JPH10101659A - Production of substituted thiazolidine-dione derivative - Google Patents
Production of substituted thiazolidine-dione derivativeInfo
- Publication number
- JPH10101659A JPH10101659A JP8279874A JP27987496A JPH10101659A JP H10101659 A JPH10101659 A JP H10101659A JP 8279874 A JP8279874 A JP 8279874A JP 27987496 A JP27987496 A JP 27987496A JP H10101659 A JPH10101659 A JP H10101659A
- Authority
- JP
- Japan
- Prior art keywords
- dione
- thiazolidine
- derivative
- substituted
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Thiazole And Isothizaole Compounds (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、置換チアゾリジン
ジオン誘導体の製造方法に関するものである。本発明に
よって得られる化合物は、医薬、農薬などの原料として
有用なものである。The present invention relates to a method for producing a substituted thiazolidinedione derivative. The compounds obtained by the present invention are useful as raw materials for medicines, agricultural chemicals and the like.
【０００２】[0002]
【従来技術】置換チアゾリジンジオン誘導体の製造法と
しては、α−ハロ−β−フェニルプロピオン酸誘導体を
チオ尿素と反応させた後、加水分解する方法（たとえ
ば、Chemical Pharmaceutical Bulletin, 30,3563(198
2) ）が知られている。しかし、この方法は原料のα−
ハロ−β−フェニルプロピオン酸誘導体の入手が困難で
あること、その製造には煩雑な工程を必要とし、廃棄が
困難な銅触媒を用いる必要があることなどの欠点があ
る。2. Description of the Related Art As a method for producing a substituted thiazolidinedione derivative, an α-halo-β-phenylpropionic acid derivative is reacted with thiourea and then hydrolyzed (for example, see Chemical Pharmaceutical Bulletin, 30 , 3563 (198).
2)) is known. However, this method uses the α-
There are drawbacks in that it is difficult to obtain a halo-β-phenylpropionic acid derivative, a complicated process is required for its production, and a copper catalyst that is difficult to dispose must be used.
【０００３】ベンジリデンチアゾリジンジオン誘導体は
分子内に硫黄を含むため、通常の水素添加では硫黄の触
媒毒作用により還元され難く、また、脱硫反応によりＳ
結合の開裂が起こることが知られている（たとえば、Or
g.Reactions,12,356(1962)）。接触水素添加の触媒とし
てパラジウムを使用する場合（特表平６ー５０３３５３
号）は、触媒活性が低下する傾向があり、原料と同重量
以上の触媒を用いなければならず経済的に不利であっ
た。[0003] Since benzylidenethiazolidinedione derivatives contain sulfur in the molecule, they are difficult to be reduced by the catalytic poisoning of sulfur by ordinary hydrogenation, and S is also reduced by desulfurization.
It is known that bond cleavage occurs (eg, Or
g. Reactions, 12 , 356 (1962)). When palladium is used as a catalyst for catalytic hydrogenation (Tokuhei 6-503353)
No. 2) tends to decrease the catalytic activity, and it is economically disadvantageous that a catalyst having the same weight or more as the raw material must be used.
【０００４】本発明者らは、ベンジリデンチアゾリジン
ジオン誘導体をニッケル、コバルト等の触媒の存在下に
水素添加すると、環状内にＳ結合が存在するにもかかわ
らず、環状内のＳ結合が開裂あるいは脱離することな
く、二重結合が選択的に水素添加されて、目的とするベ
ンジルチアゾリジンジオン誘導体を製造する方法を見い
だした（特願平７−１０３２２０号）。しかしながら、
反応濃度をあまりあげることができず、装置効率は満足
できるものではなかった。The inventors of the present invention have found that when a benzylidene thiazolidinedione derivative is hydrogenated in the presence of a catalyst such as nickel or cobalt, the S bond in the ring is cleaved or removed despite the presence of the S bond in the ring. A method for producing a target benzylthiazolidinedione derivative by selectively hydrogenating a double bond without separation was found (Japanese Patent Application No. 7-103220). However,
The reaction concentration could not be increased so much, and the efficiency of the apparatus was not satisfactory.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上述の従来技
術の種々の問題を解決するためなされたものであり、そ
の目的は、製造が容易なベンジリデンチアゾリジンジオ
ン誘導体を原料として用い、高収率でベンジルチアゾリ
ジンジオン誘導体を製造することのできる方法を提供す
ることにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned various problems of the prior art, and an object of the present invention is to use a benzylidenethiazolidinedione derivative which is easy to produce as a raw material and to provide a high yield. To provide a method by which a benzylthiazolidinedione derivative can be produced.
【０００６】[0006]
【課題を解決するための手段】本発明者らは上記目的を
達成するために鋭意検討を重ねた結果、ベンジリデンチ
アゾリジオン誘導体を炭素数２以下のアルコール系溶媒
中でニッケルを含有する触媒の存在下に接触水素化する
ことにより、目的とする置換チアゾリジオン誘導体を高
収率で製造できることを見いだし、本発明に到達した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a benzylidene thiazolidione derivative can be converted into a catalyst containing nickel in an alcohol solvent having 2 or less carbon atoms. The present inventors have found that the desired substituted thiazolidione derivative can be produced in high yield by catalytic hydrogenation in the presence of the compound, and have reached the present invention.
【０００７】すなわち、本発明は一般式（１） （式中、Ｒ1 およびＲ2 は同一または異なって、水素原
子、水酸基、炭素数１〜４の直鎖状もしくは分岐状のア
ルキル基、炭素数１〜４の直鎖状もしくは分岐状のアル
コキシ基、または、Ｒ1 およびＲ2 が一緒になってメチ
レンジオキシ基を示す）で表わされる置換チアゾリジン
ジオン誘導体を製造するに当たり、一般式（２） （式中、Ｒ1 およびＲ2 は前記のものと同義である）で
表わされるベンジリデンチアゾリジンジオン誘導体を、
炭素数２以下のアルコール溶媒中で、ニッケルを含有す
る触媒の存在下に、０〜４０℃の温度で水素添加するこ
とを特徴とする置換チアゾリジンジオン誘導体の製造方
法に関する。That is, the present invention provides a compound represented by the general formula (1): (Wherein, R 1 and R 2 are the same or different and each represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms) Group, or R 1 and R 2 together represent a methylenedioxy group) to produce a substituted thiazolidinedione derivative represented by the general formula (2) (Wherein R 1 and R 2 are as defined above),
The present invention relates to a method for producing a substituted thiazolidinedione derivative, which comprises hydrogenating an alcohol solvent having 2 or less carbon atoms in the presence of a catalyst containing nickel at a temperature of 0 to 40 ° C.
【０００８】[0008]
【発明の実施の形態】以下、本発明を詳しく説明する。
本発明で原料として用いる前記一般式（２）で表わされ
るベンジリデンチアゾリジンジオン誘導体は、具体的に
は、５−ベンジリデンチアゾリジン−２，４−ジオン、
５−（４−ヒドロキシベンジリデン）チアゾリジン−
２，４−ジオン、５−（４−メトキシベンジリデン）チ
アゾリジン−２，４−ジオン、５−（４−エトキシベン
ジリデン）チアゾリジン−２，４−ジオン、５−（４−
メチルベンジリデン）チアゾリジン−２，４−ジオン、
５−（４−ｔ−ブチルベンジリデン）チアゾリジン−
２，４−ジオン、５−（３、４−メチレンジオキシベン
ジリデン）チアゾリジン−２，４−ジオン、５−（３−
ヒドロキシベンジリデン）チアゾリジン−２，４−ジオ
ン、５−（３−メトキシベンジリデン）チアゾリジン−
２，４−ジオン、５−（３−メチルベンジリデン）チア
ゾリジン−２，４−ジオン、５−（２−ヒドロキシベン
ジリデン）チアゾリジン−２，４−ジオン、５−（２−
メトキシベンジリデン）チアゾリジン−２，４−ジオ
ン、５−（２−メチルベンジリデン）チアゾリジン−
２，４−ジオン、５−（３、４−ジヒドロキシベンジリ
デン）チアゾリジン−２，４−ジオン、５−（３、４−
ジメトキシベンジリデン）チアゾリジン−２，４−ジオ
ン、５−（３−ヒドロキシ−４−メトキシベンジリデ
ン）チアゾリジン−２，４−ジオン、５−（４−ヒドロ
キシ−３−メチルベンジリデン）チアゾリジン−２，４
−ジオンなどを挙げることができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The benzylidenethiazolidinedione derivative represented by the general formula (2) used as a raw material in the present invention is, specifically, 5-benzylidenethiazolidine-2,4-dione,
5- (4-hydroxybenzylidene) thiazolidine-
2,4-dione, 5- (4-methoxybenzylidene) thiazolidine-2,4-dione, 5- (4-ethoxybenzylidene) thiazolidine-2,4-dione, 5- (4-
Methylbenzylidene) thiazolidine-2,4-dione;
5- (4-t-butylbenzylidene) thiazolidine-
2,4-dione, 5- (3,4-methylenedioxybenzylidene) thiazolidine-2,4-dione, 5- (3-
(Hydroxybenzylidene) thiazolidine-2,4-dione, 5- (3-methoxybenzylidene) thiazolidine-
2,4-dione, 5- (3-methylbenzylidene) thiazolidine-2,4-dione, 5- (2-hydroxybenzylidene) thiazolidine-2,4-dione, 5- (2-
(Methoxybenzylidene) thiazolidine-2,4-dione, 5- (2-methylbenzylidene) thiazolidine-
2,4-dione, 5- (3,4-dihydroxybenzylidene) thiazolidine-2,4-dione, 5- (3,4-
Dimethoxybenzylidene) thiazolidine-2,4-dione, 5- (3-hydroxy-4-methoxybenzylidene) thiazolidine-2,4-dione, 5- (4-hydroxy-3-methylbenzylidene) thiazolidine-2,4
-Dione and the like.
【０００９】これらのベンジリデンチアゾリジン誘導体
は、それぞれに対応するベンズアルデヒド誘導体とチア
ゾリジン−２，４−ジオンを脱水縮合することにより容
易に得ることができる。These benzylidene thiazolidine derivatives can be easily obtained by dehydrating and condensing the corresponding benzaldehyde derivative with thiazolidine-2,4-dione.
【００１０】本発明において用いられる触媒は、ニッケ
ルを含有するものである。本触媒は、それらの金属単体
またはそれら元素の硝酸塩、硫酸塩、塩化物等の塩、酸
化物、水酸化物などの化合物で用いることができる。ま
た、担体に担持して使用することもできる。この場合、
担体としては、活性炭、シリカ、アルミナ、シリカアル
ミナなどが用いられ、触媒の担持量は、５〜７０重量％
の範囲で用いるのがよい。好ましい触媒の具体例として
は、ラネーニッケル、ニッケル−シリカゲル、ニッケル
−アルミナなどが挙げられる。[0010] The catalyst used in the present invention contains nickel. The present catalyst can be used as a simple substance of these metals or a compound such as a salt such as a nitrate, a sulfate or a chloride, an oxide or a hydroxide thereof. Further, it can be used by being supported on a carrier. in this case,
Activated carbon, silica, alumina, silica-alumina and the like are used as the carrier, and the amount of the supported catalyst is 5 to 70% by weight.
It is good to use within the range. Specific examples of preferred catalysts include Raney nickel, nickel-silica gel, nickel-alumina and the like.
【００１１】触媒の使用量は、原料のベンジリデンチア
ゾリジン誘導体に対して通常１から１／１０００重量の
範囲で、好ましくは１／１０から１／１００重量の範囲
とするのがよい。The amount of the catalyst used is usually in the range of 1 to 1/1000 weight, preferably 1/10 to 1/100 weight, based on the benzylidene thiazolidine derivative as the raw material.
【００１２】本発明の方法における反応溶媒としては、
メタノール、エタノールなどの炭素数が２以下のアルコ
ール系溶媒が、原料のベンジリデンチアゾリジオン誘導
体の溶解性が高く、反応濃度を高く設定できることか
ら、生産効率上有利であり、溶解性の高さ及び経済性の
面から特にメタノールが好ましい。The reaction solvent in the method of the present invention includes:
Alcohol-based solvents having 2 or less carbon atoms, such as methanol and ethanol, have high solubility of the benzylidenethiazolidione derivative as a raw material and can be set to have a high reaction concentration. Particularly, methanol is preferable from the viewpoint of economy.
【００１３】反応温度としては、０〜４０℃の範囲で適
用されるが、これより高い温度では生成した置換ジアゾ
リジンジオン誘導体の分解が起こる傾向がある。好まし
い反応温度は０〜３５℃、より好ましくは０〜３０℃が
よい。反応の水素圧は、通常１〜１００ｋｇ／ｃｍ2 の
範囲で適用されるが、１０〜５０ｋｇ／ｃｍ2 の範囲が
好ましい。反応時間は、触媒量、反応温度、水素圧など
の反応条件によって変動するが、通常は１０時間以内、
０．５〜６時間の範囲で適用される。The reaction temperature is in the range of 0 to 40 ° C., but at a higher temperature, the formed substituted diazolidinedione derivative tends to be decomposed. The preferred reaction temperature is 0 to 35 ° C, more preferably 0 to 30 ° C. Hydrogen pressure reaction is applied in the range of usually 1 to 100 kg / cm 2, the range of 10 to 50 kg / cm 2 is preferred. The reaction time varies depending on the reaction conditions such as the amount of the catalyst, the reaction temperature, and the hydrogen pressure.
It is applied in the range of 0.5 to 6 hours.
【００１４】本発明の方法により生成したベンジルチア
ゾリジンジオン誘導体は、反応系から蒸留、再結晶、抽
出などの一般的操作によって分離、精製することができ
る。The benzylthiazolidinedione derivative produced by the method of the present invention can be separated and purified from the reaction system by general operations such as distillation, recrystallization and extraction.
【００１５】[0015]
【実施例】以下、実施例により本発明を更に具体的に説
明するが、本発明はこれら実施例に何ら限定されるもの
ではない。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００１６】原料ベンジリデンチアゾリジンジオン誘導
体の合成を参考例として示す。 参考例 ５−（４−ヒドロキシベンジリデン）チアゾリジン−
２，４−ジオンの合成 ４−ヒドロキシベンズアルデヒド１２２．２ｇ、チアゾ
リジン−２，４−ジオン１１７．２ｇ、ピペリジン８．
５ｇ、酢酸６．０ｇおよびトルエン２０００ｍｌを混合
し、２時間加熱還流した。反応後室温まで冷却し、析出
した結晶を濾過し、メタノール５００ｍｌおよび水４０
０ｍｌで洗浄した。得られた結晶を真空乾燥し、５−
（４−ヒドロキシベンジリデン）チアゾリジン−２，４
−ジオンの黄色結晶を１９８．８ｇ得た。The synthesis of the starting benzylidenethiazolidinedione derivative is shown as a reference example. Reference Example 5- (4-hydroxybenzylidene) thiazolidine-
Synthesis of 2,4-dione 122.2 g of 4-hydroxybenzaldehyde, 117.2 g of thiazolidine-2,4-dione, 8 of piperidine.
5 g, 6.0 g of acetic acid and 2,000 ml of toluene were mixed and heated under reflux for 2 hours. After the reaction, the reaction solution was cooled to room temperature, and the precipitated crystals were filtered.
Washed with 0 ml. The obtained crystals were dried under vacuum to give 5-
(4-hydroxybenzylidene) thiazolidine-2,4
198.8 g of yellow crystals of -dione were obtained.
【００１７】実施例１ 加圧反応容器に５−（４−ヒドロキシベンジリデン）チ
アゾリジン−２，４−ジオン１０ｇとメタノール１５０
ｍｌを加え、次にラネーニッケル３．５ｇを加え、容器
内を水素で置換し、水素圧３０ｋｇ／ｃｍ2 、３０℃で
１時間撹拌した。反応後、反応混合物を濾過して触媒を
除き、濾液を減圧で濃縮して、５−（４−ヒドロキシベ
ンジル）チアゾリジン−２，４−ジオンの無色結晶を１
０．１ｇ得た。収率は９９％であった。EXAMPLE 1 10 g of 5- (4-hydroxybenzylidene) thiazolidine-2,4-dione and 150 g of methanol were placed in a pressurized reaction vessel.
Then, 3.5 g of Raney nickel was added, the inside of the vessel was replaced with hydrogen, and the mixture was stirred at a hydrogen pressure of 30 kg / cm 2 and 30 ° C. for 1 hour. After the reaction, the reaction mixture was filtered to remove the catalyst, and the filtrate was concentrated under reduced pressure to give 5- (4-hydroxybenzyl) thiazolidine-2,4-dione as colorless crystals.
0.1 g was obtained. The yield was 99%.
【００１８】実施例２〜９ 原料のベンジリデンチアゾリジンジオン誘導体を下記表
１に記載のものに代えた以外は、実施例１と同様の方法
で反応を行い、対応する置換チアゾリジンジオン誘導体
を製造した。原料と反応時間を表１に、目的生成物とそ
の収率を表２にそれぞれ示した。Examples 2 to 9 The corresponding substituted thiazolidinedione derivatives were produced in the same manner as in Example 1, except that the starting benzylidenethiazolidinedione derivative was changed to those shown in Table 1 below. The raw materials and the reaction times are shown in Table 1, and the target products and the yields are shown in Table 2.
【００１９】 表１ ──────────────────────────────────── 実施例 原料 反応時間 ベンジリデンチアゾリジンジオン誘導体 （ｈｒ） ──────────────────────────────────── ２ ５−（４−メトキシベンジリデン）チアゾリジン− ２，４−ジオン ２ ３ ５−（４−エトキシベンジリデン）チアゾリジン− ２，４−ジオン １ ４ ５−（３−ヒドロキシベンジリデン）チアゾリジン− ２，４−ジオン ２ ５ ５−（３、４−メチレンジオキシベンジリデン） チアゾリジン−２，４−ジオン ２ ６ ５−（３，４−ジヒドロキシベンジリデン） チアゾリジン−２，４−ジオン ４ ７ ５−（２−ヒドロキシベンジリデン）チアゾリジン− ２，４−ジオン ２ ８ ５−ベンジリデンチアゾリジン−２，４−ジオン ２ ９ ５−（４−メチルベンジリデン）チアゾリジン− ２，４−ジオン ２ ────────────────────────────────────Table 1 Example Raw material Reaction time Benzylidenethiazolidinedione derivative (Hr) ────────────────────────────────────25- (4-methoxybenzylidene) thiazolidine- 2,4-dione 23 5- (4-ethoxybenzylidene) thiazolidine-2,4-dione 14 5- (3-hydroxybenzylidene) thiazolidine-2,4-dione 25 5- (3,4-methylenedi Oxybenzylidene) thiazolidine-2,4-dione 26 5- (3,4-dihydroxybenzylidene) thiazolidine-2,4-dione 47 5- (2-hydroxybenzylidene) thiazolidine-2,4-dione 28 5- Benzili Denthiazolidine-2,4-dione 29 5- (4-methylbenzylidene) thiazolidine-2,4-dione 2} ────────────
【００２０】 表２ ──────────────────────────────────── 実施例 目的生成物 収率 置換チアゾリジンジオン誘導体 （％） ──────────────────────────────────── ２ ５−（４−メトキシベンジル）チアゾリジン− ２，４−ジオン ９８ ３ ５−（４−エトキシベンジル）チアゾリジン− ２，４−ジオン ９７ ４ ５−（３−ヒドロキシベンジリデン） チアゾリジン−２，４−ジオン ９５ ５ ５−（３、４−メチレンジオキシベンジリデン） チアゾリジン−２，４−ジオン ９３ ６ ５−（３，４−ジヒドロキシベンジリデン） チアゾリジン−２，４−ジオン ９２ ７ ５−（２−ヒドロキシベンジリデン）チアゾリジン− ２，４−ジオン ９５ ８ ５−ベンジリデンチアゾリジン−２，４−ジオン ９６ ９ ５−（４−メチルベンジリデン）チアゾリジン− ２，４−ジオン ９７ ────────────────────────────────────Table 2 Example Example Target Product Yield Substituted Thiazolidine Dione derivative (%) ──────────────────────────────────── 25- (4-methoxybenzyl) Thiazolidine-2,4-dione 98 3 5- (4-ethoxybenzyl) thiazolidine-2,4-dione 97 4 5- (3-hydroxybenzylidene) thiazolidine-2,4-dione 955 5- (3,4- Methylenedioxybenzylidene) thiazolidine-2,4-dione 93 6 5- (3,4-dihydroxybenzylidene) thiazolidine-2,4-dione 92 7 5- (2-hydroxybenzylidene) thiazolidine-2,4-dione 958 5-benzylidene Thiazolidine-2,4-dione 96 9 5- (4-methylbenzylidene) thiazolidine-2,4-dione 97 ───────────
【００２１】比較例１ 加圧反応容器に５−（４−ヒドロキシベンジリデン）チ
アゾリジン−２，４−ジオン１０ｇとメタノール１５０
ｍｌを加え、次にラネーニッケル３．５ｇを加え、容器
内を水素で置換し、水素圧３０ｋｇ／ｃｍ2 、５０℃で
３時間撹拌した。反応後、反応混合物を濾過して触媒を
除き、濾液を減圧で濃縮して、８．８ｇの黄色固形物を
得たが、この固形物は、目的の５−（４−ヒドロキシベ
ンジル）チアゾリジン−２，４−ジオンと原料の５−
（４−ヒドロキシベンジリデン）チアゾリジン−２，４
−ジオンの比が４：１の混合物であった。この混合物を
再結晶にて精製を試みたが、原料の除去は困難であっ
た。Comparative Example 1 10 g of 5- (4-hydroxybenzylidene) thiazolidine-2,4-dione and 150 g of methanol were placed in a pressurized reaction vessel.
Then, 3.5 g of Raney nickel was added, the inside of the vessel was replaced with hydrogen, and the mixture was stirred at 30 kg / cm 2 of hydrogen at 50 ° C. for 3 hours. After the reaction, the reaction mixture was filtered to remove the catalyst, and the filtrate was concentrated under reduced pressure to obtain 8.8 g of a yellow solid, which was the target 5- (4-hydroxybenzyl) thiazolidine- 2,4-dione and 5-
(4-hydroxybenzylidene) thiazolidine-2,4
A mixture having a dione ratio of 4: 1. An attempt was made to purify this mixture by recrystallization, but it was difficult to remove the raw materials.
【００２２】本発明の方法によれば、製造が容易なベン
ジリデンチアゾリジンジオン誘導体を原料として用い、
特殊な操作や装置を必要とすることなく、高収率で置換
チアゾリジンジオン誘導体を製造することができる。According to the method of the present invention, a benzylidenethiazolidinedione derivative which is easy to produce is used as a raw material,
A substituted thiazolidinedione derivative can be produced in high yield without requiring special operations or equipment.
Claims (3)
子、水酸基、炭素数１〜４の直鎖状もしくは分岐状のア
ルキル基、炭素数１〜４の直鎖状もしくは分岐状のアル
コキシ基、または、Ｒ1 およびＲ2 が一緒になってメチ
レンジオキシ基を示す）で表わされる置換チアゾリジン
ジオン誘導体を製造するに当たり、一般式（２） （式中、Ｒ1 およびＲ2 は前記のものと同義である）で
表わされるベンジリデンチアゾリジンジオン誘導体を、
炭素数２以下のアルコール系溶媒中で、ニッケルを含有
する触媒の存在下に、０〜４０℃の温度で水素添加する
ことを特徴とする置換ベンジルチアゾリジンジオン誘導
体の製造方法。1. The general formula (1) (Wherein, R 1 and R 2 are the same or different and each represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms) Group, or R 1 and R 2 together represent a methylenedioxy group) to produce a substituted thiazolidinedione derivative represented by the general formula (2) (Wherein R 1 and R 2 are as defined above),
A method for producing a substituted benzylthiazolidinedione derivative, comprising hydrogenating an alcoholic solvent having 2 or less carbon atoms in the presence of a catalyst containing nickel at a temperature of 0 to 40 ° C.
項１記載の方法。2. The method according to claim 1, wherein the temperature of the hydrogenation is from 0 to 35 ° C.
項１記載の方法。3. The method according to claim 1, wherein the temperature of the hydrogenation is 0 to 30 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8279874A JPH10101659A (en) | 1996-10-02 | 1996-10-02 | Production of substituted thiazolidine-dione derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8279874A JPH10101659A (en) | 1996-10-02 | 1996-10-02 | Production of substituted thiazolidine-dione derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10101659A true JPH10101659A (en) | 1998-04-21 |
Family
ID=17617154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8279874A Pending JPH10101659A (en) | 1996-10-02 | 1996-10-02 | Production of substituted thiazolidine-dione derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10101659A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000018746A1 (en) * | 1998-09-30 | 2000-04-06 | Roche Diagnostics Gmbh | Thiazolidine derivatives for the treatment and prevention of metabolic bone disorders |
| WO2009148195A1 (en) * | 2008-06-02 | 2009-12-10 | Daebong Ls, Ltd. | 5-(4-hydroxybenzyl)thiazolidine-2,4-dione as intermediate for synthesis of thiazolidinedione based compounds and process for preparing the same |
-
1996
- 1996-10-02 JP JP8279874A patent/JPH10101659A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000018746A1 (en) * | 1998-09-30 | 2000-04-06 | Roche Diagnostics Gmbh | Thiazolidine derivatives for the treatment and prevention of metabolic bone disorders |
| WO2009148195A1 (en) * | 2008-06-02 | 2009-12-10 | Daebong Ls, Ltd. | 5-(4-hydroxybenzyl)thiazolidine-2,4-dione as intermediate for synthesis of thiazolidinedione based compounds and process for preparing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5144088A (en) | Manufacture of neopentyl glycol (I) | |
| KR19990013522A (en) | Process for preparing substituted perhydroisoindole | |
| CA2431065C (en) | Process for the preparation of phenethylamine derivatives | |
| US5744648A (en) | Process for the manufacture of 1, 3-cyclohexanedione | |
| JPH11236341A (en) | Production of alcohol | |
| JPH10101659A (en) | Production of substituted thiazolidine-dione derivative | |
| EP0348223A2 (en) | Novel process for the preparation of serinol | |
| JPH08277279A (en) | Production of benzylthiazolidindione derivative | |
| JPH05286889A (en) | Production of arylacetic acid and its alkali metal salt | |
| US5847225A (en) | Production of naphthyl-substituted ketones from naphthaldehydes | |
| JPS6033370B2 (en) | Method for producing 2-aryl ethanol | |
| CN111960962B (en) | Nickel-catalyzed alpha-alkylation method of acetamide and thioacetamide | |
| EP0696566B1 (en) | Process for production of phenyllactic acid derivative | |
| JP2795492B2 (en) | Method for producing indole or indole derivative | |
| JP3691235B2 (en) | Process for producing optically active piperidines | |
| JP2860676B2 (en) | Method for producing 1-isoquinolines | |
| JP3971875B2 (en) | Process for producing trans-4- (4'-oxocyclohexyl) cyclohexanols | |
| EP0468727B1 (en) | Process for producing hydrazone derivative | |
| KR20010022485A (en) | Process for the preparation of 1-(3,4-dimethoxyphenyl)ethanol | |
| JP3569428B2 (en) | Method for producing homoallylamines | |
| JP2762107B2 (en) | Method for producing 1-substituted-3-hydroxypyrrolidine | |
| JPH1112238A (en) | Production of 1-(beta-hydroxyethyl)-2,5-diaminobenzene or its salt | |
| JPS63297363A (en) | Production of 3-methylindoles | |
| JPH0597778A (en) | Production of 2-aminoindane and its salts | |
| JPS63141964A (en) | Production of 4-piperidinopiperidines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060228 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20060718 |