DE1963356A1 - Quinophthalone dyes - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKUSEN-Btyerwerk ί 7. ΟθΖ, | 969 Pctent department Κ / bU

Quinophthalone dyes

The present invention relates to sulfonic acid group-free Quinophthalone parisons of the formula

(D

in which R, a cycloalkoxy radical or the radical of a cyclic amine, Rg for alkyl, alkoxy, Halogen, nitro or acylamino, each two adjacent substituents Rp the remaining members of a fused aromatic ring and η represents an integer from 0 to 3, as well as their production and use for dyeing hydrophobic fiber materials,

Suitable radicals R ₁ are optionally by halogen, preferably chlorine, or alkyl radicals with 1 to 3 carbon atoms substituted cyoloalkoxy groups with 4 to 7 ring members and radicals of 5- to 7-membered cyclic amines from the series of pyrrolidines, piperidines, morpholines, thiomorpholines , Thiomorpholine dioxides and hexamethyleneimines

Le A12 717

109826 / 172S

Suitable R ₂ radicals are in particular alkyl and alkoxy groups each having 1 to 4 carbon atoms, halogen atoms such as chlorine and bromine, and nitro, and alkylcarbonylamino groups having 2-4 C-atoms, In addition, each 2 adjacent substituents R _2, the remaining Form members of a fused-on benzene ring

The new dyes (I) are obtained by using hydroxyquinophthalone carboxylic acid halides the formula

i _H

in which R ₂ and η have the abovementioned meaning and Z is a halogenator, preferably chlorine,

with cycloaliphatic alcohols or cyclic amines in a manner known per se - preferably in the presence of acid-binding agents Reacts means and anhydrous inert solvents at elevated temperatures.

The quinophthalone carboxylic acid halides required as starting material some of the formula (II) are known.

These compounds are expediently obtained according to a specification in US Pat. No. 5,023,214 by condensation of Trimellitic anhydride with the corresponding 2-methylquinoline-4-carboxylic acids according to:

Le A 12 717 - 2 -

109 8 26/1725

(Ro)

2'n

COOH

-CO,

(Ro)

2'n

and subsequent conversion of the quinophthalone carboxylic acids formed in the process into the corresponding acid halides with the usual acid halogenating agents, preferably thionyl chloride.

Suitable 2-methyl-quinoline-4-carboxylic acids are: a-methylrJ-hydroxyquinoline - ^ - carboxylic acid, 2-methyl-j5-hydroxy-S-chloroquinoline - ^ - carboxylic acid, 2-methyl-3-hydroxy-6-chloroquinoline- 4-carboxylic acid, 2-methyl-5-hydroxy-6-bromoquinoline-4-carboxylic acid, 2-methyl-3-hydroxy-6-nitroquinoline-4-carboxylic acid, 2-methyl-3-hydroxy-6-methoxyquinoline-4- carboxylic acid, 2-methyl-3-hydroxy-o-acetylaminoquinoline - ^ - carboxylic acid, 2-methyl-3-hydroxy6, e-dichloroquinoline - ^ - carboxylic acid, 2-methyl-3-hydroxy-6,8-dibromoquinoline 4-carboxylic acid, 2-methyl-3-hydroxy-5 # 6,8-trichloroquinoline-4-carboxylic acid, 2-methyl-3 ~ hydroxy-6-chloro-8-methylquinoline-4-carboxylic acid, 2-methyl-3- hydroxy-7-chloro-8-methylquinoline-4-carboxylic acid, 2-methyl-3-hydroxy-6-chloro _-5J> 8-didinylethylquinoline-tt-carboxylic acids 2-.Methyl-3-hydroxy-5-methyl- 8-methoxy-quinoline - ^ - carboxylic acid, 2-methyl-jJ-hydroxy-e-chloro-T-bromo-S-methyl-quinoline ^ -carboxylic acid, 2-methyl-; 5-hydroxy-5-methyl-6- chloro-8-methoxyquinoln ^ -carboxylic acid, 2-methyl-3-

Le A12 717

109826/1725

2-methyl-3-hydroxy-6,7-benzenedoline-4-carboxylic acid and 2 ~ methyl-3-hydroxy-7 # 8-. benzquinoline-4-carboxylic acid.

In particular, the following cycloaliphatic alcohols are used as reaction components in the preparation of I according to the invention into consideration:

Cyclobutanol, cyclopentanone 1-chloro-cyclopentanol ^, 1-methylcyclopentanol-2, l-methyl-cyclopentanol-jJ * 1-ethyl-cyclophetanol-2, l-ethyl-cyclopentanol · ·? * Cyclohexanol, 1-chloro-cyclohexanol ^, l-methyl-cyclohexanol ^, l-methyl-cyclohexanol-O * 1-methylcyclohexanol-4, l-ethyl-cyclohexanol ^, l-ethyl-cyclohexanol- ^, l-fithyl-cyclohexanol- ^ l, 4-chloro- l-methyl-cyclohexanol-] J # 1 * 2- ^ dimethyl-cyclohexanol-3, l ^ -dimethyl-cyclohexanol- ^, 1,5-dimethyl-cyclohexanol-6,!, ^ - dimethyl-cyclohexanol ^, 1,3 -Dimethyl-cyclohexanol-5,!, ^ - Dimethyl-cyclohexanol-S and cycloheptanol.

Suitable cyclic amines of the formula II b are: 2-methyl-trimethyleneimine, pyrrolidine, 3 * 4-dichloropyrrolidine, 3,4-dibromopyrrolidine, 2-methyl-pyrrolidine, 3-methyl-pyrrolidine, 2,3-dimethyl-pyrrolidine, 3,4-dimethyl-pyrrolidine, 2,5-dimethylpyrrolidine, 2-chloro-piperidine, 3-chloro-piperidine, 4-chloro-piperidine, 2-bromo-piperidine, 3-bromo-piperidine, 4-bromo-piperidine, 2-methyl-piperidine, 3-methyl-piperidine, 4-methyl-piperidine, 2-ethyl-piperidine, 3-ethyl-piperidine, 4-ethyl-piperidine, 2,4-dimethyl-piperidine, 2,5-dimethyl-piperidine, 2,6-dimethylpiperidine, 2-methyl-5-ethyl-piperidine, 2-methoxy-piperidine, 3-methoxy-piperidine, 4-methoxy-piperidine, 2-ethoxy-piperidine, 3-ethoxy-piperidine, 4-ethoxy-piperidine, hexamethyleneimine, morpholine, 2-methylmorpholine, 3-methylmorpholine, 2,3-dimethyl-

Le A 12 717 - 4 -

1 09826/1725

morpholine, 2,6-dimethyl-raorpholine, thiomorpholine, 2-methylthiomorpholine, 3-methyl-thiomorpholine, 2,3-dimethyl-thio ~ morpholine, 2,5-dimethyl-thiomorpholine, 2,6-dimethyl-thiomorpholine, thiomorpholine dioxide, 2-methyl-thiomorpholine dioxide, 3-methyl-thiomorpholine dioxide, 2, jS-dimethyl-thiomorpholine dioxide, 2,5-dimethyl-thiomorpholine oxide, 2,6-dimethyl-thiomorpholine dioxide.

As an inert solvent in which the inventive Representation of I occurs, the following are possible: Dioxane, toluene, Tetralin, chlorobenzene, o-dichlorobenzene, trichlorobenzene, Nitrobenzene, dimethylaniline, pyridine or quinoline

Suitable acid-binding agents are: sodium acetate, pyridine, Picoline, quinoline, triethylamine and dimethylaniline

The condensation temperatures can be in a larger range In general, temperatures of 60 to 220 ° C, preferably 120 - 180 ° C, are used.

In the preparation of the new dyes, the procedure is expediently so that one is in a solution or suspension Acid halide in a suitable anhydrous solvent - preferably in the presence of at least 1 equivalent of one Acid acceptor - at temperatures of 25-100 ° C., preferably 60-90 ° C., at least 1 equivalent of a cycloaliphatic Alcohol or cyclic secondary amine is added dropwise, then refluxed for a few hours, cooled to room temperature, sucks off the precipitate, washes with alcohol and water and dries

The dyes thus obtained are excellent for dyeing and printing hydrophobic synthetic fiber materials such as Polyester fibers, in particular polyethylene terephthalate fibers or fibers from condensation products of bis-hydroxy-methyl-

Le A 12 717 - 5 -

109826/1725

cyclohexane and terephthalic acid and fibers of cellulose triacetate or polyolefins and polyamides and urethanes Super suitable · You can also for dyeing polyester fibers naoh use the so-called "thermosol. ¹¹

The dyeing methods customary for these materials give yellow in good yield on the materials mentioned Dyeings with good sublimation, light and rub fastness.

Compared to those known from US Pat. No. 3.02j $ .213 The dyes according to the invention show a number of better coloring properties.

For example, the dye of the formula which can be obtained according to the invention is distinguished

compared to the dye of the formula known from the US patent cited above

through a better drawing "and build-up ability"

The parts given in the following examples are parts by weight.

Le A 12 717 - 6 -

109826/1725

example 1

35.2 parts of 3-hydroxy-* quinophthalone-5-carboxylic acid chloride are suspended in 100 parts of o-dichlorobenzene, was heated to 90 ⁰ C and added with stirring to 9 parts of cyclopentanol and then with 12.5 parts of dimethylaniline. The mixture is refluxed for 2 hours, cooled to room temperature and the dyestuff which has precipitated out is filtered off with suction. The filter residue is washed with a little ethanol and then with water and dried. 36 parts of a yellow dye of the following constitution are obtained:

dyes the polyester or polyamide fibers a reddish yellow, The dyeings have good fastness to sublimation, fastness to rubbing and very good fastness to light.

Instead of cyclopentanol, the following cycloaliphati can also be used: see alcohols are reacted in the manner described above with 3'-hydroxy-quinophthalone-5-carboxylic acid chloride.

8 parts of cyclobutanol, 13 parts of 1-chloro-cyclopentanol-2, 11 parts of 1-methyl-cyclopentanol-3 »11 parts of cyclohexanol, 15 parts of 1-chloro-cyclohexanol-3, 12.5 parts of 1-methyl-cyclohexanol 4, 14 T _e ile 1,2-dimethyl-cyclohexanol-3, 14 parts of l ^ -dimethyl-cyclohexanol ^ Ik parts of 1,3-Dimethylcyclohe = xanol-fifth

Le A12 717

109826/1725

Example 2

35.2 parts of 3'-hydroxy quinophthalone-5-carboxylic acid chloride who = the suspended in 200 parts of o-dichlorobenzene at 90 ⁰ C = he Had it and mixed with 8 parts of pyrrolidine and equal to = time mixed with 8 parts of pyridine. The mixture is then refluxed for 2 hours, cooled to room temperature and the dyestuff which has precipitated out is filtered off with suction. The residue is washed with a little ethanol, then with water and dried. 3 ** parts of a yellow-brown dye are obtained with the following constitution:

which, finely divided, dyes polyester fibers with a reddish yellow tinge using the usual dyeing processes. The dye has very good build-up capacity, very good fastness to sublimation, fastness to rubbing and excellent fastness to light.

Instead of pyrrolidine, the following cyclic secondary amines can also be ^{reacted with 3 f-} hydroxy-quinophthalone-5-carboxylic acid chloride in the manner described above.

8 parts of 2-ltothyl-trimethylene-bin, 9 parts of 2-methylpyrrolidine, 24 parts of 3,4-dibromoprrelidine, 9 parts Piperidine, 13 parts x 3-chloro-piperidine, 27.5 parts 2-BroM-piperidine, 10 parts · 2-methylpiperidine, 10 parts 4-methylpiperidine, 12 parts 2,4-Diee.thyl-piperidine, 12 parts 2,5-Dieethyrl-piperidine, 12 parts of 2,6-diaethyl-piperidine,

Le A 12 717 - 8 -

109826/1725

12.5 parts of 2-methyl-5-ethy-piperidine, 12 parts of 4-methoxypiperidine, 9 parts of morpholine, 10.5 parts of 2-methyl-eorpholine, 12 parts of 2,5-dimethyl-morpholine, 11 parts of thiomorpholine 12 parts of 3-methylthiomorpholine, 13.5 parts of 2,3-dimethylthiomorpholine, 14 parts of thiomorpholine dioxide, 15-5 parts 2-methyl-thioeorpholine-dioxide, 17 parts of 2,5-dimethyl-thio » morpholine dioxide, 10.5 parts hexamethyleneimine.

Example 3

38,6Teile 3 ^{f-hydroxy-5'-ohlor-ohinophthalon-5-carbonsäurechlos} chloride are suspended in 200 parts of o-Diohlorbenzol, heated to 90 ⁰ C and with stirring, with 11 parts of cyclohexanol, and at the same time bit 8 parts of pyridine · added then heated the mixture is refluxed for 2 hours, cooled to room temperature and the precipitated dye is filtered off with suction. The filter residue is washed with a little ethanol and then with water and dried. 37 parts of a yellow dye of the following constitution are recovered;

the polyester or polyamide fibers stain reddish yellow. The dyeings have good sublimation and rub resistance and very good lightness.

Instead of cyclohexanol, the following cyoloaliphati = see alcohols or cyclic secondary amines in the above described manner are reacted with 3 * -hydroxy-5'-chloro-quinophthalone-5-carboxylic acid chloride.

Le A12 717. - 9 -

109826/17 25

ie

8 parts of cyclobutanol, 9 parts of cyclopentanone, 13 parts of 1-chloro-oyolopentanol-3, 11 parts of 1-methyl-oyolopentanol-2, 15 parts of 1-chloro-cyclohexanol- ^, 12.5 parts of 1-methyl-cyclo = Heianol-3, 14 parts!, S-Diaethyl-oyelohexanol-e, 14 parts 1, S-diaethyl-oyolohexanol-4, 14 parts 1,4-dimethyl-cyelohexa: nol-5 _t 8 parts 2-methyl-trimethyleneimine, 8 parts pyrrolidine,

9 parts of 2-methyl-pyrrolidine, 10.5 parts of 3,4-diraethyl-pyrros l'idine, 15 parts of 3,4-dichloropyrrolid "in, 24 parts of 3,4-dibromopyrrolidine, 9 parts of piperidine, 13 parts of 3-chloropiperidine, 17t5 parts of 2-bromopiper.idin, 10 parts of 2-methylpiperid,

10 parts of 3-methyl-piperidine, 10 parts of 4-methyl-piperidine, 12 parts of 2,4-dieethylpiperidine, 12 parts of 2,5-dimethylpiperidine, 12 parts of 2,6-dimethylpiperidine, 12.5 parts 2-methyl-5-ethyl-piperidine, 12 parts of 4-methoxy-piperidine, 9 parts of morpholine, 10.5 parts of 2-methyl-morpholine, 12 parts 2,5-diraethyl-morpholine, 11 parts of thiomorpholine, 12 parts 3-methyl-thiOBorpholine, 13.5 parts 2,3-dimethyl-thiomor = pholine, 14 parts of thionorpholine dioxide, 15.5 parts of 2-methylthiomorpholine dioxide, 17 parts of 2,5-dimethylthiomorpholine dioxide, 10.5 parts of hexamethyleneimine.

example k

38.6 parts of 3'-hydroxy-6 ^f -chloro-quinophthalone-5-carboxylic acid = chloride are suspended in 150 parts of pyridine, and 10.5 parts of hexamethylene imine are added at room temperature while stirring. The mixture is then refluxed for 2 hours, cooled to room temperature and the dyestuff which has precipitated out is filtered off with suction. The filter residue is washed with a little ethanol and then with water and dried. 38 parts of a yellow dye are obtained with the following constitution:

Le A 12 717 - 10 -

109826/17 2 5

the polyester or polyamide fibers dyes reddish yellow. The dyeings have good fastness to sublimation, fastness to rubbing and very good fastness to light.

Instead of hexamethyleneimine, the following cyclic secondary amines or cycloaliphatic alcohols can also be used can be used for condensation with 3 »-hydroxy-6'-chloro-ehinophthalone-5-carboxylic acid chloride receives valuable yellow pigment dyes.

8 parts of 2-methyl-trimethyleneimine, 8 parts of pyrrolidine, 9 parts 2-methyl-pyrrolidine, 10.5 parts of 3,4-dimethyl-pyrrolidine, 15 parts of 3,4-dichloropyrrolidine, 2k parts of 3,4-dibromopyrrolidine, 9 parts of piperidine, 13 parts of 3-chloropiperidine, 12.5 parts of 2-bromo-piperidine, 10 parts of 2-methylpiperidine, 10 parts of 3-methyl-piperidine, 10 parts of k-He thylpiperidin, 12 parts of 2,4-Dimethyl-piperidin, 12 parts of 2,5-Dimethyl-piperidin, 12 parts of 2,6-Dimethyl-piperidin, 12.5 Parts of 2-methyl-5-ethyl-piperidine, 12 parts of ^ i-methoxy-piperidine,

9 parts of morpholine, 10.5 parts of 2-methyl-morpholine, 12 parts of 2,5-dinethyl-eorpholine, 11 parts of thiomorpholine, 12 parts of 3-methyl-thioeorpholine, 13.5 parts of 2,3-dimethyl-thioeorpholine , Ik parts thiomorpholine dioxide, 15.5 parts of 2-methyl-thiomorpholine-dioxide, 17 parts of 2,5-dimethyl-thiomorpholine dioxide, 8 parts tJyolobutanol, 13 parts of l-chloro-eyolopenta "nol-2, 11 parts of l-methyl-cyclopentanol-3 , 11 parts cyclo = hexanol, 15 parts l-chloro-cyelohexanol ^, 12.5 parts l-methyl-cyolonexanol-ii, I ^ parts l, 2-dimethyl-cyclohexanol-3, Ik parts l ^ -Dieethyl-cyclohexanol- ^, Ik parts 1,3-Dimethyloyc1ohexanol-5.

Le A 12 717 -U-

109826/1725

example 5

38.2 parts of 3'-hydroxy-6'-methoxy-ohinophthalon-5-oarbon = säureohlorid are suspended in 200 parts of trichlorobenzene and treated at 90 ⁰ C with 18 parts of piperidine. The mixture is then heated to 180 ^° C. for 2 hours, cooled to room temperature and the dyestuff which has precipitated out is filtered off with suction. The filter residue is washed with a little ethanol, then with water and dried. 39 parts of a yellow dye are obtained with the following constitution:

H ₃ CO _ ^ OH

the polyester or polyamide fibers reddish yellow on = colors. The dyeings have very good build-up capacity, good fastness to sublimation, fastness to rubbing and very good light = authenticity. on.

Instead of piperidine, the following cy = ψ can also be used for condensation with 3'-hydroxy-6'-methoxy-quinophthalone-5-carboxylic acid chloride under the reaction conditions described, under which a small shot of the amine used for condensation also serves as an acid-binding agent Use clic secondary amines:

16 parts of 2-methyl-trimethyleneimine, 16 parts of pyrrolidine, 18 parts of 2-methyl-pyrrolidine, 21 parts of 3,4-dimethyl-pyrrolidine, 30 parts of 3,4-dichloropyrrolidine, 2k parts of 3-bromopyrrolidine, 26 Parts of 3-chloro-piperidine, 35 parts

Lm A 12 717 - 12 -

1 09826/1725

2-Bromo-piperidine, 20 parts of thy 2 "Me! Piperidine, 20 parts of 3-methyl ~ piperidn, 20 parts of 4-Methyl-piperidine, 2k parts of 2,4-dimethyl-piperidine, 24 parts of 2,5-dimethyl-piperidine , 2k parts of 2,6-dimethyl-piperidine, 25 parts of 2-methyl-5-ethyl-piperidine, 2k parts of ^ t-methoxy-piperidine, 18 parts of morpholine, 21 parts of 2-methyl-morpholine, 2k parts of 2.5- Di = methyl morpholine, 22 parts of thiomorpholine, 2k parts of 3-methylthiomorpholine, 27 parts of 2,3-dimethylthiomorpholine, 28 parts of thiomorpholine dioxide, 31 parts of 2-methylthiomorpholine dioxide, 24 parts of 2 , 5-dimethyl-thiomorpholine-dioxide, 21 parts of hexamethyleneimine.

Under the reaction conditions described in Example 1-5 The following quinophthalonoarboxylic acids can also be used chloride

k3 parts ^{3> 6-hydroxy-l} ~ bromo-5-quinophthalone oarbonsäureeh.lorid, 39.6 parts j'-hydroxy-ö'-nitro-quinophthalone S-carboneäure chloride, 56.5 parts of 3'-hydroxy- 6'-methyl-quinophthalone-S-carboxylic acid chloride, 40.8 parts ^ '- B ^ droxy-e'-acetylaniino-quinophthalone- 5-carboxylic acid chloride,

k2 parts 3 * -hydroxy-6 ', T'-dichloro-quinophthalone-S-carboxylic acid = chloride

with the cyoloaliphatic Aiko = fetch given in Example 1-5 or cyclic secondary amines in good yields to the analogous dyes, synthetic fiber materials, especially polyester fibers, also in red = pungent yellow tones, very good sublimation, rubbing and light = stain authenticity.

A 12 717

109826/1725

Example 6 <ff

35 »2 parts ^ '- Hydroxy-quinophthalone-S-carboxylic acid chloride suspended in 200 parts of o-dichlorobenzene, heated to 90.degree and with stirring with 10 parts of 2-ethyl-piperidine and 8 parts Fyridine added · Then heated to boiling for 2 hours under reflux, cools to room temperature and sucks the precipitated dye off «The residue is washed with a little ethanol, then washed with water and dried. 35 parts are obtained a yellow-brown dye of the following constitution;

OH which, brought into fine distribution, polyester fibers after the The usual dyeing process gives a reddish-tinged yellow color «The dye builds up very well and produces dyeings with very good lightfastness and sublimation fastness. Example 7

25 parts of the yellow dye obtained according to Example 1 who = with 75 parts of a condensation product from β-naph = thalinesulfonic acid and formaldehyde and 120 parts of water 24 Milled in a ball mill for hours. The paste is then continuously dried in vacuo at 50 ° and the residue finely ground.

1 part of this dye powder is stirred into 2000 parts of hot water which contains 8-10 parts of a carrier, e.g. o-phenyl-phenol, and which has been brought to a pH of about 4.5 with sulfuric acid. A very fine dyestuff suspension is obtained, into which 50 parts of polyester fibers are introduced at 40-60 °. The dyebath is heated to the boil within 20 minutes and kept at this temperature for 1-1.5 hours. The colored material is then rinsed thoroughly with water and dried. A yellow coloration with very good wet fastness, sublimation fastness and light fastness is obtained.
Le A 12 717 -14-

109826/172 5

Claims (1)

Claims
, # Quinophthalone dyes free of sulfonic acid groups of the formula (Rp) n in which R, a cycloalkyl radical or the radical of a cyclic amine, R _{2 stands} for alkyl, alkoxy, halogen, nitro or acylamino, two adjacent substituents R _{2 can form} the remaining members of a fused aromatic ring and η is an integer of 0 to 3 represents. 2.) Quinophthalone dyes free from sulfonic acid groups formula C-Ri ₁ in which R ¹ ^ cycloalkoxy groups with 4-7 ring members, optionally substituted by chlorine or alkyl radicals with 1-4 carbon atoms, or radicals of 5- to 7-membered cyclic amines from the series of pyrrolidines, piperidines, morpholines, thiomorpholines, thioeorpholine dioxides and hexamethylene lines in which R ' _{2 are} alkyl groups of 1-4 carbon atoms, halogen atoms, preferably chlorine and bromine, as well as nitro or acylamino groups, and in each of the adjacent substituents R' _{2 can form} the remaining members of a fused benzene ring and η is a whole Represents number from 0 to J Le A12 717 - 15 - 109826/1725 JH 3 ·) Quinophthalone free from sulfonic acid groups formula 4 ·) Quinophthalone free from sulfonic acid groups formula 5.) Quinophthalone free from sulfonic acid groups of the formula 6.) Quinophthalone free from sulfonic acid groups formula 7 ·) Quinophthalone-free quinophthalone dye of the formula > H 0 Q / 8.) Quinophthalone dye free from sulfonic acid groups formula Le A 12 0 - 109826/1725 9.) Process for the preparation of sulfonic acid group-free Quinophthalene dyes of the general formula in which R _{1 represents} a cycloalkoxy radical or the radicals of a cyclic amine, R _{2 represents} alkyl, alkoxy, halogen, nitro or acylamino. Any two adjacent substituents R _{2 can form} the remaining members of a fused-on aromatic ring and η represents an integer from 0 to 3, characterized in that one hydroxyquinophthalone carboxylic acid halides the formula (Ro) 2'n in which R ₂ and η have the abovementioned meaning and Z is a halogen atom, preferably chlorine, oycloaliphatisohen with alcohols or cyclic amines, preferably in the presence of acid-binding agents and anhydrous indifferent solvent at elevated temperatures converts · Le A 12 71? - 17 - 109826/1725 10.) Process for the preparation of quinophthalone dyes free of sulfonic acid groups, characterized in that «one Hydroxyquinophthalone carboxylic acid halides of the formula in which R ' _{2 are} alkyl groups with 1-4 C atoms, halogen atoms, in particular chlorine and bromine, as well as nitro or acylamino groups, and in each of which 2 adjacent substituents R' _{2 can form} the remaining members of a fused-on benzene ring, η is an integer represents from 0-3, and Z represents halogen, in particular chlorine, with optionally substituted by alkyl radicals with 1-4 carbon atoms or chlorine substituted cycloaliphatic alcohols with 4-7 ring members or 5- to 7-membered cyclic amines from the series of Pyrrolidines, piperidines, morpholines, thiomorpholines, thiomorpholine dioxides and hexamethyleneimines in the presence of acid-binding agents and anhydrous inert solvents at elevated temperatures 11.) Method of dyeing and printing hydrophobic Fiber materials, characterized in that the dyes of claim 1 are used. 12.) With the dyes of claim 1 dyed or printed hydrophobic fiber materials Le A 12 717 - 18 - »09526/17 25