JPH036154B2 - - Google Patents
Info
- Publication number
- JPH036154B2 JPH036154B2 JP62289286A JP28928687A JPH036154B2 JP H036154 B2 JPH036154 B2 JP H036154B2 JP 62289286 A JP62289286 A JP 62289286A JP 28928687 A JP28928687 A JP 28928687A JP H036154 B2 JPH036154 B2 JP H036154B2
- Authority
- JP
- Japan
- Prior art keywords
- bis
- group
- peak
- alkane
- formula
- 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.)
- Expired
Links
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- -1 alkylsilane compounds Chemical class 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 125000005587 carbonate group Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001793 charged compounds Chemical class 0.000 description 4
- 238000006114 decarboxylation reaction Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000460 chlorine Chemical group 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052801 chlorine Chemical group 0.000 description 2
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OLBGECWYBGXCNV-UHFFFAOYSA-N 3-trichlorosilylpropanenitrile Chemical compound Cl[Si](Cl)(Cl)CCC#N OLBGECWYBGXCNV-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002947 alkylene 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- PFMKUUJQLUQKHT-UHFFFAOYSA-N dichloro(ethyl)silicon Chemical compound CC[Si](Cl)Cl PFMKUUJQLUQKHT-UHFFFAOYSA-N 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Description
本発明は一般式
（但し、R1はアルキル基、R2はCH2CH2O又は
CH2CH2CH2Oで該酸素は上記一般式の右側のカ
ルボニルに結合し、Ｘはハロゲン原子で、ｍは１
〜２又ｎは１〜４の整数を表わす）で示されるビ
ス（ハロシリルプロポキシカルボニルオキシ）ア
ルカンを提供するものである。尚本発明で云うビ
ス（ハロシリルプロポキシカルボニルオキシ）ア
ルカンは、上記定義から明白なようにビス（ハロ
シリルプロポキシカルボニルオキシ）オキサアル
カンを含む総称である。
従来、Ｙ−Ｒ−SiX3（Ｘはハロゲン原子、Ｙは
管能基、Ｒは直鎖または分枝状のアルキレン基な
どを表わす）で示される官能性アルキルシラン化
合物、例えば２−シアノエチルトリクロロシラン
などは公知の化合物で繊維表面などへの撥水処理
剤、潤滑剤、防錆剤等に使用されることが知られ
ている。
本発明者は長年有用な種々の官能性有機珪素化
合物の合成研究を続けて来たが、新規な化合物で
ある、一般式
（但し、R1はアルキル基、R2はCH2CH2O又は
CH2CH2CH2Oで該酸素は上記一般式の右側カル
ボニルに結合し、Ｘはハロゲン原子で、ｍは１〜
２又ｎは１〜４の整数を表わす）で示される。ビ
ス（ハロシリルプロポキシカルボニルオキシ）ア
ルカンを合成し、その構造及び用途を確認、本発
明を完成し提供するに至つた。
即ち本発明の新規化合物であるビス（ハロシリ
ルプロポキシカルボニルオキシ）アルカンは一般
式
（但し、R1はアルキル基、R2はCH2CH2O又は
CH2CH2CH2Oで該酸素は上記一般式の右側カル
ボニルに結合し、Ｘはハロゲン原子、ｍは１〜２
又ｎは１〜４の整数を表わす）で示される。
式中のR1は、メチル基、エチル基、プロピル
基、ブチル基などのアルキル基であり、ハロゲン
その他の置換基が存在してもよい。また炭素数が
大きくなる程疎水性が増し、本物質を種々のコー
ト剤としての用途に応じて適宜選択できる。また
R2 oは本物質を剤などに用いる場合の基材との馴
染を調整するなどの働きがあり、プラスチツク材
などに適用する場合にはR2 oが−
CH2CH2OCH2CH2O−の形態がしばしば好まし
い場合がある。またＸはハロゲン原子であり、特
に塩素及び臭素が好ましい。
本発明のビス（ハロシリルプロポキシカルボニ
ルオキシ）アルカン、即ち、
は一般式にＸの種類ならびにｎの数によつてその
性状が多少異なるが通常、常温常圧下では無色透
明液体状で存在する。また本発明のビス（ハロシ
リルプロポキシカルボニルオキシ）アルカンは一
般に次の(イ)〜(ニ)のような手段で一般式の各化合物
であることを確認することが出来る。
(イ) 赤外線吸収スペクトル（IR）を測定するこ
とにより、1740〜1750cm-1付近にカーボネート
化合物に特有なカルボニル基にもとづく強い吸
収が現われる。なお、単離精製した無色透明液
体である生成物を高温例えば180℃以上に加熱
した場合、連続的に泡を発生して分解するこ
と、即ち脱炭酸反応を起こすことからも生成物
がカーボネート類に属していることを知ること
ができる。
(ロ) 13炭素核磁気共鳴スペクトル（13C−NMR）
を測定することによつて分子中に存在するメチ
レン基ならびにカーボネート基の個数と種類、
珪素原子上のアルキル基の個数と種類を知るこ
とが出来る。即ち、13C−NMR（テトラメチル
シラン基準）に於いて156ppm付近にカーボネ
ート化合物に特有なカルボニル基の炭素原子に
基づくピーク、70ppm付近にカーボネートの酸
素原子に隣接するメチレン基の炭素原子に基づ
くピーク、23ppm付近にプロピレン基の中央に
位置するメチレン基の炭素原子に基づくピー
ク、５〜15ppm付近に珪素原子に隣接したメチ
レン基の炭素原子に基づくピークを示す。さら
に分子中にエーテル結合が存在する場合、該エ
ーテル基に隣接するメチレン基の炭素原子に基
づくピークが70ppm付近に現われる。なお、そ
れぞれのピーク強度を相対的に比較することに
より、それぞれの結合基の個数を知ることが出
来る。
(ハ) 質量スペクトル（MS）を測定し、観察され
る各ピーク（一般にはイオンの分子量を電子の
荷電数ｅで割つたｍ／ｅで表わされる質量数）
に相当する組成式を算出することにより、測定
に供した試料の結合様式さらに終局的にはその
分子量を推定することが出来る。例えば前記一
般式に於いてＸが塩素原子でありｍが２でR1
がメチル基である場合ｍ／e159，157，155に
The present invention is based on the general formula (However, R 1 is an alkyl group, R 2 is CH 2 CH 2 O or
In CH 2 CH 2 CH 2 O, the oxygen is bonded to the carbonyl on the right side of the above general formula, X is a halogen atom, and m is 1
~2 or n represents an integer of 1 to 4). As is clear from the above definition, the term "bis(halosilylpropoxycarbonyloxy)alkane" used in the present invention is a general term that includes bis(halosilylpropoxycarbonyloxy)oxaalkane. Conventionally, functional alkylsilane compounds represented by Y-R-SiX 3 (X is a halogen atom, Y is a functional group, R is a linear or branched alkylene group, etc.), such as 2-cyanoethyltrichlorosilane. These are known compounds and are known to be used as water repellent treatment agents, lubricants, rust preventive agents, etc. for fiber surfaces. The present inventor has been conducting research on the synthesis of various useful functional organosilicon compounds for many years, and has developed a new compound with the general formula (However, R 1 is an alkyl group, R 2 is CH 2 CH 2 O or
In CH 2 CH 2 CH 2 O, the oxygen is bonded to the carbonyl on the right side of the above general formula, X is a halogen atom, and m is 1 to
2 or n represents an integer from 1 to 4). We synthesized bis(halosilylpropoxycarbonyloxy)alkane, confirmed its structure and uses, and completed and provided the present invention. That is, the novel compound of the present invention, bis(halosilylpropoxycarbonyloxy)alkane, has the general formula (However, R 1 is an alkyl group, R 2 is CH 2 CH 2 O or
In CH 2 CH 2 CH 2 O, the oxygen is bonded to the carbonyl on the right side of the above general formula, X is a halogen atom, and m is 1 to 2
Further, n represents an integer from 1 to 4). R 1 in the formula is an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, and a halogen or other substituent may be present. Furthermore, as the number of carbon atoms increases, the hydrophobicity increases, and this substance can be appropriately selected depending on the use as a coating agent. Also
R 2 o has the function of adjusting the compatibility with the base material when this substance is used in agents, etc., and when applied to plastic materials, R 2 o is -
The CH2CH2OCH2CH2O- form is often preferred. Further, X is a halogen atom, and chlorine and bromine are particularly preferred. The bis(halosilylpropoxycarbonyloxy)alkane of the present invention, i.e. Although its properties differ somewhat depending on the type of X and the number of n in the general formula, it usually exists in the form of a colorless and transparent liquid at room temperature and normal pressure. Furthermore, it can generally be confirmed that the bis(halosilylpropoxycarbonyloxy)alkane of the present invention is a compound of the general formula by the following methods (a) to (d). (b) By measuring the infrared absorption spectrum (IR), a strong absorption based on the carbonyl group characteristic of carbonate compounds appears around 1740 to 1750 cm -1 . In addition, when the product, which is an isolated and purified colorless transparent liquid, is heated to a high temperature, e.g., 180°C or higher, it continuously generates bubbles and decomposes, that is, a decarboxylation reaction occurs. You can know that you belong to (b) 13 carbon nuclear magnetic resonance spectrum ( 13 C-NMR)
By measuring the number and type of methylene groups and carbonate groups present in the molecule,
You can know the number and types of alkyl groups on silicon atoms. That is, in 13 C-NMR (tetramethylsilane standard), there is a peak at around 156 ppm based on the carbon atom of the carbonyl group specific to carbonate compounds, and a peak at around 70 ppm based on the carbon atom of the methylene group adjacent to the oxygen atom of the carbonate. , a peak based on the carbon atom of the methylene group located at the center of the propylene group is shown around 23 ppm, and a peak based on the carbon atom of the methylene group adjacent to the silicon atom is shown around 5 to 15 ppm. Furthermore, when an ether bond exists in the molecule, a peak based on the carbon atom of the methylene group adjacent to the ether group appears at around 70 ppm. Note that the number of each bonding group can be determined by relatively comparing the respective peak intensities. (c) Measure the mass spectrum (MS) and each peak observed (generally the mass number expressed as m/e, which is the molecular weight of the ion divided by the number of electron charges e)
By calculating the compositional formula corresponding to , it is possible to estimate the binding mode and ultimately the molecular weight of the sample subjected to measurement. For example, in the above general formula, X is a chlorine atom, m is 2, and R 1
If is a methyl group, m/e159, 157, 155
【式】に相当する極めて強い ピーク、ｍ／e117，115，113にextremely strong equivalent to [formula] Peak, m/e at 117, 115, 113
【式】に相
当するピークを示す。さらに極めて注意深く測
定を行なうと、強度的には弱いが対応する分子
量に相当する分子イオンピーク（Ｍ
）を観察
することができる。同様にＸ，R1，ｍが他の
組合わせの場合も特有のピークを観察すること
が出来る。
(ニ) 元素分析によつて炭素、水素、珪素の各重量
％を求め、さらに認知された各元素の重量％の
和を100から減じることにより、酸素の重量％
を算出することが出来、従つて、該生成物の組
成式を決定することが出来る。
本発明のビス（ハロシリルプロポキシカルボニ
ルオキシ）アルカンは高沸点も有する無色無臭の
透明液体であり、具体的には後述する実施例に示
すが、一般の有機化合物と同じように分子量が大
きくなる程沸点が高くなる傾向がある。
本発明のビス（ハロシリルプロポキシカルボニ
ルオキシ）アルカンはベンゼン、エーテル、ヘキ
サン、クロロホルム、四塩化炭素、アセトニトリ
ル、Ｎ，Ｎ−ジメチルホルムアミドなどの一般有
機溶媒に良く溶ける。また、前記一般式で示され
るジカーボネートを含水溶媒に添加すると発熱を
伴う加水分解反応が起こり、対応するポリシルセ
スキオキサン化合物に変化する。また、該加水分
解は溶媒に水酸化ナトリウム、水酸化カリウム、
アンモニア等の塩基類あるいは塩酸、硫酸、酢酸
等の酸類を添加することにより大いに促進され
る。本発明のビス（ハロシリルプロポキシカルボ
ニルオキシ）アルカンは無溶媒あるいは不活性溶
媒中で180℃以上に加熱した場合、連続的に脱炭
酸反応を起こす。該脱炭酸反応は加熱温度が高く
なる程、激しくなる傾向にある。なお脱炭酸反応
後の分解物も一般に無色透明の液体である。
本発明のビス（ハロシリルプロポキシカルボニ
ルオキシ）アルカンの製造方法は特に限定されず
如何なる方法によつて得てもよい。一般に好適に
採用される代表的な製造方法を以下に説明する。
即ち下記式で示されるビス（アリルオキシカルボ
ニルオキシ）アルカンと一般式
（但し、Ｘはハロゲン原子、ｍは１〜２の整数
である）で示されるシラン化合物例えばアルキル
ジハロゲノシランとを触媒存在下に反応させるこ
とによつて好収率で目的とするビス（ハロシリル
プロポキシカルボニルオキシ）アルカンを得るこ
とが出来る。
上記式で示されるビス（アリルオキシカルボニ
ルオキシ）アルカンは、その製法に限定されず例
えば公知の製法でられるものが特に制限されずに
使用出来る。またアルキルハロゲノシランは一般
式
（Ｘはハロゲン原子、ｍは１〜２の整数であ
る）で示される化合物で、その製法に限定されず
使用出来る。また該反応に用いられる触媒は、塩
化白金酸カリウム、白金黒、Pt／Ｃ、Pt／シリ
カ、Pt／アルミナ、PtCl2（Phh3）2、塩化白金酸
等の白金化合物、PdCl2、PdCl2（PPh3）2、PdCl2
（C6H5CN）2等のパラジウム化合物、RhCl3、
RhCl（PPh3）3等のロジウム化合物などのいわゆる
ヒドロジリル化反応に一般的に用いられる触媒で
あれば特に限定されず使用することが出来るが、
中でも白金黒、塩化白金酸等の白金化合物が少量
でしかも効果的である場合が多いので好適であ
る。
本発明に於けるビス（アリルオキシカルボニル
オキシ）アルカンとアルキルアルコキシシランと
の反応の代表例は後述する実施例で詳述する。該
反応は一般に無溶媒に於いても実施することが出
来るが、通常溶媒の存在下実施するのが一般的で
ある。該溶媒としては、原料或いは触媒と反応し
ない極性非水溶媒ならば特に限定されず用いるこ
とが出来、一般にはベンゼン、トルエン、ヘキサ
ン等の炭化水素系溶媒；クロロホルム、四塩化炭
素等のハロゲン化炭化水素系溶媒；ジメチルエー
テル、ジエチルエーテル等のエーテル系溶媒等が
好適に使用される。
また前記反応条件は特に限定されるものではな
いが、原料の種類、触媒の種類、溶媒の有無又は
種類等によつて異なる場合があるので予め好適な
条件を選定して実施するのが好ましい。一般には
−20〜160℃の温度下に、数10分〜40時間の範囲
で選べば十分である。また反応圧力は大気圧下に
十分に進行するので通常は常圧で実施すればよ
く、必要に応じて加圧下或いは減圧下で実施する
ことも出来る。
本発明のビス（ハロシリルプロポキシカルボニ
ルオキシ）アルカンは前記一般式から或いは前記
性状の説明からも明らかなようにカーボネート基
と両端に珪素を含む化合物である。該カーボネー
ト基は前記したように加熱することによつて炭酸
ガスとして離脱するのでこの性状を利用した発泡
剤としての用途がある。また前記含有珪素に基因
し撥水性の強いものであるので撥水剤としての用
途も有する。この場合ビス（シリルプロポキシカ
ルボニルオキシ）アルカンは部分的に又は完全に
加水分解させることによつて架橋した強固な被膜
とすることも出来るのでガラス、セメント、モル
タル等の無機材料；紙、木材、セルロース、ナイ
ロン等についての種々の形態の加工物の表面に塗
布することにより該加工物に撥水性を付与するこ
とが出来る。
本発明を更に具体的に説明するために以下実施
例を挙げて説明するが本発明はこれらの実施例に
限定されるものではない。
実施例 １
１，５−ビス（アリルオキシカルボニルオキ
シ）−３−オキサペンタン
（41.3ｇ、0.15モル）、メチルジクロロシラン
（51.8ｇ）、無水ｎ−ヘキサン（100ml）の混合物
に塩化白金酸・６水和物（100mg）を加え、磁気
撹拌下に８時間加熱還流した。反応混合物から低
沸点成分を常圧蒸留によつて除いた後、さらに高
沸点成分を油浴上70℃、最終的には130℃にまで
徐々に加熱しながら注意深く高真空（約0.1mmＨ
ｇ）留去した。該反応生成物は上記加熱蒸留によ
り淡黄色から暗黄色に変化した。少量の黒色沈殿
をドライボツクス中で濾過することにより、黒色
を帯びたやや粘稠な液体（73.0ｇ）を得た。赤外
吸収スペクトルを測定したところ1745cm-1にカー
ボネート基のカルボニル基に基づく強い吸収を示
した。その元素分析値はC33.0％、H5.17％であ
つてC14H26O7Cl4Si2（504.33）に対する計算値で
あるC33.3％、H5，20％に極めて良く一致した。
また質量スペクトルを測定したところｍ／e506，
504，502に強度的には弱いが分子量に相当する分
子イオンピーク（Ｍ
）、ｍ／e263，261，259に
The peak corresponding to [Formula] is shown. Furthermore, if measurements are carried out very carefully, a molecular ion peak (M) corresponding to the corresponding molecular weight can be observed, although the intensity is weak. Similarly, unique peaks can be observed when X, R 1 and m are used in other combinations. (d) Determine the weight percent of each of carbon, hydrogen, and silicon by elemental analysis, and then subtract the sum of the weight percent of each recognized element from 100 to determine the weight percent of oxygen.
can be calculated, and therefore the compositional formula of the product can be determined. The bis(halosilylpropoxycarbonyloxy)alkane of the present invention is a colorless and odorless transparent liquid that also has a high boiling point, and will be specifically shown in the examples below, but as with general organic compounds, the larger the molecular weight, the higher the molecular weight. The boiling point tends to be high. The bis(halosilylpropoxycarbonyloxy)alkane of the present invention is well soluble in common organic solvents such as benzene, ether, hexane, chloroform, carbon tetrachloride, acetonitrile, and N,N-dimethylformamide. Further, when the dicarbonate represented by the above general formula is added to a water-containing solvent, a hydrolysis reaction accompanied by heat occurs, and the dicarbonate is converted into the corresponding polysilsesquioxane compound. In addition, in the hydrolysis, sodium hydroxide, potassium hydroxide,
It is greatly promoted by adding bases such as ammonia or acids such as hydrochloric acid, sulfuric acid, acetic acid, etc. When the bis(halosilylpropoxycarbonyloxy)alkane of the present invention is heated to 180°C or higher without a solvent or in an inert solvent, a decarboxylation reaction occurs continuously. The decarboxylation reaction tends to become more intense as the heating temperature becomes higher. Note that the decomposed product after the decarboxylation reaction is also generally a colorless and transparent liquid. The method for producing the bis(halosilylpropoxycarbonyloxy)alkane of the present invention is not particularly limited and may be obtained by any method. A typical manufacturing method that is generally suitably employed will be described below.
That is, bis(allyloxycarbonyloxy)alkane shown by the following formula and the general formula (wherein, Silylpropoxycarbonyloxy)alkane can be obtained. The bis(allyloxycarbonyloxy)alkane represented by the above formula is not limited to its production method, and for example, those produced by known production methods can be used without particular limitation. Also, alkylhalogenosilane has the general formula (X is a halogen atom, m is an integer of 1 to 2) and can be used without being limited to its manufacturing method. Catalysts used in the reaction include potassium chloroplatinate, platinum black, Pt/C, Pt/silica, Pt/alumina, PtCl 2 (Phh 3 ) 2 , platinum compounds such as chloroplatinic acid, PdCl 2 , PdCl 2 ( PPh3 ) 2 , PdCl2
Palladium compounds such as (C 6 H 5 CN) 2 , RhCl 3 ,
Any catalyst that is commonly used in so-called hydrodylylation reactions, such as rhodium compounds such as RhCl (PPh 3 ) 3 , can be used without particular limitation.
Among these, platinum compounds such as platinum black and chloroplatinic acid are preferred because they are often effective even in small amounts. Representative examples of the reaction between bis(allyloxycarbonyloxy)alkane and alkylalkoxysilane in the present invention will be described in detail in the Examples below. Although the reaction can generally be carried out without a solvent, it is generally carried out in the presence of a solvent. The solvent is not particularly limited and can be used as long as it is a polar non-aqueous solvent that does not react with the raw materials or the catalyst, and generally includes hydrocarbon solvents such as benzene, toluene, and hexane; and halogenated carbonized solvents such as chloroform and carbon tetrachloride. Hydrogen solvent; ether solvents such as dimethyl ether and diethyl ether are preferably used. Further, the reaction conditions are not particularly limited, but may vary depending on the type of raw material, the type of catalyst, the presence or absence of a solvent, etc., so it is preferable to select suitable conditions in advance and carry out the reaction. Generally, it is sufficient to select a temperature of -20 to 160°C for several tens of minutes to 40 hours. Further, since the reaction pressure proceeds sufficiently under atmospheric pressure, it is usually sufficient to carry out the reaction at normal pressure, but it is also possible to carry out the reaction under increased pressure or reduced pressure if necessary. The bis(halosilylpropoxycarbonyloxy)alkane of the present invention is a compound containing a carbonate group and silicon at both ends, as is clear from the above general formula or from the description of the properties above. As mentioned above, the carbonate group is released as carbon dioxide gas by heating, and this property can be used as a blowing agent. Furthermore, since it has strong water repellency due to the silicon content, it can also be used as a water repellent. In this case, bis(silylpropoxycarbonyloxy)alkane can be partially or completely hydrolyzed to form a strong crosslinked film, so it can be used for inorganic materials such as glass, cement, mortar, etc.; paper, wood, cellulose; By applying it to the surface of various types of workpieces such as nylon, etc., water repellency can be imparted to the workpieces. EXAMPLES In order to explain the present invention more specifically, the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. Example 1 1,5-bis(allyloxycarbonyloxy)-3-oxapentane To a mixture of (41.3 g, 0.15 mol), methyldichlorosilane (51.8 g), and anhydrous n-hexane (100 ml) was added chloroplatinic acid hexahydrate (100 mg), and the mixture was heated under reflux for 8 hours with magnetic stirring. After removing the low-boiling components from the reaction mixture by atmospheric distillation, the high-boiling components were carefully heated under high vacuum (approximately 0.1 mm
g) Distilled away. The reaction product changed from pale yellow to dark yellow by the above-mentioned heated distillation. A small amount of black precipitate was filtered in a dry box to obtain a blackish, slightly viscous liquid (73.0 g). Measurement of the infrared absorption spectrum showed strong absorption at 1745 cm -1 due to the carbonyl group of the carbonate group. The elemental analysis values were C33.0% and H5.17%, which agreed very well with the calculated values for C14H26O7Cl4Si2 ( 504.33 ), which were C33.3%, H5, and 20%.
Also, when the mass spectrum was measured, m/e506,
The molecular ion peak (M) is weak in intensity at 504 and 502, but corresponds to the molecular weight, and m/e is at 263, 261, and 259.
【式】に対応
するピーク、ｍ／e159，157，155に
Peaks corresponding to [formula], m/e159, 157, 155
【式】に対応するピーク、ｍ／ e117，115，113にThe peak corresponding to [formula], m/ e117, 115, 113
【式】に対応するピークを
示した。さらに13C−核磁気共鳴スペクトル（13C
−nmr）を測定した。各ピーク（化学シフト値：
δppn：テトラメチルシラン基準）の解析結果は次
の通りであつた。
上記の結果から、単離生成物は原料である１，
５−ビス（アリルオキシカルボニルオキシ）−３
−オキサペンタン中の２個のアリル基がメチルジ
クロロシリル化された１，５−ビス（メチルジク
ロロシリルプロポキシカルボニルオキシ）−３−
オキサペンタンであることが明らかとなつた。収
率は用いた１，５−ビス（アリルオキシカルボニ
ルオキシ）−３−オキサペンタンに対して96.5％
であつた。
実施例 ２
１，２−ビス（アリルオキシカルボニルオキ
シ）エタン（23.0ｇ、0.1モル）、エチルジクロロ
シラン（38.7ｇ）、無水ｎ−ヘキサン（100ml）、
塩化白金酸・６水和物（50mg）の混合物につき実
施例１と同様に反応ならびに後処理を行ない、黒
みを帯びた黄色液体（48.1ｇ）を得た。赤外吸収
スペクトルを測定したところ1750cm-1にカーボネ
ート基のカルボニル結合に基づく強い吸収を示し
た。その元素分析値はC34.1％、H5.33％、
Cl29.11％であつてC14H26O6Cl4Si2（488.33）に対
する計算値であるC34.43％、H5.37％、Cl29.04％
に一致した。また質量スペクトル測定では分子イ
オンピーク（Ｍ
）の他に
The peak corresponding to [Formula] is shown. Furthermore, 13 C-nuclear magnetic resonance spectrum ( 13 C
−nmr) was measured. Each peak (chemical shift value:
The analysis results for δ ppn (based on tetramethylsilane) were as follows. From the above results, the isolated product is the raw material 1,
5-bis(allyloxycarbonyloxy)-3
-1,5-bis(methyldichlorosilylpropoxycarbonyloxy)-3- in which two allyl groups in oxapentane are methyldichlorosilylated
It turned out to be oxapentane. The yield was 96.5% based on the 1,5-bis(allyloxycarbonyloxy)-3-oxapentane used.
It was hot. Example 2 1,2-bis(allyloxycarbonyloxy)ethane (23.0 g, 0.1 mol), ethyldichlorosilane (38.7 g), anhydrous n-hexane (100 ml),
A mixture of chloroplatinic acid hexahydrate (50 mg) was reacted and post-treated in the same manner as in Example 1 to obtain a dark yellow liquid (48.1 g). Measurement of the infrared absorption spectrum showed a strong absorption at 1750 cm -1 due to the carbonyl bond of the carbonate group. Its elemental analysis values are C34.1%, H5.33%,
C34.43%, H5.37%, Cl29.04% which is Cl29.11% and calculated value for C 14 H 26 O 6 Cl 4 Si 2 (488.33)
matched. In mass spectrometry, in addition to the molecular ion peak (M),
【式】【formula】
【式】【formula】
【式】の各ピ
ークが観察された。さらに13C−nmr測定の解析
結は次の通りであつた。
上記の結果から、単離生成物が１，２−ビス
（エチルジクロロシリルプロポキシカルボニルオ
キシ）エタンであることが明らかとなつた。収率
は用いた１，２−ビス（アリルオキシカルボニル
オキシ）エタンに対して98.5％であつた。
実施例 ３
１，３−ビス（アリルオキシカルボニルオキ
シ）プロパン（24.4ｇ，0.1モル）、ジメチルクロ
ロシラン（28.4ｇ）、無水シクロヘキサン（100
ml）、塩化白金酸・６水和物（60mg）の混合物に
つき実施例１と同様に反応ならびに後処理を行な
い黒みを帯びた黄色液体（42.0ｇ）を得た。赤外
吸収スペクトル測定では1745cm-1にカルボニル結
合に基づく吸収を示した。その元素分析値は
C41.60％、H6.70％、Cl16.33％であつて
C15H30O6Cl2Si2（433.47）に対する計算値C41.56
％、H6.98％、Cl16.36％に一致した。また質量ス
ペクトル測定では分子イオンピーク（Ｍ
）の他
に
（CH3）2ClSiCH2CH2CH2
，（CH3）2ClSi
の各
ピークが観察された。以上の結果から生成物が
１，３−ビス（ジメチルクロロシリルプロポキシ
カルボニルオキシ）プロパンであることが明らか
となつた。収率は96.8％であつた。Each peak of [Formula] was observed. Furthermore, the analytical results of 13 C-nmr measurements were as follows. The above results revealed that the isolated product was 1,2-bis(ethyldichlorosilylpropoxycarbonyloxy)ethane. The yield was 98.5% based on the 1,2-bis(allyloxycarbonyloxy)ethane used. Example 3 1,3-bis(allyloxycarbonyloxy)propane (24.4 g, 0.1 mol), dimethylchlorosilane (28.4 g), anhydrous cyclohexane (100
ml), and a mixture of chloroplatinic acid hexahydrate (60 mg) was reacted and post-treated in the same manner as in Example 1 to obtain a dark yellow liquid (42.0 g). Infrared absorption spectrum measurement showed an absorption based on carbonyl bond at 1745 cm -1 . Its elemental analysis value is
C41.60%, H6.70%, Cl16.33%
Calculated value C41.56 for C 15 H 30 O 6 Cl 2 Si 2 (433.47)
%, H6.98%, Cl16.36%. In mass spectrometry, in addition to the molecular ion peak (M), Each peak of (CH 3 ) 2 ClSiCH 2 CH 2 CH 2 and (CH 3 ) 2 ClSi was observed. The above results revealed that the product was 1,3-bis(dimethylchlorosilylpropoxycarbonyloxy)propane. The yield was 96.8%.
Claims (1)
基、R2は−CH2CH2O−又は−CH2CH2CH2O−
で該酸素は上記一般式の右側のカルボニルと結合
し、ｍは１〜２又ｎは１〜４の整数である） で示されるビス（ハロシリルプロポキシカルボニ
ルオキシ）アルカン。[Claims] 1. General formula (However, X is a halogen atom, R 1 is an alkyl group, and R 2 is -CH 2 CH 2 O- or -CH 2 CH 2 CH 2 O-
The oxygen is bonded to the carbonyl on the right side of the above general formula, and m is an integer of 1 to 2 or n is an integer of 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62289286A JPS63146889A (en) | 1987-11-18 | 1987-11-18 | Bis(halosilylpropoxycarbonyloxy)alkane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62289286A JPS63146889A (en) | 1987-11-18 | 1987-11-18 | Bis(halosilylpropoxycarbonyloxy)alkane |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57226912A Division JPS59118794A (en) | 1982-12-27 | 1982-12-27 | Bis(silylpropoxycarbonyloxy)alkane and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63146889A JPS63146889A (en) | 1988-06-18 |
| JPH036154B2 true JPH036154B2 (en) | 1991-01-29 |
Family
ID=17741208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62289286A Granted JPS63146889A (en) | 1987-11-18 | 1987-11-18 | Bis(halosilylpropoxycarbonyloxy)alkane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63146889A (en) |
-
1987
- 1987-11-18 JP JP62289286A patent/JPS63146889A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63146889A (en) | 1988-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4658049A (en) | Carboxyl group-containing siloxane compound | |
| RU2651570C2 (en) | Transition-metal-free silylation of aromatic compounds | |
| US5300613A (en) | Fluorine-containing organosilicon compounds | |
| EP0444921B1 (en) | Siloxane compound containing tetrahydrophthalic anhydride group and method of producing the same | |
| US4294975A (en) | Hydroalkenyloxysilanes | |
| JP4332708B2 (en) | Chlorosilane compound having bissilylamino group and method for producing the same, and method for producing organooxysilane compound having bissilylamino group | |
| JPH036154B2 (en) | ||
| KR20200067757A (en) | Surface treatment agent and surface treatment method using the same | |
| EP0486116B1 (en) | Silane compound and processes for the preparation thereof | |
| JP3666551B2 (en) | Process for producing bis (3-aminopropyldimethylsilyl) benzene compound | |
| JPS6340437B2 (en) | ||
| JP2605340B2 (en) | Fluorine-containing silane compound and method for producing the same | |
| JPS6219434B2 (en) | ||
| JPS635036B2 (en) | ||
| US5856549A (en) | Silane compound and process for the preparation thereof | |
| EP0564047A1 (en) | Silane compound and processes for the preparation thereof | |
| JPH0259156B2 (en) | ||
| JPH07126272A (en) | Organosilicon compound and its production | |
| JP3558418B2 (en) | Fullerene derivative | |
| RU2164516C1 (en) | Functional carbosilanes containing tris-(gamma-trifluoro- -propyl)-silyl group | |
| JPS636074B2 (en) | ||
| JPH0144192B2 (en) | ||
| JPS6310157B2 (en) | ||
| JP3589740B2 (en) | Fullerene-containing compound, resin composition and cured product thereof | |
| JPH0474187A (en) | Phthalimide group-containing silane |