2955-67-1Relevant articles and documents
PRODUCTION METHOD OF AMIDE COMPOUND
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Paragraph 0134-0137, (2020/10/08)
PROBLEM TO BE SOLVED: To provide a production method of an amide compound, which can use a variety of carboxylic acid halides and can produce a desired amide compound at a yield higher than a batch process by suppressing a side reaction. SOLUTION: Provided is a production method of an amide compound using a flow type reactor, in which the flow type reactor includes: a first flow path; a second flow path; a first mixing means provided at a confluent part of the first flow path and the second flow path; and a third flow path that is connected to the first mixing means and arranged on a down stream side of the first mixing means, the production method comprising: a mixing step of obtaining a mixed liquid by circulating a first liquid containing the carboxylic acid halide in the first flow path, circulating a second liquid containing an amine compound having a molecular weight of 1,000 or less, an inorganic alkali and water in the second flow path, and mixing the first liquid and the second liquid by the first mixing means to obtain a mixture; and a reaction step of obtaining an amide compound by circulating the mixed liquid in the third flow path and reacting the carboxylic acid halide and the amine compound in the third flow path. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2020,JPO&INPIT
REACTIONS OF ESTERS WITH AMINES CATALYSED BY METAL CENTRES
Porta, Francesca,Pizzotti, Maddalena,Crotti, Corrado,Cenini, Sergio
, p. 475 - 478 (2007/10/02)
In the presence of metal catalysts such as AlCl3, SnCl2, FeCl3, CuCl2*2H2O, PhCl3*3H2O, "RuCl3*3H2O" and CuCl, the reaction of the ester RCO2Et (R = Me) with an aliphatic amine R1NH2 (R1 = nPr), at 65 deg C and under a dinitrogen atmosphere gives the corresponding amide, RCONHR1, and ethanol.The catalytic activity increases with increasing acidic nature of the metal centre.Similar results have been obtained with R1 = nBu and R = Me and Et, while no reaction was observed with R1 = Ph.A complex such as Rh(PPh3)3Cl has no catalytic activity in these reactions.From the attempted reaction of CH3CO2Et with nPrNH2 in the presence of Rh(PPh3)3Cl, a yellow complex of formula Rh(PPh3)2(nPrNH2)Cl has been isolated.Its reactivity towards CO, O2, and H2 has been also investigated.
Nucleophilic Ring Opening of 2-Oxazolines with Amines: A Convenient Synthesis for Unsymmetrically Substituted Ethylenediamines
Fazio, Michael J.
, p. 4889 - 4893 (2007/10/02)
The reaction of 2-alkyl-2-oxazolines with alkyl- and arylamines was investigated.The acid-catalyzed nucleophilic ring opening of the 2-oxazolines yields N-(2-aminoethyl)carboxamides in good to excellent yields with secondary amines and hindered primary amines.The N-(2-aminoethyl)carboxamides were hydrolyzed under acidic or basic conditions to selectively yield unsymmetrically substituted ethylenediamines.
Ester Aminolysis: New Reaction Series for the Quantitative Measurement of Steric Effects
DeTar, DeLos F.,Delahunty, Claire
, p. 2734 - 2739 (2007/10/02)
Further development of theoretical methods for computing steric effects on chemical reactivity requires a large body of new reliable quantitative data for calibration and for testing.We report here on design criteria for reaction series suitable for obtaining these data and on a successful implementation that shows promise of providing access to a particularly broad range of steric hindrance and which additionally has shown a new form of steric hindrance.The series examined in the present study is ester aminolysis in the form RCOOC6H4NO2-p + R'NH2 in acetonitrile solution.A primary purpose of the examination has been to ascertain whether aminolysis may be a useful general series or whether known or unexpected complications might render it unsuitable.We have measured rate constants for a matrix of reactions using five different R groups and four different R' groups, each reaction at a series of concentrations of amine.This is the first systematic study of the sumultaneous action of steric hindrance effects in both the acylating agent and the entering nucleophile.The reactions showed both a second-order term k2 and a relatively less important third-order term k32.The Taft equation was applied to subsets of the rate constants.For each amine there were data for a set of esters for which the R group was the variable.The slopes ρs for these sets were nearly unity.For each ester there were corresponding data for a series of amine reactions in which R' was the variable.These sets also gave good correlations, but the slopes ρs' were considerably larger, about 2.3.This unusually large difference in response to structural effects in the acylating agent and in the nucleophile is unexpected and appears to arise from a new type of steric hindrance.An obvious explanation based on bond lengths proves to be quantitatively insufficient; that explanation postulates that there is greater hindrance for the amine because the C-N bond is short in comparison with the C-C bond.The difference may be due instead to a requirement for special orientation within the transition state, a matter currently under theoretical investigation.The k2 and the k3 sets gave similar correlations, an important finding in at least two respects.It means that steric effects are well-defined in this example of ester aminolysis, and it means also that the extra molecule of amine is far enough from the reaction center so that no additional steric hindrance results.The reactions observed in the present study cover a range of 5 powers of 10 in relative rate constants.Preliminary studies with other examples of aminolysis suggest that a range of relative rate constants covering well in excess of 12 powers of 10 should be observable.
