JPS6340437B2 - - Google Patents
Info
- Publication number
- JPS6340437B2 JPS6340437B2 JP57226912A JP22691282A JPS6340437B2 JP S6340437 B2 JPS6340437 B2 JP S6340437B2 JP 57226912 A JP57226912 A JP 57226912A JP 22691282 A JP22691282 A JP 22691282A JP S6340437 B2 JPS6340437 B2 JP S6340437B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- bis
- peak
- alkane
- integer
- 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
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- -1 silane compound Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 125000005587 carbonate group Chemical group 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001793 charged compounds Chemical class 0.000 description 4
- 238000006114 decarboxylation reaction Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 2
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 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
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CCMHRVVSKFCHAX-UHFFFAOYSA-N $l^{1}-azanylmethylbenzene Chemical compound [N]CC1=CC=CC=C1 CCMHRVVSKFCHAX-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 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
- 150000003973 alkyl amines 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
- 150000001412 amines Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 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
- 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
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004508 fractional distillation Methods 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
- 238000006459 hydrosilylation reaction Methods 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
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- XJLTZAGUXSAJCZ-UHFFFAOYSA-N methyl 3-trimethoxysilylpropanoate Chemical compound COC(=O)CC[Si](OC)(OC)OC XJLTZAGUXSAJCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 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
- 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000003449 preventive effect Effects 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002023 wood Substances 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
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
本発明は一般式
（但し、R1及びR3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と結合し、ｍは１〜２又
ｎは１〜４の整数を表わす）で示されるビス（ア
ルコキシシリルプロポキシカルボニルオキシ）ア
ルカン及びその製造方法を提供するものである。
尚本発明で云うビス（アルコキシシリルプロポキ
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（アルコキシシリルプロポキシ
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−Si（OR3）3（R3はアルキル基、Ｙ
は官能基、Ｒは直鎖または分枝状のアルキレン基
などを表わす）で示される官能基アルキルシラン
化合物、例えば３−アミノプロピルトリエトキシ
シラン、２−メトキシカルボニルエチルトリメト
キシ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及びR3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、ｍは１〜２又ｎ
は１〜４の整数を表わす）で示される。ビス（ア
ルコキシ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（アルコキ
シ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及びR3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、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は本物質をコート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。またはR3はメチル基、エチル基、
ｎ−プロピル基などの炭素数が１〜６の低級アル
キル基特にメチル基、エチル基が好ましい。
本発明のビス（アルコキシシリルプロポキシカ
ルボニルオキシ）アルカン、即ち
は一般にR3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（アルコ
キシ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及びアルコキ
シ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おいてR1がメチル基、
R3がエチル基、ｍが２である場合、ｍ／e133
に極めて強い
The present invention is based on the general formula (However, R 1 and R 3 are alkyl groups, R 2 is
In 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. The present invention provides a silylpropoxycarbonyloxy)alkane and a method for producing the same.
As is clear from the above definition, the term "bis(alkoxysilylpropoxycarbonyloxy)alkane" used in the present invention is a general term that includes bis(alkoxysilylpropoxycarbonyloxy)oxaalkane. Conventionally, Y-R-Si(OR 3 ) 3 (R 3 is an alkyl group, Y
is a functional group, R is a linear or branched alkylene group, etc.) Functional group alkylsilane compounds such as 3-aminopropyltriethoxysilane and 2-methoxycarbonylethyltrimethoxysilane are known compounds. It is known to be used as a water repellent treatment agent, lubricant, rust preventive agent, etc. on 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 and R 3 are alkyl groups, R 2 is
In 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 1 to 2 or n
represents an integer from 1 to 4). We synthesized bis(alkoxysilylpropoxycarbonyloxy)alkane, confirmed its structure and uses, and completed and provided the present invention. That is, the novel compound of the present invention, bis(alkoxysilylpropoxycarbonyloxy)alkane, has the general formula (However, R 1 and R 3 are alkyl groups, R 2 is
In 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 1 to 2 or 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 as a coating agent, etc., and when applied to plastic materials, R 2 o is -
The CH2CH2OCH2CH2O- form is often preferred. or R 3 is a methyl group, an ethyl group,
Lower alkyl groups having 1 to 6 carbon atoms such as n-propyl group, particularly methyl group and ethyl group are preferred. The bis(alkoxysilylpropoxycarbonyloxy) alkanes of the present invention, viz. Generally, its properties differ somewhat depending on the type of R 3 and the number of n, but it usually exists in the form of a colorless and transparent liquid at room temperature and normal pressure. Further, the bis(alkoxysilylpropoxycarbonyloxy)alkane of the present invention can generally be confirmed to be each 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−
By measuring NMR), it is possible to know the number and type of methylene groups and carbonate groups present in the molecule, as well as the number and type of alkyl groups and alkoxy groups on the silicon atom. That is,
In 13 C-NMR (tetramethylsilane standard), there is a peak based on the carbon atom of the carbonyl group, which is unique to carbonate compounds, around 156 ppm.
A peak near 70 ppm based on the carbon atom of the methylene group adjacent to the oxygen atom of carbonate,
Peak based on the carbon atom of the methylene group located in the center of the propylene group around 23 ppm, 5-
A peak based on the carbon atom of the methylene group adjacent to the silicon atom is shown around 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 general formula above, R 1 is a methyl group,
When R 3 is an ethyl group and m is 2, m/e133
extremely strong
【式】に相当するピーク、 ｍ／e175にA peak corresponding to [formula], m/e175
【式】に相当する
ピークの他に対応する分子量に相当するピーク
（M）からエタノールが脱離したと考えられ
るピーク、即ちM−46のピークが観察され
る。同様にR1、R3、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（アルコキシシリルプロポキシカ
ルボニルオキシ）アルカンは高沸点を有する無色
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（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。また前記一般式に於ける
（R3O）と異種のアルコキシ基が誘導されるアル
コールに溶かすと、徐々にではあるが溶媒となる
アルコールの量に応じてアルコキシ基の一部ある
いは条件によつてはアルコキシ基の全てが溶媒と
して用いられた異種のアルコキシ基に変化するの
が一般的である。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。この際、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（アルコキシ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（アルコキシ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In addition to the peak corresponding to [Formula], a peak that is considered to be the result of desorption of ethanol from the peak (M) corresponding to the corresponding molecular weight, ie, a peak of M-46, is observed. Similarly, unique peaks can be observed when R 1 , R 3 , 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(alkoxysilylpropoxycarbonyloxy)alkane of the present invention is a colorless, odorless, transparent liquid with 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(silylpropoxycarbonyloxy)alkanes of the present invention are well soluble in common organic solvents such as benzene, ether, hexane, chloroform, carbon tetrachloride, acetonitrile, and N,N-dimethylformamide. In addition, when dissolved in an alcohol that induces an alkoxy group different from (R 3 O) in the above general formula, a part of the alkoxy group or depending on the conditions may gradually be dissolved depending on the amount of alcohol serving as a solvent. It is common for all of the alkoxy groups to be converted to a different type of alkoxy group used as a solvent. 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. At this time, the hydrolysis is greatly promoted by adding bases such as sodium hydroxide, potassium hydroxide, and ammonia, or acids such as hydrochloric acid, sulfuric acid, and acetic acid to the solvent.
When the bis(alkoxysilylpropoxycarbonyloxy)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(alkoxysilylpropoxycarbonyloxy)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
【式】
（但し、R1及びR3はアルキル基、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
ルジアルコキシ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（アルコ
キシ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
えば公知の製法で得られるものが特に制限されず
に使用出来る。またアルキルアルコキシシランは
一般式[Formula] (However, R 1 and R 3 are alkyl groups, m is an integer of 1 to 2) A good yield can be obtained by reacting a silane compound represented by the formula, such as an alkyldialkoxysilane, in the presence of a catalyst. The desired bis(alkoxysilylpropoxycarbonyloxy)alkane can be obtained. The bis(allyloxycarbonyloxy)alkane represented by the above formula is not limited to its production method, and for example, those obtained by known production methods can be used without particular limitation. In addition, alkylalkoxysilane has the general formula
【式】（R1及びR3はアルキル基、
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シ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、通常溶媒の存在下に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。
また本願発明の目的生成物であるビス（アルコ
キシシリルプロポキシカルボニルオキシ）アルカ
ンは前記反応式に従いビス（アリルオキシカルボ
ニルオキシ）アルカンとアルコキシシランとを反
応させることによつて得られる他に、次のような
方法によつて得ることも出来る。
即ち一般式
（但し、Ｘはハロゲン原子で、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、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
と一般式R3OH（但し、R3はアルキル基である）
で示されるアルコールとを触媒の存在下又は不存
在下に反応させることによつて得ることが出来
る。この場合一般に上記一般式中のアルキル基は
炭素原子数１〜６或いはこれ以上の直鎖状又は分
枝状のアルキル基を用いると好適である。また前
記反応に於ける触媒は一般に塩基であれば特に限
定されず使用出来、特にアンモニア、エチルアミ
ン、ｎ−プロピルアミン、イソプロピルアミン、
ｎ−ブチルアミン、ｓ−ブチルアミン、ジエチル
アミン、トリエチルアミン、イソブチルアミン、
イソアミルアミン、トリ−ｎ−プロピルアミン、
トリイソブチルアミン、シクロヘキシルアミン、
シクロペンチルアミン等の１〜３級の低級アルキ
ルアミン、ピリジン、Ｎ，Ｎ−ジメチルアニリ
ン、ｏ−トルイジン、ｍ−トルイジン、ｐ−トル
イジン、アニリン、Ｎ−メチルアニリン、α−フ
エネチルアミン、β−フエネチルアミン、ベンジ
ルアミン等の芳香族アミンなどの含窒素化合物が
好適に使用される。
更にまた前記したようにビス（アルコキシシリ
ルプロポキシカルボニルオキシ）アルカンにあつ
てはアルコキシが低級程高級アルコキシに置換さ
れ易い性質を有するので、このような性状を利用
すれば、低級アルコキシ基を含むビス（アルコキ
シシリルプロポキシカルボニルオキシ）アルカン
を該アルコキシ基よりも高級なアルコールと接触
させ置換反応により生成する低級アルコールを連
続的に分別蒸留等の手段で分離することによつ
て、目的のアルコキシ基を含むビス（アルコキシ
シリルプロポキシカルボニルオキシ）アルカンと
することが出来る。
本発明のビス（アルコキシ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（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
（85.7g、0.17モル）を食塩／水を用いた寒剤浴で
冷却しながら撹拌下に無水エタノール（80ml）と
無水ベンゼン（80ml）の混合物をゆつくり滴下し
た。滴下後も２時間冷却および撹拌を続けた後、
さらに同条件下に乾燥アンモニアガスを、もはや
塩化アンモニウムの白色沈殿が生成しなくなるま
で通気し、過剰のアンモニアガスを窒素ガスを通
気することによつて除いた。生成した塩化アンモ
ニウムの沈殿を加圧濾過することによつて除き、
さらに濾液に含まれる低沸点成分を蒸留すること
によつて除去した後、さらに高沸点成分を油浴上
70℃、最終的には120℃にまで徐々に注意深く高
真空（0.1mmHg）留去した。該真空蒸留によつて
はごくわずかの液体しか留出しなかつた。得られ
たほぼ無色透明の液体（86.7g）につき赤外吸収
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結合に基づく強い吸収を示し
た。その元素分析値はC48.41％、H8.32％であつ
てC22H46O11Si2（542.77）に対する計算値である
C48.68％、H8.54％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／e496に分子
量に相当する分子イオンピーク（M）からエタ
ノールが脱離したと考えられるピーク、即ちM+
〜46のピークが観察された。またｍ／e175に
A compound represented by the formula (R 1 and R 3 are alkyl groups, m is an integer of 1 to 2),
It can be used without being limited to the 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 ,
Catalysts commonly used in so-called hydrosilylation reactions, such as palladium compounds such as PdCl 2 (PPh 3 ) 2 and PdCl 2 (C 6 H 5 CN) 2 , and rhodium compounds such as RhCl 3 and RhCl (PPh 3 ) 3 . Although any compound can be used without any particular limitation, 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. In addition, bis(alkoxysilylpropoxycarbonyloxy)alkane, which is the target product of the present invention, can be obtained by reacting bis(allyloxycarbonyloxy)alkane and alkoxysilane according to the above reaction formula. It can also be obtained by other methods. That is, the general formula (However, X is a halogen atom, R 1 is an alkyl group,
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 1 to 2
Also, bis(halosilylpropoxycarbonyloxy)alkane represented by (n is an integer of 1 to 4) and the general formula R 3 OH (wherein R 3 is an alkyl group)
It can be obtained by reacting the alcohol represented by the formula in the presence or absence of a catalyst. In this case, it is generally preferable to use a linear or branched alkyl group having 1 to 6 or more carbon atoms as the alkyl group in the above general formula. In addition, the catalyst in the above reaction is generally a base and can be used without particular limitation, and in particular, ammonia, ethylamine, n-propylamine, isopropylamine,
n-butylamine, s-butylamine, diethylamine, triethylamine, isobutylamine,
Isoamylamine, tri-n-propylamine,
triisobutylamine, cyclohexylamine,
Primary to tertiary lower alkylamine such as cyclopentylamine, pyridine, N,N-dimethylaniline, o-toluidine, m-toluidine, p-toluidine, aniline, N-methylaniline, α-phenethylamine, β-phenethylamine, benzyl Nitrogen-containing compounds such as aromatic amines such as amines are preferably used. Furthermore, as mentioned above, bis(alkoxysilylpropoxycarbonyloxy) alkanes have the property that the lower the alkoxy group, the easier it is to be substituted with higher alkoxy, so if this property is utilized, bis(alkoxysilylpropoxycarbonyloxy) alkanes containing lower alkoxy groups can be substituted with higher alkoxy groups. By contacting the alkoxysilylpropoxycarbonyloxy)alkane with an alcohol higher than the alkoxy group and continuously separating the lower alcohol produced by a substitution reaction by means such as fractional distillation, the desired alkoxy group-containing bis (Alkoxysilylpropoxycarbonyloxy)alkane. The bis(alkoxysilylpropoxycarbonyloxy)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(methyldichlorosilylpropoxycarbonyloxy)-3-oxapentane (85.7 g, 0.17 mol) was mixed with anhydrous ethanol (80 ml) and anhydrous benzene under stirring while cooling in a salt/water cryogen bath. (80 ml) was slowly added dropwise. After continuing to cool and stir for 2 hours after dropping,
Furthermore, under the same conditions, dry ammonia gas was bubbled through the flask until no white precipitate of ammonium chloride was formed, and excess ammonia gas was removed by bubbling nitrogen gas through the flask. Remove the generated ammonium chloride precipitate by pressure filtration,
Furthermore, after removing the low boiling point components contained in the filtrate by distillation, the high boiling point components are further removed by distillation.
The temperature was gradually and carefully distilled off at high vacuum (0.1 mmHg) to 70°C and finally to 120°C. The vacuum distillation distilled very little liquid. When the infrared absorption spectrum of the obtained almost colorless and transparent liquid (86.7 g) was measured, it showed strong absorption at 1745 cm -1 due to the carbonyl bond of the carbonate group. Its elemental analysis values are C48.41% and H8.32%, which are calculated values for C 22 H 46 O 11 Si 2 (542.77).
It matched extremely well with C48.68% and H8.54%. In addition, when the mass spectrum was measured, there was a peak at m/e496 that was considered to be the desorption of ethanol from the molecular ion peak (M) corresponding to the molecular weight, that is, M +
~46 peaks were observed. Also m/e175
【式】に相当するピーク、ｍ／ e133にPeak corresponding to [formula], m/ to e133
【式】に相当するピークを示し
た。さらに 13C−nmrを測定した。各ピークの解
析結果は次の通りであつた。
以上の結果から、生成物が1.5−ビス（メチル
ジエトキシ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94.0％であつた。
実施例 ２
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（85.7g、
0.17モル）につき無水エタノールの代わりに無水
ｎ−ペンタノールを用いた以外は実施例４と同様
の方法により、ほぼ無色透明な液体（110g）を
得た。赤外吸収スペクトルでは1745cm-1にカーボ
ネート基の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C57.38％、H10.05％であ
つてC34H70O11Si2（711.08）に対する計算値であ
るC57.42％、H9.92％に一致した。また質量スペ
クトルを測定したところ分子イオンピーク
（M）からペンタノールが脱離したと考えられ
るピーク、即ちM−88のピーク、ｍ／e259に
に相当するピーク、ｍ／e217に
A peak corresponding to [Formula] was shown. Furthermore, 13 C-nmr was measured. The analysis results for each peak were as follows. From the above results, the product is 1.5-bis(methyldiethoxysilylpropoxycarbonyloxy)
It became clear that it was -3-oxapentane. The yield was 94.0%. Example 2 1.5-bis(methyldichlorosilylpropoxycarbonyloxy)-3-oxapenta (85.7g,
An almost colorless and transparent liquid (110 g) was obtained in the same manner as in Example 4, except that anhydrous n-pentanol was used in place of anhydrous ethanol (0.17 mol). The infrared absorption spectrum showed an absorption at 1745 cm -1 due to the carbonyl bond of the carbonate group. The elemental analysis values were C57.38% and H10.05 %, which matched the calculated values for C34H70O11Si2 (711.08) , which were C57.42% and H9.92%. In addition, when we measured the mass spectrum, we found a peak that is considered to be the desorption of pentanol from the molecular ion peak (M), that is, the peak of M-88, m/e259. peak corresponding to m/e217
【式】に相当するピー
クが観察された。さらに 13C−nmrを測定した。
各ピークの解析結果は次の通りであつた。
以上の結果から、生成物が1.5−ビス（メチル
ジ−ｎ−ペンチルオキシ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91.3％であつた。
実施例 ３
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１−３−オキサペンタン
（85.7g、0.17モル）につき、無水エタノールの代
わりに無水メタノールを用いた以外は実施例４と
同様の方法により、ほぼ無色透明の液体（79.0g）
を得た。赤外吸収スペクトル測定では1745cm-1に
カーボネート基の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C44.53％、H7.89％で
あつてC18H38O11Si2（486.66）に対する計算値で
あるC44.42％、H7.87％に一致した。また質量ス
ペクトルを測定したところ分子イオンピーク
（M）からメタノールが脱離したと考えられる
ピーク、即ちM−32のピーク、ｍ／e147にA peak corresponding to [Formula] was observed. Furthermore, 13 C-nmr was measured.
The analysis results for each peak were as follows. From the above results, it was revealed that the product was 1.5-bis(methyldi-n-pentyloxysilylpropoxycarbonyloxy)-3-oxapentane. The yield was 91.3%. Example 3 About 1.5-bis(methyldichlorosilylpropoxycarbonyloxy1-3-oxapentane (85.7 g, 0.17 mol)), the same method as in Example 4 was used except that anhydrous methanol was used instead of anhydrous ethanol. Colorless and transparent liquid (79.0g)
I got it. Infrared absorption spectrum measurement showed an absorption at 1745 cm -1 due to the carbonyl bond of the carbonate group. The elemental analysis values were C44.53% and H7.89 %, which matched the calculated values for C18H38O11Si2 (486.66) , which were C44.42% and H7.87%. In addition, when we measured the mass spectrum, we found a peak that is considered to be the desorption of methanol from the molecular ion peak (M), that is, the peak of M-32, m/e147.
【式】に相当するピーク、 ｍ／e105にA peak corresponding to [formula], m/e105
【式】に相当するピークが観
察された。さらに 13C−nmrを測定した。各ピー
クの解析結果は次の通りであつた。
以上の結果から、生成物が1.5−ビス（メチル
ジメトキシ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95.5％であつた。
実施例 ４
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
ジエトキシシラン（48.3g）、無水ｎ−ヘキサン
（100ml）、白金黒（50mg）の混合物を水浴上で冷
却しながら３時間撹拌した後、さらに５時間加熱
還流した。少量の不溶沈殿物を加圧濾過すること
により除き、濾液中の低沸点成分を蒸留すること
によつて除いた。さらに極少量の高沸点成分を油
浴上120℃以下で注意深く真空留去した。このよ
うにして得られた液体生成物（79.1g）につき
種々のスペクトル測定を行ない、実施例４で別途
合成法を記載して得られた1.5−ビス（メチルジ
エトキシシリルプロポキシカルボニルオキシ）−
３−オキサペンタンと同一であることを確認し
た。収率は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97.2％であ
つた。
実施例 ５
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）につき
メチルジエトキシシランの代わりにジメチルエト
キシシランを用いた以外は実施例７と同様の方法
により、ほぼ無色透明な液体を得た。赤外吸収ス
ペクトル測定では1745cm-1にカーボネート基のカ
ルボニル結合に基づく吸収を示した。その元素分
析値はC49.68％、H8.79％であつてC20H42O9Si2
（482.72）に対する計算値であるC49.76％、H8.77
％に一致した。また質量スペクトルを測定したと
ころ分子イオンピーク（M）からエタノールが
脱離したと考えられるピーク、即ちM−46のピ
ーク、ｍ／e145に
（CH3）2CH3CH2OSiCH2CH2CH2に相当するピ
ーク、ｍ／e103に（CH3）2CH3CH2OSiに相当
するピークが観察された。さらに 13C−nmrを測
定した。各ピークの解析結果は次の通りであつ
た。
以上の結果から生成物が1.5−ビス（ジメチル
エトキシ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96.7％であつた。A peak corresponding to [Formula] was observed. Furthermore, 13 C-nmr was measured. The analysis results for each peak were as follows. From the above results, the product is 1.5-bis(methyldimethoxysilylpropoxycarbonyloxy)
It became clear that it was -3-oxapentane. The yield was 95.5%. Example 4 1.5-bis(allyloxycarbonyloxy)-
A mixture of 3-oxapentane (41.3 g, 0.15 mol), methyldiethoxysilane (48.3 g), anhydrous n-hexane (100 ml), and platinum black (50 mg) was stirred for 3 hours while cooling on a water bath, and then further stirred. The mixture was heated under reflux for 5 hours. A small amount of insoluble precipitate was removed by pressure filtration, and low-boiling components in the filtrate were removed by distillation. Furthermore, a very small amount of high-boiling components were carefully distilled off under vacuum on an oil bath at a temperature below 120°C. Various spectral measurements were performed on the liquid product (79.1 g) thus obtained, and 1.5-bis(methyldiethoxysilylpropoxycarbonyloxy)- obtained by separately describing the synthesis method in Example 4.
It was confirmed that it was the same as 3-oxapentane. The yield was 97.2% based on 1.5-bis(allyloxycarbonyloxy)-3-oxapentane. Example 5 1.5-bis(allyloxycarbonyloxy)-
A substantially colorless and transparent liquid was obtained in the same manner as in Example 7, except that dimethylethoxysilane was used instead of methyldiethoxysilane for 3-oxapentane (41.3 g, 0.15 mol). Infrared absorption spectrum measurement showed an absorption at 1745 cm -1 due to the carbonyl bond of the carbonate group. Its elemental analysis values are C49.68%, H8.79 % , and C20H42O9Si2
Calculated value for (482.72) C49.76%, H8.77
% matched. In addition, when the mass spectrum was measured, a peak that was thought to be due to the desorption of ethanol from the molecular ion peak (M), that is, a peak of M-46, was found at m/e145 (CH 3 ) 2 CH 3 CH 2 OSiCH 2 CH 2 CH 2 A peak corresponding to (CH 3 ) 2 CH 3 CH 2 OSi was observed at m/e103. Furthermore, 13 C-nmr was measured. The analysis results for each peak were as follows. From the above results, the product is 1.5-bis(dimethylethoxysilylpropoxycarbonyloxy)-
It became clear that it was 3-oxapentane. The yield was 96.7%.
Claims (1)
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（アルコキシシリルプロポキシカ
ルボニルオキシ）アルカン。 ２ 一般式
【式】 （但し、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、
ｎは１〜４の整数である）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 【式】（但し、R1及びR3はアルキル基、 ｍは１〜２の整数である）で示されるシラン化合
物とを触媒の存在下に反応させることを特徴とす
る一般式 （但し、R1及びR3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（アル
コキシ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。 ３ 一般式 （但し、Ｘはハロゲン原子で、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、ｍは１〜
２又ｎは１〜４の整数である）で示されるビス
（シリルプロポキシカルボニルオキシ）アルカン
と一般式R3OH（但し、R3はアルキル基である）
で示されるアルコールとを触媒の存在下又は不存
在下に反応させることを特徴とする一般式 （但し、R1及びR3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（アル
コキシ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。[Claims] 1. General formula (However, R 1 and R 3 are alkyl groups, R 2 is -
In 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 1
-2 or n is an integer of 1 to 4) Bis(alkoxysilylpropoxycarbonyloxy)alkanes. 2 General formula [Formula] (However, R 2 is CH 2 CH 2 O or CH 2 CH 2 CH 2 O, and the oxygen is bonded to the carbonyl on the right side of the above general formula,
n is an integer of 1 to 4) and a bis(allyloxycarbonyloxy)alkane represented by the general formula [Formula] (wherein R 1 and R 3 are an alkyl group, m is an integer of 1 to 2) General formula characterized by reacting the shown silane compound in the presence of a catalyst (However, R 1 and R 3 are alkyl groups, R 2 is
In 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. A method for producing silylpropoxycarbonyloxy)alkane. 3 General formula (However, X is a halogen atom, R 1 is an alkyl group,
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 1 to
bis(silylpropoxycarbonyloxy)alkane represented by 2 or n is an integer of 1 to 4) and the general formula R 3 OH (wherein R 3 is an alkyl group)
A general formula characterized by reacting an alcohol represented by in the presence or absence of a catalyst. (However, R 1 and R 3 are alkyl groups, R 2 is
In 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. A method for producing silylpropoxycarbonyloxy)alkane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57226912A JPS59118794A (en) | 1982-12-27 | 1982-12-27 | Bis(silylpropoxycarbonyloxy)alkane and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57226912A JPS59118794A (en) | 1982-12-27 | 1982-12-27 | Bis(silylpropoxycarbonyloxy)alkane and its preparation |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62289286A Division JPS63146889A (en) | 1987-11-18 | 1987-11-18 | Bis(halosilylpropoxycarbonyloxy)alkane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59118794A JPS59118794A (en) | 1984-07-09 |
| JPS6340437B2 true JPS6340437B2 (en) | 1988-08-11 |
Family
ID=16852543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57226912A Granted JPS59118794A (en) | 1982-12-27 | 1982-12-27 | Bis(silylpropoxycarbonyloxy)alkane and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59118794A (en) |
-
1982
- 1982-12-27 JP JP57226912A patent/JPS59118794A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59118794A (en) | 1984-07-09 |
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