WO2000009471A1 - Divinylstilbenesulfonic acid derivatives - Google Patents

Divinylstilbenesulfonic acid derivatives Download PDF

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Publication number
WO2000009471A1
WO2000009471A1 PCT/EP1999/005431 EP9905431W WO0009471A1 WO 2000009471 A1 WO2000009471 A1 WO 2000009471A1 EP 9905431 W EP9905431 W EP 9905431W WO 0009471 A1 WO0009471 A1 WO 0009471A1
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Prior art keywords
formula
compound
alkyl
hydrogen
cyano
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PCT/EP1999/005431
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French (fr)
Inventor
Victor Paul Eliu
Peter Rohringer
Julia Hauser
Hans Kramer
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Ciba Specialty Chemicals Holding Inc.
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Priority to AU52892/99A priority Critical patent/AU5289299A/en
Priority to EP99938372A priority patent/EP1105366A1/en
Publication of WO2000009471A1 publication Critical patent/WO2000009471A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
    • C07C309/32—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings containing at least two non-condensed six-membered aromatic rings in the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C07C309/58—Carboxylic acid groups or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C07C309/59—Nitrogen analogues of carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3427—Organic compounds containing sulfur containing thiol, mercapto or sulfide groups, e.g. thioethers or mercaptales
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • the present invention relates to divinylstilbenesulfonic acid derivatives, to a process for the preparation of these compounds and to their use as fluorescent whitening agents.
  • the divinylstilbenesulfonic acid derivatives of this invention correspond to formula
  • Yi and Y 2 are each independently of the other hydrogen or -SO 3 " M + ; at least one Y, or Y 2 being -SO 3 " M + ;
  • Ri is hydrogen; C C 18 alkyl or C -C 18 alkenyl which is unsubstituted or substituted by cyano, -SH, d-Csalkylthio, C C 5 alkoxy, amino, d-dmonoalkylamino, C C 5 dialkyl- amino or carboxy; mono-, di- or trihydroxy-d-C 5 alkyl; a radical of formula
  • phenyl-C ⁇ -C 3 alkyl which is unsubstituted or substituted by one or several C r C 5 alkyl, d-C 5 alkoxy, hydroxy, cyano, sulfo or halogen;
  • R 2 and R 3 are each independently of the other hydrogen; C C 5 alkyl which is unsubstituted or substituted by cyano, -SH, CrC 5 alkylthio, C C 5 alkoxy or carboxy; hydroxy-CrC 5 alkyl; mono- or di-d-Csalkylamino-d-Csalkyl; phenyl or phenyl-d-C 3 alkyl which is unsubstituted or substituted by one or several C C 5 alkyl, C dalkoxy,hydroxy, cyano, sulfo or halogen; or
  • R 2 and R 3 together with the linking nitrogen atom, are a five- or six-membered heterocyclic radical
  • FU is hydrogen, d-C 5 alkyl, Ci-Csalkoxy, hydroxy, cyano, sulfo or halogen
  • M is hydrogen; an alkali metal cation or alkaline earth metal cation; or a cation formed from an amine
  • mi is a number from 1 to 5
  • n ! is a number from 1 to 3.
  • d-d ⁇ Alkyl is a straight-chain or branched radical, for example methyl, ethyl, n-propyl, iso- propyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
  • d-CsAlkyloxy or C ⁇ -C 5 alkylthio is a straight-chain or branched radical, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy or methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, tert-butylthio or amylthio.
  • C 2 -Ci 8 Alkenyl is, for example, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n- penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2- enyl or n-octadec-4-enyl.
  • Examples of d-C 5 monoalkylamino or Ci-Csdialkylamino are methylamino, ethylamino, pro- pylamino, butylamino, tert-butylamino or dimethylamino, diethylamino, methylethylamino, dipropylamino, dibutylamino or di-tert-butylamino.
  • substituent pair (R 2 and R 3 ), together with the linking nitrogen atom is a heterocyclic radical
  • this radical is, for example, pyrrolidino, piperidino, pipecolino, morpholino, thio- morpholino, piperazino, N-alkylpiperazino, such as N-methylpiperazino, N-phenylp ' perazino or N-alkylimidazolino.
  • Preferred saturated heterocyclic radicals used for -NR 2 R 3 are pyrrolidino, piperidino or morpholino.
  • Suitable compounds of formula (1 ) are preferably those, wherein
  • Ri is hydrogen; hydroxy; C C 5 alkyl; d-C 5 hydroxyalkyl; amino or a radical of formula (1 a); particularly preferably compounds of formula (1), wherein Ri is d-C 3 alkyl and, very particularly, methyl or ethyl.
  • Ri is a radical of formula -O-(CH 2 ) 2 -O-(CH 2 ) 2 -O-(CH 2 )2-OH.
  • R 2 and R 3 are each independently of the other hydrogen; mono- or di-C r C 5 alkylamino-C ⁇ -
  • R 2 and R 3 together with the linking nitrogen atom, are a mo ⁇ holino radical.
  • the inventive divinylstilbenesulfonic acid derivatives are prepared in a manner known per se by diazotising the corresponding aminostilbene compound of formula
  • X, Yi, Y 2 are as defined for formula (1).
  • X ' is a counterion.
  • Suitable diazotisation reagents are alkyl nitrite, nitrosylsulfuric acid and, preferably, sodium nitrite.
  • the temperature in this reaction step is in the range from 0 to 90°C, preferably from 10 to 40°C.
  • the diazotisation is preferably carried out in the presence of a mineral acid, for example sulfuric acid, methanesulfonic acid or tetrafluoroboric acid.
  • a mineral acid for example sulfuric acid, methanesulfonic acid or tetrafluoroboric acid.
  • the diazonium compound so obtained e.g. sodium acetate, sodium bicarbonate or sodium carbonate is used as a base.
  • the reaction of the diazonium compound with the acryl compound of formula (15) is preferably carried out in the presence of a catalyst.
  • the reaction can be carried out in aqueous or anhydrous medium.
  • Suitable non-aqueous solvents are alcohols, for example pentyl alcohol, acetic acid, dimethylformamide, N-methyl- pyrrolidone, dimethylacetamide, glycol ether, acetonitrile or DMSO.
  • the reaction can also be carried out in two-phase systems, for example mixtures consisting of water and halogenated hydrocarbons and dichloromethane or pentyl alcohol and phase transfer catalysts.
  • the inventive divinylstilbenesulfonic acid derivatives are usually used to optically brighten synthetic or natural organic materials.
  • textile fibres such as those consisting of synthetic poly- amides or of natural fibres of animal or vegetable origin based on cellulose or protein, for example cotton, wool, linen, silk or paper.
  • the textile materials can be in different forms of presentation and are preferably piece goods, such as wovens or knitgoods, or yarn on cheeses, warp beams, and the like.
  • the divinylstilbenesulfonic acid derivatives of this invention can be inco ⁇ orated for optical brightening in liquid and solid detergents, application liquors or paper coating compositions.
  • the formulations so obtained can additionally contain the conventional formulation assistants, such as dispersants, builders, protective colloids, stabilisers, preservatives, perfumes, pigments, enzymes and sequestrants.
  • conventional formulation assistants such as dispersants, builders, protective colloids, stabilisers, preservatives, perfumes, pigments, enzymes and sequestrants.
  • Dispersants used are preferably nonionic dispersants, e.g. fatty alcohols, ethoxylation products of fatty alcohols or fatty acids, or anionic dispersants, such as the condensates of aromatic sulfonic acids with formaldehyde, for example those based on ditolyl ether sulfonic acids, naphthalene sulfonates or lignin sulfonates.
  • nonionic dispersants e.g. fatty alcohols, ethoxylation products of fatty alcohols or fatty acids
  • anionic dispersants such as the condensates of aromatic sulfonic acids with formaldehyde, for example those based on ditolyl ether sulfonic acids, naphthalene sulfonates or lignin sulfonates.
  • Suitable builders or protective colloids are, for example, modified polysaccharides which are derived from cellulose, or heteropolysaccharides, such as xanthan, ca ⁇ oxymethylcellulose and also aluminium silicates or magnesium silicates. Additional stabilisation assistants which may be added are, for example, ethylene glycol, propylene glycol and further dispersants.
  • Preservatives used are, for example, compounds such as 1 ,2-benzisothiazolin-3-one, formaldehyde or chloroacetamide.
  • this invention also relates to a process for improving the SPF-value of textile fibre materials.
  • This process comprises treating the fibre material with 0.05 to 3 % by weight, based on the weight of the fibre material, of one or several of the compounds of formula (1).
  • the fibre material treated by the inventive process preferably has a density of less than 200 g/cm 2 and is as a rule dyed in pastel shades before treatment.
  • reaction mixture is separated by suction filtration, about 66 g of filter product being obtained.
  • This filter product is then dried under vacuum and recrystallised from water, resulting in 24.5 g of the compound of formula (101).
  • acetic anhydride 60 g are added dropwise to reduce the water concentration, the temperature being kept below 20°C by cooling. After stirring the mixture for 20 minutes, 16.8 g of sodium hydrogencarbonate are slowly added, the foam formation being controlled. 0.3 g of palladium dibenzylacetone and 8.0 g of acrylamide are stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 40°C over about 2 to 3 hours. If the diazo component test is negative, the mixture is worked up using the conventional methods.
  • reaction mixture is separated by suction filtration, about 50 g of filter product being obtained.
  • This filter product is dried under vacuum and recrystallised from water, resulting in 21.5 g of the compound of formula (102).
  • acetic anhydride 50 g of acetic anhydride are added dropwise to reduce the water concentration, the temperature being kept below 20°C by cooling. After stirring the mixture for 20 minutes, 10.8 g of sodium carbonate are slowly added, the foam formation being controlled. 0.3 g of palladium dibenzylacetone and 10.0 g of methyl acrylate are stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 35°C over about 2 to 3 hours. If the diazo component test is negative, the mixture is worked up using the conventional methods.
  • reaction mixture is separated by suction filtration, about 70 g of filter product being obtained.
  • This filter product is dried under vacuum and recrystallised from water, resulting in 18.5 g of the compound of formula (103).
  • acetic anhydride 60 g are added dropwise to reduce the water concentration, the temperature being kept below 20°C by cooling. After stirring the mixture for 20 minutes, 16.8 g of sodium hydrogencarbonate are slowly added, the foam formation being controlled. 0.3 g of palladium chloride solution, about 20% in hydrochloric acid, and 12.2 g of hydroxyethyl acrylate are stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 50°C over about 2 to 3 hours. If the diazo component test is negative, the mixture is worked up by the conventional methods.
  • reaction mixture is separated by suction filtration, about 110 g of filter product being obtained.
  • This filter product is dried under vacuum, about 36 g of crude product remaining, and recrystallised from water and sodium chloride, resulting in 20.0 g of the compound of formula (104).
  • acetic anhydride 60 g are added dropwise to reduce the water concentration, the temperature being kept below 20°C with cooling. After stirring the mixture for 20 minutes, 16.8 g of sodium hydrogencarbonate are slowly added, the foam formation being controlled. 0.3 g of palladium dibenzylacetone and 8.0 g of acrylic acid are stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 40°C over about 2 to 3 hours. If the diazo component test is negative, the mixture is worked up using the conventional methods.
  • the starting material used for this compound is the ethyl ester prepared according to Example 1 (compound of formula (101)).24.5 g of the dry, ground compound are suspended in 150 g of triethylene glycol and then 1 g of sodium ethoxide is added and the mixture is stirred for six hours at 80-90°C and 20 mbar, the resulting ethanol being removed by distillation. This gives a clear solution containing 34 g of the triethylene glycol ester of formula (105).
  • the starting material used for this compound is the ethyl ester prepared according to Example 1 (compound of formula (101)). 24.5 g of the dry compound are suspended in 150 g of diethanolamine and then 1 g of sodium ethoxide is added and the mixture is stirred for eight hours at 100°C and 20 mbar, the resulting ethanol being removed by distillation. This gives a clear solution containing 30 g of diethanolamide of formula (107).
  • the starting material used for this compound is the ethyl ester prepared according to Example 1 (compound of formula (101)).
  • 24.5 g of the dry, ground compound are suspended in 250 g of mo ⁇ holine and then 1 g of sodium ethoxide is added and the mixture is stirred for six hours at 100°C and 200 mbar, the resulting ethanol being removed by distillation.
  • the mo ⁇ holine is removed by distillation under a vacuum of 40 mbar, 34 g of bis-morpholinamide of formula (108) being obtained.
  • the starting material used for this compound is the ethyl ester prepared according to Example 1 (compound of formula (101)).
  • 24.5 g of the dry, ground compound are suspended in 250 g of diethylaminoethylamine.
  • 1 g of sodium ethoxide is added and the mixture is stirred for 10 hours at 100°C and 200 mbar, the resulting ethanol being removed by distillation.
  • the diethylaminoethylamine is removed by distillation under a vacuum of 40 mbar, affording 30 g of bis-diethylaminoethylamide of formula (109).
  • the starting material used for this compound is the free acid prepared according to Example 5 (compound of formula (105)). 18.0 g of the dry, ground compound are suspended in 150 g of thionyl chloride and the suspension is reacted, with stirring, at 70°C. After abundant degassing, the reaction mixture is concentrated by evaporation. The mixture is then suspended in 250 g of DMSO and then 17.5 g of orthanilic acid sodium salt and 10 g of sodium carbonate are added. This mixture is stirred for 4 hours at 60°C.
  • the starting material used for this compound is the amide prepared according to Example 2 (compound of formula (102)). 21.5 g of dry, ground material are suspended in 150 g of phosphorus oxychloride and the suspension is stirred for 3 hours at 70°C. After the reaction is complete, the mixture is separated by removing the acid chloride by distillation. The distillation residue is slurried in ice water, separated by filtration and dried, resulting in 17 g of the nitrile of formula (111).
  • IR abso ⁇ tion at 1670 cm '1 , the carbonyl group disappears and an IR band appears at 2105 cm "1 which can be assigned to the nitrile group.
  • acetic anhydride 60 g of acetic anhydride are added dropwise to reduce the water concentration, the temperature being kept below 20°C by cooling. After stirring the mixture for 20 minutes, 16.8 g of sodium hydrogencarbonate are slowly added, the foam formation being controlled. 0.3 g of palladium chloride solution (c. 20%) in hydrochloric acid and 14.2 g of butyl acrylate are stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 50°C over about 2 to 3 hours. If the diazo component test is negative, the mixture is worked up.
  • reaction mixture is separated by suction filtration, resulting in about 110 g of filter product.
  • This filter product is dried under vacuum, about 38 g of crude product remaining, and is recrystallised from water and sodium chloride, resulting in 28.0 g of the compound of formula (112).
  • acetic anhydride 60 g of acetic anhydride are added dropwise to reduce the water concentration, the temperature being kept below 20°C by cooling. After stirring the mixture for 20 minutes, 16.8 g of sodium hydrogencarbonate are slowly added, the foam formation being controlled. 0.3 g of palladium chloride solution (c. 20%) in hydrochloric acid and 29.4 g of lauryl acrylate are then stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 50°C over about 4 to 5 hours. If the diazo component test is negative, the mixture is worked up.
  • reaction mixture is separated by suction filtration, about 140 g of filter product being obtained.
  • This filter product is dried under vacuum, about 50 g of crude product remaining, and is recrystallised from water and sodium chloride, resulting in 30.0 g of the compound of formula (113).
  • the starting material used for this compound is the ethyl ester prepared according to Example 1 (compound of formula (101)).
  • 24.5 g of the dry, ground compound are suspended in 500 g of allyl alcohol and then 1 g of sodium ethoxide is added and the mixture stirred for 10 hours at 90-98°C under normal pressure, the resulting ethanol being removed by distillation by means of a rectification column.
  • the suspension of transesterified product is separated by filtration and dried, resulting in 34 g of allyl diester of formula (114).
  • the yellow reaction mixture is separated by suction filtration, about 300 g of filter product being obtained.
  • This filter product is dried under vacuum and recrystallised from methanol, resulting in 120 g of the compound of formula (115).
  • the compounds listed in Table 1 are dissolved in deionised water and are added to the paper pulp at a consistency of 2.2 %. The subsequent exhaustion time is 15 minutes. The retention agent is added shortly before sheet forming and the paper samples are dried under vacuum at 80°C (System Rapid Koethen).
  • a Spectroflash 500 is used to measure the brightness (ISO) and to calculate the difference between the brightness of a specimen with and without treatment. The results are listed as fluorescence (ISO) in Table 1:
  • Example 17 Use in a size press
  • the compounds listed in Table 3 are admixed in a concentration of 0.1% to a commercially available liquid detergent without fluorescent whitening agent and containing the following ingredients in accordance with EG recommendation: ⁇ 5% phosphonates, cationic surfactants
  • a washing liquor is prepared consisting of 0.4 g of the above detergent in 50 ml of drinking water.
  • the whiteness of the fabric is then determined by means of a DCI/SF 500 spectrophoto- meter by the Ganz method:
  • the mixture is applied to 5 g of bleached cotton and 5 g of polyamide by the pad-batch process (liquor uptake 70%).
  • the fabric samples are dried at 60 °C and are then thermofixed for 3 minutes at 160 °C.
  • the whiteness of the fabric is then determined by means of a DCI/SF 500 spectrophoto- meter by the Ganz method: Table 4
  • Example 20 Use in textile application; exhaust process
  • the compounds listed in Table 5 are dissolved and applied to cotton and polyamide by the pad-batch process as described in Example 19.
  • the cotton fabric samples are then immediately placed in 200 ml of a liquor comprising 10 g/l of sodium sulfate.
  • the polyamide fabric samples are placed in 200 ml of a liquor which is buffered at pH 7 by means of a phosphate buffer.
  • the two liquors are heated from 25 °C to 100 °C over 35 minutes and are kept at 100°C for 30 minutes. Subsequently, the liquors are cooled to room temperature. The fabric samples are rinsed, spin-dried and ironed at 160°C.
  • the whiteness of the fabric is determined by means of a DCI/SF 500 spectrophotometer by the Ganz method:

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Abstract

A description is given of divinylstilbenesulfonic acid derivatives of formula (1), wherein X is (a); (b); -CN; or (c); Y1 and Y2 are each independently of the other hydrogen or -SO3-M+; at least one Y¿1? or Y2 being -SO3?-M+; R¿1 is hydrogen; C1-C18alkyl or C2-C18alkenyl which is unsubstituted or substituted by cyano, -SH, C1-C5alkylthio, C1-C5alkoxy, amino, C1-C5monoalkylamino, C1-C5dialkylamino or carboxy; mono-, di- or trihydroxy-C1-C5alkyl; a radical of formula (1a), amino; C1-C5monoalkylamino; C1-C5dialkylamino; phenyl or phenyl-C1-C3alkyl which is unsubstituted or substituted by one or several C1-C5alkyl, C1-C5alkoxy, hydroxy, cyano, sulfo or halogen; R2 and R3 are each independently of the other hydrogen; C1-C5alkyl which is unsubstituted or substituted by cyano, -SH, C1-C5alkylthio, C1-C5alkoxy or carboxy; hydroxy-C1-C5alkyl; mono- or di-C1-C5alkylamino-C1-C5alkyl; phenyl or phenyl-C1-C3alkyl which is unsubstituted or substituted by one or several C1-C5alkyl, C1-C5alkoxy, hydroxy, cyano, sulfo or halogen; or R2 and R3, together with the linking nitrogen atom, are a five- or six-membered heterocyclic radical; R4 is hydrogen, C1-C5alkyl, C1-C5alkoxy, hydroxy, cyano, sulfo or halogen, M is hydrogen; an alkali metal cation or alkaline earth metal cation; or a cation formed from an amine; m1 is a number from 1 to 5; and n1 is a number from 1 to 3. These compounds are used for optically brightening synthetic or natural organic materials.

Description

Divinylstilbenesulfonic acid derivatives
The present invention relates to divinylstilbenesulfonic acid derivatives, to a process for the preparation of these compounds and to their use as fluorescent whitening agents.
The divinylstilbenesulfonic acid derivatives of this invention correspond to formula
Figure imgf000003_0001
wherein
Figure imgf000003_0002
Yi and Y2are each independently of the other hydrogen or -SO3 "M+; at least one Y, or Y2 being -SO3 "M+;
Ri is hydrogen; C C18alkyl or C -C18alkenyl which is unsubstituted or substituted by cyano, -SH, d-Csalkylthio, C C5alkoxy, amino, d-dmonoalkylamino, C C5dialkyl- amino or carboxy; mono-, di- or trihydroxy-d-C5alkyl; a radical of formula
(1a) -O- (CH2)- -OH , amino; CrC5monoalkylamino; d-C5dialkylamino; phenyl or
■ m, phenyl-Cι-C3alkyl which is unsubstituted or substituted by one or several CrC5alkyl, d-C5alkoxy, hydroxy, cyano, sulfo or halogen;
R2 and R3 are each independently of the other hydrogen; C C5alkyl which is unsubstituted or substituted by cyano, -SH, CrC5alkylthio, C C5alkoxy or carboxy; hydroxy-CrC5alkyl; mono- or di-d-Csalkylamino-d-Csalkyl; phenyl or phenyl-d-C3alkyl which is unsubstituted or substituted by one or several C C5alkyl, C dalkoxy,hydroxy, cyano, sulfo or halogen; or
R2 and R3, together with the linking nitrogen atom, are a five- or six-membered heterocyclic radical;
FU is hydrogen, d-C5alkyl, Ci-Csalkoxy, hydroxy, cyano, sulfo or halogen, M is hydrogen; an alkali metal cation or alkaline earth metal cation; or a cation formed from an amine; mi is a number from 1 to 5; and n! is a number from 1 to 3.
d-dβAlkyl is a straight-chain or branched radical, for example methyl, ethyl, n-propyl, iso- propyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
d-CsAlkyloxy or Cι-C5alkylthio is a straight-chain or branched radical, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy or methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, tert-butylthio or amylthio.
C2-Ci8Alkenyl is, for example, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n- penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2- enyl or n-octadec-4-enyl.
Examples of d-C5monoalkylamino or Ci-Csdialkylamino are methylamino, ethylamino, pro- pylamino, butylamino, tert-butylamino or dimethylamino, diethylamino, methylethylamino, dipropylamino, dibutylamino or di-tert-butylamino.
If the substituent pair (R2 and R3), together with the linking nitrogen atom, is a heterocyclic radical, then this radical is, for example, pyrrolidino, piperidino, pipecolino, morpholino, thio- morpholino, piperazino, N-alkylpiperazino, such as N-methylpiperazino, N-phenylp'perazino or N-alkylimidazolino. Preferred saturated heterocyclic radicals used for -NR2R3 are pyrrolidino, piperidino or morpholino.
Suitable compounds of formula (1 ) are preferably those, wherein
Ri is hydrogen; hydroxy; C C5alkyl; d-C5hydroxyalkyl; amino or a radical of formula (1 a); particularly preferably compounds of formula (1), wherein Ri is d-C3alkyl and, very particularly, methyl or ethyl.
Other interesting compounds of formula (1) are those, wherein Ri is a radical of formula -O-(CH2)2-O-(CH2)2-O-(CH2)2-OH.
Of pre-eminent interest are also those compounds of formula (1), wherein
R2 and R3 are each independently of the other hydrogen; mono- or di-CrC5alkylamino-Cι-
C5alkylamino; or a radical of formula (1b) or
Figure imgf000005_0001
R2 and R3, together with the linking nitrogen atom, are a moφholino radical.
Interesting compounds of formula (1) are also those, wherein X is -CN or phenyl.
Examples of divinylstilbenesulfonic acid derivatives of this invention are listed in Table 1.
Figure imgf000005_0002
Figure imgf000006_0001
The inventive divinylstilbenesulfonic acid derivatives are prepared in a manner known per se by diazotising the corresponding aminostilbene compound of formula
Figure imgf000006_0002
to the compound of formula X-
(14) (1st step) and then reacting the diazo-
Figure imgf000007_0001
nium compound so obtained with the compound of formula
5) =
to the compound of formula (1) (2nd step).
X, Yi, Y2 are as defined for formula (1). X' is a counterion.
Suitable diazotisation reagents are alkyl nitrite, nitrosylsulfuric acid and, preferably, sodium nitrite.
The temperature in this reaction step is in the range from 0 to 90°C, preferably from 10 to 40°C.
The diazotisation is preferably carried out in the presence of a mineral acid, for example sulfuric acid, methanesulfonic acid or tetrafluoroboric acid.
To neutralise the diazonium compound so obtained, e.g. sodium acetate, sodium bicarbonate or sodium carbonate is used as a base.
The reaction of the diazonium compound with the acryl compound of formula (15) is preferably carried out in the presence of a catalyst. Suitable catalysts are palladium salts, such as palladium acetate, Pd(dba) (dba= dibenzylacetone), palladium chloride, palladium bromide, palladium nitrate, H2PdCI4, Na2PdCI4 and the like.
The reaction can be carried out in aqueous or anhydrous medium. Suitable non-aqueous solvents are alcohols, for example pentyl alcohol, acetic acid, dimethylformamide, N-methyl- pyrrolidone, dimethylacetamide, glycol ether, acetonitrile or DMSO. However, the reaction can also be carried out in two-phase systems, for example mixtures consisting of water and halogenated hydrocarbons and dichloromethane or pentyl alcohol and phase transfer catalysts.
The inventive divinylstilbenesulfonic acid derivatives are usually used to optically brighten synthetic or natural organic materials.
Examples of such materials are textile fibres, such as those consisting of synthetic poly- amides or of natural fibres of animal or vegetable origin based on cellulose or protein, for example cotton, wool, linen, silk or paper.
The textile materials can be in different forms of presentation and are preferably piece goods, such as wovens or knitgoods, or yarn on cheeses, warp beams, and the like.
The divinylstilbenesulfonic acid derivatives of this invention can be incoφorated for optical brightening in liquid and solid detergents, application liquors or paper coating compositions.
To this puφose they are usually diluted to the optimum concentration for the respective application by adding further assistants or water.
The formulations so obtained can additionally contain the conventional formulation assistants, such as dispersants, builders, protective colloids, stabilisers, preservatives, perfumes, pigments, enzymes and sequestrants.
Dispersants used are preferably nonionic dispersants, e.g. fatty alcohols, ethoxylation products of fatty alcohols or fatty acids, or anionic dispersants, such as the condensates of aromatic sulfonic acids with formaldehyde, for example those based on ditolyl ether sulfonic acids, naphthalene sulfonates or lignin sulfonates.
Suitable builders or protective colloids are, for example, modified polysaccharides which are derived from cellulose, or heteropolysaccharides, such as xanthan, caΦoxymethylcellulose and also aluminium silicates or magnesium silicates. Additional stabilisation assistants which may be added are, for example, ethylene glycol, propylene glycol and further dispersants.
Preservatives used are, for example, compounds such as 1 ,2-benzisothiazolin-3-one, formaldehyde or chloroacetamide.
It has also been found that the inventive divinylstilbenesulfonic acid derivatives are effective UV-A- and UV-B-absorbers. They thus provide the textile fibre materials finished according to this invention with an improved UPF- (UPF = UV protection factor) or SPF-value (SPF = sun protection factor).
Accordingly, this invention also relates to a process for improving the SPF-value of textile fibre materials. This process comprises treating the fibre material with 0.05 to 3 % by weight, based on the weight of the fibre material, of one or several of the compounds of formula (1).
The fibre material treated by the inventive process preferably has a density of less than 200 g/cm2 and is as a rule dyed in pastel shades before treatment.
The following Examples illustrate the invention.
Working Examples of novel compounds
Example 1 :
Figure imgf000009_0001
A 0.5 litre four-necked flask, equipped with stirrer and cooling/heating bath, is charged with 120 ml of glacial acetic acid and then 19.1 g of 4,4'-diaminostilbene-2,2'-disulfonic acid (c. 97%) are stirred in. 10.5 g of methanesulfonic acid (c. 100%) are added dropwise. The thoroughly stirred pale slurry is cooled to 10°C in an ice bath, and 21.0 g of a solution of sodium nitrite in water (36 % by weight) are steadily added dropwise over one hour, the tempe- rature being kept below 15°C. This mixture is then heated to 25°C and allowed to react for another 3 hours. The nitrite excess is eliminated with some sulfamic acid.
60 g of acetic anhydride are added dropwise to reduce the water concentration, the temperature being kept below 20°C by cooling. The mixture is stirred for 20 minutes and then 18.5 g of sodium hydrogencarbonate are slowly added, the foam formation being controlled. Subsequently, 0.3 g of palladium dibenzylacetone and 11 g of ethyl acrylate are stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 40°C over about 2 to 3 hours. If the diazo component test is negative, the mixture is worked up using the conventional methods.
The reaction mixture is separated by suction filtration, about 66 g of filter product being obtained. This filter product is then dried under vacuum and recrystallised from water, resulting in 24.5 g of the compound of formula (101).
NMR spectrum ( in D?O):
7.86 ( s, 2H, aromatic, adjacent to the sulfo group)
7.75 ( s, 2H, olefinic, centre)
7.54 (d, 2H, aromatic, j = 8Hz)
7.48 (d, 2H, olefinic, j=16.7) superimposed
7.45 (d, 2H, aromatic, j=8) superimposed
6.34 (d, 2H, olefinic, j=16.7)
4.10 (q, 4H, aliphatic, ester)
1.25 (t, 6H, aliphatic, ester)
Figure imgf000010_0001
A 0.5 litre four-necked flask, equipped with stirrer and cooling/heating bath, is charged with 120 ml of glacial acetic acid and then 19.1 g of 4,4'-diaminostilbene-2,2'-disulfonic acid (c. 97%) are stirred in. 7.4 g of sulfuric acid (c. 100%) are added dropwise. The thoroughly stirred pale slurry is cooled to 10°C using an ice bath, and 20.5 g of a solution of sodium nitrite in water (36 % by weight) are steadily added dropwise over one hour, the temperature being kept below 15°C. The mixture is then heated to 30°C and allowed to react for another 5 hours. The nitrite excess is eliminated with some sulfamic acid.
60 g of acetic anhydride are added dropwise to reduce the water concentration, the temperature being kept below 20°C by cooling. After stirring the mixture for 20 minutes, 16.8 g of sodium hydrogencarbonate are slowly added, the foam formation being controlled. 0.3 g of palladium dibenzylacetone and 8.0 g of acrylamide are stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 40°C over about 2 to 3 hours. If the diazo component test is negative, the mixture is worked up using the conventional methods.
The reaction mixture is separated by suction filtration, about 50 g of filter product being obtained. This filter product is dried under vacuum and recrystallised from water, resulting in 21.5 g of the compound of formula (102).
NMR spectrum ( in D2O):
7.90 ( s, 2H, aromatic, adjacent to the sulfo group)
7.80 ( s, 2H, olefinic, centre)
7.63 (d, 2H, aromatic, j = 8Hz)
7.48 (d, 2H, aromatic, j= 8 Hz)
7.30 (d, 2H, olefinic, j=16.5 Hz)
6.52 (d, 2H, olefinic, j=16.5 Hz)
Example 3:
Figure imgf000011_0001
A 0.5 litre four-necked flask, equipped with stirrer and cooling/heating bath, is charged with 120 ml of glacial acetic acid and then 19.1 g of 4,4'-diaminostilbene-2,2'-disulfonic acid (c. 97%) are stirred in. 7.4 g of sulfuric acid (c. 100%) are added dropwise. The thoroughly stirred pale slurry is cooled to 10°C using an ice bath, and 20.5 g of a solution of sodium nitrite in water (36 % by weight) are steadily added dropwise over one hour, the temperature being kept below 15°C. The mixture is then heated to 25°C and allowed to react for another 5 hours. The nitrite excess is eliminated with some sulfamic acid.
50 g of acetic anhydride are added dropwise to reduce the water concentration, the temperature being kept below 20°C by cooling. After stirring the mixture for 20 minutes, 10.8 g of sodium carbonate are slowly added, the foam formation being controlled. 0.3 g of palladium dibenzylacetone and 10.0 g of methyl acrylate are stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 35°C over about 2 to 3 hours. If the diazo component test is negative, the mixture is worked up using the conventional methods.
The reaction mixture is separated by suction filtration, about 70 g of filter product being obtained. This filter product is dried under vacuum and recrystallised from water, resulting in 18.5 g of the compound of formula (103).
NMR spectrum ( in D2O):
7.84 ( s, 2H, aromatic, adjacent to the sulfo group)
7.70 ( s, 2H, olefinic, centre)
7.50 (d, 2H, aromatic, j = 8Hz)
7.43 (d, 2H, olefinic, j=16.7) superimposed
7.37 (d, 2H, aromatic, j=8) superimposed
6.34 (d, 2H, olefinic, j=16.7)
3.65 (s, 6H, aliphatic, ester) Example 4:
Figure imgf000013_0001
A 0.5 litre four-necked flask, equipped with stirrer and cooling/heating bath, is charged with 120 ml of glacial acetic acid and then 19.1 g of 4,4'-diaminostilbene-2,2'-disulfonic acid (c. 97%) are stirred in. Subsequently, 10.4 g of methanesulfonic acid (c. 100%) are added dropwise. The thoroughly stirred pale slurry is cooled to 10°C using an ice bath, and 20.5 g of a solution of sodium nitrite in water (36 % by weight) are steadily added dropwise over one hour, the temperature being kept below 15°C. The mixture is then heated to 25°C and allowed to react for another 5 hours. The nitrite excess is eliminated with some sulfamic acid.
60 g of acetic anhydride are added dropwise to reduce the water concentration, the temperature being kept below 20°C by cooling. After stirring the mixture for 20 minutes, 16.8 g of sodium hydrogencarbonate are slowly added, the foam formation being controlled. 0.3 g of palladium chloride solution, about 20% in hydrochloric acid, and 12.2 g of hydroxyethyl acrylate are stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 50°C over about 2 to 3 hours. If the diazo component test is negative, the mixture is worked up by the conventional methods.
The reaction mixture is separated by suction filtration, about 110 g of filter product being obtained. This filter product is dried under vacuum, about 36 g of crude product remaining, and recrystallised from water and sodium chloride, resulting in 20.0 g of the compound of formula (104).
NMR spectrum ( in D2O):
7.88 ( s, 2H, aromatic, adjacent to the sulfo group)
7.73 ( s, 2H, olefinic, centre)
7.54 (d, 2H, aromatic, j = 8Hz) 7.45 (d, 2H, olefinic, j=16.7) superimposed 7.42 (d, 2H, aromatic, j=8) superimposed 6.40 (d, 2H, olefinic, j=16.7) 4.10 (t, 4H, aliphatic, ester) 3.86 (t, 4H, aliphatic, ester)
Example 5:
Figure imgf000014_0001
A 0.5 litre four-necked flask, equipped with stirrer and cooling/heating bath, is charged with 120 ml of glacial acetic acid and then 19.1 g of 4,4'-diaminostilbene-2,2'-disulfonic acid (c. 97%) are stirred in. Subsequently, 7.4 g of sulfuric acid (c. 100%) are added dropwise. The thoroughly stirred pale slurry is cooled to 10°C using an ice bath, and 20.5 g of a solution of sodium nitrite in water (36 % by weight) are steadily added dropwise over one hour, the temperature being kept below 15°C. The mixture is then heated to 25°C and allowed to react for another 5 hours. The nitrite excess is eliminated with some sulfamic acid.
60 g of acetic anhydride are added dropwise to reduce the water concentration, the temperature being kept below 20°C with cooling. After stirring the mixture for 20 minutes, 16.8 g of sodium hydrogencarbonate are slowly added, the foam formation being controlled. 0.3 g of palladium dibenzylacetone and 8.0 g of acrylic acid are stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 40°C over about 2 to 3 hours. If the diazo component test is negative, the mixture is worked up using the conventional methods.
The reaction mixture is separated by suction filtration, about 44 g of filter product being obtained. This filter product is then dried under vacuum and recrystallised from water, resulting in 18.0 g of the compound of formula (105). NMR spectrum ( in D?O):
7.93 ( s, 2H, aromatic, adjacent to the sulfo group)
7.85 ( s, 2H, olefinic, centre)
7.75 (d, 2H, aromatic, j = 8Hz)
7.63 (d, 2H, aromatic, j=8 Hz)
7.26 (d, 2H, olefinic, j=16.5)
6.48 (d, 2H, olefinic, j=16.5 Hz)
Figure imgf000015_0001
Figure imgf000015_0002
The starting material used for this compound is the ethyl ester prepared according to Example 1 (compound of formula (101)).24.5 g of the dry, ground compound are suspended in 150 g of triethylene glycol and then 1 g of sodium ethoxide is added and the mixture is stirred for six hours at 80-90°C and 20 mbar, the resulting ethanol being removed by distillation. This gives a clear solution containing 34 g of the triethylene glycol ester of formula (105).
NMR spectrum ( in D2O):
7.90 ( s, 2H, aromatic, adjacent to the sulfo group)
7.75 ( s, 2H, olefinic, centre)
7.55 (d, 2H, aromatic, j = 8Hz)
7.48 (d, 2H, olefinic, j=16.7) superimposed
7.44 (d, 2H, aromatic, j=8) superimposed 6.40 (d, 2H, olefinic, j=16.7) 4.24 (q, 4H, aliphatic, ester) 3.56 (t, ca. 20H, aliphatic, ether)
Example 7:
Figure imgf000016_0001
The starting material used for this compound is the ethyl ester prepared according to Example 1 (compound of formula (101)). 24.5 g of the dry compound are suspended in 150 g of diethanolamine and then 1 g of sodium ethoxide is added and the mixture is stirred for eight hours at 100°C and 20 mbar, the resulting ethanol being removed by distillation. This gives a clear solution containing 30 g of diethanolamide of formula (107).
NMR spectrum ( in D2O):
8.06 ( s, 2H, aromatic, adjacent to the sulfo group)
7.95 ( s, 2H, olefinic, centre)
7.86 (d, 2H, aromatic, j = 8Hz)
7.75 (d, 2H, aromatic, j=8 Hz)
7.50 (d, 2H, olefinic, j=16.7 Hz)
7.10 (d, 2H, olefinic, j=16.7)
3.60 (t, 8H, aliphatic, amide)
2.60 (t, 8H, aliphatic, amide) Example 8:
Figure imgf000017_0001
The starting material used for this compound is the ethyl ester prepared according to Example 1 (compound of formula (101)). 24.5 g of the dry, ground compound are suspended in 250 g of moφholine and then 1 g of sodium ethoxide is added and the mixture is stirred for six hours at 100°C and 200 mbar, the resulting ethanol being removed by distillation. After the reaction is complete, the moφholine is removed by distillation under a vacuum of 40 mbar, 34 g of bis-morpholinamide of formula (108) being obtained.
NMR spectrum (in D2O):
7.86 ( s, 2H, aromatic, adjacent to the sulfo group)
7.78 ( s, 2H, olefinic, centre)
7.60 (d, 2H, aromatic, j = 8Hz)
7.35 (d, 2H, aromatic, j=8)
7.23 (d, 2H, olefinic, j=16.7)
6.40 (d, 2H, olefinic, j=16.7)
3.54 (t, 8H, aliphatic)
2.56 (t, 8H, aliphatic)
Example 9
Figure imgf000017_0002
The starting material used for this compound is the ethyl ester prepared according to Example 1 (compound of formula (101)). 24.5 g of the dry, ground compound are suspended in 250 g of diethylaminoethylamine. Subsequently, 1 g of sodium ethoxide is added and the mixture is stirred for 10 hours at 100°C and 200 mbar, the resulting ethanol being removed by distillation. After the reaction is complete, the diethylaminoethylamine is removed by distillation under a vacuum of 40 mbar, affording 30 g of bis-diethylaminoethylamide of formula (109).
NMR spectrum ( in D2O):
7.98 ( s, 2H, aromatic, adjacent to the sulfo group)
7.75 ( s, 2H, olefinic, centre)
7.54 (d, 2H, aromatic, j = 8Hz)
7.48 (d, 2H, olefinic, j=16.7) superimposed
7.45 (d, 2H, aromatic, j=8) superimposed
6.50 (d, 2H, olefinic, j=16.7)
3.25 (t, 4H, aliphatic)
2.50 (t, 4H, aliphatic)
2.40 (q, 8H, aliphatic)
1.00 (t, 12H, aliphatic)
Figure imgf000018_0001
The starting material used for this compound is the free acid prepared according to Example 5 (compound of formula (105)). 18.0 g of the dry, ground compound are suspended in 150 g of thionyl chloride and the suspension is reacted, with stirring, at 70°C. After abundant degassing, the reaction mixture is concentrated by evaporation. The mixture is then suspended in 250 g of DMSO and then 17.5 g of orthanilic acid sodium salt and 10 g of sodium carbonate are added. This mixture is stirred for 4 hours at 60°C. After the reaction is complete, the mixture is cooled and the precipitated product collected by filtration, dried under a vacuum of 20 mbar and recrystallised from water, yielding 30 g of bis-ortho-sulfon-anilide of formula (110).
Example 11 :
Figure imgf000019_0001
The starting material used for this compound is the amide prepared according to Example 2 (compound of formula (102)). 21.5 g of dry, ground material are suspended in 150 g of phosphorus oxychloride and the suspension is stirred for 3 hours at 70°C. After the reaction is complete, the mixture is separated by removing the acid chloride by distillation. The distillation residue is slurried in ice water, separated by filtration and dried, resulting in 17 g of the nitrile of formula (111).
IR absoφtion: at 1670 cm'1, the carbonyl group disappears and an IR band appears at 2105 cm"1 which can be assigned to the nitrile group.
NMR spectrum ( in D2O):
7.92 ( s, 2H, aromatic, adjacent to the sulfo group)
7.82 ( s, 2H, olefinic, centre)
7.70 (d, 2H, aromatic, j = 8 Hz)
7.52 (d, 2H, aromatic, j=8 Hz)
7.40 (d, 2H, olefinic, j=16.7 Hz)
6.10 (d, 2H, olefinic, j=16.7 Hz) Example 12:
Figure imgf000020_0001
A 0.5 litre four-necked flask, equipped with stirrer and cooling/heating bath, is charged with 120 ml of glacial acetic acid and then 19.1 g of 4,4'-diaminostilbene-2,2'-disulfonic acid (c. 97%) are stirred in. Subsequently, 10.4 g of methanesulfonic acid (c. 100%) are added dropwise. The thoroughly stirred, pale slurry is cooled to 10°C using an ice bath, and 20.5 g of a solution of sodium nitrite in water (36 % by weight) are steadily added dropwise over one hour, the temperature being kept below 15°C. The mixture is then heated to 25°C and allowed to react for another 5 hours. The nitrite excess is eliminated with some sulfamic acid.
60 g of acetic anhydride are added dropwise to reduce the water concentration, the temperature being kept below 20°C by cooling. After stirring the mixture for 20 minutes, 16.8 g of sodium hydrogencarbonate are slowly added, the foam formation being controlled. 0.3 g of palladium chloride solution (c. 20%) in hydrochloric acid and 14.2 g of butyl acrylate are stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 50°C over about 2 to 3 hours. If the diazo component test is negative, the mixture is worked up.
The reaction mixture is separated by suction filtration, resulting in about 110 g of filter product. This filter product is dried under vacuum, about 38 g of crude product remaining, and is recrystallised from water and sodium chloride, resulting in 28.0 g of the compound of formula (112).
NMR spectrum ( in D2O):
7.90 ( s, 2H, aromatic, adjacent to sulfo group)
7.78 ( s, 2H, olefinic, centre)
7.58 (d, 2H, aromatic, j = 8Hz) 7.47 (d, 2H, olefinic, j=16.7) superimposed
7.47 (d, 2H, aromatic, j=8) superimposed
6.40 (d, 2H, olefinic, j=16.7)
4.12 (t, 4H, aliphatic, ester)
1.65 (m, 4H, aliphatic, ester)
1.37 (m, 4H, aliphatic, ester)
0.90 (t, 6H, aliphatic, ester)
Figure imgf000021_0001
A 0.5 litre four-necked flask, equipped with stirrer and cooling/heating bath, is charged with 120 ml of glacial acetic acid and then 19.1 g of 4,4'-diaminostilbene-2,2'-disulfonic acid (c. 97%) are stirred in. 7.4 g of sulfuric acid (c. 100%) are added dropwise to this mixture. The thoroughly stirred, pale slurry is cooled to 10°C using an ice bath, and 20.5 g of a solution of sodium nitrite in water (36 % by weight) are steadily added dropwise over one hour, the temperature being kept below 15°C. The mixture is then heated to 32°C and allowed to react for another 5 hours. The nitrite excess is eliminated with some sulfamic acid.
60 g of acetic anhydride are added dropwise to reduce the water concentration, the temperature being kept below 20°C by cooling. After stirring the mixture for 20 minutes, 16.8 g of sodium hydrogencarbonate are slowly added, the foam formation being controlled. 0.3 g of palladium chloride solution (c. 20%) in hydrochloric acid and 29.4 g of lauryl acrylate are then stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 50°C over about 4 to 5 hours. If the diazo component test is negative, the mixture is worked up.
The reaction mixture is separated by suction filtration, about 140 g of filter product being obtained. This filter product is dried under vacuum, about 50 g of crude product remaining, and is recrystallised from water and sodium chloride, resulting in 30.0 g of the compound of formula (113).
Example 14:
Figure imgf000022_0001
The starting material used for this compound is the ethyl ester prepared according to Example 1 (compound of formula (101)). 24.5 g of the dry, ground compound are suspended in 500 g of allyl alcohol and then 1 g of sodium ethoxide is added and the mixture stirred for 10 hours at 90-98°C under normal pressure, the resulting ethanol being removed by distillation by means of a rectification column. The suspension of transesterified product is separated by filtration and dried, resulting in 34 g of allyl diester of formula (114).
Figure imgf000022_0002
A 1.0 litre four-necked flask, equipped with stirrer and cooling/heating bath, is charged with
150 g of water and 123 g of 60% sulfuric acid and is then cooled to 15°C.
A 1 litre beaker glass is charged with 450 ml of water and then 114.6 g of 4,4'-diaminostil- bene-2,2 '-disulfonic acid (c. 97%) are stirred in. This mixture is adjusted to pH 7-8 with about
47 g of sodium hydroxide 50%. A slightly brown solution forms which is charged with 121 g of sodium nitrite 35%. At 15°C, this solution is steadily added dropwise over one hour to the sulfuric acid solution, the temperature being kept at 15°C. The mixture is then slowly heated to 25°C and the mixture is allowed to react for one hour. The nitrite excess is eliminated with some sulfamic acid. The diazo suspension is filtered and washed with 100 g of water.
About 316 g of diazo are slurried in 600 g of acetic acid 100% and the water concentration is reduced by the dropwise addition of 843 g of acetic anhydride, the temperature being kept below 20°C by cooling. After stirring the mixture for 20 minutes, 101.1 g of sodium hydrogencarbonate are slowly added, the foam formation being controlled. Subsequently, 1 g of palladium dibenzylacetone and 63 g of styrene are stirred in. The reaction starts immediately with vigorous degassing. The temperature rises to 50°C over about one hour. If the diazo component test is negative, the mixture is worked up.
The yellow reaction mixture is separated by suction filtration, about 300 g of filter product being obtained. This filter product is dried under vacuum and recrystallised from methanol, resulting in 120 g of the compound of formula (115).
NMR spectrum (in DMSO)
8.18 ( s, 2H, aromatic, adjacent to the sulfo group)
8.02 ( s, 2H, olefinic, centre)
7.68 (m, 8H, aromatic)
7.40 (t, 4H, aromatic, j=8)
7.30 (t, 2H, aromatic , j=8) superimposed with
7.30 (q, 4H, olefinic, j=16.7)
Example 16: Application
In a laboratory sheet former, a mixture consisting of sulfate cellulose birch/pine 1/1, free ness value 35° SR, 10% carbonate as filler and 0.03% of a polymeric cationic polyacrylate (Percol 292) as retention agent is used for the production of paper samples (weight per unit area of 160 g/m2).
The compounds listed in Table 1 are dissolved in deionised water and are added to the paper pulp at a consistency of 2.2 %. The subsequent exhaustion time is 15 minutes. The retention agent is added shortly before sheet forming and the paper samples are dried under vacuum at 80°C (System Rapid Koethen).
A Spectroflash 500 is used to measure the brightness (ISO) and to calculate the difference between the brightness of a specimen with and without treatment. The results are listed as fluorescence (ISO) in Table 1:
Table 1
Figure imgf000024_0001
Example 17: Use in a size press
In a laboratory size press, neutrally sized base paper having a weight per unit area of
80 g/m2 is impregnated with an aqueous solution of 7% anionic starch (Perfectamyl A 4692) and 0.3% each of the whiteners of this invention. The liquor uptake is 35%. After drying the sheets, the brightness (ISO) is measured as described in Example 16 and the fluorescence
(ISO) is calculated in analogous manner (Table 2):
Table 2
Figure imgf000024_0002
Example 18: Use in detergents
The compounds listed in Table 3 are admixed in a concentration of 0.1% to a commercially available liquid detergent without fluorescent whitening agent and containing the following ingredients in accordance with EG recommendation: < 5% phosphonates, cationic surfactants
5-15% nonionic surfactants, soap
15-30% anionic surfactants
Further ingredients: enzymes, solvents, soil carriers, perfume oils
A washing liquor is prepared consisting of 0.4 g of the above detergent in 50 ml of drinking water.
10 g of bleached cotton are added to the liquor and are washed for 15 minutes at 25°C. The material is then rinsed, spin-dried and ironed at 160 °C. This washing process is repeated five times.
The whiteness of the fabric is then determined by means of a DCI/SF 500 spectrophoto- meter by the Ganz method:
Table 3
Figure imgf000025_0001
Example 19: Use in textile application: pad-batch process
1.0 g/l of the compounds listed in Table 4 are dissolved in an aqueous solution consisting of:
2 g I of Tinovetin JUN
4 g/l of Irgasol P
10% of ethanol.
Subsequently, the mixture is applied to 5 g of bleached cotton and 5 g of polyamide by the pad-batch process (liquor uptake 70%). The fabric samples are dried at 60 °C and are then thermofixed for 3 minutes at 160 °C.
The whiteness of the fabric is then determined by means of a DCI/SF 500 spectrophoto- meter by the Ganz method: Table 4
Figure imgf000026_0001
Example 20: Use in textile application; exhaust process
The compounds listed in Table 5 are dissolved and applied to cotton and polyamide by the pad-batch process as described in Example 19. The cotton fabric samples are then immediately placed in 200 ml of a liquor comprising 10 g/l of sodium sulfate. The polyamide fabric samples are placed in 200 ml of a liquor which is buffered at pH 7 by means of a phosphate buffer.
The two liquors are heated from 25 °C to 100 °C over 35 minutes and are kept at 100°C for 30 minutes. Subsequently, the liquors are cooled to room temperature. The fabric samples are rinsed, spin-dried and ironed at 160°C.
The whiteness of the fabric is determined by means of a DCI/SF 500 spectrophotometer by the Ganz method:
Table 5
Figure imgf000026_0002

Claims

What is claimed is
1. A compound of formula
Figure imgf000027_0001
wherein
Figure imgf000027_0002
Yi and Y2are each independently of the other hydrogen or -SO3 "M+; at least one Yi or Y2 being -SO3 'M+;
Ri is hydrogen; CrC╬╣8alkyl or C2-C╬╣8alkenyl which is unsubstituted or substituted by cyano, -SH, C╬╣-C5alkylthio, C╬╣-C5alkoxy, amino, C╬╣-C5monoalkylamino, d-C5dialkyl- amino or carboxy; mono-, di- or trihydroxy-d-C5alkyl; a radical of formula
(1a) -pO-(CH2 -OH , amino; d-C5monoalkylamino; CrC5dialkylamino; phenyl or
phenyl-CrC3alkyl which is unsubstituted or substituted by one or several d-C5alkyl, C╬╣-C5alkoxy, hydroxy, cyano, sulfo or halogen;
R2 and R3 are each independently of the other hydrogen; d-C5alkyl which is unsubstituted or substituted by cyano, -SH, d-C5alkylthio, C╬╣-C5alkoxy or carboxy; hydroxy-CrC5alkyl; mono- or di-C╬╣-C5alkylamino-C╬╣-C5alkyl; phenyl or phenyl-CrC3alkyl which is unsubstituted or substituted by one or several C╬╣-C5alkyl, C╬╣-C5alkoxy,hydroxy, cyano, sulfo or halogen; or
R2 and R3, together with the linking nitrogen atom, are a five- or six-membered heterocyclic radical;
R is hydrogen, C╬╣-C5alkyl, d-C5alkoxy, hydroxy, cyano, sulfo or halogen,
M is hydrogen; an alkali metal cation or alkaline earth metal cation; or a cation formed from an amine; mi is a number from 1 to 5; and ni is a number from 1 to 3.
2. A compound according to claim 1 , wherein in formula (1 )
Ri is hydroxy; d-C5-alkyl; d-C5-hydroxyalkyl; amino, or a radical of formula (1a).
3. A compound according to either claim 1 or claim 2, wherein Ri is C╬╣-C3-alkyl, in particular methyl or ethyl.
4. A compound according to either claim 1 or claim 2, wherein in formula (1 ) Ri is a radical of formula -O-(CH2)2-O-(CH2)2-O-(CH2)2-OH.
5. A compound according to claim 1 , wherein
R2 and R3 are each independently of the other hydrogen; mono- or di-d-C5-alkylamino-C╬╣-
C5alkylamino; or a radical of formula (1b) -a SOgM or
R2 and R3, together with the linking nitrogen atom, are a moφholino radical.
6. A compound according to claim 1 , wherein X is -CN or phenyl.
7. A process for the preparation of the compound of formula (1), which comprises diazotising the aminostilbene compound of formula
Figure imgf000028_0001
to the compound of formula
Figure imgf000028_0002
and then reacting the diazonium compound so obtained with the compound of formula (15)
to the compound of formula (1), wherein X, Yi and Y2 are as defined in claim (1).
8. Use of the compound of formula (1) as fluorescent whitening agent for synthetic or natural organic materials.
9. Use according to claim 8, wherein the compound of formula (1) is used for whitening paper in the pulp, size press or in coating.
10. Use according to claim 8, which comprises using the compound of formula (1) for whitening textile materials, in particular textile materials consisting of cotton and synthetic polyamide, as well as their blends with each other and with other types of fibre.
11. Use according to claim 8, which comprises using the compound of formula (1) in detergents for achieving an improved aspect of the detergent and for optically brightening the washed goods after the washing process.
12. A process for improving the SPF value of textile fibre materials, which comprises treating the fibre material with 0.05 to 3 % by weight, based on the weight of the fibre material, of one or more than one of the compound of formula (1).
PCT/EP1999/005431 1998-08-10 1999-07-29 Divinylstilbenesulfonic acid derivatives WO2000009471A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001092217A2 (en) * 2000-05-30 2001-12-06 Ciba Specialty Chemicals Holding Inc. Process for the preparation of amidostyrylstilbene-disulphonic acid compounds and novel amidostyrylstilbene-disulphonic acid compounds and their use as fluorescent whitening agents
WO2002055488A1 (en) * 2001-01-12 2002-07-18 Ciba Specialty Chemicals Holdings Inc. Asymmetric divinylstilbene-sulphonic acids
WO2007064809A3 (en) * 2005-12-02 2007-12-27 Sachem Inc Anion-exchange displacement chromatography process and anionic organic compounds for use as displacer compounds in anion-exchange displacement chromatography process
CN110922531A (en) * 2019-12-06 2020-03-27 陕西科技大学 Starch grafted fluorescent copolymer emulsion and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4918215A (en) * 1981-03-31 1990-04-17 Ciba-Geigy Corporation 4-halogenostilbene derivatives and processes for their preparation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4918215A (en) * 1981-03-31 1990-04-17 Ciba-Geigy Corporation 4-halogenostilbene derivatives and processes for their preparation

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001092217A2 (en) * 2000-05-30 2001-12-06 Ciba Specialty Chemicals Holding Inc. Process for the preparation of amidostyrylstilbene-disulphonic acid compounds and novel amidostyrylstilbene-disulphonic acid compounds and their use as fluorescent whitening agents
WO2001092217A3 (en) * 2000-05-30 2002-05-16 Ciba Sc Holding Ag Process for the preparation of amidostyrylstilbene-disulphonic acid compounds and novel amidostyrylstilbene-disulphonic acid compounds and their use as fluorescent whitening agents
WO2002055488A1 (en) * 2001-01-12 2002-07-18 Ciba Specialty Chemicals Holdings Inc. Asymmetric divinylstilbene-sulphonic acids
WO2007064809A3 (en) * 2005-12-02 2007-12-27 Sachem Inc Anion-exchange displacement chromatography process and anionic organic compounds for use as displacer compounds in anion-exchange displacement chromatography process
CN110922531A (en) * 2019-12-06 2020-03-27 陕西科技大学 Starch grafted fluorescent copolymer emulsion and preparation method and application thereof
CN110922531B (en) * 2019-12-06 2022-06-24 陕西科技大学 Starch grafted fluorescent copolymer emulsion and preparation method and application thereof

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