JP2002193975A - New organosilicon compound having adamantyl ester group - Google Patents
New organosilicon compound having adamantyl ester groupInfo
- Publication number
- JP2002193975A JP2002193975A JP2000400560A JP2000400560A JP2002193975A JP 2002193975 A JP2002193975 A JP 2002193975A JP 2000400560 A JP2000400560 A JP 2000400560A JP 2000400560 A JP2000400560 A JP 2000400560A JP 2002193975 A JP2002193975 A JP 2002193975A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- ester group
- adamantyl ester
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 title claims abstract description 19
- 125000004185 ester group Chemical group 0.000 title claims abstract description 12
- 150000003961 organosilicon compounds Chemical class 0.000 title claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- -1 dimethylene group Chemical group 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RJUIDDKTATZJFE-NSCUHMNNSA-N (e)-but-2-enoyl chloride Chemical compound C\C=C\C(Cl)=O RJUIDDKTATZJFE-NSCUHMNNSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000005371 silicon functional group Chemical group 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical group OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 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
- 150000001721 carbon Chemical group 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アダマンチルエス
テル基を有する新規なハロゲノシラン及びその中間体に
関する。TECHNICAL FIELD The present invention relates to a novel halogenosilane having an adamantyl ester group and an intermediate thereof.
【０００２】[0002]
【従来の技術】アダマンチル基を有する以下の化合物は
知られている。2. Description of the Related Art The following compounds having an adamantyl group are known.
【０００３】[0003]
【化３】 Embedded image
【０００４】[0004]
【化４】 Embedded image
【０００５】しかし、1-ブテン酸アダマンチルエステル
およびアダマンチルエステル基を有する有機基の末端炭
素原子にハロゲノシリル基のようなケイ素官能基が結合
した有機ケイ素化合物は知られていない。However, an organosilicon compound in which a silicon functional group such as a halogenosilyl group is bonded to a terminal carbon atom of an organic group having an adamantyl ester group and an adamantyl ester group is not known.
【０００６】[0006]
【発明が解決しようとする課題】本発明の課題は、アダ
マンチルエステル基を有する新規なハロゲノシランを提
供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel halogenosilane having an adamantyl ester group.
【０００７】[0007]
【課題を解決するための手段】本発明者は、アダマンチ
ルエステル基を有するハロゲノシランが、一方ではケイ
素官能基を有し、他方ではアダマンチルエステル基を有
するために、有機合成の中間原料や各種材料のカップリ
ング剤として有用であることに着目し、その構造上の特
徴を有する種々の化合物を検討して本発明を完成するに
至った。即ち、本発明は、下記一般式［２］で表され
る、アダマンチルエステル基を有するハロゲノシラン
（以下、本発明ケイ素系化合物［２］という）及びその
中間体として有用な下記構造式［１］で表される化合物
（以下、化合物［１］と略す）である。Means for Solving the Problems The present inventors have found that halogenosilane having an adamantyl ester group has a silicon functional group on the one hand and an adamantyl ester group on the other hand, so that intermediate raw materials and various materials for organic synthesis can be used. Focusing on its usefulness as a coupling agent, the present invention was completed by examining various compounds having structural characteristics thereof. That is, the present invention provides a halogenosilane having an adamantyl ester group represented by the following general formula [2] (hereinafter referred to as the silicon compound of the present invention [2]) and the following structural formula [1] useful as an intermediate thereof. (Hereinafter, abbreviated as compound [1]).
【０００８】[0008]
【化５】 Embedded image
【０００９】（式中、Ｒ1は炭素数１から４のアルキル
基であり、Ｒ2は炭素数２から６のアルキレン基であ
り、Ｘはハロゲンである。）Wherein R 1 is an alkyl group having 1 to 4 carbon atoms, R 2 is an alkylene group having 2 to 6 carbon atoms, and X is a halogen.
【００１０】[0010]
【化６】 Embedded image
【００１１】[0011]
【発明の実施の形態】以下、本発明について詳述する。
本発明ケイ素系化合物［２］は上記一般式［２］で表さ
れる。一般式［２］において、Ｒ1は炭素数１から４の
アルキル基である。Ｒ1の好ましい具体例として、メチ
ル基、エチル基、プロピル基、ブチル基があり、直鎖状
でも分岐状でも差し支えない。その中でも、原料が得易
く、合成が容易なことから、特にメチル基が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The silicon compound [2] of the present invention is represented by the general formula [2]. In the general formula [2], R 1 is an alkyl group having 1 to 4 carbon atoms. Preferred specific examples of R 1 include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be linear or branched. Among them, a methyl group is particularly preferable because a raw material is easily obtained and synthesis is easy.
【００１２】一般式［２］において、Ｒ2は炭素数２か
ら６のアルキレン基である。Ｒ2は直鎖状、分岐状のい
ずれでもよく、好ましい具体例として、ジメチレン基、
トリメチレン基、テトラメチレン基、ペンタメチレン
基、ヘキサメチレン基、２−メチルトリメチレン基、３
−メチルトリメチレン基などがあり、合成の容易なこと
および原料の入手のしやすさから、特にトリメチレン基
が好ましい。In the general formula [2], R 2 is an alkylene group having 2 to 6 carbon atoms. R 2 may be linear or branched, and preferred specific examples include a dimethylene group,
Trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 2-methyltrimethylene group, 3
-Methyltrimethylene group and the like, and a trimethylene group is particularly preferable because of easy synthesis and availability of raw materials.
【００１３】一般式［２］において、Ｘはハロゲンであ
り、原料入手の容易さから塩素であることが最も好まし
い。本発明ケイ素系化合物［２］の最も好ましい具体例
は、以下の構造式［５］で示される化合物（以下、化合
物［５］という）である。In the general formula [2], X is a halogen, and most preferably chlorine because of availability of raw materials. The most preferred specific example of the silicon compound [2] of the present invention is a compound represented by the following structural formula [5] (hereinafter, referred to as compound [5]).
【００１４】[0014]
【化７】 Embedded image
【００１５】本発明ケイ素系化合物［２］は、例えば次
のようにして製造することができる。即ち、Ｒ3−ＣＯ
Ｃｌ（但し、Ｒ3はＲ2と同じ炭素数を有し、１個の炭素
−炭素不飽和基を有する有機基である。具体的なＲ
3は、目的とする化合物［２］に応じて適宜決定され
る。）にアミン存在下でアダマンタノールを反応させる
ことにより容易に下記式［６］で表される化合物を得
る。The silicon compound [2] of the present invention can be produced, for example, as follows. That is, R 3 —CO
Cl (where R 3 is an organic group having the same carbon number as R 2 and having one carbon-carbon unsaturated group.
3 is appropriately determined according to the desired compound [2]. ) Is reacted with adamantanol in the presence of an amine to easily obtain a compound represented by the following formula [6].
【００１６】[0016]
【化８】 Embedded image
【００１７】好ましいアミンは、トリエチルアミン、ピ
リジンなどである。反応温度は、常温から溶媒の沸点近
くの温度範囲で適宜調整でき、例えばアダマンタノール
に溶媒とアミンを加え、氷冷下にtrans-クロトニルクロ
ライドを滴下した後、常温又は若干加温状態で保持した
り、或いは溶媒の沸点近くで還流を行うことができる。
好ましい溶媒は、ｎ−ペンタン、ｎ−ヘキサン、シクロ
ヘキサン、石油エーテル、トルエン、キシレン、ガソリ
ン、リグロイン等の炭化水素類；ジエチルエーテル、ジ
イソプロピルエーテル、テトラヒドロフラン等のエーテ
ル類である。Preferred amines are triethylamine, pyridine and the like. The reaction temperature can be appropriately adjusted in a temperature range from room temperature to a temperature close to the boiling point of the solvent. Alternatively, reflux can be carried out near the boiling point of the solvent.
Preferred solvents are hydrocarbons such as n-pentane, n-hexane, cyclohexane, petroleum ether, toluene, xylene, gasoline, and ligroin; and ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran.
【００１８】反応終了後、溶媒とアミンを留去し、減圧
蒸留によって化合物［６］を単離する。このようにして
得られた化合物［６］を、ジメチルクロロシランとハイ
ドロシリレーション反応させ、本発明ケイ素系化合物
［２］を得る。この反応は触媒の存在下で行われ、好ま
しい触媒は、コバルト、ニッケル、ルテニウム、ロジウ
ム、パラジウム、イリジウム、白金等の第８属から第１
０属金属の単体、有機金属錯体、金属塩または金属酸化
物等であり、通常、白金系の触媒が使用される。好まし
い白金系触媒は、塩化白金酸六水和物（H2PtCl6・６H
2O）、cis-PtCl2(PhCN)2、白金カーボン等である。な
お、Phはフェニル基を表わす。触媒の好ましい使用量
は、化合物［１］の量に対して、0.1ｐｐｍから1,000ｐ
ｐｍである。After completion of the reaction, the solvent and the amine are distilled off, and the compound [6] is isolated by distillation under reduced pressure. The compound [6] thus obtained is subjected to a hydrosilylation reaction with dimethylchlorosilane to obtain the silicon-based compound [2] of the present invention. This reaction is carried out in the presence of a catalyst, and preferred catalysts include those belonging to Group 8 to 1 such as cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum.
It is a simple substance of a Group 0 metal, an organometallic complex, a metal salt or a metal oxide, and usually a platinum-based catalyst is used. The preferred platinum catalyst is chloroplatinic acid hexahydrate (H 2 PtCl 6 · 6H
2 O), cis-PtCl 2 (PhCN) 2 , platinum carbon and the like. Ph represents a phenyl group. The preferred amount of the catalyst used is 0.1 ppm to 1,000 p based on the amount of the compound [1].
pm.
【００１９】また、上記触媒を用いる本発明ケイ素系化
合物［２］の製造は加熱下で行われる。反応温度の制御
操作は、外部からの加熱およびジメチルクロロシランの
供給速度に依存するため、一概に決められないが、通
常、反応温度を６０℃〜１１０℃の範囲に保持すること
で、ヒドロシリレーション反応を円滑に継続させること
ができる。この温度が６０℃未満ではヒドロシリレーシ
ョン反応が円滑に継続されず、１１０℃を超えると、暴
走反応が引き起こされる恐れがある。The production of the silicon compound [2] of the present invention using the above catalyst is performed under heating. The control operation of the reaction temperature depends on external heating and the supply rate of dimethylchlorosilane, and thus cannot be unconditionally determined. The reaction can be continued smoothly. If this temperature is lower than 60 ° C., the hydrosilylation reaction does not continue smoothly. If the temperature exceeds 110 ° C., a runaway reaction may be caused.
【００２０】最も好ましい構造を有する上記化合物
［５］を例にとると、先ずtrans-クロトニルクロライド
にアミン存在下でアダマンタノールを反応させて、アダ
マンチル基を有する下記化合物［１］を得る。Taking the above compound [5] having the most preferred structure as an example, first, trans-crotonyl chloride is reacted with adamantanol in the presence of an amine to obtain the following compound [1] having an adamantyl group.
【００２１】[0021]
【化９】 Embedded image
【００２２】次いで、このようにして得られた化合物
［１］を、ジメチルクロロシランと反応させ、下記の本
発明ケイ素系化合物［５］を得る。Next, the compound [1] thus obtained is reacted with dimethylchlorosilane to obtain the following silicon compound [5] of the present invention.
【００２３】[0023]
【化１０】 Embedded image
【００２４】上記化合物［１］は新規物質であり、本発
明ケイ素系化合物［５］を得るための中間体として有用
である。上記化合物［１］と類似の化合物として上記化
合物［３］と化合物［４］があるが、上記化合物［３］
は炭素不飽和結合が分子末端にないためハイドロシリレ
ーション反応が進行しないという問題があり、上記化合
物［４］はアダマンチル基により保護されたカルボキシ
ル基を生成物に付与することができないという問題があ
る。The above compound [1] is a novel substance and is useful as an intermediate for obtaining the silicon compound [5] of the present invention. The compound [3] and the compound [4] are similar to the compound [1].
Has a problem that the hydrosilylation reaction does not proceed because there is no carbon unsaturated bond at the molecular terminal, and the compound [4] has a problem that it cannot impart a carboxyl group protected by an adamantyl group to the product. .
【００２５】[0025]
【発明の効果】本発明の新規な有機ケイ素化合物は、ケ
イ素原子に結合した加水分解性のハロゲン原子が存在す
るため、他の有機ケイ素化合物（ポリマーを含む）との
反応によりシロキサン結合を形成したり、無機化合物中
のシラノール基とカップリング反応させることができ
る。一方、本発明ケイ素系化合物におけるアダマンチル
基は、酸性ないしアルカリ性の条件下で加水分解により
容易に脱離し、本発明ケイ素系化合物の末端にカルボキ
シル基を生成させることができる。このカルボキシル基
は炭素官能性基またはアルカリ水溶性基として機能す
る。このように、本発明ケイ素系化合物はケイ素官能性
および保護された炭素官能性をもつ複反応性ケイ素化合
物として機能する。また、アダマンチル基は、樹脂の耐
熱性およびガラス転移点の向上に、重要な役割を果た
す。本発明のケイ素系化合物は、そのため、有機合成の
中間原料、ポリマー樹脂の合成原料、ポリマーの改質
剤、無機化合物の表面処理剤として有用である。The novel organosilicon compound of the present invention forms a siloxane bond by reaction with another organosilicon compound (including a polymer) due to the presence of a hydrolyzable halogen atom bonded to the silicon atom. Or a coupling reaction with a silanol group in an inorganic compound. On the other hand, the adamantyl group in the silicon compound of the present invention can be easily eliminated by hydrolysis under acidic or alkaline conditions to form a carboxyl group at the terminal of the silicon compound of the present invention. This carboxyl group functions as a carbon functional group or an alkali water-soluble group. Thus, the silicon-based compound of the present invention functions as a double-reactive silicon compound having silicon functionality and protected carbon functionality. The adamantyl group plays an important role in improving the heat resistance and glass transition point of the resin. Therefore, the silicon-based compound of the present invention is useful as an intermediate material for organic synthesis, a synthetic material for a polymer resin, a modifier for a polymer, and a surface treating agent for an inorganic compound.
【００２６】[0026]
【実施例】以下、本発明を実施例によって具体的に説明
する。 実施例１ 攪拌機、温度計及び冷却管を備えた反応器を乾燥窒素雰
囲気下にして、アダマンタノール15.2g（100mmol）、ヘ
キサン80g、およびトリエチルアミン11.1g（110mmol）
を仕込み、攪拌下にtrans-クロトニルクロライド11.5g
（110mmol ）を徐々に滴下した。滴下終了後、2時間、
攪拌放置した。その後、ろ過により目的物を含有する溶
液層を分離し、ついで溶剤と末反応物を減圧蒸留により
留去したのち、引き続き、減圧蒸留によって、沸点104
〜105℃/507Paの無色透明の液体9.4gを得た。この液体
について270MHzの1Ｈ-ＮＭＲの測定を行ったところ、第
１図のスペクトルを得た。δ値とその帰属は第１表のと
おりであった。これにより得られた液体は、ビニル酢酸
のカルボキシル基の水素原子がアダマンチル基で置換さ
れた下記化合物［１］であることが確認できた。収率は
理論量に対して43％であった。The present invention will be specifically described below with reference to examples. Example 1 A reactor equipped with a stirrer, a thermometer and a condenser was placed under a dry nitrogen atmosphere, and 15.2 g (100 mmol) of adamantanol, 80 g of hexane, and 11.1 g (110 mmol) of triethylamine were used.
11.5 g of trans-crotonyl chloride under stirring
(110 mmol) was slowly added dropwise. After dropping, 2 hours
The mixture was left stirring. Thereafter, a solution layer containing the target substance was separated by filtration, and then the solvent and the unreacted product were distilled off under reduced pressure.
9.4 g of a colorless and transparent liquid at 105105 ° C./507 Pa was obtained. When this liquid was measured by 1 H-NMR at 270 MHz, the spectrum shown in FIG. 1 was obtained. The δ values and their assignments are as shown in Table 1. The liquid thus obtained was confirmed to be the following compound [1] in which the hydrogen atom of the carboxyl group of vinyl acetic acid was replaced with an adamantyl group. The yield was 43% of theory.
【００２７】[0027]
【化１１】 Embedded image
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【化１２】 Embedded image
【００３０】実施例２ 攪拌機、温度計及び冷却管を備えた反応器を乾燥窒素雰
囲気下にして、実施例１で合成した化合物［１］7.0g
（31.8mmol）を仕込み、系内を攪拌させながらオイルバ
スで加熱した。系内の温度が80℃に達したところで、白
金触媒であるcis-PtCl2(PhCN)2を3mg加えた。その後、
系内の温度が90℃前後になるように調整しながら、ジメ
チルクロロシラン3.91g（41.3mmol ）を徐々に滴下し
た。滴下終了後、2時間、80℃で攪拌放置した。その
後、減圧蒸留により未反応物を留去し、黄色透明の液体
9.5gを得た。この液体について270MHzの1Ｈ-ＮＭＲの測
定を行ったところ、第２図のスペクトルを得た。δ値と
その帰属は第２表のとおりであった。Example 2 A reactor equipped with a stirrer, a thermometer and a condenser was placed under a dry nitrogen atmosphere, and 7.0 g of the compound [1] synthesized in Example 1 was used.
(31.8 mmol) and heated in an oil bath while stirring the system. When the temperature in the system reached 80 ° C., 3 mg of cis-PtCl 2 (PhCN) 2 as a platinum catalyst was added. afterwards,
3.91 g (41.3 mmol) of dimethylchlorosilane was gradually added dropwise while adjusting the temperature in the system to around 90 ° C. After completion of the dropwise addition, the mixture was left to stir at 80 ° C. for 2 hours. Thereafter, unreacted substances are distilled off by distillation under reduced pressure, and the yellow transparent liquid
9.5 g were obtained. When this liquid was subjected to 1 H-NMR measurement at 270 MHz, the spectrum shown in FIG. 2 was obtained. The δ values and their assignments are as shown in Table 2.
【００３１】これにより得られた液体は、カルボキシル
基の水素原子がアダマンチル基で置換された有機置換基
を含有するクロロシランである化合物［３］であること
が確認できた。収率は理論量に対して95％であった。The obtained liquid was confirmed to be Compound [3] which is a chlorosilane containing an organic substituent in which a hydrogen atom of a carboxyl group was substituted with an adamantyl group. The yield was 95% of theory.
【００３２】[0032]
【化１３】 Embedded image
【００３３】[0033]
【表２】 [Table 2]
【００３４】[0034]
【化１４】 Embedded image
【図１】第１図は実施例１で得られた生成物の1H-NMRス
ペクトルを示す。FIG. 1 shows the 1 H-NMR spectrum of the product obtained in Example 1.
【図２】第２図は実施例２で得られた生成物の1H-NMRス
ペクトルを示す。FIG. 2 shows the 1 H-NMR spectrum of the product obtained in Example 2.
Claims (2)
エステル基を有する有機ケイ素化合物。 【化２】 （式中、Ｒ1は炭素数１から４のアルキル基であり、Ｒ2
は炭素数２から６のアルキレン基であり、Ｘはハロゲン
である。）2. An organosilicon compound having an adamantyl ester group represented by the following general formula [2]. Embedded image (In the formula, R 1 is an alkyl group having 1 to 4 carbon atoms, R 2
Is an alkylene group having 2 to 6 carbon atoms, and X is a halogen. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000400560A JP2002193975A (en) | 2000-12-28 | 2000-12-28 | New organosilicon compound having adamantyl ester group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000400560A JP2002193975A (en) | 2000-12-28 | 2000-12-28 | New organosilicon compound having adamantyl ester group |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002193975A true JP2002193975A (en) | 2002-07-10 |
Family
ID=18865130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000400560A Pending JP2002193975A (en) | 2000-12-28 | 2000-12-28 | New organosilicon compound having adamantyl ester group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002193975A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007308397A (en) * | 2006-05-17 | 2007-11-29 | Tokuyama Corp | Silicon-containing adamantane compound |
-
2000
- 2000-12-28 JP JP2000400560A patent/JP2002193975A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007308397A (en) * | 2006-05-17 | 2007-11-29 | Tokuyama Corp | Silicon-containing adamantane compound |
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