Patent GB-705734-A (GB)
Title: Improvements in or relating to the manufacture of halogen compounds
IPC: C07B39/00
Filed: 1952-01-11
Abstract: Organic compounds are halogenated by substitution in the presence of sulphur trioxide and a metal or aluminium halide. Sulphur dioxide and a sulphate of the metal of the metal or ammonium halide are also obtained.  The sulphate may be obtained combined with sulphur trioxide which may be liberated on heating. Aromatic or oxygen-containing compounds may react with the trioxide and when such feedstocks are used they should be introduced to the reactor in separate lines.  In upflow operation the organic compound is preferably introduced above the trioxide. The degree of substitution is effected by varying the proportions of trioxide and organic feed. Thus for the production of an alkyl halide from an alkane the mol. ratio of SO3 to hydrocarbon should be less than about 2.2 to 1. Poly-substituted products are obtained with higher ratios.  The preferred ratio is 0.5 to about 8.0 to 1.  A temperature of at least 250 DEG C. is preferred although higher temperatures may be used with short residence times e.g. when treating higher molecular weight hydrocarbons.  Inert gases may be present.  Product gas from a catalytic converter of a sulphuric acid plant may be used.  Mixed metal halides may be used, e.g. mixed calcium and sodium chlorides may be used in a ratio of about 1 to 1 in a fluidized solid type of operation. Other specified mixtures are ammonium and calcium chlorides, sylvinite, baeumlerite and rinnite.  When using a mixture of fluorides and chlorides products may be obtained which are both chlorinated and fluorinated.  Dichlorodifluoromethane is made by treating methane and SO3 in a vol. ratio of 1 to 8 with mixtures of calcium chloride and fluoride, calcium fluoride and sodium chloride or sodium chloride and fluoride.  About 2.8 parts of calcium chloride per part of calcium fluoride are used.  For trichlorofluoromethane this ratio is about 4.3 to 1, and for monochloro-difluoromethane about 0.7 to 1.  For the last two compounds the ratio of SO3 to methane is about 6 to 1. Other mixed products are specified representative being 1, 2-dichloro-1, 1, 2, 2-tetrafluoro-ethane. Halogenated feedstocks may be treated and their halogen replaced by a more reactive halogen.  Thus carbon tetrachloride with SO3 and calcium fluoride yields chlorofluoromethanes the liberated chlorine being obtained combined with the SO2 as sulphuryl chloride. Representative of other listed processes illustrating this modification are 1-chloro-2-bromo-ethane from ethylene bromide and 1-fluoro-1, 2, 2-trichloro-, 1, 2-difluoro-1, 2-dichloro- and 1, 1, 2-trifluoro-2-chloro-ethanes from 1, 1, 2, 2-tetra-chloroethanes. Halogen groups of products obtained via the process of the invention may be replaced in a second stage when using a different metal halide.  A diagram is provided of a suitable layout of apparatus.  In examples sulphur trioxide and (1) ethane in a vol. ratio of 56/44 are treated with sodium chloride at 350-400 DEG C. to yield ethyl chloride, dichloromethanes and sodium pyrosulphate, (2) ethane in a vol. ratio of 51/47 with calcium chloride at 300-350 DEG C. to yield ethyl chloride, (3) ethane in a vol. ratio of 6 to 4 with potassium bromide at 300-325 DEG C. to yield ethyl bromide and (4) methane in a vol. ratio of 52/48 with sodium chloride to yield methyl chloride, dichloromethane, trichloromethane, carbon tetrachloride and sodium pyrosulphate. It is also stated that propane, butane, pentane, hexane, cyclopropane, cyclobutane, cyclohexane, cyclopentane, cycloheptane, acetic acid, acetaldehyde, acetic anhydride, propionic acid, succinic acid, butanol, ethanol, methanol, benzaldehyde, benzophenone, n-butylamine, camphene, phenol, toluene, biphenyl or nitropropane may be used in place of the ethane of Example (1) to yield respectively isopropyl chloride, isobutyl chloride, amyl chlorides, hexyl chlorides, monochloro-cyclopropane-cyclobutane, -cyclohexane, cyclopentane, -cycloheptane, chloracetic acid, chloro-acetaldehyde, chloracetic anhydride, beta-chloro-propionic acid, chlorsuccinic acid, 1-chloro - 4 - hydroxy - butane, beta - chlor - ethanol, o - chlorbenzaldehyde, 2 - chlorbenzo - phenone, 1 - amino - 2 - chloro - butane, 3 - methyl - 3 - chlormethyl - 2 - methylene - norcamphene, m - chlorphenol, benzyl chloride, o - chlordiphenyl and 1-nitro-2-chloropropane.  Sodium bromide, iodide and fluoride, calcium fluoride, magnesium, ferric, ammonium, barium, potassium and aluminium chlorides, potassium iodide and aluminium bromide may be used instead of the sodium chloride of Example (1). Other specified feedstocks are octane, nonane, decane, undecane, dodecane, methyl and 1, 1-dimethyl cyclopropane and methyl cyclobutane and amongst other specified products are dichlor- and trichlor-acetic acid, chloral and dichloracetic anhydride.ALSO:In a process for the halogenation of an organic compound by substitution in which the compound is heated with a metal or ammonium halide in the presence of sulphur trioxide metal sulphates or ammonium sulphate are obtained as bye-products. Sodium, calcium, magnesium, iron, barium, potassium and aluminium are specified metal sulphates. Sulphuryl chloride may also be obtained amongst the products, e.g. CCl4+2SO3+CaF2 --> CCl2F2+SO2Cl2+CaSO4.  Mixtures of metal halides may be used when mixtures of sulphates will result. A temperature of at least 250 DEG C. is preferred.  In examples sulphur trioxide and (1) ethane in a vol. ratio of 56/44 are treated with sodium chloride at 350-400 DEG C. to yield ethyl chloride, dichloroethanes and sodium pyrosulphate, (2) ethane in a vol. ratio of 51/47 with calcium chloride at 300-350 DEG C. to yield ethyl chloride and calcium sulphate, and (4) methane in a vol, ratio of 52/48 with sodium chloride to yield methyl chloride, dichloromethane, trichloromethane, carbon tetrachloride and sodium pyrosulphate.  A large number of organic compounds are specified for use in place of those of the examples (see Group IV (b)).