DE2154477A1 - Azo compounds, process for their preparation and their use - Google Patents

Description

CIB / v-GEfGY

CIBA-GEIGY AG, CH-4002 Base!

( Case 1-722 VCIN-47 + " 2 · NOV. 1971

Germany J * """'" ■ ·.
CUU.U 2.

Azo compounds, process for their preparation and their

use

The subject of the invention are new valuable, azo compounds of the formula which are free from sulfonic acid groups

D-N = N-A-N / N

₂ C

wherein D is the radical of a diazo component, A is an optionally substituted 1,4-phenylene radical, R is an optionally substituted alkyl radical, R «an optionally substituted alkylene radical and Y an imino group Is a sulfur atom or an oxygen atom, the aromatic or partially or fully saturated ring B may have further substituents, such as halogen atoms, Nitro groups or organic substituents.

209820/1062

According to the invention, the compounds are obtained by adding a diazonium compound of a diazo component with a coupling component of the formula

HA-NR ₁ -R ₂ -C

couples and the resulting azo dye optionally treated with quaternizing agents.

The compounds of the formula which are free of acidic groups are of interest

CH ₂ CH ₂
DN = NAN N

^CH —V0 '

wherein D, A and Y are the same as above and X is Is hydrogen, a halogen atom or an organic radical, preferably an acyloxy radical or an alkyl radical.

The compounds of the formula are particularly preferred

D-N = N-A-N

209820/1062

where D, A and Y are the same as above and R ^{1 is} an acyl radical of an organic acid, a lower alkyl radical or a hydrogen atom, R ¹ can, for example, represent a methyl, ethyl, propyl, butyl radical, for a radical of a carboxylic acid , such as formic, acetic, butyric, propionic acid, also benzoic and toluic acid, also stand for (methyl, butyl, hexyl) (amino or oxy) carbonyl radicals or phenyl (oxy or amino) carbonyl radicals.

In the preceding formulas, the ring B 'can be represented by fluorine, chlorine, bromine atoms. Cyano groups, nitro groups, alkyl groups, such as methyl and ethyl groups, alkoxy groups, such as Methoxy and ethoxy groups, acylamino groups, such as fatty acid acylamino groups, e.g. formyl, acetyl, butyrylamino groups, and benzoylamino groups, and substituted 1,2-benzo groups be.

The group A advantageously corresponds to the formula

where c is in the ortho position to the azo group and d in the ortho position to the amino group.

The radicals c and d stand for hydrogen atoms, chlorine atoms, lower alkyl or alkoxy radicals, such as the methyl, ethyl, methoxy or ethoxy radical, and also phenylthio or

209820/1062

Phenoxy radicals.

The remainder c can also be used for a bromine atom, one trifluoromethyl group and one optionally on the nitrogen atom alkylated, preferably methylated, acylamino group in which the acyl radical is the radical of a carboxylic acid with up to 8 carbon atoms, such as a formyl, acetyl, propionyl, butyryl or benzoyl radical, the remainder of an organic Monosulfonic acid with preferably up to 7 carbon atoms, such as methane, ethane, butane, benzene or p-toluene monosulfonic acid radical, or the remainder of a carbonic acid monoester or monoamids with preferably 8 carbon atoms each, such as a methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, Butoxycarbonyl, phenoxycarbonyl, toluyloxycarbonyl, aminocarbonyl or ethyl amino carbonyl-, methylaminocarbon} '! -, Butylaminocarbonyl, phenylaminocarbonyl or cyclohexylaminocarbonyl radical is.

The group R, can represent a hydrogen atom, a Alkyl group or a substituted alkyl group, the alkyl radical being replaced by heteroatoms, such as oxygen atom, can be interrupted. Examples of substituted alkyl groups are: the β-chloroethyl, β, β, β-trifluoroethyl, ß, 7-dichloropropyl, alkylphenyl, such as benzyl, ß-phenethyl, halogenated alkyl groups such as ß-chloroethyl, β, β, β-trifluoroethyl, β, 7-dichloropropyl or 3-chloro-2-hydroxypropyl, ß-cyanoethyl, alkoxyalkyl, such as β-ethoxyethyl,

209820 / 1Π6?

<£ -Butoxy-butyl- or cT-methoxybutyl, hydroxyalkyl, such as ß-hydroxyethyl, ß, 7-dihydroxypropyl, 7-chloro-ß-hydroxypropyl, fatty acid acyloxyalkyl, such as formyloxyalkyl, ß-acetyloxyethyl, β , 7-diacetoxypropyl, propionyloxyäthy1-, 7-butyryloxypropyl and ethylhexanoyl groups, optionally with lower alkyl groups, which preferably have up to 10 carbon atoms, N-alkylated carbamoyl groups, such as NjN-dimethylaminocarbonyl, N-methyl-N-butylaminocarbonyl , Ν, Ν-dibutylaminocarbonyl, N-phenylaminocarbonyl, alkyl or arylcarbamoyloxyalkyl, such as β- (methyl, ethyl, propyl, butyl, dodecyl, cyclohexyl and β- phenyl) carbamoyloxyethyl, alkyloxycarbonyloxyalkyl , such as (methoxy, ethoxy, propyloxy, butoxy, decyloxy, oleloxy) carbonyloxyethyl, aryloxycarbonyloxyalkyl, such as o-, m- or ρ- (methoxy, ethoxy, ß ^f -chloroethoxy, isopropyloxy - or methyl) phenyl-carbonyloxyethyl, heterocyclic acyl radicals, such as α- or ß-pyridylcarbonyloxyäthyl-, 2-thenoyloxyäthyl- , 7-acetamidopropyl, / 3-phenoxyethyl, cinnamoyloxyethyl or -propyl-, ß- (p-hydroxyphenoxy) -ethyl, cyanoalkoxyalkyl, ß-carboxyethyl, ß-acetylethyl, ß-diethylaminoethyl, / 3 -Gyanacetoxyäthyl-, ß-Benzoyloxyathyl- and ß- (p-Alkoxy- or phenoxy-benzoyl) -oxyäthy1- groups.

The group R i generally contains no more than eighteen, preferably no more than ten carbon atoms.

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The following may be mentioned as examples of alkylene radicals R ₂ (the terminal coupling-directing amino group of the azo dye being drawn in to indicate the position):

-NR ₁ -CH ₂ CH ₂ CH ₂ -, -NR ₁ -C ₂ H ₄ -OC ₂ H ₄ - and

CH ₂ Cl

NR ₁ -CH ₂ -CH-

In the preferred dyes of the formula

wherein D, A, B ¹ and Y are the same as above, the group R- can stand for a hydrogen atom or an organic group. The organic groups are primarily alkyl groups, such as methyl, ethyl, propyl, butyl, benzyl groups, and acyl groups, such as carboxylic acid acyl radicals, preferably with up to 19 carbon atoms, for example acetyl, formyl, butyryl, dedecylcarbonyl, stearyl -, phenylacetyl, cinnamoyl, oleyl, benzoyl, p-chlorobenzoyl, p-carboxymethyl-benzoyl, 2-furancarbonyl, 2-pyridinecarbonyl, 2-thiophenecarbonyl and cyclohexylcarbonyl radicals in question. Other suitable acyl groups are the acyl radicals of carbamic acids and of carbonic acid half-esters, each preferably having up to 18 carbon atoms, such as methylaminocarbonyl, phenylaminocarbonyl, n-butylamino-

209820/106?

carbonyl, undecylaminocarbonyl, octadecylaminocarbonyl, Oleylaminocarbonyl, p-tosylaminocarbonyl, ethyloxycarbonyl, Cyclohexyloxycarbonyl, decyloxycarbonyl, octadecyloxycarbonyl, oleyloxycarbonyl, phenoxycarbonyl and benzyloxycarbonyl radicals.

The Diazorest D is mainly derived from mono- or bicyclic amines of the formula

D-NH ₂ ,

like any diazotizable amines that do not have acidic water-solubilizing agents Contain substituents, but especially of amines that have a heterocyclic five-membered ring with 2 or Heteroatoms, especially one nitrogen and one or two sulfur, oxygen or nitrogen atoms as heteroatoms and aminobenzenes, especially negatively substituted aminobenzenes (i.e. aminobenzenes which have substituents a negative sigma value according to the Hammet equation

para

have), especially those of the formula

f a

NH ₂

wherein a is a hydrogen or halogen atom, an alkyl or Alkoxy, nitro, cyano, carbalkoxy or alkyl sulfone group, b a hydrogen or halogen atom, an alkyl, cyano or trifluoromethyl group, e a nitro, cyano, carbalkoxy givenfa] Ir substituted sulfonamide or

209820/106?

Alkylsulfonyl group, f a hydrogen or halogen atom, mean a carbalkoxy or a carboxamide group.

Examples are:

2-aminothiazole,
2-Amino-5-nitrothiazole, 2-Amino-5-methylsulfonyl-thiazole, 2-Amino-5-cyanthiazole, 2-Amino-4-methyl-5-nitrothiazole, 3-Amino-5-nitro-benzisothiazole, S- Amino-S-nitro-y-bromo-benzisothiazole, 3-Amino-benzisothiazole, S-Amino-S-chloro-benzisothiazole, S-Amino-y-chloro-benzisothiazole, 3-Amino-4-chloro-benzisothiazole, 3- Amino-5,7-dichlorobenzisothiazole,

3-Amino-6-methyl-benzisothiazole, 3-Amino-5,7-dibromo-benzisothiazole,

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2-amino- ^; Ι · -methy1thiazole, "2-amino -h -phenylthiazole, 2-amino -h- {K '-chlor) -phenylthiazole, 2-amino ->! ■ - (V -nitro) -phenylthiazole, 3-aminopyridine," .

3-aminoquinoline,

3-amino-l-phenylpyrazole, 3-aminoindazole,

3-Amino- _1,2> 4-triazole, 5- (methyl-, ethyl-, phenyl- or benzyl) -1,2, k -triazole, 3-amino-1- (V ~ methoxyphenyl) -pyrazole, 2 -Aminobenzothiazole, 2-amino-6-methylbenzthiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-chlorobenzthiazole, 2-amino-6-cyanobenzthiazole, 2-amino-6-rhodanobenzthiazole, 2-amino-6-nitrobenzthiazole , 2-Amino-6-carboethoxybenzthiazole, 2-amino- (4- or 6) -methylsulfonylbenzthiazole, 2-amino-i, 3j ^ -thiadiazole, 2-amino-1,3 / 3-thiadlazole, '2-amino - H -phenyl- or - ^ - mothyl-1,3,5 ~ thladiazole, 2 ~ amino-5-phenyl-1,3, 'l ~ thiadiazal, 2-amino "3-nitro-5-methylGulfonyl-thiophbn,

209820/1062 BAOORIQtNAL

2-amino-3,5-bi.n- (methylfhilfonyl) -thiophen, 5-AMino-3- »ielhyl-lsoü" u.azole, 2 ~ Amino-ty-cyano-pyrazole, 2- (V-nitrophenyl) -3-amino -4 -cyanopyrazole, 3- or 4-aminophthalimide, aminobenzene,

l-amino ^ -trifluoromethyl-'i-chlorobenzene., l-amino-2-cyano - ^ - chlorobenzene, l-amino ^ -carbomebhoxy - ^ - chlorobenzene, l-amino ^ -carbomethoxy ^ -nitrobenzene ^ l-amino- 2-chloro - ^ - cyanobenzene, l-amino-2-chloro - ^ - nitrobenzo.l, l-Ainino-2-brorn - ^ - nibrobcnzol, 1-Am I η ο-2-chloro- ^J r -carba thoxybenzene , l-amino-2-chloro - ^ - methylsulfonyl benzene, l-amino-2-methylsulfonyl ~ h -chlorobenzene, l-amino ^^^ - dinitro-ö-methylsulfonylbGnzol, 1-amino-2, ^ - dinitro-6 - {2 '-liydroxyäthylsulfonyl) -benzene, l-amino-2,4-dinitro-6- (2'-chloroethylsulfonyl) -benzene, l-amino ^ -methylsulfonyl - ^ - nitrobenzene, l-amino ^ -methylsulfonyl- ^ -nitrobenzene ,.

1-amino-2, h- dinitrobenzene,

1 -Ami η ο-2-cyano-4 -inothylüulfonylbenzol, l-amino-2,6-dichloro - ^ - cyanobenzene,

2-cyano- ^/ l-chloroaniline _JU 2O9S2O / 1O62

2-Cyan-4-chloro-6- aibroman'ilin 2-Cyan - ^, 6-dibromani.lin,

BATH D ¹ '

l-Amino-n _J 6- (lLchlor- ^f l - nitrobenzene, 1 -Ami no -2 , h -d icyan -6 -chlorobenzene , ^ -amino-benzoic acid-cyolohexylester, l-ainino- ^ j ^ -dinitro -o-chlorbcnzol and especially 1-amino-2-cyano-h nitrobenzene, and also 1-Aminobenzole-, -3- or - * · -sulfonsäureamide how the x N Methyl7 or N, N-dimethyl- or! - Diethylamide, N, 7-Isopropyloxypropyl-2-aminonaphthaiine-6-sulfonic acid amide N ^ T-Isopropyloxypropyl-1-aminobenzene ^ -, -3- or - ^ - sulfonic acid amide

N-isopropyl-l-aminobenzene-2-, -3- or -k -sulfonic acid amide Nj ^ '- methoxypropyl-l-aminobenzoie-, -3 ~ or -h -sulfonic acid amide N, N-13is- (ß-hydroxyethyl) - l-aminobenzene-2-, -J> - or -ty-acid amide,

1-amino-2-h -chlorobenzene-sulfonic acid amide, and N-substituicrten derivatives 2-, 3- or ~ 'l-Aminophenylsulfamat, 2-amino - ^ -, -5- or -6-methylphenylsulfamate, 2-amino-5 -methoxy-phenylsulphamate, 3-amino-6-chlorophenylsulphamate, 3-amino-2,6-dichlorophenylsulphamate, ^J f-amino-2- or -3-methoxyphenylsulphamate, N, N -D line thy I -2-aminophonylr. ul f amat, N> N-Dl-11 -butyl -r? -; i! nlnophoiiy3:; ulfnmat, N, N -Dime thy 1-2 -amino - ¹ I -chlorphenylsulf amate,

N / n-Pi-Opyl ~ 'j -aminophenylsulfamat,

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BAD ORfQiNAL

N ^ N-Di-n-butyl - ^ - aminophcnylGulfaniatj 0 (3-Aminophonyl) -N-morpholine-N-.sulfonate O (3-Ami.nbphenyl) -N-pipcridine-sulfonate, N ~ CyolohGxyl-0- ( 3-aminophGnyl) sulfamate, N (N-methylaniline) -0- (3-aminophenyl) -sulfonate N ^ N-diethyl ^ -amino-o-methylphenyl-sulfamate, N-ethylenimine-0- (4-aminophGnyl) - sulfonate, NjN-dimethyl- ^ - aininophcnylisulfamat, O- (n-propyl) -0- (3 ~ aminophonyl) -sulfonat, 0, ß-chloroethyl-0- (2-aminophenyl) -sulfonat, 0-denzyl-0- (3-aminophenyl) sulfonate and 0 -Aothyl-0- (4-amino -2,6-dimethyl-phenyl) sulfonate,

■ a k

K -aminoazobenzole,

3.2 * ~ K dimethyl -aininoazobGnzol, 2-methyl-5-mGthoxy-4-aminoazobehzol, ^ - amino ^ -nitroazobenzol, 2,5-dimethoxy-4-aminoazobenzene, K '-methoxy-4-aminoazobenzene, 2-methyl -h '-inethoxy-4-aminoazobenzene, 3,6,4'-trimethoxy-4-aminoazobenzene, ^4? -Chlor-4-aminoazobenzene, 2 ¹ - or 3 '-chloro-4-aminoazobenzene, 3-nitro-4-amino-2' , h'-dichlorazobenzene and 4-aminoazobenzene-4 '-suiron.'iäurcamitl.

Instead of the above, from ion-sauced, water-solubilizing Groups of free diazo components can also

209820/10 BAD ORIGINS " cmo C-

those are used which have fiber-reactive groups contain, such as' s-triazinyl residues on the triazine ring 1 or 2 halogen atoms, also fluorine, chlorine or bromine atoms, carry pyrimidyl radicals containing one or two chlorine atoms or fluorine atoms or one or two arylsulfonyl or alkyl sulfonyl ■ carry groups on the pyrimidine ring, mono- or bis- (7 ~ halo-ßhydroxypropyl) -amino groups, ß-Halogenäthylsulfamylreste,

ß-IIalogenethoxy groups, β-Ilalogenäthy! mercapto groups, 2-chlorobenz thiazolyl -6-azo groups, 2-chlorobenzthiaz oly1-6-amino groups, 7-Haiogen-ß-hydroxy-propylsulfamyl residues, chloroacetylamino groups, α, β-dibromopropionyl groups, vinylsulfonyl groups and 2,3-epoxypropyl groups.

Suitable fiber-reactive diazo components are, for example, Niß-chloroethyl - ^ - chloro - ^ - amino-benzenesulfamide (hydrochloride), N ^ -Cliloroethyl - ^ - aminobenzene-sulfamide (hydrochloride), 3-bromine - ^ - amino-w-chloroacetophenone,
N ^ -Chlor-ß-hydroxypropyl - ^ - aminobenzene-sulfamide, N, ß-chloroethyl-l-amino - ^ - naphthyl3ulfonamid, N, β-chloroethyl-1-amino-3,5-dichlorobenzenesulfamide and ^ - ( γ-chloro-β-hydroxy-propoxy) aniline.

The diazotization of the diazo components mentioned, the position of the respective amino group accordingly, for example by means of mineral acid and sodium nitrite or for example using clin.'p 1.0, "UIiJ ^1;.. Vim Nl l.t'o .- 'y i- 1. cliworijliiäiu'o .In kon / .iMitrloi'lcr sulphurous acid.

The coupling can also be carried out in a manner known per se /

e.g. in a neutral to acidic environment, possibly in the presence

209820/1062

BAD ORiQtNM.

of sodium acetate or the like, the coupling speed influencing buffer substances or catalysts, such as dimethylformamide, pyridine or its salts, made will.

A precursor of the coupling component is obtained by adding 1 mol of one, if appropriate, to the aromatic nucleus substituted aniline condensed with 1 mole of chloroacetic acid on the nitrogen atom, and one mole of the adduct in the presence of Alkali condensed with 1 mole of ethylene chlorohydrin, with the azalactone of the formula

CH-CH
Ε-λ-W *

where A is the same as above, arises. This azalactone is made with an equimolar amount of a primary or secondary amine of the formula NHRR, condensed.

In this case, the ring oxygen atom is not exchanged while maintaining the ring structure, but rather an acyclic amide is formed with splitting of the azalactone ring. Because of this surprising mode of reaction of the lactone ring also succeeds in converting secondary amines. The reaction proceeds according to the equation

CH CH ₀ * CH ₀ CH ₀ -OH

HAN ^ * 'N) + NHRR> HA- / ^fc "

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If one uses the amines of the formula HNR 'Rp' in Anilines having ortho-position hydroxyl, amino or mercapto groups, condensation products are obtained which are can cyclize according to the following equation:

HA.-N R

CH ₂ CO N ^ X

A ^ - ^H 2 °

You can also prepare the coupling components required for the preparation of the above new dyes, by the haloalky! compounds, preferably ChIoralky! Compounds, the formula

wherein R ₂ , Y and B are the same as above, and Hal is a halogen atom, with monoalkylated anilines of the formula

H-A-N

^N R ^R l

converts, where A and R have the same meaning as above.

The reaction takes place e.g. in dry hydrocarbons at 80 to 150 C in the presence of tertiary amines Hydrogen halide acceptors.

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The invention therefore also relates to the amines of the formula

where A, R-,, R _? and Y have the same meaning as above, and preferably also the amines of the formula

A-N Jk

wherein A is an aryl radical, preferably an optionally substituted one Phenyl radical, Z a hydroxyl group, which is optionally esterified or etherified, or a halogen atom, in particular is a chlorine atom, and the ring B is aromatic, partially saturated or fully saturated and by halogen atoms, nitro groups and organic radicals can be substituted.

For the production of 2- (io-haloalkyl) -benzothiazoles, -oxazoles and -imidazoles are used in the ^ -position halogenated Fatty acid chloride or anhydride or such a fatty acid alkyl ester, optionally in the presence of a dehydrating agent, such as phosphorus pentoxide, with o-hydroxy, o-amino or o-mercaptoanilines.

The cyclic arylamines or azalactones used as starting materials are obtained from primary arylamines, e.g. Aniline, o-, m-, p-toluidine, 3,5-, 2,5- or 2,4-dimethylaniline, 2,5-dimethoxyaniline, o- or m-anisidine, o-isopropylaniline,

209820/106?

2., 5-dichloroaniliri, m-bromoaniline, o- or m-chloroaniline, Ethyl anthranilate, 3-nitro-aniline and 2-chloro-5-methyl-aniline through the implementation mentioned above.

The azalactones or the cyclic arylamines are reacted with the primary or secondary arylamines preferably in the presence of inert solvents such as cyclohexane, benzene or preferably higher-boiling, against Amines inert solvents such as toluene, xylene, 1,2-diethoxyethane, suIfolane, dimethyl sulfoxide and dioxane, at temperatures which are preferably above room temperature, in particular from 80 to 120.degree. The cyclization can take place in the same stage at 80 to 14o ° C or in a subsequent stage, with the deposited Waancr is constantly being removed.

The o-substituted anilines with which the azalactones are condensed include: o-phenylenediamine,
1,2-diamino-4-chlorobenzene,
1,2-diamino-3,6-dichlorobenzene,
l ^ -Diamino-jJjö-dibromobenzene,
1,2-diamino-J5, 5-dichlorobenzene,
l, 2-diamino-3 # 5 ~ dibromobenzene,
l, 2-diarnino-3-bromo-5-nltr.obenzene,
1, PI) I iinil ΐιο ~ Ί -nu'l.hv 1 Ιημι ·; ο1,
1,2-diamino-2-methylbenzene,

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1,2-diamino-'f, 5-dimethylbenzene, 1,2-diamino-Ί-nicthoxybenzene, 1,2-diamino-3-methoxybenzene, 1,2-diamino-4,5 ~ dimethoxybenzene, 1,2-diamino-4-ethoxybenzene, 1,2-diamino-3-phenoxybenzene, 1,2-diamino-4-nitrobenzene, 1,2-diaminonaphthalene, 2,3-diaminonaphthalene, 1,8-diaminonaphthalene, 3,4-diaminodiphenyl,.

1-amino ^ -hydroxybenzene, l-Amino-2-hydroxy-5-chlorobonzene, 1 -Ληιΐηο-2-hydroxy ~ 3,5 ~ d i chi or benzene, l-amino-2-hydroxy-3,5 ~ dibromobenzene, l-amino ^ -hydroxy-S-nitrobenzene, l-amino-2-hydroxy - ^ - nitrobenzene, l-Amino ^ -hydroxy - ^ - nitro-S-chlorobenzene,

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lA! nino-2-hydroxy-3-chloro-5-nitrobenzene, 1-ami no -2 -hydroxy ^ -nitrobenzene, 3-ainino-2-hydroxy-3i5 ~ dinitrobenzene, 1-amino-2-hydroxy-6- chlorobenzene, 1-amino-2-hydroxy-4-chlorobenzene, 1-amino-2-hydroxy- h , 6-dichlorobenzene, 1-amino-2-hydroxy-3i5iss-trichlorobenzene, 1-amino-1-hydroxy-o-nitrobenzene , 1-amino-2-hydroxy ^ -chloro ^ -nitrobenzene, 1-amino-2-mercapto-4 -chlorobenzene, l-AuiLno-2-morcnpto-3>! 3 -dich lor benzene, l-amino-2-mercapto-5-nitrobenzene and l-amino-2-mercapto-4-nitrobenzene, 1,2-diamino- cyclohcxan.

209820/1062

6AD ORIGIWAL

The residue PU becomes, if R is an acyl group i :: t, a · performed by subsequent acylation of the p-Hydr ^ xygruppe. As acylating agents in Fra.'ve come:

aliphatic acid chlorides, such as Aeovy! chloride ? vo pionyl chloride, a-bromoaryl acid chloride or bromide n-butyryl chloride> crotonic acid chloride, 2-methylniercaptopropionyl chloride,. 4-chlorobutyryl chloride, araliphatic carboxylic acid halides, such as phenylacetyl chloride or p-nitrophenylacetyl chloride, cycloaliphatic acid chlorides, such as cyclobutanecarboxylic _{acid chloride ^ 5- * norbornene-2-carboxylic acid chloride i} aromatic carboxylic acid chlorides such as benzoyl chloride, o-, m- and p-ethyl carbonate, o- and m- and p-methoxy and ethoxybenzoyl chloride, 1- or 2-naphthalenecarboxylic acid chloride, 3 # ^ -dinitrobenzoyl chloride ^ 2, ¹ J- or ~ 5, 'l-dichlorobenzoyl chloride, p-phenylazobenzoyl chloride, 2-' anthraquinone carboxylic acid chloride, heterocyclic carboxylic acid halides, such as furan halides -2-carboxylic acid chloride, 2-thenoyl chloride, 2-thienylacetyl chloride and nicotinic acid chloride and carboxylic acid anhydrides, such as acetic acid anhydride, n-butyric anhydride, isobutyric anhydride, cyclobutanecarboxylic anhydride, benzoic anhydride, p-chloranic anhydride anhydride and nicotinic anhydride anhydride, 2-chloroic anhydride.

Mixed anhydrides can also be used, such as the anhydrides of acetic acid and benzoic acid or ß-naphthoic acid, usually mixtures of dyes ent-gtehon.

Gu ^ i) bo new Ta ll: i can also be translated from üen froien üiiui'on go out when the acid halide or the anhydride are difficult to access.

• 209820/1062

BATH

-H-

As starting materials for the erf indun £ 3; _:; E; rrls: se reaction suitable · sulfonic acid halides are Benzolsulfor.fiäurechlorid, o- and p-toluene sulfonic acid chloride, ^{^;} l-, 2, $ - or 3,5-DiiriOthyl-bunzenesulfonsMurechlorid, 3>^{; |} > 5 or ^2; ·., O-triir, ethylbenzenesulfonic acid chloride, tetralin-T-sulfonic acid chloride, p-nitrober, benzenesulfonic acid chloride, 2-methyl-5-chloro-benzenesulfonic acid chloride, $ -methyl-thiophene-2-sulfonic acid chloride and foethanesulfonyl chloride.

Instead of the chlorides, it is also possible, if appropriate, to use fluorides, bromides or iodides of the acids.

The acylation is conveniently carried out by heating in an inert organic ¹ solvent, for example halogenated hydrocarbons such as carbon tetrachloride, 1,2-Aethylenohlorid, chlorobenzene, o-Dichlorbonzol, nitrohydrocarbons ^ such as nitrobenzene or Nitronaphthaiin, and carbon disulfide.

The reaction can take place at room temperature or below, but also at a slightly elevated temperature.

Examples of reactive carbonic acid derivatives are in question:

ClCOSC H _r CICOSCH ₂ CH ₂ Ci

ClCOOC H ClCOOCH ₂ CH Cl

CICONHC _O H _C 2 5

ClCONHCH ^ CH ^ Cl

ClCOSCH _p CH _,? OCH ClCOOCH ₀ CH ₀ OCh '

CICOSCh ₂ CH ₂ OCH 'ClCOOCn ₀ CH OOCCIL

ClCONHCH ₀ Cn ₀ OCH

ClCOSC

ClCOSC _r H _; .OCIL,

C1COSC ^ H ,, C1 ο 4

ClCOOC ₆ H ClCOOC ₆ H ₄ OCH

ClCOOC ₆ H ₄ Cl BAD ORIGINAL

ClCONHC _r H _r 6 5

CICONHC ^ L.OCIL. whether!>

ClCONHC Ai ,, Cl

into consideration. Further acylic agents are the alkyl and aryl isocyanato and heterocyclic isocyanates, such as, for example, Methyli socyar.3 ", Ao'cr.y 1 isocy ana ζ, η-Propy 1 i socyana t, r.-3u: y 1 isocy ?. rs ζ, Oc ty 1 isocyanate Ke thy 1-isocy ana toace tat, butyl-isocyor.atoacetat, cyclohexyl isocyanate, -phenyl isocyanate, p-tolyl isocyanate> o-, ir.- and p-chlorophenyl isocyanate, m- and p- nitrophenylisocyar.at, 2,5-Dichlorpr.ony.lisocyanatj o- and p-Mcthoxyisocyanat, 2-Ka ph thy I-isocyanate i-iMphonyliüocyanat, 2-Isocyanatotetrahydropyran, Tetrahydrofurfurylisocyanate 3-Isocyanat-pyridine, 2-? UryliGo-, cyanate ^ -Isocyanato- N-ethyl carbazole and preferably isocyanates

sulfur-containing heterocycles such as 2-carbornethoxy-3-isocyanatothiophene, 2-isocyanato - ^ - cyano-thiophene, 2-isocyanato-3-carbomethoxy - ^ - methyl-thiophene "ne 2-isocyariato-5-methyl-thiophene - ^ -. 2- _{carboxamides.} Ir _J ocynnato-5-carboiriethoxy- ^ e ^ -diinethyl thiopher-2-isocyanato-j5-carboäthüxy-3i ^ -tetramethylen-thiophene ^ and -Isocyanato-sulfolane; and isothiocyanates of the formula

Z-N-C = S, like

Ethyl isothiocyanate, n-butyl isothiocyanate and phenyl isothiocyanate

It is particularly advantageous to add small amounts of organic bases such as aniline, methyl aniline, Pyridine etc.

209820/1062
BATH ORIGINAL

Those of the above-mentioned heterocyclic diazo components which have a quaternizable nitrogen atom, can also be in N-alkylated form as hydrazones or are coupled oxidatively as azo sulfones [cf. Angewandte Chemie, Volume 7Ό, 215 (1958); Vol. 74, 818 (1962); Volume 80, 343 (1968)].

Those among the new compounds which contain a quaternized amino group can (1) in the manner can be obtained by treating the corresponding dyes which contain a non-quaternized amino group quaternized with alkylating agents; (2) by using quaternized coupling components, in particular those with aliphatic or cycloaliphatic ammonium groups, or by having already quaternized coupling components with benzoxazolium, benzimidazolium or benzthiazolium groups to the clutch.

As an alkylating or quaternizing agent, can you can use, for example: the methyl, ethyl, hydroxyethyl, cyanomethyl, n-propyl, η-butyl, ß-cyanoethyl, benzyl esters of hydrogen chloride, hydrogen bromide, hydrogen iodide, dimethyl and dimethyl sulfate, methyl, β-chloroethyl, Ethyl and butyl esters of benzenesulfonic acid or p-toluenesulfonic acid, also the alkyl bromoacetate (with an alkyl radical of preferably 1 to 4 carbon atoms) in Consideration. Other alkylating agents are the following halogen

209820/106? BATH

Hydrogen esters: hexyl bromide, benzyl bromide, chloroacetonitrile, chloroacetamide, methyl 2-chloro-propionate, 3-chloro-propene, 2-chloro-ethanol, 3-chloro-propanol, 6-chloro-hexanol, glycerol-chlorohydrin, glycerol-dichlorohydrin and 3-methoxypropyl chloride. Instead of certain substituted alkanol esters, their precursors can also be used, for example acrylonitrile or acrylamide in the presence of hydrogen chloride or hydrogen bromide instead of ß-cyanoethyl or ß-carbamoylethyl chloride or bromide. However, the preferred quaternizing agent is dimethyl sulfate or benzyl chloride.

Depending on the quaternizing agents used, the "alk" radical can be, for example: methyl, ethyl, propyl, η-butyl, n-pentyl, n-hexyl, 1-hydroxyhexyl, / 3-hydroxyethyl, chloroethyl -, cyanoethyl, H ₂ N-CO-CH ₂ -, Cl-CH ₂ -CH (OH) -CH ₂ -, benzyl and methylbenzyl, 3-hydroxypropyl, carbamoylethyl, 3-methoxypropyl, Carboxymethyl'äthyl- and Propenylreste.

209820/106?

Anion A is understood to mean both organic and inorganic ions, e.g. halogen, such as chloride, bromide or iodide, alkyl sulfate, sulfate, disulfate, perchlorate, phosphotungstate, phosphotungstate, benzene or Naphthalene sulfonate, 4-chlorobenzenesulfonate, oxalate, maleate, Acetate, propionate, methanesulfonate, chloroacetate, toluenesulfonate or benzoations.

These anions introduced according to the method can also be replaced by anions of other acids, for example phosphoric acid, Acetic acid, oxalic acid, lactic acid, tartaric acid, maleic acid, crotonic acid, citric acid, nitric acid or benzoic acid replaced will. The dyes can also be isolated in the form of the complex salts with zinc or cadmium halides.

The alkylation is expediently carried out by heating in an inert organic solvent, for example Hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as carbon tetrachloride, tetrachloroethane, Chlorobenzene, o-dichlorobenzene, or nitrohydrocarbons, such as Nitromethane, nitrobenzene or nitronaphthalene. Also acid anhydrides, Acid amides or nitriles, such as acetic anhydride, dimethylformamide or acetonitrile or also dimethyl sulfoxide, can be used as solvents in the alkylation. A large excess can also be used instead of a solvent to use alkylating agents. In this case, however, care must be taken that the mixture does not over-

209820/1062

heated moderately, since the reaction is strongly exothermic. Nevertheless it is in most balls, especially in the presence of organic ones Solvent, necessary to remove the reaction mixture from the outside heat to start the reaction. In special cases, the alkylation can also be carried out in an aqueous medium or under Use of an alcohol, possibly in the presence of small amounts of potassium iodide.

If necessary, the salts are expediently purified by dissolving them in water, but not at most converted starting dye can be filtered off as an insoluble residue. From the aqueous solution can through Adding water-soluble salts, for example sodium chloride, causes the dye to be deposited again.

The non-quaternized dyes are usually insoluble in water.

The new compounds, their mixtures with one another and their mixtures with other azo dyes are excellent for dyeing and printing leather, wool, silk and especially synthetic fibers, such as acrylic or acrylonitrile fibers, Polyacrylonitrile fibers and copolymers made from acrylonitrile and other vinyl compounds, such as acrylic esters, Acrylamides, vinyl pyridine, vinyl chloride or vinylidene chloride, copolymers from Dlcyanäthylen and vinyl acetate, as well as from Acrylonitril-Blookmi.sehpolyineron, fibers made of polyurethane, polyolefins, such as base-modified, nickel-modified or unmodified polypropylene, cellulose triacetate and 2 l / 2-acetate

209820/1062

BATH ORIGINAL. .

and in particular fibers made from polyamides, such as nylon-6, nylon-6,6 or nylon 12, and from aromatic polyesters, such as those made from terephthalic acid and ethylencnglycol or l, h -dimethylcyclohexane, and copolymers made from terephthalic and isophthalic acid and ethylene glycol.

For dyeing in aqueous liquors, the water-insoluble dyes are advantageously used in finely divided form Shape and color with the addition of dispersants, such as sulfite cellulose waste liquor or synthetic detergents, or one Combination of different wetting and dispersing agents. As a rule, it is useful to specify the dyes to be used to convert the dyeing into a dye preparation that contains a dispersant and finely divided dye in such a form, that when diluting the dye preparations with water a fine Dispersion arises. Such dye preparations can be used in known way, e.g. by grinding the dye In dry or wet form can be obtained with or without the addition of dispersants during the milling process. After wet grinding is obtained by subsequent drying from the textile auxiliary and dye preparations consisting of the dye.

209820/1062

BATH ORIGINAL.

For example, dispersants of the non-ionic group which can be used advantageously are mentioned: addition products of 8 mol of ethylene oxide with 1 mol of p-tert.-octylphenol, of 15 or 6 mol of acetylene oxide with castor oil, of 20 mol of ethylene oxide with the alcohol C-, 5 ^ 33 ⁰¹ U ethylene oxide addition products to di- [a-phenylä'thyl! -Phenole, poly-. Ethylene oxide tert. -dodecyl-thioather, polyamine-polyglycol- • ÜCher or addition products of 15 or 30 moles of ethylene oxide to 1 mole of Ami η Cj- ^ rNHo or Q ^ pli ^ yNII ^ ·

The following may be mentioned as anionic dispersants: sulfuric acid esters of alcohols of the fat series with 8 to 20 carbon atoms, of the ethylene oxide adducts - of the corresponding fatty acid amides, or of alkylated phenols with 8 up to 12 carbon atoms in the alkyl radical; Sulfonic acid ester with Alkyl radicals having 8 to 20 carbon atoms; Sulfation products of unsaturated fats and oils; Phosphoric acid ester with alkyl radicals having 8 to 20 carbon atoms; Fatty acid soaps, also alkylarylsulfonates, condensation products of formaldehyde with naphthalenesulfonic acid and Lignosulfonates. · ··

Suitable cationic dispersants are quaternilre Ammonium compounds ^ - / elche alkyl or Ai'alkylrest with Contain 8 to 20 carbon atoms.

Di.c! Karkh:; lof fprliparate künnon xuüät :;] I preferably to the DLspergatorcn more organic solvents, in particular, above 100 ⁰ C boiling solvents which

209820/1062

BAD ORfQiNAL

are miscible with water, such as mono- and dialkyl glycol ethers, Dioxane, dimethylformamide or acetamide, tetramethylene sulfone or dimethyl sulfoxide. One can advantageously dye, Grind the dispersant and solvent together. It is also possible to use only solvents instead of the dispersant; at least, however, the dye preparations contain either a dispersant or a solvent.

The dyeing of the polyester fibers with the inventive Dyes that are sparingly soluble in water from aqueous dispersion are carried out in accordance with those customary for polyester materials Procedure. Polyesters of aromatic polycarboxylic acids with polyhydric alcohols are preferably dyed at temperatures of over 100 C under pressure. The color can also be at the boiling point of the dyebath in the presence of dye carriers, for example phenylphenols, diphenyl polychlorobenzene compounds or similar aids are carried out or according to the thermosol process, i.e. padding with subsequent aftertreatment carried out in the heat, e.g. thermosetting, at 180 to 210 C. will. Cellulose-2 V2 acetate fibers are preferably dyed at temperatures of 80 to 85 ° C, while cellulose triacetate fibers with advantage at the boiling point of the dye bath to be colored. When dyeing cellulose-2 1/2 acetate or polyamide fibers, there is no need to use color transfer agents. Azo dyes according to the invention can also can be used for printing the materials mentioned by customary methods.

209820/1062

The padded is used to heat-set the dye Polycstorgewobo, two-in-one after drying, κ.13. in a warm air stream, at temperatures of over 100 C, for example between 180 to 210 ° C, heated. · · ·

The dyeings obtained according to the present process can be subjected to an after-treatment, for example by heating with an aqueous solution of an ion-free one Detergent. '..

Instead of impregnating, according to the present Method the specified compounds can also be applied by printing. For this purpose one uses e.g. a Printing inks which, in addition to the auxiliaries customary in printing, such as wetting agents and thickeners, are finely dispersed Contains dye.

Furthermore, one can e.g. in organic solvent-

color brisk, as in pcrcliloriithylen or in a mixture of Perehloroethylene and 5 to 10 $ dimethylformamide or methanol.

The present process gives strong dyeings and prints with good fastness properties, especially good ones Thermosetting, subliming, pleating, smoke gas, over-dyeing, Dry cleaning, chlorine and wet fastness, such as water, wax and blackness.

209820/10 62

Han can also use the new water-insoluble compounds for spin dyeing polyamides, polyesters and polyolefins. The polymer to be colored is expediently finished in the form of powder, grains or chips
Spinning solution or mixed in the molten state with the dye, which is introduced in the dry state or in the form of a dispersion or solution in an optionally volatile solvent. After homogeneous distribution of the dye in the solution or melt of the polymer, the mixture is processed into fibers, yarns, monofilaments, films, etc. in a known manner by casting, pressing or extrusion.

In the following examples, unless otherwise stated, parts are parts by weight, percentages are percentages by weight, and temperatures are in
Degrees Celsius. Parts by weight and parts by volume relate to one another like grams and milliliters.

209820/106?

Horst, οΊ1 un; ¹ ; dor Knpplunf.r.komporionten. Regulation 1.

a) 11.0 parts of o-phenylenediamine are added to a solution of 1- (m-tolyl) -3-oxomorpholine (19.1 parts) in 100 parts of dry xylene. The mixture is refluxed for 18 hours, water being continuously removed by means of a water separator. After cooling, it is filtered off. N- (β-II-hydroxyethyl) -N ~ (benzimidazolyl -2-methyl) -m-toluidine (melting point 198 ° to 200 °) of the formula is obtained

CH ₀ CH ₀ OH
2 2

^S CH cf Y)

CH,

> H

b) Acetyl icrunp ;.

20.0 parts of acetyl chloride are added dropwise to a solution of 16.8 parts of N- (β-hydroxyethyl) -N- (benzimidazolyl-2-methyl) -m-toluidine in 150 parts of dry pyridine , the solution being kept below 10 ° will. The mixture is stirred for 16 hours and then reduced to a concentration of conc. Hydrochloric acid acidified mixture of ice and water poured. The mixture is extracted three times with ether and the acthere extract is washed with water. Evaporation of the ether gives a residue, which after recrystallization

aqueous methanol, the acetic acid center of the formula

209820/1062

BAD ORJÄAL · - ^ "** -? *

CH ₀ CH ₀ OCOCH,
2 2 3

CH .. ^d

results, which has an Fp- of 186 to 18y.

c) The implementation of the N-hydroxyethyl compound carried out with a mixture of benzene and triethylamine Benzoyl chloride gives the analogous benzoyl ester {pp. 190 bis

d) The reaction of the N-hydroxyethyl compound with Phenoxyaeetylchlorid in dry pyridine gives the analogous phenoxyacetyl ester (pp. 156-157 °).

209120/1082

BAO OBIOINAL

Regulation P ..

a) Replace the ο-phenylenediamine in regulation 1 by the equivalent amount of 1,2-diamino-cyclohexane, see above the compound of the formula is obtained

CH ₀ CH ₀ OH _w t / 2 2 N

J ₀ σ

CH, ^{d X 5} H

which has a pp. from 155 to 156 °,

b) Acetylation in dry pyridine gives the ethyl acetate, which is used in the form of the semi-solid product will.

Yorso lift f,

a5 If you replace the 1- (Hi-ToIyI) -3 "in rule 1 morpholine by the equivalent amount of l-phenyl-3-oxomorpholine, thus one obtains the compound of the formula

CH ₀ CH ₀ OH _w 2 2 N

H P.Ü2 bli-ϊ 201 °,

209820/1062

BADORFOIN

b) Etylation with acotyl chloride / pyridine gives the acetic acid ester, (m.p. 222-223 °).

c) Bensoylation with benzoylochloride / benzene / triethylamine gives the benzoic acid ester ^ mp. 176 to 177 /

Regulation 4.

a) To a solution of 19 * 1 parts of l- (m-tolyl) -3-0x0-morpholine 12.0 parts of o-aminophenol were added in 200 parts of dry benzene. The mixture is for 18 hours boiled on reflux. After cooling, the precipitated product is filtered off and recrystallized from benzene. Man receives N- (ß-hydroxyethyl) -N-io-hydroxyphenyl-carbamoylmethyl) -m-toluidine, Mp. 121 to 122 °, whichever of the formula

is equivalent to.

b) The above carbainoyl derivative (16.0 parts) is refluxed for 70 hours in 350 parts of dry xylene together with 3 * 0 parts of boric acid, the water that is formed being continuously dissolved. Dar, xylene is then mixed with water

209820/1062

BADORlGiNAC; : ,,; *

evaporated., the residue shaken up three times with ether and the collected ethereal extract dried over anhydrous sodium sulfate. After the ether has evaporated, the The residue is distilled in vacuo. N- (β-hydroxyethyl) -N- (benzoxazolyl-2-methyl) -m-toluidine is obtained (Kp. 2 ^ 0 to 255 ° / 5 mm Hg) the formula

CH ₀ CH ₀ OH

ch

cn ²

c) Acetylation with acetyl chloride / ßenzene / triethyl amine gives the acetic acid ester (bp 235 to 245 ° / 4mm Hg).

d) Acylicx'ung with phenoxyacetyl chloride in pyridine gives the phenoxy acid ester in oily form is used.

209820/1062

BATH ORIGINAL Procurement p.

a) If you work as in procedure K, but using 1-phenyl-3-oxomorpholine instead of l- (m-tolyl) -3-oxomorpholine ', you get N- (β-hydroxyethyl) -N- ( ο-hydroxyphenylcarbamoylmethyl) aniline, m.p. 117 > which of the formula

CH ₀ CII ₀ OH ^{2 2}

^N CH —C — HN »

is equivalent to. ·.

b) If the cyclization is carried out as described in the instructions, N- (β-hydroxyethyl) is obtained after the distillation N-benzoxaxolyl-2-methyl) aniline of the formula

CH ₀ CH ₀ OH

^{2 2}

Kp. 233 to 2 ^ 0 ° / l >> '"Hg.

c) Acetylation in dry pyridine gives after

tier IViU. Π l; it. I on don Kjw. i tfrwiuroor.ter (Kp. ^ O bL: .i 2 $ 5 ° / l mm

2 0 9 8 20/1062 BATH ORIGINAL

d) Dcnr.oylation in troeknom pyridine gives the Benzoic acid ester φ "ρ. 10'3 to 104).

e) The reaction with phenoxy-acetyl chloride in dry Pyridine gives the phenoxyacetic acid ester, which is obtained as an oil.

Regulation 6.

a) 37 * 5 parts of o-aminothiophenol are added to a solution of 57 > 3 parts of 1- (m-tolyl) -3-0x0-morpholine in 350 parts of dry benzene. The mixture is refluxed for 24 hours. It is then refluxed for a further 24 hours, but with separation of water. After evaporation of the solvent, the residue is distilled in vacuo. N- (β-hydroxyethyl) -N- (benzthiazolyl- '2-methyl) -m-toluidih (boiling point 230 to 235 ° / 0> 8 mm Hg) of the formula is obtained

, CH ₂ CII ₂ OH _N

X)

\ ₂

CH ₃ ^ ^N S

b) Acetylation in pyridine gives the acetic acid ester (Kp. 238 bia ^ IO ° / O.9 now ed.)

c) Hen'zoylation with Bcnr.oylchlorid / pyridine gives (ion Ueni'.oor.nui'tMT.tci '(Kp. 93 hit; ^) H ⁰ ).

209820/1062 BAD ORlGINAl.

Regulation 7.

N- (fl-Benzoyloxyethyl) -N-benzoxazolyl-2-methyl) -m-toluidine

N- (β-hydroxy-ethyl) -N-benzoxazolyl-2-methyl) -m-toluidine (25 parts) are esterified with benzoyl chloride (42 parts) in 200 ml of pyridine, stirred for 16 hours and poured onto ice water and worked up. After recrystallization from dilute Ethanol gives 20.0 parts of the benzoyl ester (melting point 91 ° -92 ° C.).

Regulation 8.

Proceeding as in regulation 7, but using ethyl formic acid ester, N - (/ 3-ethoxycarbonylethoxy) -N- (benzoxazolyl-2-methyl) aniline is obtained as a viscous oil.

Regulation 9.

Proceeding as in regulation 7, but using butyl isocyanate as acylating agent, one obtains N- (β-butylcarbamoyloxyethyl) -N- (benzoxazolyl-2-methyl) aniline as a viscous oil.

209820/1062

Regulation 10.

a) Equivalent amounts of 2-amino-4-ehlophenol and l-Phenyl-3-oxo-morpholine are left in benzene for 24 hours Boiled under reflux. After cooling and recrystallization from dilute ethanol, N- (β-hydroxy-methyl) -N- (Z-hydroxy - ^ - chlorophenylcarbamoylmethyl) aniline is obtained (Mp. 154-155 °)

b) The compound obtained above was dissolved in dry xylene, in the presence of boric acid under reflux with a water separator boiled until there was no more water. After working up, a solid residue is obtained from the aqueous Ethanol crystallizes (mp. 123) and the formula

CH ₂ GH ₂ OH
- N .N. - ^cl

yuj η

^{2 x}

is equivalent to.

Example 11 .

Acylation of the compound of the formula above with acetyl chloride in pyridine gives the acetyl ester, an oil that can be distilled at 228 / 0.4 mm Hg.

2 09820/1062

Example 12 .

a) If one sets 1- (2 ', 5' -Dimetnoxyphenyl) -3-oxomorphDlin as in regulation 10 ä) and 2-aminophenol, the compound of the formula is obtained

OCH ₃

OCH ₃

with a melting point of 124-125 °.

b) The cyclization takes place as in regulation 10 b) and gives the oily benzoxazolyl compound, which at 225/3 rani Hg can be distilled.

Example 13 .

Acylation of the benzoxazolyl compound obtained above gives the acetic acid ester, which after recrystallization from ethanol melts at 80.

Example 14 .

If you boil a xylene solution, which in Example 12 b) The compound obtained and thiophenol contains, for 24 hours, the oxygen atom in the benzoxazole ring is replaced by sulfur

209820/1062
BATH ORIGINAL

replaced and one obtains the compound of the formula

as OeI (bp 26O ° / l ram).

Example 15 .

The compound obtained in Example 14 is acylated with acetyl chloride in pyridine, the acetic acid ester is obtained, which after recrystallization from ethanol at 76-77 ° melts.

Example 16.

N- (/ 3-hydroxyethyl) -N- (benzthiazolyl-2-methyl) -m-toluidine is acylated with Phenoxyace ty 1 chlorid, the phenoxyacetic ester is obtained as a viscous oil.

Regulation 17.

If you boil 1-phenyl-3-oxomorpholine and 2-aminothiophenol in xylene with a water separator for 24 hours, then, after steam distillation and work-up, the

209820/1062
ORIGINAL BATHROOM

oily compound of the formula

O <^ - <

which box 235 / 0.5 is distilled in Hg.

Regulation 18.

Acylation of the compound obtained according to regulation 17 with acetyl chloride in pyridine at less than gives the oily ethyl acetate, which at 235-240 / 1.0 mm 11g is distilled.

Regulation- 19.

If the same starting material is acylated with benzoyl chloride, in this way the solid benzoyl ester is obtained, which, after recrystallization from ethanol, melts at 124-125.

Regulation 20.

Analogously to instruction 18, one obtains with phenoxyacetyl chloride the phenoxyacetic acid ester, which after recrystallization from methanol at 77-78 °.

2 0 9 8 2 0/1 0 fi

BATH

Regulation 21 ..

26.1 parts of triethylamine are added to a mixture of Ν, β-cyanoethyl aniline (15.2 parts) and 2-chloroethylbenzoxazole (23.2 parts) in 200 parts of dry toluene and the mixture is placed in an autoclave for 24 hours 125-130 heated. After adding 200 parts of ether, the cooled mixture is dried over sodium sulfate, evaporated and heated in vacuo in order to remove unreacted material. Recrystallization of the residue from dilute ethanol gives the compound of the formula

, CH ₀ CH ₀ CN / V / 22

O-ν

^N 'CH ₉ C

in a yield of 14 parts (melting point 101-102 °).

Regulation 22.

N-benzyl-N- (benzoxazolyl-2-methyl) aniline (melting point 93 ° -94 °) is prepared in exactly the same way as in instruction 21.

Regulation 23.

N-ethyl-N- (benzoxazolyl-2-methyl) aniline is prepared in exactly the same way as in instruction 21, x ^ elches is obtained as a viscous oil.

209820/1062

BATH ORIGINAL

Regulation 24.

In exactly the same way as in regulation 21 N-ethyl-N- (benzojcazolyl-2-methyl) -in-toluidine as viscous OeI received.

Regulation 25-

In exactly the same way as in Regulation 21 N-ethyl-N- (benzoxazolyl-2-methyl) -m-nitro-aniline produced, which is obtained as a viscous oil. 5 parts of this compound are dissolved in 50 parts of acetic anhydride and hydrogenated at 45-50 with Raney nickel as a catalyst. The catalyst will filtered off and the mixture poured onto ice water and finally neutralized with sodium carbonate. The separating Oil is extracted with ether and dried over sodium sulfate. After evaporation, a viscous oil is obtained the formula

NH-CO-CH ₃

Regulation 26.

N-ethyl-N- (benzimidazolyl-2-methyl) -m-nitroaniline is prepared in exactly the same way as in instruction 21 (Fp. 219) .üie connection is dissolved in ethanol and mixed with

209820/1062

Raney nickel hydrogenated and worked up as in regulation 25, The compound is obtained after recrystallization from benzene the formula

N _CH C

NiH

NH ₂

with fp. 212. Dissolve the last-mentioned compound in acetic acid and add twice the amount of at room temperature Acetyl chloride is added, and N-ethyl-N- (benziraidazolyl-2-methyl) is obtained -m-acetylamino-aniline (mp. 266) -

Regulation 27.

Obtained from 2-chloromethyl-benzothiazole and N-ethylaniline one, exactly as described in regulation 21, N-ethyl-N- (benzthia zolyl-2-methyl) aniline, which is obtained as a viscous oil,

Regulation 28.

Proceeding as in regulation 27 and using N-ethyl-m-toluidine instead of N-ethylaniline, N-ethyl-N- (benzthiazolyl-2-methyl) -m-toluidine is obtained as a viscous oil.

Regulation 29.

N-ethyl-N- (benzthiazolyl-2-methyl) aniline (8.04 Parts) is dissolved in 250 parts of chlorobenzene. At 90 ° it becomes

209820/1062

a solution of freshly distilled dimethyl sulfate (6.5 parts) in 30 parts of chlorobenzene was added dropwise. The mixture is then stirred at 115-120 ° for 6 hours. After cooling, it is filtered off and the filter cake dissolved in 200 parts of hot water and filtered. The filtrate contains the coupling component the formula

, —N

CIL

—C

and is used telquel to clutch.

CH ^ SO ₂ ,

209820/1062

11 ⁿ rntoiluni ¹ ; fier azo compounds.

Be j.s nt el 1.

1j73 parts of 2-chloro-4-nitroaniline are used by Zimmer temperature with nitrosylsulfuric acid diazoticrt, which consists of 20 parts by volume of concentrated sulfuric acid and one part Sodium nitrite is produced. The reaction deletion will Discharged on an ice-water-Gcrnisch. After the nitrous acid has been destroyed by adding urea, the solution becomes filtered and at 5 to 10 ° with 3.23 parts of N- (ß-acetoxyethyl) -N- (bcnziinidazolyl-2-methyl) -tn-toluidine coupled in 200 parts of ethanol and stirred for a few hours until the

Clutch has ended. The solution, which is kept below 10, is brought to a ρ value by adding ^ n sodium acetate solution blunted by 4. The dye is then filtered off and washed with water. The dye can be dissolved by dissolving in acetone and precipitates with water. He corresponds to the formula

CH _o CH _o 0C0CH " _w

-NN ^ ^- VN / ^{2 2 5} / ■

and dyes polyester fibers in scarlet shades with aur, -go ", (? h'hnotoM Ι'ΛϊΙιΙ, ΙιοΠ-, ρη.

209820/1062

BATH ORIGINAL

The following dyes were produced in exactly analogous catfish, which polyester fibers in the specified Color nuances.

dye

nuance

O ₂ N- / VN = N

Cl

.CH ₂ CH ₂ -CN

- / V-N = N

N \

CIL

CN

reddish orange

Red

209820/1062

Example 2.

If 2-cyano-4-nitroaniline is used as the diazo component, which is diazotized as in Example 1, but with the addition of 5 parts by volume of acetic acid, so one obtains the Dye of the formula

CH ₀ CH ₀ O-COGH ^{2 2}

CN CH * ^N

^ H

which polyester fibers bluish red with excellent Dyes fastness properties.

The azo dyes mentioned in the table below are obtained in an analogous manner if the Diazonium compound of the diazo components indicated in column I with the coupling components indicated in column II clutch. The dyes dye polyester fibers in the shades given in column III.

209820/1062

2, 6-dichloro-4 · nitroaniline

! 5

! V

10

2-Βτοΐπ — 1 -iii t.ro-6-cyan: mi Lin

4-Nitroan Llin

2 -Am ino -5 - phe ny 1 1 j 3, 4-thiadi azole

2-amino-4-phenyl-1,5,5-uiiadiazole

2-Ciilor-4-nitroaniline

2,6-Diehlor-4-nj. l.roaniline

2 - Gy ; i: -. - ', - nil ro aniline

4-nitroaniline

2 -B ro :: - ί -η i I r ο - 6 cyananiline

2 -: ·: ο t.i ·.;, · 1;.; i; 1Γ ο ny 1 <i -ni troani lin

II

CH ₀ CH _n OCCCH I 2 2.

<Z> N Γ I

2 2

• N

CLL.

CH-C

² Ni H

209820/1062 ORIGINAL BATHROOM

III

yellow-brown

violet

orange scarlet

Red

Red orange

red-violet yellow Red

blue violet blauroca

2-chloro-4-nit.roaniline

CH CH ₀ -C H 2-cyano-4-nitro Il to il in 2,6-dichloro-4- It nicroaniline

2-Bromo-4-nitro-6-cyananiline

2-chloro / 1-inothylsulfonylaniline

2-Clilor · - /! , 6-diniLroaniline

4-Ni Lroaniline

2-chloro-4-nitroaniline

2-cyano-4-nitroaniline

2-chloro-4-nitroaniline

II

CH _o CH _o 0C0CH _o CKZI> ι c 2 2 -

A ^ -S V Al «\ y W V N- / AA λ \

CH ₀ CH ₀ OCOCH. ι 2 2

■ Ν

I • '

CH-C

CH ₀ CH ₀ OCOCH, ι 2 2 3

III

Red

rob

Red orange

purple orange
rolvi.o.'l cLt rotorarigo

yellowish tinge pink

blauroca

yellow Red

209820/1062

6AD ORIGINAL

22nd

II '

in

25th

24

25th

26th

27

2,6-dichloro-4-! nitroaniline

- ι

2-cyano-4-nitroaniline

4 — Ni troaniline

2-Bromo-4-Ni i; ro-6-cyananiline

2-methylsulfonyl-4-nitroaniline

2-chloro-4-nitroaniline

2, C-dichloro-4-nitroaniline

2-cyano-4-nitroane ilin

4-nitroaniline

2-Bromo-4-nitro-6-cyananiline

P-Xtj Uiyi mil fonyl 4-n i Lroani 1 in

CH ₂ CH ₂

gh-c

Red orange

blue red

Red orange blue pink

blue-red yellow-red

red-orange blue-pink orange

red purple ro ^ a

209320/1062

2-Chlor-4-nitroanil.in

34

36

2-cyano-4-nitroaniline

2,6-D.ichlor-4-ni fc roau.Llin

2-Bi'om-4-nitro-6-cyananiline

2 ~ chloro-4-ynethylulphonylaniline

2,4-Din.itro-6-chloroaniline

4-Ni broanilin

2-methylnulfonyl-4-nitroaniline

2-chloro-4-nitroaniline

2-cyano-4-nitroaniline

2, G-dichloro - ^ - nitroaniline

II

.''-- ('y.Mti-'l-n I t.i'O-6-broiaanllin

CH ₀ CH ₀ OCOCH, I 2 2 3

ClI CH ₂ -C

CH ₀ CH OCO-O

CH

209820/1082

III

Red

blue-red yellow-brown ü purple-red orange bordeaux

yellow-red blue-red

Red

blue red

yellow Red

i \ i '<. v irJ

2-chloro ~ 4,6-dinitroaniline

2-chloro-4-i; iethylsulfonyl aniline

4-nitroaniline

2-Chlor-4-nitroani3.in

2 - Cy a η -4 -n i t r ο aniline

2 _f ( ^: —D-ichlor-4 · ηitroanillη

2-bromo-1-ni lro - ('"- cynn.'in Ll Ln

2,4- Dini'i.ro-6-chloroaniline

4-nitroaniline

2-chloro-4-nitroaniline

II

CH ₀ CH ₀

• N

CIL. CH ₀ -C i

CH ₀ CH 0C0CH _o 0- <~~> I dd (L -

CH

CH ₀ CH ₀ OCOCH, I 2 2 3

CH ₂ -C _x

III

red violet

orange

gold bread

Red

bluish red red orange violet "bordeaux

red-orange yellow-red

209820/1062

BATH ORIGINAL

2-cyano-4-nitro aniline

56

57

60

61

62

2,6-dichloro-4-uitroaniline

2-Bromo-4-nitro-6-cyananiline.

2,4-nitro-6-chloroaniline

2-chloro-4-ethylsu1Γonylaniline

4-nitroaniline

2-AminoH-phunyl-1,! I, b - M j.Li id i ίΐκοί

2-chloro-4-uitroaniline

64

65

66

67

2-cyano-4-nitroaniline

2,6-dichloro- /) ni. t.ronnilin

2-Bro! N-4-nit2-o ~ 6-cyananiline

? -Chlor-4,6-din.i t.ro; in.L.I in

2-ChIOrH-Ut ^ IyI-sulfonylaniline «

II

CH ₀ CH ₀ OCOCH. I 2 2

III

CH ₂ -C

9820/1062

Red

rotorango "burgundy blue-red orange

red-orange bread

yellow Red

Red

orange red-violet or dew red orange

4 ~ Nitroiin.il in

69

70

71

aniline

2-ayan-4-niireaniline

2 ~ cyano-4-ni t ro-6 -br oisanil in

2-chloro-4-nitroaniline

2-cyano-4-nitroaniline

2 — Bro; n-4 -n i ü ro-, 6-gyananiline

2 ₁ 6-I) ichlor-4 -Jii tr pani. 1 in

2-Ami no-5 -ptiG ny 1-1,3 ^ 4-th jj._a4iazäl_

Γ? —Ami no — 4 - l

Il

If

H ₀ GH ₀ 2; 4th

2Q9820 / 1Ö62 BAD.ÖRIGiNAt

III

orange

yellow Red

Red

blue red

Red

bluish red violet red-orange yellow-red

79

80

81

chloraniline

aulTony! aniline

4-hi troaniline

! 86

aniline

2- = yan - 4 -nitres

2,6-Mchl (M ^ - it roaniline

2 -1 ν om-4 -nit i'Q-

2 -Arn i no - ^ A - 2> li e iiyl r 1j J5. _%% RZ thiacliazol

II

CH ₀ CIL ₁ OCOCH ..

GIi,

CH ₀ -C ² \ _t

) D

OH _x

III

bordca'ox

orange

yellow-red t red

pale red

violet

Red

BADOFMGfNAL

II

2-methyl-4-nitroaniline

4-chloro-2-cyananiline

5-amino-3-phenyl-1,2,4 thiadiaxol

2 - amino-6-nitrobenzothiazole

4-aminoacetophenone

2-methoxy-4-nitroaniline

2-amino-5-nitrothiazole

3-amino-5-nitrobenz 1,2-isothiazole

2,5-dichloro-4-aminobenzene -diric thy 1 sul f amid

CH ₀ CH ₀ OCOOC ₀ H, ι L c Zj

O;

CH ₉ -C Τ J 2 N ₀ -K ^

Il

Il

Il

CH ₂ CH ₂ OCONHC ₄ H ₉

O-

O- ¹

4'-nitro-4-ninoazobenzene

CH ₂ CH ₂ OCOC ₃ H ₇

Oi

CH ₂ -C

Cl

5-amino-3 -me thyl-4-nitro-1,2-isothiazol

209

820/1062 red-orange

yellow Red

Red

orange

red-orange purple

blue

Red orange

violet

I. II It III CH ₀ CH ₀ OCOCoH ₇ Il 98 S-amino-S-chloroindazole Ο " ¹ ? ^ N ^C1 Il Red orange OCH ^ I ² ^ CH ₂ CH ₂ OCOC ₂ H ₅
I ^ CH ₉ -C Y ^]
OC ₂ H ₅ 99 4-amino-3-chlorobenzene
chloroethylsulfamide It Red \ J VJιΙλ
3 it 100 2-amino-5-phenyl-1,3,4-
thiadiazole Il red-violet 101 5-amino-3-phenyl-1,2,4-
thiadiazole CH ₂ CH ^ COCH CH Il 102 4-nitro-2-trifluoromethyl-
aniline ίι ^CH2 " ^C \ s- ^ It 103 5-nitroanthranilic acid
methyl ester Il Il 104 4-amino-A ^,! -chloracetophenone Il yellow Red 105 3-aminopyridine orange 106 S-amino-S-methyl-l-phenyl-
pyrazole Il 107 4-amino-3,5-dichlorobenzene
suIfamid It 108 4-aminoazobenzene M. 109 2-amino-5-acetyl-3-nitro-
thiophene Red Blue

209820/1062

l-methyl-S-amino - ^ - nitroimidazole

4-aminobenzoic acid methoxy " thy le st he

nO-S-chlorobenzene-chloro-thyl sulfamic!

2-amino-5,6-dichlorobenzothiazole

2-amino-5-nitrothiazole

4-amino-2,5-dichlorobenzene diethyl sulfamide

4-amino-5-methoxy-2-methyl azobenzene

2-amino-6-methylsulfonylbenzthiazole

3-Amino-5-nitrobenzo-1,2 isothiazole

2-chloro-4-methylsulfonylaniline

2-chloro-6-bromo-4-nitroaniline

II

CH ₂ CH ₂ OCOCH = CH- / ~ \

Cl

CM

CH ₂ CH ₂ OCOCH ₂

Il Il Il

o-i

CH ₂ CH ₂ 0C0O- / ~ \

CH ₂ -C

It Il Il

CH ₀ CH ₀ CN

ο-

t-.lir.-t

Il

209820/1062

III

blue red

orange

Il

Red

Red Blue-

Red orange

Il

blue red

blue

yellow-orange

orange

CH ₀ CH ₀ -CN

111

5-Amino-2-phenyl-1,3,4-thiadiazole Co

5-amino-4-nitro-3-methyl.1,2-isothiazole

123

124 If

2-methoxy-4-nitroaniline

2,4-dicyaniline

l-methyl-4-nitro-5-amino imidazole

126

127

128

6-carbethoxy-2-aminobenzothiazole

5-amino-3-phenyl-1,2,4-thiadiazole

4-nitro-2-methylsulfonylaniline II

Il

Il

fl

Aiainoazobenzene

5 -Atnino-3-methyl -1-phenyl ■ pyrazole

2-Alino-5-acetyl-3-nitrothiophene

2-cyano-4-nitroanillin

CH,

Il

CH ₀ -

CH ₉ -C
²

209820/1062

orange

red-violet

Red

red-orange blue-red

Red

yellow Red

blue red

red orange orange

blue

red-violet

I. II CH ₇ -CHL III ί 133 2,6-Dicljlor-4-nitroaiiil-yne I Γ "ΤΙ _P I I
I Kjllr. — Kj J ^ I red-brown Il 134 2-amino-5-nitrothiazole It blue 135 2-amino-6-nitrobenzothiazole CH ₂ -CH ₃ red violet 136 2-Cynn-4-nitroaniline I 2 "\ _n Js ^ J
NHCOCH ₃ ^u violet It 137 2-chloro-4-methylsulfonyl-
aniline Il Red orange 13S 3 -Amino-5-niti-obenzo-l, 2-
isothiazole It blue 139 4-amino-2,5-dichlorobenzene
d ir.io thy 1 su 1 f amid / - y -J - _T Red 140 2,6-dichloro-4-cyananiline NHCOC ₂ H ₅ Hf Red Il 141 4-nitro-2,6-dicyananiline It blue 142 4'-carbethoxy ^ -methyl ^ -
aininoazobenzene I./ ^C 2 ^H 5 yellow Red 143 2,4-dinitro-6-chloroaniline V- ⁷ ^ CH ₀ -C ^ Tj
I "^ n - ^ ¹ ^^ blue NHCOCH ₃

BATH ORIGINAL

I. II Ill 2,4-D5.nitro-6-bromaniline OC ₂ H ₅
V- / "^ CH ₉ -C ^ ^ 3
NHSO CH ₃ ⁰ ^ blue 145 4 ~ nitro-2-methylsulfonyl-
aniline CH ₂ CH ₂ COOC ₂ H ₅
N— / j // N ^^ N Red 146 6 - Cy an- 2 - aminoben ;: thiazole Il Il 147 2-cyano-4-nitroaniline 1! 148 2-chloro-6-bromo-4-nitro ~
anllin Il orange 149 4-Aminobenζopb enone CH ₂ CII ₂ -OH
VV ι 'ί' ^^ - γ ^^ ι
ΓΗ _f IH 1
^LH 2 ^^ k. / ¹
H yellow-orange 150 2,4-dicyaniline CH ₂ CH ₂ -Cl
CH ₂ -C ^, jQy orange 151 2-methyl-4-nitroaniline O- N CH Il L52 2-amino-5-cyanthiazole Il red-violet 209820/106?

BATH ORIGINAL

I. II Il III 4th orange i yellow Red 153 2-methoxy-4-nitroaniline C ₀ H, COO-CH ₀
j I 4 J 209820/1062 yellow Red It CH-c "" ^ x /) orange CH ₃ C ₂ H ₄ O-CH ₃ 154 2-trifluoromethyl-4-nitro-
aniline Il blue red '· 2 2 '^ Q ^^ - ^ i 155 4-aminobenzoic acid ethoxy
ethyl ester 2 Nj ^ ^v ^ '
I. 156 2-cyano-4-chloroaniline C ₂ H ₄ COO-Q
\ / i> Ν L / L / γΙλ CH ₂ -C "XY CH ₃ 157 2-amino-5-phenyl-1,3,4-
thiadiazole Il C ₀ H ^ OCO-CH ₀
μ 6 3 158 4-aminoazobenzene CH ₂ CH ₂ CH ₂ -C TJ H 159 2-amino-6-nitrobenzothiazole

I. II III IbO 4-amino-2,5-dimethoxy -
azobenzene / ~ Λ I ^{2 2 3}
() ι w NHCOCHo
CH ₀ -C [. J Red H 161 4'-nitro-2'-chloro-4-amino-
azobenzene Ο "! .H ^^ ^CN
CH ₂ -C "^ i ^ J yellow Red H 12 4 2 4 162 4-amino- £ c'-chloro-aceto-
phenone CH ₀ -CII-C TT
CH ₃ orange 163 2-cyano-4-nitroaniline blue red 164 2-amino-5-nitrothiazole ti blue-violet 209820/1062

Color fivor script:

1 part of the dye obtained in Example 1 is mixed with 2 parts of a 50% strength aqueous solution of the sodium salt the dinaphthylmethanedisulfonic acid wet grinding and dried.

This dye preparation is mixed with 40 parts of a 10% strength aqueous solution of the sodium salt of N-benzyl-uheptadecyl-benzimidazole disulfonic acid stirred and 4 parts of a 40% acetic acid solution were added. By diluting a dyebath of 4000 parts is prepared from it with water. In this bath one goes at 50 with 100 parts of a cleaned one Polyester fiber increases the temperature within half an hour to 120 to 130 and stains for one hour in a closed vessel at this temperature. Then it is rinsed well. A strong color is obtained.

209820/1062

BATH ORIGINAL Example 3

3 parts of sodium nitrite are concentrated in 30 parts at 0 Sulfuric acid interspersed. Then will the mixture heated to 65 ° until everything is dissolved. After cooling to 0 °, 30 parts by volume of glacial acetic acid and propionic acid are added (6: 1) added dropwise with cooling. Then 5.82 parts of 6-ethoxy-2-aminobenzothiazole (dissolved in 50 parts of the Glacial acetic acid-propionic acid mixture) was added dropwise with cooling at 0-5 and stirred for 3 hours at this temperature. Then 3.5 parts of urea are slowly added and finally the solution becomes a solution of 8.04 parts of N-ethyl-N- (benzthiazolyl-2-methyl) aniline slowly added in 150 parts of glacial acetic acid, stirred for 3 hours at 0-10 and finally neutralized with sodium acetate solution. The dye of the formula is obtained

-C ₂ H ₅

H _C C "O

The methylation of this dye (4.73 parts) with 4.0 parts of freshly distilled dimethyl sulfate in chlorobenzene at 90-95 ° and stirring at 95-100 for 4 hours gives the dye of the formula

209820/1062
BAD ORIQiNAL

which is obtained by salting out an aqueous solution and dyes polyacrylic fibers in blue tones with good fastness properties.

In an analogous manner, dyes are obtained from the diazo components mentioned in column I and those mentioned in column II Coupling components. The dyes result after alkylation with the alkylating agents mentioned in column III cationic dyes that color polyarylnitrile in the shades given in column IV.

209820/1062

II

III

2-amino-6-ethoxy benzthiazole

2-aminobenzothiazole

2-amino-6-acetylamino benzthiazole

2-aminothiazole

3-amino-1,2,4-triazole

3-aminoindazole

2-amino-5-methyl-1,3,4 thiadiazole

C ₂ H

οί

Q-N

<? 2 ^H 5

CH ₉ -

C ₀ H _x OCOCHo

j 2 H J

_cl

C ₂ H ₄ OH

Γ
Cl

I.
CH ₂ -C

^C 4 ^H 9

C ₉ H, CN .2 4

209820/1062

Dimethyl sulfate

blue

Il

Il

Il

Toluenesulfonic acid methyl ester

Il

violet

Il

Red

Il

violet

Dietary sulfate

Il

I. II III IV 8th 3-aminopyridine \ / f N-
I CH ₂ -C ^ "Ύ ^)
NHCOCH ₃ ^% 0 "^^ Diethyl
sulfate orange 9 4-amino-3-chlorobenzene
dimethylaminopropylsulf-
amide / \ J XT 2-chlorine
ethanol yellow Red 10 4-aminobenzenic acid di-
ethylaminoethyl ester C ₂ H ₄ OCOC ₂ H ₅
I CH ₂ -C JJ
CH ₃ ^ N 2-chlorine
propionic
acid amide red orange 11 4 -amino - CU -morpho 1 ino -
acetophenone C ₂ H ₄ OC ₂ H ₅
Cl 2 \ 0 Benzyl
chloride Il CH ₃ 12th 4-aminobenzene-4'-pyridyl
ethyl sulfamide 2 ~ \ y ^ v / Methy1-
iodide π 13th 4-nitro-2-piperidino-
ethoxyaniline Benzene sulphate
fonsäure-
ethyl ester yellow Red 14th 4'-amino-2'-methylazo-
benzenecarboxylic acid-2 "-
pyridylethylamide Il Butyl
bromide M. 209820/1062

BATH ORIGINAL Example 4

4.57 parts of 4-aminophenacyltrimethylammonium chloride are yellow in 20 parts of water and 7 parts by volume of conc. hydrochloric acid admitted. The solution is at 0-5 by adding 5 parts by volume of 4-n. Sodium nitrite I'd sung diazotized. The diazo solution is at 0-5 ° to a solution of 5.54 parts of N- (2-cyanoethyl) -N- (benzoxazolyl-2-methyl) aniline added in 400 parts of alcohol. After the coupling has ended, the mixture is washed with sodium acetate solution Congo neutral and the alcohol is distilled off. The dye is precipitated by adding salt. It will filtered off, dissolved in hot water and, after filtering the solution, salted out from the filtrate. The failed dye the formula

(CH ₃ ) 3-N-CH ₂ OC- / VN = N- / V-

/ ^CH 2 ^CH 2- ^CN

is filtered off and dried. It dyes polyacrylonitrile fibers in orange shades with very good fastness properties.

The diazo components mentioned in the table below in column I are diazotized and they are coupled with the in Coupling components mentioned in column II, cationic dyes are obtained which contain polyacrylonitrile fibers in the in Color indicated nuances in column III.

209820/1062

BATH ORIGINAL

21S4477

ι ₃ nch ₂ oc / ~ Vn = n- / ~ Vnh ₂

CH ₀

I (C ₂ H ₅ ) ₂ NH ₄ C ₂ HNOC- / ~ V-CH "

Br (CH ₃ ) ₂ NH ₆ C ₃ HNO ₂ S - / ^) - NH ₂

C ₄ H ₉

K>

NH,

CH,

Θ ^

Cl CH ₃ -Qi-H ₄ C ₂ HNO ₂ S

C ₇ H ₇ SO ₃

OC,

M ₃ SO ₄

O ₂ NQ-

NH,

0-Q-CO-CH ₂ -N- (CH ₃ )

II

^C 2 ^H 5

III

Red

C ₀ H ₇ OCOCH

yellow Red

CH ₂ CH ₂ -Q

Il

C ₂ H ₄ OCH ₃

Il

1
CH,

) CH,

bluish red |

Il

NHCOCH

/ C ₂ H ₄ OCOC ₂ H ₅

yellow Red

209820/1062

Example 5

The solution of a coupling component obtained in accordance with regulation 29 a diazonium salt solution of 2.76 parts of p-nitroaniline was added at 0-5 °. Salting out gives the dye of the formula

CH,

O ₂ N

X)

If the coupling components indicated in column II are quaternized with the agents indicated in column III and with the Coupling diazo compounds of the amines given in column I, dyes are obtained which contain polyacrylonitrile in the in column IV color indicated nuances.

I. II III IV 1 2-cyano-4-nitroaniline r- \ / ^C 2 ^H 4 ° ^^ 3
V- ^ ~ ^N Ch ₂ -C ^ Vj
OH ₃ ^N 0 ^ Dimethyl
sulfate blue red 2 5-amino-3-phenyl-1,2,4-
thiadiazole Il Red 3 2-amino-5-nitrothiazole / C ₂ H ₄ CN Diathy1-
sulfate violet 4th 2-chloro-4-nitrobenzene / ^C 2 ^H 5 Dimethyl
sulfate Red 209820/1062

FMrbe regulations :

1 part of the "obtained dye of the formula -

CH ₃

¹ O "wx _CH2 _

is dissolved in 5000 parts of water with the addition of 2 parts of 407 acetic acid. You go into this dye bath at 60 with 100 parts dried yarn made of polyacrylonitrile staple fibers one, increases the temperature to 100 within half an hour and colors at an hour Cooking temperature. Then the dye is rinsed well and dried. A yellow-red color with very is obtained good fastness to light, sublimation and washing.

209820/1062 ORIGINAL BATHROOM

Claims (1)

Claims 1. New azo compounds free of sulfonic acid groups the formula alk anion 'R, D-N = N-A-N η - 1 where D is the residue of a diazo component, A is a p-phenylene residue, Y is an optionally alkylated imino group, a sulfur atom or "an oxygen atom. R is an optionally substituted one Alkyl group which, together with A, forms a tetrahydroquinoline ring can form, R "is an optionally substituted Alkylene group and "alk" is an optionally substituted alkyl or aralky group, the aromatic or partially or completely saturated ring B by halogen atoms, Nitro groups and organic radicals can be substituted, as well as mixtures of the azo compounds with one another, if appropriate in a mixture together with another monoazo dye. Compounds according to claim 1 of the formula D-N-N-A-N ^ CH, : N 209820/1062 BATHROOM ORIGtNM. wherein X is a hydrogen atom, a hydroxyl group, a halogen atom or an organic residue. 3. Compounds according to claim 2 of the formula .CH ₂ CH ₂ OR DN = NAN ^CH 2 wherein R is an acyl radical of an organic acid, a lower one
Is alkyl or hydrogen. 4. Compounds according to claims 1 to 3, characterized in that the ring B by bromine, fluorine, chlorine atoms,
Cyano, nitro, trifluoromethyl, alkyl, alkoxy, acylamino,
Acyloxy, carbalkoxy, optionally N-alkylated carbamoyl
and optionally N-alkylated sulfamoyl groups and can be substituted by a benzene radical. 5. Compounds according to claims 1 to 4, characterized in that that Y is an oxygen atom. 6. Compounds according to claims 1 to 4, characterized in that that Y is a sulfur atom. 7. Compounds according to claims 1 to 4, characterized in that that Y is an NH group. 8. Compounds according to claims 1 to 7, characterized in that that the remainder A of the formula 209820/1062
BADORIGiNAt corresponds and is bound to the azo bridge with the free bond on the left, and c and d are each a hydrogen or chlorine atom, a lower alkyl group or a lower alkoxy group, an optionally hydrogenated phenyl, phenoxy, phenylalkyl or phenylthio group and c is additionally a Can mean bromine atom, a Ψ trifluoromethyl group or an acylamino group. 9. Compounds according to claims 1 to 8, characterized in that that the radical D is a radical of a benzene, benzothiazole, thiazole, imidazole, isothiazole, benzisothiazole, trlazole or Is thiadiazole. 10. Compounds according to claims 1 to 9, characterized in that that the compound does not contain any ion-forming substituents. 11. Compounds according to claims 1 to 9, characterized in that that they have at least one quaternized nitrogen atom. 12. Compounds according to claim 11, characterized in that the radical D of the diazo component is quaternized. 13. Azo compounds according to claim 11, characterized in that η = 2 in them. 209820/1062 BATH ORIGINAL • ft 14. Azo compounds geraäss claim 11 characterized by the formula alk Anion D-N-N-A-N wherein D, A, R ₁ , R ₉ and alk are the same as in claim and Y is an alkylated imino group or a sulfur or oxygen atom. 15. Azo compounds genig.se claims 1, 4 to 7, characterized in that R ₉ = -GH «-. 16. Process for the production of new sulfonic acid groups free azo compounds, characterized in that one Coupling components of the formula alk anion " H-A-N η - 1 wherein A is a p-phenylene radical, Y is an optionally alkylated imino group, a sulfur atom or an oxygen atom, R _{1 is} an optionally substituted alkyl group which, together with A, can form a tetrahydroquinoline _{ring, R 9 is} an optionally 209820/1062 ORIGINAL BATHROOM substituted alkylene group and "all ^{15 is} an optionally substituted alkyl or aralkyl group, v / whether the aromatic or partially or fully saturated ring B can be substituted by halogen atoms, nitro groups and organic radicals, optionally together with another coupling component, with the diazonium compound Diazo component couples and, if necessary, then quaternized, 17. The method according to claim 16, characterized in that that you have a coupling component of the formula .CII ₂ HAN " > ■ used, wherein X is a hydrogen atom or an organic Rest is. 18. The method according to claim 16, characterized in that coupling components of the formula .CIi ₂ "- ^Λ Λ" used wherein \ 'an acyl rest restroom of an organic acid, a lower Alley]: or a water · l ο η ff is torn?. 2 (J S R ? O / 1 f \ (\ ^J BAD ORiOiNAL 19. The method according to claims 16 to 18, characterized in that that coupling components are used in which the ring B is replaced by bromine, fluorine, chlorine atoms, cyano, Nitro, trifluoromethyl, alkyl, alkoxy, acylamino, acyloxy, Carbalkoxy-, optionally N-alkylated carbamoyl-, and optionally N-alkylated sulfamoyl groups and by a Benzo radical can be substituted. 20. The method according to claims 16 to 19, characterized in that that one uses a coupling component in which the radical A of the formula corresponds to, in which c and d each represent a hydrogen atom or a chlorine atom, a lower alkyl or alkoxy group or an optionally hydrogenated phenyl, phenylthio, phenylalkyl or Are phenoxy and c is also a bromine atom, a trifluoromethyl group or can represent an acylamino group. 21. The method according to claims 16 to 20, characterized in that that coupling components are used in which Y is an oxygen atom. 209820/1062 BATH 22. The method according to claims 16 to 20, characterized in that that coupling components are used in which Y is a sulfur atom. 23. The method according to claims 16 to 20, characterized in that that coupling components are used in which Y is an NH group. 24. The method gema'ss claims characterized ψ 16, marked to 20, characterized in that the azo obtained after the coupling bonds, if they contain quaternizable nitrogen atoms, treated with quaternizing agents. 25. The method according to claims 16 to 20, characterized in that a diazonium compound of a benzene,
Benzthiazols, Thiazoles, Imidazoles, Isothiazols., Bonzisothiazols, Triazols or Thiadiazols are used. 26. The method according to claims 16 to 25, characterized in that that coupling components and diazo components !! that do not contain any ion-forming substituents. 27. The method according to claims 16 to 23, characterized in that that you have a coupling component of the formula alk AT 209820/1062 where A, R ,, R _? and "alk" mean the same as in claim and Y stands for an alkylated imino group or a sulfur or oxygen atom, vr rv. ^; :; r: öet ;. 28. The method according to claims 16 to 27, characterized in that one starts from coupling components in which R ~ = -CUy-. 29. Process for dyeing and printing hydrophobic synthetic fibers, especially those containing ester groups Fibers, characterized in that non-quaternized dyes according to Claims 1 to 15 are used. 30. A method for dyeing and printing acrylic fibers, characterized in that quaternized dyes according to claims 1 to 9 and 11 to 15 used. 31. The material dyed or printed according to claims 29 and 30. 32. Dyestuff preparations, characterized in that they contain dyes .ri \ r.: - ^: ss claims 1 to 15. 33. Amines of the formula ___ alk ^ AniOTi H-A-Ii '-'. W; I / ·. η BATH ORIGINAL wherein A is a p-phenylene radical, Y is an optionally alkylated imino group, a sulfur atom or an oxygen atom, R- is an optionally substituted alkyl group which, together with A, can form a tetrahydrochrnoline ring, Ii ^ an optionally substituted alkylene group and "alk" is an optionally substituted alkyl - Or aralkyl group, it being possible for the aromatic or partially or fully saturated ring B to be substituted by halogen atoms, nitro groups and organic radicals. 209820/1062 BATH ORIGINAL