W-Methylmorpholine

Bando and coworkers99 published a study where water-gas shift was used in an applied manner, to assist in the methylation of arylacetonitrile with formaldehyde, using RhCl3 as the homogeneous catalyst. Conditions T = 200 °C Pco = 101 atm 20 mg RhCl3 3H20 20 mmol arylacetonitrile 60-200 mmol paraformaldehyde 5 ml w-methylmorpholine 1 ml H20 and 10 ml dioxane 5 hours of reaction time. Results of their findings are presented in Table 25, and their proposed mechanism is shown in Scheme 38. 

Chloro-4,6-dimethoxy[l,3,5]triazine, formic acid, W-methylmorpholine, DMAP, CH2CI2, 20°C, 85-99% yield. ... 

Somewhat similar results are obtained in reductions of high molecular weight poly(methyl acrylate) with lithium aluminum hydride [238] in tetrahydrofuran. The reaction yields a product that is only soluble in mixtures of hydrochloric acid with either methyl alcohol, dioxane, or tetrahydrofuran. The problem is apparently due to some residual aluminum that is hard to remove [239]. If, however, the reduction is carried out in a W-methylmorpholine solution, followed by addition of potassium tartrate, a pure product can be isolated [240]. W-methylmorpholine is a good solvent for reductions of various macromolecules with metal hydrides [236]. In addition, the solvent permits use of strong NaOH solutions to hydrolyze the addition complexes that form. Other polymers that can be reduced in it are those bearing nitrile, amide, imide, lactam, and oxime pendant groups. Reduction of polymethacrylonitrile, however, yields a product with only 70% of primary amine groups [241]. 

For neutral pol5nners (cellulose being excluded), extraction can be performed using DMSO (48), W-methylmorpholine N-oxide (49), NaOH, or KOH at different concentrations. Over pH 12, alcoholate is formed on the —OH groups, increasing the solubility of polysaccharides. When hemicelluloses have to be extracted from a plant source, KOH 24% or NaOH 18% are often used these hydroxides produce... 

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