JP2001011016A - Production of tartaric acid lower alkyl diester - Google Patents
Production of tartaric acid lower alkyl diesterInfo
- Publication number
- JP2001011016A JP2001011016A JP11187554A JP18755499A JP2001011016A JP 2001011016 A JP2001011016 A JP 2001011016A JP 11187554 A JP11187554 A JP 11187554A JP 18755499 A JP18755499 A JP 18755499A JP 2001011016 A JP2001011016 A JP 2001011016A
- Authority
- JP
- Japan
- Prior art keywords
- tartaric acid
- lower alkyl
- lower alcohol
- acid
- amount
- 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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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]
【発明の属する技術分野】本発明は、酒石酸低級アルキ
ルジエステルの効率的製造法に関するものである。TECHNICAL FIELD The present invention relates to a method for efficiently producing a lower alkyl ditartaric acid diester.
【０００２】[0002]
【従来の技術】酒石酸低級アルキルジエステルは農薬、
医薬の製造中間体や不斉触媒として有用である。酒石酸
低級アルキルジエステルは酒石酸と低級アルコールを酸
触媒存在下で反応させることで製造できる。反応は平衡
反応であるので、原理的には大量の脱水低級アルコール
を使用することで、高収率で酒石酸低級アルキルジエス
テルを製造できるが、過剰の低級アルコールを脱水処理
してリサイクル使用するために煩雑な作業が必要とな
る。大量の脱水低級アルキルアルコールを使用しない方
法としては、オルト蟻酸エステルなどのエステル化剤を
酸触媒存在下で使用する（シンセティックコミニケーシ
ョンズ（Ｓｙｎｔｈ．Ｃｏｍｎ．），１４，１０８７，
（１９８４））記載の方法、低級アルキルアルコールを
酸触媒の存在下反応させ、水と共沸する有機溶媒，例え
ばクロロホルムを共存させて副生する水を共沸脱水で系
外に除去する（ヘルベチカ．ケミカ．アクタ（Ｈｅｌ
ｖ．Ｃｈｉｍ．Ａｃｔａ．）６２，１７１０（１９７
９））記載の方法等が知られている。2. Description of the Related Art Lower alkyl tartaric acid diesters are pesticides,
It is useful as a pharmaceutical intermediate or asymmetric catalyst. The lower alkyl ditartaric acid ester can be produced by reacting tartaric acid with a lower alcohol in the presence of an acid catalyst. Since the reaction is an equilibrium reaction, in principle, a large amount of dehydrated lower alcohol can be used to produce a lower alkyl tartaric diester in high yield by using a large amount of dehydrated lower alcohol. Complicated work is required. As a method not using a large amount of dehydrated lower alkyl alcohol, an esterifying agent such as orthoformate is used in the presence of an acid catalyst (Synth. Commun. (Synth. Comn.), 14, 1087,
(1984)), a lower alkyl alcohol is reacted in the presence of an acid catalyst, and an organic solvent azeotropic with water, for example, chloroform, is coexisted to remove by-product water by azeotropic dehydration (Helvetica). Chemica Acta (Hel
v. Chim. Acta. ) 62, 1710 (197)
The method described in 9)) is known.
【０００３】[0003]
【発明が解決しようとする課題】オルト蟻酸エステルを
使用する方法は反応収率も高く、酒石酸低級アルキルジ
エステルを得る方法として優れているが、オルト蟻酸エ
ステルが高価であり、工業生産に使用するには価格的に
不利である。また、クロロホルムを使用して共沸脱水す
る方法は、反応に長時間を要し、クロロホルムが環境汚
染する恐れがあり好ましくない。The method using orthoformate has a high reaction yield and is excellent as a method for obtaining a lower alkyl ditartaric acid ester. However, orthoformate is expensive and is not suitable for industrial production. Is disadvantageous in terms of price. Also, the method of azeotropic dehydration using chloroform is not preferable because the reaction requires a long time and chloroform may contaminate the environment.
【０００４】本発明の目的は、酒石酸低級アルキルジエ
ステルを製造する方法において、使用する低級アルコー
ル使用量を最小限に抑え、短時間で高収率を達成するこ
とにある。更に、光学活性酒石酸を原料に使用した場合
には、光学純度を低下させること無く光学活性酒石酸低
級アルキルジエステルを製造する方法を提供することに
ある。[0004] It is an object of the present invention to minimize the amount of lower alcohol used in a process for producing a lower alkyl ditartaric acid diester and achieve a high yield in a short time. Another object of the present invention is to provide a method for producing an optically active lower alkyl diester of tartaric acid without lowering optical purity when optically active tartaric acid is used as a raw material.
【０００５】[0005]
【課題を解決するための手段】本発明者らは前記目的を
達成するために鋭意研究を重ねた結果、酒石酸と低級ア
ルコールに塩化チオニルを加えることにより、酒石酸低
級アルキルジエステルを短時間で収率よく製造できるこ
とを見いだし、本発明を完成させた。Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, by adding thionyl chloride to tartaric acid and a lower alcohol, a lower alkyl diester of tartaric acid can be obtained in a short time. They found that they could be manufactured well and completed the present invention.
【０００６】即ち、本発明は、「酒石酸および低級アル
コールに、塩化チオニルを添加することを特徴とする酒
石酸低級アルキルジエステルの製造法。」である。[0006] That is, the present invention is "a process for producing a lower alkyl diester of tartaric acid, characterized by adding thionyl chloride to tartaric acid and a lower alcohol."
【０００７】[0007]
【発明の実施の形態】本発明の原料である酒石酸は、Ｌ
−酒石酸、Ｄ−酒石酸、ＤＬ−酒石酸、メソ−酒石酸の
何れでも使用することができる。BEST MODE FOR CARRYING OUT THE INVENTION Tartaric acid as a raw material of the present invention is L
Any of tartaric acid, D-tartaric acid, DL-tartaric acid and meso-tartaric acid can be used.
【０００８】もう一方の原料である低級アルコールは炭
素数４以下のアルキルアルコールが好ましく、不活性溶
媒で変性されたものも使用できる。具体的にはメタノー
ル、エタノール、プロパノール、イソブタノール等で、
直鎖、或いは分岐状のアルキルアルコールである。エタ
ノールの場合には、トルエン等の酒石酸や低級アルコー
ルと反応しない不活性溶媒類を添加して変性されたもの
でも同様に使用できる。[0008] The lower alcohol, which is the other raw material, is preferably an alkyl alcohol having 4 or less carbon atoms, and may be one modified with an inert solvent. Specifically, methanol, ethanol, propanol, isobutanol, etc.
It is a linear or branched alkyl alcohol. In the case of ethanol, those modified by adding an inert solvent which does not react with tartaric acid such as toluene or a lower alcohol can also be used.
【０００９】低級アルコールの使用量は酒石酸に対して
２〜３０倍モルが好ましく、さらに好ましくは２〜６倍
モルである。この範囲であれば経済効率も良好で、酒石
酸低級アルキルジエステルの収率も高い。The amount of the lower alcohol to be used is preferably 2 to 30 times, more preferably 2 to 6 times the molar amount of tartaric acid. Within this range, the economic efficiency is good and the yield of lower alkyl tartaric diester is high.
【００１０】反応は酒石酸と低級アルコールに塩化チオ
ニルを添加して進行させる。塩化チオニル添加量は未反
応カルボキシル基に対し０．２〜５倍モルが好ましく、
更に好ましくは０．５〜２倍モルである。反応温度は０
〜１２０℃が好ましく、さらに好ましくは２０〜９０℃
である。この範囲で反応を行うことで、酒石酸低級アル
キルジエステルの収率を高くすることが出来る。The reaction proceeds by adding thionyl chloride to tartaric acid and a lower alcohol. The addition amount of thionyl chloride is preferably 0.2 to 5 times mol based on unreacted carboxyl groups,
More preferably, it is 0.5 to 2 moles. Reaction temperature is 0
To 120 ° C, more preferably 20 to 90 ° C
It is. By performing the reaction in this range, the yield of the lower alkyl ditartaric acid diester can be increased.
【００１１】反応時には、塩化水素と二酸化硫黄が排ガ
スとして発生するが、塩化チオニル添加量が多いと排ガ
ス量も多く、排ガス処理の負荷が大きくなるため問題が
生ずる場合がある。そこで、酒石酸と低級アルコールを
酸触媒存在下でエステル化反応を進行させ、次いで反応
により副生した水を濃縮により除去した後、少量残存す
る未反応の酒石酸、酒石酸低級アルキルモノエステル、
および酒石酸低級アルキルジエステルの混合物に低級ア
ルコールと残存するカルボキシル基に対し、０．５〜
２．０倍モルの塩化チオニルを添加するのが好ましい。
酸触媒存在下でエステル化を行う際は、加熱をするのが
好ましい。好ましい加熱温度は、３０〜１２０℃であ
り、さらに好ましくは５０〜９０℃である。この範囲で
反応を行うことで不純物の発生を少なくすることが出来
る。During the reaction, hydrogen chloride and sulfur dioxide are generated as exhaust gas. However, if the amount of thionyl chloride added is large, the amount of exhaust gas is large and the load of exhaust gas treatment increases, which may cause a problem. Therefore, the esterification reaction of tartaric acid and a lower alcohol is allowed to proceed in the presence of an acid catalyst, and then water produced as a by-product of the reaction is removed by concentration. Then, a small amount of unreacted tartaric acid and lower alkyl tartaric acid monoester are removed.
And lower alcohol and lower carboxyl group in the mixture of lower alkyl tartaric acid diester,
It is preferred to add 2.0 moles of thionyl chloride.
When performing esterification in the presence of an acid catalyst, it is preferable to heat. A preferred heating temperature is 30 to 120C, more preferably 50 to 90C. By performing the reaction in this range, generation of impurities can be reduced.
【００１２】ここで、使用される酸触媒は、塩酸や硫酸
等の鉱酸類、ベンゼンスルホン酸、トルエンスルホン酸
等の芳香族スルホン酸類、メタンスルホン酸等の脂肪族
スルホン酸類、またＨ型の陽イオン交換樹脂、例えばナ
フィオン（デュポン（株）製）、ダイアイオンＰＫ２０
８（三菱化成（株）製）等が挙げられる。酸触媒の使用
量は酒石酸に対し０．００１〜１倍モルが好ましく、さ
らに好ましくは０．００５〜０．１倍モルである。The acid catalyst used herein includes mineral acids such as hydrochloric acid and sulfuric acid, aromatic sulfonic acids such as benzenesulfonic acid and toluenesulfonic acid, aliphatic sulfonic acids such as methanesulfonic acid, and H-type positive acids. Ion exchange resin, for example, Nafion (manufactured by DuPont), Diaion PK20
8 (manufactured by Mitsubishi Kasei Corporation). The amount of the acid catalyst to be used is preferably 0.001 to 1 mol, more preferably 0.005 to 0.1 mol, per mol of tartaric acid.
【００１３】酒石酸と低級アルコールを酸触媒の存在
下、エステル化反応を進行させる際に、低級アルコール
の使用量は少ない方が有利であり、低級アルコールの使
用量は酒石酸１モルに対し、２〜６モルが好ましい。こ
の範囲で反応を行うことで、経済的に、高純度の酒石酸
低級アルキルジエステルを得ることが出来る。しかし、
低級アルコールの使用量が少ないと、スラリー濃度が高
くなり、攪拌などに問題が生ずる場合があるので、そこ
で反応を円滑に進行させるために希釈剤を添加するのが
好ましい。ここで添加する希釈剤は、酒石酸や低級アル
コールと反応せず、かつ水と共沸する有機溶媒が好まし
く使用できる。具体的にはヘキサン等の脂肪族炭化水素
類、シクロヘキサン等の脂環式炭化水素類、トルエン、
キシレン等の芳香族炭化水素類、ジイソプロピルエーテ
ル等のエーテル類が挙げられる。When the esterification reaction of tartaric acid and a lower alcohol is carried out in the presence of an acid catalyst, it is advantageous that the lower alcohol is used in a smaller amount. The lower alcohol is used in an amount of 2 to 1 mol of tartaric acid. 6 moles are preferred. By performing the reaction in this range, a high-purity lower alkyl diester of tartaric acid can be obtained economically. But,
If the amount of the lower alcohol is small, the concentration of the slurry becomes high and there may be a problem in stirring or the like. Therefore, it is preferable to add a diluent in order to promote the reaction smoothly. As the diluent added here, an organic solvent that does not react with tartaric acid or a lower alcohol and azeotropes with water can be preferably used. Specifically, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, toluene,
Examples include aromatic hydrocarbons such as xylene and ethers such as diisopropyl ether.
【００１４】添加量は攪拌できるスラリー濃度になる量
でよく、低級アルコールの使用量によって異なるが、通
常は酒石酸に対して１〜２０倍重量が好ましく、さらに
好ましくは２〜１０倍重量である。この範囲であれば、
経済効率も良好で、作業性もよい。また、希釈剤は濃縮
工程で使用してもよい。エステル化反応終了後に過剰の
低級アルコール、および副生した水を濃縮除去するが、
濃縮工程での体積変化が小さくすることで、反応缶の熱
効率が低下して濃縮時間が延長される問題点や、局部加
熱で酒石酸低級アルキルジエステルの品質が低下する問
題点を防ぐことが出来る。そこで、濃縮工程に於いて留
出する低級アルコール、水、および希釈剤の量に見合っ
た希釈剤を系中に添加すれば、共沸脱水効率を高めると
同時に局部加熱による品質低下を防止することができ
る。The amount of addition may be such that the concentration of the slurry can be agitated and varies depending on the amount of the lower alcohol used. Usually, the amount is preferably 1 to 20 times, more preferably 2 to 10 times the weight of tartaric acid. Within this range,
Good economic efficiency and good workability. Further, the diluent may be used in the concentration step. After the esterification reaction, excess lower alcohol and by-product water are concentrated and removed,
By reducing the volume change in the concentration step, it is possible to prevent the problem that the thermal efficiency of the reaction vessel is reduced and the concentration time is extended, and the problem that the quality of the lower alkyl tartaric diester is reduced by local heating. Therefore, if a diluent corresponding to the amount of the lower alcohol, water and diluent distilled out in the concentration step is added to the system, it is possible to increase the azeotropic dehydration efficiency and at the same time prevent the quality deterioration due to local heating. Can be.
【００１５】エステル化の反応温度は３０〜１２０℃が
好ましく、さらに好ましくは５０〜９０℃である。[0015] The reaction temperature of the esterification is preferably 30 to 120 ° C, more preferably 50 to 90 ° C.
【００１６】反応時間は低級アルコール、酸触媒の種類
や使用量、反応温度によって異なるが、通常は０.５〜
２０時間が好ましく、さらに好ましくは１〜６時間であ
る。The reaction time varies depending on the type and amount of the lower alcohol and the acid catalyst and the reaction temperature.
It is preferably 20 hours, more preferably 1 to 6 hours.
【００１７】本発明法において、反応、脱水、塩化チオ
ニル添加により得た反応液から、酒石酸低級アルキルジ
エステルを単離するには、通常の方法が採用できる。例
えば反応液に水を加えて極僅かに残留した酒石酸や酒石
酸低級アルキルモノエステルを水層に移行させ、希釈剤
溶液を濃縮することにより、目的とする酒石酸低級アル
キルジエステルを単離することができる。或いは、真空
蒸留で精製することもできる。In the method of the present invention, a conventional method can be employed for isolating the lower alkyl ditartaric acid diester from the reaction solution obtained by the reaction, dehydration and addition of thionyl chloride. For example, by adding water to the reaction solution and transferring a very small amount of residual tartaric acid or lower alkyl tartaric acid monoester to the aqueous layer, and concentrating the diluent solution, the target lower alkyl tartaric acid diester can be isolated. . Alternatively, it can be purified by vacuum distillation.
【００１８】[0018]
【実施例】次に、本発明を実施例等にて具体的に説明す
る。尚、酒石酸や酒石酸低級アルキルジエステルの濃度
分析は下記の高速液体クロマトグラフィーで実施した。 装置：島津ＬＣ−１０ＡＴ カラム：ＹＭＣ−Ｐａｃｋ ＯＤＳ−ＡＭ３０３（ＹＭ
Ｃ（株）製）直径４．６ｍｍ×２５０ｍｍ カラム温度：４０℃ 検出法：ＵＶ（２１５ｎｍ） 溶媒：２０ｍＭ−ＮａＨ２ＳＯ４水溶液／アセトニトリ
ル＝９／１（Ｖ／Ｖ） 流量：０．５ｍｌ／ｍｉｎ 実施例１ 温度計、コンデンサー、滴下ロート、撹拌機を装着した
１Ｌ三ッ口フラスコに、Ｄ−酒石酸（東レ（株）製、光
学純度９９．９％ｅｅ以上）１２０．１ｇ（０．８モ
ル）、エタノール（片山化学（株）製、特級試薬）７
３．７ｇ（１．６モル）、トルエン（片山化学（株）
製、１級試薬）４３２．３ｇを加え攪拌した。これに、
塩化水素ガスをエタノールに吹き込み調製した１０％塩
化水素エタノール溶液８．８ｇ（塩化水素０．０２４モ
ル）を加え、２時間８０℃下で加熱した。次いで苛性ソ
ーダ（片山化学（株）製、１級試薬）を水に溶解させ調
製した４８％苛性ソーダ水溶液２．０ｇ（苛性ソーダ
０．０２４モル）を加えた後、単蒸留装置を装着し、滴
下ロートによりトルエン１８０．１ｇを加えながら、減
圧下でフラスコ中の水とエタノールをトルエンとともに
７０℃下で留出させた。水、エタノール、トルエンの混
合物約２４０ｇを留出させた後、冷却し、その液中のＤ
−酒石酸およびＤ−酒石酸モノエチルエステル濃度を分
析した結果、仕込みＤ−酒石酸に対し、Ｄ−酒石酸残存
率は１４％、Ｄ−酒石酸モノエチルエステル生成率は３
４％であった。エタノール６４．５ｇ（１．４モル）を
加え、３０〜４０℃下で塩化チオニル（片山化学（株）
製、特級試薬）６１．９ｇ（０．５２モル）を約３０分
で滴下した。２時間撹拌の後、滴下ロートによりトルエ
ン７２．０ｇを加えながら、減圧下でフラスコの中の水
とエタノールをトルエンとともに５０℃下で蒸発させ、
水、エタノール、トルエンの混合物約１０８ｇを留出さ
せた。反応液を３５℃以下まで放冷し、炭酸水素ナトリ
ウム（片山化学（株）製、１級試薬）６．７ｇ（０．０
８モル）、塩化ナトリウム（片山化学（株）製、１級試
薬）を水に溶解させ調製した８％食塩水３３ｇを反応液
に加え、良く撹拌した後、有機層を分取した。有機層は
再度飽和食塩水３３ｇで２回洗浄を行った。分離した水
層はトルエン３５０ｇで再度抽出を行い、先の分取した
有機層に加えた。ついで有機層を減圧下、４０℃下で濃
縮乾固し、溶媒を留去した後、ろ過してＤ−酒石酸ジエ
チルエステル１５６．７ｇを得た。仕込みＤ−酒石酸に
対するＤ−酒石酸ジエチルエステルの収率は９５．０％
であった。また、光学純度は９９．９％ｅｅ以上で光学
純度は低下していなかった。Next, the present invention will be specifically described with reference to examples and the like. The concentration analysis of tartaric acid and lower alkyl ditartaric acid was performed by the following high performance liquid chromatography. Apparatus: Shimadzu LC-10AT Column: YMC-Pack ODS-AM303 (YM-Pack ODS-AM303)
4.6 mm x 250 mm diameter Column temperature: 40 ° C Detection method: UV (215 nm) Solvent: 20 mM-NaH2SO4 aqueous solution / acetonitrile = 9/1 (V / V) Flow rate: 0.5 ml / min 1 In a 1 L three-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer, 120.1 g (0.8 mol) of D-tartaric acid (manufactured by Toray Industries, Inc., optical purity of 99.9% ee or more), Ethanol (Katayama Chemical Co., Ltd., special grade reagent) 7
3.7 g (1.6 mol), toluene (Katayama Chemical Co., Ltd.)
432.3 g was added and stirred. to this,
8.8 g (0.024 mol of hydrogen chloride) of a 10% ethanol solution of hydrogen chloride prepared by blowing hydrogen chloride gas into ethanol was added, and the mixture was heated at 80 ° C. for 2 hours. Then, 2.0 g of a 48% aqueous solution of caustic soda (0.024 mol of caustic soda) prepared by dissolving caustic soda (a first-class reagent manufactured by Katayama Chemical Co., Ltd.) in water was added, and a simple distillation apparatus was attached. Water and ethanol in the flask were distilled off at 70 ° C. together with toluene under reduced pressure while adding 180.1 g of toluene. After distilling out about 240 g of a mixture of water, ethanol and toluene, the mixture was cooled, and the D
As a result of analyzing the concentrations of -tartaric acid and D-tartaric acid monoethyl ester, the residual ratio of D-tartaric acid to the charged D-tartaric acid was 14%, and the yield of D-tartaric acid monoethyl ester was 3%.
4%. 64.5 g (1.4 mol) of ethanol was added, and thionyl chloride (Katayama Chemical Co., Ltd.) was added at 30 to 40 ° C.
61.9 g (0.52 mol) were added dropwise in about 30 minutes. After stirring for 2 hours, water and ethanol in the flask were evaporated at 50 ° C. together with toluene under reduced pressure while adding 72.0 g of toluene with a dropping funnel.
About 108 g of a mixture of water, ethanol and toluene was distilled off. The reaction solution was allowed to cool to 35 ° C. or lower, and 6.7 g of sodium hydrogen carbonate (a first-class reagent manufactured by Katayama Chemical Co., Ltd.)
8 mol) and sodium chloride (Katayama Chemical Co., Ltd., primary reagent) were dissolved in water, and 33 g of 8% saline solution was added to the reaction solution. After stirring well, the organic layer was separated. The organic layer was washed twice with 33 g of saturated saline again. The separated aqueous layer was extracted again with 350 g of toluene, and added to the previously separated organic layer. Then, the organic layer was concentrated to dryness under reduced pressure at 40 ° C., the solvent was distilled off, and the residue was filtered to obtain 156.7 g of diethyl D-tartaric acid. The yield of D-tartaric acid diethyl ester based on the charged D-tartaric acid is 95.0%.
Met. The optical purity was 99.9% ee or more, and the optical purity did not decrease.
【００１９】実施例２ 実施例１の方法において塩化チオニルの添加量を、３
１．０ｇ（０．２６モル）とした以外は同様の操作を行
い、Ｄ−酒石酸ジエチルエステル１５２．２ｇを得た。
仕込みＤ−酒石酸に対するＤ−酒石酸ジエチルエステル
の収率は９２．３％であった。また、光学純度は９９．
９％ｅｅ以上で光学純度は低下していなかった。Example 2 In the method of Example 1, the amount of thionyl chloride added was changed to 3
The same operation was performed except that the amount was changed to 1.0 g (0.26 mol), to obtain 152.2 g of diethyl D-tartaric acid.
The yield of D-tartaric acid diethyl ester based on the charged D-tartaric acid was 92.3%. The optical purity is 99.
At 9% ee or more, the optical purity did not decrease.
【００２０】実施例３ 実施例１の方法において塩化チオニルの添加温度を、７
０℃とし、Ｄ−酒石酸の代わりにＬ−酒石酸（片山化学
（株）製、特級試薬、光学純度９９．５％ｅｅ以上）を
使用した以外は同様の操作を行い、Ｌ−酒石酸ジエチル
エステル１５３．７ｇを得た。仕込みＬ−酒石酸に対す
るＬ−酒石酸ジエチルエステルの収率は９３．２％であ
った。また、光学純度は９９．９％ｅｅ以上で光学純度
は低下していなかった。Example 3 In the method of Example 1, the addition temperature of thionyl chloride was changed to 7
The same operation was carried out except that the temperature was 0 ° C. and L-tartaric acid (Katayama Chemical Co., Ltd., special grade reagent, optical purity of 99.5% ee or more) was used instead of D-tartaric acid. 0.7 g was obtained. The yield of L-tartaric acid diethyl ester based on the charged L-tartaric acid was 93.2%. The optical purity was 99.9% ee or more, and the optical purity did not decrease.
【００２１】実施例４ 実施例１の方法においてエタノールの代わりに２−プロ
パノール（片山化学（株）製、１級試薬）を使用し、添
加量を９６．０ｇ（初期仕込み時）、８４．０ｇ（塩化
チオニル添加時）とした以外は同様の操作を行い、Ｄ−
酒石酸ジイソプロピルエステル１７９．８ｇを得た。仕
込みＤ−酒石酸に対するＤ−酒石酸ジエチルエステルの
収率は９６．０％であった。また、光学純度は９９．９
％ｅｅ以上で光学純度は低下していなかった。Example 4 In the method of Example 1, 2-propanol (a first-class reagent manufactured by Katayama Chemical Co., Ltd.) was used in place of ethanol, and the added amount was 96.0 g (at the time of initial preparation) and 84.0 g. (At the time of addition of thionyl chloride).
179.8 g of diisopropyl tartrate were obtained. The yield of D-tartaric acid diethyl ester based on the charged D-tartaric acid was 96.0%. The optical purity is 99.9.
The optical purity did not decrease at% ee or more.
【００２２】比較例 実施例１の方法において塩化チオニルの添加をなくした
以外は同様の操作を行い、Ｄ−酒石酸ジエチルエステル
６７．６ｇを得た。仕込みＤ−酒石酸に対するＤ−酒石
酸ジエチルエステルの収率は４１．０％と低かった。ま
た、光学純度は９９．９％ｅｅ以上で光学純度の低下は
なかった。Comparative Example The same operation as in Example 1 was carried out except that the addition of thionyl chloride was omitted, to obtain 67.6 g of diethyl D-tartaric acid. The yield of D-tartaric acid diethyl ester based on the charged D-tartaric acid was as low as 41.0%. The optical purity was 99.9% ee or more, and there was no decrease in the optical purity.
【００２３】[0023]
【発明の効果】本発明によれば、酒石酸と低級アルコー
ルに、塩化チオニルを加えることで、低級アルコール使
用量を最低限に抑え、短時間で収率よく高純度の酒石酸
低級アルキルジエステルを製造することができ、酒石酸
低級アルキルジエステル製造コスト削減に大きく貢献で
きる。According to the present invention, by adding thionyl chloride to tartaric acid and a lower alcohol, the amount of lower alcohol used can be minimized, and a high-purity lower alkyl diester of tartaric acid can be produced in a short time and with good yield. And can greatly contribute to the reduction of the production cost of lower alkyl tartaric diester.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０７Ｃ 69/70 Ｃ０７Ｃ 69/70 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｍ 7:00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C07C 69/70 C07C 69/70 // C07B 61/00 300 C07B 61/00 300 C07M 7:00
Claims (5)
ニルを添加することを特徴とする酒石酸低級アルキルジ
エステルの製造法。1. A method for producing a lower alkyl ditartaric acid, comprising adding thionyl chloride to tartaric acid and a lower alcohol.
エステル化する工程、系中の副生水を除去する濃縮工
程、低級アルコールと塩化チオニルを加える工程からな
ることを特徴とする請求項１記載の酒石酸低級アルキル
ジエステルの製造法。2. The method according to claim 1, comprising the steps of esterifying tartaric acid and a lower alcohol in the presence of an acid catalyst, concentrating to remove by-product water in the system, and adding a lower alcohol and thionyl chloride. The method for producing a lower alkyl diester of tartaric acid according to the above.
低級アルコールとも反応せず、かつ水と共沸する有機溶
媒を用いることを特徴とする請求項２記載の酒石酸低級
アルキルジエステルの製造法。3. The lower alkyl diester of tartaric acid according to claim 2, wherein an organic solvent which does not react with tartaric acid or lower alcohol and azeotropes with water is used when removing by-product water in the system. Manufacturing method.
対し、２〜６モルであり、酒石酸とも低級アルコールと
も反応せず、かつ水と共沸する有機溶媒を希釈剤として
用いることを特徴とする請求項１〜３のいずれか１項記
載の酒石酸低級アルキルジエステルの製造法。4. The use amount of the lower alcohol is 2 to 6 mol per 1 mol of tartaric acid, and an organic solvent which does not react with tartaric acid or lower alcohol and azeotropes with water is used as a diluent. The method for producing a lower alkyl diester of tartaric acid according to any one of claims 1 to 3.
いずれか１項記載の酒石酸低級アルキルジエステルの製
造法。5. The method for producing a lower alkyl ditartaric acid ester according to claim 1, wherein tartaric acid is an optically active substance.
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|---|---|---|---|
| JP18755499A JP4314600B2 (en) | 1999-07-01 | 1999-07-01 | Method for producing tartaric acid lower alkyl diester |
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|---|---|---|---|
| JP18755499A JP4314600B2 (en) | 1999-07-01 | 1999-07-01 | Method for producing tartaric acid lower alkyl diester |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002128738A (en) * | 2000-10-18 | 2002-05-09 | Toray Ind Inc | Method for producing tartaric acid lower alkyl diester |
| CN104003883A (en) * | 2013-02-26 | 2014-08-27 | 东丽精细化工株式会社 | Method for manufacturing high purity tartaric acid dialkyl esters |
| JP2014162758A (en) * | 2013-02-26 | 2014-09-08 | Toray Fine Chemicals Co Ltd | Method for producing high purity dialkyl tartrate |
| JP2014169233A (en) * | 2013-03-01 | 2014-09-18 | Toray Fine Chemicals Co Ltd | Method for producing high purity optically active tartaric acid dialkyl ester |
-
1999
- 1999-07-01 JP JP18755499A patent/JP4314600B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002128738A (en) * | 2000-10-18 | 2002-05-09 | Toray Ind Inc | Method for producing tartaric acid lower alkyl diester |
| CN104003883A (en) * | 2013-02-26 | 2014-08-27 | 东丽精细化工株式会社 | Method for manufacturing high purity tartaric acid dialkyl esters |
| JP2014162758A (en) * | 2013-02-26 | 2014-09-08 | Toray Fine Chemicals Co Ltd | Method for producing high purity dialkyl tartrate |
| CN104003883B (en) * | 2013-02-26 | 2016-08-17 | 东丽精细化工株式会社 | The manufacture method of high-purity dialkyl tartrate |
| JP2014169233A (en) * | 2013-03-01 | 2014-09-18 | Toray Fine Chemicals Co Ltd | Method for producing high purity optically active tartaric acid dialkyl ester |
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| Publication number | Publication date |
|---|---|
| JP4314600B2 (en) | 2009-08-19 |
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