USRE27031E - Method of optical brightening - Google Patents

Method of optical brightening Download PDF

Info

Publication number
USRE27031E
USRE27031E US27031DE USRE27031E US RE27031 E USRE27031 E US RE27031E US 27031D E US27031D E US 27031DE US RE27031 E USRE27031 E US RE27031E
Authority
US
United States
Prior art keywords
compounds
crystals
parts
compound
formula
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.)
Expired
Application number
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed filed Critical
Application granted granted Critical
Publication of USRE27031E publication Critical patent/USRE27031E/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/60—Naphthoxazoles; Hydrogenated naphthoxazoles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/614—Optical bleaching or brightening in aqueous solvents
    • D06L4/636—Optical bleaching or brightening in aqueous solvents with disperse brighteners

Definitions

  • This invention relates to methods of optical brightening utilizing novel Z-styryloxazole compounds.
  • novel 2-styryloxazole compounds of this invention have the structure represented by the general formula:
  • 2-styryloxazole compounds were little known in the past, although, for example, 2-styrylbenzoxazole and 2- (4'-dimethylaminostyryl)-benzoxazole were found (D.M. Brown, A. R. Kon, J. Chem. Soc., 1948, 2147).
  • novel Z-styryloxazole compounds of this invention can be prepared by condensation under dehydration of a Z-methyloxazole compound represented by the following general formula (wherein A is the same as that in the general Formula I), with a benzaldehyde derivative represented by the following general formula:
  • the compounds of this invention can be prepared by intra-molecular ring closure under dehydration of a novel cinnamic acid-(O-oxyaryl)-arnide derivative represented by general formula:
  • the condensation reaction under dehydration of 2- methyloxazole compound of the general Formula II with benzaldehyde derivative of the general Formula Ill can 4-methyl-2aminophenol 4,6-dimethyl-2-aminophenol l0 4-e-thyl-2-aminophenol 4-phenyL2-aminophenol l-amino-2-naphthol Z-amino-l-naphthol and the like,
  • the intra-modecular ring closure reaction under dehydration of cinnamic acid- (O-oxyaryD-amide thus obtained can be carried out in an inert organic solvent such as xylene, chloiobenzene, dichlorobenzene and the like by adding a dehydrating agent and causing a reaction by heating.
  • CCH HC-F 21 O Greenish yellow pillar-like crystals, Blue-green.
  • EXAMPLE 4 2-methyl-a-naphthoxazole (18.3 parts), benzaldehyde 11 parts) and zinc chloride (7 parts) are thoroughly mixed and are caused to react at l60200 C. for 8 hours with stirring. To the reaction product is added methanol of 3 times volume at hot state and after cooling the precipitate is filtered out. The precipitate is recrystallized from a mixture of ethanol and glacial acetic acid to give light yellow pillar-like crystals (M.P. 3 C.). This one is a double salt of 2-styryl-a-naphthoxazole and zinc chloride. On heating with water, 2-styryl-a-naphthoxazole is easily separated. Recrystallization from ligroin gives colorless needle-like crystals (M.P. 124-125 C.).
  • a of said formula is a benzene ring having at least one alkyl group as the substituent.
  • A is a benzene ring having an aryl group as the substituent.
  • a method as claimed in claim 1 wherein said compound is Z-styryl-fi-naphthoxazole having the formula: Refemlces Clted o
  • N UNITED STATES PATENTS 2,639,282 5/1953 Sprague et al. 260240.9X 3,120,520 2/1964 Buell l1733.5 3,158,610 11/1964 Buell 11733.5 1O 20.
  • a method as claimed in claim 1 wherein said ma- FOREIGN PATENTS terial is an organic fibrous material. 569 402 4 1952 Great Britain 0 240 21.

Abstract

THIS INVENTION RELATES TO METHODS FOR OPTICAL BRIGHTENING UTILIZING CERTAIN NOVEL 2-STYRYLOXAZOLE COMPOUNDS. THE METHODS ARE PARTICULARLY APPLICABLE TO ORGANIC FLBROUS MATERIALS ESPECIALLY OF SYNTHETIC NATURE, AQUEOUS DISPERSIONS OF THE COMPOUNDS, TOGETHER WITH DISPERSING AIDS BEING SUITABLE. THE SAID COMPOUNDS MAY BE EITHER BENZOXAZOLES OR NAPHTHOXAZOLES AND VARIOUS SUBSTITUENTS MAY BE PRESENT IN THEIR MOLECULAR STRUCTURES. SOME OF THE COMPOUNDS ARE FOUND TO BE ESPICALLY SUPERIOR AND CERTAIN FIBROUS MATERIALS ARE NOTABLY BENEFITED.

Description

United States Patent Ofice Re. 27,031 Reissued Jan. 12, 1971 Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
ABSTRACT OF THE DISCLOSURE This invention relates to methods for optical brightening utilizing certain novel 2-styryloxazole compounds. The methods are particularly applicable to organic fibrous materials, especially of synthetic nature, aqueous dispersions of the compounds, together with dispersing aids being suitable. The said compounds may be either benzoxazoles or naphthoxazoles and various substituents may be present in their molecular structures. Some of the compounds are found to be especially superior and certain fibrous materials are notably benefited.
This application is a division of our prior application Ser. No. 220,904, now Patent No. 3,262,929.
This invention relates to methods of optical brightening utilizing novel Z-styryloxazole compounds.
It is an object of this invention to provide new and useful methods for optical brightening of organic fibrous materials.
The novel 2-styryloxazole compounds of this invention have the structure represented by the general formula:
wherein A is a member selected from the group consisting of substituted benzene rings and unsubstituted naphthalene ring, which is condensed with the oxazole ring, substitutes of said benzene rings being selected from the group consisting of alkyl-, aryl, and alkylene-groups, and R and R are selected from hydrogen, halogen, cyano group, carboxyl group and its ester residue, alkyl group and aryl group.
2-styryloxazole compounds were little known in the past, although, for example, 2-styrylbenzoxazole and 2- (4'-dimethylaminostyryl)-benzoxazole were found (D.M. Brown, A. R. Kon, J. Chem. Soc., 1948, 2147).
The present inventors have synthesized a number of 2- styryloxazole compounds to study precisely on their properties, and have found that the novel 2-styryloxazole compounds having the general Formula 1 exhibit a strong fluorescence and produce an excellent optical brightening effect when organic fibrous materials are treated with these novel compounds. That is, the novel Z-styryloxazole compounds are very useful substances as the optical brigntening agent for organic fibrous materials, particularly various man-made fibers, and light-fastness is excellent.
The novel Z-styryloxazole compounds of this invention can be prepared by condensation under dehydration of a Z-methyloxazole compound represented by the following general formula (wherein A is the same as that in the general Formula I), with a benzaldehyde derivative represented by the following general formula:
R III (wherein R and R are the same as those in the general Formula I).
Alternatively the compounds of this invention can be prepared by intra-molecular ring closure under dehydration of a novel cinnamic acid-(O-oxyaryl)-arnide derivative represented by general formula:
\/ H R n (wherein A, R and R are the same as those in the general Formula I).
The following compounds can be cited as examples of Q-methyloxazole compound of the general Formula 11 among the starting materials employed for preparing the novel 2-styryloxazole compounds of this invention:
Z-methylbenzoxazole 2,5-dimethylbenzoxazole 2,5 ,7-trimethylbenzoxazole 2-methyl-4,5-cyclotetramethylenebenzoxazole Z-Inethyl-S-ethylbenzoxazole Z-methyl-5-isopropy1benzoxazole Z-methyl-5-tert-butylbenzoxazole 2-methyl-5-phenylbenzoxazole 2-methyl-S-acetylaminobenzoxazole Z-methyl-a-naphthoxazole Z-methyl-fi-naphthoxazole and the like.
And also the following compounds can be cited as examples of benazldehyde derivative of the general Formula III among the starting materials:
The condensation reaction under dehydration of 2- methyloxazole compound of the general Formula II with benzaldehyde derivative of the general Formula Ill can 4-methyl-2aminophenol 4,6-dimethyl-2-aminophenol l0 4-e-thyl-2-aminophenol 4-phenyL2-aminophenol l-amino-2-naphthol Z-amino-l-naphthol and the like,
or their inorganic acid salts with cinnamic acid halogenide, for example,
cinnamic acid chloride 3-chlorocinnamic acid chloride 4-chlorocinnamic acid chloride 4-cyano-3 chlorocinnamic acid chloride according to a conventional method. The intra-modecular ring closure reaction under dehydration of cinnamic acid- (O-oxyaryD-amide thus obtained can be carried out in an inert organic solvent such as xylene, chloiobenzene, dichlorobenzene and the like by adding a dehydrating agent and causing a reaction by heating.
The examples of novel 2-styryl0xazole compounds of 15 this invention are shown in Table 1.
TABLE 1 Fluorescence No. Structural Formula Property and melting point in blenizene so u on 1 A 0\ Colorless needle-like crystals, lot-155 Violet.
CCH:HC Cl 2 0 Light yellow pillar-like crystals 196- D0.
/OCH:HC -CN N 3 0 Slightly yellow plate crystals 146-147 Do.
4 0 Light yellow pillar-like crystals 310 Do.
C-CH=HC -oN C*on=uc -GN II5CJ- o cn=11o co011 H;C
Colorless needle-like crystals, 14l-142 Do.
Liggt yellow noodle-like crystals, 221 Do.
Light yellow noodle-like crystals, 155- Do.
Light yellow needlelike crystals, 260- Blue.
Slightly yellow needle-like crystals, Blue-violet.
XVI-209 C.
TABLE 1Contlnued Fluorescence No. Structural Fonnula Property and melting point in benzene solution 10 O Sllverwhito flnkwlike crystals, 134- \"lnlnL 11 0 Light yellow needle-like crystals, 1S4 Bluei let,
/C--CH:HCCN N 12 0 Light yellow plIlar-llkr: crystals, 295- D c-cn=nc c OOH 01mmv 13 0\ Colorless flake-like crystals, 175476C Violet-blue,
C-CII=HCGN 14 l Colorlessfiake-llkecrystals, 12+125 c. Blue-violet,
CCH==HC- 15 A Slightly yallow lum-4m crystals, Blum C C H=H C 16 O Llght yellow pillar-like crystals, 12? (neon-blue.
123" c. I (l C H: H O l N 17 7 0 Cl Slightly yellow medlelike crystals, llluv-gnon.
158-169" 0. /ccn=11 06 L) N 18 0 Elm.
Light yellow flake-like crystals, 114- TABLE 1-Continued No. Structural Formula. Property and melting point Fluorescence in benzene solution 19 Yellow needle-like crystals, L'HHGU" C. Green-blue.
oon=nc ci U N 20 0 Light yellow pillar-like crystals, Violet-blue.
125-126" C. CCH=HC-F 21 O Greenish yellow pillar-like crystals, Blue-green.
C-CH:HC-Br U l N 22 -r 0 Light yellow flake-like erystuls, lL3- Violet-blue.
124C. c-cn=nc-cm [j t N 23 0 Yellow long flake-like crystals, Blue.
c-cn=nc--ooou N As shown in Table 1, the novel Z-styryloxazole com- TABLE 9 pounds of this invention have fluorescence of blue violet Compound Treatment Treatment Light to violet also q exceuflm infinity to orga lc FibcrMutcriuls COIlCUlltl'tlr temperatimes tmlu.) [astnuss fibrous materials from its aqueous dispersed y t m so 60 tionporcout turoCU.) that they are very useful for optical brightening of manmade fibers, particularly polyester, polyacrylonitrile, poly- Emmet: Q 2 120 45 4 amide, acetalized polyvinyl alcohol, polyolefin and cellugggggflg 3g 2g lose acetate fibers and their light fastness is remarkable. gigggjjj o,
' f Acetalized poly- For example, the compound No. 18 n Table is made vinylalcoholn M 45 3 mto aqueous dispersed system by using anionic surface Po]ypy'opylene Q1 45 active agent of alkylbenzene sulfonic acid type, and when the above-mentioned man-made fibers are treated in a treating bath which is prepared in such a way as the amount of this compound is 0.1% or 0.2% to the material to be treated, an excellent optical brightening effect can be obtained. The treating conditions and the light fastness (according to I18 L 10454959, Xenon light source) of man-made fibers in this case are shown in Table 2.
It is convenient to use a composition which in previously mixed with a surface active agent in order to treat 0 organic fibrous materials by using the compound of The process for preparing 2-styryloxazole compounds of this invention and the method of optical brightening of organic fibrous materials by using such compounds are illustrated by the following examples. Percents and parts herein are by weight.
EXAMPLE 1 2,5-dimethylbenzoxazole (14.7 parts), 4-carboxybenzaldehyde (15 parts) and zinc chloride (5 parts) are thoroughly mixed and are caused to react at 160-200 C. for 8 hours with stirring. The reactants are boiled and dissolved in methanol of 10 times volume. On cooling the methanol solution, S-methyl-Z-(4-carboxystyryl)-benzoxazole is precipitated as yellow crystals. When crystallized from ethanol containing glacial acetic acid, light yellow pillar-like crystals (M.P. 310 C.) are obtained.
EXAMPLE 2 2,5 dimethylbenzoxazole (14.7 parts), 4 cyano 3- chlorobenzaldehyde (18 parts) and zinc bromide (13 parts) are thoroughly mixed and are caused to reaction at 160 C. for 6 hours with stirring. In this case the water formed by the reaction is successively driven out of the reaction system. The reactants are boiled and dissolved in 50 parts of methanol. On cooling the methanol solution, 5 methyl-2-(4'-cyano-3chlorostyryl)-benzoxazole is precipitated as yellow crystals. When recrystallized from dimethyl formamide, light yellow needle-like crystals (M.P. 221 C.) are obtained.
EXAMPLE 3 2,5,7 trimethylbenzoxazole (16.1 parts), 4 cyanobenzaldehyde (13.1 parts) and zinc chloride (7 parts) are mixed thoroughly and are caused to react at 160-200" C. for 8 hours with stirring while the formed water is successively taken out of the reaction system. Then, the reactants are subjected to steam distillation and unreacted starting materials are distilled out. The distillation residue is treated with hot xylene and the resulting xylene solution is allowed to cool to precipitate 5,7-dimethyl-2-(4'- cyanostyryl)-benzoxazole as yellow needle-like crystals. When recrystallized from ligroin containing benzene, slightly yellow needle-like crystals (M.P. 207209 C.) are obtained.
EXAMPLE 4 2-methyl-a-naphthoxazole (18.3 parts), benzaldehyde 11 parts) and zinc chloride (7 parts) are thoroughly mixed and are caused to react at l60200 C. for 8 hours with stirring. To the reaction product is added methanol of 3 times volume at hot state and after cooling the precipitate is filtered out. The precipitate is recrystallized from a mixture of ethanol and glacial acetic acid to give light yellow pillar-like crystals (M.P. 3 C.). This one is a double salt of 2-styryl-a-naphthoxazole and zinc chloride. On heating with water, 2-styryl-a-naphthoxazole is easily separated. Recrystallization from ligroin gives colorless needle-like crystals (M.P. 124-125 C.).
EXAM PLE Z-methyl-B-naphthoxazole (28 parts), 3-chlorobenzaldehyde (22 parts) and zinc chloride parts) are mixed and are caused to react at 160165 C. for 6 hours while the formed water is successively taken out of the reaction system. The reactants are dissolved in 150 parts of isopropanol. The isopropanol solution is allowed to cool to precipitate 2-(3'-chlorostyryl)-fl-naphthoxazole as yellow crystals. Recrystallization from methanol gives light yellow flake-like crystals (M.P. 114-115 C.).
EXAMPLE 6 Cinnamic acid (2'-oxynaphthyl-1') amide obtained from l-amino-Z-naphthol hydrochloric acid salt parts) and cinnamic acid chloride (17 parts) is boiled 10 with 10 parts of phosphor oxychloride in 50 parts of O- dichlorobenzene for 8 hours while water formed by the reaction is successively distilled out of the system. Then, O-dichlorobenzene is taken out b steam distillation and the distillation residue is treated with ligroin. The ligroin solution is allowed to cool to precipitate Z-Styryl-B-naphthoxazole as yellow crystals. Recrystallization from ligroin gives light yellow pillar-like crystals (M.P. 121.5423" C.).
EXAMPLE 7 One part of 2 (4'-cyanostyryl)-5,7-dimethylbenzoxazole of the following formula:
HHZW M on.
is thoroughly mixed with 9 parts of surface active agent of alkylbenzene sulfonic acid type to give a sample, and 0.2 part of the sample thus prepared per 10 parts of the polyester cloth to be treated is put into 400 parts of water to give a dispersed system. In this dispersed system the polyester cloth is treated at C. for 45 minutes. The treated cloth is washed with water and dried to give the remarkable brightening effect as compared with nontreated cloth.
What is claimed is:
1. A method for optical brightening of solid polymeric materials selected from the class consisting of polyesters, polyamides, acetalized polyvinyl alcohols, cellulose acetate and polyolefins, comprising treating said materials with an oxazole compound of the formula wherein A is a member selected from the group consisting of substituted benzene rings and an unsubstituted naphthalene ring, A being condensed with the oxazole ring, substituents of said benzene rings being selected from the group consisting of alkyl-, aryl-, and alkylenegroups and [when A is said unsubstituted naphthalene ring], R and R are selected from hydrogen, halogen, cyano group, carboxyl group and its ester residue, alkyl group and aryl group, [R being a cyano group when A is said benzene ring with R being selected as aforesaid,] said treating being effected by contacting the said materials with an aqueous dispersion containing said oxazole in an amount sufiicient to impart optical brightening effects to the material undergoing treatment.
2. A method as claimed in claim 1 wherein A of said formula is a benzene ring having at least one alkyl group as the substituent.
3. A method as claimed in claim 1 wherein the said compound is 5-methyl-2-(3'-chloro 4-cyanostyryl)-benzoxazole having the formula:
4. A method as claimed in claim 1 wherein the said compound is 5,7-dimethyl-2- 3'-chloro-4-cyanostyryl benzoxazole having the formula:
11 5. A method as claimed in claim 1 wherein the said compound is S-ethyl-Z-(3'-chlor0-4'-cyanostyryl)-benzoxazole having the formula:
6. A method as claimed in claim 1 wherein the said compound is S-methyl-Z-(4'-cyanostyryl)-benzoxazole having the formula:
\ -c11:110- CN Q 7. A method as claimed in claim 1 wherein the said compound is -methyl-2-(4'-carboxythoxystyryl)-benzoxazole havin the formula:
8. A method as claimed in claim 1 wherein A is a naphthalene ring.
9. A method as claimed in claim 1 wherein said compound is 2-(3'-chlorostyryl)-fl-naphthoxoazole having the formula:
10. A method as claimed in claim 1 wherein said compound is 2-(4'-chlorostyryl)-fi-naphthoxazole having the formula:
11. A method as claimed in claim 1 wherein said compound is 2-(3'-chlorostyryl)a-naphthoxazole having the formula:
l 2 12. A method as claimed in claim 1 wherein said compound is 2-(2'-chlorostyryl)-a-naphthoxazo1e having the formula:
13. A method as claimed in claim 1 wherein said compound is 2-(4-fluorostyryl)-fi-naphthoxazole having the formula:
16. A method as claimed in claim 1 wherein A is a benzene ring having an aryl group as the substituent.
17. A method as claimed in claim 1 wherein said compound is S-phenyl-Z-(4-cyanostyryl)-benzoxazo1e having the formula:
18. A method as claimed in claim 1 wherein said compound is 5-phenyl-2-styrylbenz/oxazole having the formula:
13 14 19. A method as claimed in claim 1 wherein said compound is Z-styryl-fi-naphthoxazole having the formula: Refemlces Clted o The following references, cited by the Examiner, are of record in the patented file of this patent or the original CCH=HC 5 patent. N UNITED STATES PATENTS 2,639,282 5/1953 Sprague et al. 260240.9X 3,120,520 2/1964 Buell l1733.5 3,158,610 11/1964 Buell 11733.5 1O 20. A method as claimed in claim 1 wherein said ma- FOREIGN PATENTS terial is an organic fibrous material. 569 402 4 1952 Great Britain 0 240 21. A method for optical brightening as claimed in 573,303 5/1959 Canada 260 240 claim 1 wherein the material treated is selected from the grboug colnsistinlg firlaaf polyester dfilzielr [prilyacrlyllrinfiitgile 15 WILLIAM D. MARTIN, Primary Examiner er p0 yam1 e er, aceta ize po in aco 0 er,
cellulose acetate fiber, and polyolefin hbe l'. DAVIS Asslstam Exammer 22. A method as claimed in claim 1 wherein A is a Us Cl X R substituted benzene ring.
23. A method as claimed in claim I wherein A is an 20 117-4383,
unsubstituted naphthalene ring.
US27031D 1961-09-12 1969-05-26 Method of optical brightening Expired USRE27031E (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP3330261 1961-09-12
JP3330361 1961-09-20
JP2964162 1962-07-21

Publications (1)

Publication Number Publication Date
USRE27031E true USRE27031E (en) 1971-01-12

Family

ID=27286670

Family Applications (3)

Application Number Title Priority Date Filing Date
US220904A Expired - Lifetime US3262929A (en) 1961-09-12 1962-08-31 2-styrylbenzoxazole compounds
US550957A Expired - Lifetime US3400124A (en) 1961-09-12 1966-05-18 Optical brightening and new compositions of matter
US27031D Expired USRE27031E (en) 1961-09-12 1969-05-26 Method of optical brightening

Family Applications Before (2)

Application Number Title Priority Date Filing Date
US220904A Expired - Lifetime US3262929A (en) 1961-09-12 1962-08-31 2-styrylbenzoxazole compounds
US550957A Expired - Lifetime US3400124A (en) 1961-09-12 1966-05-18 Optical brightening and new compositions of matter

Country Status (6)

Country Link
US (3) US3262929A (en)
CH (1) CH387585A (en)
DE (1) DE1210764B (en)
FR (1) FR1336949A (en)
GB (1) GB967483A (en)
MY (1) MY6600133A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1985004652A1 (en) * 1984-04-06 1985-10-24 Laboratoires Chauvin-Blache Vinyl-4 benzoic acid derivatives, preparation method and application thereof

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB967483A (en) * 1961-09-12
DE1419330A1 (en) * 1962-06-09 1970-02-19 Hoechst Ag Optical brighteners
US3366630A (en) * 1963-10-26 1968-01-30 Hoechst Ag 2-(4'-amidostyryl)-benzoxazoles and method for using the same for the optical brightening of textiles
US3158610A (en) * 1964-01-03 1964-11-24 American Cyanamid Co 2-styrylbenzoxazole brighteners
CH902165A4 (en) * 1964-05-27 1968-12-31
US3274184A (en) * 1964-07-30 1966-09-20 American Cyanamid Co Method for the preparation of 2-styrloxazole compounds
CH475301A (en) * 1964-10-27 1969-07-15 Ciba Geigy Process for the production of shaped bodies which are optically brightened with oxazole compounds
US3546127A (en) * 1967-11-24 1970-12-08 Magnaflux Corp Fluorescent penetrant for and method of detecting surface discontinuities
US3912697A (en) * 1973-04-27 1975-10-14 Eastman Kodak Co Light-sensitive polymers
DE2331444A1 (en) * 1973-06-20 1975-01-23 Hoechst Ag NEW STYRYL BENZOXAZOLE, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS AN OPTICAL LIGHTENING AGENT
CH597335A5 (en) * 1973-09-14 1978-03-31 Ciba Geigy Ag
DE2712686C2 (en) * 1977-03-23 1986-09-04 Bayer Ag, 5090 Leverkusen 4-Triazinyl-4'-benzoxazolyl or 4'-phenyl-stilbene derivatives
GB9312853D0 (en) * 1993-06-22 1993-08-04 Euro Celtique Sa Chemical compounds
US5922751A (en) * 1994-06-24 1999-07-13 Euro-Celtique, S.A. Aryl pyrazole compound for inhibiting phosphodiesterase IV and methods of using same
US5591776A (en) * 1994-06-24 1997-01-07 Euro-Celtique, S.A. Pheynl or benzyl-substituted rolipram-based compounds for and method of inhibiting phosphodiesterase IV
US6372770B1 (en) 1994-10-12 2002-04-16 Euro-Celtique, S.A. Benzoxazoles
US6025361A (en) * 1994-12-13 2000-02-15 Euro-Celtique, S.A. Trisubstituted thioxanthines
EP0814809B1 (en) * 1994-12-13 2003-08-13 Euroceltique S.A. Aryl thioxanthines
DE69531555T2 (en) * 1994-12-13 2004-06-17 Euroceltique S.A. TRIPLE SUBSTITUTED THIOXANTHINE
US6166041A (en) * 1995-10-11 2000-12-26 Euro-Celtique, S.A. 2-heteroaryl and 2-heterocyclic benzoxazoles as PDE IV inhibitors for the treatment of asthma
US6075016A (en) * 1996-04-10 2000-06-13 Euro-Celtique S.A. 6,5-fused aromatic ring systems having enhanced phosphodiesterase IV inhibitory activity
US5864037A (en) * 1996-06-06 1999-01-26 Euro-Celtique, S.A. Methods for the synthesis of chemical compounds having PDE-IV inhibitory activity
US5744473A (en) * 1996-09-16 1998-04-28 Euro-Celtique, S.A. PDE IV inhibitors: "bis-compounds"

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2875089A (en) * 1959-02-24 Process for the optical brightening of
CA578303A (en) * 1959-06-23 Ackermann Franz Process for the optical brightening of polyacrylonitrile fibers
BE442515A (en) * 1940-07-30
GB669402A (en) * 1949-01-28 1952-04-02 George Malcolm Dyson Improvements relating to the preparation of benziminazoles and benzoxazoles
US2639282A (en) * 1949-09-29 1953-05-19 Eastman Kodak Co Resin-dyes of the cyanine type
US2953561A (en) * 1957-09-24 1960-09-20 Gen Aniline & Film Corp Nitrostyryl dye bases and vinylogs thereof derived from 2-cyanomethylazoles
DE1163542B (en) * 1959-02-03 1964-02-20 Glanzstoff Ag Process for the production of polyamides with improved light and wash resistance by polycondensation of caprolactam
GB967483A (en) * 1961-09-12
US3158610A (en) * 1964-01-03 1964-11-24 American Cyanamid Co 2-styrylbenzoxazole brighteners
US3274184A (en) * 1964-07-30 1966-09-20 American Cyanamid Co Method for the preparation of 2-styrloxazole compounds

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1985004652A1 (en) * 1984-04-06 1985-10-24 Laboratoires Chauvin-Blache Vinyl-4 benzoic acid derivatives, preparation method and application thereof
EP0161156A1 (en) * 1984-04-06 1985-11-13 Laboratoires Chauvin S.A. 4-Vinylbenzoic-acid derivatives, their preparation and their use as therapeutical compositions and as ligands
US4929635A (en) 1984-04-06 1990-05-29 Laboratoires Chauvin-Blache New derivatives of 4-vinyl benzoic acid, process for their preparation and their uses in therapeutics and as ligands

Also Published As

Publication number Publication date
CH1080362A4 (en) 1964-10-31
CH387585A (en) 1965-05-15
GB967483A (en)
US3400124A (en) 1968-09-03
DE1210764B (en) 1966-02-17
FR1336949A (en) 1963-09-06
US3262929A (en) 1966-07-26
MY6600133A (en) 1966-12-31

Similar Documents

Publication Publication Date Title
USRE27031E (en) Method of optical brightening
US3712888A (en) Bis-pyridoxazole-stilbene derivatives for optical brightening
US3158610A (en) 2-styrylbenzoxazole brighteners
US2415373A (en) Substituted 4-hydroxyalkylamino-1, 8-naphthalic acid imides
US4006158A (en) Fluorescent 1,2,3-triazole derivatives of 3-phenylcoumarin
US3076812A (en) Certain benzoxazole-2-acrylic acids
US4110246A (en) Mixture of benzoxazole derivatives
US3996210A (en) Monobenzoxazolylstilbenes
US3772282A (en) Novel 3-indenecarboxylic acid-1-methine derivatives
US3347694A (en) Method for optical brightening of polymeric substrates utilizing 2-styryloxazole compounds
DE1444006C3 (en) Use of azolyl thiophene compounds as optical brightening agents for organic materials
US3637672A (en) Azole compounds
US4179578A (en) Para-phenyl stilbene derivatives
US3641051A (en) Naphthylene-bis-2-benzimidazoles
US3873531A (en) 2{55 P-{8 2-(2-benzoxazolyl)vinyl{9 phenyl{56 oxazolo{8 5,4-b{9 pyridine fluorescent whitening agents
DE1594835A1 (en) New tolane derivatives and their use as optical brightening agents
US3660125A (en) Brightening plastics with 2-aryl-5-cyanonaphthoxazole brighteners
US2657228A (en) Sulfonic acid aryl esters of polyarylethylene derivatives and a process of making same
US4005098A (en) Triazolyl-coumarins
US3728339A (en) Styryl compounds
EP0000346A1 (en) Quinoxaline compounds, process for their manufacture and their use as brighteners for organic materials, and the materials brightened therewith
KR100248295B1 (en) Polycyclic dyes
US4182861A (en) Fluorescent 1,2,3-triazole derivatives of 3-phenylcoumarin
US3840528A (en) Azole compounds
US4082769A (en) Benzothioxanthenes