DE1020026B - Process for the preparation of 2-stilbylmononaphtho-1, 2, 3-triazole compounds - Google Patents

Description

GERMAN

In patent specification 942 395 there is a process for the preparation of 2- (stilbyl-4 ") - (naphtho-1 ', 2': 4.5) 4,2,3-triazole compounds of the general formula I described, which are in the form of their water-soluble salts as optical brighteners are suitable for cellulose fibers.

, N.

CH = CH-B

N "

SO ₃ H

In this formula, A denotes a naphthalene radical connected to the triazole ring at adjacent α, / J positions, which can be further substituted with the exclusion of chromophoric and auxochromic groups can, and B is a benzene residue that has neither auxochromic and chromophoric groups, nor strongly positive acylamino- andtriazinylamino groups, in particular in the o- or p-position to the ethylene bridge, may contain, otherwise but can also contain other customary substituents.

Auxochromic and chromophore groups here as well as in the following are the classic ones Understood substituents of Witt's color theory, for example the aromatically bound hydroxyl, Amino, alkyl, dialkyl, aralkyl, cycloalkyl or arylamino group or the nitro or arylazo group. Permissible substituents in the naphthalene and stilbene radicals are, for example, the alkyl, alkoxy, cyano, carboxyl, Sulfonic acid groups and the halogens.

In the further processing of the subject matter of the invention it has now been found that one likewise valuable optical Whitening agent for textile fibers or paper is obtained if one observes the limits given Conditions relating to the auxochromic and chromophoric, acylamino and triazinylamino groups the general formula I prepares analogous compounds in which the sulfated benzene ring is changed.

The change can consist in the fact that this sulfonic acid group is modified, for example by a Aryl sulfonate, the sulfonic acid amide, one on the nitrogen atom aliphatic, araliphatic, cycloaliphatic, replaced aromatically or heterocyclically substituted or a sulfonic acid amide group acylated on nitrogen is. It can also consist in that this sulfonic acid group is replaced by another substituent, preferably an electrophilic substituent such as the carboxyl, cyano, an alkyl or arylsulfonyl group or optionally also by a halogen atom, an alkyl or alkoxy group. Under certain conditions it can also consist of a there is no o-position substituent for the ethylene bridge bond. It can also consist in the fact that if there is a 2-position

Method of manufacture

of 2-stilbylmononaphtho-l, 2,3-triazole-

links

Addendum to patent 942 395

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

Representative: Dr. F. Zumstein, patent attorney,
Munich 2, Bräuhausstr. 4th

Claimed priority:
Switzerland from 23 August 1954

Dr. Reinhard Zweidler, Basel,

and Dr. Ernst Keller, Binningen (Switzerland),

have been named as inventors

diger sulfonic acid group another substituent, preferably in the other o-position to the ethylene bridge, is available. Finally, it can consist in the fact that several permissible groups other than the sulfonic acid group are permitted Substituents are present, of which at least one and preferably two in the o-position to the ethylene bridge. Provided that the benzene ring connected to the triazole ring does not have a substituent in the o-position to the ethylene bond has, the benzene ring B must in this case either in turn in the o-position to the ethylene bridge contain a substituent, preferably an electrophilic substituent, such as the sulfonic acid group, the carboxyl or cyano group, or a halogen atom, or then in the p-position to form ethylene bridges preferably be substituted negatively, in particular by an optionally modified one Sulfonic acid group or an alkyl or arylsulfonyl group. The meaning of this substitution of the stilbene residue is evident from the fact that similar 2-stilbylnaphthotriazole compounds with an unsubstituted stilbene residue, none or at least one which is insufficient for practical purposes, have very little fluorescence.

71 »8017/266

The new auxochrome and chromophore-free 2-stilbylnaphthotriazole compounds correspond to the general formula II

\ -CH = CH-

Inadmissible substituents, which are easily removed in the finished triazole compound or in permissible substituents The 4-aminostilbene compounds which can be used according to the invention may be converted 5 optionally contain nitro or acylamino groups. The 4-aminostilbene compounds which can be used according to the invention are either indirectly diazotized by dripping on a sodium nitrite, depending on the substitution containing solution of the water-soluble alkali salts on i ° cold mineral acids or directly in the presence of inert organic or inorganic solvents and mineral acid with alkali nitrite or nitrosylsulfuric acid. Lower alcohols are used as inert solubilizers. In these, the aromatic rings can be used to the exclusion of fatty acids or ketones or concentrated sulfuric acid the color-producing and color-deepening substituents 15 into consideration.

in the sense of Witt as well as the inadmissible in the stilbene residue as coupling components are those in the main patent

Acylamino and triazinylamino groups can also be used as desired, namely further substituted in the 1-position copper substituents, with 2-aminonaphthalene compounds in pelling.
X _r position as the only substituent in the associated The new 2-stilbyl-naphthotriazole compounds

Benzene ring however no sulfonic acid group may stand in the form of their alkali salts pale yellow powder, which are in front of themselves and the further condition applies that there is at least more or less in water, depending on the composition

Xi

II

an X position must have a preferably electrophilic substituent, while Z is an acidic group which solubilizes water with salt formation and η is an integer from 1 to 4.

The sulfonic acid group is preferably used as the acidic groups which make water-soluble with salt formation and the carboxyl group, possibly also sulfamide groups acylated on the nitrogen, as enclosed dissolve to form practically colorless solutions that fluoresce in violet-blue to green-blue in ultraviolet light and depending on their substitution a more or less great affinity for cellulose, super polyamide and super polyurethane fibers. They give more or less white substrates already in a very good way low, usual concentrations a whiter aspect in daylight, which is due to a remarkably good

For example, a sulfonic acid-alkyl sulfimide, a sulfone 3 ° resistance to oxidizing agents, as they are with acid-aryl sulfimide, a sulfonic acid-alkoylimide or, for example, in chemical bleaching of cellulose fibers a sulfonic acid aroylimide group. It can be common at the same time, is excellent.

different types of acidic, water-solubilizing The new 2-stilbyl-naphthotriazole compounds can

Groups exist, and these can be either like the compounds of the main soap patent incorporated only in the naphthalene residue or only in the stilbene residue or in 35 or synthetic detergents, in both washing Remnants are located at the same time. or rinsing liquors or also in chemical containing hypochlorite

The new 2-stilbyl-naphthotriazolverbin- see bleaching liquors are obtained because they are good fertilize according to the chlorine fastness described in the main patent.

drive by coupling suitably substituted The new monotriazole compounds point to building

4-aminostilbene compounds with a position adjacent to 40 wolle compared to the naphthalene compounds coupling an amino group which have become known from US Pat. No. 2,668,777, 4,4'-bis- [sulfonaphtho-r, 2 ': 4,5-tri- and oxidation of the obtained o-Aminoazo dye for azolyl (2)] stilbene disulfonic acids have a whiter, bes-1,2,3-triazole compound according to methosene known per se and have a lightening effect compared to the substituents from German patent 913, which are inadmissible in the end product 164 that have become known, such as the nitro or amino group, also 45 l, 4-bis- [sulfonaphtho-r, 2 ': 4,5-triazolyl- (2)] - benzenes only subsequently removed by chemical means or in
permissible substituents can be converted.

Some examples of 4-aminostilbene compounds useful in the process of the invention to which the Invention, however, is by no means restricted, are listed below: 2-cyano-4-aminostilbene, 2-carboxy-4-aminostilbene, 2-sulfonic acid phenyl-, -0- or -p-cresyl ester-4-aminostilbene, 2- methylsulfonyl-, 2-ethylsulfonyl-, 2-vinylsulfonyl-, 2-butylsulfonyl-4-aminostilbene, 2-p-toluylsulfonyl- or 2- (2 ', 4'- or 3', 4'-xylylsulfonyl) -4-aminostilbene, 4-aminostilbene-2-sulfonic acid dimethyl

a better lightfastness. Also in the USA. Patent 2,684,966 1,4-di- (4'-arylotriazolyl-styryl) -benzene compounds described, but these dye cotton yellow on.

The following examples illustrate the invention without restricting it. The parts are provided in it nothing else is noted, understood as parts by weight and the temperatures are given in degrees Celsius. Parts by weight are in the same proportion to parts by volume as kilograms to liters.

or diethylamide, 2-methyl-4-aminostilbene-2'- or -4'-sulfonic acid, 2-fluoro- or 2-chloro-4-aminostilbene-2'- or -4'-sulfonic acid, 2-methoxy- or 2-ethoxy-4-aminostilbene-2'- or -4'-sulfonic acid, 4-aminostilbene-2'-sulfonic acid, 4-amino-2'-chlorostilbene-5'-sulfonic acid, 4-aminostilbene-4'-sulfonic acid, 4-Amino-2'- or 4'-methylsulfonyl- or ethylsulfonylstilbene, 4-aminostilbene-2'- or -4'-sulfonic acid-dimethyl- or -diethylamide, 6-methyl ^ aminostilbene ^ -sulphonic acid, o-chloro ^ -aminostilbene-2 -sulfonic acid, 4-aminostilbene - 2 - sulfonic acid - acetimide, 4-aminostilbene-2-sulfonic acid benzoylimide, 4-aminostilbene-2 - sulfonic acid - methylsulfimide, 4 - aminostilbene - 2 - sulfonic acid benzene sulfimide, 4 - aminostilbene - 2 - sulfonic acid -pchlor- or p-methylbenzenesulfimide.

example 1

HSO, -;

CN

y - CH - CH -

22.0 parts of 4-amino-2-cyanstilbene are dissolved in 300 parts of 80% acetic acid with 25 parts of concentrated hydrochloric acid dissolved, mixed with 150 parts of ice and at a temperature of 5 to 8 ° with an aqueous solution of 6.9 parts of sodium nitrite diazotized. The diazo compound obtained is then with an aqueous solution of the

5 6

The sodium salt of 22.3 parts of 2-aminonaphthalene-pyridinic layer was washed several times with ammonia-containing 6-sulfonic acid and 25 parts of crystallized sodium sodium chloride solution and then combined with additional acetate. After coupling is complete, 10 parts of sodium hydroxide and 2 to 5 parts of dye are salted out and filtered off. The moist o-ami-sodium hydrosulfite, the pyridine, with steam, abnoazo dye, is distilled with the addition of an aqueous solution. For further purification, the product is dissolved in 6 parts of sodium hydroxide in 500 parts of pyridine hot, aqueous ethylene glycol monomethyl ether, dissolved warm and then filtered hot at a temperature of 30 to with the addition of some animal charcoal and the 35 ° within ^ hour 150 parts of an approximately 17 % filtrate was added dropwise to 4 to 5 times the volume of an approximately 10% sodium hypochlorite solution. One increases the saline solution poured. The precipitated product temperature slowly to 70 to 80 ° and stirred until io _wu -d, filtered off, washed with water and dried, complete disappearance of the dye. This gives the sodium salt of 2- (stilbyl-4 ") - (naphtho, the pyridine is distilled off with steam, where r, 2 ^/ : 4,5) -l, 2,3-triazol-2" -carboxylic acid as a yellowish, in water sparingly soluble powder reducible at the beginning of steam distillation. The product is an oxidation product by adding 3 to 8 parts of valuable lightening agent for cellulose, linear poly-sodium hydrosulfite can be destroyed. The precipitated amide fibers, plastics such as polyvinyl chloride, poly-triazole compounds are filtered off from the mother liquor, vinylidene chloride, copolymers, etc.
washed with water and dried in vacuo. One is also optically effective on cellulose fibers

the sodium salt of the 2- (2 "-Cyanstilbyl-4") - compound is obtained when the 2-amino- (naphtho-l ', 2 ^/ : 4,5) -l, 2,3-triazole-6 '-sulfonic acid as yellow naphthalene through 22.3 parts of 2-aminonaphthalene-6-sulfonic white powder that is sparingly soluble in water. The pro-acid replaces. Oxidation of the o-amine product obtained is a valuable brightening agent for cellulose azo dyes, and the disodium salt of 2- (stiletto fibers, linear polyamide fibers such as nylon, as well as for byl-4 ") - (naphtho-r, 2 ': 4.5) is obtained ) -l, 2,3-triazole-2 "-carboxylic acid soaps and synthetic detergents. 6'-sulfonic acid as a yellowish, sparingly soluble in water

Used in the example above instead of the 2-amino powder.

naphthalene-6-sulphonic acid 30.3 parts of 2-aminonaphthalene-25 _e-called Di in the example above using 4-aminostilbene-2-5.7-disulfonic acid and the thus obtained o-amino carboxylic acid is obtained in the following manner:
noazo dye in aqueous solution with a sodium 27 parts of 4-nitrostilbene-2-carboxylic acid (obtainable from

hypochlorite solution oxidized to the triazole compound, according to Pfeiffer, vol. 44, p. 1119) 30 parts are obtained to obtain the disodium salt of 2- (2 "-Cyanstilbyl-4") - etched cast iron filings in a mixture of ethylene (naphtho-r, 2 ': 4,5) -l, 2,3-triazole-5', 7 ^/ -disulfonic acid reduced as 30 glycol monomethyl ether and water. One yellowish, moderately water-soluble powder. The product considers the 4-aminostilbene-2-carboxylic acid as pale yellowish and represents a valuable lightening agent for cellulose fiber powder,
as well as for soaps and synthetic detergents. Example 3

The 4-amino-2-cyano-SO ₃ H used in the above example

stilbene is represented in the following way: 35 |

25 parts of 4-nitro-2-cyanstilbene (available from Uli- / \, -.,

Mann, Vol. 41, p. 2296) are etched with 30 parts> j SO ₂ -O ^ <^ ^>

Cast iron filings in a mixture of ethylene glycol HSO ₃ -V. _x ^ [- · .—

monomethyl ether and water reduced. You get the " ( \ r / ■ ₁ _rn_rti_ / \

4-Amino-2-cyanstilbene as a light yellow powder. It shows 40 \ A /. / ~~ \ /

recrystallized from alcohol, melting point 125 to ^ - N

127 ^y . 35.1 parts of 4-aminostilbene-2-sulfonic acid phenyl ester

Example 2 in 120 parts of glacial acetic acid with the addition of 25 parts

\ concentrated hydrochloric acid and after the further

COOH ⁴ ^ Addition of 100 parts of ice at a temperature of 10

to 12 ° with an aqueous solution of 6.9 parts of sodium

/. /, nitrite diazotized. The diazo compound is with a

. ■■ -> - c ± i = LJrl; ■ aqueous solution of the sodium salt of 30.3 parts

, .-- 'N ^/ 2-aminonaphthalene-5,7-disulfonic acid and 25 parts of

50 crystallized sodium acetate combined. As a solution

In 250 parts of 8O ° / _O acetic acid, 23.9 parts are mid dissolved advantageously still 2 to 5% of technical 4-aminostilbene-2-carboxylic acid, was added 25 parts concen- pyridine. After the coupling is complete, trated hydrochloric acid and 150 parts of ice are added and the o-aminoazo dye is isolated, then dissolved in an aqueous solution of pyridine in a warm temperature of 5 to 8 ° and diazotized with a solution of 60 parts of 6.9 parts of sodium nitrite. To the well-crystallized copper sulfate in 240 parts of water with a cooled diazo compound, a temperature of 40 to 45 ° and a temperature of 90 to 95 ° is oxidized to the triazole. Solution of 14.3 parts of 2-aminonaphthalene and 10 parts. After the oxidation has ended, hydrochloric acid concentrated at room temperature in 200 parts of water is run in. cooled and 120 parts of concentrated ammonia to-This is set at a temperature of 15 to 18 °. Then, as described in Example 2, aqueous solution of 40 parts of crystallized sodium benzene, first the copper salts and then the pyridine acetate are added dropwise so that the coupling reaction separates. The disodium salt of 2- (stilbyl always in the weakly mineral acid region is obtained. dissolves it in the case of a temphenyl ester-5 ', 7'-disulfonic acid as a yellow, in water temperature of 90 to 95 ° in pyridine, gives a mixture of moderately soluble powder.

from 60 parts of crystallized copper sulfate in 240 parts of 65 of the 4-aminostilbene water used in the above example and 120 parts of concentrated ammonia to phenyl 2-sulfonate is produced in the following manner and stirred at a temperature of 90 to 95 ° to keep:

complete oxidation of the dye. According to Er- 35.1 parts of 4-nitrostilbene-2-sulfonic acid phenyl ester

Cold becomes aqueous with the addition of table salt, using the Be champ method with 30 parts copper salt-containing layer separated from the pyridine, the 70 etched cast iron filings in a mixture of

Ethylene glycol monomethyl ether and water reduced. The phenyl 4-aminostilbene-2-surfonate is obtained as a yellowish white powder. Recrystallized from alcohol, the product has a melting point of 121 ° to 123 °.

Example 4

HSO,

SO ₂ CH ₃

N-

-CH = CH-

N "

27.3 parts of 4-aminostilbene-2-methylsulfone are with 25 parts of concentrated hydrochloric acid dissolved in 200 parts of warm glacial acetic acid, 150 to 200 parts of ice and water were added and diazotized at a temperature of 10 to 12 ° with an aqueous solution of 6.9 parts of sodium nitrite. The diazo compound is combined with an aqueous solution of 22.3 parts of 2-aminonaphthalene-6-sulfonic acid, 4.0 parts of sodium hydroxide and 25 parts of crystallized sodium acetate. After the coupling is completed the dye isolated and washed. The moist o-aminoazo dye is then dissolved in warm pyridine, a mixture of 60 parts of crystallized copper sulfate in 240 parts of water and 120 parts of ammonia was added and stirred at water bath temperature until the dye is completely oxidized. After it has cooled down the aqueous, copper-salt-containing layer was separated from the pyridine by adding sodium chloride, the pyridinic layer washed several times with ammonia-containing sodium chloride solution and then with the addition of 10 parts of sodium hydroxide and 2 to 5 parts of sodium hydrosulfite, the pyridine is distilled off with steam. The raw product is dissolved in hot, aqueous dimethylformamide for further purification and with the addition of something Animal charcoal filtered hot. The filtrate is poured into 4 to 5 times the volume of an approximately 10% saline solution, the precipitated product is filtered off, washed with water and dried in vacuo. You get that Sodium salt of 2- (Stübyl-4 ") - (naphtho-1 ', 2': 4,5) -l, 2, 3-triazole-2" -methylsulfane-6'-sulfonic acid as a yellow, in Heavy water, in dimethylformamide or ethylene glycol monoethyl ether easily soluble powder. The product can be used for lightening linear polyamide fibers, such as Nylon, can be used. Like the compound described in Example 1, it is excellent in chlorine and very good lightfast.

A product of similar properties is obtained when the 2-aminonaphthalene-6-sulfonic acid in the above Example is replaced by 22.3 parts of 2-aminonaphthalene-5-sulfonic acid. The sodium salt of 2- (stilbyl-4 ") - (naphtho-1 ', 2': 4,5) -l, 2,3-triazole-2" -methylsulfonic-5'-sulfonic acid is obtained as a poorly water-soluble, yellow powder.

If in the above example the 4-aminostilbene-2-methylsulfone is replaced by 36.3 parts of 4-aminostilbene-2- (l ^/ , 3'-dimethylphenylsulfon) and the o-aminoazo dye obtained is oxidized to the triazole compound by the method described above, the sodium salt is obtained of 3-triazole-2 "- (1,3-dimethylphenylsulfone) - 5 ', 7'-disulfonic acid as a yellow powder that is moderately soluble in water.

The starting materials used in the above example can be obtained in the following way: 22.3 parts of sodium 4-nitrotoluenesulfinate are used in 100 parts of toluene with 12 parts of dimethyl sulfate and 10 parts of magnesium oxide stirred under reflux for 3 to 4 hours. The 4-nitrotoluene-2-methylsulfone thus obtained is a white powder and, recrystallized from alcohol ίο, has a melting point of 118 to 120 °. 21.5 parts this 4-nitrotoluene-2-methylsulfone are mixed with 12 parts of benzaldehyde and 2 parts of piperidine at one temperature from 145 to 150 ° for 4 hours to 4-nitrostilbene-2-methylsulfone condensed. Recrystallized from glacial acetic acid, the product turns into a yellow powder with a melting point 196 to 198 °.

30.3 parts of this 4-nitrostilbene-2-methylsulfone are reduced by the method of Bechamp with 30 parts of etched cast iron filings in a mixture of Äthylenao glycol mononiethyl ether and water. The 4-aminostilbene-2-methylsulfone is obtained as an orange-yellow powder. Recrystallized from alcohol, the compound has a melting point of 131 to 133 ^D.

The 4-aminostilbene -2 - (V, 3 ' - dimethylphenylsulfone) is obtained as follows:

118 parts of 4-nitrotoluene-2-sulfonic acid chloride are heated with 400 parts of m-xylene and 10 parts of ferric chloride to boiling under reflux until the elimination of hydrochloric acid has ended. The excess m-xylene is through Separated by steam distillation. 71 parts of the 3 - nitro - 6,2 ', 4' - trimethyl -1,1 '- diphenylsulfon obtained are mixed with 25 parts of benzaldehyde with the addition of 2 parts of piperidine to form 4-nitrostilbene-2- (l ', 3'-dimethylphenylsulfone) condensed. 39.3 parts of this compound are made using the Bechamp method with 30 parts etched cast iron chips in a mixture of ethylene glycol monomethyl ether and water. The 4-aminostilbene-2- (r, 3'-dimethylphenylsulfone) is obtained as a yellowish powder; recrystallized from a benzene-gasoline mixture, it has a melting point of 138 up to 140 °.

Example 5

HSO, -

"N

N-

CH ₃

SO, —N -

-CH = CH-

2- (Stilbyl-4 ") - (naphtho-1 ^/ , 2 ': 4,5) -1, 2,3-triazol-2" - (1,3-dimethylphenylsulfone) -6'-sulfonic acid as a yellowish powder. This compound is difficult to dissolve in water and easily soluble in dimethylformamide or ethylene glycol monomethyl ether.

The disodium salt of 2- (stilbyl- 4 ") - (naphtho-1 ', 2': 4,5) -l, 2, 30.2 parts of 4-aminostilbene-2-sulfonic acid dimethylamide are dissolved with 25 parts of concentrated hydrochloric acid in 300 parts of glacial acetic acid, 150 parts of ice are added and diazotized with an aqueous solution of 6.9 parts of sodium nitrite at a temperature of 10 to 12. The diazo compound obtained is then treated with an aqueous solution of 22.3 parts of 2-aminonaphthalene-6-sulfonic acid, 4.0 parts of sodium hydroxide and 25 parts When the coupling is complete, the o-aminoazo dye obtained is dissolved in warm pyridine and, as described in Example 2, oxidized with ammoniacal copper sulfate solution to give the triazole compound and then purified. The sodium salt of 2- (stilbyl-4 ^// ) - is obtained. (naph tho-l ', 2 ^/ : 4,5) -l, 2,3-triazole-2 "-sulphonic acid-dimethylamide-6'-sulphonic acid as a yellowish powder which is sparingly soluble in water. The product is a valuable lightening agent for linear polyamide fibers, such as nylon.

θ 10

A product with very similar properties is r, 2 ': 4,5) -l, 2,3-triazole-6'-sulfonic acid, thus one obtains if in the above example the 2-aminonaphthalene falls a valuable lightening agent for linear poly-6-sulfonic acid by 22.3 parts of 2-aminonaphthalene-5-sul- amide fibers, such as nylon.

fonsäure is replaced. The sodium salt of 2- (stilbyl- If you also replace the 4-amino-2-chlorostilbene-4'-sulfone

4 ") - (naphtho-l ', 2': 4,5) -l, 2,3-triazol-2" -sulfonic acid di-5 acid by 22.6 parts of 4-amino-2-methoxystilbene, kupmethylamid-5 ' sulfonic acid is a yellowish, in water pelt its diazo compound with 2-aminonaphthalene sparingly soluble Powder received. 6-sulfonic acid and oxidizes the o-amino

The 4-aminostilbene azo dye used in the above example for the corresponding triazole compound, see above 2-sulfonic acid dimethylamide is produced in the following way, the sodium salt of 2- (2 "-methoxystilbyl-4") is obtained: io (naphtho-r, 2 ': 4,5) -l, 2,3-triazole-6'-sulfonic acid as yellow,

32.4 parts of 4-nitrilobes-2-sulfonic acid chloride become a powder which is sparingly soluble in water.

with ice cooling in 100 parts of an approximately 23% strength The 4-aminostilbene used in the above example

registered aqueous dimethylamine solution and some compounds are obtained by the method of sea hours at a temperature of 0 to 5 °, then during wine (Journal für Prakt. Chemie [2], 152, p. 256 [1939]) Stirred for 1 hour at a temperature of 60 to 65 °. 15 as follows:

After cooling, it is filtered off with cold water a) By reacting the diazo compound of

washed well and the precipitate with 30 parts of cast 17.3 parts of 4-nitro-2-chloro-1-aminobenzene with the solution iron filings and 5 parts of acetic acid in a mixture of 22.8 parts of cinnamic acid-4-sulfonic acid, 4 parts of Navon Ethylene glycol monomethyl ether and water redu- triumhydroxyd, 40 parts of sodium acetate and 10 parts adorns. The 4-aminostilbene-2-sulfonic acid-discrystallized copper (II) chloride in 200 parts of water is obtained methylamide as a yellowish powder. It shows that alcohol becomes die with elimination of nitrogen and carbon dioxide

recrystallized, melting point 134 to 136 °. 4-nitro-2-chlorostilbene-4'-sulfonic acid obtained, which one

". . . , in aqueous solution with cast iron filings and hydrochloric acid

^b "reduced to 4-amino-2-chlorostilbene-4'-sulfonic acid;

25 b) by reacting the same diazo compound with a mixture of the solutions of 14.8 parts of cinnamic acid in 200 parts of acetone and 40 parts of sodium acetate SO ₃ H and 10 parts of copper (II) chloride in 200 parts of water

one obtains the 4-nitro-2-chlorostilbene as a yellow powder, 30, the one in a mixture of ethylene glycol mono-30.95 parts of 4-amino-2-chlorostilbene-4'-sulfonic acid advertising methyl ether and W ^r ater with Gußeisenspänen and with 4.0 parts of sodium hydroxide dissolved in water, hydrochloric acid reduced to 4-amino-2-chlorostilbene, which 6.9 parts of sodium nitrite is added and obtained as a pale yellow powder at a temperature;
temperature of 10 to 12 ° with 25 parts of concentrated salt c) by reacting the diazo compound of

acid indirectly diazotized. The suspension of the diazover 35 16.8 parts of 4-nitro-2-methoxy-l-aminobenzene with 14.8 Binding is with an aqueous solution of 14.3 parts parts of cinnamic acid under the Bedin-2-aminonaphthalene communicated under b) and 10 parts of concentrated salts and reduction of the nitro to the amino group acid combined at a temperature of 12 to 15 ° and 4-amino-2-methoxystilbene is obtained as a light yellow the mineral acid reaction of the coupling by adding powder.

an aqueous solution of 40 parts of crystallized Example 7

Sodium acetate gradually dulled. After finished
Coupling, the dye is filtered off and washed. ί | SO ₃ H

The moist o-aminoazo dye is then dissolved in / \ N.

hot pyridine and oxidizes it with a mixture of j N- / CH = CH / -

60 parts of crystallized copper sulfate in 240 parts of 45 \. _ / \ /

Water and 120 parts concentrated ammonia at "'N

a temperature of 90 to 95 ° to the triazole compound. 27.5 parts of 4-aminostilbene-2'-sulfonic acid are with

The copper is removed and the crude product is purified, as in the case of 4.0 parts of sodium hydroxide dissolved in water, 6.9 parts game 2, and dry it in a vacuum. The . Sodium nitrite added and kept at a temperature of 2- (2 "-Chlorst.ilbyl-4") - (naphtho-1 ', 2': 4,5) -l, 2,3-triazole 50 10 to 12 ° with 25 parts of concentrated hydrochloric acid indirectly 4 "'- sulfonic acid is a yellow powder diazotized as the sodium salt. The diazo suspension obtained is treated with a The compound is difficult in water, in a dimethyl aqueous solution of 14.3 parts of 2-aminonaphthalene formamide or ethylene glycol monomethyl ether easily and 10 parts of concentrated hydrochloric acid at a temperature soluble and represents a valuable brightening agent for doors from 15 to 18 ° combined. By gradually adding linear polyamide fibers, such as nylon. Those which crystallized with it in an aqueous solution of 40 parts Treated fibers show a pure white tint, which sodium acetate will make the coupling reaction weak good fastness properties, in particular an excellent chlorine mineral acid. After the coupling is completed fastness and good lightfastness. the dye is filtered off and washed. The wet one

If the 2-aminonaphthalene o-aminoazo dye is replaced in the above example, it is now dissolved in pyridine at a temperature of 22.3 parts of 2-aminonaphthalene-6-sulfonic acid and 60 ° to 95 °, and a mixture of 60 parts oxidizes the o- Aminoazo dye for tri-crystallized copper sulfate in 240 parts of water and azole compound, the din atrium salt of 120 parts of concentrated ammonia is obtained and 2- (2 "-Chlorstilbyl-4 ^// ) - (naphtho-1 ', 2': 4, 5) -l, 2,3-triazole- stirred in a water bath until the 6 ', 4 "' - disulfonic acid is completely oxidized as a yellowish, water-soluble dye. After cooling, it is under powder. 65 Addition of common salt the aqueous copper salt containing

If the 4-amino-2-chlorostilbene-4'-sulfonic acid layer is removed from the pyridine, the pyridinic layer is replaced by 23.05 parts of 4-amino-2-chlorostilbene, the couple washed several times with ammoniacal saline Diazo compound with 2-aminonaphthalene-6-sulfonic acid and then with the addition of 10 parts of sodium hydroxide and oxidizes the resulting o-aminoazo dye to and 2 to 5 parts of sodium hydrosulfite with the pyridine Sodium salt of 2- (2 "-Chlorstilbyl-4") - (naphtho- 7 ° water vapor is distilled off. For further purification is

709 807/266

the crude product dissolved in hot, aqueous dimethylformamide and filtered hot with the addition of animal charcoal. The filtrate is poured into an approximately 10 ° / ₀ by weight sodium chloride solution in 4 to 5 times the volume, the precipitated product filtered off, washed and dried in vacuo. The sodium salt of 2- (stilbyl-4 ") - (naphthol ', 2': 4, S) -l, 2,3-triazole-2 '" - sulfonic acid is a yellow powder that is sparingly soluble in water. The compound is a valuable lightening agent for cellulose fibers, linear polyamide fibers such as nylon, as well as for soaps and synthetic detergents. The lightening effects thus obtained are distinguished by excellent fastness to chlorine and very good fastness to light.

Replacing the 2-aminonaphthalene in the above example by a solution of the sodium salt of 22.3 parts of 2-aminonaphthalene-5- or -6-sulfonic acid and 25 parts crystallized sodium acetate and then oxidized the o-aminoazo dye obtained to the disodium salt of 2- (stilbyl-4 ") - (naphtho4 ', 2': 4,5) -1, 2,3-triazole-2 '" - 5'- or -ö'-disulfonic acid, products are obtained which also have very valuable properties.

The 4-aminostilbene-2'-sulfonic acid used in this example is obtained in the following way:

18.3 parts of 4-nitrophenylacetic acid, 18.6 parts of 2-sulfobenzaldehyde and 5 parts of piperidine are condensed for 4 hours at a temperature of 150 to 160 °. The 4-nitrostilbene-2'-sulfonic acid is obtained as a yellowish powder. 30.5 parts of 4-nitrostilbene-2'-sulfonic acid are in water using the Be champ method reduced with 30 parts etched cast iron filings. The 4-aminostilbene-2'-sulfonic acid appears as a pale yellowish powder obtain.

Example 8

HSO, -,

Cl

CH = CH

SO ₃ H

30.95 parts of 4-ammo-2'-chlorostbene-5'-sulfonic acid become with 4.0 parts of sodium hydroxide dissolved in water, 6.9 parts of sodium nitrite were added and at a temperature indirectly diazotized from 10 to 12 ° with 25 parts of concentrated hydrochloric acid. The diazo suspension thus obtained is with an aqueous solution of 22.3 parts of 2-aminonaphthalene-6-sulfonic acid, 4.0 parts of sodium hydroxide and 25 parts of crystallized sodium acetate combined at a temperature of 12 to 15 °. After finished Coupling, the o-aminoazo dye is filtered off and washed. The dye is then applied, as in the example 7 described, dissolved in hot pyridine, with a mixture of 60 parts of crystallized copper sulfate in 240 parts of water and 120 parts of concentrated ammonia at a temperature of 90 to 95 ° for Triazolverbradung oxidized and then decoppered and cleaned. The disodium salt of 2- (2 '"- Chlorstilbyl-4") - (naphtho-1', 2 ': 4,5) 4,2,3-triazole-5 '", 6'-disulfonic acid is a yellowish powder which is readily soluble in water. The Compound draws on cellulose fibers from their dilute, aqueous solutions and gives them a whiter appearance Appearance in daylight. The lightening effects obtained in this way are distinguished by excellent fastness to chlorine and very good lightfastness.

A product which is sparingly soluble in water and also has valuable properties is obtained if the Diazo suspension of 4-amino-2'-chlorostilbene-5'-sulfonic acid with an aqueous solution of 14.3 parts of 2-aminonaphthalene and 10 parts of concentrated hydrochloric acid combined and the mineral acid reaction of the coupling gradually by adding an aqueous solution of 40 parts of crystallized sodium acetate and the o-aminoazo dye obtained is oxidized to the triazole compound as described above. After cleaning the sodium salt of 2- (2 '"- chlorostilbyl-4") - (naphtho-1', 2 ': 4,5) -l, 2,3-triazole-5' "- sulfonic acid is obtained as a yellowish powder.

The 4-amino-2'-chloro mentioned in this example

stilbene-5'-sulfonic acid is obtained in the following way:

18.3 parts of 4-nitrophenylacetic acid, 22 parts of 2-chloro

benzaldehyde-5-sulfonic acid and 6 parts of piperidine condensed at a temperature of 150 to 160 ° for 4 hours. 4-Nitro-2'-chlorostilbene-5'-sulfonic acid is obtained as a yellowish powder that is reduced using the Be champ method. 4-Amino-2'-chlorostilbene-5'-sulfonic acid is a pale yellowish powder.

Example 9

HSO, -

CH = CH-

-SO ₃ H

27.5 parts of 4-aminostilbene-4'-sulfonic acid are dissolved in water with 4.0 parts of sodium hydroxide, 6.9 parts of sodium nitrite are added and the mixture is indirectly diazotized at a temperature of 10 to 12 °. The diazo suspension obtained is combined with an aqueous solution of 22.3 parts of 2-aminonaphthalene-6-sulfonic acid, 4.0 parts of sodium hydroxide and 25 parts of crystallized sodium acetate at a temperature of 12 to 15 °. After the coupling has ended, the dye is salted out, filtered off and washed. Then, the wet o-aminoazo with 20 parts of an aqueous concentrated ammonia in 20 is dissolved ° / ₀ aqueous pyridine solution hot and combined, this solution concentrated with a mixture of 60 parts of crystalline copper sulfate in 240 parts of water and 120 parts of ammonia water and up to complete oxidation of the dye kept at a temperature of 90 to 95 °. The mixture is then separated by adding sodium chloride, the pyridinic layer is washed several times with ammoniacal sodium chloride solution and the pyridine is then driven off with steam with the addition of 10 parts of sodium hydroxide and 4 to 8 parts of sodium hydrosulfite. The Rohtriazol is released for further cleaning in hot ethylene glycol monomethyl ether, the hot solution with the addition of animal charcoal filtered hot and then poured into 4 to 5 times volume of a 10 ° / ₀ by weight sodium chloride solution. After filtering off and drying, the disodium salt of 2- (Stübyl-4 ") - (naphtho-1 ', 2': 4,5) -l, 2,3-triazole-4 '" - 6'-disulfonic acid is obtained as a yellowish , powder readily soluble in water. The product is a valuable lightening agent for cellulose fibers. The lightening effects obtained are distinguished by excellent fastness to chlorine and very good fastness to light.

A suspension of the diazo compound of 4-aminostilbene-4'-sulfonic acid obtained according to the above example is combined with an aqueous solution of 14.3 parts

13 14

2-aminonaphthalene and 10 parts of concentrated hydrochloric acid, 2-aminonaphthalene-6-sulfonic acid by 30.3 parts

acid is replaced with the gradual addition of 40 parts of crystalline 2-aminonaphthalene-5,7-disulfonic acid. That

sated sodium acetate, the oxy-obtained disodium salt of 2- (stilbyl-4 ") - (naphtho-l ',

dation of the o-aminoazo dye the sodium salt of 2 ': 4,5) -l, 2,3-triazole-2 "' - sulfonic acid dimethylamide-5 ', 7'-

2- (Stilbyl-4 ") - (naphtho-r, 2 ': 4,5) -l, 2,3-triazole-4" -sulfonic-5-disulfonic acid is a yellowish acid which is readily soluble in water

acid as yellowish, difficult in water, in dimethyl powder. Its dilute, aqueous solutions are

formamide or ethylene glycol monomethyl ether easily dissolvable - practically colorless.

Lich powder. The 4-aminostilbene-2'-sulfonic acid dimethylamide can

The 4-aminostilbene used in this example in the above example also by 35.6 parts of 4-aminostilbene

4'-sulfonic acid is produced in the following ways: io 2'-sulfonic acid cyclohexylamide can be replaced. By

a) 18.3 parts of 4-nitrophenylacetic acid, 18.6 parts of 4-Sul- setting of the diazo compound with 2-aminonaphthalenobenzaldehyde (obtainable by reacting 4-chloro-6-sulfonic acid and oxidizing the o-aminoazo dye benzaldehyde with sodium sulfite at 180 to 185 °) and the triazole compound is the sodium salt of 2- (StU-6 parts Piperidine are heated for 4 hours at a byl-4 ") - (naphtho-r, 2 ': 4,5) -l, 2,3-triazole-2'" sulfonic acid temperature condensed from 160 to 170 °. The cyclohexylamide-δ'-sulfonic acid is obtained as a yellowish in water 4-nitrostilbene-4'-sulfonic acid as a yellowish powder; heavy, in dimethylformamide or ethylene glycol mono-

b) 13.8 parts of 4-nitroaniline are obtained with 22.8 parts of 4-sulfomethyl ether, readily soluble powder. The product Focinnamic acid according to the method of Meerwein under is an excellent lightening agent for fibers the conditions described in Example 6 to give 4-nitro-linear polyamides, such as nylon or perlon. stilbene-4'-sulfonic acid implemented. 30.5 parts 4-Nitrostil- 20 A product with similar properties is obtained-4'-sulfonic acid are by the method of th when the 2-aminonaphthalene-6-sulfonic acid by Bechamp replaced 30.3 parts of 2-aminonaphthalene-5,7-disulfonic acid in water with 30 parts of etched cast iron iron chips in the presence of 5 parts of hydrochloric acid is reduced. The disodium salt of 2- (stilbyl-4 ") - (naphtho-l ', adorns. The 4-aminostilbene-4'-sulfonic acid is obtained as 2 ': 4,5) -l, 2,3-triazole-2 "' - sulfonic acid cyclohexylamide-5 ', 7'-pale yellowish Powder. 25 disulfonic acid is a yellowish, moderately soluble in water

. · Ι ·) η like powder.

Example 10 _{The in whether} j _gen example used 4-aminostilbene 2 '

CH ₃ sulf onsäuredimethylamid is in the following way -

/ -. I placed: 32.7 parts of the sodium salt in Example 7

HSO ₃ - CH ₃ -N-SOo 3 ° described 4-nitrostilbene-2'-sulfonic acid are in

] sj I "a mixture of 200 parts of phosphorus oxychloride and

/ \ / '', 40 parts of phosphorus pentachloride entered and during

., ~ \ _/ / - ^{CH = CH} - ^ / 4 hours at a temperature of 102 to 105 °

stirs. By introducing the reaction mixture in ice 35 and water at a temperature of below 5 °

30.2 parts of 4-aminostilbene 2 '- sulfonic acid - dimethyl - decomposes the phosphoric acid halides. The eject amid are in 100 parts of glacial acetic acid with 25 parts of concentrated 4-nitrostilbene-2'-sulfonic acid chloride is filtered off, Trated hydrochloric acid dissolved, 80 parts of ice were added and washed well with water and in a vacuum at a dried an aqueous solution of 6.9 parts of sodium nitrite at a temperature of 30 to 35 °, diazotized at a temperature of 10 to 12 °. The 40 obtained are 32.4 parts of 4-nitrostilbene-2'-sulfonic acid chloride Diazo compound is then with an aqueous solution at a temperature of 0 to 5 ° in 100 parts of an approximately of 22.3 parts of 2-aminonaphthalene-6-sulfonic acid, 4.0 parts of 23% strength aqueous dimethylamine solution, len sodium hydroxide and 25 parts of crystallized Na- Then a few hours at 0 to 5 ° and then trium acetate combined at a temperature of 12 to 15 °. Stirred for 1 hour at 40 to 50 °. After cooling down When coupling is complete, the o-aminoazo dye 45 is filtered off and the precipitate which has separated out is filtered off with dissolved in hot pyridine and then washed well with a mixture of cold water. Then the obtained of 60 parts of crystallized copper sulfate in 240 parts of product by the method of Bechamp Water and 120 parts of concentrated ammonia with 30 parts of cast iron turnings in the presence of 5 parts a temperature of 90 to 95 ° to the triazole compound hydrochloric acid monooxidized in a mixture of ethylene glycol. As in Example 2, the crude product is further reduced with methyl ether and water. You get that described, decoppered and cleaned. The 4-aminostilbene-2'-sulfonic acid dimethylamide is obtained as weak Sodium salt of 2- (stilbyl-4 ") - (naphtho-l ', 2': 4,5) -l, 2,3- yellowish powder. It shows, recrystallized from benzene, triazole-2 '"- sulfonic acid dimethylamide-6'-sulfonic acid as the melting point 121 to 123 °.

yellowish powder. Difficult in water, in dimethyl. The dimethylamine is replaced by a mixture of

formamide or ethylene glycol monomethyl ether easily soluble 55 100 parts of water and 25 TeUen of cyclohexylamine and Lent product draws the resulting 4-nitrostilbene-2'-sulfonic acid solutions from its dilute aqueous solution on cellulose fibers and on linear polyamide-cyclohexylamide, 4-aminostilbene-2'-fibers are obtained. sulfonic acid cyclohexylamide as a light yellowish powder. That

A similar product used for lightening cellulose fibers, recrystallized from benzene, shows the melt lignite Product is obtained when in the above example 60 point 139 to 141 °.

Example 11

- CH = CH- < > - SO ₂ -CH ₃

27.3 parts of 4-aminostilbene-4'-methylsulfone are diazotized as in Example 10 for 4-aminostilbene-2'-sulfonic acid dimethylamide described. By coupling the diazo compound with 2-aminonaphthalene-6-sulfonic acid and oxidation of the o-aminoazo dye under the same conditions as in Example 10 to give the triazole compound becomes the sodium salt of 2- (stilbyl-4 ") - (naphtho-l ', 2': 4,5) -1,2,3-triazole-4 "'- methylsulfone-6'-sulfonic acid was obtained as a yellowish powder Product is an excellent means of lightening cellulose fibers. It can further lighten up linear polyamide fibers such as nylon can be used.

A product with similar properties is obtained if instead of 4-aminostilbene-4'-methylsulfone 27.3 parts of 4-aminostilbene-2'-methylsulfone were used. The sodium salt of 2- (stilbyl-4 ") - (naphthol ', 2': 4,5) - 1,2,3-triazole-2 '"- methylsulfone-6'-sulfonic acid is a yellowish powder that is sparingly soluble in water.

a) The 4-aminostilbene-4'-methylsulfone is obtained as follows: 18.4 parts of 4-methylsulfonylbenzaldehyde are obtained with 18.3 parts of 4-nitrophenylacetic acid and 2 parts of piperidine for 4 hours at a temperature of 150 to 160 ° condensed. The 4-nitrostilbene-4'-methylsulfone is obtained as a yellow powder.

Recrystallized from glacial acetic acid, it has a melting point of 235 to 237 °. 30.3 parts of this 4-nitrostilbene

4'-methylsulfons are reduced in a mixture of ethylene glycol monomethyl ether and water using the Be champ method. The 4-aminostilbene-4'-methylsulfone is a yellowish powder.
"b) The 4-aminostilbene-2'-methylsulfone is prepared in the following way: 32.4 parts of 4-nitrostilbene-2'-sulfonic acid chloride are mixed with a solution of 32 parts of sodium sulfite and 5 parts of sodium hydroxide

ίο in 200 parts of water at a temperature of 20 to 30 ° converted into the sodium salt of 4-nitrostilbene-2'-sulfinic acid. The sodium hydroxide becomes over the course of some Hours added so that the reaction mixture always a weak phenolphthalein alkaline reaction having. Thereupon 31.1 parts of 4-nitrostilbene-2'-sulfinic acid are added Sodium in 200 parts of xylene with 20 parts of dimethyl sulfate and 20 parts of magnesium oxide during Stirred under reflux for 4 to 5 hours. The 4-nitrostilbene-2'-methylsulfone obtained is a yellow powder which, recrystallized from alcohol, has a melting point of 147 to 149 °. Will be 30.3 parts of this 4-Nitrostilben-2'-methylsulfone by the method of Bechamp with 30 parts of etched cast iron filings in a mixture of ethylene glycol monomethyl ether and

As water is reduced, 4-aminostilbene-2'-methylsulfone is obtained as a yellow powder which, recrystallized from alcohol, has a melting point of 147 ° to 149 °.

Example 12

HSO, - / '

SO ₉ -O-

, ■ - -N

CH = CH- /

35.1 parts of 4-aminostilbene-2'-sulfone-28.9 parts of 4-amino-6-methylstilbene-2-sulfonic acid are diazotized.

acid phenyl ester, coupled with 2-aminonaphthalene-6-sulphides with 4.0 parts of sodium hydroxide in 300 parts of fonsäure and oxidized the o-aminoazo-carbohydrate obtained, 6.9 parts of sodium nitrite were added and the substance to the triazole compound under those in Example 10 was added - at a temperature of 10 to 12 ° with 25 parts congenital conditions. The sodium salt of the centered hydrochloric acid is thus obtained indirectly diazotized. The obtained 2- (stilbyl-4 ") - (naphtho-r, 2 ': 4.5) -l, 2,3-triazole-2'" - sulfone diazo suspension is acid phenyl ester with a solution of 14.3 parts 6'-sulfonic acid as a yellowish, in water 2-aminonaphthalene and 10 parts concentrated salt sparingly soluble powder. The product is a valuable acid in 250 parts of water at a temperature of brightening agent for linear polyamide fibers such as nylon. 10 to 12 ^C combined and the strongly mineral acid reaction

The phenyl 4-aminostilbene-2'-sulfonate becomes like 45 of the mixture by gradually adding 40 parts obtained as follows: 32.4 parts of 4-nitrostilbene-2'-sulfonic acid-crystallized sodium acetate blunted. After beenchlorid slowly in a mixture of 10 parts of deter coupling, the o-aminoazo dye is filtered off Phenol, 4.5 parts of sodium hydroxide and 20 parts and washed. The dye is then divided into 300 parts Water at a temperature of 60 to 65 ° and phenol-hot pyridine dissolved and a mixture of 60 parts registered phthalein-alkaline reaction. Then 50 crystallized copper sulfate in 240 parts of water and is added for 1 hour at a temperature of 60 to 65 ° 120 parts of concentrated ammonia and stirred, then cooled, the resulting precipitate then filtered off until the color is completely oxidized and washed out well with water. After the substance is stirred at a temperature of 90 to 95 °. the Drying in vacuo provides the 4-nitrostilbene-2'-sulfone separation of the copper salts and the purification of the acid phenyl ester is a slightly brownish powder. 55 crude product is carried out as described in Example 2

35.1 parts of this 4-nitrostilbene-2'-sulfonic acid phenylbene. The sodium salt of the 2- (6 "-methyl esters) is obtained are made according to the Bechamp method with stilbyl-4 ") - (naphtho-1 ', 2': 4,5) -l, 2,3-triazol-2" -sulfon-30 Share etched cast iron filings in a mixture acidic as yellow, heavy in water, in dimethylformamide of ethylene glycol monomethyl ether and water redu- or ethylene glycol monomethyl ether on the other hand slightlyziert. The 4-aminostilbene-2'-sulfonic acid-60 soluble powder is obtained. The new triazole compound is a

phenyl ester as a yellowish, resinous mass.
Example 13

CH,

CH = CH-

SO »H

Excellent agent for lightening linear polyamide fibers such as nylon. The resulting whiteness shows excellent fastness to chlorine and very good fastness to light.

A product which is more readily soluble in water is obtained
when the diazo suspension obtainable according to the above example with an aqueous solution of 22.3 parts
^ -Aminonaphthalene-S-sulfonic acid, 4.0 parts of sodium hydroxide and 25 parts of crystallized sodium acetate

implemented and the o-aminoazo dye to the triazole

bond is oxidized. The disodium salt of 2- (6 "-Methylstilbyl-4") - (naphtho-1 ', 2': 4,5) -1, 2,3-triazol-2 ", 5'-disulfonic acid is obtained as a yellowish powder.

A product with almost the same properties is obtained when the 2-aminonaphthalene-5-sulfonic acid is replaced by 22.3 parts of 2-aminonaphthalene-6-sulfonic acid. The disodium salt of 2- (6 "-Methylstilbyl-4") - (naphtho-1 ', 2': 4,5) -1, 2,3-triazol-2 ", 6'-disulfonic acid is also a yellowish powder that is readily soluble in water.

Example 14

SO ₉ -NH

CH = CH

The 4-aminostilbene-2- (p-methylphenyl) disulfimide is replaced by 41.1 parts of 4-aminostilbene-2-phenyl disulfimide or by 44.8 parts of 4-aminostilbene-2- (pchlorphenyl) disulfimide and sets the diazo suspension thus obtained with an aqueous solution of 14.3 parts of 2-aminonaphthalene and 10 parts of concentrated hydrochloric acid in the weakly mineral acid range, one obtains after oxidation of the corresponding o-aminoazo dye the 2- (stilbyl-4 ") - (naphtho-r, 2 ': 4,5) -l, 2,3-triazole-2" -phenyldisulfimide or the -2 "- (p-chlorophenyl) disulfimide. As sodium salts, these compounds produce yellowish powders that are sparingly soluble in water They are very valuable lightening agents for linear polyamide fibers such as nylon or perlon. Similar effective products are obtained when the 4-aminostilbene-2- (p-methyrphenyl) disulfimide is replaced by 35.2 parts of 4-aminostilbene-2-methyldisulfimide or by 39.3 parts of 4-aminostilbene-2-benzoylsulfimide. That so obtained 2- (stilbyl-4 ") - (naphtho-l ', 2': 4,5) -l, 2,3-triazole-

42.8 parts of 4-aminostilbene-2- (p-methylphenyl) disulfimide are mixed with 4.0 parts of sodium hydroxide in water
dissolved, 6.9 parts of sodium nitrite added and with a 20 2 "-methyldisulnmid or the 2- (stilbyl-4") - (naphtho temperature of 10 to 12 ° with 25 parts of concentrated r, 2 ': 4.5) -l, 2,3-triazol-2 "-benzoylsulnmid are also yellowish compounds which are sparingly soluble in water.

Compounds which are more readily soluble in water are obtained when the diazo compounds of 4-aminostilbene-2-phenyldisulfimide or the -2- (p-chlorophenyl) -disulfi-

Hydrochloric acid indirectly diazotized. The diazo suspension obtained is mixed with a solution of 14.3 parts of 2-aminonaphthalene and 10 parts of concentrated hydrochloric acid in 250 parts of water at a temperature of 12 to 15 ° combined and the strongly mineral acid reaction of the mixture by adding about 40 parts of crystallized sodium acetate kept in the weakly mineral acid range. After the Kuppmids or of the -2-methyldisulfimide or the -2-benzoylsulfimide with an aqueous solution of 22.3 parts of 2-aminonaphthalene-6-sulfonic acid, 4.0 parts of sodium

The o-aminoazo dye is filtered off, washed hydroxide 30 and 25 parts of crystallized sodium acetate and then dissolved in 500 parts of warm pyridine. To be implemented. By oxidation of the o-amino-oxidation of the dye is a mixture of 60 parts of azo dyes, the disodium salts of the 2- (Stilcrystallized Copper sulfate in 240 parts of water and byl-4 ") - (naphtho-1 ', 2': 4,5) -1, 2,3-triazol-2" -phenyldisulf-120 Parts of concentrated ammonia and added to imide-6'-sulfonic acid or the -2 "- (p-chlorophenyl) -disulfzum complete disappearance of the dye with a 35 imide-6'-sulfonic acid or the ^ "- methyldisulfimide-o'-sul-

Stirred temperature from 90 to 95 °. After cooling down, the addition of table salt becomes the copper-salt-containing Layer separated from the pyridine, the pyridinic layer several times with ammoniacal saline solution washed out and then with the addition of 10 parts of sodium hydroxide and 3 to 6 parts of sodium hydrosulfite the pyridine is distilled off. The precipitated product is filtered off and washed with warm water washed. For further purification, the crude product is dissolved in hot, aqueous dimethylformamide and filtered hot with the addition of animal charcoal. The resulting solution is then increased by 4 to 5 times Volume of an approximately 10% saline solution poured, the precipitated product filtered off, with water washed and dried. The sodium salt of 2- (stilbyl-4 ") - (naphtho-1 ', 2': 4,5) -1, 2,3-triazol-2" - (p-methylphenyl) -disulfimide is yellowish, heavy in water, in ethylene glycol monomethyl ether or dimethylformamide Easily soluble powder obtained. This product is an excellent lightening agent for linear polyamide fibers such as nylon or perlon.

A compound which is more readily soluble in water and which is also readily brightening is obtained when the diazo compound mentioned in the above example is treated with an aqueous solution of 22.3
acid, 4.0 parts

crystallized sodium acetate is combined. By oxidation of the o-aminoazo dye in aqueous solution with a mixture of 60 parts of crystallized copper sulfate in 240 parts of water and 120 parts of concentrated ammonia in aqueous solution are obtained after work-up and purification of the disodium salt of 2- (stilbyl-4 ") - (naphtho-l ', 2': 4,5) -l, 2,3-triazole-2" - (p-methylphenyl) -disulfimide-6'- sulfonic acid than a yellowish powder.

Fonsäure or the -2 "-benzoylsulfimid-6'-sulfonic acid obtained as a yellowish powder.

The aminostilbene used in the example above are obtained in the following way: 32.4 parts of 4-nitrostilbene-2-sulfonic acid chloride of an aqueous 5 ° / _o ammonia solution are added under ice cooling in 100 parts, only a few hours at a temperature of 0 to 5 ° and then stirred for 1 hour at 60 to 65 °. After cooling, it is filtered off, washed well with cold water and then dried. 4-Nitrostilben-2-sulfamide is a yellow powder.

30.5 parts of this 4-nitrostilbene-2-sulfamide are in a mixture of ethylene glycol monomethyl ether and Water with 21 parts of p-toluenesulfochloride and 9 bis 10 parts of sodium hydroxide stirred at a temperature of 70 to 80 °. The 4-nitrostilbene-2- (p-methylphenyl) disulfimide thus obtained is according to the method of Bechamp with 30 parts of cast iron turnings in a mixture of ethylene glycol monomethyl ether and water reduced to 4-aminostilbene-2- (p-methylphenyl) disulfimide. The product turns yellowish after drying Powder.

The compounds mentioned further are obtained,

Share 2-aminonaphthalene-6-sulfone- ⁶ ° by adding the p-toluenesulfonyl chloride by 18 parts of benzene-sodium hydroxide and 25 parts of sulfochloride or 23 parts of 4-chlorobenzenesulfonyl chloride or

12 parts of methyl sulfochloride is replaced. 4-Nitrostilbene-2-sulfamide is used to produce 4-nitrostilbene-2-benzoylsulfimide reacted with benzoyl chloride in pyridine and reduced the nitro group to the amino group.

Claims (2)

Claims: 1. Further development of the method according to Patent 942 395 for the preparation of 2-stilbyl-mononaphtho-l, 2,3-triazole compounds, characterized by 709 '807/266 draws that diazotized, possibly further substituted, but no acylamino groups, 4-aminostilbene compounds of the formula containing triazinylamino groups or azole rings H ₂ N- < V-CH = CH- where in the X ₁ position only the sulfonic acid group is excluded as the only substituent of the associated benzene ring and the further condition applies that at least one preferably electrophilic substituent must be present _{in the X 1} , X ₂ and X _{3 positions, with in o-position to} Amino group coupling, optionally further substituted aminonaphthalene compounds are combined to form the o-aminoazo dye and this in a manner known per se for 1,2,3-triazole compound is oxidized, whereby the Components are chosen in such a way that the aromatic residues are neither through chromophores nor through aromatic bonded hydroxyl or amino groups are further substituted, but one to four acidic, under Salt formation contain water-solubilizing groups. 2. Process for the preparation of the 2-stilbyl-mononaphtho-1,2,3-triazole compounds characterized in more detail in claim 1, characterized in that diazotized 4-aminostilbene compounds are used which have nitro or acylamino groups contained as substituents, and in the 2 - stilbyl-mononaphtho -1,2,3 - triazole compound obtained Nitro group converted into the amino group by reduction or the acylamino group by saponification, this is diazotized, whereupon the diazo group is replaced by hydrogen by methods known per se or other substituents. Ten boards were displayed when the application was announced.