JPS6360012B2 - - Google Patents
Info
- Publication number
- JPS6360012B2 JPS6360012B2 JP56134557A JP13455781A JPS6360012B2 JP S6360012 B2 JPS6360012 B2 JP S6360012B2 JP 56134557 A JP56134557 A JP 56134557A JP 13455781 A JP13455781 A JP 13455781A JP S6360012 B2 JPS6360012 B2 JP S6360012B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- formula
- aluminum hydride
- lithium aluminum
- reducing
- 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.)
- Expired
Links
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 11
- 150000004820 halides Chemical class 0.000 claims description 10
- 150000003608 titanium Chemical class 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- JIVANURAWUCQIG-UHFFFAOYSA-N 1,1,2,4,4,7-hexamethyl-2,3-dihydronaphthalene Chemical compound C1=C(C)C=C2C(C)(C)C(C)CC(C)(C)C2=C1 JIVANURAWUCQIG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 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
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は有機ハライドの新規還元方法に関する
ものである。さらに詳しくは本発明は式（）で
示される有機ハライドを水素化リチウムアルミニ
ウムで還元して、式（）で示される還元体を製
造するに際し、反応系に触媒量の活性チタンを共
存させることを特徴とする還元方法である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for reducing organic halides. More specifically, the present invention involves the coexistence of a catalytic amount of activated titanium in the reaction system when producing the reduced product represented by the formula () by reducing the organic halide represented by the formula () with lithium aluminum hydride. This is a unique reduction method.
（式中、Ｘはハロゲンを、Ｒは水素もしくは低級
アキル基を表わす。）
（式中、Ｒは前記と同じ意味を表わす。）
従来、有機ハライドを還元して水素還元体を得
る方法としては、水素化リチウムアルミニウムで
還元する方法（ジヤーナル・オブ・アメリカン・
ケミカル・ソサエテイ：J.A.C.S.、70、3664
（1948））や他の方法が知られているが、反応時間
が長い上、満足すべき収率も得られないという難
点があつた。最近、四塩化チタン―水素化リチウ
ムアルミニウムを還元試剤として使用してアリー
ルハライドを還元する方法が報告されている（ケ
ミストリー・レターズ；Chem.Lett.、291
（1973））が、この方法では四塩化チタンを基質に
対して化学量論以上用いる必要があり、より有効
な還元方法が望まれる。 (In the formula, X represents a halogen, and R represents hydrogen or a lower alkyl group.) (In the formula, R represents the same meaning as above.) Conventionally, as a method of reducing an organic halide to obtain a reduced hydrogen product, a method of reducing with lithium aluminum hydride (Journal of American
Chemical Society: JACS, 70 , 3664
(1948)) and other methods are known, but they have the drawbacks of long reaction times and unsatisfactory yields. Recently, a method for reducing aryl halides using titanium tetrachloride-lithium aluminum hydride as a reducing agent has been reported (Chemistry Letters; Chem. Lett., 291
(1973)), but in this method it is necessary to use titanium tetrachloride in a stoichiometric amount or more with respect to the substrate, and a more effective reduction method is desired.
本発明者らはかかる状況のもとに、より簡便で
有利な有機ハライドの還元方法を見い出すべく研
究した結果、水素化リチウムアルミニウムに触媒
量の活性チタンを共存させることにより、短時間
に高収率で還元体を得る方法を見い出し、本発明
を完成するに至つた。 Under such circumstances, the present inventors conducted research to find a simpler and more advantageous method for reducing organic halides. As a result, they found that by coexisting lithium aluminum hydride with a catalytic amount of activated titanium, they achieved high yields in a short period of time. They discovered a method to obtain a reduced product at a high rate and completed the present invention.
本発明の方法についてさらに詳しく説明すれ
ば、有機ハライドを還元（水素化分解）するに際
して効果的に用いる触媒量の活性チタンは適当な
溶媒中で、チタン化合物を還元することによつて
得られる。このときに用いるチタン化合物として
は四塩化チタン、三塩化チタン、（二塩化チタン）
あるいは四臭化チタンなどをあげることができ
る。またチタンアルコキサイドたとえばチタンイ
ソプロポキサイドなどを用いることもできる。こ
れらの中で、ハロゲン化チタン、特に四塩化チタ
ンが好適に用いられる。これらの化合物より活性
チタンを得る還元剤としては水素化リチウムアル
ミニウムや水素化リチウムホウ素などが用いら
れ、なかでも水素化リチウムアルミニウムが好適
に用いられる。溶媒としてはジエチルエーテル、
テトラヒドロフラン、ジメトキシエタン等のエー
テル系溶媒が適当であり、反応は０℃及至沸点下
で行なうことができる。 To explain the method of the present invention in more detail, a catalytic amount of active titanium effectively used in reducing (hydrocracking) an organic halide can be obtained by reducing a titanium compound in a suitable solvent. Titanium compounds used at this time include titanium tetrachloride, titanium trichloride, (titanium dichloride)
Alternatively, titanium tetrabromide may be used. It is also possible to use titanium alkoxides such as titanium isopropoxide. Among these, titanium halides, particularly titanium tetrachloride, are preferably used. As a reducing agent for obtaining active titanium from these compounds, lithium aluminum hydride, lithium boron hydride, etc. are used, and among them, lithium aluminum hydride is preferably used. Diethyl ether as a solvent,
Ether solvents such as tetrahydrofuran and dimethoxyethane are suitable, and the reaction can be carried out at temperatures ranging from 0°C to the boiling point.
ここで活性チタンとは水素化チタンあるいは金
属チタンまたは両者の混合物と推定される。反応
の進行とともにこれらの析出が認められる。 Here, the activated titanium is presumed to be hydrogenated titanium, metallic titanium, or a mixture of both. These precipitates are observed as the reaction progresses.
次にかくして得られる活性チタンの存在下に有
機ハライドを水素化リチウムアルミニウム（以
下、LAHと略称する。）で還元する方法について
説明すると、LAHに対して存在させる活性チタ
ンの量は１／200〜１／５、好ましくは１／100〜
１／20当量である。効率よく反応を実施するに
は、有機ハライドを還元するに要するよりもやや
過剰のLAHと前記チタン化合物、好ましくはハ
ロゲン化チタンを１／200〜１／５、より好まし
くは１／100〜１／20当量加えて前述のように活
性化チタンを生成せしめ、この還元試剤を単離す
ることなく直ちに使用することである。この場
合、式（）で示される有機ハライド１モルに対
して用いるLAHの量は通常0.3モルから２モル、
好ましくは0.5モル及至1.2モルである。 Next, to explain the method of reducing organic halide with lithium aluminum hydride (hereinafter abbreviated as LAH) in the presence of the thus obtained activated titanium, the amount of active titanium to be present relative to LAH is 1/200 to 1/5, preferably 1/100~
It is 1/20 equivalent. In order to carry out the reaction efficiently, a slightly excess amount of LAH and the titanium compound, preferably titanium halide, is mixed in a proportion of 1/200 to 1/5, more preferably 1/100 to 1/5 of that required to reduce the organic halide. 20 equivalents are added to produce activated titanium as described above, and the reducing agent is used immediately without isolation. In this case, the amount of LAH used per 1 mol of the organic halide represented by formula () is usually 0.3 mol to 2 mol,
Preferably it is 0.5 mol to 1.2 mol.
このようにして得られる還元試剤は適当な溶媒
中で当該被還元化合物と撹拌反応させることによ
り実施できる。溶媒としてはテトラヒドロフラ
ン、ジメトキシエタンなどのエーテル類を使用す
るのが好ましい。反応は０℃乃至使用する溶媒の
沸点下に好適に進行し、目的とする還元体を高収
率で得ることができる。より確実に反応を進める
には窒素、ヘリウム、アルゴンなどの不活性ガス
雰囲気下で行なえばよい。 The reducing agent thus obtained can be stirred and reacted with the compound to be reduced in an appropriate solvent. As the solvent, it is preferable to use ethers such as tetrahydrofuran and dimethoxyethane. The reaction proceeds suitably at 0°C or below the boiling point of the solvent used, and the desired reduced product can be obtained in high yield. In order to proceed with the reaction more reliably, the reaction may be carried out under an atmosphere of an inert gas such as nitrogen, helium, or argon.
反応の進行はガスクロマトグラフイー、薄層ク
ロマトグラフイー等の分析手段によつて知ること
ができる。還元剤や溶剤を除いた後の生成物はそ
のままでも高純度であるが、必要によつては再結
晶、蒸留、クロマトグラフイー等によりさらに精
製することも可能である。 The progress of the reaction can be determined by analytical means such as gas chromatography and thin layer chromatography. The product after removing the reducing agent and solvent is highly pure as it is, but if necessary, it can be further purified by recrystallization, distillation, chromatography, etc.
以下、実施例によつて本発明の方法を説明す
る。 The method of the present invention will be explained below by way of examples.
実施例 １
窒素雰囲気中、水素化アルミニウムリチウム
1.74g（45.8mmol）をテトラヒドロフランに懸濁
させ、四塩化チタン0.22ml（2mmol）を徐々に滴
下した。滴下終了後３―（クロロメチル）―１，
１，４，４，６―ペンタメチル―１，２，３，４
―テトラヒドロナフタレン10.0g（39.9mmol）の
テトラヒドロフラン溶液（10ml）を徐々に滴下し
た。滴下終了後５分間加熱還流した。Example 1 Lithium aluminum hydride in nitrogen atmosphere
1.74 g (45.8 mmol) was suspended in tetrahydrofuran, and 0.22 ml (2 mmol) of titanium tetrachloride was gradually added dropwise. After finishing dropping 3-(chloromethyl)-1,
1,4,4,6-pentamethyl-1,2,3,4
- A solution of 10.0 g (39.9 mmol) of tetrahydronaphthalene in tetrahydrofuran (10 ml) was gradually added dropwise. After the dropwise addition was completed, the mixture was heated under reflux for 5 minutes.
冷却後、希塩酸で反応液を処理し、ｎ―ヘキサ
ンで抽出した。抽出液を飽和食塩水で洗浄後、芒
硝で乾燥し、濃縮、蒸留し7.5g（34.7mmol、87
％）の１，１，３，４，４，６―ヘキサメチル―
１，２，３，４―テトラヒドロナフタレンを得
た。 After cooling, the reaction solution was treated with dilute hydrochloric acid and extracted with n-hexane. The extract was washed with saturated saline, dried with Glauber's salt, concentrated, and distilled to give 7.5 g (34.7 mmol, 87
%) of 1,1,3,4,4,6-hexamethyl-
1,2,3,4-tetrahydronaphthalene was obtained.
bp0.5＝91℃
NMR（CCl4）δ（ppm）＝0.96（3H、ｄ）、1.03
（3H、ｓ）、1.21（3H、ｓ）、1.24（3H、
ｓ）、1.28（3H、ｓ）、1.34〜1.86（3H、
ｍ）、2.25（3H、ｓ）、6.71〜7.14（3H、ｍ）
参考例 １
窒素中水素化リチウムアルミニウム9.56g
（0.252mol）をTHF70mlに懸濁させ、３―（クロ
ロメチル）―１、１、４、４、６―ペンタメチル
―１、２、３、４―テトラヒドロナフタレン
62.9g（0.251mol）のTHF溶液を滴下した。15時
間加熱還流後、窒素中含水THFで反応液を処理
後５％塩酸600mlを加え、ｎ―ヘキサンで抽出し
た。抽出液を飽和食塩水で洗浄後、乾燥、濃縮、
蒸留し、46.0g（0.213mol、85％）の１、１、３、
４、４、６―ヘキサメチル―１、２、３、４―テ
トラヒドロナフタレンを得た。bp 0.5 = 91℃ NMR (CCl 4 ) δ (ppm) = 0.96 (3H, d), 1.03
(3H, s), 1.21 (3H, s), 1.24 (3H,
s), 1.28 (3H, s), 1.34-1.86 (3H,
m), 2.25 (3H, s), 6.71-7.14 (3H, m) Reference example 1 9.56 g of lithium aluminum hydride in nitrogen
(0.252 mol) was suspended in 70 ml of THF, and 3-(chloromethyl)-1,1,4,4,6-pentamethyl-1,2,3,4-tetrahydronaphthalene was added.
62.9 g (0.251 mol) of THF solution was added dropwise. After heating under reflux for 15 hours, the reaction solution was treated with aqueous THF under nitrogen, 600 ml of 5% hydrochloric acid was added, and extracted with n-hexane. After washing the extract with saturated saline, drying, concentrating,
Distilled and 46.0g (0.213mol, 85%) of 1, 1, 3,
4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene was obtained.
bp、NMRスペクトルは実施例のものと同じで
あつた。 bp, NMR spectrum was the same as that of the example.
Claims (1)
チウムアルミニウムで還元して式（）で示され
る還元体を製造するに際し、反応系に、水素化リ
チウムアルミニウムに対して１／200〜１／５当
量の四塩化チタンと水素化リチウムアルミニウム
から得られる触媒量の活性チタンを共存させるこ
とを特徴とする式（）で示される有機ハライド
の還元方法。 （式中、Ｘはハロゲンを、Ｒは水素もしくは低級
アキル基を表わす。） （式中、Ｒは前記と同じ意味を表わす。）[Claims] 1. When producing the reduced product represented by the formula () by reducing the organic halide represented by the formula () with lithium aluminum hydride, the reaction system contains 1/1/2 of the lithium aluminum hydride. A method for reducing an organic halide represented by the formula (), which comprises coexisting 200 to 1/5 equivalents of titanium tetrachloride and a catalytic amount of activated titanium obtained from lithium aluminum hydride. (In the formula, X represents a halogen, and R represents hydrogen or a lower alkyl group.) (In the formula, R represents the same meaning as above.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56134557A JPS5835129A (en) | 1981-08-26 | 1981-08-26 | Reducing method of organic halide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56134557A JPS5835129A (en) | 1981-08-26 | 1981-08-26 | Reducing method of organic halide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5835129A JPS5835129A (en) | 1983-03-01 |
| JPS6360012B2 true JPS6360012B2 (en) | 1988-11-22 |
Family
ID=15131104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56134557A Granted JPS5835129A (en) | 1981-08-26 | 1981-08-26 | Reducing method of organic halide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5835129A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4774802B2 (en) * | 2005-05-16 | 2011-09-14 | セントラル硝子株式会社 | Reduction method using lithium aluminum hydride |
-
1981
- 1981-08-26 JP JP56134557A patent/JPS5835129A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| CHEMISTRY LETTERS * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5835129A (en) | 1983-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0459499B1 (en) | Process for preparing silacycloalkanes | |
| JP3003327B2 (en) | Preparation of optically active amines | |
| Stork et al. | An efficient synthesis of alkenyl and alkynyl silyl ethers | |
| CN106573874B (en) | The method for manufacturing 2- amino substituted benzoyl aldehyde compounds | |
| JPS6360012B2 (en) | ||
| JPH0332548B2 (en) | ||
| JP2001525838A (en) | Method for chemical reduction of 1-substituted-3-hydroxymethyl-4- (4-fluorophenyl) tetrahydropyridine | |
| JPH07701B2 (en) | Method for producing polysilane | |
| JP2005511700A (en) | Production method of polysulfide monoorganooxysilane | |
| JP3905340B2 (en) | New preparation method of organometallic compounds | |
| JP2003292495A (en) | Copper complex and method for producing copper-containing thin film using the same | |
| JPH0717660B2 (en) | Method for producing 1,1-dichloro-1,2,2-trimethyl-2-phenyldisilane | |
| JP4345118B2 (en) | Method for producing ethynylcyclopropane | |
| JP2622747B2 (en) | Method for producing cis-7-decene-4-olide | |
| JP4807549B2 (en) | Siloxanes, silanols and silanes, and methods for producing the same | |
| JP2991818B2 (en) | Condensed 2-membered cyclic disilanilene-acetylene compound and method for producing the same | |
| US6700019B2 (en) | Process for the preparation of tetrakis (pentafluorophenyl) borate derivatives | |
| JP3864648B2 (en) | Process for producing 1,3-bis (carboxyalkyl) tetraalkyldisiloxane | |
| JP3680422B2 (en) | Production method of phosphonium chloride | |
| JP2864985B2 (en) | Method for producing tri (secondary alkyl) silane compound | |
| JP2946678B2 (en) | Chiral ferrocene derivatives | |
| JPH0678346B2 (en) | Method for preparing alkylhalodisilane | |
| JPH03109389A (en) | Production of bis(3,4-dimethylphenyl)dimethylsilane | |
| JPS63135393A (en) | Production of alkylsilyl cyanide | |
| JPH0481981B2 (en) |