Patent GB-437573-A (GB)
Title: A process for the treatment of vinyl type monohalides
IPC: C07C49/16
Filed: 1935-03-19
Abstract: Vinyl type monohalides are reacted with halogen and water, hypohalogenous acid and hydrogen halide in the presence of water, or an alkyl or aralkyl hypohalite in the presence of water, to give halogenated carbonyl compounds or halogenated compounds with or without hydroxyl groups, or both.  Vinyl type monohalides are compounds containing at least one <FORM:0437573/IV/1> grouping which may comprise part of an iso or normal alkyl chain which may be attached to a cyclic radical or include part of an alicyclic structure.  When neither of the vicinal vinylic or unsaturated carbon atoms is tertiary, the main product is a halogenated carboxyl compound which may be aldehydic or ketonic. Where a vinylic carbon atom is of tertiary character and not once removed from a tertiary or quaternary carbon atom, the product is a polyhalohydrin, but where it is once removed from such a carbon atom, the double bond is taken up by two halogen atoms and hydrogen may be substituted by halogen.  The monohalide may be in the liquid or gaseous state.  A solution of halogen or its equivalent may be atomized into an atmosphere of the monohalide in presence or absence of water, diluents or solvents such as alcohols, ethers, esters, hydrocarbons or halogenated hydrocarbons.  Contact with free or undissolved halogen is obviated as by absorbing the halogen in a separate stage.  The concentration of hydrogen halide present should not exceed 1,5N, while the product of the concentrations of hypohalogenous acid and hydrogen halide should not exceed 1N.  Primary, secondary or tertiary alkyl or aralkyl esters of HOCl or HOBr or mixtures thereof may be used.  Room or higher temperatures may be used, while in some cases it is preferably to operate substantially below 20 DEG  C.  Pressure is usually atmospheric, but may be greater or less.  According to examples: (1) A cyclic system comprising reaction chamber, a separator stage for breaking up emulsions in the reaction products and an absorption column for saturating circulating water with chlorine is employed.  The system is charged with water, carbon tetrachloride and 2-chlor-butene-2, <FORM:0437573/IV/2> These are agitated in the reaction chamber and the water circulated through the system, chlorine being introduced continuously into the column. 2-Chlor-butene-2 is intermittently admitted to the reaction chamber. The HCl content at the end of the run is about 1.1N.  The product is mainly a chlor-butanone, probably CH3--CO--CHCl--CH3, together with some dichlor secondary butyl alcohol, probably CH3--CCl2--CHOH--CH3. (2) A cyclic system comprising a spray chamber filled with vinyl chloride, a chlorine absorption tower, and pump is employed.  The solution of chlorine in water is atomized into the spray chamber, vinyl chloride being continuously introduced to maintain a constant pressure.  The product is the hydrate of chloracetaldehyde, probably CH2Cl.CHO.\ba1/2\beH2O.  (3) The apparatus of (1) is employed for reacting isocrotyl chloride.  Water is introduced continuously to maintain the HCl concentration at or below 4 per cent.  Portions of the liquid are withdrawn when necessary to keep the volume substantially constant.  The product separates into two phases, the non-aqueous phase and an ether extract of the aqueous phase being dried and fractionated.  After removal of ether and CCl4, a dichlor tertiary butyl alcohol, probably <FORM:0437573/IV/3> , distils.  (4) Phenylisocrotyl chloride <FORM:0437573/IV/4> is reacted as in (1) and (3), the products being 2.3.3.-trichlor-2-methyl-1-phenyl-propane and 3-chlor-2-(chlormethyl)-1-phenyl-propene-3.  (5) Isocrotyl chloride, water and tertiary butyl hypochlorite are stirred together to give tertiary butyl alcohol and a dichlor tertiary butyl alcohol <FORM:0437573/IV/5> (6) Bromine is added to a mixture of 1.3.dibrom-propene-1 and water.  The product is CH2Br--CHBr--CHO. The products of the present process may be used as solvents and extractants, e.g. in refining mineral oils or purifying refinery and manufactured gases.  The polyhalogenated tertiary alcohols may be hydrolyzed to polyhydric alcohols.  Specification 402,880 is referred to.ALSO:Halogenated carbonyl compounds, hydrocarbons, and hydroxy compounds, prepared by the reaction of vinyl type monohalides with halogen and water, hypohalogenous acid and hydrogen halide in the presence of water, or alkyl or aralkyl hypohalites in the presence of water, are used as solvents and extractants in the refining of mineral oils.  Products specified are dichlor-tertiary and secondary butyl alcohols, chlor-butanone, chlor-acetaldehyde, 2.3.3-trichlor-2-methyl-1-phenyl-propane, 3-chlor-2 - (chlor-methyl) - 1-phenyl-propene-3, and 1.2-dibrom-propanol-3.