DD272861A1 - METHOD FOR PRODUCING NEW CUMARIN COMPOUNDS - Google Patents

Abstract

The invention relates to a process for preparing 3- (1,3,3-trimethylindolen-2-yl) substituted 7-dialkylaminocoumarins by reacting 4-dialkylamino-2-hydroxybenzaldehydes with 1,3,3-trimethyl-2-methylenindoline-v -carbonsaeurederivaten in aqueous mineral acid medium.

Description

Alk «= C« - C

 or these reaction solutions containing, with indoline derivatives of the general formula

CH-R.

(Hl)

R = H, Alk, OAlk, -NO ₂ , -Hai Alk = C ₁ -C ₄ R ₁ = CO ₂ Alk, CN, -CONHC ₆ H ₅

in mineral acid aqueous solution and at elevated temperature to quaternary salts of 3- (1,3,3-trimethylindolen-2-yl / substituted 7-Dialkylarninocoumarine the general formula I.

(D

auk

auk

R = H, Alk, OALk, -Hal, -NO ₂ Alk = C ₁ -C ₄ X = Hal, ZnCl _{3 is} reacted by methods known per se.

2. The method according to claim 1, characterized in that is used as indoline derivatives preferably 1 AS-trimethyl ^ -mathylenindoline-carboxylic acid anilides.

Field of application of the invention

The invention relates to a process for the preparation of novel 3- (1,3,3-trimethylindolen-2-yl) -7-dialkylaminocoumarine, which can be used as a textile dye ^, mainly for polyacrylonitrile fibers.

Characteristic of the known state of the art

DE-OS 2415661 describes the preparation of 3- (1,2,4-triazol-5-yl) -7-diethylaminocoumarinimines, in which, however, the triazole ring is unsubstituted in contrast to the compounds in the 1-position claimed by us , * As W. Kuzmierkiewicz (Liebigs Ann. Chem. 1987,541-543) demonstrated, such iminocoumarins tend to follow-up reactions, so that only condensed pyrimidines could be isolated from the reaction solution and only under specific conditions 3- (1,2,4- Triazol-5-yi) coumarinimines are accessible in moderate yields.

The known from DE-OS 2142411 3-quinolyl-substituted coumarins do not show the desired bluish red nuances. In addition, alkylation and workup are associated with additional equipment.

Object of the invention

The aim of the invention is to complement the range of coumarin dyes ' .or polyacrylonitrile, which has hitherto mainly composed of greenish yellow to orange shades to complement easily accessible brilliant red marks that are well combinable with each other and as single and mixed dyes of interest.

Disclosure of the essence of the invention

The invention has for its object to provide a method that allows to provide new coumarin compounds of general formula I from readily available starting materials in high yield.

AlkAlk

R = H, Alk, -OAlk, -Hal, -NO ₂ X = Hal, ZnCl ₃ and others According to the invention, the object is achieved by reacting 4-dialkylamino-2-hydroxybenzaldehyde of the general Formula II, or these containing reaction solutions,

CHO

AlkAlk

in aqueous mineral acid solution with 1,3,3-trimethyl-2-methylenindoline <i) -carboxylic acid derivatives of the general formula I.

III

R = H, Alk -, - OAlk, Hal -, - NO ₂ R, = -COOAlk ₁ -CN ₁ -CONHC ₆ H ₆

heated according to known methods in short reaction times of 1 to 3 hours to 90 to 10O ⁰ C and after cooling the dye with excess Zincchloridlöpung and with the addition of sodium chloride falls. Surprisingly, it has been found that, as compounds of formula III, the readily available 1,3,3-trimethyl-2-meshylenedininecarboxylic anilides can be used to advantage and after a reaction time of about 2 hours, the formation of the desired

Coumarin compounds is completed, although heterocyclic substituted acetic anilides not at all or extremely inert in

the coumarin synthesis react.

1,3,3-trimethyl-2 · methylenindoline-co-carboxylic acid anilides are known from the literature and arise z. B. from the technical

Available 1,3,3-trimethyl-2-methylenindolines in the reaction with phenyl isocyanate. This procedure allows the coumarin compounds of formula I in one step without the usual

to produce subsequent alkylation. The coumarin compounds according to the invention are new valuable dyes which color polyacrylonitrile fibers in brilliant pink to violet shades and thus the range cationic

Coumarin dyes complement and allow the production of brilliant mixed dyes. embodiments example 1

10 g of 4-diethylamino-2-hydroxybenzaldehyde and 14.6 g of I.S.S-trimethyleneindoline-iu-carboxylic acid anilide are dissolved in 100 ml of water and 40 ml of concentrated hydrochloric acid and heated to 100 ° C. for 2 hours. After cooling, prediluted with 400 ml of water and the dye with 25 ml of 20% aqueous zinc chloride solution and SOg sodium chloride like. You get 23g dry

Dye which dyes polyacrylonitrile fibers in brilliant pink shades with good wet fastness properties. Lightfastness 3-4

^x max: 550nm / ethanol

With otherwise the same procedure, the following dyes of the general are obtained in similarly good yields Formula I (X = ZnCl ₃ ")

at R nuance Aa bs. Lichtecht- " Naßecht- " game Max Ness units 2 5-CH ₃ b.illantesRosa 555 / methanol 3-4 Well 3 5-OCH ₃ brilliant 560 / methanol 3-4 Well pink 4 5-NO ₂ brilliant 580 / methanol 3- ^ 1 Well violet 1) Dyeings on Wolpryla P 65 in the stripping process

Example 5

In otherwise the same procedure as in Example 1 is obtained from 12.5 parts (g) 1,3,3-trimethylindoline <ocarbonsäureethylester 19 Teilelg) of a brilliant pink dye, which is identical to the product described in Example 1.

Claims (1)

claims: 1. A process for preparing new coumarin compounds, characterized in that 4-dialkylamino-2-hydroxybenzaldehyde of the general formula II CHO auk auk