93675-40-2Relevant academic research and scientific papers
N-Methylation of poorly nucleophilic aromatic amines with dimethyl carbonate
Yan, Huidong,Zeng, Liufang,Xie, Yaqiang,Cui, Yu,Ye, Liyi,Tu, Song
, p. 5951 - 5960 (2016/06/01)
Abstract: Dimethyl carbonate (DMC), an environmentally friendly methylation agent, is a substitute for traditional methylation agents such as methyl halides (CH3X, X?=?I, Br, Cl) or dimethyl sulfate. An efficient, convenient, and green method has been developed for N-methylation of poorly nucleophilic aromatic amines with DMC. It was found that the couple PEG400/K2CO3 provides good selectivity for the N-methylation product. Finally, the mechanism for reaction of amines with DMC was investigated, and a plausible multistep mechanism proposed and verified. Graphical Abstract: [Figure not available: see fulltext.]
N-Methyl-N-(o-nitrophenyl)carbamates as photolabile alcohol protecting groups
Loudwig, Sandra,Goeldner, Maurice
, p. 7957 - 7959 (2007/10/03)
N-Methyl-N-(o-nitrophenyl)carbamates represent new photoremovable alcohol protecting groups. This protecting group is easily incorporated by chemical coupling of the corresponding alcohol to N-methyl-N-(o-nitrophenyl)carbamoyl chloride. High yield and clean deprotection are induced by photolysis in protic solvents (water, ethanol or ethanol/water mixtures) from 254 to 365 nm.
Basic Hydrolysis of Some N-Phenylcarbamates and Basic Methanolysis of Some N-Phenylacetamides Containing an ortho Nitro Substituent.
Broxton, Trevor J.
, p. 2005 - 2011 (2007/10/02)
Kinetic studies of the basic methanolysis of N-(2-nitrophenyl)acetamides indicate that unlike the 4-nitro isomer, no change of mechanism occurs on inclusion of N-methyl group.Reaction occurs with rate-determining C-N bond breaking for both the N-H and N-methyl compounds.Basic hydrolysis of some methyl N-(2-nitrophenyl)carbamates occurred by the BAC2 mechanism and the tetrahedral intermediate formed during the hydrolysis decomposed with preferential C-O bond breaking.This is in contrast to the basic hydrolysis of methyl N-methyl-N-4-nitrophenylcarbamate, which has previously been shown to occur with preferential C-N bond breaking.For the hydrolysis of methyl N-methyl-N-(2-nitrophenyl)carbamate, an induction period in amine production was detected at 0.45 M hydroxide ion.This was interpreted to mean that the tetrahedral intermediate breaks down by loss of methoxide ion.At 0.93 M hydroxide ion, however, no induction period in amine production was observed.The possibility of reaction through a dianionic intermediate was raised to explain this observation.The amide ion (2-NO2C6H4NMe-) is poorer leaving group than its 4-nitro isomer thi is explained by steric crowding in the 2-nitro compound, resulting in twisting of the nitro group out of the plane of the benzene ring and a consequent reduction in the electron-withdrawing resonance effect of the 2-nitro group compared to the 4-nitro gruop.
