DE2750779A1 - AZO DISPERSION DYES, THEIR PRODUCTION AND USE - Google Patents

Description

SANDOZ-PATENT-GMBH Loerrach

Case 150-3981

Azo disperse dyes, their manufacture and use

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The invention relates to azo disperse dyes, their manufacture and use for dyeing or printing hydrophobic fiber material.

The new dyes correspond to the formula

^R l
DN = NKN "(I),

R ₂ -CO-OX

wherein D is a diazo component of the phenyl, pyrazole, thienyl, thiazolyl, isothiazolyl or Thiadiazolyl series,

K 1,4-phenylene or 1,4-naphthylene optionally containing further substituents,

Rj when K is 1,4-naphthylene, hydrogen or C,. -alkyl,

or if K is unsubstituted or substituted 1,4-phenylene, hydrogen, C _1- . -alkyl, which is a chlorine, bromine, vinylsulfonyl, hydroxyl, cyano, C, _2- alkoxy, phenyl, acetyl, phenoxy, formyloxy, C, ., - Alkyl-carbonyloxy, benzoyloxy, C, _ ₂ -alkoxy-carbonyl, C, _ ₂ -alkoxycarbonyloxy, C, "-alkyl-aminocarbonyl, di- (C," -alkyl) -aminocarbonyl or a group of the formula - CO-OX, or hydroxy-C 1 -alkyl, which can carry a further substituent from the group consisting of chlorine, C ._.-alkoxy, hydroxy, phenoxy and benzyloxy, C _3-4 -alkenyl or chloro- or bromine - C 1-4 alkenyl

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R ₂ straight-chain or branched C 1 -alkylene or a group of the formula -CH ₂ CH ₂ -O-CH ₂ CH ₂ -,

X is a group of the formula a, b or c

-CH ₂ -C = CR ₄ (a), -CH-CH = CH-T ₁ (b) or ^ü l ^Ü 2

- C - C = CU ₃ (c),

R- and Rl one hydrogen and the other halogen,

R- hydrogen or C _1-4 -AlCyI,

T _{1 hydrogen, optionally C 1-4} substituted once by chlorine or bromine or up to two substituents from the group consisting of chlorine, bromine, hydroxy, C _1-2 -AlCyI and nitro-bearing phenyl,

T ₂ hydrogen or optionally once

substituted by chlorine, bromine or C, ₄ alkoxy, C, ₄ alkyl ~

U ₁ and U ₂ independently of one another are hydrogen, alkyl or, if U denotes hydrogen, together with the carbon atom bonded to them, also cyclohexyl.

U _{3 is} hydrogen or a group of the formula U, U ₂
- C - 0 - U ₄

and U ₄ denotes hydrogen, C, ₄ ~ alkyl or C, ₄ ~ alkylcarbonyl.

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where only in the chemistry of disperse dyes usual substituents on the molecule, including one optionally further substituents-bearing phenylazo groups are bonded.

The alkyl radicals R., T .., T_, U ,, Uy and U. preferably contain 1 or 2, in particular 1, carbon atom.

Halogen is to be understood as meaning fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.

Regardless of the other substituents, preferably mean in formula I:

D Phenyl, which can carry 1, 2, 3 or 4 substituents, including up to four from the group chlorine, bromine, iodine and / or up to two from the group nitro, cyano, methyl, trifluoromethyl, methoxy and C, ₂ ~ Alkylsulfonyl and / or one from the group formyl, C, _ _? -Alkyl-carbonyl, C, _- alkoxy-carbonyl, benzoyl, phenyl-C, -alkyl-carbonyl, phenoxycarbonyl, rhodan, phenylsulfonyl, benzylsulfonyl, toluylsulfonyl, aminosulfonyl, C, ₂ ~ alkyl- or di- (C, ₂ ~ alkyl) -aminosulfonyl, C, _ ₂ -alkoxy-C ₂ _.- aikylamino-sulfonyl or -carbonyl, phenylaminosulfonyl, NC._ ₂ -alkyl-N-phenylaminosulfonyl, aminocarbonyl, C, -alkyl- or di- ( C ₂ ~ alkyl) -aminocarbonyl, NC, ₂ -alkyl-N-phenylaminocarbonyl, phenylaminocarbonyl, phenyl, C _3-3 -alkanoylamino and phenylazo, in which the phenyl nucleus can carry up to 3 substituents, namely up to 3 chlorine or bromine and / or up to two methyl C._ ₂ ~ alkoxy, cyano and / or nitro,

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Thienyl bearing 1, 2 or 3 substituents, including none, one or two from the group consisting of chlorine, bromine, nitro, cyano and methyl and / or none or one from the group phenyl, C », - alkanoyl and C,, alkoxycarbonyl,

Thiadiazolyl, which can have phenyl, C ₁ _- alkylthio or C, ₂ ~ alkoxy as substituents,

Thiazolyl or isothiazolyl, which can have up to two substituents, including up to two from the group chlorine, bromine, nitro and cyano and / or one from the group methyl, rhodan, aminosulfonyl, C, _-alkylaminosulfonyl, di- (C, --alkyl) aminosulfony1, phenylaminosulfonyl, NC, --alkyl-N-phenylaminosulfonyl and C, ₂ ~ alkylsulfonyl,

or a group of the formula

d hydrogen, C, ₂ -alkyl, cyanoethyl, phenyl, chlorine or bromophenyl or toluyl,

e C, - alkyl, C _1-3 -AIkOXy, C, ₂ ~ ^alk y ^ltnio »cyano-

methyl, phenyl, C,. -alkoxycarbonyl, aminocarbonyI, C1 -C2 alkyl aminocarbonyl, di- (C1 -C4 alkyl) aminocarbonyl or N-C, -alkyl-N-phenylaminocarbonyl

f cyano or C, -alkoxycarbonyl

mean,'

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In particular is

D Phenyl, which can have up to three substituents, including up to two from the group chlorine, Bromine, iodine, nitro, cyano, methyl, trifluoromethyl and methoxy and / or one from the group C, - alkylsulfonyl, phenylsulfonyl, toluylsulfonyl, Aminosulfonyl, C, "-alkyl- or di- (C," -alkyl) -aminosulfonyl, Phenyl-aminosulfonyl, N-C, -Alkyl-N-phenyl-aminosulfonyl, Rhodan and / or phenylazo, in which the phenyl nucleus has up to 3 substituents, including up to two chlorine, bromine Can carry methyl or methoxy and / or a nitro or cyano,

Thienyl, which carries up to three substituents, including up to two chlorine, bromine, nitro, cyano and / or methyl and / or one from the group phenyl, C ₂ _, - alkanoyl and C, - alkoxycarbonyl, thiazolyl or Isothiazolyl, which can carry up to two substituents, including up to two chlorine or bromine and / or one methyl, cyano, nitro or C, ₂ ~ alkylsulfonyl, in particular

D Phenyl, which can have up to three substituents, including up to two chlorine, bromine, iodine, nitro and / or cyano and / or a C1-6 alkylsulfonyl or phenylazo;

K unsubstituted 1,4-naphthylene or a radical of formula IV

(IV),

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wherein

Is hydrogen, chlorine, bromine, C, j alkyl, C,, alkoxy, substituted by chlorine, bromine, hydroxyl, cyano, C, ₂ ~ alkoxy, C, -Alkoxyäthoxy or phenyl C _3-4 alkoxy or benzyloxy, especially hydrogen, C 1 -C -alkyl or C, ₂ -alkoxy, in particular hydrogen or C 1 -alkoxy, especially C _1-2 -alkoxy,

Hydrogen, chlorine, bromine, cyano, C, ₂ ~ alkyl, C, .- alkoxy, formylamino, C ._.- alkylcarbonylamino. Chlorine or bromine-C, ₄ -alky1-carbonylamino, C ₁ --AIkOXy-C. _{1-alkyl-carbonylamino,} C ₂ alkoxycarbonyl-C, ₂ -alky1-carbonylamino, C -.- alkoxycarbonylamino, phenoxy-C ₁ _ ₂ -alkyl-carbonylamino, C ₁ _ ₂ -alkoxy-C ₂ _ ₃ -alkoxy-carbonylamino, C _1-4 -alkoxy-carbonylamino-C ₁ -alkylamino-carbonylamino, benzoylamino, PhBnYl-C ₁ -alkyl -carbonylamino. Phenoxycarbonylamino, phenyl-C, ₂ -alkoxycarbonylamino or C _1-2 -alkylsulfonylamino, and the phenyl nuclei mentioned can carry one or two chlorine, bromine, iodine, C, ₂ -alkyl or a C, _{2 -alkoxy, especially hydrogen} , Chlorine, bromine, C, _2- alkyl, C, ₂ -alkoxy, formylamino, C -.- alkylcarbonylamino, chloro- or bromo-C, -alkyl-carbonylamino, C ₁ __- alkoxy-C ₁ _.- alky1 -carbonylamino, phenoxy-Cj-alkyl-carbonylamino, C, ₂ -alkoxycarbonyl-C, ₂ -alkyl-carbonylamino, C _1-4 -alkOXycarbonylamino, C, ₂ -alkoxy-C _2-3 -alkoxy-carbony1-amino, C - ^ - Alkoxy-carbonyl-C. _-3 ~ alkylaminocarbonylamino, benzoylamino, phenyl-C. _-2 ~ alky1-carbonylamino. Phenoxycarbonylamino, phenyl-C. _-2 ~ alkoxy-carbonylamino or C ₁ _ ₂ -alkylsulfonylamino,

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especially hydrogen, chlorine, bromine, C 1 -C 4 -alkyl, C _1-2 -AlkOXy or C 1 -C 4 -alkyl carbonylamino, in particular hydrogen, methyl or acetylamino;

R ,, if K is 1,4-naphthylene, hydrogen or ethyl, or if K is optionally substituted 1,4-phenylene, hydrogen, C -.- alkenyl, chloro- or bromine-C,. -Alkenyl or C, - -Alkyl, which has a substituent from the group consisting of chlorine, bromine, vinylsulfonyl, hydroxy, cyano, C. _-2 -alkoxy, phenyl, acetyl, phenoxy, formyloxy, C. -.- alkanoyloxy, benzoyloxy, C._ ₂ -alkoxycarbonyl , C, - alkoxy-carbonyloxy, C. - alkyl- and -di (C. - alkyl) -aminocarbonyloxy or a group of the formula -CO-OX or a hydroxyl and chlorine as the second substituent, C _1-4 -AIkOXy, hydroxy, phenoxy or benzyloxy can carry; is special

R, hydrogen or ethyl, or if K is optionally substituted 1,4-phenylene, also C ₁ -alkyl, which has a substituent from the group consisting of hydroxy, cyano, C 1-3 alkoxy, formyloxy, C _3-4 alkanoyloxy , Benzoyloxy and C ₁ ″ -alkoxycarbonyloxy or a hydroxyl and chlorine, C, ₂ -alkoxy, hydroxy, phenoxy or benzyloxy as the second substituent, especially if K is a radical of the formula IV and R ₁ . Is hydrogen, a group of the formula -CO-OX, especially hydrogen or ethyl,

R_ straight-chain C _2-4 alkylene or a group of the formula -CH (CH ₃ J-CH ₂ -, -CH ₂ -CH (CH ₃ ) - or -CH ₂ -CH ₂ -O-CH ₂ CH ₂ -, in particular C -alkylene, especially 1,2-ethylene;

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one of

R-, and Ri chlorine or bromine, the other hydrogen;

R. hydrogen or methyl;

T. hydrogen, methyl, ethyl, chloromethyl or bromomethyl or optionally up to twice Chlorine, bromine, hydroxy, methyl, ethyl, methoxy, ethoxy and / or nitro-substituted phenyl, in particular hydrogen, methyl, chloromethyl or phenyl, especially hydrogen, methyl or Phenyl;

T _{2 is} hydrogen, methyl, ethyl, chloromethyl or bromomethyl or C 1 -alkoxymethyl, in particular hydrogen, methyl or chloromethyl, in particular hydrogen;

_{U 1} and U 2 independently of one another are hydrogen or methyl, in particular hydrogen;

U_ hydrogen, C, _ ₂ -Akoxy-C, ₂ ~ alkyl or acetoxy-

^C l-2 ~ ^alky1 '
X is a group of formula a or c.

In general, substituted phenyl is preferred as the diazo component.

The preparation of the new compounds of the formula I is characterized in that the diazonium compound from an Amiη of the formula II

D - NH, (II)

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with a compound of the formula III

H-K-N (III)

^ R -CO-O-X 2

clutch.

The coupling component of the formula III is preferably prepared by condensation of a Esters of formula IV or V

HaI-R ₂ -CO-OX (IV)

CH ₂ = CH-CO-OX (V)

wherein Hal is chlorine or bromine, with an amine of the formula VI

H - K - NH R ₁ (VI)

or by condensation of a compound of the formula VII

H-K-N (VII)

R ₂ COOH

or a functional acid derivative, preferably of the acid chloride, with an alcohol of the formula VIII

HO-X (VIII)

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It is also possible to prepare the coupling component of the formula III in a "one-pot process", e.g. by adding an amine of the formula VI with acrylic acid, methacrylic acid or crotonic acid, in the presence an excess of the alcohol of the formula VIII, or by condensation of a compound of the formula VII with a compound of the formula IX

Shark - X (IX)

where Hai is chlorine or bromine, preferably in an anhydrous medium, in the presence of an acid acceptor (e.g. an aliphatic or heterocyclic amine).

Finally, the compounds of formula III are also obtained in a "one-pot process", e.g. Addition of an amine of the formula VI with acrylic or crotonic acid, optionally in the presence of a catalyst, e.g. a Lewis acid or glacial acetic acid, optionally diluting the reaction product with an organic solvent and adding the compound of the formula IX and an acid-binding one Means.

All of these conversions take place analogously to known, similar reactions. The alcohol of formula VIII can also be used analogously to known methods, e.g. by hydrolysis of the dihaloalkenyl of the formula IX, getting produced.

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It is often possible to treat the dyes by a heat, solvent and / or grinding treatment or by recrystallization to be converted into another, thermally stable modification. Suitable methods and those involved achievable advantages are known to the person skilled in the art.

The processing of the new compounds of the formula I into coloring preparations takes place in a generally known manner, e.g. by grinding in the presence of dispersants and / or fillers. With the possibly in a vacuum or Preparations dried by spraying can, after adding more or less water, in so-called dye, pad or print long or short liquors. The dyes are excellent in aqueous suspension on textile material made of fully synthetic or semi-synthetic, hydrophobic, high molecular organic Fabrics on. They are particularly suitable for dyeing, padding or printing textile material from linear, aromatic polyesters, as well as from cellulose-2 1/2 acetate, cellulose triacetate and synthetic Polyamides.

It is colored, padded or printed according to known methods, e.g. that in French patent specification No. 1.445.371 described procedure.

The dyeings obtained have good all-round fastness properties; to be emphasized are the lightfastness, the Thermosetting, sublimation and pleating fastness. she are excellent wetfast.

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In the following examples, parts are parts by weight and percentages are percentages by weight; the Temperatures are given in degrees Celsius.

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example 1

Preparation of the dye of the formula

OC ₂ H ₅

NK-CH ₂ CH ₂ -COOCH ₂ -CH = Ch-CI

52.4 parts of 2-bron-4,6-dinitroaniline are in 220 parts concentrated sulfuric acid stirred in and cooled to 10 °. To this suspension are in the course of 35 min. 18.8 parts of 40% nitrosylsulfuric acid were added dropwise.

After stirring for 2 hours, the resulting diazonium salt solution is at 5-10 ° in 30 minutes to a coupling solution of 68.1 parts of 5-acetylamino- -2-methoxy-N- [3'-chloropropene- (2 ') -vloxycarbonylethyl] aniline in 180 parts of glacial acetic acid, with cooling by direct addition of ice, added. After the coupling is completed diluted with 1000 parts of ice water, stirred for 1 hour, the precipitate was filtered off and washed acid-free. The dye is then redistributed in 500 parts of water while stirring at approx. 90 ° for 3-5 hours, filtered off again, washed with water and dried

The dye dyes polyester fiber material in pure, navy blue shades with excellent fastness properties.

The coupling component mentioned in the above example can be produced as follows:

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4 parts of 4-methoxyphenol, 144 parts of acrylic acid and 200 parts of acetone are placed in a Sulfer flask. Then 240 parts of triethylamine are added with stirring and with external cooling in such a way that the temperature does not exceed ^{50 β.} After the addition of 225 parts of ice, trans-1,3-dichloropropene-1, the mixture is stirred for 6 hours at 50 °, the tristhylamine hydrochloride formed is filtered off and the filtrate is subjected to fractionation, the desired acrylic acid 3-chloro-propene - (2 ) -y! ester in good yield at 73-75 ° under a vacuum of 18-19 Torr, distilled.

35.6 parts of the acrylic ester obtained in this way are further mixed with 38.8 parts of 5-acetylamino-2-ethoxyaniline, 10 parts of glacial acetic acid, 0.4 part of zinc chloride and 0.2 part of 4-methoxyphenol at 110 ° -115 ° for 5-6 hours touched. After cooling, the resulting 5-acetylamino-2-ethoxy-N- [3 ¹ -chloropropene - (2 ') -yloxycarbonylethyl] aniline is dissolved in 100 parts of glacial acetic acid and can thus be used directly for the preparation of the dye.

Examples 2-17

The procedure described in Example 1 is followed, but instead of 5-acetylamino-2-ethoxy-N- (3'-chloropropen-2'-yl-oxycarbonylethyl) aniline is used equivalent amounts of the following coupling components, one obtains blue dyes with very similar properties -

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S-acetylamino-2-methoxy-N- (3 ¹ -chloropropene-2'- yloxycarbonylethyl) aniline,

S-propionylamino ^ -ethoxy-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline,

S-propionylamino ^ -methoxy-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline,

S-acetylamino-2-ethoxy-N-ethyl-N- (3'-chloropropene-2'-yloxycarbonylethyl) aniline, S-acetylaraino ^ -methoxy-N-ethyl-N- (3 ¹ -chloropropene-2 ¹ -yloxycarbonylethyl) -aniline, S-acetylamino ^ -methoxy-N-propyl-N- (3'-chloropropene-2 '-yloxycarbonylethyl) -aniline, S-acetylamino ^ -methoxy-N-butyl-N- (3 ¹ - chloropropene-2 ¹ -yloxycarbonylethyl) aniline, S-acetylamino ^ -ethoxy-N- (propyn-2'-yloxycarbonylethyl) -aniline,

5-acetylamino-2-ethoxy-N- (4'-methoxybutyn-2 ¹ -yloxycarbonylethyl) aniline,

5-acetylamino-2-methoxy-N- (4'-ethoxybutyn-2'-yloxycarbonylethyl) -aniline,

5-acetylamino-2-ethoxy-N- (2 ¹ -chlororopen-2'-yloxycarbonylethyl) aniline,

S-acetylamino ^ -methoxv-N- (2'-bromopropen-2'-yloxycarbonylethyl) -aniline,

5-acetylamino-2-ethoxy-N- (3 ¹ -chlorproDen-2'-yloxycarbonylethoxyethyl) -aniline, 5-acetylainino-2-methoxy-N- [ß- (3 ¹ -chlorprooen-2 '-yloxycarbonyl) -ß -methy1-ethyI] -aniline, S-acetylamino ^ -methoxy-N- [cu- (3 ¹ -chloropropene-2 '-yloxycarbonyl) -butyl] -aniline, 5- acetylamino- 2- ethoxy-N- 6uj- (3'-chloropropene-2'-yloxycarbonyl) propyl] aniline.

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Examples 1.8 - 51

If you instead of 2-bromo-4,6-dinitro-aniline in the Examples 1 to 17 use the equivalent amount of 2-chloro-4,6-dinitro-aniline or 2-iodo-4,6-dinitroaniline, one obtains dyes, the polyester fiber material likewise Dye in a navy blue shade and with excellent fastness properties.

Example 52

In a mixture of 60 parts of water and 40 parts of conc. Hydrochloric acid is stirred at room temperature, 17.2 parts of 2-chloro-4-nitroaniline for 3 hours. The suspension obtained is cooled by adding 100 parts of ice and dlazotiert at 0-5 ° within 2 hours with 7 parts of sodium nitrite in 100 parts of water. After a further 30 minutes, the excess sodium nitrite is destroyed by adding aminosulfonic acid. The diazonium salt solution thus obtained is after clear filtration within 30 minutes to a solution, cooled to 0-5 °, of 35.0 parts of 3-acetylamino-N- (2 ¹ - -cyanethy1) -N- (3'-chloropropene-2'- yloxycarbonylethyl) aniline in 100 parts of 40% acetic acid was added dropwise. When the coupling is complete, it is neutralized with sodium hydroxide solution and the coupling solution is heated to 90-95 ° for 2-3 hours. It is then filtered, washed free of salt and dried. The obtained dye of the formula

Cl

[O]

CH ₂ CH ₂ -CO-O-CH ₂ -Ch = CHCl

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dyes polyester fiber material in red tones with excellent Fastnesses.

Examples 53-71

Analogously to the information in Example 52, diazotized 2-chloro-4-nitroaniline can be prepared with the following compounds can be coupled to dyes with similar properties and also red nuances on polyester fiber material:

Example No.

3-acetylamino-N-ß-cyanoethyl-N- (propyn-2'-yloxycarbonylethyl) aniline,

3-acetylamino-N-ethyl-N- (3'-chloropropene-2-yloxycarbonylethyl) -aniline, 3-acetylamino-N-ethyl-N- (2 * -bromopropen-2 ¹ -yloxycarbonylethyl) -aniline,

3-acetylamino-N-ß-hydroxyethyl-N- (3 ¹ -chlorpropen-2 ¹ -yloxycarbonylethyl) -aniline, 3-acetylamino-N, N-di- (3 ¹ -chlorpropen-2 ¹ -yloxycarbonylethyl) -aniline,

3-acetylamino-N, N-di- (2'-chloropropen-2'-yloxycarbonylethyl) -aniline,

3-acetylamino-N, N-di- (propyne-2 ¹ -yloxycarbonylethyl) aniline,

3-acetylamino-N, N-di- (4'-methoxybutyn-2'-yloxycarbonylethyl) -aniline,

N-ß-cyanoethyl-N- (3'-chloropropen-2'-yloxycarbonylethyl) -aniline

N-ethyl-N- (3'-chloropropen-2'-yloxycarbonylethyl) -aniline,

3 N-0-hydroxyethyl-N- (3 ¹ -chloropropen-2'-yloxycarbonylethyl) aniline,

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Example No.

64 N, N-di- (3'-chloropropen-2'-yloxycarbonylethyl) - -aniline,

65 N, N-di- (propyn-2'-yloxycarbonylethyl) aniline,

66 N, N-di (allyloxycarbonylethyl) aniline,

67 N-ß-cyanoethyl-N- (propin-2'-yloxycarbonylethyl) - -aniline,

68 N-ß-hydroxyethyl-N- (propyne-2-yloxycarbonylethyl) aniline

69 N-ethyl-N- (propyn-2'-yloxycarbonylethyl) aniline,

70 N-ß-cyanoethyl-N- (allyloxycarbonylethyl) -aniline,

71 N-ß-hydroxyethyl-N- (allyloxycarbonylethyl) - -aniline,

Example 72

40 parts of glacial acetic acid, 16.3 parts of 2-cyano-4-nitroaniline and another 40 parts of glacial acetic acid are added to 9.4 parts of 40 A nitrosylsulfuric acid, the temperature being constantly kept at 10-15 " thus obtained diazonium salt solution slowly added to a solution of 35.0 parts of 3-acetylamino-N-ß-cyanoethyl-N- (3'-chloro-dropen-2 ^l -yloxycarbonylethyl) aniline in 60 parts of 50% acetic acid, the temperature is kept at 0-5 ° After the coupling is complete, the mixture is diluted with 500 parts of water, stirred for 1 hour, filtered, washed acid-free with water and dried

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ο, ¹ * - <O> - ^{n =} n- <o) -ν

CH_CH_-CO-O-CH, -CH = CHCl NHCOCH ₃ * ^Z

dyes polyester fiber material in violet shades with excellent fastness properties.

Examples 73-91

If the diazotized 2-cyano-4-nitroaniline with the coupling components is used analogously to the procedure of Example 72 of Examples 53-71 implemented, one obtains dyes, the polyester fiber material in red to purple shades, coloring with excellent properties.

Examples 92-111

Analogously to the procedure of Example 52, 13.8 parts are used instead of 17.2 parts of 2-chloro-4-nitroaniline 4-Nitroaniline reacted with the coupling components of Examples 52 to 71. In this way dyes are obtained dye the polyester fiber material in yellowish-red to red shades with very good fastness properties.

Examples 112-113

Analogously to the procedure of Example 1, the diazotized 2-bromo-4,6-dinitroaniline with (Ex. 112)

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N- (propyn-2'-yloxycarbonylethy1) -α-naphthylamine, or (Ex. 113) N- [4'-Methoxybutyn-2'-yloxycarbonyl) -anaphthylamine coupled. This gives dyes that contain polyester fiber material in reddish-blue tones, with excellent dyeing properties.

If the procedure is as in Example 1, but instead of 2-bromo-4,6-dinitroaniline
If equivalent amounts of the anilines specified here are used, dyes of the shades specified next to it are obtained:

2-cyano-4-nitro-6-bromaniline blue

2,4-dinitro-6-cyananiline do.

2,4-Dinitro-6-methylsulfonylaniline do.

2,4-Dinitro-6-ethylsulfonylaniline do.

2,6-dicyano-4-nitroaniline do.

2-cyano-4-nitro-6-methylsulfonylaniline do.

2-cyano-4-nitro-6-chloro- or -iodaniline do.

2,5-dichloro-4,6-dinitroaniline do.

Instead of 5-acetylamino-2-ethoxy-N- [3'-chloropropene- (2 ') -yloxycarbonylethyl] aniline Equivalent amounts of a compound of the formula can also be used

OC ₂ H ₅

NH-CH ₂ CH ₂ -CO-OX

NHCOCH ₃
are used, whereby dyes are obtained that

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Polyester fiber material also in blue tones, with dyeing comparable fastness properties:

-CH ₂ CH = CHCl, -CH-CH = CHBr,

-CH ₂ CCl = CH ₂ , -CH ₃ CBr = CH ₂ , -CH ₂ CH = CH ₂ , -CH ₂ CH = CH-CH ₃ , -CH ₂ CH = CH-C ₆ H ₅ ,

-CH ₂ C = CH, CH ₂ C = C-CH ₂ OCH ₃ , CH ₂ C = C-CH ₂ OC ₂ H ₅ , CH ₂ C = C-CH ₂ OCOCH ₃ , C (CH ₃ ) ₂ -C = CH,

-CH (CH ₃ ) -C = C-CH (CH ₃ ) -OCH ₃ ,

In the following table 1 are further, according to the invention Dyes of the formula

CH CH -CO-O-CH-CH = CHCl

and the nuance of their coloring on polyester fiber material specified.

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TABEL

Ο »O (O OB fS> N »

O O)

E.g.
No. D. ^R l ^R 5 ^R 6 nuance 138 2-cyano-4-nitro-6-chlorophenyl -CH ₂ CH ₂ OCHO H -NHCOC ₂ H ₅ blue 139 2-cyano-4-nitro-6-brotnpheny 1 -CH ₂ Ch ₂ OCOCH ₂ CH ₂ CH ₃ H -NHCOCH ₂ CH ₂ Cl do. ILO 2,5-dichloro-4-nitropheny1 -CH ₂ CH ₂ CO-OCH ₂ Ch-CHCl H -CH ₃ yellowish
Red 141 2,4-dinitropheny1 -CH ₂ CH ₂ O-COCH ₃ H -NHCOCH ₃ violet 142 2-chloro-4-methylsulfonylphenyl -C ₂ H ₅ H Cl reddish
yellow 143 Phenyl -CH ₂ CH ₂ OH H -C ₂ H ₅ yellow 144 4-phenylazophenyl -CH ₂ CH ₂ O-COC ₂ H ₅ H -NHCOC ₂ HS Red 145 2-chloro-4-aminosulfonylphenyl -CH ₂ CH ₂ CH ₂ CH ₃ H • do. do. 146 2,5-dichloro-4-amino8ulfonylphenyl -CH ₂ CH ₂ OH H H orange 147 2-chloro-4-methylaminosulfonylphenyl -CH ₂ CH ₂ C ₆ H ₅ H -NHCOCH ₃ Red 148 2, S-dichloro-A-dimethylaminosulfonyl
phenyl -C ₂ H ₅ H do. do.

CJ cn

«J

00

TABLE 1 (continued)

oo O CO OO PO

cn

E.g.
No. D. ^R l ^R 5 ^R 6 nuance 149 3-methyl-4-meta-toluylazophenyl -CH (CH ₃ ) ₂ H -NHCOCH ₃ Red 150 2-bromo-4-nitropheny1 -CH ₀ CH ₀ O-COC ^ H-
ZZ OD H do. bluish tint
Red 151 2-cyano-4-nitro-6-ethylsulfonylphenyl -CH ₂ CHOHCH ₂ Cl K) C ₂ H ₅ do. greenish
blue 152 2-methylsulfonyl-4-nitrophenyl -CH ₂ CH = CH ₂ -OCH ₃ —CH ₀ reddish
blue 153 2-iodo-4-nitrophenyl -CH ₂ CH ₂ SO ₂ -CH-CH ₂ H do. bluish tint
rnf 154 -4-rhodanephenyl -CH ₂ CH ₂ O-CONHCH ₃ H -NHCOCH ₃ yellow 155 2,5-dichlorophenyl -CH ₂ CH ₂ O-CON (C ₂ H ₅ ) 2 H do. do. 156 2,6-dichloro-4-nitropheny1 -CH _O C, H _C
z 0 5 H -C ₂ H ₅ Brown 157 5-nitrothiazolyl-2 H H -NHCO ₂ H ₅ blue 158 4-methyl-5-nitrothiazolyl-2 H -OCH ₃ -NHCOCH ₃ do. 159 3-phenyl-1,2,4-thiadiazoly1-5 -CH ₂ CH ₂ CN H -CH ₃ Red

U) I

O) cn ro

Cn

u> v £ OO

TABLE 1 (continued)

09

to CO N> ro - *. ο m

E.g.
No. D. " ⁶ A ^R 5 ^R 6 ₂ CN H nuance 160 1-phenyl-1,3,4-thiadiazolyl-5 -CH ₂ CH ₂ O-COC ₂ H ₅ H -CH ₃ Red 161 2-cyano-3-methyl-4-methoxycarbonylthienyl -CH ₂ CH ₂ CO-OCH ₂ CH-Ch ₂ H do. blue 162 1-phenyl-3-methyl-4-cyano-pyrazolyl-5 -CH ₂ CH ₂ CH ₃ H -NHCOCH ₃ Red 163 2-cyano-4-nitro-6-chlorophenyl -CH ₂ CH ₂ OCH ₃ H -NHCOOCH ₃ blue 164 2-cyano-4-nitro-6-bromophenyl -C ₂ H ₅ H -NHCOOC H ₇ do. 165 do. do. H -NHCOOCH ₂ CH ₂ Oc ₂ H ₅ do. 166 do. -CH ₂ CH ₂ OH H -NHSO ₂ CH ₃ do. 167 2-chloro-4-nitrophenyl do. H -5IHCOCH ₂ Ch ₂ OCH ₃ Red. 168 2-bromo-4-nitropheny1 H p < H -OC ₂ H ₅ do. 169 2,4-dinitro-6-bromophenyl -CH ₂ CH ₂ CN
H .CH ₂ C ₆ T ^ -NHCOCH ₃ navy blue 170
171 2-chloro-4-nitrophenyl
2-cyano-4-nitrophenyl H p ~ Cl
-CH ₃ H
H yellowish
Red
Red 172 4-nitrophenyl orange

to I

(0

cn O I OJ VO 00

2 '7 5 U 7 1 9

Case 150-3981

In the following table 2 are further according to the invention Dyes of the formula

D-N = N

Λ \

CH ₂ CH ₂ -CO-OX

and the nuance of their coloring on polyester fiber material indicated, where X has the following meanings in all cases:

-CH ₂ CH = CHCl, -CH ₂ -CH = CH ₂ , -CH ₂ -ChCH, and -CH ₂ C = C-CH ₂ O-COCH ₃

TABLE 2

Example no. D. ^R l nuance 172-176 2,4-dinitro-6-bromophenyl H red-tinged
blue 177-181 2,4-dinitro-6-chlorophenyl -C ₂ H ₅ do. 182-186 2,4-dinitro-6-cyanophenyl H blue 187-891 2,6-dicyano-4-nitrophenyl H do. 192-196 2-cyano-4-nitro-6-bromophenyl -CH ₂ CH ₂ CH ₂ CH ₃ reddish
blue

809822/064

^Case 150-3981

ANWEHDONGS EXAMPLE

7 parts of the dye prepared according to Example 1 are with 4 parts of sodium dinaphthylmethandisulfonsaurem, 4 parts of sodium cetyl sulfate and 5 parts anhydrous sodium sulfate was ground to a fine powder in a ball mill for 48 hours.

1 part of the dye preparation obtained in this way is made into a paste with a little water and the suspension obtained through a Sieve added to a dyebath containing 3 parts of sodium lauryl sulfate in 4000 parts of water. The fleet ratio is 1:40. 100 parts of purified polyester fiber material are then added to the bath at 40-50 ° 20 parts of a chlorinated benzene emulsified in water, slowly heats the bath to 100 ° and colors 1-2 Hours at 95-100 °. The deep blue colored fibers are washed, soaped, washed again and dried. The level dyeing is excellent light, over-dyeing, washing, water, sea water, sweat, subliming, Resistant to smoke gas, thermosetting, pleating and permanent press.

809822/0641

Claims (1)

Claims Pyrazolyl, thienyl, thiazolyl, isothiazolyl or thiadiazolyl series, K 1,4-phenylene, or 1,4-naphthylene, optionally containing further substituents, R ,, when K is 1,4-naphthylene, hydrogen or C,. -alkyl, or when K is unsubstituted or substituted 1,4-phenylene, hydrogen, C,. -alkyl, which is a chlorine, bromine, vinylsulfonyl, hydroxyl, cyano, C._ ₂ -alkoxy, phenyl, acetyl, phenoxy, formyloxy, C, _3- alkyl-carbonyloxy, benzoyloxy, C, ₂ -alkoxy-carbonyl, C, _ -alkoxy-carbonyloxy, C._ ₂ -alky1-aminocarbonyl, di- (C._ ₂ ^ alkyl) -aminocarbonyl or a group of the formula -CO-OX, or hydroxy-C. .-alkyl, which can carry a further substituent from the group consisting of chlorine, C,. -alkoxy, hydroxy, phenoxy and benzyloxy, 809822/0641 ORIGINAL INSPECTED - 3r- Case 150-3981 C ₂ _ ₄ alkenyl, or chlorine or bromine-C _3-4 alkenyl. R »straight-chain or branched C 1 -alkylene or a group of the formula -CH ₂ CH ₂ -O-CH ₂ CH ₂ -, X is a group of the formula a, b or c R3R3 T ₂ -CH ₂ -C = CR ₄ (a), -CH-CH = CH-T ₁ (b) U ₁ U ₀ or -CC = C- U ₃ (c) R_ and R 'the hydrogen and the other halogen, R _{4 is} hydrogen or C. -Alkyl, T _{1 hydrogen, optionally C, 4} -alkyl substituted once by chlorine or bromine or up to two substituents from the group consisting of chlorine, bromine, hydroxy, C. "-alkyl, C," -alkoxy and nitro-bearing phenyl, T_ hydrogen or optionally C 1 -C alkyl substituted once by chlorine, bromine or C, _{4 -alkoxy,} U, and U- independently of one another are hydrogen, alkyl or, if U, hydrogen means, together with the carbon atom attached to it, also cyclohexyl , U ^ hydrogen or a group of the formula UU
- C - O - U ₄ 809822/064 1 275Q779 JT- Case 150-3981 and U ₄ denotes hydrogen, C1-alkyl or C1-alkyl-carbonyl, with substituents customary in the chemistry of disperse dyes, including on the molecule a phenylazo group optionally carrying further substituents, are bonded. 2. Azo compounds of the formula I _r according to claim I. where D is phenyl which has up to 4 substituents can carry, including up to four from the group chlorine, bromine, iodine and / or up to two from the group nitro, cyano, methyl, trifluoromethyl, methoxy and C, -alkylsulfonyl and / or one from the group formyl, C, ₂ -alkyl-carbonyl, C,, -alkoxy-carbonyl, benzoyl, Pheny1-C, ₂ -alkyl-carbonyl, phenoxy-carbony1, rhodan, phenylsulfonyl, benzylsulfonyl, toluyl-sulfonyl, aminosulfonyl, C, ₂ ~ alkyl or di- (C .-- alkyl) aminosulfonyl, C. _2 ~ ^A ^ ^cox y ~ ^C 2-4 ~ ^a ^ ^lc ylaminosulfonyl or carbonyl, phenylaminosulfonyl, NC, j-alkyl-N-phenylaminosulfonyl, aminocarbonyl, C, ₂ ~ Alkyl or di (C, ₂ -alkyl) -aminocarbonyl, NC, j-alkyl-N-phenylaminocarbonyl, phenyl-aminocarbonyl, phenyl, C _3-3 -alkanoylamino and phenylazo, in which the phenyl nucleus can carry up to 3 substituents and up to 3 chlorine or bromine and / or up to two methyls, 809822/0641 - y- Case 150-3981 C, --alkoxy, cyano and or nitro, Thienyl which has 1, 2 or 3 substituents, including none, one or two from the group chlorine, bromine, nitro, cyano and methyl and / or none or one from the group phenyl, C ^ _.- alkanoyl and C, _ -Alkoxy-carbonyl, Thiadiazole, which can have phenyl, C ₁ _ ₂ -alkylthio or C, ₂ ~ alkoxy as substituents, Thiazolyl or isothiazolyl, which can have up to two substituents, including up to two from the group chlorine, bromine, nitro and cyano and / or one from the group methyl, _{rhodan, aminosulfonyl, C 1} __- alkylarninosulfonyl, di- (C ₁ "-alkyl) -aminosulfonyl, phenylaminosulfonyl, NC ₁ _ -alkyl-N-phenylaminosulfonyl and C _,? -Alkylsulfonyl or a group of the formula wherein d is hydrogen, C, - alkyl, cyanoethyl, phenyl, chloro- or bromophenyl or Toluyl, e C ₁ _ ₂ ~ alkyl, C _1-3 -AIkOXy, C ^^ thio, cyanomethyl, phenyl, C _1-4 -AlkOXy- 809822/0641 Case 150-3981 carbonyl, aminocarbonyl, C, ₂ -alkylaminocarbony1, di- (C, --alkyl) -aminocarbonyl or NC, _-alkyl-N-phenylaminocarbony1 and f is cyano or C1- alkoxycarbonyl. 3. Azo compounds of the formula I according to claim 1, where D is phenyl which has up to three substituents can carry, including up to two from the group chlorine, bromine, iodine, nitro, cyano, methyl, trifluoromethyl and methoxy and / or one from the group C, - alkylsulfonyl, phenylsulfonyl, toluylsulfonyl, aminosulfonyl, C, - alkyl- or di- (C, ₂ -alkyl) -aminosulfonyl, phenylaminosulfonyl, NC, -alkyl-N-phenylarainosulfonyl, rhodane and / or phenylazo, in which the phenyl nucleus has up to 3 substituents, including up to two chlorine, bromine, methyl or methoxy and / or can carry a nitro or cyan, Thienyl, which has up to three substituents including up to two chlorine, bromine, nitro, cyano and / or methyl and / or one from the group phenyl, C ₂ _ ₃ ~ alkanoyl and C, ₂ ~ alkoxycarbonyl, Thiazolyl or isothiazolyl, which has up to two substituents, including up to 809822/0641 Case 150-3981 two chlorine or bromine and / or one methyl, cyano, nitro or C, ₂ ~ alkylsulfonyl can carry, means. Azo compounds of the formula I according to claim 1, wherein D is phenyl, which can have up to three substituents, including up to two Chlorine, bromine, iodine, nitro and / or cyano and or a C, - alkylsulfonyl or Phenylazo means. Azo compounds of the formula I according to one of the preceding claims, wherein K is unsubstituted 1,4-naphthylene or a radical of the formula IV (IV), wherein R _{5 is} hydrogen, chlorine, bromine, C, ₂ -alkyl, C _{1-2 -AIkOXy, C 2} _.- substituted by chlorine, bromine, hydroxyl, cyano, C, ₂ -alkoxy, C, ₂ -alkoxyethoxy or phenyl Alkoxy, or benzyloxy, R, hydrogen, chlorine, bromine, cyan, Alkyl, C _1-3 -AIkOXy, formylamino, 809822/064 1 Case 150-3981 Alky 1-carbonylami.no, chlorine or bromine -rC. ^ - alkyl-carbony lamino, C, ₂ ~ alkoxy- -C, _{.-Alkyl-carbonylamino, C, 2} ~ alkoxycarbonyl-C, _ ₂ -alky1- carbonylamino, C 1 -C 4 -alkoxy-carbonylamino, phenoxy-C, ₂ -alkyl-carbonylamino, C _1-2 -alkoxy-C -C -alkoxy-carbonylamino, C _1-4 -alkoxycarbonyl-C ₁ -alkylamino-carbonylamino , Benzoylamino, Phenyl-C-_ ₂ -alkyl-carbonylamino, Phenoxycarbonylamino, Phenyl- is kylsulfonylamlno, and the phenyl nuclei mentioned can carry one or two chlorine, bromine, iodine, C, ₂ -alkyl or a C _{1-2 -alkyl.} 6. Azo compounds according to claim 5, in which K is 1,4-naphthylene. 7. Azo compounds according to claim 5, wherein K is a radical of the formula IV and R _{5 is} hydrogen, C ^ -alkyl or C -alkoxy and R ₆ hydrogen, chlorine, bromine, C _1-2 -AlKyI, C _1-2 -alkoxy, formylamino, C _1-4 -alkyl carbonylamino, chlorine or bromine C, .- alkyl-carbonylamino, C _1-3 -alkOXy-C _1-4 -alky1-carbonylamino, phenoxy-C _1-2 -alkylcarbonylamino, Cj -alkoxy-carbony1-C _1-2 -alkyl-carbonylamino, C _1-4 -alkOXy - 809822 / 06A1 JT- Case 150-3981 carbonylamino, C, ₂ -alkoxy-C __., - alkoxycarbonylamino, C, ^ alkoxy-carbony1-C., - alkylamino-carbonylamino, Benzoy1-amino, phenyl-C._ ₂ -alkyl-carbonylamino, phenoxycarbonylamino, phenyl-C. , __- alkoxy-carbonylamino or C, »-Alkylsulfonylamino mean. 8. Azo compounds according to claim 5, wherein K is a radical of the formula IV and R_ hydrogen or C _1-3 -AlkOXy, in particular C ₁₂ and R- is hydrogen, chlorine, bromine, C, -C -alkyl, C _1-2 -AIkOXy or C. ^ alkyl-carbonylamino, in particular hydrogen, methyl or acetylamino and especially acetylamino. 9. Azo compounds according to claim 1, of the formula I, wherein R ₁ when K is 1,4-naphthylene. Hydrogen or ethyl, or if K is optionally substituted 1,4-phenylene, hydrogen, C _2- . -Alkenyl, chloro- or bromo-C _3-4 -alkenyl or C 1-4 -alkyl, the one substituent from the group chlorine , Bromine, vinylsulfonyl, hydroxy, cyano, C _1-3 -AIkOXy, phenyl, acetyl, phenoxy, formyloxy, C _3-4 -alkanoyloxy, benzoyloxy, C, ₂ ~ alkoxycarbonyl, C ₁ -alkoxy-carbonyloxy, 809822/0641 3ΛΓ- Case 150-3981 - and -Di- (C - ^ - amlnocarbonyloxy or a group of Formula -CO-O-X or a hydroxyl and the second substituent is chlorine, C -, - alkoxy, Hydroxy, phenoxy, benzyloxy can carry means. Azo compounds according to claim 9, wherein R. is hydrogen or ethyl, or if K is optionally substituted 1-4-phenylene, also C, ^ -alkyl, which has a substituent from the group hydroxy, cyano, C, ₂ -alkoxy, formyloxy, C ₂ -alkanoyloxy, Benzoyloxy and C, _- alkoxy-carbonyloxy or a hydroxyl and chlorine, C _1-2 -AIkOXy, hydroxy, phenoxy or benzyloxy can carry as the second substituent. 11. Azo compounds according to claim 5, wherein R., when K is a radical of the formula IV and R _{5 is} hydrogen, is a group of the formula -CH ₂ CH ₂ CO-OX. 12. Azo compounds of the formula I according to claim 1, wherein R _{1 is} ethyl or, above all, hydrogen. 13. azo compounds according to claim 1 of the formula I wherein R ₂ is straight-chain C ₂ _ ₄ ~ alkylene or a group of formula -CH (CH ₃₎ -CH ₃ -, -CH ₂ -CH (CH ₃₎ - or -CH _{2 means} CH-O-CH ₂ CH ₂ -. 809822/0641 Case 150-3981 14. Azo compounds according to claim 13, wherein R_ C__. Alkylene, preferably 1,2-ethylene. 15. Azo compounds of the formula I according to one of the preceding claims, wherein one of R ^ and Rl is chlorine or bromine, the other is hydrogen. 16, - azo compounds of the formula I, according to one of the preceding Claims in which R. is hydrogen or methyl. 17. Azo compounds of the formula I according to one of the preceding claims, wherein T is hydrogen, methyl, Ethyl, chloromethyl or bromomethyl or optionally up to twice with chlorine, bromine, hydroxy, methyl, Substituted ethyl, methoxy, ethoxy and / or nitro Phenyl, especially hydrogen, methyl, chloromethyl or phenyl, especially hydrogen, Means methyl or phenyl. 18. Azo compounds of the formula I according to one of the preceding claims, wherein T is hydrogen, methyl, Ethyl, chloro- or bromomethyl or C, -alkoxy- methyl, in particular hydrogen, methyl or Means chloromethyl, especially hydrogen. 19. Azo compounds of the formula I according to one of the preceding claims, wherein U. and U independently denote one another hydrogen or methyl, in particular hydrogen. 809822/0641 Case 150-3981 AA 20. Azo compounds of the formula I according to one of the preceding claims, wherein ü_ is hydrogen, C _1-2 - alkoxy-C, ₂ ~ alkyl or acetoxy-Cj ^ -alkyl, 21. Azo compounds of the formula I according to any one of the preceding claims, wherein X of the formula a or c according to claim 1 corresponds. 22. Process for the preparation of the azo compounds of the formula I according to claim 1, characterized in that the diazonium compound is selected from an amine of the formula II D - NH ₂ (II) with a compound of the formula III H-K- ΝίΓ ■ "■ (III) R "- CO-O-X clutch. 23. Use of the azo compounds of the formula I according to claim 1 as disperse dyes for dyeing or printing of fibers or threads or materials made from them made of fully or semi-synthetic, hydrophobic, high molecular weight organic matter. 24. Process for dyeing or printing fibers or threads or materials made therefrom fully or semi-synthetic, hydrophobic, high molecular weight organic substances with disperse dyes of the formula I according to claim 1. 809822/0641 Case 150-3981 25. Those with the disperse dyes of the formula I, Article colored according to claim 1. 809822/0641