JPS6241712B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides novel compounds, 3,5-disubstituted-
The present invention relates to a 1,4,2-dithiazolium salt, and more particularly to a novel sulfur-containing 1,4,2-dithiazolium salt compound having a heteroaromatic cation ring structure. Conventionally, sulfur-containing cyclic cationic compounds, such as 1,3-dithiolium salts and 1,2,4-dithiazolium salts, have been widely used as agricultural chemicals, cationic dyes, organic conductive compounds, or as intermediates for their synthesis. Ta. However, with the spread of pesticides, there are extremely high expectations for new pesticides that do not provide chemical resistance as a countermeasure against the emergence of chemically resistant pests. Furthermore, the new development of organic conductive compounds as new materials is viewed as extremely promising. Therefore,
The present invention was conceived in view of the current situation, and synthesizes various sulfur-containing cyclic cation compounds,
As a result of intensive research into the pharmacological effects of these pesticides and the conductivity of organic compounds, various types of 1, 4, and 2 expressed by the general formula below were discovered.
- It was discovered that a dithiazolium salt compound is a new and useful compound, and the present invention was completed. The various compounds of the present invention are all new compounds and can be synthesized from easily available raw materials through simple reactions and in high yields, and are not only promising as medicines and agrochemicals, cationic dyes, etc., but also in the electronics industry. It can also be used as an intermediate raw material for the synthesis of materials. The novel compounds of the present invention, 1,4,2-dithiazolium salts, have the general formula (In the formula, R ¹ and R ² are lower alkyl groups, and R ¹ ,
The ends of R ² may be bonded to each other, and R ³
is a substituted or unsubstituted phenyl group, and X represents an anion. ) 3-aryl-5
-disubstituted amino-1,4,2-dithiazolium salt. And novel 1, 4, 2 of the present invention
-Dithiazolium salts include, for example, the compounds shown by the following compound numbers. 3-phenyl-5-diethylamino-1,4,
2-dithiazolium perchlorate 3-(p-methoxyphenyl)-5-diethylamino-1,4,2-dithiazolium perchlorate 3-(p-chlorophenylamino-1,4,2
-Dithiazolium perchlorate 3-(p-tolu)-5diethylamino-1,4,
2-dithiazolium perchlorate 3-phenyl-5-dimethylamino-1,4,
2-dithiazolium perchlorate 3-phenyl-5-(1-piperidino)-1,
4,2-dithiazolium perchlorate 3-phenyl-5-diethylamino-1,4,
2-dithiazolium tetrafluoroborate The novel substance 1,1,2-dithiazolium salts of the present invention are N-aroyl-S-disubstituted thiocarbamoylsulfenamides represented by the general formula (). (In the formula, R ¹ and R ² are both lower alkyl groups such as methyl and ethyl groups, or an alkylene group to which the terminals of these lower alkyl groups are bonded, for example, a pentamethylene group. R ³ is represents a substituted or unsubstituted phenyl group such as phenyl group, p-tolyl group, p-methoxyphenyl group, or p-chlorophenyl group) in a strongly dehydrating and strongly acidic solvent. It is synthesized by 1, 4, 2 shown in the above compound number (1)
- Taking dithiazolium salt as an example, its reaction route is estimated as follows. This reaction can generally be completed by simply heating the aqueous solution slightly. A dehydration reaction occurs by carrying out the reaction in a solvent such as acetic anhydride or phosphoryl chloride, which have strong dehydrating properties, in the presence of a concentrated strong acid such as perchloric acid or boric tetrafluoride. , 2-dithiazolium salt is formed and precipitates in a stable crystalline state in good yield. The 1,4,2-dithiazolium salt thus obtained was purified by recrystallization if necessary, and identified by characteristic absorption in an infrared absorption spectrum and elemental analysis. The 1,4,2-dithiazolium salts of the present invention as described above are all new compounds, but they are in a structural isomer relationship with the known compound 1,2,4-dithiazolium salts, and have heteroaromatic cations. Since it is a type of compound and has similar chemical properties, it is not only effective as a sensitizer, pesticide, cationic dye, etc., but also an important intermediate raw material for the synthesis of nitrogen-containing cyclic compounds. It will also happen.
Furthermore, all of these 1,4,2-dithiazolium salts can be obtained by simple reactions and in good yields, and their raw materials are extremely easily available, making them industrially advantageous. Next, the present invention will be explained in more detail with reference to Examples. Example 1 2.68 g (0.01 mol) of N-benzoyl-S-diethylthiocarbamoylsulfenamide was dissolved in a solution prepared by pre-mixing 15 ml of acetic anhydride with 1 ml of 70% perchloric acid, and the solution was heated for 2 hours over the aqueous solution. do. After that, let it cool and once the reaction solution has cooled down to room temperature, add dry ether.
Add 20ml to the reaction mixture. Separate the precipitated white plate-like crystals and recrystallize them with acetonetrile to find the melting point.
2.79 g (yield: 80%) of white plate-like crystals of 3-phenyl-5-diethylamino-1,4,2-dithiazolium perchlorate was obtained at 141°C. The characteristic absorption in the infrared absorption spectrum of this product was as follows. 3050cm ^-1 , 2968cm ^-1 , 1582cm ^-1 , 1571cm ^-1 ,
1538cm ^-1 , 1465cm ^-1 , 1441cm ^-1 , 1283cm ^-1 ,
1068cm ^-1 , 761cm ^-1 , 688cm ^-1 , 617cm ^-1 . The elemental analysis value as C ₁₂ H ₁₅ N ₂ G ₂ ClO ₄ was as follows. Calculated values (%) C: 41.08, H: 4.31, N: 7.98. Measured values (%) C: 41.02, H: 4.30, N: 8.07. Example 2 Same as above, add 1 ml of 70% perchloric acid to 15 ml of acetic anhydride.
0.01 mol of N-aroyl-S-disubstituted thiocarbamoylsulfenamide shown in the table below is dissolved in a pre-mixed solution, and the mixture is heated over an aqueous solution for 2 hours. Thereafter, the reaction mixture is allowed to cool, and when the reaction mixture reaches room temperature, dry ether is added to promote precipitation of the product. The product is separated and recrystallized from acetonetrile to yield white microcrystalline 3-aryl-5-disubstituted amino-1,4,2-dithiazolium perchlorate. The melting point yield and elemental analysis results of the dithiazolium salt thus obtained are shown in Table 1.

[Table] Example 3 2.68 g (0.01 mol) of N-benzoyl-S-diethylthiocarbamoylsulfenamide was dissolved in a solution prepared by pre-mixing 1.5 ml of 40% tetrafluoroboric acid in 15 ml of acetic anhydride. Warm for 2 hours. After that, let it cool, and when the reaction solution drops to room temperature,
Dry ether is added to the reaction to promote precipitation of the product. Separate the precipitated white powder,
When recrystallized with acetonetrile, 3 with a melting point of 120℃ is obtained.
-phenyl-5-diethylamino-1,4,2-
Dithiazolium tetrafluoroborate 1.12g (yield
33%). The characteristic absorption in the infrared absorption spectrum of this product is as shown in Example 1, 3-phenyl-5-
All of the characteristic absorptions of diethylamino-1,4,2-dithiazolium perchlorate were consistent except for the absorption at 1068 cm ^-1 (attributable to perchlorate).
The elemental analysis value as C ₁₂ H ₁₅ N ₂ S ₂ BF ₄ was as follows. Calculated values (%) C: 42.62, H: 4.47, N: 8.28. Measured values (%) C: 42.58, H: 4.43, N: 8.29.

Claims (1)

[Claims] 1. General formula (In the formula, R ¹ and R ² are lower alkyl groups, and R ¹ , R 2 are lower alkyl groups,
R ² may be bonded at its terminal, R ³ is a substituted or unsubstituted phenyl group, and X represents an anion. ) 3-aryl-5-disubstituted amino-1,4,2-dithiazolium salt.