Methoxymethyl oxirane

Methoxymethyl methyl ether. See Methylal (Methoxymethyl)-oxirane. See Methyl glycidyl ether... 

Detailed structural calculations have been carried out for this system. This is because the neutral isomer, C2HsO, which is implicated in the thermochemistry of ethanol, is of interest in pollution control, atmospheric chemistry, and combustion. Also, there is new information available from photoionization experiments with which to compare theoretical calculations. For details of these comparisons, see Curtiss et al.73 In the earlier theoretical studies of Nobes et al.,74 calculations were performed at the MP2 and MP3 levels with basis sets of double plus polarization (6-13G ) with electron correlation. These studies revealed four stable minima for the system protonated acetaldehyde, CHj-C H-OH <-> CH3-CH=0+H the methoxymethyl cation, CH3OCH2 protonated oxirane, (CH2)2OH+ and vinylox-... 

The reaction usually occurs at the less substituted carbon of the oxirane ring (Scheme 62 and Scheme 67) 293,297 However regioisomeric dithianyl alcohols are obtained from 2-lithio-1,3-dithianes and the protected 3, y-epoxy alcohols shown in Scheme 66 (entry b). The observed regioselectivity is very different when methoxymethyl or benzyl protecting groups are used. This has been explained by the different... 

Methoxymethyl)-5-nitrofuran (Methoxymetliyl)oxirane 3-Methoxy-5-methyl-4-oxo-2,5-hexadienoicacid... 

Carbon-Oxygen Bond Formation. CAN is an efficient reagent for the conversion of epoxides into /3-nitrato alcohols. 1,2-cA-Diols can be prepared from alkenes by reaction with CAN/I2 followed by hydrolysis with KOH. Of particular interest is the high-yield synthesis of various a-hydroxy ketones and a-amino ketones from oxiranes and aziridines, respectively. The reactions are operated under mild conditions with the use of NBS and a catalytic amount of CAN as the reagents (eq 25). In another case, N-(silylmethyl)amides can be converted to A-(methoxymethyl)amides by CAN in methanol (eq 26). This chemistry has found application in the removal of electroauxiliaries from peptide substrates. Other CAN-mediated C-0 bondforming reactions include the oxidative rearrangement of aryl cyclobutanes and oxetanes, the conversion of allylic and tertiary benzylic alcohols into their corresponding ethers, and the alkoxylation of cephem sulfoxides at the position a to the ester moiety. 

Computational studies of the carbenoid cyclopropanation reactions of methoxymethyl-lithium and intra- and intermolecular carbenoid reactions of lithiated oxiranes have been reported. Computations suggest that methoxymethyllithium reacts with ethylene exclusively by a stepwise carbolithiation mechanism. The intramolecular reaction of lithiated l,2-epoxy-5-hexene was found to proceed by both the carbohthiation and the methylene transfer pathways, but the former is expected to dominate at room and low temperatures because the free energy of activation is less than half that of the latter pathway. 

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