JPH11255748A - Production of isothiuronium salt and 2-(4-pyridyl) ethanethiol - Google Patents
Production of isothiuronium salt and 2-(4-pyridyl) ethanethiolInfo
- Publication number
- JPH11255748A JPH11255748A JP6079498A JP6079498A JPH11255748A JP H11255748 A JPH11255748 A JP H11255748A JP 6079498 A JP6079498 A JP 6079498A JP 6079498 A JP6079498 A JP 6079498A JP H11255748 A JPH11255748 A JP H11255748A
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- Prior art keywords
- acid
- salt
- pyridyl
- ethanethiol
- reaction
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- Pyridine Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、イソチウロニウム
塩及び２−（４−ピリジル）エタンチオールの製造方法
に関する。詳しくは、４−ビニルピリジン、チオ尿素及
び酸を特定の溶媒中で反応させることによりイソチウロ
ニウム塩を製造する方法、及び得られたイソチウロニウ
ム塩をアンモニアで分解することにより２−（４−ピリ
ジル）エタンチオールを製造する方法に関する。２−
（４−ピリジル）エタンチオールは各種医農薬中間体
や、フェノールとアセトンとの縮合反応によりビスフェ
ノールＡを製造する際の触媒（変性剤）として有用な化
合物である。The present invention relates to a method for producing isothiuronium salt and 2- (4-pyridyl) ethanethiol. Specifically, a method for producing an isothiuronium salt by reacting 4-vinylpyridine, thiourea and an acid in a specific solvent, and 2- (4-pyridyl) ethane by decomposing the obtained isothiuronium salt with ammonia The present invention relates to a method for producing a thiol. 2-
(4-Pyridyl) ethanethiol is a compound useful as a catalyst (denaturing agent) when producing bisphenol A by a condensation reaction between various medical and agricultural chemical intermediates and phenol and acetone.
【０００２】[0002]
【従来の技術】ピリジルアルキルチオール類（メルカプ
トアルキルピリジン類）の合成については、従来からい
ろいろな提案がなされている。例えば、オーストラリア
ン・ジャーナル・オブ・ケミストリー（Ａｕｓｔ．Ｊ．
Ｃｈｅｍ．），１９，１８３５（１９６６）には、２−
ビニルピリジンと硫化水素から２−（２−ピリジル）エ
タンチオールを製造する方法が、米国特許第２，６０
７，７７６号明細書には、２−ビニルピリジンとチオ酢
酸よりアセチルチオ体を合成し塩酸により２−（２−ピ
リジル）エタンチオールを製造する方法が、ジャーナル
・オブ・ヘテロサイクリック・ケミストリー（Ｊ．Ｈｅ
ｔｅｒｏｃｙｃｌｉｃ．Ｃｈｅｍ．），１５，１４３１
（１９７８）には、２−（２−ピリジル）エタノールを
塩化チオニルで塩素化し水硫化カリウムと反応させ２−
（２−ピリジル）エタンチオールを製造する方法が、ヒ
ェーミッシェ・ベリヒテ（Ｃｈｅｍ．Ｂｅｒ．），８
６，７８１（１９５３）には、２−（２−ピリジル）エ
タンチオールをチオ尿素と臭化水素酸水溶液からイソチ
ウロニウム塩を合成し、水酸化ナトリウムで分解し２−
（２−ピリジル）エタンチオールを製造する方法が、ま
た、ジャーナル・オブ・オーガニック・ケミストリー
（Ｊ．Ｏｒｇ．Ｃｈｅｍ．），２６，８２（１９６１）
には、４−ビニルピリジンとチオ尿素、パラトルエンス
ルホン酸よりイソチウロニウム塩を合成し、７〜８当量
倍のアンモニア水で塩分解し２−（４−ピリジル）エタ
ンチオールを製造する方法等が報告されている。これら
公知の製造方法の中では、原料、助剤の入手の難易、取
り扱い易さ、収率の点で、前記ジャーナル・オブ・オー
ガニック・ケミストリーの方法が最も優れている。2. Description of the Related Art Various proposals have been made for the synthesis of pyridylalkylthiols (mercaptoalkylpyridines). For example, the Australian Journal of Chemistry (Aust.
Chem. ), 19, 1835 (1966)
A method for producing 2- (2-pyridyl) ethanethiol from vinylpyridine and hydrogen sulfide is disclosed in US Pat.
No. 7,776 describes a method of synthesizing an acetylthio form from 2-vinylpyridine and thioacetic acid to produce 2- (2-pyridyl) ethanethiol with hydrochloric acid, according to the Journal of Heterocyclic Chemistry (J. .He
terocyclic. Chem. ), 15,1431
(1978) describes that 2- (2-pyridyl) ethanol was chlorinated with thionyl chloride and reacted with potassium hydrosulfide to obtain 2- (2-pyridyl) ethanol.
A method for producing (2-pyridyl) ethanethiol is disclosed in Chem. Berchte, Chem.
No. 6,781 (1953), 2- (2-pyridyl) ethanethiol is synthesized from thiourea and an aqueous solution of hydrobromic acid to synthesize an isothiuronium salt, which is decomposed with sodium hydroxide to give 2- (2-pyridyl) ethanethiol.
A method for producing (2-pyridyl) ethanethiol is also described in Journal of Organic Chemistry (J. Org. Chem.), 26, 82 (1961).
Reported a method of synthesizing an isothiuronium salt from 4-vinylpyridine, thiourea, and p-toluenesulfonic acid, and decomposing the salt with 7 to 8 equivalents of aqueous ammonia to produce 2- (4-pyridyl) ethanethiol. Have been. Among these known production methods, the above-mentioned Journal of Organic Chemistry method is the most excellent in terms of difficulty in obtaining raw materials and auxiliaries, ease of handling, and yield.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、この製
造方法についても、イソチウロニウム塩の収率が９０％
であり、引き続く２−（４−ピリジル）エタンチオール
の全収率が６４％と低く、また溶媒であるエタノール
は、沸点が低く且つ高価であり、工業的には有利な製造
方法とは言えない。本発明は、イソチウロニウム塩及び
２−（４−ピリジル）エタンチオールの、安価且つ高収
率な工業的製造方法を提供することを目的とする。However, even in this production method, the yield of isothiuronium salt is 90%.
The total yield of subsequent 2- (4-pyridyl) ethanethiol is as low as 64%, and ethanol as a solvent has a low boiling point and is expensive, and cannot be said to be an industrially advantageous production method. . An object of the present invention is to provide an inexpensive and high-yield industrial production method of isothiuronium salt and 2- (4-pyridyl) ethanethiol.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、かかる事
情に鑑み鋭意検討した結果、イソチウロニウム塩製造時
に、溶媒として２−プロパノールを用いると、塩の溶解
度が低下し、イソチウロニウム塩が析出しやすくなり、
そのためイソチウロニウム塩の回収率が向上することを
見い出し、本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted intensive studies in view of the above circumstances. As a result, when 2-propanol is used as a solvent during the production of an isothiuronium salt, the solubility of the salt is reduced, and the isothiuronium salt precipitates. Easier,
As a result, the inventors have found that the recovery of isothiuronium salt is improved, and have completed the present invention.
【０００５】即ち、本発明の要旨は、１．４−ビニルピ
リジン、チオ尿素及び酸を２−プロパノール中で反応さ
せることを特徴とする下記一般式（Ｉ）で示されるイソ
チウロニウム塩の製造方法、That is, the gist of the present invention is to provide a method for producing an isothiuronium salt represented by the following general formula (I), which comprises reacting 1.4-vinylpyridine, thiourea and an acid in 2-propanol.
【０００６】[0006]
【化２】 Embedded image
【０００７】（式中、Ｘ- は使用する酸に対応するアニ
オンを示す）[0007] (wherein, X - represents an anion corresponding to the acid used)
【０００８】２．１項に記載された方法により得られた
式（Ｉ）で示されるイソチウロニウム塩をアンモニア水
により分解することを特徴とする２−（４−ピリジル）
エタンチオールの製造方法、にある。以下、本発明につ
いて詳細に説明する。2- (4-pyridyl) characterized in that the isothiuronium salt of the formula (I) obtained by the method described in section 2.1 is decomposed with aqueous ammonia.
Production method of ethanethiol. Hereinafter, the present invention will be described in detail.
【０００９】[0009]
【発明の実施の形態】本発明における目的化合物の一つ
である式（Ｉ）で示されるイソチウロニウム塩は、４−
ビニルピリジン、チオ尿素及び酸を２−プロパノール中
で反応させることにより得られる。BEST MODE FOR CARRYING OUT THE INVENTION The isothiuronium salt represented by the formula (I) which is one of the target compounds in the present invention is
It is obtained by reacting vinylpyridine, thiourea and acid in 2-propanol.
【００１０】原料の中、４−ビニルピリジンについて
は、市販の試薬をそのまま用いても特に大きな問題はな
いが、古い試薬では着色が濃い場合や、多少重合による
変質が懸念されるため反応前に単蒸留等の前処理を行う
ことが好ましい。酸としては、塩酸、硝酸、硫酸等の一
般的な無機酸やパラトルエンスルホン酸、ベンゼンスル
ホン酸、トリフルオロメタンスルホン酸等の有機酸を使
用することができる。イソチウロニウム塩の取り扱い易
さ等から、パラトルエンスルホン酸、ベンゼンスルホン
酸、塩酸が好ましく、パラトルエンスルホン酸、ベンゼ
ンスルホン酸が特に好ましい。本発明の特徴である反応
時の溶媒としては、２−プロパノールを使用するが、本
発明の効果を損なわない限りにおいて、他の低級アルコ
ール、例えばエタノール等を５０％以下、好ましくは２
０％以下併用することも可能である。[0010] Among the raw materials, 4-vinylpyridine is not particularly problematic even if a commercially available reagent is used as it is, but the old reagent may have a strong coloration or may be slightly deteriorated due to polymerization. Pretreatment such as simple distillation is preferably performed. As the acid, a common inorganic acid such as hydrochloric acid, nitric acid, and sulfuric acid, and an organic acid such as paratoluenesulfonic acid, benzenesulfonic acid, and trifluoromethanesulfonic acid can be used. From the viewpoint of easy handling of the isothiuronium salt, paratoluenesulfonic acid, benzenesulfonic acid and hydrochloric acid are preferable, and paratoluenesulfonic acid and benzenesulfonic acid are particularly preferable. 2-propanol is used as a solvent during the reaction, which is a feature of the present invention. However, as long as the effects of the present invention are not impaired, other lower alcohols, such as ethanol, may be 50% or less, preferably 2% or less.
It is also possible to use 0% or less together.
【００１１】以下、反応条件の詳細について、酸とし
て、パラトルエンスルホン酸を使用した場合について説
明する。イソチウロニウム塩製造時の２−プロパノール
に対するパラトルエンスルホン酸の仕込み量は、５〜６
０重量％であり、好ましくは３０〜５０重量％である。
パラトルエンスルホン酸の仕込み量が５重量％よりも少
ない場合には、生成するイソチウロニウム塩の析出量が
減るために回収量が減少し、６０重量％よりも多い場合
には、パラトルエンスルホン酸が十分に溶解せずイソチ
ウロニウム塩の収率低下を招く。Hereinafter, the reaction conditions will be described in detail when para-toluenesulfonic acid is used as the acid. The amount of paratoluenesulfonic acid charged to 2-propanol during production of the isothiuronium salt is 5-6.
0% by weight, preferably 30 to 50% by weight.
When the charged amount of paratoluenesulfonic acid is less than 5% by weight, the amount of recovered isothiuronium salt is reduced because the amount of precipitated isothiuronium salt is reduced, and when the charged amount is more than 60% by weight, paratoluenesulfonic acid is reduced. It does not dissolve sufficiently and causes a decrease in the yield of the isothiuronium salt.
【００１２】反応は４−ビニルピリジンとモル比で０．
５〜１．５、好ましくは０．８〜１．２のチオ尿素、モ
ル比で１．８〜３．６好ましくは２．２〜３．０のパラ
トルエンスルホン酸を仕込み、その後に、２−プロパノ
ール溶媒を加え、好ましくは窒素等の不活性ガス雰囲気
下、５０〜１００℃、好ましくは７０〜８０℃に加温
し、チオ尿素等を溶解させる。その後、７０〜９０℃に
加熱、撹拌下、４−ビニルピリジンを滴下し、その後、
還流下１〜５時間反応を行う。反応終了後、反応液を冷
却することにより、塩を析出させ、該塩を濾過し、乾燥
エーテル等で洗浄する。好ましくは、更にエーテル／イ
ソプロピルアルコール混合液等でもう一度洗浄する。洗
浄後の塩を、好ましくは乾燥後、２−（４−ピリジル）
エタンチオールの製造に使用する。The reaction is carried out with 4-vinylpyridine in a molar ratio of 0.1.
5 to 1.5, preferably 0.8 to 1.2 thiourea, and 1.8 to 3.6, preferably 2.2 to 3.0, molar ratio of paratoluenesulfonic acid are charged. -A propanol solvent is added, and the mixture is heated to 50 to 100C, preferably 70 to 80C, preferably in an atmosphere of an inert gas such as nitrogen to dissolve thiourea and the like. Thereafter, 4-vinylpyridine is added dropwise while heating and stirring at 70 to 90 ° C.
The reaction is performed under reflux for 1 to 5 hours. After completion of the reaction, the reaction solution is cooled to precipitate a salt, and the salt is filtered and washed with dry ether or the like. Preferably, it is further washed once with an ether / isopropyl alcohol mixture or the like. The salt after washing, preferably after drying, is 2- (4-pyridyl)
Used for the production of ethanethiol.
【００１３】本発明における最終目的化合物である、下
記式（II）で示される２−（４−ピリジル）エタンチオ
ールは、イソチウロニウム塩をアンモニア水で分解する
ことにより、容易に製造することができる。この２−
（４−ピリジル）エタンチオールは、各種医農薬中間体
や、フェノールとアセトンとの縮合反応によりビスフェ
ノールＡを製造する際の触媒（変性剤）として有用な化
合物である。The final target compound of the present invention, 2- (4-pyridyl) ethanethiol represented by the following formula (II), can be easily produced by decomposing an isothiuronium salt with aqueous ammonia. This 2-
(4-Pyridyl) ethanethiol is a compound useful as a catalyst (denaturing agent) for producing bisphenol A by a condensation reaction between various medical and agricultural chemical intermediates and phenol and acetone.
【００１４】[0014]
【化３】 Embedded image
【００１５】２−（４−ピリジル）エタンチオールの製
造方法としては、イソチウロニウム塩のアンモニア水に
よる塩分解反応であるが、この時、使用するアンモニア
は塩に対して１．５〜７．５当量が好ましく、１．５〜
２．５当量が更に好ましい。アンモニア量が１．５当量
よりも少ない場合には反応が十分に進行せず、７．５当
量よりも多い場合には不必要なアンモニアの中和に多大
の労力を費やすことや、目的物の２−（４−ピリジル）
エタンチオールの一部劣化によると思われる収率低下を
招く。The method for producing 2- (4-pyridyl) ethanethiol is a salt decomposition reaction of an isothiuronium salt with aqueous ammonia. At this time, the amount of ammonia used is 1.5 to 7.5 equivalents to the salt. Is preferred, and 1.5 to
2.5 equivalents are more preferred. When the amount of ammonia is less than 1.5 equivalents, the reaction does not proceed sufficiently. When the amount of ammonia is more than 7.5 equivalents, a great deal of labor is required for neutralizing unnecessary ammonia, 2- (4-pyridyl)
This leads to a decrease in yield, which is considered to be caused by partial degradation of ethanethiol.
【００１６】使用するアンモニア水のアンモニア濃度
は、低いことが好ましく、５〜３０重量％の範囲で使用
することが更に好ましく、５〜１５重量％が最も好まし
い。５重量％より低い場合には反応が遅くなり且つ釜効
率が著しく低下して好ましくなく、また３０重量％より
も高い場合には、塩分解反応時の撹拌が難しくなり、こ
れまた好ましくはない。塩分解反応温度は５０〜７０℃
で行うことが好ましい。また反応時間はおよそ０．５〜
１０時間の範囲が好ましく、０．５〜３時間の範囲がよ
り好ましい。この際、アンモニアが加熱により発生する
ため、酸、水等による発生アンモニアの吸着等何らかの
手段でアンモニアの除去を行うことが好ましい。The ammonia concentration of the aqueous ammonia used is preferably low, more preferably in the range of 5 to 30% by weight, most preferably 5 to 15% by weight. If the amount is less than 5% by weight, the reaction becomes slow and the kettle efficiency remarkably decreases, which is not preferable. If the amount is more than 30% by weight, stirring during the salt decomposition reaction becomes difficult, which is not preferable. Salt decomposition reaction temperature is 50-70 ° C
It is preferable to carry out in. The reaction time is about 0.5 ~
A range of 10 hours is preferable, and a range of 0.5 to 3 hours is more preferable. At this time, since ammonia is generated by heating, it is preferable to remove ammonia by some means such as adsorption of the generated ammonia by acid, water or the like.
【００１７】塩分解反応後、反応液から目的の２−（４
−ピリジル）エタンチオールを得るには、公知の任意の
方法が採用できるが、具体例を示せば、反応液を１０℃
程度まで冷却し、反応液中にクロロホルム等の抽出溶媒
を加えた後、濾過を行う。得られた固体（グアニジウム
塩）を更に溶媒で一〜二回洗浄した後、母液を分液して
有機層を回収し水層を更に数回溶媒で抽出し２−（４−
ピリジル）エタンチオールを回収する。得られた有機層
は先ず溶媒を留去して残液から減圧蒸留により目的の２
−（４−ピリジル）エタンチオールを得る等の方法が例
示できる。After the salt decomposition reaction, the desired 2- (4
-Pyridyl) ethanethiol can be obtained by any known method. In a specific example, the reaction solution is heated at 10 ° C.
After cooling to a degree, an extraction solvent such as chloroform is added to the reaction solution, followed by filtration. After the obtained solid (guanidium salt) is further washed once or twice with a solvent, the mother liquor is separated, the organic layer is recovered, and the aqueous layer is further extracted several times with the solvent.
The pyridyl) ethanethiol is recovered. The obtained organic layer is first distilled off the solvent, and the remaining liquid is distilled under reduced pressure to obtain the desired 2
A method of obtaining-(4-pyridyl) ethanethiol can be exemplified.
【００１８】[0018]
【実施例】次に実施例及び比較例により、本発明をさら
に具体的に説明するが、本発明は、その要旨を超えない
限り実施例に限定されるものではない。Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the examples unless it exceeds the gist thereof.
【００１９】実施例１ 容積２００ｍｌの四つ口フラスコに温度計、ジムロート
冷却管、滴下ロートを取り付けパラトルエンスルホン酸
−水和物（和光純薬工業株式会社製）２０．９ｇ（０．
１１モル）チオ尿素（和光純薬工業株式会社製）３．８
ｇ（０．０５モル）と２−プロパノール５０ｍｌを仕込
んだ。窒素雰囲気下、撹拌しながら７０℃まで昇温し
た。パラトルエンスルホン酸及びチオ尿素は５０〜６０
℃で全量溶解した。反応液が７０℃到達後、滴下ロート
より４−ビニルピリジン（和光純薬工業株式会社製）
５．２５ｇ（０．０５モル）を発熱に注意しながら約
０．５時間で滴下し、その後還流下３時間反応を行っ
た。反応終了後、反応液を冷却し、約６０℃で固体の析
出が確認されたが、冷却を続け５℃まで冷却した。析出
した固体：Ｓ−［２−（４−ピリジニウム）エチル］イ
ソチウロニウム ビ−パラ−トルエンスルホネート
（略；イソチウロニウム塩）を濾過により分取し、得ら
れた塩をエーテル３０ｍｌで洗浄し、更に冷却したエー
テル／イソプロピルアルコール混合液（１：１）６０ｍ
ｌで洗浄し、過剰のパラトルエンスルホン酸を除去し
た。洗浄後の塩を減圧乾燥し秤量したところ、２６．０
ｇ（０．０４９モル）収率９８．０％であった。得られ
たイソチウロニウム塩２６．０ｇを２５％アンモニア水
１３．５ｇ（アンモニア；０．１９８モル）と水２０．
２ｍｌの混合液に溶解し、０．５時間６０℃で反応後、
冷却しクロロホルム１３．０ｍｌを加えて、濾別して生
成塩を分離した。濾液を分液後、更にクロロホルム１０
ｍｌで八回抽出を繰り返し得られたクロロホルム層を合
わせ減圧下クロロホルムを回収し、残液を減圧蒸留し
た。沸点８７〜８８℃／２．２ｍｍＨｇで２−（４−ピ
リジル）エタンチオール５．０ｇ（０．０３５モル）が
得られた。得られた２−（４−ピリジル）エタンチオー
ルはガスクロマトグラフィー分析の結果、純度９９．６
％であった。４−ビニルピリジンよりの全収率は７１〜
７２％であった。 Example 1 A thermometer, a Dimroth condenser, and a dropping funnel were attached to a 200 ml four-necked flask, and 20.9 g of paratoluenesulfonic acid hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added.
11 mol) thiourea (manufactured by Wako Pure Chemical Industries, Ltd.) 3.8
g (0.05 mol) and 50 ml of 2-propanol were charged. The temperature was raised to 70 ° C. while stirring in a nitrogen atmosphere. 50-60 for paratoluenesulfonic acid and thiourea
The whole amount was dissolved at ℃. After the reaction solution reaches 70 ° C., 4-vinylpyridine (manufactured by Wako Pure Chemical Industries, Ltd.) is dropped from the dropping funnel.
5.25 g (0.05 mol) was added dropwise in about 0.5 hour while paying attention to heat generation, and then the reaction was carried out under reflux for 3 hours. After the completion of the reaction, the reaction solution was cooled, and solid deposition was confirmed at about 60 ° C. However, the cooling was continued and cooled to 5 ° C. Precipitated solid: S- [2- (4-pyridinium) ethyl] isothiuronium bi-para-toluenesulfonate (abbreviation; isothiuronium salt) was separated by filtration, and the obtained salt was washed with 30 ml of ether and further cooled. Ether / isopropyl alcohol mixture (1: 1) 60m
1 to remove excess paratoluenesulfonic acid. The washed salt was dried under reduced pressure and weighed to find that it was 26.0.
g (0.049 mol) The yield was 98.0%. The obtained isothiuronium salt (26.0 g) was combined with 25% aqueous ammonia (13.5 g, ammonia; 0.198 mol) and water (20.50 g).
After dissolving in 2 ml of the mixture and reacting at 60 ° C. for 0.5 hour,
The mixture was cooled, 13.0 ml of chloroform was added, and the mixture was filtered to separate the formed salt. After separating the filtrate, chloroform 10 was added.
The chloroform layer obtained by repeating extraction eight times with ml was combined, chloroform was recovered under reduced pressure, and the remaining liquid was distilled under reduced pressure. 5.0 g (0.035 mol) of 2- (4-pyridyl) ethanethiol was obtained at a boiling point of 87 to 88 ° C./2.2 mmHg. The obtained 2- (4-pyridyl) ethanethiol was analyzed by gas chromatography to find that the purity was 99.6.
%Met. The total yield from 4-vinylpyridine is 71 to
72%.
【００２０】比較例１［Ｊ．Ｏｒｇ．Ｃｈｅｍ．，２
６，８２（１９６１）の追試］ 容積２００ｍｌの四つ口フラスコに温度計、ジムロート
冷却管、滴下ロートを取り付け、パラトルエンスルホン
酸−水和物（和光純薬工業株式会社製）２０．９ｇ
（０．１１モル）、チオ尿素（和光純薬工業株式会社
製）３．８ｇ（０．０５モル）とエタノール５０ｍｌを
仕込んだ。窒素雰囲気下、撹拌しながら７０℃まで昇温
した。パラトルエンスルホン酸及びチオ尿素は５０〜６
０℃で全量溶解した。反応液が７０℃到達後、滴下ロー
トより４−ビニルピリジン（和光純薬工業株式会社製）
５．２５ｇ（０．０５モル）を発熱に注意しながら約
０．５時間で滴下し、その後還流下３時間反応を行っ
た。反応終了後、反応液を冷却し、約６０℃で固体の析
出が確認されたが、冷却を続け５℃まで冷却した。析出
したイソチウロニウム塩を濾過により分取し、得られた
塩をエーテル３０ｍｌで洗浄し、更に冷却したエーテル
／エタノール混合液（１：１）６０ｍｌで洗浄し、過剰
のパラトルエンスルホン酸を除去した。洗浄後の塩を、
実施例１と同様に、減圧乾燥し、秤量したところ、２
３．５ｇ（０．０４５モル）収率８９．６％であった。
得られたイソチウロニウム塩２３．５ｇを２５％アン
モニア水１２．２ｇ（アンモニア；０．１７９モル）と
水１８．３ｍｌの混合液に溶解し、０．５時間６０℃で
反応後、冷却しクロロホルム１２．１ｍｌを加えて、濾
別して生成塩を分離した。濾液を分液後、更にクロロホ
ルム１０ｍｌで八回抽出を繰り返し得られたクロロホル
ム層を合わせ減圧下クロロホルムを回収し、残液を減圧
蒸留した。沸点８７〜８８℃／２．２ｍｍＨｇで２−
（４−ピリジル）エタンチオール４．５ｇ（０．０３２
モル）が得られた。得られた２−（４−ピリジル）エタ
ンチオールはガスクロマトグラフィー分析の結果、純度
９９．５％であった。４−ビニルピリジンよりの全収率
は６４％であった。［文献値 ４−ビニルピリジンより
の収率６４．８％］ Comparative Example 1 [J. Org. Chem. , 2
6,82 (1961)] A thermometer, a Dimroth condenser, and a dropping funnel were attached to a 200 ml four-necked flask, and 20.9 g of paratoluenesulfonic acid-hydrate (manufactured by Wako Pure Chemical Industries, Ltd.)
(0.11 mol), 3.8 g (0.05 mol) of thiourea (manufactured by Wako Pure Chemical Industries, Ltd.) and 50 ml of ethanol were charged. The temperature was raised to 70 ° C. while stirring in a nitrogen atmosphere. 50 to 6 for paratoluenesulfonic acid and thiourea
The whole amount was dissolved at 0 ° C. After the reaction solution reaches 70 ° C., 4-vinylpyridine (manufactured by Wako Pure Chemical Industries, Ltd.) is dropped from the dropping funnel.
5.25 g (0.05 mol) was added dropwise in about 0.5 hour while paying attention to heat generation, and then the reaction was carried out under reflux for 3 hours. After the completion of the reaction, the reaction solution was cooled, and solid deposition was confirmed at about 60 ° C. However, the cooling was continued and cooled to 5 ° C. The precipitated isothiuronium salt was separated by filtration, and the obtained salt was washed with 30 ml of ether, and further washed with 60 ml of a cooled ether / ethanol mixture (1: 1) to remove excess paratoluenesulfonic acid. After washing the salt,
After drying under reduced pressure and weighing in the same manner as in Example 1, 2
The yield was 3.5 g (0.045 mol) 89.6%.
23.5 g of the obtained isothiuronium salt was dissolved in a mixture of 12.2 g of 25% aqueous ammonia (ammonia; 0.179 mol) and 18.3 ml of water, reacted for 0.5 hour at 60 ° C., cooled, and cooled. .1 ml was added, and the resulting salt was separated by filtration. After separating the filtrate, extraction was further repeated eight times with chloroform (10 ml). The obtained chloroform layers were combined, chloroform was recovered under reduced pressure, and the remaining liquid was distilled under reduced pressure. Boiling point 87-88 ° C / 2.2mmHg 2-
4.5 g of (4-pyridyl) ethanethiol (0.032
Mol) was obtained. As a result of gas chromatography analysis, the obtained 2- (4-pyridyl) ethanethiol had a purity of 99.5%. The overall yield from 4-vinylpyridine was 64%. [Literature: 64.8% yield from 4-vinylpyridine]
【００２１】[0021]
【発明の効果】本発明の方法によれば、各種医農薬中間
体又はビスフェノールＡ製造触媒等に使用される２−
（４−ピリジル）エタンチオール製造の中間体であるイ
ソチウロニウム塩を、溶媒に安価な２−プロパノールを
使用することによって、従来法のエタノールを使用する
場合よりも高収率で、しかも安価に製造することができ
る。According to the method of the present invention, 2- (2) -dichloromethane used as an intermediate for various medical and agricultural chemicals or a catalyst for producing bisphenol A is used.
By using inexpensive 2-propanol as a solvent, an isothiuronium salt, which is an intermediate for the production of (4-pyridyl) ethanethiol, is produced at a higher yield and at lower cost than when using conventional ethanol. be able to.
Claims (5)
２−プロパノール中で反応させることを特徴とする下記
一般式（Ｉ）で示されるイソチウロニウム塩の製造方
法。 【化１】 （式中、Ｘ- は使用する酸に対応するアニオンを示す）1. A method for producing an isothiuronium salt represented by the following general formula (I), wherein 4-vinylpyridine, thiourea and an acid are reacted in 2-propanol. Embedded image (Wherein, X - represents an anion corresponding to the acid used)
を特徴とする請求項１に記載のイソチウロニウム塩の製
造方法。2. The method for producing an isothiuronium salt according to claim 1, wherein the acid is paratoluenesulfonic acid.
スルホン酸の仕込み量が５〜６０重量％であることを特
徴とする請求項２に記載のイソチウロニウム塩の製造方
法。3. The method for producing an isothiuronium salt according to claim 2, wherein the amount of paratoluenesulfonic acid charged to 2-propanol is 5 to 60% by weight.
た式（Ｉ）で示されるイソチウロニウム塩をアンモニア
水により分解することを特徴とする２−（４−ピリジ
ル）エタンチオールの製造方法。4. A method for producing 2- (4-pyridyl) ethanethiol, comprising decomposing an isothiuronium salt represented by the formula (I) obtained by the method according to claim 1 with aqueous ammonia.
アンモニア水を用いる請求項４に記載の２−（４−ピリ
ジル）エタンチオールの製造方法。5. The method for producing 2- (4-pyridyl) ethanethiol according to claim 4, wherein aqueous ammonia having an ammonia concentration of 5 to 15% by weight is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06079498A JP3960678B2 (en) | 1998-03-12 | 1998-03-12 | Method for producing isothiuronium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06079498A JP3960678B2 (en) | 1998-03-12 | 1998-03-12 | Method for producing isothiuronium salt |
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| Publication Number | Publication Date |
|---|---|
| JPH11255748A true JPH11255748A (en) | 1999-09-21 |
| JP3960678B2 JP3960678B2 (en) | 2007-08-15 |
Family
ID=13152580
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|---|---|---|---|
| JP06079498A Expired - Fee Related JP3960678B2 (en) | 1998-03-12 | 1998-03-12 | Method for producing isothiuronium salt |
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