Patent GB-435096-A (GB)
Title: A process for the treatment of unsaturated monohalides
IPC: C07C17/10
Filed: 1935-04-18
Abstract: Unsaturated monohalides containing at least four carbon atoms and the halogen linked to a saturated carbon atom are reacted with hypohalogenous acids, aqueous halogen solutions, solutions of hypohalogenous acids and hydrogen halides, or alkyl or aralkyl hypohalites in the presence of water, to give polyhalogenated hydroxy compounds or hydrocarbons, or both.  The monohalide may comprise an iso or normal alkyl chain which may be attached to a cyclic radical or include an alicyclic structure.  Suitable halides have the probable formul : <FORM:0435096/IV/1> and <FORM:0435096/IV/2> Where the monohalide employed comprises the grouping <FORM:0435096/IV/3> , polyhalogenated primary or secondary alcohols are obtained when C+ is not quaternary or tertiary, and substitution of halogen for hydrogen and sometimes addition at the double bond occurs if C+ is quaternary or tertiary.  Where the grouping <FORM:0435096/IV/4> or <FORM:0435096/IV/5> is present, the product is a polyhalogenated hydroxy compound, which may be regarded as a polyhalogenated tertiary alcohol when C+ is not tertiary or quaternary, while halogen substitution occurs if C+ is tertiary or quaternary.  The unsaturated halides and reaction product should not be permitted to contact with free or undissolved halogen, thus the solution of halogen in water is preferably effected in a separate stage.  Solutions of hypohalogenous acid can be made by electrolysis of metal halide solutions, treatment of metal hypohalites with dilute acids, or decomposition of alkyl hypohalites in aqueous solution.  The optimum concentration of hydrogen halide in the system varies with the reagents and products desired, but the HCl concentration is preferably at or below 1.5N, while that of HBr or HI is less.  The concentration of HOCl is generally below 0.1N, preferably .005--.015N, while higher concentrations of HOBr and HOI can be present.  Varying the concentration controls the relative amounts of useful products formed.  Primary, secondary or tertiary esters of hypohalogenous acids may be employed.  The reaction is illustrated by the following: <FORM:0435096/IV/6> <FORM:0435096/IV/7> The mixture of products may be used as solvents or intermediates or the non-halogenated alcohols separated and used to prepare hypohalites.  The addition to the reaction mixture of carbon tetrachloride, or of a solvent for the product such as hydrocarbons, ethers, esters, alcohols or halogenated hydrocarbons is often advantageous.  Room temperature and atmospheric pressure are usually employed, but higher or lower values thereof can be used.  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, CCl4 and isobutenyl chloride.  These are agitated in the reaction chamber and the water circulated through the system, chlorine being introduced into the column continuously and isobutenyl chloride into the reaction chamber.  Water is introduced to maintain the HCl concentration at .07N.  A portion of the circulating liquid is intermittently withdrawn to maintain the volume substantially constant.  The product is separated into two layers and the non-aqueous phase, together with an ether extract of the other, distilled to remove ether and CCl4. The main product is a dichlor-tertiary butyl alcohol, probably <FORM:0435096/IV/8> (2) A mixture of isomers of isoamylene monochlorides were treated as in (1) to yield dichlor-tertiary amyl alcohols <FORM:0435096/IV/9> and <FORM:0435096/IV/100> (3) Isopentenyl chloride <FORM:0435096/IV/111> is treated with .5N HOCl to give a dichlortertiary amyl alcohol, probably <FORM:0435096/IV/122> p  (4) Crotyl bromide CH3--CH = CH--CH2Br is treated as in (1) but without addition of CCl4.  The product is 1-brom-3-chlorbutanol-2 with some 1-brom-2-chlorbutanol-3. (5) Tertiary butyl hypochlorite and water are added to isobutenyl chloride kept at 18--22 DEG  C.  The product is 1.3-dichlor-2-methyl-propanol-2.  (6) Isobutenyl chloride is reacted with chlorine and water in a cyclic process similar to (1).  The HOCl concentration is maintained around .02N and that of the HCl at or below 2.5 per cent.  The aqueous phase of the product is used for preparing the corresponding epichlorhydrin. The non - aqueous phase yields dichlor- and trichlor-tertiary butyl alcohols as well as tri- and tetra-chlorides and aldehydic substances.  (7) Chlorine is added to a mixture of chlor di-isobutylene, probably <FORM:0435096/IV/133> , and water.  The product is <FORM:0435096/IV/144> The products of the present process may be used as solvents, e.g. in refining mineral oils or purifying refinery and manufactured gases.  The polyhalogenated tertiary alcohols are used for preparing unsaturated aldehydes and ketones, polyhydric alcohols and derivatives. Specification 402,880 is referred to.ALSO:Polyhalogenated hydrocarbons and hydroxycompounds, prepared by the reaction of an unsaturated monohalide containing at least four carbon atoms in the molecule and the halogen linked to a saturated carbon atom with hypohalogenous acids, aqueous solutions of halogens, solutions of hypohalogenous acid and hydrogen halide, or alkyl or aralkyl hypohalites in the presence of water, are used as solvents for refining mineral oils.  Products specified are 1,4.dichlor-butanol-2, dichlor-and trichlor-tertiary butyl alcohols, dichlor-tertiary amyl alcohols, 1-brom-3 chlor-butanol-2, 1 brom-2 chlor-butanol-3, 1,3 dichlor-2 methyl-propanol-2, and C8H14Cl2.