JP2016040233A - Bicyclo amino organoxysilane compound and method for producing the same - Google Patents
Bicyclo amino organoxysilane compound and method for producing the same Download PDFInfo
- Publication number
- JP2016040233A JP2016040233A JP2014164153A JP2014164153A JP2016040233A JP 2016040233 A JP2016040233 A JP 2016040233A JP 2014164153 A JP2014164153 A JP 2014164153A JP 2014164153 A JP2014164153 A JP 2014164153A JP 2016040233 A JP2016040233 A JP 2016040233A
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- JP
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- Prior art keywords
- aza
- silabicyclo
- dioxa
- group
- undecane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- -1 silane compound Chemical class 0.000 claims description 84
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 150000002430 hydrocarbons Chemical group 0.000 claims description 26
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 20
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 18
- 238000002329 infrared spectrum Methods 0.000 description 16
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 16
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 15
- 238000009835 boiling Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 238000001819 mass spectrum Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000007363 ring formation reaction Methods 0.000 description 6
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 5
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 239000006087 Silane Coupling Agent Substances 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
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical compound CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- WWFAABCJPAUPDW-UHFFFAOYSA-N 2-[diethoxy(methyl)silyl]ethanamine Chemical compound CCO[Si](C)(CCN)OCC WWFAABCJPAUPDW-UHFFFAOYSA-N 0.000 description 1
- CZVSRHMBQDVNLW-UHFFFAOYSA-N 2-[dimethoxy(methyl)silyl]ethanamine Chemical compound CO[Si](C)(OC)CCN CZVSRHMBQDVNLW-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- BCJPEZMFAKOJPM-UHFFFAOYSA-N 2-ethyl-3-methyloxirane Chemical compound CCC1OC1C BCJPEZMFAKOJPM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 1
- BHWUCEATHBXPOV-UHFFFAOYSA-N 2-triethoxysilylethanamine Chemical compound CCO[Si](CCN)(OCC)OCC BHWUCEATHBXPOV-UHFFFAOYSA-N 0.000 description 1
- YHFFINXFNYQPQA-UHFFFAOYSA-N 4-[diethoxy(methyl)silyl]butan-1-amine Chemical compound CCO[Si](C)(OCC)CCCCN YHFFINXFNYQPQA-UHFFFAOYSA-N 0.000 description 1
- ZQJUGNSCGMEIHO-UHFFFAOYSA-N 4-[dimethoxy(methyl)silyl]butan-1-amine Chemical compound CO[Si](C)(OC)CCCCN ZQJUGNSCGMEIHO-UHFFFAOYSA-N 0.000 description 1
- SWDDLRSGGCWDPH-UHFFFAOYSA-N 4-triethoxysilylbutan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCCN SWDDLRSGGCWDPH-UHFFFAOYSA-N 0.000 description 1
- RBVMDQYCJXEJCJ-UHFFFAOYSA-N 4-trimethoxysilylbutan-1-amine Chemical compound CO[Si](OC)(OC)CCCCN RBVMDQYCJXEJCJ-UHFFFAOYSA-N 0.000 description 1
- RFHXUALAYUACIF-UHFFFAOYSA-N 5-methoxy-4,6-dioxa-1-aza-5-silabicyclo[3.3.3]undecane Chemical compound C1CCN2CCO[Si]1(OC)OCC2 RFHXUALAYUACIF-UHFFFAOYSA-N 0.000 description 1
- WFKNGXPBGXULKU-UHFFFAOYSA-N 5-methyl-4,6-dioxa-1-aza-5-silabicyclo[3.3.3]undecane Chemical compound C1CCN2CCO[Si]1(C)OCC2 WFKNGXPBGXULKU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 0 CC1N(*2)C(*)C(*)O*2(C)OC1* Chemical compound CC1N(*2)C(*)C(*)O*2(C)OC1* 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- LTRPLRHNXPTOIN-UHFFFAOYSA-N [diethoxy(methyl)silyl]methanamine Chemical compound CCO[Si](C)(CN)OCC LTRPLRHNXPTOIN-UHFFFAOYSA-N 0.000 description 1
- KIUCLRQNNKHLDB-UHFFFAOYSA-N [dimethoxy(methyl)silyl]methanamine Chemical compound CO[Si](C)(CN)OC KIUCLRQNNKHLDB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- GYBMSOFSBPZKCX-UHFFFAOYSA-N sodium;ethanol;ethanolate Chemical compound [Na+].CCO.CC[O-] GYBMSOFSBPZKCX-UHFFFAOYSA-N 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical compound CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- ARKBFSWVHXKMSD-UHFFFAOYSA-N trimethoxysilylmethanamine Chemical compound CO[Si](CN)(OC)OC ARKBFSWVHXKMSD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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Abstract
Description
本発明は、塗料添加剤や、接着剤、シランカップリング剤、繊維処理剤、表面処理剤として有用なビシクロアミノオルガノキシシラン化合物及びその製造方法に関するものである。 The present invention relates to a bicycloaminoorganoxysilane compound useful as a coating additive, an adhesive, a silane coupling agent, a fiber treatment agent, and a surface treatment agent, and a method for producing the same.
アミノ基を有するシラン化合物は、塗料添加剤、接着剤、シランカップリング剤、繊維処理剤、表面処理剤等として有用であり、このようなアミノ基を有するシラン化合物としては、例えばアミノプロピルトリメトキシシラン等の１級アミノ基を有するアルコキシシラン化合物や、Ｎ−フェニルアミノプロピルトリメトキシシラン等の２級アミノ基を有するアルコキシシラン化合物、また、ジメチルアミノプロピルトリメトキシシラン等の３級アミノ基を有するアルコキシシラン化合物等が知られている。 Silane compounds having an amino group are useful as paint additives, adhesives, silane coupling agents, fiber treatment agents, surface treatment agents and the like. Examples of such silane compounds having an amino group include aminopropyltrimethoxy. An alkoxysilane compound having a primary amino group such as silane, an alkoxysilane compound having a secondary amino group such as N-phenylaminopropyltrimethoxysilane, and a tertiary amino group such as dimethylaminopropyltrimethoxysilane Alkoxysilane compounds and the like are known.
しかしながら、これらのシラン化合物は、１分子あたり１つの官能基、即ちアミノ基しか有していないため、塗料添加剤、接着剤、シランカップリング剤、繊維処理剤、表面処理剤として使用した場合、官能基導入による効果の発現が少ない場合がある。 However, since these silane compounds have only one functional group per molecule, that is, an amino group, when used as a coating additive, an adhesive, a silane coupling agent, a fiber treatment agent, or a surface treatment agent, In some cases, the effect of introducing a functional group is small.
上記問題を解決するため、特許文献１（米国特許第３０３２５７６号明細書）記載のビシクロアミノオルガノキシシラン化合物が提案されており、この化合物は水分と反応することにより元々有しているアミノ基に加えて水酸基が２つ生成し、上記官能基導入による効果が大きくなる。また、上記ビシクロアミノオルガノキシシラン化合物は使用時に低沸アルコールの生成量が少なくなるため、環境負荷が少ない化合物としても有用である。 In order to solve the above problem, a bicycloaminoorganoxysilane compound described in Patent Document 1 (US Pat. No. 3,325,576) has been proposed, and this compound reacts with moisture to form an amino group originally possessed. In addition, two hydroxyl groups are generated, and the effect of introducing the functional group is increased. In addition, the above bicycloaminoorganoxysilane compound is useful as a compound having a low environmental load because the amount of low boiling alcohol produced during use is reduced.
上記ビシクロアミノオルガノキシシラン化合物を製造する方法として、特許文献１に記載のように、アミノオルガノキシシラン化合物とエポキシ化合物を反応させ、オルガノキシ基を有するアミノオルガノキシシランとし、続いて分子内脱アルコール環化による方法が挙げられるが、上記方法において特に分子内脱アルコール環化反応の進行が遅いため、単離収率が４０％程度であり、収率よく目的とするビシクロアミノオルガノキシシラン化合物を製造することが困難であった。また、エポキシ化合物としてエチレンオキシド、プロピレンオキシドを用いて製造したビシクロアミノオルガノキシシラン化合物は、常温で固体である場合が多く、製造及び取り扱いに困難を生じることがあった。
As a method for producing the bicycloaminoorganoxysilane compound, as described in
本発明は、上記事情に鑑みなされたもので、収率よくビシクロアミノオルガノキシシラン化合物を製造できる方法及び取り扱いが容易なビシクロアミノオルガノキシシラン化合物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a bicycloaminoorganoxysilane compound with good yield and a bicycloaminoorganoxysilane compound that is easy to handle.
本発明者らは、上記目的を達成するため鋭意検討を重ねた結果、塩基性又は酸性触媒の存在下、分子内脱アルコール環化反応を行うことによって、収率よく効率的にビシクロアミノオルガノキシシラン化合物を製造することが可能であること、また、炭素数２以上の非置換又は置換の１価炭化水素基を有するエポキシ化合物を用いた場合に、目的とするビシクロアミノオルガノキシシラン化合物の融点が０℃以下となり、製造及び取り扱いが容易であることを見出し、本発明を完成するに至った。 As a result of intensive investigations to achieve the above object, the present inventors have carried out an intramolecular dealcoholization cyclization reaction in the presence of a basic or acidic catalyst, thereby efficiently and efficiently producing a bicycloaminoorganoxy group. It is possible to produce a silane compound, and when an epoxy compound having an unsubstituted or substituted monovalent hydrocarbon group having 2 or more carbon atoms is used, the melting point of the target bicycloaminoorganoxysilane compound Was found to be 0 ° C. or lower, and it was found that production and handling were easy, and the present invention was completed.
従って、本発明は、下記に示すビシクロアミノオルガノキシシラン化合物及びその製造方法を提供する。
［１］ 下記一般式（１）
で示されるアミノオルガノキシシラン化合物と下記一般式（２）
で示されるエポキシ化合物を反応させ、下記一般式（３）
で示されるビシクロアミノオルガノキシシラン化合物を製造する方法において、塩基性又は酸性の触媒を用いることを特徴とする上記一般式（３）で示されるビシクロアミノオルガノキシシラン化合物の製造方法。
［２］ 前記触媒が、塩基性触媒である［１］記載のビシクロアミノオルガノキシシラン化合物の製造方法。
［３］ 式（２）、（３）中、Ｒ4が水素原子であり、Ｒ5が炭素数２〜２０の非置換又は置換の１価炭化水素基である［１］又は［２］記載のビシクロアミノオルガノキシシラン化合物の製造方法。
［４］ 下記一般式（４）
で示されるビシクロアミノオルガノキシシラン化合物。
［５］ 式（４）で示される化合物が、１−メトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−エトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メチル−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンである［４］記載のビシクロアミノオルガノキシシラン化合物。
Accordingly, the present invention provides the following bicycloaminoorganoxysilane compounds and methods for producing the same.
[1] The following general formula (1)
And the following general formula (2)
Is reacted with an epoxy compound represented by the following general formula (3):
A method for producing a bicycloaminoorganoxysilane compound represented by the general formula (3), wherein a basic or acidic catalyst is used.
[2] The method for producing a bicycloaminoorganoxysilane compound according to [1], wherein the catalyst is a basic catalyst.
[3] [1] or [2], wherein in formulas (2) and (3), R 4 is a hydrogen atom, and R 5 is an unsubstituted or substituted monovalent hydrocarbon group having 2 to 20 carbon atoms. Process for producing a bicycloaminoorganoxysilane compound.
[4] The following general formula (4)
A bicycloaminoorganoxysilane compound represented by:
[5] The compound represented by the formula (4) is 1-methoxy-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane, 1-ethoxy-3. , 7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane, 1-methyl-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] The bicycloaminoorganoxysilane compound according to [4], which is undecane.
本発明によれば、収率良く効率的にビシクロアミノオルガノキシシラン化合物を製造することができ、取り扱いが容易なビシクロアミノオルガノキシシラン化合物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, a bicycloamino organoxysilane compound can be efficiently manufactured with a sufficient yield, and the bicycloamino organoxysilane compound which is easy to handle can be provided.
本発明のビシクロアミノオルガノキシシラン化合物の製造方法は、下記一般式（１）
で示されるアミノオルガノキシシラン化合物と下記一般式（２）
で示されるエポキシ化合物を反応させ、下記一般式（３）
で示されるビシクロアミノオルガノキシシラン化合物を製造する方法において、塩基性又は酸性の触媒を用いるものである。
The production method of the bicycloaminoorganoxysilane compound of the present invention comprises the following general formula (1):
And the following general formula (2)
Is reacted with an epoxy compound represented by the following general formula (3):
In the method for producing a bicycloaminoorganoxysilane compound represented by the formula (1), a basic or acidic catalyst is used.
ここで、上記式中、Ｒ1は炭素数１〜２０、好ましくは１〜６の直鎖状又は分岐状の２価炭化水素基であり、炭素数１〜２０の２価炭化水素基として、具体的には、メチレン基、エチレン基、メチルエチレン基、プロピレン基、メチルプロピレン基、テトラメチレン基、ヘキサメチレン基、オクタメチレン基、デカメチレン基、イソブチレン基等のアルキレン基、フェニレン基等のアリーレン基、メチレンフェニレン基、メチレンフェニレンメチレン基等のアラルキレン基が例示される。Ｒ1としては、これらの中でもメチレン基、エチレン基、プロピレン基が好ましい。 Here, in the above formula, R 1 is a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, and as a divalent hydrocarbon group having 1 to 20 carbon atoms, Specifically, alkylene groups such as methylene group, ethylene group, methylethylene group, propylene group, methylpropylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group and isobutylene group, and arylene groups such as phenylene group And an aralkylene group such as a methylenephenylene group and a methylenephenylenemethylene group. The R 1, a methylene group. Among these, an ethylene group, a propylene group are preferable.
Ｒ2、Ｒ3は炭素数１〜２０、好ましくは炭素数１〜１０の非置換又は置換の１価炭化水素基であり、直鎖状、分岐鎖状又は環状のアルキル基、アルケニル基、アリール基、アラルキル基等が挙げられる。具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、イコシル基等の直鎖状のアルキル基、イソプロピル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、テキシル基、２−エチルヘキシル基等の分岐鎖状のアルキル基、シクロペンチル基、シクロヘキシル基等の環状のアルキル基、ビニル基、アリル基、プロペニル基等のアルケニル基、フェニル基、トリル基等のアリール基、ベンジル基等のアラルキル基等が例示され、また、炭化水素基の水素原子の一部又は全部が置換されていてもよく、該置換基としては、具体的には、例えば、メトキシ基、エトキシ基、（イソ）プロポキシ基等のアルコキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、シアノ基、アミノ基、炭素数２〜１０のアシル基、アルキル基、アルコキシ基がそれぞれ炭素数１〜５であるトリアルキルシリル基、トリアルコキシシリル基、ジアルキルモノアルコキシシリル基もしくはモノアルキルジアルコキシシリル基が挙げられ、これらを組み合わせて用いることもできる。Ｒ2、Ｒ3としては、特に原料の入手容易性、生成物の有用性の点からメチル基、エチル基が好ましい。 R 2 and R 3 are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group, alkenyl group, aryl Group, aralkyl group and the like. Specifically, straight chain such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, etc. -Like alkyl groups, isopropyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, texyl groups, 2-ethylhexyl groups and other branched alkyl groups, cyclopentyl groups, cyclohexyl groups and other cyclic alkyl groups, vinyl Groups, allyl groups, propenyl groups and other alkenyl groups, phenyl groups, tolyl groups and other aryl groups, benzyl groups and other aralkyl groups, and some or all of hydrogen atoms of hydrocarbon groups are substituted. Specific examples of the substituent include an methoxy group, an ethoxy group, and an (iso) propoxy group. Trialkyls each having a Coxy group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a cyano group, an amino group, an acyl group having 2 to 10 carbon atoms, an alkyl group or an alkoxy group, each having 1 to 5 carbon atoms. A silyl group, a trialkoxysilyl group, a dialkyl monoalkoxysilyl group or a monoalkyl dialkoxysilyl group can be mentioned, and these can also be used in combination. As R 2 and R 3 , a methyl group and an ethyl group are particularly preferable from the viewpoint of availability of raw materials and usefulness of the product.
Ｒ4、Ｒ5は水素原子又は炭素数１〜２０、好ましくは炭素数１〜１０の非置換又は置換の１価炭化水素基であり、上記Ｒ2、Ｒ3と同様の基が例示されるが、得られる目的物の融点が０℃以下となることから、Ｒ4は水素原子、Ｒ5は炭素数２〜２０の非置換又は置換の１価炭化水素基であることが好ましく、特にＲ5は、下記一般式（５）
−ＣＨ2−（Ｏ）a−Ｒ6 （５）
（式中、Ｒ6は炭素数１〜１０の飽和１価炭化水素基、ａは０又は１である。）
で示される基であることが好ましい。上記式（５）として、具体的には、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、２−オキサプロピル基、２−オキサブチル基、２−オキサペンチル基、２−オキサヘキシル基等が例示され、原料の入手容易性、目的物が比較的低沸点化合物となる点から特にエチル基が好ましい。
R 4 and R 5 are each a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and examples thereof are the same groups as R 2 and R 3 above. However, since the melting point of the target product to be obtained is 0 ° C. or less, R 4 is preferably a hydrogen atom, and R 5 is preferably an unsubstituted or substituted monovalent hydrocarbon group having 2 to 20 carbon atoms. 5 is the following general formula (5)
—CH 2 — (O) a —R 6 (5)
(In the formula, R 6 is a saturated monovalent hydrocarbon group having 1 to 10 carbon atoms, and a is 0 or 1.)
It is preferable that it is group shown by these. Specific examples of the formula (5) include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a 2-oxapropyl group, a 2-oxabutyl group, a 2-oxapentyl group, and a 2-oxahexyl group. In particular, an ethyl group is preferable from the viewpoint of availability of raw materials and that the target product is a relatively low boiling point compound.
上記一般式（１）で示されるアミノオルガノキシシラン化合物として、具体的には、アミノメチルトリメトキシシラン、アミノメチルメチルジメトキシシラン、アミノメチルトリエトキシシラン、アミノメチルメチルジエトキシシラン、２−アミノエチルトリメトキシシラン、２−アミノエチルメチルジメトキシシラン、２−アミノエチルトリエトキシシラン、２−アミノエチルメチルジエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルメチルジメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルメチルジエトキシシラン、４−アミノブチルトリメトキシシラン、４−アミノブチルメチルジメトキシシラン、４−アミノブチルトリエトキシシラン、４−アミノブチルメチルジエトキシシラン等が例示される。 Specific examples of the aminoorganoxysilane compound represented by the general formula (1) include aminomethyltrimethoxysilane, aminomethylmethyldimethoxysilane, aminomethyltriethoxysilane, aminomethylmethyldiethoxysilane, and 2-aminoethyl. Trimethoxysilane, 2-aminoethylmethyldimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoethylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltri Ethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutylmethyldimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxy Silane and the like.
上記一般式（２）で示されるエポキシ化合物として、具体的には、エチレンオキシド、プロピレンオキシド、１，２−エポキシブタン、２，３−エポキシブタン、１，２−エポキシペンタン、２，３−エポキシペンタン、１，２−エポキシヘキサン、メチルグリシジルエーテル、エチルグリシジルエーテル、プロピルグリシジルエーテル、ブチルグリシジルエーテル、アリルグリシジルエーテル、シクロヘキセンオキシド等が例示される。 Specific examples of the epoxy compound represented by the general formula (2) include ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxypentane, and 2,3-epoxypentane. 1,2-epoxyhexane, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, cyclohexene oxide and the like.
一般式（１）で示されるアミノオルガノキシシラン化合物と、一般式（２）で示されるエポキシ化合物の配合比は特に限定されないが、反応性、生産性の点から、一般式（１）で示されるアミノオルガノキシシラン化合物１モルに対し、一般式（２）で示されるエポキシ化合物１〜１０モル、特に１．５〜５モルの範囲が好ましい。 The compounding ratio of the aminoorganoxysilane compound represented by the general formula (1) and the epoxy compound represented by the general formula (2) is not particularly limited, but it is represented by the general formula (1) from the viewpoint of reactivity and productivity. The range of 1 to 10 mol, particularly 1.5 to 5 mol of the epoxy compound represented by the general formula (2) is preferable with respect to 1 mol of the aminoorganoxysilane compound.
また、本発明においては塩基性又は酸性の触媒を用いる。塩基性触媒としては、水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムメトキシドのメタノール溶液、ナトリウムエトキシドのエタノール溶液等が例示され、酸性触媒としては、硫酸、メタンスルホン酸、ベンゼンスルホン酸、トルエンスルホン酸、ドデシルベンゼンスルホン酸、トリフルオロメタンスルホン酸、塩酸、硝酸、酢酸、トリフルオロ酢酸及び上記酸の塩、塩化アルミニウム、四塩化チタン、塩化亜鉛等のルイス酸化合物が例示されるが、反応性向上の点から塩基性触媒を用いるのが好ましく、特にナトリウムメトキシド、ナトリウムエトキシド、ナトリウムメトキシドのメタノール溶液、ナトリウムエトキシドのエタノール溶液が好ましい。 In the present invention, a basic or acidic catalyst is used. Examples of basic catalysts include sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium methoxide in methanol, sodium ethoxide in ethanol, etc., and acidic catalysts include sulfuric acid and methanesulfonic acid. Examples include Lewis acid compounds such as benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, nitric acid, acetic acid, trifluoroacetic acid, and salts of the above acids, aluminum chloride, titanium tetrachloride, and zinc chloride. However, it is preferable to use a basic catalyst from the viewpoint of improving the reactivity, and sodium methoxide, sodium ethoxide, a methanol solution of sodium methoxide, and an ethanol solution of sodium ethoxide are particularly preferable.
本発明の反応は、下記スキームのように、一般式（１）で示されるアミノオルガノキシシラン化合物と一般式（２）で示されるエポキシ化合物が反応し、水酸基を有するアミノオルガノキシシランがまず生成し、続いて分子内脱アルコール環化により、目的とするビシクロアミノオルガノキシシラン化合物が生成するものと考えられる。
上記反応において、脱アルコール環化の段階は反応速度が遅いため、触媒を用いないと高温条件が必要であるが、高温で反応を行うと目的の分子内環化反応の他に分子間反応が進行し、目的物の収率が低下してしまう。これに対し、触媒を用いると高温としなくても反応が進行し、その結果、高温条件で進行する分子間反応を抑制できることから、分子内環化反応の選択性を向上させ、収率を向上させることができる。つまり、触媒は反応速度を向上させるだけでなく、反応選択性を向上させる効果を有している。 In the above reaction, the stage of dealcoholization cyclization has a slow reaction rate, so a high temperature condition is necessary unless a catalyst is used. However, when the reaction is carried out at a high temperature, intermolecular reaction occurs in addition to the intended intramolecular cyclization reaction. It progresses and the yield of a target object falls. On the other hand, when the catalyst is used, the reaction proceeds even at a high temperature, and as a result, the intermolecular reaction that proceeds under high temperature conditions can be suppressed, improving the selectivity of the intramolecular cyclization reaction and improving the yield. Can be made. That is, the catalyst has the effect of improving not only the reaction rate but also the reaction selectivity.
なお、触媒は、主に脱アルコール反応の際に効果を発現するため、脱アルコール環化反応の際に添加すればよいが、予めアミノオルガノキシシラン化合物とエポキシ化合物の反応の際から添加しておいてもよい。 In addition, since the catalyst exhibits an effect mainly during the dealcoholization reaction, it may be added during the dealcoholization cyclization reaction. However, the catalyst is added in advance during the reaction between the aminoorganoxysilane compound and the epoxy compound. It may be left.
用いられる触媒の使用量は特に限定されないが、反応性、生産性の点から、一般式（１）で示されるアミノオルガノキシシラン化合物１モルに対し０．０００１〜０．１モル、特に０．００１〜０．０５モルの範囲が好ましい。 The amount of the catalyst to be used is not particularly limited, but from the viewpoint of reactivity and productivity, 0.0001 to 0.1 mol, particularly 0.001 with respect to 1 mol of the aminoorganoxysilane compound represented by the general formula (1). A range of 001 to 0.05 mol is preferred.
上記反応の反応温度は特に限定されないが、０〜２５０℃、特に２０〜１８０℃が好ましく、反応時間も特に限定されないが、１〜４０時間、特に１〜２０時間が好ましい。特に、一般式（１）で示されるアミノオルガノキシシラン化合物と一般式（２）で示されるエポキシ化合物とを０〜２５０℃、特に２０〜１８０℃にて３０分〜３０時間、特に３０分〜１５時間反応させた後に、上記塩基性又は酸性の触媒を添加し、０〜２５０℃、特に２０〜１８０℃にて３０分〜１０時間、特に３０分〜５時間反応させることが好ましい。 The reaction temperature for the above reaction is not particularly limited, but is preferably 0 to 250 ° C., particularly 20 to 180 ° C., and the reaction time is not particularly limited, but is preferably 1 to 40 hours, particularly 1 to 20 hours. Particularly, the aminoorganoxysilane compound represented by the general formula (1) and the epoxy compound represented by the general formula (2) are heated at 0 to 250 ° C., particularly 20 to 180 ° C. for 30 minutes to 30 hours, particularly 30 minutes to After reacting for 15 hours, it is preferable to add the above basic or acidic catalyst and react at 0 to 250 ° C., particularly 20 to 180 ° C. for 30 minutes to 10 hours, particularly 30 minutes to 5 hours.
なお、上記反応は無溶媒でも進行するが、溶媒を用いることもできる。用いられる溶媒としては、ペンタン、ヘキサン、シクロヘキサン、ヘプタン、イソオクタン、ベンゼン、トルエン、キシレン等の炭化水素系溶媒、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン等の非プロトン性極性溶媒、ジクロロメタン、クロロホルム等の塩素化炭化水素系溶媒、メタノール、エタノール、１−プロパノール、２−プロパノール等のアルコール系溶媒等が例示される。これらの溶媒は１種を単独で使用してもよく、あるいは２種以上を混合して使用してもよい。
なお、溶媒を用いる場合の使用量は、一般式（１）で示されるアミノオルガノキシシラン化合物１モルに対し０．１〜２０モル、特に０．５〜１０モルの範囲が好ましい。
In addition, although the said reaction advances even without a solvent, a solvent can also be used. Solvents used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and ester solvents such as ethyl acetate and butyl acetate. , Aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, chlorinated hydrocarbon solvents such as dichloromethane and chloroform, alcohol solvents such as methanol, ethanol, 1-propanol and 2-propanol Etc. are exemplified. These solvents may be used alone or in combination of two or more.
In addition, when using a solvent, the usage-amount is 0.1-20 mol with respect to 1 mol of aminoorganoxysilane compounds shown by General formula (1), Especially the range of 0.5-10 mol is preferable.
本発明の製造方法によれば、下記一般式（３）
で示されるビシクロアミノオルガノキシシラン化合物を高収率で効率よく得ることができる。
According to the production method of the present invention, the following general formula (3)
Can be efficiently obtained in a high yield.
上記一般式（３）で示されるビシクロアミノオルガノキシシラン化合物としては、１−メトキシ−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−エトキシ−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−メチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−メトキシ−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−エトキシ−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−メチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−メトキシ−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−エトキシ−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メトキシ−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−エトキシ−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−メチル−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−メトキシ−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−エトキシ−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−メチル−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−メトキシ−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−エトキシ−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メチル−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−エトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−メチル−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−メトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−エトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−メチル−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−メトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−エトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メチル−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メトキシ−３，７−ジブチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−エトキシ−３，７−ジブチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−メチル−３，７−ジブチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−メトキシ−３，７−ジブチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−エトキシ−３，７−ジブチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−メチル−３，７−ジブチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−メトキシ−３，７−ジブチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−エトキシ−３，７−ジブチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メチル−３，７−ジブチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メトキシ−３，７−ジ（２−オキサプロピル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−エトキシ−３，７−ジ（２−オキサプロピル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−メチル−３，７−ジ（２−オキサプロピル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−メトキシ−３，７−ジ（２−オキサプロピル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−エトキシ−３，７−ジ（２−オキサプロピル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−メチル−３，７−ジ（２−オキサプロピル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−メトキシ−３，７−ジ（２−オキサプロピル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−エトキシ−３，７−ジ（２−オキサプロピル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メチル−３，７−ジ（２−オキサプロピル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メトキシ−３，７−ジ（２−オキサヘキシル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−エトキシ−３，７−ジ（２−オキサヘキシル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−メチル−３，７−ジ（２−オキサヘキシル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．１］ノナン、１−メトキシ−３，７−ジ（２−オキサヘキシル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−エトキシ−３，７−ジ（２−オキサヘキシル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−メチル−３，７−ジ（２−オキサヘキシル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．２］デカン、１−メトキシ−３，７−ジ（２−オキサヘキシル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−エトキシ−３，７−ジ（２−オキサヘキシル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メチル−３，７−ジ（２−オキサヘキシル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン等が例示され、生成物の融点が０℃以下となる点から上記一般式（３）のＲ4が水素原子、Ｒ5が炭素数２〜２０の非置換又は置換の１価炭化水素基である化合物が好ましく、更にＲ4が水素原子、Ｒ5がエチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、２−オキサプロピル基、２−オキサブチル基、２−オキサペンチル基、２−オキサヘキシル基である化合物がより好ましく、比較的低沸点化合物となる点から、１−メトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−エトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカン、１−メチル−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンが特に好ましい。生成物の融点が０℃以下となると、製造及び取り扱いが容易になる。 Examples of the bicycloaminoorganoxysilane compound represented by the general formula (3) include 1-methoxy-2,8-dioxa-5-aza-1-silabicyclo [3.3.1] nonane, 1-ethoxy-2, 8-dioxa-5-aza-1-silabicyclo [3.3.1] nonane, 1-methyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.1] nonane, 1-methoxy- 2,8-dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1-ethoxy-2,8-dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1- Methyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1-methoxy-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane, 1-ethoxy-2,8-dioxa -Aza-1-silabicyclo [3.3.3] undecane, 1-methyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane, 1-methoxy-3,7-dimethyl -2,8-dioxa-5-aza-1-silabicyclo [3.3.1] nonane, 1-ethoxy-3,7-dimethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3 .1] Nonane, 1-methyl-3,7-dimethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.1] nonane, 1-methoxy-3,7-dimethyl-2,8 -Dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1-ethoxy-3,7-dimethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.2] decane 1-methyl-3,7-dimethyl-2,8-dioxy -5-aza-1-silabicyclo [3.3.2] decane, 1-methoxy-3,7-dimethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane, -Ethoxy-3,7-dimethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane, 1-methyl-3,7-dimethyl-2,8-dioxa-5-aza -1-silabicyclo [3.3.3] undecane, 1-methoxy-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.1] nonane, 1-ethoxy-3 , 7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.1] nonane, 1-methyl-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.1] Nonane, 1-methoxy-3,7 -Diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1-ethoxy-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3 3.2] decane, 1-methyl-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1-methoxy-3,7-diethyl-2 , 8-Dioxa-5-aza-1-silabicyclo [3.3.3] undecane, 1-ethoxy-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3. ] Undecane, 1-methyl-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane, 1-methoxy-3,7-dibutyl-2,8-dioxa -5-aza-1-silabicyclo [3.3.1] Nan, 1-ethoxy-3,7-dibutyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.1] nonane, 1-methyl-3,7-dibutyl-2,8-dioxa 5-aza-1-silabicyclo [3.3.1] nonane, 1-methoxy-3,7-dibutyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1- Ethoxy-3,7-dibutyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1-methyl-3,7-dibutyl-2,8-dioxa-5-aza- 1-silabicyclo [3.3.2] decane, 1-methoxy-3,7-dibutyl-2,8-dioxa-5-aza-1-silabicyclo [33.3] undecane, 1-ethoxy-3, 7-Dibutyl-2,8-dioxa-5-aza-1-silabi Chlo [3.3.3] undecane, 1-methyl-3,7-dibutyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane, 1-methoxy-3,7- Di (2-oxapropyl) -2,8-dioxa-5-aza-1-silabicyclo [3.3.1] nonane, 1-ethoxy-3,7-di (2-oxapropyl) -2,8- Dioxa-5-aza-1-silabicyclo [3.3.1] nonane, 1-methyl-3,7-di (2-oxapropyl) -2,8-dioxa-5-aza-1-silabicyclo [3. 3.1] Nonane, 1-methoxy-3,7-di (2-oxapropyl) -2,8-dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1-ethoxy-3, 7-di (2-oxapropyl) -2,8-dioxa-5-aza-1-si Rabicyclo [3.3.2] decane, 1-methyl-3,7-di (2-oxapropyl) -2,8-dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1- Methoxy-3,7-di (2-oxapropyl) -2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane, 1-ethoxy-3,7-di (2-oxapropyl) ) -2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane, 1-methyl-3,7-di (2-oxapropyl) -2,8-dioxa-5-aza- 1-silabicyclo [3.3.3] undecane, 1-methoxy-3,7-di (2-oxahexyl) -2,8-dioxa-5-aza-1-silabicyclo [3.3.1] nonane, 1-ethoxy-3,7-di (2-oxahexyl) -2,8- Oxa-5-aza-1-silabicyclo [3.3.1] nonane, 1-methyl-3,7-di (2-oxahexyl) -2,8-dioxa-5-aza-1-silabicyclo [3. 3.1] Nonane, 1-methoxy-3,7-di (2-oxahexyl) -2,8-dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1-ethoxy-3, 7-di (2-oxahexyl) -2,8-dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1-methyl-3,7-di (2-oxahexyl) -2, 8-Dioxa-5-aza-1-silabicyclo [3.3.2] decane, 1-methoxy-3,7-di (2-oxahexyl) -2,8-dioxa-5-aza-1-silabicyclo [ 3.3.3] Undecane, 1-ethoxy-3,7-di (2-oxahe Syl) -2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane, 1-methyl-3,7-di (2-oxahexyl) -2,8-dioxa-5-aza -1-silabicyclo [3.3.3] undecane and the like are exemplified, and from the point that the melting point of the product is 0 ° C. or less, R 4 in the general formula (3) is a hydrogen atom, and R 5 is 2 to 20 carbon atoms. And a compound in which R 4 is a hydrogen atom, R 5 is an ethyl group, propyl group, butyl group, pentyl group, hexyl group, 2-oxapropyl group, 2- A compound which is an oxabutyl group, a 2-oxapentyl group or a 2-oxahexyl group is more preferable, and 1-methoxy-3,7-diethyl-2,8-dioxa-5-aza is preferable because it becomes a relatively low boiling point compound. -1-silabicyclo [3.3.3] Decane, 1-ethoxy-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane, 1-methyl-3,7-diethyl-2,8-dioxa- 5-Aza-1-silabicyclo [3.3.3] undecane is particularly preferred. When the melting point of the product is 0 ° C. or less, the production and handling become easy.
以下、実施例及び比較例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
［実施例１］ナトリウムエトキシドのエタノール溶液を触媒として用いた１−エトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンの合成
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、３−アミノプロピルトリエトキシシラン１７７．１ｇ（０．８モル）、エタノール７３．８ｇ（１．６モル）を仕込み、７０℃に加熱した。内温が安定した後、１，２−エポキシブタン１３８．４ｇ（１．９モル）を２時間かけて滴下し、更にその温度で８時間撹拌した。得られた反応液に２０質量％ナトリウムエトキシドのエタノール溶液２．７ｇ（０．００８モル）を添加し、７０℃にて３時間反応させた後、蒸留を行い、沸点１４２℃／０．４ｋＰａの留分を１９３．９ｇ得た。
[Example 1] Synthesis of 1-ethoxy-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane using ethanol solution of sodium ethoxide as catalyst A flask equipped with a machine, a reflux condenser, a dropping funnel and a thermometer was charged with 177.1 g (0.8 mol) of 3-aminopropyltriethoxysilane and 73.8 g (1.6 mol) of ethanol and heated to 70 ° C. did. After the internal temperature was stabilized, 138.4 g (1.9 mol) of 1,2-epoxybutane was added dropwise over 2 hours, and the mixture was further stirred at that temperature for 8 hours. After adding 2.7 g (0.008 mol) of an ethanol solution of 20% by mass sodium ethoxide to the obtained reaction solution and reacting at 70 ° C. for 3 hours, distillation was performed to obtain a boiling point of 142 ° C./0.4 kPa. 193.9 g of the fraction was obtained.
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル、ＩＲスペクトルを測定した。
質量スペクトル
ｍ／ｚ ２７３，２５８，２４４，２２８，２１６，２０２
1Ｈ−ＮＭＲスペクトル（重クロロホルム溶媒）
図１にチャートで示す。
ＩＲスペクトル
図２にチャートで示す。
以上の結果より、得られた化合物は、１−エトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンであることが確認された。また、得られた化合物の融点を測定したところ、−１０℃以下であった。
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 273, 258, 244, 228, 216, 202
1 H-NMR spectrum (deuterated chloroform solvent)
A chart is shown in FIG.
IR spectrum FIG. 2 is a chart.
From the above results, it was confirmed that the obtained compound was 1-ethoxy-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane. Moreover, when melting | fusing point of the obtained compound was measured, it was -10 degrees C or less.
［比較例１］触媒を用いない１−エトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンの合成
２０質量％ナトリウムエトキシドのエタノール溶液を添加しなかった以外は、実施例１と同様に行った。沸点１４２℃／０．４ｋＰａの留分は７２．５ｇしか得られず、実施例１と比較して収率が低下する結果となった。
[Comparative Example 1] Synthesis of 1-ethoxy-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane without using
［実施例２］ナトリウムエトキシドのエタノール溶液を触媒として用いた１−メチル−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンの合成
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、３−アミノプロピルメチルジエトキシシラン１５３．０ｇ（０．８モル）、エタノール７３．８ｇ（１．６モル）を仕込み、７０℃に加熱した。内温が安定した後、１，２−エポキシブタン１３８．４ｇ（１．９モル）を２時間かけて滴下し、更にその温度で８時間撹拌した。得られた反応液に２０質量％ナトリウムエトキシドのエタノール溶液２．７ｇ（０．００８モル）を添加し、７０℃にて３時間反応させた後、蒸留を行い、沸点１１０℃／０．４ｋＰａの留分を１６０．３ｇ得た。
[Example 2] Synthesis of 1-methyl-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane using an ethanol solution of sodium ethoxide as a catalyst A flask equipped with a machine, a reflux condenser, a dropping funnel and a thermometer was charged with 153.0 g (0.8 mol) of 3-aminopropylmethyldiethoxysilane and 73.8 g (1.6 mol) of ethanol and brought to 70 ° C. Heated. After the internal temperature was stabilized, 138.4 g (1.9 mol) of 1,2-epoxybutane was added dropwise over 2 hours, and the mixture was further stirred at that temperature for 8 hours. 2.7 g (0.008 mol) of an ethanol solution of 20% by mass sodium ethoxide was added to the obtained reaction solution and reacted at 70 ° C. for 3 hours, followed by distillation to have a boiling point of 110 ° C./0.4 kPa. 160.3 g of a fraction was obtained.
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル、ＩＲスペクトルを測定した。
質量スペクトル
ｍ／ｚ ２４３，２２８，２１４，２００，１８６，１７２
1Ｈ−ＮＭＲスペクトル（重クロロホルム溶媒）
図３にチャートで示す。
ＩＲスペクトル
図４にチャートで示す。
以上の結果より、得られた化合物は、１−メチル−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンであることが確認された。また、得られた化合物の融点を測定したところ、−１０℃以下であった。
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 243,228,214,200,186,172
1 H-NMR spectrum (deuterated chloroform solvent)
FIG. 3 shows a chart.
IR spectrum FIG. 4 is a chart.
From the above results, it was confirmed that the obtained compound was 1-methyl-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane. Moreover, when melting | fusing point of the obtained compound was measured, it was -10 degrees C or less.
［比較例２］触媒を用いない１−メチル−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンの合成
２０質量％ナトリウムエトキシドのエタノール溶液を添加しなかった以外は、実施例１と同様に行った。沸点１１０℃／０．４ｋＰａの留分は５０．３ｇしか得られず、実施例１と比較して収率が低下する結果となった。
[Comparative Example 2] Synthesis of 1-methyl-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane without using catalyst Ethanol of 20 mass% sodium ethoxide The same procedure as in Example 1 was performed except that no solution was added. Only 50.3 g of a fraction having a boiling point of 110 ° C./0.4 kPa was obtained, and the yield was reduced as compared with Example 1.
［実施例３］ナトリウムメトキシドのメタノール溶液を触媒として用いた１−メチル−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンの合成
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、３−アミノプロピルメチルジメトキシシラン９８．０ｇ（０．６モル）、メタノール３８．４ｇ（１．２モル）を仕込み、７０℃に加熱した。内温が安定した後、１，２−エポキシブタン１０３．８ｇ（１．４モル）を２時間かけて滴下し、更にその温度で８時間撹拌した。得られた反応液に２８質量％ナトリウムメトキシドのメタノール溶液１．２ｇ（０．００６モル）を添加し、７０℃にて３時間反応させた後、蒸留を行い、沸点１１０℃／０．４ｋＰａの留分を１１１．２ｇ得た。
[Example 3] Synthesis of 1-methyl-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane using methanol solution of sodium methoxide as a catalyst A flask equipped with a condenser, a reflux condenser, a dropping funnel and a thermometer was charged with 98.0 g (0.6 mol) of 3-aminopropylmethyldimethoxysilane and 38.4 g (1.2 mol) of methanol and heated to 70 ° C. did. After the internal temperature was stabilized, 103.8 g (1.4 mol) of 1,2-epoxybutane was added dropwise over 2 hours, and further stirred at that temperature for 8 hours. After adding 1.2 g (0.006 mol) of methanol solution of 28% by mass sodium methoxide to the obtained reaction liquid and reacting at 70 ° C. for 3 hours, distillation was performed to obtain a boiling point of 110 ° C./0.4 kPa. 11.2 g of this fraction was obtained.
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル、ＩＲスペクトルを測定したところ、実施例２と同様であり、得られた化合物は、１−メチル−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンであることが確認された。 When the mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured, it was the same as in Example 2. The obtained compound was 1-methyl-3,7-diethyl-2,8-. It was confirmed that it was dioxa-5-aza-1-silabicyclo [3.3.3] undecane.
［実施例４］ナトリウムメトキシドのメタノール溶液を触媒として用いた１−メトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンの合成
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、３−アミノプロピルトリメトキシシラン１４３．４ｇ（０．８モル）、メタノール５１．２ｇ（１．６モル）を仕込み、７０℃に加熱した。内温が安定した後、１，２−エポキシブタン１３８．４ｇ（１．９モル）を２時間かけて滴下し、更にその温度で７時間撹拌した。得られた反応液に２８質量％ナトリウムメトキシドのメタノール溶液１．５ｇ（０．００８モル）を添加し、７０℃にて３時間反応させた後、蒸留を行い、沸点１４６℃／０．４ｋＰａの留分を１６０．２ｇ得た。
[Example 4] Synthesis of 1-methoxy-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane using methanol solution of sodium methoxide as catalyst Stirring A flask equipped with a heat exchanger, a reflux condenser, a dropping funnel and a thermometer was charged with 143.4 g (0.8 mol) of 3-aminopropyltrimethoxysilane and 51.2 g (1.6 mol) of methanol and heated to 70 ° C. did. After the internal temperature was stabilized, 138.4 g (1.9 mol) of 1,2-epoxybutane was added dropwise over 2 hours, and the mixture was further stirred at that temperature for 7 hours. After adding 1.5 g (0.008 mol) of methanol solution of 28% by mass sodium methoxide to the obtained reaction solution and reacting at 70 ° C. for 3 hours, distillation was performed to obtain a boiling point of 146 ° C./0.4 kPa. 160.2 g of the fraction was obtained.
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル、ＩＲスペクトルを測定した。
質量スペクトル
ｍ／ｚ ２５９，２４４，２３０，２１６，２０２，１８８
1Ｈ−ＮＭＲスペクトル（重クロロホルム溶媒）
図５にチャートで示す。
ＩＲスペクトル
図６にチャートで示す。
以上の結果より、得られた化合物は、１−メトキシ−３，７−ジエチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンであることが確認された。また、得られた化合物の融点を測定したところ、−１０℃以下であった。
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 259, 244, 230, 216, 202, 188
1 H-NMR spectrum (deuterated chloroform solvent)
FIG. 5 shows a chart.
IR spectrum FIG. 6 is a chart.
From the above results, it was confirmed that the obtained compound was 1-methoxy-3,7-diethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane. Moreover, when melting | fusing point of the obtained compound was measured, it was -10 degrees C or less.
［実施例５］ナトリウムエトキシドのエタノール溶液を触媒として用いた１−メチル−３，７−ジ（２−オキサヘキシル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンの合成
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、３−アミノプロピルメチルジエトキシシラン７６．５ｇ（０．４モル）、エタノール３６．９ｇ（０．８モル）を仕込み、７０℃に加熱した。内温が安定した後、ブチルグリシジルエーテル１２５．０ｇ（１．０モル）を２時間かけて滴下し、更にその温度で３時間撹拌した。得られた反応液に２０質量％ナトリウムエトキシドのエタノール溶液１．４ｇ（０．００４モル）を添加し、７０℃にて３時間反応させた後、蒸留を行い、沸点１８５℃／０．４ｋＰａの留分を１３６．６ｇ得た。
[Example 5] 1-Methyl-3,7-di (2-oxahexyl) -2,8-dioxa-5-aza-1-silabicyclo [3.3. Using an ethanol solution of sodium ethoxide as a catalyst. 3] Synthesis of undecane In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 76.5 g (0.4 mol) of 3-aminopropylmethyldiethoxysilane and 36.9 g (0.8 mol) of ethanol And heated to 70 ° C. After the internal temperature was stabilized, 125.0 g (1.0 mol) of butyl glycidyl ether was added dropwise over 2 hours, and the mixture was further stirred at that temperature for 3 hours. After adding 1.4 g (0.004 mol) of an ethanol solution of 20% by mass sodium ethoxide to the obtained reaction solution and reacting at 70 ° C. for 3 hours, distillation was performed to obtain a boiling point of 185 ° C./0.4 kPa. Of 136.6 g was obtained.
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル、ＩＲスペクトルを測定した。
質量スペクトル
ｍ／ｚ ３４４，３０２，２８６，２７２，２１４，１８６
1Ｈ−ＮＭＲスペクトル（重クロロホルム溶媒）
図７にチャートで示す。
ＩＲスペクトル
図８にチャートで示す。
以上の結果より、得られた化合物は、１−メチル−３，７−ジ（２−オキサヘキシル）−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンであることが確認された。また、得られた化合物の融点を測定したところ、−１０℃以下であった。
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 344, 302, 286, 272, 214, 186
1 H-NMR spectrum (deuterated chloroform solvent)
FIG. 7 shows a chart.
IR spectrum FIG. 8 is a chart.
From the above results, the obtained compound is 1-methyl-3,7-di (2-oxahexyl) -2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane. It was confirmed. Moreover, when melting | fusing point of the obtained compound was measured, it was -10 degrees C or less.
［実施例６］ナトリウムエトキシドのエタノール溶液を触媒として用いた１−メチル−３，７−ジブチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンの合成
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、３−アミノプロピルメチルジエトキシシラン７６．５ｇ（０．４モル）、エタノール３６．９ｇ（０．８モル）を仕込み、７０℃に加熱した。内温が安定した後、１，２−エポキシヘキサン９６．２ｇ（１．０モル）を２時間かけて滴下し、更にその温度で６時間撹拌した。得られた反応液に２０質量％ナトリウムエトキシドのエタノール溶液１．４ｇ（０．００４モル）を添加し、７０℃にて３時間反応させた後、蒸留を行い、沸点１５１℃／０．４ｋＰａの留分を１０１．９ｇ得た。
[Example 6] Synthesis of 1-methyl-3,7-dibutyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane using ethanol solution of sodium ethoxide as catalyst A flask equipped with a machine, a reflux condenser, a dropping funnel and a thermometer was charged with 76.5 g (0.4 mol) of 3-aminopropylmethyldiethoxysilane and 36.9 g (0.8 mol) of ethanol and brought to 70 ° C. Heated. After the internal temperature was stabilized, 96.2 g (1.0 mol) of 1,2-epoxyhexane was added dropwise over 2 hours, and the mixture was further stirred at that temperature for 6 hours. After adding 1.4 g (0.004 mol) of an ethanol solution of 20% by mass sodium ethoxide to the obtained reaction solution and reacting at 70 ° C. for 3 hours, distillation was performed to obtain a boiling point of 151 ° C./0.4 kPa. 101.9 g of this fraction was obtained.
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル、ＩＲスペクトルを測定した。
質量スペクトル
ｍ／ｚ ２９９，２８４，２７０，２５６，２４２，２１４
1Ｈ−ＮＭＲスペクトル（重クロロホルム溶媒）
図９にチャートで示す。
ＩＲスペクトル
図１０にチャートで示す。
以上の結果より、得られた化合物は、１−メチル−３，７−ジブチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンであることが確認された。また、得られた化合物の融点を測定したところ、−１０℃以下であった。
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 299,284,270,256,242,214
1 H-NMR spectrum (deuterated chloroform solvent)
FIG. 9 is a chart.
IR spectrum FIG. 10 is a chart.
From the above results, it was confirmed that the obtained compound was 1-methyl-3,7-dibutyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane. Moreover, when melting | fusing point of the obtained compound was measured, it was -10 degrees C or less.
［実施例７］ナトリウムエトキシドのエタノール溶液を触媒として用いた１−メチル−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンの合成
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、３−アミノプロピルメチルジエトキシシラン１９１．３ｇ（１．０モル）、エタノール９２．２ｇ（２．０モル）を仕込み、６０℃に加熱した。内温が安定した後、プロピレンオキシド１３９．４ｇ（２．４モル）を２時間かけて滴下し、更にその温度で８時間撹拌した。得られた反応液に２０質量％ナトリウムエトキシドのエタノール溶液３．４ｇ（０．０１モル）を添加し、７０℃にて３時間反応させた後、蒸留を行い、１−メチル−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンを沸点１１３℃／１．０ｋＰａの留分として１８４．１ｇ得た。得られた化合物の融点を測定したところ、７２℃であった。
[Example 7] Synthesis of 1-methyl-3,7-dimethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane using an ethanol solution of sodium ethoxide as a catalyst Into a flask equipped with a condenser, a reflux condenser, a dropping funnel and a thermometer, 191.3 g (1.0 mol) of 3-aminopropylmethyldiethoxysilane and 92.2 g (2.0 mol) of ethanol were charged, and the temperature was adjusted to 60 ° C. Heated. After the internal temperature was stabilized, 139.4 g (2.4 mol) of propylene oxide was added dropwise over 2 hours, and the mixture was further stirred at that temperature for 8 hours. To the obtained reaction liquid, 3.4 g (0.01 mol) of an ethanol solution of 20% by mass sodium ethoxide was added and reacted at 70 ° C. for 3 hours, followed by distillation to obtain 1-methyl-3,7. 184.1 g of dimethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane was obtained as a fraction having a boiling point of 113 ° C./1.0 kPa. It was 72 degreeC when melting | fusing point of the obtained compound was measured.
［実施例８］ナトリウムメトキシドのメタノール溶液を触媒として用いた１−メトキシ−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンの合成
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、３−アミノプロピルトリメトキシシラン１７９．３ｇ（１．０モル）、メタノール６４．０ｇ（２．０モル）を仕込み、６０℃に加熱した。内温が安定した後、プロピレンオキシド１３９．４ｇ（２．４モル）を３時間かけて滴下し、更にその温度で６時間撹拌した。得られた反応液に２８質量％ナトリウムメトキシドのメタノール溶液１．９ｇ（０．０１モル）を添加し、７０℃にて３時間反応させた後、蒸留を行い、１−メトキシ−３，７−ジメチル−２，８−ジオキサ−５−アザ−１−シラビシクロ［３．３．３］ウンデカンを沸点１３２℃／０．４ｋＰａの留分として１７０．６ｇ得た。得られた化合物の融点を測定したところ、９６℃であった。
[Example 8] Synthesis of 1-methoxy-3,7-dimethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane using methanol solution of sodium methoxide as catalyst Stirring A flask equipped with a heat exchanger, a reflux condenser, a dropping funnel and a thermometer was charged with 179.3 g (1.0 mol) of 3-aminopropyltrimethoxysilane and 64.0 g (2.0 mol) of methanol and heated to 60 ° C. did. After the internal temperature was stabilized, 139.4 g (2.4 mol) of propylene oxide was added dropwise over 3 hours, and the mixture was further stirred at that temperature for 6 hours. To the obtained reaction solution, 1.9 g (0.01 mol) of a 28 mass% sodium methoxide methanol solution was added and reacted at 70 ° C. for 3 hours, followed by distillation to give 1-methoxy-3,7. 170.6 g of dimethyl-2,8-dioxa-5-aza-1-silabicyclo [3.3.3] undecane was obtained as a fraction having a boiling point of 132 ° C./0.4 kPa. The melting point of the obtained compound was measured and found to be 96 ° C.
Claims (5)
で示されるアミノオルガノキシシラン化合物と下記一般式（２）
で示されるエポキシ化合物を反応させ、下記一般式（３）
で示されるビシクロアミノオルガノキシシラン化合物を製造する方法において、塩基性又は酸性の触媒を用いることを特徴とする上記一般式（３）で示されるビシクロアミノオルガノキシシラン化合物の製造方法。 The following general formula (1)
And the following general formula (2)
Is reacted with an epoxy compound represented by the following general formula (3):
A method for producing a bicycloaminoorganoxysilane compound represented by the general formula (3), wherein a basic or acidic catalyst is used.
で示されるビシクロアミノオルガノキシシラン化合物。 The following general formula (4)
A bicycloaminoorganoxysilane compound represented by:
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019015809A1 (en) * | 2017-07-21 | 2019-01-24 | Henkel Ag & Co. Kgaa | Method for preparing silicon-containing heterocycles |
| JP2020527584A (en) * | 2017-07-21 | 2020-09-10 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ | Method for producing silicon-containing heterocycle |
| US11306109B2 (en) | 2017-07-21 | 2022-04-19 | Henkel Ag & Co. Kgaa | Method for preparing silicon-containing heterocycles |
| CN109694383A (en) * | 2017-10-24 | 2019-04-30 | 信越化学工业株式会社 | Polycyclic amino silane compounds and manufacturing method |
| EP3476851A1 (en) * | 2017-10-24 | 2019-05-01 | Shin-Etsu Chemical Co., Ltd. | Polycyclic aminosilane compounds and making method |
| KR20190045847A (en) * | 2017-10-24 | 2019-05-03 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Polycyclic aminosilane compounds and making method |
| JP2019077631A (en) * | 2017-10-24 | 2019-05-23 | 信越化学工業株式会社 | Polycyclic aminosilane compound and method for producing the same |
| TWI734939B (en) * | 2017-10-24 | 2021-08-01 | 日商信越化學工業股份有限公司 | Polycyclic aminosilane compound and its manufacturing method |
| KR102423384B1 (en) | 2017-10-24 | 2022-07-22 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Polycyclic aminosilane compounds and making method |
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