JPH02270887A - Organosilicon compound and production thereof - Google Patents
Organosilicon compound and production thereofInfo
- Publication number
- JPH02270887A JPH02270887A JP1092164A JP9216489A JPH02270887A JP H02270887 A JPH02270887 A JP H02270887A JP 1092164 A JP1092164 A JP 1092164A JP 9216489 A JP9216489 A JP 9216489A JP H02270887 A JPH02270887 A JP H02270887A
- Authority
- JP
- Japan
- Prior art keywords
- group
- halogen
- formula
- substituted
- general formula
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000003961 organosilicon compounds Chemical class 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 11
- 125000006239 protecting group Chemical group 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 7
- 150000003944 halohydrins Chemical class 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 abstract 1
- -1 silane compound Chemical class 0.000 description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 229910000077 silane Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 2
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 2
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 2
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 2
- UPYSACBOPSZOMB-UHFFFAOYSA-N 4-chlorobutoxy(trimethyl)silane Chemical compound C[Si](C)(C)OCCCCCl UPYSACBOPSZOMB-UHFFFAOYSA-N 0.000 description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-UHFFFAOYSA-N 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000004863 4-trifluoromethoxyphenyl group Chemical group [H]C1=C([H])C(OC(F)(F)F)=C([H])C([H])=C1* 0.000 description 1
- DCBJCKDOZLTTDW-UHFFFAOYSA-N 5-chloropentan-1-ol Chemical compound OCCCCCCl DCBJCKDOZLTTDW-UHFFFAOYSA-N 0.000 description 1
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 1
- DPNLUCKAZIFDLB-UHFFFAOYSA-N 7-chloroheptan-1-ol Chemical compound OCCCCCCCCl DPNLUCKAZIFDLB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001646398 Pseudomonas chlororaphis Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- BMZJKRWQEVUKJU-UHFFFAOYSA-N chloro-(chloromethyl)-(4-chlorophenyl)-methylsilane Chemical compound ClC[Si](Cl)(C)C1=CC=C(Cl)C=C1 BMZJKRWQEVUKJU-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は文献未載の新規な有機けい素化合物及びその製
造方法に係り、特には、合成用中間体等として有用な、
クロロメチル基がけい素原子に結合したヒドロキシアル
キルシラン、及びクリ二ヤール反応を応用したその製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel organosilicon compound that has not been published in any literature and a method for producing the same, and particularly relates to a novel organosilicon compound that is useful as a synthetic intermediate, etc.
The present invention relates to a hydroxyalkylsilane in which a chloromethyl group is bonded to a silicon atom, and a method for producing the same using Clinillard reaction.
（従来の技術）
従来、クロロメチル基がけい素原子に結合したヒドロキ
シアルキルシランは知られておらず、その合成法も報告
されていなかった。しかし、このシラン化合物は有用物
質生産のための合成用中間体等として、その必要性が認
められるものであった。(Prior Art) Hitherto, hydroxyalkylsilanes in which a chloromethyl group is bonded to a silicon atom have not been known, and no method for their synthesis has been reported. However, the necessity of this silane compound was recognized as a synthetic intermediate for producing useful substances.
Ｃ発明の構成）
本発明者らは、前記の新規な化合物であるヒドロキシア
ルキルシランの合成について鋭意研究の結果、ハロアル
コールを原料に用い、その水酸基を保護基により保護し
、ついでグリニヤール試薬に誘導し、これをクロロメチ
ル基を有するハロシランまたはアルコキシシランと反応
させ、生成物から前記の保護基を脱離させれば、目的と
するシランを収率よく取得できる可能性があることを見
出し、さらに検討を重ねて本発明を完成させた。C) Structure of the Invention) As a result of intensive research into the synthesis of hydroxyalkylsilane, which is the above-mentioned novel compound, the present inventors used a haloalcohol as a raw material, protected its hydroxyl group with a protecting group, and then induced it into a Grignard reagent. However, they discovered that the desired silane could be obtained in good yield by reacting it with a halosilane or alkoxysilane having a chloromethyl group to remove the above-mentioned protecting group from the product, and conducted further studies. The present invention was completed by repeating the steps.
この出願の第１の発明は、一般式Ｉ
ＣＩ（３
（式中、Ｒ’、Ｒ”は独立に、水素原子、ハロゲン原子
、−０ＣＨ３基、−０ＣＨＦ２基、−０ＣＦ３基、フェ
ニル基、ハロゲンで置換されたフェニル基、フェノキシ
基、ハロゲンで置換されたフェノキシ基、−ＣＦ３基ま
たは炭素数１〜４のアルキル基を表わし、ｎは３〜７の
整数を表わす。）で示されるヒドロキシアルキルシラン
化合物を要旨とするものである。The first invention of this application is based on the general formula I CI(3 (wherein R' and R'' independently represent a hydrogen atom, a halogen atom, a -0CH3 group, a -0CHF2 group, a -0CF3 group, a phenyl group, a halogen represents a phenyl group substituted with a phenyl group, a phenoxy group, a phenoxy group substituted with a halogen, a -CF3 group, or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 3 to 7.) Hydroxyalkylsilane represented by The gist is compounds.
第２の発明は前記のシラン化合物を製造する方法の発明
であって、一般式２
％式％
（式中、Ｘはハロゲン原子を表わし、ｎは３〜７の整数
を表わす。）で示されるハロアルコールの水酸基を保護
基により保護し、ついでグリニヤール試薬に誘導し、こ
れを一般式３
（式中、Ｒ’、Ｒ２は独立に、水素原子、ハロゲン原子
、−０ＣＨ，基、−０ＧＨＦ２基、−０ＣＦ３基、フェ
ニル基、ハロゲンで置換されたフェニル基、フェノキシ
基、ハロゲンで置換されたフェノキシ基、−ＣＦ３基ま
たは炭素数１〜４のアルキル基を表わし、Ｙはハロゲン
原子または炭素数１〜４のアルコキシ基を表わす。）で
示されるハロシランまたはアルコキシシランと反応させ
、生成物から前記の保護基を脱離させることを特徴とす
る、一般式１０式中、Ｒ１、Ｒ２、ｎは前記に同じ。）
で示されるヒドロキシアルキルシラン化合物の製造方法
を要旨とするものである。The second invention is an invention of a method for producing the above-mentioned silane compound, which is represented by the general formula 2% (wherein, X represents a halogen atom, and n represents an integer from 3 to 7). The hydroxyl group of the haloalcohol is protected with a protecting group, and then induced into a Grignard reagent, which is converted into the general formula 3 (wherein R' and R2 are independently a hydrogen atom, a halogen atom, a -0CH group, a -0GHF2 group, -0CF3 group, phenyl group, halogen-substituted phenyl group, phenoxy group, halogen-substituted phenoxy group, -CF3 group, or an alkyl group having 1 to 4 carbon atoms, and Y is a halogen atom or a C1 to 4 alkyl group; In the general formula 10, R1, R2, and n are as defined above. same. )
The gist of this article is a method for producing a hydroxyalkylsilane compound shown in the following.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明のヒドロキシアルキルシラン化合物は一般式Ｉ Ｈ３ で示される。The hydroxyalkylsilane compounds of the present invention have the general formula I H3 It is indicated by.
前記式中、Ｒ’、Ｒ”は独立に、水素原子、ハロゲン原
子、−〇ＣＨ３基、−０にＨＦ２基、−００Ｆ３基、７
ｓ−１−ル基、ハロゲンで置換されたフェニル基、フ
ェノキシ基、ハロゲンで置換されたフェノキシ基、−Ｃ
Ｆ３基または炭素数１〜４のアルキル基を表わすもので
あるが、このようなＲ’、Ｒ”を有しけい素原子に結合
した前記式中のフェニル基としては、例えば、フェニル
基、４−フルオロフェニル基、３−フルオロフェニル基
、４−クロロフェニル基、３−クロロフェニル基、４−
ブロモフェニル基、３．４−ジフルオロフェニル基、３
．５−ジフルオロフェニル基、３，４−ジクロロフェニ
ル基、３．５−ジクロロフェニル基、４−メチルフェニ
ル基、３−メチルフェニル基、３，４−ジメチルフェニ
ル基、３．５−ジメチルフェニル基、４−エチルフェニ
ル基、４−プロピルフェニル基、４−１−ブチルフェニ
ル基、４−クロロ−３−メチルフェニル基、３−クロロ
−４−メチルフェニル基、４−メトキシフェニル基、３
−メトキシフェニル基、２−メトキシフェニル基、４−
エトキシフェニル基、４−ｎ−プロポキシフェニル基、
４−ｎ−ブトキシフェニル基、４−トリフルオロメトキ
シフェニル基、４−ジフルオロメトキシフェニル基、３
−ジフルオロメトキシフェニル基、４−トリフルオロメ
チルフェニル基、３−トリフルオロメチルフェニル基、
２−トリフルオロメチルフェニル基、４−フェニルフェ
ニル基、４−フェノキシフェニル基、４−（４−クロロ
フェニル）フェニル基等が挙げられる。しかしこれらに
限定されるものではない。In the above formula, R' and R'' are independently hydrogen atom, halogen atom, -0CH3 group, -0 is HF2 group, -00F3 group, 7
s-1-l group, halogen-substituted phenyl group, phenoxy group, halogen-substituted phenoxy group, -C
It represents an F3 group or an alkyl group having 1 to 4 carbon atoms, and the phenyl group in the above formula having such R', R'' and bonded to a silicon atom is, for example, a phenyl group, 4 -Fluorophenyl group, 3-fluorophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 4-
Bromophenyl group, 3,4-difluorophenyl group, 3
．． 5-difluorophenyl group, 3,4-dichlorophenyl group, 3.5-dichlorophenyl group, 4-methylphenyl group, 3-methylphenyl group, 3,4-dimethylphenyl group, 3.5-dimethylphenyl group, 4- Ethylphenyl group, 4-propylphenyl group, 4-1-butylphenyl group, 4-chloro-3-methylphenyl group, 3-chloro-4-methylphenyl group, 4-methoxyphenyl group, 3
-methoxyphenyl group, 2-methoxyphenyl group, 4-
Ethoxyphenyl group, 4-n-propoxyphenyl group,
4-n-butoxyphenyl group, 4-trifluoromethoxyphenyl group, 4-difluoromethoxyphenyl group, 3
-difluoromethoxyphenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group,
Examples include 2-trifluoromethylphenyl group, 4-phenylphenyl group, 4-phenoxyphenyl group, and 4-(4-chlorophenyl)phenyl group. However, it is not limited to these.
また、前記式中のヒドロキシアルキル基は炭素数３〜７
の直鎖状のものであり、これには、３−ヒドロキシプロ
ピル基、４−ヒドロキシブチル基、５−ヒドロキシペン
チル基、６−ヒドロキシヘキシル基、７−ヒドロキシへ
ブチル基等が例示される。Furthermore, the hydroxyalkyl group in the above formula has 3 to 7 carbon atoms.
Examples thereof include 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, and 7-hydroxyhebutyl group.
次に本発明のヒドロキシアルキルシラン化合物の製造方
法について説明する。Next, the method for producing the hydroxyalkylsilane compound of the present invention will be explained.
本発明の製造方法においては、原料として前記の一般式
２
％式％）
（式中のＸ、ｎは前記のとおり）で示されるハロアルコ
ールを用いるが、これには、公知のものを用いることが
でき、３−クロロプロパツール、４−クロロブタノール
、５−クロロペンタノール、６−クロロへキサノール、
７−クロロヘプタノール等が例示される。In the production method of the present invention, a haloalcohol represented by the general formula 2% formula %) (in which X and n are as described above) is used as a raw material, but known ones may be used. 3-chloropropanol, 4-chlorobutanol, 5-chloropentanol, 6-chlorohexanol,
Examples include 7-chloroheptanol.
このハロアルコールは、その水酸基を保護基によって保
護したものとして用いるが、保護基としては通常のグリ
ニヤール反応の条件下に安定なものであれば特に制限は
なく、これには公知のもの、例えば、トリメチルシリル
基、トリエチルシリル基、ｔ−ブチルジメチルシリル基
、クミルジメチルシリル基等のシリル基、メチル基、テ
トラヒドロピラニル基を挙げることができ、また、ハロ
マグネシウム塩として保護することもできる。This haloalcohol is used with its hydroxyl group protected by a protecting group, but there are no particular restrictions on the protecting group as long as it is stable under the conditions of a normal Grignard reaction. Examples include silyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, and cumyldimethylsilyl group, methyl group, and tetrahydropyranyl group, and they can also be protected as halomagnesium salts.
水酸基に保護基を結合するには公知の方法によればよい
。A known method may be used to bond a protecting group to a hydroxyl group.
水酸基を保護されたハロアルコールは、公知の方法によ
りグリニヤール試薬に導くことができる。A haloalcohol with a protected hydroxyl group can be converted into a Grignard reagent by a known method.
他方の原料は一般式３
で示されるシランであり、式中のＲ１，Ｒ２を有するフ
ェニル基は先に例示したとおりであるが、Ｙとしてはハ
ロゲンのフッ素原子、塩素原子、臭素原子、ヨウ素原子
やアルコキシ基のメトキシ基、エトキシ基、プロポキシ
基、ブトキシ基が挙げられる。The other raw material is a silane represented by the general formula 3, and the phenyl groups having R1 and R2 in the formula are as exemplified above, and Y is a halogen fluorine atom, chlorine atom, bromine atom, or iodine atom. and alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups.
このシランは公知のクロロメチルメチルジハロシランま
たはクロロメチルメチルジアルコキシシランに対して、
アリールハロゲン化物から誘導される一般式４
（式中、）ｔｌ、Ｒ２は前記に同じ、２はハロゲン原子
を表わす。）で示される有機金属試薬を反応させること
によって容易に合成することができる。この反応はジエ
チルエーテル、テトラヒドロフラン、ジオキサン等のエ
ーテル系の溶媒中で行うことができる。This silane is different from known chloromethylmethyldihalosilane or chloromethylmethyldialkoxysilane.
General formula 4 derived from aryl halide (wherein) tl and R2 are the same as above, and 2 represents a halogen atom. ) can be easily synthesized by reacting organometallic reagents shown in This reaction can be carried out in an ether solvent such as diethyl ether, tetrahydrofuran or dioxane.
ついで、前記のグリニヤール試薬と一般式３で示される
シランを含む溶液とを用いて、０〜１００℃、望ましく
は５〜５０℃の温度範囲で反応させる。この反応はジエ
チルエーテル、テトラヒドロフラン、ジオキサン等のエ
ーテル系の溶媒中で行うことができる。Then, using the Grignard reagent and a solution containing the silane represented by general formula 3, a reaction is carried out at a temperature range of 0 to 100°C, preferably 5 to 50°C. This reaction can be carried out in an ether solvent such as diethyl ether, tetrahydrofuran or dioxane.
反応終了後に、水酸基の保護基を離脱させるが、これは
前記の保護基を離脱させるための通常の反応条件下に行
うことができる。After the reaction is completed, the hydroxyl protecting group is removed, and this can be done under the usual reaction conditions for removing the above-mentioned protecting groups.
目的物の単離は通常のグリニヤール反応の場合と同様に
して行われ、冷却下、水、希塩酸または塩化アンモニウ
ム水溶液を加え、撹拌した後、酢酸エチルまたはエチル
エーテル等の水と混じり合わない溶媒で抽出し、抽出液
から減圧上溶媒をストリップし、残渣を必要に応じて減
圧蒸留またはクロマトグラフィーで分離すれば、目的の
ヒドロキシアルキルシランが得られる。Isolation of the target product is carried out in the same manner as in the usual Grignard reaction. Water, dilute hydrochloric acid or ammonium chloride aqueous solution is added under cooling, and after stirring, the target product is isolated with a water-immiscible solvent such as ethyl acetate or ethyl ether. The desired hydroxyalkylsilane is obtained by extraction, stripping the solvent from the extract under reduced pressure, and separating the residue by distillation under reduced pressure or chromatography as required.
本発明のヒドロキシアルキルシランは新規な化合物であ
り、医薬、農薬等の生理活性物質合成のための中間体、
及びこれらのビルディングブロック合成のための中間体
として重要であり、また、これらの化合物自体が酸化防
止剤、表面処理剤、接着促進剤、生物制御剤等として有
用である。The hydroxyalkylsilane of the present invention is a new compound, and is an intermediate for the synthesis of physiologically active substances such as medicines and agricultural chemicals.
and are important as intermediates for the synthesis of these building blocks, and these compounds themselves are useful as antioxidants, surface treatment agents, adhesion promoters, biological control agents, and the like.
本発明の製造方法によれば、新規な化合物である広範囲
のメチレン鎖長をもつヒドロキシアルキルシランを高収
率で得ることができる。According to the production method of the present invention, a novel compound, hydroxyalkylsilane having a wide range of methylene chain lengths, can be obtained in high yield.
次に本発明の実施例を挙げる。Next, examples of the present invention will be described.
実施例１
金属マグネシウム０．５ｇ （２０，６ミｌＪモル）の
２０ｍｊ２乾燥Ｔ肝懸濁液に４−トリメチルシリルオキ
シ−１−クロロブタン３．７２ｇ （２０，６ミｌＪ（
ル）をゆっくり滴下することによってグリニヤール試薬
を得た。これとは別に、４−クロロフェニルクロロメチ
ルメチルクロロシラン４．９３ｇ （２０，６ミリモル
）を乾燥ＴＨＦ２０ｍ、１２に溶解した溶液を水冷して
５℃としておき、これを撹拌しながら、さきに調製した
グリニヤール試薬の溶液を３０分間かけて滴下した。こ
の間反応液の温度は５〜２０℃に保った。さらに３０分
間同温度に保ったのち、塩化アンモニウムの希塩酸溶液
３０ｍ℃を加えよく攪拌した。これを酢酸エチル５０ｍ
ｆ２で抽出し、抽出液を無水硫酸ナトリウムで乾燥した
のち、溶媒を留去すると無色の油状物が得られた。この
油状物をシリカゲルカラムクロマトグラフィーによって
分離したところ、４−ヒドロキシブチル−４−クロロフ
ェニルクロロメチルメチルシラン４．２ｇを純品として
得た。（収率８４％）このものが上記のシランであるこ
とは下記の分析により確認した。Example 1 To a suspension of 0.5 g (20.6 ml J mol) of magnesium metal in 20 mJ2 dry T-liver was added 3.72 g (20.6 ml J) of 4-trimethylsilyloxy-1-chlorobutane.
A Grignard reagent was obtained by slowly dropping the solution. Separately, a solution of 4.93 g (20.6 mmol) of 4-chlorophenylchloromethylmethylchlorosilane dissolved in 20 m, 12 dry THF was cooled with water and kept at 5°C, and while stirring, the previously prepared Grignard The reagent solution was added dropwise over 30 minutes. During this time, the temperature of the reaction solution was maintained at 5 to 20°C. After maintaining the same temperature for an additional 30 minutes, a dilute hydrochloric acid solution of ammonium chloride at 30 m°C was added and stirred well. Add this to 50ml of ethyl acetate
After extracting with f2 and drying the extract over anhydrous sodium sulfate, the solvent was distilled off to obtain a colorless oil. When this oily substance was separated by silica gel column chromatography, 4.2 g of 4-hydroxybutyl-4-chlorophenylchloromethylmethylsilane was obtained as a pure product. (Yield: 84%) It was confirmed by the following analysis that this product was the above-mentioned silane.
質量スペクトル ｍ／ｅ
２２７ （Ｍ”−ＣＨ，（Ｉ２） 、 １７１ （ｂａ
ｓｅ）核磁気共鳴スペクトル （δ＋ ｐｐｍ ）０、
４０３ ｆ６Ｈ，ｓ） 、 ０．９４ （２Ｈ，ｍｌ
、１．４３ （２Ｈ，ｍｌ、、 １．６０７ ｆ２Ｈｍ
ｌ 、 ２．９７ ｆ２Ｈ，ｓ） 、 ３．６２ （２
Ｈ，ｔ、 Ｊ＝６．３Ｈｚｌ 、 ７．３６ （２Ｈ，
ｄ。Mass spectrum m/e 227 (M”-CH, (I2), 171 (ba
se) Nuclear magnetic resonance spectrum (δ+ ppm) 0,
403 f6H, s), 0.94 (2H, ml
, 1.43 (2H, ml,, 1.607 f2Hm
l, 2.97 f2H,s), 3.62 (2
H, t, J=6.3Hzl, 7.36 (2H,
d.
Ｊ＝８．３１ 、７．４４ ｆ２Ｈ，ｄ、 Ｊ＝８．３
１実施例２
実施例１における４−トリメチルシリルオキシ−１−ク
ロロブタンの代りに６−ドリメチルシリルオキシー１−
クロロヘキサンを用いたほかは、実施例１と同様にして
６−ヒドロキシへキシル−４−クロロフェニルクロロメ
チルメチルシランを合成した。（収率６６％）
このものが上記のシランであることは下記の分析により
確認した。J=8.31, 7.44 f2H,d, J=8.3
1 Example 2 In place of 4-trimethylsilyloxy-1-chlorobutane in Example 1, 6-trimethylsilyloxy-1-
6-Hydroxyhexyl-4-chlorophenylchloromethylmethylsilane was synthesized in the same manner as in Example 1 except that chlorohexane was used. (Yield 66%) It was confirmed by the following analysis that this product was the above-mentioned silane.
質量スペクトル ｌＴｌ／ｅ
２５５ （Ｍ”−ＣＨ，Ｃｌ２） 、 ２３７．１７１
（ｂａｓｅｌ核磁気共鳴スペクトル （δ＋ ｐｐｍ
）０、３８５ ｆ３Ｈ，ｓ） 、 ０．９１３ （２
Ｈ，ｍｌ 、 １．３５９ ｆ８Ｈ，ｍｌ 、 １．５
３ｆ２Ｈ，ｍ） 、 ２．９５３ （２Ｈ，ｓｌ 、
３．６０２ （２Ｈ，ｔ、 Ｊ＝６．３Ｈｚｌ 、 ７
．３５（２Ｈ，ｄ、 Ｊ＝８．３） 、 ７．４３ （
２Ｈ，ｄ、 Ｊ＝８．３１実施例３〜３１
一般式
オロフェニル基、４−フルオロフェニル基、３−クロロ
フェニル基、４−クロロフェニル基、２−メトキシフェ
ニル基、３−メトキシフェニル基、４−メトキシフェニ
ル基、３−トリル基、４−トリル基、３，５−ジフルオ
ロ）千ニル基、３，４−ジクロロフェニル基、３，５−
ジクロロフェニル基、３−クロロ−４−メチルフェニル
基、４−クロロ−３−メチルフェニル基、４− ｔｅｒ
ｔ−ブチルフェニル基または４−トリフルオロメチルフ
ェニル基を有する化合物、及び一般式
％式％）
においてｎが３〜７の整数である化合物を原料として用
い、実施例１と同様の方法により前記一般式Ｉ
ＣＨ。Mass spectrum lTl/e 255 (M”-CH, Cl2), 237.171
(basel nuclear magnetic resonance spectrum (δ+ ppm
)0, 385 f3H,s), 0.913 (2
H, ml, 1.359 f8H, ml, 1.5
3f2H,m), 2.953 (2H,sl,
3.602 (2H, t, J=6.3Hzl, 7
．． 35 (2H, d, J=8.3), 7.43 (
2H, d, J=8.31 Examples 3 to 31 General formula orophenyl group, 4-fluorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxy Phenyl group, 3-tolyl group, 4-tolyl group, 3,5-difluoro)thousandyl group, 3,4-dichlorophenyl group, 3,5-
Dichlorophenyl group, 3-chloro-4-methylphenyl group, 4-chloro-3-methylphenyl group, 4-ter
Using a compound having a t-butylphenyl group or a 4-trifluoromethylphenyl group, and a compound having the general formula (%) in which n is an integer of 3 to 7 as raw materials, the above general formula was prepared in the same manner as in Example 1. Formula I CH.
化合物を合成した。The compound was synthesized.
これらの化合物についての質量スペクトルの分析結果は
第１表に併記したとおりであった。The mass spectrum analysis results for these compounds are shown in Table 1.
第１表Table 1
Claims (1)
原子、−ＯＣＨ＿３基、−ＯＣＨＦ＿２基、−ＯＣＦ＿
３基、フェニル基、ハロゲンで置換されたフェニル基、
フェノキシ基、ハロゲンで置換されたフェノキシ基、−
ＣＦ＿３基または炭素数１〜４のアルキル基を表わし、
ｎは３〜７の整数を表わす。） で示されるヒドロキシアルキルシラン化合物。 ２、一般式２ ▲数式、化学式、表等があります▼ （式中、Ｘはハロゲン原子を表わし、ｎは３〜７の整数
を表わす。） で示されるハロアルコールの水酸基を保護基により保護
し、ついでグリニヤール試薬に誘導し、これを一般式３ ▲数式、化学式、表等があります▼ （式中、Ｒ＾１、Ｒ＾２は独立に、水素原子、ハロゲン
原子、−ＯＣＨ＿３基、−ＯＣＨＦ＿２基、−ＯＣＦ＿
３基、フェニル基、ハロゲンで置換されたフェニル基、
フェノキシ基、ハロゲンで置換されたフェノキシ基、−
ＣＦ＿３基または炭素数１〜４のアルキル基を表わし、
Ｙはハロゲン原子または炭素数１〜４のアルコキシ基を
表わす。） で示されるハロシランまたはアルコキシシランと反応さ
せ、生成物から前記の保護基を脱離させることを特徴と
する、一般式１ ▲数式、化学式、表等があります▼ （式中、Ｒ＾１、Ｒ＾２、ｎは前記に同じ。）で示され
るヒドロキシアルキルシラン化合物の製造方法。[Claims] 1. General formula 1 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 independently represent a hydrogen atom, a halogen atom, -OCH_3 group, -OCHF_2 group, -OCF_
3 groups, phenyl group, phenyl group substituted with halogen,
Phenoxy group, halogen-substituted phenoxy group, -
Represents a CF_3 group or an alkyl group having 1 to 4 carbon atoms,
n represents an integer from 3 to 7. ) A hydroxyalkylsilane compound represented by 2. General formula 2 ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents a halogen atom, and n represents an integer from 3 to 7.) The hydroxyl group of the haloalcohol represented by the formula is protected with a protective group. , then induced into a Grignard reagent, which is expressed by the general formula 3 ▲ There are mathematical formulas, chemical formulas, tables, etc. Group, -OCF_
3 groups, phenyl group, phenyl group substituted with halogen,
Phenoxy group, halogen-substituted phenoxy group, -
Represents a CF_3 group or an alkyl group having 1 to 4 carbon atoms,
Y represents a halogen atom or an alkoxy group having 1 to 4 carbon atoms. ) General formula 1 ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, R^2, n are the same as above.) A method for producing a hydroxyalkylsilane compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1092164A JPH0720976B2 (en) | 1989-04-12 | 1989-04-12 | Organic silicon compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1092164A JPH0720976B2 (en) | 1989-04-12 | 1989-04-12 | Organic silicon compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02270887A true JPH02270887A (en) | 1990-11-05 |
| JPH0720976B2 JPH0720976B2 (en) | 1995-03-08 |
Family
ID=14046789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1092164A Expired - Lifetime JPH0720976B2 (en) | 1989-04-12 | 1989-04-12 | Organic silicon compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0720976B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0800525A4 (en) * | 1994-07-25 | 1997-10-15 | ||
| US5912378A (en) * | 1994-07-25 | 1999-06-15 | Fmc Corporation | Process for preparing trimethylsilyloxy functionalized alkyllithium compounds |
| KR100379300B1 (en) * | 2000-11-06 | 2003-04-10 | 주식회사 중외제약 | Sequential catalytic asymmetric allyl transfer reactions for the enantioselective synthesis of new pyran derivatives |
-
1989
- 1989-04-12 JP JP1092164A patent/JPH0720976B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0800525A4 (en) * | 1994-07-25 | 1997-10-15 | ||
| US5912378A (en) * | 1994-07-25 | 1999-06-15 | Fmc Corporation | Process for preparing trimethylsilyloxy functionalized alkyllithium compounds |
| KR100379300B1 (en) * | 2000-11-06 | 2003-04-10 | 주식회사 중외제약 | Sequential catalytic asymmetric allyl transfer reactions for the enantioselective synthesis of new pyran derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0720976B2 (en) | 1995-03-08 |
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