JP2003342271A - Method for producing 2(3h)-furanone derivative - Google Patents

Method for producing 2(3h)-furanone derivative

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Publication number
JP2003342271A
JP2003342271A JP2002150478A JP2002150478A JP2003342271A JP 2003342271 A JP2003342271 A JP 2003342271A JP 2002150478 A JP2002150478 A JP 2002150478A JP 2002150478 A JP2002150478 A JP 2002150478A JP 2003342271 A JP2003342271 A JP 2003342271A
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JP
Japan
Prior art keywords
furanone derivative
furanone
oxide
producing
derivative
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.)
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JP2002150478A
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Japanese (ja)
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JP2003342271A5 (en
Inventor
Takashi Sugioka
尚 杉岡
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to JP2002150478A priority Critical patent/JP2003342271A/en
Publication of JP2003342271A publication Critical patent/JP2003342271A/en
Publication of JP2003342271A5 publication Critical patent/JP2003342271A5/ja
Withdrawn legal-status Critical Current

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  • Furan Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for inexpensively, efficiently and industrially advantageously producing thermodynamically unstable 2(3H)-furanone derivative. <P>SOLUTION: This method for producing the 2(3H)-furanone derivative represented by formula (II) involves distilling the 2(3H)-furanone derivative while isomerizing a 2(5H)-furanone derivative represented by formula (I) in the presence of a metal oxide or a metal salt of a carboxylic acid (in the formulas, R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each hydrogen atom or an alkyl group). <P>COPYRIGHT: (C)2004,JPO

Description

【発明の詳細な説明】 【0001】 【発明の属する技術分野】本発明は、2(5H)−フラ
ノン誘導体を異性化することにより2(3H)−フラノ
ン誘導体を製造する方法に関する。本発明により得られ
る2(3H)−フラノン誘導体は、医薬の合成中間体、
バッテリーの電解液溶媒(特開平4−190574号公
報参照)などとして有用である。 【0002】 【従来の技術】2(3H)−フラノン誘導体の製造方法
としては、例えば、フルフラールを過酸化水素と反応さ
せる方法[シンセシス(Synthesis)、8巻、
786頁(1985年);オーガニック プレパレーシ
ョンズ アンド プロセデュアーズ インターナショナ
ル(Organic Preparations &P
rocedures International)、
215頁(1995年)参照]などが知られている。 【0003】 【発明が解決しようとする課題】上記の従来法では、生
成物である2(3H)−フラノン誘導体は熱力学的に安
定な2(5H)−フラノン誘導体へと異性化し易いた
め、反応終了後は両者の混合物として得られる。2(3
H)−フラノン誘導体は、該混合物を蒸留することによ
り分離されるが、20%程度の低収率でしか得られな
い。したがって、従来法は2(3H)−フラノン誘導体
の工業的に有利な製造方法とは言い難い。 【0004】本発明の目的は、2(3H)−フラノン誘
導体を安価に、効率よく、工業的に有利に製造し得る方
法を提供することにある。 【0005】 【課題を解決するための手段】本発明者は、上記の課題
を解決するために鋭意検討した結果、熱力学的に安定で
単離し易い2(5H)−フラノン誘導体を2(3H)−
フラノン誘導体へと異性化する方法を見出し、かつ両者
の物性値を利用して2(3H)−フラノン誘導体を異性
化させながら取り出す手法として、沸点差[2.67k
Paにおける沸点:2(5H)−フラノンは96℃、2
(3H)−フラノンは56℃である]を利用した蒸留方
法を見出し、本発明を完成するに至った。 【0006】本発明は、一般式(I) 【0007】 【化3】 【0008】(式中、R、RおよびRは水素
原子またはアルキル基を表す。)で示される2(5H)
−フラノン誘導体[以下、これを2(5H)−フラノン
誘導体(I)と称する]を、金属酸化物またはカルボン
酸金属塩の存在下に異性化させながら蒸留することを特
徴とする一般式(II) 【0009】 【化4】 【0010】(式中、R、RおよびRは前記
定義のとおりである。)で示される2(3H)−フラノ
ン誘導体[以下、これを2(3H)−フラノン誘導体
(II)と称する]の製造方法である。 【0011】 【発明の実施の形態】上記一般式中、R、Rおよ
びRが表すアルキル基としては、炭素数1〜6の直
鎖状または分岐鎖状のアルキル基が好ましく、例えばメ
チル基、エチル基、プロピル基、イソプロピル基、ブチ
ル基、イソブチル基、tert−ブチル基、ヘキシル基
などが挙げられる。 【0012】本発明における異性化反応は、金属酸化物
またはカルボン酸金属塩(以下、これらを触媒と総称す
る)の存在下に進行する。金属酸化物としては、例え
ば、酸化マグネシウム、酸化カルシウム、酸化チタン、
酸化ジルコニウム、酸化バナジウム、酸化ニオブ、酸化
クロム、酸化モリブデン、酸化タングステン、酸化マン
ガン、酸化レニウム、酸化鉄、酸化ルテニウム、酸化オ
スミウム、四三酸化コバルト、酸化コバルト(II)、
酸化コバルト(III)、酸化ロジウム、酸化イリジウ
ム、酸化ニッケル、酸化パラジウム、酸化白金、酸化
銅、酸化銀、酸化亜鉛、酸化カドミウム、酸化スズ、酸
化アルミニウム、酸化ホウ素、二酸化ケイ素などの典型
金属または遷移金属の酸化物が挙げられる。カルボン酸
金属塩としては、例えば、ギ酸リチウム、ギ酸ナトリウ
ム、ギ酸カリウム、酢酸リチウム、酢酸ナトリウム、酢
酸カリウム、酢酸マンガン、酢酸銅、酢酸スズ、酢酸パ
ラジウム、酢酸ロジウム、酢酸コバルトなどの典型金属
または遷移金属のカルボン酸塩が挙げられる。これらの
中でも、四三酸化コバルト(Co)およびギ酸
カリウムが特に好ましく使用される。触媒の使用量は、
2(5H)−フラノン誘導体(I)に対して0.001
〜30重量%の範囲であるのが好ましく、0.01〜5
重量%の範囲であるのがより好ましい。 【0013】異性化反応は溶媒の存在下に行うことがで
きる。溶媒としては、2(3H)−フラノン誘導体(I
I)よりも高沸点であれば反応に悪影響を与えない限り
特に限定されるものではなく、例えば、ドデカン、ペン
タデカン、1−メチルナフタレン、テトラリン、流動パ
ラフィンなどの炭化水素類;ジフェニルエーテルなどの
エーテル類;N−メチルピロリドン、N,N−ジメチル
イミダゾリジノン、ジメチルスルホキシド、N,N−ジ
メチルホルムアミド、ヘキサメチルリン酸トリアミドな
ど非プロトン性極性溶媒などが挙げられる。これらの溶
媒は単独でも2種以上を混合して使用してもよい。溶媒
の使用量は、2(5H)−フラノン誘導体(I)に対し
て0.5〜1000倍重量の範囲であるのが好ましい。 【0014】異性化反応の温度は、50〜200℃の範
囲であるのが好ましく、80〜150℃の範囲であるの
がより好ましい。反応時間は、0.5〜30時間の範囲
であるのが好ましい。 【0015】異性化反応は、常圧下または減圧下に行う
のが好ましい。本発明においては、異性化により生成し
た2(3H)−フラノン誘導体(II)を蒸留により連
続的に系外に取り出す。かかる操作により、2(3H)
−フラノン誘導体(II)を主成分とする留分を得るこ
とができる。例えば、蒸留塔を装備した反応器に2(5
H)−フラノン誘導体(I)と触媒を添加し、常圧下ま
たは減圧下に加熱することにより、低沸点の2(3H)
−フラノン誘導体(II)を主成分とする留分を容易に
得ることができる。なお、蒸留塔の理論段数は留分の組
成に大きく影響し、理論段数が大きい程、高純度の2
(3H)−フラノン誘導体(II)が得られる。また、
得られた2(3H)−フラノン誘導体(II)が所期の
純度に達していない場合には、再蒸留によりその純度を
高めることができる。 【0016】 【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明は実施例により何ら制限されるものではな
い。 【0017】実施例1 温度計、マグネチックスターラおよび蒸留塔(内径15
mm、塔長250mm、充填物:ヘリパック)を装備し
た内容積50mlの3口フラスコに、2(5H)−フラ
ノン20.00gおよび四三酸化コバルト100mgを
入れ、系内を15mmHgに減圧した後、内温が100
℃に保たれるように加熱した。定常状態になった後、塔
頂より温度50〜53℃の成分を留出させ、その留出量
と同重量の2(5H)−フラノンをフラスコ内にフィー
ドした。留出量が20.0gに達した時点で蒸留を終了
した。留出分をガスクロマトグラフィーにより分析した
結果、2(3H)−フラノン/2(5H)−フラノン=
90/10の混合物であった。 【0018】実施例2 実施例1において、四三酸化コバルト100mgの代り
にギ酸カリウム100mgを使用した以外は同様の反応
および操作を行った。留出分をガスクロマトグラフィー
により分析した結果、2(3H)−フラノン/2(5
H)−フラノン=75/25の混合物であった。 【0019】 【発明の効果】本発明によれば、2(3H)−フラノン
誘導体を安価に、効率よく、工業的に有利に製造するこ
とができる。
Description: TECHNICAL FIELD The present invention relates to a method for producing a 2 (3H) -furanone derivative by isomerizing a 2 (5H) -furanone derivative. BACKGROUND ART The 2 (3H) -furanone derivative obtained by the present invention is a synthetic intermediate of a pharmaceutical,
It is useful as an electrolyte solvent for a battery (see JP-A-4-190574). [0002] As a method for producing 2 (3H) -furanone derivatives, for example, a method of reacting furfural with hydrogen peroxide [Synthesis, Vol.
786 (1985); Organic Preparations & Procedures International (Organic Preparations & P)
procedures International),
215 (1995)]. [0003] In the above-mentioned conventional method, the product, 2 (3H) -furanone derivative, is easily isomerized into a thermodynamically stable 2 (5H) -furanone derivative. After completion of the reaction, it is obtained as a mixture of both. 2 (3
The H) -furanone derivative is separated by distilling the mixture, but can be obtained only in a low yield of about 20%. Therefore, the conventional method cannot be said to be an industrially advantageous method for producing a 2 (3H) -furanone derivative. An object of the present invention is to provide a method for producing a 2 (3H) -furanone derivative at low cost, efficiently and industrially advantageously. The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that a 2 (5H) -furanone derivative which is thermodynamically stable and easy to isolate is 2 (3H) -furanone. )-
As a method of finding a method of isomerizing to a furanone derivative and extracting the 2 (3H) -furanone derivative while isomerizing by utilizing the physical property values of both, a boiling point difference [2.67 k
Boiling point at Pa: 2 (5H) -furanone at 96 ° C, 2
(3H) -furanone is 56 ° C.], and the present invention was completed, and the present invention was completed. The present invention relates to a compound represented by the general formula (I): (Wherein R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group).
A general formula (II) characterized in that a -furanone derivative [hereinafter referred to as 2 (5H) -furanone derivative (I)] is distilled while isomerizing in the presence of a metal oxide or a metal carboxylate. [0009] (Wherein R 1 , R 2 and R 3 are as defined above) [hereinafter referred to as 2 (3H) -furanone derivative (II) The manufacturing method is referred to as BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula, the alkyl group represented by R 1 , R 2 and R 3 is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, and a hexyl group. [0012] The isomerization reaction in the present invention proceeds in the presence of a metal oxide or a metal carboxylate (hereinafter, these are collectively referred to as a catalyst). As the metal oxide, for example, magnesium oxide, calcium oxide, titanium oxide,
Zirconium oxide, vanadium oxide, niobium oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, rhenium oxide, iron oxide, ruthenium oxide, osmium oxide, cobalt trioxide, cobalt (II) oxide,
Typical metals or transitions such as cobalt (III) oxide, rhodium oxide, iridium oxide, nickel oxide, palladium oxide, platinum oxide, copper oxide, silver oxide, zinc oxide, cadmium oxide, tin oxide, aluminum oxide, boron oxide, silicon dioxide Oxides of metals are mentioned. Examples of the metal carboxylate include, for example, typical metals or transition metals such as lithium formate, sodium formate, potassium formate, lithium acetate, sodium acetate, potassium acetate, manganese acetate, copper acetate, tin acetate, palladium acetate, rhodium acetate, and cobalt acetate. Metal carboxylate is exemplified. Of these, cobalt trioxide (Co 3 O 4 ) and potassium formate are particularly preferably used. The amount of catalyst used is
0.001 based on 2 (5H) -furanone derivative (I)
-30% by weight, preferably 0.01-5% by weight.
More preferably, it is in the range of weight%. [0013] The isomerization reaction can be carried out in the presence of a solvent. As the solvent, a 2 (3H) -furanone derivative (I
The boiling point is not particularly limited as long as it does not adversely affect the reaction as long as it has a higher boiling point than I). For example, hydrocarbons such as dodecane, pentadecane, 1-methylnaphthalene, tetralin, liquid paraffin; ethers such as diphenyl ether Aprotic polar solvents such as N-methylpyrrolidone, N, N-dimethylimidazolidinone, dimethylsulfoxide, N, N-dimethylformamide and hexamethylphosphoric triamide. These solvents may be used alone or in combination of two or more. The amount of the solvent used is preferably in the range of 0.5 to 1000 times the weight of the 2 (5H) -furanone derivative (I). The temperature of the isomerization reaction is preferably in the range of 50 to 200 ° C, more preferably in the range of 80 to 150 ° C. The reaction time is preferably in the range from 0.5 to 30 hours. The isomerization reaction is preferably performed under normal pressure or reduced pressure. In the present invention, the 2 (3H) -furanone derivative (II) produced by isomerization is continuously taken out of the system by distillation. With this operation, 2 (3H)
-A fraction containing the furanone derivative (II) as a main component can be obtained. For example, in a reactor equipped with a distillation column, 2 (5
H) -Furanone derivative (I) and a catalyst are added, and the mixture is heated under normal pressure or reduced pressure to obtain 2 (3H) having a low boiling point.
-A fraction containing the furanone derivative (II) as a main component can be easily obtained. The number of theoretical plates in the distillation column greatly affects the composition of the fraction.
(3H) -furanone derivative (II) is obtained. Also,
When the obtained 2 (3H) -furanone derivative (II) does not reach the expected purity, the purity can be increased by redistillation. EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. Example 1 A thermometer, a magnetic stirrer and a distillation column (inner diameter 15
2 (5H) -furanone and 100 mg of cobalt tetroxide were placed in a 50-ml three-necked flask equipped with a 2 mm (mm), a tower length of 250 mm, and a packing: Helipak), and the pressure in the system was reduced to 15 mmHg. Internal temperature is 100
Heated so as to maintain the temperature. After a steady state was reached, a component having a temperature of 50 to 53 ° C. was distilled from the top of the column, and 2 (5H) -furanone having the same weight as the distilled amount was fed into the flask. The distillation was stopped when the amount of distillate reached 20.0 g. As a result of analyzing the distillate by gas chromatography, 2 (3H) -furanone / 2 (5H) -furanone =
It was a 90/10 mixture. Example 2 The same reaction and operation as in Example 1 were carried out except that 100 mg of potassium formate was used instead of 100 mg of cobalt trioxide. As a result of analyzing the distillate by gas chromatography, 2 (3H) -furanone / 2 (5
H) -Furanone = 75/25 mixture. According to the present invention, a 2 (3H) -furanone derivative can be produced inexpensively, efficiently and industrially advantageously.

Claims (1)

【特許請求の範囲】 【請求項1】 一般式(I) 【化1】 (式中、R、RおよびRは水素原子またはア
ルキル基を表す。)で示される2(5H)−フラノン誘
導体を、金属酸化物またはカルボン酸金属塩の存在下に
異性化させながら蒸留することを特徴とする一般式(I
I) 【化2】 (式中、R、RおよびRは前記定義のとおり
である。)で示される2(3H)−フラノン誘導体の製
造方法。
Claims: 1. A compound represented by the general formula (I): (Wherein R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group) while isomerizing the 2 (5H) -furanone derivative represented by the formula ( 1 ) in the presence of a metal oxide or a metal carboxylate. General formula (I) characterized by distillation
I) (Wherein R 1 , R 2, and R 3 are as defined above). A method for producing a 2 (3H) -furanone derivative represented by the formula:
JP2002150478A 2002-05-24 2002-05-24 Method for producing 2(3h)-furanone derivative Withdrawn JP2003342271A (en)

Priority Applications (1)

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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2002150478A JP2003342271A (en) 2002-05-24 2002-05-24 Method for producing 2(3h)-furanone derivative

Publications (2)

Publication Number Publication Date
JP2003342271A true JP2003342271A (en) 2003-12-03
JP2003342271A5 JP2003342271A5 (en) 2005-06-16

Family

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Country Status (1)

Country Link
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