DE735079C - Process for the introduction of sulfonic acid halide groups into liquid aliphatic or cycloaliphatic mono- or dihalohydrocarbons - Google Patents

Description

Process for introducing sulfonic acid halide groups into liquid aliphatic or cycloaliphatic mono- or dihalohydrocarbons It has been found that sulfonic acid halide groups can be obtained without significant further halogenation into liquid aliphatic or cycloaliphatic mono- or dihalohydrocarbons can be introduced if the starting materials are irradiated with short-wave light Treated at .a temperature up to about 20 ° free sulfur dioxide and halogen.

As starting materials are z. B. i- or 2-monochloropropane, i- or 2-monochloro-butane and its isomers mentioned, z. B. Monochloroisobutane, i, 2-dichloro-n-butane, Dichlördodecan, Monobromoctadecan, also cychsche halogenated hydrocarbons, z. B. Cyclohexyl chloride.

Mixtures of different halogenated hydrocarbons can also be used be applied, e.g. B. mono- or dihalohydrocarbons produced by exposure to from HaJogen to that in the catalytic hydrogenation of carbon monoxide in ordinary or moderately elevated pressure available hydrocarbons are formed, which may be before the halogenation of a pre-cleaning, e.g. B. by hydrogenation are subjected.

These halogenated hydrocarbons are in liquid form, if appropriate also under pressure, subjected to the action of sulfur dioxide and halogen. Particularly if you start from solid or very low-boiling halogenated hydrocarbons, the use of solvents is advantageous. As a solvent, for. B. Halohenkohlenwa.sserstoffe-are used, which at each carbon atom or contain several halogen atoms, e.g. B. carbon tetrachloride or ethylene chloride.

For example, one leads into a z. B. enamelled iron or ceramic material existing vessel, in which the starting material is located, through a floor-mounted distributor for a mixture of halogen and sulfur dioxide. The reaction mixture is simultaneously irradiated with short-wave light; for example one uses a mercury vapor immersion lamp or lets the short-wave light from one suitable light source through a quarr window. or one for Short-wave radiation permeable glass get into the implementation room. Rays with a shorter wavelength than about 2200 Äns ström-Einlieiten cause up to% vezlen a brown coloration of the end products and are therefore best passed through suitable filters held back.

Equal parts of the volume of sulfur dioxide and halogen can be allowed to act. However, it is advisable to use an excess of sulfur dioxide, for example 100% or more, to be used, because this results in the entry of halogen into the hydrocarbon radical is pushed back.

The resulting halosulfonic acid halides are high-boiling liquids or crystallized substances; they can be distilled or recrystallized getting cleaned. -It is known to use halogen and sulfur dioxide under the influence of light to act on saturated hydrocarbons. However, this suggestion offered no incentive, Ilüss: ige mono- or di-dialog carbons with a mixture of halogen and sulfur dioxide in order to avoid further halogenation among the to treat claimed conditions.

The parts given in the following examples are parts by weight. Example i In iooo parts of i-monochlorobutane a total of 74.6 Parts of chlorine and 74.6 parts of sulfur dioxide under irradiation with short-wave light initiated; the temperature in the reaction space is kept at i8 #. From the The reaction mixture becomes the unreacted monochlorobutane at ordinary pressure distilled off, the higher-boiling components under reduced pressure.

This gives moo parts of chlorobutanesulphonic acid chloride at the boiling point 118 to i 2o 'at i mm mercury pressure, next to it parts of unchanged monochlorobutane, 2 14 parts of i, 2- and i, 3-dichlorobutane and 100 parts of trichlorobutane. i 9o Tsile Monochlorobutane. those of the escaping, consisting mainly of hydrogen chloride Gases that are entrained can be separated by cooling after washing with water and returned to the implementation area. Example 2 In 7 10 parts of cyclohexyl chloride - become a total of 426 during 5 hours in the manner described in example i Parts of chlorine and .12o parts of sulfur dioxide initiated. 870, 'o des C' ;:, -lohexyl chloride -are converted into C'lilorcyclohelansulfonsäurechlorid.

EXAMPLE 3 In 60o parts of a hydrocarbon mixture from the zoo to 37o boiling range which has been produced by the catalytic hydrogenation of carbon monoxide at ordinary pressure. -: -: ground under irradiation with km-celligenr light 12o parts of chlorine introduced. In the resulting mixture of mono- and dichlorohydrocarbons with an average chlorine content of 9.100, 120 parts of chlorine and 120 parts of sulfur dioxide are then passed in for 10 hours in the manner described in Example 1. A product is obtained which contains 1.60% chlorine and 6.30% sulfur. Chlorine are bound to sulfur. EXAMPLE 100 parts of dichlorododecane -erden treated in 10 hours with 40o parts of chlorine and 38o of sodium oxide in the manner described in Example i. A product is obtained which contains 320 g of chlorine and 9.7 T0 sulfur; io, 7o, o chlorine are bound to sulfur. EXAMPLE 5 130 parts of chlorine are introduced into 60o parts of a hydrocarbon mixture from the zoo boiling range to 30 ° from a Hanoverian petroleum which has been purified by hydrogenation over sulfidic catalysts, while irradiating with short-wave light. Thereafter, 120 parts of chlorine and 120 parts of sulfur dioxide are introduced into the resulting mixture of mono- and dichlorohydrocarbons with about 100% chlorine content for 10 hours in the manner described in Example 1. A product is obtained which contains i 5, i 0'o chlorine and 6, i o'o sulfur; 6.70'o chlorine are bound to sulfur.

Claims (1)

PATENT CLAIM: Process for the introduction of sulfonic acid halide groups into liquid aliphatic or cycloaliphatic mono- or dihalohydrocarbons, thereby e -ennzeiclinet that the exit tunnel under irradiation with short-wave Light to avoid further halogenation at temperatures up to about 2o 'treated with sulfur dioxide and halogen.