JP2004277417A - シロキサン類,シラノール類及びシラン類,並びにその製造方法 - Google Patents
シロキサン類,シラノール類及びシラン類,並びにその製造方法 Download PDFInfo
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- -1 Siloxanes Chemical class 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 16
- 150000004819 silanols Chemical class 0.000 title description 9
- 150000004756 silanes Chemical class 0.000 title description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 54
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 48
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 47
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 40
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 38
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 34
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 32
- 125000006178 methyl benzyl group Chemical group 0.000 claims abstract description 21
- 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 claims abstract description 21
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 19
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 16
- 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 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000077 silane Inorganic materials 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 11
- KDBDXHQLWCNIFG-UHFFFAOYSA-N 1,2-dimethylcyclohexa-3,5-diene-1,2-diol Chemical group CC1(O)C=CC=CC1(C)O KDBDXHQLWCNIFG-UHFFFAOYSA-N 0.000 claims description 5
- NMEXRVUAXZJVJZ-UHFFFAOYSA-N 2-methylnaphthalene-1,8-diol Chemical compound C1=CC=C(O)C2=C(O)C(C)=CC=C21 NMEXRVUAXZJVJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 150000003961 organosilicon compounds Chemical class 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- QHOQHJPRIBSPCY-UHFFFAOYSA-N pirimiphos-methyl Chemical compound CCN(CC)C1=NC(C)=CC(OP(=S)(OC)OC)=N1 QHOQHJPRIBSPCY-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000011914 asymmetric synthesis Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004296 chiral HPLC Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- OCXPCSGIIJESOA-UHFFFAOYSA-N tert-butyl-dichloro-phenylsilane Chemical compound CC(C)(C)[Si](Cl)(Cl)C1=CC=CC=C1 OCXPCSGIIJESOA-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 0 C1OOC*=C1 Chemical compound C1OOC*=C1 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 3
- 239000012280 lithium aluminium hydride Substances 0.000 description 3
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SHAHPWSYJFYMRX-GDLCADMTSA-N (2S)-2-(4-{[(1R,2S)-2-hydroxycyclopentyl]methyl}phenyl)propanoic acid Chemical compound C1=CC([C@@H](C(O)=O)C)=CC=C1C[C@@H]1[C@@H](O)CCC1 SHAHPWSYJFYMRX-GDLCADMTSA-N 0.000 description 1
- SYTBZMRGLBWNTM-SNVBAGLBSA-N (R)-flurbiprofen Chemical compound FC1=CC([C@H](C(O)=O)C)=CC=C1C1=CC=CC=C1 SYTBZMRGLBWNTM-SNVBAGLBSA-N 0.000 description 1
- RYHGQTREHREIBC-UHFFFAOYSA-N 3,4-dimethylbenzene-1,2-diol Chemical group CC1=CC=C(O)C(O)=C1C RYHGQTREHREIBC-UHFFFAOYSA-N 0.000 description 1
- 241000349731 Afzelia bipindensis Species 0.000 description 1
- 238000006027 Birch reduction reaction Methods 0.000 description 1
- SVQYKJJIKPLSBU-UHFFFAOYSA-N CC(C)(C)C(C)(C1=CC=CC=C1CO)O[SiH2]C2=CC=CC=C2 Chemical compound CC(C)(C)C(C)(C1=CC=CC=C1CO)O[SiH2]C2=CC=CC=C2 SVQYKJJIKPLSBU-UHFFFAOYSA-N 0.000 description 1
- IBSSHWOSPVNKSE-UHFFFAOYSA-N CCCCC(C(C)(C)C)(C1=C(C(CO)=CC=C2)C2=CC=C1)O[SiH2]C1=CC=CC=C1 Chemical compound CCCCC(C(C)(C)C)(C1=C(C(CO)=CC=C2)C2=CC=C1)O[SiH2]C1=CC=CC=C1 IBSSHWOSPVNKSE-UHFFFAOYSA-N 0.000 description 1
- XLSSWOHDNCIRSO-UHFFFAOYSA-N CCCCC(C1=CC=CC=C1CO)(C(C)(C)C)O[SiH2]C2=CC=CC=C2 Chemical compound CCCCC(C1=CC=CC=C1CO)(C(C)(C)C)O[SiH2]C2=CC=CC=C2 XLSSWOHDNCIRSO-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- NVQOFWZLYDVFMU-UHFFFAOYSA-N azane;oxolane Chemical compound N.C1CCOC1 NVQOFWZLYDVFMU-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229940088623 biologically active substance Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- ZEFAZUWHBLWCAN-GFCCVEGCSA-N tert-butyl-methyl-phenylsilane Chemical compound C(C)(C)(C)[Si@@H](C1=CC=CC=C1)C ZEFAZUWHBLWCAN-GFCCVEGCSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
【効果】 汎用性が高く様々な光学活性有機ケイ素化合物へと誘導可能であり,市販の化合物から2工程で合成できるので工業的な利用に展開することができる。
【選択図】 図1
Description
(1)アキラルシロキサンの合成
ジハロシランとして市販のtert−ブチルフェニルジクロロシランを用い,アルコールとしてo−ジヒドロキシキシレンを用いた。tert−ブチルフェニルジクロロシラン(1a)に対してTHF中でイミダゾールを作用させ,60℃に加熱した後,その温度を保った状態でo−ジヒドロキシキシレンのTHF溶液をゆっくりと滴下することにより,1工程でアキラルなシロキサン2"aを調製した(化22)。
7−tert−ブチル−7−フェニル5,9−ジヒドロ−6,8−ジオキサ−7−シランベンゾヘプタン(2"a)
1H NMR(300MHz,CD3COCD3)δ7.68−7.65(m,2H),7.46−7.40(m,3H),7.39−7.23(m,4H),5.13(d,J=12.9Hz,2H),4.79(d,J=12.6Hz,2H),0.82(s,9H).
13C NMR(300MHz,CD3COCD3)δ140.82,135.87,132.89,130.92,130.14,129.08,128.80,66.57,25.66,18.20.
IR(neat,cm-1)2931,2857,1470,1430,1067,1040,821,698.
上記アルコールとして,1,8−ジヒドロキシメチルナフタレンを用いて同様の実験を行った。物性データは以下の通りであった。
1H NMR(300MHz,CDCl3) δ7.87−7.83(m,2H),7.74−7.70(m,2H),7.56−7.53(m,2H),7.45−7.39(m,5H),5.65(d,J=12.9Hz,2H),5.07(d,12.9Hz,2H),0.82(s,9H)
13C NMR(300MHz,CDCl3)δ135.94,135.80,135.45,132.52,131.89,130.92,130.26,130.08,127.88,125.21,68.41,25.46,17.41
IR(neat,cm−1) 1112,1051,836,782,739,701
(2)アキラルシロキサンのエナンチオ選択的求核置換反応
アキラルシロキサンとして上記第一工程で得られた環状シロキサン2"aを用い,不斉配位剤6として光学活性ビスオキサゾリン6aを用い,アルキルリチウムとしてnBuLiを用いた。原料となるベンゾヘプタンの骨格を有するシロキサン2"aと触媒量もしくは当量の光学活性ビスオキサゾリン6a(10mol%)のヘキサン溶液に対し,−40℃下で過剰量のnBuLiをゆっくり作用させると,ケイ素原子上での求核置換反応がエナンチオ選択的に進行し,対応するシロキサン3'''aが収率83%,光学純度53%eeで得られた(化23)。
[2−(n−ブチル−tert−ブチルフェニルシラニルオキシメチル)フェニル]メタノール(3'''a)
1H NMR(300MHz,CDCl3)δ7.55−7.51(m,2H),7.42−7.31(m,7H),4.89(s,2H),4.74(dd,J=6.3,3.0Hz,2H),3.13(t,J=6.3Hz,1H),1.50−1.42(m,4H),1,15−0.96(m,2H),0.94(s,9H),0.89(t,7.2Hz,3H)
13C NMR(300MHz,CDCl3)δ139.72,138.56,134.87,134.20,129.64,129.24,128.74,128.32,128.06,127.80,65.03,63.96,26.98,26.55,25.88,18.88,13.74,10.87.
IR(neat,cm-1)3392,3069,2928,2857,1462,1428,1112,1081,824,702.
53%ee:[α]27 D+2.86(c2.03,CHCl3).
キラルHPLC分析:CHIRALPAK AD−H,hexane:iPrOH=200:1,flow 0.7mL/min,press.23kg/cm-1,Rt=31.58min(minor isomer),33.48min(major isomer)
上記アルキルリチウムとしてMeLiを用いて同様の試験を行った。物性データは以下のとおりであった。
[2−(tert−ブチルメチルフェニルシラニルオキシメチル)フェニル]メタノール(3"a)
1H NMR(300MHz,CDCl3)δ7.56−7.53(m,2H),7.41−7.26(m,7H),4.80(s,2H),4.72(d,J=6.3Hz,2H),3.14(t,J=6.3Hz,1H),0.93(s,9H),0.46(s,3H)
13C NMR(300MHz,CDCl3)δ139.69,138.32,134.67,134.56,129.70,129.22,128.79,128.29,127.99,127.73,64.71,64.01,26.02,18.39,−6.95.
IR(neat,cm-1)3392,2930,2857,1472,1428,1255,1113,1077,826,736
(R)−enriched(21%ee):[α]25 D+5.43(c1.08,CHCl3).
キラルHPLC分析:CHIRALCEL OD−H,hexane:iPrOH=100:1,flow 0.6mL/min,Press.20kg/cm-1,Rt=35.03min(R体),45.35min(S体)
上記アキラルシロキサンとして環状シロキサン2’’’aを,アルキルリチウムとしてノルマルブチルリチウムを用い同様の試験を行った結果,シロキサン3’’’aを収率62%,光学純度76%eeで得た。物性データは以下の通りであった。
[8−(n−ブチル−tert−ブチルフェニルシラニルオキシメチル)ナフタレン−1−イル]−メタノール(3’’’a)
1H NMR(300MHz,CDCl3)δ7.88−7.82(m,2H),7.59−7.52(m,4H),7.47−7.34(m,5H),5.50(s,2H)5.26(d,J=5.4Hz,2H),2.87(t,J=6.0Hz,2H),1.34−1.27(m,4H),1.14−1.08(m,2H),0.938(s,9H),0.835(t,J=6.9Hz,3H)13C NMR(300MHz,CDCl3)δ137.05,136.35,135.75,134.80,134.60,130.38,130.12,129.95,129.36,129.00,127.57,125.16,125.09,67.16,66.87,27.12,26.70,25.93,19.202,13.86,11.27
IR(neat,cm−1) 3392,2928,1601,1471,1427,1171,1110,825,824,771,702
44%ee:[α]26 D+1.00(c,2.90,CHCl3)
キラルHPLC分析:CHIRALPAK AD−H,hexane:iPrOH=100:1,flow 0.6mL/min,press. 17kg/cm−1,Rt=26.6min(minor isomer),29.3min(major isomer)
(3)光学活性シラノールの合成
又,光学活性シロキサン3'''aをBrich還元条件下に付すことで光学活性シラノール4aへと誘導した。すなわち,−78℃下,液体アンモニア−THF混合溶媒にシロキサン3'''aを溶解させた金属リチウムを作用させることで還元的にジヒドロキシキシレン部位を除去し光学純度を損なうことなくシラノール4aを得た(化24)。
1H NMR(300MHz,CDCl3)δ7.59−7.56(m,2H),7.40−7.35(m,3H),1.82(s,1H),1.39−1.30(m,4H),0.94(s,9H),0.87(t,3H)
13C NMR(300MHz,CDCl3)δ136.00,134.25,129.38,127.67,26.69,26.25,25.51,18.54,13.80,11.46
IR(neat,cm-1)3435,2928,2857,1464,1428,1113,823,701
33%ee:[α]27 D−2.66(c1.37,CHCl3)
キラルHPLC分析:CHIRALCEL OD−H,hexane:iPrOH=100:1,flow 0.6mL/min,press.20kg/cm-1,Rt=11.58min(major isomer),13.01min(minor isomer)
(4)光学活性シランの合成
光学活性シロキサン3"aに有機金属反応剤,もしくは金属ヒドリド反応剤を作用させることで光学活性シラン5aへと誘導した。すなわち,室温下,Et2Oに3"aを溶解させ水素化リチウムアルミニウムを作用させることで5aを得た(化25)。尚,この実試験は本願発明の方法によって物性データが既知の化合物5aを合成することにより光学活性シロキサン3"aの立体化学を確認するためのものである。
1H NMR(300MHz,CDCl3)δ7.55−7.52(m,2H),7.39−7.33(m,3H),1.40(q,J=3.9Hz,1H),0.95(s,9H),0.35(d,J=3.9Hz,3H)
13C NMR(300MHz,CDCl3)δ135.44,135.03,129.18,127.59,26.99,16.82,−8.21.
IR(neat,cm-1)3650,2924,2854,2114,1732,1462,1377,1115.
(S)−37(10% ee,Based on[α]20 D −4.1(c6.15,hexane)):[α]27 D +0.426(c3.51,hexane)
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JP2007262025A (ja) * | 2006-03-29 | 2007-10-11 | Yuki Gosei Kogyo Co Ltd | ジアルキルシラノール化合物およびその製造方法 |
JP2013170123A (ja) * | 2012-02-17 | 2013-09-02 | National Institute Of Advanced Industrial Science & Technology | 無水条件におけるシラノールの製造方法 |
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US3542833A (en) * | 1968-08-15 | 1970-11-24 | Dow Corning | Higher alkyl containing methylphenylsilanes |
JPH0311083A (ja) * | 1989-06-08 | 1991-01-18 | Toray Dow Corning Silicone Co Ltd | シリル化剤 |
JPH03505326A (ja) * | 1988-05-19 | 1991-11-21 | シエーリング アクチエンゲゼルシヤフト | 新規ロイコトリエン―b↓4―誘導体、その製造方法および医薬としての使用 |
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US3542833A (en) * | 1968-08-15 | 1970-11-24 | Dow Corning | Higher alkyl containing methylphenylsilanes |
JPH03505326A (ja) * | 1988-05-19 | 1991-11-21 | シエーリング アクチエンゲゼルシヤフト | 新規ロイコトリエン―b↓4―誘導体、その製造方法および医薬としての使用 |
JPH0311083A (ja) * | 1989-06-08 | 1991-01-18 | Toray Dow Corning Silicone Co Ltd | シリル化剤 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2007262025A (ja) * | 2006-03-29 | 2007-10-11 | Yuki Gosei Kogyo Co Ltd | ジアルキルシラノール化合物およびその製造方法 |
JP2013170123A (ja) * | 2012-02-17 | 2013-09-02 | National Institute Of Advanced Industrial Science & Technology | 無水条件におけるシラノールの製造方法 |
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