DE2525679A1 - Sulphonated distyryl benzenes prodn - by condensing 4-methylstilbenes and sulphoanils in presence of strong base - Google Patents

Abstract

Preparing 1,4-distyrylbenzenes (I) comprises reacting a 4-methyl stilbene (II) with anil (III) in presence of a strongly basic alkali cpd. in a strongly polar neutral-to-basic org. solvent. (rings, A, B, and C are opt. substd. by nonchromophoric gps. and 1 of A and C has a SO3M substit M=H or salt-forming cation; ring A can also represent naphthalene; Ar=opt. substd. aryl). Yields of (I) are food. (I) are optical brighteners for high mol. wt. org. materials e.g. for incorporation into detergent compsns or spinning melts.

Description

Process for the preparation of distyrylbenzenes containing sulfo groups.

The present invention relates to a new method of distribution sulfo-containing distyrylbenzenes.

There are already several methods of making distyrylbenzenes known. Such a versatile process is known under the name "anil synthesis" became known [cf. e.g. Helvetica Chimica Acta 50 (1967) 906 ff and 52 (1969) 2521 ff]. However, the condition for the course of the anil synthesis has hitherto been Absence of substituents capable of forming salts, such as sulfonic acid groups, indicated in the reactants [cf. llelvetica Chimica Acta 50 (1967) 912 and 52 (1969) 2524].

Surprisingly, it has now been found that by means of the anil synthesis Distyrylbenzenes containing sulfo groups can also be prepared in good yields. This process enables a particularly inexpensive production of technically important ones Links.

The present invention accordingly relates to a process for the preparation of 1,4-distyrylbenzenes of the formula in which the benzene nuclei A, B and C can be non-chromophoric substituted, of the benzene rings A and C at least one contains an SO3M group, in which M is hydrogen or a salt-forming cation and the benzene radical A can also have the addition of a naphthalene radical, which is characterized in that there is a 4-methyl-stilbene compound of the formula with an anil of the formula where Ar is an optionally substituted aromatic radical, is reacted in the presence of a strongly basic alkali compound in a preferably polar, neutral to basic organic solvent.

Non-chromophoric substituents, which are preferably located on a sulfo group-free terminal phenyl radical are, for example, alkyl with 1 to 4 carbon atoms, Alkoxyalkyl with 2 to 5 carbon atoms, phenyl, fluorine, chlorine, alkoxy with 1 to 8 carbon atoms, benzyloxy, phenoxy, alkyl mercapto with 1 to 4 carbon atoms, Alkenyloxy with 3 to 4 carbon atoms, phenylmercapto, phenylsulfonyl, cyano, Carboxy, carbamoyl, sulfo or sulfamoyl.

Preferred carbamoyl and sulfamoyl radicals can be represented by the formulas are shown in which R and R1 are independently hydrogen, alkyl having 1 to 4 carbon atoms or together with the nitrogen, the addition to a 5- to 7-membered non-aromatic ring, for example morpholino or piperidino.

"Carboxy" and "sulfo" include the radicals -COOM and -SO3M, respectively to understand where M is hydrogen or a salt-forming cation. as Salt-forming cations M generally come from those of alkaline earth metals, e.g.

Calcium, barium or magnesium and especially alkali metals, e.g. sodium or potassium, but also optionally by alkyl or hydroxyalkyl ammonium substituted with 1 to 4 carbon atoms or cyclic amine salt ions Amines such as pyridine, morpholine or piperidine are suitable. Are preferred in the Significance of M besides hydrogen, especially the potassium and sodium cations.

The aromatic radical Ar is generally made up of one or more six-membered carbocycia, preferably it stands for an unsubstituted one or substituted naphthalene or phenyl radical, in particular for an unsubstituted one or phenyl radical substituted by chlorine.

In the context of the present study, the preparation of compounds of the formula is of particular interest where M is hydrogen or a salt-forming cation, R1 is hydrogen, alkyl with 2 to 4 carbon atoms, phenyl, chlorine, alkoxy with 1 to 4 carbon atoms, alkenyloxy with 3 to 4 carbon atoms, benzyloxy, alkoxyalkyl with 2 to 5 carbon atoms, phenoxy, alkylmercapto with 1 up to 4 carbon atoms, phenylmercapto, alkylsulfonyl with 1 to 8 carbon atoms, phenylsulfonyl, cyano, carboxy or sulfo, R2 hydrogen, alkyl with 2 to 4 carbon atoms, chlorine or alkoxy with 1 to 4 carbon atoms, or R1 and R2 in ortho position to one another a fused benzene radical, a methylenedioxy, a trimethylene or a tetramethylene group, R3 is hydrogen or alkoxy with 1 to 4 carbon atoms, R4 is hydrogen, chlorine or alkoxy with 1 to 4 carbon atoms (preferably methoxy), R5 is hydrogen, chlorine, alkyl with 1 to 4 carbon atoms, whereby the methyl group is preferably in the 3-position or alkoxy with 1 to 4 carbon atoms (preferably methoxy) , R6 is hydrogen or alkoxy having 1 to 4 carbon atoms (preferably methoxy) or R5 and R6 together are a trimethylene or tetramethylene group in the 3,4-position, which is characterized; that you can get a 4-methyl-stilbene compound of the formula with an anil of the formula in which Arl is an unsubstituted or substituted naphthyl or, in particular, phenyl radical, and the preparation of compounds of the formula wherein M1 is a hydrogen, alkali metal, alkaline earth or amine salt ion, R'1 is hydrogen, chlorine, alkyl with 2 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkyl mercapto with 1 to 4 carbon atoms, cyano or together with R'2 in the 3,4-position a trimethylene or tetramethylene group, R'2 is hydrogen, chlorine, alkoxy with 1 to 4 carbon atoms or together with R'1 in the 3,4-position a trimethylene or tetramethylene group, R'4 is hydrogen or alkoxy 1 to 4 carbon atoms, R'5 denotes hydrogen, chlorine, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms and R'6 denotes hydrogen or alkoxy with 1 to 4 carbon atoms which is characterized in that a 4-methyl- stilbene compound of the formula with an anil of the formula in which M1, R1 ', R2', R4 ', R5' and R6 'are as defined above and Arl is an unsubstituted or substituted phenyl or naphthyl radical.

The production of 1,4-distyrylbenzenes of the formula should be emphasized here wherein R "1 is hydrogen, chlorine, alkyl illite 2 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, R112 is hydrogen, chlorine or alkoxy with 1 to 4 carbon atoms, R" material, chlorine or alkoxy with 1 to 4 carbon atoms, preferably methoxy , M1 is a hydrogen, alkali metal, alkaline earth metal, ammonium or amine salt ion, which is characterized in that there is a 4-methyl-stilbene compound of the formula with an anil of the formula in which X is hydrogen or chlorine.

The preparation of 1,4-distyrylbenzenes of the formula is of particular practical interest wherein R "1 is hydrogen, alkyl having 2 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or chlorine and M1 is a hydrogen, alkali metal, alkaline earth metal, ammonium or amine salt ion, which is characterized in that the compound of the formula with an anil of the formula in which X is hydrogen or chlorine, (13) converts 1,4-distyrylbenzene of the formulas (1), (4), (7), (10) and are also obtained if, in a modification of the process according to the invention, 4-methyl-stilbene -compounds of the formulas respectively.

respectively.

or or

with the corresponding anil compounds of the formulas respectively.

respectively.

respectively.

respectively.

wherein R1, R2, R3, R4, R5, R6, M, R1 ', R2', M1, R1 ", R2" and X are the Have the meaning given above, in the presence of a strongly basic alkali compound implemented in a strongly polar, neutral to basic organic solvent will.

The starting materials for the preparation of the compounds of the formulas (1), (4), (7), (10) and (13), i.e. the compounds of the formulas (2), (3), (5), (6), (8), (9), (11), (12), (14), (15) and (16) to (20) are known or are analogous to methods known per se.

Compounds of the formula (4) in which R1 is alkylsulfonyl or phenylsulfonyl means are advantageously also by oxidation of compounds of the formula (4), wherein Rl is alkyl mercapto or phenyl mercapto.

The oxidation takes place e.g. by means of hydrogen peroxide in aqueous Glacial acetic acid in the presence of molybdenum or vanadium salts at 20 to 120 "C.

The reaction with the anilene can preferably be carried out in the presence of a suitable one strongly polar, neutral to alkaline organic solvents be, which is free of atoms, especially hydrogen atoms, by alkali metals are replaceable. In practice, dialkylamides are primarily used as such solvents formic acid and phosphoric acid and tetraalkylureas are considered, wherein "Alkyl" means an alkyl group containing lower 1 to 4 carbon atoms, in particular means a methyl group. The following are important representatives of such solvents: Diethylformamide, hexamethyl-phosphoric acid triamide, tetramethylurea and in particular Dimethylformamide. Solvent mixtures can also be used.

As mentioned, a strongly basic alkali compound is also required for the reaction necessary. Depending on the type of solvent used and the reactivity Of the anil used, certain sodium alcoholates are suitable for this purpose how Sodium t-butylate and especially potassium compounds of the composition (26) KOC lH2m 1, where m is an integer from 1 to 6, preferably 2 to 6, such as e.g. potassium hydroxide or especially potassium tertiary butoxide. In the case of such alkali alcoholates is to work here in a practically anhydrous medium, while with potassium hydroxide a low water content up to about 15% (e.g.

Water of crystallization) is still allowed. Potassium hydroxide or sodium t-butoxide is used, for example, advantageously in combination with hexamethyl-phosphoric acid triamide at 110-1300C.

The compounds containing methyl groups are equivalent to the anilene Quantities implemented. However, an excess of anil up to approx. 25% is possible generally beneficial. At least one of the alkali compounds is advantageously used the equivalent amount, i.e. at least 1 mole, of a compound having, for example, a KO group on a mole of anil. When using potassium hydroxide, the 4- applied up to 8 times the amount. Particularly good yields are obtained when using K-tertiary butoxide in 1 to 6 times, preferably 2 to 4 times, equivalents Lot.

The inventive reaction can generally at temperatures in Range carried out between about 10 and 1500C will. With especially Reactive anilene, the reaction succeeds at room temperature, in which No external heat supply is necessary. This is especially beneficial when the reactants have ring compounds or substituents by Alkali can easily be opened or split off or otherwise chemically changed. This applies, for example, to alloys with easily removable chlorine substituents. The cheapest however, it is better to work at a higher temperature, especially when using Sodium t-butoxide or potassium hydroxide.

For example, the reaction mixture is slowly increased to 30 to 100 ° C heated and then for some time, e.g. 1/2 to 2 hours and at this temperature held. The preparation of the anil leaves its reaction with the tolyl compound can also be carried out using the egg-pot method. For example, clay aldehyde is heated with excess aniline in dimethylformamide, evaporated completely in vacuo, adds the tolyl component and dimethylformamide and proceeds as usual. the end The end products can be mixed with the reaction by customary methods known per se be worked up. Isolation takes place, for example, by means of failures Water, for water-soluble products by salting out, e.g. with NaC1, KC1 or by Neutralization, if necessary by acidification with a strong mineral acid such as e.g. HC1, in this latter case optionally the free sulfonic acids can be eliminated. If desired, these can be mixed with alkali or alkaline earth metal salts, with Ammonium hydroxide or amines into the corresponding alkali metal, Alkaline earth metal, ammonium or amine salts are transferred.

The amine salts of the sulfonic acid can also be obtained, for example, by conversion an alkali salt of the sulfonic acid in the sulfochloride by means of e.g. phosphorus oxychloride, Thionyl chloride or phosphorus pentachloride and subsequent saponification in the presence of the desired amine.

The raw products are usually cleaned by boiling them out with chloroform and recrystallized serums or boiling (depending on solubility) e.g. with Water, aqueous potassium chloride solution, n-propanol-water, ethylene glycol monomethyl ether, Dimethylformamide, dimethylformamide-water, dimethyl sulfoxide or dimethyl sulfoxide-water.

According to the method described above and its modification are a considerable number better known per se, but so far only partially Detour accessible connections have become easy to establish (cf.French Patent Specification 2,049,945). Another large number of new connections were able to follow the process according to the invention are produced for the first time.

The compounds of formulas (1), (4), (7), (10) and (13) are mostly valuable optical brighteners. They can be used in a manner known per se for lightening can be used by various high molecular weight organic materials.

Example 1 To a solution of 4.85 g of 4-methylstilbene and 7.4 g of the sodium salt of p-benzaldehyde-sulfonic acid-anil in 280 ml of anhydrous dirnethylformamide carries while stirring vigorously and while passing nitrogen over it, 12.7 g of potassium t-butoxide are added a, whereby violet color occurs. The temperature is initially held by weak Cool for 1/2 hour at room temperature and then by heating for 1/2 hour at 60 ° C and one hour at 80 ° C. After cooling in an ice bath, 140 ml of distilled water are added.

Water, the precipitated product is filtered off with suction, washed twice with 20 ml of methanol each time and then with water until neutral. It is dried in vacuo at 100 ° C. and 8.0 g (80% of theory) of the compound of the formula (101) mixed with a little sodium salt are obtained as a pale yellow powder.

This is made from dimethyl sulfoxide with the help of fuller's earth recrystallized and boiled with alcohol.

Analysis: C22H17K03S (400.54) calculated: C 65.97 H 4.28 S 8.00 found: C 65.99 H 4.38 S 7.90 The sodium salt of p-benzaldehyde sulfonic acid anil is obtained as follows: 62 , 5 g of the crude sodium salt of p-sulfobenzaldehyde are briefly boiled in 500 ml of dimethylformamide and the solution is clarified by filtration at room temperature to remove insoluble salts. 28 g of aniline are added to the filtrate and the mixture is heated to boiling temperature for 10 minutes, anil already crystallizing out. 200 ml of solvent are distilled off, cooled, filtered and the residue is washed with 50 ml of dimethylformamide and twice 50 ml of methanol. 51> 3 g of colorless crystals of the formula are obtained Analysis: C13HlONNaO3S (283.28) calculated: C 55.12 H 3.56 S 11.32 found: C 55.42 H 3.65 S 11.31 The filtrate is obtained by concentrating the filtrate to about 1/3 of the original volume another 7.4 g of almost equally pure product.

Example 2 To a solution of 5.83 g of 4-methylstilbene and 9.3 g of the sodium salt of o-benzaldehyde sulfonic acid anil in 50 ml of anhydrous dimethylformamide carries 20.3 g of potassium t-butoxide are added while stirring vigorously and while passing nitrogen over it a.

The temperature is initially maintained for 1/2 hour by gentle cooling at room temperature and then by heating for 1/2 hour at 60 "C and one hour at 800C. After cooling in an ice bath, 150 ml of distilled water are added. Water, sucks the precipitated product and washed with a 1% potassium chloride solution.

It is dried in vacuo at 100 ° C. and 10.7 g (89% of theory) of the sulfonic acid of the formula are obtained mainly as a hygroscopic potassium salt with a little sodium salt in the form of a pale yellow powder. This is distilled from about 300 ml. Water recrystallizes with the aid of activated charcoal to decolorize and the addition of 0.5 g of potassium chloride after hot filtration.

If, instead of the sodium salt of o-benzaldehyde sulfonic acid anil, the sodium salt of m-benzaldehyde sulfonic acid anil is used in 80 mol of dimethylformamide and the procedure described above, the sulfonic acid of the formula is obtained after recrystallization from dimethyl sulfoxide and water and boiling with alcohol mainly as the potassium salt mixed with a little sodium salt.

The anil required for the preparation of the compound of the formula (103) is obtained as follows: 208 g of crude sodium salt of o-sulfobenzaldehyde are in 1040 ml of ethylene glycol monomethyl ether briefly boiled and the solution at room temperature Clarified by filtration to remove insoluble salts. 93.1 are added to the filtrate g freshly dist. Aniline, heated for one hour at reflux temperature and filtered again of precipitated salts. 300 ml are first distilled at atmospheric pressure and then the remaining solvent off under reduced pressure. The residue is crystallized from one liter of n-butanol, filtered off and at 1000C in a vacuum dried.

152 g of a colorless hygroscopic product of the formula are obtained (after recrystallization from n-butanol).

This anil is obtained in an even simpler way when using 1.2 1 n-butanol instead of ethylene glycol monomethyl ether, which it turns out on cooling crystallized.

The sodium salt required to prepare the compound of formula (104) m-benzaldehyde-sulfonic acid anil is obtained in an analogous manner. For isolation becomes the residue obtained after distillation of the solvent in alcohol Boiled (instead of in n-butanol) and the anil, which is insoluble in it, at room temperature filtered off, washed with alcohol and dried.

Example 3 The procedure is essentially as in Example 1 or 2 using appropriate aldehydaniles and 4-methylstilbene derivatives and 3 moles of potassium t-butoxide per mole of 4-methylstilbene derivative, and the compounds of the formula (106) listed in Table I are obtained mainly in the form of their potassium salts . The dimethylamine salts which sometimes form can be converted into their potassium salts by boiling in aqueous potassium carbonate or potassium hydroxide solution, the dimethylamine released being distilled off with water. To prepare the chlorine-containing compounds of the formulas (107), (109), (113) and (116), the reaction is carried out at room temperature, that of the formulas (120) and (121) at 60 ° C, and that of the formulas (139 ), (140) and (141) at 40 "C.

TABLE 1 Formula No. Substituents (107) 2-chloro 5-SO3H (108) 2,3-dimethoxy 5-SO3H (109) 4-chloro 3-SO3H (110) 3-methyl 5-SO3H (111) 2-methyl 5-SO3H (112) 3'-methoxy 3-SO3H (113) 3 ', 4'-dichloro 3-SO3H (114) 2 ', 3'-dimethoxy 3-SO3H (115) 3'-chloro 4-SO3H (116) 4'-CN3-SO3H (117) 4'-isopropyl 2-SO3H (118) 2 "-methoxy 2-SO3H (119) 2'-SCH3 3-SO3H (120) 3 ', 4l-dichloro 2-SO3H (121) 3 ', 4'-dichloro 4-SO3H (122) 3'-methoxy 2-SO3H (123) 2 ', 3'-dimethoxy 4-SO3H (124) 3'-methoxy 4-SO3H (125) 2'-methoxy 3-SO3H (126) 2'-methoxy 4-SO3H Formula No. Substituents (127) 3'chlor 3-SO3H (128) 3'chlor 2-SO3H (129) 2'-chloro 3-SO3H (130) 2'-chloro # 4-SO3H (131) 4'-chloro 3-SO3H (132) 4'chlor 2-SO3H (133) 4'-chloro-2-methoxy 5-SO3H (134) 4'-chloro 4-SO3H (135) 4'-isopropyl 3-SO3H (136) # 4'-Isopropyl 4-SO3H (137) 3 ', 4'-tetramethylene 2-SO3H (138) 3 ', 4'-trimethylene 2-SO3H (139) '2', 4'-dichloro 4-SO3H (140) 2 ', 4'-dichloro 3-SO3H (141) 2 ', 4'-dichloro 2-SO3H The 4-methylstilbene derivatives required for the preparation of the distyrylbenzenes are obtained by Horner-Wittig condensation according to method a) or b): a) p-methylbenzylphosphonic acid ester and benzaldehyde derivative b) benzylphosphonic acid ester and p-tolylaldehyde derivative in Presence of sodium methylate in dimethylformamide. Representatives of such 4-methylstilbenes and their method of preparation are shown in Table II.

TABLE II Method 4-methylenestilbene derivative melting point a) O CH - CH - O CH3 116 ° a) CH = CH-CH3 76 " CH3 0 a) c1-CH = CH-CH3 1210 C1 a) Q CH = CH ~ O CH3 60 ° CH 0 OCH3 3 a) CH = CH O CH3 116 ° Cl a) NC o CH = CH ~ O CH3 182 ° a) (CH3) 2CH-CH = CH-CH3 1160 Method | 4-methylenestilbene derivative melting point a) HOOC e CH = CH- O CH3 3000 (trtib) b) O CH = cH½cH3 liquid CH30 a) CHSCH - CH3 69 " SCH3 a) Cl e CH = CH- 9 CH3-2000 a) Na03SCH = CH CH3> 360 ° a) Q CH = CH- 9 CH3 800 OCH3 a) y½ cH - CH- CH3 liquid Method 4-methylenestilbene derivative melting point a) Q CH = CH 9 CH3 liquid Cl a) Cl <CH = CH- O CH3 660 Cl Anil components: The potassium salt of 2,3-dimethoxy-5-sulfobenzaldehyde-anil used as the starting material for the compound of formula (108) is obtained by boiling 2,3-dimethoxy-5-sulfobenzaldehyde (K salt) with aniline (10 % Excess) in alcohol. The dilute solution is filtered while hot, concentrated and cooled, whereupon the product crystallizes.

In an analogous manner, from 3-methyl-5-sulfobenzaldehyde (K salt) the potassium salt required as the starting material for the compound of formula (110) of 3-methyl-5-sulfobenzaldehyde anil. This is also obtained for the connection of the formula (111) required potassium salt of 2-methyl-5-sulfobenzaldehyde-anil.

In an analogous manner, from 4-chloro-3-sulfobenzaldehyde (Na salt) the sodium salt required as a starting material for the compound of the formula (109) of 4-chloro-3-sulfobenzaldehyde anil.

The sodium salt des required for the compound of the formula (107) 2-Chloro-5-sulfobenzaldehyde-anil is obtained according to the details of the potassium salt of m-Benzaldehyde sulfonic acid canil.

The sodium salt des required for the compound of the formula (133) 2-Methoxy-5-sulfobenzaldehyde-anil is obtained by boiling 15.8 g of 2-methoxybenzaldehyde sulfonic acid (Na salt) in 100 ml of aniline and 23 ml of dimethylformamide, distilling off 30 ml Solvent and cooling.

Example 4 To a fine suspension of 2.7 g of the compound of the formula and 2.37 g of benzaldehyde-p-chloranil in 100 ml of anhydrous dimethylformamide are introduced, with nitrogen being passed and vigorous stirring, 3.36 g of potassium t-butoxide. The temperature is kept at 250 for 1/2 hour, at 60 ° for 1/2 hour and at 80 ° C. for 1/2 hour. After cooling in an ice bath, 50 ml of water are added, the product which has precipitated is filtered off with suction and washed with alcohol and After boiling with water and drying, 2.65 g of a mixture of the compound of the formula (101) and its sodium salt in an approximately 1: 1 ratio are obtained.

Example 5 A solution of 0.05 g of ammonium molybdate in 30 ml of water is added to a solution of 6.7 g of the compound of the formula (119) in 90 ml of glacial acetic acid. The mixture is heated to 100 ° C. and a solution of 2.9 ml of 35% strength hydrogen peroxide in 10 ml of glacial acetic acid is added dropwise in the course of 1/2 hour. After brief stirring until the end of the reaction (peroxide detection with KJ negative), it is completely evaporated in vacuo and the residue is crystallized from about 80% aqueous alcohol. 2.7 g of the compound of the formula are obtained mainly in the form of the hygroscopic potassium salt (light yellow, shiny leaves, melting point around 210 ° C).

Example 6 A polyamide fiber fabric (Perlon-Helanca) is used in the liquor ratio Washed 1:20 for 15 minutes in a 50 "C warm liquor, the following per liter Additives contains: 0.004 to 0.016 g of the whitening agent of the formulas (103), (104), (107), (108), (109), (112), (114), (117) or (143) 0.25 g active chlorine (Javel lye) 4 g of a washing powder with the following composition: 15.00% dodecylbenzenesulfonate 10.00% sodium lauryl sulfonate 40.00% sodium tripolyphosphate 25.75% sodium sulfate anhydrous 7.00% sodium metasilicate 2.00% carboxymethyl cellulose 0.25% ethylenediaminetetraacetic acid.

The polyamide fiber fabric is only 15 minutes after the 50 ° C has been prepared warm washing bath brought into the same. After bobbin winding and drying, the Fabric has a good whitening effect.

The washing powder of the composition given above can be the brightener of the above formulas also incorporated directly.

Example 7 Bleached cotton fabric has a liquor ratio of 1:20 washed for 15 minutes in a 50 "C warm liquor, the following per liter Additives contains: 0.004 g of the whitening agent of the formulas (103), (107) or (112) 0.25 g of active chlorine (Javel lye) 4 g of a washing powder with the following composition: 15.00% dodecylbenzenesulfonate 10.00% sodium laurylsulfonate 40.00% sodium tripolyphosphate 25.75% sodium sulfate anhydrous 7.00% sodium metasilicate 2.00% carboxymethyl cellulose 0.25% ethylenediaminetetraacetic acid.

The cotton fabric is not used until 15 minutes after the 50 ° C warm wash bath introduced into the bath. After rinsing and drying it has the fabric has a good lightening effect with good chlorine fastness.

The washing powder of the composition given above can be the brightener of formulas (103), (107) or (112) also incorporated directly.

Example 8 A polyamide fiber fabric (Perlon) is used in the liquor ratio 1:40 at 600C placed in a bath that (based on the weight of the fabric) 0.05% des Brighteners of the formulas (101), (103), (104), (107), (108), (109), (110), (112), (114), (115), (117), (119) or (143) and 1 g of 80% acetic acid and 0.25 g per liter of an adduct of 30 to 35 mol of ethylene oxide with one mol of technical Contains stearyl alcohol. It is heated to boiling temperature within 30 minutes and keeps boiling for 30 minutes. After rinsing and drying, one obtains a good lightening effect.

If you use a fabric made of polyamide-6 instead of a fabric Polyamide-66 (nylon) leads to similar lightening effects.

Finally, it can also be used under high temperature conditions, e.g. during 30 minutes at 1300C.

For this type of application, an addition of 3 g / l hydrosulphite is recommended.

EXAMPLE 9 10000 g of one made from hexamethylenediamine adipate in known Polyamides produced in a manner in the form of chips are mixed with 30 g of titanium dioxide (rutile modification) and 5 g of the compound of the formulas (101), (107), (110), (119) or (143) in one Rolled container mixed for 12 hours. The schnitzels treated in this way are in one Boiler heated to 300 to 310 ° C with 0e1 or diphenyl vapor, after displacement of atmospheric oxygen and melted by steam for half an hour touched. The melt is then passed through a spinneret under a nitrogen pressure of 5 atmospheres and the cooled filament spun in this way is wound onto a spinning bobbin. The resulting threads show a good lightening effect.

Used instead of one made from hexamethylenediamine adipate Polyamides a polyamide made from ε-caprolactam, so one arrives at similar good results.

Example 10 Bleached cotton fabric is made in a liquor ratio of 1:20 washed at 95 ° C. for 30 minutes. The laundry contains the following additives per liter: 0.004 g of the whitening agent of the formulas (103), (107) or (112) 4 g of a washing powder the following composition: 40.0% soap flakes 15.0% sodium tripolyphosphate 8.0 % Sodium perborate 1.0% magnesium silicate 11.0% sodium metasilicate (9 H2O) 24.6 % Soda, calc.

0.4% ethylenediaminetetraacetic acid.

After rinsing and drying, the cotton fabric has a strong appearance Lightening effect on.

Claims (17)

Claims X Process for the preparation of 1,4-distyrylbenzenes of the formula in which the benzene nuclei A, B and C can be non-chromophoric substituted, of the benzene rings A and C at least one contains an SO3M group, in which M is hydrogen or a salt-forming cation and the benzene radical A can also have the addition of a naphthalene radical, characterized in that there is a 4-methyl-stilbene compound of the formula wherein the benzene nuclei A and B have the meaning given above, with an anil of the formula wherein Ar is an optionally substituted aromatic radical, is reacted in the presence of a strongly basic alkali compound in a strongly polar, neutral to basic organic solvent. 2. The method according to claim 1 for the preparation of 1,4-distyrylbenzenes of the formula where M is hydrogen or a salt-forming cation, R1 is hydrogen, alkyl with 2 to 4 carbon atoms, phenyl, chlorine, alkoxy with 1 to 4 carbon atoms, alkenyloxy with 3 to 4 carbon atoms, benzyloxy, alkoxyalkyl with 2 to 5 carbon atoms, phenoxy, alkylmercapto with 1 up to 4 carbon atoms, phenylmercapto, alkylsulfonyl with 1 to 8 carbon atoms, phenylsulfonyl, cyano, carboxy or sulfo, R2 hydrogen, alkyl with 2 to 4 carbon atoms, chlorine or alkoxy with 1 to 4 carbon atoms or R1 and R2 together in ortho position to one another fused benzene radical or a methylenedioxy, a trimethylene or a tetramethylene group, R3 hydrogen or alkoxy with 1 to 4 carbon atoms, R4 hydrogen, chlorine or alkoxy with 1 to 4 carbon atoms, R5 hydrogen, chlorine, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms, R6 is hydrogen or alkoxy Tait 1 to 4 carbon atoms or R5 and t> together are in the 3,4-position mean trimethylene or tetramethylene group, characterized in that there is a 4-methyl-stilbene compound of the formula with an anil of the formula where Ar1 denotes an unsubstituted or substituted phenyl or naphthyl radical and R1, R2, R3, R4, R5, R6 and M have the meaning given above. 3. The method according to claim 2 for the preparation of 1,4-distyrylbenzenes of the formula wherein M1 is a hydrogen, alkali metal, alkaline earth, ammonium or amine salt ion, R'1 is hydrogen, chlorine, alkyl with 2 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylmercapto with 1 to 4 carbon atoms, cyano or together with R '2 is a trimethylene or tetramethylene group in the 3,4-position, R'2 is hydrogen, chlorine, alkoxy having 1 to 4 carbon atoms or together with R 1 in the 3,4-position is a trimethylene or tetramethylene group, R'4 is hydrogen or alkoxy with 1 to 4 carbon atoms, R1 5 denotes hydrogen, chlorine, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms and R'6 denotes hydrogen or alkoxy with 1 to 4 carbon atoms, characterized in that one is a 4-methyl-stilbene Compound of formula with an anil of the formula in which M1, R2 ', R4', R5 'and R6' are as defined above and Arl is an unsubstituted or substituted phenyl or naphthyl radical. 4. The method according to claim 3 for the preparation of 1,4-distyrylbenzenes of the formula wherein R "1 is hydrogen, chlorine, alkyl with 2 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, R" is hydrogen, alkoxy with 1 to 4 carbon atoms or chlorine, R "5 is hydrogen, chlorine or alkoxy with 1 to 4 carbon atoms and M1 a hydrogen, alkali metal, alkaline earth metal, ammonium or amine salt ion, characterized in that a 4-methyl-stilbene compound of the formula with an anil of the formula in which X is hydrogen or chlorine. 5. The method according to claim 4 for the preparation of 1,4-distyrylbenzenes of the formula wherein R111 is hydrogen, alkyl having 2 to 4 carbon atoms, alkoxy rit 1 to 4 carbon atoms or chlorine and M1 is hydrogen. Alkali metal, alkaline earth metal, ammonium or amine salt ion, characterized in that the compound of the formula with an anil of the formula in which X is hydrogen or chlorine. 6. The method according to any one of claims 1 to 5, characterized in that that as a strongly basic alkali compound, potassium or sodium alcoholates are used uses a maximum of 6 carbon atoms. 7. The method according to any one of claims 1 to 5, characterized in that that a strongly basic alkali compound is an alkali metal compound of the formula KOCm-1H2m-1 used, in which m is an integer with a value of at most 6. 8. The method according to claim 7, characterized in that as strongly basic alkali compound potassium tert-butoxide used. 9. The method according to claim 7, characterized in that as strongly basic alkali compound potassium hydroxide with a water content of 0 to about 15% used. 10. The method according to claim 7, characterized in that as strongly basic alkali compound sodium t-butylate is used. 11. The method according to any one of claims 1 to 10, characterized in, that one as strongly polar, neutral to weakly basic organic solvents Dialkylamides of formic acid or phosphoric acid and tetraalkylureas used, the alkyl groups containing 1 to 4 carbon atoms. 12. The method according to claim 11, characterized in that as Solvent dimethylformamide used. 13. Process for the preparation of 1,4-distyrylbenzenes of the formula in which the benzene nuclei A, B and C can be non-chromophoric substituted, of the benzene rings A and C at least one contains an SO3M group, in which M is hydrogen or a salt-forming cation and the benzene radical A can also have the addition of a naphthalene radical, characterized in that there is a 4-methyl-stilbene compound of the formula in which the benzene nuclei B and C have the meaning given above, with an anil compound of the formula in which the benzene nucleus A has the meaning given above and X is hydrogen or chlorine, in the presence of a strongly basic alkali compound in a strongly polar, neutral to basic organic solvent. 14. The method according to claim 13 for the preparation of 1,4-distyrylbenzenes of the formula where M is hydrogen or a salt-forming cation, R1 is hydrogen, alkyl with 2 to 4 carbon atoms, phenyl, chlorine, alkoxy with 1 to 4 carbon atoms, alkenyloxy with 3 to 4 carbon atoms, benzyloxy, alkoxyalkyl with 2 to 5 carbon atoms, phenoxy, alkylmercapto with 1 up to 4 carbon atoms, phenylmercapto, alkylsulfonyl with 1 to 8 carbon atoms, phenylsulfonyl, cyano, carboxy or sulfo, R2 hydrogen, alkyl with 2 to 4 carbon atoms, chlorine or alkoxy with 1 to 4 carbon atoms or R1 and R2 together in ortho position to one another fused benzene radical or a methylenedioxy, a trimethylene or a tetramethylene group, R3 hydrogen or alkoxy with 1 to 4 carbon atoms, R4 hydrogen, chlorine or alkoxy with 1 to 4 carbon atoms, R5 hydrogen, chlorine, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms or R6 is hydrogen or alkoxy with 1 to 4 carbon atoms or R5 and R6 together have a 3,4-position un located trimethylene or tetramethylene group, by reaction of a 4-methylstilbene compound of the formula in which R4, R5, R6 and M have the meanings given above, with an anil compound of the formula where R1, R2 and R3 are as defined above and X is hydrogen or chlorine. 15. The method according to claim 13 for the preparation of 1,4-distyrylbenzenes of the formula wherein M1 is a hydrogen, alkali metal, alkaline earth, ammonium or amine salt ion, R'1 is hydrogen, chlorine, alkyl with 2 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylmercapto with 1 to 4 carbon atoms, cyano or together with R '2 is a trimethylene or tetramethylene group in the 3,4-position, R'2 is hydrogen, chlorine, alkoxy having 1 to 4 carbon atoms or together with R'1 in the 3,4-position is a trimethylene or tetramethylene group, R'4 is hydrogen or Alkoxy with 1 to 4 carbon atoms, R1 5 denotes hydrogen, chlorine, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms and R'6 denotes hydrogen or alkoxy with 1 to 4 carbon atoms, by reacting a 4-methylstilbene compound of the formula wherein R'4, R15, R'6 and M1 have the meanings given above, with an anil compound of the formula wherein R'1 and R'2 have the meaning given above and X is hydrogen or chlorine. 16. The method according to claim 13 for the preparation of 1,4-distyrylbenzenes of the formula wherein R "1 is hydrogen, chlorine, alkyl with 2 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, R" 2 is hydrogen, alkoxy with 1 to 4 carbon atoms or chlorine, "5 is hydrogen, chlorine or alkoxy with 1 to 4 carbon atoms and M1 mean a hydrogen, alkali metal, alkaline earth metal, ammonium or amine salt ion, by reacting a 4-methyl-stilbene compound of the formula wherein R? V'5 and M1 have the meaning given above, with an anil compound of the formula where R "and R" 2 are as defined above and X is hydrogen or chlorine. 17. The method according to claim 13 for the preparation of 1,4-distyrylbenzenes of the formula where R "1 is hydrogen, alkyl having 2 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or chlorine and M1 is a hydrogen, alkali metal, alkaline earth metal, ammonium or amine salt ion, by reaction of a 4-methylstilbene compound of the formula in which M1 has the meaning given above, with an anil compound of the formula where Rrr1 has the meaning given above and X is hydrogen or chlorine.