Alcohols epichlorohydrin

Chloropropene, allyl chloride, CH2=CH-CH2C1, is very reactive both as an organic halide and as an olefin and is, therefore, a starting material for further synthesis. Derivates of commercial importance are allyl alcohol, epichlorohydrin, and glycerol [370],... 

Glycerol ct-dichlorohydrin, sym-dichloroiso-propyl alcohol, 1,3-dichloro-2-hydroxypropane, CH2CI-CHOH-CH2C1. Colourless liquid with an ethereal odour b.p. 174-175" C. Prepared by passing dry HCl into glycerin containing 2% elhanoic acid at 100-1 lO C. Converted to x-epichlorohydrin by K.OH, Used as a solvent for cellulose nitrate and resins. 

Glycerol -dichlorohydrin, 2.3-dichloro-propanol, CH2CI CHC1 CH2 0H. Colourless liquid, b.p. 182 C. Prepared by the chlorination of propenyl alcohol. Oxidized by nitric acid to 1,2-dichloropropionic acid. Reacts with NaOH to give epichlorohydrin. 

More recendy, however, the technology of introducing a new functional group to the double bond of allyl alcohol has been developed. Adyl alcohol is accordingly used as an intermediate compound for synthesizing raw materials such as epichlorohydrin and 1,4-butanediol, and this development is bringing about expansion of the range of uses of allyl alcohol. 

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 ... 

In the synthesis of AGE with an acid as the catalyst, aHyl alcohol is added to the epoxy group of epichlorohydrin, yielding 3-aHyloxy-l-chloro-2-propanol [4638-03-3], which then undergoes cyclization with alkaU to yield AGE. Catalysts such as H2SO4, SnCl, BE (C2H )20 (33), heteropolyacids, HQO, andy -CH CgH SO H (34) are used. 

Reaction of pyroc techol with epichlorohydrin in the presence of base affords the benzodioxan derivative, 136, (The reaction may well involve initial displacement of halogen by phenoxide followed by opening of the oxirane by the anion from the second phenolic group.) Treatment of the alcohol with thio-nyl chloride gives the corresponding chloro compound (137). Displacement of halogen by means of diethylamine affords piper-oxan (138), a compound with a-sympathetic blocking activity. 

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). ... 

Bepridil (59) blocks the slow calcium channel and serves as an antianginal agent and a vasodilator. In its synthesis, alcohol (derived from epichlorohydrin) is converted to the corresponding chloride with thionyl chloride and displaced with the sodium salt of ]i-benzylaniline to give bepridil (59) °... 

To a well-stirred solution of 740 parts by weight of epichlorohydrin in 200 parts by volume of isopropyl alcohol are added 600 parts by weight of methylamlnoethanol during about 3... 

Allyl chloride is a colorless liquid, insoluble in water but soluble in many organic solvents. It has a strong pungent odor and an irritating effect on the skin. As a chemical, allyl chloride is used to make allyl alcohol, glycerol, and epichlorohydrin. 

Hydrolytic Kinetic Resolution (HKR) of epichlorohydrin. The HKR reaction was performed by the standard procedure as reported by us earlier (17, 22). After the completion of the HKR reaction, all of the reaction products were removed by evacuation (epoxide was removed at room temperature ( 300 K) and diol was removed at a temperature of 323-329 K). The recovered catalyst was then recycled up to three times in the HKR reaction. For flow experiments, a mixture of racemic epichlorohydrin (600 mmol), water (0.7 eq., 7.56 ml) and chlorobenzene (7.2 ml) in isopropyl alcohol (600 mmol) as the co-solvent was pumped across a 12 cm long stainless steel fixed bed reactor containing SBA-15 Co-OAc salen catalyst (B) bed ( 297 mg) via syringe pump at a flow rate of 35 p,l/min. Approximately 10 cm of the reactor inlet was filled with glass beads and a 2 pm stainless steel frit was installed at the outlet of the reactor. Reaction products were analyzed by gas chromatography using ChiralDex GTA capillary column and an FID detector. 

Epoxytin compounds are obtained by either hydrostannylation of unsaturated epoxides or condensation of organotin alcohols with epichlorohydrin 70). Extensive applications of these compounds in plastic industry have been suggested. 

Eicosene, i2 Elaidic acid, oil Enanthic alcohol, hll Enanthylic acid, h9 Epibromohydrin, b328 Epichlorohydrine, cl20 1,4-Epoxybutane, t69... 

Examples Nitric acid + most chemicals Ammonia + methacrylic acid Caustic soda + epichlorohydrin Examples Phosphoric acid + hexane Ammonia + ethylenediamine Gasoline + ethyl alcohol... 

EPA Shaughnessy code 057501, see Parathion a-Epichlorohydrin, see Epichlorohydrin (o0-a-Epichlorohydrin, see Epichlorohydrin Epichlorophydrin, see Epichlorohydrin Epihydric alcohol, see Glycidol Epihydrin alcohol, see Glycidol EPN 300, see EPN... 

Acrylonitrile, Alachlor. Allyl chloride, Allyl alcohol. Benzene, Butane, Chloroethane, Cyclohexene, Chloroprene, Cvclonentene. Dazomet. 1,1-Dichloroethylene, s/m-Dichloromethyl ether, Dimethylamine, A,lV-Dimethylaniline, 2,3-Dimethylbutane, 1,4-Dioxane, Epichlorohydrin,... 

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