27970-32-7Relevant articles and documents
Heterocyclization of amino alcohols into saturated cyclic quaternary ammonium salts
Bulatov, Pavel V.,Petrov, Evgeny Yu.,Tartakovsky, Vladimir A.,Vinogradov, Dmitry B.
, p. 781 - 784 (2020)
Cyclodehydration of available N-alkylethanolamines with aldehydes and simultaneous or subsequent quaternization afford functionalized quaternary ammonium salts of N-nitroimidazolidine, oxazolidine and annulated bismorpholine type. Further replacement of their anions with residues of explosive acids provides a series of energyintensive quaternary salts with a rich hydrogen content possessing satisfactory energy characteristics and sufficiently high thermal stability.
Magnesium-catalyzed mild reduction of tertiary and secondary amides to amines
Lampland, Nicole L.,Hovey, Megan,Mukherjee, Debabrata,Sadow, Aaron D.
, p. 4219 - 4226 (2015/11/11)
The first example of a catalytic hydroboration of amides for their deoxygenation to amines is reported. This transformation employs an earth-abundant magnesium-based catalyst. Tertiary and secondary amides are reduced to amines at room temperature in the presence of pinacolborane (HBpin) and catalytic amounts of ToMMgMe (ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). Catalyst initiation and speciation is complex in this system, as revealed by the effects of concentration and order of addition of the substrate and HBpin in the catalytic experiments. ToMMgH2Bpin, formed from ToMMgMe and HBpin, is ruled out as a possible catalytically relevant species by its reaction with N,N-dimethylbenzamide, which gives Me2NBpin and PhBpin through C-N and C-C bond cleavage pathways, respectively. In that reaction, the catalytic product benzyldimethylamine is formed in only low yield. Alternatively, the reaction of ToMMgMe and N,N-dimethylbenzamide slowly gives decomposition of ToMMgMe over 24 h, and this interaction is also ruled out as a catalytically relevant step. Together, these data suggest that catalytic activation of ToMMgMe requires both HBpin and amide, and ToMMgH2Bpin is not a catalytic intermediate. With information on catalyst activation in hand, tertiary amides are selectively reduced to amines in good yield when catalytic amounts of ToMMgMe are added to a mixture of amide and excess HBpin. In addition, secondary amides are reduced in the presence of 10 mol % ToMMgMe and 4 equiv of HBpin. Functional groups such as cyano, nitro, and azo remain intact under the mild reaction conditions. In addition, kinetic experiments and competition experiments indicate that B-H addition to amide C-O is fast, even faster than addition to ester C=O, and requires participation of the catalyst, whereas the turnover-limiting step of the catalyst is deoxygenation.
The functionalisation of electron rich aromatic compounds with 1,3-oxazolidines and 1,3-dimethylimidazolidine
Heaney, Harry,Papageorgiou, George,Wilkins, Robert F.
, p. 14381 - 14396 (2007/10/03)
N-Phenyl- and N-alkyl-oxazolidines react with alkyl chlorosilanes in the presence of electron rich aromatic compounds with the formation of the expected Mannich bases: 2-methoxycarbonyl-3-methyloxazolidine also reacts with 2-methylfuran in the presence of thionyl chloride to give an a-amino acid derivative: the iminium salt derived from 1,3-dimethylimidazolidine was also shown to react with 2-methylfuran.
Synthesis of unsymmetrical dinucleating ligands bearing nitrogen and oxygen donor atoms
Fenton, David E.,Papageorgiou, George
, p. 5913 - 5928 (2007/10/03)
The synthesis of unsymmetrical dinucleating ligands bearing nitrogen and oxygen donor atoms is described. The Schiff-base condensation of functionalised salicylaldehyde derivatives with primary amines gave rise to unsymmetrical unsaturated ligands, whereas condensation with secondary amines followed by in situ reduction of the iminium species with sodium borohydride, led to the formation of unsymmetrical saturated ligands. The latter were also prepared by the tandem Mannich reactions of 4-chlororesorcinol.
