Ethylene oxide hydrolysis reactions

Reaction of olefin oxides (epoxides) to produce poly(oxyalkylene) ether derivatives is the etherification of polyols of greatest commercial importance. Epoxides used include ethylene oxide, propylene oxide, and epichl orohydrin. The products of oxyalkylation have the same number of hydroxyl groups per mole as the starting polyol. Examples include the poly(oxypropylene) ethers of sorbitol (130) and lactitol (131), usually formed in the presence of an alkaline catalyst such as potassium hydroxide. Reaction of epichl orohydrin and isosorbide leads to the bisglycidyl ether (132). A polysubstituted carboxyethyl ether of mannitol has been obtained by the interaction of mannitol with acrylonitrile followed by hydrolysis of the intermediate cyanoethyl ether (133). 

In the reaction of ethylene with sulfuric acid, several side reactions can lead to yield losses. These involve oxidation, hydrolysis—dehydration, and polymerization, especially at sulfuric acid concentrations >98 wt % the sulfur thoxide can oxidize by cycHc addition processes (99). 

A competing reaction that consumes ethylene oxide is hydrolysis to ethylene glycol and oligomeric glycol by-products. 

Benzyl chloride readily forms a Grignard compound by reaction with magnesium in ether with the concomitant formation of substantial coupling product, 1,2-diphenylethane [103-29-7]. Benzyl chloride is oxidized first to benzaldehyde [100-52-7] and then to benzoic acid. Nitric acid oxidizes directly to benzoic acid [65-85-0]. Reaction with ethylene oxide produces the benzyl chlorohydrin ether, CgH CH20CH2CH2Cl (18). Benzylphosphonic acid [10542-07-1] is formed from the reaction of benzyl chloride and triethyl phosphite followed by hydrolysis (19). 

An earlier procedure for the production of choline and its salts from natural sources, such as the hydrolysis of lecithin (23), has no present-day apphcation. Choline is made from the reaction of trimethyl amine with ethylene oxide [75-21-8] or ethylene chlorohydrin [107-07-5J. 

About 60% of the ethylene oxide produced is converted to ethylene glycol by reaction of ethylene oxide ia the presence of excess water and an acidic catalyst at 50—70°C. This is followed by hydrolysis at relatively high temperatures (140—230°C) and 2—4 MPa (20—40 bar) (see Glycols, ethylene glycol). When the water concentration is lowered, poly(ethylene glycol) is obtained. 

The reaction occurs at approximately 80-130°C using the proper catalyst. Many catalysts have been tried for this reaction, and there is an indication that the best catalyst types are those of the tertiary amine and quaternary ammonium functionalized resins. This route produces ethylene glycol of a high purity and avoids selectivity problems associated with the hydrolysis of ethylene oxide. 

Further evidence for the Aa11 mechanism was obtained from a solvent kinetic isotope study. The theoretical kinetic isotope effects for intermediates in the three reaction pathways as derived from fractionation factors are indicated in parentheses in Scheme 6.143,144 For the Aa11 mechanism (pathway (iii)) a solvent KIE (/ch2o A d2o) between 0.48 and 0.33 is predicted while both bimolecular processes (pathways (i) and (ii)) would have greater values of between 0.48 and 0.69. Acid-catalysed hydrolysis of ethylene oxide derivatives and acetals, which follow an A1 mechanism, display KIEs in the region of 0.5 or less while normal acid-catalysed ester hydrolyses (AAc2 mechanism) have values between 0.6 and 0.7.145,146... 

Thioetherification of PECH is feasibly performed in DA-solvents as already described in the patent (20J. For example, the highest substitution was obtained by the reaction of P(ECH-EO)(1 1 copolymer of epichloro-hydrin and ethylene oxide) and equimolar thiophenoxide in HMPA at 100°C for 10 h as DS 83% for sodium and 93% for potassium salts. The DS in our nucleophilic substitution was estimated by the elemental analysis as well as the titration of liberated chloride ion with mercuric nitrate (21). In the latter method, reacted medium was pretreated with hydrogen peroxide when the reductive nucleophiles which can react with mercuric ion were used. As described before for PVC, thiolation was also achieved conveniently with iso-thiuronium salt followed by alkaline hydrolysis without the direct use of ill-smelling thiolate. The thiolated PECH obtained are rubbery solids, soluble in toluene, methylene chloride, ethyl methyl ketone and DMF and insoluble in water, acetone, dioxane and methanol. 

Table 10.3 summarizes the uses of propylene oxide. Propylene glycol is made by hydrolysis of propylene oxide. The student should develop the mechanism for this reaction, which is similar to the ethylene oxide to ethylene glycol conversion (Chapter 9, Section 8). Propylene glycol is a monomer in the manufacture of unsaturated polyester resins, which are used for boat and automobile bodies, bowling balls, and playground equipment. 

Palladium chloride or the chloropalladite ion catalyze the oxidation of olefins to aldehydes or ketones, presumably by forming unstable palladium-olefin complex intermediates 196). A reaction of great industrial importance is the palladium chloride/cupric chloride catalyzed oxidation of ethylene to acetaldehyde 195). The first stage is presumably the oxidative hydrolysis of ethylene,... 

Ethylene adds hypochlorous acid more readily than it adds either moist chlorine or hydrogen chloride. Bubbled into chlorine water, it is converted completely into ethylene chlorohydrin, and by the hydrolysis of this substance glycol is obtained. Ethylene chlorohydrin is important also because of its reaction with ammonia whereby mono-, di-, and triethanolamine are formed, substances which are used in the arts and are not without interest for the explosives chemist. Ethylene may be oxidized catalytically in the gas phase to ethylene oxide which reacts with water to form glycol and with glycol to form diglycol which also is of interest to the dynamite maker. 

The base-catalysed hydrolysis of ethylene oxide has been studied by the MNDO method.28 The structures of tire reactant, product, and transition state were optimized and a reaction mechanism was proposed. 

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