Epichlorohydrin alcohol reactions

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 ... 

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). ... 

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. 

Glycidol is commercially produced by two methods (1) epoxidation of allyl alcohol with hydrogen peroxide and a catalyst (tungsten or vanadium) and (2) reaction of epichlorohydrin with caustic (Grigor ev et al, 1979 Yoshida Koyama, 1992 Richey, 1993 Hutchings et al, 1995). 

Sodium azide reacts with various epoxides at 25°-30°C at pH 6-7 to give azido alcohols [57-59]. The use of harsh conditions as earlier employed by Van der Werf et al. [59] (16-40 hr reflux in dioxane) led to the production of 1,3-diazidopropanol instead of l-azido-3-chloro-2-propanol when starting with epichlorohydrin. Several representative examples of the conditions and products of the reaction of azides with epoxides are shown in Table V. 

CH OH - CHOH CH Cl. which is made by reaction of hypochlorous acid and allyl alcohol with barium hydroxide. With hydrogen chloride, glycide alcohol yields epichlorohydrin... 

Another major group of epoxy monomers derived from epichlorohydrin is that comprising monomers synthesized with an aromatic amine, such as aniline (DGA), para-aminophenol (TGpAP) and methylene dianiline (TGMDA) - (Table 2.1 e, f, and g). The reaction of epichlorohydrin with an alcohol is more difficult. Liquid monomers based on butanediol, neo-pentylglycol, and polypropylene oxide (molar mass in the range of 500 g mol-1), are the most common. 

To a mixture of 176 g (2 M) of isoamyl alcohol and 4 ml of a 10% solution of BF3 in anhydrous ether, were added, with stirring, 278 g (3 M) of epichlorohydrin while maintaining the temperature at approximately 45°C. After the addition, the reaction was maintained for an additional hour at 60°C. It was then cooled and a solution of 160 g of NaOH in pellets in 200 ml H20 was added while maintaining the temperature at approximately 15°C. Stirring was continued for an additional 2 hours, the NaCI formed was filtered and the organic phase decanted. Vacuum fractionation gave 142 g of 3-isoamyloxy-1,2-epoxypropane. Boiling point 67-68°C. 

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 methylaminoethanol during about 3 hours at 15°C to 20°C. The heat generated by the condensation is removed by means of a cooling bath. After the addition of the total quantity of methylaminoethanol, stirring is continued for 1 hour at 25°C. The condensation reaction is completed when development of heat reaction can no longer be observed. The solution thus produced of the raw l-chloro-3-(methylhydroxyethylamino)-propanol-2 in isopropyl alcohol is a colorless viscous liquid which is used without further purification for the subsequent condensation with theophylline. 

Other substances are also used as polymerization processing aids, like solvents (e.g. benzyl alcohol) and accelerators (e.g. nonylphenol). These processing aids are not significantly or not to a measurable degree chemically incorporated into the crosslinked polymer. Under the conditions of the epoxy thermoset reaction the epichlorohydrin, for example, is completely decomposed. Under the current, state of the art hardening technology, practically no epichlorohydrin can be detected in the finished product. 

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