Patent GB-909364-A (GB)
Title: Improvements relating to the production of fluorine-containing organic compounds
IPC: C08G63/91
Filed: 1960-11-09
Abstract: Liquid fluoroformic esters of a -fluoroalcohols (see Group IV(b)) are useful as liquid media for the preparation of carbon black and graphite dispersions.ALSO:Fluorine-containing polymers are obtained by reacting polymers containing carbonyl groups, such as polyamides, polyesters and ethylene/carbon monoxide polymers of the type described in U.S.A. Specification 2,495,286, with carbonyl fluoride under substantially anhydrous conditions, preferably in the presence as catalyst of a basic compound, a phosphine oxide or an inorganic or tetraalkylammonium fluoride.  An example uses a polyamide derived from adipic acid and hexamethylenediamine; and an ethylene-carbon monoxide copolymer.  Compounds of the formula ROCOF, where R is an organic radical containing fluorine attached to the carbon atom itself attached to the oxygen (see Group IV(b)) are useful as solvents for highly fluorinated polymers, e.g. poly(tetrafluoroethylene) and poly(chlorotrifluoroethylene). Compounds of formulae HCF2N(CH3)COF, HCON(CH3)COF, CH3CF2N(CH3)COF, and CH3CON(CH3)COF and N-fluoroformyl-1,1-difluorohexamethyleneimine are also useful as solvents for highly fluorinated polymers.  Such solutions impart water-repellency (see Group VIII).ALSO:Fluorine compounds are prepared by reacting carbonyl fluoride under substantially anhydrous conditions with an organic carbonyl compound in which the carbonyl carbon is joined by single bonds to two atoms of which not more than one is halogen and not more than one is oxygen; preferably in the presence, as catalyst, of a basic compound, a phosphine oxide, or an inorganic or tetraalkylammonium fluoride. The carbonyl fluoride may be prepared in situ, e.g. from phosgene and a fluoride.  In general, compounds C-CO-C, C-CO-H and C-CO-NR2 give C-CF2-C, C-CF2H and C-CF2NR2 respectively; and compounds -CO-Hal, -CO-O-, -CO-NH2 and -CO-NHR give -COF or -CF3.  Aldehydes and ketones give as intermediate products compounds of type RR1CF.OCOF; these are claimed as novel, and on heating give RCF2R1.  Examples prepare (1) and (2) 1-fluorocyclohexyl fluoroformate and 1,1 -di-fluorocylochexane from cyclohexanone; (3) di-fluorodiphenylmethane from benzophenone; (4) benzylidene difluoride from benzaldehyde; (5) p - methoxybenzylidene difluoride from anisaldehyde; (6) p-dimethylaminobenzylidene difluoride from p-dimethylaminobenzaldehyde; (7) benzoyl fluoride and benzotrifluoride from benzoic acid; (8) trifluoroacetyl fluoride from trifluoroacetic acid; (9) perfluorobutyryl fluoride from perfluorobutyric acid; (10) perfluorooctanoyl fluoride from perfluorooctanoic acid; (11) perfluoroglutaryl fluoride from perfluoroglutaric acid; (12) perfluorosuccinyl fluoride from perfluorosuccinic acid; (13) phthaloyl fluoride and o-trifluoromethylbenzoyl fluoride from phthalic anhydride; (14) benzoyl fluoride from methyl benzoate; (15) benzotrifluoride from benzoyl fluoride; (16) the compounds HCF2.N(CH3)COF and HCON(CH3)-COF from N-methylformamide; (17) the compounds CH3CF2N(CH3)COF and CH3CON-(CH3)COF from N-methylacetamide; (18) and (23) HCF2N(CH3)2 from HCON(CH3)2; (19) a ,a -difluorobenzyldimethylamine from N,N-dimethylbenzamide; (20) benzoyl fluoride from benzamide; (21) N-fluoroformyl-1,1-difluorohexamethyleneimine from caprolactam; and (22) (CH3)2NCF2N(CH3)2 from tetramethylurea.  Other reactions specified are of (i) formaldehyde to bis-fluoromethyl ether and fluoromethyl fluoroformate; (ii) phenyl fluoroformate to a fluorinated ether; (iii) of sodium benzoate to benzoyl fluoride; (iv) of sodium propionate to propionyl fluoride; and (v) the preparation of the following novel fluoroformates from the appropriate aldehyde or ketone: a  - fluoroethyl, 2 - fluoro - 2 - propyl, a -fluorocyclopentyl, a -fluorododecyl, a -fluorobenzyl, a -fluoro-a -phenylethyl, diphenylfluoromethyl, a -fluorooctadecyl and 2-fluoro-2-butyl fluoroformate.  Other aldehyde, ketone, carboxylic acid, carboxylic acid anhydride, carboxylic ester, carboxylic acid halide, and carboxylic acid amide and imide starting materials are specified.