DE2345159A1 - TRIAZOLYLA ETHYLENE COMPOUNDS - Google Patents

Description

onw Dipl.-hg. P.

O2 A.G.

Case 150-3414

Triazolylethylene compounds

The invention relates to new triazolylethylene compounds the formula

R ₁ R

CH = CH-

No,

R,

^R 3 (I)

in which

R., R_ and R ^ can be the same or different and

any hydrogen, optionally substituted aryl,

Aryloxy, alkyl or alkyloxy, halogen, cyano, carboxyl,

409812/1221

Case 150-3414

an optionally substituted carboxylic acid or sulfonic acid amide or ester residue, a sulfonic acid group or the group -SOJ ^ M ^, in which M ^ is an equivalent of a cation; Hydrogen, halogen, alkyl, cyano, the H ₂ NCO group, the R_OOC group, where R_ is hydrogen or an alkyl radical,

R- and R _{fi can be} identical or different and each represent hydrogen, optionally substituted alkyl or alkoxy, halogen, cyano, carboxyl, an optionally substituted carboxylic acid or sulfonic acid amide or ester radical, a sulfonic acid group or the group -S0_ ^ M ^, and stands for the numbers 1 to 4, each of the

Phenyl residues A at least one sulfonic acid residue or the M

° 3 ^p

-Group carries.

The process for the preparation of the compounds of the formula is characterized in that one a) a compound of the formula

(II)

in which R ^, R _fi and η have the meaning given above with a compound of the formula

/ V ^Y

(III)

409812/1221

- 3 - Cese 150-3414

and a compound of the formula

(IV)

in which R. , R ₂ , R and R. have the meaning given above, one of the radicals X, and Y, or X "and Y" is the OHC group or a functional derivative thereof and the other is the remainder of the formula

-CH ₂ Z ₁ (V)

mean,

wherein Z. is hydrogen, a carboxyl group, a substituted or unsubstituted carboxylic acid ester or amide group, or a group of the formula

-i> = O < ^VI > -ρ- ο < ^VII >, / (VIII)

ι- - yj -L ^J - υ -P = G

«3 9 ^K 8

/ S

-P = o. ^(IX) - _P © _(R , _Λ © ' ^x '

ν · ■ ^{8 3} "

in which R _ß a substituted or unsubstituted

409812/1221

Case 150-2414

tuted aryl radical, R _{q is} a substituted or unsubstituted alkyl radical with 1 to 6 carbon atoms, or a substituted or unsubstituted cycloalkyl radical and A. is a monovalent / mion, where if the imßidproduct the radical Z is different from hydrogen, this is replaced by hydrogen , or that one
b) a compound of the formula

.N

—N

-X.

(XI)

in which

R, R.,

-, R and η the above

₁ , R ₂ ,

have given meaning, with a compound of the formula (III)

wherein X ₁ and Y ₁ are as defined above, and each Z 1, which is not a hydrogen atom, is replaced by one in the end product, or e) a diazo derivative of the compound of the formula

H = CH-

(XII)

in which R

, R., R ₅ , R and η have the meaning given above, in the presence of a catalyst

409812/1221

- 5 - Cr.se 150-3414

with a compound of the formula

(XIII)

in which R ₁ , R 2, R and R have the meaning given above and Z_ denotes a carboxyl group or a substituted or unsubstituted carboxamide or ester group, reacts and, if necessary, splits off the radical Z “in the end product.

The process described under a) is preferably carried out with exclusion of air and at temperatures from 0 to 200.degree carried out, a temperature range of 20 to 160 C is particularly favorable. The procedure can be done by mere Melting together of the reactants can be carried out, but it has been shown to be advantageous works in the presence of an inert organic solvent, such as in the presence of an aliphatic or aromatic or halogenated hydrocarbon, alcohol, ether, glycol, of formamide, dimethylformamide or acetamide, of N-methylpyrrolidone, Acetonitrile, dimethyl sulfoxide, tetramethylene sulf on or phosphoric acid hexamethyltriamide.

In the compound of the formula (II), the radicals X ₁ and X- can be the same, in which case Y ₁ and Y are also the same and consequently also the compounds (III) and (IV). If the compounds (III) and (IV) are identical, it is expedient to use at least two moles of these compounds per mole of the compound (II). If the compounds (III) and (IV) are different, at least one mole of is used each connection to one mole of the

409812/1221

- 6 - Case'150-3414

bond (II).

The process is preferably carried out in the presence of condensing agents or catalysts, e.g. in the presence of boric acid, zinc chloride, aryl sulfonic acids, alkali and alkaline earth salts of aryl sulfonamides, Acetic anhydride, piperidine, alkali acetates and alkali or alkaline earth hydroxides or alcoholates.

If in the end products Z- is different from hydrogen it can subsequently be replaced by hydrogen in the usual way.

Process b) can be carried out under the same reaction conditions as those described above Procedure a).

In process c), the reaction of the Hazoderivates of the compound of the formula (XII) with the compound of the formula (XIII) is advantageously carried out in a polar solvent, for example water, acetone, glacial acetic acid or pyridine, preferably in a mixture of such solvents, where it is advantageous to operate at temperatures from -IO to +60.degree. C., preferably from 5.degree. C. to 25.degree. Suitable catalysts are those customary for similar purposes, for example copper, copper bronze or cuprous chloride or cupric chloride, which catalysts can be used in combination with acetone. The use of cuprous chloride is preferred, which is generated in situ by slowly reacting a mixture of copper or copper bronze with cupric chloride. The process can advantageously be carried out in the presence of an alkali salt of a weak acid which buffers the reaction mixture in the weakly acidic range. Suitable salts of this type are, for example, sodium acetate and monosodium phosphate or monosodium citrate or mixtures of the latter with the corresponding disodium salts. The reaction takes place under

409812/1221

- ■ T - Case 150-3414

material development, often with simultaneous splitting off of the remainder Z “. As the reaction proceeds, the evolution of nitrogen decreases, and the reaction product usually crystallizes off and can be worked up in this form, if desired after removal of the acetone by distillation. If necessary, the remainder of Z ₉ in the end product can be split off in the usual way. It is advantageous to use equimolecular amounts of the reactants. If the radical Z _{2 is} a carboxyl group, it is preferably the free carboxyl group or an alkali salt thereof, e.g. the potassium salt

The compounds of the formula (I) can be isolated and purified by known methods, e.g. by suction, optionally after previous precipitation, by evaporation of the solvent with subsequent filtration of the residue.

The compounds of the formulas (II), (III) and (IV) which are used as starting materials in the abovementioned process a) are either known compounds or those which can be prepared from available starting materials by known processes. Suitable functional derivatives of the aldehyde groups which may be present in the compounds are, for example, oximes, hydrazones, azines or, preferably, aniles. The R _fi radical which may be present is preferably a substituted phenyl radical. If the radical Rq is present and denotes a cycloalkyl radical, it is preferably a cyclohexyl radical. A ₁ ^ is, for example, Cl, Br, I ^w , CH ₃ OSO ₃ ^w or CH ₃ SO ₃ ^w . If Ζ _χ denotes a carboxyl group, this is preferably the free carboxyl group or an alkali salt, for example the potassium salt thereof.

409812/1221

Case 150-3414

The compounds of formula (XI) which are used as starting materials in process b) can e.g. be produced according to processes which are characterized in that d) a compound of the formula

, —CH = CH '

_Z.

² !. (XIV)

wherein R ₁ , R ", R_, R., R _e , R_, η and Z, the above

X Δ 3 4 DD 1

have given meaning, produced by a compound of the formula

(XV)

where R_, R _ß and η have the meaning given above and Q is the radical -CHO or a functional derivative thereof and U is a radical which is converted into a radical of the formula -CH ₃ -Z. can be converted with a compound of the formula

409812/1221

Case 150-3414

(XVI)

converts, in which R ,, R ₂ / R ^ / R ₄ and Z, have the meaning given above, where, if the radical Z in the end product is not a hydrogen atom, this is converted into such and in the end product the radical ü into the radical - CH-Z transferred, or that one

e) a compound of the formula

^R 3

/ "^ i-CH = CH-N

(XVII)

wherein R-, R_, R, R, R, R, η and Q have the meaning given above, by preparing a Compound of formula

(XVIII)

where R

^, Rg, Z .. and η have the meaning given above and V signifies a residue which is converted into a residue Q

409812/1221

- 10 - Cci & e 150-3414

can be converted with a compound of the formula

in which R ₁ , R ₂ , R ₃ , R ₄ and Q have the meaning given above, and radicals Z .. which are not hydrogen atoms present in the end product are converted into such, and radicals V present in the end product are converted into Q radicals .

The first steps in processes d) and e) can be carried out in a manner similar to that above described method a).

The meaning of the radical U in the compounds of the formula (XV) is generally known. For example, if in the compound of the formula (XIV) Z denotes a radical of the formulas (VI) or (VII), U can preferably represent the radical -CH ₂ Br, which is subsequently converted into the by reaction with a trialkyl or triaryl phosphite desired radical -CH ₂ -Z ₁ can be converted.

Suitable meanings of the radical V in compounds of the formula (XVIII) and its reactions are also known in principle.

The starting materials used in the above methods b), c), d) and e) "are known or can be prepared from accessible starting materials by methods known per se.

409812/1221

- 11 - Case 150-3414

The alkyl or alkoxy radicals in the compounds of the formula (I) preferably contain 1 to 6 carbon atoms. Examples include methyl, ethyl, n-propyl, Isopropyl, η-butyl, isobutyl, tert-butyl, n-amyl, tert-amyl, Isoamyl, sec.Amy1, n-hexyl, methoxy, ethoxy or n-butoxy; preferred alkyl and alkoxy groups are the methyl and methoxy groups. The aryl and aryloxy radicals are preferably mononuclear and unsubstituted and the preferred halogens are bromine or chlorine.

Representative compounds of the formula (I) are above all those of the formula

CH-CH

(XX)

in which the radicals R,., R, ^ and R, ~ can be identical or different and are hydrogen, phenyl, phenoxy, -C, g-alkyl, C _n --alkoxy, chlorine, bromine, a cyano group, a group -COOR -, -CON (R ₁ -J ₂ , -SO ₃ R ₁₈ or -SO ₂ N (R ₁₇ ) "mean, in which substituents the radicals R ₁ _ which can be the same or different , hydrogen or C, _fi - Alkyl and R ^ ₈ a C _1- ^ -alkyl or a sulfonic acid radical or the group -SO ₃ ö _M (±> mean, in which M © has the meaning given above, R ₁₄ hydrogen, chlorine or bromine, the H ₂ NOC group, C ^ g-alkyl, represent a cyano group ^{or R} X7 ^00C ~ ^Gru PP ^e, wherein R ₁₇ has the abovementioned meaning, R ₁₅ and R _16, which may be the same or different, are hydrogen, C ₁ - alkyl, C ₁ , -

J.- b 1-6

Alkoxy, chlorine, bromine, the cyano group, the R ₁₇ OOC-,

409812/1221

-] 2 - Case 15G-3414

: -, ^R io ° 3 ^S ~ or (R ₁₇ ) ₂ NO ₂ S group, in which groups the R ₁₇ and R _ radicals have the meaning given above, also a sulfonic acid group or the group -SO. ^ M ^, where M ^ has the meaning given above and η stands for the numbers 1, 2, 3 or 4, the phenyl radicals A _{bearing a sulfonic acid group or the M ^ O 3} S group as substituents.

M can be a monovalent cation or an equivalent of a polyvalent cation, in general such Cations come into consideration, which are customary for salt formation in anionic optical brighteners. M ^ means preferably an alkali metal cation, especially the sodium cation. But it can also do that, for example cation

(+) - x
HN s ~~ ^R mean in which the radicals R _x , R

R.
Z

and R, independently of one another, denote hydrogen or a C _1-6 "", in particular C. .. -alkyl which, if they contain two or more carbon atoms, can carry one or optionally two hydroxyl groups (for example ß-hydroxyethyl, ß- or ii-hydroxypropyl or ß, & -dihydroxypropyl)

The alkyl or alkoxy radicals in the compounds of the formula (XX) preferably contain 1 to 4 carbon atoms. Examples of the radicals Rj, R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and ^R 16 ' ^{when they represent the} R ₁₇ OOC group include: the free carboxyl group, the methoxy, ethoxy or n-butoxycarbonyl radical . As examples of the radicals R ₁₁ / R ₁ ^R 13 ' ^R 15 ^{and R} 16' ^{If you} mean ( ^R ₁₇ ) ₂ ^NOC ""' ^R 18 ° 3 ^S ~ ^and * ^R 17 *, the following are mentioned: the free aminocarbonyl group, the mono- and dimethyl, ethyl and -n-butylaminocarbonyl group, the methyl, ethyl and n-butylsulfonyl ester group, the free sulfamide group and the mono- and

409812/12 21

150-3414

Dimethyl -, - ethyl and -n-butylarainosulfonylgruppej η stands preferably for the numbers 1, 2 or 3 / in particular for 1 or 2.

The preferred compounds of the formulas (I) and (XX) are those in which the radicals R-, and R ,, with one another, the radicals R ₂ and R, "with one another, the radicals R ₃ and R ₁₃ and the radicals R. and R ,. are equal to each other. .

Examples of preferred compounds of the formula (I) are those of the following formula

CIl = CH

L- 26 ^y

(XXI)

mentioned, in which the radicals R ₀₁ and R _00, which can be the same or different, mean a sulfonic acid group, the M ^ OS group, chlorine, hydrogen, an alkyl or alkoxy radical containing 1 to 4 carbon atoms, one of the radicals mentioned being a Sulfonic acid group or the M ^ OS ^ group,
^R 24 ^hydrogen, chlorine or C, alkyl, R ₂ c and R26 ' ^we ^ ^cne radicals can be identical or different from each other hydrogen, C,. -Alkoxy, the cyano group, a sulfonic acid group or the M Md S ^ - Group and m are the numbers 1, 2 or 3.

Further preferred compounds of the formula (I) are those of the formula

409812/1221

Casa IbO-3414

(XXII)

to mention, in which one of the radicals R_, and R _{00 is} a sulfonic acid group or the M O3S ^ group and the other is hydrogen, chlorine, an alkyl or alkoxy radical with 1 to 4 carbon atoms,
R _{34 is} hydrogen, chlorine or methyl, R 1 and R 1, which radicals can be identical or different from one another, hydrogen, a sulfonic acid group or the M ^ OS group and ρ 1 or 2.

In the compounds of the formula (XXII), one of the radicals R ₀₁ and R ₀₀ is preferably a sulfonic acid group or the M ^ O_S ^ group and the other is chlorine or hydrogen. R. preferably denotes hydrogen or methyl. R _x . and R _{ofi are} both preferably hydrogen. In most of the preferred compounds of the formula (XXII), ρ is 2.

The compounds of the formula (I) are outstandingly suitable for use as optical brighteners, which are particularly suitable for lightening polyamide (especially wool, or nylon) or cellulose (especially cotton) are. They are used in the usual way, e.g. from aqueous solutions. The resulting lightening are characterized by a remarkable lightfastness. In addition, these compounds have a high Substantivity on. They are particularly suitable for

409812/1221

-Ib- Cese 350-3414

Lightening of wool and nylon from long liquor and can also be used together with bleaching agents, e.g. sodium chlorite come to use. Generally favorable concentrations of the brighteners for use are e.g. 0/001 to 1.0%, preferably 0.05-0.5% based on the Substrate, the liquor ratio preferably being 1:20 - 1:40 in the case of a long liquor.

The invention is illustrated by the following Examples 1-15 which illustrate the preparation of the compounds relate, while Examples A to D relate to the treatment of textile materials, with the compounds

of Examples 1, 2 and 7 and analogously with the compounds of Examples 3 to 6 and 8 to 15 carried out can be.

409812/1221

- 16 - Case 3 50-3414

example 1

The monosulfonic acid of 2-phenyl-vic-triazolyl-4-aldehyde is obtained as follows by sulfonating the 2-phenyl-vic-triazolyl-4-aldehyde manufactured:

2-Phenyl-vic-triazolyl-4-aldehyde is added to 20% oleum (40 g) with stirring in the course of 45 minutes at 20 ° -4O ° C (8.65 g) was added and the temperature of the mixture was increased to 70 ° and held at 60-70 ° C for 15 minutes. The resulting red-brown solution is then cooled to 10 ° C and poured onto ice (60g). Sodium chloride (6 g) is then added and the whole is stirred for 90 minutes at 20 ° C. The resulting white product is filtered off with a 25% strength (weight / volume) sodium chloride solution (25 ml) and dried in a drying cabinet at 70 ° C., 17 g of a white product being obtained, which contains the monosulfonic acid of 2-phenyl-vic-triazolyl-4-aldehyde and sodium chloride.

A 250 ml flask is charged with dimethylformamide (50 ml) and nitrogen is slowly blown over the surface of the liquid directed. Powdered potassium hydroxide (12 g) is then added to the liquid and the whole is added Stirred at 25 ° C for 15 minutes. A homogeneous mixture of 1: 4-bis (diethoxyphosphonomethyl) -benzene (7.6g) and the monosulfonic acid of 2-phenyl-vic-triazolyl-4-aldehyde (10.7 g) added in portions within 30 minutes, the temperature rises to 30 C. The mixture is then warmed to 40 C and the reaction temperature kept at 40-45 C for 3 hours. During this period the Mixture is very thick, so an additional amount of dimethylsormamide (70 ml) has to be added to prevent the To be able to stir the mixture further. The latter is finally diluted with water (500 ml) and the whole thing to 90 ° C heated. Sodium chloride (100 g) is then added and the pale yellow product which has precipitated is then filtered off at 10 ° C away. The yellow-colored filter cake is then treated with a 10% (weight / volume) sodium chloride solution (50 ml).

409812/1221

- 17 - Case 15o — 1 · < ^ίι 1 ^

wash and dry at 70 ° C, leaving 12.5 g of the sodium chloride containing crude product are obtained. This (12.5 g) is made from a mixture of 2-ethoxy-ethanol (200 ml), water (150 ml) and 4 N sodium hydroxide (5 ml) recrystallized to give 4.2 g of a compound of the formula

NaO ₃ S ^S0 3 ^Na

can be obtained.

Example 2

A 250 ml flask is charged with dimethylformamide (50 ml) and nitrogen is slowly passed over the surface of the liquid. Powdered potassium hydroxide (12.65g) is then added to the liquid and the whole is stirred at 25 ° C. for 15 minutes. A homogeneous mixture of 4,4'-bis (diethoxyphosphonomethyl) diphenyl (11.35 g) and the monosulfonic acid of 2-phenyl-vic-triazolyl-4-aldehyde (12.65 g) is then added in portions within 45 minutes. The mixture is then warmed to 40.degree. C. and the reaction temperature is maintained at 40.degree.-45.degree. C. for 3 hours, then diluted with water (350 ml) and warmed to 70.degree. Sodium chloride (150 g) is then added, the mixture is cooled to 20 ° C., and the pale yellow product which has precipitated is filtered off and washed with water (50 ml). The result is a very wet cake, which was stirred in water (500 ml) for 30 minutes, then filtered, washed with water (200 ml) and dried at 70 ⁰ C. 9.4 g of a light yellow product are obtained, which is recrystallized from pyridine. The result is the pyridine salt, which is treated with sodium hydroxide

409812/1221

- 18 - Case 150-3414

is converted into the sodium salt, which has the formula

SO ^ Well

r \ t ν

/ ^N V_ CH = CH

comes to.

Example 3

i? onosulfonic acid

There are 77.8 parts of 2-phenyl-5-methyl-vic-triazolyl-4-carboxylic acid anilide mixed with 100 parts of benzene. 60 parts are then added to the mixture in portions at 50.degree Phosphorus pentachloride is added, the mixture is kept at 75 ° C. for 40 minutes and finally the benzene and distilled the resulting phosphorus oxychloride is removed at 95.degree. A yellow crystalline residue (imide chloride) remains is stirred into 50 parts of diethyl ether, a homogeneous broth being formed.

A solution is added to this broth, which is obtained by passing dry hydrogen chloride into a mixture for 3 hours from 450 parts of diethyl ether and 100 parts of tin (II) chloride and leaves the whole thing overnight. To the 200 parts of ice and 200 parts of water are then added to the reaction mixture, and the diethyl ether is then distilled off. Steam distillation of the residue gives the aldehyde of the formula

CH ₃ OHC

409812/1221

in the form of white crystals with a melting point of 99-100 ° C. 17.3 parts of the above-described 2-phenyl-5-methyl-vic-triazolyl-4-aldehyde are added to 80 parts of 25% strength oleum at 30 ° -40 ° C. over the course of 30 minutes. The mixture is then heated to 60-70 ° C., kept at this temperature for 15 minutes, then cooled to 10 ° C. and poured onto 90 parts of ice with stirring. After adding 15 g of sodium chloride, the product is isolated by filtration after stirring for one hour at room temperature. It is washed with a little 25% strength aqueous sodium chloride solution and dried at 50-70 ° C. in vacuo. That received
from the aldehyde of the formula

70 ° C dried. The white product obtained exists

SO ₃ Na

OHC

Level_B

In Example 1, the 10.7 parts of the monosulfonic acid are replaced of 2-phenyl-vic-triazolyl-4-aldehyde by 11.3 parts of the monosulfonic acid of 2-phenyl-5-methyl-vic-triazolyl-4-aldehyde, so obtained after recrystallization from 10% aqueous acetic acid a light yellow compound that of the formula

SO Na SO ^ Na

³ < ^NCH ^

CH = CH

and in aqueous ethanol there is an absorption maximum (\ max) at 368 mm on v / e.

409812/1221

Case 150-3414

Example 4

If in Example 3, stage B, the 11.35 parts of 1,4-bis (diethoxyphosphonomethyl) benzene are replaced by 14 parts of 4,4'-bis- (diethoxyphosphonomethyl) -diphenyl, thus a light yellow compound is obtained, that of the formula

SO well

N.

CH = CH

and its maximum absorption (Xmax) at 360 nm lies. The procedure is as indicated in Example 1, but using other, suitable starting materials in approximately equivalent amounts, compounds of the formula are obtained

in which R-, R ₄ , R ₅ , R _g and η have the meanings given in the table below, and which compounds result in the lightening shades listed in the last column of this table on nylon 6,6.

409.812 / 1221

Tabel

example SO well R _r and R_
5 0 ^R 4 η Nuance of Aufhe11
effect on
Nylon 6.6 5 SO, well OCH ₃ H 1 greenish 6th SO .Na H II 3 slightly green 7th SO ₃ Na R ₅ = H; Rg = SO Na H 1 neutral 8th SO ₃ Na R _C = H; R ^ = CN H 1 neutral 9 m-SO Ma
p-Cl ^J H ^CH 3 3 slightly blue IO m-SO Well
pC 1 ^y H CU ₃ 1 slightly blue 11 m-SO Well
P-Cl H II 1 neutral 12th p-CIl
m-SO Well II II 2 neutral 13th P-CH ^
1-SO ₃ Na II ^CII 3 2 neutral 14th v-SO Well
p-Cl II II 2 neutral 15th II CH ₃ 2 greenish

409812/1221

Usage examples Example A.

5 g of a piece pre-bleached with hydrogen peroxide Wool is wetted in a dilute, aqueous solution of a surfactant, spun off and then added Treated room temperature in 200 ml of an aqueous solution containing 5 mg of a compound obtained according to Example 1 and contains 1 gram of puttered sodium hydrosulfite. The compound obtained according to example 1 (brightener) is added as a 0.1% stock solution in 50% aqueous Cellosolve. The bath containing the wool is heated to 70 ° C within 15 minutes, kept at this temperature for 30 minutes and then with 1 ml of 10%, aqueous acetic acid added. The temperature of the bath is then kept at 70 C, after which the wool taken out of the bath, rinsed thoroughly in cold water and dried at 8O C. The wool so treated is much whiter than those treated in the absence of the mentioned brightener.

Example B.

5 g of a piece of nylon 6.6 (Banlon) are added at room temperature to 2OO ml of an aqueous solution containing 25 mg of a compound obtained according to Example 2 and 150 mg of acetic acid. This compound is added as a 0.1% stock solution in 50% aqueous dimethylformamide. The temperature of the solution (treatment liquor) is increased to 90 ° C. within 30 minutes and kept at 90 ° -95 ° C. for a further 30 minutes, during which time the nylon piece is moved mechanically. The latter is then rinsed thoroughly in cold water, spun off and dried in a drying cabinet at 80 ° C. This treatment turns it nice and white.

409812/1221

£ O4 3IÜ3 -23- Case lbO-3414

Example C

5 g of a piece of cotton are added at room temperature to 2OO ml of an aqueous solution containing 10 mg of a compound obtained according to Example 2 and 500 mg of sodium sulfate hydrate (the brightener is in the form of a 1% stock solution in 50% aqueous Dimethylformamide added), the cotton is agitated in this solution (treatment liquor), the temperature of the solution being increased to 70 ° C. within 15 minutes and held at 70 ° C. for a further 30 minutes. The cotton is then thoroughly rinsed in cold water, spun off and dried at 80 ^° C. in a drying cabinet. It is then characterized by a brilliant white compared to untreated cotton.

Example D

5 g of a piece of white nylon 6.6 (Banlon) are treated in 200 ml of a solution which contains 10 mg of the compound prepared according to Example 7 and 400 mg of sodium chlorite, which is buffered to pH 3.5. The sodium chlorite is buffered with a buffer consisting of 140 mg sodium perborate, 120 mg sodium nitrate, 120 mg trisodium polyphosphate, 20 mg of an adduct of ethylene oxide with di-sec-butylphenol and 2.5 ml of 10% formic acid. The nylon piece is added to the solution at 40 ° C., whereupon it is heated to 90-95 ° C. within 30 minutes and held at this temperature for a further 30 minutes % aqueous sodium metabisulphite solution and then again thoroughly rinsed in cold demineralized water and finally dried at 80 ° C. In contrast to a piece of nylon which was treated in the absence of the compound obtained according to Example 7, that treated as described above a brilliant, neutral Weir-auf.4Q981 2/1221

Claims (9)

Claims R ₃ , R ₂ and R_ can be identical or different and each hydrogen, optionally substituted aryl, aryloxy, alkyl or alkyloxy, halogen, cyano, carboxyl, an optionally substituted carboxylic acid or sulfonic acid amide or ester radical, a sulfonic acid group or the group -S0_ ^ M ^, in which M ^ is an equivalent of a cation; . Hydrogen, halogen, alkyl, cyano, the H ₂ NCO group, the R-OOC group, in which R _{7 is} hydrogen or an alkyl radical, and R _{6 can be} identical or different and each is hydrogen, optionally substituted alkyl or alkoxy, halogen, cyano, carboxyl, an optionally substituted carboxylic acid or sulfonic acid amide or ester radical, a sulfonic acid group mean and η for the or the group -SO- Numbers 1 to 4, each of the phenyl radicals A having at least one sulfonic acid radical or the M Group carries. ^Q 3 ^S 2. Compounds according to claim 1, of the formula 409812/12 2-1 - 25 - Case 150-343.4 ^14th in which the radicals R -, -, / R ₁₂ and R _{13 can be} identical or different and are hydrogen, phenyl, phenoxy, C 1, -C -alkyl, C, g-alkoxy, chlorine, bromine, a cyano group, a group -COOR ₁₇ , -CON (R ₁₇ J ₂ , -SO ₃ R ₁₈ or -SO ₂ N (R ₁₇ J ₂ mean in which substituents the radicals R _17, which can be identical or different, are hydrogen or C 1, -alkyl and R _1o a C ₁ , -alkyl or a sulfonic acid radical or the group -SO ₃ ^w M ^w , in v / which M ^ has the meaning given above, R,. hydrogen, chlorine or bromine, the H ₂ N0C group, C, _fi represents alkyl, a cyano group or the R, ₇ 00C group, wherein R ₁₇ has the abovementioned meaning, R-yy- and R ₁₆ / which radicals may be the same or different, are hydrogen, C, alkyl, C , _ _ß -Alkoxy, chlorine, bromine, the cyano group, the R 00C -, (R ₁₇ ) ₂ NOC, R ₁ qO_S or (R, -) _? NO _? S group mean in which groups the R ₁₇ - and R, "- radicals have the meaning given above, also a sulfonic acid group or the group - SO M, where M ^ has the meaning given above and η stands for the numbers 1, 2, 3 or 4, the phenyl radicals A _{bearing a sulfonic acid group or the M ^ 0 3} S group as substituents. 3. Compounds according to claim 1, of the formula 409812/1221 Case 15O-3414 22 - 25th (XXI) wherein the radicals R ₀₁ and R _00, which can be the same or different, mean a sulfonic acid group, the M ^ OS ^ group, chlorine, hydrogen, an alkyl or alkoxy radical containing 1 to 4 carbon atoms, one of the radicals mentioned being a Sulfonic acid group or the M ^ OS group, R ₀ . Hydrogen, chlorine or C. _1-alkyl-4 ZQ χ R _oc and R ₀ , -, which radicals are identical or different from- Zo Zo each other can be hydrogen, C ..- alkoxy, the cyano * group, a sulfonic acid group or the M ^ O_S ^ group and m are the numbers 1, 2 and 3. 4. Compounds according to claim 1, of the formula CH = CH (XXII) to mention in which one of the radicals R ₀ , and R ₀₀ a / qs / ^ yJ 1 32 Sulfonic acid group or the M ^ OS ^ group and the other Hydrogen, chlorine, an alkyl or alkoxy radical with 1 to 4 carbon atoms, 409812/1221 Cas ^ 150-343 R_. Hydrogen, chlorine or methyl _{,, c} and R - ,, -, which radicals can be identical or different from one another, hydrogen, a sulfonic acid group or the M ^ 0_S ^ group and ρ 1 or 2. 5. Process for the preparation of the compounds of the formula (I) according to Claim 1, characterized in that a) a compound of the formula R .. (ID in which Rj., R, and η have the meaning given above have with a compound of the formula (III) and a compound of the formula (IV) 409812/1221 in which R ₁ , R ₂ , R ₃ and R _{4 have} the meaning given above, one of the radicals X and Y or X ₃ and Y _{3 is} the OHC group or a functional derivative thereof and the other is the radical of the formula - CH ₂ Z ₁ (V) mean, wherein Z _{1 is} hydrogen, a carboxyl group, a substituted or unsubstituted carboxylic acid ester or amide group, or a group of the formula -P = 0 < ^VI > -ρ = π ^(VII) -, / r, < ^VIII > ^ül! 8 O '< ₉ \ / S ' (IX) - ° ■ in which R "is a substituted or unsubstituted aryl radical, R _{g is} a substituted or unsubstituted alkyl radical having 1 to 6 carbon atoms, or a substituted or unsubstituted cycloalkyl radical and A ₁ ^ is a monovalent anion, where if the radical Z in the end product -. , is different from hydrogen, replacing it with hydrogen, or that one
b) a compound of the formula 409812/1221 Case 130-3414 .N V-CH = CIi- -X. (XI) in which R ,, R ₂ , R_, R ₄ , R ₅ , R, and η have the meaning given above, with a compound of Formula (III) wherein X, and Y _{1 have} the meaning given above, and in the end product each Z ,, which does not Is hydrogen atom, replaced by one, or that one c) a diazo derivative of the compound of the formula H = CH (XII) in which R ₁ , R ~, R-, R., R ₁ -, R-. and η the above X Z 3 4 DD have given meaning, in the presence of a catalyst with a compound of the formula CH = CH-Z (XIII) N '^ R- 409812/1221 in which R ,, R ,,, R and R have the meaning given above have and Z is a carboxyl group or a substituted or unsubstituted carboxamide or ester group means, converts and, if necessary, splits off the radical Z “in the end product. 6. Use of the compounds of the formula (I) according to Claim 1 as an optical brightener. 7. Use according to claim 6 for optical brightening of polyamide or cellulose. 8. Use according to claim 7 for the optical brightening of synthetic polyamide. 9. The materials brightened with the brighteners of the formula (I) according to claim 1. 409812/1221