Patent GB-860309-A (GB)
Title: Method for the preparation of aromatic perchloryl compounds
IPC: F02B3/06
Filed: 1958-09-25
Abstract: The invention comprises compounds of the formula Ar-ClO3, where Ar is a substituted or unsubstituted aromatic radical.  The aromatic radical may be a phenyl, biphenylyl, a - or b -naphthyl, a -, b -, or g -anthryl, phenanthryl, naphthacenyl, pyrenyl, or triphenylyl radical.  It may contain substituents of various kinds including alkyl groups of 1-12 carbon atoms; carbonyl, carboxyl, hydroxyl, alkoxy, esterified, nitrated, sulphonated, cyanated, aminated, and closed-ring derivatives and forms of such alkyl groups; bromine, chlorine, fluorine, iodine, phenyl, nitrophenyl, hydroxy, amino, nitro, cyano, thiophenyl, sulphohydryl, thioether, sulpho, sulphonyl chloride, sulphonyl, amidosulphonyl, carbamyl, perchlorylaryl, carboxy, nitroso, azo, azoxy, hydrazo, ester, or ether groups or radicals, or an aryl or heterocyclic radical such as a phenyl, naphthyl, furan, thiophene, pyrrole, indole, pyridine, piperidine, 1, 2, 3-triazolyl or quinoline radical.  The perchloryl aromatic compounds may be produced by reacting, in presence of a Friedel-Crafts catalyst, perchloryl fluoride with an aromatic compound capable of substitution in the nucleus, the reaction being carried out at a temperature below 280 DEG  C.  The primary products may be converted by various chemical treatments, carried out below 280 DEG  C. and under such pH and other conditions that the perchloryl groups are not decomposed, into other compounds of the stated general formula.  Perchloryl fluoride may be reacted with 2,3-dichlorobenzene to form 3,4-dichloro-perchlorylbenzene, or the same product may be obtained by reacting chlorobenzene with perchloryl fluoride and then chlorinating the 4-chloro-perchlorylbenzene. Perchlorylbenzene may be made by perchlorination of benzene or by deamination of 3-amino-perchlorybenzene.  Specified perchloryl compounds include 3-iodo, 3 - sulphamido, 3 - cyano, 3 - carboxy, 3 - phenoxy, 4-chloromethyl, 4-hydroxymethyl, 4 - trichloromethyl, 4 - thiophenyl, 3 - (b  - hydroxynaphthylazo), 4 - trifluoromethyl, 3 - amino-4-methyl, 3-bromo-4-methyl, and 2,4-dichloro-5-nitro, perchlorylbenzene.  Benzene, toluene, ethyl benzene, the various xylenes, mono-, di-, and tri-halobenzenes, and the various chlorotoluenes are preferred for reaction with the perchloryl fluoride to obtain the primary products.  The perchloryl fluoride may be introduced in gaseous or liquid form into the catalyst-containing mass.  Aluminium chloride, bromide, and fluoride, and similar compounds of Sb, Sn, Fe, Ta, Ti, and boron may be used as catalyst. The aromatic compound may be used alone or dissolved in a solvent. The reaction may be carried out at temperatures ranging from -15 DEG C. to +280 DEG  C., a range of 0 DEG  to 15 DEG  C. being generally preferred.  The pressure may be above, below, or at atmospheric pressure.  The perchlorylaromatic compounds possess explosive properties and may be used for blasting and like purposes.  They may be used as high-energy fuels or as additives to fuels for internal combustion engines, or as intermediates for drugs and dyes.  In examples, details are given of the production of perchlorylbenzene; 2,4- (and 2,5-) dimethyl-, 4-fluoro-, 3 - amino (and acetylamino)-, 3 - nitro-, 4 - hydroxy-, 4-methoxy-, 3-(4-nitrophenyl)-, and 4 - thiophenyl - perchlorylbenzene; 3,31 - diperchloryl - diazoaminobenzene, and perchlorylbenzene-3-diazonium chloride.ALSO:The invention includes azo dyestuffs which contain the perchloryl group-ClO3 attached to an aromatic nucleus e.g. to that of a phenyl, biphenylyl, a -naphthyl, b -naphthyl, a -, b , or g -anthryl, phenanthryl, naphthacenyl, chrysenyl, pyrenyl, or triphenylyl radical.  The dyestuffs may be produced by diazotizing an appropriate amino-perchloryl aromatic compound (see Group IV(b)) and coupling with b -naphthol or other coupling component.  In an example 3-amino-perchloryl-benzene is diazotized to form a solution of the diazonium chloride, the precipitate of 3, 31-diperchloryl diazoaminobenzene is filtered off, b -naphthol in dilute caustic soda solution is added, and the product, 3-(b -hydroxynaphthylazo)-perchlorylbenzene is obtained as dark orange crystals which may be used for dyeing wool.  The production of m, m1-diperchloryl azobenzene from 3-amino-perchlorylbenzene is also mentioned.ALSO:Perchloryl aromatic compounds of the formula Ar-ClO3 where Ar is a substituted or unsubstituted aromatic radical (see Group IV (b)) may be used as high energy fuels or as additives to fuels used in internal-combustion engines, particularly diesel fuels. The aryl radical may be phenyl, biphenylyl, naphthyl, anthryl, phenanthryl, naphthacenyl, chrysenyl, pyrenyl, or triphenylyl.  Many optional substituents of the aryl radical are mentioned, including substituted and unsubstituted alkyl groups, halogen atoms, and groups containing oxygen, sulphur, nitrogen, and/or halogen atoms. Among groups which may be present in radical Ar are carbonyl, carboxyl, hydroxyl, esterified carboxyl, etherified hydroxyl, nitrate, nitro, cyanate, cyano, sulphonate, sulpho, thioether, sulphhydryl, sulphonyl, sulphonylchloride, amino, amino sulphonyl, carbamyl, nitroso, azo, azoxy, hydrazo and heterocyclic nitrogen groups.