6906-13-4Relevant academic research and scientific papers
Synthesis of N-methylmorpholine from morpholine and dimethyl carbonate
Zhu, Maodian,Liu, Shaoying,Deng, Zhiyong,Wang, Gongying
, p. 8427 - 8430 (2013/11/06)
The synthesis of N-methylmorpholine from morpholine and dimethyl carbonate was investigated. The effects of reaction variables upon the formation of the compounds were also examined. Under the optimized conditions, higher yield of N-methylmorpholine 83 %
Kinetics and mechanism of the aminolysis of methyl 4-nitrophenyl, methyl 2,4-dinitrophenyl, and phenyl 2,4-dinitrophenyl carbonates
Castro, Enrique A.,Aliaga, Margarita,Campodonico, Paola,Santos, Jose G.
, p. 8911 - 8916 (2007/10/03)
The reactions of methyl 4-nitrophenyl carbonate (MNPC) with a series of secondary alicyclic amines (SAA) and quinuclidines (QUIN), methyl 2,4-dinitrophenyl carbonate (MDNPC) with QUIN and 1-(2-hydroxyethyl)piperazinium ion (HPA), and phenyl 2,4-dinitrophenyl carbonate (PDNPC) with SAA are subjected to a kinetic investigation in aqueous solution, at 25.0°C and an ionic strength of 0.2 M. By following spectrophotometrically the nucleofuge release (330-400 nm) under amine excess, pseudo-first-order rate coefficients (kobsd) are obtained. Plots of kobsd VS [amine] at constant pH are linear, with the slope (kN) being pH independent. The Broensted-type plot (log kN vs amine pKa) for the reactions of SAA with MNPC is biphasic with slopes β1 = 0.3 (high pKa region) and β2 = 1.0 (low pKa region) and a curvature center at pKa0 = 9.3. This plot is consistent with a stepwise mechanism through a zwitterionic tetrahedral intermediate (T±) and a change in the rate-determining step with SAA basicity. The Broensted plot for the quinuclidinolysis of MNPC is linear with slope βN = 0.86, in line with a stepwise process where breakdown of T± to products is rate limiting. A previous work on the reactions of SAA with MDNPC was revised by including the reaction of HPA. The Broensted plots for the reactions of QUIN and SAA with MDNPC and SAA with PDNPC are linear with slopes β = 0.51, 0.48, and 0.39, respectively, consistent with concerted mechanisms. Since quinuclidines are better leaving groups from T± than isobasic SAA, yielding a less stable T±, it seems doubtful that the quinuclidinolysis of PDNPC is stepwise, as reported.
Novel Synthesis of Carbamic Ester from Carbon Dioxide, Amine, and Ortho Ester
Ishii, Shideru,Nakayama, Hidenobu,Yoshida, Yasuhiko,Yamashita, Tadataka
, p. 455 - 458 (2007/10/02)
Carbon dioxide reacted with aliphatic amines and ortho esters to form carbamic esters in good yields.The influence of different ortho esters on the carbamate synthetic reaction is described.In the case of orthocarbonates, carbamic esters were obtained in high yields.The reaction of carbon dioxide, amines, and ortho esters may involve a competitive reaction between the esterification of carbamic acid produced by a reaction of carbon dioxide with amine, and the alkylation of amine.
Model Studies on the Mechanism of Biotin-Dependent Carboxylations. 2. Site of Protonation vs. CO2 Transfer
Cravey, Melanie J.,Kohn, Harold
, p. 3928 - 3939 (2007/10/02)
Three irreversibly acidified model compounds (6-8) of N'-carboxybiotin (2) have been prepared to access the importance of proir protonation of the biotin ring system of the CO2-transfer potential of the N'-carboxy group.Substrates 6 and 7 can be considered model compounds of N'-carboxybiotin (2) in which protonation has occurred at the ureido carbonyl oxygen atom.Conversely, compound 8 was synthesized to evaluate the CO2-transfer potential of the N'-carboxy group, if protonation occurred at the N'-nitrogen atom.The reactivity of each substrate with nucleophiles has been evaluated.Of these three compounds, only 8 led to efficient transfer to the carbomethoxy group upon treatment with nitrogen-containing nucleophiles (morpholine, cyclohexylamine, and diisopropylamine).With smaller nucleophiles (i.e, water, methanol) reaction was centered at the ring C-2 position.Correspondingly, treatment of compound 6 with nucleophiles (i.e, alcohols, amines) led to products which can be explained in terms of two competing reactions.One pathway involves initial attack of the nucleophile at the C-2 position of the imidazolinium cation (an AAC2 process) to give a tetrahedral intermediate which then undergoes bond cleavage in either of two directions.The competing pathway observed was an irreversible SN2 displacement reactions (an AAL2 process) at the methylene position of the O-alkyl side chain.Factors are presented which account for the overall product distribution obtained from these reactions.Finally, the products obtained from the treatment of compound 7 with nucleophiles (i.e., alcohols, amines) could be accounted for solely by reactions which occurred at the C-2 position of the ring (an AAC2 process).The corresponding SN2 pathway is not a viably route for this substrate.The significance of these results to the mechanism of action of biotin is discussed.
