JPS5919947B2 - 2,4,6-trisubstituted-1,3,5-thiadiazinylium salt - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound, 2.4.6-trisubstituted-1.3.5-thiadiadiazinylium salt,
More specifically, the present invention relates to a novel thiadiazinylium salt compound having a heterocationic ring structure.

Conventionally, heterocationic ring compounds, such as thiopyrylium salts and 1,3-thiazinium salts, have been widely used as photosensitivity promoters, agricultural chemicals, cationic dyes, etc., or as synthetic intermediates thereof.

However, as optical machinery advances, there is a demand for the development of drugs that are more sensitive to light, and as pesticides become more widespread, there are expectations for new pesticides that do not provide chemical resistance as a countermeasure against the emergence of chemically resistant pests. is extremely strong.

The present invention was conceived in view of the current situation, and as a result of synthesizing various heterocationic ring compounds and studying the effects of these compounds as sensitizers and pharmacological effects as agricultural chemicals, the following formula was developed: The inventors have discovered that the various thiadiazinylium salt compounds shown are new compounds, and have completed the present invention.

These various compounds are all new compounds and can be synthesized from easily available raw materials through simple reactions and in high yields, and are also effective as sensitizers, agricultural chemicals, cationic dyes, etc. . The novel thiadiazinylium salt compound of the present invention has the general formula (wherein R1 and R2 represent a phenyl group, p-tolyl group, p-chlorophenyl group, or p-methoxyphenyl group, and R3 represents a phenyl group, p- It represents a chlorophenyl group, p-methoxyphenyl group, thienyl group or benzylthio group.

X is a perchlorate acid group or a tetrafluoroborate acid group, and R
1 and R2 both represent a phenyl group, R3 represents a phenyl group, thienyl group, benzylthio group, or p-methoxyphenyl group, and X represents a perchloric acid group, R1, R2
and when R3 both represent a p-tolyl group, X represents a tetrafluoroborate acid group, and when R1, R2 and R3 both represent a p-methoxyphenyl group, X represents a perchlorate acid group,
When R1 and R3 both represent a phenyl group, R2 represents a phenyl group or a p-chlorophenyl group, X represents a tetrafluoroborate acid group, and R1, R2 and R3 both represent a p-chlorophenyl group. When shown, X represents a tetrafluoroborate acid group. ). Examples of the novel thiadiazinylium salt compounds of the present invention include three compounds shown by the following compound numbers.

(1) 2,4,6-triphenyl-1,3,5-thiadiazidinylium perchlorate (2) 2,4-diphenyl-6-(2-thiophenyl)-1,3,5-thiadiazinylium perchlorate dinyllium perchlorate 3) 2,4-diphenyl-6-benzylthio-1,3,5-thiadiazidinylium perchlorate) 2,4,6-tris(p-tolyl)-1,3. 5
-Thiadiaginylium tetrafluoroborate 2, 4, 6-
Triphenyl-1,3,5-thiadiazinylium tetrafluoroborate (6) 4-(p-chlorophenyl)-2
・6--diphenyl-1,3,5-thiadiazidinylium tetrafluoroborate (7) 2,4,6-tris(p-chlorphenino(ha)1,3,5-thiadiazidinylium tetraboronate) Fluoroborate (8) 2-(p-methoxyphenyl)-4,6-diphenyl-1,3,5-thiadiazinylium perchlorate (9) 2,4,6-tris(p -methoxyphenyl) 1,3,5-thiadiazidinylium perchlorate The novel thiadiazinylium salt compounds of the present invention are N-acylimido chlorides represented by the general formula (1) (in the formula, R1 , R2 each represent a phenyl group, a dimethylamino group, or a p-tolyl group.

) with a thioamide represented by the general formula () in the presence of perchloric acid or tetrafluoroboric acid in a nonpolar organic solvent. (In the formula, R3 represents a phenyl group, a dimethylamino group, a thienyl group, a benzylthio group, or a p-tolyl group.

). Now, taking the thiadiazinylium salt shown by the above compound number (1) as an example, its synthesis is represented by the following formula ().

The reaction can generally be carried out at room temperature, in an organic solvent that is non-polar and reactive with water, such as acetic anhydride, and in the presence of perchloric acid or boron tetrafluoride, which have a dehydrating effect in a concentrated state. By carrying out this process, the desired thiadiazinylium salt is stabilized and can be obtained in a high yield in crystalline form.

Furthermore, the novel thiadiazinylium salt compound of the present invention can be obtained by reacting 4H-1.3.5-thiadiazine represented by the following formula () with a trityl salt of tetrafluoroboric acid or perchloric acid in an organic solvent. You can get it even if you twist it.

In the formula (), R'', R2, and R3 are all phenyl group, p=chlorophenyl group, or p-methoxyphenyl group, or R1 and R3 are phenyl group and R2 is p-chlorophenyl group, or R1 , R2 are both phenyl groups and R3
is a p-methoxyphenyl group.

Now, taking the thiadiazinylium salt of Compound No. (7) as an example, the reaction is represented by the following formula (V).

For example, acetonitrile, benzene, acetic anhydride,
It is easily carried out at room temperature in an organic solvent such as ether.
The raw material thiadiazine () can be easily obtained by reacting aldehyde, thioamide, and nitrile in an equimolar fluoroform solution at room temperature in the presence of BF3-ether complex, and the other raw material trityl salt is triphenyl carbinol. It can be easily synthesized by a dehydration reaction between fluorine and a strong acid such as boric tetrafluoride.

The thiadiazinylium salt obtained by reaction formula () or (V) as described above was purified by recrystallization if necessary, and identified by characteristic absorption in an infrared absorption spectrum and elemental analysis.

2.4.6-trisubstitution-1.3 of the present invention as described above
・5-Thiadiadinylium salts are all new compounds, and are similar to known compounds such as thiopyrylium salts and 1.
Like 3-thiazinylium salt, it is a type of heterocationic ring compound and has similar chemical properties, so it is not only effective as a sensitizer, pesticide, cationic dye, etc., but also useful for the synthesis of nitrogen-containing heterocyclic compounds. It is an important intermediate raw material for

In addition, all of these thiadiazinylium salts have high yields and
Moreover, it can be synthesized by a simple reaction, and each raw material is already commercially available or can be easily synthesized by a simple reaction, so it is industrially advantageous.

Next, examples of the present invention will be described.

Example 1 5 ml of acetic anhydride solution containing 1.38 parts by weight of thiobenzamide
and 10 ml of an acetic anhydride solution containing 2.50 parts by weight of N-benzoylbenzimiddle chloride, and further added 1
．． 2ml of 70% perchloric acid was slowly added dropwise.

After stirring for a while, the mixture was left at room temperature overnight. The precipitated yellow crystalline crude product was separated and recrystallized with acetonitrile to obtain 2,4,6-triphenyl-1,3,5-thiadiazinylium perchlorate (above compound number (1)). 3.71 parts of yellow crystals were obtained. The yield was 87% (based on theoretical value, the same applies hereinafter), and the decomposition point was 242.0°C. The characteristic absorption by infrared absorption spectrum and elemental analysis values of this product were as follows.

Example 2 A solution of 2.50 parts by weight of N-benzoylbenzimiddle chloride in 10 ml of acetic anhydride solution and a solution of 1.45 parts by weight of thiophenyl-2-thioamide in 5 ml of benzene were mixed,
While cooling with ice water, 1.2 ml of 70% perchloric acid was gradually added dropwise.

After stirring for a while, the mixture was left at room temperature overnight. The precipitated crude product of orange crystals was separated and recrystallized with acetonitrile to produce 2,4-diphenyl-6-(2-thiophenyl)-1,3,5-thiadiazidin with a decomposition point of 223.6°C. 3.3 of lithium perchlorate (above compound number (2))
8 parts by weight were obtained.

The yield was 78%. The characteristic absorption in the infrared absorption spectrum of this product is shown below.

Further, the elemental analysis values for Cl9Hl3N2S2ClO4 are shown below.

Example 3 2.50 parts by weight of N-benzoylbenzimide chloride and 1.85 parts by weight of benzyl dithiocarbamate were mixed into 1
It was dissolved in 0 ml of chloroform, and a mixed solution of 10 ml of acetic anhydride and 1.2 ml of 70% perchloric acid was added to this solution.

The yellow powder that precipitated after standing overnight was separated and recrystallized with acetonitrile. 2,4-diphenyl-6-benzylthio-1,3,5-thiadiazidinylium perchlorate with a decomposition point of 179.9℃ 2.84 parts by weight of Compound No. (3)) was obtained. The yield was 60%. The infrared absorption spectrum of this product showed the following characteristic absorption.

The elemental analysis value is C22Hl7N2S2ClO4. Example 4 N-(p-tolyl)-p-tolymidoyl chloride 2.
75 parts by weight of p-methylthiobenzamide and 1.70 parts by weight of p-methylthiobenzamide were dissolved in 20 ml of acetic anhydride, the solution was cooled with ice water and, with stirring, 2.5 parts of 40% tetrafluoroboric acid was dissolved.
ml was added dropwise.

After stirring for a while, 10 ml of dry ether was added, and the mixture was left in the refrigerator overnight.

The precipitated orange crude product was separated and purified by recrystallization with acetic anhydride to produce 2,4,6-tris(p-tolyl)-1,3,5-thiadiazidin with a decomposition point of 187.8°C. 3.29 parts by weight of lithium tetrafluoroborate was obtained.

The yield was 72%. The infrared absorption spectrum of this product showed the following characteristic absorption.

The elemental analysis values for C24H2 and N2SBF4 were as follows.

Example 5 2,4,6-Triphenyl-4H-1,3,5-thiadiazine 3. obtained by reacting equimolar amounts of benzaldehyde, benzonitrile and thiobenzamide with BF3-ether complex in fluoroform at room temperature. A solution of 4.00 parts by weight of trityl tetrafluoroborate in 10 ml of acetic anhydride was mixed with 30 parts by weight of acetic anhydride in 10 ml at room temperature with stirring.

After stirring for a while, 20 ml of dry ether was added, and the mixture was left in the refrigerator overnight. Separate the precipitated yellow crude product,
Recrystallization from acetonitrile yielded 3.36 parts by weight of 2,4,6-triphenyl-1,3,5-thiadiadidinylium tetrafluoride borate having a decomposition point of 246.5°C.

The yield rate was 81%. The absorption characteristics of this infrared absorption spectrum are shown below.

v]VO The elemental analysis values are as follows as C2lH, 5N2SBF4.

V-VV) U ● LJU Example 6 4-(
p-chlorophenyl)-2,6-diphenyl-4H-1
・3665 parts by weight of 3,5-thiadiazine was added to benzene 3
Boron tetrafluoride trityl salt 4
．． A solution of 20 ml of 0.00 parts of acetic anhydride was mixed.

This solution was heated to about 50° C., and when almost all insoluble matter was gone, it was quickly filtered, and the filtered solution was left in a refrigerator for 2 days.

When the precipitated yellow microcrystals were separated, the decomposition point was 176.
2.51 parts by weight (yield: 56%) of 4-(p-chlorophenyl)-2,6-diphenyl-1,3,5-thiadiadidinylium tetrafluoride borate at 6°C was obtained.

The characteristic absorption of the infrared absorption spectrum of this product was as follows, and the elemental analysis value as C2, Hl4N2SClBF4 was as follows.

Example 7 2,4,6-tris (p-
Chlorphenyl)-4H-1.3.5thiadiazine4.
35 parts by weight was completely dissolved in 130 ml of acetonitrile by heating to about 50°C.

This solution was mixed with 30 ml of an acetic anhydride solution in which 4.00 parts by weight of trityl tetrafluoroborate salt was dissolved, and quickly filtered.

When this solution was left at room temperature overnight, golden yellow needle-like crystals were precipitated, and when separated, 2,4,6-tris (p-chlorfenino(he)-1,3,5-tris) with a decomposition point of 128.5°C was separated. 2.07 parts by weight (yield: 40%) of asiadinylium tetrafluoroborate were obtained.

Characteristic absorption of infrared absorption spectrum of this substance and C2l
The elemental analysis values for Hl2N2SCl4BF4 are shown below.

Claims (1)

[Claims] 1 General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R^1 and R^2 are phenyl group, p-tolyl group, p-chlorophenyl group, or p-methoxyphenyl group) and R^3 is a phenyl group, p-chlorophenyl group, p
-Methoxyphenyl group, thienyl group or benzylthio group. X is a perchlorate group or a tetrafluoroborate group, and R
When ^1 and R^2 both represent a phenyl group, R^3 represents a phenyl group, thienyl group, benzylthio group, or p-methoxyphenyl group, and X represents a perchloric acid group, R^
1. When R^2 and R^3 both represent p-tolyl group, X
indicates a tetrafluoroborate acid group, R^1, R^2 and R
When ^3 both represent a p-methoxyphenyl group, X represents a perchloric acid group, and when R^1 and R^3 both represent a phenyl group, R^2 represents a phenyl group or a p-chlorophenyl group. , X represents a tetrafluoroborate acid group, and R
When ^1, R^2 and R^3 all represent a p-chlorophenyl group, X represents a tetrafluoroborate acid group. ) 2,4,6-tri-substituted-1,3,5-thiadiazinylium salt.