JPS63218673A - Production of 1,3-dithiol-2-thione compound - Google Patents
Production of 1,3-dithiol-2-thione compoundInfo
- Publication number
- JPS63218673A JPS63218673A JP62053701A JP5370187A JPS63218673A JP S63218673 A JPS63218673 A JP S63218673A JP 62053701 A JP62053701 A JP 62053701A JP 5370187 A JP5370187 A JP 5370187A JP S63218673 A JPS63218673 A JP S63218673A
- Authority
- JP
- Japan
- Prior art keywords
- carbon disulfide
- sulfur
- compound
- raw material
- dithiol
- 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.)
- Granted
Links
- -1 1,3-dithiol-2-thione compound Chemical class 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 10
- WYKJWNVWJOKVQP-UHFFFAOYSA-N 1,3-dithiole-2-thione Chemical class S=C1SC=CS1 WYKJWNVWJOKVQP-UHFFFAOYSA-N 0.000 description 5
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- IIGQRYLVHFWKHJ-UHFFFAOYSA-N 1,3-dithiol-1-ium Chemical class C1=C[S+]=CS1 IIGQRYLVHFWKHJ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- ACJOYTKWHPEIHW-UHFFFAOYSA-N ethyl 3-phenylprop-2-ynoate Chemical compound CCOC(=O)C#CC1=CC=CC=C1 ACJOYTKWHPEIHW-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Plural Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は１，３−ジチオール−２−チオン化合物の製造
法に関するもので、より詳細にはこれらの化合物をアセ
チレン化合物と二硫化炭素および硫黄とを塩基の存在下
に高圧で反応させることにより簡便にかつ収率よく製造
する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 1,3-dithiol-2-thione compounds, and more specifically, the present invention relates to a method for producing 1,3-dithiol-2-thione compounds, and more specifically, these compounds are prepared by combining an acetylene compound, carbon disulfide, and sulfur in the presence of a base. The present invention relates to a method for producing easily and with high yield by reacting at high pressure.
（産業上の利用分野）
従来、１，３−ジチオール−２−チオン化合物は含硫黄
の医農薬を誘導する１、３−ジチオリウム塩への中間原
料となるばかりではなく、有機導電性化合物として知ら
れているＴＴＦ （テトラチアフルバレン）の合成中間
体として利用されている。(Industrial Application Field) Conventionally, 1,3-dithiol-2-thione compounds have not only been used as intermediate raw materials for 1,3-dithiolium salts that induce sulfur-containing pharmaceuticals and agricultural chemicals, but also have been used as organic conductive compounds. It is used as an intermediate for the synthesis of TTF (tetrathiafulvalene).
（発明が解決しようとする問題点）
このように１，３−ジチオール−２−チオン化合物は合
成化学上興味ある化合物であるが、現在はカルバミン酸
塩とα−ハロケトン類から出発し、数段階の反応工程を
経て、合成するか又は、アセチレン化合物を二硫化炭素
および特殊なスルフェンアミドと反応させることによっ
て得られるが。(Problems to be Solved by the Invention) As described above, 1,3-dithiol-2-thione compounds are interesting compounds in terms of synthetic chemistry, but currently they have been developed in several steps starting from carbamates and α-haloketones. or by reacting an acetylene compound with carbon disulfide and special sulfenamides.
本発明の目的は反応工程を単純化し、ｏｎｅ−ρｏｔで
。The purpose of the present invention is to simplify the reaction process, in one-ρot.
しかも安価な原料を用いて、好収率で、所望の化合物の
製造法を開発することである。Furthermore, the objective is to develop a method for producing a desired compound at a high yield using inexpensive raw materials.
（問題点を解決する手段）
本発明者らは高圧条件下にアセチレン化合物（１）と二
硫化炭素および硫黄とを塩基の存在下で反応させること
により、１，３−ジチオール−２−チオン化合物（２）
を好収率で製造することを見出し、本発明を完成するに
至った。(Means for Solving the Problems) The present inventors produced a 1,3-dithiol-2-thione compound by reacting the acetylene compound (1) with carbon disulfide and sulfur in the presence of a base under high pressure conditions. (2)
The present inventors have discovered that they can be produced with good yield, and have completed the present invention.
すなわち１本発明は、
一般式 Ｒ’−ＣＥＣ−Ｒ”・・・・・・・・・（１
）（式中 Ｒ１，Ｒ＊は不活性な置換基又は水素を表わ
す、）で示されるアセチレン化合物と二硫化炭素および
硫黄とを塩基の存在下、高圧をかけて反応させることを
特徴とする。That is, 1 the present invention has the general formula R'-CEC-R"... (1
) (wherein R1 and R* represent an inert substituent or hydrogen) is reacted with carbon disulfide and sulfur under high pressure in the presence of a base.
一般式
（式中 Ｒ１，Ｒ２は前記と同じ意味を持つ。）で示さ
れる１、３−ジチオール−２−チオン化合物の製造法を
提供するものである。The present invention provides a method for producing a 1,3-dithiol-2-thione compound represented by the general formula (wherein R1 and R2 have the same meanings as above).
本発明の出発原料の一つであるアセチレン化合物はきわ
めて一般的な物質であり、多くのものは市販されている
。また、Ｒ１、Ｒ２として所望の置換基を導入すること
は容易であり、たやすく入手できる。なお、これらの置
換基Ｒ１、Ｒ３は本反応に不活性なものであれば如何な
るものでもよく、たとえば、アルキル基、アラルキル基
、エステル基、複素環基、などがあげられる、また、そ
れらが置換されている場合も包含する。Acetylene compounds, which are one of the starting materials of the present invention, are extremely common substances, and many are commercially available. Further, it is easy to introduce desired substituents as R1 and R2, and they are easily available. Note that these substituents R1 and R3 may be of any type as long as they are inert to this reaction, and include, for example, alkyl groups, aralkyl groups, ester groups, heterocyclic groups, etc. This also includes cases where
このほかの原料、二硫化炭素および硫黄については市販
のものをそのまま使用してもよいが、二硫化炭素自身が
硫黄を溶解する優れた溶剤であるので過剰量用いるとよ
い結果を与える。As for the other raw materials, carbon disulfide and sulfur, commercially available ones may be used as they are, but since carbon disulfide itself is an excellent solvent for dissolving sulfur, good results can be obtained if an excess amount is used.
次に本発明において、目的とする化合物（２）の生成は
塩基としてトリエチルアミンを用いて、フェニルプロパ
ルギル酸エチルと二硫化炭素および硫黄との反応を例に
とれば、下記の式（３）のように表現できる。Next, in the present invention, the production of the target compound (2) is as shown in the following formula (3) using triethylamine as a base and taking the reaction of ethyl phenylpropargylate with carbon disulfide and sulfur as an example. It can be expressed as
４０℃
（２ａ）
本発明の反応は通常第三級アミンの存在下、高圧下で行
われ、第三級アミンの添加は目的とする反応を促進する
と考えられる。アミンとしてはトリエチルアミン、ピリ
ジン、Ｎ、Ｎ−ジメチルアニリンなどのごく一般的な脂
肪族、芳香族アミンの中から選択できる。圧力は高圧は
ど好ましいが、一般には５００〜９０００ ｋｇ／ａＪ
の範囲で選択される０反応温度は特に制約されないが、
副反応の進行を抑制する意味で、室温から１００℃まで
の温度の採用が好ましい１反応時間は圧力、温度等の諸
条件によって左右されるが、通常５時間から５０時間で
充分である。40° C. (2a) The reaction of the present invention is usually carried out under high pressure in the presence of a tertiary amine, and it is believed that the addition of a tertiary amine promotes the desired reaction. The amine can be selected from common aliphatic and aromatic amines such as triethylamine, pyridine, and N,N-dimethylaniline. High pressure is preferable, but generally 500 to 9000 kg/aJ
The reaction temperature selected within the range of 0 is not particularly restricted, but
In order to suppress the progress of side reactions, it is preferable to use a temperature between room temperature and 100° C. The reaction time for one reaction depends on various conditions such as pressure and temperature, but usually 5 to 50 hours is sufficient.
反応終了後は１反応温合物から過剰の二硫化炭素又は有
機溶媒を留去した後、再結晶あるいはカラムクロマトで
分取することにより本発明の目的とする化合物が純度よ
く得られる。After the reaction is completed, the target compound of the present invention can be obtained with high purity by distilling off excess carbon disulfide or organic solvent from the reaction mixture and then fractionating it by recrystallization or column chromatography.
かくして得られた目的物はＩＲ，ＭＳスペクトルおよび
元素分析によって構造を確認できる。The structure of the target product thus obtained can be confirmed by IR, MS spectra, and elemental analysis.
（発明の効果）
本発明方法によれば、各種の１，３−ジチオール−２−
チオン化合物を単純な原料から、はとんど副生物もなく
好収率で製造することができる。(Effect of the invention) According to the method of the present invention, various 1,3-dithiol-2-
Thione compounds can be produced from simple raw materials in good yields with almost no by-products.
このことにより１，３−ジチオール−２−チオン化合物
を中間原料として誘導される有用物質のＴＴＦ、医薬、
農薬などの開発が一層容易になる。As a result, TTF, a useful substance derived from a 1,3-dithiol-2-thione compound as an intermediate raw material, a pharmaceutical,
The development of agricultural chemicals will become even easier.
（実施例） 次の本発明を実施例に基づきさらに詳細に説明。(Example) The following invention will be explained in more detail based on examples.
する。do.
テフロンチューブにアセチレン化合物、二硫化炭素、硫
黄および塩基を封入し、高圧反応装置に入れて所定の圧
力、温度で、２０時間反応させた。An acetylene compound, carbon disulfide, sulfur, and a base were sealed in a Teflon tube, placed in a high-pressure reactor, and reacted at a predetermined pressure and temperature for 20 hours.
反応終了後反応物をとり出し、カラムクロマトで分取、
精製した。このようにして得られた生成物をＩＲ，ＭＳ
、スペクトル、元素分析その構造を確認した。これらの
反応条件および収率は表１に構造確認のデータは表２に
まとめた。After the reaction is completed, the reaction product is taken out and fractionated using column chromatography.
Purified. The product thus obtained was analyzed by IR, MS
, spectrum and elemental analysis confirmed its structure. These reaction conditions and yields are summarized in Table 1, and data on structure confirmation are summarized in Table 2.
Claims (1)
）（式中Ｒ＾１、Ｒ＾２は不活性な置換基又は水素を表
わす。）で示されるアセチレン類と二硫化炭素および硫
黄とを塩基の存在下で、高圧をかけて反応させることを
特徴とする。 一般式 ▲数式、化学式、表等があります▼・・・・・・・・・
・・・（２） （式中Ｒ＾１、Ｒ＾２は前記と同じ意味を持つ。）で示
される１，３−ジチオール−２−チオン化合物の製造方
法。[Claims] General formula R^1-C≡C-R^2 (1
) (wherein R^1 and R^2 represent inert substituents or hydrogen.) Acetylenes represented by the formula (R^1 and R^2 represent inert substituents or hydrogen) are reacted with carbon disulfide and sulfur in the presence of a base under high pressure. Features. General formulas▲Mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...(2) A method for producing a 1,3-dithiol-2-thione compound represented by the formula (wherein R^1 and R^2 have the same meanings as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62053701A JPS63218673A (en) | 1987-03-09 | 1987-03-09 | Production of 1,3-dithiol-2-thione compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62053701A JPS63218673A (en) | 1987-03-09 | 1987-03-09 | Production of 1,3-dithiol-2-thione compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63218673A true JPS63218673A (en) | 1988-09-12 |
| JPH0376315B2 JPH0376315B2 (en) | 1991-12-05 |
Family
ID=12950125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62053701A Granted JPS63218673A (en) | 1987-03-09 | 1987-03-09 | Production of 1,3-dithiol-2-thione compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63218673A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100898319B1 (en) | 2007-05-29 | 2009-05-20 | 경희대학교 산학협력단 | Method of preparing alkylene trithiocarbonate by using imidazolium halides |
-
1987
- 1987-03-09 JP JP62053701A patent/JPS63218673A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100898319B1 (en) | 2007-05-29 | 2009-05-20 | 경희대학교 산학협력단 | Method of preparing alkylene trithiocarbonate by using imidazolium halides |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0376315B2 (en) | 1991-12-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |