Methyl propionate, vinylation with methanol

Methyl propionate, vinylation with methanol over Ti -TSM, 39 318 Methyl radicals ESR of, 22 298, 299... 

Vinylation of Methyl Acetate and Methyl Propionate with Methanol Over Ti -TSM°... 

Ueda et al. (37) have proposed magnesium oxide catalyst modified with a transition metal ion (M/MgO) for the vinylation of methyl propionate and acetonitrile. Acetonitrile is vinylated to acrylonitrile selectively (94% selectivity at about 10% conversion) over Cr/MgO catalysts at 350 C in the absence of oxygen. The selectivity for the vinylation of methyl propionate over Mn/MgO catalysts is not different from the value obtained with Ti -TSM in the presence of oxygen. The catalyst system, however, is not effective for the reaction of acetic acid. We conducted the reaction of acetonitrile and methanol over Ti -TSM in the presence of oxygen, and found that the vinylation does not take place but the hydrolysis to acetic acid and subsequent esterification with methanol into methyl acetate proceed preferentially. It is likely that Ti -TSM is an appropriate catalyst for the vinylation of carbonyl compounds and M/MgO is appropriate for the vinylation of nitriles. 

Di-[3-(iV-vinylformamido)propionamido]metliylcycloliexane and l-[3-(7V-vinyl-formamido)propionamido]-2-amino-methylcycloliexane. A 50 mL single-neck round bottom flask equipped with a distillation head was charged with 15.7 g ( 0.1 mol) of methyl 3-(7V-vinylformamido)propionate, 12.8 g (0.1 mol) of l,2-diamino-3-methylcyclohexane and 0.10 g of 25% sodium methoxide in methanol solution. The mixture was stirred at 90 for 2 hr and 110 °C for an additional hour. Generated methanol was removed by distillation at reduced pressure to give a viscous liquid. NMR analysis indicated that about 58.5% of methyl 3-(N-vinylformamido)propionate was consumed. 

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