JP2018197199A - Imine structure-containing cyclic organic silicon compound and manufacturing method therefor - Google Patents
Imine structure-containing cyclic organic silicon compound and manufacturing method therefor Download PDFInfo
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- JP2018197199A JP2018197199A JP2017101711A JP2017101711A JP2018197199A JP 2018197199 A JP2018197199 A JP 2018197199A JP 2017101711 A JP2017101711 A JP 2017101711A JP 2017101711 A JP2017101711 A JP 2017101711A JP 2018197199 A JP2018197199 A JP 2018197199A
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- 125000000879 imine group Chemical group 0.000 title claims abstract 6
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000004122 cyclic group Chemical group 0.000 title abstract description 8
- 150000003377 silicon compounds Chemical class 0.000 title abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 47
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- 125000004429 atom Chemical group 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 11
- -1 cyclic organosilicon compound Chemical class 0.000 claims description 121
- 125000005842 heteroatom Chemical group 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 11
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 7
- 150000001450 anions Chemical class 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 231100000989 no adverse effect Toxicity 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- 150000002466 imines Chemical group 0.000 description 27
- 150000002430 hydrocarbons Chemical group 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 21
- 150000001412 amines Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000002329 infrared spectrum Methods 0.000 description 12
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 12
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- SSKOYBZTDKUYNV-UHFFFAOYSA-N N-[2-(2-methoxy-2-methylazasilolidin-1-yl)ethyl]-1-phenylmethanimine Chemical compound CO[Si]1(CCCN1CCN=CC2=CC=CC=C2)C SSKOYBZTDKUYNV-UHFFFAOYSA-N 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 125000001841 imino group Chemical group [H]N=* 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 5
- 239000012756 surface treatment agent Substances 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- ZYKLRSSOYHAZQM-UHFFFAOYSA-N N-[2-(2-ethoxy-2-methylazasilolidin-1-yl)ethyl]-1-phenylmethanimine Chemical compound CCO[Si]1(CCCN1CCN=CC2=CC=CC=C2)C ZYKLRSSOYHAZQM-UHFFFAOYSA-N 0.000 description 4
- PCRBLBPWTKIWJY-UHFFFAOYSA-N N-[2-(2-methoxy-2-methylazasilolidin-1-yl)ethyl]-1-(4-methoxyphenyl)methanimine Chemical compound CO[Si]1(N(CCC1)CCN=CC1=CC=C(C=C1)OC)C PCRBLBPWTKIWJY-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- LZUBFHIFJAQUGS-UHFFFAOYSA-N N-[1-(2-methoxy-2-methylazasilolidin-1-yl)propan-2-yl]-2-methylpropan-1-imine Chemical compound CO[Si]1(N(CCC1)CC(C)N=CC(C)C)C LZUBFHIFJAQUGS-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 3
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 125000001544 thienyl group Chemical group 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 2
- 125000004665 trialkylsilyl group Chemical group 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000008096 xylene Substances 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
- FSJXYOZVEYHREI-UHFFFAOYSA-N 1-(furan-2-yl)-N-[2-(2-methoxy-2-methylazasilolidin-1-yl)ethyl]methanimine Chemical compound CO[Si]1(CCCN1CCN=CC2=CC=CO2)C FSJXYOZVEYHREI-UHFFFAOYSA-N 0.000 description 1
- OVONARZNQIKMGQ-UHFFFAOYSA-N 1-phenyl-n-trimethylsilylmethanamine Chemical compound C[Si](C)(C)NCC1=CC=CC=C1 OVONARZNQIKMGQ-UHFFFAOYSA-N 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000006479 2-pyridyl methyl group Chemical group [H]C1=C([H])C([H])=C([H])C(=N1)C([H])([H])* 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 0 CC(*(C)C)*(C)**(*N)*(C)C Chemical compound CC(*(C)C)*(C)**(*N)*(C)C 0.000 description 1
- XXSJNQIPORGCRG-UHFFFAOYSA-N CC(C)(C)C=NCCN1CCCC[Si]1(C)C Chemical compound CC(C)(C)C=NCCN1CCCC[Si]1(C)C XXSJNQIPORGCRG-UHFFFAOYSA-N 0.000 description 1
- WPEXJOAWGKLDSN-UHFFFAOYSA-N CC(C)(C)C=NCCN1CCC[Si]1(C)C Chemical compound CC(C)(C)C=NCCN1CCC[Si]1(C)C WPEXJOAWGKLDSN-UHFFFAOYSA-N 0.000 description 1
- QUISOABSKFCMOF-UHFFFAOYSA-N CC(C)(C)C=NCCN1CCC[Si]1(C)OC Chemical compound CC(C)(C)C=NCCN1CCC[Si]1(C)OC QUISOABSKFCMOF-UHFFFAOYSA-N 0.000 description 1
- LRURXOOZLCDPHO-UHFFFAOYSA-N CC(C)(C)C=NCCN1CCC[Si]1(OC)OC Chemical compound CC(C)(C)C=NCCN1CCC[Si]1(OC)OC LRURXOOZLCDPHO-UHFFFAOYSA-N 0.000 description 1
- MYDIDOXDISKQFN-UHFFFAOYSA-N CCO[Si]1(CCCCN1CCN=CC(C)(C)C)C Chemical compound CCO[Si]1(CCCCN1CCN=CC(C)(C)C)C MYDIDOXDISKQFN-UHFFFAOYSA-N 0.000 description 1
- PEFMQGATPAQARB-UHFFFAOYSA-N CCO[Si]1(CCCCN1CCN=CC(C)(C)C)OCC Chemical compound CCO[Si]1(CCCCN1CCN=CC(C)(C)C)OCC PEFMQGATPAQARB-UHFFFAOYSA-N 0.000 description 1
- MPFQUWUXKRQKGS-UHFFFAOYSA-N CCO[Si]1(CCCN1CCN=CC(C)(C)C)OCC Chemical compound CCO[Si]1(CCCN1CCN=CC(C)(C)C)OCC MPFQUWUXKRQKGS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-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
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 description 1
- IOOUJWIUYWAAEH-UHFFFAOYSA-N N-[2-(2,2-diethoxyazasilinan-1-yl)ethyl]-1-(4-methoxyphenyl)methanimine Chemical compound CCO[Si]1(CCCCN1CCN=CC2=CC=C(C=C2)OC)OCC IOOUJWIUYWAAEH-UHFFFAOYSA-N 0.000 description 1
- HUENTVRCGKXABZ-UHFFFAOYSA-N N-[2-(2,2-diethoxyazasilinan-1-yl)ethyl]-1-phenylmethanimine Chemical compound CCO[Si]1(CCCCN1CCN=CC2=CC=CC=C2)OCC HUENTVRCGKXABZ-UHFFFAOYSA-N 0.000 description 1
- NRADNVIBUUALPD-UHFFFAOYSA-N N-[2-(2,2-diethoxyazasilinan-1-yl)ethyl]cyclohexanimine Chemical compound C(C)O[Si]1(N(CCCC1)CCN=C1CCCCC1)OCC NRADNVIBUUALPD-UHFFFAOYSA-N 0.000 description 1
- YGCWRPAUXQAVIR-UHFFFAOYSA-N N-[2-(2,2-diethoxyazasilinan-1-yl)ethyl]octan-1-imine Chemical compound C(C)O[Si]1(N(CCCC1)CCN=CCCCCCCC)OCC YGCWRPAUXQAVIR-UHFFFAOYSA-N 0.000 description 1
- ZUHZOLFBGWWDTO-UHFFFAOYSA-N N-[2-(2,2-diethoxyazasilolidin-1-yl)ethyl]-1-(4-methoxyphenyl)methanimine Chemical compound C(C)O[Si]1(N(CCC1)CCN=CC1=CC=C(C=C1)OC)OCC ZUHZOLFBGWWDTO-UHFFFAOYSA-N 0.000 description 1
- LBHHMFJOIBJZOW-UHFFFAOYSA-N N-[2-(2,2-diethoxyazasilolidin-1-yl)ethyl]-1-(furan-2-yl)methanimine Chemical compound CCO[Si]1(CCCN1CCN=CC2=CC=CO2)OCC LBHHMFJOIBJZOW-UHFFFAOYSA-N 0.000 description 1
- MHPPNKIMXXFNGA-UHFFFAOYSA-N N-[2-(2,2-diethoxyazasilolidin-1-yl)ethyl]-1-phenylmethanimine Chemical compound CCO[Si]1(CCCN1CCN=CC2=CC=CC=C2)OCC MHPPNKIMXXFNGA-UHFFFAOYSA-N 0.000 description 1
- KRNHNKWVTSRXNT-UHFFFAOYSA-N N-[2-(2,2-diethoxyazasilolidin-1-yl)ethyl]cyclohexanimine Chemical compound C(C)O[Si]1(N(CCC1)CCN=C1CCCCC1)OCC KRNHNKWVTSRXNT-UHFFFAOYSA-N 0.000 description 1
- SETFMUKKWBLZRN-UHFFFAOYSA-N N-[2-(2,2-diethoxyazasilolidin-1-yl)ethyl]octan-1-imine Chemical compound C(C)O[Si]1(N(CCC1)CCN=CCCCCCCC)OCC SETFMUKKWBLZRN-UHFFFAOYSA-N 0.000 description 1
- WMRYHLJLQNKJLC-UHFFFAOYSA-N N-[2-(2,2-dimethoxyazasilinan-1-yl)ethyl]-1-(4-methoxyphenyl)methanimine Chemical compound COC1=CC=C(C=C1)C=NCCN2CCCC[Si]2(OC)OC WMRYHLJLQNKJLC-UHFFFAOYSA-N 0.000 description 1
- LTJYNUUGIZCKJN-UHFFFAOYSA-N N-[2-(2,2-dimethoxyazasilinan-1-yl)ethyl]-1-phenylmethanimine Chemical compound CO[Si]1(CCCCN1CCN=CC2=CC=CC=C2)OC LTJYNUUGIZCKJN-UHFFFAOYSA-N 0.000 description 1
- SUYDQGBUHYUGFC-UHFFFAOYSA-N N-[2-(2,2-dimethoxyazasilinan-1-yl)ethyl]cyclohexanimine Chemical compound CO[Si]1(CCCCN1CCN=C2CCCCC2)OC SUYDQGBUHYUGFC-UHFFFAOYSA-N 0.000 description 1
- BOMVOAIYFWIODK-UHFFFAOYSA-N N-[2-(2,2-dimethoxyazasilinan-1-yl)ethyl]octan-1-imine Chemical compound CCCCCCCC=NCCN1CCCC[Si]1(OC)OC BOMVOAIYFWIODK-UHFFFAOYSA-N 0.000 description 1
- PDKBSNGWBOETSF-UHFFFAOYSA-N N-[2-(2,2-dimethoxyazasilolidin-1-yl)ethyl]-1-(furan-2-yl)methanimine Chemical compound CO[Si]1(CCCN1CCN=CC2=CC=CO2)OC PDKBSNGWBOETSF-UHFFFAOYSA-N 0.000 description 1
- PRAVELRVVYXPAN-UHFFFAOYSA-N N-[2-(2,2-dimethoxyazasilolidin-1-yl)ethyl]-1-phenylmethanimine Chemical compound CO[Si]1(CCCN1CCN=CC2=CC=CC=C2)OC PRAVELRVVYXPAN-UHFFFAOYSA-N 0.000 description 1
- OTFYSKQYQUGAOA-UHFFFAOYSA-N N-[2-(2,2-dimethoxyazasilolidin-1-yl)ethyl]-1-pyridin-2-ylmethanimine Chemical compound CO[Si]1(N(CCC1)CCN=CC1=NC=CC=C1)OC OTFYSKQYQUGAOA-UHFFFAOYSA-N 0.000 description 1
- ISNDSHRTUDTUFO-UHFFFAOYSA-N N-[2-(2,2-dimethoxyazasilolidin-1-yl)ethyl]-1-thiophen-2-ylmethanimine Chemical compound CO[Si]1(CCCN1CCN=CC2=CC=CS2)OC ISNDSHRTUDTUFO-UHFFFAOYSA-N 0.000 description 1
- LMTZTCRQIPHGOL-UHFFFAOYSA-N N-[2-(2,2-dimethoxyazasilolidin-1-yl)ethyl]cyclohexanimine Chemical compound CO[Si]1(N(CCC1)CCN=C1CCCCC1)OC LMTZTCRQIPHGOL-UHFFFAOYSA-N 0.000 description 1
- NGGUKSZDYJEBCQ-UHFFFAOYSA-N N-[2-(2,2-dimethoxyazasilolidin-1-yl)ethyl]octan-1-imine Chemical compound CO[Si]1(N(CCC1)CCN=CCCCCCCC)OC NGGUKSZDYJEBCQ-UHFFFAOYSA-N 0.000 description 1
- TWLJTUXPXBTQTI-UHFFFAOYSA-N N-[2-(2,2-dimethylazasilinan-1-yl)ethyl]-1-(4-methoxyphenyl)methanimine Chemical compound C[Si]1(N(CCCC1)CCN=CC1=CC=C(C=C1)OC)C TWLJTUXPXBTQTI-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
本発明は、イミン構造含有環状有機ケイ素化合物およびその製造方法に関し、さらに詳述すると、アニオン末端変性剤、接着剤、樹脂改質剤、シランカップリング剤、表面処理剤、合成中間体等として有用なイミン構造含有環状有機ケイ素化合物およびその製造方法に関する。 The present invention relates to an imine structure-containing cyclic organosilicon compound and a method for producing the same. More specifically, the present invention is useful as an anionic terminal modifier, an adhesive, a resin modifier, a silane coupling agent, a surface treatment agent, a synthetic intermediate, and the like. The present invention relates to an imine structure-containing cyclic organosilicon compound and a method for producing the same.
イミン構造含有有機ケイ素化合物は、窒素上に活性水素を持たないため、そのままでは反応性を示さない。しかし、この化合物は、湿気あるいは水分と接触するとイミノ基の加水分解が起こり、一級アミノ基含有アルコキシシラン化合物とカルボニル化合物に分解され、反応性に富む一級アミノ基が再生するという特徴を有している。また、イミノ基は求核試薬と反応できるため、合成中間体やアニオン末端変性剤として使用することもできる。 Since the imine structure-containing organosilicon compound does not have active hydrogen on nitrogen, it does not exhibit reactivity as it is. However, this compound has a feature that when it comes into contact with moisture or moisture, hydrolysis of the imino group occurs, it is decomposed into a primary amino group-containing alkoxysilane compound and a carbonyl compound, and a highly reactive primary amino group is regenerated. Yes. Moreover, since an imino group can react with a nucleophile, it can also be used as a synthetic intermediate or an anion terminal modifier.
このようなイミン構造含有有機ケイ素化合物の具体例として、ベンジリデン（トリメトキシシリルプロピル）アミンやメチルイソブチリデン（トリメトキシシリルプロピル）アミン等が挙げられる。これらの化合物は、イミノ基が加水分解されることによって３−アミノプロピルトリメトキシシランを生成し、樹脂改質剤、シランカップリング剤、接着剤、表面処理剤等として使用する際に効力を発揮する。 Specific examples of such an imine structure-containing organosilicon compound include benzylidene (trimethoxysilylpropyl) amine and methylisobutylidene (trimethoxysilylpropyl) amine. These compounds produce 3-aminopropyltrimethoxysilane by hydrolysis of the imino group and are effective when used as resin modifiers, silane coupling agents, adhesives, surface treatment agents, etc. To do.
しかし、上記イミン構造含有有機ケイ素化合物の加水分解によって生じるアミノプロピルトリメトキシシランは、一分子当たり一つのアミノ基しか有していないため、樹脂改質剤、シランカップリング剤、接着剤、表面処理剤等として使用した際に、アミノ基導入の効果が十分に発揮されない場合があった。 However, since aminopropyltrimethoxysilane produced by hydrolysis of the above-mentioned imine structure-containing organosilicon compound has only one amino group per molecule, resin modifier, silane coupling agent, adhesive, surface treatment When used as an agent or the like, the effect of amino group introduction may not be sufficiently exhibited.
この問題を解決できる化合物として、イミノ基の他に二級アミノ基を有するイミン構造含有アルコキシシラン化合物であるベンジリデン（トリメトキシシリルプロピルアミノエチル）アミンや、ベンジリデン（メチルジメトキシシリルプロピルアミノエチル）アミンが知られている（特許文献１，２）。
これらの化合物では、イミノ基が加水分解されて一級アミノ基が再生すると、３−（２−アミノエチル）アミノプロピルトリメトキシシランまたは３−（２−アミノエチル）アミノプロピルメチルジメトキシシランが生成する。これらはアミノ基を二つ有しているため、一分子当たりアミノ基を一つしか有しない化合物に比べて、アミノ基導入の効果が大きくなる。
Compounds that can solve this problem include benzylidene (trimethoxysilylpropylaminoethyl) amine, which is an imine structure-containing alkoxysilane compound having a secondary amino group in addition to an imino group, and benzylidene (methyldimethoxysilylpropylaminoethyl) amine. Known (
In these compounds, when the imino group is hydrolyzed and the primary amino group is regenerated, 3- (2-aminoethyl) aminopropyltrimethoxysilane or 3- (2-aminoethyl) aminopropylmethyldimethoxysilane is produced. Since these have two amino groups, the effect of introducing an amino group is greater than that of a compound having only one amino group per molecule.
しかしながら、上記各特許文献記載の化合物は、反応性に富む二級アミノ基が分子内に存在するため、アニオン末端変性剤として使用した場合、アニオン末端と二級アミノ基上の水素が反応し、アニオン末端を失活させてしまうという問題がある。このため、アニオン末端を十分に変性できず、得られたポリマーが所望の性能を発揮しない可能性がある。
また、アミノ基と反応可能な官能基を有する化合物と当該化合物を混合し、一液化を試みた場合に保存安定性が低いという問題がある。例えば、エポキシ樹脂やイソシアネート樹脂等に上記化合物を添加した場合、二級アミノ基と樹脂中のエポキシ基あるいはイソシアネート基が反応し、樹脂中の官能基を変換してしまう。このため、例えば、上記化合物をエポキシ樹脂あるいはイソシアネート樹脂を主成分とする接着剤等として使用した場合、官能基が変換されてしまうため、一液型組成物とすることができず、所望の性能を得られない可能性がある。
However, since the compound described in each of the above patent documents has a highly reactive secondary amino group in the molecule, when used as an anion terminal modifier, the anion terminal reacts with hydrogen on the secondary amino group, There is a problem that the anion terminal is deactivated. For this reason, an anion terminal cannot fully be modified and the obtained polymer may not exhibit desired performance.
In addition, there is a problem that storage stability is low when a compound having a functional group capable of reacting with an amino group and the compound are mixed to attempt one-pack. For example, when the above compound is added to an epoxy resin, an isocyanate resin, or the like, a secondary amino group reacts with an epoxy group or an isocyanate group in the resin to convert a functional group in the resin. For this reason, for example, when the above compound is used as an adhesive having an epoxy resin or an isocyanate resin as a main component, the functional group is converted. You may not get
本発明は、上記事情に鑑みなされたもので、アニオン末端変性剤、接着剤、樹脂改質剤、シランカップリング剤、表面処理剤、合成中間体等として用いた場合に悪影響が生じず、かつ添加効果が大きい、新規なイミン構造含有環状有機ケイ素化合物およびその製造方法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 when used as an anionic terminal modifier, an adhesive, a resin modifier, a silane coupling agent, a surface treatment agent, a synthetic intermediate, and the like, no adverse effects occur, and An object of the present invention is to provide a novel imine structure-containing cyclic organosilicon compound having a large additive effect and a method for producing the same.
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、所定のイミン構造含有環状有機ケイ素化合物が、アニオン末端変性剤、接着剤、樹脂改質剤、シランカップリング剤、表面処理剤、合成中間体等として用いた場合に、悪影響が生じずに、添加による特性向上を図ることができることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have determined that the predetermined imine structure-containing cyclic organosilicon compound is an anionic terminal modifier, an adhesive, a resin modifier, a silane coupling agent, a surface treatment. It was found that when used as an agent, a synthetic intermediate or the like, the characteristics can be improved by addition without causing adverse effects, and the present invention has been completed.
すなわち、本発明は、
１． 下記一般式（１）で表されるイミン構造含有環状有機ケイ素化合物、
２． 下記一般式（２）
で示されるイミン構造含有有機ケイ素化合物を分子内環化させる１のイミン構造含有環状有機ケイ素化合物の製造方法
を提供する。
That is, the present invention
1. An imine structure-containing cyclic organosilicon compound represented by the following general formula (1):
2. The following general formula (2)
A method for producing an imine structure-containing cyclic organosilicon compound, which comprises intramolecular cyclization of an imine structure-containing organosilicon compound represented by the formula:
本発明のイミン構造含有環状有機ケイ素化合物は、接着剤、樹脂改質剤、シランカップリング剤、表面処理剤等として使用した場合に、アミノ基導入の効果を十分に発揮することができる。また、分子内に活性水素を持たないことから、アニオン末端変性剤、合成中間体等へ利用した場合に、活性末端を失活させることが無く、反応性官能基を有する化合物とも一液化させることができる。 When the imine structure-containing cyclic organosilicon compound of the present invention is used as an adhesive, a resin modifier, a silane coupling agent, a surface treatment agent or the like, the effect of amino group introduction can be sufficiently exhibited. In addition, since it has no active hydrogen in the molecule, it does not deactivate the active terminal when used for anion terminal modifiers, synthetic intermediates, etc. Can do.
以下、本発明について具体的に説明する。
本発明に係るイミン構造含有環状有機ケイ素化合物は、下記一般式（１）で示される。
Hereinafter, the present invention will be specifically described.
The imine structure-containing cyclic organosilicon compound according to the present invention is represented by the following general formula (1).
上記一般式（１）において、Ｒ1およびＲ2は、互いに独立して、水素原子、またはヘテロ原子を含んでいてもよい、置換もしくは非置換の炭素数１〜２０、好ましくは１〜１０の１価炭化水素基を表すが、Ｒ1およびＲ2が互いに結合して環構造を形成してもよく、Ｒ3は、ヘテロ原子を含んでいてもよい、置換または非置換の炭素数１〜２０、好ましくは１〜１０の２価炭化水素基を表し、Ｒ4は、ヘテロ原子を含んでいてもよい、置換または非置換の炭素数１〜２０、好ましくは２〜１０、より好ましくは３〜５の２価炭化水素基を表し、Ｒ5およびＲ6は、ヘテロ原子を含んでいてもよい、置換または非置換の炭素数１〜２０、好ましくは１〜１０の１価炭化水素基を表し、Ｒ7は、単結合、またはＳｉ原子側末端が、−Ｏ−、−Ｓ−、−ＮＨ−もしくは−Ｃ（＝Ｏ）Ｏ−で置換された、炭素数２〜１０、好ましくは２〜５の２価炭化水素基を表す。
In the general formula (1), R 1 and R 2 are each independently a hydrogen atom or a substituted or unsubstituted C 1-20, preferably 1-10, which may contain a hetero atom. Represents a monovalent hydrocarbon group, R 1 and R 2 may be bonded to each other to form a ring structure, and R 3 may contain a hetero atom, a substituted or unsubstituted C 1 -
上記炭素数１〜２０の１価炭化水素基としては、直鎖状、分岐鎖状または環状のいずれでもよく、その具体例としては、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、デシル、ドデシル、テトラデシル、ヘキサデシル、オクタデシル、イコシル基等の直鎖状のアルキル基；イソプロピル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ネオペンチル、テキシル、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、シクロヘキシル基等の環状のアルキル基；アリル、プロペニル、ブテニル、ペンテニル基等のアルケニル基；フェニル、トリル基等のアリール基；ベンジル、フェネチル基等のアラルキル基等が挙げられる。 The monovalent hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl. Linear alkyl groups such as decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl group; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, texyl, 2-ethylhexyl group Cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as allyl, propenyl, butenyl and pentenyl groups; aryl groups such as phenyl and tolyl groups; aralkyl groups such as benzyl and phenethyl groups;
また、上記１価炭化水素基は、分子鎖中に、エーテル基（−Ｏ−）、チオエーテル基（−Ｓ−）等のヘテロ原子の１種または２種以上が介在してもよく、そのような基の具体例としては、フラニル基、チエニル基、ピリジル基、テトラヒドロフラニル基、テトラヒドロチエニル基等が挙げられる。
なお、上記１価炭化水素基の水素原子の一部または全部は、その他の置換基で置換されていてもよく、この置換基の具体例としては、メトキシ、エトキシ、（イソ）プロポキシ基等の炭素数１〜６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；フェニル、トリル基等の炭素数６〜１０のアリール基；ベンジル、フェネチル基等の炭素数７〜１０のアラルキル基；それぞれ各アルキル基、各アルコキシ基が炭素数１〜６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、モノアルキルジアルコキシシリル基等が挙げられる。
The monovalent hydrocarbon group may be interspersed with one or more heteroatoms such as an ether group (—O—) and a thioether group (—S—) in the molecular chain. Specific examples of such groups include furanyl group, thienyl group, pyridyl group, tetrahydrofuranyl group, tetrahydrothienyl group and the like.
In addition, some or all of the hydrogen atoms of the monovalent hydrocarbon group may be substituted with other substituents. Specific examples of this substituent include methoxy, ethoxy, (iso) propoxy group and the like. Alkoxy groups having 1 to 6 carbon atoms; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; aryl groups having 6 to 10 carbon atoms such as phenyl and tolyl groups; and 7 to 7 carbon atoms such as benzyl and
また、Ｒ1およびＲ2が互いに結合して形成する環としては、特に限定されるものではなく、例えば、シクロプロパン環、シクロブタン環、シクロペンタン環、シクロヘキサン環等の炭素数３〜２０の脂肪族炭化水素環等が挙げられる。 In addition, the ring formed by combining R 1 and R 2 with each other is not particularly limited. For example, a C 3-20 fatty acid such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or a cyclohexane ring. Group hydrocarbon ring and the like.
Ｒ1およびＲ2としては、特に原料の入手容易性や、生成物の有用性の観点から、水素原子、炭素数１〜１０の直鎖、分岐もしくは環状アルキル基、炭素数６〜１０のアリール基、フラニル基、チエニル基、ピリジル基が好ましく、Ｒ1およびＲ2のいずれか一方が水素原子で、他方が、炭素数１〜１０の直鎖、分岐もしくは環状アルキル基、炭素数６〜１０のアリール基、フラニル基、チエニル基、ピリジル基がより好ましい。
また、Ｒ5およびＲ6としては、特に原料の入手容易性や、生成物の有用性の観点から、炭素数１〜１０の直鎖、分岐もしくは環状アルキル基が好ましく、炭素数１〜５の直鎖アルキル基がより好ましく、メチル、エチル基がより一層好ましい。
As R 1 and R 2 , particularly from the viewpoint of availability of raw materials and usefulness of the product, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl having 6 to 10 carbon atoms Group, furanyl group, thienyl group and pyridyl group are preferred, one of R 1 and R 2 is a hydrogen atom, and the other is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, 6 to 10 carbon atoms. An aryl group, a furanyl group, a thienyl group, and a pyridyl group are more preferable.
R 5 and R 6 are preferably straight-chain, branched or cyclic alkyl groups having 1 to 10 carbon atoms, particularly from the viewpoint of availability of raw materials and usefulness of the product. Straight chain alkyl groups are more preferred, and methyl and ethyl groups are even more preferred.
上記炭素数１〜２０の２価炭化水素基としては、メチレン、エチレン、トリメチレン、テトラメチレン、ヘキサメチレン、オクタメチレン、デシレン基等の直鎖状アルキレン基；プロピレン（メチルエチレン）基、メチルトリメチレン基等の分岐状アルキレン基；シクロヘキシレン基等の環状アルキレン基；プロペニレン基等のアルケニレン基；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等が挙げられる。
また、ヘテロ原子を含む２価炭化水素基としては、アルキレンアミノアルキレン基、アルキレンオキシアルキレン基、アルキレンチオアルキレン基等が挙げられ、これらのアルキレン基としては、互いに独立して、上記直鎖状、分岐状、環状アルキレン基で例示した基と同様の基が挙げられる。
上記炭素数２〜２０の２価炭化水素基およびヘテロ原子を含む炭素数２〜２０の２価炭化水素基としては、上記炭素数１〜２０の２価炭化水素基から、炭素数１のメチレン基を除いたものと同様の基が挙げられる。
Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decylene group; propylene (methylethylene) group, methyltrimethylene Branched alkylene groups such as groups; cyclic alkylene groups such as cyclohexylene groups; alkenylene groups such as propenylene groups; arylene groups such as phenylene groups; aralkylene groups such as methylenephenylene groups and methylenephenylenemethylene groups.
In addition, examples of the divalent hydrocarbon group containing a hetero atom include an alkyleneaminoalkylene group, an alkyleneoxyalkylene group, an alkylenethioalkylene group, and the like. Examples thereof include the same groups as those exemplified for the branched and cyclic alkylene groups.
Examples of the divalent hydrocarbon group having 2 to 20 carbon atoms and the divalent hydrocarbon group having 2 to 20 carbon atoms containing a hetero atom include the methylene having 1 carbon atom from the divalent hydrocarbon group having 1 to 20 carbon atoms. Examples thereof include the same groups as those excluding the group.
なお、上記２価炭化水素基の水素原子の一部または全部は、その他の置換基で置換されていてもよく、この置換基の具体例としては、メトキシ、エトキシ、（イソ）プロポキシ基等の炭素数１〜６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；フェニル、トリル基等の炭素数６〜１０のアリール基；ベンジル、フェネチル基等の炭素数７〜１０のアラルキル基；それぞれ各アルキル基、各アルコキシ基が炭素数１〜６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、モノアルキルジアルコキシシリル基等が挙げられる。
In addition, some or all of the hydrogen atoms of the divalent hydrocarbon group may be substituted with other substituents. Specific examples of this substituent include methoxy, ethoxy, (iso) propoxy group and the like. Alkoxy groups having 1 to 6 carbon atoms; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; aryl groups having 6 to 10 carbon atoms such as phenyl and tolyl groups; and 7 to 7 carbon atoms such as benzyl and
また、上記Ｓｉ原子側末端が、−Ｏ−、−Ｓ−、−ＮＨ−または−Ｃ（＝Ｏ）Ｏ−で置換された、炭素数２〜１０の２価炭化水素基の具体例としては、エチレンオキシ基、エチレン（メチル）オキシ基、エチレンアミノ基、エチレンメルカプト基、メチレンカルボキシル基等が挙げられる。 Specific examples of the divalent hydrocarbon group having 2 to 10 carbon atoms in which the Si atom side terminal is substituted with —O—, —S—, —NH— or —C (═O) O— , Ethyleneoxy group, ethylene (methyl) oxy group, ethyleneamino group, ethylene mercapto group, methylene carboxyl group and the like.
Ｒ3としては、特に原料の入手容易性や、生成物の有用性の観点から、炭素数１〜１０の直鎖、分岐または環状のアルキレン基が好ましく、炭素数１〜５の直鎖アルキレン基がより好ましく、エチレン基がより一層好ましい。
Ｒ4としては、特に原料の入手容易性や、生成物の有用性の観点から、炭素数２〜１０の直鎖、分岐または環状のアルキレン基が好ましく、炭素数３〜５の直鎖アルキレン基がより好ましく、トリメチレン基がより一層好ましい。
Ｒ7としては、特に原料の入手容易性や、生成物の有用性の観点から、単結合がより好ましい。
R 3 is preferably a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, particularly a linear alkylene group having 1 to 5 carbon atoms, from the viewpoint of availability of raw materials and usefulness of the product. Is more preferable, and an ethylene group is even more preferable.
R 4 is preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms, particularly a linear alkylene group having 3 to 5 carbon atoms, from the viewpoint of availability of raw materials and usefulness of the product. Are more preferable, and a trimethylene group is still more preferable.
R 7 is more preferably a single bond particularly from the viewpoint of availability of raw materials and usefulness of the product.
上記一般式（１）で示されるイミン構造含有環状有機ケイ素化合物の具体例としては、２−メトキシ−２−メチル−１−（２−ベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメトキシ−１−（２−ベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−エトキシ−２−メチル−１−（２−ベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジエトキシ−１−（２−ベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメチル−１−（２−ベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−メトキシ−２−メチル−１−（２−ｐ−メトキシベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメトキシ−１−（２−ｐ−メトキシベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−エトキシ−２−メチル−１−（２−ｐ−メトキシベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジエトキシ−１−（２−ｐ−メトキシベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメチル−１−（２−ｐ−メトキシベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−メトキシ−２−メチル−１−（２−メチルイソブチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメトキシ−１−（２−メチルイソブチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−エトキシ−２−メチル−１−（２−メチルイソブチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジエトキシ−１−（２−メチルイソブチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメチル−１−（２−メチルイソブチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−メトキシ−２−メチル−１−（２−シクロヘキシリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメトキシ−１−（２−シクロヘキシリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−エトキシ−２−メチル−１−（２−シクロヘキシリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジエトキシ−１−（２−シクロヘキシリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメチル−１−（２−シクロヘキシリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−メトキシ−２−メチル−１−（２−Ｎ−メチルピペリジニリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメトキシ−１−（２−Ｎ−メチルピペリジニリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−エトキシ−２−メチル−１−（２−Ｎ−メチルピペリジニリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジエトキシ−１−（２−Ｎ−メチルピペリジニリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメチル−１−（２−Ｎ−メチルピペリジニリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−メトキシ−２−メチル−１−（２−オクチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメトキシ−１−（２−オクチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−エトキシ−２−メチル−１−（２−オクチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジエトキシ−１−（２−オクチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメチル−１−（２−オクチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−メトキシ−２−メチル−１−（２−フラニルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメトキシ−１−（２−フラニルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−エトキシ−２−メチル−１−（２−フラニルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジエトキシ−１−（２−フラニルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメチル−１−（２−フラニルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−メトキシ−２−メチル−１−（２−ピリジルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメトキシ−１−（２−ピリジルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−エトキシ−２−メチル−１−（２−ピリジルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジエトキシ−１−（２−ピリジルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメチル−１−（２−ピリジルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−メトキシ−２−メチル−１−（２−チエニルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメトキシ−１−（２−チエニルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−エトキシ−２−メチル−１−（２−チエニルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジエトキシ−１−（２−チエニルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２，２−ジメチル−１−（２−チエニルメチリデンアミノエチル）−１−アザ−２−シラシクロペンタン、２−メトキシ−２−メチル−１−（２−ベンジリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメトキシ−１−（２−ベンジリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２−エトキシ−２−メチル−１−（２−ベンジリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジエトキシ−１−（２−ベンジリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメチル−１−（２−ベンジリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２−メトキシ−２−メチル−１−（２−ｐ−メトキシベンジリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメトキシ−１−（２−ｐ−メトキシベンジリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２−エトキシ−２−メチル−１−（２−ｐ−メトキシベンジリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジエトキシ−１−（２−ｐ−メトキシベンジリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメチル−１−（２−ｐ−メトキシベンジリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２−メトキシ−２−メチル−１−（２−メチルイソブチリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメトキシ−１−（２−メチルイソブチリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２−エトキシ−２−メチル−１−（２−メチルイソブチリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジエトキシ−１−（２−メチルイソブチリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメチル−１−（２−メチルイソブチリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２−メトキシ−２−メチル−１−（２−シクロヘキシリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメトキシ−１−（２−シクロヘキシリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２−エトキシ−２−メチル−１−（２−シクロヘキシリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジエトキシ−１−（２−シクロヘキシリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメチル−１−（２−シクロヘキシリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２−メトキシ−２−メチル−１−（２−Ｎ−メチルピペリジニリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメトキシ−１−（２−Ｎ−メチルピペリジニリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２−エトキシ−２−メチル−１−（２−Ｎ−メチルピペリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジエトキシ−１−（２−Ｎ−メチルピペリジニリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメチル−１−（２−Ｎ−メチルピペリジニリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２−メトキシ−２−メチル−１−（２−オクチリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメトキシ−１−（２−オクチリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２−エトキシ−２−メチル−１−（２−オクチリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジエトキシ−１−（２−オクチリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメチル−１−（２−オクチリデンアミノエチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメトキシ−６−（２−ベンジリデンアミノエチル）−１，６，２−オキサアザシラシクロオクタン、２−メトキシ−２−メチル−６−（２−ベンジリデンアミノエチル）−１，６，２−オキサアザシラシクロオクタン、２，２−ジエトキシ−６−（２−ベンジリデンアミノエチル）−１，６，２−オキサアザシラシクロオクタン、２−エトキシ−２−メチル−６−（２−ベンジリデンアミノエチル）−１，６，２−オキサアザシラシクロオクタン、２，２−ジメチル−６−（２−ベンジリデンアミノエチル）−１，６，２−オキサアザシラシクロオクタン、２，２−ジメトキシ−８−メチル−６−（２−ベンジリデンアミノエチル）−１，６，２−オキサアザシラシクロオクタン、２，８−ジメチル−２−メトキシ−６−（２−ベンジリデンアミノエチル）−１，６，２−オキサアザシラシクロオクタン、２，２−ジエトキシ−８−メチル−６−（２−ベンジリデンアミノエチル）−１，６，２−オキサアザシラシクロオクタン、２−エトキシ−２，８−ジメチル−６−（２−ベンジリデンアミノエチル）−１，６，２−オキサアザシラシクロオクタン、２，２，８−トリメチル−６−（２−ベンジリデンアミノエチル）−１，６，２−オキサアザシラシクロオクタン等が例示される。 Specific examples of the imine structure-containing cyclic organosilicon compound represented by the general formula (1) include 2-methoxy-2-methyl-1- (2-benzylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-dimethoxy-1- (2-benzylideneaminoethyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1- (2-benzylideneaminoethyl) -1-aza-2- Silacyclopentane, 2,2-diethoxy-1- (2-benzylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-dimethyl-1- (2-benzylideneaminoethyl) -1-aza- 2-silacyclopentane, 2-methoxy-2-methyl-1- (2-p-methoxybenzylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2- Methoxy-1- (2-p-methoxybenzylideneaminoethyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1- (2-p-methoxybenzylideneaminoethyl) -1-aza- 2-silacyclopentane, 2,2-diethoxy-1- (2-p-methoxybenzylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-dimethyl-1- (2-p-methoxybenzylidene) Aminoethyl) -1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1- (2-methylisobutylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-dimethoxy -1- (2-Methylisobutylideneaminoethyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1- (2-methylisobu Rideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (2-methylisobutylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-dimethyl- 1- (2-methylisobutylideneaminoethyl) -1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1- (2-cyclohexylideneaminoethyl) -1-aza-2-sila Cyclopentane, 2,2-dimethoxy-1- (2-cyclohexylideneaminoethyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1- (2-cyclohexylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (2-cyclohexylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2- Dimethyl-1- (2-cyclohexylideneaminoethyl) -1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1- (2-N-methylpiperidinylideneaminoethyl) -1-aza -2-silacyclopentane, 2,2-dimethoxy-1- (2-N-methylpiperidinylideneaminoethyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1- (2 -N-methylpiperidinylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (2-N-methylpiperidinylideneaminoethyl) -1-aza-2-silacyclo Pentane, 2,2-dimethyl-1- (2-N-methylpiperidinylideneaminoethyl) -1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1- (2-o Tylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-dimethoxy-1- (2-octylideneaminoethyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-methyl -1- (2-octylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (2-octylideneaminoethyl) -1-aza-2-silacyclopentane, 2 , 2-Dimethyl-1- (2-octylideneaminoethyl) -1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1- (2-furanylmethylideneaminoethyl) -1-aza -2-silacyclopentane, 2,2-dimethoxy-1- (2-furanylmethylideneaminoethyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1- ( -Furanylmethylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (2-furanylmethylideneaminoethyl) -1-aza-2-silacyclopentane, 2, 2-Dimethyl-1- (2-furanylmethylideneaminoethyl) -1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1- (2-pyridylmethylideneaminoethyl) -1-aza -2-silacyclopentane, 2,2-dimethoxy-1- (2-pyridylmethylideneaminoethyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1- (2-pyridylmethyl) Ridenaminoethyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (2-pyridylmethylideneaminoethyl) -1-aza-2-silacyclopentane 2,2-dimethyl-1- (2-pyridylmethylideneaminoethyl) -1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1- (2-thienylmethylideneaminoethyl) -1 -Aza-2-silacyclopentane, 2,2-dimethoxy-1- (2-thienylmethylideneaminoethyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1- (2- Thienylmethylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (2-thienylmethylideneaminoethyl) -1-aza-2-silacyclopentane, 2,2-dimethyl -1- (2-Thienylmethylideneaminoethyl) -1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1- (2-benzylideneaminoethyl) -1- The-2-silacyclohexane, 2,2-dimethoxy-1- (2-benzylideneaminoethyl) -1-aza-2-silacyclohexane, 2-ethoxy-2-methyl-1- (2-benzylideneaminoethyl)- 1-aza-2-silacyclohexane, 2,2-diethoxy-1- (2-benzylideneaminoethyl) -1-aza-2-silacyclohexane, 2,2-dimethyl-1- (2-benzylideneaminoethyl)- 1-aza-2-silacyclohexane, 2-methoxy-2-methyl-1- (2-p-methoxybenzylideneaminoethyl) -1-aza-2-silacyclohexane, 2,2-dimethoxy-1- (2- p-methoxybenzylideneaminoethyl) -1-aza-2-silacyclohexane, 2-ethoxy-2-methyl-1- (2-p-methoxybe) Dilideneaminoethyl) -1-aza-2-silacyclohexane, 2,2-diethoxy-1- (2-p-methoxybenzylideneaminoethyl) -1-aza-2-silacyclohexane, 2,2-dimethyl-1 -(2-p-methoxybenzylideneaminoethyl) -1-aza-2-silacyclohexane, 2-methoxy-2-methyl-1- (2-methylisobutylideneaminoethyl) -1-aza-2-silacyclohexane 2,2-dimethoxy-1- (2-methylisobutylideneaminoethyl) -1-aza-2-silacyclohexane, 2-ethoxy-2-methyl-1- (2-methylisobutylideneaminoethyl)- 1-aza-2-silacyclohexane, 2,2-diethoxy-1- (2-methylisobutylideneaminoethyl) -1-aza-2-silacyclo Hexane, 2,2-dimethyl-1- (2-methylisobutylideneaminoethyl) -1-aza-2-silacyclohexane, 2-methoxy-2-methyl-1- (2-cyclohexylideneaminoethyl)- 1-aza-2-silacyclohexane, 2,2-dimethoxy-1- (2-cyclohexylideneaminoethyl) -1-aza-2-silacyclohexane, 2-ethoxy-2-methyl-1- (2-cyclohex Silideneaminoethyl) -1-aza-2-silacyclohexane, 2,2-diethoxy-1- (2-cyclohexylideneaminoethyl) -1-aza-2-silacyclohexane, 2,2-dimethyl-1- (2-cyclohexylideneaminoethyl) -1-aza-2-silacyclohexane, 2-methoxy-2-methyl-1- (2-N-methylpiperidinyl) Aminoethyl) -1-aza-2-silacyclohexane, 2,2-dimethoxy-1- (2-N-methylpiperidinylideneaminoethyl) -1-aza-2-silacyclohexane, 2-ethoxy-2-methyl- 1- (2-N-methylpiperideneaminoethyl) -1-aza-2-silacyclohexane, 2,2-diethoxy-1- (2-N-methylpiperidinylideneaminoethyl) -1-aza-2- Silacyclohexane, 2,2-dimethyl-1- (2-N-methylpiperidinylideneaminoethyl) -1-aza-2-silacyclohexane, 2-methoxy-2-methyl-1- (2-octylideneaminoethyl) ) -1-aza-2-silacyclohexane, 2,2-dimethoxy-1- (2-octylideneaminoethyl) -1-aza-2-silacyclohexane, -Ethoxy-2-methyl-1- (2-octylideneaminoethyl) -1-aza-2-silacyclohexane, 2,2-diethoxy-1- (2-octylideneaminoethyl) -1-aza-2- Silacyclohexane, 2,2-dimethyl-1- (2-octylideneaminoethyl) -1-aza-2-silacyclohexane, 2,2-dimethoxy-6- (2-benzylideneaminoethyl) -1,6,2 -Oxaazasilacyclooctane, 2-methoxy-2-methyl-6- (2-benzylideneaminoethyl) -1,6,2-oxaazasilacyclooctane, 2,2-diethoxy-6- (2-benzylideneamino) Ethyl) -1,6,2-oxaazasilacyclooctane, 2-ethoxy-2-methyl-6- (2-benzylideneaminoethyl) -1,6,2-oxa Azasilacyclooctane, 2,2-dimethyl-6- (2-benzylideneaminoethyl) -1,6,2-oxaazasilacyclooctane, 2,2-dimethoxy-8-methyl-6- (2-benzylideneamino) Ethyl) -1,6,2-oxaazasilacyclooctane, 2,8-dimethyl-2-methoxy-6- (2-benzylideneaminoethyl) -1,6,2-oxaazasilacyclooctane, 2,2 -Diethoxy-8-methyl-6- (2-benzylideneaminoethyl) -1,6,2-oxaazasilacyclooctane, 2-ethoxy-2,8-dimethyl-6- (2-benzylideneaminoethyl) -1 , 6,2-oxaazasilacyclooctane, 2,2,8-trimethyl-6- (2-benzylideneaminoethyl) -1,6,2-oxaazasilacyclooctane Tan, and the like.
特に、接着剤、表面処理剤等として使用した場合に、迅速に処理ができるという点から、Ｒ7が単結合である下記一般式（３）で示される化合物が好ましく、さらに、原料調達の容易性から、Ｒ4がトリメチレン基である下記一般式（４）で示される化合物がより好ましい。 In particular, a compound represented by the following general formula (3) in which R 7 is a single bond is preferable because it can be rapidly processed when used as an adhesive, a surface treatment agent, or the like, and further, easy procurement of raw materials. In view of the properties, a compound represented by the following general formula (4), in which R 4 is a trimethylene group, is more preferable.
上記一般式（１）で示されるイミン構造含有環状有機ケイ素化合物は、例えば、下記一般式（２）で示されるイミン構造含有有機ケイ素化合物を分子内環化させて製造することができる。 The imine structure-containing cyclic organosilicon compound represented by the general formula (1) can be produced, for example, by intramolecular cyclization of the imine structure-containing organosilicon compound represented by the following general formula (2).
上記一般式（２）で示されるイミン構造含有有機ケイ素化合物において、Ｒ8は、水素原子、またはヒドロキシ基、アミノ基、チオール基もしくはカルボキシル基で置換された炭素数２〜１０の１価炭化水素基を表す。
ヒドロキシ基、アミノ基、チオール基もしくはカルボキシル基で置換された炭素数２〜１０の１価炭化水素基中の１価炭化水素基としては、上記で例示した基と同様の基が挙げられ、上記置換された炭素数２〜１０の１価炭化水素基の具体例としては、エチレンヒドロキシ基、エチレンアミノ基、エチレンメルカプト基、メチレンカルボキシル基、エチレン（メチル）ヒドロキシ基等が挙げられる。
Ｒ8としては、特に、原料調達の容易性から水素原子が好ましく、水素原子でない場合は反応性の点からヒドロキシ基を含むことが好ましい。
In the imine structure-containing organosilicon compound represented by the general formula (2), R 8 is a hydrogen atom or a monovalent hydrocarbon having 2 to 10 carbon atoms substituted with a hydroxy group, an amino group, a thiol group or a carboxyl group Represents a group.
Examples of the monovalent hydrocarbon group in the monovalent hydrocarbon group having 2 to 10 carbon atoms substituted with a hydroxy group, an amino group, a thiol group, or a carboxyl group include the same groups as those exemplified above. Specific examples of the substituted monovalent hydrocarbon group having 2 to 10 carbon atoms include an ethylene hydroxy group, an ethylene amino group, an ethylene mercapto group, a methylene carboxyl group, and an ethylene (methyl) hydroxy group.
R 8 is particularly preferably a hydrogen atom from the viewpoint of easy procurement of raw materials, and if it is not a hydrogen atom, it preferably contains a hydroxy group from the viewpoint of reactivity.
上記一般式（２）で示されるイミン構造含有有機ケイ素化合物の具体例としては、ベンジリデン（メチルジメトキシシリルプロピルアミノエチル）アミン、ベンジリデン（トリメトキシシリルプロピルアミノエチル）アミン、ベンジリデン（メチルジエトキシシリルプロピルアミノエチル）アミン、ベンジリデン（トリエトキシシリルプロピルアミノエチル）アミン、ベンジリデン（ジメチルメトキシシリルプロピルアミノエチル）アミン、ベンジリデン（ジメチルエトキシシリルプロピルアミノエチル）アミン、ｐ−メトキシベンジリデン（メチルジメトキシシリルプロピルアミノエチル）アミン、ｐ−メトキシベンジリデン（トリメトキシシリルプロピルアミノエチル）アミン、ｐ−メトキシベンジリデン（メチルジエトキシシリルプロピルアミノエチル）アミン、ｐ−メトキシベンジリデン（トリエトキシシリルプロピルアミノエチル）アミン、ｐ−メトキシベンジリデン（ジメチルメトキシシリルプロピルアミノエチル）アミン、ｐ−メトキシベンジリデン（ジメチルエトキシシリルプロピルアミノエチル）アミン、メチルイソブチリデン（メチルジメトキシシリルプロピルアミノエチル）アミン、メチルイソブチリデン（トリメトキシシリルプロピルアミノエチル）アミン、メチルイソブチリデン（メチルジエトキシシリルプロピルアミノエチル）アミン、メチルイソブチリデン（トリエトキシシリルプロピルアミノエチル）アミン、メチルイソブチリデン（ジメチルメトキシシリルプロピルアミノエチル）アミン、メチルイソブチリデン（ジメチルエトキシシリルプロピルアミノエチル）アミン、シクロヘキシリデン（メチルジメトキシシリルプロピルアミノエチル）アミン、シクロヘキシリデン（トリメトキシシリルプロピルアミノエチル）アミン、シクロヘキシリデン（メチルジエトキシシリルプロピルアミノエチル）アミン、シクロヘキシリデン（トリエトキシシリルプロピルアミノエチル）アミン、シクロヘキシリデン（ジメチルメトキシシリルプロピルアミノエチル）アミン、シクロヘキシリデン（ジメチルエトキシシリルプロピルアミノエチル）アミン、Ｎ−メチルピペリジニリデン（メチルジメトキシシリルプロピルアミノエチル）アミン、Ｎ−メチルピペリジニリデン（トリメトキシシリルプロピルアミノエチル）アミン、Ｎ−メチルピペリジニリデン（メチルジエトキシシリルプロピルアミノエチル）アミン、Ｎ−メチルピペリジニリデン（トリエトキシシリルプロピルアミノエチル）アミン、Ｎ−メチルピペリジニリデン（ジメチルメトキシシリルプロピルアミノエチル）アミン、Ｎ−メチルピペリジニリデン（ジメチルエトキシシリルプロピルアミノエチル）アミン、オクチリデン（メチルジメトキシシリルプロピルアミノエチル）アミン、オクチリデン（トリメトキシシリルプロピルアミノエチル）アミン、オクチリデン（メチルジエトキシシリルプロピルアミノエチル）アミン、オクチリデン（トリエトキシシリルプロピルアミノエチル）アミン、オクチリデン（ジメチルメトキシシリルプロピルアミノエチル）アミン、オクチリデン（ジメチルエトキシシリルプロピルアミノエチル）アミン、２−フラニルメチリデン（メチルジメトキシシリルプロピルアミノエチル）アミン、２−フラニルメチリデン（トリメトキシシリルプロピルアミノエチル）アミン、２−フラニルメチリデン（メチルジエトキシシリルプロピルアミノエチル）アミン、２−フラニルメチリデン（トリエトキシシリルプロピルアミノエチル）アミン、２−フラニルメチリデン（ジメチルメトキシシリルプロピルアミノエチル）アミン、２−フラニルメチリデン（ジメチルエトキシシリルプロピルアミノエチル）アミン、２−ピリジルメチリデン（メチルジメトキシシリルプロピルアミノエチル）アミン、２−ピリジルメチリデン（トリメトキシシリルプロピルアミノエチル）アミン、２−ピリジルメチリデン（メチルジエトキシシリルプロピルアミノエチル）アミン、２−ピリジルメチリデン（トリエトキシシリルプロピルアミノエチル）アミン、２−ピリジルメチリデン（ジメチルメトキシシリルプロピルアミノエチル）アミン、２−ピリジルメチリデン（ジメチルエトキシシリルプロピルアミノエチル）アミン、２−チエニルメチリデン（メチルジメトキシシリルプロピルアミノエチル）アミン、２−チエニルメチリデン（トリメトキシシリルプロピルアミノエチル）アミン、２−チエニルメチリデン（メチルジエトキシシリルプロピルアミノエチル）アミン、２−チエニルメチリデン（トリエトキシシリルプロピルアミノエチル）アミン、２−チエニルメチリデン（ジメチルメトキシシリルプロピルアミノエチル）アミン、２−チエニルメチリデン（ジメチルエトキシシリルプロピルアミノエチル）アミン、ベンジリデン（トリメトキシシリルプロピル（ヒドロキシエチル）アミノエチル）アミン、ベンジリデン（メチルジメトキシシリルプロピル（ヒドロキシエチル）アミノエチル）アミン、ベンジリデン（トリエトキシシリルプロピル（ヒドロキシエチル）アミノエチル）アミン、ベンジリデン（メチルジエトキシシリルプロピル（ヒドロキシエチル）アミノエチル）アミン、ベンジリデン（ジメチルメトキシシリルプロピル（ヒドロキシエチル）アミノエチル）アミン、ベンジリデン（ジメチルエトキシシリルプロピル（ヒドロキシエチル）アミノエチル）アミン、ベンジリデン（トリメトキシシリルプロピル（ヒドロキシ（メチル）エチル）アミノエチル）アミン、ベンジリデン（メチルジメトキシシリルプロピル（ヒドロキシ（メチル）エチル）アミノエチル）アミン、ベンジリデン（トリエトキシシリルプロピル（ヒドロキシ（メチル）エチル）アミノエチル）アミン、ベンジリデン（メチルジエトキシシリルプロピル（ヒドロキシ（メチル）エチル）アミノエチル）アミン、ベンジリデン（ジメチルメトキシシリルプロピル（ヒドロキシ（メチル）エチル）アミノエチル）アミン、ベンジリデン（ジメチルエトキシシリルプロピル（ヒドロキシ（メチル）エチル）アミノエチル）アミン等が挙げられる。 Specific examples of the imine structure-containing organosilicon compound represented by the general formula (2) include benzylidene (methyldimethoxysilylpropylaminoethyl) amine, benzylidene (trimethoxysilylpropylaminoethyl) amine, and benzylidene (methyldiethoxysilylpropyl). Aminoethyl) amine, benzylidene (triethoxysilylpropylaminoethyl) amine, benzylidene (dimethylmethoxysilylpropylaminoethyl) amine, benzylidene (dimethylethoxysilylpropylaminoethyl) amine, p-methoxybenzylidene (methyldimethoxysilylpropylaminoethyl) Amine, p-methoxybenzylidene (trimethoxysilylpropylaminoethyl) amine, p-methoxybenzylidene (methyldiethoxysilylpro) Ruaminoethyl) amine, p-methoxybenzylidene (triethoxysilylpropylaminoethyl) amine, p-methoxybenzylidene (dimethylmethoxysilylpropylaminoethyl) amine, p-methoxybenzylidene (dimethylethoxysilylpropylaminoethyl) amine, methylisobutylidene (Methyldimethoxysilylpropylaminoethyl) amine, methylisobutylidene (trimethoxysilylpropylaminoethyl) amine, methylisobutylidene (methyldiethoxysilylpropylaminoethyl) amine, methylisobutylidene (triethoxysilylpropylaminoethyl) ) Amine, methylisobutylidene (dimethylmethoxysilylpropylaminoethyl) amine, methylisobutylidene (dimethylethoxysilylpro) Ruaminoethyl) amine, cyclohexylidene (methyldimethoxysilylpropylaminoethyl) amine, cyclohexylidene (trimethoxysilylpropylaminoethyl) amine, cyclohexylidene (methyldiethoxysilylpropylaminoethyl) amine, cyclohexylidene (triethoxy Silylpropylaminoethyl) amine, cyclohexylidene (dimethylmethoxysilylpropylaminoethyl) amine, cyclohexylidene (dimethylethoxysilylpropylaminoethyl) amine, N-methylpiperidinylidene (methyldimethoxysilylpropylaminoethyl) amine, N -Methylpiperidinylidene (trimethoxysilylpropylaminoethyl) amine, N-methylpiperidinylidene (methyldiethoxysilylpropylamino) Noethyl) amine, N-methylpiperidinylidene (triethoxysilylpropylaminoethyl) amine, N-methylpiperidinylidene (dimethylmethoxysilylpropylaminoethyl) amine, N-methylpiperidinylidene (dimethylethoxysilylpropylaminoethyl) Amine, octylidene (methyldimethoxysilylpropylaminoethyl) amine, octylidene (trimethoxysilylpropylaminoethyl) amine, octylidene (methyldiethoxysilylpropylaminoethyl) amine, octylidene (triethoxysilylpropylaminoethyl) amine, octylidene (dimethyl) Methoxysilylpropylaminoethyl) amine, octylidene (dimethylethoxysilylpropylaminoethyl) amine, 2-furanylmethylidene ( Tildimethoxysilylpropylaminoethyl) amine, 2-furanylmethylidene (trimethoxysilylpropylaminoethyl) amine, 2-furanylmethylidene (methyldiethoxysilylpropylaminoethyl) amine, 2-furanylmethylidene (tri Ethoxysilylpropylaminoethyl) amine, 2-furanylmethylidene (dimethylmethoxysilylpropylaminoethyl) amine, 2-furanylmethylidene (dimethylethoxysilylpropylaminoethyl) amine, 2-pyridylmethylidene (methyldimethoxysilylpropyl) Aminoethyl) amine, 2-pyridylmethylidene (trimethoxysilylpropylaminoethyl) amine, 2-pyridylmethylidene (methyldiethoxysilylpropylaminoethyl) amine, 2-pyridylmethylidene (Triethoxysilylpropylaminoethyl) amine, 2-pyridylmethylidene (dimethylmethoxysilylpropylaminoethyl) amine, 2-pyridylmethylidene (dimethylethoxysilylpropylaminoethyl) amine, 2-thienylmethylidene (methyldimethoxysilyl) Propylaminoethyl) amine, 2-thienylmethylidene (trimethoxysilylpropylaminoethyl) amine, 2-thienylmethylidene (methyldiethoxysilylpropylaminoethyl) amine, 2-thienylmethylidene (triethoxysilylpropylaminoethyl) Amine, 2-thienylmethylidene (dimethylmethoxysilylpropylaminoethyl) amine, 2-thienylmethylidene (dimethylethoxysilylpropylaminoethyl) amine, benzylidene ( Trimethoxysilylpropyl (hydroxyethyl) aminoethyl) amine, benzylidene (methyldimethoxysilylpropyl (hydroxyethyl) aminoethyl) amine, benzylidene (triethoxysilylpropyl (hydroxyethyl) aminoethyl) amine, benzylidene (methyldiethoxysilylpropyl) (Hydroxyethyl) aminoethyl) amine, benzylidene (dimethylmethoxysilylpropyl (hydroxyethyl) aminoethyl) amine, benzylidene (dimethylethoxysilylpropyl (hydroxyethyl) aminoethyl) amine, benzylidene (trimethoxysilylpropyl (hydroxy (methyl)) Ethyl) aminoethyl) amine, benzylidene (methyldimethoxysilylpropyl (hydroxy (methyl) ethyl) amino Til) amine, benzylidene (triethoxysilylpropyl (hydroxy (methyl) ethyl) aminoethyl) amine, benzylidene (methyldiethoxysilylpropyl (hydroxy (methyl) ethyl) aminoethyl) amine, benzylidene (dimethylmethoxysilylpropyl (hydroxy ( And methyl) ethyl) aminoethyl) amine, benzylidene (dimethylethoxysilylpropyl (hydroxy (methyl) ethyl) aminoethyl) amine, and the like.
分子内環化させる方法としては、一般式（２）で示されるイミン構造含有有機ケイ素化合物を触媒の存在下で加熱し、生じたアルコール成分を系外に除去する第一の方法や、一般式（２）で示されるイミン構造含有有機ケイ素化合物を触媒の存在下で加熱し、生じたアルコール成分をオルトエステル化合物またはシラザン化合物で捕捉する第二の方法等が挙げられる。 As a method for intramolecular cyclization, a first method in which an imine structure-containing organosilicon compound represented by the general formula (2) is heated in the presence of a catalyst and the resulting alcohol component is removed from the system, or a general formula Examples include a second method in which the imine structure-containing organosilicon compound represented by (2) is heated in the presence of a catalyst, and the resulting alcohol component is captured by an ortho ester compound or a silazane compound.
第一の方法における触媒としては、ブレンステッド酸として、酢酸、プロピオン酸、ヘキサン酸、オクタン酸、コハク酸、安息香酸、トリフルオロ酢酸等のカルボン酸；メタンスルホン酸、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、ノナフルオロブタンスルホン酸等のスルホン酸；Ｏ−ベンズスルホンイミド、ジベンゼンスルホンイミド等のスルホンイミド、ルイス酸として、塩化亜鉛、塩化アルミニウム、塩化マグネシウム、トリメチルシリルトリフルオロメタンスルホナート等が挙げられ、これらの触媒は単独で用いても、２種以上を混合して用いてもよい。
これらの触媒の添加量は、生成するアルコール成分１モルあたり、好ましくは０．０００１〜０．１モル、より好ましくは０．００１〜０．０５モルである。
As a catalyst in the first method, as Bronsted acid, carboxylic acid such as acetic acid, propionic acid, hexanoic acid, octanoic acid, succinic acid, benzoic acid, trifluoroacetic acid; methanesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethane Sulfonic acids such as sulfonic acid and nonafluorobutanesulfonic acid; sulfoimides such as O-benzsulfonimide and dibenzenesulfonimide; Lewis acids include zinc chloride, aluminum chloride, magnesium chloride, and trimethylsilyl trifluoromethanesulfonate. These catalysts may be used alone or in combination of two or more.
The amount of these catalysts added is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.05 mol, per mol of the alcohol component to be produced.
第一の方法における反応温度は、好ましくは０〜２００℃、より好ましくは４０〜２００℃である。反応時間は、好ましくは３０〜６００分間、より好ましくは６０〜３００分間、より一層好ましくは６０〜１５０分間である。
第一の方法の反応は、常圧下でも進行するが、生じたアルコールを速やかに除去するために減圧下で行うことが好ましい。
第一の方法の反応は、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、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；アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド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等が挙げられ、これらの溶媒は、１種を単独で用いても、２種以上を混合して用いてもよい。
The reaction temperature in the first method is preferably 0 to 200 ° C, more preferably 40 to 200 ° C. The reaction time is preferably 30 to 600 minutes, more preferably 60 to 300 minutes, and even more preferably 60 to 150 minutes.
The reaction of the first method proceeds even under normal pressure, but is preferably performed under reduced pressure in order to quickly remove the alcohol produced.
The reaction of the first method proceeds even without solvent, but a solvent can also be used. Solvents used include hydrocarbon solvents such as pentane, hexane, cyclohexane, isooctane, benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aprons such as acetonitrile and N, N-dimethylformamide Polar solvents; chlorinated hydrocarbon solvents such as dichloromethane and chloroform, and the like. These solvents may be used alone or in combination of two or more.
第二の方法における触媒としては、第一の方法と同じものが挙げられ、また添加量についても同様である。
第二の方法における反応温度は、好ましくは８０℃〜２００℃、より好ましくは１１０℃〜２００℃である。反応時間は、好ましくは６０〜６００分間、より好ましくは１２０〜３００分間である。
第二の方法の反応は、減圧下でも進行するが、反応温度をできるだけ高く設定するために、常圧下で行うことが好ましい。
Examples of the catalyst in the second method include the same catalyst as in the first method, and the addition amount is the same.
The reaction temperature in the second method is preferably 80 ° C to 200 ° C, more preferably 110 ° C to 200 ° C. The reaction time is preferably 60 to 600 minutes, more preferably 120 to 300 minutes.
The reaction of the second method proceeds even under reduced pressure, but it is preferably performed under normal pressure in order to set the reaction temperature as high as possible.
第二の方法で用いられるオルトエステル化合物としては、オルトギ酸トリメチル、オルトギ酸トリエチル等が挙げられ、シラザン化合物としては、テトラメチルジシラザン、ヘキサメチルジシラザン、ジメチルアミノトリメチルシラン、ジエチルアミノトリメチルシラン、フェニルアミノトリメチルシラン、フェニルメチルアミノトリメチルシラン等が挙げられる。
これらの化合物の使用量は、生成するアルコール成分１モルあたり、好ましくは０．５〜１０モル、より好ましくは０．５〜５モルである。
第二の方法の反応は、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、第一の方法と同様のものが挙げられる。
Examples of the ortho ester compound used in the second method include trimethyl orthoformate and triethyl orthoformate, and examples of the silazane compound include tetramethyldisilazane, hexamethyldisilazane, dimethylaminotrimethylsilane, diethylaminotrimethylsilane, and phenyl. Examples include aminotrimethylsilane and phenylmethylaminotrimethylsilane.
The amount of these compounds to be used is preferably 0.5 to 10 mol, more preferably 0.5 to 5 mol, per mol of the alcohol component to be produced.
The reaction of the second method proceeds even without solvent, but a solvent can also be used. Examples of the solvent to be used include the same solvents as those used in the first method.
上記一連の反応で得られた一般式（１）で示されるイミン構造含有環状有機ケイ素化合物の単離や精製は、減圧蒸留や各種クロマトグラフィー等の通常の有機合成における精製方法から適宜選択して用いることができるが、工業的経済性の点から減圧蒸留が好ましい。 Isolation and purification of the imine structure-containing cyclic organosilicon compound represented by the general formula (1) obtained by the series of reactions described above is appropriately selected from purification methods in ordinary organic synthesis such as vacuum distillation and various chromatography. Although it can be used, vacuum distillation is preferred from the viewpoint of industrial economy.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
［実施例１］
撹拌機、還流器、滴下ロート、温度計、および充填剤を含む蒸留塔を備えたフラスコに、トルエン２１８．５ｇ、トリフルオロメタンスルホン酸０．７ｇ（０．００５モル）を仕込み、トルエン還流下でベンジリデン（メチルジメトキシシリルプロピルアミノエチル）アミン１４７．３ｇ（０．５０００モル）、ヘキサメチルジシラザン４４．３ｇ（０．２７４モル）、アセトニトリル３８．０ｇの混合物を４時間かけて滴下しながら、生成したトリメチルメトキシシラン、アセトニトリルおよびトルエンを留去し、さらに釜温１２０℃までトルエンを留去した。得られた反応液を蒸留し、１４７℃／０．４ｋＰａの留分４５．３ｇを得た。
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。ＩＲスペクトルを図１に、1Ｈ−ＮＭＲスペクトルを図２に示す。
質量スペクトル
ｍ／ｚ ２６２，２３３，１４４，１１４，７５
以上の結果より、得られた化合物は、２−メトキシ−２−メチル−１−（ベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタンであることが確認された。
[Example 1]
Into a flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a distillation column containing a filler, was charged 218.5 g of toluene and 0.7 g (0.005 mol) of trifluoromethanesulfonic acid. Benzylidene (methyldimethoxysilylpropylaminoethyl) amine 147.3 g (0.5000 mol), 44.3 g (0.274 mol) of hexamethyldisilazane, and 38.0 g of acetonitrile were added dropwise over 4 hours. Trimethylmethoxysilane, acetonitrile and toluene were distilled off, and toluene was further distilled off to a kettle temperature of 120 ° C. The obtained reaction liquid was distilled to obtain 45.3 g of a fraction of 147 ° C./0.4 kPa.
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured. The IR spectrum is shown in FIG. 1, and the 1 H-NMR spectrum is shown in FIG.
Mass spectrum m /
From the above results, it was confirmed that the obtained compound was 2-methoxy-2-methyl-1- (benzylideneaminoethyl) -1-aza-2-silacyclopentane.
［実施例２］
撹拌機、還流器、滴下ロート、温度計、および充填剤を含む蒸留塔を備えたフラスコに、トルエン２１１．３ｇ、ノナフルオロブタンスルホン酸１．５ｇ（０．００５０モル）を仕込み、トルエン還流下でｐ−メトキシベンジリデン（メチルジメトキシシリルプロピルアミノエチル）アミン１６２．３ｇ（０．５０００モル）、ヘキサメチルジシラザン４４．５ｇ（０．２７６モル）、アセトニトリル３７．８ｇの混合物を４時間かけて滴下しながら、生成したトリメチルメトキシシラン、アセトニトリルおよびトルエンを留去し、さらに釜温１２０℃までトルエンを留去した。得られた反応液を蒸留し、１４６℃／０．４ｋＰａの留分６２．２ｇを得た。
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。ＩＲスペクトルを図３に、1Ｈ−ＮＭＲスペクトルを図４に示す。
質量スペクトル
ｍ／ｚ ２９２，２６３，１４４，１１３，７５
以上の結果より、得られた化合物は、２−メトキシ−２−メチル−１−（ｐ−メトキシベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタンであることが確認された。
[Example 2]
To a flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a distillation column containing a filler, was charged with 211.3 g of toluene and 1.5 g (0.0050 mol) of nonafluorobutanesulfonic acid, and the mixture was refluxed with toluene. A mixture of 162.3 g (0.5000 mol) of p-methoxybenzylidene (methyldimethoxysilylpropylaminoethyl) amine, 44.5 g (0.276 mol) of hexamethyldisilazane and 37.8 g of acetonitrile was added dropwise over 4 hours. The produced trimethylmethoxysilane, acetonitrile and toluene were distilled off, and toluene was further distilled off to a kettle temperature of 120 ° C. The obtained reaction liquid was distilled to obtain 62.2 g of a fraction of 146 ° C./0.4 kPa.
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured. FIG. 3 shows the IR spectrum, and FIG. 4 shows the 1 H-NMR spectrum.
Mass spectrum m /
From the above results, it was confirmed that the obtained compound was 2-methoxy-2-methyl-1- (p-methoxybenzylideneaminoethyl) -1-aza-2-silacyclopentane.
［実施例３］
撹拌機、還流器、滴下ロート、温度計、および充填剤を含む蒸留塔を備えたフラスコに、Ｏ−キシレン２２７．６ｇ、ノナフルオロブタンスルホン酸１．５ｇ（０．００５０モル）を仕込み、Ｏ−キシレン還流下でベンジリデン（メチルジエトキシシリルプロピルアミノエチル）アミン１５８．９ｇ（０．４９２７モル）、ヘキサメチルジシラザン４４．３ｇ（０．２７４モル）、アセトニトリル３８．５ｇの混合物を４時間かけて滴下しながら、生成したトリメチルエトキシシラン、アセトニトリル、およびＯ−キシレンを留去し、さらに釜温１５２℃までＯ−キシレンを留去した。得られた反応液を蒸留し、１４７℃／０．５ｋＰａの留分４７．１ｇを得た。
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。ＩＲスペクトルを図５に、1Ｈ−ＮＭＲスペクトルを図６に示す。
質量スペクトル
ｍ／ｚ ２７６，２４７，１５８，１１４，９１
以上の結果より、得られた化合物は、２−エトキシ−２−メチル−１−（ベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタンであることが確認された。
[Example 3]
In a flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a distillation column containing a filler, 227.6 g of O-xylene and 1.5 g of nonafluorobutanesulfonic acid (0.0050 mol) were charged. -A mixture of 158.9 g (0.4927 mol) benzylidene (methyldiethoxysilylpropylaminoethyl) amine, 44.3 g (0.274 mol) hexamethyldisilazane, and 38.5 g acetonitrile over 4 hours under reflux of xylene. The resulting trimethylethoxysilane, acetonitrile, and O-xylene were distilled off while dropping, and further O-xylene was distilled off to a kettle temperature of 152 ° C. The obtained reaction liquid was distilled to obtain 47.1 g of a fraction of 147 ° C./0.5 kPa.
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured. FIG. 5 shows the IR spectrum and FIG. 6 shows the 1 H-NMR spectrum.
Mass spectrum m / z 276, 247, 158, 114, 91
From the above results, it was confirmed that the obtained compound was 2-ethoxy-2-methyl-1- (benzylideneaminoethyl) -1-aza-2-silacyclopentane.
［実施例４］
撹拌機、還流器、滴下ロート、温度計、および充填剤を含む蒸留塔を備えたフラスコに、トルエン２０９．９ｇ、ノナフルオロブタンスルホン酸１．５ｇ（０．００５０モル）を仕込み、トルエン還流下でメチルイソブチリデン（メチルジメトキシシリルプロピルアミノエチル）アミン１４４．５ｇ（０．５００９モル）、ヘキサメチルジシラザン４４．５ｇ（０．２７６モル）、アセトニトリル３８．０ｇの混合物を４時間かけて滴下しながら、生成したトリメチルメトキシシラン、アセトニトリル、およびトルエンを留去し、さらに釜温１２２℃までトルエンを留去した。得られた反応液を蒸留し、１１０℃／０．４ｋＰａの留分３５．３ｇを得た。
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。ＩＲスペクトルを図７に、1Ｈ−ＮＭＲスペクトルを図８に示す。
質量スペクトル
ｍ／ｚ ２５６，２４１，１５８，１４４，１１４，７５
以上の結果より、得られた化合物は、２−メトキシ−２−メチル−１−（メチルイソブチリデンアミノエチル）−１−アザ−２−シラシクロペンタンであることが確認された。
[Example 4]
Into a flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a distillation column containing a filler, was charged 209.9 g of toluene and 1.5 g (0.0050 mol) of nonafluorobutanesulfonic acid, and the mixture was refluxed with toluene. A mixture of methyl isobutylidene (methyldimethoxysilylpropylaminoethyl) amine 144.5 g (0.5009 mol), hexamethyldisilazane 44.5 g (0.276 mol) and acetonitrile 38.0 g was added dropwise over 4 hours. The produced trimethylmethoxysilane, acetonitrile, and toluene were distilled off, and toluene was further distilled off to a kettle temperature of 122 ° C. The obtained reaction liquid was distilled to obtain 35.3 g of a fraction at 110 ° C./0.4 kPa.
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured. FIG. 7 shows the IR spectrum and FIG. 8 shows the 1 H-NMR spectrum.
Mass spectrum m /
From the above results, it was confirmed that the obtained compound was 2-methoxy-2-methyl-1- (methylisobutylideneaminoethyl) -1-aza-2-silacyclopentane.
［応用例１］イミン構造含有環状有機ケイ素化合物とメタノールの反応
撹拌および還流器を備えたフラスコに、実施例１で得られた２−メトキシ−２−メチル−１−（ベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン１．０ｇ（０．００３８モル）を仕込み、メタノール１．２ｇ（０．０３８モル）を加え、室温で１時間撹拌した。得られた反応液のガスクロマトグラフィー分析を行ったところ、２−メトキシ−２−メチル−１−（ベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタンに由来するピークは消失し、ベンジリデン（メチルジメトキシシリルプロピルアミノエチル）アミンが生成した。
以上の結果から、本発明で得られたイミン構造含有環状有機ケイ素化合物は、アルコール成分や空気中の湿気で容易に環状構造が解消され、反応性に富む２級アミノ基が再生されることが示された。
Application Example 1 Reaction of Imine Structure-Containing Cyclic Organosilicon Compound with Methanol 2-Methoxy-2-methyl-1- (benzylideneaminoethyl) -1 obtained in Example 1 was added to a flask equipped with stirring and reflux. -Aza-2-silacyclopentane 1.0g (0.0038mol) was prepared, methanol 1.2g (0.038mol) was added, and it stirred at room temperature for 1 hour. When the obtained reaction liquid was analyzed by gas chromatography, the peak derived from 2-methoxy-2-methyl-1- (benzylideneaminoethyl) -1-aza-2-silacyclopentane disappeared, and benzylidene ( Methyldimethoxysilylpropylaminoethyl) amine was formed.
From the above results, the imine structure-containing cyclic organosilicon compound obtained in the present invention can be easily eliminated by the alcohol component or moisture in the air, and the secondary amino group rich in reactivity can be regenerated. Indicated.
［応用例２］イミン構造含有環状有機ケイ素化合物とブチルリチウムの反応
撹拌機、還流器、および温度計を備えたフラスコに、実施例１で得られた２−メトキシ−２−メチル−１−（ベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン２．６ｇ（０．００９９モル）とトルエン８．２ｇを仕込み、室温で撹拌した。この反応液にｎ−ブチルリチウム（２．６Ｍヘキサン溶液）７．６ｍｌ（０．０２０モル）を５分かけて滴下し、その後室温で１時間撹拌した。得られた反応液にメタノールを加えて反応を停止し、得られた反応液のＧＣ／ＭＳ分析を行った。その結果、原料の２−メトキシ−２−メチル−１−（ベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタンが消失し、２−（ブチルメチルメトキシシリルプロピル）アミノエチル（１−フェニルペンチル）アミンの生成が確認された。
以上の結果から、本発明で得られたイミン構造含有環状有機ケイ素化合物は、アニオン重合末端を失活させることなく、金属末端と反応することが示された。
[Application Example 2] Reaction of Imine Structure-Containing Cyclic Organosilicon Compound and Butyllithium To a flask equipped with a stirrer, a reflux condenser, and a thermometer, 2-methoxy-2-methyl-1- ( Benzylideneaminoethyl) -1-aza-2-silacyclopentane (2.6 g, 0.0099 mol) and toluene (8.2 g) were charged and stirred at room temperature. To this reaction solution, 7.6 ml (0.020 mol) of n-butyllithium (2.6 M hexane solution) was added dropwise over 5 minutes, and then stirred at room temperature for 1 hour. Methanol was added to the obtained reaction solution to stop the reaction, and the obtained reaction solution was subjected to GC / MS analysis. As a result, the raw material 2-methoxy-2-methyl-1- (benzylideneaminoethyl) -1-aza-2-silacyclopentane disappeared, and 2- (butylmethylmethoxysilylpropyl) aminoethyl (1-phenylpentyl) disappeared. ) Formation of amine was confirmed.
From the above results, it was shown that the imine structure-containing cyclic organosilicon compound obtained in the present invention reacts with the metal terminal without deactivating the anionic polymerization terminal.
［応用例３］イミン構造含有環状有機ケイ素化合物とエポキシ樹脂の安定性評価
エポキシ樹脂ＪＥＲ−８２７（三菱化学（株）製）３０．０ｇとトルエン３０．０ｇの混合物に、実施例１で得られた２−メトキシ−２−メチル−１−（ベンジリデンアミノエチル）−１−アザ−２−シラシクロペンタン３．０ｇを混合し、均一な組成物を調製した。この組成物を調製直後に、ウベローデ粘度計（柴田科学（株）製、粘度計定数０．００９８４）を用い、２５℃で動粘度を測定したところ、５．０であった。その後、窒素雰囲気下、３日間室温で静置した後、再び２５℃で動粘度を測定したところ、５．８であり、顕著な増粘は認められなかった。
以上の結果から、本発明で得られたイミン構造含有環状有機ケイ素化合物は、エポキシ樹脂と安定に混合できることが示された。
Application Example 3 Stability Evaluation of Imine Structure-Containing Cyclic Organosilicon Compound and Epoxy Resin A mixture of 30.0 g of epoxy resin JER-827 (Mitsubishi Chemical Corporation) and 30.0 g of toluene was obtained in Example 1. 2-Methoxy-2-methyl-1- (benzylideneaminoethyl) -1-aza-2-silacyclopentane (3.0 g) was mixed to prepare a uniform composition. Immediately after this composition was prepared, the kinematic viscosity was measured at 25 ° C. using an Ubbelohde viscometer (manufactured by Shibata Kagaku Co., Ltd., viscometer constant 0.00984), and it was 5.0. Then, after leaving still at room temperature for 3 days under nitrogen atmosphere, when kinematic viscosity was measured again at 25 degreeC, it was 5.8 and remarkable thickening was not recognized.
From the above results, it was shown that the imine structure-containing cyclic organosilicon compound obtained in the present invention can be stably mixed with an epoxy resin.
Claims (2)
で示されるイミン構造含有有機ケイ素化合物を分子内環化させる請求項１記載のイミン構造含有環状有機ケイ素化合物の製造方法。 The following general formula (2)
The method for producing an imine structure-containing cyclic organosilicon compound according to claim 1, wherein the imine structure-containing organosilicon compound represented by formula (1) is cyclized intramolecularly.
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| EP4023657A4 (en) * | 2020-07-22 | 2023-01-04 | LG Chem, Ltd. | Novel imine group-containing compound, modified conjugated diene-based polymer comprising same, method for preparing same polymer, and rubber composition comprising same polymer |
| JP7330377B2 (en) | 2020-07-22 | 2023-08-21 | エルジー・ケム・リミテッド | New imine group-containing compound, modified conjugated diene polymer containing the same, method for producing the polymer, and rubber composition containing the polymer |
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