DE2062717B2 - Azo dyes from 2,6-diamino pyridine derivatives, process for their preparation and use - Google Patents

Description

'Ν — R,

in D the remainder of a diazo component of the benzene, naphthalene, diphenyl, azobenzene, benzthiazole, benzisothiazole, thiazole, thiadiazole, triazole, benzotriazole, indazole, pyrazole, anthraquinone, naphthalic acid imide, Chromanone or diphenylene oxide series, X cyano or carboxamide, R hydrogen, allyl, Hydroxyälhoxyäthyl, optionally substituted by hydroxy, alkoxy with 1 to 8 carbon atoms, amino, mono- or dialkylamino with a total of up to 8 carbon atoms, alkyl with 1 up to 8 carbon atoms, optionally phenyl, cyclohexyl, benzyl, phenylethyl or (uN-pyrrolidonyl- and (uN-thiomorpholinyl-S-dioxide-alkyl with 2 or 3 carbon atoms in the alkyl radical, R, hydrogen, hydroxyethoxyethyl, optionally with hydroxy, alkoxy with 1 to 8 carbon atoms, amino, mono- or dialkylamino with a total of up to 8 C-atoms substituted alkyl with 1 to 8 C-atoms, or R and R, together with the nitrogen, are the remainder of pyrrolidine, piperidine, morpholine, thiomorpholine-S-dioxide, piperazine or N-methylpiperazine, and independently of one another, R _{2 has the} same meaning as R, R _{3 has the} same meaning as R, and R ₂ and R _{3 have the} same meaning as R + R ₁ .

2. Dyestuffs according to Claim 1 of the general formula

717

CH,

N = N

R-NH

NHR ₂

in the Y Nitro. Cyan, chlorine, bromine, carbomethox). Carboaelhoxy, methylsulfonyl, ethylsulfonyl, methyl or methoxy. Z hydrogen, nitro, chlorine, bromine, cyano, methyl, methoxy, carbomethoxy. Carboethoxy, methylsulphonyl or ethylsulphonyl and Z ¹ hydrogen, chlorine, bromine, cyano, methyl, methoxy, carbomethoxy, carboelhoxy. Phenylazo, p-nitrophenylazo, p-hydroxyphenylazo. p-methoxyphenylazo. p-chlorophenylazo or methylphenylazo and has R and R ₂ (as defined except WasserstofOsowieXdieiii ¹ \ nspruch. 1

3. Dyestuffs according to Claim 1. wherein D in the formula is a benzisothiazole radical.

4. A method of making dyes

«Em according to claims 1 to 3, characterized in that that one diazo compounds of amines of the general formula

D-NH ₂

with coupling components of the general formula

reacted, where D, FL, R ₁ , R ₂ , R ₃ and X have the meanings given in claims 1 to 3.

5. The use of the dyestuffs according to Claims 1 to 3 for dyeing textile material ais Aeryl nitrile polymers, synthetic polyamides, cellulose esters or synthetic, linear ones Polyesters.

The invention relates to: dyes of the general formula

R-N

R ₁

NR ₂

in the D the remainder of a diazo component of the benzene. Naphthalene, diphenyl, azobenzene, benzothiazole. Benzisothiazole, thiazole, thiadiazole, triazole. Benztriazole, indazole, pyrazole, anthraquinone. Naphthalic acid imide, chromanone or diphenylene oxide series, X cyano or carboxamide, R hydrogen, allyl, hydroxyethoxyethyl, optionally with hydroxy, alkoxy with 1 to 8 carbon atoms, amino. Mono- or dialkylamino with a total of up to 8 carbon atoms substituted alkyl with 1 to 8 carbon atoms, optionally with chlorine. Cyano, methyl. Ethyl. / i-hydroxyethyl, methoxy, ethoxy, hydroxyalhoxy. N-methylcarbamoyl or N-ß-melhoxyethylcarbamoyl substituted phenyl, cyclohexyl, benzyl, phenylethyl or («-N-pyrrolidonyl- and <-iN-thiomorpholinyl-S-dioxide-alkyl with 2 or 3 carbon atoms in the alkyl radical, R ₁ hydrogen , Hydroxyäthoxyäthyl, optionally by hydroxy, alkoxy with 1 to 8 carbon atoms, amino, mono- or dialkylamino with a total of up to 8 carbon atoms substituted alkyl with 1 to 8 carbon atoms, R and R ₁ together with the nitrogen the remainder des pyrrolidine, piperidine, morpholine, thiomorpholine-S-dioxide, piperazine or N-methylpiperazine, where, independently of one another, R _{2 has the} same meaning as R, R _{3 has the} same meaning as R ₁ and R ₂ and R, the same meaning as R -t R ₁ have.

The invention also relates to a process for the preparation of these dyes and their use for dyeing textile material made from acrylonitrile polymers, synthetic polyamides, cellulose esters or synthetic, linear polyesters.

Compared to comparable ones from the German Offenlegungsschrift 1 544446 and the USA patent specification 2,029,315 known dyes, the new dyes have advantages in terms of lightfastness and thermosetting plastic. The large color range and brilliance should also be emphasized the colors available with the new dyes. By varying the amine substituents, also achieve favorable fastness and coloring properties.

As substituents for the radicals D of the diazo components include, for example:

In the benzene series:

Chlorine, bromine, nitro, cyano, trifluoromethyl, methylsulfonyl, Ethylsulfonyl, phenylsulfonyl, p - (,; - Hydroxyäthylphenyl) -sulfonyl. Carbomethoxy, Carboiithoxy, Carbobutoxy, Carbo - ^ - methoxyäihoxy, Carbo-p'-ethylhexoxy, carbopropoxy. Carbo -,; - hydroxyethoxy, optionally N-mono- or disubstituted carbon- or sulfonamide, methyl, ethyl. Meihoxy or ethoxy;

N-Subsikuenten of the carbon or sulfonamides are z. B. methyl, ethyl, propyl, butyl, / i-ethylhexyl. Cyclohexyl, benzyl, phenylethyl, / i-hydroxyethyl. / i-hydroxypropyl, / i-methoxyethyl or ; -Nlclhoxypropyl as well as pyrrolidide, piperidide or Morpholide;

in the azobenzene series:

Chlorine, bromine, nitro. Cyano, carbalkoxy, methyl. Ethyl. Methoxy, ethoxy, hydroxy, acetylamino. Formyl, / i-Hydroxyethoxy or Äthoxycarhonylamino:

in the heterocyclic series:

Chlorine, bromine, nitro, cyano, methyl. Ethyl. Phenyl. Methoxy, ethoxy, methyl mercapto, fi-carbonmelhoxyethyl mercapto, β- carboethoxyethyl mercapto. Carbomethoxy, carboethoxy, methylsulfonyl or ethylsulfonyl;

Radicals R, R ₁ , R ₂ and R ₃ are in detail apart from the already mentioned z. B .:

Methyl, ethyl, propyl, butyl. Hexyl, i-ethylhexyl. ((-Hydroxyethyl or -propyl, γ-hydroxypropyl. i'j-Hydroxyhexyl, / (- methoxyethyl, v-methoxypropyl. /) '- Ethoxyethyl, γ-ethoxypropyl, --isopropoxypropyi. - / - Butoxypropyl, / i-Aminoälhyl, -, - Dimethylaminopropyl, y-dibutylaminopropyl or <u-aminohexyl as well as the remainder of the formulas

CH ₁ CH ₁ OCH ₁ CH ₇ OH

CH ₂ CH ₂ CH ₂ OCH ₂ CH C ₁

C ₂ H,
CH ₁ = CH-CH,

The remainders D derive z. B. from the following amines:

Aniline, o-, m- or p-toluidine. O-. m- or p-Nitrani-Hn, o-, m- or p-cyananiline: 2,4-dicyananiline. ρ-chloroaniline, 3.4-dichloroaniline. 2.5 - dichloroaniline. 2,4,5-trichloroaniline. 2,4,6-trichloroaniline. o-, m- or p-bromoaniline, 2,4,6-tribromaniline, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 2-cyano-4-nitroaniline, l-amino-4-methyl-2-nitrobenzene, 1-amino-4-methoxy-2-nitrobenzene, 1-amino-4-chloro-2-nitrobenzene, 2-cyano-4-nitro-6-bromaniline, 2-cyano-4-nitro-6 - chloro - aniline, 1 - amino - 2 - methyl - 4 - nitrobenzene.

1 -amino ^ -trifluoromethyl ^ -chlorobenzene, 1 -amino-

2 - methoxy - 4 - nitrobenzene, N - benzoyl - ρ - phenylenediamine, N - acetyl - ρ - phenylenediamine, N - phenylsulfonyl - ρ - phenylenediamine, N - phenylsulfonylm-phenylenediamine, 4-amino-acetophenone, 4-aminobenzophenone, 2-aminobenzophenone, 4-methylsulfonyl - aniline, 2 - amino - diphenylsulfone, 2-, 3- or 4 - aminobenzoic acid methyl ester, methyl ester.

-propylester, -butylester, -isobutylester, -f> - ethylhexylester, -cyclohexylester, -benzylesier, -piienylester, - {i- methoxy -äthylester, -, - J - ethoxy - ethyl ester. -fi - butoxy - ethyl ester, methyl diglycol ester, ethyl diglycol ester, methyl triglycol ester, ethyl triglycol ester, - / i-hydroxy-ethyl ester, -ji-aceloxy-ethyl ester. - /; - (jt ' - hydroxy - ethoxy) - ethyl ester, - />' - hydroxypropyl ester. - ·> - hydroxypropyl ester, -d - hydroxybutyl ester. - «.- hydroxyhexyl ester. 4-nitro-anthranilic acid - methyl ester, isobutyl ester, methyldiglycol ester, -ft - methoxyethylsier, -, ·> - butoxyethylsier. -methyldiglykolester, -p - acetoxyälhylester. -but \ le ^ ier, 3 or 4-aminophthalic acid, 5-aminoisophthalic acid or aminolerephthalic acid - di - methylesler. -di-ethyl ester, -di-propyl ester, -di-butyl ester. 3- or 4-aminobenzoic acid amide, methyl amide, propyl amide. -n-butylamide, -iso-bulylamide, -cyclohexylamide. -isooctylamide. methoxypropylamide. ethoxypropylamide. -anilide, 2-, 3- or 4-aminobenzoic acid dimethylamide. diethylamide. -pyrrolidide. -morpholide. -N - mettnl-N - [i - hydroxy - ethylamide. 5 - Aminoisophthalic acid diamide, -dimethoxypropylamide. Aminoterephthalic acid bis-diethylamide. 3- or 4-aminophthalic acid imide. - / i-hydroxyethylimide. - ■■ -hydroxy-propylimide. -phenylimide, -tolylimide. 3 - Amino - 6 - nitrophthalic acid - / (- hydroxyälhy'imid. 2-, 3- or 4 - aminobenzenesulphonic acid - dimethyl - amide, diethylamide. - pyrrolidide, - morpholide. - N - methylanilide '- or 4' - amino - phenylesler, ethylsulfonic acid 2'-, 3'- or 4'-aminophenylesier.

Bulylsulfonic acid 2-, 3- or 4'-aminophenyl ester. Benzenesulfonic acid 2'-, 3'- or 4'-aminophenyl ester. 2,4 - dinitro - 6 - bromo - aniline, 2.5 - dichloro - 4 - nilroaniline. 1-amino ^ .o-dibromobenzene ^ -methylsulfone. 2 - chloro - 4 - amino - benzonitrile. 1 - aminobenzene-4-methylsulfone. 2 - amino - 4 - chloro - benzonitrile. 1 - amino - 2,6 - dichlorobenzene - 4 - methyl sulfone. 1-Amino -2,4-dinitro-benzene-fc-carboxylic acid methyl ester. methoxy ethyl ester. 4-Amino-naphthalic acid-1.8-methoxyethylimide. methoxy propylimide.

1-amino -4-nitrobenzene-2-methylsulfone, 1-amino-4 - nitro - 2,6 - dicyanobenzene. 2.4 - Dinitroaniline. 2-amino-6,7-dichlorobenzthiazole, 2-amino-5,6-dichlorobenzlhiazole. 1-amino-2-nitrΰbenzene-4-sulfonic acid - η - bulylamide. 1 - amino - 2 - nitrobenzene -

_(l0 4 - sulfonic acid -,; - methoxyethylamide. 1 - aminoanihrachinone. 1 - amino - 4 - chloranthraquinone. I - or 2 - aminonaphthalene. 1 - amino - 2 - ethoxynaphthalene. 4 - amino - naphthalic acid - bulylimide. 3,5-dichloro anthranilic acid propyl ester.3,5-Dihrom-

(, 5 anthranilic acid - // - methoxymethyl ester. 5 - aminochromanone. 2- or 4-AmIHOdIPhCiIyI ^ or 4-aminodiphenylene oxide. 2 - amino - 3,5 - dinilro - benzonitrile. 1-Amino-2,4-di-nitro beiizol-6-methylsulfone.

Suitable diazo component !! the aminoazobenzene series are for example:

4 - aminoazobenzene, 2 ', 3 - dimethyl - 4 - arninoazobenzene, 3 \ 2 - dimethyl - 4 - aminoazobenzene. 2,5 - dimethyl-4-aminoazobenzene, 2 - methyl - 5 - methoxy-4 - aminoazobenzene, 4 '- chloro - 2 - methyl - 5 - meihoxy-4 - aminoazobenzene, 2 - methyl - 4 ', 5 - dimethoxv-4-aminoazobenzene, 4'-hydroxy-4-aminoazobenzene. 4 '- hydroxy - 3' - methyl - 4 - aminoazobenzene. 2 '- hydroxy -5'-methyl -4-aminoazobenzene. 4'-hydroxy-ιο 2-methoxy-4-aminoazobenzene. 4'-hydroxy-2-chloro-4 - aminoazobenzene. 4 '- hydroxy - 2,5 - dimethoxy-4-aminoazobenzene, 4-hydroxy-2,6-dichloro-4-aminoazobenzene, 2,5 - dimethoxy - 4 - aminoazobenzene. 4 '- chloro - 2,5 - dimethoxy - 4 - aminoazobenzene. is 4'-nitro-2,5-dimethoxy-4-aminoazobenzene, 4'-nitro 4 - aminoazobenzene, 4 '- nitro - 2 - methyl - 5 - methoxy-4 - aminoazobenzene. 4'-chloro-2-methyl-4-aminoazobenzene, 4'-chloro-2,5-dimethyl 4-aminoazobenzene. Benzene-azo-4-amino-3-ethoxynaphthalene or benzene-azo-4-aminonaphthalene and the compounds of the formulas:

O = CH

CH ₃

OCH ₃

HO CH ₁ -CH ₁ -O

CH ₃

OCH ₃

HO-CH ₉ -CH, -O

C ₂ H ₅ -O-CO-NH

-N = N-

OCH ₃

> —NH;

OCH,

HO-

-N = N--

-NH,

CH ₃

OCH ₃

ho - '/ ^v ; - N = N

CH ₃ CH ₃

V-N = N

Br

CH ₃ -O-t

-N = N

OCH ₃

5 - NH,

OCH ₃

NH,

To prepare the dyes of the formula 1, the diazonium compounds of the amines of the ai common formula II

D-NH ₂

with coupling components
Formula III

CH ₃
[X

(Π) the general

40

RN

R ₁

Ν —R,

'/ ~~ NH, 45 convert, where D, R. R ₁ . R ₂ , R ₃ and X have the meanings given above.

The amines are diazotized as usual. The coupling is also as usual in aqueous Medium, optionally with the addition of solvents, carried out with a weak to strongly acidic reaction.

The coupling components of the formula III are prepared by reacting 2,6-dichloro-3-cyano-4-methyl-pyridine or, preferably, 2,6-dichloro-4-methylpyridine- (3) -carboxamide _with amines of the general formula IV

CH ₃
CH ₃ -O <f ^ - ■ N - N - ■; -Nl-I, _(H

(XM ₃
Cl Cl

NH

or

R,

NH

in left

Primary or secondary amines can be used. By suitable choice of the acceptance conditions succeeds in gradually increasing the chloralom of the! .o-dichloro-S-cyano ^ -methyl-pyridine substitute, so that one mono- and Disubstiimionsprodukte can isolate. Reaction conditions that influence the exchange of chlorine atoms, are the temperature, the amine component. the molar ratio of the reactants and the diluent or Solvent.

In the first reaction step, I-amino-B-cyano ^ -methyl-o-chloropyridines are predominantly obtained. which then with or without intermediate isolation to 2,6-diamino-3-cyano-4-methylpyridine derivatives with identical or different amine residues can be implemented. The cyano group can then be converted to the carbonamide group as usual.

If you put 2,6-dichloro-3-cyano-4-methylpyridine with complete exchange of the chlorine atoms with a Mixing different amines in order to obtain Coupling component mixtures: When using two amines, one obtains, for example, one Mixture of 4 coupling components, if a mixture of 3 amines is selected, a mixture is obtained of 9 coupling components.

With a suitable choice of the amines and their mixing ratios, the dye mixtures which can be prepared therefrom can be used have significantly better drawability on synthetic fibers than a single dye this mixture.

Used for the preparation of 2,6-diamino-S-cyano ^ -methylpyridine derivatives as amine components ammonia or volatile amines such as methylamine, ethylamine, it is recommended. solutions to use these amines or ammonia in solvents which are inert under the reaction conditions. For reaction temperatures up to about 150 C, for example, inert solvents Alcohols such as methanol, ethanol or / I-methoxyethanol called. If the components are allowed to react at higher temperatures, then, for example, are suitable Dimethylformamide, N-methylpyrrolidone. Glycol or glycol ethers, such as ethylene glycol dimethyl ether.

You can also use the liquefied amines themselves under pressure and the reaction times raise.

To bind the HCl released during the reaction, excess amine and usually acid-binding agents used, such as tertiary amines. Magnesium oxide, alcoholates or alkalis are used will.

Amines of the formula IV are, for example: ammonia, allylamine, methylamine, ethylamine. n- or i-propylamine, n- or i-butylamine, lert-butylamine. Isoamylamine, n- or i-hexylamine. n- or i-octylamine, 2-ethylbutylamine, 2-ethylhexylamine. Cycloxylamine, / f-hydroxyethylamine. / J-hydroxypropylamine, y-hydroxypropylamine, (D-hydroxyhxylamine. ^ / I-methoxyethylamine, ß-ethoxyethylamine, / i-butoxyethylamine. Y - (/ f-ethylhexoxy) -propylamine, //-(,-."-hydroxyethoxy ) - ethylamine, y - ethoxy - propylamine y - methoxypropylamine, y - isopropoxypropylamine γ - amino - "- N - methylaminopropane;... · - amino ^ π - N - dimethylamino propane, α - amino - β - β diäthylaminoäthan - amino - / ί - ethyl - «.y - propanediol β- amino -. '/ - methyl propanol, N-ethyl-N (/>' - hydroxy-

45 ethyl amine. Diethanolamine, dimethylamine, diethyl limine. Dipropylamine, N - methyl - N - (ß - hydroxy) ethylamine, morpholine, piperidine, piperazine. N-methyl piperazine. Pyrrolidine, thiomorpholine S-dioxide. / i-Aminoäthytthiomorpholin-S-dioxide. N- (γ-aminopropylj-pyrrolidone, aniline, o-, m-, p-toluidine. O-. M-. P-methoxyaniline, o-, m-, p-chloroanilm. O-. M-, p-cyananiline . 0-, m-, p-Älhoxyanilin, o-. M-, p-Äthylanilin, p- aminobenzoic acid methylamide, p-amino - benzoic acid - // - methoxy-ethylamide, 1-amino-4 - (/ i-hydi " oxyethyl) benzene, 1 - amino - 4 - (β - hydroxyethoxy) benzene, N - β - hydroxyethylaniline, N - methylaniline, benzylamine, / I-phenylethylamine, 1,3-diaminopropane, 1.2 - diaminoethane, 1,2 - diaminopropane. 1.6 - diaminohexane or 1,4-diaminobutane.

Dyes and dye mixtures of the general formula 1 a are particularly useful from a technical point of view

Z) Z

N = N

R-NH

(Ia)

NHR ₁

in the Y Nitro. Cyan. Chlorine. Bromine. Carbomeihoxy, carboethoxy. Methylsulfonyl, ethylsulfonyl. Methyl or methoxy, Z hydrogen, nitro, chlorine. Bromine. Cyano, methyl. Methoxy, carbomethoxy, carboethoxy. Methylsulfonyl or ethylsulfonyl and Z ¹ hydrogen. Chlorine. Bromine. Cyan. Methyl. Methoxy. Carbomethoxy. Carboethoxy, phenylazo. p-nitrophenylazo. p-hydroxyphenylazo. p-methoxyphenylazo. are p-chlorophenylazo or methylphenylazo and R and R ₂ (except hydrogen) and X have the meanings given above.

Furthermore, the corresponding dyes, which may be used as a diazo component, are particularly valuable through nitro. Chlorine. Have bromine or C \ an substituted benzisothiazoi.

Some of the particularly valuable diazo components are:

1-amino-4-nitrobenzene, 1-amino-.Vchloro ^ -nitrobenzene. 1-amino-2-bromo-4-nitrobenzene. 2-amino-5 - nitro - benzonitrile, 2 - amino - 4 - chloro - benzonitrile.

3 - chloro - 4 - amino - benzonitrile, 2 - chloro - 4 - aminobenzonitrile. 2 - amino - benzonitrile. 2.5 - dichloro

4 - amino - benzonitrile. 1 - amino - 2,4 - dicyanobenzene. 1 - amino - 2,4 - dicyan - 6 - chlorobenzene. 2 - chloro-4-amino-5-nitro-benzonitrile. 1-Amino-Z.S-dichloro-4-nitrobenzene. 1-amino-2,6-dichloro-4-nitrobenzene. 1 - amino - 2.6 - dibromo - 4 - nitrobenzene. 1 - amino-2-bromo-4-nitro-6-chlorobenzene, 1 -Amino ^^ - dinitrobenzene. 1 - amino - 2,4 - dinitro - 6 - chlorobenzene. 1 - amino - 2.4 - dinitro - 6 - bromobenzene. 1 - amino-4 - nitrobenzene - 2 - methyl sulfone. 1 - amino - 4 - nitrobenzene 2-ethyl sulfone, 4-aminophenyl methyl sulfone, 1-amino ^ -chlorobenzene ^ -methylsulfone. 1-amino-2,6-dichlorobenzene -4-methyl sulfone. 1-Amino-2,6-dibromo-benzene-4-methylsulfone. 4-aminobenzoic acid ester. 1-Amino ^ -nitro-benzene ^ -carboxylic acid ester. 1 - Amino - 2 - bromo - 4 - nitro - benzene - 6 - carboxylic acid ester, 1 - amino ^^ - dichloro-benzene ^ -carboxylic acid eslcr. 1-Amino-2,4-dibromo-benzene-6-carboxylic acid. 4-amino-azobenzene. 2 ', 3-dimethyl-4-aminoazobenzene. 4 '- hydroxy-2' - methyl - 4 - amino - azobenzene. 1 - Amino ^^ - dinitrobenzene-o-carboxylic acid methyl ester or methoxy ethyl ester. 3.5 dibromo

409526/400

ίο

4-aminoazobenzene. 3 ', 2-dimethyl-4-aminoazobenzene. 2,5-dimethyl-4-aminoazobenzene, 2-methyl-5-melhoxy-4-aminoazobenzene. 4'-chloro-2-methyl-5-methoxy-4-aminoazobenzene, 4'-nitro-2,5-dimethoxy-4 - aminoazobenzene, 4 '- nitro - 2 - methyl - 5 - methoxy

4-aminoazobenzene, 4 '- chloro-2 - methyl - 5 - methoxy-4-aminoazobenzene.

Of the particularly valuable heterocyclic diazo components !! are mentioned:
2 - amino - 5 - nitrothiazole 2 - amino - 4 - methyl-

5 - nitrothiazole, 2 - amino - 5 - phenyl - thiazole -1,3.4, 3 - phenyl - 5 - amino - thiadiazo! - 1,2,4, 3 - methylmercapto-5-amino-thiadiazo! -1,2,4, 3- / i-carbomethoxyethyl - mercapto - 5 - amino - thiadiazole - 1,2,4,

3 - amino - 5 - nitro - 2,1 - benzisothiazole, 3 - amino-5-nitro-7-chloro-2, l -benzisothiazole, 3-amino-5-nitro-7-bromo-2,1 -benzisothiazole, 3-amino-7-nitrobenzisothiazole, 4 - amino - 5 - bromo - benzisothiazole,

4 - Amino - 5 - bromo - 7 - nitrobenzisoihiazoi or 4-Amino-5-cyano-7-nitro-benzisothiazo !.

The new dyes are yellow to green-blue and are suitable for dyeing textile material made from acrylonitrile polymers and, in particular, synthetic polyamides and cellulose esters, such as 2 _1/2 or triacetate. or synthetic linear polyesters such as polyethylene glycol terephthalate or chemically analogous

The likely formula is

built-up polymers. This gives strong dyeings which have good fastness properties, in particular Distinguish thermosetting and light fastness. Details of parts and percentages in the following Unless otherwise noted, examples are based on weight.

Manufacture of coupling components
Example I.

54 parts of 2,6-dichloro-3-cyano-4-methylpyridine are at 20 to 38 ° C ⁿ in a mixture of 90 parts of / i-Methoxyäthylaniiin and added 70 parts of methanol. The mixture is stirred for 3 hours at 40.degree. C. and 1000 parts of ice water are then added. After acidification with hydrochloric acid to pH 4 to 5, the deposited precipitate is filtered off with suction and washed with water. 50 parts of the product are mixed with 120 parts of i-hydroxyethylamine, then the mixture is ^{stirred at 160 to 170 °} C. for 3 to 4 hours. The mixture is then allowed to ^{cool to 120 °} C., the mixture is poured onto 500 parts of ice and 500 parts of water with stirring and acidified to pH 5 to 6 with hydrochloric acid. About 50 parts of a dark green oil are obtained, which slowly solidify. Melting point of the crude product: 108 to lirC.

HO - CH ₂ - CH ₂ - HN NH- CH ₂ - CH ₂ - O - CH ₃

The product contains a minor proportion of a coupling component of the likely formula

CH ₃ - O - CH ₂ - CH ₂ - HN

NH-CH ₂ - CH ₂ - OH

Example 2

formula

187 parts of 2,6-dichloro-3-cyano-4-methylpyridine are gradually added at 20 to 30 ° C. to a mixture of 250 parts by volume of i-hydroxyethylamine and 200 parts by volume of methanol. The mixture is stirred for 4 to 5 hours at 40 ° C., then the mixture is poured into 3000 parts of ice-water with thorough stirring and acidified to pH 6 to 4 with ₅₅ CH ₃ O-CH ₂ -CH _{2 -NH with hydrochloric acid.} The deposited precipitate is filtered off, washed with water and dried. 202 parts of a colorless one are obtained

Powder.

I (Xi parts of this powder are 300 parts by volume , .'- methyl oxyethylamine for 12 hours under reflux cooling heated. Excess AiViin is then distilled off. stirs the residue in 1500 parts Ice water and adjust the pH to 6 to 7 with hydrochloric acid. The deposited precipitate is nitrided, washed with water and dried. You get about 100 to 110 parts of a brownish one to colorless powder of probable CH,

CN

NH-CH ₂ -CH ₂ OH

which melts at 78 to 8I ^{0 C.} The product may contain a smaller amount of the coupling component of the likely formula

HO-CH, -CH, -NH

contain.

NH-CH ₂ -CH ₂ -OCH ₃

Example 3

93 parts of 2,6-dichloro-3-cyano-4-methylpyridine are mixed with 220 parts by volume / I-hydroxyethylamine and carefully heated to 165 to 170 ° C. The mixture is stirred for 2 to

3 hours at this temperature, then allowed to rise to 120.degree cool, add the mixture to 700 parts of ice water and adjust the pH to 7 to 6. After suction after the precipitate and drying, 97 parts of a colorless powder of the formula are obtained

HO-CH, -CH, -NH

CN

NH-CH ₂ -CH ₂ -OH

(F. 156 ° C)

Example 4

54 parts of 2,6-Dich] or-3-cyano-4-methylpyridine-feed at 15 to 35 ° C under cooling gradually into a mixture of 80 parts of diethylamine and the mixture 4 hours at 35 ⁰ C and then pour it into 1000 Share water. After acidification with hydrochloric acid to pH 6, the product is filtered off with suction and the product obtained is washed with water. After recrystallization from methanol, 50 parts of a colorless one are obtained

130 parts by volume of methanol entered. Mix 25 powders of the likely formula

CHc

C ₂ H ₅

(F. 88 to 90 ⁰ C)

54 parts of the product of the formula

Example 5

CH,

are added with 120 parts by volume / ϊ-Hydroxyälhylaminver hydrochloric acid up to a pH of 6 to 7. After sets and stirred at 165 ° C for 2 to 3 hours. Man 55 let cooling to room temperature, then separates the 110 ⁰ C to cool and water and 1000Teile obtained oily product of the probable formula

C ₂ H ₅

C ₂ H ₅

HO-CH, -CH, -NH N

as usual from the aqueous phase. The product gradually solidifies and melts at 106 to 108 ⁰ C.

100 parts of the product of the formula

2 717 jf

Example 6

NH-CH ₁ -CH ₇ -CH, - OH

(M.p. 118 to 120 C)

are made up of a mixture of 120 parts 3-methoxypropylamine and 120 parts by volume of n-ile \ ylamine offset. The mixture is refluxed for 12 hours. Then the excess is distilled Amin off. added the residue mil

CH, - O - CH ₂ - CH ₂ - CH ₂ - HN

1500 parts of water and mil hydrochloric acid up to one pH from 6 to 7. The precipitated oil is, as usual, separated from the aqueous phase. Yield: about 190 to 220 parts of a dark oil. that from the coupling components of the formulas

CN

NH - CH ₂ - CH, - CH, - OH

CH ₃ - CH ₂ - CH ₂ - CH ₂ - CH ₂ - CH ₂ - HN

NH - CH, - CH, - CH, - OH

consists.

Example 7

In a mixture of 108 parts of 2,6-dichloro-3-cyano-4-methylpyridine and 130 parts of N-methylpyrrolidone a mixture of 50 parts is left at 60 to 100.degree /> '- Methoxyethylamine. 50 parts / i-hydroxyethylamine and pour in 25 parts of n-butylamine. The mixture is then stirred under reflux for 10 hours then distilled off the excess amines. 2000 parts of water are added to the residue and mixed with hydrochloric acid up to a pH of 6. The precipitated oil is separated off. Yield: about 100 to 115 parts of a mixture of dcr Arnine of the formula

R ₁ -NH NH-R,

in which R ₁ and R _{2 are} the radicals

-CH ₂ -CH ₂ OH
-CH ₂ -CH ₂ -O-CH,

Example 8

54 parts of 2,6-dichloro-3-cyano-4-methylpyridine are gradually added at 35 to 40 ° C. with cooling a mixture of 30 parts / i-hydroxyethylamine and 30 parts / n'-methoxyethylamine in 100 parts Given N-methylpyrrolidone. One stirs 4 to 5 slun

_4S then sets at 40 C. 40 parts of n-hexylamine to and the mixture heated for a further 10 to 12 hours unier reflux. Excess amine is then distilled off and 1000 parts of water are added to the residue. After acidification with hydrochloric acid to pH 6 to 5, about 54 parts of a dark oil are obtained. which is separated from the aqueous phase as usual. The product has the formula

CN

R ₁ -NH NH-R ₂

in which R ₁ and R _{2 are} the radicals

or

- CH, - CH ₂ - OH
- CH ₂ - CH, - O - CH ₃

-CH, -CH, -CM, -CH,

- CH ₂ - CH ₂ - CH ₂ - CH ₂ - CH ₂ - CH ₃

heocuten and where R ₁ and R _; identical or denoted and where R ₁ and R 1 can be identical or different. can be divorced.

Example 9

130 parts of 90% strength sulfuric acid were added to 50 parts of the product described in Example 8 and stirred at 80 to 100 ° C. for 5 to 6 hours. It is then allowed to cool, poured on with stirring 800 parts of ice and neutralized with 50% sodium hydroxide solution. After extracting the mixture with ethyl acetate and removing the extractant, 48 parts of a darker one are obtained. Oil of the formula

CH ₃

CONH,

R ₁ -NH

NH-R ₂

in which R _{1 and R 2 have} the meaning mentioned in Example 8.

have lung.

Example 10

100 parts of 2,6-dichloro-3-cyano-4-methylpyridine become 250 parts of 90% sulfuric acid are added and the mixture is stirred at 70 to 100 ° C. for 4 to 8 hours. then it is allowed to cool and the mixture is poured onto 1000 parts of ice with stirring. After filtering and washing

with water, about 80 to 90 parts of a colorless powder of the formula are obtained

CONH,

that at 178 ⁰ C
1670 cm " ¹ .

melts. IR spectrum: C = O:

_1S manufacture of dyes

Example 11

25 parts of the product described in Example 10 are heated ^{to 160 to 165 ° C. with 100 parts of i-hydroxyethylamine for 4 hours.} After cooling, the mixture is mixed with 3000 parts of water and acidified to pH 3 to 4 with hydrochloric acid. It is then cooled to 0 ^° C. and the mixture is mixed with 21.2 parts of a solution of 4-amino-azobenzene diazotized as usual and then with sodium acetate solution up to pH 1 to 2. After the coupling has ended, the precipitated dye is filtered off. washes with water and dries. About 42 parts of a red-brown powder of the formula are obtained

N = N

NH -CH ₂ -CH ₁ -OH

which dissolves in dimethylformamide with a violet color and cellulose ester in red tones, polycaprolaclam- and dyes polyethylene terephthalate fabric in strong red-brown shades with very good fastness properties.

Example 12

8.3 parts of p-aminobenzoic acid-fi-methoxyalhyl ester are with 100 parts of water and 12 parts of 30% Hydrochloric acid stirred. Then 100 parts of ice and 16 parts by volume of 23% sodium nitrite solution are added and stir for 2 hours at 0 to 5 ° C. The diazonium salt solution obtained is gradually added at 0 ° C. to a solution of 12.3 parts of 2,6-di - (/ * - hydroxyethyl) -amino-3-cyano-4-methylpyridine in 350 parts of water and 12 parts by volume of 30% strength hydrochloric acid. The pH value of the is maintained during the coupling Coupling mixture by adding dropwise sodium acetate solution or 50% sodium hydroxide solution at 0 to 2. After the coupling has ended, the dyestuff which has precipitated is of the formula

CH, - O - CH ₂ - CH ₂ - O - C

CH ₃ CN

V-NH-CH, -CH, -OH
NH - CH, - CH, - OH

filtered off, washed with water and dried. A yellow powder is obtained which is in dimethylformamide dissolves with an orange-yellow color and dyes polycaprolactam and polyethylene crephthalate fabrics in yellow tones. Using the diazo and coupling components, one obtains analogously to the procedure given the following table other dyes with similar properties:

409 526/400

Diazo component OCH ₃ O
I. the same > ~ NH, Coupling comr HOCHXH ₂ HN C ₄ H ₁₁ In) HN CHj CHjOCH ₂ CH ₂ HN CHj j CH, OCH _: ('H; 11N CHj HIGH, CH _; HN Kinenle Hue of the staining Polycapro
lactam Ρ, ί \ - at UVO-Ch ₂ CH ₂ CH ₂ -NHC- Y ^v '' aUnlc
terc- game
No. CHj the same acetate phlha! O > —NH, CN Ii / -> ..
C ₂ H ₅ OC- ^} O ₂ NK ^ X NH ₂ OjN- ^; ' V-NH ₂ S - / the same yellow · = ■ ( ^ NH ₂ NH-CH ₂ CH ₂ OH yellow 13th O
j] Vl NO, the same yellow CH ₁₃ In) OC-YY -NH, yellow O
Ν yellow 14th C ₈ HpIn) OC ^ ^ y the same yellow yellow O,
Ν / <(2) -NH ₂ gdh 15th C ₀ H ₁₃ (H) OC YY) the same yellow Scarlet fever -NH ₂ Red sharp ": 16 O
Ij the same Red CHj-O-CH ₂ CH ₂ CHj-NHC- -NH ₂ yellow O Br the same gelh 17th / "X-OC- ^ J) golden yellow O
Il YOKE., the same goldgc 18th C ₂ H ₅ OC- ^ Y golden yellow goldgi 19th golden yellow yellow COOCH ₂ -CH CH, yellow 20th O ₂ N- <( Y-NH ₂ 1 yellow Scarlet fever \ - / Red sound 21 \ \ ΖΥ ^Ν " ² Red CN NH-C ₄ H ₁₁ (H) yellow 22nd CN Scarlet fever Red sharp 23 NHCH ₂ CH ₂ OCH, yellow Red CONH ₂ Red NHCH ₂ CH ₂ OCH, Dead 24 Red CONH, Red NHCHjCH ₂ OCH, Red 25th

lg on

Polyiiliiylen-

terephlhalai

pale yellow

“Idgelb

iarlach-

irlach-

Example 26

formula

CN CH ₃ CN

In-a mixture of 15 parts of nitrosylsulfuric acid "(with a content of 13.1% nitrous oxide) and 35 parts of concentrated sulfuric acid one rises at 0 to 5 ° C with stirring 12.1 parts % Amino-3-bromo-5-nitrobenzonitrile. One stirs 4 hours at 0 to 5 ° C and gives the diazcnium salt

mixing jjaun _na ch and according to a solution, cooled to OC solution of 12.3 parts of the coupling component described in Example 5 in 300 parts of water and 12 parts by volume of 30% hydrochloric acid. The pH of the coupling mixture is maintained at 0 to 15 by adding sodium hydroxide solution or sodium acetate. After coupling has ended, the precipitate which has separated out is filtered off, washed with water and dried. A dark red powder of O, N is obtained

N = N

NH

.C ₂ H ₅

C ₂ H ₅

CH, - CH ₂ - OH

10 which dissolves in dimethylformamide with a violet color and dyes polyethylene terephthalate and polycaprolactam fabric in ruby red tones.

If equivalent amounts of the diazo and coupling components listed in the table below are used and if the instructions in the previous example are followed, dyes are obtained with similar authenticity properties.

at charlach- game Ot No.

Dia7o component

Cl-

32

33

O, N

CN

- / V NH,

O, N

the same

CN

O ₂ N-if Y-NH ₂

Coupling component

CHj CN

N NH-R ₁

R ₁ = C ₂ H ₅ OH: R ,. R ₃ = C ₂ H ₅

desfil.

R ₁ = CH ₂ CH ₂ OCH,

R ₂ = CH ₃

_{R 1} = CH 2 CH ₂ OH

the same

R, = CH ₂ CH ₂ OCH ₃

R, = C ₂ H ₅

R, = CH ₂ CH ₁ OH

_{R 1} = CH 2 CH ₂ OH R ₂ . R, = C ₂ H ₅

_{R 1} = CH 2 CH ₂ OH

R, = CHXH ₂ CH ₂ OCH ₃

R., - H

N = -CN

R, CH ₂ CH ₂ CH ₂ OCH.,

R ₂ -r. CH ₂ CH ₂ OH

R, H color ion of the staining

acetate

yellow

yellow

Ruby red

Polycaprolaclam

Polyethylene terephthalate

celb

yellow

yellow

ruby

blue

yellow

blue

Red

Red

Red

Red

21

Continued 11

game no.

the same CN r "~ Coupling component Diazo component Ο, Ν ^^ - NH, CN
/ Br CH ₂ CH ₂ CH ₂ OCH ₃ O ₂ Nf;! - NH, the same R ₁ = CH ₂ CH ₂ OH
H Br R ₂ =
R ₃ = CH ₂ CH ₂ OH R ₁ = C "H, j (n) dcscl. R ₂ = H R ₃ = C "H, ₃ (n) R, = CH ₂ CH ₂ OH R ₂ = H the same R .. = CH ₂ CH ₂ OH R ₁ = - ^ ~ ' V-CH, R ₂ = H R ₃ = CH, CN the same C ) -NHR,
Vn NH-R, - (^ y-CH ₃ . *,. R, = -CH ₂ CH ₂ OH -CH ₂ CH ₂ OH. R ₁ -R- - <^ J> -OCH, CH, CN
V ζ > -NHR,
> N NH-R, -CH ₂ CH ₂ CH ₂ OCH ,. R, .R, =

dcscl.

O, N-

NO ₂

> —NH ₂ Br

the same

S (KCII, I

Ο, Ν

C ₄ H ₁₁ (H) NHSO,

NII.

NO,

Ml.

R ₁ . R ₂ = - <"\ - CH ₂ CH, OH. CH ₂ CH ₂ OH

CH, i R ₁ . R, = -CHXH-C) H.

-CHXHXIi ₂ OCH,

R ₁ , R ₂ = -CH ₂ CH ₂ OCH ,. -CH ₂ -CH ₂ -OH

Ki-K ₂ ^ CiI ₂ CH ₂ CH ₂ OCH.,. ΠΙ, (ΊΙ, OH

K ₁ . R ₂ CU, CH, OH

Color tan of the Hirbung

Λΐ-Tlal

ruby

Polycapriilaclam

bluish red

bluish gray

bluish red

Ruby red

Ruby red

ruby red! ruby red

Ruby red

ubin

CIt

Red

sih.irl.i. H

l '<: l \ .iih \ knlerephilKii.il

bluestichiiirm

bluish tints

ruby

Ruby red

Ruby red

ru there

phthalate

licliiuroi

ichiiirol

ichigroi

example
No.

47

23

Diazo component

continuation

Coupling component

4X

4 ')

O ₂ NV) -NH,
COOC ₁ H ₇ R ₁ . R ₂ CH ₂ CH ₂ OCH,
CH; CH ₂ OH Br
/
O ₁ NA-NH, dcsgl. COOCHj
CH ₂ CH ₂ OCH., I.
N
ο - Λ = ο dcsgl. \ Τ / " ^ΝΗί I.
NO ₂
COOCH ₂ CH ₂ OH ί CH, CN

50

O, N-

51

54

Br

Cl

/ "V-NH ₂

Br

Br

^ -NH,

o ₂ n- <_; Vi

-Br

O, N - <(V NH ₂ ^X Br Cl

^s > -NHR ₂

'V N

NH-R,

R ₁ = CHXH ₂ CII ₁ OCH., R, = H

R ₁ . R ₂ = - CHXH ₂ OH.

-CHXH ₂ CH ₂ OCH.,

descl.

CHXH ₂ OH. CH ₂ CH ₂ CHrOCH,

of the ill

ο, ν- /

5ft

57

5S

Cl

NH, ^ λ

■ \ - N the same.

dcsgl.

descl.

the same

R ₁ . R, - C, .H ,, (nl.

CH ₂ CH ₂ OCH,

R ₁ . R ₂ = C ₁₁ H ,, in ».

CH ₂ CH ₂ OH 24

l-'hue of l-'iirpuiig alii

l'oix.illulcn-

ΛιχΙ; ιΐ

Red

Red

scarlet

Red

scarlet

Red

Scarlet fever

idiarlach

tbrown

Scarlet fever

Scarlet fever

rothraun

M brown

I red-brown

red-brown

blue purple
blue violet

blaiiviolctt

■ • i brown

Waiiviolell blue violet

blue violet

409 526/400

example
No.

25th

Diazo component

O, N-

Br

.- NH,

N
O

O O ₂ N- ' Ml, Br CN NH

O ₂ U--

VN CH, C. N O OH - NH ₂ N Br NH CH ₂ C. CN

O, N-

NH,

ο, ν - ·

tiessil.

the same

the same

the same

NH, Br CH,
\ the same N S.
N ' s CN -CH ₂ -C CN NH NH ₂

CH,

OH

N N CH,

continuation

Coupling component

V \ U VS

MIR-NH R ₁

R ₁ , R, - CH, CH, ÜCH ,.

CH ₂ CIU (X 1I _: CH, () II j

R ₁ . R, C ^- H, - CH-CH,

R ₁ . R, :: CW ₂ C HCH ,, dl ·. -CH, - OH 26

Hue of the staining

Λ co Ui ι

Ruhin

;. · N
NH CH ₂ CH ₂ -OH

CH, CN

/ _v ~> NH CH ₂ CH ₂ N j NH -CH ₂ CH; OH

CH, CN

^ -NH- CH, - CH, - OH NH-CH ₂ CH ₂ O-CHXH ₂ CH ₂ Ch, Pohcapro-Iaet am

purple i purple

red-brown

Ruhin

Red

blue

Polyiitlv ·, tcrepiit'ti

violet

red bra ti

Red

ruby

blue

hlaustiehigrot

ruby

blue:

bluish tinge

blue

Example 70 11.5 parts of the compound of formula

COOCH, NH,

COOC ₂ H ₅

13 parts by volume of 30% hydrochloric acid and 200 parts of water were stirred. The mixture is then cooled to 0 to 5 C, 16 parts of the room at 23 ° C. are added dropwise Sodium nitrite solution is added and the mixture is stirred for 2 hours at 0 C. After adding 1 part of sulfamic acid, the mixture is left then the diazonium salt mixture gradually to form a solution of 13.5 parts cooled to OC of the coupling component mixture described in Example 7 in 300 parts of water and 12 parts by volume of 30% strength hydrochloric acid. Then you bet 10 to 50% sodium hydroxide solution up to a pH of 1.5. After the coupling is completed, the failed one Dye mixture of the formula

COOCH, CH, CN

- N = N - ^> - NH-R,

\ NH-R ₁

COOC ₂ H ₅

in which R ₁ and R _{2 have} the Bcdeu-Ui η si given in Example 7, isolated. It dissolves in dimethylformamide

orange colored and dyed polyethylene entericphlhalai fabric in strong golden yellow tones.

Example 71

> 13.1 parts of 2.4-dinilro-6-broinaniline are at 0 C. gradually in a mixture of 63 parts 85% iget Sulfuric acid and 16 parts of nilrosylsulfuric acid (with a content of 13.1% nitrous oxide) registered. After stirring for 4 to 5 hours at

ίο 0 C you add the diazonium salt mixture after and after in a cooled to 0 C solution of 13.5 parts of the coupling component mixture described in Example 7 and 1 part of sulfamic acid in 300 parts of water and 12 parts by volume of 30% hydrochloric acid. The mixture is stirred for 10 minutes and then sodium acetate and ice are added in this way. that the pH of the coupling mixture rises to 1 and the temperature 3 C does not exceeds. When the coupling is complete, the precipitated dyestuff mixture is filtered off with suction with water washed and dried. A dark-red powder is obtained which has the formula

O ₂ N--

NO, CH ₁ CN

VNN V "■; NH-R ₂

Br

NH-R,

corresponds, in which R and R _{1 have} the meanings given in Example 7. The dye mixture dissolves in dimethylformamide with a red-violet color and dyes polyethylene terephthalate fabrics in red shades.

Other dyes are obtained in an analogous way with the slides listed in the table below. and coupling components.

Diazo component

CU, <

CH ₃ O -: -; ■

O, N - <

O, N

O, N

NO;

> - NH,
NO,

NO,
V- NH,
NO,

Br
> -NH,

NO,
OCH,

■> - NH,

Coupling Composition

Example 7

desiil

desd

dcsgl

Ktrblon the 1 arbunij aiii

Oljoapro- '■ Pohjlhvien-Ι.κΊ.ιηι: tcrcphth; ilat

rar: i: c ι crap.LC

blue- j bkiu-

dcscl.

siichmroi

I «charlach

stichiuroi

stharlach

Continue Tune

30th

example

No.

Diazo component

(XN -;

O, N-

O, N

Cl

Cl

> - NH ₂

Br

V-NH ₂

COOCH ₂ CH ₂ OCH; NH,

Cl
COOC ₁ H ₇

\
Cl

COOCH,

Br- <> - ■ NH ₂

Br
CN

O, N - <\ - NH-,

Cl
NO,

O, N ■ -

O, N -

O, N

Cl
NO ₂

> - NH,

\ CN

<f 'V- NH,

S>

O, N

O, N - ·

Ο, Ν

Br

^ V- NH ₂

CN
> NH,

Br

CN

Coupling component

Example 7

devi.

the same

the same

of the el.

the same

the same

the same

the same

the same

the same

dcscl

! ■ "arblon of the Karbune

acetate

Polycaprol; u: tam

Scarlet fever

Scarlet fever

Red

orange

cirange

l'olxiilli; lercplitl ¹

Sharlai

orange

bluish tinge

Red

Waustichigrot

Red

violet

Red

blue-

sticliii ;!

blauslichic

Red

violet

Red

Scarlet scliarl red red

ing on i

Pol> äihw _L. ". i ^B ^^ l J lerephihalai I

Scarlet fever

Scarlet fever

orange

orange

bluish gr

3lauiiichiui'ii

ioleti

90

92

94

95

96

97

98

99

HK)

31

Diazo components

SOXH ₃ Ο, Ν— / V-NH,

SOX ₂ H ₅

O ₂ N

■ COOCH ₃ O ₂ N- ^ "y— NH, COOC ₃ H-
/
/ O ₂ N- ^ ^ ■) - NH,
S = / COOCH ₂ CH ₁ OCH,
/ O ₂ N -i ^ -NH ₂ ^ V
Br Br
/

O ₂ N

> - NH ₂

Br Cl

O ₂ N-

NC-

Cl Cl

J-NH ₂

Br NO ₂

V - NH,

Cl

.luirhirli-

101

O ₂ N - <( O.N - < Cl < SO ₂ CH ₃
/ JV NH ₂ V
Br SO ₂ CH ₃ ^Γ '": --- NH ₂ Cl NO, '' NH,

continuation

Clutch component

Example 7

the same

desel.

the same

the same

the same

the same

the same

the same

the same

the same

clesül.

32

Farbion de; Coloring on

AceUl

Pohcaprolacuim

Polyäl terepr

Red

Red

red-brown

red-brown rotl

red-brown

Red

Red

Example no.

102

103

K) 5

tab

• 07

KIS

IK)

112

113

33

Diazucomponcntc

Cl

O ₁ N -4 ' ;> - NH,

Cl "

Cl

CH ₃ - SO, - <f;> - NH,

α - f

ei - <<

CN

';> - NH, CK ₃

> - NH,

NH, O ₂ NJ

Cl-

Cl

Cl

NO,

CHjOCH ₂ CH ₂ NHSO ₂ -f ;> - Νίί, O

C ₂ H ₅ OCH ₂ CH ₂ OC ^> -NH,

NO,

O- = CI OC ₂ H ₅

O ₂ N ^ COOC ₂ H ₅

C ₂ H ₅ OOC NH,

N-N n '> X> - NH,

2 062

717 4 *

O, N

NH,

H ₃ C

O ₂ N < y Μ ,.

34

continuation

Coupling competent

example

desiil.

desai.

de ^ gl.

the same

the same

desul.

the same

d «sgl.

despl.

the same

Harblon's coloring on

Aectul

Polycaprolaclani

! golden yellow

orange

golden yellow

golden yellow

golden yellow I golden yellow

reddish blue

golden yellow

roiviolelt

dcsul.

Scarlet fever

scarlet

orange

Red

golden yellow

red-violet

violet violet violet

Polyethylene terephthalate

gold;.'..

gokhci!

reddish .. blue

golducih

sharp

Scarlet red

orange

Red

golden yellow

red-violet

35

continuation

yäthyleniphihaiai

)! d yellow

> ldgelb

"yellow

tslichigau

Idgclb

larlach

iarlach-

yellow

ioletl

example

No.

115

116 I.

Diazo component

! I

CH ₃ OC-CH ₁ CH, -S TN

N> -NH,

O ₂ N

H-N N

117

NH,

0, N

Br

Br

ί — Nl

Br CH ₃

O, N -ζ J- NH ₂ Cl

13)

50, C ₂ H ₄ CO ₂ CH ₃

122

123

124

125

126

127

O ₂ N

CH ₃ -S- ^ N

N> -NH ₂ ^ S ⁷

N \

S NH, NH,

O ₂ N

O ₂ N

SO ₂ CH ₃ NH ₂ CN

Ο, Ν -Υ ~ \ - NH,

" ^V " V

Br

CN

O, N

Coupling component

Example 7

the same

the same

the same

the same

the same

the same

the same

the same

Example 8

the same

the same

the same

36

Hue of the staining

Aceuu

orange

Polyeanrolactam

orange

Red

Pcilyälhylenlerephlhalat

orange

Red

blue viojell

orange

blue violetl

orange

red-brown

Red

Orange red

orange

orange

red-brown

Red

Orange red

orange

orange

blue-violet

ro ι

hlau siichigrot

ro ι

blue violet

Red

bluish tinge

Red

37

continuation

Example

No.

128

Diazo component

124

130

O _: N - <f ', - NH ₂

Br

Br

./, - ' O, N - ^, - NH,

s;.

Br

CHj-SO; < V NH,

Br

Cl

CH, -SO, - / VNH,

N - ■ C. I. NH, N N H NH NH - CH,

Cl. <(V-NH, CH, CH, OH

K ', <"■ NH,

CIU ¹ H ₂ OII

ο ■■■ - <--- ο

NH, -N - ^ '' v-NH,

O H

Coupling components lc

lurblon de 'Färbur.g; ιιιΓ Acetal

dcsiil.

the same

desnl.

Example 7 dcsjil.

the same

the same

the same

desel.

I'oljcapni- | Poh.iiln iereplilh

rol

vuelell

yellow

yellow yellow yellow

cclh

g.-lb

hot·

viol .;

i> elh i; elb

iiclb

yellow yellow yellow

yellow

yellow

Cl- <f

μ on

Polvalh \ lentereplilhalal

violet I

clb

Ib

39

example

No.

141

142

143

144

145

146

147

148

149

Diazo component

COOCpH,

j CO OC; H,

COOCH,

f Il

COOCH,

Ο, Ν

-—Η- NH,

! N

V \.-N

HO

CH, OCH, CH ₂ CH ₂ - N> = \ O

- NH,

Br

Ο, Ν - ■ <? · ■

Ο, Ν

NH,

Λ -Ν NH, CN CN O; N - * { V NH; - ■ <'"■; —NH ₂ Br SO, CH, Ο, Ν Ο, Ν

Resolution

Coupling KonipoiK'nU '

Bci-ipicl S

ilcsal.

ilesgl.

the same

CH ₁ CONII,

■ ^ V-NHR,

NH-R ₁

janaiog for example S)

R ₁ -R ₂ = CH ₂ CH ₂ OH

- CH, CH, CH, OCH,

dcscl.

des i: l.

■ lcscl.

ili'scl.

liiihlon animal läihun Λ λ · ta ι

Wan

. • ioletl

Pohuiprolailain

yellow

cd b

blue

blue

\ iolctt

blaustiehiiirol

nibin

Example no.

150

IJl

152

153

154

155

156

157

158 159

IW)

161 162

41

Diazo component Br

jN-V "> - NH ₂ Br

O ₂ N

NO ₂ > - NH ₂ Br

O ₂ N -f V-NH ₂

NO ₂ O, N -f Y-NH,

O, N

Cl

> - NH ₂ COOC ₄ H,

O, N - ~ i V NH ₃

COOC ₄ H ₁ O ₂ N- / ^ V NH ₂ Br Cl
/ O ₂ N- O- ⁿ «. Cl O ₂ N - ζ VNH ₂ S.

CH ₁ OC-CHXH ₂ -S - ^ - N

Il N

N-N

's

CN

Cl

NH ₂

continuation

Cl

Coupling component

CH., CONH,

ONLY,

• N

NH R,

(an; iloj> / u example 8 |

R ₁ . R ₂ ■ - ■ _- CH ₃ CH ₂ OH

CH ₂ CH ₂ CH ₂ OCH, C "H" lnl

the same

the same

the same

the same

the same

the same

the same

like. like. like.

the same.

42

color of the l-arhung on

acetate

violet

blue violet

scarlet

orange orange

Polycaprolaclam

ruby

Polvathy! lercphlh;

ruby

violet violet

bluish red

Red

blue stitch red

ruby

ruby

blue-violet

Red

scarlet

orangeroi scarlet

bhiusiichig

Red

I blue chi

ruby

rubii

blue

Red

scha rol

NS

43

717

continuation

44

,. , , Example

lyallnlen- _N |.

-cphthulat

. "higrol

uhigrol

ivioleu

laughing

gerol
laugh

163

164

165

166

167

168

169a

169b

170

171

Diazo component

COOCH ₃

COOCH ₁

NO ₂

N = C

Br

II C ₂ H ₅ OC

Br Cl

Br

CH ₃ -SO ₂ -

O ₂ N

O ₂ N

Br

CN

SO ₂ CH,

NO,

CN

SO ₂ CH ₃

O ₂ N

O ₂ N coupling components

CH., C ^- C) NU,

■ NHR,

> N

NH R,

(analogous to example Si

= - CHXHjOH

- CH ₂ CHXH ₂ OCH ₃

- ■ - C _1- H ₁₃ (Ii)

the same

the same

the same

the same

R _1- R ₂ = - <ζ V-CHXH ₂ OH
- CHXHXH ₂ OCH,

R "R, = -CH ₂ CHCH,

OH
- CHXH ₂ OH

CH, CONH ₂
NHR,

R ₁ -R ₂ = - \ ^ J-

"CH ₂ CH ₂ CH ₂ OCH ₃

dcsRl.

-N
NH-R ₁

Hue of the l 'staining

Acetal

bluish red

bluish red

Red

orange

Polycaprolaclam

bluish tinge

bluish tinge

Red

ruby

violet

reddish blue

violet

blue-violet

Polyethylene terephthalate

bluish tinge

bluish red

orange

Red

ruby

violet

reddish blue

violet

blue-violet

continuation

example
No. slide ^ okomponenle CN \ R ₁ . R; = Coupling component Color
Acetal O ₂ N NH ₂ the same 172 χ X y - / "V-NH ₂
^s s R ₁ . R ₂ = ^: "Φ -CH ₂ CHjCHjOH 173 J csgl. the same = - CH ₂ CHCH ₂ CH ₂ Ch ₂ CH, CH ₂ - CH,
-CH ₂ CH ₂ OH R ₁ -R ₂ 174 O ₂ N- R ₁ -R ₂ the same 175 = -CH ₂ CH ₂ OH 176 OjN- = -C ₁₁ H ₁₃ In)
-CH ₂ CHjOCH ₃ HIGH CH ₃ CONHj 177 CH ₂ CH ₂ -OH

Hue of Färbiinc j

Polycaprohetam

blue

blue

violet

violet

violet

blue

Pohalli \ leiiicreplnhalal

violet

violet

violet

example

Diazo component Coupling component Colors ι
Polyacrylic
nitrile η der Härbeun
Poly-
caprolact. g on
Polyälhy
tcrcplitli. NO; CH ₃ X; Ο, Ν- ^ ζ> - NH ₂ > N ^ - ' ruby ruby Br NH-CH ₂ CH ₂ OH X ₁ = H. X ₂ = CN and X ₁ = CN. X ₂ = H CN CH ₃ X ₂ O ₂ N- / 'S-NHj ^X ~ C VN ^ O violet violet i Br Nk-CH ₂ CH ₂ OH X, = H. X ₂ = CONHj and X ₁ = CONH ₂ . X, - H

-ing on

Polyethylene

blue

bla.i

blue

ng to l'iil) aih \ lontcrcplti i-.alal

Ruhin

violet

example

No.

180

182

183

47

Diazo component

O, N-

CN

NH,

Br

the same

the same

SOXH,

O, N

_y v.

NH,

continuation
Coupling component

CH ₃ CN

(VNHR ₁ NH-R ₂

- CH, CH, CH, OH

CN
> —NH- R,

> N
NH-R,

R ₁ . R, = - -CH ₂ CH ₂ -N ⁷ -CH ₂ CH ₃

_{/ C} H ₃

CH,

QH,

R ₁ . _{R 1} = H: - CH 2 CH ₂ N

CH,

CH ₃ CONH,

\ _j f

i (V-NH-R ₂ NH- R,

C ₂ H ₅

R ₁ . R, = - (H, CH ₂ N

scarlet

C ₂ H ₅ CH ₂ CH ₂ CH ₂ OCH ₃

SO ₂ CH, CH ₃ CN

184 0? N— <"'') - NH,!:, _X V-NH-R ₂ scarlet- scarlet-

Vn * red

H-N-R,

R ₁ . R, = - CH ₂ CH ₂ NH, CH ₂ CH ₂ CH ₂ OCIl,

Then leave to cool for 8 hours at 60 to 90 ° C. and pour the solution onto a mixture with stirring 20 parts of the dye mixture of the formula (With 300 parts of ice and 250 parts of ice water 57) fallen dye mixture is filtered off, with water

55 washed neutral and dried. You get 15 to 18 parts of a black powder of the formula

Hue of the staining

Polyacrylonitrile

Red

Red

Polycaprolact.

Polyethylene terephthalai

ruby

Red

ruby

Red

example

NO,

CH, CN

--N — Ν - Λ V - NH --- R, (, o

NH R ₁ in which R ₁ and R, the radicals - CH, CH, O CII, ^

NO,

CH., CONH,! - 4 '> --NII - R, NH-R,

and —C ₁₁ H ₁₃ (Ii) mean, at 40 to 60 (The powder dissolves in dimethylformamide with

while stirring gradually to 100 parts S5 to blue color and colors PolycaproUictam- and Poh-sulfuric acid added. One stirs - ^s hi>, älhylenlcrcphlhaiatgcwcbe in blue tones.

Example 186

100 parts of polyethylene terephthalate are finely divided in a dyebath consisting of 3000 parts of water and 9 parts o-phenylphenol and 0.3 parts of the dye from Example 104 reads 90 minutes for a Temperature of 100 "C. The yellow-colored fabric is then washed with water and then in a bath consisting of 3000 parts of water, 3 parts of sodium dithionite and 3 parts of 32% sodium hydroxide solution consists, 15 minutes reductively cleaned, washed again with water and dried.

Example 187 ' ⁵

100 parts of a fabric made of cellulose 2 ¹ ,, - acetate are dyed for 60 minutes at 80 ° C. in a bath of 30 parts of water, 1 part of the dye mixture from Example 113 and 3 parts of the reaction product of one mole of castor oil with 40 moles of ethylene oxide. A red-violet color is obtained.

Example 188

100 parts of polyester fibers are mixed with 1 part of the dye mentioned in Example 150 as usual Stained in a pressure vessel at 130 to 135 C for 1 hour. The material is then placed in a bath. which consists of 3000 parts of water, 5 parts of sodium dithionite and 5 parts of 25% sodium hydroxide solution, 15 minutes Purified reductively at 80 to 85 ° C and then washed with water. Strong red-brown colored polyester fibers are obtained. The coloring stands out characterized by excellent lightfastness and good wetfastness.

30th

35

example
No.

Diazo component

CH ₃

NH,

' Vn = N- / V-nh,

CH ₃

Example 189

100 parts of polyamide fabric are dyed for 90 minutes at 95 to 100.degree. C. in a bath containing 2,000 parts Water 1 part of the dye prepared according to Example 12 in finely divided form and 2 parts of sulfated Contains sperm oil alcohol. The golden yellow coloration obtained is characterized by good light and wet fastness properties the end.

Example 190

20Parts of p-aminoazobenzene are several hours with 120 parts of water and 0.2 parts of de.-, solution product of oleylamine stirred with about 12 moles of ethylene oxide at room temperature. To Add 40 parts by volume of 10N hydrochloric acid and fill it with ice and water to a volume of 800 parts then add 30 parts of a 23% sodium nitrite solution at 15 ° C. and stir for 2 hours at the same temperature, excess nitrous acid is then destroyed as usual.

The solution of 25 parts of 2,6-di- (1 -hydroxyethylamino-3-cyano-4-methylpyridine in 500 parts of water and 25 parts by volume of 10-hydrochloric acid) is poured into the diazonium salt mixture thus obtained 200 parts of a 55% strength sodium aceint solution are gradually added dissolves in dimethylformamide with a yellowish color . On fibers made from poly-terephthalic acid-ji: kulester or from polycaprolactam one gets fair> strong scarlet tones with excellent fastness properties.

If one uses equivalent amounts of the in <.: -: Diazo and coupling components listed in the following table and proceed according to the information; of the above example, dyes are ηι, ι obtained similar fastness properties.

Coupling component

CH,

CN

CH,

-N = -N-

NH ₂

HO-CH ₂ -CH ₂ -NH like.

the same

Kk

CH ₃

Cl-

J = N- (T

NH ₂

the same

CH,

The color of the paint

Polyester pohamiil

Scarlet fever

seharlaeh

Red

Red

Scarlet fever

Scarlet fever

grooves at ■

WHERE Share] Jy

iten coloring; No.

sulfated ~ "~ * same dye authenticity

196

rere status umihrl2Mol irt. According to mill man ^{| 97a} lOORaumleile an irt 2 Stuiisalpetrige

197b

Lisch leaves: n 2,6-dipyridine in hydrochloric acid nan then iumacetat-. If the powder is washed, tichigrolei isacid-gly- _{] 99} one stains. ler in thei nd coupling information! materials mil

II of the Aiisung on

PoK amide

198

Scarlet fever

Scarlet fever

201

202

203

204

205

51

Diazo component

Forlsel / una

52

o, f

-NH _:

Coupling component

CH,

CN

- 'N HO CH, CH, -NH NH CH. CH- OH

Hue of the paint

j upholstery j polyamide

jhordo

CH.,

O, N- <

-—NH,; \ io! etl

OCH, CH ₃ ^ - _N: = N- ^; ..- NH _;

OCH, OCH,

V-N = N- /; -NH,

OCH;

OC, H _S

VM = N - / "^%; --NH _:

violet

desj).

j ro,

cn,

i XN

HO-CH, -CH, -: ^ H NH CH, -CH, OH

desul.

j vir'.etl

! violcll

'korinlh

korintli

- N- N- /

CH, CH,

/ V-N = N - / "^ V-N

CH ₃ CH.,

CH ₃

Cl - / "" ^ - NN- / VNH, j CH ₃

_N = N - / VnH,

CH,

CH.,

/ ~ '% NN-'"-NH; i OCH, / '■ \
NH

CN

NH R,

R, I CH ₂ ClUOCH ;, R, I CHXH ₂ OlI

i -, charlach

the same

desul.

the same

Scarlet fever

! Scarlet fever

, charlach

charlach

Scarlet fever

CH,

R,

CN

= - "NH R,

rol ι ro I.

R ₁ . R ₂

CU ₂ CH; OCH, CH, CH, OH

dcsül.

continuation

Diazo component

CH ₃ coupling component

CH,

OCH ₃

CH,

Ci- <: '

V-N =

OCH, OCH ₃

- NH, CN

R ₁ . R, -

CH, - CH, OCH ₃
CH, CH, - OH

Hue of the coloring on

l'oivestcr j l'tiK.inii

Example no

the same

OCH,

CH.,

N ■■■

CHy CO

\ - - N ^ CH ₃ NH N - V; OCH, isp iel Be 208

the same

desnl.

rol

bordo

Red

A mixture that consists of the solution of 23 parts of 4 '- hydroxy - 2' - methyl - 4 - aminoazobenzene in Rough parts of a 1% sodium hydroxide solution and parts by volume of a 23% sodium nitrite solution is left within one hour at 0 to C in the mixture of 40 parts by volume of 1On salicic acid, 400 parts of ice. 6 parts of 23 "sodium nitrite solution and 4 parts of the reaction product of oleylamine with about 12 mol of ethylene oxide. The whole is stirred for a further 2 hours at 0 ° to C. Then the excess of nitrous is destroyed Acid in the usual way.

The solution of 32 parts of 2,6-di- / i-methoxyeth-I amino-3-cyano-4-methylpyridine in 400 parts of Was-.t and 12 parts by volume of 10N hydrochloric acid. Then m. N slowly pour in 300 parts by volume of a saturated sodium acetate solution. After the coupling. s the dye is isolated by suction, washed with water and dried at 80 "C. The vj The red powder obtained dissolves in 80% strength acetone with a yellowish red color. On textile matern] from polyester or polyamide, scarlet tones with a high level of fastness are obtained.

If the components given in the following examples are used instead of the aforementioned components Compounds, dyes with similar properties are obtained.

a / above groove 3Γ lind 2 5 shots additive

Zui Losun. 3-cyan f. Ach gcmisc dye washing

example

Diazo component

CH,

ho ■; · '

NH,

the same

desnl

clutch component

CH,

CN

N '
R ₁ NH NH R,

R ₁ . R; lCH; l, O CH ₁

R ₁ . R Cjll., 1111

R ,. R; CIl; CH; Oil

CH; ill, O CU,
RR CIl. CIl. OCH,

the color of the hats aiii Hurry polyester polyamide 4-me 33Te drox ' Scarlet fever Scarlet fever There from SaI zs Nat on 3 Scarlet fever Scarlet fever with verei sctiailacli sound.i Nat Estonian

the aiising on

l'nhamid

board or

hoxyüth) ί-

. · Η water

lets ma.i

Sodium-

Kupuiij

ilated. mil

et. That so

m acetone

material

Scarlet fever-

'Koinpogcnen
similar

continuation

example

No.

21?

214

215

Diazo component

Hl,

'. / ■ ■

HO ■? % NN ζ ■■; .. ■ Nil, R ₁ . R,

the same. R ₁ . R;

the same. R ₁ . R ₂ ---

the same. R ₁ . R,

Example 216

The solution of 35.5 parts of 3,5-dibromo-4-aminoa / above-zol 32 parts of nitrosylsulphuric acid (40%) are added to glacial acetic acid at 15 ° C. in 600 volume files and stirred for 2 hours at the same temperature, excess nitrosylsulfuric acid is then through /r.set of urea destroyed in the usual way.

The diazo solution is set at 15 to 20 ° C Solution of 25 parts of 2,6-di- (tf-hydroxyethylamino) -3-cyano-4-methylpyridine in 250 parts of glacial acetic acid. After the coupling has ended, enough water is gradually added to the reaction mixture that the Dye crystallized out. After suctioning off and washing with water, a brown powder is obtained.

l-arHum the I arhiingcii on
l'ohcslcr IVU.inud

H ^x
(H, CH ₂ OH

CH, ■ :( \
CII, CH ₂ OH

y
- (CH,), O CW

-CH, - CH, OH

-f Jy-CU,
CH, CH, OH

CH.,

CH ₃

Sharlaeli

Scarlet fever

Scarlet fever

Scarlet fever

Scarlet fever

Scarlet fever

Scarlet fever

scl'arlach

which dissolves in dimethylformamide with a red color. This means that they are perfectly real on polyester fibers Preserved red color.

Mils of the same diazo component are used with equivalent amounts to those in the following table The specified coupling components Rottönc obtained from similar coloring properties:

CH,

ImA

R ₁ -NH

CN

NH-R,

example

217
218

R.

HO-CH ₂ -CH ₂

HIGH,

CH ₂ - CH, - CH, - CH ₂ - CH ₂ - 0 -CH ₂ - CH, - OH CH ₂ - - CH ₂ / - "IT O -CH, - CH, - OH -O

ngen aiii
'.'!>. iniid

liarlach

harlach
li.iiiach

Example 219

A mixture of 56 parts of 2,6-dichloro-3-cyano-4-methylpyridine. 27 parts / i-Hydroxyäthjlamin. 33 parts / f-methoxy-älhylamin and 33 parts p'-hydroxy-propylamine for 2 hours at 150 C ^r stirred.

The reaction mixture is poured into the mixture of KX) O parts of ice water and 10% space parts of 10N hydrochloric acid. The pH is then set by adding 150 parts of 55% sodium acetate solution to 3.5 to 4 and shakes the aqueous phase three times with 500 Raumteüen ethyl acetate. the ■ combined ester extracts are dried with anhydrous sodium sulfate and from the filtrate Ester distilled. 66 parts by weight of a viscous oil are left behind.

The solution of 28 parts of this product in 300 parts of dimethylformamide is allowed to enter the from 20 parts of 4-aminoazobenzene according to Example 190

ss obtained diazonium salt solution slowly at 5 to 10 C. Increased 55% sodium acetate solution by gradually adding 300 parts of the room the pH is adjusted to 3 to 4. The dye thus obtained is isolated by suction, with water washed and dried at 80.degree. It is then available as a red powder in 80% aqueous acetone with a yellowish red color and the polyester and polyamide fibers in scarlet tones are excellent Dyes fastness properties.

fts Use the ones listed in the table below Aminoazobinzolc as diazo components and the same coupling component, so are Obtaining dyes with similar properties:

409526/400

example

57

Diazo component

CH ₁

NH,

HO

HO

Cl

CH ₃

// V

-NH,

CH ₃

CH,

CH ₃

■ - ^NH ;

OH

CM,

Ν Ν

^ - NH,

OCH.,

CH ₁

CHjO-Ζ \ - N

OCHj

OCH,

/ 'XX ₁ = I.

OCH ₃

7 «» 58

Color of the Λιι * Πιι1ιιΐημεη on

I'olvcslcr scarlet fever

Scarlet fever scarlet fever

bordo

polyamide

Scarlet fever

Scarlet fever

Scarlet fever

Scarlet fever

Scarlet fever

Red

Red

Red

Red

Red

bordo

Acetal

scarlet egg K

Scarlet fever

Scarlet fever

Jf

iarlach

iarlach
iarlach

Example 231

In the example 190 from 20 parts of 4-aminoazobenzene obtainable diazonium salt solution is added at 5 to 10 ° C. 1000 parts by volume of a 2.5% strength aqueous solution Solution of l-hydroxyethyl-o-aminoethyl-.Vcyan-4-methylpyridine. By adding 300 parts by volume of a saturated sodium acetate solution, the Coupling completed. The dye thus obtained is isolated by suction and washed with water and dried. A yellow-brown powder is obtained which dissolves orange-colored in hot water. In order to produced colorations on acrylonitrile polymers are orange and have very good real healing properties.

If 4-aminoazobenzene is used as the diazo component instead of the one listed in the following table Derivatives, dyes with similar coloring properties are obtained.

Hot example

No.

232

233

234

235

236

237

example

238

239

Diazo component

Color of the color on acrylonitrile polymers

-N = N

OCH ₃

NH,

CH ₃

Diazo component

CH ₃

-N = N-

NH,

OCH,

_OCH:

OCH ₃

Coupling component

Λ ' CN R ₁ Nh ' Λ _Ν - \ NHR ₂ R, .R ₂ = CH, - -CH ₂ - -O - CH _:

CH, - CH, - OH

the same

orange

orange

Scarlet fever

Scarlet fever

Red

bordo

Hue on
Polyamide polycarbonate

Red

bordo

example

61

Diazo component

V-NH ₂

CH ₁

O ₂ N- / ^ -N = N- <f VnH,

OCH,

CH,

N = N-

CH,

$ 43

244

245

246

247

248

250

CHj

-NH,

CH,

V-N = N-f V-NH

OCH,

V-N =

OCH,

CH,

H ₂ N-SO ₂

continuation

62

OCH ₅

OCH,

OCH,

the same

dcsp !.

Kuppkmgskiuiipoiienle

R ₁ . R ₂ = CH ₂ -CH ₂ -OH

CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OH

the same

the same

R ₁ -R ₂ = CH ₂ -CH ₂ -OH

CH ₂ -CH ₂ -O-CH ₂ -CH ₂ OH

R ₁ -R ₂ = CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OH

CH,

CN

H, C | i 1 CH,

\ CH ₂ CH ₂ OH CH ₂ CH ₂ OH

CH,

CN

X

R ₁ HN NHR ₂

R ₁₁ R ₂ = (CH ₂ I ₃ OCH,

the same

R ₁ . R ₂ = nC ₄ H "

the same

CH,

R ₁ -R ₂ = (CH ₂ ), -O-CH

CH ₂ -CH ₂ -OH like.

R ₁ -R ₂ = \ H y

-CH, -CH -, - OH

CH,

Harbinη on P

Polyamide 'olycslcr -

Scarlet fever

violet

Red

Scarlet fever

Scarlet fever

Scarlet fever

Scarlet fever

bordo

rol

bordo

bordo

scarlet fever

Scarlet fever

violet

Red

Scarlet fever

sfharliich

Sharia ih

scha rl a c Ii

bordo

Red

bordo

bordo

scarlet sharp Uah

.S

: || example

253

- .; 254

255

256

257

258

259

260

261

ι 262

263

63

Diazo component

continuation

64

CH ₃

NH,

OCH ₃

= N- <f V

CH ₃

V- NH,

/ CH ₃

CH,

-NH,

CH ₃

Cl

N = N- ^ f _ ^ - NH ₂

CH ₃

OCH ₃

CH ₃

CH ₃ -

^N =

CH ₃

OCH ₃

OCH ₃

V-N = N-

NHj coupling component

R ₁ . R ₂ =

-CH ₂ -CH ₂ -OH ChI ₃

CN

R ₁ -NH NH-R,

R ₁ , R ₂ = CH ₂ -CH-CH ₃

OH

desgi.

the same

the same

CN

R ₁ -NH NH-R ₂

R ₁ . R ₂ = CH ₂ -CH-CH,

OH

the same

the same

CO-NH ₂

-NH,

the same

R ₁ -NH NH-R ₂

R ₁ , R, = CH ₂ -CH ₂ -OH

CH ₂ -CH-CH ₃

OH CH ₂ -CH ₂ - OCH,

R ₁ . R, = CU ₂ -CH, OII

R ₁ . R; = CH, -CH, OH CH ₂ CH, CH ₁

Color on polyamide polyester

shariach

Scarlet fever

rol

Red

Red

board ο

red-brown

red-brown red-brown

shariach

shariach

Red

board ο

red-brown

red-brown

red-brown

409 526/400

example

65

Diazo component

continuation

CH ₃

> -N = N- <ζ y ~ NH ₂ OCH ₃

the same

OCH ₃

O ₂ N

= N- <_> -NH ₂

\ OCH ₃

the same

Coupling component

R ₁ . R ₂ = CH ₂ -CH ₂ -OH CH ₂ -CH ₂ -CH ₃

R ₁ , R ₂ = CH ₂ -CH ₂ -OH

the same

R ₁₁ R ₂ = CH ₂ -CH ₂ -OH CH ₂ -CH-CH ₃

OH
CH ₂ -CH ₂ -OCH ₃

66

Color on polyamide polyester

blue

blue

blue

blue

Be> -

blue

blue

blue

blue

The components described in the examples are obtained from the components of the table below How other dyes work:

example

Diazo component

CN

O ₂ N- <,,) - NH ₂

Br

the same

CN

the same

co; ; ch,

NO, -NI !.

Coupling component

CH ₃ CONH ₂

/ ~> -NH —R,

> N

HNR ₁

R ₁ . R ₂ = CH, -CH-CH,

OH R, = -CH ₂ -CH ₂ -OH

R ₁ . R ₂ = -CHj -CHj-OH. -CH ₂ -CH-CH ₃ OH

R ₁ . R ₂ = --CH ₂ -CH-CH ,,

OH CH ₂ -CH ₂ -CH ₂ - OCH,

the same

the same. Hue of the coloring

acetate

red violet

bluish red

bluish red

bluish red

bluish red

Pohcaprolactam

violet

roller-tinged blue

bluish red

bluish red

bluish red

bluish tinge

Polyethylene terephthalate

violet

reddish blue

bluish red

bluish red

bluish red

bluish red

67

NH ₂

279

280

281

282 283

the same

the same

the same

the same

284

CN

O ₂ N - £> -NH ₂

continuation

Coupling component 68

Hue of the staining

acetate

R ₁ , R ₂ = -CH ₂ -CH-CH ₃ ,

OH -CH ₂ -CH ₂ -CH ₂ -OCH ₃

the same

pure red

bluish red

Polycaprolactam

Polyethylene terephthalai

the same

the same

R ₁ , R ₂ = -CH ₂ -CH ₂ -OH,

OH

R ₁ = —CH ₂ —CH ₂ —CH ₂ —OCH, R ₂ = —CH ₂ —CH ₂ —OH bluish red

bluish red

bluish tinge

Red

bluish red

blue

R ₁ =
R ₂ = -QH ₁
-CH ₂ > —NH-R
■ N
R, R ₁ = -CH ₂ R ₂ = -CHj R ₁ =
R ₂ = ■ <
- -CH; R ₂ =
R ₁ = = —CH -(O
-CH-OH
ι H I.
CH ₃ -CH-CH ₃ .
j OH
, -CH ₂ -OH , -CH ₂ -OH ^) - O-CH ₃
, -CH ₂ -OH mixture
CH ₃ CN - N--

bluish red

bluish red

Red

greenish blue

bluish red

bluish tinge

Red

pure blue

greenish blue 1 pure blue

blue

R ₁ . R ₁ = -CH ₂ -CH ₂ -OH. -CH ₂ CH ₂ -OCH ₃ . -ClI ₁ -CH-CH ₃

OH charlachroi

greenish blue

green Blue

green Blue

scarlet

greenish blue

green Blue

green Blue

scarlet

example

69

Diazo component

CN

Ο, Ν — 1,; - NH,

Br NO,

O ₂ N

NO,

O, N- <> -NH,

Br SO ₂ CH ₃

Ο, Ν— < _x y ~ NH,

NH,

0, N

NH,

Br

S NH ₂

the same

the same

. -N Ο, Ν - * ^ -NH,

continuation

Coupling component

R ₁ . R, = -CH ₂ -CH ₂ -OH, -CH ₂ -CH ₂ -OCH ₃ . -CH ₂ -CH-CH ₃

OH

the same

the same

the same

X = - CONH ₂ R ₂ = - (^) - OC ₂ H ₄ OH R ₁ = _{- CH 2} -CH-CH ₃ OH

X = -CONH,

R, == —CH ₂ - ( -OH -CH. ΓΗ —CH ₃ - OH R: OH - OH X = -CH ₂ -CH = -CH ₂ -CH-CH ₃ -CH ₃ R, = -CONH ₂ OH R ₂ = -CH ₂ -CH = -CONH, -OH = -CH, -CH χ = -CH ₂ CH ₃ R, = —CONH ₂ R ₂ = -CH ₂ -CH X OH R, = —CH ₂ -CH, R:

70

Colorion of the I-iirbuni on

Acetal

X = ~ CONH, R ₁ . R, = - CH, CH-CH.,.

OH

- CH ₂ CH, ■■ CH ₂ -OCH ₃ purple

pohcuprolacuim

Red

Pol> älli \ leiilercphtlialat

Red

Red

Red

yellowishigrol

blue green

greenish bloom m

Red

violet

yellowish red

blue green

greenish blue

Red

Red

Red

violet

lcrcphtiKil.il ·. ^s P ^{ll: l}

295

om pi MKMiIe

CN
O ₂ N - <> Nile,

CN
O, N - (. V NH;

'n'

continuation

Coupling component

X;

R ₁ - - CH, CH, OH

R, ^ - CH, CH, -N SO,

X - CONH, R ₁ r- CH, CH, C) H R, = -C ¹ H, CII, CH,

1-arbtoii the 1 .iihuiii! on

Acel.ii

Pol \ ca piv
I; icl. mi

Red

rotstichicbluu

Pohällnleiilcrcphllial.n

rolstieh blue

b e ι s ρ ι e ι _v /

64 parts of 2,6-dichloro-3-carboxamide-4-methylpyridine are mixed with 80 parts of n-butylamine for 7 hours at 80 to £ stirred. Then one sets five parts ^ '- Hydroxyalhylamine added and excess Butyia mi η distilled off. The residue will last for 5 to 7 hours Stirred up to 170'C, after cooling with 100 parts of dimethylformamide and then with a mixture of 900 parts of water and 80 parts by volume 36% hydrochloric acid added. After cooling to 2s OC, the mixture is gradually added 41 parts of a customary diazotized solution of 2-chloro-4-nitro-aniline and then sodium acetate solution up to pH 2.5. After the coupling has ended, the dyestuff of the formula which has precipitated out is sucked off

blaupriiii

Cl

CH, CONH,

Ο, N - ■ /> -N = N- <'V-NH-CH ₂ -CH ₂ -CH, -CH, NH -. CH ₂ - CH ₂ - OH

i'.rüiistichichlJ

and washes it with water. After drying, a red-brown powder is obtained, which is in dimethylformamide with a bluish-red color, and polyethylene terephthalate fabric and acetate silk in red tones colors. The strong colorations obtained are characterized by very good use:; cchthciten.

Hot example

No.

298

299

300

Diazo component

O ₂ N

CN

> - NH ₂

Br

the same

CN

Coupling component

I karhton the l'arbunu on Pol valin lcntcrephthal.il

X = -CONH ₂ -CH-
I. -CH ₂ CH, Red R. R, U OH H in) R ₂ = CH ₂ - = -CONH ₂ R3 = H = H X = CH ₂ - --OH bluish red R. = - C R ₁ R,

the same

rol

409526/400

continuation

example

No.

302

303

Diazo component

O, N

// V

COOCH ₃

NH,

CH, - SO

Coupling component

X = -CONH ₂

R = H

Rl = CHj CH ₂ OH

R ₂ = -QH ₉ (Ii)

R ₁ = H

the same

the same

Color ion of the color on polyethylene terephthulal

Red

Red

orange red

Example 304

150 parts of 2,6-dichloro-3-carboxamido-4-methyl-pyridine are stirred with 250 parts of 2-hydroxypropylamine for 5 hours at 80 to 95 ° C., then allowed to cool and 800 parts of ice water are added. After acidification with hydrochloric acid to pH 6 to 4, the mixture is stirred for a further 1 hour at 0 ^° C. and the product of the formula which has precipitated out is sucked off

CH,

CONH,

Cl

> N

OH

(Melting point 140 ⁰ C)

25 parts of this compound are heated with 50 parts / Mvlethoxy-ethylamine in an autoclave 5 to 7 hours at 150 to 170 ⁰ C. Excess amine is then distilled off and the residue is treated with 150 parts of water and hydrochloric acid to pH 4. The mixture is then ^{cooled to 0 °} C. and then with a solution of 16 parts of 2-amino-5-nitro-benzonitrile diazotized as usual offset. The mixture is adjusted to a pH of 2.5 with 50% sodium acetate solution, and the precipitated dye of the formula

CN

CONH ₂

O, N- <

is isolated.

OH

NH-CH ₂ -CH ₂ -O-CH ₃ The red-brown powder dissolves in dimethylform amide with a bluish-tinted red color and dyes polyethylene terephthalate fabric with a bluish-tinted red tint. Di-staining is very good lightfast, thermosetting washfast.

Example 305

NH,

In the Diazolösuns obtained according to Example 190 des 4-Aminoazobenzene is added at 10 to 15 C 15 Teik 2,6-diamino-3-cyano ^ -methylpyridine, dissolved in a mixture of 15 parts by volume of 10N hydrochloric acid and 200 parts of water. To achieve a complete coupling, a 55% sodium acetate solution is added with 200 parts by volume set to pH = 3 to 4. The isolated and dried dye, a brown-yellow powder dissolves in dimethylformamide with a reddish yellow color. With fibers made of polyamide or polyester, golden-yellow dyeings with excellent fastness properties are obtained.

The coupling component is obtained if 94 parts of 2,6-dichloro-3-cyano-4-methylpyridine are reacted with 2000 parts by volume of 25% ammonia for 5 hours at 180 ^° C. in an autoclave. F. 226 to 227 ^C C

75

example

No

306

307

308

309

310

311

312

313

314

315

317

C)

CM ₁ OC CU, CH, S

CN

V NH,

Cl

CN

O ₂ N - <^> -NH,

CN O ₂ NZ ^- V-NH,

Cl O, N— f ^X > NH:

S NH,

S. ^N N ' / ■■ NH O ₂ N S. NH O ₂ N - < r- ^, S. \

O ₂ N- / "-NH,

CN "*> Nile,

SNN-CH, C ₂ H ₅ OOC- /> -NH ₂

CH., CH ₁ OC { > NM,

76

CH, CN

NH CM ₂ C \ l _: C, .H,

NH CH, CH ₁ - OH CH, CN

NH -CH ₂ CH, OH CH., CN

<· '"" ■ ".— NH- / O CH-CH, OH

NH -CH ₂ CH, O-CH ₁ CH, CN

f "> - NH CH, - CH ₂ O CU,

. ' —N

! NH CH, - CH, ■ - O - cn, - CH, OH

dcsjil. dcstl.

also CH, CN

-nh -ch ₁ -ch- o ch, cu, oh

CH, CN

': · ■ NH CH, CH, O-CU- CH, OH

V-NH, I.

dcspl. CH, CN

- NH CH --- :; ' ^:

'—N' - "^

NH CH ₂ CH, OH

CUy CN

-NH CH, CH, 0, H ₅

'- N

NH CH, -CH, -OH

I-; irbion dor larburm on Pol \ iilli \ leii lcrcplilhalal

riibiii

Ruby red

violet!

! \ iolet

red \ iolctt

riibin

ro!

BclhMiehiümt

Red

Bcispic

318

319

J20

322

323

324

326

77

Diazo component

CN

O ₂ NV> -

Cl

O ₂ N

NH,

CN

Br

Ii

CH ₃ -O-CCH, -CH, -S

N V N Η,

CN

O ₂ N - f> -NH,

\ Cl

CN

ζ V-NH,

CN

'VN

Br

CN

Cl

O, N

O, N-

C V-NH ₂

-NH ₂

I /

-NH, CH,

Vnh ₂

Cl

O ₂ N

continuation

Coupling component

CH, CN

\ -NH-CH ₁ -CH, -O -CH,

^ N ⁷

NH-CH ₂ -CH ₂ -0-CH ₂ -CH ₂ -OH

the same

the same

78

CH ₃ CN

<f V-NH-CH, -CH, -OH

V = N "'

NH CH ₂ -CH ₂ -O-CH, CH, CN

<f 'V-NH-CH ₂ -CH ₂ -Q ₁ H,

■; - = n nh-ch ₂ -ch ₂ -oh

CH, CN

'( V-NH-! CH, ("- OH

> = - N · "NH- (CH,)" - OH

CH, CN

<( S-NH- (CH,)., - OH

V = N ''

NH- (CH ₂ ), - OH CH ₃ CN

<(Vnh,

the same. CH, CN

V-NH- (CH,) _ft- OH NH- (CH,) ,, - OH

the same.

Hue of the l 'staining on Polyü'llnlcn tcrephtliiiliit

bluish red

rol

ruby

orange

(Acetate:

ruby

yellow (Polvamid: celbl

ruby

yellow

yellow-orange

orange

orange

Scarlet fever

example

330

O ₂ N

79

Diazo component

OCH ₃ ~ ^{Ν Η} ;

Br

331

332

333

334

Ο, Ν ^

CN

O ₂ N- ^ ~ \ - N ¹ H, NO ₂

O ₂ N

NH ₂

CN

O ₂ N- <V-NH

335

Br CN

-NH ₂

Cl NO ₂

336

337

338

Ο, Ν

O ₂ N- /

CN O ₂ N - / IV ^NHj

Br

339

340

341

CN

O ₁ N

O, N

NH ₁

NH ₂

Cl

CN

^; · NH,

continuation

80

K upplun.siskomponenle

CH ₃ CN

/ V NH- (CH,) "- OH> = Ν </
NH- (CH ₂ I ₁₁ -OH

the same

the same

the same

the same

the same

the same

the same

the same

the same

CH, CN

/ NH (CH,) ,,

'> "' - N NH (CH,) ,, OH

the same

Color ion of the coloring on Polyäihylenlerephlhalal

Scarlet fever

celbsiichigrot

rol

ruby

ruby

ruby

ruby

; itvioleU

iolelt

blauwoletl

; same

409 52i

81

continuation

Example | No.

Diazo component

342

343

J45

J46

J47

S48

J49

J50

J51

J52

353

354

O, N

SO ₂ -N (C ₂ H ₅ ), NH,

O, N

W ^S

NH,

O, N

y ν

SO ₂ -N (C ₂ H ₅

NH ₂

O ₂ N

CN

NH ₂ Br

Cl

CN

COOCH ₃

NH ₂ COOCH ₃

O, N - / ~> - NH,

COOCH ₂ -CH ₂ -OCH.,

O ₂ N - / V-NH ₂

NO,

O, N

NH,

CN

C1 ^^ J> -NH ₂ NO ₂

O ₂ N - </ ~ V-NH ₂

"ci

CN

355

O ₂ N

NH ₂

Coupling component

CH ₃ CN

-NH- (CH ₂ J ₆ -OH

NH- (CH ₂ I ₀ -OH

desul.

CH ₃ CN

-NH-CH ₂ -CH ₂ -OH

NH ₂

CH ₃ CN

NH-CH ₁ -CH ₂ -O-CH ₃

NH-LH ₂ -CH ₂ -OH CH ₃ CN

NH-CH ₂ -CH ₂ -QH ₅

NH-CH ₂ -CH ₂ -OH

the same

like. like. like. like. like. like.

the same

Shade cJlt j

Coloring on '

Pol valin lcnterephth.iij ¹ .

red scarlet

Red

ruby

orange scarlet yellow yellow red

dark roll golden yellow bluish red

yellowish red

Example no.

356

357 358

359

360

361 362 363 364 365

366 367 368 369

83

Cl

Ο, Ν

NH,

CN

CN Br

CN

Br CN

O ₂ N - <> - NH ₂

\ Cl

NO ₂

CN

O ₂ N

Cl

Br

O ₂ N

CN

Cl

O ₂ N-

NH ₂

CN

Cl- / V-NH ₂

NO ₂

O ₂ N- / VNH ₂

continuation

84

CH ₃ CN

/ V ^NH -CH, -CH, -OH

NH-CH ₂ -CH ₂ -CH ₅

the same

the same

CH ₃ CN

-NH,

NH-CH ₂ -CH ₂ -C ₁₁ H ₅

the same

the same

the same

the same

the same

CH,

<V-NH NH-CH ₂ -CH ₂ -OH

the same.

the same.

Shade of the dye on polyethylene terephthalai

Scarlet fever

yellowish red

ruby

Red

Red

Scarlet fever

Scarlet fever

Scarlet fever

yellowish red scarlet fever

ruby

Example

No. 370 371

373 374

375

376 377 378

379

85

380

Diazo component

CN

382

O, N-

O ₁ N

y /

J '

NH,

Cl

-NH,

O, N- ^ f V-NH,

O, Ν — f '> - NH,

CN

O, N — f V-NH,

Cl

O, N- <V-NH,

O, N

NH,

O ₂ N - <

CN

CN

CN

O ₂ N- ^ f 'V-NH,

O ₂ N-

O ₂ N-

CN V-NH ₂

SO ₂ CH,

γ V-NH,

continuation

(/ Cf

86

CH ₃ CN

Coupling component

CH ₃

NH-CH, -CH, -CH, -OH

desel.

the same

CH ₃ CN

NH-CH, -CH, -OH

the same

the same

OCH,

CH, / CN -CH ₂ -Q ₁ H ₅ S. V
ζ- -CH; > -NH-CH ₂ , - OH NH- , -CH ₂ -CH CHj CN -CH ₂ -CH ₅ ; - V-NH-CH ₂ , - OH NH- -CH- the same OCH, CHj / , -CH ₂ -CH CN > -NH- / ~

^ N ' ^N -'

NH-CH ₂ -CH ₂ -CH ₂ -OH

CH ₃ CN

V-NH-CH ₂ -CH ₂ -C ₁₁ H ₅

the same

the same

Hue of Färbiini! on polyallene tereplilh .i.n

yellowish seharlac !,

Scarlet fever

dark rol

yellowish igmi

rolstiehig blue

orange

yellow

dark red

ruby

ruby

87

Hot example

No.

383

384

385 386

387

388 389 390 391

continuation

88

Diazo component

COO-CH ₂ -CH ₂ -O-CH,

Coupling component

CN

Cl

0, N- /

O ₅ N

Ο, Ν-C V-NH ₂

CN

Cl - <_;> - NH ₂

COOCH ₃

CH ₃ CN

CN

NO,

O ₂ N- / VnH,

COO (CH ₂ CH ₂ O) ₃ CH ₃

NH,

the same

the same

the same. CH, CN

NH,

the same

the same

the same

the same

> - NH _{- CH 2} - CH ₂ - C ₁₁ H ₅

l-'arhtoi 1-arbiin

Polyiitli tcrcplii

Red

Sharlai

Sharia

orange

yellow

ι yellow

yellow

Claims (1)

2 claims: 1. Azo dyes made from 2,6-diaminopyridine derivatives of the general formula CH ₃
DN = NIX \ A,