DD204094A1 - PROCESS FOR PREPARING 2-ARYL-4-CUMARYL- (3 ') - BZW. 2,4-BIS-coumaryl (3 ') - thiazoles - Google Patents

Abstract

Such compounds can gain importance as dyes and as biologically active compounds. With the invention is to be achieved to produce the hitherto unknown 2-aryl-4-cumaryl- (3) - or 2,4-bis-cumaryl- (3) -thiazole in a simple manner. This is done according to the invention in such a way that 3- (bromoacetyl) coumarins with thioamides or with 3-thiocarbamoyl-coumarins or cyanthioacetamide optionally with subsequent reaction with an o-hydroxybenzaldehyde to 2-aryl-4-cumaryl- (3) -thiazolen of type I or 2,4-bis-cumaryl (3) thiazoles of type II are reacted. The invention can be used in the chemical and pharmaceutical industries.

Description

Process for the preparation of 2-aryl-4-cuiaaryl- (3 '') or 2.4-BiS-CUiHaTyI- (3 ') -thiazoles

Int. Cl. :. CO? D 417/04 Field of application of the invention

The invention relates to a process for the preparation of 2-aryl-4-cumaryl- (3 *) - or 2 '"-4-bis-cumaryl- (3') - thiazoleη Such compounds may be of importance as dyes in the dyeing erosion, as biological active compounds and as a light absorber in electrophotography. and obtain in other recording methods,

Characteristic of the known technical solution

2-aryl-4-cujr.aryl- {3 ') - or 2.4-3is-cumaryl ^ {3'! -Thiazoles are hitherto unknown.

Objective of the invention

The aim of the invention is the hitherto unknown 2-aryl-4-cumaryl- (3 ') - or 2 .4-bis-cum.a ryl- (3') - thiazoles as dyes and biologically active compounds of easily prepared Access to starting products *

- 2 -

-Z-

Darling of the essence of the invention

237330

The object of the invention is to find a method to produce the hitherto unknown 2-aryl-4-cumaryl- {3 *.) - or 2,4-sis-cumaryl-iS ¹ ) -thiazole in a simple manner »Erfindungsgemaß the object is achieved in that Z- (C ^ -3romacetyl) coumarins type I

/ Br

with type II thioamides

II

or with S-thiocarbamoyl-coumarin-iyps

III

to the 2-aryl-4-cumaryl (3 ') - thiazoles of type IV

IV

- 3 -

237330 1

or to the 2.4-3is-cumaryl- (3 *) -thiazoles of the type V,

or that Type I 3- (£ a / bromoacetyl) coumarina with cyan thioacetamide VI

VI

to the 2-cyanoethyl-4-cumaryl (3 ') - thiazoles VII,

VII

those with o-Hydroxybenzaldehyden the type VIII

VIII

with the addition of a base such as z, 3-ιriethylamin, piperidine, pyridine or NaGH to the 2-Ini.inocumaryl- (3 ') -4-cumaryl (3') thiazoles type IX,

IX

which by hydrolysis in the

¹ ) -thi-

R and R are identical or different, hydrogen, the OH, alkoxy and a; N "N-dialkylamino group or a fused in the 5.5-position benzene ring, R and R, the same and may be hydrogen, the OH, alkoxy, halogen, methyl or a N, N-dialkylamino group and R and R, which can be identical or different, and are hydrogen, the OH, alkoxy, halogeno, or , Methyl or N, N-dialkylamino group and a senzol ring fused in 5.6 position, represent »

AusfQhrungsbeispieIe

The compounds represented by the variants listed here, of the type IV ₁ V and IX are summarized in Tables 1-3.

option A

0.010 mol of 3- (LU "-3roinacetyl) -coumarin type I, prepared according to a modified synthesis procedure according to C-.F, KOELSCH, 0, Amer.chera.Soc. 72, 2993 (1950) and 0.015 mol of a Tbioaraides of the type II, III or VI are suspended in 30 ml of ethanol and refluxed for 5-30 minutes. The crystals which precipitate on cooling are filtered off with suction and subjected to ultraprecystallization from the solvent indicated in the Tables. »

Variant B

 The procedure is analogous to variant A, but the reaction mixture is added before boiling at reflux with 5-8 drops of piperidine.

Variant C

0.010 mol of 2-cyanomethyl-4-cumaryl- (3 ') - thiazole of the type VII, prepared by reacting equi-polar amounts of a 3- (or bromoacetyl) -coumarin type -I with Cyanthioacetamid type VI, analog variant A, and 0.012 h of the o-hydroxybenzaldehyde type VIII are suspended in 25 ml of ethanol, mixed with 5 drops of piperidine and refluxed for 10 minutes. * The crystals formed during cooling are filtered off with suction and the filtrate is diluted with water to separate further end product the combined filter residues from the specified solvents. Recrystallized

Variant D

The mixture of 0.010 mole of 2-Cy3nmethyl-4-cumaryl- (3 *) - thiazoT type VII, 0.012 mole of o-Hydroxybenzaldshdes type VIII and 25 ml of ethanol is added with stirring at room temperature with 5 mi 20 % sodium hydroxide solution , That soon after precipitating final product is filtered off with suction and recrystallized.

- o

23733Ö

Variant Ξ

0.010 mol of 2-Iminocuraaryl- {3 ') - 4-cumaryl- (3 *) - thiazole type IX are suspended in 30 ml of 70% ethanol and briefly boiled with the addition of 5 ml of dilute hydrochloric acid * 4-3is ^ curaaryl- (3 ') - thiazole Type V is filtered off and recrystallized,

Variant F

Analog variant E _4, but instead of ethanol, glacial acetic acid is used.

ii r, ι i '\;<

_mlm J ^^

I ύ / J J υ i

Table 1: Prepared 2-aryl-4-cumaryl- (3 ') - thiazoles type IV

Embodiment. No. R ¹ H 2 H R ³   H R ⁴ H Schmp »/ ° C (umkrist,) Training / Va % d.Th « X H H 4-CH ₃ - 3-CH ₃ O- 142 acetonitrile 89 / A 2 H H 4-CH ₃ O- N- H 203 acetonitrile 95 / A 3 H H A- (CH ₃ ) ₂ H. 157 acetonitrile 87 / A 4 H ff 4-chloro- H 201 acetonitrile 69 / A 5 5,6-3enzo 4-CH3 3-CH ₃ O- 201 acetonitrile 78 / B 6 5 '6-Senzo 4-CH ₃ O- N- H 233 DMF 8 l / A 7 5 x 6-Ββηζο 4- ₍ CH ₃ ) ₂ H 234 acetonitrile 56 / A 8th 5,6-3enz * o 4-chloro- h ^r 298 DHF 63 / Ä f 7-CC ₂ H ₅ J ₂ M - H" H H 253 DMF 49 / A ίο 7- (C ₂ Hg) ₂ N - H 4-CH ₃ - 3-CH ₃ O- 133 ethanol 86 / A 11 · 7- (C ₂ Hg) ₂ N - H 4-CH ₃ O- N- H 149 ethanol 92 / A 12 7- (C ₂ H ₅ J ₂ N - H 4- (CH ₃ J ₂ H 191 acetonitrile 78 / A 13 7- (C ₂ HJ ₂ N - H 4-chloro- 189 ethanol 52 / A 14 196 ethanol 66/3

23 7 3'J υ ι

Table 2. Prepared Type V 2 * 4-8is-cumaryl- (3 *) -thiazoles

Example # no.

R '

R "o

R Schmp, / C Ausb./Var.

% d. Th ..

(Urakrist.)

H H '7-

HH 8-CH ₃ Q-

279 DMF

307 DMF

9 β / Ξ 95 / F

84 / Ε

table

Prepared Type IX 2-iminocoumaryl- (3 ') - 4-ctimaryl- (3') thiazoles

Off / f, _ R "" beisp ♦

Schmp, / C (Ufkrist »)

Ausb, / var.

ld, Th,

H S-CH ^ O o

H 273 ril Acetonit H 241 ril Acetonit H 254 ril Acetonit

93 / G

84 / D

75 / C 87 / C

Claims (1)

- g - 3733 Srf Indication claim A process for the preparation of 2-aryl-4-cumaryl {3 ') or 2.4-bis-cumaryl-C3') = thiazoles, characterized in that 3- (u7-3roraacetyl) coumarins type I with thiomides of type II II or with 3-i-hiocarbamoyl-coumarins of type III to the 2-aryl-4-curaaryl- {3 ') - thiazoles of the type IV IV or, to the 2.4-3is-curnaryl (3 ^< ) thiazoles of type V ₁ 237330 1 or that 3- {u / -3romacetyl) -coumarins type I with Cyanthioacetamid VI CN-CH ₂ -CSNH ₂ VI to the 2-cyanomethyl-4-cumaryl {3 ') -thiazoles VIi, VII those with type VIII o-hydroxybenzidehydes «5 VIII with the addition of a base such as "3. Triethylamine, piperidine, pyridine or NaOf! to the 2-iminocoumaryl- {3 ') -4-cufsaryl- (3') thiazoles of type IX, IX which can be converted into the 2.4-3is-cumaryl- (3 ') -thiazoles of type V by hydrolysis, where R and R are identical or different, hydrogen, the OH, alkoxy or a N-N-alkylamino group or an annelierten in 5,6 position 3 4 3-membered ring, R and R, which may be the same or different and are hydrogen, the OH, alkoxy, halogen, methyl or sine - 11 - N, N-dialkylamino group and R and R, which may be the same or different, and are hydrogen, OH, alkoxy, halogen, methyl or an N, N-dialkylamino group and a benzene ring fused in 5.6-position.