Chlorohydrin acetate synthesis

Nitroimidazoles substituted by an aromatic ring at the 2-position are also active as antitrichomonal agents. Reaction of p-fluorobenzonitrile (83) with saturated ethanolic hydrogen chloride affords imino-ether 84. Condensation of that intermediate with the dimethyl acetal from 2-aminoacetaldehyde gives the imidazole 85. Nitration of that heterocycle with nitric acid in acetic anhydride gives 86. Alkylation with ethylene chlorohydrin, presumably under neutral conditions, completes the synthesis of the anti-... 

Commerciol Dichlorohydrin consists of the above two isomers, the proportions of which depend on method of prepn d 1.36-1.39, bp 175-80°, flash p 74°, Glycerol was the main source for the prepn of glycerol chloro-hydrins until the process for direct substitutive chlorination of propylene to allyl chloride paved the way for synthesis by chlorohydrination of allyl chloride. In the synthesis from glycerol, excess HCI is used in the presence of 4% acetic acid. The reaction is run at 130° to yield 90% of product which is mainly the a,y-form. Synthesis from propylene yields a mixt of approx 70% a,/8-form 8c 30% a,y-form. Addn of HCI to epichlorohydrin, CH2 CHCH> Cl, at... 

Shibasaki et al. developed a method for the direct synthesis of chlorohydrins or 2-acetoxy alcohols from disubstituted olefins [41). Various kinds of chlorohydrins are prepared from the corresponding alkenes with bis(trimethylsilyl)peroxide (BTSP) and chlorotrimethylsilane (TMSCl) in the presence of the catalyst (SnCU or (SnO) ). It is worth noting that 2-acetoxy alcohols could be obtained under similar reaction conditions using trimethylsilyl acetate (TMSOAc) instead of TMSCl with the promotion of Zr(0 Pr)4 in place of SnCU (Scheme 10.20). 

---