JPH02240086A - Production of ortholithio-substituted phenylsilane compound - Google Patents
Production of ortholithio-substituted phenylsilane compoundInfo
- Publication number
- JPH02240086A JPH02240086A JP6048589A JP6048589A JPH02240086A JP H02240086 A JPH02240086 A JP H02240086A JP 6048589 A JP6048589 A JP 6048589A JP 6048589 A JP6048589 A JP 6048589A JP H02240086 A JPH02240086 A JP H02240086A
- Authority
- JP
- Japan
- Prior art keywords
- group
- substituted
- compound
- formula
- phenylsilane
- 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 phenylsilane compound Chemical class 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 239000012442 inert solvent Substances 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims 1
- 125000000068 chlorophenyl group Chemical group 0.000 claims 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 abstract description 2
- ZBZJETKIVHSLNR-UHFFFAOYSA-N N'-[[2-(dimethylamino)ethyl-methylamino]-diphenylsilyl]-N,N,N'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)[Si](C1=CC=CC=C1)(C1=CC=CC=C1)N(CCN(C)C)C ZBZJETKIVHSLNR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical class [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LBWUDIILHLQIQJ-UHFFFAOYSA-N (4-chlorophenyl)-methylsilane Chemical compound C[SiH2]C1=CC=C(C=C1)Cl LBWUDIILHLQIQJ-UHFFFAOYSA-N 0.000 description 1
- WWSJRHRWFJXYDC-UHFFFAOYSA-N (4-methoxyphenyl)-diphenylsilane Chemical compound C1=CC(OC)=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 WWSJRHRWFJXYDC-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 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
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、農薬や医薬品などに用いる含ケイ素生理活性
物質として有用なオルト置換フェニルシラン化合物やそ
の誘導体を得るための中間体である、才ルトリチオ置換
フェニルシラン化合物の製造方法に関する。The present invention relates to a method for producing ortho-substituted phenylsilane compounds, which are intermediates for obtaining ortho-substituted phenylsilane compounds and derivatives thereof useful as silicon-containing physiologically active substances used in agricultural chemicals, pharmaceuticals, and the like.
オルト置換シランフェニル化合物は、ａ薬や医薬品など
の含ケイ素生理活性物質として種々の用途が考えられる
化合物である。しかし、この化合物は工業的製造方法が
ないため、上記用途にはあまり利用されていない。Ortho-substituted silamphenyl compounds are compounds that can be used in various ways as silicon-containing physiologically active substances such as a-drugs and pharmaceuticals. However, since there is no industrial production method for this compound, it is not widely used for the above-mentioned purposes.
【発明が解決しようとする課題１
本発明は、種々のオルｌ・置換フェニルシラン化合物誘
導体を得るための中間体となるオルトリチオ置換フェニ
ルシラン化合物を、効率良く選択的に合成する新規な合
成法を提供することを目的とする。
【課題を解決するための手段】
本発明者らはオル１・リチオ置換フェニルシラン化合物
の工業的合成法について鋭意研究を重ねた結果、フエニ
ルシランのケイ素にアミノ基を導入し、これとアルキル
リチウム化合物とを反応させると、ベンゼン環の才ルト
メタル化が高い選択住を持って進行することを見い出し
、本発明を完成するに至った。
即ち、前記の目的を達成するためのオルトリチ才置換フ
エニルシラン化合物の製造方法は、一般で示される化合
物を、不活性溶剤存在下、一般式Ｒ５Ｌｉ
［ ２ ］で示される化合物と混合し、一
般式
で示される化合物を得る方法である。
式中のｊｕｌｌは、例えばメチル基、エチル基などのア
ルキル基２クロ口メチル基、クロロプロビル基などの置
換アルキル基、ビニル基、ブロベニル基などのアルケニ
ル基、トルイル基、アニシル基、クロ口フェニル基など
の置換フェニル基またはフエニル基である。
Ｒ２は、例えばフロロ基、クロロ基、ブロモ基などのハ
ロゲン基、メトキシ基、エトキシ基などのアルコキシ基
、メチル基、エチル基などのアルキル基または水素基で
ある。
Ｒ３およびＲ４は、例えばメチル基、エチル基などのア
ルキル基、σ−Ｎ’Ｎ’−ジメチルアミノエチル基など
の置換アルキル基である。
Ｒ″は例えばアルキル基である。
ｎは０〜２の整数である。
一般式［１］で表わされる化合物は、例えばビス（トＮ
’Ｎ’−ジメチルアミノエチルーメチルアミノ）一ジフ
エニルシラン、トリス（ｊｌ−Ｎ’Ｎ”−ジメチルアミ
ノエチルーメチルアミノ）一フェニルシラン、ビス（δ
一Ｎ’Ｎ’−ジメチルアミノエチルーメチルアミノ）一
ｐ−フロロフェニルーフエニルシラン．ビス（ジメチル
アミノ）〜ｐ−クロロフェニルーメチルシラン、ビス（
ジェチルアミノ）一ｐ−メトキシフエニルーフェニルー
フエニルシラン、ビス（β一Ｎ’Ｎ’−ジメチルアミノ
エチルーメチルアミノ）一フエニルーγ−クロロブ口ビ
ルシランである。
一般式［２］で表わされる化合物としては、例えばメチ
ルリチウム、ｎ−ブチルリチウム、ｔ−ブチルリチウム
が挙げられる。
反応の際に使用する不活性の溶剤は、例えばベンタン、
ヘキサンのような脂肪族炭化水素類が好ましい。
反応は−７８〜５０℃の温度で行なうことが可能である
が、−１０−ｔｏ℃が範囲で行なうことが望ましい。
（以下余白）
得られたオルトリチ才置換フエニルシラン化合物［３］
は、以下の各反応式
なお、本発明の製造方法の反応によって合成された生成
物がオルト置換体であることは、核磁気共鳴分析によっ
て確認される。例えば下記の反応（ ３ ） Ｈ３０”
（ ６ＮＨＣｌ ）（Ｍｅはメチル基、Ｅｔはエチル
基）
のように種々の反応基質と反応させてそれに伴う様々な
オルト置換フエニルシラン化合物誘導体を得ることが出
来る。
（Ｍｅはメチル基、Ｅｔはエチル基、Ｂｕはブチル基）
によって合成された生成物の核磁気共鳴分析結果は、
’Ｈ ＮＭＲδ ０．３．４ （ｓ，１２Ｈ
）７．４０〜７．７８ （ｍ，４８）となり、文献
（Ｗ．Ｆｉｎｇ，Ｈｅｌｖ．Ｃｈｉｍ．Ａｃｔａ ５７
，１０１０（１９７４） ）で報告された式［５コの分
析値’Ｈ ＮＭＲδ ０． ３０ （ｓ， １
２Ｈ）７．１９ （ｍ．４Ｈｌ
と略一致している。このことから式［５］の生成物には
分子内シロキサン構造があることがわかり、各ＳＬはベ
ンゼン環の才ルト位以外には結合出来ないため、オルト
置換体であることが確認される。
また、下記の反応式
Ｆ
（Ｍｅはメチル基、ｉ−Ｐｒはイソブロビル基）によっ
て合成された生成物の核磁気共鳴分析結果は、
’Ｈ ＮＭＲδ （ ２００ＭＩ｛ｚ，Ｓｏｌｖｅｎ
ｔ ＣＤＣ１ａ）０．２９ （ｓ，９Ｈ ）
４．６６ （ｓ，１｝［ ）
６．６０ （ｄｄ，Ｊコ３．９Ｈｚ，８．７Ｈｚ
，ＩＨ）６．Ｆｌ８ ｆｄｄｄ．Ｊｓ３．ＯＨｚ
，Ｉｌ．ＳＨｚ，８．７｝１ｚ，ＩＨ）７．００
（ｄｄ，Ｊｌｌ３．ＯＨｚ，８．５Ｈｚ，ＩＨ）とな
り、このカップリング定数値よりオルト置換体であるこ
とが確認される。Problem to be Solved by the Invention 1 The present invention provides a novel synthetic method for efficiently and selectively synthesizing ortho-thio-substituted phenylsilane compounds, which are intermediates for obtaining various or-l-substituted phenylsilane compound derivatives. The purpose is to provide. [Means for Solving the Problems] As a result of extensive research into the industrial synthesis method of or-1-lithio substituted phenylsilane compounds, the present inventors introduced an amino group into the silicon of phenylsilane, and combined this with an alkyllithium compound. The present inventors have discovered that when the benzene ring is reacted with, the metallization of the benzene ring proceeds with high selectivity, and the present invention has been completed. That is, the method for producing an ortho-substituted phenylsilane compound to achieve the above object is to prepare a compound represented by the general formula R5Li in the presence of an inert solvent.
This is a method of mixing with the compound represented by [ 2 ] to obtain the compound represented by the general formula. jull in the formula is, for example, an alkyl group such as a methyl group or an ethyl group, a substituted alkyl group such as a methyl group, a chloroprobyl group, an alkenyl group such as a vinyl group or a brobenyl group, a tolyl group, anisyl group, or a chloropropyl group. A substituted phenyl group such as a phenyl group or a phenyl group. R2 is, for example, a halogen group such as a fluoro group, a chloro group, or a bromo group, an alkoxy group such as a methoxy group or an ethoxy group, an alkyl group such as a methyl group or an ethyl group, or a hydrogen group. R3 and R4 are, for example, an alkyl group such as a methyl group or an ethyl group, or a substituted alkyl group such as a σ-N'N'-dimethylaminoethyl group. R'' is, for example, an alkyl group. n is an integer of 0 to 2. The compound represented by the general formula [1] is, for example, bis(tN
'N'-dimethylaminoethyl-methylamino)-diphenylsilane, tris(jl-N'N''-dimethylaminoethyl-methylamino)-phenylsilane, bis(δ
-N'N'-dimethylaminoethyl-methylamino)-p-fluorophenylphenylsilane. Bis(dimethylamino) ~ p-chlorophenyl-methylsilane, bis(
p-methoxyphenyl-phenyl-phenylsilane, and bis(β-N'N'-dimethylaminoethyl-methylamino)-phenyl-γ-chlorobutylsilane. Examples of the compound represented by the general formula [2] include methyllithium, n-butyllithium, and t-butyllithium. Examples of inert solvents used in the reaction include bentane,
Aliphatic hydrocarbons such as hexane are preferred. The reaction can be carried out at a temperature of -78 to 50°C, but preferably in the range of -10 to 50°C. (Left below) Obtained orthorich-substituted phenylsilane compound [3]
is the following reaction formula. It is confirmed by nuclear magnetic resonance analysis that the product synthesized by the reaction of the production method of the present invention is an ortho-substituted product. For example, the following reaction (3) H30"
(6NHCl) (Me is a methyl group, Et is an ethyl group) By reacting with various reaction substrates, various ortho-substituted phenylsilane compound derivatives can be obtained. (Me is a methyl group, Et is an ethyl group, Bu is a butyl group)
The nuclear magnetic resonance analysis result of the product synthesized by 'H NMRδ 0.3.4 (s, 12H
) 7.40 to 7.78 (m, 48), and the literature (W.Fing, Helv.Chim.Acta 57
, 1010 (1974)) [5 analytical values 'H NMRδ 0. 30 (s, 1
2H) 7.19 (m.4Hl) This shows that the product of formula [5] has an intramolecular siloxane structure, and each SL has a Since it cannot bind, it is confirmed that it is an ortho-substituted product.In addition, the nuclear magnetic resonance analysis results of the product synthesized by the following reaction formula F (Me is a methyl group, i-Pr is an isobrobyl group) are as follows. 'H NMRδ (200MI{z,Solven
t CDC1a) 0.29 (s, 9H) 4.66 (s, 1} [ ) 6.60 (dd, J 3.9Hz, 8.7Hz
, IH)6. Fl8fddd. Js3. OHz
, Il. SHz, 8.7}1z, IH) 7.00
(dd, Jll3.OHz, 8.5Hz, IH), and this coupling constant value confirms that it is an ortho-substituted product.
本発明の製造方法では、出発物質であるフェニルシラン
化合物のケイ素にアミノ基が導入してある，そのためフ
ェニルシラン化合物のベンゼン環とアルキルリチウム化
合物とが反応する際、シランに対するベンゼン環のオル
ト位がアルキルリチウム化合物によって高位置選択度で
リチウム化される。
また、本発明の製造方法で得られたオルトリチオ置換フ
ェニルシラン化合物は、種々の反応基質と反応させて反
応基質に対応する様々な誘導体を合成することが出来る
。農薬や医薬品などの含ケイ素生理活性物質を製造する
ための中間体とじて有用である。In the production method of the present invention, an amino group is introduced into the silicon of the phenylsilane compound as a starting material. Therefore, when the benzene ring of the phenylsilane compound and the alkyllithium compound react, the ortho position of the benzene ring with respect to the silane is It is lithiated with high regioselectivity by alkyllithium compounds. Further, the orthothio-substituted phenylsilane compound obtained by the production method of the present invention can be reacted with various reaction substrates to synthesize various derivatives corresponding to the reaction substrates. It is useful as an intermediate for producing silicon-containing physiologically active substances such as agricultural chemicals and pharmaceuticals.
以下、本発明の実施例を説明する。
実施例ｌ
《原料物質の合成》
窒素雰囲気下で、Ｍｅ２Ｎ−Ｃ，Ｈｎ−ＮＭｅ （
６６ミリｍｏｌ）Ｉ
Ｕ
のＴＨＦ溶液（４０ｍｊｌをＯ℃に冷却する。その溶液
にｎ−ＢｕＬｉ６６ミリｍｏｌの１．６Ｍヘキサン溶液
を１時間かけて滴下して２時間撹拌する。ＰｈａＳｉＣ
１２（Ｐｈはフエニル基）２６ミリｍｏｌを１１０分間
かけて滴下し、室温で一夜撹拌する。溶媒を留去し、塩
が析出したらヘキサンを加え、セライト濾過同様の操作
を繰返して塩を安全に取り除くシ溶媒を留去し、１６５
〜１８０℃／０．４ｍｍｌイｇでワーゲル蒸留を行ない
、量のベンタン溶液をＯ℃で加えたのち、室温に昇温し
て２時間撹拌し、式［７］に示すオルトリチオ置換フヱ
ニルシラン化合物を合成した。以下に反応式を示す。
に示す原料物質を合成した。収率は９０％、純度は９５
％以上であった。
合成した化合物の核磁気共鳴分析結果は以下のとおりで
ある。
’Ｈ ＮＭＲδ（２００ＭＨｚ，Ｓｏｌｖｅｎｔ （：
ａＤｓ ）２．Ｑ８ ｉｓ，１２Ｈ）
２．４３ ｔ，Ｊ−７．３Ｈｚ，４Ｈｌ２．
７３ ｓ， ６Ｈ）
３．１３ ｆｔ，Ｊ−７．３Ｈｚ．４Ｈ）７．
２５〜７．３３ （ｍ，６Ｈ）
７．８０〜７．８７ ｍ，４Ｈ）
《オルトリチオ置換フエニルシラン化合物の合成》
上記で得た式［６］の原料物質１ミリｎｏｔをヘキサン
２１に溶解する．その溶液に！−ＢｕＬｉ ２．８当《
オルト置換フェニルシラン化合物誘導体の合成》
このようにして得られた式［７］の才ルトリチオ置換フ
エニルシラン化合物は，種々な反応基質と反応させるこ
とによって、反応基質に応じた様々なオルト置換フェニ
ルシラン化合物誘導体を得ることが出来る。以下はその
使用例である。
使用例１−１
式［７］で示される才ルトリチオ置換フェニルシラン化
合物を再度０℃に冷却し、反応基質として１０当量のＭ
ｅａＳｉＣｌを加え、５℃で３時間加熱する。室温でイ
ソブロビルアルコール（ｌ−ＰｒＯＨＩ ＬＯ当量を加
えて終夜撹拌する。撹拌終了後、ｌＯ％のＮＨ．Ｃｌ水
で加水分解して抽出、乾燥した後、シリカゲル力ラムで
単離し、式［８］に示すオルト位の−Ｌｉが−ＳｉＭｅ
３で置換された才ルト置換フエニルシラン化合物誘導体
を得た。収率は７２％であった。以下に反応式を示す。
Ｃ以下余白）
【７１
式［８］の化合物の核磁気共鳴分析結果は以下の通りで
ある。
’Ｈ ＮＭＲδ（２００ＭＨｚ，Ｓｏｌｖｅｎｔ ＣＤ
ＣＩｓ）（１．３２ （ ｓ，９Ｈ）
１．１３ （ ｄ，Ｊｌ１６Ｈｚ， ６Ｂ）１
．１７ （ ｄ，ＪＩＩ６Ｈｚ，６Ｈ）４．
１２ （ Ｓｅｐｔ．ＪＩＩ６Ｈｚ， ２Ｈ
）７．２０〜７．３８ （ ｍ， ＳＨ）７．５９〜
７．６１１１ （ ｍ， ４Ｈ）？た、この化合物の
元素分析により求めた組成比は、水素８．６６％、炭素
６７．８６％であり、組成式Ｃｚ＋ＨａｚＯ■Ｓｌ２に
基く計算値、水素８．９１％、炭素６７． ５０％と略
一致している。
使用例１−２
また、反応基質としてＭｅ３ＳｎＣｌを用いる他は使用
例１−２と同様な操作を行ない、オルト位がＭｅ３Ｓｎ
で置換されたオルト置換フエニルシラン化合物誘導体を
合成した。収率は５５％であった。
得られた誘導体の核磁気共鳴分析結果を以下に示す。
？ Ｎ１１１Ｒδ （２００Ｍ｝Ｉｚ，Ｓｏｌｖｅｎ
ｔ ＣＤＣＩｓ）０．２４ （ ｓ，
９Ｈ）１．１３ （ ｄ，Ｊ；６Ｈｚ，
６Ｍ）１．１６ （ ｄ，Ｊ＝６Ｈｚ，
６８）４．１４ （ Ｓｅｐｔ．ＪＩＩ
６１｛ｚ，２Ｈ ）７．１８〜７．４１ （ ｍ，
５Ｈ）７．５６ 〜７．６５ （ｍ，４Ｈ）使用
例１−３
反応基質としてＣＩＣＯ■Ｅｔ （Ｅｔはエチル基）
を用いる他は使用例１−１と同様な操作を行ない、オル
ト位がＣＯ鵞Ｅｔで置換されたオルト置換フエニルシラ
ン化合物誘導体を合成した。収率は３０％であった。以
下に核磁気共鳴分析結果を示す。
’Ｈ ＮＭＲδ（２００ＭＨｚ，Ｓｏｌｖｅｎｔ ＣＤ
Ｃ１３）１．０３ （ ｔ，Ｊ＝７．２Ｈｚ，
３８）１．１３ （ｄ，Ｊ工６Ｈｚ， ６Ｈ）
１．１６ （ ｄ，Ｊ＝６Ｈｚ，６８）３．
９６ ｆｑ， Ｊｌ１７． ２Ｈｚ， ２Ｈ）
４．１６ （Ｓｅｐｔ．Ｊｌｌ６Ｈｚ，２Ｈ
）７．２１〜７．３５ （ｍ．３Ｈ）
７．４Ｑ 〜７．６１ （ｍ．４Ｈ）７． ９４
（ｄｄ， Ｊ；２Ｈｚ， ７Ｈｚ， ＩＨ）８．
２４ （ｄｄ，Ｊ＝２Ｈｚ， ７Ｈｚ， ＩＨ
）使用例１−４
反応基質としてＣＨ．・ＣＨＣＨＪｒを用いる他は使用
例１−１と同様な操作を行ない、オルト位がＢｒで置換
されたオルト置換フエニルシラン化合物誘導体を合成し
た。取率は９６％であった。核磁気共鳴分析結果は以下
の通りである。
’Ｈ ＮＭＲδ （２ロＯＭＨｚ，Ｓｏｌｖｅｎｔ
ＣＤＣｌ３）１． １８ （ ｄ， Ｊ−６
Ｈｚ， ６Ｈ）１．２３ （ｄ，Ｊ
冨６Ｈｚ。６Ｈ）４．２０ （ Ｓｅｐｔ
．ＪＩＩ６Ｈｚ，２８ ）７．１８〜７．５０
（ ｍ．６Ｈ）７．６２〜７．６８ （ｍ，２Ｈ）
７．９４ （ｄｄ，ＪＩＩ２Ｈｚ，７Ｈ
ｚ，ＩＨ）使用例１−５
反応基質としてｌｉｌｅ２ｓＯｎを用いる他は使用例１
と同様な操作を行ない、オルト位がｌｌＩｅで置換され
た才ル１・置換フェニルシラン化合物誘導体を合成した
。収率は２４％であった。以下に核磁気共鳴分析結果を
示す。
’Ｈ ＮＭＲδ（２００ＭＨｚ，Ｓｏｌｖｅｎｔ ＣＤ
ＣＩｓ）１．１７ （ ｄ，Ｊｓ６Ｈｚ，６Ｈ
）１． １８ （ ｄ， ＪＪＨｚ， ６Ｈ）
２．２３ （ｓ，３Ｈ）
４．１５ （Ｓｅｐｔ．Ｊ弓Ｈｚ， ２Ｈ）７
．０６〜７．４４ （ ｍ，６Ｈ）７． ５７〜 ７
．６５ （ｍコ， ２ Ｈ ）７．８６
（ｄｄ，Ｊ；１．６Ｈｚ， ７．４Ｈｚ， Ｎｉ
ｌ実施例２
《原料物質の合成》
Ｐｈ＊ＳｉＣｌａの替わりにＰｈＳｉＣ１ｓを用いる他
は実施例１と略同様にして式［９］
の原料物質を合成した。この化合物の核磁気共鳴分析結
果を下記に示す。
’Ｈ ＮＭＲδ（２００ＭＨｚ，Ｓｏｌｖｅｎｔ Ｃａ
Ｄａ）２． １６ （ｓ， １８Ｈ）２．４５
（Ｌ， Ｊ；７． ５Ｈｚ， ６Ｈ）２．６
９ （ｓ，９Ｈ）
３．１０ ｆｔ，Ｊ＝７．５Ｈｚ，６Ｈ）７．
２６〜７．３８ （ｍ，３Ｈ）
７．８４ （ｄｄ，Ｊ＠１．７Ｈｚ，７．７Ｈ
ｚ，２Ｈ）《オルトリチオ置換フェニルシラン化合物の
合成》
式［９コの化合物を原料物質とする他は実施例１と略同
様にして、式［１０］に示すオル１・リチす置換フェニ
ルシラン化合物を合成した。
《オルト置換フェニルシラン化合物誘導体の合成》
このようにして害られた式［ １０］のオルトリチ才置
換フエニルシラン化合物と反応基質とを反応させて誘導
体を得る使用例を示す。
使用例２−１
オルトリチ才置換フェニルシラン化合物として式［１０
］の化合物を用いる他は前述の使用例ｔ−ｉと同様にし
て、式［１ｌ］に示すオルト置換フエニルシラン化合物
誘導体を得た。収率は６０％であった。
？．２０ （ ｄ，Ｊ：６１｛ｚ，１８
Ｈ）４．２５ ＜ Ｓｅｐｔ．Ｊ＝６Ｈ
ｚ，３１｛）７．２２ 〜７．４０ （ｍ，２Ｈ）７
．５９ 〜７．６８ （ｍ，ｌ｝Ｉ）７．８０ 〜７
．９１ （ ｍ， ＩＨ）この化合物の元素分析に
より求めた組成比は水素１０．０１％、炭素６０． ９
９％で２組成式Ｃ＋ａｌｌａｎＯ３Ｓｉｚに基《計算値
、水素９．６６％、炭素６０．９６％と略一致している
。
使用例２−２
反応基質としてＣ Ｉ Ｃ ０ ２Ｅ ｔ．を用いる他
は使用例２−１と同様な操作を行ない、式［ｌ２１に示
す才ルト位がＣＯ■Ｅｔで置換されたオル１・置換フェ
ニルシラン化合物誘導体を合成した。収率は１５％であ
った。
式［ １１］の化合物の核磁気共鳴分析結果は以下の通
りである。
ＨＮＭＲδ（２００ＭＨｚ，Ｓｏｌｖｅｎｔ ＣＤＣ１
ａ）０．３６ （ ｓ，９Ｈ）
得られた誘導体の核磁気共鳴分析結果を示す。
’Ｈ ＮＭＲδ（２００Ｍ｝Ｉｚ，Ｓｏｌｖｅｎｔ Ｃ
ＤＣ１ｓ）１．１７
１．３９
４．３１
４．３８
７．３８〜７，５３
７．８７〜７．９３
８，０５〜８．ｌＯ
実施例３
《原料物質の合成》
（ ｄ，Ｊ＝６Ｈｚ，１８Ｈ）
（ｔ，Ｊ＝７．２１１ｚ．３Ｈ）
（ Ｓｅｐｔ．Ｊ：６Ｈｚ，３Ｈ
（ ｑ．ＪＩＩ７．２Ｈｚ，２Ｈ）
（ ｍ，２Ｈ）
（ ｍ，ＬＨ）
（ ｍ，ＩＨ）
実施例ｌと略同様にして式［１３］に示す原料物質を合
成した。
合成した化合物の核磁気共鳴分析結果を下記に示す，
’ＩＩ ＮＭＲδ（ ２００ＭＨｚ，Ｓｏｌｖｅｎｔ
ＣａＤｓ）２．０８ （ｓ， １２Ｈ）
２．３９ （ｔ，Ｊ＝７．３Ｈｚ，４Ｈ）２．
６７ （ｓ，６Ｈ）３． ０７
（ｔ， Ｊ＝７． ３Ｈｚ， ４Ｈｌ６．９７
ｆｔ，Ｊ−８．８Ｈｚ，２Ｈ）７．２５ 〜
７．２６ （ｍ，３Ｈ）７．６７ （
ｄｄ，Ｊ：６．４Ｈｚ，８．８Ｈｚ，２Ｈ）７．７４〜
７．８０ （ｍ，２８）《オルトリチオ置換フエニ
ルシラン化合物の合成》
式［ｌ３］の化合物を原料物質とする他は、実施例ｌと
略同様にして式［１４コに示す才ルトリチ才置換フェニ
ルシラン化合物を合成した。
ＬＬ
《オルト置換フェニルシラン化合物誘導体の合成》
このようにして得られた式［ｌ４〕のオルトリチオ置換
フエニルシラン化合物と反応基質とを反応させて種々の
誘導体を得る使用例を示す。
使用例３−１
才ルトリチ才置換フエニルシラン化合物として式［１４
１の化合物を用いる他は実施例１の使用例１−１と同様
にして、式［ｌ５〕に示すオルト置換フェニルシラン化
合物誘導体を得た。収率は２０％であった。
式［１５］の誘導体の核磁気共鳴分析結果は以下の通り
である。
ＩＨ ＮＭＲδ（２００ＭＨｚ．Ｓｏｌｖｅｎｔ ＣＤ
ＣＩｓ）１．０３ （ ｔ，Ｊ＝７Ｈｚ，３Ｈ
）１． １ １ （ ｄ， Ｊ＝６Ｈｚ，
６Ｈｌ１．１５ （ ｄ，Ｊ＝６Ｈｚ，６Ｂ）
３．９７ （ Ｑ．Ｊ＊７Ｈｚ，２８１４．
１４ （ Ｓｅｐｔ．Ｊ−６Ｈｚ， ２ＦＩ
）７．２１〜７．３５ （ ｍ，４Ｈ）７．５１〜７
．５６ （ｍ，２８）
？．６３ （ｄｄ，Ｊ；２．６Ｈｚ，７．８
Ｈｚ，ＩＨ）８．２５ （ｄｄ，Ｊ＝６．４
Ｈｚ，８．４Ｈｚ， １８）使用例３−２
反応基質としてｌ＋ｌＲ３ｓｉｃ１を用いる他は使用例
３−１と同様な操作を行ない、式［１６］に示すオルト
位がＭｅｓＳｉで置換されたオルト置換フェニルシラン
化合物誘導体を合成した。収率は６６％であった。
得られた誘導体の核磁気共鳴分析結果を下記に示す。
’Ｈ ＮＭＲδ（２００）４Ｈｚ，Ｓｏｌｖｅｎｔ Ｃ
ＤＣＩｓ）０．３１ （ ｓ，９Ｈ）
１． １３ （ ｄ， Ｊ＝６Ｈｚ， ６Ｈ
）１．１７ （ｄ，Ｊ＝６Ｈｚ．６Ｈ）４．
１１ （ Ｓｅｐｔｊ＝６Ｈｚ，２Ｈ）６．９
３ （ ｄｔ．Ｊｌｌ２．８Ｈｚ，８．６Ｈ
ｚ， １８）７．２６〜７．４１ （ ｍ．４Ｈ）７
．５５〜７．７０ （ｍ，３｝１）実施例４
《原料物質の合成》
？ｅ
■
ＰｈｚＳｉＣｌ２の替わりにＣＩＰｈＳｉＣ１ｍを用い
る他は実施例ｌと同様な操作によって式［ｌ７］に示す
化合物を得た。
式［ｌ７］の化合物を原料物質とする他は、実施例ｌと
略同様にして式［１８］に示すオル１・リヂオ置換フェ
ニルシラン化合物を合成した。
ｌＪｏ
《オルト置換フェニルシラン化合物誘導体この化合物の
核磁気共鳴分析結果を下記に示ず。
ＩＩ ＮＭＲδ （ ２００ＭＨｚ，Ｓｏｌｖｅｎｔ
ＣａＤａ）０．３７ （ｓ，３Ｈ）
２．１２ （ｓ，１２Ｈ）２．３１〜２
．３８ （ａ＋，４｝１）２．５３
（ｓ，６８）２，９２〜３．００ ｍ，４Ｈｌ
？．３１ （ｄ，ＪＩＩ８．２．Ｈｚ，
２Ｈ）７．４７ ｆｄ，Ｊｓ８．２Ｈｚ
，２Ｈ）《オルトリチオ置換フエニルシラン化合物の合
成》
の合成》
このようにして得られたオルトリチ才置換フェニルシラ
ン化合物［ｌ８］ と反応基質と反応させてその誘導体
を得る使用例を示す。
使用例４−１
オルトリチオ置換フエニルシラン化合物として式［１８
］の化合物を用いる他は実施例１の使用例１−１と同様
にして、式［ｌ９］に示すオルト置換フェニルシラン化
合物誘導体を得た。収率は２０％であった。
式［ｌ９１で示される化合物の核磁気共鳴分析結果は以
下の通りである。
Ｈ ＮＭＲδ（２００ＭＨｚ，Ｓｏｌｖｅｎｔ （：Ｄ
Ｃｌ３）０．３６ （ｓ，９８）
０．３８ （ｓ，３Ｈ）
１． １９ （ ｄ， ＪＩＩＧＨｚ， ６Ｈ
）１．２０ （ ｄ，ＪＩＩ６Ｈｚ，６Ｈ）
４． １．８ （ Ｓｅｐｔ．Ｊｌ１６Ｈｚ，
２８）７． ３０ （ｄｄ． Ｊ−２Ｈｚ，
８Ｈｚ， ＩＨ）７．５７ （ｄ，Ｊエ２Ｈ
ｚ， ＩＨ）？． ７０ （ｄ， ＪＩ１８
Ｈｚ． ＩＨ）また、この化合物の元素分析により求め
た組成比は水素８．６１％、炭素５５．７９％であり、
組成式Ｃ１ｅＨ２ｅＯ２ＳｉｚＣｌに基く計算値、水素
８．４７％、炭素５５． ７０％と略一致していた。Examples of the present invention will be described below. Example 1 <<Synthesis of raw material>> Me2N-C, Hn-NMe (
A THF solution (40 mjl) of I U (66 mmol) is cooled to 0° C. A 1.6 M hexane solution of 66 mmol of n-BuLi is added dropwise to the solution over 1 hour and stirred for 2 hours. PhaSiC
26 mmol of 12 (Ph is a phenyl group) was added dropwise over 110 minutes, and the mixture was stirred overnight at room temperature. The solvent is distilled off, and when the salt precipitates, hexane is added, and the same operation as Celite filtration is repeated to safely remove the salt.
After performing Wagel distillation at ~180°C/0.4 mml Ig, adding an amount of bentane solution at 0°C, the temperature was raised to room temperature and stirred for 2 hours to synthesize the orthothio-substituted phenylsilane compound shown in formula [7]. did. The reaction formula is shown below. The raw materials shown in were synthesized. Yield: 90%, purity: 95
% or more. The results of nuclear magnetic resonance analysis of the synthesized compound are as follows. 'H NMRδ (200MHz, Solvent (:
aDs)2. Q8 is, 12H) 2.43 t, J-7.3Hz, 4Hl2.
73 s, 6H) 3.13 ft, J-7.3Hz. 4H)7.
25-7.33 (m, 6H) 7.80-7.87 m, 4H) <<Synthesis of orthothio-substituted phenylsilane compound>> 1 mm not of the raw material of formula [6] obtained above was dissolved in hexane 21. In that solution! -BuLi 2.8 wins《
Synthesis of ortho-substituted phenylsilane compound derivatives》 The thus obtained trithio-substituted phenylsilane compound of formula [7] can be reacted with various reaction substrates to form various ortho-substituted phenylsilane compounds depending on the reaction substrate. derivatives can be obtained. Below is an example of its use. Usage Example 1-1 The trithio-substituted phenylsilane compound represented by formula [7] was cooled again to 0°C, and 10 equivalents of M was added as a reaction substrate.
Add eaSiCl and heat at 5° C. for 3 hours. Add isobrobyl alcohol (l-PrOHI LO equivalent) at room temperature and stir overnight. After stirring, extract with 1O% NH.Cl water, extract, dry, isolate with silica gel ram, and obtain the formula [8 ] -Li at the ortho position shown in -SiMe
A phenylsilane compound derivative substituted with 3 was obtained. The yield was 72%. The reaction formula is shown below. Blank space below C) [71 The nuclear magnetic resonance analysis results of the compound of formula [8] are as follows. 'H NMRδ (200MHz, Solvent CD
CIs) (1.32 (s, 9H) 1.13 (d, Jl16Hz, 6B) 1
．． 17 (d, JII6Hz, 6H)4.
12 (Sept.JII6Hz, 2H
)7.20~7.38 (m, SH)7.59~
7.6111 (m, 4H)? In addition, the composition ratio determined by elemental analysis of this compound is 8.66% hydrogen and 67.86% carbon, and the calculated value based on the composition formula Cz+HazO■Sl2 is 8.91% hydrogen and 67% carbon. This is approximately equal to 50%. Usage Example 1-2 In addition, the same operation as Usage Example 1-2 was performed except that Me3SnCl was used as the reaction substrate, and the ortho position was Me3Sn.
Ortho-substituted phenylsilane compound derivatives substituted with were synthesized. The yield was 55%. The results of nuclear magnetic resonance analysis of the obtained derivative are shown below. ? N111Rδ (200M}Iz, Solven
t CDCIs) 0.24 (s,
9H) 1.13 (d, J; 6Hz,
6M) 1.16 (d, J=6Hz,
68) 4.14 (Sept. JII
61{z, 2H )7.18~7.41 (m,
5H) 7.56 to 7.65 (m, 4H) Usage example 1-3 CICO■Et as reaction substrate (Et is ethyl group)
An ortho-substituted phenylsilane compound derivative in which the ortho position was substituted with CO-Et was synthesized by carrying out the same operation as in Use Example 1-1, except for using . The yield was 30%. The results of nuclear magnetic resonance analysis are shown below. 'H NMRδ (200MHz, Solvent CD
C13) 1.03 (t, J=7.2Hz,
38) 1.13 (d, J engineering 6Hz, 6H)
1.16 (d, J=6Hz, 68)3.
96 fq, Jl17. 2Hz, 2H)
4.16 (Sept. Jll6Hz, 2H
)7.21~7.35 (m.3H) 7.4Q ~7.61 (m.4H)7. 94
(dd, J; 2Hz, 7Hz, IH)8.
24 (dd, J=2Hz, 7Hz, IH
) Usage Example 1-4 CH. - An ortho-substituted phenylsilane compound derivative in which the ortho position was substituted with Br was synthesized by performing the same operation as in Use Example 1-1 except for using CHCHJr. The yield rate was 96%. The nuclear magnetic resonance analysis results are as follows. 'H NMRδ (20OMHz, Solvent
CDCl3)1. 18 (d, J-6
Hz, 6H) 1.23 (d, J
6Hz. 6H) 4.20 (Sept.
．． JII6Hz, 28) 7.18-7.50
(m.6H)7.62~7.68 (m,2H)
7.94 (dd, JII2Hz, 7H
z, IH) Usage example 1-5 Usage example 1 except that lile2sOn is used as the reaction substrate
A similar operation was carried out to synthesize a 1-substituted phenylsilane compound derivative in which the ortho position was substituted with llIe. The yield was 24%. The results of nuclear magnetic resonance analysis are shown below. 'H NMRδ (200MHz, Solvent CD
CIs) 1.17 (d, Js6Hz, 6H
)1. 18 (d, JJHz, 6H)
2.23 (s, 3H) 4.15 (Sept. J bow Hz, 2H) 7
．． 06-7.44 (m, 6H)7. 57～7
．． 65 (mko, 2 H)7.86
(dd, J; 1.6Hz, 7.4Hz, Ni
l Example 2 <<Synthesis of raw material>> A raw material of formula [9] was synthesized in substantially the same manner as in Example 1 except that PhSiC1s was used instead of Ph*SiCla. The results of nuclear magnetic resonance analysis of this compound are shown below. 'H NMRδ (200MHz, Solvent Ca
Da)2. 16 (s, 18H) 2.45
(L, J; 7.5Hz, 6H)2.6
9 (s, 9H) 3.10 ft, J=7.5Hz, 6H)7.
26~7.38 (m, 3H) 7.84 (dd, [email protected], 7.7H
z, 2H) <<Synthesis of ortho-lithio-substituted phenylsilane compound>> The or-1-lithio-substituted phenylsilane compound shown in formula [10] was prepared in substantially the same manner as in Example 1 except that the compound of formula [9] was used as the starting material. was synthesized. <<Synthesis of ortho-substituted phenylsilane compound derivative>> An example of use will be shown in which a derivative is obtained by reacting the ortho-substituted phenylsilane compound of formula [10] damaged in this way with a reaction substrate. Usage Example 2-1 Ortho-substituted phenylsilane compound with formula [10
An ortho-substituted phenylsilane compound derivative represented by the formula [1l] was obtained in the same manner as in the above-mentioned usage example t-i except that the compound of formula [11] was used. The yield was 60%. ? ．． 20 (d, J:61{z,18
H) 4.25 < Sept. J=6H
z, 31 {) 7.22 ~ 7.40 (m, 2H) 7
．． 59 ~7.68 (m,l}I)7.80 ~7
．． 91 (m, IH) The composition ratio determined by elemental analysis of this compound is 10.01% hydrogen and 60.0% carbon. 9
Based on the 2 composition formula C+allanO3Siz at 9%, the calculated values are approximately equal to 9.66% hydrogen and 60.96% carbon. Usage example 2-2 C I C 0 2E t. The same operation as in Use Example 2-1 was carried out except that 1-substituted phenylsilane compound derivative represented by the formula [l21 was substituted with CO₂Et at the root position was synthesized. Yield was 15%. The nuclear magnetic resonance analysis results of the compound of formula [11] are as follows. HNMRδ (200MHz, Solvent CDC1
a) 0.36 (s, 9H) The results of nuclear magnetic resonance analysis of the obtained derivative are shown. 'H NMRδ(200M}Iz, Solvent C
DC1s) 1.17 1.39 4.31 4.38 7.38~7,53 7.87~7.93 8,05~8. lO Example 3 <<Synthesis of raw material>> (d, J=6Hz, 18H) (t, J=7.211z.3H) (Sept.J:6Hz,3H (q.JII7.2Hz, 2H) (m, 2H) ( m, LH) ( m, IH) The raw material shown in formula [13] was synthesized in substantially the same manner as in Example 1. The results of nuclear magnetic resonance analysis of the synthesized compound are shown below. 200MHz, Solvent
CaDs) 2.08 (s, 12H) 2.39 (t, J=7.3Hz, 4H)2.
67 (s, 6H)3. 07
(t, J=7.3Hz, 4Hl6.97
ft, J-8.8Hz, 2H) 7.25 ~
7.26 (m, 3H) 7.67 (
dd, J: 6.4Hz, 8.8Hz, 2H) 7.74~
7.80 (m, 28)《Synthesis of an orthotrithio-substituted phenylsilane compound》 The altrithio-substituted phenylsilane shown in formula [14] was prepared in substantially the same manner as in Example 1, except that the compound of formula [13] was used as a starting material. The compound was synthesized. LL <<Synthesis of ortho-substituted phenylsilane compound derivatives>> Examples of use will be shown in which various derivatives are obtained by reacting the ortho-thio-substituted phenylsilane compound of formula [14] thus obtained with a reaction substrate. Use example 3-1 As a substituted phenylsilane compound with the formula [14
An ortho-substituted phenylsilane compound derivative represented by formula [15] was obtained in the same manner as in Example 1, Use Example 1-1, except that compound No. 1 was used. Yield was 20%. The nuclear magnetic resonance analysis results of the derivative of formula [15] are as follows. IH NMRδ (200MHz.Solvent CD
CIs) 1.03 (t, J=7Hz, 3H
)1. 1 1 (d, J=6Hz,
6Hl1.15 (d, J=6Hz, 6B)
3.97 (Q.J*7Hz, 2814.
14 (Sept.J-6Hz, 2FI
)7.21~7.35 (m,4H)7.51~7
．． 56 (m, 28)? ．． 63 (dd, J; 2.6Hz, 7.8
Hz, IH) 8.25 (dd, J=6.4
Hz, 8.4Hz, 18) Usage Example 3-2 The same operation as Usage Example 3-1 was performed except that l+lR3sic1 was used as the reaction substrate, and the ortho-substituted phenyl substituted with MesSi at the ortho position shown in formula [16] was prepared. Silane compound derivatives were synthesized. The yield was 66%. The results of nuclear magnetic resonance analysis of the obtained derivative are shown below. 'H NMRδ (200) 4Hz, Solvent C
DCIs) 0.31 (s, 9H) 1. 13 (d, J=6Hz, 6H
)1.17 (d, J=6Hz.6H)4.
11 (Septj=6Hz, 2H)6.9
3 (dt.Jll2.8Hz, 8.6H
z, 18) 7.26~7.41 (m.4H)7
．． 55-7.70 (m, 3}1) Example 4 <<Synthesis of raw material>>? e ■ A compound represented by formula [17] was obtained in the same manner as in Example 1, except that CIPhSiClm was used instead of PhzSiCl2. An or-1-ridio-substituted phenylsilane compound represented by formula [18] was synthesized in substantially the same manner as in Example 1, except that the compound of formula [17] was used as a starting material. lJo <<Ortho-substituted phenylsilane compound derivative The results of nuclear magnetic resonance analysis of this compound are not shown below. II NMRδ (200MHz, Solvent
CaDa) 0.37 (s, 3H)
2.12 (s, 12H) 2.31~2
．． 38 (a+,4}1)2.53
(s, 68) 2,92~3.00 m, 4Hl? ．． 31 (d, JII8.2.Hz,
2H) 7.47 fd, Js8.2Hz
, 2H) <<Synthesis of orthorithio-substituted phenylsilane compound>>> An example of use will be shown in which the thus obtained orthorithio-substituted phenylsilane compound [18] is reacted with a reaction substrate to obtain a derivative thereof. Usage example 4-1 Orthothio-substituted phenylsilane compound of formula [18
An ortho-substituted phenylsilane compound derivative represented by the formula [19] was obtained in the same manner as in Use Example 1-1 of Example 1, except that the compound of formula [19] was used. Yield was 20%. The nuclear magnetic resonance analysis results of the compound represented by the formula [l91 are as follows. H NMRδ (200MHz, Solvent (:D
Cl3) 0.36 (s, 98) 0.38 (s, 3H) 1. 19 (d, JIIGHz, 6H
) 1.20 (d, JII6Hz, 6H)
4. 1.8 (Sept.Jl16Hz,
28)7. 30 (dd. J-2Hz,
8Hz, IH) 7.57 (d, JE2H
z, IH)? ．． 70 (d, JI18
Hz. IH) Also, the composition ratio determined by elemental analysis of this compound is 8.61% hydrogen and 55.79% carbon.
Calculated value based on composition formula C1eH2eO2SizCl, hydrogen 8.47%, carbon 55. It was almost the same as 70%.
Claims (1)
置換フェニル基またはアルケニル基、Ｒ＾２は水素基、
ハロゲン基、アルコキシ基、アルキル基、Ｒ＾３および
Ｒ＾４はアルキル基または置換アルキル基、ｎは０〜２
の整数） で示される化合物を不活性溶剤存在下、一般式 Ｒ＾５Ｌｉ［２］ （Ｒ＾５はアルキル基） で示される化合物と混合し、一般式 ▲数式、化学式、表等があります▼［３］ （Ｒ＾１はアルキル基、置換アルキル基、フェニル基、
置換フェニル基またはアルケニル基、Ｒ＾２は水素基、
ハロゲン基、アルコキシ基、アルキル基、Ｒ＾３および
Ｒ＾４はアルキル基または置換アルキル基、ｎは０〜２
の整数） で示される化合物を得ることを特徴とするオルトリチオ
置換フェニルシラン化合物の製造方法。 ２、前記Ｒ＾１がメチル基、エチル基、クロロメチル基
、クロロプロピル基、フェニル基、トレイル基、アニシ
ル基、クロロフェニル基、ビニル基またはプロペニル基
、Ｒ＾２が水素基、フロロ基、クロロ基、ブロモ基、メ
トキシ基、エトキシ基、メチル基、エチル基、Ｒ＾３お
よびＲ＾４がメチル基、エチル基、β−Ｎ′Ｎ′−ジメ
チルアミノエチル基、Ｒ＾５がメチル基、ｎ−ブチル基
、ｔ−ブチル基であることを特徴とする特許請求の範囲
第１項記載のオルトリチオ置換フェニルシラン化合物の
製造方法。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [1] (R^1 is an alkyl group, a substituted alkyl group, a phenyl group,
Substituted phenyl group or alkenyl group, R^2 is hydrogen group,
Halogen group, alkoxy group, alkyl group, R^3 and R^4 are alkyl groups or substituted alkyl groups, n is 0 to 2
A compound represented by the general formula R^5Li[2] (R^5 is an alkyl group) is mixed with a compound represented by the general formula R^5Li[2] (R^5 is an alkyl group) in the presence of an inert solvent to form a compound represented by the general formula▲Mathematical formula, chemical formula, table, etc.▼ [3] (R^1 is an alkyl group, a substituted alkyl group, a phenyl group,
Substituted phenyl group or alkenyl group, R^2 is hydrogen group,
Halogen group, alkoxy group, alkyl group, R^3 and R^4 are alkyl groups or substituted alkyl groups, n is 0 to 2
A method for producing an orthothio-substituted phenylsilane compound, characterized by obtaining a compound represented by (an integer of ). 2. The above R^1 is a methyl group, ethyl group, chloromethyl group, chloropropyl group, phenyl group, trail group, anisyl group, chlorophenyl group, vinyl group or propenyl group, and R^2 is a hydrogen group, fluoro group, chloro group. group, bromo group, methoxy group, ethoxy group, methyl group, ethyl group, R^3 and R^4 are methyl group, ethyl group, β-N'N'-dimethylaminoethyl group, R^5 is methyl group, 2. The method for producing an orthothio-substituted phenylsilane compound according to claim 1, wherein the compound is an n-butyl group or a t-butyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1060485A JPH0768249B2 (en) | 1989-03-13 | 1989-03-13 | Method for producing orthotrithio-substituted phenylsilane compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1060485A JPH0768249B2 (en) | 1989-03-13 | 1989-03-13 | Method for producing orthotrithio-substituted phenylsilane compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02240086A true JPH02240086A (en) | 1990-09-25 |
| JPH0768249B2 JPH0768249B2 (en) | 1995-07-26 |
Family
ID=13143628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1060485A Expired - Fee Related JPH0768249B2 (en) | 1989-03-13 | 1989-03-13 | Method for producing orthotrithio-substituted phenylsilane compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768249B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036723A (en) * | 2004-07-29 | 2006-02-09 | Sharp Corp | pi-ELECTRON-CONJUGATED MOLECULE-CONTAINING SILICON COMPOUND AND METHOD FOR PRODUCING THE SAME |
| JP2013516421A (en) * | 2009-12-31 | 2013-05-13 | 株式会社ブリヂストン | Aminosilane initiators and functionalized polymers prepared therefrom |
| US8916665B2 (en) | 2010-12-30 | 2014-12-23 | Bridgestone Corporation | Aminosilane initiators and functionalized polymers prepared therefrom |
-
1989
- 1989-03-13 JP JP1060485A patent/JPH0768249B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036723A (en) * | 2004-07-29 | 2006-02-09 | Sharp Corp | pi-ELECTRON-CONJUGATED MOLECULE-CONTAINING SILICON COMPOUND AND METHOD FOR PRODUCING THE SAME |
| JP2013516421A (en) * | 2009-12-31 | 2013-05-13 | 株式会社ブリヂストン | Aminosilane initiators and functionalized polymers prepared therefrom |
| JP2014205840A (en) * | 2009-12-31 | 2014-10-30 | 株式会社ブリヂストン | Aminosilane initiator and functionalized polymer manufactured from the same |
| JP2016074910A (en) * | 2009-12-31 | 2016-05-12 | 株式会社ブリヂストン | Aminosilane initiator and functionalized polymer prepared therefrom |
| US9884923B2 (en) | 2009-12-31 | 2018-02-06 | Bridgestone Corporation | Aminosilane initiators and functionalized polymers prepared therefrom |
| US10745497B2 (en) | 2009-12-31 | 2020-08-18 | Bridgestone Corporation | Aminosilane initiators and functionalized polymers prepared therefrom |
| US8916665B2 (en) | 2010-12-30 | 2014-12-23 | Bridgestone Corporation | Aminosilane initiators and functionalized polymers prepared therefrom |
| US9255158B2 (en) | 2010-12-30 | 2016-02-09 | Bridgestone Corporation | Aminosilane initiators, functionalized polymers prepared therefrom and related processes |
| US9676874B2 (en) | 2010-12-30 | 2017-06-13 | Bridgestone Corporation | Processes for preparing aminosilane functionalized polymers |
| US10351636B2 (en) | 2010-12-30 | 2019-07-16 | Bridgestone Corporation | Processes for preparing aminosilane functionalized polymers |
| US11104748B2 (en) | 2010-12-30 | 2021-08-31 | Bridgestone Corporation | Processes for preparing aminosilane functionalized polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0768249B2 (en) | 1995-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20230131941A (en) | Method for producing organotin compounds | |
| CN110615811B (en) | Method for preparing chiral sulfinamide monophosphine ligand in large scale | |
| JPH02240086A (en) | Production of ortholithio-substituted phenylsilane compound | |
| CA2214580A1 (en) | Catalytic enantioselective synthesis of a spirofused azetidinone | |
| JP3034305B2 (en) | Phosphinite-borane compound having chiral structure, method for producing the same and use thereof | |
| EP0593332B1 (en) | Phenylborinic acid derivatives, their preparation and their use as intermediates in syntheses | |
| JPH02108692A (en) | Production of aryldimethyl (3-arylpropyl)silane | |
| JP7131109B2 (en) | Method for producing organosilicon compound, method for producing aminoaryl group-containing organosilicon compound, and organosilicon compound | |
| JPH0959290A (en) | Ferroceny diphenylphosphine derivative and hydrosilylation method using the ligand metal complex | |
| JP6940241B2 (en) | Method for preparing bis (acyl) phosphinic acid silyl ester | |
| JP2004137165A (en) | Method for producing nitrogen-containing heterocyclic compound | |
| JPH02290885A (en) | Organosilicon compound and its production | |
| Kakusawa et al. | Synthesis of Sb-chiral Organoantimony (III) Compounds: Stepwise Nucleophilic Displacement Reaction of Tribromostibane via a Bisethynylstibane Intermediate | |
| JPH1160550A (en) | Production of sulfonyloxytropone | |
| JPH0753740B2 (en) | Five-coordinate silicon compound and method for producing the same | |
| JPH08119976A (en) | Production of asymmetric disiloxane compound | |
| JPS59144794A (en) | Heterocyclic five-membered phosphorus derivative | |
| JP3564530B2 (en) | Method for producing tetrakis (diarylsilyl) benzene | |
| JPH03123785A (en) | Cyclotetrasilane derivative, its production and intermediate for production | |
| JP3778521B2 (en) | Method for producing cyclopropenone acetal derivative | |
| JP2687955B2 (en) | Method for producing 1,4,5,8-tetrahydroxyanthraquinone | |
| Youn et al. | Substituted (2-ferrocenylethyl) methyl ethers | |
| JP4006264B2 (en) | Method for preparing lithium aluminum hydride from sodium aluminum hydride | |
| JPH01313471A (en) | Production of n-sulfamoylamidine compound | |
| JPH09176176A (en) | Tris(triorganosiloxy)antimony, its production and production of hydrolyzate thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |