JP2006321789A - Protected piperazino group-having organoxysilane compound and method for producing the same - Google Patents
Protected piperazino group-having organoxysilane compound and method for producing the same Download PDFInfo
- Publication number
- JP2006321789A JP2006321789A JP2006109347A JP2006109347A JP2006321789A JP 2006321789 A JP2006321789 A JP 2006321789A JP 2006109347 A JP2006109347 A JP 2006109347A JP 2006109347 A JP2006109347 A JP 2006109347A JP 2006321789 A JP2006321789 A JP 2006321789A
- Authority
- JP
- Japan
- Prior art keywords
- group
- trimethylsilylpiperazine
- compound
- propyl
- methyl
- 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.)
- Granted
Links
- -1 piperazino Chemical group 0.000 title claims abstract description 98
- 150000001875 compounds Chemical class 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 8
- 230000000996 additive effect Effects 0.000 abstract description 7
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 41
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 24
- 150000002430 hydrocarbons Chemical group 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000002329 infrared spectrum Methods 0.000 description 7
- 238000001819 mass spectrum Methods 0.000 description 7
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 7
- 229910000077 silane Inorganic materials 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 6
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- BRIWVFWNSIANPV-UHFFFAOYSA-N triethoxy-[3-(4-trimethylsilylpiperazin-1-yl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCN([Si](C)(C)C)CC1 BRIWVFWNSIANPV-UHFFFAOYSA-N 0.000 description 5
- JEALDEGTHUYGSC-UHFFFAOYSA-N trimethyl-(4-prop-2-enylpiperazin-1-yl)silane Chemical compound C[Si](C)(C)N1CCN(CC=C)CC1 JEALDEGTHUYGSC-UHFFFAOYSA-N 0.000 description 5
- BIGOJJYDFLNSGB-UHFFFAOYSA-N 3-isocyanopropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCC[N+]#[C-] BIGOJJYDFLNSGB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- CQERQNNEKFKVFU-UHFFFAOYSA-N triethoxy(3-piperazin-1-ylpropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCNCC1 CQERQNNEKFKVFU-UHFFFAOYSA-N 0.000 description 3
- 239000005051 trimethylchlorosilane Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000013329 compounding Methods 0.000 description 2
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 2
- LARLLKRITAIYAU-UHFFFAOYSA-N diethoxy-methyl-[3-(4-trimethylsilylpiperazin-1-yl)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCN1CCN([Si](C)(C)C)CC1 LARLLKRITAIYAU-UHFFFAOYSA-N 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 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
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-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
- OTQGDEACENBQMU-UHFFFAOYSA-N (4-but-1-enylpiperazin-1-yl)-tert-butyl-dimethylsilane Chemical compound CCC=CN1CCN([Si](C)(C)C(C)(C)C)CC1 OTQGDEACENBQMU-UHFFFAOYSA-N 0.000 description 1
- QMINIEGRHOOQAE-UHFFFAOYSA-N (4-but-1-enylpiperazin-1-yl)-tri(propan-2-yl)silane Chemical compound CCC=CN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 QMINIEGRHOOQAE-UHFFFAOYSA-N 0.000 description 1
- VGLYSHZUDDFEBV-UHFFFAOYSA-N (4-but-1-enylpiperazin-1-yl)-triethylsilane Chemical compound CCC=CN1CCN([Si](CC)(CC)CC)CC1 VGLYSHZUDDFEBV-UHFFFAOYSA-N 0.000 description 1
- PXBIRLRBRAYJRH-UHFFFAOYSA-N (4-ethenylpiperazin-1-yl)-tri(propan-2-yl)silane Chemical compound CC(C)[Si](C(C)C)(C(C)C)N1CCN(C=C)CC1 PXBIRLRBRAYJRH-UHFFFAOYSA-N 0.000 description 1
- GWINWTXIWQLLIH-UHFFFAOYSA-N (4-ethenylpiperazin-1-yl)-triethylsilane Chemical compound CC[Si](CC)(CC)N1CCN(C=C)CC1 GWINWTXIWQLLIH-UHFFFAOYSA-N 0.000 description 1
- OKNHBDQXYGQHDS-UHFFFAOYSA-N (4-ethenylpiperazin-1-yl)-trimethylsilane Chemical compound C[Si](C)(C)N1CCN(C=C)CC1 OKNHBDQXYGQHDS-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- ZWAQJGHGPPDZSF-UHFFFAOYSA-N 1-prop-2-enylpiperazine Chemical compound C=CCN1CCNCC1 ZWAQJGHGPPDZSF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RLPLWNUTMLAEAU-UHFFFAOYSA-N C(C)(C)[SiH2]N1CCNCC1 Chemical compound C(C)(C)[SiH2]N1CCNCC1 RLPLWNUTMLAEAU-UHFFFAOYSA-N 0.000 description 1
- HBERHRGDARGNRD-UHFFFAOYSA-N C[Si](CCN1C(CN(CC1)C(C)(C)C)[SiH](C)C)(OCC)OCC Chemical compound C[Si](CCN1C(CN(CC1)C(C)(C)C)[SiH](C)C)(OCC)OCC HBERHRGDARGNRD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- FNIUGHSZXXYXER-UHFFFAOYSA-N [Pt].ClC1=C(Cl)C=CCCCC1 Chemical compound [Pt].ClC1=C(Cl)C=CCCCC1 FNIUGHSZXXYXER-UHFFFAOYSA-N 0.000 description 1
- MBNZWTSAAPQLKH-UHFFFAOYSA-N [SiH3]N1CCNCC1 Chemical compound [SiH3]N1CCNCC1 MBNZWTSAAPQLKH-UHFFFAOYSA-N 0.000 description 1
- APDDLLVYBXGBRF-UHFFFAOYSA-N [diethyl-(triethylsilylamino)silyl]ethane Chemical compound CC[Si](CC)(CC)N[Si](CC)(CC)CC APDDLLVYBXGBRF-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000006165 cyclic alkyl 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
- 238000010511 deprotection reaction Methods 0.000 description 1
- TXYQJTYLXLZGHE-UHFFFAOYSA-N diethoxy-methyl-[2-(4-triethylsilylpiperazin-1-yl)ethyl]silane Chemical compound CCO[Si](C)(OCC)CCN1CCN([Si](CC)(CC)CC)CC1 TXYQJTYLXLZGHE-UHFFFAOYSA-N 0.000 description 1
- NBXYSABABNELJK-UHFFFAOYSA-N diethoxy-methyl-[2-(4-trimethylsilylpiperazin-1-yl)ethyl]silane Chemical compound CCO[Si](C)(OCC)CCN1CCN([Si](C)(C)C)CC1 NBXYSABABNELJK-UHFFFAOYSA-N 0.000 description 1
- AHYKVCPDKZZXMZ-UHFFFAOYSA-N diethoxy-methyl-[2-[4-tri(propan-2-yl)silylpiperazin-1-yl]ethyl]silane Chemical compound CCO[Si](C)(OCC)CCN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 AHYKVCPDKZZXMZ-UHFFFAOYSA-N 0.000 description 1
- SUHSWMTTYNLOPU-UHFFFAOYSA-N diethoxy-methyl-[4-[4-tri(propan-2-yl)silylpiperazin-1-yl]butyl]silane Chemical compound CCO[Si](C)(OCC)CCCCN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 SUHSWMTTYNLOPU-UHFFFAOYSA-N 0.000 description 1
- WQSKQDVJFFCAKK-UHFFFAOYSA-N diethoxy-methyl-[[4-tri(propan-2-yl)silylpiperazin-1-yl]methyl]silane Chemical compound CCO[Si](C)(OCC)CN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 WQSKQDVJFFCAKK-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- XNVZPLOIRSEVFC-UHFFFAOYSA-N dimethoxy-methyl-(4-piperazin-1-ylbutyl)silane Chemical compound CO[Si](C)(OC)CCCCN1CCNCC1 XNVZPLOIRSEVFC-UHFFFAOYSA-N 0.000 description 1
- ZQTFNSWRSCEXRH-UHFFFAOYSA-N dimethoxy-methyl-(piperazin-1-ylmethyl)silane Chemical compound CO[Si](C)(OC)CN1CCNCC1 ZQTFNSWRSCEXRH-UHFFFAOYSA-N 0.000 description 1
- RFECOKJYTHOMHC-UHFFFAOYSA-N dimethoxy-methyl-[(4-triethylsilylpiperazin-1-yl)methyl]silane Chemical compound CC[Si](CC)(CC)N1CCN(C[Si](C)(OC)OC)CC1 RFECOKJYTHOMHC-UHFFFAOYSA-N 0.000 description 1
- MLQDMHOOAAMPRO-UHFFFAOYSA-N dimethoxy-methyl-[2-(4-triethylsilylpiperazin-1-yl)ethyl]silane Chemical compound CC[Si](CC)(CC)N1CCN(CC[Si](C)(OC)OC)CC1 MLQDMHOOAAMPRO-UHFFFAOYSA-N 0.000 description 1
- DHCUEJVIZGJKEP-UHFFFAOYSA-N dimethoxy-methyl-[2-(4-trimethylsilylpiperazin-1-yl)ethyl]silane Chemical compound CO[Si](C)(OC)CCN1CCN([Si](C)(C)C)CC1 DHCUEJVIZGJKEP-UHFFFAOYSA-N 0.000 description 1
- MEDIUEFGXOUUBW-UHFFFAOYSA-N dimethoxy-methyl-[4-[4-tri(propan-2-yl)silylpiperazin-1-yl]butyl]silane Chemical compound CO[Si](C)(OC)CCCCN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 MEDIUEFGXOUUBW-UHFFFAOYSA-N 0.000 description 1
- YJQROODCRMVMOI-UHFFFAOYSA-N dimethoxy-methyl-[[4-tri(propan-2-yl)silylpiperazin-1-yl]methyl]silane Chemical compound CO[Si](C)(OC)CN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 YJQROODCRMVMOI-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- JXYJMKMHOUUINM-UHFFFAOYSA-N ethoxy-dimethyl-(2-methyl-3-piperazin-1-ylpropyl)silane Chemical compound CCO[Si](C)(C)CC(C)CN1CCNCC1 JXYJMKMHOUUINM-UHFFFAOYSA-N 0.000 description 1
- AFSGUQSHNQLQMW-UHFFFAOYSA-N ethoxy-dimethyl-(4-piperazin-1-ylbutyl)silane Chemical compound CCO[Si](C)(C)CCCCN1CCNCC1 AFSGUQSHNQLQMW-UHFFFAOYSA-N 0.000 description 1
- RVFNNUWGZGSBDV-UHFFFAOYSA-N ethoxy-dimethyl-[2-(4-triethylsilylpiperazin-1-yl)ethyl]silane Chemical compound CCO[Si](C)(C)CCN1CCN([Si](CC)(CC)CC)CC1 RVFNNUWGZGSBDV-UHFFFAOYSA-N 0.000 description 1
- BDTYLTDOXCPENT-UHFFFAOYSA-N ethoxy-dimethyl-[2-(4-trimethylsilylpiperazin-1-yl)ethyl]silane Chemical compound CCO[Si](C)(C)CCN1CCN([Si](C)(C)C)CC1 BDTYLTDOXCPENT-UHFFFAOYSA-N 0.000 description 1
- TUNCKKMRIJVWLM-UHFFFAOYSA-N ethoxy-dimethyl-[2-[4-tri(propan-2-yl)silylpiperazin-1-yl]ethyl]silane Chemical compound CCO[Si](C)(C)CCN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 TUNCKKMRIJVWLM-UHFFFAOYSA-N 0.000 description 1
- ZGDGKYZNTIVAJS-UHFFFAOYSA-N ethoxy-dimethyl-[4-(4-triethylsilylpiperazin-1-yl)butyl]silane Chemical compound CCO[Si](C)(C)CCCCN1CCN([Si](CC)(CC)CC)CC1 ZGDGKYZNTIVAJS-UHFFFAOYSA-N 0.000 description 1
- NOJAPRJTSFNZHQ-UHFFFAOYSA-N ethoxy-dimethyl-[4-[4-tri(propan-2-yl)silylpiperazin-1-yl]butyl]silane Chemical compound CCO[Si](C)(C)CCCCN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 NOJAPRJTSFNZHQ-UHFFFAOYSA-N 0.000 description 1
- CQAJQACPFIGIKS-UHFFFAOYSA-N ethoxy-dimethyl-[[4-tri(propan-2-yl)silylpiperazin-1-yl]methyl]silane Chemical compound CCO[Si](C)(C)CN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 CQAJQACPFIGIKS-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 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
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- MDLRQEHNDJOFQN-UHFFFAOYSA-N methoxy(dimethyl)silicon Chemical compound CO[Si](C)C MDLRQEHNDJOFQN-UHFFFAOYSA-N 0.000 description 1
- LITJDZKHWGVYLQ-UHFFFAOYSA-N methoxy-dimethyl-(4-piperazin-1-ylbutyl)silane Chemical compound CO[Si](C)(C)CCCCN1CCNCC1 LITJDZKHWGVYLQ-UHFFFAOYSA-N 0.000 description 1
- GZLIWTRYYXRADK-UHFFFAOYSA-N methoxy-dimethyl-[2-(4-trimethylsilylpiperazin-1-yl)ethyl]silane Chemical compound CO[Si](C)(C)CCN1CCN([Si](C)(C)C)CC1 GZLIWTRYYXRADK-UHFFFAOYSA-N 0.000 description 1
- BJHRUYZTRCZXLK-UHFFFAOYSA-N methoxy-dimethyl-[3-(4-trimethylsilylpiperazin-1-yl)propyl]silane Chemical compound CO[Si](C)(C)CCCN1CCN([Si](C)(C)C)CC1 BJHRUYZTRCZXLK-UHFFFAOYSA-N 0.000 description 1
- OGMCXHHYTKFGNV-UHFFFAOYSA-N methoxy-dimethyl-[4-[4-tri(propan-2-yl)silylpiperazin-1-yl]butyl]silane Chemical compound CO[Si](C)(C)CCCCN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 OGMCXHHYTKFGNV-UHFFFAOYSA-N 0.000 description 1
- JUTABOVXDRWWCA-UHFFFAOYSA-N methoxy-dimethyl-[[4-tri(propan-2-yl)silylpiperazin-1-yl]methyl]silane Chemical compound CO[Si](C)(C)CN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 JUTABOVXDRWWCA-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 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
- 230000003287 optical effect Effects 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229960002195 perazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- QRWMESWRAILKQV-UHFFFAOYSA-N phenylphosphane;platinum Chemical compound [Pt].PC1=CC=CC=C1 QRWMESWRAILKQV-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CYAQVHLMFIKTOK-UHFFFAOYSA-N tert-butyl-(4-ethenylpiperazin-1-yl)-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)N1CCN(C=C)CC1 CYAQVHLMFIKTOK-UHFFFAOYSA-N 0.000 description 1
- HNNFSYZAWPRLQB-UHFFFAOYSA-N tert-butyl-[4-[2-[dimethoxy(methyl)silyl]ethyl]piperazin-1-yl]-dimethylsilane Chemical compound CO[Si](C)(OC)CCN1CCN([Si](C)(C)C(C)(C)C)CC1 HNNFSYZAWPRLQB-UHFFFAOYSA-N 0.000 description 1
- ZDCLQQYILUIEKM-UHFFFAOYSA-N tert-butyl-[4-[2-[methoxy(dimethyl)silyl]ethyl]piperazin-1-yl]-dimethylsilane Chemical compound CO[Si](C)(C)CCN1CCN([Si](C)(C)C(C)(C)C)CC1 ZDCLQQYILUIEKM-UHFFFAOYSA-N 0.000 description 1
- NEQJOUGRLYLUAS-UHFFFAOYSA-N tert-butyl-[4-[4-[diethoxy(methyl)silyl]butyl]piperazin-1-yl]-dimethylsilane Chemical compound CCO[Si](C)(OCC)CCCCN1CCN([Si](C)(C)C(C)(C)C)CC1 NEQJOUGRLYLUAS-UHFFFAOYSA-N 0.000 description 1
- GKSSTQIASSJZLT-UHFFFAOYSA-N tert-butyl-[4-[4-[dimethoxy(methyl)silyl]butyl]piperazin-1-yl]-dimethylsilane Chemical compound CO[Si](C)(OC)CCCCN1CCN([Si](C)(C)C(C)(C)C)CC1 GKSSTQIASSJZLT-UHFFFAOYSA-N 0.000 description 1
- MAUCEBOGFUVOFU-UHFFFAOYSA-N tert-butyl-[4-[4-[ethoxy(dimethyl)silyl]butyl]piperazin-1-yl]-dimethylsilane Chemical compound CCO[Si](C)(C)CCCCN1CCN([Si](C)(C)C(C)(C)C)CC1 MAUCEBOGFUVOFU-UHFFFAOYSA-N 0.000 description 1
- VTZCRYZUSZCWKG-UHFFFAOYSA-N tert-butyl-[4-[4-[methoxy(dimethyl)silyl]butyl]piperazin-1-yl]-dimethylsilane Chemical compound CO[Si](C)(C)CCCCN1CCN([Si](C)(C)C(C)(C)C)CC1 VTZCRYZUSZCWKG-UHFFFAOYSA-N 0.000 description 1
- PHXUSHRZYBTJQQ-UHFFFAOYSA-N tert-butyl-[4-[[dimethoxy(methyl)silyl]methyl]piperazin-1-yl]-dimethylsilane Chemical compound CO[Si](C)(OC)CN1CCN([Si](C)(C)C(C)(C)C)CC1 PHXUSHRZYBTJQQ-UHFFFAOYSA-N 0.000 description 1
- ICSSHIYROAKUTF-UHFFFAOYSA-N tert-butyl-[4-[[ethoxy(dimethyl)silyl]methyl]piperazin-1-yl]-dimethylsilane Chemical compound CCO[Si](C)(C)CN1CCN([Si](C)(C)C(C)(C)C)CC1 ICSSHIYROAKUTF-UHFFFAOYSA-N 0.000 description 1
- XMMDOCGGSCXGTC-UHFFFAOYSA-N tert-butyl-[4-[[methoxy(dimethyl)silyl]methyl]piperazin-1-yl]-dimethylsilane Chemical compound CO[Si](C)(C)CN1CCN([Si](C)(C)C(C)(C)C)CC1 XMMDOCGGSCXGTC-UHFFFAOYSA-N 0.000 description 1
- WJGVYUNZQOCTCC-UHFFFAOYSA-N tert-butyl-dimethyl-[4-(2-triethoxysilylethyl)piperazin-1-yl]silane Chemical compound CCO[Si](OCC)(OCC)CCN1CCN([Si](C)(C)C(C)(C)C)CC1 WJGVYUNZQOCTCC-UHFFFAOYSA-N 0.000 description 1
- UUAACVTUNRXQFL-UHFFFAOYSA-N tert-butyl-dimethyl-[4-(2-trimethoxysilylethyl)piperazin-1-yl]silane Chemical compound CO[Si](OC)(OC)CCN1CCN([Si](C)(C)C(C)(C)C)CC1 UUAACVTUNRXQFL-UHFFFAOYSA-N 0.000 description 1
- NWJQZLOXKLBQDT-UHFFFAOYSA-N tert-butyl-dimethyl-[4-(triethoxysilylmethyl)piperazin-1-yl]silane Chemical compound CCO[Si](OCC)(OCC)CN1CCN([Si](C)(C)C(C)(C)C)CC1 NWJQZLOXKLBQDT-UHFFFAOYSA-N 0.000 description 1
- HVMMNXJPBFYUIN-UHFFFAOYSA-N tert-butyl-dimethyl-[4-(trimethoxysilylmethyl)piperazin-1-yl]silane Chemical compound CO[Si](OC)(OC)CN1CCN([Si](C)(C)C(C)(C)C)CC1 HVMMNXJPBFYUIN-UHFFFAOYSA-N 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- ZTSBGKITEAKURO-UHFFFAOYSA-N triethoxy(4-piperazin-1-ylbutyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCN1CCNCC1 ZTSBGKITEAKURO-UHFFFAOYSA-N 0.000 description 1
- UBQUEAFWQULZAP-UHFFFAOYSA-N triethoxy-[2-(4-trimethylsilylpiperazin-1-yl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCN1CCN([Si](C)(C)C)CC1 UBQUEAFWQULZAP-UHFFFAOYSA-N 0.000 description 1
- SKRDFEWAXGETID-UHFFFAOYSA-N triethoxy-[2-[4-tri(propan-2-yl)silylpiperazin-1-yl]ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 SKRDFEWAXGETID-UHFFFAOYSA-N 0.000 description 1
- COHVEALKYYLOMC-UHFFFAOYSA-N triethoxy-[4-[4-tri(propan-2-yl)silylpiperazin-1-yl]butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 COHVEALKYYLOMC-UHFFFAOYSA-N 0.000 description 1
- ZFIPRWKKSCBZMH-UHFFFAOYSA-N triethoxy-[[4-tri(propan-2-yl)silylpiperazin-1-yl]methyl]silane Chemical compound CCO[Si](OCC)(OCC)CN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 ZFIPRWKKSCBZMH-UHFFFAOYSA-N 0.000 description 1
- QJXRDUCRJHUQCF-UHFFFAOYSA-N triethyl-[4-(2-trimethoxysilylethyl)piperazin-1-yl]silane Chemical compound CC[Si](CC)(CC)N1CCN(CC[Si](OC)(OC)OC)CC1 QJXRDUCRJHUQCF-UHFFFAOYSA-N 0.000 description 1
- MGJOOXFCDVXSPB-UHFFFAOYSA-N triethyl-[4-(trimethoxysilylmethyl)piperazin-1-yl]silane Chemical compound CC[Si](CC)(CC)N1CCN(C[Si](OC)(OC)OC)CC1 MGJOOXFCDVXSPB-UHFFFAOYSA-N 0.000 description 1
- MCCXNRTWGOGGLM-UHFFFAOYSA-N triethyl-[4-[2-[methoxy(dimethyl)silyl]ethyl]piperazin-1-yl]silane Chemical compound CC[Si](CC)(CC)N1CCN(CC[Si](C)(C)OC)CC1 MCCXNRTWGOGGLM-UHFFFAOYSA-N 0.000 description 1
- HXYMWKLNCJPAKW-UHFFFAOYSA-N trimethoxy(3-piperazin-1-ylpropyl)silane Chemical compound CO[Si](OC)(OC)CCCN1CCNCC1 HXYMWKLNCJPAKW-UHFFFAOYSA-N 0.000 description 1
- FHXHRRLIXQSUAE-UHFFFAOYSA-N trimethoxy(4-piperazin-1-ylbutyl)silane Chemical compound CO[Si](OC)(OC)CCCCN1CCNCC1 FHXHRRLIXQSUAE-UHFFFAOYSA-N 0.000 description 1
- NUKNNYBZEVDMPB-UHFFFAOYSA-N trimethoxy(piperazin-1-ylmethyl)silane Chemical compound CO[Si](OC)(OC)CN1CCNCC1 NUKNNYBZEVDMPB-UHFFFAOYSA-N 0.000 description 1
- TWMNFNIVZQBBHN-UHFFFAOYSA-N trimethoxy-[2-(4-trimethylsilylpiperazin-1-yl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCN1CCN([Si](C)(C)C)CC1 TWMNFNIVZQBBHN-UHFFFAOYSA-N 0.000 description 1
- NYWYEURGDPWJQQ-UHFFFAOYSA-N trimethoxy-[3-(4-trimethylsilylpiperazin-1-yl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCN1CCN([Si](C)(C)C)CC1 NYWYEURGDPWJQQ-UHFFFAOYSA-N 0.000 description 1
- LKTRUVILMQVLLS-UHFFFAOYSA-N trimethoxy-[4-[4-tri(propan-2-yl)silylpiperazin-1-yl]butyl]silane Chemical compound CO[Si](OC)(OC)CCCCN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 LKTRUVILMQVLLS-UHFFFAOYSA-N 0.000 description 1
- XIJVKKRJHZLFQF-UHFFFAOYSA-N trimethoxy-[[4-tri(propan-2-yl)silylpiperazin-1-yl]methyl]silane Chemical compound CO[Si](OC)(OC)CN1CCN([Si](C(C)C)(C(C)C)C(C)C)CC1 XIJVKKRJHZLFQF-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Abstract
Description
本発明は、塗料添加剤、接着剤、シランカップリング剤、表面処理剤等として有用な保護されたピペラジノ基を有するオルガノキシシラン化合物及びその製造方法に関する。 The present invention relates to an organoxysilane compound having a protected piperazino group useful as a paint additive, an adhesive, a silane coupling agent, a surface treatment agent, and the like, and a method for producing the same.
アミノ基が保護されたオルガノキシシラン化合物は、塗料添加剤、接着剤、シランカップリング剤、表面処理剤等として有用であり、特にアミノ基がシリル基で保護されたオルガノキシシラン化合物は、保護、脱保護が容易なため、上記用途に用いるのに適している。 Organoxysilane compounds with amino groups protected are useful as paint additives, adhesives, silane coupling agents, surface treatment agents, etc. Especially organoxysilane compounds with amino groups protected with silyl groups are protected. Since deprotection is easy, it is suitable for use in the above applications.
このようなアミノ基がシリル基で保護されたオルガノキシシラン化合物としては、例えば特許第３４１４１３４号公報（特許文献１）記載のＮ，Ｎ−（ビストリメチルシリル）アミノプロピルシラン化合物が例示され、アミノ変性シリコーンオイルの変性剤として有用であることが開示されている。 Examples of such organoxysilane compounds in which an amino group is protected with a silyl group include N, N- (bistrimethylsilyl) aminopropylsilane compounds described in Japanese Patent No. 3414134 (Patent Document 1). It is disclosed that it is useful as a modifier for silicone oil.
更に、このようなアミノ基がシリル基で保護されたオルガノキシシラン化合物は、塗料や接着剤の添加剤としても有用であり、例えばエポキシ樹脂に添加することにより、アミノ系シランカップリング剤添加の効果（接着性、補強性向上）を有する一液型硬化性組成物、即ち水分を遮断した系では反応性を示さず安定な組成物であるが、水分と接触することにより加水分解による脱保護が起こり、アミノ基が再生しアミノ系シランカップリング剤を添加したのと同等の効果を示す組成物とすることができる。 Furthermore, such an organoxysilane compound in which an amino group is protected with a silyl group is also useful as an additive for paints and adhesives. For example, by adding it to an epoxy resin, an amino-based silane coupling agent can be added. One-component curable composition with effects (adhesion and reinforcement), that is, a stable composition that does not show reactivity in a system where moisture is blocked, but is deprotected by hydrolysis when in contact with moisture Thus, the amino group is regenerated and an amino-based silane coupling agent is added to obtain a composition having the same effect.
上記のようにアミノ基がシリル基で保護されたオルガノキシシラン化合物は、塗料や接着剤添加時に、官能基の保護により官能基自身が反応してしまうのを防ぐことができ、その後脱保護することにより、定量的、効率的に官能基を再生、導入可能であるため有用である。しかしながら、更に最近では、光学材料や電子材料等において、これらの樹脂、硬化物に、剛直性、高い機械的強度、紫外線領域を含んだ透明性が要求されてきているものの、既知のアミノ基がシリル基で保護されたオルガノキシシラン化合物では、満足な剛直性、高い機械的強度、紫外線領域を含んだ透明性を付与することができなかった。 The organoxysilane compound in which the amino group is protected with a silyl group as described above can prevent the functional group itself from reacting due to the protection of the functional group when adding paint or adhesive, and then deprotecting it. Therefore, it is useful because the functional group can be regenerated and introduced quantitatively and efficiently. However, recently, in optical materials and electronic materials, these resins and cured products have been required to have rigidity, high mechanical strength, and transparency including an ultraviolet region. The organoxysilane compound protected with a silyl group cannot give satisfactory rigidity, high mechanical strength, and transparency including an ultraviolet region.
本発明は上記事情に鑑みなされたもので、剛直性、高い機械的強度、紫外線領域を含んだ透明性を付与することができる塗料添加剤、接着剤等として好適に用いられるピペラジノ基を有するオルガノキシシラン化合物及びその製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and has a piperazino group suitably used as a coating additive, an adhesive, or the like that can impart rigidity, high mechanical strength, and transparency including an ultraviolet region. An object is to provide a xylsilane compound and a method for producing the same.
本発明者は、上記目的を達成するため鋭意検討を重ねた結果、下記方法によって得ることができる下記一般式（１）
（式中、Ｒは炭素数１〜１０の直鎖状又は分岐状の２価炭化水素基、Ｒ1、Ｒ2、Ｒ3、Ｒ4は炭素数１〜１０の１価炭化水素基、ｎは０、１又は２である。）
で示される保護されたピペラジノ基を有するオルガノキシシラン化合物が、塗料添加剤、接着剤等として用いた場合に、剛直性、高い機械的強度、紫外線領域を含んだ透明性を付与することができることを知見し、本発明を完成するに至ったものである。
As a result of intensive studies to achieve the above object, the present inventor has the following general formula (1) that can be obtained by the following method.
(In the formula, R is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, R 1 , R 2 , R 3 and R 4 are monovalent hydrocarbon groups having 1 to 10 carbon atoms, n Is 0, 1 or 2.)
When the organoxysilane compound having a protected piperazino group represented by is used as a paint additive, adhesive, etc., it can provide rigidity, high mechanical strength, and transparency including an ultraviolet region. As a result, the present invention has been completed.
従って、本発明は下記シラン化合物及びその製造方法を提供する。
（Ｉ）下記一般式（１）
（式中、Ｒは炭素数１〜１０の直鎖状又は分岐状の２価炭化水素基、Ｒ1、Ｒ2、Ｒ3、Ｒ4は炭素数１〜１０の１価炭化水素基、ｎは０、１又は２である。）
で示される保護されたピペラジノ基を有するオルガノキシシラン化合物。
（ＩＩ）下記一般式（２）
（式中、Ｒ5は水素原子又はメチル基であり、Ｒ5が水素原子の場合、Ｒ’は炭素数１〜８の直鎖状又は分岐状の２価炭化水素基、Ｒ5がメチル基の場合、Ｒ’は炭素数１〜７の直鎖状又は分岐状の２価炭化水素基であり、Ｒ2、Ｒ3、Ｒ4は上記と同様である。）
で示される化合物と、下記一般式（３）
ＨＳｉ（ＣＨ3）n（ＯＲ1）3-n （３）
（式中、Ｒ1、ｎは上記と同様である。）
で示されるハイドロジェンシラン化合物とを白金触媒下で反応させることを特徴とする（Ｉ）の保護されたピペラジノ基を有するオルガノキシシラン化合物の製造方法。
（ＩＩＩ）下記一般式（４）
（式中、Ｒ、Ｒ1、ｎは上記と同様である。）
で示される化合物をＲ2Ｒ3Ｒ4Ｓｉ−基（Ｒ2、Ｒ3、Ｒ4は上記と同様である。）を有するシリル化剤によってシリル化することを特徴とする（Ｉ）の保護されたピペラジノ基を有するオルガノキシシラン化合物の製造方法。
Accordingly, the present invention provides the following silane compound and a method for producing the same.
(I) The following general formula (1)
(In the formula, R is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, R 1 , R 2 , R 3 and R 4 are monovalent hydrocarbon groups having 1 to 10 carbon atoms, n Is 0, 1 or 2.)
An organoxysilane compound having a protected piperazino group represented by
(II) The following general formula (2)
(In the formula, R 5 is a hydrogen atom or a methyl group, and when R 5 is a hydrogen atom, R ′ is a linear or branched divalent hydrocarbon group having 1 to 8 carbon atoms, and R 5 is a methyl group. In this case, R ′ is a linear or branched divalent hydrocarbon group having 1 to 7 carbon atoms, and R 2 , R 3 and R 4 are the same as above.)
And a compound represented by the following general formula (3)
HSi (CH 3 ) n (OR 1 ) 3-n (3)
(Wherein R 1 and n are the same as above)
The method for producing an organoxysilane compound having a protected piperazino group according to (I), which comprises reacting with a hydrogensilane compound represented by formula (I) under a platinum catalyst.
(III) The following general formula (4)
(In the formula, R, R 1 and n are the same as above.)
Protecting (I), wherein the compound represented by the formula (I) is silylated with a silylating agent having an R 2 R 3 R 4 Si— group (R 2 , R 3 and R 4 are the same as above). For producing an organoxysilane compound having a piperazino group.
本発明によれば、保護されたピペラジノ基を有するオルガノキシシラン化合物を用いることにより、塗料添加剤、接着剤等として用いた場合に、剛直性、高い機械的強度、紫外線領域を含んだ透明性を付与することができる。 According to the present invention, by using an organoxysilane compound having a protected piperazino group, when used as a paint additive, an adhesive, etc., rigidity, high mechanical strength, transparency including ultraviolet region Can be granted.
本発明の化合物は、下記一般式（１）
（式中、Ｒは炭素数１〜１０の直鎖状又は分岐状の２価炭化水素基、Ｒ1、Ｒ2、Ｒ3、Ｒ4は炭素数１〜１０の１価炭化水素基、ｎは０、１又は２である。）
で示される保護されたピペラジノ基を有するオルガノキシシラン化合物である。
The compound of the present invention has the following general formula (1)
(In the formula, R is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, R 1 , R 2 , R 3 and R 4 are monovalent hydrocarbon groups having 1 to 10 carbon atoms, n Is 0, 1 or 2.)
An organoxysilane compound having a protected piperazino group represented by the formula:
ここで、Ｒ1、Ｒ2、Ｒ3、Ｒ4は炭素数１〜１０、好ましくは１〜６の１価炭化水素基であり、直鎖状、分岐状又は環状のアルキル基、アルケニル基、アリール基等が挙げられる。具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、デシル基、ビニル基、アリル基、メタリル基、ブテニル基、フェニル基等が例示される。Ｒは炭素数１〜１０の直鎖状又は分岐状の２価炭化水素基であり、アルキレン基、アリーレン基、アラルキレン基等が挙げられ、具体的には、メチレン基、ジメチレン基、トリメチレン基、テトラメチレン基、ヘキサメチレン基、イソブチレン基等が例示される。 Here, R 1 , R 2 , R 3 and R 4 are monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, linear, branched or cyclic alkyl groups, alkenyl groups, An aryl group etc. are mentioned. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, vinyl Group, allyl group, methallyl group, butenyl group, phenyl group and the like. R is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include an alkylene group, an arylene group, and an aralkylene group. Specifically, a methylene group, a dimethylene group, a trimethylene group, Examples include a tetramethylene group, a hexamethylene group, and an isobutylene group.
本発明の保護されたピペラジノ基を有するオルガノキシシラン化合物を具体的に例示すると、下記の通りである。 Specific examples of the organoxysilane compound having a protected piperazino group of the present invention are as follows.
１−［１−（トリメトキシシリル）メチル］−４−トリメチルシリルピペラジン、１−［１−（メチルジメトキシシリル）メチル］−４−トリメチルシリルピペラジン、１−［１−（ジメチルメトキシシリル）メチル］−４−トリメチルシリルピペラジン、１−［１−（トリエトキシシリル）メチル］−４−トリメチルシリルピペラジン、１−［１−（メチルジエトキシシリル）メチル］−４−トリメチルシリルピペラジン、１−［１−（ジメチルエトキシシリル）メチル］−４−トリメチルシリルピペラジン、１−［１−（トリメトキシシリル）メチル］−４−トリエチルシリルピペラジン、１−［１−（メチルジメトキシシリル）メチル］−４−トリエチルシリルピペラジン、１−［１−（ジメチルメトキシシリル）メチル］−４−トリエチルシリルピペラジン、１−［１−（トリエトキシシリル）メチル］−４−トリエチルシリルピペラジン、１−［１−（メチルジエトキシシリル）メチル］−４−トリエチルシリルピペラジン、１−［１−（ジメチルエトキシシリル）メチル］−４−トリエチルシリルピペラジン、１−［１−（トリメトキシシリル）メチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［１−（メチルジメトキシシリル）メチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［１−（ジメチルメトキシシリル）メチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［１−（トリエトキシシリル）メチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［１−（メチルジエトキシシリル）メチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［１−（ジメチルエトキシシリル）メチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［１−（トリメトキシシリル）メチル］−４−トリイソプロピルシリルピペラジン、１−［１−（メチルジメトキシシリル）メチル］−４−トリイソプロピルシリルピペラジン、１−［１−（ジメチルメトキシシリル）メチル］−４−トリイソプロピルシリルピペラジン、１−［１−（トリエトキシシリル）メチル］−４−トリイソプロピルシリルピペラジン、１−［１−（メチルジエトキシシリル）メチル］−４−トリイソプロピルシリルピペラジン、１−［１−（ジメチルエトキシシリル）メチル］−４−トリイソプロピルシリルピペラジン、１−［２−（トリメトキシシリル）エチル］−４−トリメチルシリルピペラジン、１−［２−（メチルジメトキシシリル）エチル］−４−トリメチルシリルピペラジン、１−［２−（ジメチルメトキシシリル）エチル］−４−トリメチルシリルピペラジン、１−［２−（トリエトキシシリル）エチル］−４−トリメチルシリルピペラジン、１−［２−（メチルジエトキシシリル）エチル］−４−トリメチルシリルピペラジン、１−［２−（ジメチルエトキシシリル）エチル］−４−トリメチルシリルピペラジン、１−［２−（トリメトキシシリル）エチル］−４−トリエチルシリルピペラジン、１−［２−（メチルジメトキシシリル）エチル］−４−トリエチルシリルピペラジン、１−［２−（ジメチルメトキシシリル）エチル］−４−トリエチルシリルピペラジン、１−［２−（トリエトキシシリル）エチル］−４−トリエチルシリルピペラジン、１−［２−（メチルジエトキシシリル）エチル］−４−トリエチルシリルピペラジン、１−［２−（ジメチルエトキシシリル）エチル］−４−トリエチルシリルピペラジン、１−［２−（トリメトキシシリル）エチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［２−（メチルジメトキシシリル）エチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［２−（ジメチルメトキシシリル）エチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［２−（トリエトキシシリル）エチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［２−（メチルジエトキシシリル）エチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［２−（ジメチルエトキシシリル）エチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［２−（トリメトキシシリル）エチル］−４−トリイソプロピルシリルピペラジン、１−［２−（メチルジメトキシシリル）エチル］−４−トリイソプロピルシリルピペラジン、１−［２−（ジメチルメトキシシリル）エチル］−４−トリイソプロピルシリルピペラジン、１−［２−（トリエトキシシリル）エチル］−４−トリイソプロピルシリルピペラジン、１−［２−（メチルジエトキシシリル）エチル］−４−トリイソプロピルシリルピペラジン、１−［２−（ジメチルエトキシシリル）エチル］−４−トリイソプロピルシリルピペラジン、１−［３−（トリメトキシシリル）プロピル］−４−トリメチルシリルピペラジン、１−［３−（メチルジメトキシシリル）プロピル］−４−トリメチルシリルピペラジン、１−［３−（ジメチルメトキシシリル）プロピル］−４−トリメチルシリルピペラジン、１−［３−（トリエトキシシリル）プロピル］−４−トリメチルシリルピペラジン、１−［３−（メチルジエトキシシリル）プロピル］−４−トリメチルシリルピペラジン、１−［３−（ジメチルエトキシシリル）プロピル］−４−トリメチルシリルピペラジン、１−［３−（トリメトキシシリル）プロピル］−４−トリエチルシリルピペラジン、１−［３−（メチルジメトキシシリル）プロピル］−４−トリエチルシリルピペラジン、１−［３−（ジメチルメトキシシリル）プロピル］−４−トリエチルシリルピペラジン、１−［３−（トリエトキシシリル）プロピル］−４−トリエチルシリルピペラジン、１−［３−（メチルジエトキシシリル）プロピル］−４−トリエチルシリルピペラジン、１−［３−（ジメチルエトキシシリル）プロピル］−４−トリエチルシリルピペラジン、１−［３−（トリメトキシシリル）プロピル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［３−（メチルジメトキシシリル）プロピル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［３−（ジメチルメトキシシリル）プロピル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［３−（トリエトキシシリル）プロピル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［３−（メチルジエトキシシリル）プロピル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［３−（ジメチルエトキシシリル）プロピル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［３−（トリメトキシシリル）プロピル］−４−トリイソプロピルシリルピペラジン、１−［３−（メチルジメトキシシリル）プロピル］−４−トリイソプロピルシリルピペラジン、１−［３−（ジメチルメトキシシリル）プロピル］−４−トリイソプロピルシリルピペラジン、１−［３−（トリエトキシシリル）プロピル］−４−トリイソプロピルシリルピペラジン、１−［３−（メチルジエトキシシリル）プロピル］−４−トリイソプロピルシリルピペラジン、１−［３−（ジメチルエトキシシリル）プロピル］−４−トリイソプロピルシリルピペラジン、１−［３−（トリメトキシシリル）−２−メチルプロピル］−４−トリメチルシリルピペラジン、１−［３−（メチルジメトキシシリル）−２−メチルプロピル］−４−トリメチルシリルピペラジン、１−［３−（ジメチルメトキシシリル）−２−メチルプロピル］−４−トリメチルシリルピペラジン、１−［３−（トリエトキシシリル）−２−メチルプロピル］−４−トリメチルシリルピペラジン、１−［３−（メチルジエトキシシリル）−２−メチルプロピル］−４−トリメチルシリルピペラジン、１−［３−（ジメチルエトキシシリル）−２−メチルプロピル］−４−トリメチルシリルピペラジン、１−［３−（トリメトキシシリル）−２−メチルプロピル］−４−トリエチルシリルピペラジン、１−［３−（メチルジメトキシシリル）−２−メチルプロピル］−４−トリエチルシリルピペラジン、１−［３−（ジメチルメトキシシリル）−２−メチルプロピル］−４−トリエチルシリルピペラジン、１−［３−（トリエトキシシリル）−２−メチルプロピル］−４−トリエチルシリルピペラジン、１−［３−（メチルジエトキシシリル）−２−メチルプロピル］−４−トリエチルシリルピペラジン、１−［３−（ジメチルエトキシシリル）−２−メチルプロピル］−４−トリエチルシリルピペラジン、１−［３−（トリメトキシシリル）−２−メチルプロピル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［３−（メチルジメトキシシリル）−２−メチルプロピル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［３−（ジメチルメトキシシリル）−２−メチルプロピル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［３−（トリエトキシシリル）−２−メチルプロピル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［３−（メチルジエトキシシリル）−２−メチルプロピル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［３−（ジメチルエトキシシリル）−２−メチルプロピル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［３−（トリメトキシシリル）−２−メチルプロピル］−４−トリイソプロピルシリルピペラジン、１−［３−（メチルジメトキシシリル）−２−メチルプロピル］−４−トリイソプロピルシリルピペラジン、１−［３−（ジメチルメトキシシリル）−２−メチルプロピル］−４−トリイソプロピルシリルピペラジン、１−［３−（トリエトキシシリル）−２−メチルプロピル］−４−トリイソプロピルシリルピペラジン、１−［３−（メチルジエトキシシリル）−２−メチルプロピル］−４−トリイソプロピルシリルピペラジン、１−［３−（ジメチルエトキシシリル）−２−メチルプロピル］−４−トリイソプロピルシリルピペラジン、１−［４−（トリメトキシシリル）ブチル］−４−トリメチルシリルピペラジン、１−［４−（メチルジメトキシシリル）ブチル］−４−トリメチルシリルピペラジン、１−［４−（ジメチルメトキシシリル）ブチル］−４−トリメチルシリルピペラジン、１−［４−（トリエトキシシリル）ブチル］−４−トリメチルシリルピペラジン、１−［４−（メチルジエトキシシリル）ブチル］−４−トリメチルシリルピペラジン、１−［４−（ジメチルエトキシシリル）ブチル］−４−トリメチルシリルピペラジン、１−［４−（トリメトキシシリル）ブチル］−４−トリエチルシリルピペラジン、１−［４−（メチルジメトキシシリル）ブチル］−４−トリエチルシリルピペラジン、１−［４−（ジメチルメトキシシリル）ブチル］−４−トリエチルシリルピペラジン、１−［４−（トリエトキシシリル）ブチル］−４−トリエチルシリルピペラジン、１−［４−（メチルジエトキシシリル）ブチル］−４−トリエチルシリルピペラジン、１−［４−（ジメチルエトキシシリル）ブチル］−４−トリエチルシリルピペラジン、１−［４−（トリメトキシシリル）ブチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［４−（メチルジメトキシシリル）ブチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［４−（ジメチルメトキシシリル）ブチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［４−（トリエトキシシリル）ブチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［４−（メチルジエトキシシリル）ブチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［４−（ジメチルエトキシシリル）ブチル］−４−ｔ−ブチルジメチルシリルピペラジン、１−［４−（トリメトキシシリル）ブチル］−４−トリイソプロピルシリルピペラジン、１−［４−（メチルジメトキシシリル）ブチル］−４−トリイソプロピルシリルピペラジン、１−［４−（ジメチルメトキシシリル）ブチル］−４−トリイソプロピルシリルピペラジン、１−［４−（トリエトキシシリル）ブチル］−４−トリイソプロピルシリルピペラジン、１−［４−（メチルジエトキシシリル）ブチル］−４−トリイソプロピルシリルピペラジン、１−［４−（ジメチルエトキシシリル）ブチル］−４−トリイソプロピルシリルピペラジン。 1- [1- (trimethoxysilyl) methyl] -4-trimethylsilylpiperazine, 1- [1- (methyldimethoxysilyl) methyl] -4-trimethylsilylpiperazine, 1- [1- (dimethylmethoxysilyl) methyl] -4 -Trimethylsilylpiperazine, 1- [1- (triethoxysilyl) methyl] -4-trimethylsilylpiperazine, 1- [1- (methyldiethoxysilyl) methyl] -4-trimethylsilylpiperazine, 1- [1- (dimethylethoxysilyl) ) Methyl] -4-trimethylsilylpiperazine, 1- [1- (trimethoxysilyl) methyl] -4-triethylsilylpiperazine, 1- [1- (methyldimethoxysilyl) methyl] -4-triethylsilylpiperazine, 1- [ 1- (Dimethylmethoxysilyl) methyl] -4-tri Tylsilylpiperazine, 1- [1- (triethoxysilyl) methyl] -4-triethylsilylpiperazine, 1- [1- (methyldiethoxysilyl) methyl] -4-triethylsilylpiperazine, 1- [1- (dimethyl) Ethoxysilyl) methyl] -4-triethylsilylpiperazine, 1- [1- (trimethoxysilyl) methyl] -4-tert-butyldimethylsilylpiperazine, 1- [1- (methyldimethoxysilyl) methyl] -4-t -Butyldimethylsilylpiperazine, 1- [1- (dimethylmethoxysilyl) methyl] -4-tert-butyldimethylsilylpiperazine, 1- [1- (triethoxysilyl) methyl] -4-tert-butyldimethylsilylpiperazine, 1- [1- (Methyldiethoxysilyl) methyl] -4-tert-butyldimethylsilylpi Razine, 1- [1- (dimethylethoxysilyl) methyl] -4-tert-butyldimethylsilylpiperazine, 1- [1- (trimethoxysilyl) methyl] -4-triisopropylsilylpiperazine, 1- [1- ( Methyldimethoxysilyl) methyl] -4-triisopropylsilylpiperazine, 1- [1- (dimethylmethoxysilyl) methyl] -4-triisopropylsilylpiperazine, 1- [1- (triethoxysilyl) methyl] -4-tri Isopropylsilylpiperazine, 1- [1- (methyldiethoxysilyl) methyl] -4-triisopropylsilylpiperazine, 1- [1- (dimethylethoxysilyl) methyl] -4-triisopropylsilylpiperazine, 1- [2- (Trimethoxysilyl) ethyl] -4-trimethylsilylpiperazine, 1 -[2- (methyldimethoxysilyl) ethyl] -4-trimethylsilylpiperazine, 1- [2- (dimethylmethoxysilyl) ethyl] -4-trimethylsilylpiperazine, 1- [2- (triethoxysilyl) ethyl] -4- Trimethylsilylpiperazine, 1- [2- (methyldiethoxysilyl) ethyl] -4-trimethylsilylpiperazine, 1- [2- (dimethylethoxysilyl) ethyl] -4-trimethylsilylpiperazine, 1- [2- (trimethoxysilyl) Ethyl] -4-triethylsilylpiperazine, 1- [2- (methyldimethoxysilyl) ethyl] -4-triethylsilylpiperazine, 1- [2- (dimethylmethoxysilyl) ethyl] -4-triethylsilylpiperazine, 1- [ 2- (Triethoxysilyl) ethyl] -4-trie Rusilylpiperazine, 1- [2- (methyldiethoxysilyl) ethyl] -4-triethylsilylpiperazine, 1- [2- (dimethylethoxysilyl) ethyl] -4-triethylsilylpiperazine, 1- [2- (tri Methoxysilyl) ethyl] -4-tert-butyldimethylsilylpiperazine, 1- [2- (methyldimethoxysilyl) ethyl] -4-tert-butyldimethylsilylpiperazine, 1- [2- (dimethylmethoxysilyl) ethyl]- 4-t-butyldimethylsilylpiperazine, 1- [2- (triethoxysilyl) ethyl] -4-t-butyldimethylsilylpiperazine, 1- [2- (methyldiethoxysilyl) ethyl] -4-t-butyl Dimethylsilylpiperazine, 1- [2- (dimethylethoxysilyl) ethyl] -4-tert-butyldimethyl Silylpiperazine, 1- [2- (trimethoxysilyl) ethyl] -4-triisopropylsilylpiperazine, 1- [2- (methyldimethoxysilyl) ethyl] -4-triisopropylsilylpiperazine, 1- [2- (dimethyl) Methoxysilyl) ethyl] -4-triisopropylsilylpiperazine, 1- [2- (triethoxysilyl) ethyl] -4-triisopropylsilylpiperazine, 1- [2- (methyldiethoxysilyl) ethyl] -4-tri Isopropylsilylpiperazine, 1- [2- (dimethylethoxysilyl) ethyl] -4-triisopropylsilylpiperazine, 1- [3- (trimethoxysilyl) propyl] -4-trimethylsilylpiperazine, 1- [3- (methyldimethoxy) Silyl) propyl] -4-trimethylsilylpiperazi 1- [3- (dimethylmethoxysilyl) propyl] -4-trimethylsilylpiperazine, 1- [3- (triethoxysilyl) propyl] -4-trimethylsilylpiperazine, 1- [3- (methyldiethoxysilyl) propyl ] -4-trimethylsilylpiperazine, 1- [3- (dimethylethoxysilyl) propyl] -4-trimethylsilylpiperazine, 1- [3- (trimethoxysilyl) propyl] -4-triethylsilylpiperazine, 1- [3- ( Methyldimethoxysilyl) propyl] -4-triethylsilylpiperazine, 1- [3- (dimethylmethoxysilyl) propyl] -4-triethylsilylpiperazine, 1- [3- (triethoxysilyl) propyl] -4-triethylsilylpiperazine , 1- [3- (Methyldiethoxysilyl) Propyl] -4-triethylsilylpiperazine, 1- [3- (dimethylethoxysilyl) propyl] -4-triethylsilylpiperazine, 1- [3- (trimethoxysilyl) propyl] -4-tert-butyldimethylsilylpiperazine, 1- [3- (methyldimethoxysilyl) propyl] -4-tert-butyldimethylsilylpiperazine, 1- [3- (dimethylmethoxysilyl) propyl] -4-tert-butyldimethylsilylpiperazine, 1- [3- ( Triethoxysilyl) propyl] -4-t-butyldimethylsilylpiperazine, 1- [3- (methyldiethoxysilyl) propyl] -4-t-butyldimethylsilylpiperazine, 1- [3- (dimethylethoxysilyl) propyl ] -4-t-butyldimethylsilylpiperazine, 1- [3- (trimetho Cysilyl) propyl] -4-triisopropylsilylpiperazine, 1- [3- (methyldimethoxysilyl) propyl] -4-triisopropylsilylpiperazine, 1- [3- (dimethylmethoxysilyl) propyl] -4-triisopropylsilyl Piperazine, 1- [3- (triethoxysilyl) propyl] -4-triisopropylsilylpiperazine, 1- [3- (methyldiethoxysilyl) propyl] -4-triisopropylsilylpiperazine, 1- [3- (dimethyl) Ethoxysilyl) propyl] -4-triisopropylsilylpiperazine, 1- [3- (trimethoxysilyl) -2-methylpropyl] -4-trimethylsilylpiperazine, 1- [3- (methyldimethoxysilyl) -2-methylpropyl ] -4-trimethylsilylpiperazine, 1- [3- (dimethylmethoxysilyl) -2-methylpropyl] -4-trimethylsilylpiperazine, 1- [3- (triethoxysilyl) -2-methylpropyl] -4-trimethylsilylpiperazine, 1- [3- ( Methyldiethoxysilyl) -2-methylpropyl] -4-trimethylsilylpiperazine, 1- [3- (dimethylethoxysilyl) -2-methylpropyl] -4-trimethylsilylpiperazine, 1- [3- (trimethoxysilyl)- 2-methylpropyl] -4-triethylsilylpiperazine, 1- [3- (methyldimethoxysilyl) -2-methylpropyl] -4-triethylsilylpiperazine, 1- [3- (dimethylmethoxysilyl) -2-methylpropyl ] -4-triethylsilylpiperazine, 1- [3- (triethoxysilyl) -2-methylpropyl] -4-triethylsilylpiperazine, 1- [3- (methyldiethoxysilyl) -2-methylpropyl] -4-triethylsilylpiperazine, 1- [3- (dimethylethoxysilyl) -2- Methylpropyl] -4-triethylsilylpiperazine, 1- [3- (trimethoxysilyl) -2-methylpropyl] -4-t-butyldimethylsilylpiperazine, 1- [3- (methyldimethoxysilyl) -2-methyl Propyl] -4-tert-butyldimethylsilylpiperazine, 1- [3- (dimethylmethoxysilyl) -2-methylpropyl] -4-tert-butyldimethylsilylpiperazine, 1- [3- (triethoxysilyl) -2 -Methylpropyl] -4-tert-butyldimethylsilylpiperazine, 1- [3- (methyldiethoxysilyl) ) -2-methylpropyl] -4-t-butyldimethylsilylpiperazine, 1- [3- (dimethylethoxysilyl) -2-methylpropyl] -4-t-butyldimethylsilylpiperazine, 1- [3- (tri Methoxysilyl) -2-methylpropyl] -4-triisopropylsilylpiperazine, 1- [3- (methyldimethoxysilyl) -2-methylpropyl] -4-triisopropylsilylpiperazine, 1- [3- (dimethylmethoxysilyl) ) -2-Methylpropyl] -4-triisopropylsilylpiperazine, 1- [3- (triethoxysilyl) -2-methylpropyl] -4-triisopropylsilylpiperazine, 1- [3- (methyldiethoxysilyl) -2-methylpropyl] -4-triisopropylsilylpiperazine, 1- [3- (dimethyl) (Luethoxysilyl) -2-methylpropyl] -4-triisopropylsilylpiperazine, 1- [4- (trimethoxysilyl) butyl] -4-trimethylsilylpiperazine, 1- [4- (methyldimethoxysilyl) butyl] -4 -Trimethylsilylpiperazine, 1- [4- (dimethylmethoxysilyl) butyl] -4-trimethylsilylpiperazine, 1- [4- (triethoxysilyl) butyl] -4-trimethylsilylpiperazine, 1- [4- (methyldiethoxysilyl) ) Butyl] -4-trimethylsilylpiperazine, 1- [4- (dimethylethoxysilyl) butyl] -4-trimethylsilylpiperazine, 1- [4- (trimethoxysilyl) butyl] -4-triethylsilylpiperazine, 1- [4 -(Methyldimethoxysilyl) butyl] -4-to Ethylsilylpiperazine, 1- [4- (dimethylmethoxysilyl) butyl] -4-triethylsilylpiperazine, 1- [4- (triethoxysilyl) butyl] -4-triethylsilylpiperazine, 1- [4- (methyldiethyl) Ethoxysilyl) butyl] -4-triethylsilylpiperazine, 1- [4- (dimethylethoxysilyl) butyl] -4-triethylsilylpiperazine, 1- [4- (trimethoxysilyl) butyl] -4-t-butyldimethyl Silylpiperazine, 1- [4- (methyldimethoxysilyl) butyl] -4-tert-butyldimethylsilylpiperazine, 1- [4- (dimethylmethoxysilyl) butyl] -4-tert-butyldimethylsilylpiperazine, 1- [ 4- (Triethoxysilyl) butyl] -4-tert-butyldimethylsilylpiperazi 1- [4- (methyldiethoxysilyl) butyl] -4-tert-butyldimethylsilylpiperazine, 1- [4- (dimethylethoxysilyl) butyl] -4-tert-butyldimethylsilylpiperazine, 1- [4 -(Trimethoxysilyl) butyl] -4-triisopropylsilylpiperazine, 1- [4- (methyldimethoxysilyl) butyl] -4-triisopropylsilylpiperazine, 1- [4- (dimethylmethoxysilyl) butyl] -4 -Triisopropylsilylpiperazine, 1- [4- (triethoxysilyl) butyl] -4-triisopropylsilylpiperazine, 1- [4- (methyldiethoxysilyl) butyl] -4-triisopropylsilylpiperazine, 1- [ 4- (Dimethylethoxysilyl) butyl] -4-triisopropylsilylpiperazi N.
一般式（１）で示される保護されたピペラジノ基を有するオルガノキシシラン化合物の製造方法は、例えば下記一般式（２）
（式中、Ｒ5は水素原子又はメチル基であり、Ｒ5が水素原子の場合、Ｒ’は炭素数１〜８の直鎖状又は分岐状の２価炭化水素基、Ｒ5がメチル基の場合、Ｒ’は炭素数１〜７の直鎖状又は分岐状の２価炭化水素基であり、Ｒ2、Ｒ3、Ｒ4は上記と同様である。）
で示される化合物と、下記一般式（３）
ＨＳｉ（ＣＨ3）n（ＯＲ1）3-n （３）
（式中、Ｒ1、ｎは上記と同様である。）
で示されるハイドロジェンシラン化合物とを白金触媒下で反応させる方法が例示される。
A method for producing an organoxysilane compound having a protected piperazino group represented by the general formula (1) is, for example, the following general formula (2):
(In the formula, R 5 is a hydrogen atom or a methyl group, and when R 5 is a hydrogen atom, R ′ is a linear or branched divalent hydrocarbon group having 1 to 8 carbon atoms, and R 5 is a methyl group. In this case, R ′ is a linear or branched divalent hydrocarbon group having 1 to 7 carbon atoms, and R 2 , R 3 and R 4 are the same as above.)
And a compound represented by the following general formula (3)
HSi (CH 3 ) n (OR 1 ) 3-n (3)
(Wherein R 1 and n are the same as above)
The method of making it react with the hydrogen silane compound shown by platinum catalyst under a platinum catalyst is illustrated.
ここで、Ｒ’はＲ5が水素原子の場合、炭素数１〜８の直鎖状又は分岐状の２価炭化水素基、Ｒ5がメチル基の場合、炭素数１〜７の直鎖状又は分岐状の２価炭化水素基であり、メチレン基、エチレン基、トリメチレン基、テトラメチレン基等のアルキレン基、フェニレン基等のアリーレン基、アラルキレン基等が挙げられる。 Here, R ′ is a linear or branched divalent hydrocarbon group having 1 to 8 carbon atoms when R 5 is a hydrogen atom, and a linear chain having 1 to 7 carbon atoms when R 5 is a methyl group. Alternatively, it is a branched divalent hydrocarbon group, and examples thereof include alkylene groups such as methylene group, ethylene group, trimethylene group, and tetramethylene group, arylene groups such as phenylene group, and aralkylene groups.
上記一般式（２）で示される化合物としては、具体的には、１−ビニル−４−トリメチルシリルピペラジン、１−ビニル−４−トリエチルシリルピペラジン、１−ビニル−４−ｔ−ブチルジメチルシリルピペラジン、１−ビニル−４−トリイソプロピルシリルピペラジン、１−アリル−４−トリメチルシリルピペラジン、１−アリル−４−トリエチルシリルピペラジン、１−アリル−４−ｔ−ブチルジメチルシリルピペラジン、１−アリル−４−トリイソプロピルシリルピペラジン、１−メタリル−４−トリメチルシリルピペラジン、１−メタリル−４−トリエチルシリルピペラジン、１−メタリル−４−ｔ−ブチルジメチルシリルピペラジン、１−メタリル−４−トリイソプロピルシリルピペラジン、１−ブテニル−４−トリメチルシリルピペラジン、１−ブテニル−４−トリエチルシリルピペラジン、１−ブテニル−４−ｔ−ブチルジメチルシリルピペラジン、１−ブテニル−４−トリイソプロピルシリルピペラジンが例示される。 Specific examples of the compound represented by the general formula (2) include 1-vinyl-4-trimethylsilylpiperazine, 1-vinyl-4-triethylsilylpiperazine, 1-vinyl-4-t-butyldimethylsilylpiperazine, 1-vinyl-4-triisopropylsilylpiperazine, 1-allyl-4-trimethylsilylpiperazine, 1-allyl-4-triethylsilylpiperazine, 1-allyl-4-t-butyldimethylsilylpiperazine, 1-allyl-4-tri Isopropylsilylpiperazine, 1-methallyl-4-trimethylsilylpiperazine, 1-methallyl-4-triethylsilylpiperazine, 1-methallyl-4-tert-butyldimethylsilylpiperazine, 1-methallyl-4-triisopropylsilylpiperazine, 1-butenyl -4-trimethylsilyl Perazine, 1-butenyl-4-triethylsilyl piperazine, 1-butenyl -4-t-butyldimethylsilyl piperazine, 1-butenyl-4-triisopropylsilyl piperazine is exemplified.
上記反応で用いられる一般式（３）で示されるハイドロジェンシラン化合物としては、具体的には、トリメトキシシラン、メチルジメトキシシラン、ジメチルメトキシシラン、トリエトキシシラン、メチルジエトキシシラン、ジメチルエトキシシラン等が例示される。 Specific examples of the hydrogensilane compound represented by the general formula (3) used in the above reaction include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, and the like. Is exemplified.
一般式（２）で示される化合物と、一般式（３）で示されるハイドロジェンシラン化合物の配合比は特に限定されないが、反応性、生産性の点から、一般式（２）で示される化合物１モルに対し、一般式（３）で表されるハイドロジェンシラン化合物０．５〜２モル、特に０．８〜１．２モルの範囲が好ましい。 The compounding ratio of the compound represented by the general formula (2) and the hydrogensilane compound represented by the general formula (3) is not particularly limited, but from the viewpoint of reactivity and productivity, the compound represented by the general formula (2). The range of 0.5-2 mol, especially 0.8-1.2 mol of the hydrogen silane compound represented by the general formula (3) is preferred with respect to 1 mol.
上記反応で用いられる白金触媒としては、塩化白金酸、塩化白金酸のアルコール溶液、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエン又はキシレン溶液、テトラキストリフェニルホスフィン白金、ジクロロビストリフェニルホスフィン白金、ジクロロビスアセトニトリル白金、ジクロロビスベンゾニトリル白金、ジクロロシクロオクタジエン白金等が例示される。 Examples of the platinum catalyst used in the above reaction include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a toluene-1, xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, tetrakistri. Examples include phenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, and the like.
白金触媒の使用量は特に限定されないが、反応性、生産性の点から一般式（２）で示される化合物１モルに対し、０．０００００１〜０．０１モル、特に０．００００１〜０．００１モルの範囲が好ましい。 Although the usage-amount of a platinum catalyst is not specifically limited, 0.000001-0.01 mol with respect to 1 mol of compounds shown by General formula (2) from the point of reactivity and productivity, especially 0.00001-0.001. A molar range is preferred.
上記反応の反応温度は特に限定されないが、０〜１２０℃、特に２０〜１００℃が好ましく、反応時間は１〜２０時間、特に１〜１０時間が好ましい。 Although the reaction temperature of the above reaction is not particularly limited, it is preferably 0 to 120 ° C, particularly preferably 20 to 100 ° C, and the reaction time is preferably 1 to 20 hours, particularly preferably 1 to 10 hours.
なお、上記反応は無溶媒でも進行するが、溶媒を用いることもできる。用いられる溶媒としては、ペンタン、ヘキサン、シクロヘキサン、ヘプタン、イソオクタン、ベンゼン、トルエン、キシレン等の炭化水素系溶媒、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド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例示される。これらの溶媒は１種を単独で使用してもよく、あるいは２種以上を混合して使用してもよい。 In addition, although the said reaction advances even without a solvent, a solvent can also be used. Solvents used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and ester solvents such as ethyl acetate and butyl acetate. And aprotic polar solvents such as acetonitrile and N, N-dimethylformamide, and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.
また、本発明における上記一般式（１）で示される保護されたピペラジノ基を有するオルガノキシシラン化合物の製造法として、下記一般式（４）
（式中、Ｒは炭素数１〜１０の直鎖状又は分岐状の２価炭化水素基、Ｒ1は炭素数１〜１０の１価炭化水素基、ｎは０、１又は２である。）
で示される化合物をＲ2Ｒ3Ｒ4Ｓｉ−基（Ｒ2、Ｒ3、Ｒ4は上記と同様である。）を有するシリル化剤によりシリル化する方法も例示される。
Moreover, as a manufacturing method of the organoxysilane compound which has the protected piperazino group shown by the said General formula (1) in this invention, following General formula (4)
(In the formula, R is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is 0, 1 or 2. )
A method of silylating the compound represented by the above with a silylating agent having an R 2 R 3 R 4 Si— group (R 2 , R 3 and R 4 are the same as described above) is also exemplified.
上記一般式（４）で示される化合物としては、具体的には、１−［１−（トリメトキシシリル）メチル］ピペラジン、１−［１−（メチルジメトキシシリル）メチル］ピペラジン、１−［１−（ジメチルメトキシシリル）メチル］ピペラジン、１−［１−（トリエトキシシリル）メチル］ピペラジン、１−［１−（メチルジエトキシシリル）メチル］ピペラジン、１−［１−（ジメチルエトキシシリル）メチル］ピペラジン、１−［２−（トリメトキシシリル）エチル］ピペラジン、１−［２−（メチルジメトキシシリル）エチル］ピペラジン、１−［２−（ジメチルメトキシシリル）エチル］ピペラジン、１−［２−（トリエトキシシリル）エチル］ピペラジン、１−［２−（メチルジエトキシシリル）エチル］ピペラジン、１−［２−（ジメチルエトキシシリル）エチル］ピペラジン、１−［３−（トリメトキシシリル）プロピル］ピペラジン、１−［３−（メチルジメトキシシリル）プロピル］ピペラジン、１−［３−（ジメチルメトキシシリル）プロピル］ピペラジン、１−［３−（トリエトキシシリル）プロピル］ピペラジン、１−［３−（メチルジエトキシシリル）プロピル］ピペラジン、１−［３−（ジメチルエトキシシリル）プロピル］ピペラジン、１−［３−（トリメトキシシリル）−２−メチルプロピル］ピペラジン、１−［３−（メチルジメトキシシリル）−２−メチルプロピル］ピペラジン、１−［３−（ジメチルメトキシシリル）−２−メチルプロピル］ピペラジン、１−［３−（トリエトキシシリル）−２−メチルプロピル］ピペラジン、１−［３−（メチルジエトキシシリル）−２−メチルプロピル］ピペラジン、１−［３−（ジメチルエトキシシリル）−２−メチルプロピル］ピペラジン、１−［４−（トリメトキシシリル）ブチル］ピペラジン、１−［４−（メチルジメトキシシリル）ブチル］ピペラジン、１−［４−（ジメチルメトキシシリル）ブチル］ピペラジン、１−［４−（トリエトキシシリル）ブチル］ピペラジン、１−［４−（メチルジエトキシシリル）ブチル］ピペラジン、１−［４−（ジメチルエトキシシリル）ブチル］ピペラジン等が例示される。 Specific examples of the compound represented by the general formula (4) include 1- [1- (trimethoxysilyl) methyl] piperazine, 1- [1- (methyldimethoxysilyl) methyl] piperazine, and 1- [1. -(Dimethylmethoxysilyl) methyl] piperazine, 1- [1- (triethoxysilyl) methyl] piperazine, 1- [1- (methyldiethoxysilyl) methyl] piperazine, 1- [1- (dimethylethoxysilyl) methyl ] Piperazine, 1- [2- (trimethoxysilyl) ethyl] piperazine, 1- [2- (methyldimethoxysilyl) ethyl] piperazine, 1- [2- (dimethylmethoxysilyl) ethyl] piperazine, 1- [2- (Triethoxysilyl) ethyl] piperazine, 1- [2- (methyldiethoxysilyl) ethyl] piperazine, 1- [2- ( Methylethoxysilyl) ethyl] piperazine, 1- [3- (trimethoxysilyl) propyl] piperazine, 1- [3- (methyldimethoxysilyl) propyl] piperazine, 1- [3- (dimethylmethoxysilyl) propyl] piperazine, 1- [3- (triethoxysilyl) propyl] piperazine, 1- [3- (methyldiethoxysilyl) propyl] piperazine, 1- [3- (dimethylethoxysilyl) propyl] piperazine, 1- [3- (tri Methoxysilyl) -2-methylpropyl] piperazine, 1- [3- (methyldimethoxysilyl) -2-methylpropyl] piperazine, 1- [3- (dimethylmethoxysilyl) -2-methylpropyl] piperazine, 1- [ 3- (triethoxysilyl) -2-methylpropyl] piperazine, 1- [3- Methyldiethoxysilyl) -2-methylpropyl] piperazine, 1- [3- (dimethylethoxysilyl) -2-methylpropyl] piperazine, 1- [4- (trimethoxysilyl) butyl] piperazine, 1- [4- (Methyldimethoxysilyl) butyl] piperazine, 1- [4- (dimethylmethoxysilyl) butyl] piperazine, 1- [4- (triethoxysilyl) butyl] piperazine, 1- [4- (methyldiethoxysilyl) butyl] Examples include piperazine and 1- [4- (dimethylethoxysilyl) butyl] piperazine.
上記反応で用いられるシリル化剤としては、トリメチルクロロシラン、トリメチルブロモシラン、トリメチルヨードシラン、トリエチルクロロシラン、ｔ−ブチルジメチルクロロシラン、トリイソプロピルクロロシラン等のＲ2Ｒ3Ｒ4ＳｉＸ（Ｒ2、Ｒ3、Ｒ4は上記の通りであり、Ｘは塩素原子等のハロゲン原子）で表されるトリオルガノハロシラン化合物、ヘキサメチルジシラザン、ヘキサエチルジシラザン等の（Ｒ2Ｒ3Ｒ4Ｓｉ）2ＮＨ（Ｒ2、Ｒ3、Ｒ4は上記の通り）で表されるジシラザン、その他のシラザン化合物等が例示される。 Examples of the silylating agent used in the above reaction include R 2 R 3 R 4 SiX (R 2 , R 3 , R 3 R 3 R 4 SiX, trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, triethylchlorosilane, t-butyldimethylchlorosilane, triisopropylchlorosilane, and the like. R 4 is as described above, and X is a (R 2 R 3 R 4 Si) 2 NH such as a triorganohalosilane compound represented by a halogen atom such as a chlorine atom), hexamethyldisilazane, hexaethyldisilazane, etc. Examples thereof include disilazane represented by (R 2 , R 3 and R 4 are as described above) and other silazane compounds.
一般式（４）で示される化合物と、シリル化剤との配合比は特に限定されないが、反応性、生産性の点から、一般式（４）で示される化合物１モルに対し、シリル化剤を、シリル基のモル数で０．５〜４モル、特に０．８〜２モルの範囲が好ましい。 The compounding ratio of the compound represented by the general formula (4) and the silylating agent is not particularly limited. However, from the viewpoint of reactivity and productivity, the silylating agent is used with respect to 1 mol of the compound represented by the general formula (4). Is preferably in the range of 0.5 to 4 mol, particularly 0.8 to 2 mol in terms of the number of moles of silyl group.
上記反応の反応温度は特に限定されないが、０〜１５０℃、特に２０〜１３０℃が好ましく、反応時間は１〜２０時間、特に１〜１０時間が好ましい。 Although the reaction temperature of the above reaction is not particularly limited, it is preferably 0 to 150 ° C., particularly preferably 20 to 130 ° C., and the reaction time is preferably 1 to 20 hours, particularly preferably 1 to 10 hours.
なお、上記反応は無溶媒でも進行するが、溶媒を用いることもできる。用いられる溶媒としては、ペンタン、ヘキサン、シクロヘキサン、ヘプタン、イソオクタン、ベンゼン、トルエン、キシレン等の炭化水素系溶媒、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド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例示される。これらの溶媒は１種を単独で使用してもよく、あるいは２種以上を混合して使用してもよい。 In addition, although the said reaction advances even without a solvent, a solvent can also be used. Solvents used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and ester solvents such as ethyl acetate and butyl acetate. And aprotic polar solvents such as acetonitrile and N, N-dimethylformamide, and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.
以下、実施例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
［合成例１］ １−アリル−４−トリメチルシリルピペラジンの合成
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、アリルピペラジン１２６．２ｇ（１．０モル）、トリエチルアミン１１１．３ｇ（１．１モル）、トルエン３００ｍｌを仕込み、トリメチルクロロシラン１１９．５ｇ（１．１モル）を２０〜３０℃で１時間かけて滴下し、その温度で１時間撹拌した。生成した塩を濾過により除去し、濾液を蒸留した。１−アリル−４−トリメチルシリルピペラジンを沸点８２℃／１ｋＰａの留分として１６８．９ｇ得た（収率８５％）。
[Synthesis Example 1] Synthesis of 1-allyl-4-trimethylsilylpiperazine In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 126.2 g (1.0 mol) of allylpiperazine and 111.3 g of triethylamine (1 0.1 mol) and 300 ml of toluene were charged, and 119.5 g (1.1 mol) of trimethylchlorosilane was added dropwise at 20 to 30 ° C. over 1 hour, followed by stirring at that temperature for 1 hour. The formed salt was removed by filtration and the filtrate was distilled. 168.9 g of 1-allyl-4-trimethylsilylpiperazine was obtained as a fraction having a boiling point of 82 ° C./1 kPa (yield: 85%).
［実施例１］ １−［３−（トリエトキシシリル）プロピル］−４−トリメチルシリルピペラジンの合成
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、１−アリル−４−トリメチルシリルピペラジン９９．２ｇ（０．５モル）、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエン溶液（白金含量３質量％）０．６５ｇを仕込み、７０℃に加熱した。内温が安定した後、トリエトキシシラン８２．２ｇ（０．５モル）を４時間かけて滴下し、その温度で１時間撹拌した。反応液を蒸留し、沸点１１９〜１２２℃／５０Ｐａの留分を１３７．５ｇ得た。
[Example 1] Synthesis of 1- [3- (triethoxysilyl) propyl] -4-trimethylsilylpiperazine In a flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer, 1-allyl-4-trimethylsilylpiperazine 99 was prepared. .2 g (0.5 mol) and 0.65 g of a platinum solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル（重クロロホルム溶媒）、ＩＲスペクトルを測定した。質量スペクトルの結果を下記に示す。また、図１には1Ｈ−ＮＭＲスペクトルのチャート、図２にはＩＲスペクトルのチャートを示した。
質量スペクトル
ｍ／ｚ ３６２， ３４７， １７１， １２８， ７３
以上の結果より、得られた化合物は１−［３−（トリエトキシシリル）プロピル］−４−トリメチルシリルピペラジンであることが確認された。
The mass spectrum, 1 H-NMR spectrum (deuterated chloroform solvent) and IR spectrum of the obtained fraction were measured. The results of the mass spectrum are shown below. FIG. 1 shows a chart of 1 H-NMR spectrum, and FIG. 2 shows a chart of IR spectrum.
Mass spectrum m / z 362, 347, 171, 128, 73
From the above results, it was confirmed that the obtained compound was 1- [3- (triethoxysilyl) propyl] -4-trimethylsilylpiperazine.
［実施例２］ １−［３−（メチルジエトキシシリル）プロピル］−４−トリメチルシリルピペラジンの合成
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、１−アリル−４−トリメチルシリルピペラジン９９．２ｇ（０．５モル）、白金−１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体のトルエン溶液（白金含量３質量％）０．６５ｇを仕込み、７０℃に加熱した。内温が安定した後、メチルジエトキシシラン６７．１ｇ（０．５モル）を４時間かけて滴下し、その温度で１時間撹拌した。反応液を蒸留し、沸点１０５〜１０６℃／３０Ｐａの留分を１３０．８ｇ得た。
Example 2 Synthesis of 1- [3- (methyldiethoxysilyl) propyl] -4-trimethylsilylpiperazine In a flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer, 1-allyl-4-trimethylsilylpiperazine 99.2 g (0.5 mol) and 0.65 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル（重クロロホルム溶媒）、ＩＲスペクトルを測定した。質量スペクトルの結果を下記に示す。また、図３には1Ｈ−ＮＭＲスペクトルのチャート、図４にはＩＲスペクトルのチャートを示した。
質量スペクトル
ｍ／ｚ ３３２， ３１７， １７１， １２８， ７３
以上の結果より、得られた化合物は１−［３−（メチルジエトキシシリル）プロピル］−４−トリメチルシリルピペラジンであることが確認された。
The mass spectrum, 1 H-NMR spectrum (deuterated chloroform solvent) and IR spectrum of the obtained fraction were measured. The results of the mass spectrum are shown below. FIG. 3 shows a chart of 1 H-NMR spectrum, and FIG. 4 shows a chart of IR spectrum.
Mass spectrum m / z 332, 317, 171, 128, 73
From the above results, it was confirmed that the obtained compound was 1- [3- (methyldiethoxysilyl) propyl] -4-trimethylsilylpiperazine.
［実施例３］ １−［３−（トリエトキシシリル）プロピル］ピペラジンを原料として用いる１−［３−（トリエトキシシリル）プロピル］−４−トリメチルシリルピペラジンの合成
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、１−［３−（トリエトキシシリル）プロピル］ピペラジン５８．１ｇ（０．２モル）、トリエチルアミン２２．３ｇ（０．２２モル）、トルエン６０ｍｌを仕込み、４０℃に加熱した。内温が安定した後、トリメチルクロロシラン２２．８ｇ（０．２１モル）を１時間かけて滴下し、その温度で１時間撹拌した。生成した塩を濾過により除去し、濾液を蒸留した。沸点１１９〜１２０℃／５０Ｐａの留分を５９．５ｇ得た。
[Example 3] Synthesis of 1- [3- (triethoxysilyl) propyl] -4-trimethylsilylpiperazine using 1- [3- (triethoxysilyl) propyl] piperazine as a raw material Stirrer, reflux, dropping funnel and A flask equipped with a thermometer was charged with 58.1 g (0.2 mol) of 1- [3- (triethoxysilyl) propyl] piperazine, 22.3 g (0.22 mol) of triethylamine, and 60 ml of toluene. Heated. After the internal temperature was stabilized, 22.8 g (0.21 mol) of trimethylchlorosilane was added dropwise over 1 hour and stirred at that temperature for 1 hour. The formed salt was removed by filtration and the filtrate was distilled. 59.5 g of a fraction having a boiling point of 119 to 120 ° C./50 Pa was obtained.
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル、ＩＲスペクトルを測定したところ、実施例１で得られた化合物のスペクトルと同じであり、得られた化合物は１−［３−（トリエトキシシリル）プロピル］−４−トリメチルシリルピペラジンであることが確認された。 When the mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured, it was the same as the spectrum of the compound obtained in Example 1, and the obtained compound was 1- [3- (triethoxy Silyl) propyl] -4-trimethylsilylpiperazine.
Claims (3)
（式中、Ｒは炭素数１〜１０の直鎖状又は分岐状の２価炭化水素基、Ｒ1、Ｒ2、Ｒ3、Ｒ4は炭素数１〜１０の１価炭化水素基、ｎは０、１又は２である。）
で示される保護されたピペラジノ基を有するオルガノキシシラン化合物。 The following general formula (1)
(In the formula, R is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, R 1 , R 2 , R 3 and R 4 are monovalent hydrocarbon groups having 1 to 10 carbon atoms, n Is 0, 1 or 2.)
An organoxysilane compound having a protected piperazino group represented by
（式中、Ｒ5は水素原子又はメチル基であり、Ｒ5が水素原子の場合、Ｒ’は炭素数１〜８の直鎖状又は分岐状の２価炭化水素基、Ｒ5がメチル基の場合、Ｒ’は炭素数１〜７の直鎖状又は分岐状の２価炭化水素基であり、Ｒ2、Ｒ3、Ｒ4は請求項１で定義した通りである。）
で示される化合物と、下記一般式（３）
ＨＳｉ（ＣＨ3）n（ＯＲ1）3-n （３）
（式中、Ｒ1、ｎは請求項１で定義した通りである。）
で示されるハイドロジェンシラン化合物とを白金触媒下で反応させることを特徴とする請求項１記載の保護されたピペラジノ基を有するオルガノキシシラン化合物の製造方法。 The following general formula (2)
(In the formula, R 5 is a hydrogen atom or a methyl group, and when R 5 is a hydrogen atom, R ′ is a linear or branched divalent hydrocarbon group having 1 to 8 carbon atoms, and R 5 is a methyl group. In this case, R ′ is a linear or branched divalent hydrocarbon group having 1 to 7 carbon atoms, and R 2 , R 3 and R 4 are as defined in claim 1).
And a compound represented by the following general formula (3)
HSi (CH 3 ) n (OR 1 ) 3-n (3)
(Wherein R 1 and n are as defined in claim 1).
The method for producing an organoxysilane compound having a protected piperazino group according to claim 1, wherein the hydrogensilane compound is reacted with a hydrogensilane compound represented by formula (1) under a platinum catalyst.
（式中、Ｒ、Ｒ1、ｎは請求項１で定義した通りである。）
で示される化合物をＲ2Ｒ3Ｒ4Ｓｉ−基（Ｒ2、Ｒ3、Ｒ4は請求項１で定義した通りである。）を有するシリル化剤によってシリル化することを特徴とする請求項１記載の保護されたピペラジノ基を有するオルガノキシシラン化合物の製造方法。 The following general formula (4)
(Wherein R, R 1 and n are as defined in claim 1).
A compound represented by the above formula is silylated with a silylating agent having an R 2 R 3 R 4 Si— group (R 2 , R 3 , R 4 are as defined in claim 1). Item 2. A process for producing an organoxysilane compound having a protected piperazino group according to Item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006109347A JP4771075B2 (en) | 2005-04-20 | 2006-04-12 | Organoxysilane compound having protected piperazino group and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005122659 | 2005-04-20 | ||
| JP2005122659 | 2005-04-20 | ||
| JP2006109347A JP4771075B2 (en) | 2005-04-20 | 2006-04-12 | Organoxysilane compound having protected piperazino group and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006321789A true JP2006321789A (en) | 2006-11-30 |
| JP4771075B2 JP4771075B2 (en) | 2011-09-14 |
Family
ID=37541716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006109347A Active JP4771075B2 (en) | 2005-04-20 | 2006-04-12 | Organoxysilane compound having protected piperazino group and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4771075B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012025788A (en) * | 2010-06-24 | 2012-02-09 | Shin-Etsu Chemical Co Ltd | Adhesive composition containing organosilicon compound having piperazinyl group |
| JP2013256477A (en) * | 2012-06-14 | 2013-12-26 | Shin-Etsu Chemical Co Ltd | Method for producing organoxysilane compound having piperazinyl group and piperazine compound |
| JP2015098459A (en) * | 2013-11-20 | 2015-05-28 | 信越化学工業株式会社 | Nitrogen-containing organoxy silane compound-containing composition, and preparation method thereof |
| JP2016084314A (en) * | 2014-10-28 | 2016-05-19 | 信越化学工業株式会社 | Method for producing n-silyl piperazine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04149183A (en) * | 1990-10-15 | 1992-05-22 | Rikagaku Kenkyusho | Bactericidal silane compound, its production, and suppressing agent of disease by microbes and suppressing method of disease by microbes |
| JPH04214470A (en) * | 1990-02-07 | 1992-08-05 | Dow Corning Ltd | Treatment of textile materials |
| JP2000212187A (en) * | 1999-01-20 | 2000-08-02 | Shin Etsu Chem Co Ltd | Organosilicon compound and its production |
| JP2002161099A (en) * | 2000-10-05 | 2002-06-04 | Consortium Elektrochem Ind Gmbh | Cyclic silazane, method for manufacturing the same and method for manufacturing disiloxane having bisaminoalkyl terminal |
-
2006
- 2006-04-12 JP JP2006109347A patent/JP4771075B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04214470A (en) * | 1990-02-07 | 1992-08-05 | Dow Corning Ltd | Treatment of textile materials |
| JPH04149183A (en) * | 1990-10-15 | 1992-05-22 | Rikagaku Kenkyusho | Bactericidal silane compound, its production, and suppressing agent of disease by microbes and suppressing method of disease by microbes |
| JP2000212187A (en) * | 1999-01-20 | 2000-08-02 | Shin Etsu Chem Co Ltd | Organosilicon compound and its production |
| JP2002161099A (en) * | 2000-10-05 | 2002-06-04 | Consortium Elektrochem Ind Gmbh | Cyclic silazane, method for manufacturing the same and method for manufacturing disiloxane having bisaminoalkyl terminal |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012025788A (en) * | 2010-06-24 | 2012-02-09 | Shin-Etsu Chemical Co Ltd | Adhesive composition containing organosilicon compound having piperazinyl group |
| JP2013256477A (en) * | 2012-06-14 | 2013-12-26 | Shin-Etsu Chemical Co Ltd | Method for producing organoxysilane compound having piperazinyl group and piperazine compound |
| JP2015098459A (en) * | 2013-11-20 | 2015-05-28 | 信越化学工業株式会社 | Nitrogen-containing organoxy silane compound-containing composition, and preparation method thereof |
| JP2016084314A (en) * | 2014-10-28 | 2016-05-19 | 信越化学工業株式会社 | Method for producing n-silyl piperazine |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4771075B2 (en) | 2011-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7053233B2 (en) | Silane compound having at least two protected functional groups and method for preparing the same | |
| JP4771075B2 (en) | Organoxysilane compound having protected piperazino group and method for producing the same | |
| JP5630458B2 (en) | Organoxysilane compound having secondary amino group protected by silyl group and method for producing the same | |
| JP5494233B2 (en) | Cyclic silazane compound having carboxylic acid ester group and method for producing the same | |
| JP6052140B2 (en) | Organoxysilane compound having bissilylamino group and process for producing the same | |
| US7569691B2 (en) | Protected piperazino group-bearing organoxysilane compound and making method | |
| EP2289898B1 (en) | Melamine-functional organosilicon compound and making method | |
| JP5359185B2 (en) | Organosilicon compound having amino group and protected hydroxyl group and method for producing the same | |
| JP4662042B2 (en) | Bisorganoxysilane compound having amino group protected by silyl group and method for producing the same | |
| JP6011475B2 (en) | Sulfur-containing organoxysilane compound having bissilylamino group and process for producing the same | |
| JP5440389B2 (en) | Silane compound having amino group and carboxylate group protected by silyl group and method for producing the same | |
| JP4433168B2 (en) | Organoxysilane compounds having protected hydroxyl groups | |
| JP4336970B2 (en) | Silane compound having protected carboxyl group and method for producing the same | |
| TWI635119B (en) | Nitrogen-containing organoxysilane compound composition and making method | |
| JP5644515B2 (en) | Unsaturated bond-containing silyl group-protected amino acid compound and method for producing the same | |
| JP5754272B2 (en) | Carboxylic acid silyl ester compound having bulky substituent and method for producing the same | |
| JP6879260B2 (en) | Organosilicon compounds having a glycoluril ring and methods for producing them | |
| JP3124910B2 (en) | Cyclotrisiloxane and method for producing the same | |
| TWI626244B (en) | Silyl-protected nitrogen-containing cyclic compounds and making method | |
| JP2011162496A (en) | Organic silicon compound having amino group protected with silyl group and method for producing the same | |
| JP4420150B2 (en) | Method for synthesizing 3- (2-oxo-1-pyrrolidinyl) propylsilanes | |
| JP2017141180A (en) | Bis-silyl compound and method for producing the same | |
| JPS62149686A (en) | Vinyltrialkoxysilane derivative | |
| JP2002193979A (en) | New cyclic organosilicon compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080225 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110223 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110525 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110607 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140701 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4771075 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |