JPS6168481A - Production of 3-aryl-5-disubstituted-1,4,2-dithiazolium salt - Google Patents

Abstract

PURPOSE:To obtain the titled substance useful as agricultural chemicals, sensitizers, cationic dyes, materials for electronic industries, etc., by subjecting an N-aroyl-S-disubstituted thiocarbamoyl sulfenamide to ring formation through dehydration in the presence of a strong acid. CONSTITUTION:A compound shown by the formula I (R<1> and R<2> are alkyl or aryl which may contain substituent group, and ends of them may be bonded; R<3> is aryl which may contain substituent group) is subjected to ring formation in a solvent (e.g., acetic anhydride, or phosphoryl chloride) in the presence of a strong acid (e.g., perchloric acid, tetrafluoroboric acid, or sulfuric acid) to give a compound shown by the formula II (X is acid radical of inorganic strong acid).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 3-aryl-5-disubstituted amino-1°4.2
- This relates to a method for producing dithiazolium salts, and more specifically, these compounds are converted into simple compounds by cyclodehydration reaction of N-aroyl-8-)fit-substituted thiocarbamoylsulfenamide in the presence of a strong inorganic acid, Alternatively, it was widely used as a synthetic intermediate for these. However, as pesticides become more widespread, there are extremely strong expectations for new pesticides that do not provide chemical resistance as a countermeasure to the emergence of chemically resistant pests.

Furthermore, the development of viTfc, an organic conductive compound as a new material, is highly promising. The present invention was conceived in view of the current situation, and involved synthesizing various sulfur-containing cyclic cationic compounds, examining the pharmacological effects of these pesticide binders, and conducting extensive studies on the conductivity of organic compounds. However, various new and useful 1.4.2
- It has been discovered that dithiazolium salts can be produced in high yield by an extremely simple method, and the present invention has been completed. That is, the present invention provides (in the formula, R1 and R2 represent an alkyl group which may have an inert substituent, and R1 and R2° may have their terminals bonded to each other, R3 represents all aryl groups which may have an inert substituent.) The method is characterized by subjecting N-aroyl-8-disubstituted thiocarbamoylsulfenamide represented by the following formula to a cyclodehydration reaction in the presence of a strong acid. (In the formula, R1 and R2 are the same as above, and X represents an acid group of a strong inorganic acid.)
, 2-dithiazolium salt.

The compound of the present invention is synthesized by reacting the general formula (1) in a strongly acidic solvent with strong t-dehydration property, and the compound is a raw material N-aroyl-S-disubstituted thiocarbamoylsulfene. Amides can be produced by reacting hydroxy/luamine-0-sulfone with a di-substituted dithiocarbamate. Therefore, for R1 and R2, desired substitution groups can be introduced by selecting the type of dithiocarbamic acid. Further, as for R3, a desired substituent can be introduced by appropriately selecting a carboxylic acid anhydride or a multi-group compound. Also, )jl
, l(,2, R3 can have an inert substituent, and examples of the inert substituent in this case include lower alkokenes and halogens.

Next, the procedure for the desired cyclodehydration reaction If! r is N-phenyl-8-)ethylcarbamoylsulfenamide (IA
) and using perchloric acid as a strong acid, it can be expressed as the following formula (■[).

This reaction can be completed by simply heating it slightly on a water bath, but in a highly dehydrating solvent such as acetic anhydride or phosphoryl chloride, a concentrated strong acid such as perchloric acid,
When carried out in the presence of tetrafluoroboric acid, sulfuric acid, etc., the desired 1,4,2-dithiazolium salt is produced, and in many cases it precipitates in a stable crystalline state with good yield.
Depending on necessity, an inert organic solvent may be added to promote precipitation of the product.

The 1,4,2-dithiazolium salt thus obtained can be further purified by recrystallization, if necessary.

New substance 3-aryl-5-disubstituted amino-1゜4.2
-The structure of the dithiazolium salt was confirmed by elemental analysis and characteristic absorption of infrared absorption spectrum.

As mentioned above, the 1.4゜2-dithiazolium salts of the present invention are all new compounds, but they can be considered as a type of 5-membered ring sulfur-containing aromatic cation compounds, and chemically,
Similar to those known compounds. Therefore, this compound is not only effective as a sensitizer, agricultural chemical, cationic dye, electronic material, etc., but also serves as an important intermediate raw material for the synthesis of nitrogen-containing cyclic compounds.

In addition, all of these 1.4.2-) thiazolium salts are not only easily obtained by reaction and in good yields, but also their raw materials are very easily available, so they are extremely advantageous from an industrial standpoint.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 2.681 (o, or mol) of N-benzoyl-8-)ethylthiocarbamoylsulfenamide was dissolved in a solution prepared by pre-mixing 1M of 70% perchloric acid in 15ml of acetic anhydride. Warm for 2 hours. Thereafter, the reaction solution is allowed to cool, and when the reaction solution reaches room temperature, 20 ml of dry ether is added to the reaction solution. The precipitated white plate A was separated from each other and recrystallized with acetonitrile to give white plate crystals 3-phenyl-5-dinithylamino-1.4.2-dithiazolium perchlorate 2.79.I with a melting point of 141'C. (yield: 80 cm). The characteristic absorption of the infrared absorption spectrum of this product was as follows.

3050cm-', 2968cm', 1582c
m-', 1571m'+1538cTrL',
1465cm-', 1441crrL-', 12
83cm-'.

1068crn-', 761cm', 688c
m-', 617 cm',.

The elemental analysis values for C1□H,, N2S, and ClO4 were as follows.

Calculated value Excellent) C: 41.08. H:4.31. Nia, 9
8゜Po11 constant value (chi) C: 41.02. H:4.30.
N: 8.07゜Example 2゜Similarly to the above, 0.0% as shown in the table below was added to a solution prepared by pre-mixing 15 ml of anhydrous vinegar C1k and 1 ml of 70% perchlorine.
Dissolve 1 mol of N-aroyl-8-disubstituted thiocarbamoylsulfenamide, heat on aqueous solution for 2 hours, then allow to cool. When the reaction solution reaches room temperature, add dry ether to obtain the product. Totally promotes precipitation. The product is separated and recrystallized from acetonitrile to yield white microcrystalline 3-aryl-5-disubstituted amino-1,4,2-)thiazolium perchlorate. The melting point yield and elemental analysis results of the dithiazolium salt thus obtained are shown in Table 1.

Example 3 2.68 F (0.01 mol) of N was added to a solution of 1.5 ml of 40% tetrafluoroboric acid mixed in advance with 15 d of anhydrous intoxicant.
-Benzoyl-8-dicherthiocarpamoylsulfenamide is dissolved and heated over the water solution for 2 hours. Thereafter, the reaction solution is allowed to cool, and when the reaction solution reaches room temperature, dry ether is added to the reaction solution to promote precipitation of the product. The precipitated white powder was separated from each other and recrystallized from acetonitrile to give 3-phenyl-5-diethylamino-
1,4,2-dithiazolium tetrafluoroborate 1.1
2F (yield 33%) was obtained. The characteristic absorption of the infrared absorption spectrum of this product is as shown in Example 1.
All of the characteristic absorptions of diethylamino-1,4,2-dithiazolium perchlorate were consistent except for the absorption of 1068m" (attributable to perchlorine salt), Cl2H1s Nz S
The elemental analysis values for 2BF4 were as follows.

Calculated value (chi) C: 42.62. H:4.47. N:8.
28° measurement value (chi) C: 42.58. H:4.43. N
:8.29. .

Claims (1)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 and R^2 are alkyl or aryl groups that may have an inert substituent, and R^ 1, R^2
may be bonded at its terminal, and R^3 represents an aryl group which may have an inert substituent. ) is a general formula characterized by subjecting N-aroyl-S-disubstituted thiocarbamoylsulfenamide to a cyclodehydration reaction in the presence of a strong acid ▲There are mathematical formulas, chemical formulas, tables, etc. ▼(II) (Formula Inside R^1, R^2, R^3 are the same as above, and X
represents the acid radical of a strong inorganic acid. ) 3-aryl-5-disubstituted amino-1,4,
Method for producing 2-dithiazolium salt.