JPH07138247A - Production of o,o'-diacyltartaric acid anhydride - Google Patents
Production of o,o'-diacyltartaric acid anhydrideInfo
- Publication number
- JPH07138247A JPH07138247A JP5314563A JP31456393A JPH07138247A JP H07138247 A JPH07138247 A JP H07138247A JP 5314563 A JP5314563 A JP 5314563A JP 31456393 A JP31456393 A JP 31456393A JP H07138247 A JPH07138247 A JP H07138247A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- acid
- chloride
- tartaric acid
- component
- 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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Classifications
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- 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、Ｏ，Ｏ´−ジアシル酒
石酸無水物の製造方法に関し、特に、Ｏ，Ｏ´−ジアシ
ル酒石酸無水物の工業的に有利な製造方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing O, O'-diacyltartaric anhydride, and more particularly to an industrially advantageous method for producing O, O'-diacyltartaric anhydride.
【０００２】[0002]
【従来の技術】従来、Ｏ，Ｏ´−ジアシル酒石酸無水物
の代表例である、Ｏ，Ｏ´−ジベンゾイル酒石酸無水物
を製造する方法として、（１）酒石酸と大過剰の塩化ベ
ンゾイルとを無溶媒下に於いて反応させる方法（Ｊ．Ａ
ｍ．Ｃｈｅｍ．Ｓｏｃ．，５５，２６０５（１９３
３））、（２）酒石酸と２倍モルの塩化ベンゾイルとを
溶媒存在下に反応させ、次いで塩化チオニルを加えて反
応を行う方法に於いて、反応させるに際して塩化鉄、塩
化亜鉛或いは塩化アルミニウム等の触媒を添加する方法
（ＨＵ３４７２０）などが提案されている。2. Description of the Related Art Conventionally, as a method for producing O, O'-dibenzoyltartaric anhydride, which is a typical example of O, O'-diacyltartaric anhydride, (1) tartaric acid and a large excess of benzoyl chloride are used. Method of reacting in a solvent (JA
m. Chem. Soc. , 55, 2605 (193
3)), (2) Tartaric acid and 2-fold molar benzoyl chloride are reacted in the presence of a solvent, and then thionyl chloride is added to carry out the reaction. In the reaction, iron chloride, zinc chloride, aluminum chloride, etc. The method of adding the catalyst of (HU34720) is proposed.
【０００３】[0003]
【発明が解決しようとする課題】（１）法においては、
酒石酸と塩化ベンゾイルの混合物を加熱して反応させる
際に、反応混合物が固化する等操作性が悪く工業的な製
造法には適さない。（２）法は操作性が良好であり、ま
た（１）法より低い温度でも反応が進行し工業的には好
ましい方法である。しかしながら、高価な酸ハロゲン化
物を使用するために製造コストが高く、より安価な製造
方法の開発が望まれていた。[Problems to be Solved by the Invention] In the method (1),
When a mixture of tartaric acid and benzoyl chloride is heated and reacted, the reaction mixture is not suitable for industrial production because the reaction mixture solidifies and the operability is poor. The method (2) has good operability, and the reaction proceeds even at a lower temperature than the method (1), which is an industrially preferable method. However, since the expensive acid halide is used, the manufacturing cost is high, and the development of a cheaper manufacturing method has been desired.
【０００４】本発明の目的は、操作性が良好で工業的生
産に適し、高価な酸ハロゲン化物を用いずに安価に行う
ことができ、高収率、高純度でＯ，Ｏ´−ジアシル酒石
酸無水物を得ることができるＯ，Ｏ´−ジアシル酒石酸
無水物の製造方法を提供することである。The object of the present invention is that the operability is good, it is suitable for industrial production, it can be carried out inexpensively without using an expensive acid halide, and high yield, high purity of O, O'-diacyltartaric acid is obtained. An object of the present invention is to provide a method for producing an O, O'-diacyltartaric acid anhydride capable of obtaining an anhydride.
【０００５】[0005]
【課題を解決するための手段】本出願人は、先に、カル
ボン酸類と酒石酸とをクロル化剤の存在下で反応させる
ことによりＯ，Ｏ´−ジアシル酒石酸無水物を製造する
方法を発明し、特許出願した（特願平４−３２１０１９
号）。この方法は、カルボン酸をそのまま用いることが
でき（すなわち、高価な酸ハロゲン化物が不要）、操作
性が良好で、高収率、高純度でＯ，Ｏ´−ジアシル酒石
酸無水物を製造することができる優れた方法である。The present applicant previously invented a method for producing an O, O'-diacyl tartaric anhydride by reacting a carboxylic acid and tartaric acid in the presence of a chlorinating agent. Filed a patent application (Japanese Patent Application No. 4-321019)
issue). In this method, a carboxylic acid can be used as it is (that is, an expensive acid halide is unnecessary), operability is good, and O, O′-diacyltartaric anhydride can be produced in high yield and high purity. It is an excellent way to
【０００６】本願発明者らは、特願平４−３２１０１９
号に記載された方法のうち、芳香族カルボン酸類を出発
原料として用いる場合に、触媒を用いることによりＯ，
Ｏ´−ジアシル酒石酸無水物をより高収率かつ高純度に
得ることができることを見出し、本発明を完成した。[0006] The inventors of the present application filed Japanese Patent Application No. 4-321019.
In the method described in No. 1, when an aromatic carboxylic acid is used as a starting material, a
The inventors have found that O'-diacyl tartaric anhydride can be obtained in higher yield and higher purity, and have completed the present invention.
【０００７】すなわち、本発明は、下記一般式（II）That is, the present invention has the following general formula (II)
【化１】 （式中Ｒ1 、Ｒ2 は水素原子、ハロゲン原子又は炭素数
１〜３のアルキル基を示し、Ｒ1 とＲ2 が同一でも、異
なってもよい。）で示される芳香族カルボン酸類と酒石
酸とをクロル化剤及び触媒の存在下に反応させる下記一
般式（Ｉ）[Chemical 1] (In the formula, R 1 and R 2 represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, and R 1 and R 2 may be the same or different.) And tartaric acid The following general formula (I) is used to react with and in the presence of a chlorinating agent and a catalyst.
【化２】 （式中Ｒ1 、Ｒ2 は一般式（II）のＲ1 、Ｒ2 と同じも
のであり、水素原子、ハロゲン原子又は炭素数１〜３の
アルキル基を示す。）で示されるＯ，Ｏ´−ジアシル酒
石酸無水物の製造方法を提供する。[Chemical 2] (Is the same as the R 1, R 2 in the formula R 1, R 2 is the formula (II), a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.) O indicated by, O A method for producing ′ -diacyl tartaric anhydride is provided.
【０００８】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【０００９】本発明の方法では、反応原料として上記式
（II) で示される芳香族カルボン酸類を用いる。芳香族
カルボン酸類の使用量は酒石酸に対して通常１．８倍モ
ル乃至４倍モル、好ましくは２．０倍モル乃至２．４倍
モルである。これより使用量が少ないと未反応の酒石酸
が製品中に混入して製品純度を低下させるので好ましく
ない。これより使用量が多いと使用薬品費用が高くなる
ので好ましくない。In the method of the present invention, an aromatic carboxylic acid represented by the above formula (II) is used as a reaction raw material. The amount of the aromatic carboxylic acid used is usually 1.8 times to 4 times, and preferably 2.0 times to 2.4 times the mol of tartaric acid. If the amount used is less than the above range, unreacted tartaric acid is mixed in the product to lower the product purity, which is not preferable. If the amount used is larger than this, the cost of chemicals used will increase, which is not preferable.
【００１０】本発明の方法においては、反応の際にクロ
ル化剤を共存させる。クロル化剤としては次のようなも
のがあげられる。例えば五塩化燐、三塩化燐、塩化チオ
ニルであり、中でも塩化チオニルが好ましい。クロル化
剤の添加量は芳香族カルボン酸類に対して通常１．４倍
モル乃至３倍モル、好ましくは１．５倍モル乃至２．０
倍モルである。In the method of the present invention, a chlorinating agent is allowed to coexist during the reaction. Examples of the chlorinating agent include the following. Examples thereof include phosphorus pentachloride, phosphorus trichloride, and thionyl chloride, with thionyl chloride being preferred. The amount of the chlorinating agent added is usually 1.4 times to 3 times, preferably 1.5 times to 2.0 times the aromatic carboxylic acid.
It is twice the mole.
【００１１】本発明の方法では反応の際に触媒を共存さ
せる。触媒としては塩化鉄、塩化アルミニウム、塩化亜
鉛、三フッ化ホウ素等のルイス酸が挙げられる。触媒の
使用量は酒石酸に対して通常０．００１乃至０．２倍モ
ル、好ましくは０．００２乃至０．１０倍モルであり、
反応開始時に一括して添加してもよく、また反応開始時
にその一部を添加し、更に反応の途中に追加してもよ
い。In the method of the present invention, a catalyst is allowed to coexist during the reaction. Examples of the catalyst include Lewis acids such as iron chloride, aluminum chloride, zinc chloride and boron trifluoride. The amount of the catalyst used is usually 0.001 to 0.2 times mol, preferably 0.002 to 0.10 times mol, relative to tartaric acid,
It may be added all at once at the start of the reaction, or a part thereof may be added at the start of the reaction and further added during the reaction.
【００１２】本発明においては、反応に際して有機溶媒
を共存させてもさせなくてもよいが、有機溶媒を共存さ
せると、生成したＯ，Ｏ´−ジアシル酒石酸無水物が反
応槽内で固化すること無く、操作性良く反応を行うこと
ができるので好ましい。加える有機溶媒としては次のよ
うなものがあげられる。例えば、ヘプタン、オクタン、
ノナンのような脂肪族炭化水素化合物、ベンゼン，トル
エン、キシレンのような芳香族炭化水素化合物であり、
中でもベンゼン，トルエン、キシレンが好ましい。な
お、２種以上の溶媒を併用することも可能である。溶媒
は酒石酸に対して通常０．５乃至１０倍重量、好ましく
は１乃至５倍重量の量で使用される。これより少ない
と、反応の際に生成したＯ，Ｏ´−ジアシル酒石酸無水
物のスラリ−濃度が高くなり、撹拌が困難になるので好
ましくない。またこれより多いと反応容積の大きい装置
が必要になり、生産性が悪くなるので好ましくない。有
機溶媒を加える時機は、反応開始時或いは反応途中のい
ずれでも良いが、好ましくは反応開始時である。In the present invention, an organic solvent may or may not be allowed to coexist during the reaction, but when the organic solvent coexists, the produced O, O'-diacyl tartaric anhydride solidifies in the reaction tank. It is preferable because the reaction can be carried out with good operability without the use. Examples of the organic solvent to be added include the following. For example, heptane, octane,
Aliphatic hydrocarbon compounds such as nonane, aromatic hydrocarbon compounds such as benzene, toluene, xylene,
Among them, benzene, toluene and xylene are preferable. It is also possible to use two or more solvents in combination. The solvent is usually used in an amount of 0.5 to 10 times, preferably 1 to 5 times the weight of tartaric acid. If it is less than this range, the concentration of the slurry of O, O'-diacyltartaric acid anhydride produced during the reaction becomes high and stirring becomes difficult, which is not preferable. On the other hand, if the amount is larger than this, an apparatus having a large reaction volume is required and productivity is deteriorated, which is not preferable. The organic solvent may be added either at the start of the reaction or during the reaction, but it is preferably at the start of the reaction.
【００１３】芳香族カルボン酸類と酒石酸とを反応させ
る場合の反応方法としては、例えば酒石酸、芳香族カル
ボン酸類および必要に応じて溶媒を加えた混合物を適当
な温度に昇温したのち塩化チオニルを徐々に加え、次い
で触媒を加えた後、更に加熱して熟成反応を行う方法、
酒石酸、芳香族カルボン酸類、触媒および必要に応じて
溶媒を加えた混合物を適当な温度に昇温したのち塩化チ
オニルを徐々に加え、更に熟成反応を行う方法がある。
また酒石酸、芳香族カルボン酸類、触媒、塩化チオニル
および必要に応じて溶媒を加えた混合物を、所定の温度
まで徐々に昇温させたのち、更に熟成反応を行う方法も
ある。触媒はこのように反応開始時に添加してもよく、
或いは反応の途中に添加してもよい。また反応開始時に
添加し、更に反応途中に追加してもよい。As a reaction method for reacting an aromatic carboxylic acid and tartaric acid, for example, a mixture of tartaric acid, an aromatic carboxylic acid and, if necessary, a solvent is heated to an appropriate temperature and then thionyl chloride is gradually added. In addition to the above, after adding a catalyst, further heating to perform an aging reaction,
There is a method in which a mixture obtained by adding tartaric acid, aromatic carboxylic acids, a catalyst and, if necessary, a solvent is heated to an appropriate temperature, and then thionyl chloride is gradually added to carry out an aging reaction.
There is also a method in which a mixture obtained by adding tartaric acid, an aromatic carboxylic acid, a catalyst, thionyl chloride and, if necessary, a solvent is gradually heated to a predetermined temperature and then subjected to an aging reaction. The catalyst may thus be added at the beginning of the reaction,
Alternatively, it may be added during the reaction. It may be added at the start of the reaction and further added during the reaction.
【００１４】本発明の方法は、一般的には４０乃至１７
０℃、好ましくは６０乃至１５０℃にて行われる。反応
温度が低い場合には反応を完結させるのに長時間を要
し、また反応温度が高い場合には短時間で反応を完結さ
せることができるが同時に分解反応が起きる。すなわ
ち、反応温度が上記範囲の下限付近である場合には、反
応時間は通常２０ないし５０時間程度であり、上記範囲
の上限付近の場合には反応時間は通常１ないし３時間程
度であり、その間の温度の場合には、反応時間もその間
になる。The method of the present invention is generally 40 to 17
It is carried out at 0 ° C., preferably 60 to 150 ° C. When the reaction temperature is low, it takes a long time to complete the reaction, and when the reaction temperature is high, the reaction can be completed in a short time, but at the same time, the decomposition reaction occurs. That is, when the reaction temperature is near the lower limit of the above range, the reaction time is usually about 20 to 50 hours, and when near the upper limit of the above range, the reaction time is usually about 1 to 3 hours. In case of the temperature of, the reaction time is also in the meantime.
【００１５】このようにして得られた反応混合物をその
まま、或いは溶媒を添加、或いは追加した後に冷却し、
析出した結晶を濾別することによってＯ，Ｏ´−ジアシ
ル酒石酸無水物が取得できる。The reaction mixture thus obtained is cooled as it is, or after adding or adding a solvent, it is cooled,
O, O'-diacyl tartaric acid anhydride can be obtained by filtering the precipitated crystals.
【００１６】[0016]
【実施例】以下、実施例により本発明を説明するが、本
発明はこれらの実施例により限定されるものではない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【００１７】実施例１ 攪拌機、温度計、コンデンサーおよび滴下ロートを装着
した３００ｍｌの反応器にＤ−酒石酸３０ｇ、トルエン
７０ｇ、塩化第二鉄０．１２ｇ及び安息香酸５３．７ｇ
を入れ、内容物を９０℃に加熱した。次いでその温度を
保ちながら、滴下ロ−トから塩化チオニル８３．７ｇを
６時間かけて添加した後、更に１０５〜１１０℃で１時
間熟成して反応を行った。反応混合物を室温まで冷却
し、析出した結晶を濾別したのち乾燥して、薄黄色結晶
のＯ，Ｏ´−ジベンゾイル−Ｄ−酒石酸無水物６１．８
ｇを得た。高速液体クロマトグラフィ−で分析したとこ
ろ、Ｏ，Ｏ´−ジベンゾイル−Ｄ−酒石酸無水物の純度
は１００％であった。（収率９０．９％） Example 1 30 g of D-tartaric acid, 70 g of toluene, 0.12 g of ferric chloride and 53.7 g of benzoic acid were placed in a 300 ml reactor equipped with a stirrer, a thermometer, a condenser and a dropping funnel.
And the contents were heated to 90 ° C. Next, while maintaining the temperature, 83.7 g of thionyl chloride was added from a dropping funnel over 6 hours, and then the reaction was carried out by further aging at 105 to 110 ° C for 1 hour. The reaction mixture was cooled to room temperature, the precipitated crystals were separated by filtration and dried to give pale yellow crystals of O, O'-dibenzoyl-D-tartaric anhydride 61.8.
g was obtained. When analyzed by high performance liquid chromatography, the purity of O, O'-dibenzoyl-D-tartaric acid anhydride was 100%. (Yield 90.9%)
【００１８】実施例２ 攪拌機、温度計、コンデンサーおよび滴下ロートを装着
した３００ｍｌの反応器にＤ−酒石酸３０ｇ、トルエン
７０ｇ、塩化第二鉄０．１２ｇ及びｐ−トルイル酸５
９．９ｇを入れ、内容物を９０℃に加熱した。次いで、
その温度を保ちながら、滴下ロ−トから塩化チオニル８
３．７ｇを６時間かけて添加した後、更に１０５〜１１
０℃で１時間熟成して反応を行った。反応混合物を室温
まで冷却し、析出した結晶を濾別したのち乾燥して、薄
黄色結晶のＯ，Ｏ´−ジ−ｐ−トルオイル−Ｄ−酒石酸
無水物６７．２ｇを得た。（純度１００％、収率９１．
３％） Example 2 30 g of D-tartaric acid, 70 g of toluene, 0.12 g of ferric chloride and 5 p-toluic acid were placed in a 300 ml reactor equipped with a stirrer, a thermometer, a condenser and a dropping funnel.
9.9g was added and the contents were heated to 90 ° C. Then
While maintaining the temperature, thionyl chloride 8 was added from the dropping funnel.
After adding 3.7 g over 6 hours, a further 105-11
The reaction was carried out by aging at 0 ° C. for 1 hour. The reaction mixture was cooled to room temperature, the precipitated crystals were separated by filtration and dried to obtain 67.2 g of light yellow crystals of O, O′-di-p-toluoyl-D-tartaric acid anhydride. (Purity 100%, yield 91.
3%)
【００１９】実施例３ 攪拌機、温度計、コンデンサーおよび滴下ロートを装着
した３００ｍｌの反応器にＤ−酒石酸３０ｇ、トルエン
７０ｇ、塩化第二鉄０．１２ｇ、塩化チオニル８３．７
ｇ及び安息香酸５３．７ｇを入れ、内容物を攪拌しなが
ら３時間かけて９０℃まで昇温した。更に内容物を９０
℃に保ちながら４時間熟成を行い、次いで１０５〜１１
０℃に昇温して１時間熟成を行った。反応混合物を室温
まで冷却し、析出した結晶を濾別したのち乾燥して、薄
黄色結晶のＯ，Ｏ´−ジベンゾイル−Ｄ−酒石酸無水物
６２．３ｇを得た。（純度１００％、収率９１．６％） Example 3 30 g of D-tartaric acid, 70 g of toluene, 0.12 g of ferric chloride and 83.7 thionyl chloride were placed in a 300 ml reactor equipped with a stirrer, a thermometer, a condenser and a dropping funnel.
g and 53.7 g of benzoic acid were added, and the contents were heated to 90 ° C. over 3 hours with stirring. 90 more contents
Aging for 4 hours while maintaining at ℃, then 105 ~ 11
The temperature was raised to 0 ° C. and aging was carried out for 1 hour. The reaction mixture was cooled to room temperature, and the precipitated crystals were filtered off and dried to obtain 62.3 g of O, O'-dibenzoyl-D-tartaric anhydride as pale yellow crystals. (Purity 100%, Yield 91.6%)
【００２０】実施例４ 攪拌機、温度計、コンデンサーおよび滴下ロートを装着
した３００ｍｌの反応器にＤ−酒石酸３０ｇ、トルエン
７０ｇ、塩化第二鉄０．１２ｇ、塩化チオニル８３．７
ｇ及びｐ−トルイル酸５９．９ｇを入れ、内容物を攪拌
しながら３時間かけて９０℃まで昇温した。更に内容物
を９０℃に保ちながら４時間熟成を行い、次いで１０５
〜１１０℃に昇温して１時間熟成を行った。反応混合物
を室温まで冷却し、析出した結晶を濾別したのち乾燥し
て、薄黄色結晶のＯ，Ｏ´−ジ−ｐ−トルオイル−Ｄ−
酒石酸無水物６７．７ｇを得た。（純度１００％、収率
９２．０％） Example 4 30 g of D-tartaric acid, 70 g of toluene, 0.12 g of ferric chloride and 83.7 thionyl chloride were placed in a 300 ml reactor equipped with a stirrer, a thermometer, a condenser and a dropping funnel.
g and p-toluic acid 59.9 g were added, and the content was heated to 90 ° C. over 3 hours while stirring. Further, the contents were aged for 4 hours while maintaining the temperature at 90 ° C., then 105
The temperature was raised to ˜110 ° C. and aging was carried out for 1 hour. The reaction mixture was cooled to room temperature, and the precipitated crystals were separated by filtration and dried to give pale yellow crystals of O, O'-di-p-toluoyl-D-.
67.7 g of tartaric anhydride was obtained. (Purity 100%, Yield 92.0%)
【００２１】実施例５ 攪拌機、温度計、コンデンサーおよび滴下ロートを装着
した３００ｍｌの反応器にＤ−酒石酸３０ｇ、トルエン
７０ｇ、塩化亜鉛０．１０ｇ及び安息香酸５３．７ｇを
入れ、内容物を９０℃に加熱した。次いでその温度を保
ちながら、滴下ロ−トから塩化チオニル８３．７ｇを６
時間かけて添加した後、更に１０５〜１１０℃で１時間
熟成して反応を行った。反応混合物を室温まで冷却し、
析出した結晶を濾別したのち乾燥して、白色結晶のＯ，
Ｏ´−ジベンゾイル−Ｄ−酒石酸無水物５８．１ｇを得
た。（純度１００％、収率８５．４％） Example 5 30 g of D-tartaric acid, 70 g of toluene, 0.10 g of zinc chloride and 53.7 g of benzoic acid were placed in a 300 ml reactor equipped with a stirrer, a thermometer, a condenser and a dropping funnel, and the contents were heated to 90 ° C. Heated to. Then, while maintaining the temperature, 63.7 g of thionyl chloride was added from the dropping funnel.
After the addition over a period of time, the reaction was carried out by further aging at 105 to 110 ° C. for 1 hour. The reaction mixture is cooled to room temperature,
The precipitated crystals are separated by filtration and dried to give white crystals of O,
58.1 g of O'-dibenzoyl-D-tartaric anhydride was obtained. (Purity 100%, Yield 85.4%)
【００２２】実施例６ 攪拌機、温度計、コンデンサーおよび滴下ロートを装着
した３００ｍｌの反応器にＤ−酒石酸３０ｇ、トルエン
７０ｇ、三フッ化ホウ素を４６％含有するジエチルエー
テル溶液１．４ｇ及び安息香酸５３．７ｇを入れ、内容
物を９０℃に加熱した。次いでその温度を保ちながら、
滴下ロ−トから塩化チオニル８３．７ｇを６時間かけて
添加した後、更に１０５〜１１０℃で１時間熟成して反
応を行った。反応混合物を室温まで冷却し、析出した結
晶を濾別したのち乾燥して、白色結晶のＯ，Ｏ´−ジベ
ンゾイル−Ｄ−酒石酸無水物６２．０ｇを得た。（純度
１００％、収率９１．２％） Example 6 In a 300 ml reactor equipped with a stirrer, a thermometer, a condenser and a dropping funnel, 30 g of D-tartaric acid, 70 g of toluene, 1.4 g of a diethyl ether solution containing 46% of boron trifluoride and 53 of benzoic acid. 0.7 g was added and the contents were heated to 90 ° C. Then while maintaining that temperature,
After adding 83.7 g of thionyl chloride from the dropping funnel over 6 hours, the reaction was carried out by further aging at 105 to 110 ° C. for 1 hour. The reaction mixture was cooled to room temperature, the precipitated crystals were filtered off and dried to obtain 62.0 g of white crystals of O, O'-dibenzoyl-D-tartaric acid anhydride. (Purity 100%, Yield 91.2%)
【００２３】実施例７ 攪拌機、温度計、コンデンサーおよび滴下ロートを装着
した３００ｍｌの反応器にＤ−酒石酸３０ｇ、トルエン
７０ｇ、塩化第二鉄０．１２ｇ及び３，４−ジメチル安
息香酸６６．０ｇを入れ、内容物を９０℃に加熱した。
次いでその温度を保ちながら、滴下ロ−トから塩化チオ
ニル８３．７ｇを６時間かけて添加した後、更に１０５
〜１１０℃で１時間熟成して反応を行った。反応混合物
を室温まで冷却し、析出した結晶を濾別したのち乾燥し
て、薄黄色結晶のＯ，Ｏ´−ジ−（３，４−ジメチルベ
ンゾイル）−Ｄ−酒石酸無水物７１．４ｇを得た。（純
度１００％、収率９０．１％） Example 7 30 g of D-tartaric acid, 70 g of toluene, 0.12 g of ferric chloride and 66.0 g of 3,4-dimethylbenzoic acid were placed in a 300 ml reactor equipped with a stirrer, a thermometer, a condenser and a dropping funnel. Then, the contents were heated to 90 ° C.
Then, while maintaining the temperature, 83.7 g of thionyl chloride was added from the dropping funnel over 6 hours, and then a further 105
The reaction was carried out by aging at ˜110 ° C. for 1 hour. The reaction mixture was cooled to room temperature, and the precipitated crystals were separated by filtration and dried to obtain 71.4 g of light yellow crystals of O, O'-di- (3,4-dimethylbenzoyl) -D-tartaric acid anhydride. It was (Purity 100%, Yield 90.1%)
【００２４】実施例８ 攪拌機、温度計、コンデンサーおよび滴下ロートを装着
した３００ｍｌの反応器にＤ−酒石酸３０ｇ、トルエン
７０ｇ、塩化第二鉄０．１２ｇ及び２−クロロ安息香酸
６８．８ｇを入れ、内容物を９０℃に加熱した。次いで
その温度を保ちながら、滴下ロ−トから塩化チオニル８
３．７ｇを６時間かけて添加した後、更に１０５〜１１
０℃で１時間熟成して反応を行った。反応混合物を室温
まで冷却し、析出した結晶を濾別したのち乾燥して、薄
黄色結晶のＯ，Ｏ´−ジ（２−クロロベンゾイル）−Ｄ
−酒石酸無水物７４．３ｇを得た。（純度１００％、収
率９０．８％） Example 8 30 g of D-tartaric acid, 70 g of toluene, 0.12 g of ferric chloride and 68.8 g of 2-chlorobenzoic acid were placed in a 300 ml reactor equipped with a stirrer, a thermometer, a condenser and a dropping funnel, The contents were heated to 90 ° C. Then, while maintaining that temperature, thionyl chloride 8 was added from the dropping funnel.
After adding 3.7 g over 6 hours, a further 105-11
The reaction was carried out by aging at 0 ° C. for 1 hour. The reaction mixture was cooled to room temperature, the precipitated crystals were filtered off and dried to give pale yellow crystals of O, O'-di (2-chlorobenzoyl) -D.
74.3 g of tartaric anhydride were obtained. (Purity 100%, Yield 90.8%)
【００２５】実施例９ 攪拌機、温度計、コンデンサーおよび滴下ロートを装着
した３００ｍｌの反応器にＤ−酒石酸３０ｇ、トルエン
７０ｇ、塩化アルミニウム０．１０ｇ及び安息香酸５
３．７ｇを入れ、内容物を９０℃に加熱した。次いでそ
の温度を保ちながら、滴下ロ−トから塩化チオニル８
３．７ｇを６時間かけて添加した後、更に１０５〜１１
０℃で１時間熟成して反応を行った。反応混合物を室温
まで冷却し、析出した結晶を濾別したのち乾燥して、白
色結晶のＯ，Ｏ´−ジベンゾイル−Ｄ−酒石酸無水物５
８．９ｇを得た。（純度１００％、収率８６．６％） Example 9 30 g of D-tartaric acid, 70 g of toluene, 0.10 g of aluminum chloride and 5 parts of benzoic acid were placed in a 300 ml reactor equipped with a stirrer, a thermometer, a condenser and a dropping funnel.
3.7 g was added and the contents were heated to 90 ° C. Then, while maintaining that temperature, thionyl chloride 8 was added from the dropping funnel.
After adding 3.7 g over 6 hours, a further 105-11
The reaction was carried out by aging at 0 ° C. for 1 hour. The reaction mixture was cooled to room temperature, and the precipitated crystals were filtered off and dried to give white crystals of O, O′-dibenzoyl-D-tartaric acid anhydride 5
8.9 g was obtained. (Purity 100%, Yield 86.6%)
【００２６】[0026]
【発明の効果】本発明により、安価、高収率、高純度に
Ｏ，Ｏ´−ジアシル酒石酸無水物を製造することができ
る方法が提供された。Industrial Applicability According to the present invention, there has been provided a method capable of producing O, O'-diacyl tartaric acid anhydride at low cost, high yield and high purity.
Claims (4)
１〜３のアルキル基を示し、Ｒ1 とＲ2 が同一でも、異
なってもよい。）で示される芳香族カルボン酸類と酒石
酸とをクロル化剤及び触媒の存在下に反応させる下記一
般式（Ｉ） 【化２】 （式中Ｒ1 、Ｒ2 は一般式（II）のＲ1 、Ｒ2 と同じも
のであり、水素原子、ハロゲン原子又は炭素数１〜３の
アルキル基を示す。）で示されるＯ，Ｏ´−ジアシル酒
石酸無水物の製造方法。1. The following general formula (II): (In the formula, R 1 and R 2 represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, and R 1 and R 2 may be the same or different.) And tartaric acid To react with chlorinating agent and catalyst in the following general formula (I) (Is the same as the R 1, R 2 in the formula R 1, R 2 is the formula (II), a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.) O indicated by, O A method for producing ′ -diacyl tartaric anhydride.
求項１記載の製造方法。2. The method according to claim 1, wherein the chlorinating agent is thionyl chloride.
２記載の製造方法。3. The production method according to claim 1, wherein the catalyst is a Lewis acid.
塩化アルミニウム又は三フッ化ホウ素である請求項３記
載の製造方法。4. The Lewis acid is ferric chloride, zinc chloride,
The manufacturing method according to claim 3, which is aluminum chloride or boron trifluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31456393A JP3149652B2 (en) | 1993-11-19 | 1993-11-19 | Process for producing O, O'-diacyltartaric anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31456393A JP3149652B2 (en) | 1993-11-19 | 1993-11-19 | Process for producing O, O'-diacyltartaric anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07138247A true JPH07138247A (en) | 1995-05-30 |
| JP3149652B2 JP3149652B2 (en) | 2001-03-26 |
Family
ID=18054793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31456393A Expired - Fee Related JP3149652B2 (en) | 1993-11-19 | 1993-11-19 | Process for producing O, O'-diacyltartaric anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3149652B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004262846A (en) * | 2003-03-03 | 2004-09-24 | New Japan Chem Co Ltd | Method for producing 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride |
-
1993
- 1993-11-19 JP JP31456393A patent/JP3149652B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004262846A (en) * | 2003-03-03 | 2004-09-24 | New Japan Chem Co Ltd | Method for producing 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3149652B2 (en) | 2001-03-26 |
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