CH560736A5 - Stilbene optical brighteners - for natural, synthetic and semi-synthetic textiles and as scintillators in photography - Google Patents

Abstract

The novel stilbene cpds. are of formula (I) sulpho or its salts, esters, amides or halides, carboxyl or its salts, esters or amides, CN, sulphonyl, Me or OH; V2 and V21 are each H, 1-18C alkyl, 1-12C alkoxy, halogen or sulpho or their salts, esters or amides; V3 and V31 are each H, or 1-4C alkyl; W1 are sulpho gps. or their esters, salts or amides, 1-4C alkyl or alkoxy, carboxyl gps. or their esters, salts or amides, CN or halogen; one of W1 and V1 and/or V11 may also be H; W1 is not H when R3 and/or R4 are diphenylyl). (I) are used as optical brighteners for textiles made of or contg. synthetic, semi-synthetic and natural materials for incorporation in amts. of pref. 0.0005-0.5%, at any convenient stage in the manufacture of the textile; as additives in soaps and detergents, in amts. of 0.005-1%, calc. on the total washing agent, marked brightening being obtained on cellulose fibres, polyamides, polyesters, wool, etc., in daylight. They are also useful as scintillators in photography, e.g. optical brightening of photographic layers, electrophotographic reproduction, supersensitisation.

Description

  

  
 



   The invention relates to the use of bis-stilbene compounds as optical brightening agents outside the textile industry.



   The subject of the main patent no. 513 785 is, in addition to a process for production, the use of bis-stilbene compounds outside the textile industry, which correspond to the formula (1) R1-CH = CH-X-CH = CG-R2, where X is an 4- and 4'-positions bonded to the = CH groups, optionally substituted, diphenylyl radical, R1 and R2, independently of one another, denote an optionally substituted phenyl or naphthyl radical, at least one of the ring systems R1, R2 and X being an optionally functionally modified one Sulfonic acid group, a sulfonic group, an optionally functionally modified carboxylic acid group, a nitrile group, a hydroxyl group, a mercapto group or a methyl group.



   The compounds of the formula (1) may at most be weakly colored and therefore contain no chromophoric groups such as nitro groups, azo groups and anthraquinone residues.



   The bisstilbene compounds of the formula (1) can be prepared by methods known per se. It is advantageous to proceed in such a way that, in a molecular ratio of 1: 2, compounds of the formula (2) Z1-X-Z1, with those of the formula (3) R-Z2 or

   (4) Z2R2 converts, where X is a diphenyl radical bonded to Z1 in the 4- and 4'-positions, R1 and R2 are a monocyclic benzene radical, a diphenyl radical or a naphthalene radical, one of the symbols Zl and Z is an O = CH group and the other one of the groupings of the formulas
EMI1.1
 where R is an optionally further substituted alkyl group, an aryl group, a cycloalkyl group or an aralkyl group, and where at least one of the ring systems present in the starting materials is an optionally functionally modified sulfonic acid group, a sulfonic acid group, an optionally functionally modified carboxylic acid group, a nitrile group, a hydroxyl group , contains a mercapto group or a methyl group,

   and that, if necessary, further reactions are carried out on these substituents.



   Accordingly, for example dialdehydes of the formula (8) O = CH-X-CH = O with monofunctional compounds of the formula (9) R1-V or monoaldehydes of the formula (10) Rl-CH = O with bifunctional compounds of the formula (II) Implement VXV, where X and R1 have the meaning given and V is one of the phosphorus-containing substituents of the formulas (5) (6) and (7).



   The phosphorus compounds of the formulas (9) and (11) required here as starting materials are obtained by adding halogenomethyl compounds, preferably chloromethyl compounds, of the formula (12) R1CH2-halogen, or



  (13) HalogenH2-XCH2-halogen with phosphorus compounds of the formulas
EMI1.2
 implements. In these formulas, R has the meaning given, radicals R bonded to oxygen preferably being lower alkyl groups, whereas R radicals bonded directly to phosphorus are preferably aryl radicals such as benzene radicals.



   Otherwise, both the reactions for the production of the starting materials and those for the production of the end materials can be carried out in the usual way.



   In a further development of the subject matter of the main patent, it was found that such compounds within the framework of the general formula (1) are particularly suitable for the stated purpose, which of the formula
EMI1.3
 correspond, in which R3 is diphenyl or a radical
EMI1.4

R4 phenyl, diphenylyl, c- or p-naphthyl or a radical
EMI2.1
 represents, and where V1 and V'1, which are the same or different, the sulfo group and their salts, esters, amides or halides, the carboxyl group and their salts, esters or amides, the nitrile group, a sulfonyl group, the methyl group or the hydroxyl group, V2 and V2, which are the same or different,

   Hydrogen, an alkyl group containing 1 to 18 carbon atoms, an alkoxy group containing 1 to 12 carbon atoms, halogen or the sulfo group and their salts, esters or amides, and Mg and V3, which are identical or different, hydrogen or a group containing 1 to 4 carbon atoms Alkyl group, W1 for the sulfo group, and their salts, esters or amides, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, the carboxyl group and their salts, esters or amides, the nitrile group or halogen, and where
I. one of the symbols W1 or V1 and / or V1, can always mean a hydrogen atom and
II. W1 is different from hydrogen if R3 and / or R4 stand for the diphenylyl radical.



   In the context of the present invention, esters, amides and halides thereof are primarily suitable as functionally modified sulfonic acid groups or carboxylic acid groups. While the phenyl (optionally substituted) and benzyl esters are of practical interest in the case of the esters of an aromatic or araliphatic nature, in the case of the aliphatic esters it is primarily alkyl esters with 1 to 18 carbon atoms that are suitable.



   Amides of the said acids should be understood as meaning not only the unsubstituted, but also the mono- and di-substituted representatives, it being possible for the substituting component to be aromatic (anilide), araliphatic and, in particular, aliphatic and cycloaliphatic. In this case too, aliphatic members generally have no more than 18 carbon atoms and can be substituted with hydroxyl groups, halogen atoms, alkoxy groups, nitrile groups, carboxy or carbalkoxy groups, sulfo groups, amino and alkylamino groups.



   Among the acid halides, the chlorides and bromides are particularly worth mentioning.



   Although the water-soluble types (alkali, ammonium or amine salts) are of predominant importance in the case of salts, other salts may be of particular interest in certain cases, e.g. Barium or calcium salts.



   The sulfones include the aryl sulfones and aralkyl sulfones such as phenyl and benzyl sulfone, and also alkyl sulfones with lower alkyl groups (1 to 4 carbon atoms).



   For the meaning of halogen as a substituent, fluorine and chlorine are particularly suitable.



   In the context of the above invention, the following groups of compounds can be used particularly advantageously:
Bis-stilbene compounds, which of the formula
EMI2.2
 correspond, where V1 is the sulfo group and their salts, esters, amides or halides, the carboxyl group and their salts, esters or amides, the nitrile group, a sulfonyl group or the methyl group or the hydroxyl group, V2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, a Alkoxy group containing 1 to 12 carbon atoms, halogen or the sulfo group as well as their salts, esters or amides and V2 represents hydrogen or an alkyl group containing 1 to 4 carbon atoms, W the sulfo group and salts thereof, esters or amides, an alkyl group with 1 to 4 Carbon atoms, an alkoxy group containing 1 to 4 carbon atoms,

   denotes the carboxyl group and their salts, esters or amides, the nitrile group or halogen, where one of the symbols W or V1 can furthermore denote a hydrogen atom.



   Bis-stilbene compounds, which of the formula
EMI2.3
 correspond, where V1 is the sulfo group and their salts, esters, amides or halides, the carboxyl group and their salts, esters or amides, the nitrile group, a sulfonyl group, the methyl group or the hydroxyl group, V2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, an alkoxy group containing 1 to 12 carbon atoms, halogen or the sulfo group and their salts, esters or amides and Vs represents hydrogen or an alkyl group containing 1 to 4 carbon atoms.

 

     Bis-stilbene compounds, which of the formula
EMI2.4
 correspond, where V4 denotes the sulfo group and their salts, esters or amides, the carboxyl group such as their salts, esters or amides or the nitrile group, and V5 denotes hydrogen, the sulfo group and their salts, esters or amides, an alkyl group with 1 to 4 carbon atoms or represents an alkoxy group having 1 to 4 carbon atoms
Bis-stilbene compounds, which of the formula
EMI2.5
 correspond, in which V6 denotes the sulfo group, its salts or amides.



   Bis-stilbene compounds, which of the formula
EMI2.6
  correspond, in which R5 is either a naphthyl radical or the radical
EMI3.1
 and where V2 denotes hydrogen, an alkyl group containing 1 to 18 carbon atoms, an alkoxy group containing 1 to 12 carbon atoms, halogen or the sulfo group and their salts, esters or amides, and V, hydrogen or an alkyl group containing 1 to 4 carbon atoms represent, and W1 for the sulfo group and their salts, esters or amides, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, the carboxyl group and their salts, esters or amides,

   represents the nitrile group or halogen
Within the above formulas and the corresponding claims, the definition of the substituents V and W is always to be understood in the context of the definition of formula (1), ie, if substituents V1, V2, V, or W1 assume the meaning of hydrogen, must nevertheless the condition of the presence of at least one of the obligatory substituents [an optionally functionally modified sulfonic acid group, a sulfonic group, an optionally functionally modified carboxylic acid group, a nitrile group, a hydroxyl group, a mercapto group or a methyl group] must always be met.



   For the preparation of the compounds to be used according to the invention, essentially two variants of the principle which are the same can be considered. They are characterized by the fact that either in a molecular ratio of 1: 2 compounds of the formula
EMI3.2
 with compounds of the formula R3-CHO or R4-CHO or in a molecular ratio of 1: 2
EMI3.3
 with those of the formula R3-Z3 or Z3-R4.

  Here, R3, R4 and W1 have the meaning given under formula (1) and Z3 represents one of the groupings of the formulas
EMI3.4
 represents, in which R is an optionally further substituted alkyl radical, an aryl radical, a cycloalkyl radical or an arallcyl radical
The reaction is carried out in both cases by reacting the components in the presence of a strongly basic alkali compound and in the presence of a preferably hydrophilic, strongly polar solvent, and in the case of using alkali hydroxides as the strongly basic alkali compound, these alkali hydroxides may have a water content of up to 25% .



   In a corresponding manner, a process for the preparation of compounds of the formula (19) is characterized in that the dialdehyde of the formula is used in a molecular ratio of 1: 2
EMI3.5
 with a compound of the formula
EMI3.6
 converts, or in a molecular ratio of 1: 2 a compound of the formula
EMI3.7
 with a compound of the formula
EMI3.8
 converts, the reaction being carried out as described above in both cases.



   Compounds of the formula (22) are obtained in a corresponding manner by adding an aldehyde of the formula
EMI3.9
  with a compound of the formula
R5-Z3 converts, or a compound of the formula
EMI4.1
 with an aldehyde of the formula Rs-CHO, the reaction being carried out as characterized above.



   The new compounds defined above show a more or less pronounced fluorescence in the dissolved or finely divided state. They can be used for the optical brightening of a wide variety of synthetic, semi-synthetic or natural organic materials outside the textile industry or substances which contain such organic materials.



   For this purpose, the following groups of organic materials outside the textile industry should be mentioned, for example, without the following overview expressing any restriction thereto, insofar as an optical brightening of the same is possible:
I. Synthetic organic high molecular materials:

   a) Polymerization products based on organic compounds containing at least one polymerizable carbon-carbon double bond, i.e. their homopolymers or copolymers and their aftertreatment products such as crosslinking, grafting or degradation products, polymer blends or products obtained by modifying reactive groups, for example polymers based on unsaturated carboxylic acids or derivatives of such carboxylic acids, especially acrylic compounds (such as e.g.

  Acrylic esters, acrylic acid, acrylonitrile, acrylamides and their derivatives or their methacrylic analogues), olefin hydrocarbons (such as ethylene, propylene, styrenes or dienes, also so-called ABS polymers) or polymers based on vinyl and vinyliene compounds ( such as vinyl chloride, vinyl alcohol, vinylidene chloride).



   b) polymerization products obtainable by ring opening, e.g. Polyamides of the polycaprolactam type, as well as polymers that are obtainable both via polyaddition and polycondensation, such as polyethers or polyacetals.



   c) Polycondensation products or precondensates based on bi- or polyfunctional compounds with condensable groups, their homo- and mixed condensation products, as well as post-treatment products, such as polyesters, especially saturated (e.g. ethylene glycol terephthalic acid polyesters) or unsaturated (e.g.



     Maleic acid-dialcohol polycondensates and their crosslinking products with polymerizable vinyl monomers), unbranched and branched (also based on higher alcohols such as alkyd resins), polyesters, polyamides (e.g.



  Hexamethylenediamine adipate), maleinate resins, melamine resins, their precondensates and analogues, polycarbonates or silicones.



   d) Polyaddition products such as polyurethanes (crosslinked and uncrosslinked) or epoxy resins.



   II. Semi-synthetic organic materials (if they are treated outside of the textile industry), e.g. Cellulose esters of various degrees of esterification (so-called 21/12 acetate, triacetate) or cellulose ethers, regenerated cellulose (viscose, copper ammonia cellulose) or their aftertreatment products, as well as casein plastics.



   III. Natural organic materials of animal or vegetable origin (insofar as their treatment takes place outside the textile industry), for example based on cellulose or proteins, for example natural varnish resins, starch, casein.



   The organic materials to be optically brightened can belong to the most diverse processing states (raw materials, semi-finished products or finished products). On the other hand, they can be in the form of the most varied of structured structures, ie. For example, as predominantly three-dimensionally extended bodies such as plates, profiles, injection moldings, various types of workpieces, chips, granulates or foams, furthermore as predominantly two-dimensional bodies such as films, foils, lacquers, coatings, impregnations and coatings or as predominantly one-dimensional bodies such as endless -Threads, bristles, flakes, wires.

  On the other hand, the said materials can also be used in unshaped states in the most disagreeable homogeneous or inhomogeneous forms of distribution, e.g. in the form of powders, solutions, emulsions, dispersions, latices, pastes or waxes.



   Fiber materials can be present, for example, as endless threads (drawn or undrawn), staple fibers, flocks, nonwovens, felts, wadding, flocked structures or as composite materials, paper, cardboard or paper pulps.



   The stated optical brightening agents can advantageously be applied from an aqueous medium in which the compounds in question are in finely divided form (suspensions, so-called microdispersions, optionally solutions). If appropriate, dispersants, stabilizers, wetting agents and other auxiliaries can be added during the treatment. Depending on the type of brightener compound used, it may prove advantageous to work preferably in a neutral, alkaline or acid bath. The treatment is usually carried out at temperatures of about 20 to 1400C, for example at the boiling point of the bath or in the vicinity (about 90 C).

  Under certain circumstances, solutions or emulsions in organic solvents can also be considered for applications outside the textile industry, as is known from dyeing practice in so-called solvent dyeing (padding thermofixing application, exhaust dyeing process in dyeing machines).



   The new optical brightening agents according to the present invention can in particular be added to or incorporated into the materials before or during their deformation. For example, they can be added to the molding compound or injection molding compound in the production of films, foils (e.g. rolling in polyvinyl chloride in the heat) or moldings.

 

   If fully or semi-synthetic organic materials are shaped by spinning processes or spinning masses, the optical brighteners can be applied according to the following processes: - Addition to the starting substances (e.g. monomers) or intermediate products (e.g. precondensates, prepolymers), ie before or during the Polymerization, polycondensation or polyaddition, - powdering onto polymer chips or granules for spinning masses, - bath coloring of polymer chips or granules for spinning masses, - metered addition to spinning melts or spinning solutions, application on tow before drawing.



   The new optical brightening agents according to the present invention can also be used, for example, in the following application forms: a) In mixtures with dyes (nuances) or pigments (color or, in particular, e.g. white pigments).



   b) In mixtures with wetting agents, plasticizers, swelling agents, antioxidants, light stabilizers, heat stabilizers, chemical bleaching agents (chlorite bleach, bleaching bath additives).



   c) Incorporation of the optical brightening agents into polymeric carrier materials (polymerization, polycondensation or polyaddition products) in dissolved or dispersed form for use e.g. in coating, impregnating or binding agents (solutions, dispersions, emulsions) for nonwovens, paper, leather.



   d) As additives to so-called master batches.



   e) As additives to a wide variety of industrial products in order to make them more marketable (e.g. aspect improvement of soaps, detergents, pigments).



   f) In combination with other optically brightening substances.



   g) In spin bath preparations, i.e. as additives to spinning baths, such as those used to improve the lubricity for the further processing of synthetic fibers, or from a special bath before the fibers are drawn.



   h) As scintillators, for various purposes of the photographic type, e.g. optical brightening of photographic layers (possibly in combination with white pigments), for electrophotographic reproduction or supersensitization.



   In certain cases, the brighteners are brought to their full effect by a subsequent treatment. This can be, for example, a chemical (e.g. acid treatment), a thermal (e.g. heat) or a combined chemical / thermal treatment.



   The amount of the new optical brighteners to be used according to the invention, based on the material to be optically brightened, can vary within wide limits. Even with very small amounts, in certain cases e.g. those of 0.0001 percent by weight, a clear and durable effect can be achieved. However, amounts of up to about 0.8 percent by weight and optionally up to about 2 percent by weight can also be used. For most practical purposes, amounts between 0.0005 and 0.5 weight percent are preferably of interest.



   The new optical brightening agents are also particularly suitable as additives for washing baths or for commercial and household detergents, and they can be added in various ways. They are expediently added to washing baths in the form of their solutions in water or organic solvents or also in finely divided form as aqueous dispersions. For household or commercial detergents, they are advantageously used at any stage of the detergent manufacturing process, e.g. added to the so-called slurry before atomizing the washing powder or when preparing liquid detergent combinations.



  The addition can take place either in the form of a solution or dispersion in water or other solvents or without auxiliaries as a dry brightener powder. The lightening agents can, for example, be mixed, kneaded or ground with the washing-active substances and thus mixed with the finished washing powder. However, they can also be dissolved or predispersed and sprayed onto the finished detergent.



   The detergents used are the known mixtures of active detergent substances such as soap in the form of chips and powder, synthetics, soluble salts of sulfonic acid half-esters of higher fatty alcohols, higher and / or polyalkyl-substituted arylsulfonic acids, sulfocarboxylic acid esters of medium to higher alcohols, fatty acid acylaminoalkyl or phosphoric acid sulfonates of fatty acid alcoholsulfonates of fatty acid alcohols, etc. , in question. As building materials, so-called builders, e.g. Alkali poly and polymetaphosphates, alkali pyrophosphates, alkali salts of carboxymethyl cellulose and other soil redeposition inhibitors, also alkali silicates, alkali carbonates, alkali borates, alkali perborates, nitrilotriacetic acid, ethylenediaminetetraacetic acid, alkanol stabilizers of higher fatty acids, such as alkanol stabilizers.

  The detergents can also contain, for example, antistatic agents, moisturizing skin protection agents such as lanolin, enzymes, antimicrobials, perfumes and dyes.



   The new optical brighteners have the particular advantage that they can also be used in the presence of active chlorine donors, e.g. Hypochlorite, are effective and without significant loss of the effects in washing baths with non-ionic detergents, e.g. Alkyl phenol polyglycol ethers. can be used.



   The compounds according to the invention are added in amounts of 0.005 to 1% or more, based on the weight of the liquid or powdery, finished detergent. When washing textiles made of cellulose fibers, polyamide fibers, highly refined cellulose fibers, polyester fibers, wool, etc.



  a brilliant aspect of daylight.



   The washing treatment is carried out, for example, as follows:
The specified textiles are treated for 1 to 30 minutes at 20 to 100 ° C. in a washing bath which contains 1 to 10 g / kg of a built-up, composite detergent and 0.05 to 1%, based on the weight of the detergent, of the claimed brightening agent. The liquor ratio can be 1: 3 to 1:50. After washing, it is rinsed and dried as usual. The washing bath can contain 0.2 g / l active chloride (eg as hypochlorite) or 0.1 to 2 g / l sodium perborate as a bleach additive .



   In the following manufacturing instructions and examples, unless otherwise stated, parts are always parts by weight and percentages are always percentages by weight. Unless otherwise noted, melting and boiling points are uncorrected.



   Manufacturing regulations
I) A solution of 32.7 g of the sodium salt of benzaldehyde-2-sulfonic acid with a content of about 70% is added to a suspension of 60 g of potassium tert-butoxide in 125 ml of anhydrous dimethylformamide with stirring at 40 to 50 "C. Free sulfonic acid and 22.7 g of 4,4'-bis- (diethoxyphosphonomethyl) -diphenyl in 50 ml of anhydrous dimethylformamide (a small insoluble residue is removed by filtration) was added dropwise over the course of 40 minutes, a red-brown suspension in a slightly exothermic reaction The reaction mixture is stirred for a further hour at 40 to 50 ° C. and then poured into 2.5 liters of cold water.

  The resulting pale yellow, cloudy solution is heated to the boil, filtered and 375 g of sodium chloride are added to the hot filtrate. The light yellow product crystallizes out on cooling. It is made twice from a mixture of 900 ml of water and 90 ml of glacial acetic acid with the addition of 18 g of sodium chloride, once from a mixture of 100 ml of dimethylformamide and 1000 ml of water with the addition of 150 g of sodium chloride u. recrystallized twice from 900 ml and 500 ml of ethanol.



   Yield: About 4.0 g (14.2% of theory) of the compound of the formula
EMI6.1
 light yellow, fine needles.



   The 4,4'-bis (diethoxyphosphonomethyl) diphenyl used as starting material can be obtained in the following way:
301 g of 4,4'-bis-chloromethyldiphenyl in 1200 ml of xylene are added to 420 g of triethyl phosphite at 142 to 146 ° C. over the course of one hour: The reaction mixture is refluxed for 20 hours and the solvent is then distilled off at normal pressure. After adding a further 410 ml of triethyl phosphite, the reaction mixture is refluxed for a further 20 hours. The excess triethyl phosphite is distilled off under normal pressure, the reaction mixture is cooled to 120 ° C., 500 ml of toluene are added and the mixture is cooled to room temperature, the product crystallizing and being isolated by filtration .

  After recrystallization from toluene, 361.5 g (66.3 of theory) of 4,4'-bis (diethoxyphosphonomethyl) diphenyl of the formula are obtained
EMI6.2
 as white crystal powder with a melting point of 108 to 110 "C.



   II) To a well stirred suspension of 126.5 g of potassium hydroxide powder with a content of about 89% in 500 ml of anhydrous dimethylformamide, a homogeneous mixture of 113.5 g of 4,4'-bis (diethoxyphosphonomethyl ) Diphenyl and 129 g of the sodium salt of benzaldehyde-2-sulfonic acid with a content of about 86% of free sulfonic acid slowly entered. The temperature gradually rises to 45 ° C. and is kept at 40 to 45 ° C. by cooling with ice. Stirring is then continued for 3 hours at 40 to 45 ° C.

  The reaction mixture is poured into 3.5 l of distilled water at about 70 ° C. 1.5 kg of sodium chloride and about 1.5 kg of ice are added to the slightly cloudy solution formed, the temperature of the pale yellow suspension falling to about 25 ° C . The pH of the suspension is adjusted to about 7 by adding 37% hydrochloric acid, stirring is continued for one hour at room temperature, suction filtered and the product is washed with 23% sodium chloride solution. After drying, about 158 g of crude product are obtained which contain 21% sodium chloride and 125 g of the compound of the formula (101), corresponding to a yield of 89% of theory.

  Recrystallization of the moist filter cake from ethanol gives about 117 g of pure product with a sodium chloride content of 13%, corresponding to a rem yield of 72% of theory. The product of the formula (101) can be obtained salt-free by further recrystallization from alcohol.



  Analysis for C2H20Na2OS2: calc .: C 59.78 H 3.58 S 11.40 found: C 59.62 H 3.54 S 11.19
Instead of 113.5 g of 4,4'-bis- (diethoxyphosphonomethyl) -diphenyl, 99.6 g of 4,4'-bis- (dimethoxy phosphonomethyl) -diphenyl and 116 g of the sodium salt of benzaldehyde-2-sulfonic acid are used with a content of about 88% of free sulfonic acid and if the process is carried out as described above, but with a reaction time of 5 hours, about 163 g of crude product with a sodium chloride content of 24.5%, corresponding to a yield of 87% of theory, are obtained.

  By dissolving the crude product in 1600 ml of boiling distilled water, clarifying filtration, rinsing with 400 ml of boiling distilled water, adding 400 g of sodium chloride to the clear filtrate, cooling, suction filtering and drying the crystallized product, about 147 g of pure product of the formula (101) are obtained with a sodium chloride content of 18%, corresponding to a pure yield of 86% of theory.



   If, in this process, an equivalent amount of sodium hydroxide with a content of about 98% is used instead of potassium hydroxide, the product of the formula (101) is obtained with a crude yield of 73% and a pure yield of 70% of theory.



   Instead of potassium hydroxide or sodium hydroxide, sodium methylate can also be used with good results.



   Finally, instead of dimethylformamide, dimethyl sulfoxide can also be used as the solvent. In this case, a concentrated aqueous solution of potassium hydroxide (e.g. 50%) can also be used as the condensing agent, the water content of the reaction mixture being about 8%.



   The 4,4'-bis- (dimethoxyphosphonomethyl) -di phenyl used can be obtained as follows:
A mixture of 261 g of 4,4'-bis- (chloromethyl) diphenyl and 372 g of trimethylphosphine is stirred at reflux temperature (117 to 119 "C) until the evolution of methylene chloride has ended, which takes about 8 hours The excess trimethyl phosphite is distilled off in vacuo, the clear, colorless solution is diluted with 600 ml of toluene and allowed to crystallize. After suction filtering, washing with a little toluene and drying, 358 g (90% of theory) bis (dimethoxyphosphonomethyl) diphenyl of the formula are obtained
EMI6.3
 as colorless crystals with a melting point of 129 to 1300C. A sample recrystallized on toluene for analysis melts at 130 to 131 "C.



  Analysis for Cl8H2406P2 (398.33): Calculated: C 54.28 H 6.07 P 15.55 found: C 54.53 H 6.02 P 15.39
If the equivalent amount of triethyl phosphite is used instead of trimethyl phosphite, bis (diethoxyphosphonomethyl) diphenyl of the formula (102) is obtained as colorless crystals with a melting point of 107 to 1090 ° C in a yield of 89% of theory at a final temperature of 1600C. A sample recrystallized from toluene melts at 108 to 11,000.



  Analysis C22HS2P20; (454.44): calc .: C 58.15 H 7.10 P 13.63 found: C 57.89 H 7.22 P 13.64
The 4,4'-bis-chloromethyl-diphenyl used as starting material is prepared as follows:
Into 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 stream of hydrogen chloride is introduced with very good stirring, whereby a temperature of 50 "is achieved by external cooling until all reactants have dissolved. C., then for 24 hours a temperature of 300 ° C. The bis-chloromethyl-diphenyl formed continuously crystallizes out.

  After suction filtering at 15 "C, washing with cyclohexane and water and drying in vacuo at 70" C, 1580 g (63% of theory) bis-chloromethyl-diphenyl are obtained as a colorless, crystalline powder with a melting point of 132 to 135 "C.



     III) 113.5 g of 4,4'-bis (diethoxyphosphonomethyl) -diphenyl and 222 g of disodium salt of benzaldehyde-2,4-disulfonic acid with a content of about 70% free acid are in 800 ml of anhydrous dimethylformamide and 126 g of potassium hydroxide powder according to Example 2 implemented. After a reaction time of one hour, the thick reaction mixture is poured into 1.4 liters of distilled water at about 80 "C, the cloudy solution is clarified by filtration, the filtrate is cooled to 15" C and the like. mixed with 5 1 itthanol. The product which has crystallized out is filtered off with suction and dried under vacuum. Yield: about 113 g (59.3% of theory, calculated on the tetrasodium salt).



   The pure tetrasodium salt of the formula (104) is obtained by recrystallization from water / ethanol, conversion into the free tetrasulfonic acid using an ion exchanger and neutralization with sodium hydroxide solution.
EMI7.1

Fine, light yellow needles.



  Analysis for C28Hl8Na40.2S4: calc .: C 43.87 H 2.37 S 16.73 found: C 43.39 H 2.67 S 16.17
In a manner similar to that described in the preceding examples, the bis-stilbene compounds listed in the table below of the formula
EMI7.2
 being represented.



   The sodium salt of 5-formyl-2-methylbenzene-sulfonic acid used as starting material for the bis-stilbene compound of the formula (111) can be obtained by sulfonating 4-methylbenzaldehyde with oleum with 66% SOa content and purifying it via the barium salt can be obtained. In the same way, the sodium salt of 5-For myl-2-methoxybenzenesulfonic acid used as the starting material for the bis-stilbene compound of the formula (112) is obtained from 4-methoxybenzaldehyde.

 

  No. R powder color
EMI7.3


<tb> <SEP> S03Na
<tb> 106 <SEP> <<SEP> light yellow
<tb> <SEP> S03Na
<tb> la7-C1
<tb> <SEP> yeast yellow
<tb> S03Na
<tb> 108 <SEP> yellow
<tb> <SEP> SO <SEP> 3Na
<tb> 109 <SEP> COONa
<tb> 109 <SEP> I <SEP> green-tinted-gdb
<tb> <SEP> SO, well.
<tb>



  110 <SEP> q <SEP> pale yellow
<tb> <SEP> SO3Na
<tb> 111 <SEP> q <SEP> 3 <SEP> pale grXy tinge
<tb> <SEP> SO <SEP> 3Na <SEP> yellow
<tb> 112 <SEP> q <SEP> -OCK,
<tb> 112 <SEP> 1 <SEP> 3 <SEP> pale green cast
<tb> <SEP> SO3Na <SEP> yellow
<tb> 113 <SEP> - <SEP> oSO <SEP> Na <SEP> light beige
<tb> <SEP> 3
<tb> <SEP> SODNg
<tb> 113a <SEP> to <SEP> light yellow
<tb> <SEP> SO3Na
<tb> IV) 200 g of the compound of the formula (101) are heated in 1000 ml of dry chlorobenzene with stirring and the addition of 500 ml of thionyl chloride and 1 ml of dimethylformamide to 950 ° C. within 35 minutes and stirred at 95 to 1000 ° C. for 20 hours. It is then cooled, the product which has crystallized out is filtered off with suction and recrystallized from dry chlorobenzene.



   Yield: about 117.3 g (60.4% of theory) of the compound of the formula
EMI8.1

Shiny yellow leaves. Melting point: 236 to 237 C.



  Analysis for C28H20C1204S2: calc .: C 60.54 H 3.63 C1 12.76 found: C 60.57 H 3.92 C1 12.63
In an analogous manner, the sulfochloride of the formula
EMI8.2

Yellow shiny leaves. Melting point) 300 C can be obtained.



   Likewise, sulfochlorides of the formulas are obtained in an analogous manner from the compounds of the formulas (104), (110) and (111)
EMI8.3

V) 11.1 g of the compound of the formula (115) are dissolved in 150 ml of dimethylformamide for 2 hours with stirring
Heated between 145 and 150 C. It is then cooled to 80 ° C., 150 ml of ethanol are added, the mixture is cooled to 5 ° C., the product which has crystallized out is suction filtered, recrystallized from 400 ml of dimethylformamide and dried under vacuum.



   Yield 4.5 g of the compound of the formula Analysis for Cs2HN2o6S2: 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
Dissolving the compound of the formula (117) in dimethylformamide / water and adding 30% strength sodium hydroxide solution to the hot solution gives the sodium salt of the formula (113).



  Analysis for C28H20Na2OS2: calc .: C 59.78 H 3.58 S 11.40 found: C 59.55 H 3.82 S 11.09
By dissolving the compound of the formula (101) in water and adding barium or calcium chloride, the corresponding barium or calcium salt is obtained.



   If the solution of the compound of the formula (101) is treated with a strongly acidic ion exchanger, a solution of the free sulfonic acid is obtained which can be isolated by evaporation. The corresponding amine salts can be obtained by neutralization with amines, for example the diethanolammonium salt with diethanolamine.



   VI) 27.8 g of the compound of the formula (114) are dissolved in 300 ml of dry chlorobenzene at 120 ° C. with stirring.



  A moderate stream of dry ammonia is then passed in for 30 hours. After cooling, the crystallized product is filtered off with suction and recrystallized twice from dimethylformamide / water.



   Yield 16.2 g of the compound of formula
EMI8.4

Pale yellow fine leaflets. Melting point: 280.5 to 282 C.



  Analysis for C28H24N204S2: calc .: 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., 20.7 g of the compound of the formula (119) are obtained after recrystallization from dimethylformamide
EMI8.5

Light yellow, shiny leaves. Melting point: 280 to 281 C.
EMI8.6
  



   If, instead of introducing dimethylamine, 42 g of diethanolamine are added dropwise at 60 ° to 650 ° C. and then heated to 120 ° to 1250 ° C. for one hour, 8.0 g of the compound of the formula are obtained after recrystallization from dimethylformamide / ethanol with the addition of activated carbon
EMI9.1

Pale yellow needles, melting point: 232 to 233 OC.



   VII) 13.9 g of the compound of the formula (114) are introduced into 200 ml of n-octylamine and heated to 75 to 80 ° C. for 45 minutes with stirring. The pale yellow solution is cooled, 100 ml of methanol are added, the precipitated product is suction filtered and recrystallized twice from chlorobenzene with the addition of fuller's earth.



   Yield: 10.4 g (corresponding to 56.3% of theory) of the compound of the formula
EMI9.2

Colorless crystal powder. Melting point: 143.5 to 1440C.



   The bis-stilbene compounds of the formula (105) listed in the following table can be prepared in a similar manner.



   Enamel
No. R point C
EMI9.3
   Melting r. R point cm
EMI9.4
  
VIII) 27.8 g of the compound of the formula (114) are slowly added to a solution of 40.8 g of 3-dimethylamino-1-propylamine in 300 ml of ethanol at room temperature, while stirring. The mixture is then stirred for 5 hours at 55 to 60 ° C., cooled, the product which has crystallized out is filtered off with suction, washed with water and ethanol and dried under vacuum. Yield: 33.5 g (corresponding to 97.7% of theory) of the compound of the formula
EMI10.1

After two recrystallizations from dimethylformamide / water with the addition of activated charcoal, 25.0 g (72.8% of theory) of yellow flakes with a melting point of 164.5 to 165.5 ° C. are obtained.



  Analysis for C; eHN4o4s2 calcd .: C 66.44 H 6.75 N 8.16 S 9.34 found: C 66.25 H 6.78 N 7.89 S 9.41
13.7 g of the compound of the formula (128) are refluxed in 1500 ml of methanol with 15 ml of dimethyl sulfate for 4 hours. 700 ml of methanol are then distilled off, the product of the formula
EMI10.2
 precipitates in the form of almost colorless crystals.



   Melting point after recrystallization from methanol / hexane 254 to 256 "C.



   In a similar manner, the compound of the formula is obtained from the compound of the formula (116a)
EMI10.3
  and therefrom the compound of the formula
EMI11.1

IX) 13.9 g of the compound of the formula (114) are slowly introduced into a solution of 9.4 g of phenol in 100 ml of anhydrous pyridine at room temperature with stirring. The mixture is then heated to 95 to 105 ° C. for 2 hours, cooled to 50 ° C., the residue is filtered off, 200 ml of hexane are added to the clear filtrate, the precipitated product is suction filtered, dried, extracted twice with boiling water, dried again and recrystallized from chlorobenzene. The product is dissolved in 200 ml of dioxane, clarified by filtration, admixed with 300 ml of ethanol and 50 ml of water and allowed to crystallize.



  1.2 g of the compound of the formula are obtained
EMI11.2
 Pale yellow needles. Melting point: 241 to 241.50C.



  Analysis for CioH3006S2: calc .: C 71.62 H 4.51 S 9.56 found: C 71.36 H 4.72 S 9.65
The corresponding p, p 'and m, m' compounds are obtained in a similar manner from the compounds of formulas (115) and (116a).

 

   X) 20 g of the crude sulfochloride of the formula (116) are introduced into 800 ml of methyl cellosolve and 100 ml of 24% ammonium hydroxide solution with stirring and the heated to 90 to 950 ° C. for 4 hours. The cloudy solution is filtered clear, concentrated with 800 ml of water and 50 ml. Hydrochloric acid added.



  The precipitated product is filtered off with suction and washed neutral with water. dried and recrystallized from dimethylformamide / water. 1.0 g of the compound of the formula is obtained
EMI11.3
 Yellow plates. Melting point) 3000C.



  Analysis for C28H26N408S4: calc .: C 49.84 H 3.88 S 19.01 found: C 49.77 H 4.03 S 18.92
XI) 10 g of the crude compound of the formula (116) are suspended in 200 ml of chlorobenzene with stirring and dimethylamine is passed in at about 60 ° C. for 6 hours. After cooling, it is suction filtered and made of dimethylformamide / ethanol, respectively. Dioxane / ethanol recrystallized. 1.9 g of the compound of the formula are obtained
EMI12.1
 Yellow crystal powder. Melting point: 257.5 to 2580C.



  Analysis for C36H42N4O8S4: calc .: C 54.94 H 5.38 S 16.30 found: C 54.68 H 5.37 S 16.12
XII) 10 g of the crude sulfochloride of the formula (116) are heated to 75 to 80 ° C. in 200 ml of ns-octylamine with stirring for 3 hours. The cloudy solution is clarified by filtration, cooled, a little water and 1.5 l of methanol are added, the precipitated product is filtered off and isolated from dimethylformamide! Recrystallized water. Yield: 3.9 g of the compound of the formula
EMI12.2
 Lemon yellow needles. Melting point: 255 to 256 C.



  Analysis for Ca0Hs0N4O8S4: calc .: C 64.14 H 8.07 N 4.99 S 11.41 found: C 64.12 H 8.20 N 5.00 S 11.42
XIII) 22.7 g of 4,4'-bis (diethoxyphosphonomethyl) -diphenyl and 14.4 g of p-toluene aldehyde are dissolved in 100 ml of anhydrous dimethylformamide with heating. After cooling to 200 ° C., 20 g of 30% strength methanolic sodium methylate solution are added dropwise with stirring over the course of 15 minutes, the temperature rising to 48 ° C. and a pale yellow, thick suspension being formed. The mixture is stirred for a further hour, diluted with 50 ml of methanol, neutralized with glacial acetic acid and the product which has crystallized out is filtered off with suction.

  After recrystallization from a mixture of 600 ml of dimethylformamide and 1200 ml of trichlorobenzene, 12.2 g (63.3% of theory) of 4,4'-bis (p-methylstyryl) diphenyl of the formula are obtained
EMI12.3
 in the form of shiny, pale yellow leaflets. Melting point:> 300 C.



  Analysis for C, 0H26: calc .: C 93.22 H 6.78 found: C 92.98 H 6.64
XIV) 22.7 g of 4,4'-bis (diethoxyphosphonomethyl) diphenyl and 15.7 g of p-cyanobenzaldehyde are dissolved in 100 ml of anhydrous dimethylformamide at 40 ° C. with stirring. Then, within 20 minutes, 20 g of 30% strength methanolic sodium methylate solution was added dropwise so that the temperature does not rise above 500C.

  The resulting orange suspension is stirred for a further 5 hours at 45 to 500C, cooled to room temperature, the product which has crystallized out is suction filtered, the filter material is washed well with methanol and made from a mixture of 500 ml of trichlorobenzene and 250 ml of dimethylformamide or from 500 ml of trichlorobenzene with the aid of Fuller's earth recrystallized
Yield: 4.2 g (20.6% of theory) of the compound of the formula
EMI13.1

Yellow crystal powder. Melting point: 276 to 277 "C.



  Analysis: C, 0H20N2: calc .: C 88.21 H 4.94 N 6.86 found: C 88.08 H 5.15 N 6.92
XV) A solution of 3.9 g of methyl benzaldehyde-4-carboxylate and 5.0 g of 4,4'-bis is added to a suspension of 13.2 g of potassium tert-butoxide in 200 ml of anhydrous dimethylformamide with stirring at 40 to 50 "C. - (diethoxyphos phonomethyl) diphenyl in 20 ml of anhydrous dimethylformamide is added dropwise. The resulting, yellow, thick suspension is stirred for a further 4 hours at 40 to 45 ° C.



  cooled and the product sucked off. After recrystallization from a mixture of 1000 ml of trichlorobenzene and 500 ml of dimethylformamide, or from 500 ml of dimethylformamide, 1.0 g (19.2% of theory) of the compound of the formula is obtained
EMI13.2
 as yellow crystal powder.



   Melting point:> 3000C.



   51.6 g of the diester of the formula (136) are stirred in 1500 ml of methyl cellosolve with 60 g of a 30% strength aqueous sodium hydroxide solution for 5 hours at 95 to 100.degree.



  After cooling and suction filtration, the disodium salt obtained is converted into the free dicarboxylic acid by acidification with aqueous hydrochloric acid. You suck on, wash with water and dry.



   13.4 g of the dicarboxylic acid are heated to 95 ° C. in 200 ml of chlorobenzene and 0.5 ml of dimethylformamide with 20 ml of thionyl chloride and stirred at 95 to 100 ° C. for 3 hours. The reaction product obtained after cooling is recrystallized twice from o-chlorobenzene: 7.3 g (50.3% of theory) of the compound of the formula
EMI13.3
 as yellow, shiny leaves.



   Melting point: 281 to 283 "C.



  Analysis for C80H20O2C: calc .: C 75.54 H 4.17 Cl 14.67 found: C 74.72 H 4.17 Cl 14.50
4.85 g of the compound of the formula (136a) are stirred in 200 ml of chlorobenzene for 6 to 7 hours at 55 to 60 ° C. while passing in dry dimethylamine. After cooling, suction filtering, washing with methanol and drying, 4.8 is obtained g (96% of theory) of the compound of the formula
EMI14.1
 in the form of light-colored, green-tinted, fine needles that melt above 300 "C and can be further purified by recrystallization from o-dichlorobenzene or dimethylformamide.



   If monomethylamine is used instead of dimethylamine, the compound of the formula is obtained
EMI14.2

XVI) In a suspension of 25.5 g of potassium hydroxide powder with a water content of about 12% in 120 ml of dimethylformamide, a solution of 22.7 g of 4,4'-bis- (diethoxyphosphonomethyl) -diphenyl is added with stirring at 40 to 45 ° C and 14.4 g of p-toluene aldehyde in 50 ml of dimethylformamide are added dropwise. The resulting yellow suspension is stirred for a further 2 hours at 40 to 45 ° C., after adding 500 ml of water it is suction filtered and the product is washed with water and methanol.



   Yield: 18.1 g, corresponding to 93.8% of the theory of the compound of the formula
EMI14.3
 as a light yellow powder; Melting point:> 3000C.



   After recrystallization from 1500 ml of trichlorobenzene with the aid of fuller's earth, or from a mixture of 750 ml of trichlorobenzene and 750 ml of dimethylformamide, 8.6 g (44.6% of theory) of pale yellow crystals are obtained.



  Melting point:> 3000C
The bis-stilbene compounds of the formula shown in the table below are similar
EMI14.4
 shown, where for the compound of formula (139), the reaction mixture is acidified with aqueous hydrochloric acid after the reaction has ended.



     Melting point number R in 0C
EMI14.5

XVII) To a suspension of 25.2 g of potassium hydroxide powder with a water content of about 11% in 100 ml of dimethylformamide, a solution of 10.5 g of 4,4'-bis-formyl-diphenyl and with exclusion of air is added 25.3 g of 1-diethoxyphosphonomethyl-2-cyano-benzene of the formula
EMI 14.6
 in 50 ml of dimethylformamide is added dropwise so that the temperature does not rise above 40 "C. The reaction mixture is stirred for a further 3 hours at 40 to 45" C., cooled to 50 ° C. and 200 ml of water are added dropwise.

  After suction filtering, washing with water and methanol and drying, 18.2 g (89.3% of theory) brownish-yellow fine needles of 4,4'-bis- (2-cyanostyryl) -diphenyl of the formula
EMI 14.7
  behave from the melting point 271 to 2720C. Twice recrystallization from o-dichlorobenzene (fuller's earth) gives 13.5 g (66.3% of theory) of pale yellow, glossy flakes which melt at 274 to 275.degree.



  Analysis for C, 0H20N2: Calculated: C 88.21 H 4.94 N 6.86 found: C 88.20 H 5.22 N 6.86
The l-diethoxyphosphonomethyl-2-cyano-benzene of the formula (140) used as an intermediate can be obtained from o-toluonitrile by reaction with N-bromosuccinic acid to form the bromomethyl compound and further reaction of the same with triethylphosphite; Boiling point: 138 to 140 C at 0.09 mm.



   If 1-diethoxyphosphonomethyl-3-cyano-benzene is used instead of 1-diethoxyphosphonomethyl-2-cyano-benzene, the compound of the formula is obtained
EMI15.1

Melting point:> 3000C.



   To prepare the bis-stilbene compounds of forms (141) and (142), dimethyl sulfoxide can also be used as a solvent instead of dimethylformamide.



   According to the information in this example, the bis-stilbene compounds of the formula listed in the table below can also be used
EMI15.2
 getting produced.



     
Enamel
No. R1 R2 point in C
EMI15.3
 Enamel
No. R1 R2 point in C
EMI15.4

The 4,4'-bis-formyl-3,3'-dimethyl-diphenyl used as the starting material for the bis-stilbene compounds (143) and (150) to (152) is produced by reacting diazotized tolidine with potassium cyanide / copper sulfate and reducing the obtained dinitriles are represented by means of Raney nickel / formic acid.



   Melting point 108 to 1090C.



   The 4,4'-bis-formyl-3,3'-dimethoxydiphenyl, melting point 241 to 243 C, and the 4 used for the compound (145) are used in an analogous manner for the compounds (144) and (149) , 4'-bis-formyl-3,3'-dichloro-diphenyl, melting point 220 to 222 ° C
The 4,4'-bis-formyl-diphenyl-3,3'-disulfonic acid is obtained via the following reaction stages:
Sulfonation of 4,4'-Dimethykiiphwyl by means of conc.



  Sulfuric acid at 80 ° C. for 4 to 5 hours; Conversion of the 4,4'-dimethyl-diphenyl-3,3'-disulfonic acid obtained with thionyl chloride into the disulfonic acid dichloride; Melting point 192 to 193 C, oxidation with chromic anhydride in acetic anhydride / glacial acetic acid to form the acetate chloride of the formula
EMI15.5

Melting point: 185 to 1880C, and finally hydrolysis in dilute hydrochloric acid to form aldehyde sulfonic acid.



   The 4,4'-bis-formyl-diphenyl-3,3'-bis-sulfonic acid dimethylamide is produced from the sulfochloride acetate of the formula (153) by reaction with dimethylamine in chloroform and hydrolysis in dilute hydrochloric acid
Melting point: 219 to 221 ° C.



   XVIII) In Example 2, the 4,4'-bis- (diethoxyphosphono-methyl) -diphenyl is replaced by the equivalent amount of 4,4'-bis- (phenylethoxyphosphonomethyl) -diphenyl of the formula
EMI16.1
 in this way the compound of the formula (101) is obtained in a yield of 23% of theory with otherwise the same test procedure and work-up.



   The phosphinic ester of the formula (154) used as the starting material is obtained by reacting 4,4-bis-chloromethyldiphenyl with 2.5 mol of phenyldiethoxyphosphine.



   Colorless crystals of alcohol.



   Melting point: 232 to 2340C.



  Analysis for CBoHs204P2 calcd .: C 69.49 H 6.22 P 11.95 found: C 69.30 H 6.28 P 11.93
XIX) 45.4 g of 4,4 '- (diethoxyphosphonomethyl) diphenyl, 13.1 g of p-cyanobenzaldehyde and 21.2 g of the sodium salt of Benzaldehya-2-sulfonic acid with a content of 88% free sulfonic acid are in a suspension of 51.1 g of potassium hydroxide powder with a water content of about 12% are added to 200 ml of dimethylformamide and implemented according to the information in Example 2. After drying, the compound of the formula (135) is removed by boiling with trichlorobenzene, and the compound of the formula is removed from the residue by crystallization from water and 800 ml of dimethylformamide
EMI16.2
 isolated in the form of yellow leaflets.



     Analysis for C2DH2003N S Na @ ¸ 1 H2O: calc .: C 70.50 H 4.28 N 2.83 S 6.48 found: C 70.41 H 4.56 N 2.76 S 6.65
The asymmetric bisstilbene compounds of the formulas listed below can be used in a similar manner
EMI16.3
 and
EMI16.4
 being represented.



   XX) 22.2 g of the disulfonic acid dichloride of the formula (114) are suspended with 0.2 g of a commercially available wetting agent in 50 ml of water and added to a solution of 40.3 g of sodium sulfite hydrate in 500 ml of water with stirring.



  The reaction mixture is heated to 90 ° C. and at this temperature 15 ml of a 30% strength aqueous sodium hydroxide solution is gradually added dropwise so that the pH is 9 to 9.5. After stirring for 12 hours at 90 to 95 ° C., the hot solution is filtered and the reaction product is salted out from the filtrate with 50 g of sodium chloride. After suction filtering and drying, the disodium salt becomes disulfinic acid of the formula
EMI16.5
 recrystallized twice from methanol-water. Light yellow leaves which melt above 300 ° C. are obtained.



  Analysis for C28H2004S2Na2 1 H2O: calc .: C 61.30 H 4.04 S 11.69 found: C 61.47 H 3.88 S 12.38
16.0 g of the disodium salt of disulfinic acid of the formula (158) are stirred in 100 ml of water and 150 ml of ethanol with 50 g of methyl iodide for 22 hours at 50.degree. The excess methyl iodide is then distilled off with the ethanol and the remaining reaction mixture is decolorized with sodium thiosulfate, suction filtered and the suction filter is dried in vacuo. It is recrystallized once from ethanol / dimethylformamide / water and then twice from chloroform / ethanol, the compound of the formula
EMI16.6
 is obtained in the form of light beige, glossy flakes which melt at 301 to 302 C :.

 

  Analysis for C30H2604S2: calc .: C 70.01 H 5.09 S 12.46 found: C 69.77 H 5.03 S 12.46
XXI) A homogeneous mixture of 19.9 g of 4,4'-bis is added to a well-stirred suspension of 6.8 g of sodium methylate (content: 95.6%) in 250 ml of anhydrous dimethylformamide while displacing the air with a stream of nitrogen - (Dimethoxyphosphonomethyl) diphenyl and 24.2 g of the sodium salt of 4-chlorobenzaldehyde-3-sulfonic acid entered in the course of about 10 minutes. The temperature rises to 45 ° C. and is kept at 40 to 45 ° C. by ice cooling. The mixture is then stirred at 40 to 45 ° C. for a further 2 hours.

  The pale yellow thick suspension is poured onto 1000 ml of deionized water, the suspension is cooled to 15 ° C. with stirring, the product is suction filtered, washed with 100 ml of deionized water and recrystallized from a mixture of 900 ml of dimethylformamide and 600 ml of deionized water Recrystallization from 600 ml of dimethylformamide and 400 ml of deionized water and after drying in vacuo at 100 to 110 ° C. gives about 16.4 g of the compound of the formula
EMI17.1
 Light yellow powder.



   Instead of 4,4'-bis (dimethoxyphosphonomethyl) diphenyl, the equivalent amount of 4,4'-bis (diethoxyphosphonomethyl) diphenyl can be used.



   The bis-stilbene compounds of the formula shown in the table below can be prepared in a similar manner
EMI17.2
 being represented.



   No. R
EMI17.3

The sulfobenzaldehydes used as starting materials for the compound (153) can be obtained by sulfonating the corresponding benzaldehydes with oleum having an SO3 content of 66%.



   XXII) To a well stirred suspension of 37.3 g of sodium methoxide (content: 95.6%) in 500 ml of anhydrous dimethylformamide, a solution of 136.2 g of 4,4'-bis- (diethoxy-phosphonomethyl) -diphenyl and 98.4 g of methyl benzaldehyde-3-carboxylate in 600 ml of anhydrous dimethylformamide were added dropwise in the course of 10 minutes. The temperature rises to 45 "C and is kept at 40 to 45" C by ice cooling. The mixture is then stirred for a further hour at 40 to 45 ° C., 500 ml of methanol are added, and the product which has crystallized out is filtered off with suction and washed neutral with deionized water.



  Yield 117.8 g of the compound of formula
EMI17.4

Light yellow powder; Melting point: 232 to 234 "C. For further purification, crystallization is first carried out from dimethylformamide with the addition of activated carbon, then twice from chlorobenzene with the addition of fuller's earth. The product is obtained in the form of pale yellow, fine flakes with a melting point of 236 to 237" C.



   Instead of dimethylformamide, it is also possible to use dimethyl sulfoxide and instead of solid sodium methylate a methanolic sodium methylate solution. It is also possible to use the equivalent amount of 4,4'-bis (di methoxyphosphonomethyl) diphenyl instead of 4,4'-bis (diethoxyphosphonomethyl) diphenyl.



   The bis-stilbene compounds of the formula shown in the table below can be prepared in a similar manner
EMI17.5


<tb> (1 <SEP> 05c)
<tb> are displayed <SEP>.
<tb>



  No. R
EMI17.6
   No. R
EMI18.1

XXIII) 19.0 g of the compound of the formula (154) are heated to 92 ° C. in 700 ml of methyl cellosolve with stirring. 30 g of 30% sodium hydroxide solution are added dropwise to the pale yellow suspension over the course of 5 minutes Stirred to 103 "C, the pale yellow suspension cooled to 200C, the crystallized product filtered off with suction, washed with 150 ml of deionized water and dried under vacuum at 100 to 110" C.



   Yield: 19.2 g of the compound of the formula
EMI18.2

Pale yellow powder.



   74.2 g of the compound of the formula (171) are suspended in 500 ml of chlorobenzene and 2 ml of dimethylformamide with stirring. Over the course of about 5 minutes, 100 ml of thionyl chloride are added dropwise, the temperature rising from 350 ° C. to 45 ° C. Over the course of about 30 minutes, the mixture is heated to 110 ° C. and held for 3 hours at 105 to 110 ° C. After cooling, the product crystallized out suction filtered, recrystallized from 400 ml of chlorobenzene and dried at 80 to 85 "C under vacuum.



   Yield: 45.1 g of the compound of the formula
EMI18.3

Light yellow powder; Melting point: 213 to 214 "C.



   7.2 g of the compound of the formula (172) are dissolved in 150 ml of chlorobenzene at 920 ° C. with stirring. 20 ml of diethanolamine are added dropwise in the course of 5 minutes. The mixture is stirred for a further 4 hours at 90 to 95 "C, cooled to 70" C, 100 ml of methanol added, kept at 70 "C for 10 minutes, cooled to 20" C, suction filtered and the product from 100 ml of dimethyl sulfoxide / 100 ml Recrystallized ethanol.



   Yield: 7.1 g of the compound of the formula
EMI18.4

Pale yellow powder, melting point: 247 to 248 "C.



   The condensation can also be carried out directly in 100 ml of diethanolamine at about 60 ° C. For working up, the warm reaction mixture is mixed with 50 ml of deionized water and 200 ml of ethanol, cooled and the recrystallized product is suction filtered.



   XXIV) 7.25 g of the compound of the formula (172) are heated in 100 ml of pyridine for one hour with stirring to 95 to 99 ° C. Then 100 ml of deionized water are added dropwise, the pale yellow suspension is cooled to 200 ° C. and suction filtered. The product is suspended in deionized water, neutralized with hydrochloric acid, suction filtered, washed with deionized water and dried under vacuum.

 

   Yield: 6.3 g of the compound of the formula
EMI18.5

Light yellow powder, melting point: over 3000C.



   XXV) 14.5 g of the compound of the formula (122) are suspended in a mixture of 250 ml of isopropanol and 250 ml of o-dichlorobenzene with stirring at 20 ° C. The whole is heated to 80 ° C. and at 80 to 87 for 8 hours C. After cooling, the product which has crystallized out is filtered off with suction and recrystallized from 500 ml of o-dichlorobenzene with the aid of fuller's earth.



   Yield: 5.3 g of the compound of the formula
EMI18.6
  
Pale yellow leaflets; Melting point: 2900C (decomposition).



   In a manner similar to that described above or in Example 15, the bis-stilbene compounds of the formula shown in the table below can be used
EMI19.1
 being represented.



   No. R
EMI19.2
 No. R
EMI19.3

XXVI) To a solution of 2.6 g of 4-methylbenzaldehyde and 7.75 g of the phosphonium salt of the formula
EMI19.4
 2.4 g of potassium tert-butoxide are added to 100 ml of absolute ethanol. The yellow solution warms up immediately to about 40 ° C. and after about one minute a light beige precipitate forms. The mixture is stirred for 3 hours at room temperature, then heated briefly to 80 ° C. and then cooled again. After suction filtering, washing with ethanol and water and drying, 2.7 g of the compound of the formula (134) are obtained.



   Melting point:> 300 "C.



   The phosphonium salt of the formula (195) can be obtained in a yield of 90% by reacting 4,4-bis-chloromethyldiphenyl with triphenylphosphine in dimethylformamide.



  White dust; Melting point:> 3000C.



   Example I.
10,000 g of a polyasnide prepared in a known manner from hexamethylerediamine adipate in chip form are mixed with 30 g of titanium dioxide (rutile modification) and 5 g of one of the compounds of the formula (101), (127), (134), (127b), (119), (136b), (139a), (141) or (141a) mixed in a Roliss vessel for 12 hours. The chips treated in this way are melted in a kettle heated to 300 to 310 ° C. with oil or diphenyl vapor, after the atmospheric oxygen has been displaced by steam, and stirred for half an hour.

  The melt is then pressed out through a spinneret under nitrogen pressure of 5 atm and the cooled filament spun in this way is cemented onto a spinning bobbin. The resulting threads show an excellent lightening effect with good lightfastness.



   If, instead of a polyamide made from adipate hexamethylenediamine, a polyamide made from ± -caprolactam is used, similarly good results are obtained.



   Example 2
100 g of polypropylene fiber grade are intimately mixed with 0.8 g of the compound of the formula (141) or (143) and melted at 280 to 290 ° C. with stirring. The melt is spun out and drawn by conventional spinnerets according to known melt spinning processes Highly lightened polypropylene fibers are obtained.



   Example 3
100 g polyester granules made from terephthalic acid ethylene glycol.



  polyesters are intimately mixed with Q05 g of one of the compounds of the formulas (119), (135), (136), (136b), (141), (139a), (141a), (145) or (159) and at 285 "C melted with stirring. After spinning through conventional spinnerets, heavily lightened polyester fibers are obtained.



   The compounds of the formulas (119), (135), (136), (136b), (139a), (141), (141a), (145) or (159) can also be used before or during the polycondensation to give the polyester Add starting materials.



   Example 4
An intimate mixture of 100 parts of polyvinyl chloride, 3 parts of stabilizer (Advastat BD 100; Ba / Cd complex), 2 parts of titanium dioxide, 59 parts of dioctyl phthalate and 0.01 to 0.2 parts of one of the compounds of the formulas (119), (135 ), (141) or (143) rolled out on a calender at 150 to 1550C into a film. The opaque polyvinyl chloride film obtained in this way has a significantly higher whiteness content than a film which does not contain the optical brightener.



   Example 5
100 parts of polystyrene and 0.1 part of one of the compounds of the formulas (119), (134) and (138) are melted with the exclusion of air for 20 minutes at 210 ° C. in a tube 1 cm in diameter. After cooling, an optically brightened polystyrene mass of good lightfastness is obtained.



   Example 6
A paper pulp containing 100 parts of bleached cellulose se, 2 parts of resin size are added in the Hollander. After 10 to 15 minutes, first 0.05 to 0.3 parts of the compound of the formula (101), which were dissolved in 20 parts of water, are added, then - after a further 15 minutes, -3 parts of aluminum sulfate are added. The mass treated in this way then reaches the paper machine via the mixing vat, on which the paper is produced in a known manner. The paper obtained in this way shows an excellent lightening effect with good lightfastness.

 

   Example 7
2 parts of resin size are added to a paper pulp containing 100 parts of bleached cellulose in the Hollander. After 15 minutes, 3 parts of aluminum sulfate are added.



  The paper web produced on the paper machine is then surface-sized with a size press, starch or alginates containing 0.05 to 0.3 parts of one of the compounds of formulas (101) or (104) being used as adhesive. The paper obtained in this way has a very high white content.

 

Claims (1)

PATENT CLAIM Use of stilbene compounds as optical brightening agents outside the textile industry, which of the formula EMI20.1 correspond, in which R3 diphenylyl or a residue EMI20.2 R is phenyl, diphenylyl-, a- or frnaphthyl or a radical EMI20.3 represents, and in which V1 and V1 ,, which are identical or different, the sulfo group and their salts, esters, amides or halides, the carboxyl group and their salts, esters or amides, the nitrile group, a sulfonyl group, the methyl group or the hydroxyl group, V2 and V2 ,, which are identical or different, hydrogen, an alkyl group containing 1 to 18 carbon atoms, an alkoxy group containing 1 to 12 carbon atoms, halogen or the sulfo group and salts thereof, Esters or amides, and V31 and V8 ,, which are identical or different, denote hydrogen or an alkyl group containing 1 to 4 carbon atoms, W1 for the sulfo group, and their salts, esters or amides, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, the carboxyl group and their salts, esters or amides, the nitrile group or halogen, and where L one of the symbols W1 or V1 and / or V1, can always also mean a hydrogen atom and II. W1 is different from hydrogen when R and / or R4 are the diphenylyl radical. SUBClaims 1. Use according to claim of bis-stilbene compounds which have the formula EMI21.1 correspond, where V1 is the sulfo group and their salts, esters, amides or halides, the carboxyl group and their salts, esters or amides, the nitrile group, a sulfonyl group, the methyl group or the hydroxyl group, V2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, a Alkoxy group containing 1 to 12 carbon atoms, halogen or the sulfo group and their salts, esters or amides and V3 represent hydrogen or an alkyl group containing 1 to 4 carbon atoms, W, the sulfo group and their salts, esters or amides, an alkyl group with 1 to 4 Carbon atoms, an alkoxy group with 1 to 4 carbon atoms, the carboxyl group and their salts, esters or amides, denotes the nitrile group or halogen, where one of the symbols W1 or Vt can furthermore denote a hydrogen atom. 2. Use according to claim of bis-stilbene compounds which have the formula EMI21.2 correspond, where V1 is the sulfo group and their salts, esters, amides or halides, the carboxyl group and their salts, esters or amides, the nitrile group, a sulfonyl group, the methyl group or the hydroxyl group, V2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, an alkoxy group containing 1 to 12 carbon atoms. Halogen or the sulfo group and their salts, esters or amides and V3 represent hydrogen or an alkyl group containing 1 to 4 carbon atoms. 3. Use according to claim of bis-stilbene compounds which have the formula EMI21.3 correspond, where V4 is the sulfo group and their salts, esters or amides, the carboxyl group and their salts, esters or amides or the nitrile group, and V, hydrogen, the sulfo group and their salts, esters or amides is an alkyl group with 1 to 4 carbon atoms or represents an alkoxy group having 1 to 4 carbon atoms. 4. Use according to patent claim of bis-stilbene compounds which have the formula EMI21.4 correspond, in which V6 denotes the sulfo group, its salts or amides. 5. Use according to claim of stilbene compounds which have the formula EMI21.5 correspond, in which R5 is either a naphthyl radical or the radical EMI21.6 and where V2 is hydrogen, an alkyl group containing 1 to 18 carbon atoms, an alkoxy group containing 1 to 12 carbon atoms, halogen or the sulfo group and their salts, esters or amides, and V, hydrogen or an alkyl group containing 1 to 4 carbon atoms, and Wl represents the sulfo group and its salts, esters or amides, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, the carboxyl group and their salts, esters or amides, the nitrile group or halogen. 6. Use according to patent claim and dependent claims 1 to 5 of stilbene bonds as optical brightening agents in soaps and detergents.