DD272860A1 - METHOD FOR PRODUCING NEW CUMARIN COMPOUNDS - Google Patents

Abstract

The invention relates to a process for the preparation of novel 3- (1,2,4-triazol-5-yl) -7-dialkylaminocoumarines and their quaternary salts by condensation of 4-dialkylamino-2-hydroxybenzaldehydes with 1,2,4-triazole 5-yl-acetic acid derivatives, preferably 1,2,4-triazol-5-yl-acetonitriles, in alcoholic / aqueous solution with the addition of hydrochloric acid, wherein the quaternary color salts by subsequent alkylation of the dyes according to the invention or by condensation of the aldehyde with the previously quaternized 1,2,4-triazol-5-yl-acetonitrile. The new coumarin compounds are suitable as textile dyes for polyester or polyacrylonitrile fibers for embedding polymeric compositions and as fluorescent dyes and have high fastness properties.

Description

Formula I

E r is attained finduivjE'jeniäß the Aufgabe- by reacting <tO! ^'L 3l .y! 3mino-2-hyciroxybsnz3! Dehyde dor general formula or containing them Heaktionslösungen

CHO

AIk: C, to C ₄

with Triazclygligsigsäurederivaten of the general formula III

ii

 II

Formula Il

R ₁ ί Π, alk-, -

Formula III

R ₃ : II, Alk-, OAlk, Hol-, -Ii R _A : -CO ₀ Alk, -CIi, COOIi

heated according to known methods in aqueous alcoholic solution with the addition of acids, preferably hydrochloric acid, under reflux and deposited daboi coumarins of the general formula I by dilution with water and neutralization of Reaktioiislösung separates. By methods known per se, the quaternary salts of the general formula IV are obtained from the compounds of the formula I by alkylation in organic solvents such as, for example, benzene, toluene, chlorobenzene or dimethylformamide with alkylating agents, preferably dimethyl sulfate

CII ₃

auk

- -V-- R-

R ₁ J II, Alk-,

R ₂ : Alk, -

R _3: Ii, Alk, OAlk, fetch, _-II0? A ": ZnCl ₃ " *, Hol ~, CII ₃ SO ₇ , "

Formol IV

-5- 272 8CO

However, the compounds of the general formula IV are obtained particularly advantageously if one condenses compounds of the formula II according to the process already described with compounds of the formula V.

CH.

+ "ti ^X 3

Jb GH ₂ GlT

Formula V

R.

H, alk, -

R ₀ : Alk, ~

R ₃ : II, Alk, OAlk, Hal, -HO ₂

A ": CII ₃ SO ^", Hai ", ZnGl ₃ ~, 011

and isolated by salting out of the reaction solution.

The compounds of the general formula I and IV are valuable textile dyes, preferably polyester and

color modified polyacrylonitrile fibers with good fastness properties in greenish-yellow shades.

embodiments example 1

13 parts (g) of 3,4-diphenyl-1,2,4-triazol-5-yl-acetonitrile and 10 parts of (g) 4-diethylamino-2-hydroxybenzaldehyde are dissolved in 100 ml

Ethanol and 10ml of concentrated hydrochloric acid for 1 hour reflux. After cooling, it is diluted with 300 parts of water

and sucked off. This gives 18.5 parts of (g) 3- (3,4-diphenyl-1,2,4-triazol-5-yl) -7-diethylaminocoumarin, mp. 242-244 ⁰ C. Das

Product dissolves in organic solvents with a greenish yellow color. Xmax. 415nm. The elemental analysis is correct

the molecular formula C ₂₇ H ₂₄ N ₄ C ₂ .

In an analogous procedure, the following coumarin compounds of the general formula I are obtained (Alk = C ₂ H ₆ )

at Ri R2 to hum (Mol. fp Y. Section. game formula Wt.) ^A max. 2 Ph -P-CHPH C ₂₇ H ₂₃ N ₄ O ₂ Cl (470.0) 248-249 ⁰ C / 93% 416nm methanol 3 Ph -P-CH ₁ -Ph C ₂₈ H ₂₆ N ₄ O ₂ (450.5) 267-270 ⁰ C / 70% 414nm methanol 4 Ph -P-OCH ₃ Ph C ₂₈ H ₂₆ N ₄ O ₃ (466.5) 276-278 ⁰ C / 65% 415nm methanol 5 pH -P-NO ₂ -Ph C ₂₇ H ₂₃ N ₆ O ₄ (481.4) 279-281 ⁰ C / 65% 417nm methanol

Example β

23.5 parts (g) of the coumarin compound from Example 2 are dissolved in 200 ml of dimethylformamide and 12.5 ml of dimethyl sulphate are added. The mixture is heated for 10 minutes under reflux and diluted after cooling with 1000 parts of water. The dye is precipitated by adding 100 ml of 20% zinc chloride solution. This gives 24 parts (g) of a dye salt, which dyes polyacrylonitrile ingruenichichig-yellow shades with good fastness properties.

Lightfastness ": 3 Wet fastness ": good In an analogous procedure, the following color salts of the general formula V (Alk = C ₂ H ₆ ) A "= V: ZnCl ₄ ² *")

examples R rj Section. Lightfastness ¹¹ wet fastness " Viax »7 Ph Ph 430 nm 3 Well 8th Ph -P-CH ₃ -Ph 430 nm 3 Well 9 Ph -P-OCH ₃ -Ph 430 nm 3 Well 10 Ph -P-NO ₁ -Ph 440 nm 2-3 Well

1) (dyeings on Wolpryla P 65 by exhaustion)

Example 11

13 parts (g) of 3,4-diphonyl-1,2,4-triazol-5-yl-acetonitrile are dissolved in 50m! Chlorobenzene reacted with 7 ml of dimethyl sulfate. 20 parts (g) of the quaternary salt thus prepared are heated with 10 parts (g) of 4-diethyiamino-2-hydroxybenzaldehyde in 100 ml of ethanol and 10 ml of concentrated hydrochloric acid for 1 h reflux.

After cooling, it is diluted with water to 500 ml total volume and the dye is precipitated with sodium chloride. This gives 20 parts (g) of color salts with the same properties as the product described in Example 7.

Claims (3)

claims: 1. A process for preparing new coumarin compounds, characterized by reacting 4-dialkylamino-2-hydroxybenzaldehyde of the general formula II or these containing reaction solutions GHO al !: AU: Alk: C ₁ to C ₄ with 1,2,4-triazol-5-yl-acetic acid derivatives of the general formula III (II) R ₁ : H, all · -. - R. Alk, - < Ii R ₃ : Ii, Alk-, OAlk, Hal-, -MO ₂ R _/ : -GO ₂ AIk, -GIi, COOH in aqueous-alcoholic solution with addition of acids, and at elevated temperature, to give 3- (1,2,4-triazol-5-yl) -7-dialkylaminocoumarine of general formula I. (I) Ί ' R. iv K ₃ :: ΐ, AlV.-, OAlk, ilyl-, -IiO ₂ reacted according to methods known per se and if appropriate subsequently converted into alkylated solvents in the quaternary compounds of the general formula IV in organic solvents, \ ι ν X v ^ \ R. birj (IV) - Yi. iU::, Alk-, OAl ':, HnI-. -. "ΙΟ, ^ ti or the compounds of general formula II with quaternary Triazolylessigsäurederivaten of the general formula V Ιί _ο : Al;:, - (V) condensed directly to the quaternary compounds of the general formula IV according to the above-claimed procedure. 2. The method according to claim 1, characterized in that are preferably used as compounds of formula III, 1,2,4-triazol-5-yl-acetonitriles. 3. Process according to Claim 1, characterized in that the alkylation of the compounds of the general formula I is advantageously achieved by dissolving them in dimethylformamide. , id heated for 0.5 to 2 hours with the addition of 1 to 2 equivalents of dimethyl sulfate. Field of application of the invention The invention relates to a process for the preparation of novel 3- (1,2,4-triazol-5-yl) -7-dialkylaminocoumar and their quaternary salts which are used as textile dyes for dyeing polymer compositions or as fluorescein. enzfarbstoffe are suitable. Characteristic of the known state of the art In DE-OS dor 2-115661 dio representation vun 3- described -7-diethyl aminocumariniminen! (1,2,4-triazol-5-yl) but in which the Ti iazolring in contrast to the compounds beanspruchton by us in 1-position is unsubstituted. As W. Kuzmierkiewicz (Liebigs Ann. Chem. 1987, 5Ί1-543) demonstrated, such Iminocoumarine tend to follow-up reactions, so that only condensed pyrimidines from the reaction solution could be isolated and only under special conditions 3- (1,2,4 Triazole-5-yl) coumar; nimines are accessible in moderate yields. Object of the invention The aim of the invention is to make new brilliant grünstichiggelbc Cumarinfarbstoffe, dio for a Cumarine guv ^ s level of authenticity, accessible in a simple manner and from readily available intermediates. Presentation of the essence of the invention The invention has for its object to develop a technologically simple process for the preparation of new Cumprinvcrbindungon the general formula I and their quaternary salts, which exploits these compounds in Ikhen! free from by-products.