NO131456B - - Google Patents

Description

New bis-stilbene compounds for

use as optical brighteners and as

are colorless to maximally faintly colored.

The invention relates to bis-stilbene compounds for use as optical brighteners and which are colorless to at most weakly colored, the compound being characterized in that they correspond to the formula

in which at least one of the ring systems defined under R- and Ru or one of the substituents contains a sulfonic acid group, a sulfonic acid amide group or sulfonic acid ester group, a sulfo group, a carboxyl

acid group, carboxylic acid amide group or carboxylic acid ester group, a nitrile group or a methyl group, R ^ means phenyl, diphenyl, α-or β-naphthyl or a residue

R^l means phenyl, diphenyl, a- or g-naphthyl or a residue in which V-^ and ' may be the same or different and means a sulfonic acid group as well as their salts, esters, amides or halides, a carboxylic acid group as well as its salts, esters or amides, the nitrile group, a sulfone group, a methyl group or hydroxyl group, V"2 and ' may be the same or different and mean hydrogen, an alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, halogen or a sulfonic acid group and its salts, esters or amides, and V^ and V^' may be the same or different and mean hydrogen or an alkyl group of 1 to 4 carbon atoms, W-^ means a sulfonic acid group, as well as its salts, esters or amides, an alkyl group of 1 to 4 carbon atoms .

II. is different from hydrogen if R^ and/or R^

means the diphenylyl residue.

As functionally modified sulfonic acid groups resp. carboxylic acid groups come within the scope of the invention predominantly in consideration of their esters, amides and halides. While for the esters of an aromatic or araliphatic nature phenyl (optionally substituted) and benzyl residues are of practical interest, for the aliphatic esters alkyl esters with 1 to 18 carbon atoms are primarily taken into account.

The amides of the mentioned acids should not only be understood

the unsubstituted but also the mono- and disubstituted representatives, - as the substituting components can be both aromatic (anilide), araliphatic and also especially aliphatic and cycloaliphatic in nature. Also in this case, aliphatic links usually do not have more than 18 carbon atoms and may be substituted with hydroxy groups, halogen atoms, alkoxy groups, nitrile groups, carboxy or carboxy-alkoxy groups, sulfo groups, amino and alkylamino groups.

Among the acid halides it should be mentioned above all

the chlorides and bromides.

Although the salts in the water-soluble types (alkali, ammonium or amine salts) are predominantly important, other salts can in certain cases be very interesting, e.g. barium or calcium salts.

Among the sulfones, mention should be made of aryl sulfones and aralkyl sulfones such as phenyl and benzyl sulfone, further alkyl sulfones with lower alkyl groups (1 to 4 carbon atoms).

For the meaning halogen as a substituent it comes

above all considering fluorine and chlorine.

The compounds of preferred interest within the framework of formula (2) are such bis-stilbene compounds as listed below under A and B:

A: Compounds with formula

in which at least one and preferably at most two of the symbols U-^ to means an optionally functionally converted sulfonic acid group, a benzene residue further substituted by a sulfonic acid group, a sulfone group, an optionally functionally modified carboxylic acid group, a nitrile group or a methyl group and the remaining U-^ to Uh mean independently of each other a hydrogen atom, a 1 to 18 carbon alkyl group, a 1 to 12 carbon alkoxy group, a chlorine atom, a benzene residue.

B. Compounds with formula

wherein means a sulfonic acid group as well as their salts, esters, amides or halides, a carboxylic acid group as well as their salts, esters or amides, the nitrile group, a sulfonic group, a methyl group or hydroxyl group, v"2 means hydrogen, a 1 to 18 carbon-containing alkyl group, a 1 to 12 carbon-containing alkoxy group,

halogen or a sulfonic acid group as well as their salts, esters or amides and V-^ means hydrogen or a 1 to 4 carbon-containing alkyl group, means a sulfonic acid group as well as their salts, esters or amides, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a carboxyl group as well as their salts, esters or amides, the nitrile group or halogen, one of the symbols or further can mean a hydrogen atom.

Within the above-mentioned formulas, two important subgroups must be highlighted, one of which contains the central diphenylene link unsubstituted (type C to H), while the other group contains the obligatory substituents according to formula (2) in the central diphenylene link (type J to N). There are the following connection groups:

C. Compounds with formula

wherein means a sulfonic acid group as well as their salts, esters, amides or halides, a carboxylic acid group as well as their salts, esters or amides, the nitrile group, a sulfonic group, a methyl group, a hydroxyl group, V2 means hydrogen, a 1 to 18 carbon empty alkyl group, a 1 to 12 carbon-containing alkoxy group, halogen or a sulfonic acid group as well as their salts, esters or amides and means hydrogen or a 1 to 4 carbon-containing alkyl group. D. Compounds with formula

in which means an optionally functionally modified sulfonic acid group, a benzene residue further substituted with a sulfonic acid group, a sulfonic group, an optionally functionally modified carboxylic acid group, a nitrile group or a methyl group and U\ means one of the just given definitions of U-, corresponding substituents or a hydrogen atom, a 2 to 8 carbon-containing alkyl group, a 1 to 12 carbon-containing alkoxy group, a chlorine atom or a benzene residue.

E. Compounds with formula

wherein Vn means a sulfonic acid group as well as its salts, esters or amides, a carboxylic acid ester group as well as its salts, esters or amides or nitrile groups, V,- means hydrogen, a sulfonic acid group as well as its salts, esters or amides, an alkyl group with 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms.

F. Compounds with formula

in which U-j^-j means a sulphonic acid group and U^^ a hydrogen atom, a chlorine atom or an alkyl group with a maximum of 4 carbon atoms. G. Compounds with formula

in which Y means a cation and the YO^S group is preferably in the o-position to the -CH= group.

H. Compounds with formula

wherein Vg means a sulfonic acid group, its salts or amides. J. Compounds of formula in which R,- either means a naphthyl residue or the residue

and wherein V 2 means hydrogen, a 1 to 18 carbon alkyl group, a 1 to 12 carbon alkoxy group, halogen or a sulfonic acid group as well as its salts, esters or•amides, and V-, hydrogen

or a 1 to 4 carbon-containing alkyl group and W-^ means a sulfonic acid group as well as its salts, esters or amides, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, a carboxyl group as well as its salts, esters or amides, the nitrile group or halogen.

K. Compounds with formula

in which one of the symbols U^, Ug and U ? means an optionally functionally converted sulfonic acid or carboxylic acid group or a nitrile group and the other two mean hydrogen atoms.

L. Compounds with formula

in which one of the symbols U=., and U-^ means a sulfonic acid group and the other a hydrogen atom, a chlorine atom, an alkyl group with a maximum of 4 carbon atoms or a nitrile group.

M. Compounds with formula

in which U-^c- means a hydrogen atom, a chlorine atom, a nitrile group, an alkyl or alkoxy group with a maximum of 4 carbon atoms, an optionally sulfonic acid group-containing phenyl group, a phenoxy group, a benzene residue or an optionally functionally converted carboxylic acid group and Y means a cation.

N. Compounds with formula

in which one or two of the symbols Ug, Ug and U-^q mean a sulfonic acid group and the other two symbols mean hydrogen atoms or the second symbol means a hydrogen atom. The bis-stilbene compounds of formula (2) to (15) can be prepared analogously in known methods. Generally, the procedure is such that, in a molecular ratio of 1:2, compounds of the formula are reacted with those of the formula where X means a diphenyl radical bound in the 4- and 4'-position to Z-^, and R2 means a monocyclic benzene radical, a diphenyl radical or a naphthalene residue, one of the symbols Z-L and Z2 means an 0=CH group and the other one of the groupings of formula

in which R means an optionally further substituted alkyl radical, preferably one with up to 6 carbon atoms, an aryl radical, preferably phenyl-

residue, a cycloalkyl residue, preferably a cyclohexyl residue or an aralkyl residue, preferably a benzene residue and at least one of the ring systems present in the starting material contains an optionally functionally converted sulfonic acid group, a sulfonic group, an optionally functionally converted carboxylic acid group, a nitrile group, a hydroxyl group, a mercapto group or a methyl group (as also defined in the preceding description of the substances) and that, if necessary, further conversions are also carried out on these substituents.

Consequently, one can, for example, react with dialdehydes

formula

with monofunctional compounds of formula or monoaldehydes of formula with bifunctional compounds of formula where X and has the indicated meaning and V means one of the phosphorus-containing substituents of formula (19), (20) and (21). The phosphorus compounds with formulas (23) and (25) required as starting materials are obtained by reacting halomethyl compounds, preferably chloromethyl compounds with the formula with phosphorus compounds with the formulas

In these formulas, R has the indicated meaning, since to oxygen-bound residues R is preferably lower alkyl groups, directly to phosphorus-bound residues, R, on the other hand, is aryl residues such as benzene residues.

In this way, both the turnover for the production of the starting materials as well as the turnover for the production of the end products can be carried out in the usual way.

For the production of the compounds of particular practical interest with formula (2), essentially two variants come into consideration. One can either react in a molecular ratio of 1:2 with compounds of formula

with those with formula

(32) R3 - CHO resp. (33) Rj, - CHO

or in molar ratio 1:2 react compounds with formula

with those with formula Hereby, R^, R^ and W-^ have the meaning indicated under formula (2), and Z-, is one of the groupings with the formulas

wherein R means an optionally further substituted alkyl residue, an aryl residue, a cycloalkyl residue or an aralkyl residue.

The reaction is carried out in both cases by reaction of the components in the presence of a strongly basic alkali compound and in the presence of a preferably hydrophilic, strong polar solvent, in the case of using alkali hydroxides as strongly basic alkali compounds and these alkali hydroxides have a water content of up to 25/".

In a similar way, compounds with formula (5) can be prepared by reacting dialdehydes with formula in a molecular ratio of 1:2

with a compound of formula or in a molecular ratio of 1:2 reacts a compound of formula with a compound of formula, in both cases the reaction is carried out as mentioned above. In a similar way, compounds of formula (11) are obtained by reacting an aldehyde of formula with a compound of formula or reacting a compound of formula with an aldehyde of formula

as here too the turnover is carried out as indicated above.

Examples of solvents for the above-mentioned method for preparing compounds with formula (2) include toluene, xylene, chlorobenzene, alcohols such as e.g. ethanol, ethylene glycol monomethyl ether, preferably however N-methylpyrrolidine, dimethylformamide, diethylformamide, dimethylacetamide or dimethylsulphoxide•

The temperature at which the turnover is carried out can vary within wide limits. It is determined a) by the resistance of the used solvent to the reaction participants, especially to the strongly basic alkali compounds,

g) by the reactivity of the condensation participants and

y) by the action of the solvent-base combination as a condensing agent.

Preferably it lies approximately in the range from 30 - 60°C, however, in many cases satisfactory results can already be achieved at room temperature (approx. 20°C) on the one hand or on the other hand at temperatures of 100°C, even at the solvent's boiling temperature when this is desirable for time-saving reasons or by using a less active but cheaper condensation agent. In principle, reaction temperature intervals from 10 to 180°C are thus also possible.

As strongly basic alkali compounds, the hydroxides, amides and alcoholates (preferably of such primary alcohols containing 1 to 4 carbon atoms) of the alkali metals come into consideration, the ones of lithium, sodium and potassium being of interest for economic reasons. However, alkali sulphides and carbonates, aryl alkali compounds such as e.g. phenyllithium or strongly basic amines (including ammonium bases, e.g. trialkylammonium hydroxides).

The new compounds of formula (2) have a remarkable fluorescence in dissolved or finely divided state. They can be used for optical illumination of the various high-molecular or low-molecular organic materials resp. materials containing organic substances.

In addition, the following groups of organic materials must be mentioned, for example, as far as optical lighting is taken into account: I. Synthetic organic high-molecular or higher-molecular materials: a) Polymerization products based on polymerizable organic compounds containing carbon-carbon double bonds, i.e. their homo- or copolymers as well as "their finishing products such as for example network formation, grafting or degradation products, polymer mixtures, etc., to which examples should be mentioned: Polymers based on a, (3-unsaturated carboxylic acids, especially of acrylic compounds, of olefinic hydrocarbons (especially poly-α-olefins), polymers based on vinyl and vinylidene compounds of halogenated hydrocarbons, of unsaturated aldehydes, ketones or allyl compounds, their graft polymerization crosslinking products (for example, bi- or multifunctional crosslinkers) or by partial dismantling, modification of

reactive groupings etc. obtainable products,

b) other polymerization products such as those e.g. are achievable by ring opening, e.g. polyamides of the polycaprolactam type, further

formaldehyde polymers or polymers which are both obtainable via polyaddition and also polycondensation such as polyethers, polythioethers, polyacetals, thioplast,

c) polycondensation products or precondensates based on bi- or polyfunctional compounds with condensable properties

groups, their homo- and mixed condensation products as well as products from the post-treatment, to which examples must be mentioned: polyesters, saturated (especially aromatic such as e.g. polyethylene terephthalate) or unsaturated (e.g. maleic acid dialcohol polycondensates as well as their network formation products with on-polymerizable vinyl monomers), unbranched as well as branched (such as alkyd resins), polyamides (e.g. hexamethylene diamine adipate), maleate resin, melamine resins, phenolic resins (novolacquers), aniline resins, furan resins, carbamide resins, resp. also their precondensates and analogously built products,

polycarbonates, silicone resins,

d) polyaddition products such as polyurethane (cross-linked and non-cross-linked), epoxy resins. II. Semi-synthetic organic materials such as cellulose esters or mixed esters (acetate, propionate), nitrocellulose, cellulose ethers, regenerated cellulose (viscose, copper ammonia cellulose) or their finishing products, casein plastics. III. Natural organic materials of animal or vegetable origin, for example on the basis of cellulose or proteins, such as wool, cotton, silk, bast, jute, hemp, felt and hair, leather, wood pulp in fine distribution, natural resins (such as rosin, especially varnish resins) , further rubber, gutta-percha, balata as well as their finishing and modification products, decomposition products, which are obtained by modifying reactive groups.

The organic materials in question can exist in a wide variety of processing states (raw materials, semi-finished products or finished products) and aggregate states. On the one hand, they can exist in the form of different shaped structures, i.e. e.g. as predominantly three-dimensionally extended bodies such as plates, pro-filters, injection molded bodies and the most diverse pieces of material, cuts or granules, foams; predominantly as two-dimensionally designed bodies such as film, foil, varnish, impregnations and coatings or as predominantly one-dimensionally designed bodies, such as threads, fibres, strands, thread. On the other hand, the mentioned materials can also be present in unformed states in the most diverse homogeneous and inhomogeneous forms of distribution and aggregate states, e.g. such as powders, solutions, emulsions, dispersions, latex, sols, gels, putty, paste, wax, adhesives and fillers, etc.

The fiber materials can, for example, be in the form of endless threads, staple fibres, skeins, string goods, yarn, fiber pile, felt,

wadding, population structures or as textiles, woven fabrics or textile composite substances, works as well as paper and cardboard or paper pulp etc.

Of importance are the compounds to be used according to the invention also for the treatment of textile organic materials,

such as textile fabrics. If the fiber substrates as mentioned above according to the invention are to be optically illuminated, this advantageously takes place in an aqueous medium, in which the compounds in question are present in finely divided form. (Suspension, possibly solutions). Optionally, dispersants such as e.g. soaps, polyglycol ethers of fatty alcohols, fatty amines or alkylphenols, cellulose sulphite liquor or condensation products of optionally alkylated naphthalene sulphonic acids with formaldehyde. It turns out to be particularly appropriate to work in a neutral, weakly alkaline or acidic bath. Likewise, it is advantageous when the treatment takes place at elevated temperatures of approx. 50 to 100°C, for example at the boiling temperature of the bath or close to this (approx. 90°C). For the processing according to the invention, solutions in organic solvents are also taken into consideration.

The new optical brighteners to be used

according to the invention can further be added to the materials before or during their shaping or embodied. Thus, they can be added, for example, during the production of films or other molded bodies to the press compounds, injection molding compounds, etc. or before spinning dissolve, disperse or otherwise finely distribute it in the spinning compound. The optical brighteners can also be added to the starting materials, reaction mixtures or intermediate products for the production of fully or semi-synthetic organic material, i.e. also before or during the chemical reaction, for example in a polycondensation (so also precondensates), in a polymerization (so also prepolymers ) or a polyaddition.

The new optically brightening substances are characterized by very good heat resistance, light fastness and migration resistance as well as high profitability.

The quantities of the new optical brighteners to be used according to the invention, referred to the material to be optically brightened, can fluctuate within wide limits. Already with very small amounts, in certain cases e.g. such at 0.01% by weight, a clear and lasting effect can be achieved. Quantities of up to approx. 0.5% by weight and more. For most practical needs, amounts between 0.01 and 0.2 percent by weight are preferably of interest.

The new compounds that serve as lightening agents can, for example, also be used in the following way: a) in a mixture with dyes or pigments or as an additive to dye baths, thick, etching or reserve pastes. Furthermore also to

finishing of colourings, prints or etchings.

b) In a mixture with so-called "Carrier", antioxidants, light protection agents, heat stabilizers, chemical bleaching agents or as an additive to bleaching baths. c) In a mixture with net formers, finishing agents such as starch or synthetic available finishing materials. The products according to the invention

can advantageously also be added to the baths that are used to achieve a wrinkle-free finish.

d) In combination with detergents. The detergents and lightening agents can be placed separately in the wash baths to be used. It is

it is also advantageous to use detergents that contain the lightening agents mixed in. Suitable detergents are, for example, soaps,

salts of sulfonate detergents, such as e.g. of sulfonated benzimidazoles substituted at the 2-carbon atom by higher alkyl residues, further salts of monocarboxylic acid esters of 4-sulfofthalic acid. with higher fatty alcohols, further salts of fatty alcohol sulfonates, alkylarylsulfonic acids or condensation products of higher fatty acids with aliphatic oxy- or aminosulfonic acids. Furthermore, non-ionic detergents can be used, e.g. polyglycol ethers, which derive from ethylene oxide and higher fatty alcohols, alkylphenols or fatty amines.

e) In combination. with polymeric carrier materials (polymerisation, polycondensation or polyaddition products), in which the brighteners

possibly next to other substances are embedded in dissolved or dispersed form, e.g. by coating, impregnating or binding agents (solutions, dispersions, emulsions) for textiles, felt, paper, leather. f) As an addition to a wide variety of industrial products to make them more suitable for the market or to avoid disadvantages in usability, e.g. as an addition to glues, adhesives, spreaders, etc. g) In combination with other optical brighteners to achieve a shade equalization and/or a synergistic effect.

The compounds with the formulas given at the outset can be used as scintillators, for various purposes of a photographic nature, such as for electrophotographic reproduction or for supersensitisation.

If the lightening procedure is combined with other treatment or processing methods, then the combined treatment takes place advantageously with the help of correspondingly resistant preparations. Such preparations are characterized by the fact that they contain the optically brightening compounds of the general formula stated at the outset as dispersants, detergents, carriers, dyes, pigments or finishing agents.

In the formulas no. (2), (4), (11) the definition of the substituents V resp. W always to be assumed so that if the substituents V-^, V2» Vj or W-^ have the meaning of hydrogen, the condition of the presence of at least one of the obligatory substituents must nevertheless always be fulfilled (an optionally functionally converted sulfonic acid group,

a sulfone group, an optionally functionally converted carboxylic acid group, a nitrile group, a hydroxyl group, a mercapto group or a methyl group).

Example 1.

To a suspension of 60 g of potassium tertiary butylate i

125 ml of anhydrous dimethylformamide are added dropwise over the course of 50 min. with stirring at 40 to ^ 0°C a solution of 32.7 g of the sodium salt of benzaldehyde-2-sulfonic acid with a content of approx. 10% of free sulfonic acid and 22.7 g of 4,4'-bis-(diethoxyphosphonomethyl)-diphenyl in 50 ml of anhydrous dimethylformamide (a small insoluble part is removed by filtration), as a slightly exothermic reaction results in a reddish-brown suspension. The reaction mixture is further stirred for 1 hour at 40 to 50°C and then poured into 2.5 liters of cold water. The pale yellow cloudy solution formed is heated to boiling, filtered and the hot filtrate is mixed with 375 g of sodium chloride. On cooling, the pale yellow product crystallizes out. It is recrystallized twice from a mixture of 900 ml water and 90 ml glacial acetic acid with the addition of 18 g sodium chloride, once from a Manding of 100 ml dimethylformamia and 1000 ml water with the addition of 150 g sodium chloride and twice from 900 ml resp. 500 ml of ethanol.

Yield: approx. 4.0 g (14.2% of the theoretical.) of compounds of formula

like light yellow, fine little needles.

The 4,4'-iso-(aiethoxyphosphono-methyl)-diphenyl used as starting material can be obtained in the following way:

301 g of 4,4'-bis-chloromethyldiphenyl in 1200 ml of xylol are added to 420 g of triethyl phosphite at 142 to 146°C over the course of 1 hour. The reaction mixture is boiled for 20 hours under reflux and then the solvent is distilled off at normal pressure. After adding a further 410 ml of triethyl phosphite, the reaction mixture is boiled for a further 20 hours under reflux. Excess triethyl phosphite is distilled off under normal pressure, the reaction mixture is cooled to 120°G, ^ 00 ml of toluene is added and cooled to room temperature, the product being crystallized out and isolated by filtration. After recrystallization from toluene, 3^1.5 g (66.3 u/<> of ^a theoretical) 4,4'-bis-(diethoxyphosphonomethyl)-diphenyl with formula

as white crystalline powder of melting point 108 to 110°C.

' Example 2.

To a well-stirred suspension of 126.5 g of potassium hydroxide powder with a content of approx. 89% in 500 ml of anhydrous dimethylformamide is introduced slowly under displacement of the air by means of a stream of nitrogen with a homogeneous mixture of 113.5 g of 4»4'-bis-(diethoxy-phosphonomethyl)-diphenyl and 129 g of the sodium salt of benzaldehyde-2- sulphonic acid with a content of approx. 86% of free sulfonic acid. The temperature gradually increases to 45°C and is maintained by ice cooling at 40 to 45°C. The mixture is then stirred again for 3 hours at 40 to 45°C. The reaction mixture is poured into 3>5 liters of distilled water of approx. 70°C. Add 1.5 kg of sodium chloride and approx. 1.5 kg of ice, the temperature of the pale yellow suspension falling to approx. 25°C. By adding 37% hydrochloric acid, the suspension's pH value is set to approx. 7, is stirred for a further 1 hour at room temperature, sucked off and the product is washed with a 23% sodium chloride solution. After drying, you get approx. 158 g of crude product, which contains 21% sodium chloride and 125 g of the compound of formula (101), corresponding to a yield of 89% of the theoretical. During the recrystallization of the moist nut cake from ethanol, approx. 117 g pure product with a sodium chloride content of 13% corresponding to a pure yield of 72% of the theoretical. By further recrystallization from alcohol, the product of formula (LOI) can be obtained salt-free.

Analysis: C 2 g H 2 O Na 2 O g S 2

Instead of 113.5 S 4,4'-bis-(diethoxyphosphonomethyl)-diphenyl, 99.6 g of 4,4'-bis-(dimethoxyphosphonomethyl)-diphenyl and 116 g of the sodium salt of benzaldehyde-2-sulfonic acid with a content of of approx. 88% of free sulphonic acid and carry out the procedure as mentioned above, however with a reaction duration of 5 hours, you get approx. 163 g of crude product with a sodium chloride content of 24.5%, corresponding to a yield of 87% of the theoretical. By dissolving the crude product in 1600 ml of boiling distilled water, clear filtration, rinsing with 400 ml of boiling distilled water, adding 400 g of sodium chloride to the clear filtrate, cooling, suctioning off and drying the crystallized product, you get approx. 147 S" pure product of formula (101) with a sodium chloride content of 18%, corresponding to a pure yield of 86% of the theoretical.

In this method, an equivalent amount of sodium hydroxide with a content of approx. 98%, then you get the product with formula (101) with a crude yield of 73%

and a net yield of 70% of the theoretical. Finally, instead of dimethylformamide, dimethylsulfoxide can also be used as a solvent.

It used 4,4'-bis-(dimethoxyphosphonomethyl)-diphenyl

can be obtained in the following way:

A mixture of 26l g of 4,4'-bis-(chloromethyl)-diphenyl and

372 g of trimethyl phosphite is stirred at reflux temperature (117 to 119°G), until the development of the methyl chloride is finished, which lasts approx.

8 hours. After distilling off excess trimethylphosphite in vacuum, the clear, colorless solution is diluted with 600 ml of toluene and allowed to crystallize. After extraction, washing with a little toluene and drying, 358 g (90% of the theoretical) of bis-(dimethoxyphosphonomethyl)-diphenyl with the formula

as colorless crystals of melting point 129 to 130°C. A sample recrystallized for analysis from toluene melts at 130 to 131°C. Cl8H24°6P2 (39<8,>33)

If an equivalent amount of triethylphosphite is used instead of trimethylphosphite, then at a final temperature of 160°C, a yield of 89% of the theoretical bis-(diethoxyphosphonomethyl)-diphenyl with formula (102) is obtained as colorless crystals of melting point 107 to 109 °C. A sample recrystallized from toluene melts at 108 to 110°C.

<C>22<H>32<P>2°6 U54.44)

The starting material used 4,4'-bis-chloromethyl-

diphenyl is produced in the following way:

In a mixture of 1542 g of biphenyl, 671 g of paraformaldehyde (98%), 927 g of zinc chloride (98%) and 2000 ml of cyclohexane, a strong flow of chlorine hydrogen is introduced with very good stirring, with the aid of external cooling until dissolution of all reaction participants is observed temperature of 50°C, then for 24 hours a temperature of 30°C.

The formed bis-chloromethyl-diphenyl constantly crystallizes out. After extraction with suction at 15°C, washing with cyclohexane and water and drying in vacuum at 70°C, 1580 g (63% of theory) of bis-chloromethyl-diphenyl is obtained as a colorless, crystalline powder of melting point 132° to 135°C.

Example 3.

113.5 g of 4,4'-bis-(diethoxyphosnomethyl)-diphenyl and

222 g of the disodium salt of benzaldehyde-2,4-isulfonic acid with a content of approx. -" JOfo free acid is reacted in 800 ml of anhydrous dimethylformamide and 126 g of potassium hydroxide powder according to example 2. After a reaction time of one hour, the thick reaction mixture is poured into 1.4 1 of distilled water and approx. 80°C, the cloudy solution is filtered clear, the filtrate is cooled to 15° C. and mixed with 5 1 of ethanol. The crystallized product is sucked off and dried under vacuum.

Yield: approx. 113 g (59>3% of the theoretical, calculated on the tetrasodium salt).

By recrystallization from water/ethanol, transfer using an ion exchanger in the free tetrasulfonic acid and neutralization with sodium hydroxide solution, the pure tetrasodium salt with the formula is obtained

Fine light yellow small needles.

Analysis: CggH-^Na^O-^S„

In a similar way as in the previous examples, the bis-stilbene compounds with formula listed in the following table can be

is produced.

The sodium salt of 5-formyl-2-methylbenzenesulfonic acid used as starting material for bis-stilbene compounds of formula (111) can be obtained by sulfonation of 4-methylbenzaldehyde mea oleum of 66% SO^ content and purification over the barium salt. In the same way, it is obtained as starting material for bis-stilbene compounds with formula

(112) used the sodium salt of 5-formyl-2-methoxybenzenesulfonic acid from 4-methoxybenzaldehyde.

Example 4.

200 g of the compound with formula (101) is heated in

1000 ml of dry chlorobenzene with stirring and addition of 500 ml of thionyl chloride and 1 ml of dimethylformamide during 35 minutes at 95°C °S are stirred for 20 hours at 95 to 100°C. It is then cooled, the crystallized product is sucked off and recrystallized from 2 liters of dry chlorobenzene.

Yield: approx. 117.3 5 (60.4% of ^a theoretical) of the compound with formula

Shiny yellow leaflets. Melting point 236 to 237°G.

Analysis: C28*20^2^4^2 ;;In an analogous way, the sulphochloride of formula ;can be obtained as yellow glistening leaflets with a melting point above jrOO°G. Similarly, from the compounds of formula (104), (HO) and (111) sulfochlorides with the formulas are obtained in an analogous manner Example 5. 11.1 g of the compound of formula (115) is heated in 150 ml of dimethylformamide over the course of 2 hours unaer stirring to I45 to 150°C. It is then cooled to 80°C, 150 ml of ethanol is added, cooled to 5°C, the crystallized product is sucked off, recrystallized from 400 ml of dimethylformamide and dried under vacuum. ;Yield 4.5 S of compound with formula ;;Analysis: C32<H>3<6N2>°6<S>2 ;calculated: C 63.14 H 5.96 N 4.60 S 10.53 ;found: C 63.02 H 5.93 N 4.47 S 10.54 ;By dissolving the compound with formula (117) in dimethylformamide/water and adding 303 mg of sodium hydroxide solution to the hot solution, you get the sodium salt with formula (113)« ;Analysis: C28H20<N>a2^6S2;By dissolving compounds with formula (101) in water and adding barium or calcium chloride, the corresponding barium or calcium salt. ;Example 6. ;27.8 g of the compound of formula (114) is dissolved in ;300 ml of dry chlorobenzene with stirring at 120°C. A suitable flow of dry ammonia is then introduced for 30 hours. After cooling, the crystallized product is suctioned off and recrystallized twice from dimethylformamide/water. ;Yield: 16.2 g of compound of formula ;;Bright yellow fine leaves with melting point 280.5 to 282°C. ;Analysis: C28<H>24<N2>°4<S>2 ;calculated: C 65.10 H 4.68 N 5.42 S 12.41 ;found: C 64.92 H 4.69 N 5, 15 S 12.35 ; If, instead of ammonia, dimethylamine is introduced for 6 hours at 60 to 65°C, after recrystallization from dimethylformamide 20.7 S of the compound with formula ;; is obtained as pale yellow glistening leaves with a melting point of 280 to 28l°C . ;If, instead of introducing dimethylamine, 42 g of diethanolamine are added dropwise at 60 to 65°C and then heated for 1 hour at 120 to 125°C, after recrystallization from dimethylformamide/ethanol with the addition of activated carbon, 8.0 g of the compound mea is obtained formula ;pale yellow small needles, melting point 323 to 233°G. Example 7. 13.9 g of the compound of formula (114) are introduced into 200 ml of n-octylamine and heated with stirring for 45 min. at 75" to 80°C. The pale yellow solution is cooled, mixed with 100 ml of methanol and the precipitated product is suctioned off and recrystallized twice from chlorobenzene with the addition of bleaching earth. ;Yield: 10.4 g (corresponding to 56.3% of the theoretical) of compound with formula ;;colourless crystal powder with melting point 143>5 to 144°C. ;In a similar way, the bis-stilbene compounds with formula (105) listed in the following table can be prepared. ;Example 8. ;27> 8 g of the compound of formula (114) are slowly introduced into a solution of 40.8 g of 3-dimethylamino-1-propylamine in 300 ml of ethanol without stirring at room temperature. Then the mixture is stirred for 5 hours at 55 to 60°C, cooled, the crystallized product is suctioned off, washed with water and ethanol and dried under vacuum. Yield: 33" 5 g (corresponding to 97.7% of the theoretical) of compound ice with the formula ; After recrystallization twice from dimethylformamide/water and adding activated carbon man 25.0 g (72.8% of the theoretical) yellow small plates of sm melting point 165.5 to 165.5°C« ;Analysis: C^H^N.^ ;13.7 g of compound of formula (128) is boiled in 1500 ml of methanol with 15 ml of dimethyl sulphate for 4 hours under reflux. Then 700 ml of methanol is distilled off, the product with formula ;precipitating in the form of approximately colorless crystals. Melting point after recrystallization from methanol/hexane 254 to 256°C. Example 9 13.9 g of compound of formula (114) are introduced at room temperature into a solution of 9>4 g of phenol in 100 ml of anhydrous pyridine with slow stirring. It is then heated for 2 hours at 95 to 105°C, cooled to 5°C, the residue is filtered off, the clear filtrate is mixed with 200 ml of hexane, the precipitated product is suctioned off, dried, extracted twice with boiling water, dried again and recrystallized from chlorobenzene. The product is dissolved in 200 ml dioxane, filtered clear, mixed with 300 ml ethanol and 50 ml water and allowed to crystallize. One obtains 1.2 g of the compound with formula ;;Light yellow small needles with melting point 241 to 241.5°c« ;Analysis: C^gH^OgSg ;;Example 10. ;20 g of the crude sulfochloride with formula (ll6) is introduced with stirring in 800 ml of methyl cellulose solution and 100 ml of 24% ammonium hydroxy solution and heated for 4 hours at 90 to 95°C. The cloudy solution is clearly filtered, mixed with 800 ml of water and 50 ml of concentrated hydrochloric acid. The precipitated product is suctioned off, washed neutrally with water, dried and recrystallized from dimethylformamide/water. You get 1.0 g of the compound with formula ;;Yellow small plates with a melting point above 3°0°C';Analysis: C28<H2>6<N>4°8<S>4 ;;Example 11. ;10 g of the crude compound of formula (ll6) is suspended in 200 ml of chlorobenzene with stirring and during 6 hours at approx. 60°C, dimethylamine is introduced. After cooling, suck off and recrystallize from dimethylformamide/ethanol resp. dioxane/ethanol. 1.9 g of the compound with formula ;; Yellow crystal powder with melting point 257.5 to 258°C is obtained. ;Analysis: C^H^O^ ;;Example 12. ;10 g of the crude sulfochloride mea formula (116) is heated in 200 ml of n-octylamine with stirring for 3 hours at 75 to 80°C. The cloudy solution is clearly filtered, cooled, mixed with a little water and 1.5 1 methanol, the precipitated product is filtered off and recrystallized from dimethylformamide/water. Yield: 3>9 g of the compound of formula ;Lemon yellow small needles with a melting point of 255 to 256°C. ;Analysis: C^H^OgS^ ;;Example 13»; 22.7 g of 4»4'-bis-(diethoxyphosphonomethyl)-diphenyl and 14.4 g of p-toluylaldehyde are dissolved under heating in 100 ml of anhydrous dimethylformamide. After cooling to 20°C, 20 g of 3% methanolic sodium methylate solution are added dropwise with stirring over the course of 15 minutes, the temperature rising to /\ Q°G and a pale, yellow, thick suspension forming. It is stirred for a further hour, diluted with 50 ml of methanol, neutralized with glacial acetic acid and the crystallized product is sucked off. After recrystallization from a mixture of 600 ml of dimethylformamide and 1200 ml of trichlorobenzene, 12.2 g (63.3% of the theoretical) of 4>4'-bis-(p-methylstyryl)-diphenyl of formula ;; are obtained in the form of glistening , pale yellow leaves with a melting point above 300°C. ;Analysis: C^Q^g ;;Example 14»;22.7 g of 4,4'-bis-(diethoxyphonomethyl)-diphenyl and 15.7 g of p-cyanobenzaldehyde are dissolved in 100 ml of anhydrous dimethylformamide at 40°C with stirring . Then, over the course of 20 minutes, 20 g of a 30% methanolic sodium methylate solution are added dropwise so that the temperature does not rise above 50°C. The orange colored suspension formed is stirred for a further 5 hours at 45 to 0°C, cooled to room temperature, the crystallized product is sucked off, the solids are washed well with methanol and recrystallized from a mixture of 500 ml of trichlorobenzene and 250 ml of dimethylformamide resp. of 500 ml of trichlorobenzene with the help of bleaching earth. ;Yield: 4.2 g (20.6% of theoretical) of the compound of formula ;;Yellow crystalline powder with melting point 271 to 272°C. ;Analysis: C^qH^I^ ;;Example 15» ;To a suspension of 13>2 g of potassium tertiary butylate in 200 ml of anhydrous dimethylformamide, a solution of 3>9 S benzaldehyde is added dropwise with stirring at 40 to 50°C -4-carboxylic acid methyl ester and 5.0 g of 4>4'-bis-(diethoxyphosphonomethyl)-diphenyl in 20 ml of anhydrous dimethylformamide. The resulting thick yellow suspension is stirred for a further 4 hours at 40 to 45°C, cooled and the product is suctioned off. After recrystallization from a mixture of 1000 ml of trichlorobenzene and 500 ml of dimethylformamide, resp. of 500 ml of dimethylformamide gives 1.0 g (19.2% of the theoretical) of the compound with formula ;; as a yellow crystalline powder with a melting point above 300°C. 51.6 g of the diester with formula (136) is stirred in 1500 ml of methyl cellulose solution with 60 g of a 30% aqueous sodium hydroxide solution for 5 hours at 95 to 100°C. After cooling and extraction, the formed disodium salt is transferred by acidification with aqueous hydrochloric acid into the free dicarbonic acid. You vacuum, wash with water and dry. ;13.4 g of the dicarboxylic acid is heated in 200 ml of chlorobenzene; and 0.5 ml of dimethylformamide with 20 ml of thionyl chloride at 95°C and stirred for 3 hours at 95 to 100°C. The reaction product formed after cooling is recrystallized twice from o-dichlorobenzene: 7.3 g (50.3%; of the theoretical) of the compound of formula ; as yellow, shiny petals with a melting point of 28l to 283°C. Analysis: C^B^^Clg ; 4.85 g of the compound of formula (136a) is stirred in ; 200 ml of chlorobenzene for 6 to 7 hours at 55 to 60°C while introducing dry dimethylamine. After cooling, suction, washing with methanol and drying, 4.8 g (96% of the theoretical) of the compound with formula ;; are obtained in the form of light, greenish yellow, fine needles which melt above 300°C and can be further purified by recrystallization from o-dichlorobenzene or dimethylformamide. ;Example 16. ;In a suspension of 25.5 g of potassium hydroxide powder with a water content of approx. 12% in 120 ml of dimethylformamide is added dropwise without stirring at 40 to 45°C a solution of 22.7 g of 4,4'-bis-(diethoxy-phosphonomethyl)-diphenyl and 14.4 g of p-toluylaldehyde in 50 ml of dimethylformamide . The yellow suspension formed is stirred for a further 2 1/2 hours at 40 to 45°c> after addition of 500 ml of water is suctioned off and the product is washed with water and methanol. ;Yield: 18.1 g, corresponding to 93.8% of the theoretical of the compound of formula ;;as pale yellow powder; melting point above 300°C. ;After recrystallization from 1500 ml of trichlorobenzene using bleaching earth or from a mixture of 750 ml of trichlorobenzene and 750 ml of dimethylformamide, 8.6 g (44.6% of the theoretical) of pale yellow crystals are obtained, melting point above 300°C. In a similar way, the bis-stilbene compounds listed in the following table are prepared with formula, in that for the compound with formula (139), the reaction mixture is acidified after the reaction has ended with aqueous hydrochloric acid. ;Example 17. ;To a suspension of 25.2 g of potassium hydroxide powder with a water content of approx. 11% in 100 ml of dimethylformamide is added dropwise with stirring and with the exclusion of air a solution of 10.5 S 4,4'-bis-formyl-diphenyl and 25.3 g of 1-diethoxyphosphonomethyl-2-cyano-benzene with formula in 50 ml dimethylformamide so that the temperature does not rise above 40°C. The reaction mixture is further stirred for a further 3 hours at 40 to 45°C, cooled to 5°C and 200 ml of water are added dropwise. After extraction, washing with water and methanol and drying, 18.2 g (89.3% of the theoretical) of brownish yellow fine needles of 4,4'-bis-(2-cyanostyryl)-diphenyl with formula ; with melting point 271 to 272°C. Twice recrystallization from o-dichlorobenzene (pale earth) yields 13.5 g (66.3% of theory) of pale yellow, glistening leaflets, melting at 274 to 275°C. ;Analysis: C3qH20<N>2 ;The intermediate product l-dioxyphosphonomethyl-2-cyanobenzene of formula (140) can be obtained from o-tolunitrile by reaction with M-bromosuccinimide to the bromomethyl compound and further reaction of this with triethylphosphite, boiling point 138 to 140°C at 0.09 rcm' If, instead of l-diethoxyphosphonomethyl-2-cyano-benzene, l-diethoxyphosphonomethyl-3-cyano-benzene is used, the compound of formula ; with a melting point above 300°C is obtained. For the preparation of the bis-stilbene compounds with the formulas (I4I) and 142), dimethylsulfoxide can also be used as a solvent instead of dimethylformamide. According to the information in this example, the bis-stilbene compounds with formula listed in the following table can also be prepared. ;The 4,4,-bis-formyl-3,3,-dimethyl-aphenyl used as starting material for the bis-stiiben compounds ;(143) and (150) to (154) can be prepared by reacting diazotized tolidine with potassium cyanide/ copper sulfate and reduction of the dinitrile formed using Raney nickel/formic acid. Melting point 108 to 109°C. In an analogous manner, the 4,4'-bis-formyl-3,3'-dimethoxy-diphenyl required for compounds (144) and (I49) is prepared, melting point 241 to 243°C, and the 4 used for compound (145) ,4'-bis-formyl-3,3'-dichloro-diphenyl, mp 220 to 222°C. 4,4,-bis-formyl-diphenyl-3,3'-isosulfonic acid is obtained via the following reaction steps. ;Sulfonation of 4»4'-dimethyl-diphenyl using concentrated sulfuric acid at 80°C for 4" to 5 hours; transfer of the aanneae 4,4'-dimethyl-diphenyl-3»3'-disulfonic acid with thionyl chloride in disulfone -acid dichloride; melting point 192 to 193°C» oxidation with chromic anhydride in acetic anhydride/glacial acetic acid to acetate chloride with formula Melting point 185 to 188°C and final hydrolysis in dilute hydrochloric acid to aldehyde sulphonic acid. 4,4'-bis-formyl-diphenyl-313 '-bis-sulfonic acid dimethylamide is prepared from sulfochloride acetate of formula (155) by reaction with dimethylamine in chloroform and hydrolysis in dilute hydrochloric acid. Melting point 219 to 221°G. ;Example 18. ;In example 2, if one replaces 4,4'-bis -(diethoxyphosphono-methyl)-diphenyl with the equivalent amount of 4,4'-bis-(phenylethoxyphosphono-methyl)-diphenyl with formula ;; then, with otherwise identical experimental conditions and preparation, compounds with formula (101) are obtained in a yield of 23 % of the theoretical. ;The phosphinic acid ester of formula (156) used as starting material is obtained by reaction of 4»4'-bis-chloromethyldiphenyl with 2.5 mol of phenyl-diethoxyphosphine. ;Colorless crystals from alcohol with melting point 232 to 234°C. ;Analysis: C30<H>3<2>°<4>P2;;Example lq. ; 45.4 g of 4,4'-(diethoxyphosphonomethyl)-diphenyl, 13.1 g of p-cyanobenzaldehyde and 21.2 g of the sodium salt of benzaldehyde-2-sulfonic acid with a content of 88% free sulfonic acid are introduced into a suspension of 51 .1 g of potassium hydroxide powder with a water content of approx. 12% in 200 ml of dimethylformamide and reacted according to what is stated in example 2. After drying, the compound with formula (135) is removed by boiling with trichlorobenzene and from the residue the compound with formula is isolated by crystallization from 2 1 water and 800 ml of dimethylformamide in the form of yellow leaflets. Analysis: C^H^C^N s Na. 1/2 HgO In a similar way, the below listed asymmetric bis-stilbene compounds with formula ; can be prepared. ;Example 20. ;22.2 g of the disulfonic acid dichloride of formula (H4) is suspended with 0.2 g of a commercially available wetting agent in 50 ml of water and introduced into a solution of 40.3 6 sodium sulphite hydrate in 500 ml of water under stirring. The reaction mixture is heated to 90°C and at this temperature 15 ml of a 30% aqueous sodium hydroxide solution is gradually added dropwise so that the pH value is 9 to 9.5. After 12 hours of stirring at 9° to 95°C, the hot solution is filtered and the reaction product is desalted from the filtrate with 50 g of sodium chloride. After extraction and drying, the disodium salt of disulfinic acid with formula ;; is recrystallized twice from methanol-water. You get light yellow leaves, which melt at over 300°C. ;Analysis: CggHggO^SgNag.l HgO ;l6.0 g of the disodium salt of disulfinic acid with formula (l60) is stirred in 100 ml of water and 150 ml of ethanol with 50 g of methyl iodide during 22 hours at 50°C. The excess of methyl iodide is then distilled off with the ethanol and the remaining reaction mixture is de-coloured with sodium thiosulphate, sucked off and the nut material is dried in a vacuum. It is crystallized once from ethanol/dimethylformamide/water and then twice from chloroform/ethanol, whereby compounds of formula ; are obtained in the form of light beige, glistening leaflets which melt at 301 to 302°C. ;Analysis: C3oH260ÆS2 ;;Example 21. ;Bleached cotton fabric is washed in a bath ratio of 1:30 for 30 min. in a 60°C hot bath which per liter contains the following addition: 0.032 g of the brightener with formula (101) or (110) ; 1 g of active chlorine (lye) ; 4 g of a washing powder of the following composition: ; 15.00% dodecylbenzene sulphonate, ; 10.00% sodium lauryl sulfonate, ;40.00% sodium tripolyphosphate, ;25.75% sodium sulfate anhydrous, ;7.00% sodium metasilicate, ;2.00% carboxymethylcellulose, ;0.25%"ethylenediaminetetraacetic acid. ;After rinsing and drying, the fabric has a strong brightening effect of good acid and chlorine resistance.; The washing powder of the above-mentioned composition can contain brighteners with formula (101) or (110) also incorporated directly. ;You also get a strong brightening effect when you carry out the washing process for 30 minutes at 20°C. ;Example 22. ;Bleached cotton fabric is washed in a bath ratio of 1:20 for 30 min. at 60 to 95°0« The laundry contains per liter of the following addition: ;0.04 g of brightener with formula (101), ;4 g of a washing powder of the following composition: ;40.0% soap flakes, ;15.0% sodium tripolyphosphate, ;8.0% sodium perborate, ;1 .0% magnesium silicate, ;11.0% sodium metasilicate (9 HgO), ;24.6% soda ash, calcined, ;0.4% ethylenediaminetetraacetic acid. After rinsing and drying, the cotton fabric has a strong brightening effect. ;Example 23«;Tissue sections of polyamide-6, bleached wool and "Koratron" finished cotton are treated together in a bath ratio of 1:20 for 20 min. at 30°C in a bath, which contains 0.1% of the brightener with formula (101), calculated for fiber goods and 0.5 g/l sodium fluorosilicate. After rinsing and drying, the three fiber materials have a strong lightening effect with good lightfastness. ;Example 24»;Boiled cotton fabric is treated in a bath ratio of 1:30 for ;60 minutes at room temperature in a bath of the following composition: 0.1% brightener with formula (101) or (110), calculated on fiber weight, ;2 g/ l active chlorine such as Javel lye. It is then rinsed and dechlorinated. After drying, compared to unlightened cotton, a very strong lightening effect is visible. Example 25 Bleached cotton poplin is impregnated with a urea-formaldehyde precondensate and ammonium nitrate, adding 1.5 g/l of the bis-stilbene compound of formula (101) to the solution. After the tissue has been squeezed to approx. 80% bath uptake, the resin is condensed out for 5 minutes at 150°C. You get brilliant whiteness and good curl resistance. ;Example 26. ;Bleached wool fabric is treated in bath ratio 1:4-0 for 60 min. ;in a bath containing 0.1 to 0.4% of one of the brighteners with formulas (101), (104) or (110), calculated on fiber weight and 4 g/l hydrosulphite. After rinsing and drying, you get strong lysjøång effects with good light fastness. You also get strong lightening effects when you add 5% acetic acid, calculated on fiber weight, to the bath instead of hydrosulphite. "Example 27" A polyamide fiber fabric (Perlon) is introduced in a bath ratio of 1:40 at 6o°C in a bath containing (calculated in fabric weight) 0.1% of one of the brighteners with formula (101), (110), (113), (117), (H8) or (124) as well as per liter 1 g of 80% acetic acid and 0.25 g of an addition product of 30 to 35 m°l of ethylene oxide to 1 mol of technical stearyl alcohol. It is heated to boiling temperature within 30 minutes and kept for "} 0 minutes when boiling. After rinsing and drying, a strong lightening effect with good light fastness is obtained. Instead of the weave of polyamide-6, one of polyamide-66 (nylon) is used. , then you get similarly good light effects. ;Finally, you can also work under HT conditions, for example for 30 minutes at 130° C. For this type of application, it pays to add 3 g/l hydrosulphite to the bath. ;Example 28. ;Polyacrylonitrile fibers (Orlon 42) are introduced in a bath ratio of 1:40 into an aqueous bath which per liter contains 1 g of 85% formic acid and 0.2% of the compound with formula (128), calculated on fiber weight. heats the treatment bath to boiling within 3° min. and continues for 30 to 60 minutes at this temperature. After rinsing and drying, polyacrylonitrile fibers with an excellent lightening effect are obtained. ;You also get a good lightening effect when treating Courtelle fibers according to this example. ; Example 29. ;Mon foularder at room temperature (approx. 20°C) a polyester fabric (e.g. "Dacron") with an aqueous dispersion which per liter contains 0.1 to 1 g of a bis-stilbene compound of formula ; (121) to (124) or (I4I) as well as 1 g of an impurity product; of approx. 35 m°l ethylene oxide to 1 mol octodecyl alcohol and drying at approx. 100°C. The dry material is then subjected for 30 seconds to a heat treatment at approx. 220°C. The polyester fabric treated in this way has a strong optical brightening effect. ;Example 30» ;One foulards at room temperature (approx. 20°C) a weave of polyvinyl chloride fibers ("Thermovyl") with an aqueous dispersion which per liter contains 1 to 2 g of the bis-stilbene compound with formula (113) as well as 1 g of an addition product of approx. 35 m°l ethylene oxide to 1 mol octodecyl alcohol and drying at approx. 70°C. The dry material is then subjected to 3 min. at 100°C a heat treatment. The fabric of polyvinyl chloride fibers treated in this way has a significantly higher softness content than an untreated fabric of polyvinyl chloride fibers. ;Example 31»;A web of cellulose acetate is placed in a bath ratio of 1:30 to 1:40 at 50°C in an aqueous bath containing 0.15% of the bis-stilbene compound of formula (128), intended for fiber goods. The temperature of the treatment bath is brought to 90 to 95°C and held for 30 to 45 minutes. at this temperature. After rinsing and drying, you get a good lightening effect. ;Example 32. ;10,000 g of a polyamide produced in a known manner from hexamethylenediamine adipate in cut form is mixed with 30 g of titanium dioxide (Rutile modification) and 5 g of a compound with the formulas (101), ;(134) or (119) in a roller tub for 12 hours. The thus treated cuts are melted in a boiler heated to 300 to 310°C with oil or diphenyl steam, after displacing the air oxygen with steam and stirred for 1/2 hour. The melt is then extruded under nitrogen pressure of 5 ato through a spinning nozzle and the thus spun cooled filament is wound up on a spinning coil. The threads formed show an excellent brightness effect and good washing and light fastness. If, instead of a polyamide produced from hexamethylenediamine adipate, a polyamide produced from £-caprolactam is used, correspondingly good results are obtained. ;Example 33. ;100 g of polypropylene "Fibergråd" is mixed well with 0.8 g of the compound with formula (14D or (I43) °S is melted at 280 to 290°C with stirring. The melt is spun according to melt spinning methods known per se , through ordinary spinning nozzles and stretched. Highly lightened polypropylene fibers are obtained. ;Example 34. ;100 g of polyester granules of terephthalic acid-ethylene glycol polyester are mixed well with 0.05 S of one of the compounds of formula (119), (135), (HD » (143) or (I45) and melted with stirring at 285°C. After spinning through ordinary spinning nozzles, highly lightened polyester fibers are obtained. ;One can also add the compounds with the formulas (H9), ;(135), (141), (143) or (I45) also before or during the polycondensation to polyester of the starting materials. ;Example 35. ;A good mixture of 100 parts polyvinyl chloride, 3 parts stabilizer (Advastat BD 100; Ba/Cd complex), 2 parts titanium dioxide , 59 parts of dioctyl phthalate and 0.01 to 0.2 parts of one of the compounds with fo The strips (119), (135), (141) or (I43) are rolled out on a calender at 150 to 155°C into a foil. The opaque polyvinyl chloride film produced in this way has a significantly higher whiteness content than a film which does not contain the optical brightener. ;Example 36. ;100 parts of polystyrene and 0.1 part of one of the compounds of the formula (H9), (134) °S (13$) are melted under exclusion of air for 20 minutes at 210°C in a tube of 1 cm diameter. After cooling, you get an optically lightened polystyrene mass with a good light net. Example 37. A pulp containing 100 parts bleached cellulose is added to the Hollenderen 2 parts resin glue. After 10 to 15 minutes, first add 0.05 tH 0>3 parts of one of the compounds with formula (101) or (110), which was dissolved in 20 parts of water, then after a further 15 minutes 3 parts of aluminum sulphate. The thus treated pulp then comes over the mixing bucket of the paper machine, whereupon the paper is produced in a known manner. The paper produced in this way shows an outstanding lighting effect of good light netting. ;Example 38. ;A paper pulp containing 100 parts of bleached cellulose, ;is added in the Hollenderen with 2 parts of resin glue. After 15 min. 3 parts of aluminum sulphate are also added. The paper web produced on the paper machine is now glued superficially with a "Size-Press", the adhesive being used is starch or alginate containing 0.05 to 0.3 parts of one of the compounds with the formulas (101) or (110). The paper thus formed has a very high whiteness content. ;Example 1 39 ;To a solution of 2.6 g of 4-methylbenzaldehyde and ;7.75 g of the phosphonium salt with formula ;;in 100 ml of absolute ethanol, 2.4 g of potassium tertiary butylate is added. The yellow solution immediately heats up to approx. 40°C, and after a few minutes a light beige precipitate occurs. Stir for 3 hours at room temperature, then heat briefly at 80°C and cool again. After extraction, washing with ethanol and washing and drying, 2.7 g of the compound with formula (134) are obtained. Melting point above 300°C. The phosphonium salt of formula (162) is available by reacting 4,4'-bis-chloromethyldiphenyl with triphenylphosphine in dimethylformamide in a yield of 90%. White powder: melting point above 300°C.*

Claims (3)

1. Bis-stilbene compounds for use as optical brighteners and which are colorless to at most slightly colored, characterized in that they correspond to formula in which at least one of the ring systems defined under FU and R^ or one of the substituents W-^ contains a sulfonic acid group, a sulfonic acid amide group or sulfonic acid ester group, a sulfonic group, a carboxylic acid group, carboxylic acid amide group or carboxylic acid ester group, a nitrile group or a methyl group, R^ means phenyl , diphenyl, α-or g-naphthyl or a residue Rj. means phenyl, diphenylyl, α- or g-naphthyl or a residue wherein V-^ and ' may be the same or different and mean a sulfonic acid group as well as their salts, esters, amides or halides, a carboxylic acid group. as well as its salts, esters or amides, the nitrile group, a sulfone group, a methyl group or hydroxyl group, Vp and 1 may be the same or different and mean hydrogen, an alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, halogen or a sulfonic acid group as well as their salts, esters or amides, and V-j and V-^' may be the same or different and mean hydrogen or an alkyl group with 1 to 4 carbon atoms, W-^ means a sulfonic acid group, as well as its salts, esters or amides, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a carboxyl group and its salts, esters or amides, the nitrile group or halogen, and where 1. one of the sylbols W-^ or V, and/or ' can mean a hydrogen atom, II. W-, is different from hydrogen if R-, and/or R^ means the diphenylyl radical. 2. Bis-stilbene compounds according to claim 1, characterized in that they have the formula in which means a sulfonic acid group and its salts, esters or amides or halides, a carboxylic acid group and its salts, esters or amides, nitrile group, a sulfonic group, a methyl group, a hydroxyl group, Vp means hydrogen, an alkyl group with 1-18 C atoms, an alkoxy group with 1-12 C atoms, halogen or a sulfonic acid group and their salts, esters or amides, and V-, means hydrogen or an alkyl group with 1- 4 C atoms.. 3. Bis-stilbene compounds according to claim 2, characterized in that they have the formula in which Vjj means a sulfonic acid group and its salts, esters or amides, a carboxylic acid group and its salts, esters or amides or the nitrile group, and V,- means hydrogen , a sulfonic acid group as well as its salts, esters or amides, an alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms.