DE1951409A1 - Phthalocyanine dyes - Google Patents

Description

1951 409 COLOR FACTORY BAYERAG

LEVERXUSEN-Beyeswerk, fc * ^ * OKl. I-3UC * Patent department

M / ¥ k

Phthalocyanine dyes

The invention relates to new water-soluble phthalocyanine dyes, those in the form of their free acids of the formula

(SO «li-alkylene-IT-OO-X-arylen-N-Z)

and their mixtures as well as procedures for their Manufacture and its use.

Herein mean the radical of a Pc phthalocyanines, R ₁ and Rp V / on Hydrogen or identical or different alkyl radicals, the ring-closed and / or can be substituted or optionally substituted cycloalkyl, aralkyl or aryl radicals _f, R ,, R. and R ^ hydrogen or identical or different alkyl radicals with 1-3 carbon atoms, which are optionally substituted by hydroxyl groups, "alkylene" is an alkylene chain with 2-6 carbon atoms, X is a direct bond or a

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—N group, where Rg is hydrogen or an optionally alkyl radical substituted by a hydroxyl group with 1-3 Represents carbon atoms, "arylene" means an optionally by lower alkyl groups, lower alkoxy groups, halogen atoms, Sulfo groups carboxy groups carbonamido groups and / or Carbon ester groups with 1 - 4 carbon atoms in the alcohol radical substituted arylene radical and Z is a reactive group; a and c stand for an integer from 1 to 3 and b for an integer from 0 to 2, whereby the sum of a, b and c is not greater than is 4. .

In the dyes of the formula (I), any sulfonic acid or Sulfonamide group bonded to another benzene ring of the phthalocyanine in the 3- or 4-position. The phthalocyanine residue Pc can be metal-free, but is preferably metal-containing. The metals cobalt, nickel and copper come into play Consideration. .

Examples of substituted or unsubstituted hydrocarbon radicals ^ R ^ and Rg are: low molecular weight alkyl radicals such as methyl, ethyl, propyl, butyl and amyl, substituted low molecular weight alkyl radicals, for example hydroxyalkyl radicals such as β-hydroxyethyl, β-hydroxypropyl, β. y-Dihyd-roxypropyl and pentahydroxyhexyl, low molecular weight carboxyalkyl, such as ß-carboxyethyl, and low molecular weight SuIfo- 'are alkyl radicals, such as .beta.-sulfoethyl, cycloalkyl radicals such as cyclohexyl, aralkyl groups such as benzyl, aryl groups such as chlorophenyl, methoxyphenyl, SuIfophenyl and carboxyphenyl. - '

Examples of the groups denoted by R ^ jR ^ and R ^ are lower alkyl radicals, such as methyl, ethyl and propyl radicals, or lower hydroxyalkyl radicals, w, ie ß-hydroxyethyl and K-hydroxypropyl.

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Suitable alkylene chains are, for example: CH _x CH,

CH-CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH-CH ₂ -CH ₂ -, -CH ₂ -

_{3 3}

-CH-CH ₀ -CH ₀ -CH ₀ -CH ₀ -, -CH ₀ -CH-CH-CH ₀ -CH ₀ - and

1 C.. ei C. £. tL yy c. c ~

-CH ₂ -CH ₂ -CH ₂ -Ch ₂ -CH ₂ -CH ₂ -,

-xCH-t

Examples of Rg are: hydrogen, methyl, Ethyl, ß-hydroxyethyl, propyl and iso-propyl.

Suitable, optionally by lower alkyl groups, lower alkoxy groups, halogen atoms, sulfo groups, carboxy groups, Carbonamido and / or carbon ester groups substituted arylene radicals are, for example: 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1.4-naphthylene, 1.5-naphthylene, 4-methyl-1.3-phenylene, 2-methyl-1,4-phenylene, 2-methyl-5-chloro-1,4-phenylene, 4-methoxy-1,3-phenylene, 3-methoxy-1,4-phenylene, 4-chloro-1,3-phenylene, 2-chloro-1,4-phenylene, 5-carbonamido-i.3-phenylene, 3-carboxy-methyl-1.4-phenylene, 5-CaTbOXy-ISO-PrOPyI-T ^ - phenylene, 2-chloro-5-carboxy-n-butyl-1,3-phenylene, 4-sulfo-1,3-phenylene, 3-sulfo-T.4-phenylene, 5-sulfo-1.4-napthtylene, 4-sulfo-1,5-naphthylene, 4-carboxy-1,3-phenylene and 3-carboxy-1,4-phenylene.

Reactive groups of the radical Z are understood to mean those which have one or more reactive groups or substituents which can be split off, which when the dyes are applied on cellulose materials in the presence of acid-binding agents and optionally under the action of heat with the

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Hydroxyl groups of the cellulose or during application Super polyamide fibers, such as wool, with the NH groups of these Fibers are able to react with the formation of covalent bonds. Such fiber-reactive groups are off known in large numbers in the literature. -. ,

Reactive groups which are suitable according to the invention and which contain at least one removable substituent bonded to a heterocyclic or an aliphatic radical are, inter alia. those which contain at least one reactive substituent attached to a 5- or 6-membered heterocyclic ring, such as a monazine, diazine, triazine, e.g., pyridine, pyrimidine, pyridazine, pyrazine, thiazine -, oxazine or asymmetrical or symmetrical triazine ring, or on such a ring system which has one or more fused aromatic rings, such as a quinoline, phthalazine, ginnoline, quinazoline, quinoxaline, acridine, phenazine and phenanthridine Ring system; the 3- or 6-membered heterocyclic rings which have at least one reactive substituent are therefore preferably those which contain one or more nitrogen atoms and can contain 5- or preferably 6-membered carbocyclic rings fused on Heterocyclic are, for example, halogen (Cl, Br or F), ammonium, including hydrazinium, sulfonium, sulfonyl, AzIdO- (N,), rhodanido, thio, thiols A 12 577 - 4 -

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ether, oxyether, sulfinic acid, and sulfonic acid. Examples include mono- or dibalogen-sym.-triazinyl radicals, e.g. B. 2,4-dichlorotriazinyl-6-, 2-amino-4-cbl'ortriazinyl-6-, 2-alkylamino-4-cblortriazinyl-6-, such as 2-metbylamino-4-chlorotriazinyl-6-, 2-ethylamino - or 2-propylamino - ^ - cblortriazinyl-6-, 2-ß-0xätbylamino-4-cblortriazinyl-6-, 2-di-ß-oxätbylamino-4-cblortriazinyl-6- and the corresponding sulfuric acid balloesters, 2-dietbylamino-4 -chlorotriazinyl-6-, 2-morpholino- or 2-piperidino-4-cblortriazinyl-6-, 2-cyclohexylamino-4-cblortriazinyl-6-, 2-arylamino and subst * arylamino - ^ - chlorotriazinyl-δ-, such as 2-pbenylamino- ^/ ^ -cblortriazinyl-6-, 2- (o-, m- or p-carboxy- or sulfophenyl) -amino- ^ '- cblortriazinyl-6-, 2-alkoxy-4- chlorotriazinyl-6-, such as 2-metboxy- or -ethoxy-4-cblortriazinyl-6-, 2- (pbenylsulfonylmetboxy) - ^z l · -cblortriazinyl-6-, 2-aryloxy- and subst. Aryloxy-4- cblortriazinyl-6-, such as 2-phenoxy-1-4 -cblortriazinyl-6-, 2- (p-sulfopbenyl) -oxy-4-chlorotriazinyl-6-, 2- (o-, m- or p-methyl - or methoxyphenyl) -oxy-4-chlorotriazinyl-6-, 2-alkylmercapto- or 2-arylmercapto- or 2- (substituted aryl) -mercapto-4-cblortriazinyl-6-, such as 2- (ß-hydroxyethyl) - niercapto-4-cblortriazinyl-6-, 2-phenylmercapto-4-cblortriazinyl-6-, 2- (4'-metbylpbenyl) -mercapto-4-cblortriazinyl-6- _t 2- (2 ·, 4 · - dinitro) - pbenylmercapto- ^/ i-cblortriazinyl-6-, 2-methyl-4-chlorotriazinyl-6-, 2-pbenyl-4-chlorotriazinyl-6-, mono-,

Le A 12 577 - 5 -

1 0 9 8 1 8 / 2Q32

Di- or trihalopyrimidinyl radicals, such as 2,4-dicblorpyrimidinyl-6-, 2,4,5-tricblorpyriinidinyl-6-, 2,4-dichloro-5-nitro- or ^ -methyl- or -5-carboxyinetbyl- or -5 -carboxy- or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-mono-, -di- or -tricblomethyl- or - ^ - carboalkoxy-pyrimidinyl-e-, 2,6- Dichloropyrimidine- ^z ^ - carbonyl- _t 2,4-dicblorpyrimidine-5-carbonyl-, 2-chloro-4-methylpyriraidin-5-carbonyl-, 2-methyl-4-chloropyrimidine-5-carbonyl-, 2-methyltbio-4 -fluoropyrimidine-5-carbonyl-, e-methyl ^ j ^ -dicblorpyrimidin ^ -carbonyl-, 2,4,6-trichloropyriraidin-5-carbonyl-, 2,4 * dichloropyrimidine-5-sulfonyl-, ^ -Cblorquinoxaline-J -earbonyl-, 2- or 3-monocblorquinoxaline-6-carbonyl-, 2- or 3-monochloroquinoxaline-6-sulfonyl-, 2 _# 3-dicblorquinoxaline-6-carbonyl-, 2,3-dichlorocbinoxaline-6-sulfonyl-, 1, ^ - Dicblorphtbalazin-e-sulfonyl- or -6-carbonyl-, ^, ^ - Dicblorcbinazolin -? - or -6-sulfonyl- or -carbonyl-, 2- or 3- or 4- (4 ¹ , 5 '-DiCbIOrpyridazon-6'-yl-1') - pbenylsulfonyl- or -carbonyl-, ß- (4 ', 5'-dichloropyridazon-e'-yl-i 4-cblortriazinyl-6) -carbamyl-, N-methyl-N- (2-dimethylamino-4-chlorotriazinyl-6) -carbamyl-, N-metbyl- or N-ethyl-N- (2,4-dicblortriazinyl-6 ) -aminoacetyl-, N-methyl-N-C2,3-dichlorobinoxaline-6-sulfonyl) -aniinoacetyl-, N-methyl-N- (2,3-dichloroquinoxaline-6-carbonyl) -aminoacetyl-, as well as the corresponding bromine - and fluoro derivatives of the above

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mentioned chlorine-substituted heterocyclic radicals, among these for example a-iuoro - ^ - pyrimidinyl-, 2,6-difluoro-4-pyrimidinyl-, 2,6-difluoro-5-chloro-4-pyrimidinyl-, 2-fluoro-5 , ^{6-dichloro-£} »-pyriinidinyl-, 2,6-difluoro-5-methyl-4-pyrimidinyl, 2,5-difluoro-6-methyl-4 ~ pyrimidinyl, 2-fluoro-5-methyl-6 ~ cblor-4-pyrimidinyl, 2-fluoro-5-nitro-6-cblQr-4-pyrimidinyl, 5-BroIn-2-fluoro-4-pyrimidinyl ₎ 2-fluoro-ί? -cyan-4'-pyriInidinyl _! , 2-fluoro-5-methyl - ^ - pyriinidinyl, 2,5,6-trifluoro-4-pyrimidinyl, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl, 2,6-bifluoro-5-bromo -4-pyrimidinyl, 2-fluoro-5-bromo-6-raethyl-4-pyrimidinyl, 2-fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5-chloromethyl-4-pyrimidinyl , 2, e-Diiluor - ^ - nitro - ^ - pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-6-methyl- ^/ ipyrimidinyl, 2-fluoro ~ 5-chloro- 4-pyrimidinyl, 2-fluoro-6-chloro-4-pyrimidinyl, 6-trifluoromethyl-5-chloro-2-fluoro ~ 4-pyrimidinyl, 6-trifluoromethyl-2-fluoro-4-pyrimidinyl, 2-fluoro ~ 5- nitro-4-pyrimidinyl, 2-fluoro-5-trifluorιaethyl-4-pyrimidinyl, 2-fluoro-5-phenyl- or ^ -methylsulfonyl- ^ - pyrimidinyl, 2-fluoro-5-carbonamido-4-pyrimidinyl, 2-fluoro -5-carbomethoxy-.4-pyrimidinyl, 2-fluoro-5-bromo-6-trifluoromethoxy-4-pyrimidinyl, 2-fluoro-6-carbonamido-4-pyrimidinyl, 2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimidinyl _> 2-fluoro-6-cyano-4-pyrimidinyl, 2,6-difluoro-5-diethylsulfonyl-4-pyrimidinyl, 2-fluoro-5-sulfonamido-4-pyrimidinyl, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl, 2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl;

- 7 Le A 12 577

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■■ * ■ - ' ^: .- ■■■■■ :.'

triazine radicals containing sulfonyl groups, such as 2,4-bis- (pbenyl- ■. -sulfonyl.) -triazinyl-6-, 2- (3'-carboxyphenyl) -sulfonyl-4-chlorotriazinyl-6-, 2- (3 ^f -sulfophenyl ) -sulfonyl-4-chlorotriazinyl-6-, 2,4-bis- (3 * -carboxyphenylsulfonyl-1 ') - triazinyl-6-; pyrimidine rings containing sulfonyl green, such as 2-carboxymethylsulfonyl-pyrimidinyl-49, 2-methylsulfonyl-G-raetbyl-pyrimidinyl- ^ -, 2-methylsulfonyl-6-ethyl-pyrimidinyl-4-, 2-pbenylsulfonyl-5-methyl-cbylor ^ , 2,6-bis-methylsulfony-1-pyrimidinyl-4, 2,6-bis-methylsulfonyl-5-chloropyrimidinyl-4, 2,4-bis-P>'metbylsulfonyl-pyrimidine-5-sulfonyl, 2- Me tbyl sulfonyl -

pyrimidinyl-4, 2-Phenylsulfonyl-pyrimidinyl- ^, 2-Tricblormetbylsulfonyl-e-metbyl-pyrimidinyl- ^ j 2-Metbylsulfonyl-5-cblor-ö-metbyl-pyrimidinyl- ^, 2-Metbylsulfonyl - ^ - brora-öniet pyrimidinyl- ^, 2-methylsulfonyl -5-cblor-6 ^ ätbyl pyrimidinyl-4, 2-methylsulfonyl-5-chloro-6-chloΓraethyl-_ pyrimidinyl-4, 2-methylsulfonyl-4-cbloΓ-6-metbyl ; pyΓiraidin-5-sulfonyl, 2-metbylsulfonyl-5-nitΓo-6-metbyl-pyΓiInidinyl-4, aj ^ .e-Tris-methylsulfonyl-pyrimidinyl - ^, '. 2-Metbylsulfonyl-5,6-dimethyl-pyriniid- ynyl-4, 2-Ätbylsulfonyl-5-chloΓ-6-methylpyrimidinyl- ^, 2-methylsulfonyl-6-cblor-pyrimidinyl- ^£ 4-, 2,6-bis-raetbylsulfonyl-5-chloropyrimidinyl-4 _s 2- Methylsulfonyl-6-carboxy-pyrimidinyl- ^, 2-methylsulfonyl-5-sulfopyriraidinyl-4, 2-Metbylsulfonyl-6-carbomethoxy-pyriπlidinyl-4, ^ -Metbylsulfonyl - ^ - carboxy-pyrimidinyl- ^, 2-Metbylsulfonyl-4, ^ -Metbylsulfonyl- ^ - . cyano-e-inethoxy-pyrimidinyl- ^, 2-methyl-sulfonyl-5-chloropyrmidinyl-4, 2-sulfoethylsulfonyl-6-methyl-pyΓimidinyl-4,

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2-methylsulfonyl-5-bromo-pyrimidinyl-4, 2-phenylsulfonyl-5-chloro-pyrimidinyl-4, 2-carboxymetbylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4, 2-methylsulfonyl-6-cnloropyrimidine-4- and -5-carbonyl-, 2,6-bis- (metbylsulfonyl) -pyrimidine-4-
or -5-carbonyl-, 2-ethylsulfonyl-6-chloropyimidine-5-carbonyl-, 2,4-bis- (methylsulfonyl) -pyrimidine-5-sulfonyl-, 2-metbylsulfonyl- ^ - chloro-e-metbylpyrimidine-5 -sulfonyl- or -carbonyl-; triazine rings containing ammonium groups, such as 2-trimethylammonium-4-phenylamino- or -4-Co-, m- or p-sulfo-, phenyl) -aminotriazinyl-6-, 2- (1,1-dimethylhydrazinium) -4-phenylamino - or -4- (o-, m- or p-sulfοphenyl) -aminotriazinyl -6-, 2- (2-1sopropylidene-1,1-dimethyl) -bydrazinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6-, 2-N-AiEinopyrrolidinium- or 2-N-aminopiperidinium-4-pbenylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6- , also 4-Pheny! amino or 4- (SuIfοphenylamino) -triazinyl-6 radicals, which in the 2-position via a nitrogen bond, the 1,4-bis-aza-bicyclo- / 2 ~, 2,27-octane or the
Contain 1,2-bis-aza-bicyclo- / Ü, 5 »27-octane quaternary bonded, ^ -Fyridinium ^ -pbenylamino- or -4- (o-, m- or p-sulfophenyl) -amino-triazinyl-6 -as well as corresponding 2-0niumtriazinyl-6 radicals, which are in the 4-position by alkylamino, such as metbylamino, ethylamino or ß-hydroxyethylamino, or alkoxy, such as metboxy or alkoxy, or aroxy, such as phenoxy or sulfophenoxy groups are substituted; 2-Cblorbenzthiazol-5- or -6-carbonyl- or -5- or -6-sulfonyl-, 2-arylsulfonyl- or -alkylsulfonylbenzthiazol-5- or -6-carbonyl- or -5- or -6-

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sulfonyl, such as 2-methysulfonyl or 2-ethylsulfonyl-benzothiazole-5- or -6-sulfonyl- or -carbonyl-, 2-phenylsulfonylbenztbiazol-5- or -6-sulfonyl or -carbonyl- and the corresponding sulfo groups in the fused-on benzene ring containing 2-sulfonylbenzobiazole-5- or -6-carbonyl- or -sulfonyl derivatives, 2-Cblorbenzoxazol-5- or -6-carbonyl- or -sulfonyl-, 2-chlorobenzimidazole-5- or -6-carbonyl- or -sulfonyl-, 2-chloro-1-methylbenzimidazole-5- or -6-carbonyl- or -sulfonyl-, 2-chloro-4-metbylthiazole- (1,3) -5-carbonyl- or -4- or -5-sulfonyl-, N-oxide of 4-chloro- or 4-nitroquinoline-5-jk carbonyl. ,

Reactive groups of the aliphatic series should also be mentioned, such as acryloyl, mono-, di- or trichloroacryloyl, such as -CO-CH = CH-Cl, -CO-CCl = CH ₂ , -CO-CCl = CH-CH ₃ , also -CO-CCl = CH-COOH, -CO-CH = CCl-COOH, ß-chloropropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, 3-phenylsulfonylpropionyl, ß-sulfato-ethylaminosulfonyl, vinylsulfonyl ß-chloroethylsulfonyl-, ß-sulfatoethylsulfonyl-, ß-methylsulfonyl-ethylsulfonyl-, ß-phenylsulfonyl-ethylsulfonyl-, 2-fluoro-2-chloro-3, J-difluorocyclobutane-i-carbonyl-, 2,2,3,3 -Tetrafluorocyclobutanecarbonyl-1- or -sulfonyl-1-, ß- (2,2,3,3-tetrafluorocyclobutyl-1) -acryloyl-, OC- or ß-bromoacryloyl-, QL- or ß-alkyl- or -arylsulfonyl- acryloyl groups, such as Gt- or ß-methylsulfonylacryloyl.

- 10 -

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A preferred group within those of the invention Dyes are those of the general formula

Pe— ( ₂ | _t

(SOpNH-alkylen-NH-CO-X-arylen-lTH-Z)

and their mixtures

where Pc denotes the radical of a phthalocyanine, which can be metal-free or also metal-containing. Such metals are cobalt, nickel and copper. Each sulfonic acid or sulfonamide group is bonded to a different benzene ring of the phthalocyanine in the 3- or 4-position. In the formula, R ₁ , Rp, "alkylene", "arylene", Z, a, b and c have the meanings given above.

Particularly preferred among the new dyes are those in which Z is a halotriazine radical or halopyrimidine radical represents, where fluorine, chlorine and / or bromine are possible as halogen.

An excellent range among the new phthalocyanine dyes are those of the general formula

(C! A XJ λ
OU ^ Xl J

• Pc— (SO ₀ TA), 'Cl F (III)

'c

and their mixtures F

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^: ' ^: ■:' ■ Λ; ■■■ where the symbols Pc, R ₁ , RgV "alkylene"} "arylene", a, b and c have the meaning given above. Here, Pc can be metal-free or else contain metal, with cobalt, nickel and copper being considered as metals. Each sulfonic acid or sulfonamide group is bonded to a different benzene ring of the phthalocyanine in the 3- or 4-position.

The new dyes of the formula (I) are produced by condensation suitable starting components shown. The most advantageous process is such that in dyes the formula

Pe— (so ₂ 3src | i) _b

(SOpN-alkylene-N-OO-X-arylen-N-HV E _3. R ₄ R ₅

wherein Pc, R ₁ , R ₂ , R ₃ , R ^, R ₅ , "alkylene", "arylene", 'a, b and c have the meaning given, the terminal group -WH in a manner known per se

by reacting with suitable, at least bifunctional ^; nellen reactive components YZ into a group -EZ

converts, in which Z has the meaning given above and Y is a removable substituent. The conversion of the amino group -N (R ₅ ) H into the grouping -N (R ₅ ) Z is generally an acylation

Le A 12 577 - 12 - ■

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Lind can be used in aqueous, aqueous organic or organic, ■ prefers weak, acidic to weakly alkaline medium Temperatures of, for example, 0-80 ° C can be carried out.

Reactive components YZ suitable for this purpose are, for example, those on which the aforementioned reactive groups are based, ie generally the halides, in particular the chlorides and fluorides of the acyl components Z mentioned. triazines, such as cyanuric chloride and cyanuric bromide, dihalo-monoamino- and mono-substituted-amino-sym.-triazines, such as 2,6-dichloro-4-aminotriazine, 2,6 ~ Mchlor-4-methylaminotriazines, 2,6 -Dichlor-4-ethylaminotriazine, 2, o-dichloro ^ -oxäthylaminotriazine, 2,6- dichloro-4-phenylaminotriazine, 2,6-dichloro-4- (o-, m- or psulfophenyl) -aminotriazine, 2,6- Dichloro-4- (2 ', 3'-, -2', 4'- »-3 ^f , 4'- or -3 ·, ^ '- disulfophenylj-aminotriazine, dihaloalkoxy- and -aryloxy-sym.triazines, such as 2,6-dichloro-4-niethoxytriazine, 2,6-dichloro-4-ethoxytriazine, 2,6-dichloro-4-phenoxytriazine, 2/6-dichloro-4- (o-, m- or p-sulfophenyl ) -oxytriazine, dihalo-alkylmercapto- and -arylmercapto-sym.triazine, such as 2,6-dichloro-4-ethylInercapto-triazine, 2,6-dichloro-4-phenylmercaptotriazine, 2,6-dichloro-4 ~ (p-niethylphenyl) mercaptotriazine; Tetrahalopyrimidines, such as tetrachloro-, tetrabromo- or tetrafluoropyrimidines, 2,4,6-trihalopyrimidines, such as 2,4,6-trichloro-, tribromo- or trifluoropyrimidines, dihalopyrimidines, such as 2,4-dichloro-, -dibromine - or -difluoropyrimidine; 2,4,6, -Trichlor-5-nitro- or -5-methyl- or -5-carbomethoxy- or -S-carboethoxy- or -5-carboxymethyl- or -5-mono-, -di- or -trichloromethyl - or -5-carboxy- or -5-sulfo- or -5-cyano- or -5-vinyl-pyrimidine, 2,4-difluoro-6-methylpyrimidine, 2,6-difluoro-4-methyl-5-chloropyrimidine , 2,4-difluoro-5-ethylsulfonyl-pyrimidine, 2,6-difluoro-4-

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chlorpyrimiain, 2,4,6-trifluoro-5-chloropyrimidine, 2,6-difluoro * 4-met] iyl-5-i) rompyrimidine, 2,4-MfIuor-5, j6-dichloro or -dittromopyrimidine, 4,6-difluoro-2,5-dic] ilor- or -dibromopyrimidine, 2,6-difluoro-4-bromopyrimidine, 2,4,6-trifluoro-5-chloromethylpyriinidine, 2,4,6-trifluoro-5-nitropyrimidine, 2 ,,. 4,6 ~ trifluoro-5-cyanopyrimidine, 2,4,6-trifluoro-pyrimidine-5- carboxylic acid alkyl esters or ^ -carboxamides, 2,6-difluoro-5-methyl-4-chloropyrimidine, 2,6-difluoro-5-clilorpyrimidine, 2,4,6

2,4-difluoro-5-nitro-6-chloropyrimidine, 2,4 ~ difluoro-5-cyanopyrimidine, 2,4-difluoro-5-methylpyrimidine, 6-trifluoromethyl-5-chloro-2,4-difluoropyrimidine, e-phenyl ^ j ^ -difluoropyrimidine,

Wk, 6-trifluoromethyl-2,4-difluoropyriraidine, 5-trifluoromethyl-2,4,6-

trifluoropyrimidine, 2,4-difluoro-5-nitro-pyrimidine, 2,4-difluoro-5-trifluoromethyl-pyrimidine, 2,4 ~ Difluoro-5-methyl sulfonyl pyrimidine, 2,4-difluoro-5-pbenyl-pyrimidine, 2,4-difluoro-5-carbonamido-pyrimidine, 2,4-difluoro-5-carbomethboxy-pyriInidine, 2,4-Difluoro-6-trifluoromethyl-pyrimidine, 2,4-Difluoro-5-bromo-6-trifluorobyl-pyrimidine, 2,4-Difluoro-6-carbonamido-pyrimidine, 2,4-Dii * luor-6-carbometboxy-pyrimidine, 2,4-Difluoro-6-phenylpyrimidine, 2,4-difluoro-6-cyano-pyrimidine, 2,4,6-trifluoro-5-methylsulfonyl-pyrimidine, 2,4-difluoro-5-sulfonamido-pyrimidine,

f 2,4-Difl ^ or-5-cblor-6-carbomethoxy-pyrimidine, 5-Trii "luormethyl-

2,4-difluoropyrimidine, ^^ - dicblorpyrimidine - ^ - carboxylic acid chloride, ^^, e-Trichloropyrimidine - ^ - carboxylic acid chloride, ^ - pyrimidine-5-carboxylic acid chloride, ^ -Chlor ^ carboxylic acid chloride, 2,6-dicblorpyrimidine-4-carboxylic acid chloride; Pyrimidine reactive components with removable sulfonyl groups,

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195H09

such as α-carboxymethylsulfonyl - ^ - chloropyrimidine, 2-methylsulfonyl-4-chloro-6-methylpyrimidine, 2,4-bis-methylsulfonyl-6-methylpyrimidine, 2,4-bis-pbenylsulfonyl-5-cbloro-6-methylpyrimidine, 2 , 4,6-tris-methylsulfonylpyrimidine, 2,6-bis-methylsulfonyl-4,5-dichloropyrimidine, 2,4-bis-methylsulfonylpyrimidine-5- sulfonic acid chloride, 2,4-ble-trichloromethylsulfonyl-6-methyl pyrimidine, 2, 4-bis-methylsulphonyl-5-chloro-6-methylpyrimidine, 2,4-bis-methylsulphonyl-5-bromo-! 6-methylpytimidine, 2-methylsulphonyl-4, ^ - dichloro-δ-methylpyrimidine, 2-methylsulphonyl-4 , 5-dichloro-6-chloromethylpyrimidine, 2-methylsulfonyl-4-ChIoX-O-methylpyrimidine-5-sulfonic acid chloride, 2-methylsulfonyl-4-chloro - ^ - nitro-e-methylpyrimide in, 2,4,5,6- Tetra-methylsulfonylpyrimidine, 2-methylsulfonyl-4-chloro-5 | 6-dimetbylpyrimidine, 2-ethylsulfonyl-4, ^ - dichloro-ö-metbylpyrimidine, 2-methylsulfonyl-4,6-dichloropyrimidine, 2,4,6-TΓis- methylsulfonyl-5-chloropyrimidine, 2-methylsulfonyl ^ -cbloro-e-carboxypyrimidine, 2-methylsulfonyl-4-chloropyrimidine-5-sulfonic acid, 2 -Methyl sulf onyl ^ -chlor-e-carbomethoxypyrimidine, 2-methylsulfonyl-4-chloropyrimidine-5-carboxylic acid, 2-methyl sulf onyl ^ -cblor ^ -eyan-e-methoxypyrimidine, 2-methylsulfonyl-4,5-dichloropyrimidine , 4,6-bis-methylsulfonylpyrimidine, 4-methylsulfonyl-6-chloropyrimidine, 2-sulfoethylsulfonyl-4-chloro-6-methylpyrimidine, 2-methylsulfonyl-4-chloro-5-bromopyrimidine, 2-methyl sulfonyl ^ -eblor ^ -bromo-e-methyl pyrimidine, 2,4-bismethylsulfonyl-5-chloropyrimidine, 2-phenylsulfonyl-4,5-dichloropyrimidine, 2-phenylsulfonyl-4,5-dichloro-6-methylpyrimidine, 2-carboxymethylsulfonyl-4,5 -dichloro-6-methylpyrimidine, 2- (2'-

- 15 Le A 12 577

1098 18/203 ^

or 3>'- or 4'-carboxyphenylsulfonyl) -4, ^ - dicbloro-e-methylpyrimidine, 2,4-bis- (2'- or 3'- or 4 ¹ -carboxyphenylsulfonyl) - ^ -cbloro-G-methylpyrimidine , 2-methylsulfonyl-ö-chloropyrimidine - ^ - or - ^ - carboxylic acid chloride, 2 ~ Ätbylsulfonyl-6-chlorpyrimidin-4- or -5-carboxylic acid chloride, 2,6-bis- (methyl sulfonyl) -pyri midi nr- 4-carboxylic acid chloride, 2-methylsulfonyl-6-methyl-4-chloro - or - ^ - bromopyrimidine - ^ - carbonyl chloride or bromide, 2,6-bis (methylsulfonyl) -4-cblorpyriraidin - ^ - carboxylic acid chloride; further reactive components of the heterocyclic series with reactive sulfonyl substituents are for example

fe 3 »6-bis-phenylsulfonylpyridazine, 3-methylsulfonyl-6-chloropyridazine, 396-Bis-tricblormethylsulfonylpyridazin, 3 _t 6-bis-methylsulfonyl-4-metbylpyridazin, 2,5,6-Trismethylsulfonylpyrazin, 2,4-bis-methylsulfonyl -i, 3j5-triazine, 2,4-bis-methylsulfonyl-6- (3'-sulfophenylamino) -1,3,5-triazine, 2,4-bis-methylsulfonyl-6-N-methylanilino-1,3 , 5-triazine, 2,4-bis-methylsulfonyl-6-phenoxy-1,3,5-triazine, 2., 4-bismethylsulfonyl-G-tricbloroethoxy-i, 3,5-triazine, 2, A, 6- Trispbenylsulfonyl-1 ^^ - triazine, 2,4-bis-metbylsulfonylquinazoline, 2,4-bis-tricblormetbylsulfonylquinoline, 2,4-bis-carboxymethyl-

W sulfonylquinoline, 2,6-bis (methylsulfonyl) pyridine-4-carboxylic acid chloride and 1- (4 '- (chlorocarbonylphenyl or 2'-chlorocarbonylethyl) -4,5-bis-methylsulfonyl-pyridazon- (6); others Heterocyclic reactive components with mobile halogen include 2- or 3-monocblorquinoxaline - 6-carbo, acid chloride or -6-sulfonic acid chloride, 2- or ■ J-monobromoquinoxaline-6-carboxylic acid.

Ie A 12 577 .. ₁₆ _ /

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bromide or -6-sulfonic acid bromide, 2,35-dichloroquinoxaline-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2,3-dibromobinoxaline-6-carboxylic acid bromide or -6-sulfonic acid bromide, 1,4-dichlorophthalazine-e-carboxylic acid chloride or -6- sulfonic acid chloride and the corresponding bromine compounds, 2,4-dichloroquinazoline-6- or -7-carboxylic acid chloride or sulfonic acid chloride and the corresponding bromine compounds, 2- or 3- or 4- (4 ¹ , S'-dicblorpyridazon-6'-yl -i ') - pbenylsulfonic acid chloride or -carboxylic acid chloride and the corresponding bromine compounds, ß- (4', ^ '- dichloropyridazon-S'-yl-i') - ethyl carboxylic acid chloride, 2-chloroquinoxaline-3-carboxylic acid chloride and the corresponding bromine compound, N- Methyl-N- (2,4-dichlorotriazinyl-6) -carbamic acid chloride, N-methyl-N- (2-ChIOr - ^ - metbylamino-triazinyl-öi-carbamic acid chloride, N-methyl-N- (2-chloro-4- dimetbylamino-triazinyl-6) -carbamic acid chloride, N-methyl- or N-ethyl-N- (2,4-dicblortriazinyl-6) -aminoacetyl chloride, N-methyl-, N-ethyl- or N-hydroxyeth yl-N - <(2,3-dlchloroquinoxaline-6-sulfonyl- or -6-carbonyl) -aminoacetyl chloride and the corresponding bromine derivatives, also 2-chlorobenzbiazole-5- or -6-carboxylic acid chloride or -5- or -6-sulfonic acid chloride and the corresponding bromine compounds, 2-arylsulfonyl- or 2-alkylsulfonyl-benztbiazole-5- or -e-carboxylic acid chloride or -5- or -6-sulfonic acid chloride, such as 2-methylsulfonyl- or 2-ethylsulfonyl- or 2-phenylsulfonyl-benzthiazole 5- or -e-sulfonic acid chloride or -5- or -ö-carboxylic acid chloride and the corresponding 2-

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10 9 8 18/2032

/ Γ

Sulphonylbenzthiazole derivatives, 3,5-bis-methylsulphonyl-isotbiazo.l-4-carboxylic acid chloride, 2-chlorobenzene-oxazoi-5- or -6-carboxylic acid chloride or sulfonic acid chloride and the like corresponding bromine derivatives, 2-0310 ^ 6 ^ 1111133201-5- or -S-carboxylic acid chloride or sulfonic acid chloride and the corresponding bromine derivatives, 2-chloro-1-methyl-benzimidazole-5- or -ö-carboxylic acid chloride or -sulphonic acid chloride and the corresponding bromine derivatives, 2-chloro-4-methylthiazole (1,3) -5-carboxylic acid chloride or -4- or -5-sulfonic acid chloride, ^ -chlorobiazole- ^ - or -5-sulfonic acid; chloride and the corresponding bromine derivatives.

From the series of aliphatic reactive components, for example, the following should be mentioned: acrylic acid chloride, mono-, di- or trichloroacrylic acid chloride, 3-chloropropionic acid chloride, 3-phenylsulfonyl-propionic acid chloride, 3-methylsulfonyl-propionic acid chloride, 5-ethylsulfonyl-propionic acid chloride, 3-chloropropionic acid chloride, 3-chloropropionic acid chloride , • 2-chloroacetyl chloride, 2,2,3,3-tetrafluorocyclobutane-i-carboxylic acid chloride, β- (2,2,3,3-tetrafluorocyclobutyl-i) -acrylic acid chloride, β- (2,3,3-trifluoro-2 -cblor-cyclobutane-1) -carboxylic acid- * chloride, ß-methylsulfonyl-acrylic acid chloride, Ot-methylsulfonylacrylic acid chloride and oc-bromoacrylic acid chloride and ß-bromoacrylic acid chloride.

The conversion leads to dyes that have more than one reactive group in the radical Z or elsewhere on the dye molecule have, these can partly be replaced by other residues, both

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1098 18/2032

for example, amino radicals are replaced, which in turn are reactive Groups, 'e.g. B. in the form of esterified oxyalkyl groups can. Basically the presence of two or several different reactive groups in the dye possible.

The "phthalocyanine inversions used in the process according to the invention of the formula (IY) can be prepared in that a phthalocyaninesulfonic acid chloride is preferred in the form of an aqueous suspension - which of the formula

(SO ₂ Cl) _n
Pc (V)

corresponds to, ■. ■

where Pc has the meaning given above, m the numbers 0, 1. or 2 and η the numbers 2, 3 or 4 denote, where the sum of m and η is not greater than 4,

either with a compound of the formula

H-IT-alkylene-NG OXa rylene-NH, _yi s

wherein R ₃ , R. and R, - and "alkylene", "arylene" and X have the meaning given above ■ and optionally with a compound of the formula

H-W

R ₂

Le A 12 577 - 19 -

10 981 8V 2t) '3Ü

where R ^ and Rp have the meaning given above, or - with a compound of the formula:

H-N-alkylene-E-CO-X-arylene-NCU -,. Ii ^ (VIII)

R R

wherein R ,, R ₄ , "alkylene", "arylene" and X have the meaning given above,

and optionally with a compound of the formula (VII) is condensed and in the latter case the nitro groups contained in the condensation product are reduced to amino groups will. During this condensation, unhydrolyzed and unreacted sulfonic acid chloride groups can be converted into sulfonic acid groups by hydrolysis.

If necessary, one can for the representation of the dyes (IV) also proceed so that Phthalocyaninsulfonsäureehloridsulfonsäuren with monoformylated D.iamines of the formula

HN-alkylene-N-CO-X-arylene-N-CHO ! I _x 1 (IX)

in which R ₂ , R. and R ₁ -, X, "alkylene" and "arylene" have the meaning given above, condensed and the formyl group then saponified.

Phthalocyaninesulfonic acid chloride sulfonic acids of the formula (V) can be obtained by mixing the corresponding phthalocyanine or .Phthalocyaninesulfonic acid with chlorosulfonic acid and optionally an acid halide such as

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195KQ9

Thionyl chloride, phosphorus pentachloride, phosphorus oxychloride or phosphorus trichloride as in the British patents 708,543, 784,834 and 785,629 and in U.S. Patent 2 219 330 described, treated.

According to the invention, uniform phthalocyanine dyes can be used are used, those are those in which the letters a, b and c characterize the numbers 0, 1, 2 and 3 respectively. Furthermore however, mixtures of these dyes can also be used. Such mixtures sometimes show solubility and substantivity have particular advantages. In such Mixtures vary the numbers in the averaged value.

Such mixtures according to the invention are prepared for example from two or more, each of the unitary Endfarbstoffen ¹ formula (i) or, particularly advantageously by using a mixtures of the starting components. The latter often inevitably arises since the phthalocyaninesulfonic acid chloride-sulfonic acids (IV) with regard to the degree of sulfonation and their ratio of sulfonic acid chloride and sulfonic acid groups are often obtained industrially as a mixture.

Suitable diamines of the formula (VI) are, for example, N- (ß-aminoethyl) -N ^l - (2-aminophenyl) urea, !! - (ß-Amtnoäthyl) -N '- (3-aminophenyl) urea, U- (ß-Aminoethyl) -Ii ^l - (4-aminophenyl) -urea, M- (ß-methylaminoethyl) -U-methyl-H '- (4-aminophenyl) -urea, F- (ß-aminoethyl) -N ^t - (3-amino-4-sulfophenyl) -urea, N- (ß-amino-ethyl) -N ^t - (4-amino-3-sulfophenyl) -urea, N-methyl-N - ^ - amlnobenzoyl ^ propylenediamine- 1.3, W-methyl-N- (3-aminobenzoyl) -propylenediamine-1.3, N- (p-aminobenzoyl) -ethylenediamine-1.2, K- (m-aminobenzoyl) -ethylenediamine-1.2 ·, N- (p-methylaminobenzoy 1 ) -ethylenediamine-1.2.

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10-98 T 87 2 0 32

_:: U ■■■■ ■■■ · ■■■■■

Examples of amines of the formula (VIX) are ammonia, methylamine, itliylamine, propylamine, taurine, methyltaurine, aminoacetic acid, Sarcosine, ethanolamine, diethanolamine, morpholine, benzylamine, Aniline, m-sulfanilic acid, p-anisidine, 4-amino-benzoic acid.

Suitable amines of the formula (VIII) are, for example, H- (B-aminoethyl) -N ^I - (2 '-. Nitrophenyl) urea, H- (β-aminoethyl) -N - (3-nitrophenyl) urea> N - (β-Aminoethyl) -N ^f - (4-nitrophenyl) urea, IT- (γ-aminopropyl) -H-methyl-l ^f - (4-nitrophenyl) urea, N- (Y-methylaminopropyl) -Ii ^! - (4-nitrophenyl) urea,]! Ί ~ (ß-methylaminoethyl) -l · I-methyl-H '- (4-nitrophenyl) urea, N- (ß-aminoethyl) -li ^l -methyl-] ! ir ^! - (4-nitrophenyl) urine-; substance, E "- (ß-Amino-a-methyl-ethyl) -E"'- (4-nitrophenyl) urine

Wk substance, N- (ß-amino-ethyl) -N ^l - (4-nitro-2-chlorophenyl) urea, W- (ß-amino-ethyl) -N ^l - (4-nitro-2- methyl.-phenyl) urea, H- (ß-amino-ethyl) -lT ^r - (3-nitro-5-car'boxy-phenyl) -urea, Ή- (ß-amino-ethyl) -Ή · - (4 * -n itro-2-methoxy ^ phenyl) urea, N- (β-amino-ethyl) -II ^l - (3-nitro-5-carbonamido-phenyl) -urea, N- (B-AmInO -EtIIyI) -H ¹ - (3-nitro-5-isopropylcarboxyphe.nyl) -urea, N- (ß-amino-ethyl) -IT ^l - (4-nitro-5-sulfonaphthy1) -urea, W- (ß -Amino-ethy1) -Έ '-äthyl-N' (4-nitrophenyl) urea, H- (ß-amino-ethyI) -N ¹ - (ß-hydroxyethyI) -H - (4-.nitrophenyl) - urea, H- (aJ-Amino-butyl) -H ^l - (4-r-nitrophe.nyl) -urea, H- (iJ-Amtno-hexyl) -H ¹ - (4-nitrophenyl) -urea, H- (m-Hitrobenzoyl) -ethylenediamine-1.2, H- (p-Hitrobenzoyl) -ethylenediamine-1,2, H- (p-Hitrobenzoyl) -propylenediamine-1.3,

ψ ' N- (p-Hitrobenzoyl) -propylenediamine-1.2 *

G-suitable monoformylated diamines of the formula (IX) are, for example: H- (B-Amino-ä thy 1) -H ^f - (4-formylmethylamino-phenyl) urine, H- (ß-amino-ethyl ) -H ^l - (4-formylethylamino-phenyl) -urea, N- (ß-amino-ethyl) -H ^l - ("4-formylhydroxyethylamino-phenyl) -urea, N- (4-formylmethylamino-benzoyl-ethylenediamine -1.2

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195U09

av

The reaction of the phthalocyaninesulfonic acid chloride sulfonic acid with the compound of the formula (VI) and the compound of the formula (VII) or the compound of the formula (VIII) and the compound of the formula (VII) can be carried out in a single reaction stage or in separate stages. In general, the simultaneous conversion (in the event that b should be greater than 0) is advantageous. Here, a compound of the formula (VII) can serve as an acid-binding agent.

The turnover of PhthaloeyaninsulfonsäureChloriden der Formula (V) obtained with amines of the formula (VIII) and optionally amines of the formula (VII) bearing nitro groups Intermediate products can be replaced by alkali sulfides or alkali hydrogen sulfides, such as sodium sulfide or sodium hydrogen sulfide, be converted into the corresponding amino compounds.

The new dyes are extremely valuable products that are suitable for a wide variety of applications. As water-soluble compounds, they are of interest for dyeing hydroxyl-containing and nitrogen-containing textile materials, in particular textile materials made from native and regenerated cellulose, as well as from wool, silk, synthetic polyamide and polyurethane fibers. They are particularly suitable as reactive dyes for dyeing cellulosic materials using the techniques that have recently become known for this purpose. The fastness properties obtained, especially wet fastness properties, are excellent.

For dyeing cellulose, the dyes are preferably used in an aqueous solution which reacts with alkaline agents Substances such as alkali hydroxide or alkali carbonate, or with compounds that change into alkaline substances, such as alkali bicarbonate, 01, C-COONa, are added can. Further auxiliaries can be added to the solution, but they are not mixed with the dyes in an undesired manner

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1Ö9 818/2032

to react, Such additives are, for example, surface-active substances, such as alkyl sulfates, or migration the dye preventing substances or dyeing auxiliaries, such as urea, or indifferent Verdieku ^ such as oil-water emulsions, tragacanth, starch, or alginate Methyl cellulose. ·

The solutions or pastes produced in this way are applied to the material to be colored, for example by padding in a poulard ^: (short liquor) or by printing and then heated to an elevated temperature, preferably from 4-0 to 150 ° C., for some time. The heating can be carried out in the hot flue, in the steamer, on heated rollers or by placing in heated, concentrated salt baths, either on its own or in any order one after the other.

When using a padding or dye liquor without alkali a passage of the dry goods through an alkaline reacting solution, the table salt or Glauber's salt is added, connected. The addition of salt reduces migration of the dye from the fiber.

The material to be colored can also be mixed with one of the aforementioned Pretreat acid-binding agents, then treat with the solution or paste of the dye and finally, as indicated, fix at elevated temperature.

For dyeing from a long liquor one goes into an aqueous solution of the dye (liquor ratio 1: 5 to 1:40) at room temperature and colors 40 to 90 minutes, if necessary under Increase the temperature up to 95 ° C and if necessary ■ with partial addition of salt, e.g. B. sodium sulfate, and

: - 24 -

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109818/203

then alkali, "for example sodium phosphates, sodium carbonate, NaOH or KOH.

The former reaction between dye and laser on. After chemical fixation has taken place, the material to be dyed becomes Rinsed with hot water and then soaped, removing non-fixed residues of the dye. You get excellent real, especially wet and lightfast dyeings »

In the so-called block cold dwell process, you can see one Subsequent heating of the padded fabric saves you from having to leave the fabric for some time, e.g. 2 to 2Q Hours, stored at room temperature. In this method, a stronger alkali than that described above is used Dyeing process from a long liquor used.

For printing on materials containing hydroxyl groups is made of a printing paste. the dye off solution, a ■ thickening agent, like sodium alginate, and one alkaline reactive compounds or compounds that split off alkali when heated, such as sodium carbonate, sodium phosphate, potassium carbonate, Potassium acetate or sodium * and potassium hydrogen carbonate are used and the printed material is spooled and soaped,

Textile materials containing amide groups, such as wool, silk, Synthetic polyamide and polyurethane fibers are generally made using the usual dyeing methods in acidic colored to neutral area. ·

The colorations available with the new dyes' draw generally look good to very good fastness properties, in particular through excellent wet fastness properties.

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1098-1.8 / 203?

195 H.

In the following examples "the degrees mean degrees Celsius and the parts by weight,

Example 1; ■

11.1 parts of the dye are in 150 parts of water formula

(SQ ₃ Na) ^ Pc- (3) -

dissolved, the dye solution is adjusted to P ™ 8.0 and cooled to QV 5C. At this temperature, 2.35 parts of 2,4,6-trifluoro-5-chloropyrimidine are allowed to run in for half an hour and a half hour, while the P ^ value is kept at 7-8 with dilute sodium hydroxide solution you stir for a few more hours at 0-5 ⁰ C, with the

jj continues to hold at 7 - 8. It is then acidified slightly, the dye is salted out, filtered off with suction and washed with 5 Taiger, weakly acidic saline solution. After the filter material has been dried at 50 ° C., the dye, which is in the form of its sodium salt of the formula W, is obtained in a practically quantitative yield

A 12 5.77 ^ 26 -.

is equivalent to,

The dye used as the starting material (formula see above) can be obtained as follows:

9.5 parts of a mixture consisting of 3.8 parts of copper phthalocyaninesulfonic acid chloride sulfonic acid the formula

SO ₃ II

Cu-Pc- (3) '

and 5.7 parts of copper phthalocyanine sulfonic acid chloride sulfone acid of the formula

Cu-Pc-O)

(obtained by treating Cu-Pc with chlorosulfonic acid and a little thionyl chloride) are in the form of their aqueous paste whipped in 100 parts of ice water and neutralized. Under Adherence to a P ^ value of 9.6-10 is then left to a Solution of 2.7 parts of N- (ß-aminoethyl) -1 '- (4-nitrophenyl) urea the formula

H ₂ H-CH ₂ -CH ₂ -Jm-C0-NH- // Λ -

in 50 parts of H-methylpyrrolidone and 20 parts of methanol with 3 parts of 5N ammonia solution and 5 parts of Sn sodium hydroxide solution, flow in. The temperature is increased to 35 ° G over the course of 1 hour. Stirring is carried out to complete the reaction one more time at this temperature, whereby one the

le A 12 577 - 27 - · ^; '

1Ö9818 / 2032

The P "value of the solution is kept at 9> 6-10 with 1N sodium hydroxide solution. After all sulfonic acid chloride groups have reacted or saponified, the mixture is cooled to 10 ° C. and add a solution of 12 parts of Na ₂ S.9H ₂ O in 15 parts of water and stir until the reduction is complete at 10-25 ° C. The phthalocyanine derivative is precipitated at P ^ 5 by adding sodium bisulfite solution, sodium chloride and hydrochloric acid , suctioned off and washed with weakly acidic, dilute sodium chloride solution.

Is used in paragraph 1 instead of 2,4,6-trifluoro-5 ~ chlor-pyrimidines a corresponding amount of the following ^, listed reactive components, whereby the condensation at temperatures between 0 - 80 ° C in organic, organic-aqueous or aqueous weakly acidic to weakly alkaline medium, which is carried out with the help of soda, Bicarbonate or sodium hydroxide solution, valuable reactive dyes are also obtained:

2,4j6-trifluoropyrimidine

2-phenylamino-4j6-difluorotriazine

2-ethoxy-4> 6-difluorotriazine

2, S-dichloro-quinoxaline-G-sulfonic acid chloride

• -

2,3-dichloro-quinoxaline-6-carboxylic acid chloride 1 ^ -Bichlorophthalazine-6-sulfonic acid chloride 1 ^ -Dichlorophthalazine-6-carboxylic acid chloride 2-01110 ^^ 6. ^^ 1113201-5- or -ö-carboxylic acid chloride

2-chloro-benzthiazole-5- or -6-sulfonic acid chloride 2-ethylsulfonyl-benzthiazole-5- or -6-carboxylic acid chloride 2-ethylsulfonyl-benzthiazole-5- or -6-sulfonic acid chloride 3,5-bis-methylsulfonyl-isothiazole- 4-carboxylic acid chloride, 2-methylsulfonyl-4, S-dichloro-δ-methyl-pyrimidine, tetrachloropyrimidine
4,5,6-Trichloro-pyrimidine
2 ₃ K, 6-trichloropyrimidine
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ta

2,4-dichloro-pyrimidin-5-carbohsaurechlorid 2.4 i 6-trichloro-triazine

2-amino-4,6-dichlorobriazine

2-phenylamino-4j6-dichlorotriazine

ß- (4 ", 5'-dichloropyridazon-6'-yl ~ 1 ^! ) -äthyibbnsäürec3ilörid 4- ( 4'i 5 '-Dichlor-pyridazön-6 i-yl-1 *) -phenyläulf btts ^ iirechlbrid 4 - (4 ' i 5'-Diclilör-pyriä.azö'n-6'-yl-i') -phe ± iylc-ättjbiiäätt'iei6iiiöriä acrylic acid chloride

^ -ölilof-prepionic acid Glilotid

3-methylsulfonyl-propionic acid chloride ^ -ihenylsuifonyl-propionsätireclilorid or ß-Methylsülföriylacrylaäurfechlorid

Balsplei 2 *. ■

lii i5ö parts.ii of water become 11 * 1 parts of the! fbrirlel

solved. The dye _{solution is adjusted to P H} 8.0 and cooled down to 5 ° C at least. At this temperature iöän allows 2 _f 35 parts of a ^^ pyriraidin to run in within half an hour and keeps the Pg value at 7-8 with dilute sodium hydroxide solution. To complete the reaction is allowed to noöh several hours at east * - 5 ° C wherein _r .nachrühren to continue the P ^ value to 7 - holds. 8 It is then acidified slightly, the dye is salted out, filtered off with suction and washed with 5% weakly acidic sodium chloride solution. The dye

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paöte itfird "dried at 50 G. One obtains in practically quantitative yield of the dye, which is in the form of his Hfatriufisäizes of the formula -

C ¹ I

Cu-Pc- (3 j- SO ₂ NH ₂ \ m- ^ JJ

SO ₂ NH-CH ₂ -CH ₂ -NH-Co-NH- % ~ y f

eiits'pribht.

The colorants of the formulas are not more analogous

SO ₂ NH ₂

and

(SO _x Na) ₉ Cl F

^ -σσ-ΝΗ- / ~ 7

- SO ₂ NH ₂

^ SO ₀ NH-CH ₉ -CHo-NH

^L 2

Ie A 12 577

fÖSe187

obtained if one proceeds as described in paragraph 1, as starting compounds, however, the corresponding nickel phthalocyanine dyes are used. After one of the application methods customary for reactive dyes both dyes on cellulosic! Material clear, greenish turquoise tones with very good general fastness properties.

The dyes used as starting compounds in this example can, starting from copper phthalocyaninesulfonic acid chloride-sulfonic acid or nickel phthalocyaninesulfonic acid chloride-sulfonic acid, using N- (ß-aminoethyl) -N '- (3-nitrophenyl) urea or N- (ß- Aminoethyl) -N ^I - (4-nitrophenyl) urea in the manner described in Example 1, paragraph 2 win.

Likewise valuable reactive dyes are obtained if the copper and nickel phthalocyanine dyes used as starting compounds in this example paragraph 1 and paragraph 2 instead of 2,4,6-trifluoro-5-chloropyrimidine with the Reactive components listed in the final part of Example 1.

example

11.0 parts of the dye are in 150 parts of water formula

(SO ₅ Na) ₂

Cu-Pc- (3) - SC

-NH 2

Le A 12 577 - 31 -

ORIGINAL INSPECTED 109818/2032 J ^ _

195Uüa

^: . . .,. ■■■■■■ st

solved. The dye solution is adjusted to P "8 and cooled to 0-5 ° C. At this temperature, 2.35 parts of 2,4-pyrimidine are run in over the course of half an hour and the Ρττ value is kept at 7-8 with dilute sodium hydroxide solution. To stop the reaction is allowed to stir for a few hours at 0-5 ⁰ C, where,

the Ρ ,, value is kept at 7-8. Then you acidify n

weakly, salt out the dye, suction off and wash with 5 figs weakly acidic saline solution. The dye paste is dried at 50 ° C. The dye, which is obtained in the form of its sodium salt of the formula, is obtained in a practically quantitative yield

Cu-Pc- (3) -SO ₂ UH ₂ Cl F

CH ₅ -Ch ₀ -NH-CO- // '% -NH- / f ^X N

is equivalent to. According to one of the usual for reactive dyes Application methods are obtained on cellulose-containing! Material clear turquoise tones of very good generality.

The dyes of the formulas are used in an analogous manner

O ₃ Na) ₂ - Cl Ρ;

Cu-Pc- (3) - SO ₉ NH ₉ , NH-

le A 12 577 - 32-

ORIGSNAL INSPECTHD 109818/2032

Ni-Pc- (3) - SO ₂ NH ₂ Cl i »

SO ₂ NH-CH ₂ -CH ₂ -IiH-GO- / A /

~ F

(SO ₅ Na) ₂

Ni-Pc- (3) - SO ₂ NH ₂

obtained if one proceeds as described in paragraph 1 ", however, the amino yerbindings on which these dyes are based are used as starting compounds. You surrender on cellulosic! Material clear turquoise tones or with the Clear greenish turquoise tones of very good general fastness properties.

The dye used in paragraph 1 as the starting compound (Formula see above) can be obtained as follows; 9.5 parts of a mixture consisting of 3.8 parts of copper \ phthalocyanine sulfonic acid chloride sulfonic acid of the formula

S SO ₅ H

Cu-Pc- (3)

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and 5/7 parts of copper phthalocyaninesulfonic acid chloride sulfonic acid of the formula ⁷

0u-Pc- (3)

(obtained by treating Cu-Pc with chlorosulfonic acid and some thionyl chloride) are whipped in the form of their aqueous paste in 100 parts of ice water and neutralized. Under Compliance with a Ρττ value .von. 9-10 you leave a Solution of 2.5 parts of E- (4-nitrobenzoyl) -ethylenediamine-1,2 the formula

H ₂ H-CH ₂ -CH ₂ -EH-C0-

in 50 parts of E-methylpyrrolidone and 20 parts of methanol mixed with 3 parts of 5N ammonia solution and 5 parts of sodium hydroxide solution. The temperature is increased to 35 ° C. within one hour. To end the reaction, the mixture is stirred for some time at this temperature, the Ρττ value of the solution being kept to 9-10 with sodium hydroxide solution Sulfonic acid chloride groups have reacted or saponified, the mixture is cooled to .10 ° C. and a solution of 12 parts of Ea _{2 S.9H 2} O in 15 parts of water is added and the mixture is stirred at 10-25 ° C. until the reduction is complete. By adding sodium bisulfite solution, sodium chloride and hydrochloric acid, the phthalocyanine derivative is precipitated at P "3, filtered off with suction and washed with weakly acidic, dilute sodium chloride solution.

In an analogous way, one also obtains the ones for the production of the in Paragraph 2 described dyes required starting compounds. . "■■": '■

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1-95U09

Likewise valuable reactive dyes are obtained if the copper and nickel phthalocyanine used as starting compounds in this example, paragraph 1 and paragraph 2 dyes instead of 2,4,6-trifluoro-5-chloropyrimidine with the reactive components listed in connection with Example 1 implements.

Example 4:

11.4 parts of the dye are in 150 parts of water formula

Gu-Pc- (3)

SO ₂ HH-CH ₂ -CH ₂ -HH-CO-Im-

solved. The dye off solution is adjusted to Pg-9.0 and cooled to 0-5 ° G. At this temperature one leaves within half an hour 4.70 parts of 2,4,6-trifluoro-5-chloropyrimidine and keeps the P ^ -value with diluted Caustic soda to 8 - 8.5. To end the reaction, the mixture is stirred for a few more hours at 0-5 ° C., with the P ^ value is kept at 8 - 8.5. Then sour one weakly, the dye is salted out, filtered off with suction and washed with dilute sodium chloride solution. The dye is at 50 ° C dried. The dye is obtained in a very good yield which is in the form of its sodium salts of the formula

Cu-Pc- (3)

(SO ₃ IIa)

SO ₂ HH-CH ₂ -CH ₂ -HH-CO-HH- ^ y -SO ₃ Ha

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; '. ,. ■■■

is equivalent to. It dyes cellulosic material in clear Turquoise tones of very good general classes.

A dye of similar properties., But which is im Hue is clearly gnawed, you get, if you instead of the copper phthalocyanine derivative used in paragraph 1, line 2 the corresponding nickel phthalocyanine derivative is used.

Likewise valuable reactive dyes are obtained if the in this example, paragraph 1 and paragraph 2 as starting compounds related copper and nickel phthalocyanine dyes instead of 2,4,6-trifluoro-5-chloropyrimidine the reactive components listed in connection with Example 1 implements.

The starting dyes used in paragraph 1 and paragraph 2 can be obtained as follows:

8.53 parts of copper or nickel phthalocyaninesulfonic acid chloride sulfonic acid the formula

SO ₅ H
Gu-Pc- (3) 'or

(SO ₂ Ci) ₂ -.

(obtained by treating Cu-Pc or Ni-Pc with chlorosulfonic acid and some thionyl chloride) are in the form of their aqueous paste suspended in 150 parts of ice water and neutralized. Then 3.6 parts of the li (ß-aminoethyl) -Iifs_ (3-amino-4-sulfo-phenyl) urine are added the formula

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1098 18/2032

H ₂ U-CH ₂ -GH ₂ -HH-CO-3SH-

to, increases the temperature to 20-25 ° G and ..stirring while maintaining a P ^ value of about 9 by adding dilute sodium hydroxide solution until the reaction is complete. To the
Saponification of any remaining sulfonic acid chloride groups is briefly heated to 60 ° C. The dye is precipitated by stirring in hydrochloric acid, filtered off with suction and washed with dilute hydrochloric acid.

Example 5 '· .

10.4 parts of the dye are in ISO parts of water formula

. (SO ₃ Na) ₂ .
Ou-Pc- (3)

^ SQ ₂ NH-Gh ₂ -OH ₂ -NH-CO-NH ^ // ^ y-

solved. The dye solution is adjusted to Pg 8.0 and cooled to 0-5 ° C. At this temperature, 3.30 parts of 2,4-trifluoro-5-chloropyrimidine are allowed to run in over the course of half an hour and the P ^ - Value with dilute sodium hydroxide solution to 7-8. To stop the reaction
the mixture is allowed to stir for a few more hours at 0-5 ° C., the P _H value still being kept at 7-8. It is then acidified slightly, the dye is salted out, filtered off with suction and washed with 5% weakly acidic sodium chloride solution. After drying
of the nutritive goods at 50 ° G are obtained in practically quantita-

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tive yield of the dye, which is in the form of its liatrium salt the formula

Cu-Pc- (3) Cl F

SO ₂ IfH-CH ₂ -CH ₂ -NH-CO-IIH- <? \ -KH- / ^x

is equivalent to. Each one of the usual for reactive dyes Application process produces clear turquoise tones of very good generality on cellulose-containing material.

Likewise valuable reactive dyes can be obtained analogous to the reaction of paragraph 1, if instead of the dye mentioned in line 2, the following phthalocyanine derivatives uses as output connections:

Cu-Pe- (3j.

SO ₂ IH-CH ₂ -CH ₂ -KlI-CO-IiH-

Ni-Pc- (3)

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195U09

Cu-Pc- (3)

KH,

SO ₂ NH-CH ₂ -CH ₂ -KH-C 0-KH-

-Ni-Pc- (3)

Ni-Pc- (3)

KHr

SO ₂ NH-CH ₂ -CH ₂ -KH-C 0-KH- <f Λ

(SO ₃ Na) ₂

Co-Pc- (3) Cu-Pc- (3)

. (SO ₃ Na) ₂

SO ₂ N-CH ₂ -CH ₂ -CH ₂ -KH-Co-KH- ^ _ ^x > -KH ₂

CH,

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195 H.

Cu-Pc- (3)

SO ₀ N-CH ₀ -CH ₀ -N-CO-NH- <'\ -NH CH, CH,

J J

Cu-Pc- (3) -SO

SO ₂ -NH-CH ₂ -CH ₂ -Nh-CO-NH- / ~ \ -NH

~ CH

. (SO ₅ Na) ₂ Cu-Pc- (3) - SO ₂ NH ₂

SO ₂ NH-CH ₂ -CH ₂ -NH-CO-Nh-

^ΝΝ · -NH C ₂ H ₅

Cu-Pc- (3)

, (SO ₅ Na) ₅

■ SQ ₂ Nh-CH ₂ -CH ₂ -NH-CO-NH- / ⁷ > -NH

C ₀ H.OH

(SO ₅ Na) ₅

Cu-Pe- (3)

NH,

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So ₂ NH-CH ₂ -CH ₂ -NH-CO-N- - CH - 40 -

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CU-Pc-O)

(SO ₃ Ia) ₅

G ₂ H ₅

(S 0-, Ia

Cu-Pc- (3)

-IH-CHo-CHo-IH-C 0-1- <f > -IH

ο-υϋο - ΙΝ11-υυ-1 \! - γ / -1MiIo

CgH.OH

Cu-Pc- (3) -

SQ ₂ IH ₂
SO ₀ -IH-CH ₀ -CH-IH-CO-Ih-

7-

CH

Gu-Pc- (3) -

(SQ ₃ Ia) ₂

(SO ^ Ia).

Cu-Pc- (3)

SQ ₂ IH-CH ₂ -CH ₂ -CH ₂ -CH ₂ -Ch ₂ -CH ₂ -IH-CO-IH- / T

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Cu-Pc- (3) '- SO ₂ NH ₂

Cl

Cu-Pc- (3 ) - SO ₂ NH ₂

c \

-NH-CQ-NH- / ^7ν \ -NH

CH,

Cu-Pc- (3) - SO ₂ NH ₂

H ₃ C

SQ ₂ NH-CH ₂ -CH ₂ -NH-CO-Nh- / ' ^x \ -

Cu-Pc- (3) - SO ₀ NH

CQQNa

SQ ₂ NH-CH ₂ -CH ₂ -NH-C Q-NH- <^ _ ^ν ^.

(SQ ₂ NH-QH ₂ -CH ₂ -NH-QQNh- ^ J

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Gu-Pc- (3 ί

COlH,

UH,

Cu-Pc- (3)

HH,

COO-CH

(SO ₃ Na) ₂

Cu-Pc- (3) So ₂ NH-CH ₂ -CH ₂ -NH-CO- <^ Α -NH ₂

-NH

Cu-Pc- (3) (SO ₃ Na) ₃

SO ₂ NH-CH ₂ -

CH,

Ni-Pc- (3) (SO ₃ Ha) ₂

SO ₂ HH-CH ₂ -CH ₂ -NH-C 0- <^

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(SO ₃ Na) ₂

Cu * Pc- (3)

NH ₂ .

Cu-Pc- (3)

CH,

Cu-Pc- (3

(SO ₅ Na) ₂

So ₂ NH-CH ₂ -CH ₂ -NH-CO-

. (SO ₃ Na) ₂

Cu-Pc- (3) - SO ₂ NH-CH ₃

NH,

SO ₂ NH-CH ₂ -Ch ₂ -NH-CO-NH- <' ^N > -S0, Na

Cu-Pc- (3) -SO ₂ NH-CH ₂ -CH ₂ OH

NH,

SO ₂ NH-CH ₂ -CH ₂ -NH-C 0 -NH- < ^y

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195U09

. (SO ₃ Na) ₂
Cu-Po-C3) - SO ₂ NH-CH ₂ -CH ₂ -SO ₃

N / A

SO ₂ NH-Ch ₂ -CH ₂ -NH-CO-NH-

-NH,

Cu-Pc- (3) - SO ₂ NH-CH ₂ -CH ₂ -SO ₃ Na SO ₂ NH-CH ₂ -CH ₂ -NH-C 0-

Λ-

, (SO ₃ Na) ₂

Cu-Pc- (3)

SO ₂ NH-CH ₂ -COONa

pAV 14.— \ Jiin-

^X \ -NH,

Ni-Pc- (3) - SO ₂ NH-CH ₂ -CH ₂ -SO ₃ Na? ^H 2

(SO ₃ Na) ₂ "
Ni-Pc- (3) - SO ₂ NH-CH ₂ -COONa

SO ₂ NH-CH ₂ -CH ₂ -Nh-CO- ^ ^AN y-NH,

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1351409

Cu-Pc- (3) - SO ₂ NH-CH ₂ -CH ₂ -SO ₅

N / A

SO ₂ NH-CH ₂ -CH ₂ -NH-CO-Nh-

(SO ₅ Na) ₂

Cu-Pc- (3) -SO ₂ N (CH ₅ ) -CH ₂ -COONa SO

.Cu-Pc- (J) - SOoNH- / ^{7 Λ}

SO ₂ NH-CH ₂ -CH ₂ -NH-CO-NH

Gu-Pc- (4)

(SO ₇ Na) ₅

SOoNH-CHo-CHo-NH-CO-NH- / ^% -NH

(SO ₅ Na).

Cu-Pc- (4)

SO ₂ NH-CH ₂ -CH ₂

Η,

Ie i 12 577

Cu-Pc-

SO ₀ NH-CH ₀ -Ch ₀ -NH-CO - // ^x > -L ± _o 2 2 2 \ _ / 2

(SO ₃ Ia) ₃

Cu-Pc- (4)

SO ₀ NH-CH ₂ -CH ₂ -NH-CO-

(SO ₃ Ia) ₃

Cu-Pc- (4)

Ni-Pc- (4)

CH ₃

(SO ₃ Na) ₃

SO ₂ NH-Ch ₂ -CH ₂ -NH-CO-NH- / " ^x \ -NH ₂

Reactive dyes, which are also valuable, are obtained if the amount used in paragraph 1 ran, 3.3 parts of 2,4,6-trifluoro-5-chloro-pyrimidine increased to 6.5 parts and instead of the dye mentioned in line 2, equimolecular parts the following phthalocyanine derivatives as starting compounds uses:

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19 5H09

Cu-Pc- (J) -

SO ₃ Na

NH,

(SO ₂ NH-CH ₂ -CH ₂ -KH-C 0-NH- / ΓΛ-SO JSTa)

SO ₃ Na

■ Cu-Pc- (5)

SO ₅ Well

(SO ₂ NH-CH ₂ -CH ₂ -NH-C 0-NH- // ^x ) -NH ₃ )

(SO ₅ Na) ₂

i-Pc- (37

NH,

(SO ₂ NH-CH ₂ -CH ₂ -NH-CO-NH- ^ A-SO ₅ Na) ₂

Cu-Pe- (3)

SO ₅ Well

S 0, Na

7th

(SO ₅ Na) ₂

Cu-Pc- (47 'y ° 3 ^Na

(SO ₂ NH-CH ₂ -CH ₂ -NH-Co-NH- / ~ Λ-NH ₂ ) _;

Cu-Pc- (4)

. SO ₅ Well

NH,

(SO ₂ NH-Ch ₂ -CH ₂ -M-CO-NH-

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The starting dyes listed in this example " can be obtained by taking from Phthalocyaninsulfonsäureehloriden "or Phthalocyaninesulfonsäurechlorid-sulfonic acids and this either based on Example 1, paragraph 2 with the corresponding nitro-amines and, if applicable Ammonia or monoamines bearing no nitro groups are reacted, reduced and optionally with oleum or chlorosulfonic acid after sulfonated or based on example 4, paragraph 4 with the corresponding diamines and, if necessary Ammonia or monoamines set and, if necessary, re-sulfated.

To likewise valuable reactive dyes is obtained if in this example related as starting compounds of copper, nickel and Kobaltphthalocyaninfarbstoffe one instead of 2,4,6-Trifluo _t r-5-chloro-pyrimidine is reacted with the above in connection with Example 1, the reactive components .

Example 6:

5 g of dye, which is obtained according to Example 1, paragraph 1, are mixed with 5 g of urea and Ig m-nitrobenzene-sulfonic acid sodium, made into a paste with 10 ml of water at 20-25 ° C and mixed with 80 ml of water at 20 ° C Stirring at Pt 7-8 dissolved. 20 ml of a 10 % sodium carbonate solution are added to this solution. With the padding liquor thus obtained, 20 g of cotton-G-ewebe are padded on a laboratory pad, the rollers of which are pressed together with such a pressure that the liquor pick-up of the cotton fabric is about 80 i <3 of its dry weight Tenter frame stretched and in

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-: ■■■■■ ■■■■. ■■■ ' ^ί0 ':

Drying oven for 15 minutes at 60-70 ° C and then steamed at 102 ° C for 3 minutes. One rinses then the dyed material thoroughly, first with cold Water and then with hot water until the wash liquor is no longer bled. Then the. colored material in 500 ml of a liquor containing 0.5 g of sodium alkyl sulfonate contains, soaped for 20 minutes at boiling temperature, 'rinsed again and in a drying cabinet at 60 - 70 ° C dried.

The dye is absorbed in a wet-fast, clear, turquoise-blue tone. .

■ ■.

Turquoise-blue colorations are also obtained if the dye used in paragraph 1 is replaced by the dyes obtained according to Example 2, paragraph 1, example 3 ₅ paragraph 1 or example 5> paragraph 1.

Example 7; -. _:

3 g of dye obtained according to Example 2, paragraph 1, are mixed with 15 g of urea and 1 g of sodium m-nitrobenzene sulfonic acid, made into a paste with 10 ml of water at 20-25 ° C and mixed with 80 ml of water at 20 ° C with stirring at Pjj 7 - 8 dissolved. 20 ml of a 10% sodium carbonate solution are added to this solution. With the padding liquor thus obtained, 20 g of cotton fabric are padded on a laboratory padding, the rollers of which are pressed onto one another with such a pressure that the liquor pick-up of the cotton fabric -. is about $ 80 of its dry weight. The.:., G-ewebe padded in this way is placed on a stenter for 15 minutes in the; Drying cabinet at 60 - 70 ° C and dried at 150 ° Q

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Treated for 3 minutes. The dyed material is then rinsed Thoroughly first with cold water and then with hot water until the wash liquor is no longer bled. The colored material is then placed in 500 ml of a liquor containing 0.5 g of sodium alkyl sulfonate for 20 minutes Soaped at boiling point, rinsed again and at 60 - 70 ° C dried in a drying cabinet. A turquoise-blue, wet-fast coloring is obtained.

Turquoise-blue colorations that are also wet-fast can be obtained if, instead of the above-mentioned dye, the dyes are used, which can be obtained by converting the in Example 1, Paragraph 1 related initial connection with those in the final part of Example 1 mentioned reactive components is obtained.

Example 8;

220 ml of water at 20-25 ° C. are placed in a staining beaker with a capacity of 500 ml, which is located in a heatable water bath. One teigt 0.3 g of dye obtained according to Example 1, paragraph 1, with 2 ml of cold water well and add 48 ml of hot water (70 ⁰ G). The dye solution with a P ^ value of 7-8 is added to the water initially taken, 10 g of cotton yarn being kept in constant motion in this dye liquor. The temperature of the dye liquor is increased to 95 ° 0 within 10 minutes, 15 g of sodium sulfate (anhydrous) are added and the dyeing is continued for 30 minutes. 2 g of sodium carbonate are then added to the dye liquor and it is dyed at 95 ° G for 60 minutes the dyed material of the dye liquor, removes the adhering liquor by wringing out or pressing it off and rinses the material thoroughly first with cold water and then with hot water for so long

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ο.

"until the wash liquor is no longer bled. Then the dyed material is in 500 ml of a liquor containing 0.5 g Contains sodium alkyl sulfonate, soaped for 20 minutes at boiling temperature, rinsed again and in dried in a drying cabinet. The cotton is dyed in a clear, turquoise-blue shade that is fast to wet.

Is used instead of the dye mentioned in paragraph 1 the Mckelphthalocyanine dyes, which are obtained according to Example 2, Paragraph 2 or Example 3, Paragraph 2 is obtained, you get wet-fast, clear, turquoise colors *

Example 9:

5 g of dye, obtained according to Example 2, paragraph 1, are made into a paste with 2 ml of water at 20-25 ° C. and dissolved with 68 ml. 30 ml of a 10% sodium carbonate solution are added to this solution. The padding liquor thus obtained is used to pad 20 g of cotton fabric on a laboratory padding, the rollers of which are pressed together with such a pressure that the liquor pick-up of the cotton fabric is about 80 % of its dry weight. The fabric padded in this way is rolled up and stored in a closed glass tube for 10 hours at 20-25 °. The dyed material is then rinsed thoroughly, first with cold water and then with hot water until the wash liquor is no longer bled. The dyed material is then soaped in 500 ml of a liquor containing 0.5 g of sodium alkyl sulfonate for 20 minutes at the boiling point, rinsed again and dried at 60-70 ° C. in a drying cabinet. Mari takes on a wet-fast, turquoise-blue color.

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Example 10:

A cotton piece is made with a printing paste consisting of 50 g of the dye of Example 1, paragraph 1, 150 g of urea, 20 g of sodium bicarbonate, 10 g of m-nitrobenzene sulfonic acid ¥ atrium, 450 g of a highly viscous alginate thickening and 320 g Water, printed and in a damper, e.g. B of the Mather-Platt type, steamed at 103 ° 0 .. The print is then rinsed with cold, then with hot and finally again with cold water. A wet-fast, turquoise-blue coloration is obtained.

You can also get turquoise blue or turquoise colorations, if, instead of the above-mentioned dye, the dyes from Example 4, paragraph 1 or 2 are used, or the Dyes used according to Example 5 »Paragraph 1 using the starting compounds specified in the table in Example 5 receives.

Example 11;

Cellulose nettle is mixed with a printing paste of the following composition printed: '

50 g dye according to example 2, paragraph 1, 50 g urea,

10 g of sodium m-nitrobenzene sulfonic acid, 500 g of highly viscous alginate thickening
390 g of water.

! After drying, you pad on a padder that is loaded with a solution of the following composition: 200 g of soda,
200 g potassium carbonate,
600 g water,.

30 g sodium hydroxide solution 38 ° Be.

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Then steam manually - continuously - 30 minutes at 120 ° C, washes with cold ^ then with hot and finally again with cold water. You get a wet, real, turquoise-blue one Pressure.

Example 12;

A piece of cotton nettle will follow with a pressure approach Composition 'printed:

50 g of dye, obtained according to Example 3, paragraph 1, 50 g of urea,

10g of sodium m-nitrobenzene sulfonic acid. 500 g highly viscous alginate thickener,
390 g water.

The dried print goes through a padding liquor heated to 100 ° C. on a padder in 15 seconds, as in Example 11 indicated, and v / ird continuously with cold, then with 90 G warm and then washed again with cold water. A wet-fast, turquoise-blue print is obtained.

Example 13:

A 20 g wool skein is put into a dye bath at 40 ° C received that from ■

0.5 g dye, obtained according to Example 1, paragraph 1 (at % 7 - 8 solved),

3.0 g of a polyglycol ether, manufactured according to DAS 1.041.003, Example 9,

5.0 g sodium sulfate and

1.2 g acetic acid per liter and heated to 80 ° G within 15 minutes. At this tem-

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temperature is allowed to linger for 30 minutes, heated to a boil and maintains this temperature for about an hour. After rinsing with water a potting- and whale-fast, turquoise-blue coloration is obtained. .

Turquoise-blue or turquoise colors are also obtained if, instead of the above dye, the in Example 2, Paragraphs 1 and 2, Example 3, Paragraphs 1 and 2 or Example 5, Paragraph 1 used dyes.

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Claims (11)

Claims 1.) Phthalocyanine reactive dyes of the formula Po- ( ₂ ^ ₁₁ (SCUN-alkylene-N-CO-X-.arylene-NZ) Ί II ° R,. R,. Rr-3.4 5 where Pc is the radical of a phthalocyanine, R 1 and R _{2 are} hydrogen atoms or identical or different alkyl radicals which can be ring-closed and / or substituted, or optionally substituted cycloalkyl, aralkyl or aryl radicals, R 1, R and R 2 are hydrogen or the same or various alkyl radicals with 1-3 carbon atoms, which can be substituted by hydroxyl groups, "alkylene" is an alkylene chain with 2-6 carbon atoms, X is a direct bond or a -H (.R ^) - group, where Rg Y represents hydrogen or an alkyl radical with T - 3 carbon atoms which is optionally substituted by a hydroxyl group, "arylene" represents an optionally substituted by lower alkyl groups, lower alkoxy groups, halogen atoms, sulfonic acid groups, carboxy groups, carbamide groups and / or carboxylic ester groups with T - 4 C - Atoms in the alcohol radical and Z represent a reactive group, and a and c represent numbers from 1-3 and b represent a number from 0-2, the sum of a, b and c not being greater than 4. Le A 12 577 - .56.- TO 9 8 18/20 3 2 1951403 2.) Phthalocyanine reactive dyes of the formula Pc (SO ₂ HCgI) _b R ₆ in which Pc, R _{1, R, R 5} , Rg, "alkylene", Z and a, b and c have the meaning given in claim 1, R / and Rp are hydrogen, lower alkyl radicals with 1-3, optionally substituted by hydroxyl groups C atoms and "arylene" denote a phenyl radical optionally substituted by lower alkyl groups, lower alkoxy groups, halogen atoms, sulfonic acid groups, carboxyl groups, carbonamide groups and / or carbon ester groups with 1-4 carbon atoms in the alcohol radical. 3.) Phthalocyanine reactive dyes of the formula Po- (SO ₂ NCgI) _b (SOoir-alkylene-N-CO-arylen-N-Z -) .- R ₃ -E ₄ ■ R ₅ - where Pc, R ,, R., R ^, "alkylene" Z and a, b and c have the meaning given in claim T, R. and R _{2 are} hydrogen, lower alkyl radicals with 1 - 3 G- Atoms - 57 Le A 12 577 and "arylene", an optionally substituted by lower alkyl groups, lower alkoxy groups, halogen atoms, sulfonic acid groups, carboxy groups, carbonamide groups and / ^; - · or carbon ester groups with 1-4 C atoms in the alcohol radical are substituted phenyl radicals. 4.) Phthalocyanine dyes of the formula (SO ₂ WH-alkylene-NH-CO-X-arylene-1TH-Z) _c wherein Pc, R ₁ , R ₂ , "alkylene", X, "arylene", Z, and a, b and c have the meaning given in claim 1. 5.). Phthalocyanine dyes of claims 1 to 4, characterized in that Z halotriazine and halogen— represents pyrimidine radicals, where "halogen" is fluorine, chlorine and Means bromine. 6.) Phthalocyanine dyes of the formula ^ (SO ₅ H) ₃ Pe— ■■ (SO ₉ ITcJrK 'ei F V- ^ K ₂ D y ^ (SO ₂ lIH-alkylene- ^ H-CO-X-arylene * NH - <^^ Iir) _β wherein Pc, R ₁ , R ₂ , "alkylene", X, "arylene" »and a, b and c have the meaning given in claim T. Ie A 12 577 - 58 - 109818/2032 7.) - ..: · ■: ■■; Process for the preparation of phthalocyanine reactive dyes ^ open », characterized in that amino group-containing phthalocyanine dyes of the formula pe- ( ₂ | _t (SOgK-alkylen-N-CO-X-arylen-li-H) _Q where Pc is the radical of a phthalocyanine, R ^ and Rg are hydrogen atoms or identical or different alkyl radicals which can be ring-closed and / or substituted, or optionally substituted cycloalkyl, aralkyl or aryl radicals, R ₃ , R. and R, - hydrogen or the same or various alkyl radicals with 1-3 O atoms, which can be substituted by hydroxyl groups, "alkylene" is an alkylene chain with 2-6 carbon atoms, X is a direct bond or an -N (Rg) group, where 'Rg is hydrogen or represents an alkyl radical with 1-3 carbon atoms optionally substituted by a hydroxyl group, "arylene" represents an optionally substituted with lower alkyl groups, lower alkoxy groups, halogen atoms, sulfonic acid groups, carboxy groups, carbonamide groups and / or carbon ester groups with 1-4 carbon atoms in the alcohol radical substituted arylene radical, and a and c represent numbers from 1-3 and b represent a number from 0-2, the sum of a, b and c not being greater than 4, with a reactive component Y-Z, where Z is a reactive group and Y is a removable substituent stands. Le A-12 577 - 59 - 109818/20 32 8.) Procedure for batches and printing. containing hydroxyl groups Materials, in particular textile materials made from native or regenerated cellulose, characterized in that that you can use these materials in any order or applying several dyes of claims 1 to 6 and optionally increasing the exposure to the material treated in this way Temperature subjects. 9.) Process for dyeing N-containing materials, preferred of wool, silk, synthetic superpolyamide and '-polyurethane fibers, characterized in that they are Materials with one or more dyes of claims 1-5 from acidic to neutral liquor dyes and optionally then increased the P ^ range of the dyebath. 10.) By the method of claim 8 colored or printed materials containing hydroxyl groups. 11.) According to the method of claim 9 colored N-containing Materials. - 60 - Le Λ 12 577. "