2424-02-4Relevant articles and documents
Synthesis of Oxazolidinones by a Hypervalent Iodine Mediated Cyclization of N-Allylcarbamates
Das, Mirdyul,Rodríguez, Arantxa,Lo, Pui Kin Tony,Moran, Wesley J.
supporting information, p. 1646 - 1650 (2021/02/11)
The preparation of oxazolidinones by the hypervalent iodine mediated cyclization of allylcarbamates is described. A versatile range of substrates can be converted into substituted oxazolidinones primed for further transformations. Derivatization of the products at both ends is demonstrated. A preliminary attempt at the enantioselective formation of an oxazolidinone using a chiral iodane is also presented. (Figure presented.).
Synthesis of Mixed Secondary and Tertiary Amines
Ayrapetyan, L. V.,Chukhajian, E. O.,Mkrtchyan, H. S.,Panosyan, H. A.
, p. 353 - 355 (2020/04/17)
Abstract: A one-stage and facile method of synthesis of expensive methyl- and ethyl(allyl)amines, methyl- and ethyl(prop-2-ynyl)amines, and methyl- and ethyl(allyl)(3-phenylprop-2-ynyl)amines is developed. The synthesized amines present practical interest, because some (prop-2-ynyl)amines are used in the therapy cancer.
Triazinines: Synthesis and proteolytic decomposition of a new class of cyclic triazenes
Schmidt,Schmidt, Brigitte F.,Snyder,Snyder, Emily J.,Carroll,Carroll, Robin M.,Farnsworth,Farnsworth, David W.,Michejda,Michejda, Christopher J.,Smith R.H.,Smith Jr., Richard H.
, p. 8660 - 8665 (2007/10/03)
The reaction of 1-azido-3-chloropropane with various Grignard reagents and subsequent treatment with anhydrous isopropylamine results in the formation of the corresponding azimine. If the initial magnesium-triazene complex if first hydrolyzed with Dowex resin and then concentrated, the resultant linear triazene begins self-catalyzed cyclization to form the six- membered-ring triazenes as the major product, with HCl as the byproduct. Addition of an amine, at reduced temperature, allows for the neutralization of the byproduct, HC1, which would otherwise react with the linear triazene and the cyclic six-membered-ring triazene to form hydrolysis products. We have assigned the trivial name of triazinines to this new class of cyclic triazenes. The hydrolytic decomposition of these compounds in mixed acetonitrile-aqueous buffers predominantly forms 3-(alkylamino)-1-propanol and lesser amounts of the rearranged alcohol 1-(alkylamino)-2-propanol and N- alkyl-2-propenamine. The rate of hydrolysis of 1-alkyltriazinines is approximately equal to that of the analogous 1,3,3-trialkyltriazenes, about three times slower than that of the analogous 1-alkyltriazolines, and varies in the order ethyl > butyl > 3,3-diethoxypropyl > benzyl. As was true for other triazenes, the mechanism of the decomposition was found to be specific acid-catalyzed (A1), involving rapid reversible protonation followed by rate- limiting formation of a 3-(alkylamino)propyldiazonium ion. The slopes of the log k(obs) versus pH plots were near -1.0 The solvent deuterium isotope effect, k(H)2O/k(D)2O, was in all cases 1.0 and ranges from 0.82 for 1- benzyltriazinine to 0.89 for 1-ethyltriazinine. The activation parameters of the proteolytic decomposition of a series, 1-ethyltriazinine, 1- ethyltriazoline, 1,3,3-triethyltriazene, and 1-ethyl-3-methyltriazene, had similar values for ΔH(+) (+9 → 12 kcal/mol) and ΔS(+) (+7 → 15 eu), respectively.
ELECTROCHEMICAL REDUCTIVE AMINATION. II. AMINATION OF ALIPHATIC ALDEHYDES WITH PRIMARY AMINES
Smirnov, Yu. D.,Pavlichenko, V. F.,Tomilov, A. P.
, p. 374 - 380 (2007/10/02)
The formation of a secondary amine by the electrolysis of an aqueous solution containing an aldehyde and a primary amine was studied.The formation of the secondary amines passes through the intermediate stage of an aldimine.The highest yield of secondary amine is attained at a molar ratio of primary amine to aldehyde of 1.2:1.As electrode material lead, cadmium, zinc, and copper may be used.As supporting electrolyte a phosphate buffer with a pH close to the pKa of the primary amine is recommended.By the method developed 32 amines with various structures were synthesized.
PHOSPHONIUM DIAZA-DIYLIDS AND AZA-YLDIID AS NEW AND EFFICIENT REAGENTS FOR PRIMARY AND SECONDARY AMINES SYNTHESIS
Cristau, Henri-Jean,Garcia, Chantal,Kadoura, Jumah,Torreilles, Eliane
, p. 151 - 154 (2007/10/02)
Metallated aminophosphonium ylids, diaza-diylids and aza-yldiid, are investigated as reagents for primary and secondary amines synthesis.
Heterocyclisations radicalaires d'aminothiols ethyleniques. I. Generalites sur la formation de composes thiazolidiniques
Kaafarni, Mustapha,Crozet, Michel P.,Surzur, Jean-Marie
, p. 449 - 457 (2007/10/02)
Free radical initiation or photolysis of N-allyl-2-aminothiols 1 leads not only to a mixture of heterocyclic compounds b and c resulting from intramolecular addition of the thiyl radical to the terminal double bond but also to 2-alkyl-thiazolidines a.The ratios of these two types of heterocyclic compounds are very sensitive to the experimental conditions and the structures of the reagents.Compounds b and c are the major ones at low reaction temperature, low aminothiol concentration, in a poor hydrogen-donating solvent and with starting compounds 1 containing a tertiary amino group.Thiazolidines a are the major products at high reaction temperature, high aminothiol concentration, in a good hydrogen-donating solvent and with starting compounds 1 containing a secondary amino group.Thiazolidines a are assumed to arise from intramolecular allylic hydrogen abstraction by the thiyl radical.This unusual reactivity of the thiyl radical towards hydrogen abstraction (rather than addition) is discussed.
