WO2000047550A1 - Bis-styrylbiphenyl compounds - Google Patents
Bis-styrylbiphenyl compounds Download PDFInfo
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- WO2000047550A1 WO2000047550A1 PCT/EP2000/000726 EP0000726W WO0047550A1 WO 2000047550 A1 WO2000047550 A1 WO 2000047550A1 EP 0000726 W EP0000726 W EP 0000726W WO 0047550 A1 WO0047550 A1 WO 0047550A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
- C07C255/51—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings containing at least two cyano groups bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/56—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and doubly-bound oxygen atoms bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
Definitions
- the present invention relates to novel asymmetrical bis-styrylbiphenyl compounds, to a process for their preparation and to their use as optical brighteners, in particular for polyester spinning melts.
- Bis-styrylbiphenyl compounds which are suitable as optical brighteners are already known, e.g. from GB-A-1 , 247,934 which also discloses processes for their preparation. However, those processes provide almost exclusively symmetrical compounds, i.e. compounds which carry the same substituents in the same positions at the terminal phenyl radicals.
- the preparation of asymmetrical bis-styrylbiphenyl compounds is described only in admixture with symmetrical compounds from which they must be separated by elaborate measures, e.g. by recrystallisation. Naturally, the resulting yield of asymmetrical compounds is unsatisfactory.
- this invention relates to asymmetrical bis-styrylbiphenyl compounds of formula
- R, and R 2 are each independently of the other hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyioxy, aryl oraralkyl, wherein R, and
- R are not both hydrogen at the same time and which substituents are different if they are in the same position of the phenyl ring, and
- R 3 , R , R5 and R 6 are each independently of one another hydrogen, halogen, alkyl, cycloalkyl or alkoxy.
- Ri and R 2 are each independently of the other hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, at least one of which substituents is not hydrogen, and
- R3, R , s and R 6 are each independently of one another hydrogen, halogen, alkyl or alkoxy.
- R1 and R 2 are independently of each other cyano, chloro, hydroxy, C C 4 alkyl, C C 4 alkoxy or phenyl.
- R 3 to R 6 are preferably each independently of one another hydrogen, chloro, C C 4 alkyl or C r C 4 alkoxy. In particularly preferred compounds of formula (1) or (2), all of these substituents are hydrogen.
- Halogen is fluoro, bromo, iodo or, preferably, chloro.
- alkyl groups in the alkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy and aralkyl radicals contain, for example, 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms and, most preferably, 1 to 4 carbon atoms.
- alkyl is preferably C C alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
- Cycloalkyl is preferably Cs-C ⁇ ycloalkyl, more preferably cyclohexyl.
- Alkoxy preferably means C C 4 alkoxy, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert-butoxy.
- Aryl is, for example, naphthyl or, preferably, phenyl, and these radicals can be substituted, for example by alkyl, alkoxy, sulfo, carboxy, halogen or alkoxycarbonyl.
- Aralkyl preferably means C C 4 alkylenephenyl, more preferably benzyl.
- R is hydrogen, cyano, halogen, hydroxy, alkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl.
- Rt is C 1 -C 2 alkyl, CrC-salkoxy, cyano or phenyl.
- the compounds of formula (1 ) are prepared, for example, by reacting 1 mole of a dialdehyde of formula
- R 3 , R . Rs and R 6 are each independently of one another hydrogen, halogen, alkyl or alkoxy, with 1 mole of a compound of formula
- R T is hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, and
- R 7 and R 8 are alkyl, cycloalkyl, aryl or aralkyl, to give an intermediate of formula
- R 2 is hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, and
- R 7 and R 8 are alkyl, cycloalkyl, aryl or aralkyl, wherein Ri and R 2 are not both hydrogen at the same time and which substituents are different if they are in the same position of the phenyl ring, to give a compound of formula (1).
- R 7 and R 8 are preferably C ⁇ -C 4 alkyl, phenyl or benzyl. In particularly preferred compounds of formula (5) and (7) these substituents are d-Caalkyl.
- the compounds (4), (5) and (7) are known or can be prepared in a manner known per se.
- the reaction of a compound of formula (4) with a compound of formula (5) and the reaction of an intermediate of formula (6) with a compound of formula (7) are carried out in the presence of a strongly basic compound.
- a strongly basic compound are for example: alkali metal hydroxides, alkali metal amides, alkali metal carbonates, alkali metal hydrogen- carbonates or alkali metal alcoholates, in particular the lithium, potassium or sodium compounds.
- the potassium or sodium alcoholates of aliphatic C 1 -C 4 alcohols are particularly preferred.
- the solvent used for the reaction of a compound of formula (4) with a compound of formula (6) is a solvent which is inert towards the reactants, preferably an aliphatic alcohol and, more preferably, a CrC 6 alcohol.
- Suitable are, for example, methanol, ethanol, n-propanol, isopro- panol, butan-1-ol, butan-2-ol, tert-butanol, pentan-1-ol and hexan-1-ol. Of these, methanol is preferred.
- the reaction temperature is usually in the range from room temperature to the boiling temperature of the solvent. It is preferred to work at about 20 to 80° C, more preferably at 30 to 70° C.
- the reaction time depends, inter alia, on the kind of reactants used and on the reaction temperature.
- the temperature is usually in the range from 2 to 48 hours.
- Ri is hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, and
- R3, R 4 , R 5 and R 6 are each independently of one another hydrogen, halogen, alkyl or alkoxy, at least one of the substituents R 3 , R 4 , R5 and R 6 not being hydrogen, are novel and are also an object of this invention.
- an aprotic solvent is used which is inert towards the reactants and in which the compound of formula (6) is at least partially soluble. It is possible to use e.g. dimethylformamide, diethylformamide, di- methylacetamide, dimethylsulfoxide and N-methylpyrrolidone.
- the reaction temperature is usually in the range from room temperature to the boiling temperature of the solvent. It is preferred to work at about 20 to 80° C, more preferably at 20 to 40° C.
- the reaction time depends, inter alia, on the kind of reactants used and on the reaction temperature and is generally in the range from 2 to 48 hours.
- the reaction mixture is worked up in customary manner and the compound of formula (1) is isolated, e.g. by evaporation or by filtration if it is insoluble in the solvent used.
- the compounds of formula (1) have marked fluorescence in the dissolved or finely divided state. They can thus be used for optically brightening a range of materials, in particular organic materials.
- This invention thus also relates to the use of the compounds of formula (1 ) for optically brightening organic materials, and to organic materials comprising at least one compound of formula (1), as well as to a process for optically brightening organic materials, which process comprises incorporating into, or applying to, these materials at least one compound of formula (1).
- the organic materials which can be brightened according to this invention by means of compounds of formula (1) include synthetic, semi-synthetic or natural, especially polymeric, materials.
- Suitable materials are, for example, a) polymerisation products based on organic compounds containing at least one polyme- risable carbon-carbon double bond, for example polymers based on unsaturated carboxylic acids or derivatives thereof (such as acryl esters, acrylic acids, acrylonitrile and their derivatives), on olefin hydrocarbons (such as ethylene, propylene, styrene) or on vinyl compounds or vinylidene compounds (such as vinyl chloride, vinyl alcohol, vinylidene chloride); b) polymerisation products which are obtainable by ring-opening, for example polyamides of the caprolactam type, and also polymers which are obtainable both via polyaddition and via polycondensation, such as polyethers or polyacetals; c) polycondensates, such as polyesters, polyamides, melamine
- novel compounds are particularly preferably used for optically brightening polyesters, in particular polyethylene glycol terephthalate, in the spinning melt, since they do not decompose at the required temperatures.
- novel asymmetrical compounds of formula (1) have a higher degree of whiteness on the cited materials than the corresponding symmetrical compounds. They are furthermore distinguished by particularly good fastness to sublimation.
Abstract
Asymmetrical bis-styrylbiphenyl compounds of formula (1) wherein R1 to R6 are as defined in claim 1, are excellently suitable as optical brighteners, for example for polyesters in the spinning melt.
Description
Bis-styrylbiphenyl compounds
The present invention relates to novel asymmetrical bis-styrylbiphenyl compounds, to a process for their preparation and to their use as optical brighteners, in particular for polyester spinning melts.
Bis-styrylbiphenyl compounds which are suitable as optical brighteners are already known, e.g. from GB-A-1 , 247,934 which also discloses processes for their preparation. However, those processes provide almost exclusively symmetrical compounds, i.e. compounds which carry the same substituents in the same positions at the terminal phenyl radicals. The preparation of asymmetrical bis-styrylbiphenyl compounds is described only in admixture with symmetrical compounds from which they must be separated by elaborate measures, e.g. by recrystallisation. Naturally, the resulting yield of asymmetrical compounds is unsatisfactory.
A process has now been found for the preparation of asymmetrical bis-styrylbiphenyl compounds which provides them in high yields and good purity. When used as optical brighteners in polyester spinning melts, the bis-styrylbiphenyl compounds obtained surprisingly have improved whiteness compared to the corresponding symmetrical compounds.
Accordingly, this invention relates to asymmetrical bis-styrylbiphenyl compounds of formula
R, and R2 are each independently of the other hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyioxy, aryl oraralkyl, wherein R, and
R are not both hydrogen at the same time and which substituents are different if they are in the same position of the phenyl ring, and
R3, R , R5 and R6 are each independently of one another hydrogen, halogen, alkyl, cycloalkyl or alkoxy.
Preferred compounds of this invention correspond to formula
Ri and R2 are each independently of the other hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, at least one of which substituents is not hydrogen, and
R3, R , s and R6 are each independently of one another hydrogen, halogen, alkyl or alkoxy.
Preferred meanings of R1 and R2 are independently of each other cyano, chloro, hydroxy, C C4alkyl, C C4alkoxy or phenyl.
R3 to R6 are preferably each independently of one another hydrogen, chloro, C C4alkyl or CrC4alkoxy. In particularly preferred compounds of formula (1) or (2), all of these substituents are hydrogen.
Halogen is fluoro, bromo, iodo or, preferably, chloro.
The alkyl groups in the alkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy and aralkyl radicals contain, for example, 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms and, most preferably, 1 to 4 carbon atoms.
In the optical brighteners of formulae (1) and (2), alkyl is preferably C C alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
Cycloalkyl is preferably Cs-C^ycloalkyl, more preferably cyclohexyl.
Alkoxy preferably means C C4alkoxy, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert-butoxy.
Aryl is, for example, naphthyl or, preferably, phenyl, and these radicals can be substituted, for example by alkyl, alkoxy, sulfo, carboxy, halogen or alkoxycarbonyl.
Aralkyl preferably means C C4alkylenephenyl, more preferably benzyl.
Very particularly preferred novel compounds correspond to formula
R is hydrogen, cyano, halogen, hydroxy, alkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl.
Of these compounds, those are particularly preferred, wherein Rt is C1-C2alkyl, CrC-salkoxy, cyano or phenyl.
The compounds of formula (1 ) are prepared, for example, by reacting 1 mole of a dialdehyde of formula
FL
R5 R6
wherein
R3, R . Rs and R6 are each independently of one another hydrogen, halogen, alkyl or alkoxy, with 1 mole of a compound of formula
O
RT is hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, and
R7 and R8 are alkyl, cycloalkyl, aryl or aralkyl, to give an intermediate of formula
R„ R„
O
R2 is hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, and
R7 and R8 are alkyl, cycloalkyl, aryl or aralkyl, wherein Ri and R2 are not both hydrogen at the same time and which substituents are different if they are in the same position of the phenyl ring, to give a compound of formula (1).
R7 and R8 are preferably Cι-C4alkyl, phenyl or benzyl. In particularly preferred compounds of formula (5) and (7) these substituents are d-Caalkyl.
The compounds (4), (5) and (7) are known or can be prepared in a manner known per se.
The reaction of a compound of formula (4) with a compound of formula (5) and the reaction of an intermediate of formula (6) with a compound of formula (7) are carried out in the presence of a strongly basic compound. Such strongly basic compounds are for example: alkali metal hydroxides, alkali metal amides, alkali metal carbonates, alkali metal hydrogen- carbonates or alkali metal alcoholates, in particular the lithium, potassium or sodium
compounds. The potassium or sodium alcoholates of aliphatic C1-C4alcohols are particularly preferred.
The solvent used for the reaction of a compound of formula (4) with a compound of formula (6) is a solvent which is inert towards the reactants, preferably an aliphatic alcohol and, more preferably, a CrC6alcohol. Suitable are, for example, methanol, ethanol, n-propanol, isopro- panol, butan-1-ol, butan-2-ol, tert-butanol, pentan-1-ol and hexan-1-ol. Of these, methanol is preferred.
The reaction temperature is usually in the range from room temperature to the boiling temperature of the solvent. It is preferred to work at about 20 to 80° C, more preferably at 30 to 70° C.
The reaction time depends, inter alia, on the kind of reactants used and on the reaction temperature. The temperature is usually in the range from 2 to 48 hours. After the reaction is complete, the reaction mixture is worked up in customary manner and the compounds of formula (6) are isolated, if desired, e.g. by evaporation or by filtration if they are insoluble in the solvent used.
The intermediates of formula
Ri is hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, and
R3, R4, R5 and R6are each independently of one another hydrogen, halogen, alkyl or alkoxy, at least one of the substituents R3, R4, R5 and R6 not being hydrogen, are novel and are also an object of this invention.
To react a compound of formula (6) with a compound of formula (7) an aprotic solvent is used which is inert towards the reactants and in which the compound of formula (6) is at least partially soluble. It is possible to use e.g. dimethylformamide, diethylformamide, di- methylacetamide, dimethylsulfoxide and N-methylpyrrolidone.
The reaction temperature is usually in the range from room temperature to the boiling temperature of the solvent. It is preferred to work at about 20 to 80° C, more preferably at 20 to 40° C.
The reaction time depends, inter alia, on the kind of reactants used and on the reaction temperature and is generally in the range from 2 to 48 hours. After the reaction is complete, the reaction mixture is worked up in customary manner and the compound of formula (1) is isolated, e.g. by evaporation or by filtration if it is insoluble in the solvent used.
The compounds of formula (1) have marked fluorescence in the dissolved or finely divided state. They can thus be used for optically brightening a range of materials, in particular organic materials. This invention thus also relates to the use of the compounds of formula (1 ) for optically brightening organic materials, and to organic materials comprising at least one compound of formula (1), as well as to a process for optically brightening organic materials, which process comprises incorporating into, or applying to, these materials at least one compound of formula (1).
The organic materials which can be brightened according to this invention by means of compounds of formula (1) include synthetic, semi-synthetic or natural, especially polymeric, materials. Suitable materials are, for example, a) polymerisation products based on organic compounds containing at least one polyme- risable carbon-carbon double bond, for example polymers based on unsaturated carboxylic acids or derivatives thereof (such as acryl esters, acrylic acids, acrylonitrile and their derivatives), on olefin hydrocarbons (such as ethylene, propylene, styrene) or on vinyl compounds or vinylidene compounds (such as vinyl chloride, vinyl alcohol, vinylidene chloride); b) polymerisation products which are obtainable by ring-opening, for example polyamides of the caprolactam type, and also polymers which are obtainable both via polyaddition and via polycondensation, such as polyethers or polyacetals; c) polycondensates, such as polyesters, polyamides, melamine resins or polycarbonates;
d) polyaddition products, such as polyurethanes, or e) semi-synthetic materials, such as cellulose ester, cellulose ether, regenerated cellulose.
The novel compounds are particularly preferably used for optically brightening polyesters, in particular polyethylene glycol terephthalate, in the spinning melt, since they do not decompose at the required temperatures.
Surprisingly, the novel asymmetrical compounds of formula (1) have a higher degree of whiteness on the cited materials than the corresponding symmetrical compounds. They are furthermore distinguished by particularly good fastness to sublimation.
The following Examples illustrate the invention in more detail. Parts and percentages are by weight and temperatures are given in degrees Celsius.
Example 1 :
4-r2-(4'-FormylH .1 '-biphenyl -vOethenyllbenzonitrile
3.15 g (15 mmol) of 4,4'-biphenyldialdehyde are suspended in 100ml of methanol at room temperature. A solution of 1.62 g (30 mmol) of sodium methylate in 4.7 ml of methanol is added dropwise to this suspension over 10 minutes, and this mixture is then heated to 40° C. A solution of 3.38 g (15mmol) of 4-(dimethoxyphosphonomethyl)benzonitrile in 16 ml of methanol is then added dropwise over 30 minutes. After the addition is complete, the reaction mixture is allowed to cool to room temperature and is then stirred for another 20 hours at room temperature. The precipitated solid is subjected to filtration, washed with 2 x 50 ml of methanol and once with 50 ml of hexane and is then dried at 80° C under vacuum.
This yields 3.89 g (12.6 mmol) of the compound of formula
1H-NMR spectrum: (360 MHz, [D6]DMSO): δ = 7.4 (d); 7.6 (m); 7.8 (m); 8.0 (AA'XX');
10.1 (s) Example 2:
2-r2-(4'-Formviπ .1 '-biphenyll-4-yl)ethenyllbenzonitrile
3.15 g (15mmol) of 4,4'-biphenyldialdehyde are suspended in 100 ml of methanol at room temperature. A solution of 1.62 g of sodium methylate in 4.7 ml of methanol is added drop- wise to this suspension over 10 minutes, and this mixture is then heated to 40° C. A solution of 3.38 g (15 mmol) of 2-(dimethoxyphosphonomethyl)benzonitrile in 16 ml of methanol is added dropwise over 30 minutes at this temperature. After the addition is complete, the reaction mixture is allowed to cool to room temperature and is stirred for another 20 hours at room temperature. The precipitated solid is subjected to filtration, washed with 2 x 50 ml of methanol and once with 50 ml of hexane and is then dried at 80°C under vacuum.
This yields 3.2 g (10.3 mmol) of the compound of formula
2.2 g of this compound are recrystallised in 40 ml of chlorobenzene. The mixture is heated until the solid is completely dissolved and is then cooled and charged with 0.5 g of tonsil. The mixture is refluxed and subjected to hot filtration. The filtrate is again refluxed and is then cooled in an oil bath. This yields 1.25 g of the analytically pure compound of the above formula.
1H-NMR spectrum: (360 MHz, [Dβ]DMSO): δ = 7.4 - 8.1 (m); 10.1 (s)
Example 3:
2.4 ΪH .1 '-Biphenyll-4.4 '-diyldi-2.1 -ethenedivDbisbenzonitrile
46.41 g (0.15 mol) of 4-[2-(4'-formyl[1 ,1 '-biphenyl]-4-yl)ethenyl]benzonitrile, obtained according to Example 1 , and 37.16 g (0.165 mol) of 2-(di-methoxyphosphonomethyl)ben- zonitrile are suspended in 400 ml of N.N-dimethylformamide. A solution of 10.80 g of sodium methylate in 32 ml of methanol is added dropwise to this suspension over 60 minutes. A beige to brown suspension is obtained which is stirred for another 3 hours at room temperature. After adding 150 ml of methanol, the mixture is stirred for 10 minutes and the pre- cipated solid is subjected to filtration. The filtrate is washed with 2 x 25 ml of water and then with 2 x 50 ml of methanol and dried at 80° C under vacuum. This yields 53.83 g of the compound of formula
48.83 g of this compound are recrystallised in 500 ml of 1 ,2-dichlorobenzene. The mixture is heated until the solid is completely dissolved and is then cooled and charged with 3.0 g of tonsil. This mixture is refluxed and subjected to hot filtration. The filtrate is again refluxed and is then cooled in an oil bath. This yields 41.5 g of the analytically pure compound of the above formula.
1 H-NMR spectrum, (360 MHz, [D6]DMSO): δ = 7.44 (m); 7.53 (d); 7.64 (d); 7.75 - 8.05 (m); 8.15 (d)
Example 4:
3,4'-(H , 1 '-Biphenvn-4.4'-diyldi-2, 1 -ethenedivObisbenzonitrile
late
Under a weak stream of nitrogen, 4.64g (0.015mol) of 4-[2-(4'-formyl[1 ,1 '-biphenyl]-4-yl)- ethenyljbenzonitrile, obtained according to Example 1 , and 4.39g (0.0165mol) of 3-(dimeth- oxyphosphonomethyl)benzonitrile are suspended in 40ml of N,N-dimethylformanπide. A solution of 3.6 g (0.02mol) of sodium methylate 30% is then added dropwise to this suspension over 25 minutes. This mixture is stirred for four hours at room temperature and then for another hour at 50°C. After allowing the mixture to cool, 25ml of methanol are added. After filtration, the product is washed with methanol and water and then dried at 70°C under vacuum. This yields 4.9g of the product in the form of pale yellow crystals.
Example 5:
2.3'-(f 1.1 '-Biphenyl1-4.4'-diyldi-2.1 -ethenedivhbisbenzonitrile
ate
Under a weak stream of nitrogen, 4.64g (0.015mol) of 2-[2-(4'-formyl[1 ,1 '-biphenyl]-4-yl)- ethenyljbenzonitrile, obtained according to Example 2, and 4.39g (0.0165mol) of 3-(dimeth- oxyphosphonomethyl)benzonitrile are suspended in 40ml of N,N-dimethylformamide. A solution of 3.6 g (0.02mol) of sodium methylate 30% is added dropwise to this suspension over 25 minutes. This mixture is stirred for five hours at room temperature and then for another hour at 50°C. After allowing the mixture to cool, 35ml of methanol are added and the product is subjected to filtration, washed with methanol and water and then dried at 70°C under vacuum. This yields 4.45g of the product in the form of pale yellow crystals.
Claims
1. A bis-styrylbiphenyl compound of formula
R,
R, and R2 are each independently of the other hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, wherein R, and
R2 are not both hydrogen at the same time and which substituents are different if they are in the same position of the phenyl ring, and
R3. R4. Rs and R6 are each independently of one another hydrogen, halogen, alkyl, cycloalkyl or alkoxy.
2. A compound according to claim 1 of formula
R_ R.
R, and R2 are each independently of the other hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, at least one of which substituents is not hydrogen, and
R3. R . Rs and R6 are each independently of one another hydrogen, halogen, alkyl or alkoxy.
3. A compound according to either claim 1 or claim 2, wherein
Ri and R2 are each independently of the other cyano, chloro, hydroxy, C C4alkyl, CrC4- alkoxy or phenyl.
4. A compound according to any one of claims 1 to 3, wherein
R3 to R6 are each independently of one another hydrogen, chloro, C1-C4alkyl or C C4alkoxy.
5. A compound according to any one of claims 1 to 4, wherein R3 to R6 are each hydrogen.
6. A compound according to claim 1 of formula
RT is hydrogen, cyano, halogen, hydroxy, alkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl.
7. A compound according to claim 6, wherein Ri is CrC2alkyl, Cι-C2alkoxy, cyano or phenyl.
8. A process for the preparation of the compound of formula (1) according to claim 1 , which comprises reacting 1 mole of a dialdehyde of formula
wherein
R3. R , Rs and R6are each independently of one another hydrogen, halogen, alkyl or alkoxy, with 1 mole of a compound of formula 
wherein
R! is hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, and
R7 and R8 are each alkyl, cycloalkyl, aryl or aralkyl, to give an intermediate of formula
O
R2 is hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, and
R7 and R8 are each alkyl, cycloalkyl, aryl or aralkyl, wherein Ri and R2 are not both hydrogen at the same time and which substituents are different if they are in the same position of the phenyl ring, to give a compound of formula (1 ).
9. A process according to claim 8, which comprises using compounds of formulae (5) and
(7), wherein
R7 and R8 are each C1-C4alkyl, phenyl or benzyl.
10. A process according to claim 8, which comprises using compounds of formulae (5) and (7), wherein R7 and R8 are identical and are each C,-C2alkyl.
1 1. A process according to any one of claims 8 to 10, which comprises using a compound of formula (4), wherein R3, R4, R5 and R6 are each hydrogen.
12. An intermediate of formula
Ri is hydrogen, cyano, halogen, hydroxy, alkyl, cycloalkyl, alkoxy, carboxy, alkoxycarbonyl, alkylcarbonyloxy, aryl or aralkyl, and
R3. R , Rs and R6are each independently of one another hydrogen, halogen, alkyl or alkoxy, at least one of the substituents R3, R4, R5 and R6 not being hydrogen.
13. Use of the compound of formula (1) according to claim 1 for optically brightening organic materials.
14. An organic material comprising at least one compound of formula (1) according to claim 1.
15. A process for optically brightening organic materials, which comprises incorporating into, or applying to, these materials at least one compound of formula (1 ) according to claim 1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000598471A JP2002536506A (en) | 1999-02-11 | 2000-01-31 | Bis-styryl biphenyl compounds |
| KR1020017009934A KR20010101802A (en) | 1999-02-11 | 2000-01-31 | Bis-styrylbiphenyl compounds |
| AU26680/00A AU2668000A (en) | 1999-02-11 | 2000-01-31 | Bis-styrylbiphenyl compounds |
| EP00904986A EP1153011A1 (en) | 1999-02-11 | 2000-01-31 | Bis-styrylbiphenyl compounds |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP99810119 | 1999-02-11 | ||
| EP99810119.0 | 1999-02-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2000047550A1 true WO2000047550A1 (en) | 2000-08-17 |
Family
ID=8242673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2000/000726 WO2000047550A1 (en) | 1999-02-11 | 2000-01-31 | Bis-styrylbiphenyl compounds |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1153011A1 (en) |
| JP (1) | JP2002536506A (en) |
| KR (1) | KR20010101802A (en) |
| CN (1) | CN1364154A (en) |
| AU (1) | AU2668000A (en) |
| ID (1) | ID29984A (en) |
| WO (1) | WO2000047550A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004026197A2 (en) * | 2002-09-17 | 2004-04-01 | Cph Innovations Corporation | Novel photostabilizers, uv absorbers, and methods of photostabilizing a sunscreen composition |
| CN102911509A (en) * | 2012-10-26 | 2013-02-06 | 山西青山化工有限公司 | Environment-friendly preparation method of toluylene-based biphenyl type fluorescent brightener |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH582134A5 (en) * | 1973-11-19 | 1976-11-30 | Ciba Geigy Ag | |
| EP0054511A2 (en) * | 1980-12-12 | 1982-06-23 | Ciba-Geigy Ag | 4-Styryl-4'-vinylbifenyls, methods for their preparation and their use as optical whiteners |
| US4380514A (en) * | 1980-01-12 | 1983-04-19 | Basf Aktiengesellschaft | Preparation of optical brighteners |
| EP0136259A1 (en) * | 1983-08-05 | 1985-04-03 | Ciba-Geigy Ag | 4-Heterocyclyl-vinyl-4'-styryl-biphenyls |
| DE4330968A1 (en) * | 1993-09-13 | 1995-03-16 | Basf Ag | Brightener mixtures based on bisstyryl compounds |
-
2000
- 2000-01-31 KR KR1020017009934A patent/KR20010101802A/en not_active Application Discontinuation
- 2000-01-31 ID IDW00200101865A patent/ID29984A/en unknown
- 2000-01-31 CN CN00803540A patent/CN1364154A/en active Pending
- 2000-01-31 EP EP00904986A patent/EP1153011A1/en not_active Withdrawn
- 2000-01-31 JP JP2000598471A patent/JP2002536506A/en active Pending
- 2000-01-31 WO PCT/EP2000/000726 patent/WO2000047550A1/en not_active Application Discontinuation
- 2000-01-31 AU AU26680/00A patent/AU2668000A/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH582134A5 (en) * | 1973-11-19 | 1976-11-30 | Ciba Geigy Ag | |
| US4380514A (en) * | 1980-01-12 | 1983-04-19 | Basf Aktiengesellschaft | Preparation of optical brighteners |
| EP0054511A2 (en) * | 1980-12-12 | 1982-06-23 | Ciba-Geigy Ag | 4-Styryl-4'-vinylbifenyls, methods for their preparation and their use as optical whiteners |
| EP0136259A1 (en) * | 1983-08-05 | 1985-04-03 | Ciba-Geigy Ag | 4-Heterocyclyl-vinyl-4'-styryl-biphenyls |
| DE4330968A1 (en) * | 1993-09-13 | 1995-03-16 | Basf Ag | Brightener mixtures based on bisstyryl compounds |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004026197A2 (en) * | 2002-09-17 | 2004-04-01 | Cph Innovations Corporation | Novel photostabilizers, uv absorbers, and methods of photostabilizing a sunscreen composition |
| WO2004026197A3 (en) * | 2002-09-17 | 2004-07-22 | Cp Hall Co | Novel photostabilizers, uv absorbers, and methods of photostabilizing a sunscreen composition |
| US6962692B2 (en) | 2002-09-17 | 2005-11-08 | Cph Innovations Corp. | Photostabilizers, UV absorbers, and methods of photostabilizing a sunscreen composition |
| CN102911509A (en) * | 2012-10-26 | 2013-02-06 | 山西青山化工有限公司 | Environment-friendly preparation method of toluylene-based biphenyl type fluorescent brightener |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2668000A (en) | 2000-08-29 |
| CN1364154A (en) | 2002-08-14 |
| ID29984A (en) | 2001-10-25 |
| JP2002536506A (en) | 2002-10-29 |
| KR20010101802A (en) | 2001-11-14 |
| EP1153011A1 (en) | 2001-11-14 |
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