CN104211725A - 甲硅烷基保护的含氮环状化合物和制备方法 - Google Patents
甲硅烷基保护的含氮环状化合物和制备方法 Download PDFInfo
- Publication number
- CN104211725A CN104211725A CN201410228912.4A CN201410228912A CN104211725A CN 104211725 A CN104211725 A CN 104211725A CN 201410228912 A CN201410228912 A CN 201410228912A CN 104211725 A CN104211725 A CN 104211725A
- Authority
- CN
- China
- Prior art keywords
- silyl
- piperazine
- methylethyl
- hexahydropyrimidine
- imidazolidine
- 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
Links
- -1 Silyl-protected nitrogen Chemical class 0.000 title abstract description 52
- 150000001923 cyclic compounds Chemical class 0.000 title abstract 2
- 238000000034 method Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 25
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 6
- 229920005668 polycarbonate resin Polymers 0.000 abstract 1
- 239000004431 polycarbonate resin Substances 0.000 abstract 1
- 229920001225 polyester resin Polymers 0.000 abstract 1
- 239000004645 polyester resin Substances 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- 229920005749 polyurethane resin Polymers 0.000 abstract 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 127
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 46
- DKYBVKMIZODYKL-UHFFFAOYSA-N 1,3-diazinane Chemical group C1CNCNC1 DKYBVKMIZODYKL-UHFFFAOYSA-N 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- CAXIRAPVUUWWOJ-UHFFFAOYSA-N 3-(3-silyl-1,3-diazinan-1-yl)propanenitrile Chemical compound [SiH3]N1CN(CCC1)CCC#N CAXIRAPVUUWWOJ-UHFFFAOYSA-N 0.000 description 5
- PVBBHKIUHMTBBI-UHFFFAOYSA-N 3-(3-silylimidazolidin-1-yl)propanenitrile Chemical compound [SiH3]N1CN(CC1)CCC#N PVBBHKIUHMTBBI-UHFFFAOYSA-N 0.000 description 5
- NOEOVKPVQQTBFN-UHFFFAOYSA-N ethyl 2-methyl-3-(3-silyl-1,3-diazinan-1-yl)propanoate Chemical compound [SiH3]N1CN(CCC1)CC(C)C(=O)OCC NOEOVKPVQQTBFN-UHFFFAOYSA-N 0.000 description 5
- OGPJONZGIJSVQL-UHFFFAOYSA-N ethyl 2-methyl-3-(3-silylimidazolidin-1-yl)propanoate Chemical compound [SiH3]N1CN(CC1)CC(C)C(=O)OCC OGPJONZGIJSVQL-UHFFFAOYSA-N 0.000 description 5
- KPFPIYGCBPDESR-UHFFFAOYSA-N ethyl 2-methyl-3-(4-silylpiperazin-1-yl)propanoate Chemical compound [SiH3]N1CCN(CC1)CC(C)C(=O)OCC KPFPIYGCBPDESR-UHFFFAOYSA-N 0.000 description 5
- MXHYQRAFQWYGSJ-UHFFFAOYSA-N methyl 2-methyl-3-(3-silyl-1,3-diazinan-1-yl)propanoate Chemical compound [SiH3]N1CN(CCC1)CC(C)C(=O)OC MXHYQRAFQWYGSJ-UHFFFAOYSA-N 0.000 description 5
- QMNXVEASSWVZQD-UHFFFAOYSA-N methyl 2-methyl-3-(4-silylpiperazin-1-yl)propanoate Chemical compound [SiH3]N1CCN(CC1)CC(C)C(=O)OC QMNXVEASSWVZQD-UHFFFAOYSA-N 0.000 description 5
- LATGBXWIZRTLHS-UHFFFAOYSA-N piperazin-1-yl-tri(propan-2-yl)silane Chemical compound CC(C)[Si](C(C)C)(C(C)C)N1CCNCC1 LATGBXWIZRTLHS-UHFFFAOYSA-N 0.000 description 5
- SUQBVXFGGATXQO-UHFFFAOYSA-N tert-butyl-dimethyl-piperazin-1-ylsilane Chemical compound CC(C)(C)[Si](C)(C)N1CCNCC1 SUQBVXFGGATXQO-UHFFFAOYSA-N 0.000 description 5
- PXUXRPHQWHGBLZ-UHFFFAOYSA-N 3-(4-silylpiperazin-1-yl)propanenitrile Chemical compound [SiH3]N1CCN(CC1)CCC#N PXUXRPHQWHGBLZ-UHFFFAOYSA-N 0.000 description 4
- WRCGNRHXRPXTGR-UHFFFAOYSA-N 3-[4-[tert-butyl(dimethyl)silyl]piperazin-1-yl]propanenitrile Chemical compound CC(C)(C)[Si](C)(C)N1CCN(CCC#N)CC1 WRCGNRHXRPXTGR-UHFFFAOYSA-N 0.000 description 4
- UCKGSFYZTDYEAF-UHFFFAOYSA-N 3-[4-tri(propan-2-yl)silylpiperazin-1-yl]propanenitrile Chemical compound CC(C)[Si](C(C)C)(C(C)C)N1CCN(CCC#N)CC1 UCKGSFYZTDYEAF-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- LVQQCKBOSIOPPK-UHFFFAOYSA-N methyl 2-methyl-3-(3-silylimidazolidin-1-yl)propanoate Chemical compound [SiH3]N1CN(CC1)CC(C)C(=O)OC LVQQCKBOSIOPPK-UHFFFAOYSA-N 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- RWTKDXMCDQQEFA-UHFFFAOYSA-N 1,3-diazinan-1-ylsilane Chemical compound [SiH3]N1CNCCC1 RWTKDXMCDQQEFA-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- MBNZWTSAAPQLKH-UHFFFAOYSA-N [SiH3]N1CCNCC1 Chemical compound [SiH3]N1CCNCC1 MBNZWTSAAPQLKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- AASHTZXZPFCYKW-UHFFFAOYSA-N imidazolidin-1-ylsilane Chemical compound [SiH3]N1CNCC1 AASHTZXZPFCYKW-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 125000004193 piperazinyl group Chemical group 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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 compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229940043232 butyl acetate Drugs 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003335 secondary amines Chemical group 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 2
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- LPSYJLUKTAGVLU-UHFFFAOYSA-N (1-hexylimidazolidin-2-yl)-dimethylsilane Chemical compound C(CCCCC)N1C(NCC1)[SiH](C)C LPSYJLUKTAGVLU-UHFFFAOYSA-N 0.000 description 1
- FCZISCSSXWYEHT-UHFFFAOYSA-N (1-hexylpiperazin-2-yl)-dimethylsilane Chemical compound C(CCCCC)N1C(CNCC1)[SiH](C)C FCZISCSSXWYEHT-UHFFFAOYSA-N 0.000 description 1
- LPSATGHVVVBQST-UHFFFAOYSA-N 1,3-diazinan-1-yl(triethyl)silane Chemical compound CC[Si](CC)(CC)N1CCCNC1 LPSATGHVVVBQST-UHFFFAOYSA-N 0.000 description 1
- OLQZTYSRLXEPRP-UHFFFAOYSA-N 1,3-diazinan-1-yl-tris(2-methylpropyl)silane Chemical compound CC(C)C[Si](CC(C)C)(CC(C)C)N1CCCNC1 OLQZTYSRLXEPRP-UHFFFAOYSA-N 0.000 description 1
- QLPZEDHKVHQPAD-UHFFFAOYSA-N 2,2,2-trifluoro-n-trimethylsilylacetamide Chemical compound C[Si](C)(C)NC(=O)C(F)(F)F QLPZEDHKVHQPAD-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- TYOYZEXBEOWVND-UHFFFAOYSA-N 3-(1,3-diazinan-1-yl)propanenitrile Chemical compound N#CCCN1CCCNC1 TYOYZEXBEOWVND-UHFFFAOYSA-N 0.000 description 1
- VLMHJHCIAIDKLX-UHFFFAOYSA-N 3-(2-dimethylsilyl-3-hexyl-1,3-diazinan-1-yl)propanenitrile Chemical compound C(CCCCC)N1C(N(CCC1)CCC#N)[SiH](C)C VLMHJHCIAIDKLX-UHFFFAOYSA-N 0.000 description 1
- LGRHUVICHVJKOY-UHFFFAOYSA-N 3-(2-dimethylsilyl-3-hexylimidazolidin-1-yl)propanenitrile Chemical compound C(CCCCC)N1C(N(CC1)CCC#N)[SiH](C)C LGRHUVICHVJKOY-UHFFFAOYSA-N 0.000 description 1
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- BLKCEKCPGKJVAX-UHFFFAOYSA-N 3-[4-[tert-butyl(diphenyl)silyl]piperazin-1-yl]propanenitrile Chemical compound CC(C)(C)[Si](N1CCN(CCC#N)CC1)(c1ccccc1)c1ccccc1 BLKCEKCPGKJVAX-UHFFFAOYSA-N 0.000 description 1
- KWMXUICVVGPCMG-UHFFFAOYSA-N 3-[4-[tris(2-methylpropyl)silyl]piperazin-1-yl]propanenitrile Chemical compound CC(C)C[Si](CC(C)C)(CC(C)C)N1CCN(CCC#N)CC1 KWMXUICVVGPCMG-UHFFFAOYSA-N 0.000 description 1
- LKOVOMZHFZBQFP-UHFFFAOYSA-N 3-imidazolidin-1-ylpropanenitrile Chemical compound N#CCCN1CCNC1 LKOVOMZHFZBQFP-UHFFFAOYSA-N 0.000 description 1
- MVOFPBMQTXKONX-UHFFFAOYSA-N 3-piperazin-1-ylpropanenitrile Chemical compound N#CCCN1CCNCC1 MVOFPBMQTXKONX-UHFFFAOYSA-N 0.000 description 1
- QIICJUWNVJOFPS-UHFFFAOYSA-N 4,4,5,5,6,6-hexaethyl-3H-azadisiline Chemical compound C(C)C1(C(C(N=[SiH][SiH2]1)(CC)CC)(CC)CC)CC QIICJUWNVJOFPS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 0 CC*(C(*)*)*(*)*N(C)C Chemical compound CC*(C(*)*)*(*)*N(C)C 0.000 description 1
- LTAAZFNTIYUSTB-UHFFFAOYSA-N CCCC(C)(C)N1CCNC1[SiH](C)C Chemical compound CCCC(C)(C)N1CCNC1[SiH](C)C LTAAZFNTIYUSTB-UHFFFAOYSA-N 0.000 description 1
- YCLOWEKXUBLDOQ-UHFFFAOYSA-N CCCC(C)(C)N1CCNCC1[SiH](C)C Chemical compound CCCC(C)(C)N1CCNCC1[SiH](C)C YCLOWEKXUBLDOQ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- QFHMNFAUXJAINK-UHFFFAOYSA-N [1-(carbamoylamino)-2-methylpropyl]urea Chemical group NC(=O)NC(C(C)C)NC(N)=O QFHMNFAUXJAINK-UHFFFAOYSA-N 0.000 description 1
- 125000001118 alkylidene 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 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
- 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
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- VWKHMIVQJFIBNU-UHFFFAOYSA-N ethyl 2-methyl-3-(3-triethylsilyl-1,3-diazinan-1-yl)propanoate Chemical compound CCOC(=O)C(C)CN1CCCN(C1)[Si](CC)(CC)CC VWKHMIVQJFIBNU-UHFFFAOYSA-N 0.000 description 1
- MUXRAHKFVIHSMI-UHFFFAOYSA-N ethyl 2-methyl-3-(3-triethylsilylimidazolidin-1-yl)propanoate Chemical compound CCOC(=O)C(C)CN1CCN(C1)[Si](CC)(CC)CC MUXRAHKFVIHSMI-UHFFFAOYSA-N 0.000 description 1
- AGZKUCUFBKZGDW-UHFFFAOYSA-N ethyl 2-methyl-3-(4-triethylsilylpiperazin-1-yl)propanoate Chemical compound CCOC(=O)C(C)CN1CCN(CC1)[Si](CC)(CC)CC AGZKUCUFBKZGDW-UHFFFAOYSA-N 0.000 description 1
- LPSYEJWRLRLZAV-UHFFFAOYSA-N ethyl 2-methyl-3-[3-[tris(2-methylpropyl)silyl]-1,3-diazinan-1-yl]propanoate Chemical compound CCOC(=O)C(C)CN1CCCN(C1)[Si](CC(C)C)(CC(C)C)CC(C)C LPSYEJWRLRLZAV-UHFFFAOYSA-N 0.000 description 1
- SCHZFHHEOJTVDM-UHFFFAOYSA-N ethyl 2-methyl-3-[3-[tris(2-methylpropyl)silyl]imidazolidin-1-yl]propanoate Chemical compound CCOC(=O)C(C)CN1CCN(C1)[Si](CC(C)C)(CC(C)C)CC(C)C SCHZFHHEOJTVDM-UHFFFAOYSA-N 0.000 description 1
- GUVRHFGZGPMLET-UHFFFAOYSA-N ethyl 2-methyl-3-[4-[tris(2-methylpropyl)silyl]piperazin-1-yl]propanoate Chemical compound CCOC(=O)C(C)CN1CCN(CC1)[Si](CC(C)C)(CC(C)C)CC(C)C GUVRHFGZGPMLET-UHFFFAOYSA-N 0.000 description 1
- FMZHIYFGWQHOAL-UHFFFAOYSA-N ethyl 2-methyl-3-piperazin-1-ylpropanoate Chemical compound CCOC(=O)C(C)CN1CCNCC1 FMZHIYFGWQHOAL-UHFFFAOYSA-N 0.000 description 1
- ZINLJGSUUOQJTD-UHFFFAOYSA-N ethyl 3-(1,3-diazinan-1-yl)-2-methylpropanoate Chemical compound CCOC(=O)C(C)CN1CCCNC1 ZINLJGSUUOQJTD-UHFFFAOYSA-N 0.000 description 1
- HFYNARAYYGGHBY-UHFFFAOYSA-N ethyl 3-(2-dimethylsilyl-3-hexyl-1,3-diazinan-1-yl)-2-methylpropanoate Chemical compound C(CCCCC)N1C(N(CCC1)CC(C)C(=O)OCC)[SiH](C)C HFYNARAYYGGHBY-UHFFFAOYSA-N 0.000 description 1
- PJBUDGRAGCIIQB-UHFFFAOYSA-N ethyl 3-(2-dimethylsilyl-3-hexylimidazolidin-1-yl)-2-methylpropanoate Chemical compound C(CCCCC)N1C(N(CC1)CC(C)C(=O)OCC)[SiH](C)C PJBUDGRAGCIIQB-UHFFFAOYSA-N 0.000 description 1
- WFVKKRHFZLAQEO-UHFFFAOYSA-N ethyl 3-(3-dimethylsilyl-4-hexylpiperazin-1-yl)-2-methylpropanoate Chemical compound C(CCCCC)N1C(CN(CC1)CC(C)C(=O)OCC)[SiH](C)C WFVKKRHFZLAQEO-UHFFFAOYSA-N 0.000 description 1
- SSAGOOHEHRRRLF-UHFFFAOYSA-N ethyl 3-[3-[tert-butyl(dimethyl)silyl]-1,3-diazinan-1-yl]-2-methylpropanoate Chemical compound [Si](C)(C)(C(C)(C)C)N1CN(CCC1)CC(C)C(=O)OCC SSAGOOHEHRRRLF-UHFFFAOYSA-N 0.000 description 1
- OBOLHYGTLGIJNH-UHFFFAOYSA-N ethyl 3-[3-[tert-butyl(dimethyl)silyl]imidazolidin-1-yl]-2-methylpropanoate Chemical compound CCOC(=O)C(C)CN1CCN(C1)[Si](C)(C)C(C)(C)C OBOLHYGTLGIJNH-UHFFFAOYSA-N 0.000 description 1
- OQJSIHOJUDLFMX-UHFFFAOYSA-N ethyl 3-[3-[tert-butyl(diphenyl)silyl]-1,3-diazinan-1-yl]-2-methylpropanoate Chemical compound [Si](C1=CC=CC=C1)(C1=CC=CC=C1)(C(C)(C)C)N1CN(CCC1)CC(C)C(=O)OCC OQJSIHOJUDLFMX-UHFFFAOYSA-N 0.000 description 1
- VJXXBDHIYDCYIP-UHFFFAOYSA-N ethyl 3-[3-[tert-butyl(diphenyl)silyl]imidazolidin-1-yl]-2-methylpropanoate Chemical compound CCOC(=O)C(C)CN1CCN(C1)[Si](c1ccccc1)(c1ccccc1)C(C)(C)C VJXXBDHIYDCYIP-UHFFFAOYSA-N 0.000 description 1
- PARAHKVIOLHJSJ-UHFFFAOYSA-N ethyl 3-[4-[tert-butyl(dimethyl)silyl]piperazin-1-yl]-2-methylpropanoate Chemical compound CCOC(=O)C(C)CN1CCN(CC1)[Si](C)(C)C(C)(C)C PARAHKVIOLHJSJ-UHFFFAOYSA-N 0.000 description 1
- BFNYQGAQWMYPMY-UHFFFAOYSA-N ethyl 3-[4-[tert-butyl(diphenyl)silyl]piperazin-1-yl]-2-methylpropanoate Chemical compound CCOC(=O)C(C)CN1CCN(CC1)[Si](c1ccccc1)(c1ccccc1)C(C)(C)C BFNYQGAQWMYPMY-UHFFFAOYSA-N 0.000 description 1
- XAXRVXUWOKPIAI-UHFFFAOYSA-N ethyl 3-imidazolidin-1-yl-2-methylpropanoate Chemical compound CCOC(=O)C(C)CN1CCNC1 XAXRVXUWOKPIAI-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 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
- 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 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- CEFXUTZNHDLCDC-UHFFFAOYSA-N imidazolidin-1-yl-tris(2-methylpropyl)silane Chemical compound CC(C)C[Si](CC(C)C)(CC(C)C)N1CCNC1 CEFXUTZNHDLCDC-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- MBLYSUDOWZIRQK-UHFFFAOYSA-N methyl 2-methyl-3-(3-triethylsilyl-1,3-diazinan-1-yl)propanoate Chemical compound CC[Si](CC)(CC)N1CCCN(CC(C)C(=O)OC)C1 MBLYSUDOWZIRQK-UHFFFAOYSA-N 0.000 description 1
- FYPFGMQWMLYCSH-UHFFFAOYSA-N methyl 2-methyl-3-(3-triethylsilylimidazolidin-1-yl)propanoate Chemical compound CC[Si](CC)(CC)N1CCN(CC(C)C(=O)OC)C1 FYPFGMQWMLYCSH-UHFFFAOYSA-N 0.000 description 1
- MJOGXTBYZLMZPZ-UHFFFAOYSA-N methyl 2-methyl-3-(4-triethylsilylpiperazin-1-yl)propanoate Chemical compound CC[Si](CC)(CC)N1CCN(CC(C)C(=O)OC)CC1 MJOGXTBYZLMZPZ-UHFFFAOYSA-N 0.000 description 1
- IENLXDHTIKYZOU-UHFFFAOYSA-N methyl 2-methyl-3-[3-[tris(2-methylpropyl)silyl]-1,3-diazinan-1-yl]propanoate Chemical compound COC(=O)C(C)CN1CCCN(C1)[Si](CC(C)C)(CC(C)C)CC(C)C IENLXDHTIKYZOU-UHFFFAOYSA-N 0.000 description 1
- VJXQHMMOSAILQV-UHFFFAOYSA-N methyl 2-methyl-3-[4-[tris(2-methylpropyl)silyl]piperazin-1-yl]propanoate Chemical compound COC(=O)C(C)CN1CCN(CC1)[Si](CC(C)C)(CC(C)C)CC(C)C VJXQHMMOSAILQV-UHFFFAOYSA-N 0.000 description 1
- RRHPJFYNGFZSBN-UHFFFAOYSA-N methyl 2-methyl-3-piperazin-1-ylpropanoate Chemical compound COC(=O)C(C)CN1CCNCC1 RRHPJFYNGFZSBN-UHFFFAOYSA-N 0.000 description 1
- ANIYNEVBLOHOGG-UHFFFAOYSA-N methyl 3-(1,3-diazinan-1-yl)-2-methylpropanoate Chemical compound COC(=O)C(C)CN1CCCNC1 ANIYNEVBLOHOGG-UHFFFAOYSA-N 0.000 description 1
- IRYSIZXCCUYZSY-UHFFFAOYSA-N methyl 3-(2-dimethylsilyl-3-hexyl-1,3-diazinan-1-yl)-2-methylpropanoate Chemical compound C(CCCCC)N1C(N(CCC1)CC(C)C(=O)OC)[SiH](C)C IRYSIZXCCUYZSY-UHFFFAOYSA-N 0.000 description 1
- GTFKNQKRUUVJBF-UHFFFAOYSA-N methyl 3-(2-dimethylsilyl-3-hexylimidazolidin-1-yl)-2-methylpropanoate Chemical compound C(CCCCC)N1C(N(CC1)CC(C)C(=O)OC)[SiH](C)C GTFKNQKRUUVJBF-UHFFFAOYSA-N 0.000 description 1
- YLQQMUMODKHXDV-UHFFFAOYSA-N methyl 3-(3-dimethylsilyl-4-hexylpiperazin-1-yl)-2-methylpropanoate Chemical compound C(CCCCC)N1C(CN(CC1)CC(C)C(=O)OC)[SiH](C)C YLQQMUMODKHXDV-UHFFFAOYSA-N 0.000 description 1
- RLPJKBKJSWPLRC-UHFFFAOYSA-N methyl 3-[3-[tert-butyl(dimethyl)silyl]-1,3-diazinan-1-yl]-2-methylpropanoate Chemical compound [Si](C)(C)(C(C)(C)C)N1CN(CCC1)CC(C)C(=O)OC RLPJKBKJSWPLRC-UHFFFAOYSA-N 0.000 description 1
- GCGUOBJLFZOAEA-UHFFFAOYSA-N methyl 3-[3-[tert-butyl(dimethyl)silyl]imidazolidin-1-yl]-2-methylpropanoate Chemical compound COC(=O)C(C)CN1CCN(C1)[Si](C)(C)C(C)(C)C GCGUOBJLFZOAEA-UHFFFAOYSA-N 0.000 description 1
- FJBJHULNQWATBL-UHFFFAOYSA-N methyl 3-[3-[tert-butyl(diphenyl)silyl]-1,3-diazinan-1-yl]-2-methylpropanoate Chemical compound [Si](C1=CC=CC=C1)(C1=CC=CC=C1)(C(C)(C)C)N1CN(CCC1)CC(C)C(=O)OC FJBJHULNQWATBL-UHFFFAOYSA-N 0.000 description 1
- ATXOMAQRFUXLPO-UHFFFAOYSA-N methyl 3-[3-[tert-butyl(diphenyl)silyl]imidazolidin-1-yl]-2-methylpropanoate Chemical compound COC(=O)C(C)CN1CCN(C1)[Si](c1ccccc1)(c1ccccc1)C(C)(C)C ATXOMAQRFUXLPO-UHFFFAOYSA-N 0.000 description 1
- CSUCIXHAKRTLGX-UHFFFAOYSA-N methyl 3-[4-[tert-butyl(dimethyl)silyl]piperazin-1-yl]-2-methylpropanoate Chemical compound COC(=O)C(C)CN1CCN(CC1)[Si](C)(C)C(C)(C)C CSUCIXHAKRTLGX-UHFFFAOYSA-N 0.000 description 1
- LEGPELTVVSJXON-UHFFFAOYSA-N methyl 3-[4-[tert-butyl(dimethyl)silyl]piperazin-1-yl]propanoate Chemical compound COC(=O)CCN1CCN(CC1)[Si](C)(C)C(C)(C)C LEGPELTVVSJXON-UHFFFAOYSA-N 0.000 description 1
- OIXHPVSGILUQCM-UHFFFAOYSA-N methyl 3-[4-[tert-butyl(diphenyl)silyl]piperazin-1-yl]-2-methylpropanoate Chemical compound COC(=O)C(C)CN1CCN(CC1)[Si](c1ccccc1)(c1ccccc1)C(C)(C)C OIXHPVSGILUQCM-UHFFFAOYSA-N 0.000 description 1
- VLFCQWUCFDLODJ-UHFFFAOYSA-N methyl 3-imidazolidin-1-yl-2-methylpropanoate Chemical compound COC(=O)C(C)CN1CCNC1 VLFCQWUCFDLODJ-UHFFFAOYSA-N 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
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WDFKBRQZGBFDAB-UHFFFAOYSA-N n-triethylsilylacetamide Chemical compound CC[Si](CC)(CC)NC(C)=O WDFKBRQZGBFDAB-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen 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
- 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000006884 silylation reaction Methods 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
- YXXOEPOAKDYCIU-UHFFFAOYSA-N tert-butyl-(1,3-diazinan-1-yl)-dimethylsilane Chemical compound [Si](C)(C)(C(C)(C)C)N1CNCCC1 YXXOEPOAKDYCIU-UHFFFAOYSA-N 0.000 description 1
- MLNRYZPGDBUORJ-UHFFFAOYSA-N tert-butyl-(1,3-diazinan-1-yl)-diphenylsilane Chemical compound [Si](C1=CC=CC=C1)(C1=CC=CC=C1)(C(C)(C)C)N1CNCCC1 MLNRYZPGDBUORJ-UHFFFAOYSA-N 0.000 description 1
- HLMOLFJFBVIKHW-UHFFFAOYSA-N tert-butyl-diphenyl-piperazin-1-ylsilane Chemical compound CC(C)(C)[Si](N1CCNCC1)(c1ccccc1)c1ccccc1 HLMOLFJFBVIKHW-UHFFFAOYSA-N 0.000 description 1
- GMWUTDCEJDAIEE-UHFFFAOYSA-N tert-butyl-imidazolidin-1-yl-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)N1CCNC1 GMWUTDCEJDAIEE-UHFFFAOYSA-N 0.000 description 1
- WRNVOYILULRVQG-UHFFFAOYSA-N tert-butyl-imidazolidin-1-yl-diphenylsilane Chemical compound CC(C)(C)[Si](N1CCNC1)(c1ccccc1)c1ccccc1 WRNVOYILULRVQG-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- KIRNNHTVECROAX-UHFFFAOYSA-N triethyl(imidazolidin-1-yl)silane Chemical compound CC[Si](CC)(CC)N1CCNC1 KIRNNHTVECROAX-UHFFFAOYSA-N 0.000 description 1
- QZYRDEYZWLOYGR-UHFFFAOYSA-N triethyl(piperazin-1-yl)silane Chemical compound CC[Si](CC)(CC)N1CCNCC1 QZYRDEYZWLOYGR-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- MWHTTZHGWQATOD-UHFFFAOYSA-N tris(2-methylpropyl)-piperazin-1-ylsilane Chemical compound CC(C)C[Si](CC(C)C)(CC(C)C)N1CCNCC1 MWHTTZHGWQATOD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5445—Silicon-containing compounds containing nitrogen containing at least one Si-N bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
本发明提供具有式(1)的甲硅烷基保护的含氮环状化合物,其中R1、R2和R3各自为单价烃基,R4和R5各自为二价烃基,R6、R7和R8各自为H或者单价烃基,A为-C(O)OR9或-C≡N,R9为单价烃基,并且a为0或1。该化合物添加到聚氨酯、聚酯或聚碳酸酯树脂以形成单组分型固化性组合物从而对其赋予刚度、机械强度和透明性。
Description
技术领域
本发明涉及可用作树脂添加剂、涂料添加剂、粘合剂等的甲硅烷基保护的含氮环状化合物和其制备方法。
背景技术
如专利文献1和2中所述,含氮环状化合物、典型地为哌嗪用作树脂添加剂(特别是环氧树脂固化剂)、涂料添加剂、粘合剂等。由于哌嗪具有仲胺结构,因此,哌嗪作为环氧树脂的固化剂的使用,例如,确保通过仲胺部分与环氧基的反应将哌嗪环引入环氧树脂中,由此对环氧树脂赋予哌嗪环结构固有的刚度、机械强度和透明性(包括UV区)。
但是,专利文献1和2中描述的哌嗪因其具有在氮原子上的活性氢产生问题。哌嗪用作环氧树脂的固化剂时,如果预先将哌嗪加入环氧树脂中,粘度增加和凝胶化可能随着时间的经过而发生。单组分型固化性组合物是不可行的。该组合物必须作为要求繁杂的操作如使用时精确的称量和混合的双组分型来配制。
引用文献列表
专利文献 1:JP-A S50-69200(USP 3943104)
专利文献 2:USP 4800222
发明内容
本发明的目的是提供化合物及其制备方法,将该化合物加入聚氨酯、聚酯、聚碳酸酯或其它树脂以形成单组分型组合物而对其赋予刚度、机械强度以及UV和可见区域中的透明性。
如前所述,专利文献1和2中描述的哌嗪在用作环氧树脂的固化剂时不能作为单组分型组合物来配制。将考虑用甲硅烷基如三甲基甲硅烷基保护哌嗪中的氮原子上的活性氢。这样的甲硅烷基团保护的哌嗪可预先加入环氧树脂等中以形成单组分型固化性组合物,因为:只要将水隔离,该组合物为非反应性和稳定的,但是在与水接触时,水解发生而导致去保护,由此再生出氨基以便哌嗪用作固化剂。需要指出,该甲硅烷基保护的哌嗪具有氨基作为唯一的官能团。该甲硅烷基保护的哌嗪在加入到环氧、丙烯酸系和相似的树脂时赋予刚度、机械强度和包括紫外区的透明性完全有效,但是在添加到具有较弱的与氨基的相互作用的聚氨酯、聚酯、聚碳酸酯和相似的树脂时效果较低。
发明人已经发现,具有酯基或氰基的甲硅烷基保护的含氮环状化合物可添加到聚氨酯、聚酯、聚碳酸酯和相似的树脂以形成单组分型固化性组合物,并且对于对其赋予刚度、机械强度和包括UV和可见区的透明性有效。
在一个方面中,本发明提供甲硅烷基保护的含氮环状化合物,其具有通式(1):
此处R1、R2和R3各自为取代或未取代的1-20个碳原子的单价烃基,R4和R5各自为1-10个碳原子的二价烃基,R6、R7和R8各自为氢或者取代或未取代的1-20个碳原子的单价烃基,A为-C(O)OR9或-C≡N,R9为取代或未取代的1-20个碳原子的单价烃基,并且a为0或1。
在优选的实施方式中,其中R4和R5各自为亚乙基。
在另一方面中,本发明提供甲硅烷基保护的含氮环状化合物的制备方法,包括使通式(2)的化合物与通式(3)的化合物反应的步骤,由此,形成具有通式(1a)的甲硅烷基保护的含氮环状化合物,
其中R1、R2、R3、R4和R5如上述定义,
其中R10为氢或者取代或未取代的1-20个碳原子的单价烃基,A为如上述定义,
其中R1、R2、R3、R4、R5、R10和A如上述定义。
在另一方面中,本发明提供甲硅烷基保护的含氮环状化合物的制备方法,包括用具有其中R1、R2、R3如上述定义的基团R1R2R3Si-的甲硅烷基化剂将通式(4)的含氮环状化合物甲硅烷基化的步骤,由此形成具有通式(1)的甲硅烷基保护的含氮环状化合物,
其中R4、R5、R6、R7、R8,A和a如上述定义,
其中R1、R2、R3、R4、R5、R6、R7、R8、A和a如上述定义。
发明的有益效果
在添加到聚氨酯、聚酯、聚碳酸酯和相似的树脂中时,本发明的甲硅烷基保护的含氮环状化合物对赋予刚度、机械强度和包括UV和可见区的透明性有效并且可配制成单组分型固化性组合物。因此,该化合物用作树脂添加剂、涂料添加剂和粘合剂。
附图说明
图1为实施例1中得到的1-叔丁基二甲基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪的1H-NMR谱。
图2为实施例1中得到的1-叔丁基二甲基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪的IR光谱。
图3和4分别为实施例2中得到的1-叔丁基二甲基甲硅烷基-4-(2-氰基乙基)哌嗪的1H-NMR谱和IR光谱。
图5和6分别为实施例3中得到的1-三异丙基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪的1H-NMR谱和IR光谱。
图7和8分别为实施例4中得到的1-三异丙基甲硅烷基-4-(2-氰基乙基)哌嗪的1H-NMR谱和IR光谱。
优选实施方式
本发明的一个实施方式为具有通式(1)的甲硅烷基保护的含氮环状化合物,
此处R1、R2和R3各自为取代或未取代的1-20个碳原子的单价烃基,R4和R5各自为1-10个碳原子的二价烃基,R6、R7和R8各自为氢或者取代或未取代的1-20个碳原子的单价烃基,A为-C(O)OR9或-C≡N,R9为取代或未取代的1-20个碳原子的单价烃基,并且a为0或1。
R1、R2、R3和R9各自选自取代或未取代的1-20个碳原子、优选1-10个碳原子、以及更优选1-5个碳原子的单价烃基,例如,直链、支化或环状的烷基,烯基,芳基,和芳烷基。实例包括直链烷基如甲基,乙基,丙基,丁基,戊基,己基,庚基,辛基,癸基,十二烷基,十四烷基,十六烷基,十八烷基,和二十烷基;支化的烷基如异丙基,异丁基,仲丁基,叔丁基,叔己基(thexyl)和2-乙基己基;环烷基如环戊基和环己基;烯基如乙烯基、烯丙基和丙烯基;芳基如苯基和甲苯基;和芳烷基如苄基。特别地,优选甲基、乙基、异丙基、仲丁基和叔丁基。在这些烃基中,一些或全部氢原子可被取代基取代。合适的取代基包括烷氧基如甲氧基、乙氧基、(异)丙氧基;卤素原子如氟、氯、溴和碘;氰基;氨基;C6-C18芳基如苯基和甲苯基;C7-C18芳烷基如苄基和苯乙基;C2-C10酰基;其中每个烷基或烷氧基部分具有1-5个碳原子的三烷基甲硅烷基、三烷氧基甲硅烷基、二烷基单烷氧基甲硅烷基或单烷基二烷氧基甲硅烷基。此外,酯部分(-COO-)、醚部分(-O-)或硫醚部分(-S-)可以介入任意的上述基团中。任意的两种以上的上述基团的组合也是可接受的。
R4和R5各自选自1-10个碳原子、优选1-5个碳原子、并且更优选1-3个碳原子的的二价烃基,例如,亚烷基如亚甲基,亚乙基,三亚甲基,四亚甲基,六亚甲基,八亚甲基,十亚甲基和亚异丁基;亚芳基如亚苯基;和亚芳烷基如亚甲基亚苯基和亚甲基亚苯基亚甲基。
含R4和R5的环状结构的优选实例为咪唑烷(imidazolidine)、哌嗪和六氢嘧啶结构。特别地,优选其中R4和R5均为亚乙基的,即、其中下式
的环状结构为哌嗪结构的式(1)的那些化合物,因为它们在添加至树脂时能赋予高机械强度。
R6、R7和R8各自选自氢和取代或未取代的1-20个碳原子的单价烃基。单价烃基的实例与上述对于R1、R2和R3所例示的相同。特别地,优选甲基、乙基、异丙基、仲丁基和叔丁基。
具有式(1)的甲硅烷基保护的含氮环状化合物的示例性而非限制性的实例包括
1-三甲基甲硅烷基-3-(2-甲氧基羰基乙基)咪唑烷,
1-己基二甲基甲硅烷基-3-(2-甲氧基羰基乙基)咪唑烷,
1-癸基二甲基甲硅烷基-3-(2-甲氧基羰基乙基)咪唑烷,
1-三乙基甲硅烷基-3-(2-甲氧基羰基乙基)咪唑烷,
1-三异丁基甲硅烷基-3-(2-甲氧基羰基乙基)咪唑烷,
1-叔丁基二甲基甲硅烷基-3-(2-甲氧基羰基乙基)咪唑烷,
1-叔丁基二苯基甲硅烷基-3-(2-甲氧基羰基乙基)咪唑烷,
1-叔己基二甲基甲硅烷基-3-(2-甲氧基羰基乙基)咪唑烷,
1-三异丙基甲硅烷基-3-(2-甲氧基羰基乙基)咪唑烷,
1-三(仲丁基)甲硅烷基-3-(2-甲氧基羰基乙基)咪唑烷,
1-三环戊基甲硅烷基-3-(2-甲氧基羰基乙基)咪唑烷,
1-三环己基(hexylyl、ヘキシリル)甲硅烷基-3-(2-甲氧基羰基乙基)咪唑烷,
1-三甲基甲硅烷基-3-(2-乙氧基羰基乙基)咪唑烷,
1-己基二甲基甲硅烷基-3-(2-乙氧基羰基乙基)咪唑烷,
1-癸基二甲基甲硅烷基-3-(2-乙氧基羰基乙基)咪唑烷,
1-三乙基甲硅烷基-3-(2-乙氧基羰基乙基)咪唑烷,
1-三异丁基甲硅烷基-3-(2-乙氧基羰基乙基)咪唑烷,
1-叔丁基二甲基甲硅烷基-3-(2-乙氧基羰基乙基)咪唑烷,
1-叔丁基二苯基甲硅烷基-3-(2-乙氧基羰基乙基)咪唑烷,
1-叔己基二甲基甲硅烷基-3-(2-乙氧基羰基乙基)咪唑烷,
1-三异丙基甲硅烷基-3-(2-乙氧基羰基乙基)咪唑烷,
1-三(仲丁基)甲硅烷基-3-(2-乙氧基羰基乙基)咪唑烷,
1-三环戊基甲硅烷基-3-(2-乙氧基羰基乙基)咪唑烷,
1-三环己基甲硅烷基-3-(2-乙氧基羰基乙基)咪唑烷,
1-三甲基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)咪唑烷,
1-己基二甲基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)咪唑烷,
1-癸基二甲基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)咪唑烷,
1-三乙基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)咪唑烷,
1-三异丁基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基-)咪唑烷,
1-叔丁基二甲基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)咪唑烷,
1-叔丁基二苯基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)咪唑烷,
1-叔己基二甲基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)咪唑烷,
1-三异丙基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)咪唑烷,
1-三(仲丁基)甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基))咪唑烷,
1-三环戊基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)咪唑烷,
1-三环己基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)咪唑烷,
1-三甲基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-己基二甲基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-癸基二甲基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-三乙基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-三异丁基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-叔丁基二甲基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-叔丁基二苯基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-叔己基二甲基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-三异丙基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-三(仲丁基)甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-三环戊基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-三环己基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-三甲基甲硅烷基-3-(2-氰基乙基)咪唑烷,
1-己基二甲基甲硅烷基-3-(2-氰基乙基)咪唑烷,
1-癸基二甲基甲硅烷基-3-(2-氰基乙基)咪唑烷,
1-三乙基甲硅烷基-3-(2-氰基乙基)咪唑烷,
1-三异丁基甲硅烷基-3-(2-氰基乙基)咪唑烷,
1-叔丁基二甲基甲硅烷基-3-(2-氰基乙基)咪唑烷
1-叔丁基二苯基甲硅烷基-3-(2-氰基乙基)咪唑烷,
1-叔己基二甲基甲硅烷基-3-(2-氰基乙基)咪唑烷,
1-三异丙基甲硅烷基-3-(2-氰基乙基)咪唑烷,
1-三(仲丁基)甲硅烷基-3-(2-氰基乙基)咪唑烷,
1-三环戊基甲硅烷基-3-(2-氰基乙基)咪唑烷,
1-三环己基甲硅烷基-3-(2-氰基乙基)咪唑烷,
1-三甲基甲硅烷基-3-(2-氰基-2-甲基乙基)咪唑烷,
1-己基二甲基甲硅烷基-3-(2-氰基-2-甲基乙基)咪唑烷,
1-癸基二甲基甲硅烷基-3-(2-氰基-2-甲基乙基)咪唑烷,
1-三乙基甲硅烷基-3-(2-氰基-2-甲基乙基)咪唑烷,
1-三异丁基甲硅烷基-3-(2-氰基-2-甲基乙基)咪唑烷,
1-叔丁基二甲基甲硅烷基-3-(2-氰基-2-甲基乙基)咪唑烷,
1-叔丁基二苯基甲硅烷基-3-(2-氰基-2-甲基乙基)咪唑烷,
1-叔己基二甲基甲硅烷基-3-(2-氰基-2-甲基乙基)咪唑烷,
1-三异丙基甲硅烷基-3-(2-氰基-2-甲基乙基)咪唑烷,
1-三(仲丁基)甲硅烷基-3-(2-氰基-2-甲基乙基)咪唑烷,
1-三环戊基甲硅烷基-3-(2-氰基-2-甲基乙基)咪唑烷,
1-三环己基甲硅烷基-3-(2-氰基-2-甲基乙基)咪唑烷,
1-三甲基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪,
1-己基二甲基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪,
1-癸基二甲基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪,
1-三乙基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪,
1-三异丁基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪,
1-叔丁基二甲基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪,
1-叔丁基二苯基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪,
1-叔己基二甲基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪,
1-三异丙基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪,
1-三(仲丁基)甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪,
1-三环戊基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪,
1-三环己基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪,
1-三甲基甲硅烷基-4-(2-乙氧基羰基乙基)哌嗪,
1-己基二甲基甲硅烷基-4-(2-乙氧基羰基乙基)哌嗪,
1-癸基二甲基甲硅烷基-4-(2-乙氧基羰基乙基)哌嗪,
1-三乙基甲硅烷基-4-(2-乙氧基羰基乙基)哌嗪,
1-三异丁基甲硅烷基-4-(2-乙氧基羰基乙基)哌嗪,
1-叔丁基二甲基甲硅烷基-4-(2-乙氧基羰基乙基)哌嗪,
1-叔丁基二苯基甲硅烷基-4-(2-乙氧基羰基乙基)哌嗪,
1-叔己基二甲基甲硅烷基-4-(2-乙氧基羰基乙基)哌嗪,
1-三异丙基甲硅烷基-4-(2-乙氧基羰基乙基)哌嗪,
1-三(仲丁基)甲硅烷基-4-(2-乙氧基羰基乙基)哌嗪,
1-三环戊基甲硅烷基-4-(2-乙氧基羰基乙基)哌嗪,
1-三环己基甲硅烷基-4-(2-乙氧基羰基乙基)哌嗪,
1-三甲基甲硅烷基-4-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1-己基二甲基甲硅烷基-4-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1-癸基二甲基甲硅烷基-4-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1-三乙基甲硅烷基-4-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1-三异丁基甲硅烷基-4-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1-叔丁基二甲基甲硅烷基-4-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1-叔丁基二苯基甲硅烷基-4-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1–叔己基二甲基甲硅烷基-4-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1-三异丙基甲硅烷基-4-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1-三(仲丁基)甲硅烷基-4-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1-三环戊基甲硅烷基-4-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1-三环己基甲硅烷基-4-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1-三甲基甲硅烷基-4-(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-己基二甲基甲硅烷基-4-(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-癸基二甲基甲硅烷基-4-(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-三乙基甲硅烷基-4-(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-三异丁基甲硅烷基-4-(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-叔丁基二甲基甲硅烷基-4-(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-叔丁基二苯基甲硅烷基-4-(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-叔己基二甲基甲硅烷基-4-(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-三异丙基甲硅烷基-4--(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-三(仲丁基)甲硅烷基-4-(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-三环戊基甲硅烷基-4-(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-三环己基甲硅烷基-4-(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-三甲基甲硅烷基-4-(2-氰基乙基)哌嗪,
1-己基二甲基甲硅烷基-4-(2-氰基乙基)哌嗪,
1-癸基二甲基甲硅烷基-4-(2-氰基乙基)哌嗪,
1-三乙基甲硅烷基-4-(2-氰基乙基)哌嗪,
1-三异丁基甲硅烷基-4-(2-氰基乙基)哌嗪,
1-叔丁基二甲基甲硅烷基-4-(2-氰基乙基)哌嗪,
1-叔丁基二苯基甲硅烷基-4-(2-氰基乙基)哌嗪,
1-叔己基二甲基甲硅烷基-4-(2-氰基乙基)哌嗪,
1-三异丙基甲硅烷基-4-(2-氰基乙基)哌嗪,
1-三(仲丁基)甲硅烷基-4-(2-氰基乙基)哌嗪,
1-三环戊基甲硅烷基-4-(2-氰基乙基)哌嗪,
1-三环己基甲硅烷基-4-(2-氰基乙基)哌嗪,
1-三甲基甲硅烷基-4-(2-氰基-2-甲基乙基)哌嗪,
1-己基二甲基甲硅烷基-4-(2-氰基-2-甲基乙基)哌嗪,
1-癸基二甲基甲硅烷基-4-(2-氰基-2-甲基乙基)哌嗪,
1-三乙基甲硅烷基-4-(2-氰基-2-甲基乙基)哌嗪,
1-三异丁基甲硅烷基-4-(2-氰基-2-甲基乙基)哌嗪,
1-叔丁基二甲基甲硅烷基-4-(2-氰基-2-甲基乙基)哌嗪,
1-叔丁基二苯基甲硅烷基-4-(2-氰基-2-甲基乙基)哌嗪,
1-叔己基二甲基甲硅烷基-4-(2-氰基-2-甲基乙基)哌嗪,
1-三异丙基甲硅烷基-4-(2-氰基-2-甲基乙基)哌嗪,
1-三(仲丁基)甲硅烷基-4-(2-氰基-2-甲基乙基)哌嗪,
1-三环戊基甲硅烷基-4-(2-氰基-2-甲基乙基)哌嗪,
1-三环己基甲硅烷基-4-(2-氰基-2-甲基乙基)哌嗪,
1-三甲基甲硅烷基-3-(2-甲氧基羰基乙基)六氢嘧啶,
1-己基二甲基甲硅烷基-3-(2-甲氧基羰基乙基)六氢嘧啶,
1-癸基二甲基甲硅烷基-3-(2-甲氧基羰基乙基)六氢嘧啶,
1-三乙基甲硅烷基-3-(2-甲氧基羰基乙基)六氢嘧啶,
1-三异丁基甲硅烷基-3-(2-甲氧基羰基乙基)六氢嘧啶,
1-叔丁基二甲基甲硅烷基-3-(2-甲氧基羰基乙基)六氢嘧啶,
1-叔丁基二苯基甲硅烷基-3-(2-甲氧基羰基乙基)六氢嘧啶,
1-叔己基二甲基甲硅烷基-3-(2-甲氧基羰基乙基)六氢嘧啶,
1-三异丙基甲硅烷基-3-(2-甲氧基羰基乙基)六氢嘧啶,
1-三(仲丁基)甲硅烷基-3-(2-甲氧基羰基乙基)六氢嘧啶,
1-三环戊基甲硅烷基-3-(2-甲氧基羰基乙基)六氢嘧啶,
1-三环己基甲硅烷基-3-(2-甲氧基羰基乙基)六氢嘧啶,
1-三甲基甲硅烷基-3-(2-乙氧基羰基乙基)六氢嘧啶,
1-己基二甲基甲硅烷基-3-(2-乙氧基羰基乙基)六氢嘧啶,
1-癸基二甲基甲硅烷基-3-(2-乙氧基羰基乙基)六氢嘧啶,
1-三乙基甲硅烷基-3-(2-乙氧基羰基乙基)六氢嘧啶,
1-三异丁基甲硅烷基-3-(2-乙氧基羰基乙基)六氢嘧啶,
1-叔丁基二甲基甲硅烷基-3-(2-乙氧基羰基乙基)六氢嘧啶,
1-叔丁基二苯基甲硅烷基-3-(2-乙氧基羰基乙基)六氢嘧啶,
1-叔己基二甲基甲硅烷基-3-(2-乙氧基羰基乙基)六氢嘧啶,
1-三异丙基甲硅烷基-3-(2-乙氧基羰基乙基)六氢嘧啶,
1-三(仲丁基)甲硅烷基-3-(2-乙氧基羰基乙基)六氢嘧啶,
1-三环戊基甲硅烷基-3-(2-乙氧基羰基乙基)六氢嘧啶,
1-三环己基甲硅烷基-3-(2-乙氧基羰基乙基)六氢嘧啶,
1-三甲基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-己基二甲基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-癸基二甲基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-三乙基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-三异丁基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-叔丁基二甲基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-叔丁基二苯基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-叔己基二甲基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-三异丙基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-三(仲丁基)甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-三环戊基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-三环己基甲硅烷基-3-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-三甲基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-己基二甲基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-癸基二甲基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-三乙基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-三异丁基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-叔丁基二甲基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-叔丁基二苯基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-叔己基二甲基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-三异丙基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-三(仲丁基)甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-三环戊基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-三环己基甲硅烷基-3-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-三甲基甲硅烷基-3-(2-氰基乙基)六氢嘧啶,
1-己基二甲基甲硅烷基-3-(2-氰基乙基)六氢嘧啶,
1-癸基二甲基甲硅烷基-3-(2-氰基乙基)六氢嘧啶,
1-三乙基甲硅烷基-3-(2-氰基乙基)六氢嘧啶,
1-三异丁基甲硅烷基-3-(2-氰基乙基)六氢嘧啶,
1-叔丁基二甲基甲硅烷基-3-(2-氰基乙基)六氢嘧啶,
1-叔丁基二苯基甲硅烷基-3-(2-氰基乙基)六氢嘧啶,
1-叔己基二甲基甲硅烷基-3-(2-氰基乙基)六氢嘧啶,
1-三异丙基甲硅烷基-3-(2-氰基乙基)六氢嘧啶,
1-三(仲丁基)甲硅烷基-3-(2-氰基乙基)六氢嘧啶,
1-三环戊基甲硅烷基-3-(2-氰基乙基)六氢嘧啶,
1-三环己基甲硅烷基-3-(2-氰基乙基)六氢嘧啶,
1-三甲基甲硅烷基-3-(2-氰基-2-甲基乙基)六氢嘧啶,
1-己基二甲基甲硅烷基-3-(2-氰基-2-甲基乙基)六氢嘧啶,
1-癸基二甲基甲硅烷基-3-(2-氰基-2-甲基乙基)六氢嘧啶,
1-三乙基甲硅烷基-3-(2-氰基-2-甲基乙基)六氢嘧啶,
1-三异丁基甲硅烷基-3-(2-氰基-2-甲基乙基)六氢嘧啶,
1-叔丁基二甲基甲硅烷基-3-(2-氰基-2-甲基乙基)六氢嘧啶,
1-叔丁基二苯基甲硅烷基-3-(2-氰基-2-甲基乙基)六氢嘧啶,
1-叔己基二甲基甲硅烷基-3-(2-氰基-2-甲基乙基)六氢嘧啶,
1-三异丙基甲硅烷基-3-(2-氰基-2-甲基乙基)六氢嘧啶,
1-三(仲丁基)甲硅烷基-3-(2-氰基-2-甲基乙基)六氢嘧啶,
1-三环戊基甲硅烷基-3-(2-氰基-2-甲基乙基)六氢嘧啶,
1-三环己基甲硅烷基-3-(2-氰基-2-甲基乙基)六氢嘧啶等。
在本发明的另一实施方式中,上述定义的式(1)的甲硅烷基保护的含氮环状化合物可以例如通过使通式(2)的化合物与通式(3)的化合物反应来制备,
其中R1、R2、R3、R4和R5如上述定义,
其中R10为氢或者取代或未取代的1-20个碳原子的单价烃基,A为如上述定义。在该实施方式中,得到具有通式(1a)的化合物,
其中R1、R2、R3、R4、R5、R10和A如上述定义。
在R10表示取代或未取代的1-20个碳原子的单价烃基时,烃基的实例与上述对于R1、R2、R3和R9所例示的相同。
式(2)的化合物的实例包括:
1-三甲基甲硅烷基咪唑烷,
1-己基二甲基甲硅烷基咪唑烷,
1-癸基二甲基甲硅烷基咪唑烷,
1-三乙基甲硅烷基咪唑烷,
1-三异丁基甲硅烷基咪唑烷,
1-叔丁基二甲基甲硅烷基咪唑烷,
1-叔丁基二苯基甲硅烷基咪唑烷,
1-叔己基二甲基甲硅烷基咪唑烷,
1-三异丙基甲硅烷基咪唑烷,
1-三(仲丁基)甲硅烷基咪唑烷,
1-三环戊基甲硅烷基咪唑烷,
1-三环己基甲硅烷基咪唑烷,
1-三甲基甲硅烷基哌嗪,
1-己基二甲基甲硅烷基哌嗪,
1-癸基二甲基甲硅烷基哌嗪,
1-三乙基甲硅烷基哌嗪,
1-三异丁基甲硅烷基哌嗪,
1-叔丁基二甲基甲硅烷基哌嗪,
1-叔丁基二苯基甲硅烷基哌嗪,
1-叔己基二甲基甲硅烷基哌嗪,
1-三异丙基甲硅烷基哌嗪,
1-三(仲丁基)甲硅烷基哌嗪,
1-三环戊基甲硅烷基哌嗪,
1-三环己基甲硅烷基哌嗪,
1-三甲基甲硅烷基六氢嘧啶,
1-己基二甲基甲硅烷基六氢嘧啶,
1-癸基二甲基甲硅烷基六氢嘧啶,
1-三乙基甲硅烷基六氢嘧啶,
1-三异丁基甲硅烷基六氢嘧啶,
1-叔丁基二甲基甲硅烷基六氢嘧啶,
1-叔丁基二苯基甲硅烷基六氢嘧啶,
1-叔己基二甲基甲硅烷基六氢嘧啶,
1-三异丙基甲硅烷基六氢嘧啶,
1-三(仲丁基)甲硅烷基六氢嘧啶,
1-三环戊基甲硅烷基六氢嘧啶,
1-三环己基甲硅烷基六氢嘧啶等。
式(3)的化合物的实例包括丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯腈、和甲基丙烯腈。
尽管式(2)的化合物和式(3)的化合物可以任意希望的比例使用,从反应性和生产率的角度出发,优选对于每摩尔的式(2)的化合物使用0.1-4摩尔,更优选0.2-2摩尔的式(3)的化合物。
尽管反应温度并不特别限定,优选的温度为0-200℃,尤其为20-150℃的范围。尽管反应时间并不特别限定,优选的时间为1-40小时,尤其为1-20小时。反应气氛优选非活性气体氛围如氮气或氩气。
虽然上述反应可以在无溶剂体系中进行,但可以使用溶剂。合适的溶剂包括烃溶剂如戊烷、己烷、环己烷、庚烷、异辛烷、苯、甲苯和二甲苯;醚溶剂如乙醚、四氢呋喃和二噁烷;酯溶剂如乙酸乙酯和乙酸丁酯;非质子极性溶剂如乙腈、N,N-二甲基甲酰胺和N-甲基吡咯烷酮;和氯化烃溶剂如二氯甲烷和氯仿,它们可以单独或两种以上混合使用。
本发明的另一实施方式中,上述定义的式(1)的甲硅烷基保护的含氮环状化合物可以例如通过用具有其中R1、R2、R3为如上定义的基团R1R2R3Si-的甲硅烷基化剂将通式(4)的含氮环状化合物甲硅烷基化来制备,
其中R4、R5、R6、R7、R8,A和a如上述定义。
在式(4)中,由R4、R5、R6、R7、R8和A表示的基团如上所说明和示例的。式(4)化合物的示例性的实例包括
1-(2-甲氧基羰基乙基)咪唑烷,
1-(2-乙氧基羰基乙基)咪唑烷,
1-(2-甲氧基羰基-2-甲基乙基)咪唑烷,
1-(2-乙氧基羰基-2-甲基乙基)咪唑烷,
1-(2-氰基乙基)咪唑烷,
1-(2-氰基-2-甲基乙基)咪唑烷,
1-(2-甲氧基羰基乙基)哌嗪,
1-(2-乙氧基羰基乙基)哌嗪,
1-(2-甲氧基羰基-2-甲基乙基)哌嗪,
1-(2-乙氧基羰基-2-甲基乙基)哌嗪,
1-(2-氰基乙基)哌嗪,
1-(2-氰基-2-甲基乙基)哌嗪,
1-(2-甲氧基羰基乙基)六氢嘧啶,
1-(2-乙氧基羰基乙基)六氢嘧啶,
1-(2-甲氧基羰基-2-甲基乙基)六氢嘧啶,
1-(2-乙氧基羰基-2-甲基乙基)六氢嘧啶,
1-(2-氰基乙基)六氢嘧啶,
1-(2-氰基-2-甲基乙基)六氢嘧啶等。
可用于甲硅烷基化反应的具有基团R1R2R3Si-的合适的甲硅烷基化剂包括:式R1R2R3SiX的三有机卤硅烷化合物,其中R1、R2和R3为如上定义,并且X为卤素原子如氯、溴或碘,例如,三甲基氯硅烷、三甲基溴硅烷、三甲基碘硅烷、三乙基氯硅烷,叔丁基二甲基氯硅烷、以及三异丙基氯硅烷;式:(R1R2R3Si)2NH的硅氮烷化合物,其中R1、R2和R3为如上定义,例如,六甲基二硅氮烷和六乙基二硅氮烷;式:CR3C(-OSiR1R2R3)=NSiR1R2R3的甲硅烷基酰胺化合物,其中R为氢或氟,R1、R2和R3为如上定义,例如,双(三甲基甲硅烷基)乙酰胺、双(三乙基甲硅烷基)乙酰胺、和双(三甲基甲硅烷基)三氟乙酰胺;以及式:CR3SO3Si R1R2R3的磺酸甲硅烷基酯化合物,其中R为氢或氟,R1、R2和R3为如上定义,例如,甲磺酸三甲基甲硅烷基酯和三氟甲磺酸三甲基甲硅烷基酯。
尽管式(4)的化合物和甲硅烷基化剂可以任意希望的比例使用,从反应性和生产率的角度出发,优选对于每摩尔式(4)的化合物使用1-4摩尔、更优选1-2摩尔的甲硅烷基化剂(以甲硅烷基计)。
尽管反应温度并不特别限定,优选的温度为0-200℃,尤其为20-150℃的范围。尽管反应时间并不特别限定,优选的时间为1-40小时,尤其为1-20小时。
催化剂可以用于反应,尽管该反应可以在没有催化剂下进行。合适的催化剂可以为碱性或酸性的化合物,并且包括:叔胺如三甲基胺、三乙基胺和三苯基胺;季铵盐如四丁基氯化铵和四丁基溴化铵;以及酸如硫酸和磺酸,其衍生物和其无机盐。
虽然上述反应可以在无溶剂体系中进行,但可以使用溶剂。合适的溶剂包括烃溶剂如戊烷、己烷、环己烷、庚烷、异辛烷、苯、甲苯和二甲苯;醚溶剂如乙醚、四氢呋喃和二噁烷;酯溶剂如乙酸乙酯和乙酸丁酯;非质子极性溶剂如乙腈、N,N-二甲基甲酰胺和N-甲基吡咯烷酮;和氯化烃溶剂如二氯甲烷和氯仿,它们可以单独或两种以上混合使用。
实施例
通过示例的方式而非通过限制的方式如下给出本发明的实施例。
合成例 1
1-叔丁基二甲基甲硅烷基哌嗪
在安装有搅拌器、回流冷凝器、滴液漏斗和温度计的烧瓶中装入1076.3g(12.5mol)的哌嗪和500ml的二甲苯,并在110℃下加热。一旦内部温度变稳定,用3小时逐滴添加1507.0g(5.0mol)的叔丁基二甲基氯硅烷的50wt%甲苯溶液。在该温度下连续搅拌2小时。将反应溶液冷却至室温,向其中加入2500g的10wt%氢氧化钠水溶液。分离有机层。蒸馏后,收集646.6g的具有沸点70-71℃/0.2kPa的馏分,其为1-叔丁基二甲基甲硅烷基哌嗪。
实施例 1
1-叔丁基二甲基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪
在安装有搅拌器、回流冷凝器、滴液漏斗和温度计的烧瓶中装入160.3g(0.8mol)的1-叔丁基二甲基甲硅烷基哌嗪(合成例1)并在70℃下加热。一旦内部温度变稳定,用2小时逐滴添加75.8g(0.88mol)丙烯酸甲酯。在该温度下连续搅拌4小时。反应溶液蒸馏后,收集219.9g的具有沸点135-137℃/0.4kPa的馏分。
通过质谱、1H-NMR谱和IR光谱分析该馏分。
MS
m/z 286,229,187,89,73,59
1H-NMR谱(重氯仿溶剂中)
参见图1
IR光谱
参见图2
由这些分析结果,鉴定该化合物为1-叔丁基二甲基甲硅烷基-4-(2-甲氧基羰基-乙基)哌嗪。
实施例 2
1-叔丁基二甲基甲硅烷基-4-(2-氰基乙基)哌嗪
在安装有搅拌器、回流冷凝器、滴液漏斗和温度计的烧瓶中装入160.3g(0.8mol)的1-叔丁基二甲基甲硅烷基哌嗪(合成例1)并在70℃下加热。一旦内部温度变稳定,用2小时逐滴添加46.7g(0.88mol)的丙烯腈。在该温度下连续搅拌4小时。反应溶液蒸馏后,收集194.1g的具有沸点145-147℃/0.4kPa的馏分。
通过质谱、1H-NMR谱和IR光谱分析该馏分。
MS
m/z 253,238,196,155,73,59
1H-NMR谱(重氯仿溶剂中)
参见图3
IR光谱
参见图4
由这些分析结果,鉴定该化合物为1-叔丁基二甲基甲硅烷基-4-(2-氰基乙基)哌嗪。
合成例 2
1-三异丙基甲硅烷基哌嗪
在安装有搅拌器、回流冷凝器、滴液漏斗和温度计的烧瓶中装入189.4g(2.2mol)的哌嗪,200ml的二甲苯和1.0g(0.01mol)甲磺酸,并在130℃下加热。一旦内部温度变稳定,用2小时逐滴添加192.8g(1.0mol)的三异丙基氯硅烷。在该温度下连续搅拌10小时。将反应溶液冷却至室温,向其中加入500g的10wt%氢氧化钠水溶液。分离有机层。蒸馏后,收集132.6g的具有沸点109-111℃/0.4kPa的馏分,其为1-三异丙基甲硅烷基哌嗪。
实施例 3
1-三异丙基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪
在安装有搅拌器、回流冷凝器、滴液漏斗和温度计的烧瓶中装入194.0g(0.8mol)的1-三异丙基甲硅烷基哌嗪(合成例2)并在70℃下加热。一旦内部温度变稳定,用2小时逐滴添加75.8g(0.88mol)的丙烯酸甲酯。在该温度下连续搅拌4小时。反应溶液蒸馏后,收集250.0g的具有沸点163-164℃/0.4kPa的馏分。
通过质谱、1H-NMR谱和IR光谱分析该馏分。
MS
m/z 328,285,243,198,97,59
1H-NMR谱(重氯仿溶剂中)
参见图5
IR光谱
参见图6
由这些分析结果,鉴定该化合物为1-三异丙基甲硅烷基-4-(2-甲氧基羰基乙基)哌嗪。
实施例 4
1-三异丙基甲硅烷基-4-(2-氰基乙基)-哌嗪
在安装有搅拌器、回流冷凝器、滴液漏斗和温度计的烧瓶中装入194.0g(0.8mol)的1-三异丙基甲硅烷基哌嗪(合成例2)并在70℃下加热。一旦内部温度变稳定,用2小时逐滴添加46.7g(0.88mol)的丙烯腈。在该温度下连续搅拌4小时。反应溶液蒸馏后,收集224.8g的具有沸点179-180℃/0.4kPa的馏分。
通过质谱、1H-NMR谱和IR光谱分析该馏分。
MS
m/z 295,252,211,169,97,59
1H-NMR谱(重氯仿溶剂中)
参见图7
IR光谱
参见图8
由这些分析结果,鉴定该化合物为1-三异丙基甲硅烷基-4-(2-氰基乙基)-哌嗪。
Claims (4)
1.甲硅烷基保护的含氮环状化合物,其具有通式(1):
其中R1、R2和R3各自为取代或未取代的1-20个碳原子的单价烃基,R4和R5各自为1-10个碳原子的二价烃基,R6、R7和R8各自为氢或者取代或未取代的1-20个碳原子的单价烃基,A为-C(O)OR9或-C≡N,R9为取代或未取代的1-20个碳原子的单价烃基,并且a为0或1。
2.权利要求1的化合物,其中R4和R5各自为亚乙基。
3.甲硅烷基保护的含氮环状化合物的制备方法,包括使通式(2)的化合物与通式(3)的化合物反应的步骤,由此,形成具有通式(1a)的甲硅烷基保护的含氮环状化合物,
其中R1、R2和R3各自为取代或未取代的1-20个碳原子的单价烃基,R4和R5各自为1-10个碳原子的二价烃基,
其中R10为氢或者取代或未取代的1-20个碳原子的单价烃基,A为-C(O)OR9或-C≡N,并且R9为取代或未取代的1-20个碳原子的单价烃基,
R1、R2、R3、R4、R5、R10和A如上述定义。
4.甲硅烷基保护的含氮环状化合物的制备方法,包括用具有其中R1、R2、R3各自为取代或未取代的1-20个碳原子的单价烃基的基团R1R2R3Si-的甲硅烷基化剂将通式(4)的含氮环状化合物甲硅烷基化的步骤,由此形成具有通式(1)的甲硅烷基保护的含氮环状化合物,
其中R4和R5各自为1-10个碳原子的二价烃基,R6、R7和R8各自为氢或者取代或未取代的1-20个碳原子的单价烃基,A为-C(O)OR9或-C≡N,R9为取代或未取代的1-20个碳原子的单价烃基,并且a为0或1,
其中R1、R2、R3、R4、R5、R6、R7、R8、A和a如上述定义。
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