Occidental Chemical Corporation

Hooker Chemicals & Plastics Corporation

Other

Henry C Lin

Neil J O'Reilly

Lawrence B Fertel

Jeffrey S Stults

William S Derwin

Robert A Buchanan

Byron R Cotter

Deanne M Nowak

Ramesh Krishnamurti

James J Maul

Robert L Ostrozynski

Mahendra K Dosi

Joseph A Pawlak

Stephen Robota

Karl W Seper

Stanley A Sojka

Garra C Lester

Disclosed are bis-meta-benzotrifluoride compounds having the general formula ##STR1## where each A is independently selected from the group consisting of NO.sub.2, NH.sub.2, and NH.sub.3.sup.+ Z.sup.-, Z.sup.- is an anion and B is selected from the group consisting of O, CO, S, SO, and SO.sub.2. The diamine compounds are useful as monomers in making polyimides, polyamide-imides, and polyamides.

Bis-m-benzotrifluoride compounds

3,4,6-trifluorophthalic acid is prepared in high yield by reaction of a 3,4,6-trichloro-N-substituted phthalimide with potassium fluoride at temperatures in the range of 200.degree. to 270.degree. C. in the absence of a catalyst to form the corresponding trifluoro-N-substituted phthalimide which, in turn, is hydrolyzed to form the 3,4,6-trifluorophthalic acid.

Preparation of 3,4,6-trifluorophthalic acid

A process for the preparation of 4,4'-dinitro-2,2'-di(trifluoromethyl)diphenyl ether according to the equation ##STR1## where X is F, Cl, Br or I, where the inorganic base is selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates, in the presence of a catalytic quantity of a benzoate catalyst. 2,8-Dinitro-6,6,12,12,-tetrafluoro-6H,12H-dibenzo[b,f][1,5]dioxocin, the corresponding diamine and polyimides formed from the diamine are also disclosed.

Method for ether formation

3,5-Diaminobenzotrifluoride is prepared by reaction of 4-chloro-3,5-dinitrobenzotrifluoride with sodium formate in acetic acid, in the presence of sodium acetate and palladium on charcoal.

Process for the preparation of 3,5-diaminobenzotrifluoride

Disclosed is a method of making 1,1'-sulfonylbis[3-nitro-5-(trifluoromethyl) benzene] by reacting dibenzotrifluoride sulfide with at least four equivalents of fuming nitric acid and at least four equivalents of fuming sulfuric acid at a temperature below 20.degree. C., until the sulfide link is oxidized to a sulfone link, then raising the temperature to above 20.degree. C. until the reaction is complete. Also disclosed is the preparation of 1,1'-sulfonylbis[3-nitro-(5-trifluoromethyl) benzenamine] by reducing the benzene compound.

Method of making 1,1'-sulfonylbis[3-nitro-5-(trifluoromethyl)benzene]

3,4,6-Trifluorophthalic acid may be decarboxylated in a controlled manner to form 2,4,5-trifluorobenzoic acid by heating the phthalic acid in a dipolar aprotic solvent in the absence of any catalyst.

Preparation of 2,4,5-trifluorobenzoic acid by decarboxylation of

Novel halogenated trifluoromethylbenzenes have the structural formula ##STR1## wherein X is halogen, preferably Cl, F or Br, and R is a group selected from the group consisting of --COOH, --C(O)NH.sub.2 and --CN. These compounds are intermediates for pesticidal trifluoromethyl diphenyl ethers and are converted thereto by replacing the fluorine para to the trifluoromethyl with substituted phenoxy group in aromatic nucleophilic substitution. A novel intermediate which is converted by reaction with cuprous cyanide and HONO to compound having the above structural formula where X is F and R is --CN is 2,3-difluoro-5-(trifluoromethyl)aniline and has the formula ##STR2##

Halogenated trifluoromethylbenzenes

3,5-Diaminobenzotrifluoride can be produced, in a single step, by reacting 4-chloro-3,5-dinitro benzotrifluoride in a suitable solvent, with hydrogen gas, in the presence of a catalyst comprising palladium on a suitable carrier, and in the presence of a suitable base.

Preparation of 3,5-diamino benzotrifluoride

p-Trifluoromethyl benzaldehydes are prepared by the catalytic reduction reaction of p-trifluoromethyl benzonitriles with hydrogen in an aqueous formic acid media in the presence of a nickel/aluminum alloy catalyst.

Catalytic reduction of nitriles to aldehydes

This invention relates to novel fluorinated N,N-bis-imides of the formula ##STR1## wherein R is a bivalent radical of the formula ##STR2## The compounds are particularly useful as monomers in the preparation of high performance polymer.

Fluorinated N,N-bis-imides

Plychlorophthalimides, specifically, N-substituted tetrachlorophthalimides and N-substituted trichlorophthalimides may be treated with zinc and a base in aqueous soluction to yield, after acidification, the product 3,5-dichlorophthalic acid or salts thereof.

Preparation of 3,5-dichlorophthalic acid and 3,5-dichlorophthalic

Polyfluorobenzenes are prepared by the decarboxylation of polyfluorophthalic acids or polyfluorobenzoic acids, in the presence of a Cu, CuO or Cu.sub.2 O catalyst in either quinoline or N-methyl-2-pyrrolidone as a solvent.

Preparation of fluorobenzenes by the decarboxylation of fluorophthalic

A process for the aromatization of 4-chlorotetrahydrophthalic anhydride and 4,5-dichlorotetrahydrophthalic anhydride which comprises heating a solution of either substance in the presence of activated carbon and in the partial absence of air.

Preparation of halogenated phthalic anhydrides

Chlorinated phthalic anhydrides are converted to fluorinated phthalic acids without dilactone formation by reacting an anhydride with a primary amine under anhydrous conditions to form the corresponding chlorinated-N-substituted phthalimide which in turn is reacted with a fluorinating agent under anhydrous conditions to form the corresponding fluorinated phthalimide which is hydrolyzed to form the corresponding fluorinated phthalic acid. In a preferred embodiment tetrachlorophthalic anhydride is refluxed with aniline in the presence of glacial acetic acid for 5 to 10 hours to form tetrachloro-N-phenylphthalimide which is reacted with KF in sulfolane in the presence of tributylhexadecylophosphonium bromide under nitrogen at 140.degree. C. to 160.degree. C. for 10 to 15 hours to form tetrafluoro-N-phenylphthalimide which in turn is hydrolyzed by refluxing with 50% H.sub.2 SO.sub.4 for 15 to 25 hours. The tetrafluoro-N-phenylphthalimide is a novel compound. The fluorinated phthalic acid products are intermediates for the corresponding fluorinated phthalic anhydrides, fluorinated benzoic acids and fluorinated benzenes.

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Grand Island, NY, United States of America

Henry C Lin