DD140144A1 - PROCESS FOR THE PREPARATION OF P-AMINOPHENYL SUBSTITUTED 2-AMINO-1,3-THIAZINIUM SALTS - Google Patents

Abstract

Such compounds can be important as dyes. The invention aims to make the previously unknown p-aminophenyl-substituted 2-amino-1,3-thiazinium salts accessible. This is achieved according to the invention by reacting 2-amino-1,3-thiazinium salts with a free 4- or 6-position in an acidic medium with N,N-disubstituted arylamines, optionally with the addition of an oxidizing agent, to form the p-aminophenyl-substituted 2-amino-1,3-thiazinium salts of type I, where X and Y are different sulfur or nitrogen. The invention is applicable in the chemical industry. - Formula I -

Description

Process for the preparation of p-aminophenyl-substituted 2-amino-1,3-thiazinium salts

Field of application of the invention

The invention relates to a process for the preparation of p-aminophenyl-substituted 2-amino-1,3-thiazinium salts. Such compounds may be useful as dyes.

Characteristics of known technical solutions

ρ-Aminophenyl substituted 2~amino-1,3-thiazinium salts are unknown so far,,

Aim of the invention

The aim of the invention is to make such compounds accessible.

Statement of the meaning of the invention

The object of the invention is to prepare the previously unknown p-aminophenyl-substituted 2-amino-1,3-thiazinium salts in a simple manner.

According to the invention, this object is achieved by using 2-amino-1,3-thiazinium salts of type I

in acidic medium with Η,Ν-disubstituted arylamines of type II

R ¹ R ² N

—2 —

G a

optionally with the addition of an oxidizing agent to the p-aminophenyl-substituted 2-amino-1,3-thiasinium salts of type III, .

R ¹ RTi

III

where Ar is a substituted or unsubstituted aryl or

Heteroaryl radical, R and R identical or different represent a substituted or unsubstituted alkyl, aryl or benzyl group.

3 4

together form a cycloalkyl or cycloheteroalkyl radical, R and R

5 6 or R and R are identical or different and are hydrogen, an alkyl, aryl, acyl or aroyl radical or together a cycloalkyl or cycloheteroalkyl radical, X and Y are different and are sulfur or nitrogen and Z" is an acid radical anion, such as ClO," PO ₀ Cl ₀ ", HSO," or SbCl,

J Λ

-r represent, are implemented.

Examples of implementation . ,

The p-aminophenyl-substituted 2-amino-1,3-thiazinium salts of type III prepared according to the different variants are listed in Table 1.

Variant A .

0.01 mol of 2-amino-1,3-thiazinium salt of type I is treated with 8 ml of glacial acetic acid, 7 ml of acetic anhydride, and 0.01 mol of N,N-disubstituted arylamine of type II. The mixture is heated to reflux for one hour, the deep-colored precipitate that forms upon cooling is filtered off with suction and recrystallized.

Variant B .

Analogous to variant A, but only glacial acetic acid (20 ml) is used as solvent and the reaction mixture is heated to boiling for 30 minutes.

• -3·

n/

Variant C

Analogous to variant B, with the addition of 0.7 g K ₂ Gr ₂ Oy as oxidizing agent«,

Variant D .

A mixture of 0.01 mol of 2-amino-1,3-thiazinium salt of type I, 20 ml of glacial acetic acid, 2 ml of acetic anhydride and 0.01 mol of N,N-disubstituted amine of type II is heated to boiling for 5 hours and then worked up analogously to variant A.

Variant E

Analogous to variant A, but only acetic anhydride (20 ml) is used as solvent and the mixture is heated to boiling for 30 minutes

“4.

Table 1: Prepared p-aminophenyl-substituted 2-amino-1,3-thiazinium salts of type III (Z=ClO).

Ar X Y ^{R1 R2 R3} · ^R4 Melting point ⁰ C (recrystallization) Training/Var. ^d.Th. ^y P-CH ₃ CgH ₄ S N f ΠΙΤ ^ VV/XIo J 2 ( _CH3 255-257 (glacial acetic acid) 36/ ^{A1 P} " 3 6 4 S N (CH₃) 2 ( _CH2 290-292' (glacial acetic acid) 27/A ¹ ) BC ₁₀ H ₇ S N (C ₂ H ₅ h, .(C ₂ H ₄ )O(C ₂ H ₄ ι) 314-315 ^Γ ( glacial acetic acid/ .CH ₃ NO ₂ ) 17/ ^C1 P-CH ₃ CgH ₄ N S ( _CH3 ) 2 (C ₂ H ₄ JO(C ₂ H^ ,) ^> 360 (glacial acetic acid) 46/ ^B1 V P-ClCgH ₄ N S (C ₂ H ₅ ( _CH2 296-298 (glacial acetic acid) 23/B ^? ) P-ClCgH ₄ N S _CH3Cg ( _CH2 303-305 (glacial acetic acid/ CH ₃ NO ₂ ) 12/ ^B1 ) \ BC ₁₀ H ₇ N S ( _CH3 ) 2 (C ₂ H 5>2 138-140 (glacial acetic acid) 47/3^ \ BC ₁₀ H ₇ N S ( _CH3 ) ro _CH3CO CgH ₅ 263-265 (glacial acetic acid/ CH ₃ NO ₂ ) ) BC ₁₀ H ₇ N S _{CH3Cg H5CH2 ​} (C ₂ H 5 2 128-130 (glacial acetic acid) 27/c'

R ⁵ /R ⁶ =R ² /R ³

R ⁵ =C ₆ H ₅ ; R ⁶ =H

Claims (2)

-ν * · "as" c w Brfindungs ans pruch 1. A process for the preparation of p-arainophenylsubstituierten 2-amino-1,3-thiazinium salts characterized in that 2-amino-1,3-thiazinium salts of the type I ^V Y Θϊ. : 5 _π 6 in acid medium with N, N-disubstituted arylamines of type II II optionally with the addition of an oxidizing agent to the p-aminophenyl-substituted 2-amino-1,3-thiazinium salts of the type III,. , R ¹ R ² IT III wherein Ar is a substituted or unsubstituted aryl or 12 Heteroaryl, R and R, identically or differently, represent a substituted or unsubstituted alkyl, aryl or benzyl or together a cycloalkyl or cycloheteroalkyl radical, R 1 and R 'or R " ⁵ and R ° are identical or different and are hydrogen, an alkyl -, aryl, acyl or aroyl or together a cycloalkyl or Cycloheteroalkylrest, X and Y different sulfur or nitrogen and Z ~ an "acid residue anion, such as a, B. Clö, ~ ", POpClp""H ^so a ~ r" or SbCIR ".