DE1769436C - Disperse dyes of the quinophthalone series, process for their preparation and their use - Google Patents

Description

SO ₂ -R

in which R is an aryl radical, an alkyl radical with 1 to 12C AtOmCn, a cyclohexyl radical or a benzothiazolyl radical, Y is a hydrogen atom, a halogen atom, a nitro group or a phenyl radical, Z is a hydrogen atom or a halogen atom, m is an integer between 1 and 4 and η 1 or 2, characterized in that 4-halo-3-hydroxy-quinophthalones of the general formula

45

in which Q denotes a chlorine or bromine atom and Y, Z, m and η have the meanings given above, with sulfinic acid salts of the formula

R - SO ₂ Me "

in which R has the meaning given above and Me is an alkali metal ion.

3. The method according to claim 2, characterized in that .the implementation at a Tem »temperature between ÖÖ and! 180 ⁰ C stirred.

4. Use of the in claims 1 to 3 described F £ -b = töffe for coloring and printing of hydrophobic fiber materials, preferably those made of polyethylene terephthalates, from aqueous dispersion,

5 Use of the dyes described in claims 1 to 3 for dyeing Polyäthylenterephthalatsn in the spinning mass.

IO The invention relates ChinophthalonfarbstoEfe of the general formula

in which R is an aryl radical, an alkyl radical with 1 to 12 carbon atoms, a cyclohexyl radical or a benzothiazolyl radical, Y a hydrogen atom, a halogen atom, a Nitro group or a phenyl radical, Z a hydrogen atom or a halogen atom, m an integer between 1 and 4 and η 1 or 2 mean a process for their preparation and their use.

Compounds of the quinophthalone series are used as dyes that are used to dye polyester fibers suitable, known from the German Auslegeschrift 1 168 862.

Of the substituted quinophthalones, ^ bromo-hydroxy-quinophthalone is a particularly light one true dye for polyester fibers with moderate fastness to heat set, in the British patents 865 308 and 1 036 389.

It has now been found that there are new thermosetting quinophthalone dyes of the general

^Fd SO ₂ -R

in which R is an aryl radical, an alkyl radical with 1 to 12 carbon atoms, a cyclohexyl radical or a benzthiazolyl radical, Y is a hydrogen atom, a halogen atom, a nitro group or a phenyl radical. Z denotes a hydrogen atom or a halogen atom, m denotes an integer between 1 and 4 and η 1 or 2, is obtained by 4-halo-3-hydroxyquinophthalones of the general formula

in which Q is a chlorine or bromine atom and Y,

I 769436

2, m and η have the meanings given above, with sulfinic acid salts of the formula

R - SO ₂ Me

in which R has the meaning given above and Me is an alkali metal ion

The aryl radical R in the above formulas is a phenyl, naphthyl, anthraquinonyl or fluorenyl radical. These radicals can be substituted one or more times. Examples of such substituents are hydroxy, alkoxy, hydroxyalkoxy, nitro, carboalkoxy, carboxyl, amino, alkyl, phenyl, naphthyl or benzyl groups or halogen atoms, where the alkyl groups 1 to 12 and the alkoxy _t5 groups contain 1 to 4 carbon atoms. The alkyl radical with 1 to 12 carbon atoms or the cyclohexyl radical R or the benzothiazolyl radical in the above formulas can also be substituted by hydroxy, alkoxy, phenoxy, cyano, sulfone. Amino or phenyl or naphthyl groups or halogen atoms.

Suitable starting materials of the quinophthalone series are, for. B. ^ Bromo-S-hydroxy-quinophthalone. 4 - chloro - 3 - hydroxy - quinophthalone. 4.5'.6'-tribromo-3-hydroxyquinophthalone. 4.4'.5'.6 ', 7'-pentabromo-3-hydroxy-quinophthalone. 4 - bromo-4.7 '- dichloro - 3 - hydroxy - quinophthalone, 4 - bromo-4.5'.6'.7 ^: - tetrachloro - 3 - hydroxy - quinophthalone, 4 - bromo - 4' - fluoro - 3 - hydroxy - diinophthalone , 4 - bromo - 5 '- nitro - 3 - hydroxy - quinophthalone.

4.6 - Dibromo - 3 - hydroxy - quinophthalone. 4 - bread

5. ⁷ - dichloro - 3 - hydroxy - quinophthalone and 4 - bromo - 5 '- phenyl - 3 - hydroxy - quinophthalone.

Suitable sulphonic acid salts are, for example Sodium or potassium salts of methanesulfinic acid c. Athanesulfinic acid, pentane-1-sulfinic acid, octane-1 -sulnic acid, dodecane-1-sulphinic acid, chloromethane sultinic acid, 2-hydroxy-ethane-1-sulfinic acid, aminomethane - sulfinic acid. Benzene sulfinic acid, 4 - toluenesulfinic acid, 3.4 - dimethylbenzene sulfinic acid, 2.4,5 - trimethylbenzenesulfinic acid. 4 - nitrobenzenesulfinic acid, 2,4-dinitrobenzene - sulfinic acid, 4-chlorobenzene - sulfinic acid. 4 - fluorobenzenesulfinic acid, 4 - iodobenzenesulfinic acid, 2 - chloro - 5 - nitrobenzenesulfinic acid, 4 - hydroxy - 3 - carboxy - benzene - sulfinic acid, 3,5 - dicarboxy - benzene - sulfinic acid. 4 - aminotoluene - 2 - sulfinic acid, 1 - methoxy - 2 - acetylaminobenzene - 4 - sulfinic acid, 2 - methoxybenzene - sulfinic acid, 4 - methoxy - benzenesulfinic acid, 4 - η - dodecylbenzene - sulfinic acid, cyclohexane - sulfinic acid. naphthalene - 1 - sulfinic acid. Anthraquinone-1-sulfinic acid, fluorene-1-sulfinic acid and benzothiazole-2-sulfinic acid.

The reaction is advantageously carried out in a polar solvent with good dissolving power for the alkali salts of sulfinic acids. Such solvents are, for example, phosphoric acid tris-dimethylamide, dimethylformamide, N-methylacetamide, dimethyl sulfoxide and the like are suitable.

In general, the calculated amounts of the reactants are used. In some cases is a slight excess of the alkali salt of sulfinic acid, for example an excess of about 10 to 20%, advantageous.

The temperature at which the reaction is carried out depends on the reactants and the type of solvent used, generally a temperature between 50 and 180 ° C

25th

30th

35

40

₄₅

50 appropriate. It is preferred to work at temperatures between about 100 and 150 ^° C.

The dye is isolated either by cooling the solution and filtering off the crystallized one Dye or by pouring the solution into water or a lower alcohol, for example, methanol, and sank the precipitated color.

The dyes prepared according to the invention give on synthetic fiber materials, in particular those made from polyethylene terephthalates, yellow dyeings with good fastness to washing, solvents and light and surprisingly good heat-setting and ironing fastnesses. Compared to those with 3-hydroxy-quinophthalone or 4-bromo-3-hydroxy-quinophthalone available dyeings are distinguished by those according to the invention Dyes obtained dyeings through better heat-setting fastness.

For producing real PoIyestermaterialien dyeings are treated in the presence of carriers, between 80 and H0 ^c C or in the absence of carriers between 110 and 140 ° C with the respective dyes. To produce prints, aqueous printing pastes are printed onto the polyester fabric and this is then steamed between 95 and 110 ° C. in the presence of a carrier or between 120 and 140 ° C. in the absence of a carrier.

The dyeing or printing can also be done according to the so-called thermosol process by briefly dry heat treatment between 180 and 200 C for the padded or printed goods subject.

The dyes prepared according to the invention can also be used for dyeing polyethylene terephthalates use in the spinning pulp with good success.

example 1

10 parts by weight of 4-bromo-3-hydroxy-quinophthalone and 5 parts by weight of the sodium salt of methanesulfinic acid are added to 100 parts by weight of phosphoric acid tris-dimethylamide, and the mixture is heated to 100 ° C until no more starting material can be detected. Then that will The mixture was cooled to room temperature and added to 500 parts by weight of methanol. The dye is filtered off with suction, washed with methanol and then with water and dried. 9 parts by weight are obtained that is 94% of theory of the dye of the formula

SO ₂ - CH ₃

Melting point: 280 ° C.

The dye dyes fibers and films made of polyethylene terephthalate in yellow shades with very good fastness to light, washing and rubbing and excellent Thermoset fastness.

Example 2

Parts by weight ^ bromo-S-hydroxy-chinopbthalon and 6 parts by weight of the sodium salt of benzenesulfinic acid are added to 100 weight parts of dimethylformamide, and the! Mixture is heated so Jange at 140 to 150 ⁰ C, until no starting material prove more It is then d bkühl with 500 parts by weight D5 * ~ f4 in 50 parts by weight

ure are in S

· Entered, and throw the mixture & heated up in a sample

är10 Shtsteüe, that's 76% of the ff d Frmel

more material to be assigned isi. uwm wu «» »« - «~ _{receives 10} Gewicütsteue, u,

Cooled room temperature and with 5ÜOGe% icnts- ^ 2. ^ of the dye of the formula

teflenWas ^ · diluted The dye is sucked off, to theory, the rar

- ι 1 *

share water diluted D
washed with water and dried
11 parts by weight are obtained, that is 95% of the fe d area

You get 11 weights,
Theory, of the dyes of the formula

Ο ^θ
Melting point: 287 ° C.

The dye dyes fibers and films made from polyethylene terephthalates in yellow shades with very good fastness properties, in particular with excellent heat-setting fastness B e i s ρ i e 1 3

Parts by weight of 4-chloro-3-hydroxy-quinophthalone and 6 parts by weight of the potassium salt of the 3-chloro

Melting point: 250 ¹ C

The dye dyes fibers and foils made from polyether terephthalates in yellow tones, with very good fastness to light, washing and heat setting.

Additional dyes are shown in the table below listed, which can be prepared according to the processes described in Examples 1 to 3:

Source material

4-bromo-3-hydroxyquinophthalone

the same
the same
the same
the same
the same
the same

the same

the same
the same
the same
the same
the same

Implementation with dye

Ethane sulfinic acid, sodium salt

Pentane (1) sulfinic acid, Sodium salt

Octan (1) sulfinic acid, Sodium salt

Chloromethane sulfinic acid, sodium salt

2-Hydroxyethane sulfinic acid, sodium salt

4-toluenesulfinic acid, Sodium salt

3,4-dimethylbenzenesulfinic acid, Sodium salt

2-methoxy-benzenesulfinic acid, sodium salt

4-nitro-benzene-sulfinic acid, Sodium salt

4-chloro-benzene-sulfinic acid, Sodium salt

4-fluoro-benzene-sulfinic acid, Sodium salt

4-iodobenzene sulfinic acid, sodium salt

2-chloro-5-nitro-benzenesulfinic acid, sodium salt

4-ethylsulfonyl-3-hydroxy-

quinophthalone
4-n-pentylsulfonyl 3-hydΓoxy-

quinophthalone
4-n-octylsulfonyl-3-hydroxy-

quinophthalone
4-chloromethylsulfonyl-3-hydroxy-

quinophthalone
4 - ^ - Hydroxy-ethylsulfonyl-3-hydroxy-

quinophthalone
4- (4'-methyl-phenyl-sulfonyl) -

3-hydroxy-quinophthalone
4- (3 ', 4'-dimethyl-phenyl «-sulfonyl * -

3-hydroxy-quinophthalone

4- (2'-methoxyphenyl-sulfonyl) -3-hydroxy-quinophthalone

4- (4'-nitro-phenyl-sulfouyl) -

3-hydroxy-quinophthalone
4- (4'-chloro-phenyl-sulfonyl) -

3-hydroxy-quinophthalone 4- (4'-Flubr-phenyl-sulfonyl) -

3-hydroxy-quinophthalone 4- (4'-iodo-phenyl-sulfonyl) -3-hydroxy-

quinophthalone
4- (2'-chloro-5'-nitro-phenyl-sulfonyl) -

3-hydroxy-quinophthalone

hue

Yellow Yellow Yellow Yellow Yellow Yellow Yellow

yellow

Yellow yellow yellow yellow yellow

continuation

Source material Implementation with dye hue 4-bromo-3-hydroxy 4-hydroxy-3-carboxy- 4- (4'-Hydroxy-3'-carboxy-phenyU yellow quinophthalone benzene sulfinic acid,
N ^ 31ΓΊ lim QH17 sulfonyl) -3-hydroxy-quinophthalone the same 3,5-dicarboxy-benzene- 4- (3 ', 5'-dicarboxy-phenyl-sulfonyl) - yellow sulfinic acid, sodium
05 * 1 * 7 3-hydroxy-quinophthalone the same Oai £>
4-amino-toluene-2-sulfine 4- (5'-Amino-2'-methyl-phenyl-sulfo- yellow acid, sodium salt nyl-3-hydroxy-quinophthalone the same 4-n-dodecyl-benzene- 4- (4'-n-Dodecyl-phenyl-sulfonyl) - yellow sulfinic acid, potassium 3-hydroxy-quinophthalone the same Cyclohexane sulfinic acid, 4-cyclohexyl-sulfonyl-3-hydroxy- yellow Sodium salt chinophlhalon the same Naphthalene-1-sulfine- 4- (l'-naphthyl-sulfonyl) -3-hydroxy- yellow acid, sodium salt quinophthalone the same Anthraquinone-1-sulfine- 4- (l '-anthraquinonyl-sulfonyl) - yellow acid, sodium salt 3-hydroxy-quinophthalone the same Fluoicn-l-sulfonic acid, 4- {1 '-Fluorenyl-sulfonyO-S-hydroxy- yellow Sodium salt quinophthalone the same Benzothiazole-2-sulfine- 4- (2'-Benzthiazolyl-sulfonyl) - yellow acid, sodium salt. 3-hydroxy-quinophthalone 4'-chloro-4-bromo- Benzenesulfinic acid, 4'-chloro-4-phenylsulfonyl-3-hydroxy- yellow 3-hydroxy-quinoph- Sodium salt quinophthalone thalon 5'-phenyl-4-bromo- Methanesulfinic acid, S'-phenyl ^ methyl-sulfonyl- yellow 3-hydroxy-quinoph- Sodium salt 3-hydrox] quinophthalone thalon 5'-nitro-4-bromo 4-toluenesulfinic acid, 5'-nitro-4- {4'-methylphenyl-sulfonyl) - yellow 3-hydroxy-quinoph- Sodium salt 3-hydroxy-quinophthalone thalon 4 \ 5 \ 6 \ 7'-tetrachloro 4-chloro-benzene-sulfine- 4 ', 5', 6 ', 7'-tetrachloro-4- (4 "-chlor- yellow 4-bromo-3-hydroxy acid, sodium salt phenyl-sulfonyl) -3-hydroxy- quinophthalone quinophthalone 4-bromo-5,7-dichloro Benzenesulfinic acid, SJ-dichloro- ^ phenylsulfonyl- yellow 3-hydroxy-quino
phthalone
4-bromo-3-hydroxy Sodium salt 3-hydroxy-quinophthalone quinophthalone 4 - (/ i-hydroxyethoxy) - 4- [4 '- (/ i-Hydroxyethoxy) -phenyl- yellow . 4-bromo-3-hydroxy benzenesullinic acid,
Sodium sal7 sulfonyij-3-hydroxy-quinophtha! on quinophthalone 2-OJ-hydroxyethoxy) - 4- [2'-l / J-hydroxyethoxy) -phenyl- yellow 4-bromo-3-hydroxy benzenesulfinic acid,
NatTiuTnsal 7 suu "onyl] -3-hydroxy-chiophthalone quinophthalone 4-butoxy-benzene 4-14'-butoxy-phenyl-sulfonyl) - yellow 4-bromo-3-hydroxy sulfinic acid, sodium
salt 3-hydroxy-quinophthalone quinophthalone 4-bromo-benzene-sulfm- 4- (4'-Bromo-phenyl-sulfonyl) - yellow 4,4 \ 5 ', 6', 7'-PeDtabrom- acid, sodium salt 3-hydroxy-quinophthalone 3-hyäroxy-quino-
phthalone
4,7-dibromo-3-hydroxy Benzene sulfinic acid, 4 '^', 6 ', 7'-tetrabromo-4-phenyl- Geib quinophthalone Sodium salt sulfonyl-3-hydroxy-quinophthalone Benzene sulfinic acid, 7-bromo-4-phenylsulfyl-3-hydΓoxy- yellow Sodium salt quinophthalone

Claims (2)

Patent claims: 1. Chiiiophthaloniarbiiofre
formula the general SO ₂ -R «5 in which R is an aryl radical, an alkyl radical with 1 to 12 carbon atoms, a cyclohexyl radical or a benzthiazolyl radical, Y is a hydrogen atom. a halogen atom, a nitro group or a phenyl radical, Z a hydrogen atom or a halogen atom, m an integer between 1 and 4 and η 1 or 2. 2. Process for the preparation of quinophthalone dyes of the general formula