FR2504130A1 - FLUORO-BENZOPHENONES, METHODS FOR THEIR PREPARATION AND THEIR APPLICATION - Google Patents
FLUORO-BENZOPHENONES, METHODS FOR THEIR PREPARATION AND THEIR APPLICATION Download PDFInfo
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Abstract
Description
La présente invention concerne des fluoro-4 benzophénones, des procédés permettant de les préparer et leur application comme absorbeurs de rayons ultra-violets ou comme corps intermédiaires. The present invention relates to 4-fluorophenophenones, processes for their preparation and their application as absorbers of ultraviolet rays or as intermediate bodies.
On sait que les dérivés de la benzophénone répondant à la formule
dans laquelle R représente un radical méthoxy ou hydroxy et X un atome de fluor, un radical fluoralkyle ou un radical fluoralcényle contenant chacun de 1 à 9 atomes de carbone, conviennent comme absorbeurs de rayons ultra-violets (voir le brevet US 3 387 035). Ces dérivés de la benzophénone se préparent par réaction de l'éther diméthylique du résorcinol avec un chlorure de benzoyle a substituant fluoré, en présence d'un catalyseur d'acylation, plus spécialement de chlorure d'aluminium,et d'un diluant, tel que le n-hexane ou le sulfure de carbone. Comme fluoro-4 benzophénone porteuse d'un groupe hydroxy le document cité mentionne la fluoro-4 hydroxy-2' méthoxy-4' benzophénone fondant a 88-890C.We know that the benzophenone derivatives corresponding to the formula
in which R represents a methoxy or hydroxy radical and X a fluorine atom, a fluoralkyl radical or a fluoralcenyl radical each containing from 1 to 9 carbon atoms, are suitable as absorbers of ultraviolet rays (see US Pat. No. 3,387,035) . These benzophenone derivatives are prepared by reaction of the dimethyl ether of resorcinol with a fluorinated substituent benzoyl chloride, in the presence of an acylation catalyst, more especially of aluminum chloride, and of a diluent, such than n-hexane or carbon sulfide. As fluoro-4 benzophenone carrying a hydroxy group the cited document mentions fluoro-2-hydroxy-2 'methoxy-4' benzophenone melting at 88-890C.
L'invention fournit un moyen pour préparer d'autres fluoro-4 benzophénones porteuses d'au moins un groupe hydroxy, qui peuvent être préparées par synthèse d'une manière simple et qui sont utilisables comme absorbeurs de rayons ultra-violets ainsi que comme corps intermédiaire pour la synthèse de substances actives de différents types. The invention provides a means for preparing other 4-fluoro benzophenones carrying at least one hydroxy group, which can be prepared by synthesis in a simple manner and which can be used as absorbers of ultraviolet rays as well as as a body. intermediate for the synthesis of active substances of different types.
L'invention a pour objet des fluoro-4 benzophénones répondant à la formule (1)
dans laquelle R représente un atome d'hydrogène ou un radical alkyle contenant de 3 à 12 atomes de carbone.The subject of the invention is 4-fluoro benzophenones corresponding to formula (1)
in which R represents a hydrogen atom or an alkyl radical containing from 3 to 12 carbon atoms.
Elle a en outre pour objet des fluoro-4 benzophénones répondant à la formule (2)
dans laquelle R' représente un radical alkyle contenant de 1 à 6 atomes de carbone.It further relates to 4-fluoro benzophenones corresponding to formula (2)
in which R 'represents an alkyl radical containing from 1 to 6 carbon atoms.
L'invention a trait en outre à un procédé de préparation de fluoro-4 benzophénones, procédé caractérisé en ce qu'on acyle le résorcinol de manière à le convertir en un composé de formule (3)
et on alkyle éventuellement le produit réactionnel pour obtenir un composé répondant à la formule (1)
dans laquelle R représente un radical alkyle contenant de 3 à 12 atomes de carbone.The invention further relates to a process for the preparation of 4-fluoro benzophenones, a process characterized in that the resorcinol is acylated so as to convert it into a compound of formula (3)
and optionally alkylating the reaction product to obtain a compound corresponding to formula (1)
in which R represents an alkyl radical containing from 3 to 12 carbon atoms.
L'invention concerne aussi un procédé permettant de préparer des fluoro-4 benzophénones, procédé selon lequel on acyle le résorcinol de manière à le convertir en un composé de formule (3)
puis on alkyle le produit réactionnel afin d'obtenir un composé répondant à la formule (4)
dans laquelle R' représente un radical alkyle contenant de 1 à 6 atomes de carbone, et on sulfone l'éther obtenu afin d'obtenir un composé répondant à la formul-e (2)
dans laquelle R' représente un radical alkyle contenant de 1 à 6 atomes de carbone.The invention also relates to a process for preparing 4-fluoro-benzophenones, a process in which the resorcinol is acylated so as to convert it into a compound of formula (3)
then the reaction product is alkylated in order to obtain a compound corresponding to formula (4)
in which R 'represents an alkyl radical containing from 1 to 6 carbon atoms, and the ether obtained is sulfonated in order to obtain a compound corresponding to formula (2)
in which R 'represents an alkyl radical containing from 1 to 6 carbon atoms.
L'invention a en outre pour objet des fluoro-4 benzophénones répondant à la formule (5)
dans laquelle R représente un atome d'hydrogène ou un radical alkyle contenant de 3 à 12 atomes de carbone.The invention further relates to 4-fluoro benzophenones corresponding to formula (5)
in which R represents a hydrogen atom or an alkyl radical containing from 3 to 12 carbon atoms.
On prépare ces fluoro-4 benzophénones de formule (5) en acylant le pyrogallol, c'est-à-dire le trihydroxy-1,2,3 benzène, de manière à le convertir en un composé de formule (6)
et en alkylant éventuellement le produit réactionnel, afin d'obtenir un composé répondant à la formule (5)
dans laquelle R représente un radical alkyle contenant de 3 à 12 atomes de carbone.These 4-fluorophenones of formula (5) are prepared by acylating the pyrogallol, that is to say 1,2,3,3-trihydroxy benzene, so as to convert it into a compound of formula (6)
and optionally alkylating the reaction product, in order to obtain a compound corresponding to formula (5)
in which R represents an alkyl radical containing from 3 to 12 carbon atoms.
Les composés conformes à l'invention sont en particulier
- parmi les composés de formule (1), la fluoro-4 dihydroxy2',4' benzophénone et les mono-éthers suivants de celle-ci : la fluoro-4 hydroxy-2' propoxy-4' benzophénone, la fluoro-4 hydroxy2' butoxy-4' benzophénone, la fluoro-4 hydroxy-2' hexyloxy-4' benzophénone et la fluoro-4 hydroxy-2' octvloxy-4' benzophénone.The compounds according to the invention are in particular
- among the compounds of formula (1), fluoro-4 dihydroxy2 ', 4' benzophenone and the following mono-ethers thereof: fluoro-4 hydroxy-2 'propoxy-4' benzophenone, fluoro-4 hydroxy2 'butoxy-4' benzophenone, fluoro-4 hydroxy-2 'hexyloxy-4' benzophenone and fluoro-4 hydroxy-2 'octvloxy-4' benzophenone.
- parmi les composés de formule (2), l'acide fluoro-4 hydroxy2' méthoxy-4' benzophénone-sulfonique-5, l'acide fluoro-4 hydroxy-2' éthoxy-4' benzophénone-sulfonique-5, l'acide fluoro-4 hydroxy-2' propoxy-4' benzophénone-sulfonique-5 et les alcoxy benzophénones homologues, et
- parmi les composés de formule (5), la fluoro-4 trihydroxy2',3-',4' benzophénone et les alcoxy-4' benzophénones homologues.- among the compounds of formula (2), 4-fluoro-hydroxy2 '4-methoxy-benzophenone-sulfonic-5 acid, 4-fluoro-2-hydroxy-2' ethoxy-4 'benzophenone-sulfonic acid-5, l'4-hydroxy-2-hydroxypropoxy-4'-benzophenone sulfonic-5 acid and the homologous alkoxy benzophenones, and
- among the compounds of formula (5), fluoro-4 trihydroxy2 ', 3 -', 4 'benzophenone and alkoxy-4' benzophenones homologous.
L'acylation du résorcinol ou du pyrogallol est effectuée de préférence en présence d'un catalyseur de Friedel et Crafts dans un solvant organique inerte, à une température de 40 à 800C, de préférence de 50 à 700C. The acylation of resorcinol or pyrogallol is preferably carried out in the presence of a Friedel and Crafts catalyst in an inert organic solvent, at a temperature of 40 to 800C, preferably 50 to 700C.
Comme catalyseur pour l'acylation on utilisera plus particulièrement le chlorure d'aluminium ainsi que le chlorure de. zinc, le chlorure ferriaue et le trifluorure de bore . Le catalyseur est mis en jeu en une quantité de 0,8 à 1,2 mole par mole de résorcinol ou de pyrogallol. L'agent d'acylation pourra être un halogenure de fluoro-4 benzoyle, tel que le bromure de fluoro-4 benzoyle ou, mieux, le chlorure de fluoro4 benzoyle, ou plus spécialement le trichlorométhyl-l fluoro-4 benzène. On peut faire réagir ce dernier de manière connue dans un alcanol inférieur, plus particulièrement le méthanol ou l'e- thanol, en ajoutant ou non de l'eau, en l'absence d'un catalyseur. As catalyst for the acylation, use will be made more particularly of aluminum chloride as well as chloride. zinc, ferria chloride and boron trifluoride. The catalyst is used in an amount of 0.8 to 1.2 moles per mole of resorcinol or pyrogallol. The acylating agent may be a 4-fluoro benzoyl halide, such as 4-fluoro benzoyl bromide or, better, fluoro-4 benzoyl chloride, or more especially trichloromethyl-4-fluoro benzene. The latter can be reacted in a known manner in a lower alkanol, more particularly methanol or ethanol, with or without the addition of water, in the absence of a catalyst.
Comme solvant organique inerte on utilise autrement le nitrobenzène ou un halogéno-alcane contenant de 1 à 3 atomes de carbone, de préférence un chloralcane, par exemple le dichloro-1,2 éthane ou le tricAloro-l,l,l éthane. La réaction peut être effectuée aussi dans de l'acide fluorhydrique, lequel sert en même temps de catalyseur et de solvant.As inert organic solvent, nitrobenzene or a haloalkane containing 1 to 3 carbon atoms, preferably a chloralkane, for example 1,2-dichloroethane or tricAloro-1,1,1 ethane, is otherwise used. The reaction can also be carried out in hydrofluoric acid, which serves at the same time as catalyst and solvent.
La fluoro-4 dihydroxy-2',4' benzophénone ou la fluoro-4 trihydroxy-2',3',4' benzophénone qui a été obtenue par l'acylation de Friedel et Crafts est éventuellement mono-éthérifiée, cela par alkylation avec un halogéno-l alcane contenant soit de 3 à 12 atomes de carbone1 de préférence de 3 à 8, auquel cas on obtient un mono-éther de formule (1) ou de formule (5), soit de 1 à 6 atomes de carbone, de préférence de 1 à 4, auquel cas on obtient un mono-éther de formule (4). Cette alkylation est effectuée à une température de 20 à 1600C, de préférence de 60 à 1600C, en présence d'une base, dans un solvant organique inerte. Fluoro-4 dihydroxy-2 ', 4' benzophenone or fluoro-4 trihydroxy-2 ', 3', 4 'benzophenone which was obtained by the acylation of Friedel and Crafts is optionally mono-etherified, this by alkylation with a halo-l alkane containing either from 3 to 12 carbon atoms1 preferably from 3 to 8, in which case a mono-ether of formula (1) or of formula (5) is obtained, or from 1 to 6 carbon atoms, preferably from 1 to 4, in which case a mono-ether of formula (4) is obtained. This alkylation is carried out at a temperature of 20 to 1600C, preferably from 60 to 1600C, in the presence of a base, in an inert organic solvent.
Comme base on utilisera ici plus particulièrement un carbonate de métal alcalin ou un hydrogénocarbonate de métal alcalin, par exemple le carbonate de sodium ou l'hydrogénocarbonate de sodium.As a base, an alkali metal carbonate or an alkali metal hydrogen carbonate, for example sodium carbonate or sodium hydrogen carbonate, will be used here more particularly.
La base est mise en jeu en une quantité de 20 à 35 % en poids (par rapport à la fluoro-4 dihydroxy-2',4' benzophén9ne ou à la fluoro-4 trihydroxy-2',3',4' benzophénone). Comme solvant organique inerte on utilisera ici une cétone, telle que la cyclohexanone, ou un hydrocarbure aromatique contenant de préférence de 6 à 8 atomes de carbone, par exemple le toluène ou un xylène.The base is used in an amount of 20 to 35% by weight (relative to fluoro-4 dihydroxy-2 ', 4' benzophen9ne or fluoro-4 trihydroxy-2 ', 3', 4 'benzophenone) . As inert organic solvent, a ketone, such as cyclohexanone, or an aromatic hydrocarbon preferably containing from 6 to 8 carbon atoms, for example toluene or a xylene, will be used here.
L'éthérification est éventuellement effectuée aussi avec un sulfate de dialkyle, par exemple avec le sulfate de diméthyle ou le sulfate de diéthyle. The etherification is optionally also carried out with a dialkyl sulphate, for example with dimethyl sulphate or diethyl sulphate.
Le mono-éther de formule (4) fourni par l'alkylation est éventuellement transformé par sulfonation en un composé de formule (2), cela par réaction avec un acide halogénosulfonique, à une température de 20 à 800C, de préférence de 40 à 60"C, dans un solvant organique inerte. L'acide halogénosulfonique est de préférence l'acide chlorosulfonique. Le solvant organique inerte est l'un de ceux que l'on peut utiliser pour l'acylation de Friedel et Crafts. The mono-ether of formula (4) provided by the alkylation is optionally transformed by sulfonation into a compound of formula (2), this by reaction with a halosulfonic acid, at a temperature of 20 to 800C, preferably from 40 to 60 "C, in an inert organic solvent. The halosulfonic acid is preferably chlorosulfonic acid. The inert organic solvent is one of those which can be used for the acylation of Friedel and Crafts.
Les fluoro-4 benzophénones conformcs à l'in.ention sont obtenues avec un rendement d'au moins 70 t. Ell se signalent par une grande pureté, qui est d'-au moirs 99 '-b (chromatoraphie en phase liquide 5 haute performance).Elles conviennent comme absorbeurs de rayons ultra-violets, plus particulièrement dans des matières plastiques ou dans des compositions cosmétiques, ainsi que comme corps de départ pour la préparation de médica mentis, de produits phytosanitaires ou de matières plastiques. The fluoro-4 benzophenones conformcs to the in.ention are obtained with a yield of at least 70 t. They are distinguished by a high purity, which is from m to 99 m-b (high performance liquid chromatography 5). They are suitable as absorbers of ultra-violet rays, more particularly in plastics or in cosmetic compositions. , as well as as a starting material for the preparation of medicinis, phytosanitary products or plastics.
Les exemples suivants illustrent la présente invention. The following examples illustrate the present invention.
Dans ces exemples les pourcentages relatifs à des quantités de matière s'entendent en poids.In these examples, the percentages relating to quantities of material are understood by weight.
Exemple 1 a) On dissout 110 g (1 mole) de résorcinol dans -650 ml de dichlo
ro-1,2 éthane. A la solution obtenue on ajoute peu à peu 133 g
(1 mole) de chlorure d'aluminium, tout en maintenant la tempé
rature du mélange à 50"C au plus. A la suspension on ajoute
goutte-à-goutte en 1 heure, tout en agitant et en maintenant
la température de 500C, 159 g (1 mole) de chlorure
de fluoro-4 benzoyle, puis on maintient le mélange pendant en
core 30 minutes à 50"C. Après cela on verse le mélange réac
tionnel sur un mélange de glace et d'eau et on extrait le pro
duit solide obtenu par du dichloro-1,2 éthane chaud. Après
avoir éliminé l'agent d'extraction on obtient 208.,g (90 % de
la quantité théorique) de fluoro-4 dihydroxy-2',4' benzophé
none brute.Par recristallisation dans du méthanol aqueux à
80 % on obtient un produit ayant un point de fusion de 171
1720C et une pureté supérieure à 99 %.Example 1 a) 110 g (1 mole) of resorcinol are dissolved in -650 ml of dichlo
ro-1,2 ethane. To the solution obtained is gradually added 133 g
(1 mole) of aluminum chloride, while maintaining the temperature
stripping of the mixture at 50 ° C. at most. To the suspension is added
drip in 1 hour, while stirring and maintaining
the temperature of 500C, 159 g (1 mole) of chloride
of 4-fluoro benzoyl, then the mixture is maintained for
core 30 minutes at 50 "C. After that pour the reaction mixture
tional on a mixture of ice and water and extract the pro
solid product obtained with hot 1,2-dichloroethane. After
having eliminated the extraction agent, 208., g (90% of
the theoretical amount) of 4-fluoro-dihydroxy-2 ', 4' benzophé
none gross. By recrystallization from aqueous methanol to
80% we get a product with a melting point of 171
1720C and a purity greater than 99%.
b) On ajoute 700 g d'une solution à 10 96 d'hydroxyde de potassium
(1,25 mole de KOH) à 232 g (1 mole) de la fluoro-4 dihydroxy
2',4' benzophénone purifiée obtenue selon (a), et on ajoute
goutte-à-goutte au mélange, à 350C, tout en agitant, 62 g
(1 mole) de sulfate de diméthyle. Cela fait, on chauffe le
mélange à reflux pendant encore 30 rinutes.Après refroidisse
ment à la température ambiante on sépare la phase organique
et on l'extrait par du toluène. .X. partir de l'extrait on ob
tient, après avoir éliminé l'agent d extraction, 194 g (79 t;
de la quantité théorique) de flaorc- hydroxy-2' méthoxy-4'
benzophénone fondant à 86-88"C. b) 700 g of a 10% solution of potassium hydroxide are added.
(1.25 moles of KOH) to 232 g (1 mole) of 4-fluoro dihydroxy
2 ', 4' purified benzophenone obtained according to (a), and added
drip to the mixture, at 350C, while stirring, 62 g
(1 mole) dimethyl sulfate. That done, we heat the
reflux for another 30 rins. After cooling
at room temperature the organic phase is separated
and extracted with toluene. .X. from the extract on ob
holds, after removing the extractant, 194 g (79 t;
theoretical amount) of flaorc-hydroxy-2 'methoxy-4'
benzophenone melting at 86-88 "C.
Exemple 2
On dissout dans 300 ml de dichloro-1,2 éthane 49,2 g (0,2 mole) de la fluoro-4 hydroxy-2' méthoxy-4' benzophénone obtenue à l'exemple 1 b) et, à la solution ainsi obtenue, on ajoute en 10 minutes,- à 700C,tout en agitant, 11,8 g (0,2mole) d'acide chlorosulfonique. On sépare par essorage le précipité qui s'est formé après refroidissement du mélange à 10 C, on le lave avec du dichloro-1,2 éthane froid et on le sèche. On obtient 55 g (84 E de la quantité théorique) d'acide fluoro-4 hydroxy-2' méthoxy-4' benzophénone-sulfonique-5 qui a une teneur en acide supérieure à 98 % et qui se décompose à partir de 1800C.Example 2
Is dissolved in 300 ml of 1,2-dichloroethane 49.2 g (0.2 mole) of 4-fluoro-2-hydroxy-4-methoxy-benzophenone obtained in Example 1 b) and, to the solution thus obtained, 11.8 g (0.2 mol) of chlorosulfonic acid are added over 10 minutes, at 700C, with stirring. The precipitate which formed after cooling the mixture to 10 ° C. is separated by wringing, washed with cold 1,2-dichloroethane and dried. 55 g (84 E of the theoretical amount) of 4-hydroxy-2'-methoxy-4 'benzophenone-sulfonic-5 acid which has an acid content of over 98% and which decomposes from 1800C are obtained.
Exemple 3
On chauffe à 1500C pendant 5 heures 92,8 g (0,4 mole) de la fluoro-4 dihydroxy-2',4' benzophénone obtenue selon l'exemple 1 a) avec 77,2 g (0,4 mole) de bromo-l octane et 33,6 g (0,4 mole d'hydrogénocarbonate de sodium dans 400 ml de cyclohexanone. On sépare ensuite les corps solides par filtration et on évapore le filtrat à siccité. Le résidu cireux obtenu à partir de ce filtrat est recristallisé dans du méthanol. On obtient 100 g (72 % de la quantité théorique) de fluoro-4 hydroxy-2' octyloxy-A' benzophénone fondant à 48-490C et ayant une pureté de 99 %.Example 3
Heated at 1500C for 5 hours 92.8 g (0.4 mole) of 4-fluoro-dihydroxy-2 ', 4' benzophenone obtained according to Example 1 a) with 77.2 g (0.4 mole) of bromo-l octane and 33.6 g (0.4 mole of sodium hydrogencarbonate in 400 ml of cyclohexanone. The solid bodies are then separated by filtration and the filtrate is evaporated to dryness. The waxy residue obtained from this filtrate is recrystallized from methanol to give 100 g (72% of the theoretical amount) of 4-fluoro-2-hydroxy-octyloxy-A 'benzophenone melting at 48-490C and having a purity of 99%.
Exemple 4
On dissout 63 g (0,5 mole) de pyrogallol dans- 300 ml d'éthanol. On chauffe la solution obtenue à 650C et on y ajoute goutte-à-goutte en 30 minutes, tout en agitant, 214 g (2 moles) de trichlorométhyl-l f2uoro-4 benzène. On verse ensuite le mélange réactionnel dans 1,5 litre d'eau et on sépare par filtration le produit solide obtenu. Après l'avoir séché pendant 8 heures à 90 C on obtient 100 g (80,6 % de la quantité théorique) de fluoro-4 trihydroxy-2',3',4' benzophénone brute. Par recristallisation dans de l'éthanol aqueux à 80 % on obtient un produit fondant à 149-1500C et ayant une pureté supérieure à 99 t. Example 4
63 g (0.5 mole) of pyrogallol are dissolved in 300 ml of ethanol. The solution obtained is heated to 650C and is added dropwise over 30 minutes, while stirring, 214 g (2 moles) of 1-trichloromethyl-4-uoro-4 benzene. The reaction mixture is then poured into 1.5 liters of water and the solid product obtained is filtered off. After having dried it for 8 hours at 90 ° C., 100 g (80.6% of the theoretical amount) of 4-fluoro-trihydroxy-2 ′, 3 ′, 4 ′ benzophenone are obtained. By recrystallization from 80% aqueous ethanol, a product is obtained which melts at 149-1500 ° C. and has a purity greater than 99 t.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3115363 | 1981-04-16 | ||
| DE19823206129 DE3206129A1 (en) | 1981-04-16 | 1982-02-20 | Fluorobenzophenone derivative, process for its preparation, and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2504130A1 true FR2504130A1 (en) | 1982-10-22 |
| FR2504130B1 FR2504130B1 (en) | 1985-07-05 |
Family
ID=25792722
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8206565A Expired FR2504130B1 (en) | 1981-04-16 | 1982-04-16 | FLUORO-BENZOPHENONES, METHODS FOR THEIR PREPARATION AND THEIR APPLICATION |
| FR8215778A Granted FR2511672A1 (en) | 1981-04-16 | 1982-09-20 | FLUORO-4-TRIHYDROXY-2 ', 3', 4 'BENZOPHENONE DERIVATIVES, PROCESS FOR PREPARING THEM AND THEIR APPLICATION |
| FR8215777A Granted FR2513635A1 (en) | 1981-04-16 | 1982-09-20 | 4-FLUORO-BENZOPHENONE-SULFONIC-5 DERIVATIVES, PROCESSES FOR PREPARING THEM AND THEIR APPLICATION |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8215778A Granted FR2511672A1 (en) | 1981-04-16 | 1982-09-20 | FLUORO-4-TRIHYDROXY-2 ', 3', 4 'BENZOPHENONE DERIVATIVES, PROCESS FOR PREPARING THEM AND THEIR APPLICATION |
| FR8215777A Granted FR2513635A1 (en) | 1981-04-16 | 1982-09-20 | 4-FLUORO-BENZOPHENONE-SULFONIC-5 DERIVATIVES, PROCESSES FOR PREPARING THEM AND THEIR APPLICATION |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE3206129A1 (en) |
| FR (3) | FR2504130B1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2892872A (en) * | 1957-10-09 | 1959-06-30 | American Cyanamid Co | Chlorinated benzophenone ultraviolet absorbers |
| US3387035A (en) * | 1963-11-04 | 1968-06-04 | Air Force Usa | Fluorine substituted benzophenone ultraveiolet absorbers |
| GB1145318A (en) * | 1966-05-05 | 1969-03-12 | American Cyanamid Co | Substituted benzophenones as light stabilizers |
| FR2084325A5 (en) * | 1970-03-11 | 1971-12-17 | Ciba Geigy Ag | |
| US3769349A (en) * | 1967-01-27 | 1973-10-30 | Kyodo Chem Co Ltd | Process for preparing 2,4-dihydroxybenzophenones |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3468938A (en) * | 1966-10-21 | 1969-09-23 | Gaf Corp | Method of preparing sulfonated hydroxybenzophenone |
-
1982
- 1982-02-20 DE DE19823206129 patent/DE3206129A1/en not_active Withdrawn
- 1982-04-16 FR FR8206565A patent/FR2504130B1/en not_active Expired
- 1982-09-20 FR FR8215778A patent/FR2511672A1/en active Granted
- 1982-09-20 FR FR8215777A patent/FR2513635A1/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2892872A (en) * | 1957-10-09 | 1959-06-30 | American Cyanamid Co | Chlorinated benzophenone ultraviolet absorbers |
| US3387035A (en) * | 1963-11-04 | 1968-06-04 | Air Force Usa | Fluorine substituted benzophenone ultraveiolet absorbers |
| GB1145318A (en) * | 1966-05-05 | 1969-03-12 | American Cyanamid Co | Substituted benzophenones as light stabilizers |
| US3769349A (en) * | 1967-01-27 | 1973-10-30 | Kyodo Chem Co Ltd | Process for preparing 2,4-dihydroxybenzophenones |
| FR2084325A5 (en) * | 1970-03-11 | 1971-12-17 | Ciba Geigy Ag |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3206129A1 (en) | 1982-11-04 |
| FR2513635B1 (en) | 1984-02-10 |
| FR2513635A1 (en) | 1983-04-01 |
| FR2511672B1 (en) | 1984-03-16 |
| FR2511672A1 (en) | 1983-02-25 |
| FR2504130B1 (en) | 1985-07-05 |
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| Date | Code | Title | Description |
|---|---|---|---|
| ER | Errata listed in the french official journal (bopi) | ||
| ST | Notification of lapse |