Hydrogen chloride, telomerization

Another byproduct of the reaction was a mixture of alkyl chlorides in which the alkyl groups had an even number of carbon atoms. These were obviously formed by telomerization of ethylene and hydrogen chloride 2). 

The pathway by which the hydrogen chloride inhibits the telomerization and thus produces mono-ethylcyclohexane was supported by use of a solution of deuterium chloride (38%) in heavy water (99% deuterium oxide) as promoter under the standard conditions. The reaction mixture included 1.15 mols of cyclohexane and... 

The peroxide-induced ethylation of isobutyl chloride in the presence of 19% hydrochloric acid involved monoethylation at all of the carbon atoms in the molecule (Expt. 23). As might be expected, the chief product was l-chloro-2,2-dimethylbutane, produced via abstraction of the hydrogen atom attached to the tertiary carbon atom. Also formed were l-chloro-2-methylpentane (ethylation at a methyl group) and 3-chloro-2-methylpentane (ethylation at the carbon at< n holding the chlorine atom). Some 1-chlorohexane was also obtained in this case, its formation was undoubtedly due to telomerization of the ethylene with hydrogen chloride rather than by a reaction involving the isobutyl chloride. 

Zinc chloride hydrogen chloride 1,4-Addition of halides to 1,3-dienes Prevention of telomerization... 

CH2 CH C CH. Colourless gas with a sweet odour b.p. 5°C. Manufactured by the controlled low-temperature telomerization of ethyne in the presence of an aqueous solution of CuCI and NH Cl. Reduced by hydrogen to butadiene and, finally, butane. Reacts with water in the presence of HgSO to give methyl vinyl ketone. Forms salts. Forms 2-chloro-butadiene (chloroprene) with hydrochloric acid and certain metallic chlorides. 

If water serves as telogen together with 2 mol of taxogen, the telomerization becomes a special hydrodimerization (Eq. 2). The consequent product in the case of butadiene as taxogen can be hydrogenated to produce 1-octanol, which has a considerable market as a raw material for plastidzers for poly(vinyl chloride). 

Telomerization of 1,4-butadiene with water, alcohols, amines, and acids is an extremely useful reaction since it leads to the formation of practically important products. (179,180). For example, the telomer with water, 2,7-octadiene-l-ol can be further hydrogenated to 1-octanol which is a raw material for plasticizers for poly(vinyl chloride). In fact, this reaction was among the processes disclosed in the first patents on the use of TPPTS in biphasic solvent mixtures (58). The catalyst for such telomerizations usually consists of palladium(O) and an excess of TPPTS, TPPMS, or other water-soluble phosphines (eg, with quaternary ammonium substituents). The telomerization of 1,4-butadiene with water was developed into an industrial process by Kuraray Ind. (Scheme 26). Interestingly, the best ligand was the phosphonium salt shown in (Scheme 26) and the catalyst could be prepared in situ from this ligand and [Pd(OAc)2] (179). It is assumed that under the reaction conditions the corresponding tertiary phosphine can be formed to some extent and coordinates to palladium. In any case with a large excess of... 

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