JPH069471A - Photo-dehydrogenative dimerization of tert-butyl methyl ether - Google Patents
Photo-dehydrogenative dimerization of tert-butyl methyl etherInfo
- Publication number
- JPH069471A JPH069471A JP5085496A JP8549693A JPH069471A JP H069471 A JPH069471 A JP H069471A JP 5085496 A JP5085496 A JP 5085496A JP 8549693 A JP8549693 A JP 8549693A JP H069471 A JPH069471 A JP H069471A
- Authority
- JP
- Japan
- Prior art keywords
- methyl ether
- butyl methyl
- tert
- reaction
- halide
- 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
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)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はターシャリーブチルメチ
ルエーテルを脱水素二量化し、エチレングリコールジタ
ーシャリーブチルエーテル及び水素を製造する新規な方
法に関するものである。さらに詳しくいえば、光化学反
応によりターシャリーブチルメチルエーテルを選択的脱
水素二量化する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel process for producing ethylene glycol ditertiary butyl ether and hydrogen by dehydrogenative dimerization of tertiary butyl methyl ether. More specifically, it relates to a method for selectively dehydrogenating dimerization of tertiary butyl methyl ether by photochemical reaction.
【０００２】[0002]
【従来の技術】光反応を化学反応に応用し、新規な反応
を構築しようという試みが近年注目されている。本発明
者らは、先にウィルキンソン錯体（特許１２３６５６４
号）や、ロジウム化合物（特許１２７８４０８号）が空
気雰囲気下で２−プロパノールに対して非常に高い脱水
素活性を示すことを見い出し、光脱水素反応触媒の発明
を完成した。また、さらに研究を進めて、アセトン及び
ロジウム錯体の共存下にメタノールを光照射することに
より効率よくエチレングリコールを製造する方法（特公
昭６０−００６９３０号）の発明も完成した。2. Description of the Related Art In recent years, attention has been paid to attempts to construct new reactions by applying photoreactions to chemical reactions. The inventors of the present invention have previously proposed the Wilkinson complex (Japanese Patent No. 1236564).
No. 1) and a rhodium compound (Japanese Patent No. 1278408) showed a very high dehydrogenation activity for 2-propanol under an air atmosphere, and completed the invention of a photodehydrogenation reaction catalyst. Further, by further researching, the invention of a method for efficiently producing ethylene glycol by irradiating methanol in the presence of acetone and a rhodium complex (Japanese Patent Publication No. 60-006930) was completed.
【０００３】一方、ターシャリーブチルメチルエーテル
は、イソブテンにメタノールを反応させることによって
生成する物質であり、通常には原料として石油精製によ
り分けられた、イソブテンを含むＣ4留分混合物が用い
られている。近年、Ｃ4留分の新しい利用として注目さ
れ、現在も生産量が増加しつつある化合物である。今
回、本発明者らは先の光触媒反応にさらに研究を重ね、
このターシャリーブチルメチルエーテルの新規な使途と
しての脱水素二量化反応を探索した結果、ハロゲン化ロ
ジウムとアセトンあるいはハロゲン化オミニウムとアセ
トンを共存させてターシャリーブチルメチルエーテルを
光照射することによって、ターシャリーブチルメチルエ
ーテルに対して非常に高い選択率で一段反応でエチレン
グリコールジターシャリーブチルエーテル及び水素が得
られることを見い出し、この知見に基づき本発明を成立
させた。On the other hand, tert-butyl methyl ether is a substance produced by reacting isobutene with methanol. Usually, a C 4 fraction mixture containing isobutene separated by petroleum refining is used as a raw material. There is. In recent years, it has attracted attention as a new use of the C 4 fraction, and it is a compound whose production is still increasing. This time, the present inventors have conducted further research on the above photocatalytic reaction,
As a result of exploring the dehydrogenation dimerization reaction as a novel use of this tertiary butyl methyl ether, the tertiary butyl methyl ether was irradiated with light in the coexistence of rhodium halide and acetone or ominium halide and acetone. It was found that ethylene glycol ditertiary butyl ether and hydrogen can be obtained in a one-step reaction with very high selectivity to butyl methyl ether, and the present invention was completed based on this finding.
【０００４】[0004]
【発明が解決しようとする課題】従って、本発明は工業
的に有利なターシャリーブチルメチルエーテルの脱水素
二量化の方法を提供することを目的とするものである。SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide an industrially advantageous method for the dehydrogenative dimerization of tertiary butyl methyl ether.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明によれ
ば、ターシャリーブチルメチルエーテルを、ハロゲン化
ロジウムとアセトンの存在下あるいはハロゲン化オスミ
ニウムとアセトンの共存下に光照射することを特徴とす
る、ターシャリーブチルメチルエーテルの脱水素二量化
方法が提供される。That is, according to the present invention, tertiary butyl methyl ether is irradiated with light in the presence of rhodium halide and acetone or in the presence of osmium halide and acetone. A method for dehydrogenation dimerization of tertiary butyl methyl ether is provided.
【０００６】本発明方法は、次式により、表わされる。 ２ＣＨ3−Ｏ−Ｃ（ＣＨ3）3→Ｈ2＋［ＣＨ2−Ｏ−Ｃ（ＣＨ3）3］2 The method of the present invention is represented by the following equation. 2CH 3 -O-C (CH 3 ) 3 → H 2 + [CH 2 -O-C (CH 3) 3] 2
【０００７】本発明を好ましく実施するためには、ター
シャリーブチルメチルエーテルとアセトン、光脱水素光
触媒反応用のハロゲン化ロジウム又はハロゲン化オスミ
ニウムを内部照射型反応器に仕込み、一定時間、撹拌し
つつ不活性ガスを通気した後に光照射を行う。この場合
に撹拌しつつ不活性ガスを通気する時間は任意である
が、１５分程度で十分である。本発明においては反応は
通常常温で行われる。必要に応じて、０〜５３℃の範囲
で任意に行うことが出来るが、室温付近で十分である。In order to carry out the present invention preferably, tertiary butyl methyl ether and acetone, rhodium halide or osmium halide for photodehydrogenation photocatalytic reaction are charged into an internal irradiation type reactor and stirred for a certain period of time. Light is irradiated after aeration with an inert gas. In this case, the time for ventilating the inert gas while stirring is arbitrary, but about 15 minutes is sufficient. In the present invention, the reaction is usually carried out at room temperature. If necessary, it can be optionally carried out in the range of 0 to 53 ° C., but it is sufficient at around room temperature.
【０００８】光照射を行う光源については、高圧水銀灯
から発せられる白色光が適用されるが、４００ｎｍ以下
の紫外光を発する光源であれば任意に用いることができ
る。光照射を行う時間については特に制限はなく、反応
に用いる基質の量、光源の種類、強度等の反応条件に応
じて適宜定めることができる。As the light source for irradiating light, white light emitted from a high-pressure mercury lamp is applied, but any light source emitting ultraviolet light of 400 nm or less can be used. The time for light irradiation is not particularly limited and can be appropriately determined according to reaction conditions such as the amount of substrate used in the reaction, the type of light source, and the intensity.
【０００９】本発明においては、アセトン共存下に光照
射を行うことが必要である。このアセトンの添加量は、
少なくとも反応中に光脱水素光触媒反応用のハロゲン化
ロジウム又はハロゲン化オスミニウムが溶解する限りに
おいて任意であるが、好ましくは、０．０５〜２のター
シャリーブチルメチルエーテルに対する体積比の範囲で
添加される。In the present invention, it is necessary to perform light irradiation in the presence of acetone. The amount of acetone added is
It is optional as long as at least rhodium halide or osmium halide for photodehydrogenation photocatalytic reaction is dissolved during the reaction, but preferably added in a volume ratio range of 0.05 to 2 to tertiary butyl methyl ether. It
【００１０】本発明において用いられる光脱水素光触媒
反応用の化合物としては、ハロゲン化ロジウム又はハロ
ゲン化オスミニウムが用いられる。ハロゲン化ロジウム
又はハロゲン化オスミニウムとしては、少なくとも反応
中に溶解性を示すならば任意であるが、好ましくは塩化
ロジウム（ＲｈＣｌ3・３Ｈ2Ｏ）塩化オスミニウム（Ｏ
ｓＣｌ3）などが使用される。これらの光脱水素光触媒
反応用の化合物はその使用量に特に制限はなく反応条件
に応じて任意の量を用いることができるが、１×１０-4
〜１×１０-4ｍｍｏｌ／ｍｏｌのターシャリーブチルメ
チルエーテルの範囲が好ましい。本発明は、通常不活性
ガス雰囲気下で行われる。空気雰囲気下においても行う
ことは可能であるが、反応速度は不十分となる。As the compound for the photodehydrogenation photocatalytic reaction used in the present invention, rhodium halide or osmium halide is used. Any rhodium halide or osmium halide may be used as long as it exhibits solubility at least during the reaction, but rhodium chloride (RhCl 3 .3H 2 O) and osmium chloride (O 2
sCl 3 ) or the like is used. The amount of these compounds used for the photodehydrogenation photocatalytic reaction is not particularly limited, and any amount can be used depending on the reaction conditions, but 1 × 10 −4
A range of ˜1 × 10 −4 mmol / mol tertiary butyl methyl ether is preferred. The present invention is usually performed under an inert gas atmosphere. Although it is possible to carry out the reaction under an air atmosphere, the reaction rate becomes insufficient.
【００１１】[0011]
【発明の効果】このような本発明方法によれば、常温常
圧下においてターシャリーブチルメチルエーテルから水
素と、エチレングリコールジターシャリーブチルエーテ
ルを高選択的に一段で製造するという優れた反応方法が
提出され、その意義は大きい。EFFECTS OF THE INVENTION According to the method of the present invention, an excellent reaction method has been proposed in which hydrogen and tertiary glycol tert-butyl ether are produced from tertiary butyl methyl ether at room temperature and normal pressure with high selectivity in a single step. , Its significance is great.
【００１２】[0012]
【実施例】次に本発明を実施例により、さらに詳細に説
明する。EXAMPLES Next, the present invention will be described in more detail by way of examples.
【００１３】実施例１ ガスビューレットを接続した内部照射型反応装置に、タ
ーシャリーブチルメチルエーテル２００ｍｌ、アセトン
１００ｍｌ及び塩化ロジウム（ＲｈＣｌ3・３Ｈ2Ｏ）２
６．３ｇを仕込み、窒素気流を１０分間撹拌しつつ通気
した後光照射を開始した。撹拌はマグネッチクスターラ
ーで行った。反応温度は恒温槽により２０℃に制御し
た。光源として、４００Ｗ高圧水銀灯を水冷式石英製ジ
ャケットを通して用いた。このようにして６時間光照射
したところ、６２３ｍｌの水素が発生した。反応液をガ
スクロマトグラフにより分析したとこらエチレングリコ
ールジターシャリーブチルエーテル３１．０ｍｍｏｌが
生成した。Example 1 200 ml of tertiary butyl methyl ether, 100 ml of acetone and rhodium chloride (RhCl 3 .3H 2 O) 2 were placed in an internal irradiation type reactor connected with a gas buret.
After charging 6.3 g of the mixture, the mixture was aerated with a nitrogen stream for 10 minutes while being aerated, and then irradiation with light was started. Stirring was performed with a magnetic stirrer. The reaction temperature was controlled at 20 ° C. by a constant temperature bath. A 400 W high-pressure mercury lamp was used as a light source through a water-cooled quartz jacket. When light was thus irradiated for 6 hours, 623 ml of hydrogen was generated. When the reaction solution was analyzed by gas chromatography, 31.0 mmol of ethylene glycol ditertiary butyl ether was produced.
【００１４】実施例２ ガスビューレットを接続した内部照射型反応装置に、タ
ーシャリーブチルメチルエーテル２００ｍｌ、アセトン
１００ｍｌ及び塩化オスミニウム２９．７ｍｇを仕込
み、窒素気流を１０分間撹拌しつつ通気した後光照射を
開始した。撹拌はマグネッチクスターラーで行った。反
応温度は恒温槽により２０℃に制御した。光源として、
４００Ｗ高圧水銀灯を水冷式石英製ジャケットを通して
用いた。このようにして３時間光照射したところ、３４
３ｍｌの水素が発生した。反応液をガスクロマトグラフ
により分析したところエチレングリコールジターシャリ
ーブチルエーテル３０．０ｍｍｏｌが生成した。 比較例１ ガスビューレットを接続した内部照射型反応装置に、タ
ーシャリーブチルメチルエーテル１２５ｍｌ、アセトン
２５ｍｌを仕込み、窒素気流を１０分間撹拌しつつ通気
した後光照射を開始した。撹拌はマグネッチクスターラ
ーで行った。反応温度は恒温槽により２０℃に制御し
た。光源として、１００Ｗ高圧水銀灯を水冷式石英製ジ
ャケットを通して用いた。このようにして６時間光照射
したところ、水素は発生しなかった。反応液をガスクロ
マトグラフにより分析したところエチレングリコールジ
ターシャリーブチルエーテル２０．４ｍｍｏｌが生成し
た。Example 2 200 ml of tertiary butyl methyl ether, 100 ml of acetone and 29.7 mg of osmium chloride were charged into an internal irradiation type reaction apparatus connected with a gas buret, and a nitrogen stream was aerated while stirring for 10 minutes, followed by light irradiation. Started. Stirring was performed with a magnetic stirrer. The reaction temperature was controlled at 20 ° C. by a constant temperature bath. As a light source
A 400 W high pressure mercury lamp was used through a water cooled quartz jacket. When light was irradiated for 3 hours in this way,
3 ml of hydrogen evolved. When the reaction liquid was analyzed by gas chromatography, 30.0 mmol of ethylene glycol ditertiary butyl ether was produced. Comparative Example 1 125 ml of tertiary butyl methyl ether and 25 ml of acetone were charged into an internal irradiation type reaction device connected to a gas buret, and a nitrogen stream was aerated while stirring for 10 minutes, and then light irradiation was started. Stirring was performed with a magnetic stirrer. The reaction temperature was controlled at 20 ° C. by a constant temperature bath. A 100 W high pressure mercury lamp was used as a light source through a water-cooled quartz jacket. When light was thus irradiated for 6 hours, hydrogen was not generated. When the reaction liquid was analyzed by gas chromatography, 20.4 mmol of ethylene glycol ditertiary butyl ether was produced.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松崎 武彦 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 (72)発明者 杉 義弘 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takehiko Matsuzaki 1-1, Higashi Tsukuba-shi, Ibaraki Institute of Industrial Science and Technology, Institute of Materials Engineering (72) Inventor Yoshihiro Sugi 1-1-chome, Tsukuba, Ibaraki Institute of Engineering and Technology
Claims (1)
ハロゲン化ロジウムとアセトンの存在下あるいはハロゲ
ン化オスミニウムとアセトンの存在下で光照射すること
により脱水素二量化させることを特徴とするターシャリ
ーブチルメチルエーテルの脱水素二量化方法1. Tertiary butyl methyl ether,
Method for dehydrogenation dimerization of tertiary butyl methyl ether characterized by dehydrogenation dimerization by light irradiation in the presence of rhodium halide and acetone or in the presence of osmium halide and acetone
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5085496A JPH0713032B2 (en) | 1993-03-19 | 1993-03-19 | Method for photodehydrogenation dimerization of tertiary butyl methyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5085496A JPH0713032B2 (en) | 1993-03-19 | 1993-03-19 | Method for photodehydrogenation dimerization of tertiary butyl methyl ether |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1034817A Division JPH02215739A (en) | 1989-02-14 | 1989-02-14 | Method for photodehydrating dimerization of tertiary butyl methyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH069471A true JPH069471A (en) | 1994-01-18 |
| JPH0713032B2 JPH0713032B2 (en) | 1995-02-15 |
Family
ID=13860549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5085496A Expired - Lifetime JPH0713032B2 (en) | 1993-03-19 | 1993-03-19 | Method for photodehydrogenation dimerization of tertiary butyl methyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0713032B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07312635A (en) * | 1994-05-18 | 1995-11-28 | Aakitekuto Ink:Kk | Waist holder for hanging and holding communication equipment upside down |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2824559A1 (en) * | 1977-06-10 | 1979-01-04 | Yamanouchi Pharma Co Ltd | 7 ALPHA -METHOXY-7 BETA- (1,3- DITHIETAN-2-CARBOXAMIDO) CEPHALOSPORANIC ACID DERIVATIVES AND THE PROCESS FOR THEIR PRODUCTION |
| DE2824575A1 (en) * | 1977-07-28 | 1979-02-15 | Yamanouchi Pharma Co Ltd | 1,3-DITHIETAN-2-CARBONIC ACIDS AND THE PROCESS FOR THEIR PRODUCTION |
-
1993
- 1993-03-19 JP JP5085496A patent/JPH0713032B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2824559A1 (en) * | 1977-06-10 | 1979-01-04 | Yamanouchi Pharma Co Ltd | 7 ALPHA -METHOXY-7 BETA- (1,3- DITHIETAN-2-CARBOXAMIDO) CEPHALOSPORANIC ACID DERIVATIVES AND THE PROCESS FOR THEIR PRODUCTION |
| DE2824575A1 (en) * | 1977-07-28 | 1979-02-15 | Yamanouchi Pharma Co Ltd | 1,3-DITHIETAN-2-CARBONIC ACIDS AND THE PROCESS FOR THEIR PRODUCTION |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07312635A (en) * | 1994-05-18 | 1995-11-28 | Aakitekuto Ink:Kk | Waist holder for hanging and holding communication equipment upside down |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0713032B2 (en) | 1995-02-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |