JP3149651B2 - Process for producing O, O'-diacyltartaric anhydride - Google Patents

Process for producing O, O'-diacyltartaric anhydride

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Publication number
JP3149651B2
JP3149651B2 JP31447793A JP31447793A JP3149651B2 JP 3149651 B2 JP3149651 B2 JP 3149651B2 JP 31447793 A JP31447793 A JP 31447793A JP 31447793 A JP31447793 A JP 31447793A JP 3149651 B2 JP3149651 B2 JP 3149651B2
Authority
JP
Japan
Prior art keywords
reaction
chloride
anhydride
tartaric acid
added
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.)
Expired - Fee Related
Application number
JP31447793A
Other languages
Japanese (ja)
Other versions
JPH07138246A (en
Inventor
年弘 藤野
治代 佐藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
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Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP31447793A priority Critical patent/JP3149651B2/en
Publication of JPH07138246A publication Critical patent/JPH07138246A/en
Application granted granted Critical
Publication of JP3149651B2 publication Critical patent/JP3149651B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【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 Method of reacting in a solvent (JA
m. Chem. Soc. , 55, 2605 (193)
3)), (2) a method of reacting tartaric acid with twice the molar amount of benzoyl chloride in the presence of a solvent and then adding thionyl chloride to carry out the reaction. In the reaction, iron chloride, zinc chloride, aluminum chloride, etc. (HU34720) has been 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)法は操作性も良好であり、また
(1)法より低い反応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、触媒として塩化鉄
を用いると反応収率は高いものの反応混合物の着色が激
しく、製品の色調も悪い。また触媒として塩化亜鉛或い
は塩化アルミニウム等を用いると、塩化鉄を用いた場合
より反応収率が低く好ましくない。
(1) In the method,
When a mixture of tartaric acid and benzoyl chloride is heated and reacted, the operability is poor such that the reaction mixture solidifies, and the method is not suitable for an industrial production method. The method (2) has good operability, and the reaction proceeds even at a lower reaction temperature than the method (1), which is industrially preferable. However, when iron chloride is used as a catalyst, although the reaction yield is high, the reaction mixture is strongly colored and the color of the product is poor. Also, when zinc chloride or aluminum chloride is used as a catalyst, the reaction yield is lower than when iron chloride is used, which is not preferable.

【0004】従って、本発明の目的は、操作性が良好で
工業的製造に適し、O,O´−ジアシル酒石酸無水物へ
の選択性が高く、かつ良好な品質の製品を得ることがで
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。
Accordingly, an object of the present invention is to provide a product which has good operability and is suitable for industrial production, has high selectivity to O, O'-diacyltartaric anhydride, and can provide a product of good quality. , O'-diacyltartaric anhydride.

【0005】[0005]

【課題を解決するための手段】本発明者らは、操作性が
良好で、O,O´−ジアシル酒石酸無水物への選択性が
高く、かつ着色のない良好な品質の製品を得る方法につ
いて鋭意研究した結果、反応触媒に三フッ化ホウ素を用
いることにより、上記目的を達成できることを見出し、
本発明を完成するに至った。
Means for Solving the Problems The present inventors have developed a method for obtaining a product of good operability, high selectivity to O, O'-diacyltartaric anhydride and no coloration. As a result of intensive research, they have found that the above object can be achieved by using boron trifluoride as a reaction catalyst.
The present invention has been completed.

【0006】すなわち、本発明は、下記一般式(II)That is, the present invention provides a compound represented by 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 、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塩化物類
と酒石酸とを反応させるに際し、触媒として三フッ化ホ
ウ素を使用することを特徴とする下記一般式(I)
Embedded image (Wherein R 1 and R 2 each 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). Wherein boron trifluoride is used as a catalyst in the reaction of the compounds with tartaric acid.

【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、ハロゲン原子或いは炭素数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。
Embedded image (Are those same as R 1, R 2 in the formula R 1, R 2 is the formula (II), a hydrogen atom, a halogen atom or 1 to 3 carbon atoms
Represents an alkyl group. The present invention provides a method for producing O, O'-diacyltartaric anhydride represented by the formula:

【0007】また、本発明は、下記一般式(III)Further, the present invention provides a compound represented by the following general formula (III):

【化3】 (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 、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無水物類
と酒石酸とを反応させるに際し、触媒として三フッ化ホ
ウ素を使用することを特徴とする下記一般式(I)
Embedded image (Wherein R 1 and R 2 each 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). Wherein boron trifluoride is used as a catalyst in the reaction of the compounds with tartaric acid.

【化2】 (式中R1 、R2 は一般式(III)のR1 、R2 と同じも
のであり、水素原子、ハロゲン原子或いは炭素数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。
Embedded image (Are those same as R 1, R 2 in the formula R 1, R 2 is formula (III), a hydrogen atom, a halogen atom or 1 to 3 carbon atoms
Represents an alkyl group. The present invention provides a method for producing O, O'-diacyltartaric anhydride represented by the formula:

【0008】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.

【0009】本発明の方法に用いられる特有の触媒は三
フッ化ホウ素である。公知の方法では、酒石酸と芳香族
カルボン酸塩化物類或いは芳香族カルボン酸無水物類と
を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存在下で行われる場合がある。しか
し、塩化鉄媒を用いた場合には製品の色調が悪く、また
塩化亜鉛或いは塩化アルミニウム等を用いた場合には反
応収率が低く好ましくない。この点において、本発明の
特有の触媒である三フッ化ホウ素を用いた場合、公知の
触媒を用いた場合に比べて反応収率が高く、且つ製品の
色調も良く工業的には非常に有利である。用いる三フッ
化ホウ素は、ホウフッ化ナトリウムと三酸化ホウ素およ
び濃硫酸を加熱して発生させたものを用いてもよく、ま
た市販の三フッ化ホウ素をエーテル等に吸収させたもの
を用いてもよい。ホウフッ化ナトリウムと三酸化ホウ素
および濃硫酸を加熱して発生させた場合には、発生した
三フッ化ホウ素を反応開始時に酒石酸と溶媒および場合
によっては芳香族カルボン酸塩化物類或いは芳香族カル
ボン酸無水物類が存在する混合物中に吸収させるか、或
いは反応途中に反応混合物中に吸収させてもよい。市販
の三フッ化ホウ素をエーテル等に吸収させたものを用い
る場合には、そのまま反応開始時、或いは反応途中に添
加すればよい。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。
The specific catalyst used in the process of the present invention is boron trifluoride. In a known method, the reaction of tartaric acid with an aromatic carboxylic acid chloride or an aromatic carboxylic acid anhydride may be performed in the presence of a catalyst such as iron chloride, zinc chloride or aluminum chloride. However, the color tone of the product is poor when an iron chloride medium is used, and the reaction yield is unfavorably low when zinc chloride or aluminum chloride is used. In this regard, the use of boron trifluoride, which is a specific catalyst of the present invention, has a higher reaction yield and a better color tone of the product than the case of using a known catalyst, and is industrially very advantageous. It is. The boron trifluoride used may be one generated by heating sodium borofluoride, boron trioxide and concentrated sulfuric acid, or one obtained by absorbing commercially available boron trifluoride in ether or the like. Good. When sodium borofluoride, boron trioxide and concentrated sulfuric acid are generated by heating, the generated boron trifluoride is converted into tartaric acid and a solvent at the start of the reaction, and optionally aromatic carboxylic acid chlorides or aromatic carboxylic acids. It may be absorbed in the mixture in which the anhydrides are present, or may be absorbed in the reaction mixture during the reaction. When a commercially available product obtained by absorbing boron trifluoride in ether or the like is used, it may be added at the start of the reaction or during the reaction. The amount of the catalyst used is usually 0.1 to tartaric acid.
001 to 0.2 times mol, preferably 0.002 to 0.10 times mol, 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. May be added.

【0010】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なく、操作性よく反応を行うこと
ができるので好ましい。加える有機溶媒としては次ぎの
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。
In the present invention, an organic solvent may or may not be allowed to coexist during the reaction. However, when an organic solvent coexists, the produced O, O'-diacyltartaric anhydride solidifies in the reaction tank. It is preferable because the reaction can be carried out with good operability. The following are examples of the organic solvent to be added. For example, heptane, octane,
Aliphatic hydrocarbon compounds such as nonane, benzene, toluene, aromatic hydrocarbon compounds such as xylene,
Among them, benzene, toluene and xylene are preferred. In addition, it is also possible to use two or more solvents in combination. The solvent is used in an amount of usually 0.5 to 10 times, preferably 1 to 5 times the weight of tartaric acid. If the amount is less than this, the slurry concentration of O, O'-diacyltartaric anhydride generated during the reaction increases, and it is not preferable because stirring becomes difficult. On the other hand, if the amount is larger than this, an apparatus having a large reaction volume is required, and productivity is deteriorated.

【0011】芳香族カルボン酸塩化物類の使用量は酒石
酸に対して通常2.6倍モル乃至5倍モル、好ましくは
3.0倍モル乃至3.5倍モルである。また、反応に際
して塩化チオニルを存在させる場合(後述)には、芳香
族カルボン酸塩化物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。また、本発明に於いては、芳香
族カルボン酸塩化物類の代わりに芳香族カルボン酸無水
物類を用いることができる。この場合、芳香族カルボン
酸無水物類の使用量は酒石酸に対して通常2.6倍モル
乃至5倍モル、好ましくは3.0倍モル乃至3.5倍モ
ルである。また、塩化チオニルを存在させる場合(後
述)には、芳香族カルボン酸無水物類の使用量は酒石酸
に対して通常0.9倍モル乃至2倍モル、好ましくは
1.0倍モル乃至1.2倍モルである。これより使用量
が少ない場合は酒石酸の一部が未反応のまま残存して収
率が低下し、また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。
The amount of the aromatic carboxylic acid chloride to be used is usually 2.6 to 5 times, preferably 3.0 to 3.5 times the molar amount of tartaric acid. When thionyl chloride is present in the reaction (described later), the amount of the aromatic carboxylic acid chloride to be used is usually 1.8 to 4 times, preferably 2.0 to 4 times the molar amount of tartaric acid. It is 2.4 times mol. In the present invention, aromatic carboxylic acid anhydrides can be used instead of aromatic carboxylic acid chlorides. In this case, the amount of the aromatic carboxylic acid anhydride to be used is usually 2.6 to 5 times, preferably 3.0 to 3.5 times the molar amount of tartaric acid. When thionyl chloride is present (described later), the amount of the aromatic carboxylic acid anhydride to be used is usually 0.9 to 2 times, preferably 1.0 to 1 times the molar amount of tartaric acid. It is 2 times mol. If the amount used is less than this, a part of tartaric acid remains unreacted and the yield decreases, and 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 increases, which is not preferable.

【0012】酒石酸と芳香族カルボン酸塩化物類或いは
芳香族カルボン酸無水物類のどちらを反応させる場合に
於いても、安価な塩化チオニルを共存させると、高価な
芳香族カルボン酸塩化物類或いは芳香族カルボン酸無水
物類の使用量が少なくて済むために使用薬品費用が低減
でき、また高純度の製品を取得することができるので好
ましい。塩化チオニルの添加量は、例えば酒石酸と芳香
族カルボン酸塩化物類とを反応させる場合には、芳香族
カルボン酸塩化物類に対して通常0.3倍モル乃至1.
5倍モル、好ましくは0.5倍モル乃至1.0倍モルで
ある。また、酒石酸と芳香族カルボン酸無水物類とを反
応させる場合には、芳香族カルボン酸無水物類に対して
通常0.9倍モル乃至2.5倍モル、好ましくは1.0
倍モル乃至2.0倍モルである。塩化チオニルの添加量
が前記の量より少ないと、製品中に芳香族カルボン酸類
が混入して、製品純度が低下するので好ましくない。ま
た、添加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 case of reacting tartaric acid with an aromatic carboxylic acid chloride or an aromatic carboxylic acid anhydride, if an inexpensive thionyl chloride is present, an expensive aromatic carboxylic acid chloride or It is preferable because the amount of the aromatic carboxylic acid anhydride used can be small, the cost of chemicals used can be reduced, and a product with high purity can be obtained. For example, when tartaric acid is reacted with an aromatic carboxylic acid chloride, the amount of thionyl chloride to be added is usually 0.3 to 1 mol of the aromatic carboxylic acid chloride.
It is 5 moles, preferably 0.5 mole to 1.0 mole. When tartaric acid is reacted with an aromatic carboxylic acid anhydride, it is usually 0.9 to 2.5 times, preferably 1.0 to 1.0 times the amount of the aromatic carboxylic acid anhydride.
The molar ratio is twice to 2.0 times. If the addition amount of thionyl chloride is smaller than the above amount, aromatic carboxylic acids are mixed in the product, and the purity of the product is undesirably reduced. On the other hand, if the amount of addition is large, the cost of chemicals used increases, which is not preferable.

【0013】芳香族カルボン酸塩化物類と酒石酸とを反
応させる場合の反応方法としては、例えば酒石酸、触媒
および溶媒を加えた混合物を適当な温度に昇温したのち
芳香族カルボン酸塩化物類を添加して所定の時間反応さ
せる方法、或いは酒石酸,触媒、芳香族カルボン酸塩化
物類および必要に応じて溶媒を加えた混合物を徐々に加
熱して所定の温度まで昇温させる方法がある。また、塩
化チオニルを存在させる場合には、例えば酒石酸、溶
媒、触媒の混合物を適当な温度に昇温したのち芳香族カ
ルボン酸塩化物類を添加して所定の時間反応させ、次い
で塩化チオニルを添加する方法、酒石酸,触媒、芳香族
カルボン酸塩化物類、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徐々に加熱して所定の温度まで昇
温させる方法、或いは酒石酸,溶媒および触媒の混合物
を適当な温度に昇温し、その混合物中に芳香族カルボン
酸塩化物類と塩化チオニルの混合溶液を添加して反応さ
せる方法がある。
As a reaction method for reacting an aromatic carboxylic acid chloride with tartaric acid, for example, a mixture containing tartaric acid, a catalyst and a solvent is heated to an appropriate temperature, and then the aromatic carboxylic acid chloride is converted to a mixture. There is a method of adding and reacting for a predetermined time, or a method of gradually heating a mixture to which tartaric acid, a catalyst, an aromatic carboxylic acid chloride and, if necessary, a solvent are added, to a predetermined temperature. When thionyl chloride is present, for example, a mixture of tartaric acid, a solvent, and a catalyst is heated to an appropriate temperature, and then an aromatic carboxylic acid chloride is added, and the mixture is reacted for a predetermined time, and then thionyl chloride is added. A method in which tartaric acid, a catalyst, an aromatic carboxylic acid chloride, thionyl chloride, and a solvent, if necessary, are gradually heated to a predetermined temperature, or a mixture of tartaric acid, a solvent and a catalyst. Is raised to an appropriate temperature, and a mixed solution of an aromatic carboxylic acid chloride and thionyl chloride is added to the mixture to cause a reaction.

【0014】芳香族カルボン酸無水物類と酒石酸とを反
応させる場合の反応方法としては、例えば酒石酸,触媒
および溶媒の混合物を適当な温度に昇温したのち芳香族
カルボン酸無水物類を添加して所定の時間反応させる方
法、或いは酒石酸,触媒、芳香族カルボン酸無水物類お
よび必要に応じて溶媒を加えた混合物を徐々に加熱して
所定の温度まで昇温させる方法がある。また、塩化チオ
ニルを存在させる場合には、例えば酒石酸、溶媒、触媒
の混合物を適当な温度に昇温したのち芳香族カルボン酸
無水物類を添加して所定の時間反応させ、次いで塩化チ
オニルを添加する方法、酒石酸、触媒、芳香族カルボン
酸無水物類、塩化チオニルおよび必要に応じて溶媒を加
えた混合物を徐々に加熱して所定の温度まで昇温させる
方法、或いは酒石酸,溶媒および触媒の混合物を適当な
温度に昇温し、その混合物中に芳香族カルボン酸無水物
類と塩化チオニルの混合溶液を添加して反応させる方法
がある。
As a reaction method for reacting an aromatic carboxylic anhydride with tartaric acid, for example, a mixture of tartaric acid, a catalyst and a solvent is heated to an appropriate temperature, and then the aromatic carboxylic anhydride is added. And a method in which tartaric acid, a catalyst, an aromatic carboxylic anhydride, and a solvent, if necessary, are added to the mixture to gradually heat the mixture to a predetermined temperature. When thionyl chloride is present, for example, a mixture of tartaric acid, a solvent, and a catalyst is heated to an appropriate temperature, and then aromatic carboxylic anhydrides are added to react for a predetermined time, and then thionyl chloride is added. A method in which tartaric acid, a catalyst, an aromatic carboxylic anhydride, thionyl chloride, and a solvent, if necessary, are gradually heated to a predetermined temperature, or a mixture of tartaric acid, a solvent and a catalyst. Is raised to an appropriate temperature, and a mixed solution of an aromatic carboxylic anhydride and thionyl chloride is added to the mixture to cause a reaction.

【0015】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こる。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。
[0015] The method of the present invention generally comprises from 40 to 17
It is carried out at 0 ° C, preferably at 60 to 150 ° C. When the reaction temperature is low, it takes a long time to complete the reaction. When the reaction temperature is high, the reaction can be completed in a short time, but at the same time, a 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 the reaction temperature is near the upper limit of the above range, the reaction time is usually about 1 to 3 hours. In the case of the above temperature, the reaction time is also between them.

【0016】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,
O, O'-diacyltartaric anhydride can be obtained by filtering the precipitated crystals by filtration.

【0017】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 a solvent, and the precipitated crystals are separated by filtration to obtain O, O'-diacyltartaric anhydride.

【0018】[0018]

【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.

【0019】比較例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L−酒石酸30gとトルエン
70gを入れ、攪拌下90〜95℃で滴下ロートから塩
化ベンゾイル89.9gを3時間かけて添加した。次い
で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て結晶を析出させ、これを濾
別し、乾燥して白色結晶68.1g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−L−酒石酸無水物の純度は76.5%であっ
た。(収率76.6%)
Comparative Example 1 30 g of L-tartaric acid and 70 g of toluene were placed in a 300 ml reactor equipped with a stirrer, a thermometer, a condenser and a dropping funnel, and 89.9 g of benzoyl chloride was added from the dropping funnel at 90 to 95 ° C. with stirring. Added over time. Then, the mixture was aged at 105 to 110 ° C. for 1 hour to carry out a reaction. The reaction mixture was cooled to room temperature to precipitate crystals, which were separated by filtration and dried to obtain 68.1 g of white crystals. When analyzed by high performance liquid chromatography, the purity of O, O'-dibenzoyl-L-tartaric anhydride was 76.5%. (Yield 76.6%)

【0020】比較例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L−酒石酸30gとトルエン
70gおよび無水塩化鉄0.12gを入れ、攪拌下90
〜95℃で滴下ロートから塩化ベンゾイル62gを3時
間かけて添加した。次いで同様に滴下ロ−トから塩化チ
オニル28.5gを3時間かけて添加したのち105〜
110℃で1時間熟成して反応を行った。反応混合物を
室温まで冷却して結晶を析出させた。これを濾別し、乾
燥して黄色結晶のO,O´−ジベンゾイル−L−酒石酸
無水物62.1gを得た。(純度100%、収率91.
3%)
Comparative Example 2 30 g of L-tartaric acid, 70 g of toluene and 0.12 g of anhydrous iron chloride were placed in a 300 ml reactor equipped with a stirrer, thermometer, condenser and dropping funnel.
At -95 ° C, 62 g of benzoyl chloride was added from the dropping funnel over 3 hours. Next, 28.5 g of thionyl chloride was similarly added from the dropping funnel over 3 hours, and then 105-
The reaction was performed by aging at 110 ° C. for 1 hour. The reaction mixture was cooled to room temperature to precipitate crystals. This was separated by filtration and dried to obtain 62.1 g of O, O'-dibenzoyl-L-tartaric anhydride as yellow crystals. (Purity 100%, yield 91.
3%)

【0021】比較例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L−酒石酸30gとトルエン
70gおよび無水塩化亜鉛0.10gを入れ、攪拌下9
0〜95℃で滴下ロートから塩化ベンゾイル62gを3
時間かけて添加した。次いで同様に滴下ロ−トから塩化
チオニル28.5gを3時間かけて添加したのち105
〜110℃で1時間熟成して反応を行った。反応混合物
を室温まで冷却して結晶を析出させた。これを濾別し、
乾燥して白色結晶のO,O´−ジベンゾイル−L−酒石
酸無水物58.1gを得た。(純度100%、収率8
5.4%)
Comparative Example 3 30 g of L-tartaric acid, 70 g of toluene and 0.10 g of anhydrous zinc chloride were placed in a 300 ml reactor equipped with a stirrer, thermometer, condenser and dropping funnel.
62 g of benzoyl chloride was added from a dropping funnel at 0 to 95 ° C.
Added over time. Next, 28.5 g of thionyl chloride was similarly added from the dropping funnel over 3 hours.
The reaction was carried out by aging at 110110 ° C. for 1 hour. The reaction mixture was cooled to room temperature to precipitate crystals. This is filtered off,
Drying yielded 58.1 g of O, O'-dibenzoyl-L-tartaric anhydride as white crystals. (Purity 100%, yield 8
5.4%)

【0022】比較例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L−酒石酸30gとトルエン
70gおよび無水塩化第二鉄0.12gを入れ、攪拌下
90〜95℃で滴下ロートから塩化p−トルオイル68
gを3時間かけて添加した。次いで同様に滴下ロ−トか
ら塩化チオニル28.5gを3時間かけて添加したのち
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て結晶を析出させた。これを濾
別し、乾燥して黄色結晶のO,O´−ジ−p−トルオイ
ル−L−酒石酸無水物67.7gを得た。(純度100
%、収率92.0%)
Comparative Example 4 30 g of L-tartaric acid, 70 g of toluene and 0.12 g of anhydrous ferric chloride were placed in a 300 ml reactor equipped with a stirrer, thermometer, condenser and dropping funnel, and dropped at 90 to 95 ° C. with stirring. From the funnel p-toluene chloride 68
g was added over 3 hours. Then, similarly, 28.5 g of thionyl chloride was added from the dropping funnel over 3 hours, and the mixture was aged at 105 to 110 ° C. for 1 hour to carry out a reaction. The reaction mixture was cooled to room temperature to precipitate crystals. This was separated by filtration and dried to obtain 67.7 g of O, O'-di-p-toluoyl-L-tartaric anhydride as yellow crystals. (Purity 100
%, Yield 92.0%)

【0023】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L−酒石酸30gとトルエン
70gおよび三フッ化ホウ素を46%含有するジエチル
エーテル溶液1.4gを入れ、攪拌下90〜95℃で滴
下ロートから塩化ベンゾイル89.9gを3時間かけて
添加した。次いで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て結晶を析出
させ、これを濾別し、乾燥して白色結晶71.1g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−L−酒石酸無水物の純度は8
6.6%であった。(収率90.5%)
Example 1 A 300 ml reactor equipped with a stirrer, thermometer, condenser and dropping funnel was charged with 30 g of L-tartaric acid, 70 g of toluene and 1.4 g of a diethyl ether solution containing 46% of boron trifluoride and stirred. At below 90-95 ° C, 89.9 g of benzoyl chloride was added from the dropping funnel over 3 hours. Then, the mixture was aged at 105 to 110 ° C. for 1 hour to carry out a reaction. The reaction mixture was cooled to room temperature to precipitate crystals, which were separated by filtration and dried to obtain 71.1 g of white crystals. When analyzed by high performance liquid chromatography,
The purity of O, O'-dibenzoyl-L-tartaric anhydride is 8
It was 6.6%. (Yield 90.5%)

【0024】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とトルエン
70gおよび三フッ化ホウ素を46%含有するジエチル
エーテル溶液1.4gを入れ、攪拌下90〜95℃で滴
下ロートから塩化ベゾイル62gを3時間かけて添加し
た。次いで同様に滴下ロ−トから塩化チオニル28.5
gを3時間かけて添加したのち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
て結晶を析出させた。これを濾別し、乾燥して白色結晶
のO,O´−ジベンゾイル−D−酒石酸無水物61.9
gを得た。(純度100%、収率91.0%)
Example 2 30 g of D-tartaric acid, 70 g of toluene and 1.4 g of a diethyl ether solution containing 46% of boron trifluoride were placed in a 300 ml reactor equipped with a stirrer, thermometer, condenser and dropping funnel, and stirred. At 90 to 95 ° C, 62 g of bezoyl chloride was added from the dropping funnel over 3 hours. Subsequently, 28.5 thionyl chloride was similarly added from the dropping funnel.
g was added over 3 hours, and the mixture was aged at 105 to 110 ° C. for 1 hour to carry out a reaction. The reaction mixture was cooled to room temperature to precipitate crystals. This was filtered off and dried to give O, O'-dibenzoyl-D-tartaric anhydride as white crystals, 61.9.
g was obtained. (Purity 100%, yield 91.0%)

【0025】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L−酒石酸30gとトルエン
70gおよび三フッ化ホウ素を46%含有するジエチル
エーテル溶液1.4gを入れ、攪拌下90〜95℃で滴
下ロートから塩化p−トルオイル68gを3時間かけて
添加した。次いで同様に滴下ロ−トから塩化チオニル2
8.5gを3時間かけて添加したのち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
冷却して結晶を析出させた。これを濾別し、乾燥して白
色結晶のO,O´−ジ−p−トルオイル−L−酒石酸無
水物67.7gを得た。(純度100%、収率92.0
%)
Example 3 A 300 ml reactor equipped with a stirrer, thermometer, condenser and dropping funnel was charged with 30 g of L-tartaric acid, 70 g of toluene and 1.4 g of a diethyl ether solution containing 46% of boron trifluoride and stirred. At 90 to 95 ° C, 68 g of p-toluene chloride was added from the dropping funnel over 3 hours. Subsequently, thionyl chloride 2 was similarly added from the dropping funnel.
After adding 8.5 g over 3 hours, 105-110 ° C
And reacted for 1 hour. The reaction mixture was cooled to room temperature to precipitate crystals. This was separated by filtration and dried to obtain 67.7 g of O, O'-di-p-toluoyl-L-tartaric anhydride as white crystals. (Purity 100%, yield 92.0
%)

【0026】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L−酒石酸30gとトルエン
70gおよび三フッ化ホウ素を46%含有するジエチル
エーテル溶液0.2gを入れ、攪拌下90〜95℃で滴
下ロートから塩化p−トルオイル68gを3時間かけて
添加した。反応混合物中に更に三フッ化ホウ素を46%
含有するジエチルエーテル溶液1.2gを追加した後、
同様に滴下ロ−トから塩化チオニル28.5gを3時間
かけて添加したのち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て結晶を析
出させた。これを濾別し、乾燥して白色結晶のO,O´
−ジ−p−トルオイル−L−酒石酸無水物67.4gを
得た。(純度100%、収率91.6%)
Example 4 A 300 ml reactor equipped with a stirrer, thermometer, condenser and dropping funnel was charged with 30 g of L-tartaric acid, 70 g of toluene and 0.2 g of a diethyl ether solution containing 46% of boron trifluoride and stirred. At 90 to 95 ° C, 68 g of p-toluene chloride was added from the dropping funnel over 3 hours. 46% more boron trifluoride in the reaction mixture
After adding 1.2 g of diethyl ether solution containing,
Similarly, 28.5 g of thionyl chloride was added from the dropping funnel over 3 hours, and the mixture was aged at 105 to 110 ° C. for 1 hour to carry out a reaction. The reaction mixture was cooled to room temperature to precipitate crystals. This is separated by filtration and dried to obtain white crystals of O, O '.
67.4 g of di-p-toluoyl-L-tartaric anhydride were obtained. (Purity 100%, yield 91.6%)

【0027】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L−酒石酸30g、トルエン
70g、安息香酸無水物49.7g、塩化チオニル8
8.9gおよび三フッ化ホウ素を46%含有するジエチ
ルエーテル溶液1.4gを入れ、攪拌しながら6時間か
けて90〜95℃に昇温した。次いで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
冷却して結晶を析出させた。これを濾別し、乾燥して白
色結晶のO,O´−ジベンゾイル−L−酒石酸無水物6
3.2gを得た。(純度100%、収率92.9%)
Example 5 30 g of L-tartaric acid, 70 g of toluene, 49.7 g of benzoic anhydride, 89.7 g of thionyl chloride were placed in a 300 ml reactor equipped with a stirrer, thermometer, condenser and dropping funnel.
8.9 g and 1.4 g of a diethyl ether solution containing 46% of boron trifluoride were added, and the temperature was raised to 90 to 95 ° C. over 6 hours with stirring. Then 105-110 ° C
And reacted for 1 hour. The reaction mixture was cooled to room temperature to precipitate crystals. This was separated by filtration and dried to obtain white crystalline O, O'-dibenzoyl-L-tartaric anhydride 6
3.2 g were obtained. (Purity 100%, yield 92.9%)

【0028】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とトルエン
70gおよび三フッ化ホウ素を46%含有するジエチル
エーテル溶液1.4gを入れ、攪拌下90〜95℃で滴
下ロートから2−クロロベゾイルクロライド77gを3
時間かけて添加した。次いで同様に滴下ロ−トから塩化
チオニル28.5gを3時間かけて添加したのち105
〜110℃で1時間熟成して反応を行った。反応混合物
を室温まで冷却して結晶を析出させた。これを濾別し、
乾燥して白色結晶の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10
0%、収率90.8%)
Example 6 A 300 ml reactor equipped with a stirrer, thermometer, condenser and dropping funnel was charged with 30 g of D-tartaric acid, 70 g of toluene and 1.4 g of a diethyl ether solution containing 46% of boron trifluoride and stirred. 77 g of 2-chlorobezoyl chloride from the dropping funnel at 90 to 95 ° C.
Added over time. Next, 28.5 g of thionyl chloride was similarly added from the dropping funnel over 3 hours.
The reaction was carried out by aging at 110110 ° C. for 1 hour. The reaction mixture was cooled to room temperature to precipitate crystals. This is filtered off,
Drying yielded 74.3 g of O, O'-di (2-chlorobenzoyl) -D-tartaric anhydride as white crystals. (Purity 10
0%, yield 90.8%)

【0029】[0029]

【発明の効果】本発明によれば、酒石酸と芳香族カルボ
ン酸塩化物類或いは芳香族カルボン酸無水物類とを反応
させるに際して、反応触媒として三フッ化ホウ素を共存
させることによって、着色のない高品質のO,O´−ジ
アシル酒石酸無水物が高収率で製造することができる。
また、その際にクロル化剤を共存させると、安価に高品
質のO,O´−ジアシル酒石酸無水物を製造することが
できる。
According to the present invention, when tartaric acid is reacted with an aromatic carboxylic acid chloride or an aromatic carboxylic anhydride, boron trifluoride is allowed to coexist as a reaction catalyst so that no coloration occurs. High quality O, O'-diacyltartaric anhydride can be produced in high yield.
In addition, when a chlorinating agent is allowed to coexist at that time, high-quality O, O'-diacyltartaric anhydride can be produced at low cost.

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) C07D 307/56 B01J 27/12 C07B 61/00 300 CA(STN) REGISTRY(STN)──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C07D 307/56 B01J 27/12 C07B 61/00 300 CA (STN) REGISTRY (STN)

Claims (3)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 下記一般式(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 、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塩化物類
と酒石酸とを反応させるに際し、触媒として三フッ化ホ
ウ素を使用することを特徴とする下記一般式(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、ハロゲン原子或いは炭素数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): (Wherein R 1 and R 2 each 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). Wherein boron trifluoride is used as a catalyst in the reaction of the compounds with tartaric acid, characterized by the following general formula (I): (Are those same as R 1, R 2 in the formula R 1, R 2 is the formula (II), a hydrogen atom, a halogen atom or 1 to 3 carbon atoms
Represents an alkyl group. )), A method for producing O, O'-diacyltartaric anhydride.
【請求項2】 下記一般式(III) 【化3】 (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 、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無水物類
と酒石酸とを反応させるに際し、触媒として三フッ化ホ
ウ素を使用することを特徴とする下記一般式(I) 【化2】 (式中R1 、R2 は一般式(III)のR1 、R2 と同じも
のであり、水素原子、ハロゲン原子或いは炭素数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。
2. The following general formula (III): (Wherein R 1 and R 2 each 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). Wherein boron trifluoride is used as a catalyst in the reaction of the compounds with tartaric acid, characterized by the following general formula (I): (Are those same as R 1, R 2 in the formula R 1, R 2 is formula (III), a hydrogen atom, a halogen atom or 1 to 3 carbon atoms
Represents an alkyl group. )), A method for producing O, O'-diacyltartaric anhydride.
【請求項3】 反応に際し、塩化チオニルを共存させる
ことを特徴とする請求項1又は請求項2に記載の製造方
法。
3. The method according to claim 1, wherein thionyl chloride is allowed to coexist during the reaction.
JP31447793A 1993-11-19 1993-11-19 Process for producing O, O'-diacyltartaric anhydride Expired - Fee Related JP3149651B2 (en)

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JP31447793A JP3149651B2 (en) 1993-11-19 1993-11-19 Process for producing O, O'-diacyltartaric anhydride

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Application Number Priority Date Filing Date Title
JP31447793A JP3149651B2 (en) 1993-11-19 1993-11-19 Process for producing O, O'-diacyltartaric anhydride

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JPH07138246A JPH07138246A (en) 1995-05-30
JP3149651B2 true JP3149651B2 (en) 2001-03-26

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