DE2030507B2 - Oxazolyl coumarins, their manufacture and use - Google Patents

Description

H-N

wherein R ₁ and R _{2 are} independently hydrogen, alkyl, cycloalkyl or aralkyl radicals or together with the nitrogen atom to which they are bonded and optionally including further heteroatoms as ring members form a heterocyclic ring, to form a cyanoacetic acid amide of the formula

OR ₁

N = C-CH, -C-N

in which R ₁ and R 2 are as defined above, and this is reacted without intermediate isolation with an o-aminohydroxy compound of the formula

has, to an oxazolyl (2) acetic acid amide of the formula

OR ₁

N Il /

Il

CH ₂ -C- N

R ₂

B-C

Il ο

in which A has the meaning given in claim 1 and B is an OH, alkoxy, aralkoxy or - NR ₁ R ₂ group, where R ₁ and R _{2 are} independently hydrogen, alkyl, cycloalkyl, aralkyl - Or aryl radicals or together with the nitrogen atom and optionally with the inclusion of further heteroatoms as ring members form a heterocyclic ring which subjects the aldol condensation and, optionally after conversion of the o-alkoxy group into the hydroxyl group, brings about the ring closure to the coumarin, which is then free of sulfonic acid groups when used Starting materials is sulfonated if desired.

11. The method according to claim 10, characterized in that that in a one-pot reaction, first a cyanoacetic ester in a manner known per se the formula

Il

N = C - CH ₂ - C - OR "

wherein R "represents a lower alkyl or benzyl radical with an amine of the formula

in which A, R ₁ and R _{2 have} the meaning given above, condensed and this in turn without intermediate isolation with an aldehyde of the formula

CHO

wherein Z ₁ , Z ₂ and Z _{3 have} the meaning given in claim 10, reacts to bring about the coumarin ring closure according to claim 10. 12. A process for dyeing and printing organic fiber materials, characterized in that coumarin dyes of claim I are used.

The invention relates to oxyzolyl-coumarins of the general formula

- (SO ₃ Y) _n

OH

in which A has the meaning given in claim 1 in which A for the remaining members of one optionally substituted by chlorine, alkyl, alkoxy, cyclohexyl, phenoxy, phenyl, benzyl, phenylsulfonyl, alkylcarbonylamino, phenylcarbonylamino, alkylsulfonylamino, phenylsulfonylamino -, alkylsulfonyl, sulfamoyl or carbamoyl radicals substituted benzene or naphthaene radicals, Z ₁ and Z ₂ independently of one another are hydrogen, an alkyl radical optionally substituted by CN, OH, Cl, phenyl, methoxy or acetoxy or the remaining members of a pyrrolidine, N -Methylpiperazine, piperidine or morpholine radicals, where alkyl or alkoxy are to be understood as meaning radicals with 1 to 5 carbon atoms, Y stands for hydrogen or a cation, η represents a number 0.1 or 2, with the proviso that in the event that η denotes the number 0 and A denotes an alkyl-substituted benzene radical, this alkyl substituent either has at least 2 carbon atoms or represents the methyl radical, as well as a Process for their production and their use as fluorescent dyes.
Suitable alkyl radicals in nucleus A are those with 1 to 5 carbon atoms which can have further substituents, such as halogen, hydroxyl and alkoxy. Suitable alkyl radicals are, for. B. methyl, ethyl, chloroethyl, bromoethyl, hydroxyethyl, n-Pro-

pyl, i-propyl and η-, i- and t-butyl. The mentioned Sulfamoyl and carbamoyl radicals can preferably be substituted by alkyl groups.

Suitable cations Y are: sodium, potassium, lithium and ammonium ions and cations more basic Dyes.

The new coumarin compounds of the formula I are obtained when «-hydroxyaldehydes or a-Alkoxyaldehydes of the formula

CHO

No. ₁

(II)

in which Z and Z _{2 have} the abovementioned meaning, Z _{3 stands} for hydrogen or an alkyl radical and in which the benzene ring can also be substituted by a sulfonic acid group, and oxazolyl-2-acetic acid derivatives of the formula

(III)

CH ₂
BC

Il ο

in which A has the abovementioned meaning and B represents an OH, alkoxy, aralkoxy or the --NR ₁ R ₂ group, where R ₁ and R _{2 are} independently hydrogen, alkyl, cycloalkyl, aralkyl or aryl radicals or together with the nitrogen atom and optionally including further heteroatoms as ring members form a heterocyclic ring which subjects the aldol condensation and, optionally after conversion of the o-alkoxy group into the hydroxyl group, brings about the ring closure to form the coumarin, which then, if desired, sulfonates when using starting materials free from sulfonic acid groups will.

In general, reactants II and III are used in approximately equimolar amounts, but have a small excess of one of the compounds has no effect on the course of the reaction.

Suitable aldehydes of the formula II for the reaction according to the invention are, for example Consideration: ·

50

4-dimethylaminosalicylaldehyde,
^ Dimethylamino-S-methyl-salicylaldehyde,
4-diethylamino-salicylaldehyde,
4- / I-cyanoethyl-methylamino-salicylaldehyde,
^ Hexahydrobenzyl-methylamino-Z-methoxy-

benzaldehyde,
4 - /) - cyanoethyl-methylamino-2-methoxy-benz-

aldehyde,

't-Phenyl-methylamino-l-methoxy-benzaldehyde, 4-di- (n-butyl) -amino-salicylaldehyde, 4-benzyl-methyl-amino-salicylaldehyde,
4-cyclohexylamino-salicylaldehyde,
4 - (/? - Methoxyethyl) -methyl-amino-salicylaldehyde, 4-hydroxyethyl-ethyl-amino-salicylaldehyde,
4-n-propylamino-salicylaldehyde, 4- (j? -Chloroethyl) -methyl-ainino-salicylaldehyde,
4-di-n-propyl-amino-salicylaldehyde,
4- (jJ-cyanoethyl) -amino-salicylaldehyde, 4-hydroxyethyl-methylamino-salicylaldehyde, 4-benzylamino-salicylaldehyde, 4-bromoethyl-amino-salicylaldehyde, 4-methoxyethyl-amino-salicylaldehyde, 4 - (/ 9-acetoxyethyl) -amino-salicylaldehyde, 4 - (/ 5-acetylethyl) -amino-salicylaldehyde, 4-N- pyrrolidyl-salicylaldehyde, 4-N- piperidyl-salicylaldehyde, 4-N-morpholinyl-salicylaldehyde, 4-acetamino-salicylaldehyde- anil, 4- (p-ethoxyphenyl) -methyl-amino-salicylaldehyde.

As suitable oxazolyl-2-acetic acid derivatives of Formula III are for example:

Benzoxazolyl- (2) -acetic acid ethyl ester, 5-methyl-benzoxazolyl- (2) -acetic acid methyl ester, 4,5-dimethyl-benzoxazolyl- (2) -acetic acid propyl ester,

5-chloro-benzoxazolyl- (2) -acetic acid-ethyl ester, 5-bromobenzoxazolyl- (2) -acetic acid-methoxyethyl ester,

Naphth [l, 2-d] oxazolyl- (2) -acetic acid ethyl ester, Naphth [2,3-d] oxazole- (2) -acetic acid methyl ester, 5-ethylsulfonyl-benzoxazolyl- (2) -acetic acid ethyl ester,

Benzoxazolyl- (2) -acetamide,
5-methyl-benzoxazolyl- (2) -acetamide, 5-chloro-benzoxazolyl- (2) -acetamide, 5-ethylsulfonyl-benzoxazolyl- (2) -acetamide, 5-dimethylaminosulfonyl-benzoxazolyl- (2) -acetamide,

5-methyl-benzoxazolyl- (2) -acetic acid methylamide, 4,5-dimethyl-benzoxazolyl- (2) -acetic acid methyl-

amide,
5-cyclohexyl-benzoxazolyl- (2) -acetic acid cyclo-

hexylamide,
5-phenyl-benzoxazolyl- (2) -acetic acid isophoryl-

amide,
Naphth- (l, 2-d) -oxazolyl- (2) -acetic acid methyl-

amide,
5-methoxy-benzoxazolyl- (2) -acetic acid propylamide,

5-bromo-benzoxazolyl- (2) -acetic acid-methylamide, 5-benzyl-benzoxazolyl- (2) -acetic acid-methyl-

amide,
5- (l ', l', 3 ', 3'-tetramethyl-n-butyl) -

benzoxazolyl- (2) -acetic anilide, 5-phenylsulfonyl-benzoxazolyl- (2) -acetic acid-

anilide,
5-Benzylsulfonyl-benzoxazolyl- (2) -acetic acid-

methylamide,
5-diethylaminocarbonyl-benzoxazolyl- (2) -acetic-

acid-n-butylamide,
5-methoxy-benzoxazolyl- (2) -acetic acid cyclohexylamide,

5-ethoxy-benzoxazolyl- (2) -acetic acid anilide, 5-phenoxy-benzoxazolyl- (2) -acetic acid-anilide, 5-acetylamino-benzoxazolyl- (2) -acetic acid-

3-methoxy-n-propylamide, 5-bromo-benzoxazolyl- (2) -acetic acid methylamide, 5-trifluoromethyl- (2) -acetic acid-n-propylamide, Anthra [2, l-d] oxazole- (2) -acetic acid methylamide, phenanthreno [9,10-d] oxazole- (2) -acetic acid methylamide,

yp
acid methylamide,

Oxazolo (5,4-b) pyridine- (2) -acetic acid anilide, Oxazolo (4,5-g) quinoline- (2) -acetic acid-methyl-

amide,
OxazoIo (4,5-c) quinoline- (2) -acetic acid-methyl-

amide,
Oxazolo (5,4-d) pyrimidine- (2) -acetic acid-methyl-

amide,
Oxazolo (4,5-d) pyridazine- (2) -acetic acid-methyl-

atnid,
Oxazolo (4,5-b) quinoxaline- (2) -acetic acid-methyl-

amide,
Oxazolo (4,5-b) phenazine- (2) -acetic acid-

methylamide,
5-oxazolo (4,5-b) phenoxazine- (2) -acetic acid methylamide,

Oxazolo (4,5-a) dibenzofuran (2) acetic acid anilide, 5-methylbenzoxazolyl (2) acetic acid ethylamide, 5-methyl-benzoxazolyl- (2) -acetic acid-

n-propylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

2'-hydroxyethylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

3'-methoxy-n-propylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

3'-dimethylamino-n-propylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

3'-morpholino-n-propylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

2'-bromoethylamide,
5-methyl-benzoxazolyl- (2) -acetic acid isobutyl-

amide,
5-methyl-benzoxazolyl- | 2) acetic acid hexy) amide,

5-methyl-benzoxazolyl- (2) -acetic acid benzylamide, 5-methyl-benzoxazoly! - (2) -acetic acid-

2'-phenylethylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

4-picolylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

furfurylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

thcnvlamid,
5-methyl-benzoxazoIyl- (2) -acetic acid tetruhydrofurfuryl amide,

5-Methy! -Benzoxazo! Yl- (2) -acetic acid anilul. 5-methylben7oxazolyl- (2) -acetic acid-

4'-toluidide.
5-methyl-benzoxazo! Yl- (2) -acetic acid-2'-hydro;<y-

5-methyl anilide,
5Chlor-benzo-azolyi- (2l-acetic acid-2'-hydroxyl-

5-chloro-anilide.
5-tertiarybulyl-benzoxa / .olyt- (2) -acetic acid-

2-hydroxy-5'-tertiary butyl anilide,
Benzoxazolyl- (2-acetic acid: iure-2'-hydroxy-anilKi.

4-phcnetidid.
5-methylben / oxazolyl- (2) -acetic acid-

l'-naphthylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

dimethylamide,
5-methylbenzoxazolyl- (2) acetic acid

diethylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-di-n-biityl-

amide,
5-methyl-benzoxazolyl- (2l-acetic acid-

aziridide,
5-methyl-benzoxazolyl- (2) -acetic acid pyrrolidide.

5-Methy] -benzoxazolyl- (2) -acetic acid-piperidide, 5-methyl-benzoxazolyl- (2) -acetic acid-azepid,
5-methyl-benzoxazo! Yl- (2) -acetic acid-piperazid, 5-methyl-benzoxazolyl- (2) -acetic acid-morpholide, 5-methyl-benzoxazolyl- (2) -acetic acid-

N-methylanilide,
5-methyl-benzoxazolyl- (2) -N'-methyl-

N-piperazid,

5-methyl-benzoxazolyl- (2) -acetyl-2'-methylindoline.

The above-mentioned oxazolylacetic acid derivativesc are partly known. These compounds are obtained either by processes known per se (cf. for example Liebigs Ann. 537, 53 [1938]; CA. 67, 64 126m [1967]; Chem. Ber. 100, 1661 [1967]) or - advantageously - by condensation of o-aminohydroxy compounds with cyanoacetamides and - if desired - subsequent replacement of the amide group for one other amide or ester grouping.

The aldol condensation is known to be preferred in polar organic solvents, optionally containing water, in the presence basic catalysts carried out. Suitable solvents are methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, Dioxane, formamide, dimethylformamide or dimethyl sulfoxide.

Suitable basic catalysts are potassium carbonate, sodium acetate, potassium hydroxide and sodium ethylate or organic nitrogen bases such as diethylamine, indoline, pyridine, but especially pyrrolidine or piperidine.

The reaction temperatures can be varied within a substantial range, for example 0 to 160 ⁰ C. In general, already achieved in the range of 0 to 50 ° C complete conversion to the compounds of formula I.

The cyclization of the aldol condensation product to give the coumarin compounds of the formula I can in the case of R = H by heating for several hours in the original condensation medium - expedient at the reflux temperature of the solvent used - be carried out. By addition an acidic catalyst such as hydrochloric acid, sulfuric acid. Phosphoric acid, p-toluenesulfonic acid. Oxalic acid. Boric acid. Boron trifluoride, zinc chloride or aluminum chloride can accelerate the ring closure reaction will. In the case R = alkyl, the cyclization under the usual conditions of an ether cleavage takes place. for example with aluminum chloride, pyridine hydrochloride, Hydrochloric acid, hydrobromic acid or hydrogen chloride.

_o The Noohsulfonicrunji of the> sulfo group-free Ox-.l / olylcoumarins! can be carried out in SOj-hooked sulfuric acid by the usual methods.

Hine particularly advantageous embodiment of the claimed process for the preparation of the oxazolyl-coumarins I is characterized by the fact that in a backpot reaction one starts with in itself known wisdom; a cyanoacetic ester of the formula

.1

N vi = C-CH _; -C- OR "

(IV)

where R "is lower alkyl or benzylreM

409 538/312

represents, with an amine of the formula

H-N

(V)

wherein R ₁ and R _{2 are} independently hydrogen, alkyl, cycloalkyl or aralkyl radicals or together with the nitrogen atom and optionally including further heteroatoms as ring members form a heterocyclic ring, to form a cyanoacetic acid amide of the formula

15 9 Ri

N = C-CH ₂ -C -N

(Vl)

in which R ₁ and R _{2 have} the meaning given above, and this is reacted without intermediate isolation with an o-aminohydroxy compound of the formula

(VII)

)H

to an oxazolyl (2) acetic acid amide of the formula

N;

CH ₂ -CN

(VIII)

condensed and this in turn without intermediate isolation with an aldehyde of the formula II to the Compounds of formula I converts.

A further variant of the process according to the invention for the preparation of I consists in that one according to the principle of Perkin's synthesis starting from the free oxazolyl-acetic acids of the formula III (B = OH) sodium acetate is used as the basic catalyst and acetic anhydride as the solvent.

The new coumarin dyes of the formula I are predominantly yellow to red crystalline powders that are in organic media, especially solvents such as alcohols, esters, amides, lower fatty acids, Dissolve ethers and ketones with intense yellow-green fluorescence. The coumarin dyes containing sulfo groups of formula I also dissolve in water, but no fluorescence is observed.

The coumarin dyes of the formula I are highly suitable for coloring oils and macromolecular organic materials such as coatings, films, sheets, fibers and molded parts, such as those made of Celluloseestern as CeIIuIoSe ^ V ₂ - and triacetate, polyvinyl compounds such as polyvinyl chloride, polyvinyl acetate, Polyolefins such as polyethylene and polypropylene, polyamides, polyurethanes, polystyrene and polyesters in bulk in (extraordinarily) brilliant, predominantly bright yellow to orange tones. Particularly suitable for this application are the compounds of the formula I which do not contain sulfo groups and those which contain sulfo groups and are in the form of amine salts which make fat-solubilizing alkylamines.

These compounds can also be used together with pigment dyes, especially yellow pigments, in the materials mentioned are rolled in, which results in a significant improvement in the aspect.

A preferred field of application for the coumarin dyes of the formula I according to the invention is the dyeing and printing of natural and synthetic fiber and fabric materials, in particular those made of wool, synthetic polyamides, polyurethanes and polyesters. While the sulfo-containing Dyes are particularly good for dyeing polyamide, polyurethane and wool fibers are particularly good effects and fastness properties with sulfo group-free dyes on polyester fibers and fabrics achieved.

The dyes of the formula I according to the invention are used on the fibers and fabrics mentioned extremely brilliant, yellow-green fluorescent colors in yellow to orange in ultraviolet and daylight Tones produced, which are characterized by high color strength, good build-up and drawing power and very good Characteristics of fastness properties such as washing, rubbing, sublimation, perspiration, exhaust gas and light fastness.

These advantageous properties have so far been available as fluorescent yellow and orange dyes proposed compounds are not to the same extent. Compared to those from the German interpretative document 1098125 (and U.S. Patent 3,458,880) known, next comparable 3-benzimidazolylcoumarin dyes the dyes of the formula I according to the invention have a higher brilliance and a better drawability and better lightfastness on polyester as well as low sensitivity to pH changes and better wash fastness on polyamide. Compared to the cited above The closest comparable 3-benzothiazolyl-coumarin dyes known to the German interpretation is the To emphasize significantly better solubility in benzyl alcohol, as they door the production of ballpoint pen pastes is required.

In the British patent 867 592 an S-benzoxazolyl-T-hydroxycoumarin is described in example 8, which, however, in contrast to the dyes according to the invention, is only empty and completely in terms of textile technology results in worthless staining on polyester fibers.

The dyes of the formula I according to the invention can be colored and printed by conventional methods, for example in the form of aqueous solutions, dispersions or printing pastes. The dye baths and Printing pastes can contain the usual additives for dyeing auxiliaries such as leveling agents, dispersants and Color accelerators, for example substituted polyglycol ethers, Condensation products from aromatic sulfonic acids and formaldehyde, condensation products higher molecular weight aliphatic amines and ethylene oxide, higher molecular weight alkyl sulfates and Alkyl sulfonates in the form of their aqueous sodium or cyclohexylamine salts, condensation products higher molecular weight alcohols and ethylene oxide, cellulose sulphite waste liquor products, o-Oxydiphenyl, halogenated aromatic hydrocarbons and / or esters contain aromatic carboxylic acids.

The dyes according to the invention can also advantageously be colored from organic solutions, for example from those in which water-immiscible solvents such as tetrachlorethylene, tri-

chlorethylene, 1,1,2-trichloroethane or 1,1,1-trichloropropane be used.

Unless otherwise specified, the parts given in the following examples are parts by weight, the specified temperature degrees Celsius degrees.

example 1

22.6 parts of ethyl cyanoacetate and 18 parts 3-Methoxypropylamine are mixed with cooling and heated to 60 ° for 30 minutes. Afterward 25 parts of 3-amino-4-hydroxytoluene are added. The mixture is left on for 6 hours under nitrogen 180 ° (bath temperature) heated, allowing liquid to distill off. When it cools down, it solidifies Crystalline melt. The compound of the formula thus obtained

CH ₂ -C -NH-CH _{2 -Ch 2} -CH ₂ -OCH ₃

(D

is without intermediate isolation with 38.5 parts of 4-diethylamino-salicylaldehyde, 300 parts by volume of isopropanol and 2 parts by volume of piperidine are added and Heated to boiling under reflux and stirring for 20 hours. After cooling to 5 °, the crystalline Sucked off precipitate, washed with ice-cold alcohol and dried at 70 ° in vacuo. You get 33.7 parts of compound of formula

CH,

(2)

35

40

propyl ester, isobutyl ester or benzyl ester or if instead of 3-methoxypropylamine one equivalent amount of n-propylamine, n-butylamine, dimethylamine (as a 30% aqueous solution), pyrrolidine or piperidine is used.

Following the same procedure using 4-dimethylaminosalicylaldehyde is the compound the formula

CH ₁

from melting point 279 to 28 Γ or when used o-aminophenol instead of 3-amino-4-hydroxytoluene the compound of formula

C ₂ H ₅

obtained from melting point 184.5 to 185.5 °.

Also follow the same procedure using the table below indicated salicylaldehydes the compounds of the formula

from melting point 204 to 206 ^c .

The same result is achieved if, instead of ethyl cyanoacetate, an equivalent amount on methyl cyanoacetate, -n-propylester, -iso- 45 obtained:

Salicylaldehyde of the formula II

4- / i-cyanoethyl-methylaminosalicylaldehyde

4-di-n-butylaminosalicyclic aldehyde

4-benzyl-methylamino-salicyla I den yd

4- di-benzylamino-salicylaldehyde

4 - /) - Phenylethylamino-salicylaldehyde

CH ₃ NC - CH ₂ -CH ₂ -N-

I ₃ - CH ₂ - CH ₂ - CH ₂ I ₂ N CH ₃

- CH, - N -

CH _:

N--

CH ₂ - CH ₂ - N - H compound no

(5)

(6)

(7)

(8th)

(9)

hue

greenish yellow

greenish yellow

greenish yellow

greenish yellow

greenish yellow

13th 2,030 507 14th - l.irbton continuation greenish yellow Salicylaldehyde of the formula II IJ Connect
application no greenish yellow 4 - ^ - methoxyethyl-methylamino-
salicylaldehyde CH ₃ O - CH ₂ - CH ₂ - N -
CH ₃ (10) greenish yellow 4-hydroxyethyl-ethylamino-
salicylaldehyde HO - CH ₂ -CH ₂ -N- (Π) greenish yellow 4-n-propylamino-salicylaldehyde CH ₃ - CH ₂ -CH ₂ -N-
H (12) greenish yellow 4 - / (- chloroethyl-methyiamino-
salicylaldehyde Cl - CH ₂ -CH ₂ -N-
CH ₃ (13) greenish yellow 4-di-n-propylamino-salicylaldehyde (CH ₃ - CH ₂ - CH ₂ ) jN - (14) 4-bromoethylamino-salicylaldehyde Br - CH ₂ -CH ₂ -N- (15) greenish yellow O
|| 4 - ^ - Acetoxyäthylamino-salicyl-
aldehyde CH ₃ -CO-CH ₇ -CH ₂ -N-
H (16) greenish yellow O
I. greenish yellow 4- / i-acetylethylamino-salicyl-
aldehyde I.
CH ₃ - C - CH ₂ - CH, - N - (17) greenish yellow 4-cyclopentylamino-salicylaldehyde ' ^{/ X} x
N -
IJ (18) greenish yellow 4-N-pyrrolidyl-salicylaidehyde N - (19) greenish yellow 4-N-piperidyl-salicylaldehyde N - (20) 4-N-Morpholinyi-salicylaldehyde Ί Ν - (21)

4-N- (N'-methyl-piperazyl (-salicyl- i aldehyde j

4-N- (Phenylpyrazolinyl) -salicyi- | aldehyde

4-N-indolinyl-salicyi <i! Deh> d

CH ₃ - N

CH ₃

4-isobutylaminosulicylaldehyde

4-di-hexylamino-salieylaldehyde j 4-n-dodecylamino-salicylaldehyde I

CH- ^r ) U N H CH ₃

[CH ₃ (CH,),, N-

CH ₃ - (CHi, -N - H

(22)! greenish geib

i N-- (23) i grüriMidnui'.eib

(24)

(25)

(26) 1

ι i

ί (27) 1 green cast ^ L 'ib

continuation

Salicylaldehyde the form! Il

4-n-stearylamino-salicylaldehyde
4-allyl-methylamino-salicylaldehyde

Example 2
15 parts of compound of formula

CH ₃ - (CH ₂ J ₁₇ -NH

CH ₂ = CH - CH ₂ - N - CH ₃

the formula

Connection no

(28)
(29)

hue

greenish yellow greenish yellow

Cl

O
CH ₂ -C-NH,

SO ₂ -N

CH ₃

(32)

C, H

(30)

2 "5

from melting point 201 to 202 °, 14 parts of 4-diethylamino-salicylaldehyde, 200 parts by volume of ethanol and 1 part by volume of piperidine are heated to boiling under reflux and stirring for 23 hours, with ammonia escapes, and then cooled to 10 °. The crystalline precipitate obtained is filtered off with suction, washed with ice-cold alcohol and dried at 60 ° in vacuo. 26 parts of compound are obtained the formula

from melting point 223 to 225 °.

If instead of compound (30) an equivalent amount of 5-ethylsulfonyl-benzoxazoIyl- (2) -acetamide is used (Melting point 194 °), the compound of the formula is obtained in an analogous manner

SO ₂ C ₂ H ₅

(33)

(31)

45

from melting point 202 to 204 ° (from dimethylformamide).

If the compound (30) is replaced by an equivalent amount of 5-dimethylaminosulfonyl-benzoxazolyl- (2) -acetamide (Melting point 230 to 23Γ), the compound is obtained in an analogous manner from melting point 186 to 188 ° (from chlorobenzene).

Likewise in an analogous manner, using the corresponding benzoxazolyl- (2) -acetamides, the compounds of the formula listed in the table below

C ₂ H

C ₂ H ₅
manufactured:

Benzoxa / olyl- (2) -ueetamide

5-PhenyIsulfonyl-benzoxazolyl- (2) -acetamide

5-Bromoethyl-benzoxazolyl- (2) -acetamide
5-methoxy-benzoxazolyl- (2) -acetamide

5-acetylamino-benzoxazolyl- (2) -acetamide

W. O link
No. hue SO ₂ - -0 -C-CH ₃ (34) greenish yellow CH ₂ - CH ₂ - Br (35) greenish yellow OCH 3 (36) yellow NH- (37) yellow

409 538/312

17th 2 030 507
continuation 18th Color ion Benzoxazolyl (2) acelamide W. link
No yellow 5-benzenesulfonylamino-benzoxazolyl- (2) -acet-
amide (38) greenish yellow
greenish yellow 5- / S-hydroxyethyl-benzoxazoyl- (2) -acetamide
5-benzyl-benzoxazoyl- (2) -acetamide - CH ₂ - CH ₂ - OH (39)
(40) Example 3

12 parts of compound of formula

CH ₂ -C -NH-CH ₃

from melting point 195 to 197 °, 9.7 parts of 4-diethylamino-salicylaldehyde, 90 parts by volume of ethanol and 0.3 parts by volume of pyrrolidine are taken for 20 hours Reflux and stirring heated to boiling, with methylamine escaping and then cooled to 10 °. The resulting crystalline precipitate is filtered off, washed with methanol and im at 70 ° Vacuum dried. 14.5 parts of the compound of the formula are obtained

200 ⁰ C melts. Compound (42) is obtained in the same way if instead of naphth [1,2-d] oxazolyl- (2) -acetic acid methylamide (41)

i $ which uses dimethylamide, pyrrolidide, piperidide, anilide or p-toluidide of the same acid.

In an analogous manner, using the corresponding benzoxazolyl- (2) -acetic acid methylamides are the compounds listed in the table below the formula

(42)

- ₂ ™ 5

C ₂ H ₅

which after recrystallization from toluene at 198 to prepared:

Benzotazole> 1- (2) -acetic acid-methyIamide

5-Benzylsulfonyl-benzoxazolyl- (2) -acetic acid methylamide

5-Ethoxy-benzoxazolyl- (2) -acetic acid methylamide

5-methylaminosulfonyl-benzoxazolyl- (2) -acetic acid-methylamide

5-Diethylaminocarbonyl-benzoxazolyl- (2) -acetic acid-methylamide

5-n-propylaminocarbonyl-benzoxazolyl- (2) -acetic acid ure-methylamide

5 - /? - chloroethyl-benzoxazolyl- (2) -acetic acid methylamide

CH ₂ - SO ₂ -
C ₂ H ₅ O-CH ₃ - NH - SO ₂ -

C ₂ H ₅

N —CO-

C ₂ H ₅ CH ₃ - CH ₂ - CH ₂ - NH - CO -

Ci - CH, - CH,

Connection no.

(43)
(44)
(45)

(46)
(47)
(48)

Color ion

greenish yellow

yellow

greenish yellow

greenish yellow greenish yellow greenish yellow

19th

continuation

20th

Benzoxazolyl- (2Ksigsaure-me (hylamide

5-ß-Methoxyethylbenzoxazolyl- (2) -acetic acid methylamide

5-phenoxy-benzoxazolyl- (2) -acetic acid methylamide

5- propyl-benzoxazolyl- (2) -acetic acid methylamide

CH ₃ O - CH ₂ - CH ₂

O -
CH ₃ - CH ₂ - CH ₂ -

Connection no

(49)

(50)

(51)

hue

greenish geib

yellow

greenish geib

Likewise in an analogous manner using the corresponding oxazolyl- (2) -acetic acid methylamides the connections listed in the following table are established:

Oxazolyl- (2) -acetic acid methylamides

4,5-tetramethylene-benzoxazolyl- (2) -acetic acid-methylamide

5,6-trimethylene-benzoxazolyl- (2) -acetic acid-methylamide

5,6-dimethyl-benzoxazolyl- (2) -acetic acid methylamide

5-Methyl-benzoxazolyl- (2) -acetic acid-methylamide-6-sulfonic acid

Naphth [], 2-d] oxazolyl- (2) -acetic acid-methylamide disulfonic acid Coumarin compounds of the formula I.

Il [

CH ₃

CH ₃

CH ₃

SO ₃ H

SO ₃ H

Connection no.

(52)

(53)

(54)

(55)

(56)

hue

greenish geib

greenish geib

greenish geib

greenish geib

yellow

When preparing the acidic compounds (55) and (56), it is advisable to reduce the amount of pyrrolidine so far to increase that an alkaline reaction medium is also present here.

The following oxazolyl- (2) -acetic acid methylamides can also be prepared in an analogous manner with 4-diethylamino-salicylaldehyde convert to corresponding coumarin dyes:

the compound of the formula is obtained in an analogous manner

Anthra [2,1 -d] oxazolyl- (2) -acetic acid methylamide

Phenanthreno [9,10-d] oxazolyl- (2) -acetic acid methylamide

Fluoreno [2,3-d] oxazolyl- (2) -acetic acid methylamide

4,5-dihydroacenaphth [5,4-d] ox-

azolyl- (8) -acetic acid methylamide

Acenaphth [5,4-d] oxazolyl- (8) -acetic acid methylamide

Example 4 10.2 parts of a compound of the formula

CH ₂ -C -NH

IO

Color of the coumarin

Orange · 5 Orange Orange _J0 Orange Orange

(59)

from melting point 244 to 245 ° (from dimethylformamide).

Example 5
11.3 parts of compound of formula

CH ₂ -C

35

(57)

from a melting point of 170 to 171.5 °, 5.8 parts of 4-diethylaminosalicylaldehyde, 60 parts by volume of ethanol and 0.2 parts by volume of piperidine are heated to boiling under reflux and stirring for 20 hours and then cooled to 10 °. The crystalline precipitate is filtered off with suction, washed with alcohol and made from methylglycol recrystallized. 6.1 parts of the compound of the formula are obtained

40

from a melting point of 169 to 170 °, 5.8 parts of 4-diethylamino-salicylaldehyde, 110 parts by volume of ethanol and 0.5 parts by volume of piperidine are stirred and Reflux heated to boiling for 20 hours. After cooling to 10 °, the crystalline precipitate formed is suctioned off, washed with ice-cold alcohol and dried at 60 ° in vacuo. 6.6 parts of the compound of the formula are obtained

50

(58)

55

60 N.
C ₂ H ₅
from melting point 184 to 186.

Example 6
13 parts of compound of formula

(61)

CH ₃

O
CH ₂ -C- NH

CH ₃

(62)

after recrystallization from dimethylform- from melting point 197 to 199 ', 8 parts of 4-dimethylamide melts at 167 to 169 °. 65 aminosalicylaldehyde, 400 parts by volume of ethanol and If 4-diethylaminosalicylaldehyde is used instead of 2 parts by volume of pyrrolidine, 20 hours of reconnection (57) heated to the boil with the equivalent amount of 5-tertiary flow and stirring and then heated to 10 " butyl-benzoxazolyl- (2) -acetic acid-cyclohexylamide. cooled down. The crystalline precipitate obtained

is washed with ice-cold methanol and dried at 80 ° in vacuo. 13.5 parts of compound are obtained the formula

CH ₁

(63)

from melting point 306 to 308 ° (from chlorobenzene).

In an analogous manner, using the 15 corresponding benzoxazolyl- (2) -acetanilide produced the following compounds:

From 5- (Γ, Γ, 3 ', 3'-tetramethyl-n-butyl) -benzoxazolyl- (2) -acetanilide

amino-salicylaldehyde, 1000 parts by volume of ethanol and 5 parts by volume of piperidine are heated to boiling under reflux and stirring for 24 hours and then cooled. The resulting crystalline precipitate is filtered off, washed with ice-cold methanol and dried at 60 ° in vacuo. 76 parts of the compound of the formula are obtained

(67)

CH ₃ CH ₃

C-CH ₂ -C-CH ₃ CH ₃ CH ₃

which melts after recrystallization from methylglycol at 184.5 to 185.5 ° [cf. with connection of the formula (4) in example l! ].

In an analogous manner, the compound of the compound (66) and 4-dimethylamino-salicylaldehyde formula

(68)

(64) 30

From 5-fluoro-benzoxazolyl- (2) -acetanilide

from melting point 304 to 306 ° (from dimethylformamide). With 4-dimethylamino-5-methylsalicylaldehyde the compound of the formula is formed in an analogous manner

(65)

CH

CH ₃

Example 7 67 parts of compound of formula

(69)

H-O

CH, - C - NH

(66)

from melting point 158 to 159 °, 48 parts of 4-diethyl

If compound (66) is replaced by equivalent amounts of substituted compounds in the procedure given above Benzoxazolyl - (2) - acetic acid - 2 '- hydroxyanilide. in an analogous manner, those in the the connections given in the following table:

Benzoxazolyl (2) acetic acid
2'-hydro \> -. Iniliil N Coumarin compound CH ₃ Connect
application no. hue C ₂ H ₅ Ί
CH CH ₃ 5-isopropyl-benzoxazolyl- (2) -acetic-
acid-2'-hydroxy-5'-isopropyl-
anilide if \ ° ^^
\ Λο \
O (70) greenish yellow

409 538/312

continuation

Benzoxazolyl- (2) -acetic acid-
2'-hydroxy anilide C ₂ H ₅
\ /
N Cumann connection Br I. Connect
application no. hue 5-bromo-benzoxazolyl- (2) -acetic acid-
2'-hydroxy-5'-bromo-anilide C ₂ H ₅ O (71) greenish yellow C ₂ H ₅ C ₂ H ₅
\ /
N / ΝγΛ 5-ethyl-benzoxazolyl- (2) -acetic acid-
2'-hydroxy-5'-ethyl anilide C ₂ H ₅ AAAoXy
0 (72) greenish yellow

Example 8
24 parts compound of formula

CH, - C - NH

dried. 30 parts of the compound of the formula are obtained

35

(73)

C ₃ H,

from melting point 216 to 218 °, 13.3 parts of 4-diethylamino-salicylaldehyde, 300 parts by volume of ethanol and 1 part by volume of piperidine are refluxed for 22 hours and stirring heated to boiling and then cooled.

The crystalline precipitate is filtered off with suction, washed with methanol and at 70 ° in vacuo which melts at 285 to 287 ° after dissolving from benzene.

In an analogous manner, 4-diethylaminosalicylaldehyde is obtained and the corresponding heterocyclic fused oxazolyl- (2) -acetanilides are those in the following Coumarin dyes indicated in the table:

Acetanilide

Oxazolo [5,4-b] pyridine- (2) -acetanilide

Oxazolo [4,5-g] quinoline- (2) -acetanilide

Coumarin dyes

Connection no.

(75)

(76)

hue

greenish yellow

yellow

27

continuation

28

Acetanilide Cumann dyes

Connection no.

hue

Oxazolo [4 ^ -c] quinoline- (2) -acetanilide

OxazoIo [5,4-d] pyrimidine- (2) -acetanilide

Oxazolo [4,5-d] pyridazine- (2) acetanilide

Oxazolo [4,5-b] quinoxaline- (2) -acetanilide

Oxazolo [4,5-b] phenazine- (2) -acetanilide

5 H-Oxazolo [4,5-b] phenoxazine acetanilide

Example 9 20.4 parts of the formula

C ₇ H

C ₂ H ₅ (77)

(78)

(79)

(80)

(81)

(82)

yellow

greenish yellow

greenish yellow

yellow

orange

orange

Water bath distilled off (last in vacuo). 40 parts of the compound of the formula are obtained as residue

CH,

CH ₂ -C -NH -CH _{3 6o}

(83)

from melting point 154 to 155 °, 22.1 parts of 4-diethyI-amino-2-ethoxybenzaldehyde, 220 parts by volume of ethanol and 1 part by volume of piperidine are taken for 12 hours Reflux and stirring heated to boiling and then cooled to 10 °. The solvent is on the

CO -NH-CH ₃

OC ₂ H ₅

from melting point 179 to 181 ° (alcohol). 22 parts of this compound are divided into 120 parts by volume of water

suspended free benzene, mixed with 34 parts of anhydrous aluminum chloride and then 24 hours heated to boiling. The reaction mixture is made up of 25 parts by volume of 30% strength hydrochloric acid and 25 parts Discharged ice and then azeotropically distilled off the benzene. The crystalline precipitate is filtered off with suction and washed with water. 20 parts of compound of formula 2 with a melting point of 204 bis are obtained 206 ° (from dimethylformamide).

Replaces 4-diethylamino-2-ethoxy-benzaldehyde in the above procedure by equivalent amounts of the following 2-alkoxybenzaldehydes the coumarin dyes listed in the following table are used in an analogous manner:

2-alkoxybenzaldehyde

Coumarin dye

Connection no.

hue

4- / S-Cyanmethyl-methylamino-2-methoxy-benzaldehyde

CH

NC-CH, -

4-hexahydrobenzyl-methylamino-2-methoxy-benzaldehyde

(5)

greenish yellow

(85)

greenish yellow

H) —CH,

4-cyclohexylamino-2-methoxybenzaldehyde

NH

(86)

greenish yellow

4-diethylamino-2-ethoxybenzaldehyde-5-sulfonic acid

(87)

greenish yellow

C ₂ H ₅

Example 10

20.4 parts of the compound of formula 83, 19.5 parts of 4-diethylamino-salicylaldehyde, 230 parts by volume of ethanol and 2 parts by volume of piperidine are heated to boiling under reflux and stirring for 18 hours then cooled to 15 °. The crystalline precipitate is filtered off, washed with alcohol and stored at 60 ° dried in vacuum. 31.2 parts of compound of formula 2 with a melting point of 204 bis are obtained 206 ° (see example 1).

The same compound is obtained if an equivalent is used instead of the compound of the formula 83 Amount of one of the following 5-methyl-benzoxazolyl- (2) -acetic acid amides uses:

5-methyl-benzoxazolyl- (2) -acetic acid-

diethylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-di-

n-butylamide.

5-methyl-benzoxazolyl- (2) -acetic acid-pyrrolidide, 5-methyl-benzoxazo1yl- (2) -acetic acid-piperidide, 5-methyl-benzoxazolyl- (2) -acetic acid-morpholide, 5-methyl-benzoxazolyl- (2) -acetic acid- (2) -azepid, 5-methyl-benzoxazolyl- (2) -acetic acid aziridide, 5-methyl-benzoxazolyH2) -acetic acid-N'-methyl-

piperazid,
5-methyl-benzoxazoIyl- (2) -acetic acid-N-methyl-

anilide,

5-methyl-benzoxazolyl- (2) -acetic acid tetrahydrofurfurylamide,

5-methyl-benzoxazolyl- (2) -acetic acid-

furfurylamide,
5-methyl-benzoxazolyl- (2) -acetic acid urethenylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

benzylamide,

5-methyl-benzoxazolyl- (2) -acetic acid ß-phenylethylamide,

5-methyl-benzoxazolyl- (2) -acetic acid-

4'-picolylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

2'-hydroxyethylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

3'-dimethylamino-n-propylamide, 5-methyl-benzoxazoIyl- (2) -acetic acid-

3 '-morpholino-n-propylamide, 5-methyl-benzoxazolyl- (2) -acetic acid-

2-bromoethylamide,
5-MethyI-benzoxazoIyl- (2) -acetic acid-

n-butylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

n-hexylamide,
5-methyl-benzoxazolyl- (2) -acetic acid-

p-toluidid,
5-methyl-benzoxazolyl- (2) -acetic acid-

phenetidid,
5-methyl-benzoxazolyl- (2) -acetic acid-1'-naphthylamide.

"5

40

45

C, H

In organic solvents such as dimethylformamide, compound (88) shows a very intense green Fluorescence; in aqueous solution, however, the fluorescence is quenched.

Monosulfonated dyes are also obtained if, instead of the compound of the formula 2 equivalent amounts of one of the following coumarin dyes are used:

Compounds of formula 3, 4, 5, 6, 10, 11, 12. 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 25, 26, 27. 28, 29, 31, 32, 33, 35, 36, 37, 39, 44, 45, 46, 47, 48, 49, 51, 52, 53. 54, 58, 59, 63, 64, 65, 68, 69, 70, 71, 72, 75, 76, 77, 78, 79, 80.

Disulfonated as well as monosulfonated dyes are obtained if in place of the compound Formula 2 equivalent amounts of one of the following coumarin coloring agents are used:

Compounds of formula 7, 9, 23, 24, 40, 42, 43, 50, 61, 74.

Example 12
25.7 parts of the compound of the formula

C ₂ H ₅ -SO ₂

CH ₂ -C-OC ₂ H ₅
(89)

Example 11

24 parts of the compound of the formula 2 are gradually introduced into 150 parts of sulfuric acid (density: 1.85) with cooling and stirring, and the mixture is stirred at 20 to 25 ° for 15 minutes. When everything has dissolved, 60 parts of oleum (65% SO _r content) are added dropwise with cooling and stirring over the course of 10 minutes. The mixture is then heated to 60 ° for 16 hours, cooled and poured onto 750 parts of ice. After adding 1500 parts by volume of saturated sodium acetate solution and 600 parts by volume of saturated sodium chloride solution, the crystalline precipitate is filtered off with suction, washed with dilute sodium chloride solution and dried at 60 ° in a vacuum. 34 parts of the compound of the formula are obtained

from melting point 110 to 111 °, 19.5 parts of 4-diethylamino-salicylaldehyde, 300 parts by volume of ethanol and 2 parts by volume of piperidine are refluxed for 10 hours and stirring heated to boiling and then cooled to room temperature. The crystalline precipitate is filtered off with suction, washed with methanol and dried at 70 ° in vacuo. You get 36.5 parts of compound of formula 33 with a melting point of 186 to 188 ° (see Example 2!).

If equivalent amounts of one of the following compounds are used instead of compound (89), then the coumarin dyes listed in the following table are obtained:

Oxii / .olyl- (2) -essigesler

Ethyl benzoxazolyl (2) acetic acid ester
5-methyl-benzoxazolyl- (2) -acetic acid-

methyl ester

5-chloro-benzoxazolyl- (2) -acetic acid-

isopropyl ester

5-bromobenzoxazolyl- (2) -acetic acid-

methoxyethyl ester

Benzyl naphth [1,2-d] oxazolyl- (2) -acetate

Coumarin
I arbsiofr

(4)

(2)

(31)

(71)

(42)

Example 13

An approximately 0.25% dyeing with dye (4) on polyethylene terephthalate fabric was produced as follows:

The fabric is at 50 ° and a liquor ratio of 1:40 in a dye bath containing the finely divided dye, 2 g / l of a conventional anionic dispersant, 5 g / l o-cresotinic acid methyl ester and Ig NaH ₂ PO ₄ and with acetic acid pH 4.5 to 5 is adjusted, introduced. In the course of 15 to 20 minutes, the temperature is increased to 80 to 85 ° and remains in this temperature range for a further 20 minutes. The liquor is then gradually brought to the boil. The dyeing process is ended after a cooking time of 1 to ¹ _{1/2 hours.}

After rinsing and drying, greenish yellow colorations of extraordinary brilliance are obtained and very good fastness properties (compared to the next comparable 7 - diethylamino - 3 - benzimidazolyl- (2) -coumarin [German Auslegeschrift 1 098 125, Example 2] higher brilliance, significantly better drawability and better lightfastness).

Likewise, brilliantly brilliant, greenish colorations are obtained if instead of a compound (4) one of the following dyes is used:

Compound of Formula 2. 3, 5, 6, 7, 8, 10, 12, 13, 14, 15, 16, 17, 21, 29, 31, 32, 33, 34, 35, 40, 42, 43, 45 , 46, 51, 52, 53, 54, 58, 59, 61, 63, 64, 65, 68, 69, 70, 71, 72, 75, 79, 85, 86.

409538/312

. ,, α parts by weight thiodiglycol, 20 parts by weight pressure oil

Example 14 _and 160 parts by volume of water dissolved. One dilutes

About 0.12% coloring with dye (2) on with 200 parts of water, thickened with 400 parts of crystal

Polyamide 6 fabrics were made as follows: rubber and made with a further 60 to 100 parts of water

The fabric becomes a printable paste at 40 ° and a liquor ratio 5. Be with this paste

nis from 1:40 to 1:30 in a dye bath containing 1 g of a fabric made of polyethylene terephthalate in the usual

conventional anion-active dispersant and manner printed and then in a damper

contains the finely divided dye, introduced. Im steamed at 103 to 105 ° for 20 minutes. After this

Over the course of 40 to 60 minutes, increasing the soaps, rinsing with water and drying is obtained

Liquor temperature to 98 ° (boiling temperature) and a very brilliant, greenish yellow color print,

left at this temperature for about 60 minutes. which is characterized by good washing, rubbing, light and sublimation

It is then rinsed and dried. mierfastness distinguishes itself.

High greenish yellow colorations are obtained

Brilliance with very good fastness properties. Same - example 18

if excellent brilliant, greenish colorations 15

are obtained when, instead of compound (2), 1 part of dye of the formula 2 is used in 4000 parts

one of the following dyes is used: water with the help of 8 parts of oleic acid-N-methyl-

Compound of formula 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, finely dispersed tauride. Then at 40 °

13, 14, 15, 17, 18, 19, 20, 21, 22, 25, 29, 31, 32, 35, 39, 100 parts of cellulose triacetate fabric in the bath

40,46,47,48,49,51,52,53,54,58,59,61,63,65,68,20 brought. The bath temperature is within

69, 70, 71, 72, 75, 78, 79, 85, 86. 30 minutes increased to 100 °. It will be 1.5 hours

. colored at boiling temperature. After rinsing with

Example 15 warm, then cold water and drying

Polyethylene terephthalate fabric is impregnated with an aqueous liquor at 40 ° with an aqueous liquor to give a very brilliant dyeing with very padder, good fastness properties,
10 g of finely dispersed coumarin dye per liter. . .
of formula 2, 7.5 g of sodium alginate, 20 g of triethanol example iy
amine and 20g octylphenyl polyglycol ether. 0.16 parts of dye of the formula 88 are dissolved in 160 parts to a liquor content of about len water, 50 parts by volume of 10% ammo · 100% are squeezed off, dried at 100 ° and then nium acetate solution is added and with Water fixed for 30 seconds at 200 to 210 °. After that diluted a Fiotten weight of 5000 parts. On-rinsing and drying, an extremely brilliant finish is obtained, then one goes at 50 ° with 100 parts of fabric-green-tinged dyeing with very good inherent fastness material made of poly-f-caprolactam in the dyebath. and heated this to 100 ° within 15 minutes. . _{The dyebath is kept} at this temperature for 1 hour, but 3 g of acetic acid _{are added after} 3Q minutes

A fabric made of polyethylene terephthalate is used in after. After rinsing and drying, a very room temperature is impregnated with a clear padding liquor with a brilliant greenish yellow coloration with very good fastness properties, the 5.5 parts of the compound of the formula 58,
Contains tetrachlorethylene in 994.5 parts. After 40 dyeings of similar high brilliance and fastness, squeezing off to a weight increase of 60%, the fabric is dried for 1 minute at 80 ° instead of the dye. Using formula 88, one of the other dyes in Example 11, the dye is fixed in mono- or disulfated dyes written at 220 ° for 45 seconds. The tissue is placed in cold tetras for 20 seconds.

washed out chlorethylene. After drying 45 B e i s d i e 1 20

if you hold an extraordinarily brilliant greenish ^p

yellow coloring with very good fastness properties. 0.2 parts of the dye of the formula 88 are

The fixing yield is 98%. Dissolve hot water and add water to it

A color of similar brilliance and also diluted liquor weight of 5000 parts. Subsequent

excellent fastness properties are obtained, you go 50 ßend at 40 ° with 100 parts of wool fibers in

if a clear padding liquor is used which incorporates the dyebath, add 3 parts acetic acid, heat

0.95 parts of compound (2) in 999 parts of Perchloräthy- boil within 15 minutes and color

len contains. The fixation yield is 1 hour at boiling temperature, after 30 minutes

Fall at 190 ° 97% and at 220 ° 99%. 2 parts of formic acid are added. To

For dyeing from tetrachlorethylene, especially rinsing and drying, a brilliant green

The other suitable coumarin dyes correspond to the pungent yellow coloration with good fastness properties

Formula 6, 14, 20, 26, 27, 40, 51, 52, 53, 54, 59, 64, 70, are obtained.

72.85. Colorations of similar high brilliance and fastness

_R. 117 are obtained if in place of the dye

υ e 1 s ρ 1 e 1 1/60 of the formula 88 one of the others in example 11

30 parts by weight of the dispersed dye of the mono- or disulfonated dyes described

Example 13 are used in a mixture of 50 weights.

Claims (1)

Claims: 1. Oxazolyl-coumarins of the general formula 5. Oxazolylcoumarin of the formula IO (SO ₃ Y) _n wherein A for the remaining members of an optionally by chlorine, alkyl, alkoxy, cyclohexyl, phenoxy, phenyl, benzyl, phenylsulfonyl, alkylcarbonylamino, phenylcarbonylamino, alkylsulfonylamino, phenylsulfonylamino, alkylsulfonyl, sulfamoyl or Carbamoyl radicals substituted benzene or naphthalene radicals, Z ₁ and Z ₂ independently of one another are hydrogen, an alkyl radical optionally substituted by CN, OH, Cl, phenyl, methoxy or acetoxy, or the remaining members of a pyrrolidine, N-methylpiperazine, piperidine or morpholine radical mean, where alkyl or alkoxy are to be understood as meaning those radicals with 1 to 5 carbon atoms, Y stands for hydrogen or a cation, η is a number O, 1 or 2, with the proviso that in the event that « the number 0 denotes and A denotes an alkyl-substituted benzene radical, this alkyl substituent either has at least 2 carbon atoms or denotes the methyl radical. 2. Oxazolylcoumarin of the formula 3. Oxazolylcoumarin of the formula CH, 40 45 QH ₅ N
/
QH ₅ 4. Oxazolylcoumarin of the formula 55 60 SO ₇ -N CH ₃ CH ₃ 6. Oxazolylcoumarin of the formula SO ₂ C ₂ H ₅ C ₂ H ₅ N
C ₂ H ₅ 7. Oxazolylcoumarin of the formula N O /
C ₂ H ₅ 8. Oxazolylcoumarin of the formula SO ₃ Na 9. Oxazolylcoumarin of the formula SO ₃ Na 10. Process for the preparation of oxazolylcoumarins according to claim 1, characterized in that that one a-hydroxyaldehydes or a-alkoxyaldehydes the formula CHO in which Z ₁ and Z _{2 mentioned} in claim 1 Have meaning, Z _{3 stands} for hydrogen or an alkyl radical and in which the benzene ring can also be substituted by a sulfonic acid group, with oxazolyl-2-acetic acid derivatives of the formula CH _: