Epichlorohydrin, reaction with alcohols

URANIUM HEXAFLUORIDE (7783-81-5) FjU Radioactive. Violent reaction with water, steam, ethanol, producing hydrogen fluoride gas. Violent reaction with alcohols, aromatic hydrocarbons (benzene, toluene, xylenes, etc.), bromine trifluoride. Aqueous solution increases the explosive sensitivity of nitromethane and is incompatible with sulfuric acid, alkalis, alcohols, ammonia, aliphatic amines, alkanolamines, alkylene oxides, amides, epichlorohydrin, ethers. 

In this process, the fine powder of lithium phosphate used as catalyst is dispersed, and propylene oxide is fed at 300°C to the reactor, and the product, ahyl alcohol, together with unreacted propylene oxide is removed by distihation (25). By-products such as acetone and propionaldehyde, which are isomers of propylene oxide, are formed, but the conversion of propylene oxide is 40% and the selectivity to ahyl alcohol reaches more than 90% (25). However, ahyl alcohol obtained by this process contains approximately 0.6% of propanol. Until 1984, ah ahyl alcohol manufacturers were using this process. Since 1985 Showa Denko K.K. has produced ahyl alcohol industriahy by a new process which they developed (6,7). This process, which was developed partiy for the purpose of producing epichlorohydrin via ahyl alcohol as the intermediate, has the potential to be the main process for production of ahyl alcohol. The reaction scheme is as fohows ... 

Substitution of an additional nitrogen atom onto the three-carbon side chain also serves to suppress tranquilizing activity at the expense of antispasmodic activity. Reaction of phenothia zine with epichlorohydrin by means of sodium hydride gives the epoxide 121. It should be noted that, even if initial attack in this reaction is on the epoxide, the alkoxide ion that would result from this nucleophilic addition can readily displace the adjacent chlorine to give the observed product. Opening of the oxirane with dimethylamine proceeds at the terminal position to afford the amino alcohol, 122. The amino alcohol is then converted to the halide (123). A displacement reaction with dimethylamine gives aminopromazine (124). ... 

This methodology has been extended successfully to polymer-supported chiral (salen)Co complexes [88] and to intramolecular kinetic resolution of epoxy alcohols (with (R,R)-L Co OAc)) [82]. The ceiling of 50 % yield in kinetic resolution reactions can be extended if the starting material undergoes racemization under the reaction conditions. This has been shown to be possible with epichlorohydrin in reaction with TMSN3, the dynamic kinetic resolution process affording now a 76 % product yield (97 % ee) and 12 % each of the dichloro and diazido products [89]. 

The most widely used epoxy resins and adhesives are based on a prepolymer made from bisphenol A and epichlorohydrin. On treatment with base under carefully controlled conditions, bisphenol A is converted into its anion, which acts as a nucleophile in an S142 reaction with epichlorohydrin. Each epichlorohydrin molecule can react with two molecules of bisphenol A, once by S 2 displacement of chloride ion and once by opening of the epoxide ring. At the same time, each bisphenol A molecule can react with two epichlorohydrins, leading to a long polymer chain. Each end of a prepolymer chain has an unreacted epoxy group, and each chain has numerous secondary alcohol groups. 

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