Hydroxylation of ethylenic compounds

D. Swern, Epoxidation and Hydroxylation of Ethylenic Compounds with Organic Peracids, Org. React. 1953, 7, 378 133. 

Kpoxidation and Hydroxylation of Ethylenic Compounds with Organic... 

Note that, in some studies, poly(ethylene oxide) oligomers, micelle-forming surfactants derived from them, and their complexes were used to perform such reactions in aqueous and alcohol solutions as hydroformylation [31-33], Wacker oxidation [34,35], hydroxylation of aromatic compounds [36-38], carbon dioxide hydrogenation [39], and epoxidation [40]. It was shown that using poly(ethylene oxide)s substantially increases the reaction rate and, in some cases, allows us to separate a metal complex containing oligo(ethylene oxide) [31,40]. 

Water-soluble macromolecular metal complexes based on terminally functionalized ethylene oxides and ethylene oxide-propylene oxide block copolymers have been used as catalysts for hydroformylation, hydrogenation, Wacker oxidation of imsaturated compounds, hydroxylation of aromatic compounds, oxidation of saturated and alkylaromatic hydrocarbons, metathesis, Heck reaction, and some asymmetric reactions. 

Polyhydric alcohols are compounds containing two or more hydroxyl groups in the molecule. The two most important are ethylene glycol HOCHjCHjOH (a dihydric alcohol) and glycerol HOCHjCH(OH)CH. OH (a trihydric alcohol). Ethylene glycol may be obtained by the hydrolysis of ethylene dibromide or ethylene dichloride with dilute aqueous sodium hydroxide or sodium carbonate solution ... 

Eyrol 51 is a water-soluble Hquid containing about 21% phosphoms. It is made by a multistep process from dimethyl methylphosphonate, phosphoms pentoxide, and ethylene oxide. The end groups are principally primary hydroxyl and the compound can thus be incorporated chemically into aminoplasts, phenoHc resins, and polyurethanes. Eyrol 51, or 58 if diluted with a small amount of isopropanol, is used along with amino resins to produce a flame-retardant resin finish on paper used for automotive air filters, or for backcoating of upholstery fabric to pass the British or California flammabiHty standards. 

Hydroxypyrroles. Pyrroles with nitrogen-substituted side chains containing hydroxyl groups are best prepared by the Paal-Knorr cyclization. Pyrroles with hydroxyl groups on carbon side chains can be made by reduction of the appropriate carbonyl compound with hydrides, by Grignard synthesis, or by iasertion of ethylene oxide or formaldehyde. For example, pyrrole plus formaldehyde gives 2-hydroxymethylpyrrole [27472-36-2] (24). The hydroxymethylpyrroles do not act as normal primary alcohols because of resonance stabilization of carbonium ions formed by loss of water. 

Ethylene glycol, or 1,2-ethanediol, HOCH2CH2OH (2), is an example of a diol, which is a compound with two hydroxyl groups. Ethylene glycol is used as a component of antifreeze mixtures and in the manufacture of some synthetic fibers. 

Reaction LXXVI. Addition of Hydroxyl to Ethylenic Bonds. (B., 21, 919 A., 268, 27.)—When compounds containing ethylenic linkages are treated with mild oxidising agents, e.g., bromine and caustic potash, dilute nitric acid and especially very dilute (2%) potassium permanganate solution, addition of hydroxyl at the double bond to form a 1 2-dihydroxy compound occurs. 

Diffusion of ethylene glycol through the high-viscosity reaction system is the apparent rate-determining step in PET polycondensation. Preliminary examination of many univalent hydroxyl compounds shows that water and phenol diffuse much more readily through molten PET than does ethylene glycol. Therefore, a bifunctional reagent that re-... 

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