55モル） を仕込み、三方コックより窒素を流し、系内を窒素置換
した。次いで、 ジエチル亜鉛10ml（ 0.1モル濃度のヘキサン溶液： 0.0
01モル） を窒素を流しながら三方コックより注射器で滴下を開始
した。水浴で20〜40℃に保ちながら、約５時間かけてジ
エチル亜鉛を滴下したのち、原料のアイオダイドがほぼ
消失した時点で、減圧蒸留を行なった。沸点89〜91℃／
３mmHgの留分として、 Ｃ8 Ｆ17CH2 CHＩSiMe3 309ｇ（収率96％） が得られた。尚、生成物の同定は、以下の分析を行な
い、標品と比較同定することにより確認した。 [文献：
T.Fuchikami, I.Ojima, Tetrahedron Letters, 25, 30
3(1984)]EXAMPLES Example 1 500 equipped with a stirrer, thermometer, Dimroth, and three-way cock
ml 4-necked flask, perfluorooctyl iodide (C 8 F 17 I) 273
55 g (0.55 mol) of g (0.5 mol) trimethylvinylsilane was charged, and nitrogen was flowed from a three-way cock to replace the inside of the system with nitrogen. Then, 10 ml of diethyl zinc (0.1 molar hexane solution: 0.0
(01 mol) was added with a syringe from a three-way cock while flowing nitrogen. Diethyl zinc was added dropwise over about 5 hours while maintaining the temperature at 20 to 40 ° C. in a water bath, and vacuum distillation was carried out when the raw material iodide almost disappeared. Boiling point 89-91 ℃ /
As a fraction of 3 mmHg, 309 g of C 8 F 17 CH 2 CHISiMe 3 (96% yield) was obtained. The identification of the product was confirmed by performing the following analysis and comparing and identifying it with a standard product. [Reference:
T. Fuchikami, I. Ojima, Tetrahedron Letters, 25 , 30
3 (1984)]
【００２０】ＧＣ−マス：分子ピーク 646 ＩＲ：チャートを図１に示す。1 Ｈ−ＮＭＲ； CCl4 溶液：CHCl3 内部標準 (ppm) 0.30 （ｓ, Si−Me, 9H） 2.30〜3.13 （ｍ, −CH2 −, 2H） 3.13〜3.43 （ｍ, −CHＩ−, 1H）19 Ｆ−ＮＭＲ；CF3 COOH標準GC-mass: molecular peak 646 IR: chart is shown in FIG. 1 H-NMR; CCl 4 solution: CHCl 3 internal standard (ppm) 0.30 (s, Si-Me, 9H) 2.30 to 3.13 (m, -CH 2- , 2H) 3.13 to 3.43 (m, -CHI-, 1H ) 19 F-NMR; CF 3 COOH standard
【化１４】 (ppm) ａ: − 4.51 ｂ：−37.91 ｃ：−44.93 ｄ：−46.58 ｅ：−49.39Embedded image (ppm) a: −4.51 b: −37.91 c: −44.93 d: −46.58 e: −49.39
【００２１】実施例２ パーフルオロブチルアイオダイド及びトリメチルビニル
シランを使用し、表１に示す反応条件（ジエチル亜鉛の
使用量及び滴下時間）を使用した以外は実施例１と同様
にして反応及び蒸留を行ない、沸点57〜58℃／４mmHgの
留分として、 Ｃ4 Ｆ9 CH2 CHＩSiMe3 （収率92％） が得られた。尚、生成物の同定は、実施例１と同様にし
て行ない、以下の結果であった。 Example 2 Reaction and distillation were carried out in the same manner as in Example 1 except that perfluorobutyl iodide and trimethylvinylsilane were used and the reaction conditions shown in Table 1 (amount of diethyl zinc used and dropping time) were used. As a result, C 4 F 9 CH 2 CHISiMe 3 (yield 92%) was obtained as a fraction having a boiling point of 57 to 58 ° C./4 mmHg. The product was identified in the same manner as in Example 1 and the following results were obtained.
【００２２】ＩＲ：チャートを図２に示す。1 Ｈ−ＮＭＲ； CCl4 溶液：CHCl3 内部標準 (ppm) 0.32 （ｓ, Si−Me, 9H） 1.30〜3.12 （ｍ, −CH2 −, 2H） 3.12〜3.43 （ｍ, −CHＩ−, 1H）19 Ｆ−ＮＭＲ；CF3 COOH標準IR: The chart is shown in FIG. 1 H-NMR; CCl 4 solution: CHCl 3 internal standard (ppm) 0.32 (s, Si-Me, 9H) 1.30 to 3.12 (m, -CH 2- , 2H) 3.12 to 3.43 (m, -CHI-, 1H ) 19 F-NMR; CF 3 COOH standard
【化１５】 (ppm)ａ：− 4.70 ｂ：−38.21 ｃ：−47.80 ｄ：−49.08Embedded image (ppm) a: -4.70 b: -38.21 c: -47.80 d: -49.08
【００２３】実施例３ パーフルオロブチルアイオダイド及びトリエトキシビニ
ルシランを使用し、表１に示す反応条件（ジエチル亜鉛
の使用量及び滴下時間）を使用した以外は実施例１と同
様にして反応及び蒸留を行ない、沸点74〜76℃／２mmHg
の留分として、 Ｃ4 Ｆ9 CH2 CHＩSi (OEt)3 （収率92％） が得られた。尚、生成物の同定は、実施例１と同様にし
て行ない、以下の結果であった。 Example 3 Reaction and distillation were carried out in the same manner as in Example 1 except that perfluorobutyl iodide and triethoxyvinylsilane were used and the reaction conditions shown in Table 1 (amount of diethyl zinc used and dropping time) were used. Boiling point 74-76 ℃ / 2mmHg
C 4 F 9 CH 2 CHISi (OEt) 3 (yield 92%) was obtained as a fraction of The product was identified in the same manner as in Example 1 and the following results were obtained.
【００２４】ＩＲ：チャートを図３に示す。1 Ｈ−ＮＭＲ； CCl4 溶液：CHCl3 内部標準 (ppm) 1.30 （ｔ, −Me, 9H） 2.10〜3.00 （ｍ, −CF2 CH2 −, 2H） 3.00〜3.30 （ｍ, −CHＩ−, 1H） 3.93 （ｑ, Ｏ−CH2 −Ｃ, 6H）19 Ｆ−ＮＭＲ；CF3 COOH標準IR: The chart is shown in FIG. 1 H-NMR; CCl 4 solution: CHCl 3 internal standard (ppm) 1.30 (t, −Me, 9H) 2.10 to 3.00 (m, −CF 2 CH 2 −, 2H) 3.00 to 3.30 (m, −CHI−, 1H) 3.93 (q, O- CH 2 -C, 6H) 19 F-NMR; CF 3 COOH standard
【化１６】 (ppm) ａ：− 4.58 ｂ：−38.46 ｃ：−47.74 ｄ：−49.02Embedded image (ppm) a: −4.58 b: −38.46 c: −47.74 d: −49.02
【００２５】実施例４ パーフルオロオクチルアイオダイド及びメトキシジメチ
ルビニルシランを使用し、表１に示す反応条件（ジエチ
ル亜鉛の使用量及び滴下時間）を使用した以外は実施例
１と同様にして反応及び蒸留を行ない、沸点 108〜110
℃／４mmHgの留分として、 Ｃ8 Ｆ17CH2 CHＩSi(Me)2 (OMe) （収率84％） が得られた。尚、生成物の同定は、実施例１と同様にし
て行ない、以下の結果であった。 Example 4 Reaction and distillation were carried out in the same manner as in Example 1 except that perfluorooctyl iodide and methoxydimethylvinylsilane were used and the reaction conditions shown in Table 1 (diethyl zinc usage and dropping time) were used. Boiling point 108-110
C 8 F 17 CH 2 CHISi (Me) 2 (OMe) (yield 84%) was obtained as a fraction at ℃ / 4 mmHg. The product was identified in the same manner as in Example 1 and the following results were obtained.
【００２６】ＩＲ：チャートを図４に示す。1 Ｈ−ＮＭＲ； CCl4 溶液：CHCl3 内部標準 (ppm) 1.42 （ｓ, Si−Me, 6H） 2.26〜3.15 （ｍ, −CH2 −, 2H） 3.15〜3.42 （ｍ, −CHＩ−, 1H） 3.53 （ｓ, Ｏ−Me, 3H）19 Ｆ−ＮＭＲ；CF3 COOH標準IR: The chart is shown in FIG. 1 H-NMR; CCl 4 solution: CHCl 3 internal standard (ppm) 1.42 (s, Si-Me, 6H) 2.26 to 3.15 (m, -CH 2- , 2H) 3.15 to 3.42 (m, -CHI-, 1H ) 3.53 (s, O-Me, 3H) 19 F-NMR; CF 3 COOH standard
【化１７】 (ppm) ａ：− 4.51 ｂ：−38.03 ｃ：−44.87 ｄ：−46.52 ｅ：−49.26Embedded image (ppm) a: −4.51 b: −38.03 c: −44.87 d: −46.52 e: −49.26
【００２７】実施例５ パーフルオロオクチルアイオダイド及びジメトキシメチ
ルビニルシランを使用し、表１に示す反応条件（ジエチ
ル亜鉛の使用量及び滴下時間）を使用した以外は実施例
１と同様にして反応及び蒸留を行ない、沸点97〜98℃／
１mmHgの留分として、 Ｃ8 Ｆ17CH2 CHＩSi(Me) (OMe)2 （収率82％） が得られた。尚、生成物の同定は、実施例１と同様にし
て行ない、以下の結果であった。 Example 5 Reaction and distillation were carried out in the same manner as in Example 1 except that perfluorooctyl iodide and dimethoxymethylvinylsilane were used and the reaction conditions shown in Table 1 (diethyl zinc usage and dropping time) were used. Boiling point 97-98 ℃ /
As a fraction of 1 mmHg, C 8 F 17 CH 2 CHISi (Me) (OMe) 2 (yield 82%) was obtained. The product was identified in the same manner as in Example 1 and the following results were obtained.
【００２８】ＩＲ：チャートを図５に示す。1 Ｈ−ＮＭＲ； CCl4 溶液：CHCl3 内部標準 (ppm) 0.42 （ｓ, Si−Me, 3H） 2.10〜3.32 （ｍ, −CH2 CHＩ−, 3H） 3.53 （ｓ, Ｏ−Me, 6H）19 Ｆ−ＮＭＲ；CF3 COOH標準IR: The chart is shown in FIG. 1 H-NMR; CCl 4 solution: CHCl 3 internal standard (ppm) 0.42 (s, Si-Me, 3H) 2.10 to 3.32 (m, -CH 2 CHI-, 3H) 3.53 (s, O-Me, 6H) 19 F-NMR; CF 3 COOH standard
【化１８】 (ppm) ａ：− 4.51 ｂ：−38.15 ｃ：−44.87 ｄ：−46.52 ｅ：−49.26Embedded image (ppm) a: −4.51 b: −38.15 c: −44.87 d: −46.52 e: −49.26
【００２９】実施例６ パーフルオロオクチルアイオダイド及びトリエトキシビ
ニルシランを使用し、表１に示す反応条件（ジエチル亜
鉛の使用量及び滴下時間）を使用した以外は実施例１と
同様にして反応及び蒸留を行ない、沸点 113〜115 ℃／
１mmHgの留分として、 Ｃ8 Ｆ17CH2 CHＩSi (OEt)3 （収率63％） が得られた。尚、生成物の同定は、実施例１と同様にし
て行ない、以下の結果であった。 Example 6 Reaction and distillation were carried out in the same manner as in Example 1 except that perfluorooctyl iodide and triethoxyvinylsilane were used and the reaction conditions shown in Table 1 (diethyl zinc usage and dropping time) were used. Boiling point 113-115 ℃ /
C 8 F 17 CH 2 CHISi (OEt) 3 (yield 63%) was obtained as a fraction of 1 mmHg. The product was identified in the same manner as in Example 1 and the following results were obtained.
【００３０】ＩＲ：チャートを図６に示す。1 Ｈ−ＮＭＲ； CCl4 溶液：CHCl3 内部標準 (ppm) 1.30 （ｔ, −Me, 9H） 2.17〜3.30 （ｍ, −CH2 CHＩ−, 3H） 3.95 （ｑ, Ｏ−CH2 −, 6H）19 Ｆ−ＮＭＲ；CF3 COOH標準IR: The chart is shown in FIG. 1 H-NMR; CCl 4 solution: CHCl 3 internal standard (ppm) 1.30 (t, −Me, 9H) 2.17 to 3.30 (m, −CH 2 CHI−, 3H) 3.95 (q, O—CH 2 −, 6H ) 19 F-NMR; CF 3 COOH standard
【化１９】 (ppm) ａ：− 4.51 ｂ：−38.34 ｃ：−44.93 ｄ：−46.76 ｅ：−49.32Embedded image (ppm) a: −4.51 b: −38.34 c: −44.93 d: −46.76 e: −49.32
【００３１】実施例７ アイオダイドとして表１に示すパーフルオロアルキルエ
ーテルアイオダイドを使用し且つメトキシジメチルビニ
ルシランを使用し、表１に示す反応条件（ジエチル亜鉛
の使用量及び滴下時間）を使用した以外は実施例１と同
様にして反応及び蒸留を行ない、沸点 69 〜 71 ℃／３
mmHgの留分として、下記式： Example 7 Except that the perfluoroalkyl ether iodide shown in Table 1 was used as the iodide, methoxydimethylvinylsilane was used, and the reaction conditions (the amount of diethylzinc used and the dropping time) shown in Table 1 were used. Reaction and distillation were carried out in the same manner as in Example 1, and the boiling point was 69 to 71 ° C / 3.
As the fraction of mmHg, the following formula:
【化２０】 で表されるシラン化合物を得た（収率75％）。尚、生成
物の同定は、実施例１と同様にして行ない、以下の結果
であった。Embedded image A silane compound represented by was obtained (yield 75%). The product was identified in the same manner as in Example 1 and the following results were obtained.
【００３２】ＩＲ：チャートを図７に示す。1 Ｈ−ＮＭＲ； CCl4 溶液：CHCl3 内部標準 (ppm) 0.43 （ｓ, −SiMe, 6H） 2.27〜3.37 （ｍ, −CH2 CHＩ−, 3H） 3.54 （ｓ, −ＯMe, 3H）19 Ｆ−ＮＭＲ；CF3 COOH標準IR: The chart is shown in FIG. 1 H-NMR; CCl 4 solution: CHCl 3 internal standard (ppm) 0.43 (s, −SiMe, 6H) 2.27 to 3.37 (m, −CH 2 CHI−, 3H) 3.54 (s, −OMe, 3H) 19 F -NMR; CF 3 COOH standard
【化２１】 (ppm) ａ：− 3.48 ｂ：− 5.00 ｃ：− 6.58 ｄ：−52.80 ｅ：−56.12 f: −67.70Embedded image (ppm) a: -3.48 b: -5.00 c: -6.58 d: -52.80 e: -56.12 f: -67.70
【００３３】[0033]
【表１】 [Table 1]
【００３４】実施例８ 攪拌子、温度計、ジムロート、三方コックを備えた 500
ml四つ口フラスコに、 ＩＣ4 Ｆ8 Ｉ 227ｇ(0.5モル) ジメチルメトキシビニルシラン 139ｇ(1.2モル) を仕込んだ。三方コックより窒素を流し、系内を窒素置
換した。次いで、ジエチル亜鉛20mlを注射器により三方
コックから滴下を開始する。水浴で20〜40℃に保ちなが
ら、約７時間かけて滴下した。その後、２時間後攪拌
し、原料がほぼ消失したことを確認し、減圧蒸留を行な
い、 150〜151 ℃／ 2.0×10-5Torrの留分として下記
式： Example 8 500 equipped with stirrer, thermometer, Dimroth, three-way cock
Into a ml four-necked flask, 227 g (0.5 mol) of IC 4 F 8 I and 139 g (1.2 mol) of dimethylmethoxyvinylsilane were charged. Nitrogen was flown from the three-way cock to replace the inside of the system with nitrogen. Then, 20 ml of diethyl zinc is started to be dropped from a three-way cock by a syringe. While maintaining the temperature at 20 to 40 ° C in a water bath, the solution was added dropwise over about 7 hours. Then, after stirring for 2 hours, it was confirmed that the raw material had almost disappeared, vacuum distillation was carried out, and the following formula was used as a fraction of 150 to 151 ° C./2.0×10 −5 Torr:
【化２２】 のシラン化合物 292ｇ（収率85％）を得た。尚、生成物
の同定は、実施例１と同様にして行ない、以下の結果で
あった。Embedded image 292 g (yield 85%) of the silane compound of The product was identified in the same manner as in Example 1 and the following results were obtained.
【００３５】ＧＣ−マス： 686 ＩＲ；チャートを図８に示す。1 Ｈ−ＮＭＲ； CCl4 溶液：CHCl3 内部標準 (ppm) 0.40 （ｓ, −SiMe, 12H） 2.10〜3.47 （ｍ, −CH2 CHＩ−, 6H） 3.54 （ｓ, −ＯMe, 6H）19 Ｆ−ＮＭＲ；CF3 COOH標準GC-mass: 686 IR; chart is shown in FIG. 1 H-NMR; CCl 4 solution: CHCl 3 internal standard (ppm) 0.40 (s, --SiMe, 12H) 2.10 to 3.47 (m, --CH 2 CHI--, 6H) 3.54 (s, --OMe, 6H) 19 F -NMR; CF 3 COOH standard
【化２３】 (ppm) ａ：−38.59 ｂ：−46.94 Embedded image (ppm) a: −38.59 b: −46.94
【００３６】[0036]
【発明の効果】本発明によれば、安価で且つ取扱い容易
な亜鉛化合物を反応触媒として使用することにより、含
フッ素アイオダイドとビニルシランとの反応により含フ
ッ素シラン化合物を得ることが可能となった。この反応
は比較的低温で行なうことができ、工業的に極めて有用
である。According to the present invention, it becomes possible to obtain a fluorine-containing silane compound by reacting a fluorine-containing iodide with vinylsilane by using a zinc compound which is inexpensive and easy to handle. This reaction can be carried out at a relatively low temperature and is industrially extremely useful.
【図１】実施例１で合成されたシラン化合物のＩＲチャ
ート。FIG. 1 is an IR chart of a silane compound synthesized in Example 1.
【図２】実施例２で合成されたシラン化合物のＩＲチャ
ート。FIG. 2 is an IR chart of the silane compound synthesized in Example 2.
【図３】実施例３で合成されたシラン化合物のＩＲチャ
ート。FIG. 3 is an IR chart of the silane compound synthesized in Example 3.
【図４】実施例４で合成されたシラン化合物のＩＲチャ
ート。FIG. 4 is an IR chart of the silane compound synthesized in Example 4.
【図５】実施例５で合成されたシラン化合物のＩＲチャ
ート。5 is an IR chart of the silane compound synthesized in Example 5. FIG.
【図６】実施例６で合成されたシラン化合物のＩＲチャ
ート。FIG. 6 is an IR chart of the silane compound synthesized in Example 6.
【図７】実施例７で合成されたシラン化合物のＩＲチャ
ート。FIG. 7 is an IR chart of the silane compound synthesized in Example 7.
【図８】実施例８で合成されたシラン化合物のＩＲチャ
ート。8 is an IR chart of the silane compound synthesized in Example 8. FIG.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 小池 則之 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社 シリコーン電 子材料技術研究所内 (72)発明者 松田 高至 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社 シリコーン電 子材料技術研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location // C07B 61/00 300 C07B 61/00 300 (72) Inventor Noriyuki Koike Matsui Usui-gun Gunma Prefecture Tamachi Oji Hitomi 1-10 Shin-Etsu Chemical Co., Ltd. Silicon Silicon Electronic Materials Research Laboratory (72) Inventor Takashi Matsuda Matsuda-cho, Gunma Pref. In-house
Claims (2)
またはパーフルオロポリエーテル基を示す〕で示される
ヨウ素化合物と、下記一般式(2): 【化１】 〔式中、Ｘは炭素数１〜５のアルコキシ基、Ｒ1 は炭素
数１〜10の非置換もしくは置換炭化水素基、ａは０〜３
の整数である〕で表されるビニルシランとを、下記一般
式(3): Ｒ2 Zn (3) 〔式中、Ｒは炭素数１〜５の非置換の一価炭化水素基で
ある〕で表される亜鉛化合物の存在下に反応させる工程
を有する、下記一般式(4): 【化２】 〔式中、Rf1 , Ｒ1 及びａは前述の通りである〕で表さ
れる含フッ素シラン化合物の製造方法。1. An iodine compound represented by the following general formula (1a): Rf 1 I (1a) [wherein, Rf 1 represents a perfluoroalkyl group or a perfluoropolyether group having 1 to 15 carbon atoms] , The following general formula (2): [In the formula, X is an alkoxy group having 1 to 5 carbon atoms, R 1 is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and a is 0 to 3
A vinyl silane represented by the following general formula (3): R 2 Zn (3) [wherein, R is an unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms] The following general formula (4) has a step of reacting in the presence of a zinc compound represented by: A method for producing a fluorine-containing silane compound represented by the formula: wherein Rf 1 , R 1 and a are as described above.
基もしくは二価のパーフルオロポリエーテル基である〕
で示されるヨウ素化合物と、一般式(2): 【化３】 〔式中、Ｘ及びａは前述の通りである〕で表されるビニ
ルシランとを、一般式(3): Ｒ2 Zn (3) 〔式中、Ｒは前述の通りである〕で表される亜鉛化合物
の存在下に反応させる工程を有する、一般式(5): 【化４】 〔式中、Rf2 , Ｘ, Ｒ1 及びａは前述の通りである〕で
表される含フッ素シラン化合物の製造方法。Wherein the following formula (1b): I-Rf 2 -I (1b) wherein, Rf 2 is a perfluoroalkylene group or a divalent perfluoropolyether group having 1 to 15 carbon atoms]
With an iodine compound represented by the general formula (2): [Wherein X and a are as described above] and a vinylsilane represented by the general formula (3): R 2 Zn (3) [wherein R is as described above] General formula (5) having a step of reacting in the presence of a zinc compound: [In the formula, Rf 2 , X, R 1 and a are as described above].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4227986A JP2684296B2 (en) | 1992-08-04 | 1992-08-04 | Method for producing fluorine-containing organosilicon compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4227986A JP2684296B2 (en) | 1992-08-04 | 1992-08-04 | Method for producing fluorine-containing organosilicon compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0656854A JPH0656854A (en) | 1994-03-01 |
| JP2684296B2 true JP2684296B2 (en) | 1997-12-03 |
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ID=16869376
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4227986A Expired - Fee Related JP2684296B2 (en) | 1992-08-04 | 1992-08-04 | Method for producing fluorine-containing organosilicon compound |
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| US10745524B2 (en) | 2016-01-20 | 2020-08-18 | Ochanomizu University | Fluorine-containing and silicon containing compound |
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| Publication number | Publication date |
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| JPH0656854A (en) | 1994-03-01 |
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