JPS61275241A - Production of deuterated acrylic acid or methacrylic acid - Google Patents
Production of deuterated acrylic acid or methacrylic acidInfo
- Publication number
- JPS61275241A JPS61275241A JP60113963A JP11396385A JPS61275241A JP S61275241 A JPS61275241 A JP S61275241A JP 60113963 A JP60113963 A JP 60113963A JP 11396385 A JP11396385 A JP 11396385A JP S61275241 A JPS61275241 A JP S61275241A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- methacrylic acid
- deuterated
- catalyst
- acrylic acid
- 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
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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は重水素化アクリル酸又は重水素化メタクリル酸
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing deuterated acrylic acid or deuterated methacrylic acid.
従来、重水素化メタクリル酸を製造する方法としては１
重水素化アセトンシアンヒドリンを経由して重水素化メ
タクリル酸メチルを製造する方法がジャーナル・オプ・
ポリマーサイエンス６２巻９５頁（１９６２年）に提案
されている。Conventionally, the method for producing deuterated methacrylic acid is 1.
A method for producing deuterated methyl methacrylate via deuterated acetone cyanohydrin was published in the Journal Op.
It was proposed in Polymer Science Vol. 62, p. 95 (1962).
またこの中間生成物である重水素化メタクリルアミドを
加水分解する方法、すなわち重水素化アセトンと青酸よ
り重水素化アセトンシアンヒドリンを製造し、これを硫
酸で処理して生成するメタクリルアミドの硫酸塩を重水
で加水分解して重水素化メタクリル酸を製造する方法も
知られている。しかしこれらの方法は重水素化アセトン
及び重水など重水素化した原料を使用し。There is also a method of hydrolyzing this intermediate product, deuterated methacrylamide, in which deuterated acetone cyanohydrin is produced from deuterated acetone and hydrocyanic acid, and this is treated with sulfuric acid to produce sulfuric acid of methacrylamide. A method for producing deuterated methacrylic acid by hydrolyzing a salt with heavy water is also known. However, these methods use deuterated raw materials such as deuterated acetone and heavy water.
多くの反応工程を必要とするため、経済上充分なものと
はいえず、より工程の少ない改良法が望まれていた。・
〔問題点を解決するための手段〕
本発明者らは重水素化メタクリル酸の合理的な製造法に
ついて鋭意研究した結果、メタクリル酸中の水素を直接
重水素交換する新規な製造法を見い出し、本発明を完成
した。Since it requires many reaction steps, it cannot be said to be economically sufficient, and an improved method with fewer steps has been desired.・ [Means for solving the problem] As a result of intensive research into a rational production method for deuterated methacrylic acid, the present inventors discovered a new production method in which hydrogen in methacrylic acid is directly exchanged with deuterium. , completed the invention.
本発明は、触媒の存在下にアクリル酸又はメタクリル酸
の水素な手暗重水素交換することを特徴とする、重水素
化アクリル酸又は重水素化メタクリル酸の製造方法であ
る。The present invention is a method for producing deuterated acrylic acid or deuterated methacrylic acid, which is characterized by carrying out manual dark deuterium exchange of acrylic acid or methacrylic acid with hydrogen in the presence of a catalyst.
アクリル酸又はメタクリル酸の水素を垂−重水素交換す
るための重水素源としては１重水又は重水及び重水素ガ
スの混合物を用いることができる。アクリル酸又はメタ
クリル酸に対して少なくとも化学量論以上の重水素が反
応系に存在することが必要である。As the deuterium source for hydrogen-deuterium exchange of hydrogen in acrylic acid or methacrylic acid, mono-deuterated water or a mixture of deuterated water and deuterium gas can be used. It is necessary that at least a stoichiometric amount of deuterium exists in the reaction system relative to acrylic acid or methacrylic acid.
触媒としてはパラジウム、ルテニウム、イリジウム及び
／又は白金を含む化合物例えばヘキサクロロイリジウム
酸、テトラキス（トリフェニルホスフィン）パラジウム
、臭化白金酸カリウム、ペンタクロロルテニウム酸カリ
ウム、硝酸パラジウム、ヘキサヒドロキン白金酸カリウ
ムなどが好ましい。これらの２種以上の混合物を用いる
こともできる。これらの化合物は、必要に応じて適当な
担体、例えばアルミナ、シリカ、シリカ−アルミナ、珪
藻土、活性炭などに担持させて用いることもできる。Catalysts include compounds containing palladium, ruthenium, iridium and/or platinum, such as hexachloroiridic acid, tetrakis(triphenylphosphine)palladium, potassium bromideplatinate, potassium pentachlororuthenate, palladium nitrate, potassium hexahydroquineplatinate, etc. is preferred. A mixture of two or more of these can also be used. These compounds can also be used by being supported on a suitable carrier such as alumina, silica, silica-alumina, diatomaceous earth, or activated carbon, if necessary.
反応は気相、液相のいずれでもよ（、また加圧下で行う
こともできる。重合反応を抑制するため、適当な重合防
止剤例えばフェノチアジン、ハイドロキノン等を必要に
応じて添加することができる。また、反応液中に少量の
酸素を共存させることによって重合を抑制することもで
きる。The reaction can be carried out in either a gas phase or a liquid phase (and can also be carried out under pressure). In order to suppress the polymerization reaction, a suitable polymerization inhibitor such as phenothiazine or hydroquinone can be added as necessary. Moreover, polymerization can also be suppressed by allowing a small amount of oxygen to coexist in the reaction solution.
本発明を実施するに際しては、アクリル酸又はメタクリ
ル酸を重水素源例えば重水と反応させ、アクリル酸又は
メタクリル酸の水素を寺≠重水素交換する。In practicing the present invention, acrylic or methacrylic acid is reacted with a deuterium source, such as heavy water, to exchange hydrogen from the acrylic or methacrylic acid.
本反応は、必要に応じ１反応源度で安定な溶媒例えばジ
メチルアセトアミド、ジメチルホルムアミド等の存在下
に行われる。本反応は室温ないし６００℃で行われるが
、反応速度、副反応及び重合の抑制の面から６０〜２０
０℃で行うことが好ましい。反応時間は通常２０分ない
し１００時間である。This reaction is carried out, if necessary, in the presence of a stable solvent such as dimethylacetamide, dimethylformamide, etc. at one reaction level. This reaction is carried out at room temperature to 600°C, but from the viewpoint of reaction rate, side reactions and inhibition of polymerization,
Preferably, it is carried out at 0°C. The reaction time is usually 20 minutes to 100 hours.
下記実施例中の部は重量部を意味する。分析はガスクロ
マトグラフ及び質量分析装置によった。重水素化率及び
転化率は以下のように定義される。Parts in the following examples mean parts by weight. Analysis was performed using a gas chromatograph and a mass spectrometer. Deuteration rate and conversion rate are defined as follows.
実施例１
メタクリル酸８．６部、重水４０部、ヘキサクロロイリ
ジウム酸０．６部及び重合防止剤として微量のハイドロ
キノンを小型オートクレーブに入れ、攪拌下、１１０℃
で２４時間反応させた。Example 1 8.6 parts of methacrylic acid, 40 parts of heavy water, 0.6 parts of hexachloroiridic acid, and a trace amount of hydroquinone as a polymerization inhibitor were placed in a small autoclave and heated to 110°C under stirring.
The mixture was allowed to react for 24 hours.
冷却後１反応生成物を分析したところ、転化率１００％
で重水素化率２６％の重水素化メタクリル酸が得られた
。Analysis of one reaction product after cooling revealed that the conversion rate was 100%.
Deuterated methacrylic acid with a deuteration rate of 26% was obtained.
実施例２
ヘキサクロロイリジウム酸０．６部をテトラキス（トリ
フェニルホスフィン）ハラシウム０．５８部に替え、そ
の他は実施例１と同様にして反応させた。その結果、転
化率１００％で重水素化率８４％の重水素化メタクリル
酸が得られた。Example 2 The reaction was carried out in the same manner as in Example 1, except that 0.6 part of hexachloroiridic acid was replaced with 0.58 part of tetrakis(triphenylphosphine)halacium. As a result, deuterated methacrylic acid with a conversion rate of 100% and a deuteration rate of 84% was obtained.
実施例６
アクリル酸７．２部、重水４０部、ヘキサクロロイリジ
ウム酸ナトリウム１．４部、ジメチルアセトアミド２２
部及び微量のハイドロキノンを冷却器付のフラスコに入
れ、攪拌しながら９０℃で６００時間反応せた。その結
果、転化率７９％で重水素化率２５％の重水素化アクリ
ル酸が得られた。Example 6 7.2 parts of acrylic acid, 40 parts of heavy water, 1.4 parts of sodium hexachloroiridate, 22 parts of dimethylacetamide
and a trace amount of hydroquinone were placed in a flask equipped with a condenser, and the mixture was reacted at 90° C. for 600 hours with stirring. As a result, deuterated acrylic acid with a conversion rate of 79% and a deuteration rate of 25% was obtained.
実施例４〜８
触媒、とじて臭化白金酸カリウム０．６８部（実施例４
）、ペンタクロロルテニウム酸カリウム０．２部（実施
例５）、硝酸パラジウム０．２３部（実施例６）、ヘキ
サヒドロキソ白金酸カリウラ０．２部（実施例７）又は
パラジウム及びルテニウムを活性炭粉末に各１％担持し
た触媒２部（実施例８）を用い１反応源度及び時間を下
記表のように変更し、その他は実施例１と同様にして反
応させた。Examples 4-8 Catalyst, 0.68 parts of potassium bromide platinate (Example 4
), 0.2 parts of potassium pentachlororuthenate (Example 5), 0.23 parts of palladium nitrate (Example 6), 0.2 parts of potassium hexahydroxoplatinate (Example 7), or palladium and ruthenium on activated carbon powder. The reaction was carried out in the same manner as in Example 1, except that 2 parts of the catalyst (Example 8) each having 1% of the catalyst supported thereon was used, and the reaction rate and time were changed as shown in the table below.
その結果を次表に示す。The results are shown in the table below.
Claims (1)
を重水素交換することを特徴とする、重水素化アクリル
酸又は重水素化メタクリル酸の製造方法。 ２、触媒としてパラジウム、ルテニウム、イリジウム及
び／又は白金を含む化合物を使用することを特徴とする
、特許請求の範囲第１項に記載の方法。[Claims] 1. A method for producing deuterated acrylic acid or deuterated methacrylic acid, which comprises exchanging hydrogen in acrylic acid or methacrylic acid with deuterium in the presence of a catalyst. 2. The method according to claim 1, characterized in that a compound containing palladium, ruthenium, iridium and/or platinum is used as a catalyst.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60113963A JPS61275241A (en) | 1985-05-29 | 1985-05-29 | Production of deuterated acrylic acid or methacrylic acid |
| CA000510055A CA1265814A (en) | 1985-05-29 | 1986-05-27 | Process for the production of deuterated acrylic acid or deuterated methacrylic acid |
| NO862126A NO163953C (en) | 1985-05-29 | 1986-05-28 | PROCEDURE FOR THE PREPARATION OF DEUTRATED ACRYLIC ACID OR DEUTRATED METACRYLIC ACID. |
| EP86107250A EP0203588B1 (en) | 1985-05-29 | 1986-05-28 | Process for the production of deuterated acrylic acid or deuterated methacrylic acid |
| DE19863689206 DE3689206T2 (en) | 1985-05-29 | 1986-05-28 | Process for the preparation of deuterated acrylic or methacrylic acid. |
| US07/522,418 US5221768A (en) | 1985-05-29 | 1990-05-07 | Process for the production of deuterated acid or deuterated methacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60113963A JPS61275241A (en) | 1985-05-29 | 1985-05-29 | Production of deuterated acrylic acid or methacrylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61275241A true JPS61275241A (en) | 1986-12-05 |
Family
ID=14625588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60113963A Pending JPS61275241A (en) | 1985-05-29 | 1985-05-29 | Production of deuterated acrylic acid or methacrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61275241A (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005070853A1 (en) * | 2004-01-23 | 2005-08-04 | Wako Pure Chemical Industries, Ltd. | Method of deuteration using mixed catalyst |
| WO2006001236A1 (en) * | 2004-06-25 | 2006-01-05 | Wako Pure Chemical Industries, Ltd. | Method for deuterating haloacrylic acid or its salt |
| US7517990B2 (en) | 2002-11-15 | 2009-04-14 | Wako Pure Chemical Industries, Ltd. | Method for deuteration of a heterocyclic ring |
| WO2011136369A1 (en) | 2010-04-28 | 2011-11-03 | 協和発酵キリン株式会社 | Cationic lipid |
| WO2011136368A1 (en) | 2010-04-28 | 2011-11-03 | 協和発酵キリン株式会社 | Cationic lipid |
| US8093422B2 (en) | 2002-07-26 | 2012-01-10 | Wako Pure Chemical Industries, Ltd. | Method for deuteration of an aromatic ring |
| WO2013018899A1 (en) | 2011-08-03 | 2013-02-07 | 協和発酵キリン株式会社 | Dibenzooxepin derivative |
| WO2013031931A1 (en) | 2011-09-02 | 2013-03-07 | 協和発酵キリン株式会社 | Chemokine receptor activity regulator |
| WO2013065825A1 (en) | 2011-11-02 | 2013-05-10 | 協和発酵キリン株式会社 | Cationic lipid |
| WO2013089151A1 (en) | 2011-12-12 | 2013-06-20 | 協和発酵キリン株式会社 | Lipid nanoparticles for drug delivery system containing cationic lipids |
| WO2013089152A1 (en) | 2011-12-12 | 2013-06-20 | 協和発酵キリン株式会社 | Lipid nanoparticles containing combinations of cationic lipids |
| WO2014002967A1 (en) | 2012-06-25 | 2014-01-03 | 協和発酵キリン株式会社 | 4,6-hexadecadiene-2,4-dicarboxylic acid derivative |
| WO2014021383A1 (en) | 2012-07-31 | 2014-02-06 | 協和発酵キリン株式会社 | Condensed ring heterocyclic compound |
| WO2014084330A1 (en) | 2012-11-30 | 2014-06-05 | 協和発酵キリン株式会社 | Nitrogen-containing heterocyclic compound |
| WO2014088085A1 (en) | 2012-12-06 | 2014-06-12 | 協和発酵キリン株式会社 | Pyridone compound |
| WO2015016195A1 (en) | 2013-07-29 | 2015-02-05 | 協和発酵キリン株式会社 | Wnt SIGNALING INHIBITOR |
| WO2017111076A1 (en) | 2015-12-24 | 2017-06-29 | 協和発酵キリン株式会社 | α, β UNSATURATED AMIDE COMPOUND |
| WO2018235926A1 (en) | 2017-06-23 | 2018-12-27 | 協和発酵キリン株式会社 | α, β-UNSATURATED AMIDE COMPOUND |
| WO2019189778A1 (en) | 2018-03-30 | 2019-10-03 | 協和発酵キリン株式会社 | Compound with anticancer activity |
| WO2021065980A1 (en) | 2019-09-30 | 2021-04-08 | 協和キリン株式会社 | Bet degrader |
-
1985
- 1985-05-29 JP JP60113963A patent/JPS61275241A/en active Pending
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8093422B2 (en) | 2002-07-26 | 2012-01-10 | Wako Pure Chemical Industries, Ltd. | Method for deuteration of an aromatic ring |
| US7517990B2 (en) | 2002-11-15 | 2009-04-14 | Wako Pure Chemical Industries, Ltd. | Method for deuteration of a heterocyclic ring |
| US9255070B2 (en) | 2004-01-23 | 2016-02-09 | Wako Pure Chemical Industries, Ltd. | Method of deuteration using mixed catalyst |
| JP4839839B2 (en) * | 2004-01-23 | 2011-12-21 | 和光純薬工業株式会社 | Deuteration method using mixed catalyst |
| WO2005070853A1 (en) * | 2004-01-23 | 2005-08-04 | Wako Pure Chemical Industries, Ltd. | Method of deuteration using mixed catalyst |
| WO2006001236A1 (en) * | 2004-06-25 | 2006-01-05 | Wako Pure Chemical Industries, Ltd. | Method for deuterating haloacrylic acid or its salt |
| WO2011136369A1 (en) | 2010-04-28 | 2011-11-03 | 協和発酵キリン株式会社 | Cationic lipid |
| WO2011136368A1 (en) | 2010-04-28 | 2011-11-03 | 協和発酵キリン株式会社 | Cationic lipid |
| WO2013018899A1 (en) | 2011-08-03 | 2013-02-07 | 協和発酵キリン株式会社 | Dibenzooxepin derivative |
| WO2013031931A1 (en) | 2011-09-02 | 2013-03-07 | 協和発酵キリン株式会社 | Chemokine receptor activity regulator |
| WO2013065825A1 (en) | 2011-11-02 | 2013-05-10 | 協和発酵キリン株式会社 | Cationic lipid |
| EP3301086A1 (en) | 2011-11-02 | 2018-04-04 | Kyowa Hakko Kirin Co., Ltd. | Production of a composition containing a complex between a membrane composed of a lipid monolayer and a nucleic acid, and, a lipid membrane for encapsulating the complex therein |
| WO2013089151A1 (en) | 2011-12-12 | 2013-06-20 | 協和発酵キリン株式会社 | Lipid nanoparticles for drug delivery system containing cationic lipids |
| WO2013089152A1 (en) | 2011-12-12 | 2013-06-20 | 協和発酵キリン株式会社 | Lipid nanoparticles containing combinations of cationic lipids |
| WO2014002967A1 (en) | 2012-06-25 | 2014-01-03 | 協和発酵キリン株式会社 | 4,6-hexadecadiene-2,4-dicarboxylic acid derivative |
| WO2014021383A1 (en) | 2012-07-31 | 2014-02-06 | 協和発酵キリン株式会社 | Condensed ring heterocyclic compound |
| WO2014084330A1 (en) | 2012-11-30 | 2014-06-05 | 協和発酵キリン株式会社 | Nitrogen-containing heterocyclic compound |
| WO2014088085A1 (en) | 2012-12-06 | 2014-06-12 | 協和発酵キリン株式会社 | Pyridone compound |
| WO2015016195A1 (en) | 2013-07-29 | 2015-02-05 | 協和発酵キリン株式会社 | Wnt SIGNALING INHIBITOR |
| WO2017111076A1 (en) | 2015-12-24 | 2017-06-29 | 協和発酵キリン株式会社 | α, β UNSATURATED AMIDE COMPOUND |
| WO2018235926A1 (en) | 2017-06-23 | 2018-12-27 | 協和発酵キリン株式会社 | α, β-UNSATURATED AMIDE COMPOUND |
| WO2019189778A1 (en) | 2018-03-30 | 2019-10-03 | 協和発酵キリン株式会社 | Compound with anticancer activity |
| WO2021065980A1 (en) | 2019-09-30 | 2021-04-08 | 協和キリン株式会社 | Bet degrader |
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