DD254004A1 - PROCESS FOR THE PRODUCTION OF 2-POSITION BY NUCLEOFUG EASILY REPLACEABLE RESTE SUBSTITUTED 3,5-DIARYLTHIAZOLIUM SALTS - Google Patents

Abstract

Such compounds are important as intermediates for the preparation of dyes, in particular sensitizing dyes and biologically active substances. The aim of the invention is to achieve the synthesis of the 3,5-diarylthiazolium salts substituted in the 2-position by nucleofug which are easily exchangeable radicals from more readily available and more conveniently manageable starting materials in a greater variety and higher yields than hitherto. This is erfindungsmaessig in such a way that Halogenmethylarylketone with Arylaminothiokohlensaeurederivaten to the in position 2 by nucleofug easily replaceable radicals substituted 3,5-Diarylthiazoliumsalzen type I, wherein X is a dialkylamino, alkylthio or arylthio or aryloxy or alkoxy radical, Z is the anion of the metal salt used or halogen and Ar1, Ar2 are each a substituted or unsubstituted aryl group, are reacted.

Description

where Ar ¹ , Ar ^{2 is} a substituted or unsubstituted aryl radical, X is a dialkylamino, aryl or alkylthio or aryl or alkoxy radical and Z is the anion of the metal salt or halogen.

Field of application of the invention

The invention relates to a process for the preparation of in 2-position by nucleofug easily exchangeable radicals substituted 3,5-Diarylthiazoliumsalzen. Such compounds are important as intermediates for the preparation of dyes, in particular sensitizing dyes and biologically active substances.

Characteristic of the known technical solutions

Of the claimed compounds, only 2-alkylthio-3,5-diarylthiazolium salts are known. These are represented by the alkylation of corresponding thiazoline-2-thiones with reactive alkylating agents. Disadvantages of this method are the use of toxic Dialkylsuifate or expensive Alkyijodide and the mostly low yields of 2-Alkylthiq-3,5-Diarylthiazoliumsalzen. 2-aryl- and 2-alkoxy- and 2-dialkylamino-substituted 3,5-diarylthiazolium salts are hitherto unknown.

Object of the invention

The aim of the invention is to produce the novel 2-aryl or alkoxy and 2-dialkylamino-substituted 3,5-diarylthiazolium salts from readily available starting materials in high yields and also the 2-aryl- and 2-alkylthio-substituted 3 To make 5-Diarylthiazoliumsalze cheaper and easier to handle starting materials in higher yields than previously available.

Explanation of the essence of the invention

The object of the invention is to produce the in 3,5-position by nucleofug easily exchangeable groups substituted 3,5-Diarylthiazoliumsalze from easily accessible and convenient manageable starting materials in high yields.

According to the invention, this object is achieved in that Halogenmethylarylketone type I

with arylaminothiocarbonic acid derivatives of the type II

S Arjflbfi-X

in a condensing agent, such as acetic anhydride and optionally in the presence of a metal salt of a mineral acid, such as. B. Mg (CIO ₄ I ₂ , to the 2-position by nucleofug easily exchangeable groups substituted 3,5-diarylthiazolium salts of the type III _# .

wherein Ar ¹ , Ar ² each represents a substituted or unsubstituted aryl radical X is a dialkylamino, Aiylthio or alkylthio or an aryloxy or alkoxy radical and Z "represents the anion of the metal salt used, such as CIO ₄ " or halide, are reacted.

embodiments

The 3,5-diarylthiazolium salts prepared according to the different variants and substituted in the 2-position by nucleofug which are easily exchangeable radicals are summarized in Table 1.

option A

A mixture of 0.05 mol of a Arylaminothiokohlensäurederivats the general formula II and 0.05 mol of a halomethylaryl ketone type I are suspended in the presence of 6.5g (0.025mol) Mg (CIO ₄ I ₂ in 80ml acetone hydride and then heated for 5 min to reflux. After cooling, 100 ml of dry ether or ethyl acetate are added and the resulting oil is washed after decanting from the solution with 50 ml of a 37% strength aqueous HCl solution, and the residue is recrystallized from isopropanol or glacial acetic acid.

Variant B

0.05 mol of a type II arylaminothiocarbonic acid derivative and 0.05 mol of a halomethylaryl ketone of the formula I are boiled in the presence of 6.5 g (0.025 mol) of Mg (CIO ₄ I ₂ in 40-55 ml of acetic anhydride, boiled for 1 min and cooled ,

By adding 20 ml of ether or ethyl acetate, the crystallization is completed. The salts are filtered off with suction and the isopropanol recrystallized.

Variant C

Analog variant B, except that the reaction mixture is refluxed for 10 minutes.

Variant D

Analog variant A, except that the resulting oil is dissolved in acetonitrile at 8O ⁰ C. The precipitating solid on cooling becomes solid

filtered off and recrystallized from isopropanol. , , , ,

Table 1

Prepared, in the 2-position by nucleofug easily exchangeable radicals substituted 3,5-diarylthiazolium salts of type III

Ar ' Ar " X Z Schmp./ Ausb./Variante ° C (% D.Th.) C ₆ H ₅ C ₆ H ₅ pyrrolidino CIO ₄ 131-4 89 / A PC ₆ H ₅ -C ₆ H ₄ C ₆ H ₅ pyrrolidono CIO ₄ 223 92 / A P-Br-C ₆ H ₄ C ₆ H ₅ morpholino CIO ₄ 116 81 / A P-Br-C ₆ H ₄ C ₆ H ₅ SC ₆ H ₅ CIO ₄ 101 73 / B P-CI-C ₆ H ₄ C ₆ H ₅ SC ₆ H ₅ CIO ₄ 191 83 / D 82 / B P-NO ₂ -C ₆ H ₄ C ₆ H ₅ SC ₆ H ₅ CIO ₄ 254 76 / B C ₆ H ₅ C ₆ H ₅ SC ₆ H ₅ CIO ₄ 193 91 / B 96 / D PC ₆ H ₅ -C ₆ H ₄ C ₆ H ₅ OCH ₂ C ₆ H ₅ CIO ₄ 123-4 93 / D 73 / D P-CI-C ₆ H ₄ C ₆ H ₅ OCH ₂ C ₆ H ₅ CIO ₄ 105 96 / C 62 / D

Claims (2)

1. Process for the preparation of in 2-position by nucleofug easily exchangeable radicals substituted 3,5-Diarylthiazoliumsalzen, characterized in that Halogenmethylarylketone type I ArC-CH ₁ HoL with arylaminothiocarbonic acid derivatives of the type II in a condensing agent such as acetic anhydride and optionally in the presence of a metal salt of a mineral acid such as Mg (CIO ₄ J ₂₎ to the 3,5-diarylthiazolium salts of type III which are substituted in the 2-position by nucleofugically exchangeable radicals,