Alkenes reaction with hypochlorous acid

The C = C bond in 3,3,3-trifluoro-2-methylprop-l-eneis readily oxidized in 76 % yield by bubbling the substrate into a cooled solution of hypochlorous acid (Table 6).98 Chlorohydrins together with 1,2-dichloro derivatives arc obtained by oxidation of alkenes with tert-butyl hypochlorite when the reaction is performed in acetic acid instead of water, chlorohydrin acetate is formed (Table 6)."... 

The reaction of chloro- or bromohydrins with bases provides an economical route for the preparation of epoxides. Halohydrins are readily accessible by treatment of an alkene with either hypochlorous acid (Clj -1- H2O —> HOCl), hypochlorite bleach solution (NaOCl), or hypobromous acid (NBS -1- HjO HOBr). These reactions involve the... 

It is known that dissolving chlorine in water leads to a solution that contains hypochlorous acid (HOCl) and bromine dissolved in water contains hypobromous acid (HOBr). In one experiment, 1-pentene is mixed with chlorine and water (HOCl in aqueous media) and the major product is l-chloro-2-pentanol (48), in 43% isolated yield. ° In the previous section, chlorine reacted with 1-pentene in a nonaqueous solvent such as carbon tetrachloride to give a dichloride. To ascertain why this reaction is different, the first useful observation is that HOCl is in solution rather than Cl-Cl. The polarization of HOCl is HO -Cl, where chlorine is the electrophilic atom. The 7t-bond of an alkene should react with the positive chlorine atom, and cleavage of the Cl-H bond will give hydroxide ion, which is a... 

It has recently been reported that more highly substituted alkenes produce allylic chlorides rather than chlorohydrins when treated in dichloromethane with aqueous hypochlorous acid. ° The reaction is often regioselective, discriminating between double bonds, as exemplified by (78) - (79). Allylic dithiocarbamates... 

In the reaction of chlorine dioxide with water, hypochlorous, hydrochloric and chloric acids are formed temporarily, and in alkaline solutions chlorites (C102 ), chlorates (ClOj ) and other products arise. The cation H20C1 formed in aqueous solutions of chlorine, chlorine dioxide and hypochlorites may react with alkenes and other unsaturated compounds. The electrophilic addition of HOCl to alkenes is an established reaction mechanism for a, P-chloroalcohol (chlorohydrin) and a, -dichloro derivative formation (Figure 11.16). The reaction yielding chlorohydrins follows the Markovnikov rule with the hydroxyl group adding to the more substituted carbon. Oxidation of chlorohydrins by hypochlorites... 

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