JPH0987277A - Production of 1,2-dithiol-3-thione derivative - Google Patents
Production of 1,2-dithiol-3-thione derivativeInfo
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- JPH0987277A JPH0987277A JP25117595A JP25117595A JPH0987277A JP H0987277 A JPH0987277 A JP H0987277A JP 25117595 A JP25117595 A JP 25117595A JP 25117595 A JP25117595 A JP 25117595A JP H0987277 A JPH0987277 A JP H0987277A
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- group
- carbon atoms
- dithiol
- general formula
- sulfur
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- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、１，２−ジチオー
ル−３−チオン誘導体の製造法に関する。TECHNICAL FIELD The present invention relates to a method for producing a 1,2-dithiol-3-thione derivative.
【０００２】[0002]
【従来の技術】一般式（１）で示される１，２−ジチオ
ール−３−チオン誘導体は、医薬品として有用である一
般式（３）［化３］BACKGROUND OF THE INVENTION A 1,2-dithiol-3-thione derivative represented by the general formula (1) is useful as a drug in the general formula (3) [Chemical Formula 3]
【０００３】[0003]
【化３】 （式中、Ａはメチレン基または酸素原子を表し、Ｒ1、
Ｒ2はそれぞれ独立して水素原子、ヒドロキシル基、ハ
ロゲン原子、炭素数１から４の低級アルキル基または炭
素数１から４の低級アルコキシ基を表す。またＡがメチ
レン基のとき、ｎは０から３の整数を表し、Ａが酸素原
子のとき、ｎは１から３の整数を表す。Ｍはアルカリ金
属またはアルカリ土類金属であり、ｍはＭがアルカリ金
属の場合１、Ｍがアルカリ土類金属の場合１／２であ
る）で示される化合物の製造において重要な中間体であ
る。Embedded image (In the formula, A represents a methylene group or an oxygen atom, R 1 ,
R 2's each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms or a lower alkoxy group having 1 to 4 carbon atoms. When A is a methylene group, n represents an integer of 0 to 3, and when A is an oxygen atom, n represents an integer of 1 to 3. M is an alkali metal or alkaline earth metal, m is 1 when M is an alkali metal, and 1/2 when M is an alkaline earth metal) is an important intermediate in the production of the compound.
【０００４】一般式（１）で示される化合物の製造につ
いては、ヨーロッパ公開特許EP0641792に例示されるベ
ンゼン、トルエン、ピリジンなどの溶媒中、一般式
（２）で示される化合物または一般式（４）［化４］Regarding the production of the compound represented by the general formula (1), the compound represented by the general formula (2) or the general formula (4) in a solvent such as benzene, toluene or pyridine exemplified in European Patent Publication EP0641792. [Chemical 4]
【０００５】[0005]
【化４】 （式中、Ａ、Ｒ1、Ｒ2およびｎは前記と同義であり、Ｒ
4は炭素数１から４までの低級アルキル基を表す）で示
される３−オキソエステルを五硫化リンもしくはローソ
ン試薬［２，４−ビス（４−メトキシフェニル）−１，
３−ジチア−２，４−ジホスホエタン−２，４−ジスル
フィド］などのチオネート剤と反応させる方法が知られ
ている。しかしこれらは一般に収率が低く（30〜40%程
度）、工業的な製造を考慮すると好ましい方法ではな
い。また、Liebigs Annalen der Chemie, 129 (1960)に
開示されている３−オキソエステルと五硫化リンの反応
に硫黄を添加する方法によれば、収率の若干の改善が報
告されているものの、これも満足し得るものではない。Embedded image (In the formula, A, R 1 , R 2 and n are as defined above, and R
4 represents a lower alkyl group having 1 to 4 carbon atoms) and a 3-oxoester represented by phosphorus pentasulfide or Lawesson's reagent [2,4-bis (4-methoxyphenyl) -1,
A method of reacting with a thionate agent such as 3-dithia-2,4-diphosphoethane-2,4-disulfide] is known. However, these are generally low in yield (about 30 to 40%) and are not preferable methods in view of industrial production. According to the method of adding sulfur to the reaction of 3-oxoester and phosphorus pentasulfide disclosed in Liebigs Annalen der Chemie, 129 (1960), although a slight improvement in yield is reported, Is not satisfactory either.
【０００６】[0006]
【発明が解決しようとする課題】本発明の課題は、効率
的な１，２−ジチオール−３−チオン誘導体の製造法を
提供することにある。An object of the present invention is to provide an efficient method for producing a 1,2-dithiol-3-thione derivative.
【０００７】[0007]
【課題を解決するための手段】本発明者らは上記課題を
解決すべく鋭意検討したところ、驚くべきことに一般式
（２）で示される化合物を出発原料にし、かつ五硫化リ
ンと反応させる際に、硫黄を添加した場合にのみ収率が
著しく向上することを見い出し、本発明を完成した。す
なわち、本発明は一般式（１）［化５］Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems, and surprisingly found that the compound represented by the general formula (2) is used as a starting material and reacted with phosphorus pentasulfide. At this time, it was found that the yield was significantly improved only when sulfur was added, and the present invention was completed. That is, the present invention has the general formula (1)
【０００８】[0008]
【化５】 （式中、Ａはメチレン基または酸素原子を表し、Ｒ1、
Ｒ2はそれぞれ独立して水素原子、ヒドロキシル基、ハ
ロゲン原子、炭素数１から４の低級アルキル基または炭
素数１から４の低級アルコキシ基を表す。またＡがメチ
レン基のとき、ｎは０から３の整数を表し、Ａが酸素原
子のとき、ｎは１から３の整数を表す）で示される化合
物の製造において、一般式（２）［化６］で示される化
合物Embedded image (In the formula, A represents a methylene group or an oxygen atom, R 1 ,
R 2's each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms or a lower alkoxy group having 1 to 4 carbon atoms. Further, when A is a methylene group, n represents an integer of 0 to 3, and when A is an oxygen atom, n represents an integer of 1 to 3) in the production of the compound represented by the general formula (2) 6]
【０００９】[0009]
【化６】 （式中、Ａはメチレン基または酸素原子を表し、Ｒ1、
Ｒ2はそれぞれ独立して水素原子、ヒドロキシル基、ハ
ロゲン原子、炭素数１から４の低級アルキル基または炭
素数１から４の低級アルコキシ基を表す。またＡがメチ
レン基のとき、ｎは０から３の整数を表し、Ａが酸素原
子のとき、ｎは１から３の整数を表す。Ｒ3は、炭素数
１から４の低級アルキル基またはＲ3同士連結して炭素
数２から４のアルキレン基を表す）を五硫化リンと反応
させる際に、硫黄を添加することを特徴とする製造法を
提供するものである。[Chemical 6] (In the formula, A represents a methylene group or an oxygen atom, R 1 ,
R 2's each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms or a lower alkoxy group having 1 to 4 carbon atoms. When A is a methylene group, n represents an integer of 0 to 3, and when A is an oxygen atom, n represents an integer of 1 to 3. R 3 is a lower alkyl group having 1 to 4 carbon atoms or R 3 is linked to each other to represent an alkylene group having 2 to 4 carbon atoms), and sulfur is added when reacting with phosphorus pentasulfide. It provides a manufacturing method.
【００１０】[0010]
【発明の実施の形態】以下、本発明をさらに詳しく説明
する。先ず、一般式（１）および一般式（２）で示され
る化合物について説明を加える。ハロゲン原子として
は、フッ素原子、塩素原子、臭素原子、ヨウ素原子を挙
げることができる。炭素数１から４の低級アルキル基と
は、例えばメチル基、エチル基、ｎ−プロピル基、イソ
プロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブ
チル基、ｔｅｒｔ−ブチル基などを挙げることができ
る。炭素数１から４の低級アルコシキ基とは、例えばメ
トキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポ
キシ基、アリルオキシ基、ｎ−ブトキシ基、イソブトキ
シ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基を挙
げることができる。添加する硫黄の量は、一般式（２）
で示される化合物１モルに対して、１モルから１０モル
であり、好ましくは２モルから１０モルであり、さらに
好ましくは２モルから５モルである。一般式（２）で示
される化合物１モルに対して、硫黄の添加量が１モル未
満では収率の向上が見られず、一方１０モルを越えると
脱水素反応などの副反応が起こる不都合がある。なお、
本発明の一般式（１）で示される化合物の製造におい
て、原料として用いる一般式（２）で示される化合物
は、ヨーロッパ公開特許EP0641792、Chemical and Phar
maceutical Bulletin, 36, 401 (1988)などに開示され
ている方法により製造することができる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. First, the compounds represented by the general formula (1) and the general formula (2) will be described. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the lower alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. . Examples of the lower alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, allyloxy group, n-butoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group. be able to. The amount of sulfur added is determined by the general formula (2)
The amount is 1 mol to 10 mol, preferably 2 mol to 10 mol, and more preferably 2 mol to 5 mol, relative to 1 mol of the compound represented by. When the amount of sulfur added is less than 1 mol per 1 mol of the compound represented by the general formula (2), the yield is not improved. On the other hand, when it exceeds 10 mol, a side reaction such as dehydrogenation reaction occurs. is there. In addition,
In the production of the compound represented by the general formula (1) of the present invention, the compound represented by the general formula (2) used as a raw material is a compound disclosed in European Patent Publication EP0641792, Chemical and Phar.
It can be produced by the method disclosed in maceutical Bulletin, 36 , 401 (1988) and the like.
【００１１】すなわち、一般式（５）［化７］That is, the general formula (5) [Chemical formula 7]
【００１２】[0012]
【化７】 （式中、Ａ、Ｒ1、Ｒ2およびｎは前記と同義）で示され
るケトンを適当な塩基存在下、二硫化炭素および適当な
ハロゲン化アルキルまたは硫酸エステルなどのアルキル
化剤と反応させる方法により製造することができる。[Chemical 7] A method of reacting a ketone represented by the formula (wherein A, R 1 , R 2 and n are as defined above) with carbon disulfide and an alkylating agent such as a suitable alkyl halide or sulfuric ester in the presence of a suitable base. Can be manufactured by.
【００１３】[0013]
【実施例】以下、実施例、比較実施例を挙げて本発明を
さらに具体的に説明するが、本発明はこれらによって限
定されるものではない。 実施例１４，５−ジヒドロ−７−メトキシ−３Ｈ−ナフト［１，
２−ｃ］−１，２−ジチオール−３−チオンの製造 第１工程 ２−ビス（メチルチオ）メチリデン−６−メ
トキシ−１−テトラロンの合成 ６−メトキシ−１−テトラロン20gのＤＭＳＯ（100ml）
溶液に、30%水酸化ナトリウム水溶液36mlを加え、室温
にて１時間攪拌した。次に、二硫化炭素8.6g、ジメチル
硫酸40gを各々30分かけて滴下し、さらに1時間攪拌し
た。反応溶液を水200mlにあけ、析出した結晶を濾集し
た。水100mlおよびメタノール100mlで洗浄後、メタノー
ルから再結晶を行い、目的物19.7gを得た（収率62%）。 融点78℃ 1H NMR(CDCl3,δ):2.39(3H,s), 2.45(3H,s), 2.95(2H,
t), 3.23-3.28(2H,m), 3.85(3H,m), 6.69(1H,d), 6.84
(1H,dd), 8.08(1H,d).EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1 4,5-Dihydro-7-methoxy-3H-naphtho [1,
Preparation of 2-c] -1,2-dithiol-3-thione 1st step 2-bis (methylthio) methylidene-6-me
Synthesis of toxy-1-tetralone 6-methoxy-1-tetralone 20 g DMSO (100 ml)
36 ml of 30% aqueous sodium hydroxide solution was added to the solution, and the mixture was stirred at room temperature for 1 hour. Next, 8.6 g of carbon disulfide and 40 g of dimethylsulfate were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour. The reaction solution was poured into 200 ml of water, and the precipitated crystals were collected by filtration. After washing with 100 ml of water and 100 ml of methanol, recrystallization from methanol was performed to obtain 19.7 g of the desired product (yield 62%). Melting point 78 ° C 1H NMR (CDCl3, δ): 2.39 (3H, s), 2.45 (3H, s), 2.95 (2H,
t), 3.23-3.28 (2H, m), 3.85 (3H, m), 6.69 (1H, d), 6.84
(1H, dd), 8.08 (1H, d).
【００１４】第２工程 ４，５−ジヒドロ−７−メトキ
シ−３Ｈ−ナフト［１，２−ｃ］−１，２−ジチオール
−３−チオンの合成 加熱還流した五硫化リン7.9gおよび硫黄2.3gのピリジン
（60ml）懸濁液に、２−ビス（メチルチオ）メチリデン
−６−メトキシ−１−テトラロン10gのピリジン（17m
l）溶液を30分かけて滴下した。同温度でさらに30分攪
拌した。室温に冷却後、反応混合物に水120mlを加え
た。析出した結晶を濾集し、水100mlおよびメタノール1
00mlで洗浄後、シリカゲルカラムクロマトグラフィー
（溶媒：クロロホルム）にて精製を行い、目的物8.3gを
得た（収率87%）。 融点150-153℃ 1H NMR(CDCl3,δ):2.88-3.00(4H,m), 3.88(3H,s), 6.83
-6.86(2H,m), 7.59(1H,d).Second step 4,5-dihydro-7-methoki
Ci-3H-naphtho [1,2-c] -1,2-dithiol
Synthesis of 3-thione To a suspension of 7.9 g of phosphorus pentasulfide and 2.3 g of sulfur which had been heated under reflux, and pyridine (60 ml), 2-bis (methylthio) methylidene-6-methoxy-1-tetralone (10 g of pyridine (17 m
l) The solution was added dropwise over 30 minutes. The mixture was stirred at the same temperature for 30 minutes. After cooling to room temperature, 120 ml of water was added to the reaction mixture. The precipitated crystals were collected by filtration, 100 ml of water and 1 ml of methanol.
After washing with 00 ml, the product was purified by silica gel column chromatography (solvent: chloroform) to obtain 8.3 g of the desired product (yield 87%). Melting point 150-153 ° C 1H NMR (CDCl3, δ): 2.88-3.00 (4H, m), 3.88 (3H, s), 6.83
-6.86 (2H, m), 7.59 (1H, d).
【００１５】比較実施例１ 実施例１の第２工程におい
て五硫化リン、硫黄の添加量を変えた製造例 実施例１の第２工程と同様の方法に従って、五硫化リ
ン、硫黄の添加量を変えた場合の合成実験を行い、目的
化合物４，５−ジヒドロ−７−メトキシ−３Ｈ−ナフト
［１，２−ｃ］−１，２−ジチオール−３−チオンの収
率を求めた。その結果を表−１［表１］に示す。Comparative Example 1 In the second step of Example 1.
According to the same method as in the second step of Production Example Example 1 in which the addition amounts of phosphorus pentasulfide and sulfur were changed, a synthetic experiment was performed in which the addition amounts of phosphorus pentasulfide and sulfur were changed to obtain the target compounds 4, 5 The yield of -dihydro-7-methoxy-3H-naphtho [1,2-c] -1,2-dithiol-3-thione was determined. The results are shown in Table 1 [Table 1].
【００１６】[0016]
【表１】 表−１ 五硫化リン、硫黄の添加量を変えた場合 五硫化リン 硫黄 収率（％） ──────────────────── １．５ ２．０ ９１ １．５ ０ ３６ １．０ ２．０ ８７ ０．６ ２．０ ８６ 表中、五硫化リンと硫黄の数字は２−ビス（メチルチ
オ）メチリデン−６−メトキシ−１−テトラロン１モル
当たりの五硫化リンおよび硫黄のモル数を表す。[Table 1] Table-1 When the addition amounts of phosphorus pentasulfide and sulfur are changed: phosphorus pentasulfide, sulfur yield (%) ───────────────────── 1. 5 2.0 91 1.5 0 36 36 1.0 2.0 87 87 0.6 2.0 86 In the table, the numbers of phosphorus pentasulfide and sulfur are 2-bis (methylthio) methylidene-6-methoxy-1-tetralone. It represents the number of moles of phosphorus pentasulfide and sulfur per mole.
【００１７】比較実施例２ 実施例１の第２工程におい
て、原料に３−オキソエステルを用いた製造例 原料に２−エトキシカルボニル−６−メトキシ−１−テ
トラロンを用い、実施例１の第２工程と同様の方法によ
り合成実験を行った。反応温度、反応時間などの条件は
同一にし、目的化合物４，５−ジヒドロ−７−メトキシ
−３Ｈ−ナフト［１，２−ｃ］−１，２−ジチオール−
３−チオンの収率を求めた。その結果を表−２［表２］
に示す。Comparative Example 2 In the second step of Example 1.
Then, a synthesis experiment was carried out in the same manner as in the second step of Example 1 using 2-ethoxycarbonyl-6-methoxy-1-tetralone as a raw material in a production example using 3-oxoester as a raw material. The conditions such as reaction temperature and reaction time were the same, and the target compound 4,5-dihydro-7-methoxy-3H-naphtho [1,2-c] -1,2-dithiol-
The yield of 3-thione was determined. The results are shown in Table-2 [Table 2].
Shown in
【００１８】[0018]
【表２】 表−２ 原料に３−オキソエステルを用いた場合 五硫化リン 硫黄 収率（％） ───────────────────── １．５ ２．０ ４１ １．５ ０ ３５ 表中、五硫化リンと硫黄の数字は、２−エトキシカルボ
ニル−６−メトキシ−１−テトラロン１モル当たりの五
硫化リンおよび硫黄のモル数を表す。実施例１により合
成した１，２−ジチオール−３−チオン誘導体（４，５
−ジヒドロ−７−メトキシ−３Ｈ−ナフト［１，２−
ｃ］−１，２−ジチオール−３−チオン）から、医薬品
として有用な４，５−ジヒドロ−７−メトキシ−８−ス
ルホ−３Ｈ−ナフト［１，２−ｃ］−１，２−ジチオー
ル−３−チオン ナトリウムには、次の参考例１に示す
ようになんら問題なく製造することができた。[Table 2] Table-2 When 3-oxoester is used as a raw material Phosphorus pentasulfide Sulfur Yield (%) ────────────────────── 1.5 2.0 41 1.50 35 In the table, the numbers of phosphorus pentasulfide and sulfur represent the number of moles of phosphorus pentasulfide and sulfur per mole of 2-ethoxycarbonyl-6-methoxy-1-tetralone. 1,2-Dithiol-3-thione derivative synthesized according to Example 1 (4,5
-Dihydro-7-methoxy-3H-naphtho [1,2-
c] -1,2-dithiol-3-thione) to 4,5-dihydro-7-methoxy-8-sulfo-3H-naphtho [1,2-c] -1,2-dithiol As shown in Reference Example 1 below, 3-thione sodium could be produced without any problems.
【００１９】参考例１４，５−ジヒドロ−７−メトキシ−８−スルホ−３Ｈ−
ナフト［１，２−ｃ］−１，２−ジチオール−３−チオ
ン ナトリウムの製造 濃硫酸6mlに25%発煙硫酸18.8gを加え攪拌した。10℃に
冷却後、４，５−ジヒドロ−７−メトキシ−３Ｈ−ナフ
ト［１，２−ｃ］−１，２−ジチオール−３−チオン6g
を加えた。室温に戻し30分攪拌した後、水200mlにあけ
た。40℃に加熱して、30%炭酸ナトリウム水溶液140gを
加え中和した。同温度で1時間攪拌後、静置し、上澄み
（100ml）を除いた。温水200mlを加え、再び40℃に加熱
して20分攪拌後、結晶を濾集した。水から再結晶を行
い、目的物6.7gを得た（収率80%）。 融点352℃(dec.) 1H NMR (DMSO-d6):2.76(2H,t), 3.00(2H,t), 3.87(3H,
s), 7.11(1H,s), 8.02(1H,s).Reference Example 1 4,5-Dihydro-7-methoxy-8-sulfo-3H-
Naphtho [1,2-c] -1,2-dithiol-3-thio
Production of sodium salt To 6 ml of concentrated sulfuric acid, 18.8 g of 25% fuming sulfuric acid was added and stirred. After cooling to 10 ° C, 4,5-dihydro-7-methoxy-3H-naphtho [1,2-c] -1,2-dithiol-3-thione 6g
Was added. After returning to room temperature and stirring for 30 minutes, the mixture was poured into 200 ml of water. It heated at 40 degreeC and neutralized by adding 140 g of 30% sodium carbonate aqueous solution. After stirring at the same temperature for 1 hour, the mixture was allowed to stand and the supernatant (100 ml) was removed. 200 ml of warm water was added, the mixture was heated again to 40 ° C. and stirred for 20 minutes, and then crystals were collected by filtration. Recrystallization from water gave 6.7 g of the desired product (yield 80%). Melting point 352 ° C (dec.) 1H NMR (DMSO-d6): 2.76 (2H, t), 3.00 (2H, t), 3.87 (3H,
s), 7.11 (1H, s), 8.02 (1H, s).
【００２０】[0020]
【発明の効果】 本発明によれば、一般式（１）で示さ
れる１，２−ジチオール−３−チオン誘導体を従来の方
法に比較してはるかに高い収率で製造することができ
る。EFFECTS OF THE INVENTION According to the present invention, the 1,2-dithiol-3-thione derivative represented by the general formula (1) can be produced in a much higher yield as compared with the conventional method.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 逆井 一也 千葉県茂原市東郷1144番地 三井東圧化学 株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuya Sakai 1144, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.
Claims (2)
Ｒ2はそれぞれ独立して水素原子、ヒドロキシル基、ハ
ロゲン原子、炭素数１から４の低級アルキル基または炭
素数１から４の低級アルコキシ基を表す。またＡがメチ
レン基のとき、ｎは０から３の整数を表し、Ａが酸素原
子のとき、ｎは１から３の整数を表す）で示される化合
物の製造において、一般式（２）［化２］で示される化
合物 【化２】 （式中、Ａはメチレン基または酸素原子を表し、Ｒ1、
Ｒ2はそれぞれ独立して水素原子、ヒドロキシル基、ハ
ロゲン原子、炭素数１から４の低級アルキル基または炭
素数１から４の低級アルコキシ基を表す。またＡがメチ
レン基のとき、ｎは０から３の整数を表し、Ａが酸素原
子のとき、ｎは１から３の整数を表す。Ｒ3は、炭素数
１から４の低級アルキル基またはＲ3同士連結して炭素
数２から４のアルキレン基を表す）を五硫化リンと反応
させる際に、硫黄を添加することを特徴とする製造法。1. A compound represented by the general formula (1): (In the formula, A represents a methylene group or an oxygen atom, R 1 ,
R 2's each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms or a lower alkoxy group having 1 to 4 carbon atoms. Further, when A is a methylene group, n represents an integer of 0 to 3, and when A is an oxygen atom, n represents an integer of 1 to 3) in the production of the compound represented by the general formula (2) A compound represented by 2] (In the formula, A represents a methylene group or an oxygen atom, R 1 ,
R 2's each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms or a lower alkoxy group having 1 to 4 carbon atoms. When A is a methylene group, n represents an integer of 0 to 3, and when A is an oxygen atom, n represents an integer of 1 to 3. R 3 is a lower alkyl group having 1 to 4 carbon atoms or R 3 is linked to each other to represent an alkylene group having 2 to 4 carbon atoms), and sulfur is added when reacting with phosphorus pentasulfide. Manufacturing method.
合物１モルに対し、１から１０モルである請求項１に記
載の製造法。2. The production method according to claim 1, wherein the amount of sulfur is 1 to 10 mol with respect to 1 mol of the compound represented by the general formula (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25117595A JPH0987277A (en) | 1995-09-28 | 1995-09-28 | Production of 1,2-dithiol-3-thione derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25117595A JPH0987277A (en) | 1995-09-28 | 1995-09-28 | Production of 1,2-dithiol-3-thione derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0987277A true JPH0987277A (en) | 1997-03-31 |
Family
ID=17218807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25117595A Pending JPH0987277A (en) | 1995-09-28 | 1995-09-28 | Production of 1,2-dithiol-3-thione derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0987277A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776489A (en) * | 2019-02-26 | 2019-05-21 | 温州大学 | The method of copper catalysis bis- sulphur -3- 40 thione derivatives of phenylpropyl alcohol ynamine sulphur Cyclization 1,2- |
-
1995
- 1995-09-28 JP JP25117595A patent/JPH0987277A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776489A (en) * | 2019-02-26 | 2019-05-21 | 温州大学 | The method of copper catalysis bis- sulphur -3- 40 thione derivatives of phenylpropyl alcohol ynamine sulphur Cyclization 1,2- |
| CN109776489B (en) * | 2019-02-26 | 2021-03-30 | 温州大学 | Method for synthesizing 1, 2-disulfide-3-thioketone derivative by copper-catalyzed thiocyclization of amphetamine |
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