JPH0687784A - Production of crotonic acid and crotonic acid derivative - Google Patents
Production of crotonic acid and crotonic acid derivativeInfo
- Publication number
- JPH0687784A JPH0687784A JP4239371A JP23937192A JPH0687784A JP H0687784 A JPH0687784 A JP H0687784A JP 4239371 A JP4239371 A JP 4239371A JP 23937192 A JP23937192 A JP 23937192A JP H0687784 A JPH0687784 A JP H0687784A
- Authority
- JP
- Japan
- Prior art keywords
- crotonic acid
- acid derivative
- acetic acid
- acetaldehyde
- coor
- 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
- 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、クロトン酸及びクロト
ン酸誘導体の製造方法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing crotonic acid and crotonic acid derivatives.
【０００２】[0002]
【従来の技術】クロトン酸及びクロトン酸誘導体は優れ
た合成樹脂共重合モノマー、医薬、香料、農業、可塑剤
として工業的に有用な化合物であり、現在までに様々な
合成方法が提案されている。例えば、クロトンアルデヒ
ドを酸化する方法としては、(1) 空気或いは酸素のみで
酸化する方法（PBレポート91665)、(2) 金属酸化物など
の触媒の存在下、酸素含有ガスで酸化する方法（特公昭
40-24176、同42-5852 など) 、(3) セレン化合物の存在
下、過酢酸で酸化する方法（特公昭49-41175) 、(4) 可
溶性マンガン塩存在下、過酢酸で酸化する方法（特開昭
57-62238) 、及び(5) ルテニウム触媒の存在下、過酸化
水素で酸化する方法（特公昭46-2967)などがある。BACKGROUND OF THE INVENTION Crotonic acid and crotonic acid derivatives are industrially useful compounds as excellent synthetic resin copolymerizable monomers, drugs, fragrances, agriculture and plasticizers, and various synthetic methods have been proposed to date. . For example, as a method for oxidizing crotonaldehyde, (1) a method of oxidizing only with air or oxygen (PB Report 91665), (2) a method of oxidizing with an oxygen-containing gas in the presence of a catalyst such as a metal oxide (see Kosho
40-24176, 42-5852, etc.), (3) Method of oxidizing with peracetic acid in the presence of selenium compound (JP-B-49-41175), (4) Method of oxidizing with peracetic acid in the presence of soluble manganese salt ( JPA
57-62238), and (5) oxidation with hydrogen peroxide in the presence of a ruthenium catalyst (Japanese Patent Publication No. 46-2967).
【０００３】[0003]
【発明が解決しようとする課題】しかし、クロトンアル
デヒドを酸化する方法のうち(1) 、(2) 、(5) の方法に
おいては、クロトン酸選択率を高めるため、或いは、結
晶の析出などプロセス上の問題のため、クロトンアルデ
ヒドの転化率を50〜60％に制限しなければならない。そ
れでもなお選択率は最良の場合で85〜89％、クロトンア
ルデヒドの収率は30〜40％であって、工業的に考えて満
足すべき技術とは言えない。(3) の方法はクロトンアル
デヒドの酸化に関する具体的な実施例がないばかりでな
く触媒として極めて毒性の強いセレン化合物を高濃度で
用いなくてはならず、これも実用的とは言い難い。(4)
の方法は、(3) の触媒のセレン化合物より毒性の低いマ
ンガン化合物を使用しているが、酸化物質として爆発性
の過酸化物を使用しているためあまり好ましいとは言え
ない。However, in the methods (1), (2), and (5) of the methods for oxidizing crotonaldehyde, in order to increase the crotonic acid selectivity, or to perform a process such as crystal precipitation. Due to the above problem, the conversion of crotonaldehyde must be limited to 50-60%. Nevertheless, the selectivity is 85 to 89% in the best case, and the yield of crotonaldehyde is 30 to 40%, which is not a satisfactory technology from an industrial viewpoint. The method (3) does not have a specific example concerning the oxidation of crotonaldehyde, and also requires the use of a highly toxic selenium compound as a catalyst at a high concentration, which is also not practical. (Four)
The method of (3) uses a manganese compound, which is less toxic than the selenium compound of the catalyst of (3), but is not so preferable because it uses an explosive peroxide as an oxidizing substance.
【０００４】従って、穏和な条件下、より短い製造工程
で安全に収率良くクロトン酸及びクロトン酸誘導体を製
造できる方法の開発が強く望まれている。Therefore, it has been strongly desired to develop a method capable of safely producing crotonic acid and a crotonic acid derivative under mild conditions in a shorter production process and in a high yield.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記課題
を解決すべく鋭意検討した結果、酢酸又は酢酸誘導体と
アセトアルデヒドとのアルドール型反応をルイス酸触媒
を用いることによって活性化し、より穏和な条件下で収
率良くクロトン酸及びクロトン酸誘導体を製造する方法
を見出した。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have activated the aldol-type reaction of acetic acid or an acetic acid derivative with acetaldehyde by using a Lewis acid catalyst to make the reaction more mild. We have found a method to produce crotonic acid and crotonic acid derivatives in good yield under various conditions.
【０００６】即ち、本発明は、一般式、 CH3−COOR （Ｉ） （式中、R は、水素原子、炭素数１〜５のアルキル基、
アリール基又はアシル基を示す。）で表される酢酸又は
酢酸誘導体（以下、酢酸誘導体（Ｉ）と略する。）とア
セトアルデヒドをルイス酸触媒下で反応させることを特
徴とする一般式、 CH3−CH＝CH−COOR （II) （式中、R は、水素原子、炭素数１〜５のアルキル基、
アリール基又はアシル基を示す。）で表されるクロトン
酸及びクロトン酸誘導体（以下、クロトン酸誘導体（I
I) と略する。) の製造方法に関する。That is, the present invention has the general formula CH 3 --COOR (I) (wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
An aryl group or an acyl group is shown. ), An acetic acid derivative or acetic acid derivative (hereinafter, abbreviated as acetic acid derivative (I)) and acetaldehyde are reacted under a Lewis acid catalyst, a general formula: CH 3 —CH═CH—COOR (II (In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
An aryl group or an acyl group is shown. Crotonic acid and crotonic acid derivative (hereinafter referred to as crotonic acid derivative (I
Abbreviated as I). ) Related to the manufacturing method.
【０００７】本発明の出発物質として使用される酢酸誘
導体（Ｉ）の一般式中に示されている置換基R は、水素
原子、炭素数１〜５のアルキル基、アリール基又はアシ
ル基を示しているが、アシル基としてはR'CO−（R'は炭
素数１〜５のアルキル基）が好ましい。アルキル基は直
鎖であっても分岐したものであっても良く、又、アリー
ル基及びアシル基の持つ置換基についても限定されな
い。本発明に使用される酢酸誘導体（Ｉ）の一部を例示
すると、酢酸、酢酸メチル、酢酸エチル、酢酸プロピ
ル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、
酢酸フェニル、酢酸ベンジル、酢酸クロロフェニル、酢
酸ブロモフェニル、酢酸メトキシフェニル、無水酢酸等
がある。The substituent R shown in the general formula of the acetic acid derivative (I) used as the starting material of the present invention is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group or an acyl group. However, as the acyl group, R′CO— (R ′ is an alkyl group having 1 to 5 carbon atoms) is preferable. The alkyl group may be linear or branched, and the substituents of the aryl group and acyl group are not limited. Some examples of the acetic acid derivative (I) used in the present invention are acetic acid, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate,
Examples include phenyl acetate, benzyl acetate, chlorophenyl acetate, bromophenyl acetate, methoxyphenyl acetate and acetic anhydride.
【０００８】一方、本発明において使用されるアセトア
ルデヒドは、モノマーでも三量体でも良いが、モノマー
を使用する時は脱水処理した後に使用する方が好まし
い。On the other hand, the acetaldehyde used in the present invention may be a monomer or a trimer, but when the monomer is used, it is preferably used after dehydration treatment.
【０００９】本発明で使用するルイス酸触媒は、特に限
定されるものではないが、好ましくはAl,Cu,Sn,Zn のア
ルコキシド、カルボキシレート、ハライド、オキシド等
である。又、仕込む段階では、金属単体でも良い。The Lewis acid catalyst used in the present invention is not particularly limited, but preferably is Al, Cu, Sn, Zn alkoxide, carboxylate, halide, oxide or the like. In addition, at the stage of charging, a single metal may be used.
【００１０】本発明において、酢酸誘導体（Ｉ）とアセ
トアルデヒドのモル比は規制されるものではないが、酢
酸誘導体（Ｉ）１モルに対してアセトアルデヒド１〜10
モルにすることが好ましい。酢酸誘導体（Ｉ）１モルに
対してアセトアルデヒドが１モル未満であると、反応速
度が著しく遅く、生成したクロトン酸誘導体（II) が重
合変質する場合があるため好ましくない。また、酢酸誘
導体（Ｉ）１モルに対してアセトアルデヒドが10モルよ
り多く存在すると、過剰量のアセトアルデヒドを回収す
る必要があり経済的に問題であり、また、しばしばアセ
トアルデヒドの重合物による配管閉塞も起こる。In the present invention, the molar ratio of the acetic acid derivative (I) to acetaldehyde is not limited, but 1 to 10 mol of acetaldehyde relative to 1 mol of the acetic acid derivative (I).
It is preferable to make it molar. If the amount of acetaldehyde is less than 1 mol with respect to 1 mol of the acetic acid derivative (I), the reaction rate is remarkably slow and the produced crotonic acid derivative (II) may undergo polymerization alteration, which is not preferable. Further, when acetaldehyde is present in an amount of more than 10 mols per mol of the acetic acid derivative (I), it is necessary to recover an excessive amount of acetaldehyde, which is economically problematic, and often the piping of the acetaldehyde polymer is clogged. .
【００１１】一方、ルイス酸触媒の使用量は特に限定す
るものではないが、好ましくは、酢酸誘導体（Ｉ）１モ
ルに対して 0.001〜５モルの範囲で、特に好ましくは
0.1〜２モルの範囲で使用するのが有利である。On the other hand, the amount of the Lewis acid catalyst used is not particularly limited, but is preferably in the range of 0.001 to 5 mol, and particularly preferably in the range of 1 mol of acetic acid derivative (I).
It is advantageous to use it in the range from 0.1 to 2 mol.
【００１２】本発明の反応は、反応温度50〜400 ℃の範
囲で実施するのが好ましく、特に好ましくは 100〜250
℃の範囲である。反応温度が50℃より低いと反応速度が
著しく低下し 400℃を超えると生成するクロトン酸誘導
体（II) の一部が重合変質する。The reaction of the present invention is preferably carried out at a reaction temperature of 50 to 400 ° C, particularly preferably 100 to 250 ° C.
It is in the range of ° C. When the reaction temperature is lower than 50 ° C, the reaction rate is remarkably reduced, and when it exceeds 400 ° C, a part of the crotonic acid derivative (II) produced is polymer-altered.
【００１３】本発明の反応は、次の様に実施できる。酢
酸誘導体（Ｉ）、アセトアルデヒド、ルイス酸触媒の混
合物をオートクレーブ中に充填し、上記反応温度に 0.5
〜10時間保持する。次いで、反応混合物からクロトン酸
誘導体（II) を常法により、例えば蒸留により分離す
る。The reaction of the present invention can be carried out as follows. A mixture of acetic acid derivative (I), acetaldehyde and Lewis acid catalyst was charged into an autoclave and the reaction temperature was adjusted to 0.5.
Hold for ~ 10 hours. Then, the crotonic acid derivative (II) is separated from the reaction mixture by a conventional method, for example, by distillation.
【００１４】[0014]
【実施例】以下に実施例を挙げて、より具体的に本発明
を説明するが、本発明はその主旨を超えない限り、本実
施例に限定されるものではない。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.
【００１５】実施例１ 無水酢酸 1.0モル、アセトアルデヒド 9.0モル、ルイス
酸触媒として塩基性酢酸アルミニウム0.1 モルをオート
クレーブ中に充填し、反応温度180.0 ℃にて 2.0時間保
持した。その後、反応混合液をガスクロマトグラフィー
法により分析し無水酢酸転化率、クロトン酸収率を求め
た。表１にその結果を示す。Example 1 1.0 mol of acetic anhydride, 9.0 mol of acetaldehyde, and 0.1 mol of basic aluminum acetate as a Lewis acid catalyst were charged in an autoclave and kept at a reaction temperature of 180.0 ° C. for 2.0 hours. Then, the reaction mixture was analyzed by gas chromatography to determine the acetic anhydride conversion rate and crotonic acid yield. The results are shown in Table 1.
【００１６】[0016]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 69/56 8018−4Ｈ // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C07C 69/56 8018-4H // C07B 61/00 300
Claims (1)
アリール基又はアシル基を示す。）で表される酢酸又は
酢酸誘導体とアセトアルデヒドをルイス酸触媒下で反応
させることを特徴とする一般式、 CH3−CH＝CH−COOR （II) （式中、R は、水素原子、炭素数１〜５のアルキル基、
アリール基又はアシル基を示す。）で表されるクロトン
酸及びクロトン酸誘導体の製造方法。1. A general formula, CH 3 —COOR (I) (wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
An aryl group or an acyl group is shown. ), Acetic acid or acetic acid derivative and acetaldehyde are reacted under a Lewis acid catalyst, a general formula, CH 3 -CH = CH-COOR (II) (In the formula, R is a hydrogen atom, carbon number 1 to 5 alkyl groups,
An aryl group or an acyl group is shown. ) A method for producing crotonic acid and a crotonic acid derivative represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4239371A JPH0687784A (en) | 1992-09-08 | 1992-09-08 | Production of crotonic acid and crotonic acid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4239371A JPH0687784A (en) | 1992-09-08 | 1992-09-08 | Production of crotonic acid and crotonic acid derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0687784A true JPH0687784A (en) | 1994-03-29 |
Family
ID=17043780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4239371A Pending JPH0687784A (en) | 1992-09-08 | 1992-09-08 | Production of crotonic acid and crotonic acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0687784A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6844447B2 (en) | 2001-12-18 | 2005-01-18 | Metabolix Inc. | Methods of making intermediates from polyhydroxyalkanoates |
| CN114349631A (en) * | 2022-01-14 | 2022-04-15 | 北京富盛嘉华医药科技有限公司 | Preparation method and application of 4-methoxy crotonic acid |
-
1992
- 1992-09-08 JP JP4239371A patent/JPH0687784A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6844447B2 (en) | 2001-12-18 | 2005-01-18 | Metabolix Inc. | Methods of making intermediates from polyhydroxyalkanoates |
| US6897338B2 (en) | 2001-12-18 | 2005-05-24 | Metabolix, Inc. | Methods of making intermediates from polyhydroxyalkanoates |
| US6933404B2 (en) | 2001-12-18 | 2005-08-23 | Metabolix Inc. | Methods of making intermediates from polyhydroxyalkanoates |
| US7001969B2 (en) | 2001-12-18 | 2006-02-21 | Metabolix Inc. | Methods of making intermediates from polyhydroxyalkanoates |
| US7166743B2 (en) | 2001-12-18 | 2007-01-23 | Metabolix, Inc. | Methods of making intermediates from polyhydroxyalkanoates |
| US7230144B2 (en) | 2001-12-18 | 2007-06-12 | Metabolix Inc. | Methods of making intermediates from polyhydroxyalkanoates |
| CN114349631A (en) * | 2022-01-14 | 2022-04-15 | 北京富盛嘉华医药科技有限公司 | Preparation method and application of 4-methoxy crotonic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3374863B2 (en) | Method for producing dialkyl carbonate | |
| JPH0687784A (en) | Production of crotonic acid and crotonic acid derivative | |
| JP2002322122A (en) | Method for producing carboxylic ester, and its 'onium' salt and salt mixture | |
| JP2976245B2 (en) | Method for producing hydroxyphenylpropionate | |
| JPH03173846A (en) | Preparation of chlorocarboxylic acid chloride | |
| JPS6261965A (en) | Bis(2-gluconamidoalkyl)disulfide | |
| JP2708548B2 (en) | Method for producing unsaturated carboxylic acid amide | |
| JP2711517B2 (en) | Method for producing 6-alkyl-2-naphthalenecarboxylic acid and 6-isopropyl-2-naphthalenecarboxylic acid | |
| JP3402499B2 (en) | Method for producing cyano norbornene | |
| JP2608724B2 (en) | Method for producing benzotriazoles | |
| SU1685915A1 (en) | Method for obtaining monochloroacetic acid | |
| JP2903233B2 (en) | Method for producing high-purity dimethyl diphenyldicarboxylate | |
| JP3446761B2 (en) | Method for producing alkylene carbonate | |
| EP0230916B1 (en) | Process for the preparation of the esters of an alkyltartronic acid | |
| JPS6261961A (en) | Carbamic acid ester having keto group | |
| JPS6287529A (en) | Production of alcohol or such | |
| JP2816618B2 (en) | Method for removing bischloromethyl ether contained in pivalic acid chloromethyl ester | |
| JPH04217948A (en) | Process for synthesizing amide from vinyl acetate | |
| JPH0248559A (en) | Production of unsaturated carboxylic acid amide | |
| JP2928673B2 (en) | Method for producing benzyl dicarboxylic acid ester | |
| JPS6261950A (en) | Carbonate having keto group | |
| JP2813231B2 (en) | Highly efficient production method of optically active cyanohydrins | |
| JPH0753692B2 (en) | Method for producing aromatic carboxylic acid esters | |
| JPS6130672B2 (en) | ||
| JPH0513937B2 (en) |