DE1101660B - Process for the preparation of monoazo dyes - Google Patents

Description

The present invention relates to a process for the preparation of monoazo dyes, which wool and Really dye wool-like fibers from neutral to slightly acidic baths.

It has been found that valuable monoazo dyes are obtained if a diazotized 2-aminobenzene-1-sulfonyl compound, optionally further substituted nonionogenically in the benzene ring, with the sulfonyl substituent —SO ₂ R, in which R is an aryl, aryloxy or organic amine radical containing the sulfonic acid group optionally combined in an acid medium with a coupled, in position 1 and in position-8 containing a hydroxyl group 2-Aminonaphthalinsulfonsäureamid whose sulfonic acid amide group may be substituted organic still, but should be free acid groups S ¹ of sulfonic.

If R is an aryl radical, this is primarily one of the benzene or naphthalene series. the Sulphonic acid group present by definition can either directly or via a bridge member be bound to an aromatic ring. As substituents, which both in the amino group-containing Benzene ring as well as in the radical R can be present, those customary in azo dyes come into consideration, for example halogens, alkyl, alkoxy, aryloxy, alkylcarbonyl, arylcarbonyl and acylated amino groups. Among the diazo components substituted on the aminobenzene ring, those are preferred which are nucleophilic Contain groups, especially acylamino groups, such as low molecular weight alkyl or alkoxycarbonylamino groups, Aryl or aryloxyacetylamino groups, aralkyl or cycloalkyloxycarbonylamino groups or alkylsulfonylamino groups.

As examples of 2-aminobenzene-l-aryl sulfones, which contain the sulfonic acid group in the arylsulfonyl radical, the following may be mentioned: 2-amino-l, l'-diphenylsulfone - 3 '- sulfonic acid, 2 - amino - 3' - sulfoacetylaminol, l'-diphenylsulfone, 2-Amino-4- or -5-carbethoxyamino - 4 '- methyl -1,1' - diphenylsulfone - 3 '- sulfonic acid, 2-Amino-4- or -S-carbobutoxyamino ^ '- methyl-l.r'-diphenylsulfone-S'-sulfonic acid, 2-amine p-4- or -5-carbobenzyloxy- or -carbocyclohexyloxyamino - ^ '- methyl 1,1'-diphenylsulfone-3'-sulfonic acid and 2-aminophenyl, 2'-naphthylsulfonic acid.

If R is a sulfated aryloxy group, this is primarily derived from a monohydroxy compound of the benzene or naphthalene series. Here, too, the sulfonic acid group can be bonded directly to an aromatic ring or then connected to one via a non-aromatic bridge ring. 13er aryloxy radical can optionally, as indicated above, be further substituted. Examples of aryl 2-aminobenzdl-1-sulfonate which can be used according to the invention are 2-aminobenzene-1-sulfonic acid-4'-sulfophenyl ester, processes for preparation
of monoazo dyes

Applicant:
JR Geigy A.-G., Basel (Switzerland)

Representative: Dr. F. Zumstein,

Dipl.-Oiem. Dr. rer. nat. E. Assmann.

and Dipl.-Chem, Dr. R. Koenigsberger, patent attorneys,

Munich 2, Bräuhausstr. 4th

Claimed priority:
Switzerland from February 28 , 1958

Dr. Jean-Pierre Jung, Riehen, Basel,

and Dr. 'Guido Sdietty, Basel (Switzerland),

■ have been named as he & nder

2-aminobenzene-l-sulfonic acid 4'-sulfoacetylamnophenyl ester, 2-aminobenzene-l-sulfonic acid (2'-methyl-4'-sulfoacetylamino) phenyl ester, 2-aminobenzene-l -sulfonic acid- (2 '- chloro - 4' - sulfoacetylamino) - phenyl ester, 4 - chloro-2-aminobenzene-l-sulfonic acid-4'-sulΐoacety ^ aminophenyiester, 2-aminobenzene-1-sulfonic acid 4 '- (4 "-sulfophenoxy) -phenyl ester and 2-AnUnObCnZoI-I-SuIfOnSaUTe ^ -SuIfO-diphenyl- (4'J -ester.

Finally, R can represent an organic amine black. Possible organic radicals are optionally substituted hydrocarbon radicals of the aliphatic, cycloaliphatic, araliphatic, heterocyclic and especially those of the aromatic series, containing a sulfonic acid group. These 2-aminobenzdl-1-sulfonic acid amides can be derived from primary or secondary organic amines. With regard to the substituents and with regard to the way in which the sulfonic acid group present according to the definition is bound, what has already been said about the 2-aminobenzene-1-aryl sulfones is also good. Examples of such o-diazobenzenesulfonic acid amides which can be used according to the present invention are the diazonium compounds of the following amines: 2-aminobenzene-1-sulfonic acid-N-methyl ^ -sulioethylamide, 2-aminobenzene-1-sulfonic acid-N - ethyl - 4 '- sulfophenylamide, 2 - aminobenzene -1 - sulfonic acid - N - benzyl - 4 '- sulfophenylamide, 2 - aminobenzene-1 -sulfonic acid-N-cyclohexyW-sulfophenylamide, 2-aminobenzene-l-sulfonic acid-N-methyl-3'- or ^' -sulfoacetyl-

109 529/596

3 4

aminophenylamide, ^ CHor ^ -aminobenzene-l-sulfonic acid furylamide groups and the sulfonic acid-3-pyridylamide-N-methyl-3'- or ^ '- sulfoaeetylaininophenylamid, group.

2 - aminobenzene -1 - sulfonic acid - 4 '- (4 "- sulfophenoxy) - The suitable azo components,

phenylamide and the corresponding N-methyl derivative, optionally substituted 2-aminonaphthaHnsulfon-2-aminobenzene-1 -sulfonic acid-N-methyl-2 '(2 "-sulfo- 5 acid amides can be obtained, for example, in the following way: phenoxy) -S'-chlorophenylamide, 2-aminobenzene-1-sulfone-2-aminonaphthalenesulfonic acids, their amino- and acid-4 "-sulfodiphenyl- (4 ') - amide and its N-methyl hydroxyl groups, if any, by an acyte derivative, 2-aminobenzene-l-sulfonic acid [5'- or -6'- or lation are protected by means of phosphorus penta- -7'-sulfonaphthyl- (2 ')] amide and 2-aminobenzene-1-sulfone chloride into the corresponding sulfonic acid halides acid-N-methyl- [5'- or -6'- or -7'-sulfonaphthyl- (2 ')] - converted and this with ammonia or primary amide. or secondary amines implemented, whereupon in the doing

The 2-acylamrqonaphthaunosulfonic acid amides obtained for use in accordance with the present invention are obtained ble diazo components by z. B. o-nitro acylamino and any acyloxybenzenesulfonic acid chlorides saponified with aromatic carbon groups.

Hydrogen in the presence of Friedel-Craftschen 15 The coupling of these azo components with the Catalysts or o-nitrochlorobenzene compounds with sulfonic acid group-containing o-diazobenzenesulfonylaromatic sulfonic acids to 2-nitrobenzene-1-aryl sulfones compounds takes place in acidic, for example congocondensed, the nitrodiarylsulfones sulfonated and then acidic or acetic acidic agent. In many cases the Andie Reduced nitro to amino group. According to the invention, the essence of water-soluble organic solutions can be used Aryl o-aminobenzenesulfonate contains 20 intermediaries, such as ethyl alcohol or dioxane, an advantage, one z. B. from optionally substituted o-nitrobenzene- Sometimes it is advantageous to use the halides in the coupling reaction sulfonic acid Mineral acid released by reaction with phenolate, for example with sodium or Naphtholates, sulfonation and reduction of acetate to blunt.

Nitro to amino group. o-Aminobenzenesulfonic acid- For the preparation of dyes according to the invention are

Finally, amides are obtained from o-nitrobenzenesulfonic acid halides, especially o-diazobenzenesulfonyl compounds, by condensation with primary or valuable organic amines that are not or only secondary organic amines on the aminobenzene ring, sulfonation and, by positive groups such as acylamino groups, reduction of the nitro to the amino group. Instead of the sulfon are substituted. Subsequent introduction of the o-diazobenzenesulfonic acid amide acid group into the amide residue is preferred because they give more lightfast dyes, the o-nitrobenzenesulfonic acid halides can be condensed directly from the azo components, the 2-aminonaphthalene with sulfated amines. The corresponding orange and the 2-amino-8-hydroxynaphthaene sulfonic acid group present in the 5- and 7-sulfonic acid amides for the preparation of the diazo components which can be used according to the invention can optionally also be replaced by 6-sulfonic acid amides for red dyes, exchanging a mobile halogen atom , for example, those azo components whose chlorine is introduced into chloroacetylamino groups by means of alkali metal sulfonic acid amide groups from secondary amines are metal sulfites. The diazotization of the derived, somewhat more valuable dyes than ento-aminobenzenesulfonyl compounds is expediently speaking components in which the sulfonic acid amide is carried out according to the indirect method, that is, whose hydrogen atoms are only partially replaced,
aqueous, with the theoretical amount of alkali metal nitrite. The monoazo dyes are advantageously used in

alkali metal salt solutions are used in dilute form of their alkali salts, e.g. B. the potassium and sodium mineral acids poured. salts isolated. They represent orange, red, to purple powders

The azo components which can be used according to the invention and which are readily soluble in hot water. The color are optionally substituted 2-aminonaphthaJin fabrics dye natural and artificial polypeptide fibers, sulfonic acid amides, which couple in the 1-position. It is especially wool, already in a neutral bath or in amkommen the derivatives of the 2-aminonaphthalene-5-, 45-monsulfate-containing baths under complete -6- or -7-sulfonic acids, but especially those of their creation in very even, pure oranges 2-Amino-8-hydroxynaphthaUn-6-sulfonic acid into consideration. to bluish-tinged red tones. Where there is a sour stain The sulfonic acid amide groups can be recommended by ammonia without affecting the properties or are colored acidic by primary or secondary aliphatic, cyclo- des colored material. As well as aliphatic, araliphatic, aromatic or hetero- 5 ° those obtained in neutral and acidic baths be derived from cyclic amines. Substituted colorations are distinguished by remarkable light sulfonic acid amide groups come z. B. the following in question: fastness, very good fastness to washing, fulling and sea water the sulfonic acid methyl, ethyl, propyl, butyl, tert. and good rubfastness from. Particularly lightfast dyeings amyl- and -octylamidgruppen, the sulfonic acid-jS-hydroxy- give those dyes which, according to the definition ethyl and y-methoxypropylamide groups, the sulfonic 55 o-aminobenzenesulfonic acid amides are built up, wähsäuredimethyl-, -diethyl-, -dibutyl- and -di-2- (ethyl- rend the analogous sulfones and sulfonic acid esters here hexyl) -amide groups, the sulfonic acid-N-methyl-jö-hy- a little behind, but still very good light hydroxyethyl amide group, have sulfonic acid benzyl-4-chlorine fastness.

benzyl, -3,4-dichlorobenzyl and dibenzylamide groups, compared to that from the French patent

the sulfonic acid cyclohexyl, methylcyclohexyl, dicyclo 60 871 731 known azo dye with the composition hexyl and hexahydrobenzyl amide groups, the sulfone 2-amino-4-acetylammo-4'-methyl-l, l'-diphenylsulfonic acid-N-methyl - or -N-ethyl- or -N-propylcyclo- 3'-sulfonic acid - * - 2-amino-8-hydroxynaphthalene-6-sulhexyl or -benzyl- or -phenylamide groups, the sulfonic acid shows the comparative acid available according to the invention N-methyl- or -N-ethyl-2-methylphenyl- or bare azo dye of the composition 2-amino- -4-methoxyphenyl- or -4-chlorophenylamide groups, the 65 4-acetylamino-4'-methyl-l, l'- diphenylsulfon-3'-suh ^c on-sulfonic acid-N-methyl- or -N-ethyl- or -N-cyclo- acid - »- 2-amino-8-hydroxynaphthalene-6-sulfonic acid-hexyl-4- (methylsulfonylamino) -phenylamide group , the amide a better leveling capacity, and compared to the sulfonic acid-a- or -ß-naphthyl- and -tetrahydronaph- from the French patent 1113 026 known thylamide groups and the corresponding the N-methylating azo dye of the composition 2-amino-4-methylten amide groups, the sulfonic acid morpholide or -fur- 70 sulfonyl-4'-methyl-l, r-diphenylsuh ^c on-3'-sulfonic acid -> -

1 IUl ÖÖU

The comparable azo dye obtainable according to the invention and having the composition 2-amino-4-methylsulfonyl-4'-methyl 1,1'-diphenylsulfone-3'-sulfonic acid - * - 2-aminonaphthalene-6-sulfonic acid amide also shows 2-aminonaphthalene-6-sulfonic acid better leveling ability.

Further details can be found in the following examples. In these examples, unless they mean nothing otherwise expressly stated, the parts are parts by weight and the temperatures are given in degrees Celsius. Parts by weight are related to parts by volume as grams are to cubic centimeters.

HO ₁₁ SCH ₉ CONH

Example 1 -0-SO ₂

NH

38.6 parts of 2-ammobenzene-1-sulfonate 4'-sulfacetylaminophenyl ester are dissolved as the sodium salt in 500 parts of water, 6.9 parts of sodium nitrite are added, the solution is dissolved in 30 parts of concentrated hydrochloric acid and 100 parts with stirring and external cooling Dripped in ice. After stirring for 1 hour at 0 to 3 °, the excess nitrous acid is destroyed and the diazonium salt solution is added to the solution of 34.2 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid-N-ethyl-N-phenylamide in 300 parts of glacial acetic acid and pour in 500 parts of ethanol. Coupling occurs immediately with the formation of a red dye. The C ₂ H _{5 is stirred}

Mixture for a further 8 hours at 10 to 20 °, then diluted with 1000 parts of water, heated to 50 °, added 150 parts of sodium chloride and sucks off the separated red dye. One washed with a 2 ° / ₀ aqueous solution of sodium chloride until neutral and dried in vacuo at 80 to 85 °.

The dye is a brownish red powder that dissolves in hot water with a red color and wool from one neutral or from a weakly acidic bath containing ammonium sulfate when boiled in uniform, clear, shades of blue-tinged red. The wool dyes are very lightfast, alkali and millfast.

Example 2
NH ₂

C ₂ H ₅ -N

SO, —N — CH ₅ ,

SO ₃ H

35.6 parts of 2-aminobenzene-1-sulfonic acid-N-ethyl-N- (4'-sulfophenyl) -amide are dissolved as the sodium salt in 500 parts of hot water. The solution is 6.9 parts Added sodium nitrite and added to the mixture of 30 parts of concentrated hydrochloric acid and 100 parts of ice at 0 to 5 ° added dropwise with stirring and external cooling. The colorless diazo suspension is stirred for a further hour 0 to 5 ° and destroys the excess nitrous acid. Then the diazonium salt suspension is left in Stir slowly at 0 ° to 10 ° into the solution of 40.4 parts of 2 - amino - 8 - hydroxynaphthalene - 6 - sulfonic acid N-benzyl-N-phenylamide flow in 250 parts of glacial acetic acid and 500 parts of ethanol. The coupling is quick forming a red dye. After stirring the mixture for 8 hours at 5 to 10 °, it is warmed up to 60 °, 2,000 parts of hot water are added and the acid is partially sprinkled with 80 parts of sodium carbonate neutralized. The dye is excreted as the sodium salt with the help of sodium chloride, Sucked off, washed well with 2% sodium chloride solution and dried.

The red dye is soluble in hot water and dyes wool from a neutral to weakly acidic bath in pure, bluish-tinged red tones. The wool dyeings are very light, alkali and wet fast.

100 parts of well-wetted wool are introduced into a dyebath at 40 °, which in 300 parts of water is 2 parts this contains monoazo dyes and 5 parts Glauber's salt. The bath is heated to the boil within 45 minutes and with good changing of the wool for 1 and a half hours kept at boiling temperature. A very uniform, pure, bluish-tinged red wool dyeing is obtained in this way is characterized by very good fastness properties.

Equally good wool dyeings can also be obtained using an acid dye bath, e.g. B. in the present of 1 part of 40% acetic acid.

Example 3

HO ₃ S

N = N

SO ₉ NH-CrH ₁ ,

39.2 parts of 2-aminobenzene-1-sulfonic acid-N-methyl-N- [7'-sulfonaphthyl- (2 ')] - amide are dissolved as the sodium salt in 1000 parts of water, 6.9 parts of sodium nitrite are added, and the 40 ° warm solution is added dropwise to 30 parts of concentrated hydrochloric acid and 100 parts of ice at 0 to 8 °. After stirring for 1 hour at 0 ° to 5 ° and destruction of the excess nitrous acid, the colorless diazonium salt suspension is allowed to flow into the solution of 33.4 parts of 2-aminonaphthaline-5-sulfonic acid octylamide in 500 parts of ethanol. After addition of 25 parts of crystallized sodium acetate, the dye suspension is stirred for 6 hours at 10 to 15 °, then diluted with 1000 parts of hot water, 200 parts of sodium chloride are added and the orange dye which has separated out is filtered off with suction. One washed on the funnel with a 2 ° / ₀ aqueous solution of sodium chloride until neutral and dried thereon at 80 ° to 85 ° in vacuo.

The dye dissolves in hot water with an orange color and dyes wool from an ammonium sulfate containing Bath when cooking in even, clear, orange tones. The colorations are characterized by remarkable light and wet fastness properties.

Example 4

HO ₃ S ■

> - O - SUN

N = N

SO ₂ -N

40.5 parts of 2-ammobenzene-1-sulfonic acid-4 "-sulfodiphenyl- (4 ') - ester are dissolved as the sodium salt in 1000 parts of hot water, 6.9 parts of sodium nitrite are added, and the solution is in the mixture of 30 parts of concentrated hydrochloric acid and 100 parts of ice at 0 to 10 ° added dropwise with stirring and external cooling. The mixture is stirred for a further 1 hour at 0 ° to 5 ° and destroyed then the excess nitrous acid. The colorless diazonium salt suspension is then left with stirring at 5 to 10 ° slowly in 32.6 parts of 2-aminonaphthalene-7-sulfonic acid-N-ethyl-N-phenylamide, which are dissolved in 500 parts of ethanol and 200 parts of glacial acetic acid, flow in.

Coupling occurs rapidly with the formation of an orange dye which precipitates immediately. One stirs them Dye suspension for several hours at 10 to 20 °, the acid partially neutralized with 80 parts of sodium carbonate sucks off the excreted dye and dries it.

The dye is an orange powder that dissolves in hot water with a yellow-orange color and dyes wool from a neutral or from a weakly acidic bath containing ammonium sulphate when boiled in clear, even, orange tones. The wool dyeings are light and wet fast.

Example 5

'CH,

SO, -N- C

46.8 parts of 2-Än ^ äno-4-carlocyclohexyloxyamino-4 "- methyM, r-diphenylsulfon-3 ^v -sulfonic acid are dissolved in 10'6 parts of water at 80 ° as sodium salt, with 6 '9 parts of sodium nitrite are added, and the warm solution is added dropwise to 30 parts of concentrated hydrochloric acid and' 200 'parts of ice -at Ό * to 1Ό ° with stirring and external cooling. After stirring for 1 hour * at 0 to 5 °, the excess is destroyed nitrous acid and combined the aqueous suspension of the diazonium salt with a solution of 32.5 parts of a-amino-S ^ hydroxynapilthaTln-6-sulfoic acid-N-methyl-Ni>h'er ^ yaänn'd and 25 parts of faistaUisieftein sodium acetate in 50 parts of ethanol and 100 parts of water. The formation of a red dye occurs immediately. After stirring the

Mixture at 10 to 20 ° it is warmed to 60 ° and mixed with 1000 parts of hot water. The dye is precipitated with 100 parts sodium chloride, filtered, washed well with a 2 ° / _o solution of aqueous sodium chloride and dried in vacuo at 80 to 85 ° dried.

The dye is a brown powder that dissolves in hot water with a red color, and wool is made from an ammonia

10

Sulphate-containing bath colors in even, pure, bluish-tinged red tones when cooked. The colorations are very lightfast, washfast and washfast.

In the table below, further dyes according to the invention are indicated, which when used corresponding amounts of diazo and azo components according to the procedures described in Examples 1 to S can be produced.

Tabel

No. Diazo component Azo component Color of
Wool dye 1 2-aminobenzene-1-sulfonic acid-4 "-sulfo- 2-amino-8-hydroxynaphthalene-6-sulfone Bluish red diphenyl (4 ') ester acid di-n-butylamide 2 the same 2-amino-8-hydroxynaρhthalin-6-sulfone- Red acid morpholide 3 2-A minobenzene-1-sulfonic acid-3 '-sulfoacetyl- 2-aniino-8-hydroxynaphthalene-o-sulfone- Bluish red aminophenyl ester acid-N-methyl-N-phenylamide 4th 2-amino-4-chlorobenzene-l-sulfonic acid the same the same 4'-sulfoacetylaminophenyl ester 5 2-aminobenzene-l-sulfonic acid-2'-chloro- the same the same 4'-suHoacetylaminophenyl ester 6th the same 2-aminonaphthaUn-6-sulfonic acid-N-methyl- orange N-phenylamide 7th 2-aminobenzene-l-sulfonic acid-4 '- (4 "-sulfo- the same the same phenoxy) phenyl ester 8th the same 2-aminonaphthalene-7-sulfonic acid-Nn-butyl-
amide the same 9 the same 2-amino-8-hydroxynaphthalene-6-sulfone Bluish red acid-N-ethyl-N-phenylamide 10 2-aminobenzene-l-sulfonic acid-4'-sulfophenyl- 2-amino-8-hydroxynaphthalene-6-sulfone the same ester acid-N-benzyl-N-phenylamide 11 2-aminobenzene-l-sulfonic acid-N-ethyl- 2-amino-8-hydroxynaphthalene-6-sulfonic acid the same N- (4'-sulfophenyl) amide N-methyl-N-p- (p'-tolylsulfonyl) -phenyl- amide 12th the same 2-aminonaphthaHn-7-sulfonic acid-N-di- orange n-butylamide 13th 2-aminobenzene-l-sulfonic acid-4'-sulfoaeetyl- 2-aminonaphthaUn-5-sulfonic acid dicyclo- the same aminophenyl ester hexylamide 14th 2-Airu'nobenzol-l-sulfonic acid-N-methyl- 2-aminonaphthalene-5-sulfonic acid morpholide the same N- [4 "-sulfodiphenyl- (4 ')] - amide 15th 2-aminobenzene-l-sulfonic acid-N-ethyl- 2-Amίno-8-hydroxynaphthalene-6-sulfone Bluish red N- (4'-sulfophenyl) amide acid-N-octylamide 16 2-aminobenzene-l-sulfonic acid-N-cyclohexyl- 2-Amino-8-hydroxynaphtha ^ n-6-sulfone- the same N- (4'-sulfophenyl) amide acid-N-methyl-N-phenylamide 17th 2-aminobenzene-l-sulfonic acid-N-benzyl- 2-amino-8-hydroxynaphthalene-6-sulfone the same N- (4'-sulfophenyl) amide acid ethylamide 18th the same 2-aminonaphthalene-7-sulfonic acid dimethyl
amide orange 19th 2-aminobenzene-l-sulfonic acid-N-methyl- 2-Aπlino-8-hydroxynaphthahn-6-sulfone- Bluish red N- (4'-sulfoacetylamino-phenyl) -amide acid-N-ethyl-N- (2'-methylphenyl) -amide 20th the same 2-amino-8-hydroxynaphthalene-6-sulfonic acid the same N-methyl-N-phenylamide 21 2-aminobenzene-l-sulfonic acid-N-ethyl- 2-amino-8-hydroxynaphthalene-6-sulfone the same N- (4'-sulfophenyl) amide acidicyclohexylamide 22nd 2-aminobenzene-l-sulfonic acid-N-methyl- 2-amino-8-hydroxynaphthane-6-sulfonic acid the same N- [4 '- (4 "-sulfophenoxy) phenyl] amide N-methyl-N-phenylamide 109 529/596

continuation

No. Diazo component Azokömpöneiite Color of
"Wool dye 23 2-ammobenzene-l-sulfonic acid-N-methyl- the same - - - the same N- [2 '- (4 "-chlor-2" -sulfophenoxy) -4'-chloro- phenyl] amide 24 2-aminobenzene-l-sulfonic acid-N-methyl- 2-aminonaph.thalene-7-sulfonic acid-n-butyl- orange N- [3'-sulfoacetylaminophenyl] amide amide 25th 2-aminobenzoH-sulfonic acid-N-methyl- 2 ^ ammonaphthalene-7 - su ^ fonsäure-N-methyl- the same N- (2'-chloro-4'-sulfoacetylaminophenyl) - N- (2 ', 5'-dimethylphenyl) amide amide 26th the same 2-aminonaphthalene-7-sulfonic acid morpholide the same 27 2-aminobenzene-l-sulfonic acid-N-methyl- the same the same N- (2,4'-sulfonaphthyl) ainide 28 2-aminobenzene-l-sulfonic acid-N-methyl- 2-ammonaphthaHn-6-sulfonic acid-methyl- the same N- (2,6'-sulfonaphthyl) -amide N-phenylamide 29 2-Amino-4- (4 "-tert.amylbenzoylamino) - 2-ammonaphtha-5-sulfonic acid-di- the same 4'-methyl-l, l'-diphenylsulfone-3 '»sulfone- n-butylamide acid 30th 2-amino ■ -4-carbocyclollexyloxyalnino- 2-amino-8-liydroxynaplitlialin-6-sulfone- Bluish red 4'-methyl-l, l'-diplienylsulfone-3'-sulfone- acid-N-methyl-N-phenylamide acid 31 2-Anüno-5-carboamyloxyammo-4'-methyl- the same the same 1,1'-diphenylsulfone-3'-sulfonic acid 32 2-amino-5- (carbo-4 '' - chlorbenzyloxyamino) - the same the same 4'-methyl-l, l'-diphenyl sulfone-3'-sulfone ~ acid 33 2-Amino-1 ₎ l'-diphenylsulfon-3'-sulfonic acid 2-ammo-8-hydroxynaphthalm-6-sulfone- the same acid-N-benzyl-N-pnenylamide 34 the same 2-An ^ inonapllthalin-7-sulfonic acid-N-octyl-
amide orange 35 2-Ammo-1,2'-phenylnaphthylsulfone- 2-aminonap] ithalin-7-sulfonic acid-N-methyl- the same x'-sulfonic acid N-ph.enylamide 36 2-Amino-3'-sulphoacetylamino-l ₎ l''diplienyl- the same the same sulfone 37 the same 2-AInino-8-llydroxynaρlltllann-6-sulfone- Bluish red acid-N-octylamide 38 the same 2-amino-8-hydroxynaph.thalene-6-sulfone the same acid'di-n-butylamide 39 2-amino oil 1,2'-phenymaphthylsulfone 2-amino-8-hydroxynapllthalene-7-sulfone the same x'-sulfonic acid acid-N-methyl-N-phenylamide

Claims (3)

Patent claims: 1. A process for the preparation of monoazo dyes, characterized in that a diazotized 2-aminobenzene-1-sulfonyl compound with the sulfonyl substituent —SO ₂ R, in which R is a sulfonic acid group-containing aryl, aryloxy or organic amine radical, which is optionally further substituted nonionogenically in the benzene ring means, combined in an acidic medium with a 2-aminonaphtha-sulfonic acid amide coupling in the 1-position and optionally containing a hydroxyl group in the 8-position, the sulfonic acid amide group of which can still be organically substituted but should be free of sulfonic acid groups. 2. The method according to claim 1, characterized by the use of such a 2-aminobenzene-1-sulfonyl compound in which the symbol R of the sulfonyl substituent a —SO ₂ R denotes an arylamine radical which contains a sulfonic acid group. 3. Process according to Claims 1 and 2, characterized in that an azo component is used 2-Amino-8-hydroxynaphthane-6-sulfonic acid amide is used, in which the amide nitrogen is still organic can be substituted. Considered publications:
French patents nos. 871 731, 1 113 026. When the application was announced, two coloring tables with explanations were displayed. © 109 529/596 2.61