DE1644370C - Process for the preparation of azo compounds which are poorly soluble in water - Google Patents

Description

The invention relates to the preparation of azo compounds of the formula which are sparingly soluble in water

DE

N = N

NH

(I)

A hydrogen, chlorine, bromine, cyano, nitro, methoxy, methoxycarbonyl or methylsulfonyl,

B nitro, methylsulfonyl, cyanomethylsulfonyl, aminosulfonyl, Methylaminosulfonyl, dimethylaminosulfonyl, ethylaminosulfonyl or diethylaminosulfonyl,

D hydrogen or chlorine,

E hydrogen, chlorine or bromine,

F hydrogen, chlorine, bromine, cyano, methyl, methoxy, acetylamino, chloroacetylamino, propionylamino, Methoxycarbonylamino or ethoxycarbonylamino,

G hydrogen, chlorine, bromine, methyl, methoxy, formylamino, acetylamino, propionylamino, butylrylamino, Valeroylamino, chloroacetylamino, chlorpropionylamino, methoxycarbonylamino, ethoxycarbonylamino, chloromethoxycarbonylamino or chloroethoxycarbonylamino, chlorine, bromine, cyano, nitro, acetyl, acetoxy,

^ Aib

IO

15th

20th

25th

30th

y y

MethoxycarbonyUÄthoxycarbony ^ aminocarbonyl, methylaminocarbonyl, Äthylaminocarbonyl, dimethylaminocarbonyl, Diäthylaminocarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy, propoxycarbonyloxy, Methoxypropylaminocarbonyl, methylsulfonyl, chloromethylsulfonyl, ethylsulfonyl, phenylsulfonyl, aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, ethylaminosulfonyl, Diäthylaminosulfonyl or Methoxypropylaminosulfonyl and
K is hydrogen, methoxy or ethoxy.

Examples of diazo components are:

1 -Amino ^ -chloM-nitrobenzene, 1 -amino ^ -chlor ^ -nitrobenzene, l-amino-l.o-dichloro- ^ nitrobenzene, 1-amino-2,5-dichloro-4-nitrobenzene, 1-amino-2-bromo-4-nitrobenzene, l-amino-2,6-dibromo-4-nitrobenzene, l-amino-6-chloro-2,4-dinitrobenzene, l-amino-6-bromo-2,4-dinitrobenzene, 2-amino-3-chloro-5-nitrobenzonitrile, ^ Amino-S-bromo-S-chloro-1-methyl-sulfonylbenzene,

2-amino-3-bromo-5-nitrobenzonitrile, 2-amino-5-nitrobenzonitrile,

l-amino-4-nitrobenzene, 1-amino - ^^ - dinitrobenzene,
2-AmInO-S-ChIOr-S-HiIrO-1-methylsulfonylbenzene, formula 4-amino-3-cyano-1-methylsulfonylbenzene, 4-amino-1-methylsulfonylbenzene, 1-amino-4-dimethylaminosulfonylbenzene, 1-amino-4 -aminosulfonylbenzene, 4-amino-3-chloro-1-methylsulfonylbenzene, 4-amino-3-chloro-1-methylsulfonylbenzene, 1-amino- ^ aminosulfonyl ^ -chlorobenzene, i-amino ^ -chloro- ^ methyl-aminosulfonylbenzene

l-Amino ^ -Chlor- ^ dimeihylaminosulfonyl-

benzene.
Preferred coupling components are, for. B .:

N- (4'-chloro-phenyl) -aminobenzene,

N- (4'-nitro-phenyl) -amino-benzene,

N- (4'-cyanophenyl) aminobenzene,

N- (4'-acetylphenyl) aminobenzene _?

N- (4'-methylsulfonyl-phenyl) -aniinobenzene,

N- (4'-methoxycarbonyl-phenyl) -aminobenzene,

N- (4'-Amino-carbonylphenyl) -aminobenzene,

N- (4'-aminosulfonyl-phenyl) -aminobenzene,

^ f. (4'-Methylaminocarbonyl-phenyl) -amino-

benzene,
N- (4'-ethylsulfonyl-phenyl) -aminobenzene,

N- (2'-chloro-4'-methylsulfonyl-phenyl) -amino-

benzene,
N- (2'-methyl-4'-methylsulfonyl-phenyl) -amino-

benzene,
N- (2'-methoxy-4'-methylsulfonyl-phenyl) -

aminobenzene,
N- (2'-Acetylamino-4'-methylsulfonyl-phenyl) -

aminobenzene,
N- (2'-methoxycarbonylamino-4'-methylsulfonyl-

phenyl) aminobenzene,
N- (2'-acetylamino-4'-chlorophenyl) -amino-

benzene,
N- (2'-propionylamino-4'-chloro-phenyl) -aminobenzene,

N- (2'-Acetylamino-4'-cyano-phenyl) -aminobenzene, N- (2'-Acetylamino-4'-nitro-phenyl) -amiuo-

benzene,
N- (2'-propionylamino-4'-nitro-phenyl) -amino-

benzene,
N- (2'-butylrylamino-4'-nitro-phenyl) -amino-

benzene,
N- (2'-Acetylamino-4'-aminocarbonyl-phenyl) -

aminobenzene,
N- (2'-Acetylamino-4'-methoxycarbonyl-phenyl) -

aminobenzene,
N- (2'-Acetylamino-4'-ethoxycarbonyl-phenyl) -

aminobenzene,
N- (2'-Acetylamino-4'-aminosulfonyl-phenyl) -

aminobenzene,
N- (2'-Butyrylamino-4'-methylsulfonyl-phenyl) -

aminobenzene,
N- (2'-acetylamino-4'-methylaminocarbonyl-

phenyl) aminobenzene,
N- (2'-Acetylamino-4'-ethylsulfonyl-phenyl) -aminobenzene,

N- (4'-nitro-phenyl) -3-methyl-1-aminobenzene, N- (4'-nitro-phenyl) -3-methoxy-1-aminobenzene

or
N- (4'-chloro-phenyl) -2-methoxy-5-acetylamino-1-aminobenzene.

The new compounds of the formula (I) are prepared by diazotizing an amine

NH,

(H)

and coupling the resulting diazonium compound with an amine of the formula

(IH)

In general, coupling is carried out in an acidic, optionally buffered, medium with cooling, for example at temperatures between 0 and 5 ° C.

The new dyes thus obtained are excellent disperse dyes. It is particularly beneficial to convert them from their use into dye preparations in a known manner. This is what they become crushed until the average particle size is about 0.01 hi-. 10 microns and especially about 0.1 to 5 microns amounts to. The comminution can take place in the presence of dispersants or fillers. For example the dried dye with a dispersant, optionally in the presence of fillers, ground or kneaded in paste form with a dispersant and then in a vacuum or dried by spraying. With the preparations obtained in this way, after adding more or less water, dye or pad or print in so-called long or short liquor.

When dyeing in a long liquor, up to about 20 g of dye per liter are generally used Pad up to about 150 g per liter, preferably 0.1 up to 100 g per liter, and when printing up to about 150 g in the kilogram of printing paste. The liquor ratio can be chosen within wide limits, e.g. B. between about 1: 3 and 1: 200, preferably between 1: 3 and 1:80.

The dyes are extremely well absorbed from aqueous suspension on moldings made from fully synthetic or semi-synthetic high molecular weight substances. They are particularly suitable for dyeing, padding or printing fibers, threads or fleeces, woven or knitted fabrics made from linear, aromatic polyesters, and from cellulose 2V ₂ acetate or cellulose triacetate. Synthetic polyamides, polyolefins, acrylonitrile polymerization products and polyynyl compounds can also be colored with them. Particularly valuable dyeings are obtained on linear, aromatic polyesters. These are generally polycondensation products from terephthalic acid and glycols, especially ethylene glycol.

It is dyed according to methods known per se. Polyester fibers can be dyed in the presence of carriers at temperatures between about 80 and 125 ° C. or in the absence of carriers under pressure at about 100 to 140 ° C. by the exhaust process. They can also be padded or printed with the aqueous dispersions of the new dyes and the impregnation obtained can be fixed at about 140 to 230 ° C., e.g. B. with the help of steam or air. In the particularly favorable temperature range between 180 and 220 ^° C., the dyes quickly diffuse into the polyester fiber and do not sublime again, even if these high temperatures are allowed to act for a longer period of time. This avoids annoying soiling of the dyeing equipment.

Cellulose-2 '/ 2-acetate is preferably dyed between about 65 and 80 ^u C and cellulose triacetate at temperatures up to about 115 ° C. The lowest pH range is between 2 and 9, and particularly 4 to 8

Usually the usual dispersants, which are preferably anionic or nonionic, are added can also be used in a mixture with one another. About 0.5 g of dispersant per liter of dye preparation are often sufficient, but larger amounts, e.g. B. up to about 3 g per liter, applied will. Amounts in excess of 5 g usually result in no further benefit. Known anionic Dispersants which are suitable for the process are, for example, condensation products from naphthalenesulfonic acids and formaldehyde, especially

special Dinaphthylmethandisulfonate, esters of sulfonated Succinic acid, Turkish red oil and alkali salts of sulfuric acid esters of fatty alcohols, e.g. B. Sodium lauryl sulfate, sodium cetyl sulfate, sulfite cellulose waste liquor or their alkali salts, soaps or alkali

sulfates of monoglycerides of fatty acids. Examples known and particularly suitable nonionic dispersants are addition products of about 3 to 40 moles of ethylene oxide on alkylphenols, fatty alcohols or fatty amines and their neutral sulfuric acid esters.

When padding and printing you will use the usual thickeners, such. B. modified or unmodified natural products, crystal gum, locust bean gum, tragent, carboxymethyl cellulose, Hydroxyethyl cellulose, starch or synthetic products such as polyacrylamides or polyvinyl alcohol.

The dyeings obtained are extremely fast, e.g. B. excellent thermosetting, subliming, Pleated, smoke gas, over-dyeing, dry cleaning, chlorine and wet fast, z. B. water, wash and sweat resistant. The etchability and reserve of wool and cotton are good. The lightfastness is excellent, even in light tones, so that the new dyes can also be used as mixing components for manufacture pastel fashion tones are very suitable. The dyes are at temperatures up to at least 220 ° C and especially at 80 to 140 ° C, resistant to boiling and reduction. This persistence will neither still adversely affected by the liquor ratio by the presence of dye accelerators. Due to their excellent sublimation fastness, the dyes are ideal for fabrics, which are subjected to a permanent pressing process in the course of their further processing.

The next comparable ones, from the French patent specification 1 261 349 and the Swiss patent specification 367 254 known dyes are the dyes according to the invention in the light fastness or inferior in fastness to sublimation.

The parts mentioned in the examples are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius.

example 1

To be 120 parts of concentrated sulfuric acid slowly added 6.9 parts of sodium nitrite at 60 to 70 ° with vigorous stirring. One is still stirring 10 minutes at 60 °, then cools to 10 ° and adds 6; i 16.3 parts of 2-amino-5-nitro at this temperature benzonitrile too. The diazotization is complete after 3 hours. The sulfuric acid diazonium salt is poured solution to a mixture of 30.4 parts of N- (2'-acetyl

amino - 4 '- methyl - sulfonyl - phenyl) - aminobenzenes 200 parts of glacial acetic acid, 150 parts of ice and 10 parts Aminosulfonic acid. The coupling is made in acidic medium by blunting with sodium acetate the pH value 2.0 to 2.5 brought to an end. The dye forms quickly and fails. It is filtered off, washed free of acid, dried and recrystallized from dioxane. The pure dye melts at 208 to 209 ° and colors synthetic fibers in red tones excellent fastness properties.

Example 2

6.9 parts are powdered to 120 parts of concentrated sulfuric acid at 60 ° to 70 ° with vigorous stirring Given sodium nitrite. Stirring is continued for 10 minutes at 60 °, then cooled to 10 ° and added at 10 to 20 ° 100 parts of glacial acetic acid and then 20.7 parts of 1-amino-2,6-dichloro-4-nitrobenzene and 100 parts of glacial acetic acid. The mixture is stirred at 10 to 15 "for 2 hours and the resulting mixture is poured Diazonium solution to a mixture of 30.4 parts of N- (2'-acetylamino-4'-methylsulfonyl-phenyl) -aminobenzene, 200 parts of glacial acetic acid, 150 parts of ice and 10 parts of aminosulfonic acid. The clutch will in acidic medium by blunting with sodium acetate to pH 2.0 to 2.5 to the end. The dye forms immediately and falls out. He will filtered off, washed acid-free, dried and made from a mixture of equal parts of alcohol and Recrystallized acetone. The pure dye melts at 223 to 224 ° and colors synthetic fibers in yellow-brown Shades with very good fastness properties.

Example 3

In a mixture of 60 parts of water and 40 parts of concentrated hydrochloric acid are at room temperature 17.2 parts of 1-amino-2-chloro-4-nitro-benzene were stirred for 3 hours. The suspension obtained is through Addition of 100 parts of ice and cooled at 0 to 5 ° within 2 hours with a solution of 6.9 parts Sodium nitrite diazotized in 100 parts of water. The mixture is stirred for a further 15 minutes and the resulting solution is added with 10 parts of aminosulfonic acid and filtered it. A mixture is added to the clarifying diazonium salt solution from 30.4 parts of N- (2'-acetylamino-4'-methylsulfonylphenylj-aminobenzene and 200 parts of glacial acetic acid. The coupling is achieved in acidic medium by blunting with sodium acetate to a pH of 2.0 to 2.5 End led. The dye forms quickly and precipitates. It is filtered off, washed free of acid and dried and recrystallized from a mixture of equal parts of ethanol and acetone. The pure dye melts at 202 to 203 ° and dyes synthetic fibers in scarlet shades with very good fastness properties.

Example 4

55

To 120 parts of concentrated sulfuric acid are slowly added at 60 to 70 ° with vigorous stirring 6.9 parts of sodium nitrite are added. The mixture is stirred for a further 10 minutes at 60 °, then cooled to 10 ° and added 20.7 parts of 1-amino-2,6-dichloro-4-nitrobenzene. The diazotization has ended after 3 hours. One relocates with 8 parts of urea and stir for a further 15 minutes 10 °. The resulting diazonium salt solution is poured into a mixture of 30.5 parts of N- (2'-acetyl-4'-aminosulfonyl-phenyl) -aminobenzene, 300 parts of glacial acetic acid and 150 parts of ice. The coupling reaction is carried out in acidic Medium was brought to an end by blunting with sodium acetate to pH 2.0 to 2.5. The dye forms quickly and fails. It is filtered off, washed free of acid and dried, recrystallized Chlorobenzene melts the pure dye at 244 to 248 °. He dyes synthetic fibers in yellow-brown Shades with very good fastness properties.

Eg game 5

To 120 parts of concentrated sulfuric acid are slowly added at 60 to 70 ° with vigorous stirring 6.9 parts of sodium nitrite are added. The mixture is stirred for a further 10 minutes at 60 °, then cooled to 10 ° and added at this temperature 20.7 parts of 1-amino-2,6-dichloro-4-nitrobenzene to. The diazotization has ended after 3 hours. The diazonium salt solution obtained is poured to a mixture of 31.8 parts of N- (2'-propionylamino - 4 '- methylsulfonyl - phenyl) - aminobenzene, 300 parts glacial acetic acid, 150 parts ice and 10 parts Aminosulfonic acid. The coupling is made in acidic medium by blunting with sodium acetate the pH value 2.0 to 2.5 brought to an end. The dye forms quickly and precipitates. It is filtered off washed acid-free and dried. Recrystallized from a mixture of equal parts alcohol and Dioxane melts the pure dye at 211 to 214 °. It dyes synthetic fibers in yellow-brown shades with very good fastness properties.

Example 6

6.9 parts are powdered to 120 parts of concentrated sulfuric acid at 60 ° to 70 ° with vigorous stirring Given sodium nitrite. The mixture is stirred for a further 10 minutes at 60 °, cooled to 10 ° and then 20.7 parts are added Amino-2,6-dichloro-4-nitro-benzene to. The mixture is stirred for 2 hours at 10 ° and the resulting diazonium salt solution is poured to a mixture of 26 parts of N- (2'-acetylamino-4'-chlorophenyl) aminobenzene, 300 parts of glacial acetic acid, 150 parts of ice and 10 parts of aminosulfonic acid. The coupling is completed in an acidic medium. The dye forms quickly and precipitates. It is filtered off, washed free of acid and dried. The pure dye dyes synthetic fibers in yellow-brown shades with excellent fastness properties.

Dyeing instruction 1

7 parts of the dye obtained according to Example 1 are mixed with 4 parts of dinaphthylmethandisulfonsaurem Sodium, 4 parts of sodium cetyl sulfate and 5 parts of sodium sulfate in a ball mill for 48 hours ground to a fine powder. 2 parts of the dye preparation obtained in this way are dissolved in 3000 parts of water which 3 parts of a 30% solution of a highly sulfonated castor oil and 20 parts of an emulsion of a contains chlorinated benzene, dispersed. At 20 to 25 " if 100 parts of polyester fiber fabric are introduced, the » the bath in about 30 minutes to 95 to 100 ° and dye 1 hour at 95 to 100 °. The material to be dyed is made from derr Taken bath, rinsed, 15 minutes at 70 ° with a egg 0.1% solution of an alkylphenyl polyglycol ether! soaped, rinsed again and dried. You get a red dyeing with excellent fastness properties

Staining instruction 2

30 parts of the dye obtained according to Example 2: are mixed with 40 parts of dinaphthylmethandisulfonsau rem sodium, 50 parts of sodium cetyl sulfate and 50 parts of anhydrous sodium sulfate in a ball mill Ground to a fine powder for 48 hours.

To 4 parts of the dye preparation obtained in 1000 parts of 40 to 50 ° warm water are added 100 parts purified. Polyester fiber material and heats slowly. Staining takes about 60 minutes under pressure at 130 ° and becomes yellow-brown in color after rinsing, soaking, rinsing and drying with excellent fastness properties.

Dyeing instruction 3

An aqueous, finely dispersed suspension of 30 parts of the dye obtained according to Example 2 , 70 parts of sodium dinaphthylmethanedisulphonic acid and 3 parts of sodium alginate is made up to 1000 parts with water and mixed well. A polyester fabric is padded with the padding liquor obtained at 20 °, dried with air at 60 to 100 ° and then treated with hot, dry air at 230 ° for 60 seconds. The fabric is then rinsed, soaped, rinsed again and dried. A yellow-brown, level dyeing with good fastness properties is obtained.

Dyeing instruction 4

15 parts of the dye obtained according to Example 1 are mixed with 20 parts of sodium dinaphthylmethandisulfonsaurem, 25 parts of sodium cetyl sulfate and 25 parts of anhydrous sodium sulfate in a ball mill Ground to a fine powder for 48 hours.

100 parts of purified water are added to 5 parts of the dye preparation obtained in 4000 parts of water Cellulose triacetate fiber fabric and slowly heated to 95 to 100 °. The material to be dyed is taken out of the bath, rinsed, 15 minutes at 70 ° with a 0.1% solution of an alkylphenol polyglycol ether soaped, rinsed again and dried a red dyeing with good fastness properties.

Dyeing instruction 5

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

2 parts of the dye preparation thus obtained are in

3000 parts of water, which contains 3 parts of a 30% solution of a highly sulfonated castor oil, dispersed. At 20 to 25 °, 100 parts of Cellu-

loose-27 ₂ acetate fiber fabric and heats the bath to 80 to 82 ° in about 30 minutes. This is followed by dyeing at 80 to 82 ° for 1 hour. The dyed material is made from the

Taken a bath, rinsed, soaped, rinsed again and

then dried. A red color is obtained with good fastness properties.

Staining instruction 6

7 parts of the dye obtained according to Example 5 are with 13 parts sulfite cellulose liquor powder and Milled 100 parts of water in a ball mill.

The paste obtained is dried by spraying.

4 parts of the dye preparation obtained are with A little water made into a paste and put through a sieve 4 parts of N-oleyl-N'-hydroxy-ethyl-N '- (3'-sulfo-2'-hydroxypropyl) -ethylenediamine in 4000 parts of water containing dye bath added. 100 parts of polyamide fiber material are now added to the bath at 20 °, heats this to 100 ° within 30 minutes and colors at 100 ° for 1 hour. The yellow-brown obtained The dyeing is rinsed and dried. It does not matter and has good fastness properties.

The colors given in the following table

shocks are made by the method according to Example 1 from a diazotized amine of the formula (II) and a compound of the formula (III) produced. The constitution of the specified dyes corresponds the formula

A-N = N-B-NH-D

the azo group in each case in the 1-position on nuclei A and B and the amino nitrogen in the 4-position to the nucleus B and in the 1-position aa the benzene nucleus D is bound.

example A. B. D. Shade on polyester S. 7th 2-bromo-4-nitro-phenyl -C ₆ H ₄ - 2-acetylamino-4-methyl-
^ iilfnnvi-nlipnvl Scarlet fever 8th 2,6-dibromo-4-mtro-phenyl C ₆ H ₄ the same Yellow-brown 9 2-chloro-4-methylsulfonyl- -C ₆ H ₄ - the same orange phenyl 10 2,4-dinitro-phenyl -C ₆ H ₄ - the same Red 11th 2,4-dinitro-6-bromophenyl -C ₆ H ₄ - desgL violet 12th 2-chloro-4-nitro-phenyl -C ₆ H ₄ - 2-acetylamino-4-nitro-
phenyl Scarlet fever 13th 2-cyano-4-nitro-phenyl -C ₆ H ₄ - the same Red 14th the same -C ₆ H ₄ - 2-propionylamino-4-nitro-
ηϊιβπνΐ Red 15th 2,6-dichloro-4-nitro-phenyi -C ₆ H ₄ - 2-AcetylamiiH> 4-nitrQ-
ohenyl · Yellow-brown 16 2,6-dibromo-4-nitro-phenyl -C ₆ H ₄ - 4-methylsalphonyl-phenyI Yellow-brown 17th the same -C ₆ H ₄ - 2-methoxycarbonylamffio- j Scarlet fever 4-methylsulfonyl-phenyi 18th 2-Ογ3ΐι> 4-ηϊίΓθ-ρ1ιβην1 -C ₆ H ₄ - desgL Red 19th 2-cyano-4-nitro-6-bromo ^ C ₆ H ₄ - the same ruby phenyl 20th 2-cyano-4 ^ utrophenyl -C ₆ H ₄ - 2-acetyiamino-4-ciiloro ^; RoI phenyl

209632/252

continuation

ok

10

example A. the same B. D. Shade on polyester 21 -C ₆ H ₄ - 2-acetylamino-4-amino- Red 2,6-dichloro-4-nitro-phenyl sulfonyl-phenyl 22nd 2-chloro-4-nitro-6-bromo -C ₆ H ₄ - 2-acetylamino-4-amino-
carhnnvl-nhpnvl Yellow-brown 23 phenyl Z * " ¹ TJ
1 ^ ₆ H ₄ ^ dI VJ Wl Ij 1 LJ k IV ^ 11 V 1
2-acetylamino-4-methyl- Yellow-brown 2,6-dichloro-4-nitro-phenyl aminocarbonyl-phenyl 24 2,4-dinitro-6-bromophenyl -C ₆ H ₄ - the same Yellow-brown 25th 2-chloro-4-nitro-6-bromo C ₆ H ₄ 2-acetylamino-4-nitro-
phenyl violet 26th phenyl -C ₆ H ₄ - 2-acetylamino-4-methyl- Yellow-brown 2-0110 ^ 4 - ^^ 0-6- ^ 001-
nhf * nv1 sulfonyl-phenyl 27 Li UCIl j X
the same C ₆ H ₄ 4-methylsulfonyl-phenyl Yellow-brown 28 -C ₆ H ₄ - 2-acetylamino-4-amino- Yellow-brown 2,6-dichloro-4-nitro-phenyl carbonyl-phenyl 29 2,6-dibromo-4-nitro-phenyl -C ₆ H ₄ - 4-methylsulfonyl-phenyl Red 30th the same -C ₆ H ₄ - l-acetylamino ^ amino-
es rhf> n vl -nli ρύ \ v1 Yellow-brown 31 C ₆ H ₄ VhL UVU Jf 1 Ullbll J1
2-acetylamino-4-methyl- Yellow-brown 2,6-dibromo-4-nitro-phenyl aminocarbonyl-phenyl 32 2,5-dichloro-4-nitro-phenyl -C ₆ H ₄ - 2-formylamino-4-methyl-
<5ul fön vl-nil pn vl Yellow-brown 33 2,6-dichloro-4-nitro-phenyl C ₆ H ₄ the same Scarlet fever 34 2-chloro-5-methylsulfonyl- C ₆ H ₄ l-propionylamino ^ methyl-
sulfonvl-nlietivl Yellow-brown 35 phenyl C ₆ H ₄ 2-acetylamino-4-amino- orange 2-chloro-4-nitro-6-bromo carbonyl-phenyl 36 phenyl . T "C ₆ H ₄ the same Yellow-brown 4-nitro-phenyl 37 -C ₆ H ₄ - 2-acetylamino-4-amino- orange 2-methoxycarbonyl-phenyl sulfonyl-phenyl 38 2-chloro-4-aminosulfonyl-
nViPnvl -C ₆ H ₄ - 2-chloro-4-methylsulfonyl-
phenyl orange 39 tjiiciiyi
l-Melhyisuifooyl- ^ hlor-
plienyl -C ₆ H ₄ - 4-chlorophenyl orange 40 S ^ -Dichlor- ^ - nitro-phenyl -CA- 2-acetylamino-4-nitro-
phenyl orange 41 2-methoxycarbonyl- -C ₆ H ₄ - the same orange 42 4-methylsulfonyl-phenyl -C ₆ H ₄ - 2-acetylamino-4-methyl- orange 2-cyano-4-nitro-phenyl sulfonyl-phenyl 43 -C ₆ H ₄ - 3-acetylamino-4-chloro- Reddish 2-cyano-4-nitro-6-chloro phenyl violet 44 phenyl -C ₆ H ₄ - desgL violet 2,6-dichloro-4-nitro-phenyl 45 2-chloro-4-nitro-6-bromo -C ₆ H ₄ - 4-acetyl-phenyl Yellow-brown 46 phenyl -C ₆ H ₄ - 2-propionylamino-4-methyl- Yellow-brown 2-cyano-4-nitro-phenyl sulfonyl-phenyl 47 -C ₆ H ₄ - 2-acetylamino-4-chloro Red 2,4-dinitro-6-bromophenyl methylsulfonyl-phenyl 48 2-cyano-4-nitro-phenyl -C ₆ H ₄ - l-acetylamino- ^ nitro-
τΛρτϊ vl - ' violet 49 -C ₆ H ₄ - 2-acetylamino-4-bromo Red 2-methoxy-4-nitro-phenyl 5-acetylamino-phenyl 50 2-methylsulfonyl-4-nitro- -C ₆ H ₄ - 4 <3ilor-phenyl Hot 51 phenyl -C ₆ H ₄ - 2-acetylanuno-4-chloro-; Red 2-chloro-4-nitro-phenyl phenyl 52 * ■ ⁼ C ₆ H ₄ 2 ^ 00 ^ 1310 ^ 10-4-0160 ^ 1-; i ■ scarlet fever sulfonyl-pheoyl

11th

continuation

example A. B. * -C ₆ H ₄ - D. the same Shade on polyester 53 2,6-dichloro-4-nitrophenyl -C ₆ H ₄ - 2-formylamino-4-methyl- Yellow-brown 54 2-chloro-4-nitro-6-bromo- C ₆ H ₄ 2-acetylamino
"nVienvlen sulfonyl-p'henyl Scarlet fever phenyl C ₆ H ₄ the same 55 2-cyano-4-nitro-phenyl -C ₆ H ₄ - the same Red '56 2-chloro-4-methylsulfonyl-
nhenvi C ₆ H ₄ -C ₆ H ₄ - the same orange 57 UllwllJ L
2,5-dichloro-4-methyl- C ₆ H ₄ Scarlet fever sulfonyl-phenyl 2,5-dimethyl the same 58 2-NitΓO-4-methylsulfonyl-
nVien vi -C ₆ H ₄ - phenylene the same Red 59 2-methylsulfonyl-4-nitro-
phenyi C ₆ H ₄ -C ₆ H ₄ - 2-formylamino-4-nitro- Red 60 2-chloro-4-nitro-6-methyl- C ₆ H ₄ C ₆ H ₄ -, phenyl Red sulfonyl-phenyl 4-nitro-phenyl 61 2-cyano-4-nitro-phenyl -C ₆ H ₄ - -C ₆ H ₄ - 2- / 3-chloroethoxycarbonyl Red 62 2-bromo-4-nitro-phenyl -C ₆ H ₄ - -C ₆ H ₄ - amino-4-methylsulfonyl- Scarlet fever -C ₆ H ₄ phenyl 2-acetylamino-4-methyl-
sulfonyl-phenyl
2-acetylamino-4-acetyl- 63 2,5-dichloro-4-nitro-phenyl C ₆ H ₄ C ₆ H ₄ . ■ sulfonyl-phenyl Scarlet fever 64 2,6-dichloro-4-nitro-phenyl C ₆ H ₄ the same Yellow-brown 2-methoxycarbonylamino 65 2-chloro-4-nitro-6-bromo
nhpnvi -C ₆ H ₄ - 4-methylsulfonyl-phenyl Yellow-brown 66 the same -C ₆ H ₄ - the same Yellow-brown the same 67 2,5-dichloro-4-nitro-phenyl C ₆ H ₄ 2-propionylamino-4-amino- Yellow-brown 68 2-cyano-4-nitro-phenyl -C ₆ H ₄ - sulfonyl Red 69 2,6-dichloro-4-nitro-phenyl -C ₆ H ₄ - 2-Aoetylanuno-4-methylyl- Yellow-brown aminosuifonyl-phenyl 70 2-cyano-4-nitro-phenyl -C ₆ H ₄ - 4-phenylsulfonyl-phenyl Red 2-methyl-4-ethoxycarbonyl- 71 2,6-dichloro-4-nitro-phenyl -C ₆ H ₄ - phenyl Yellow-brown 72 2-chloro-4-methylsulfonyl- -C ₆ H ₄ - 2-ethoxycarbonyl-4-nitro- orange phenyl phenyl 73 2-CbIoro-4-nitro-phenyl -C ₆ H ₄ - 2-acetylamino-4-cyano- Scarlet fever phenyl 74 2-cyano-4-nitro-phenyl 4-nitro-phenyl ...; Red 2-acetylamino-4-amino- 75 2,6-dichloro-4-nitro-phenyl sulfonyl-phenyl Yellow-brown 76 desgL 2 - ^ - chlorpropionylainJno- Yellow-brown 4-methylsulfonyl-phenyl 77 the same 2 ₃ 5-dimethoxy-4-nitro7 _. Yellow-brown phenyl 78 2-Bromo-6-chloro-4-methyl: 4-cyano-phenyl Yellow-brown sulfonyl-phenyl 2-acetylamino-4-cyano- 79 2-cyano-4-nitro-phenyl : phenyl. -. Red 80 2-nitro-4-methylsulfonyl- 2-Metiiöxycarbonylainmo Red phenyl 4-acetyl-phenyl - i _t / 81 2,6-dibromo-4-nitro-phenyl 2-Acetylamino-4-acetyl- - ..
ohenvl JGibbratm 82 2-cyano-4-nitro-phenyl desgL,: _{j ;;} Red 83 desgL 3-nitro-phenyl, s' : Rpt 84 2-chloro-4-nitro-phenyl ,-Scarlet fever ' 85 2-cyano-4-nitro-phenyl Red-

■ V

continuation

ir

example A. > 2,6-dichloro-4-nitro-phenyl ■ B. D. Shade on polyester 86 2-cyano-4-nitro-phenyl dcogl. 2-cyano-4-nitro-phenyl -C ₆ H ₄ - 2-methoxy-4-chlorophenyl ruby 87 2,6-dichloro-4-nitro-phenyl 2-cyano-4-nitro-phenyI C ₆ H ₄ 4-methoxycarbonyloxy Yellow-brown the same 2-methylsulfonyl-4-nitro- phenyl 88 the same phenyl -C ₆ H ₄ - 4-ethoxycarbonyloxy-phenyl Yellow-brown 89 the same 2-methylsulfonyl-4-nitro- 2-chloro-4-methylsulfonyl-
phenyl -C ₆ H ₄ - 4-propyloxycarbonyloxy-
nnpnvi Yellow-brown 90 2-cyano-4-nitro-phenyl phenyl 2-chloro-4-aminosulfonyl-
Γ * ϊΐΡΤΐν1 -C ₆ H ₄ - LJiiviiyi
4-ethoxycarbonyloxy-phenyl Yellow-brown 91 the same 2,6-dicblor-4-nitro-phenyl jjUwiujri
• l ^ Mor- ^ methylamino ^ -C ₆ H ₄ - 4-acetoxyphenyl Yellow-brown 92 2-methylsulfonyl-4-nitro- the same ^ adfonyl-phenyl C ₆ H ₄ 4-nitro-phenyl Red phenyl desgL 93 2-chloro-4-methylsulfonyl- -C ₆ H ₄ - the same orange phenyl 94 Z-ChloM-aminosulfonyl- -C ₆ H ₄ - the same orange phenyl 95 2-chloro-4-methylamino -C ₆ H ₄ - the same orange sulfonyl-phenyl 96 2-chloro-4-dimethylamino C ₆ H ₄ the same orange sulfonyl-phenyl 97 the same -C ₆ H ₄ - 2-acetylamino-4-nitro-
nhenvi orange 98 2-chloro-4-methylamino -C ₆ H ₄ - l / llvllj 1
the same orange sulfonyl-phenyl 99 2-chloro-4-aminosulfonyl-
nit pn from left -C ₆ H ₄ - the same orange 100 LF11 till jr 1
2-ChloΓ ■ 4-methylsulfonyl-
Till pn from left -C ₆ H ₄ - 2-acetylamino-4-nitro-
ohenvl orange 101 % J 11WU j L
2-methylsulfonyl-4-nitro- C ₆ H ₄ L / UvUj Ä
the same Red phenyl 102 the same C ₆ H ₄ 2-propionylamino-4-nitro- Red phenyl 103 the same -C ₆ H ₄ - 2-PrOPiODyIaTnUiO ^ ChIOr- Red phenyl 104 2-methyl
nil pn vl cn 2-nitro-phenyl Red 105 Lyii wiiy iwu
2-methoxy the same Red phenylene 106 2-acetyiamino the same Roi phenylene 107 2-methyl the same violet phenylene 108 2-methyl
nnpnvien 4-methoxycarbonyloxy
nhptivl violet 109 LyIl vll V Jl vl 1
2-methyl
nii en vl en L / lJlw 11 j I
_v 4-ethoxycarbonyloxy-phenyl violet 110 uiiviiy iwii
2-methyl 4-propyloxycarbonyloxy- violet phenylene phenyl in 2-methyl
nhenvlen 4-ethoxycarbonyloxy-phenyl Red 112 Lrliviij Λ \ ^ Α4
2-methyl
nnenvien 4-acetoxyphenyl Red 113 ifiivuy ivu
-C ₆ H ₄ - 4-nitro-phenyl Red 114 -C ₆ H ₄ - desgL -Orange 115 C ₆ H ₄ . the same orange 116 -QH ₄ - desgL Orange;

2478

Example 117 118 119 120 121 122

123 124 125 126

127 128

129

130 131 132

133 134 135

136

137 138

139 140 141 142 143 144

145 146 147 148

2-chloro-4-dimethylaminosulfonyl-phenyl the same

2-cyano-4-nitro-phenyl like.

2-methylsulfonyl-4-nitrophenyl

2-chloro-4-n? Tro-phenyl

2-chloro-4-nitro-6-cyano

phenyl 2,4-dinitro-6-bromophenyl

2-chloro-4-nitro-6-bromo

phenyl 2,6-dibromo-4-nitro-phenyl

the same

2-chloro-4-nitro-6-bromo

phenyl 2,6-dichloro-4-nitro-phenyl

the same. 2-chloro-4-nitro-6-bromo-

phenyl 2,6-dibromo-4-nitro-phenyl

desg'i. 2-chloro-4-nitro-6-bromo

phenyl 2-chloro-4-nitro-6-bro-i-

phenyl

2,6-dibromo-4-nitro-phenyl desgl.

2,6-dichloro-4-nitro-phenyl 2-methylsulfonyl-4-nitro-

phenyl 2-chloro-4-methylsulfonyl-

phenyl 2-chloro-4-aminosulfonyl-

phenyl 2,6-dichloro-4-nitro-phenyl

l-chlorine ^ -nitro-o-bromine-

phenyl 2,6-dibromo-4-nitro-phenyl

the same.

2 ~ chloro-4-nitro-6-bromophenyl

-C ₆ H ₄ - -C ₆ H ₄ -

2-acetylaminophenylene

2-methoxy

phenylene 2,5-dimethoxy

phenylene 2-methoxy carbon

nylamino

phenylene 2-chloramino

phenylene 2-acetyl-5-ether

oxyphenylene

2,5-dimethoxy

phenylene -C ₆ H ₄ -

-C ₆ H ₄ - -C ₆ H ₄ -

-C ₆ H ₄ -

-C ₆ H ₄ - -C ₆ H ₄ - -C ₆ H ₄ -

-C ₆ H ₄ - -C ₆ H ₄ - -C ₆ H ₄ -

-C ₆ H ₄ -

-C ₆ H ₄ - -C ₆ H ₄ -

-C ₆ H ₄ - -C ₆ H ₄ -

-C ₆ H ₄ - -C ₆ H ₄ -

- C ₆ H ₄ C ₆ H ₄

-C ₆ H ₄ -C ₆ H ₄

-C ₆ H ₄ -C ₆ H ₄

2-acetylamino-4-nitro-

phenyl
4-methylsulfonyl-phenyl

the same
the same
the same

4-nitro-phenyl
4-nitro-phenyl
4-methyl-sulfonyl-phenyl

2-acetylatenino-4-nitrophenyl

the same

2-propionylamino-4-nitrophenyl
the same

the same

4-chloro-phenyl
the same

the same

4-nitro-phenyl
the same

2-acetylamino-4-chloro

phenyl
the same
2-butyrylamino-4-methyl-

sulfonyl-phenyl

the same

2-acetylamino-4-cyanophenyl
the same

the same. '

2-acetylamino-4-chloromethylsulfonyl-phenyl

the same
the same

2-propionylamino-4-methyl sulfonyl-phenyl

2-acetylamino-4-ethylsulfonyl-phenyl

2-acetylamino-4-aminosulfonyl-phenyl

Nuance on polyester orange orange violet violet violet violet

Red blue purple yellow brown

Yellow-brown Yellow-brown

Yellow-brown

Yellow-brown Yellow-brown Yellow-brown

Yellow-brown Yellow-brown Yellow-brown

Yellow-brown

Yellow-brown Yellow-brown

Yellow-brown red

Orange orange yellow brown yellow brown

Yellow-brown Yellow-brown

Yellow-brown Yellow-brown

t "i

Γ ¹ ' 17th A. the same 1644 370 If) continuation D. Shade on polyester B. 2-propionylamino-4-amino- Yellow-brown 2,6-dibromo-4-nitro-phenyl l ^v 18 -QH ₄ - sulfonyl-phenyl example the same the same Yellow-brown 149 -QH ₄ - 2-acetylamino-4-methyl- Yellow-brown 2-chloro-4-nitro-6-bromo -QH ₄ - aminosulfonyl-phenyl 150 phenyl the same Yellow-brown 151 2,6-dichloro-4-nitrorphenyl -QH ₄ - the same the same Yellow-brown 152 -QH ₄ - - 2-propionylamino-4-methyl- Yellow-brown 2,6-dibromo-4-nitro-phenyl QH ₄ aminosulfonyl-phenyl 153 2-chloro-4-methylamino the same Yellow-brown 154 sulfonyl-phenyl - QH ₄ - 2-acetylamino-4-cyano- orange the same -QH ₄ - phenyl 155 2-chloro ^ r-aminosulfonyl-
phenyl 2-acetylamino-4-chloro orange 156 2-chloro-4-methylsulfonyl- -QH ₄ - the same orange phenyl -QH ₄ - the same orange 157 2-bromo-4-methylsulfonyl- -QH ₄ - 158 phenyl 2-acetylamino-4-chloro orange 159 the same - QH ₄ - phenyl 2-acetylamino ^: 4-amino- orange 160 2-chloro-4-methylsulfonyl- -QH ₄ - sulfonyl-phenyl phenyl the same orange 161 2-chloro-4-aminosulfonyl-
nlipnvl -QH ₄ - | J1 It'll J k
2-chloro-4-methylamino the same orange 162 sulfonyl-phenyl -QH ₄ - the same orange 2-methylsulfonyl-4-nitro- -QH ₄ - 163 phenyl the same Red 164 the same -QH ₄ - 2-acetylamino-4-methyl- Red 165 2-methylsulfonyl-4-chloro
nhpnvl -QH ₄ - aminosulfonyl-phenyl 2-chloro-4-methylsulfonyl- the same orange 166 phenyl -QH ₄ - the same orange 2-chloro-4-aminosulfonyl- -QH ₄ - 167 phenyl the same orange 168 2-chloro-4-methylamino - QH ₄ - sulfonyl-phenyl the same orange 169 2-chloro-4-dimethylamino -QH ₄ - sulfonyl-phenyl the same orange 170 2,6-dichloro-4-nitro-phenyl -QH ₄ - 2-acetylamino-4-dimethyl- Yellow-brown 171 2-chloro-4-nitro-6-bromo -QH ₄ - amino-sulfonyl-phenyl phenyl the same Yellow-brown 172 2,6-dibromo-4-nitro-phenyl -QH ₄ - the same the same Yellow-brown 173 QH ₄ 2- propionylamino-4-di- Yellow-brown -QH, - methylaminosulfonyl- 174 2,6-dichloro-4-nitro-phenyl phenyl 175 the same the same Yellow brown;: -QH, - 2-AcetyIamino-4-ethyl- Yellow-brown 2-chloro-4-nitro-6-bromo QH, aminosulfonyl-phenyl 176 phenyl the same Yellow brown i 177 2,6-dibromo-4-nitro-phenyl L ₆ M, thegl. Yellow brown | 178 -QH, - 179

continuation

example A. desgL B. D. Shade on polyester 180 -C ₆ H ₄ - 2-acetylamino-4- (3'-meth- Yellow-brown oxypropyl) -amino- 2-ChloΓ-4-nitro-6-bromine-
nhpfivl sulfonyl-phenyl 181 2,6-dichloro-4-nitro-phenyl -C ₆ H ₄ - the same Yellow-brown 182 desgL -C ₆ H ₄ - desgL Yellow-brown 183 -C ₆ H ₄ - 2-AcetylaInirio-4-phenyl- Yellow-brown 2,6-dibromo-4-nitro-phenyl aminosulfonyl-phenyl 184 the same -C ₆ H ₄ - 3-methyl-4-nitro-phenyl Yellow-brown 185 the same 2-chloro-phenylene 3-chloro-4-nitro-phenyl Yellow-brown 186 2,5-dimethyl 2,5-dimethoxy-4-nitro- Yellow-brown 2,6-dichloro-4-nitro-phenyl phenylene phenyl 187 the same 2 - / ^ chloropropionyl-amino- Yellow-brown 2-chloro-4-nitro-6-bromo
nfipnvi 4-methylsulfonyl-phenyl 188 2,6-dichloro-4-nitro-phenyl the same the same Yellow-brown 189 2,6-dibromo-4-nitro-phenyl the same 2-methyl-4-nitro-phenyl Yellow-brown 190 2-ChloΓ-4-nitΓO-6-bΓom-
nlipnvl the same the same Yellow-brown 191 JJIL / IXJ 1
the same the same the same Yellow-brown 192 2,6-dichloro-4-nitro-phenyl the same 2-chloro-4-nitro-phenyl Yellow-brown 193 the same the same the same Yellow-brown 194 2,6-dibromo-4-nitro-phenyl the same 2,4-dichloro-phenyl Yellow-brown 195 the same the same the same Yellow-brown 196 2,6-dichloro-4-nitro-phenyl the same 2-methoxy-4-nitro-phenyl Yellow-brown 197 the same 2-methoxy-4-nitro-phenyl Yellow-brown 198 2,6-dibromo-4-nitro-phenyl -C ₆ H ₄ - 2-chloro-4-methylsulfonyl-
phenyl Yellow-brown 199 2,5-dichloro-4-nitro-phenyl -C ₆ H ₄ - the same Yellow-brown 200 4-aminosulfonyldaphthyl 2-chloro-phenylene 4-diethylaminosulfonyl-
T ^ Ii f »n vi orange 201 2-propionyl LJ U ^ / kl J 1
4-ethylaminocarbonyl- orange 2-chloro-4-dimethylamino atnino-pheny- phenyl 202 sulfonyl-phenyl IVlI
2-nitro-phenylene 4- (3'-methoxypropyl) - orange 2,5-dichloro-4-dimethyl- aminocarbonyl-phenyl 203 aminosulfonyl-phenyl 2-acetylamino 4-nitro-phenyl orange 5-ethoxy 2,6-dichloro-4-dimethyl- phenylene 204 aminosulfonyl-phenyl -C ₆ H ₄ - 2-butyroylamino-amino- orange the same 4-methylsulfonyl-phenyl 205 -C ₆ H ₄ - 2-acetylamino-4-cyano- orange 2,6-dichloro-4-diethyl methylsulfonyl-phenyl 206 aminosulfonyl-phenyl -C ₆ H ₄ - 2-valcroylamino-4- / 3-hy- orange 2,6-dibromo-4-dimethyl- hydroxyethylsulfonyl-phenyl 207 aminosulfonyl-phenyl -C ₆ H ₄ - 2- / 3-chloropropionylamino- orange 2,6-dibromo-4-dimethyl- 4-nitro-phenyl 208 aminosulfonyl-phenyl -C ₆ H ₄ - 2-ethoxycarbonylamino Yellow-brown 4-methylsulfonyl-phenyl

Claims (2)

Patent claims: 1. Process for the production of azo compounds, characterized in that an amine of the formula 60 diazotized and the diazonium compound obtained with a compound of the formula NH, (H) to a compound of the formula A K coupling, where in the formulas (I), (II) and (III) A hydrogen, chlorine, bromine, cyano, nitro, methoxy, methoxycarbonyl or methylsulfonyl, B nitro, methylsulfonyl, cyanomethylsulfonyl, aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, Ethylaminouilfonyl or diethylaminosulfonyl, D hydrogen or chlorine, E hydrogen, chlorine or bromine, F hydrogen, chlorine, bromine, cyano, methyl, methoxy, acetylamino, chloroacetylamino, Propionylamino, methoxycarbonylamino or ethoxycarbonylamino, G hydrogen, chlorine, bromine, methyl, methoxy, formylamino, acetylamino, propionylamino, Butyrylamino, valeroylamino, chloroacetylamino, Chloropropionylamino, methoxycarbonylamino, ethoxycarbonylamino, chloromethoxycarbonylamino or chloroethoxycarbonylamino, Chlorine, bromine, cyan, nitro. Acetyl, acetoxy, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, methylaminocarbonyl, Äthylaminocarbonyl, dimethylaminocarbonyl, Diäthylaminocarbonyl, methoxycarbonyloxy, Athoxycarbonyloxy, propoxycarbonyloxy, Methoxypropylaminocarbonyl, methylsulfonyl, chloromethylsulfonyl, Athylsulfonyl, phenylsulfonyl, aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, ethylaminosulfonyl, Diäthylaminosulfonyl or MethoxypropylaminosuUOnyl and
K is hydrogen, methoxy or ethoxy. 2. Process for dyeing, padding or printing fibers, threads or fleeces, fabrics or knitted from fully or semi-synthetic high molecular weight fabrics, characterized in that according to the method according to claim 1 prepared dyes are used.