DE2529434B2 - COLORS OF THE CUMARIN SERIES AND THEIR USE - Google Patents

Description

R '

(Ib)

R- ¹

in which R ^{1 is} alkyl having 1 to 4 carbon atoms, preferably methyl or ethyl, and R and X have the meanings given.

3. Use of the dyes according to claim 1 for dyeing synthetic and semi-synthetic Fibers.

4. Use of the dyestuffs according to Claim 1 for coloring plastics in bulk or you the transfer printing.

The invention relates to dyes of the formula 1

Ν — Ν

in the RC ₁ - to C ₄ -alkyl, benzyl, / J-hydroxyethyl

or -propyl, / JC ₁ - to C ₄ -alkoxyethyl or -propyl. / I-cyanoethyl, />'- carb-C, - to C ₄ -alkoxyethyl. / Hp'-Äihylmercapto- or Äthylsulfonyläthoxy) -äthyl, / 7-phenoxyethyl, cyclohexyl, optionally phenyl, naphthyl, pyridyl, furyl or thienyl, R ¹ hydrogen, C.sub.1, optionally substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy or cyano ₁ - to C ₄ -alkyl, optionally with cyano, C ₁ - to C ₄ -alkoxy, chlorine. Bromine, carboxyl, carb-C _{1 -C 4} -alkoxy, carbonamide or acetoxy-substituted C _{1 -C 4} -AlKyI.

Cyclohexyl, benzyl, phenylethyl or phenyl, R ^{2 is} hydrogen, _{C 1 to C 4} alkyl or optionally by cyano, C 1 to C ₄ alkoxy, chlorine, bromine. Carboxyl. Carb-C, - to C ₄ -alkoxy, carbonamide or acetoxy-substituted C ₁ - to C ₄ -alkyl, R ¹ and R ² together with the nitrogen the remainder of a 5- or 6-membered saturated, heterocyclic ring, R ² together with the Nitrogen is a radical of the formula which is condensed on in the ortho position to the nitrogen

R ¹ CH ₃

-N-CH-CH ₂ -

R ¹

and X is oxygen or imino.
2. Dyestuffs according to Claim 1 of the formula

N-N

or

CH ₃ CH ₃

-NC-CH ₂ -CH-R ¹ CH ₃

-N-CH-CH ₂ -R ¹ CH ₃

QH ₅

-N-CH-CH ₂ -R ¹

and X is oxygen or imino.

In addition to the radicals already mentioned, the following are examples of substituents: for R ¹ and R ² : methyl, ethyl, n- or i-propyl, n- or i-butyl, / i-methoxyethyl, / I-ethoxyethyl, fi-acetoxyethyl , / i-chloroethyl, / 5-carbomethoxyethyl, / MTarboethoxyethy), / i-carbobutoxyethyl, / I-methoxypropyl, / i-eth-

impropyl, /, '- methoxy-y-chloropropyl or,; - acetoxyprnpyl.

Together with the nitrogen, R ¹ and R ² mean ι. B. the remainder of the pyrrolidine, piperidine, morpholine, piperazines or N-methylpipcrazines.

Chemicals are of particular technical importance of formula 1 a

c) compounds of formula V

A A

C-NH-HNC-R

R ²

(la)

(V)

in which R ^{1 is} alkyl having 1 to 4 carbon atoms, preferably methyl or ethyl, and R and X have the meaning given. Door X is preferably oxygen and door R is optionally substituted phenyl.

The new fluorescent dyes are of high brilliance, the color tones are yellow-green Area. They are suitable for dyeing textile material made of synthetic and semi-synthetic Fibers, e.g. B. from polyamides, cellulose esters. Acrylonilrilpolymcrisaten and in particular polyesters as well as bulk coloring of plastics. Easy subliming dyes are also suitable for transfer printing.

The dyes of the present invention are very extensive (brightly colored) and result in colorations with good lightness and thermal stability.

To prepare the compounds of formula 1, one can

al compounds of the formula II

in which one A is sulfur and the other is oxygen, cyclize according to DT-PS 1249 873.

Compared to the known processes, there are no deviations in the preparation of the dyes according to the invention; the reactions take place analogously.
Compounds of formula IV are, for. B. by reacting compounds of formula 11 with compounds of formula VI

NC-Ch ₂ CONH-NHCOR (Vl)

accessible.

In the following examples, data relate to by parts and percentages, unless otherwise noted, by weight.

CHO

with compounds of formula III

N-N

Y-CH,

in which Y denotes cyano or carb-Q- to C ₄ -alkoxy, condense according to DT-PS 1098 125 or DT-OS 20 11 500 or
b) compounds of the formula IV

CONH- NHOC- R

cyclize according to DT-PS 11 34 080 or

example 1

7 parts of 4-diethylaminosalicylaldehyde in 50 percent by volume Isopropanol are made with 9 parts

2 - [5 '- Phenyl - ihiadiazolyl - (2')] - acetic acid ethyl ester and 2 parts by volume of pyrrolidine heated to boiling under reflux for 15 minutes, then cooled and sucked off.

K) parts (73% of theory) of 3- [5'-phenylthiadiazolyl- (2 ')] - 7-diethylaminocoumarin are obtained Melting point 270-272 ° C (from DMF).

Example 2

(II) Used instead of 4-diethylaminosalicylaldehyde 4-Dimethylaminosalicylaldehyde and processes otherwise as indicated in Example 1, one obtains

3 - [5 '- Phenylthiadiazolyl - (2')] - 7 - dimethylaminocoumarin in 55% yield of theory. with a melting point of 286 290 ¹ C.

Example 3

19.3 parts of diethylaminosalicylaldehyde and 20.1 parts 2-Cyanmethyl-5-phenyl-thiadiazole in 100 parts by volume of isopropanol with 5 parts by volume of pyrrolidine Heated to boiling under reflux for 15 minutes. After cooling, the 3- [5'-phenyl-ihiadiazolyl is sucked - (2 ')] - 7 - diethylamino - 2 - iminocoumarin, melting point 228-230 "C, in 79% yield away.

4.6 parts of the iminocoumarin are dissolved in 40 parts by volume of ethanol with 10 parts by volume of water and 10 parts by volume of concentrated hydrochloric acid heated to boiling for 1 hour. After cooling down, it is suctioned off, suspended the filter material in water, made alkaline with ammonia and filtered off again with suction. 4 parts (87% of theory) of 3- [5'-Phcnyl-thiadiazolyl- (2 ')] - 7-diethylaminocoumarin are obtained from melting point 272-275 ° C.

The compounds listed in Table I are obtained analogously to Example 3.

(IV)

N N - N > S. \ "ο

R-

Example R 'R ² R ¹ R ^J

4 -CH ₃ --CHj HH

5 -C ₂ H ₅ -C ₂ H ₅ 4-Cl H

6 -C ₂ H ₅ -C ₂ H ₅ 2-Cl H

7 -GH, -CHj 4-Cl H

8 -CH ₃ -CH ₃ 2-Cl H

9 -C ₂ H ₅ -C ₂ H ₅ 2-Cl 4-Cl

10 - CHj -CHj 2-Cl 4-Cl

11 -C ₂ H ₅ -C ₂ H ₅ 2-Cl 6-Cl

12 -CH ₃ -CH ₃ 2-Cl 6-Cl

13 -CH ₃ -CHj 4-CHj H

14 -C ₂ K ₅ -C ₂ H ₅ 4-CHj H

15 -CHj -CHj 4-OCHj H

16 -C ₂ H ₅ -C ₂ H ₅ 4-OCHj H

17 -CH ₃ -CHj 4-OC ₂ H ₅ H

18 -C ₂ H ₅ -C ₂ H ₅ 4-OC ₂ H ₅ H

19 - CHj -CHj 2-OCHj H

20 -C ₂ H ₅ -C ₂ H ₅ 2-OC Hj H

21 - CHj -CHj 4-NH

CH ₃
CH ₃

22 -C ₂ H ₅ -C ₂ H ₅ 4-NH

CHj

23 -C ₂ H ₅ -C ₂ H ₅ 4-NO ₂ H

24 -CH ₃ -CH ₃ 4-NO ₂ H

25 -CH ₃ -CH ₃ 4-CN H

26 -C ₂ H ₅ -C ₂ H ₅ 4-CN H

27 -CH ₃ -CH ₃ 4-CO ₂ C ₂ H ₅ H

28 -C ₂ H ₅ -C ₂ H ₅ 4-CO ₂ C ₂ H ₅ H

Example 29

Parts of N- [7-diethylaminocumaroyl- (3)] - N'-buty-, the precipitate is filtered off with suction. 6.5 parts are obtained

rylhydrazine in 60 parts by volume of pyridine with (95% of theory) 3- [5'-propyl-thiadiazolyl- (2 ')] - 7-diethyl-

13.3 parts of phosphorus pentasuind verseUi. Eraminocoumarin with a melting point of over 30O ⁰ C. is heated to 60 ° C. for 1 hour and below 65 for a further 5 hours.

Reflux. After cooling, the reaction compounds, which can be prepared analogously,

mixture mixed with 60 parts by volume of ethanol and listed:
carefully stirred into ice water. After 1 hour

R ¹

Example R ¹

30th -CH ₃ Propyl 31 - C ₂ H ₅ isopropyl 32 -CH ₃ Butyl 33 -C ₂ H ₅ Butyl 34 -CH ₃ isobutyl 35 -C ₂ H ₅ isobutyl 36 -CH., -CH ₃ 37 -C ₂ H ₅ -CH ₃ 38 -CH ₃ -C ₂ H ₅ 39 -C ₂ H ₅ -C ₂ H ₅ 40 -CH ₃ -CH ₂ - 41 -C ₂ H ₅ -CH ₂ -

42

43

44 45 46 47

48

49 50

_CH, -CH ₂ -O-CH ₂ -CH ₂
-CH ₇ -CH ₂ -OO-CH ₂ -CH ₃

-CH ₃

-0-CH ₁ -CH ₂ -SC ₂ H ₅

-CH ₃

-CH _{5 the} same.

-CH ₁ -CH ₁ -O-CH ₂ -CH ₂ -S-QHs
-CH, -CH ₂ -O-CH ₂ -CH ₂ -SO ₂ -QH ₅

-C ₂ H ₅ like.

-CH ₃ -CH ₂ -CH ₂ -O-

-CH _{5 the} same.

example

1.4 parts of N- [7-diethylaminocumaroyl- (3'0-N'-isonicotinylhydrazine are in 50 parts by volume of pyridine with 10 parts by volume of pyrrolidine and then at room temperature mixed with 20 parts of phosphorus pentasulfide. The mixture is then stirred at 60 ° C. for 1 hour and then gradually increases the temperature to C. The mixture is stirred at this for a further 5 hours Temperature, then cools, 100 parts of ethanol are added and the reaction mixture is poured into 2C

Ice water. The mixture is stirred for 2 hours

then the precipitate from. You get

(82% of theory) 3- [5 '- (Pyridyl- (4) -lhiadiazu

t._s 7-diethylaminucumarin from the melting point

283C (from DMF).

The results in Table 3 are obtained analogously

Links:

example

_ _{r H} ²

_H ^{2 5}

-CH ₃

ίο

example

R ²

-CH,

-CH ₃

Example 58

A solution of 19.3 parts of 4-diethylaminosalieylaldehyde and 20.1 parts of 5-phenyl-2-cyanomethylthiadiazole in 80 parts by volume of dimethylformamic is mixed with 20 parts by volume of 32% hydrochloric acid and stirred at 100 ° C. for 1 hour. It entsteh ¹ a Krislallbrei, which is at 80 ⁰ C with 2-n Natronlaugt to a pH of 4-5 provided, suction filtered then cooled, washed with water and getrockne. 30 parts (79.5% of theory) of 3- [5'-phenylthiadiazolyl- (2 ')] - 7-diethylaminocoumarin are obtained.

Claims (1)

Patent claims:
1. Dyes of the formula N-N (la) in the RC ₁ - to C ₄ -alkyl, benzyl, / i-hydroxyethyl or -propyl, / iC, - to C ₄ -alkoxyethyl or -propyl, / ϊ-cyanoethyl, / i-carb-C, - to Q- alkoxyethyl, / Hff'-ethylmercapto- or Älhylsulfonyläthoxy) -äthyl, / i-phenoxyethyl, cyclohexyl, optionally phenyl, naphthyl, pyridyl, furyl or thienyl substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy or cyano, R ¹ hydrogen , C ₁ to C ₄ alkyl optionally substituted by cyano, C, - to C ₄ -alkoxy, chlorine, bromine, carboxyl, carb-C, - to C ₄ -alkoxy, carboxamide or acetoxy-substituted C ₁ - to C ₄ -Alkyl, cyclohexyl, benzyl, phenyl or phenyl, R ² hydrogen, C ₁ - to C ₄ -alkyl or optionally by cyano, C ₁ - to C ₄ -alkoxy, chlorine, bromine, carboxyl, carb-C, - to C _4- alkoxy, carbonamide or acetoxy-substituted C ₁ - to C ₄ -alkyl. R ¹ and R ² together with the nitrogen form the remainder of a 5- or 6-membered saturated, heterocyclic ring, R ² together with the nitrogen form a remainder of the formula which is condensed ortho to the nitrogen CH ₃ CH ₃ -NC-CH ₂ -CH-R ¹ CH ₃
-N-CH-CH ₂ -