EP1153011A1 - Bis-styrylbiphenyl compounds - Google Patents
Bis-styrylbiphenyl compoundsInfo
- Publication number
- EP1153011A1 EP1153011A1 EP00904986A EP00904986A EP1153011A1 EP 1153011 A1 EP1153011 A1 EP 1153011A1 EP 00904986 A EP00904986 A EP 00904986A EP 00904986 A EP00904986 A EP 00904986A EP 1153011 A1 EP1153011 A1 EP 1153011A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- alkyl
- hydrogen
- compound
- alkoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- ZMLPKJYZRQZLDA-UHFFFAOYSA-N 1-(2-phenylethenyl)-4-[4-(2-phenylethenyl)phenyl]benzene Chemical group C=1C=CC=CC=1C=CC(C=C1)=CC=C1C(C=C1)=CC=C1C=CC1=CC=CC=C1 ZMLPKJYZRQZLDA-UHFFFAOYSA-N 0.000 title abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 58
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 150000002431 hydrogen Chemical class 0.000 claims description 25
- 125000003545 alkoxy group Chemical group 0.000 claims description 23
- 229910052736 halogen Inorganic materials 0.000 claims description 22
- 150000002367 halogens Chemical class 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 17
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 16
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 16
- -1 bis-styrylbiphenyl compound Chemical class 0.000 claims description 15
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 14
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011368 organic material Substances 0.000 claims description 8
- 238000005282 brightening Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 2
- 230000003287 optical effect Effects 0.000 abstract description 5
- 229920000728 polyester Polymers 0.000 abstract description 5
- 238000009987 spinning Methods 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- 239000000203 mixture Substances 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 210000002741 palatine tonsil Anatomy 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MFNGPXDOHFAZSN-UHFFFAOYSA-N 3-[bis(methylperoxy)phosphorylmethyl]benzonitrile Chemical compound COOP(=O)(OOC)CC1=CC=CC(C#N)=C1 MFNGPXDOHFAZSN-UHFFFAOYSA-N 0.000 description 2
- FEHLIYXNTWAEBQ-UHFFFAOYSA-N 4-(4-formylphenyl)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=C(C=O)C=C1 FEHLIYXNTWAEBQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000006526 (C1-C2) alkyl group Chemical group 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- YFGHBSALOSGQFT-UHFFFAOYSA-N 2-[bis(methylperoxy)phosphorylmethyl]benzonitrile Chemical compound COOP(=O)(OOC)CC1=CC=CC=C1C#N YFGHBSALOSGQFT-UHFFFAOYSA-N 0.000 description 1
- CVQMRHBBIKDPFM-UHFFFAOYSA-N 4-[2-[4-(4-formylphenyl)phenyl]ethenyl]benzonitrile Chemical compound C1=CC(C=O)=CC=C1C(C=C1)=CC=C1C=CC1=CC=C(C#N)C=C1 CVQMRHBBIKDPFM-UHFFFAOYSA-N 0.000 description 1
- DWZSDRLPLBRONP-UHFFFAOYSA-N 4-[bis(methylperoxy)phosphorylmethyl]benzonitrile Chemical compound COOP(=O)(OOC)CC1=CC=C(C#N)C=C1 DWZSDRLPLBRONP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
wherein
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
wherein
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
wherein
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
wherein
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„
and then reacting this intermediate with 1 mole of a compound of formula
O
wherein
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
wherein
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
2.5 g of this compound are recrystallised in 50 ml of 1 ,2-dichlorobenzene. The mixture is heated until the solid is completely dissolved and is then cooled and charged with 1.5 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 1.18 g of the analytically pure compound of the above 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,
wherein
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.
wherein
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
wherein
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
and then reacting this intermediate with 1 mole of a compound of formula
O
wherein
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
wherein
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.
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EP00904986A EP1153011A1 (en) | 1999-02-11 | 2000-01-31 | Bis-styrylbiphenyl compounds |
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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 |
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EP0054511B1 (en) * | 1980-12-12 | 1987-05-13 | Ciba-Geigy Ag | 4-styryl-4'-vinylbifenyls, methods for their preparation and their use as optical whiteners |
US4666627A (en) * | 1983-05-08 | 1987-05-19 | Ciba-Geigy Corporation | 4-Heterocyclylvinyl-4-'styryl-biphenyls |
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