Ynaziridines and their reactions with amines

On the basis of the results of IR and UV spectroscopy, a considerable decrease in the efficacy of the conjugation of the unshared pair of the nitrogen atom with a carbonyl group in ynaziridines as compared with ynamines has been shown. The difference in the electronic structures of these compounds finds its reflection in their chemical behavior: the electrophilicity of the triple bond in an ynaziridine is higher than that in the analogous ynamine in reactions with amines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 618–622, May, 1985.     

On reactions of spirostane sapogenins with benzeneseleninic anhydride

Direct dehydrogenation of spirostane sapogenins with benzeneseleninic anhydride/iodoxybenzene afforded the Δ²² derivatives in low yields. The reactions catalyzed by BF₃/Et₂O produced the 23-oxo-sapogenins in addition to their 22-oxo-23-spiro-isomers. The reactions of sapogenins with benzeneseleninic anhydride carried out in the presence of TiCl₄ afforded products chlorinated at C23.     

Products of endic anhydride reaction with cyclic amines and their heterocyclization

Products of reaction between bicyclo[2.2.1]hept-5-ene-endo-endo-2,3-dicarboxylic anhydride (endic anhydride) and cyclic amines were obtained. By an example of one of amido acids a conformational analysis was performed and character of hydrogen bonds was studied using quantum-chemical calculations by PM3 procedure. endo-3-(4-Antipyrylcarbomoyl)-bicyclo[2.2.1]hept-5-ene-endo-2-carboxylic acid with a secondary amide group was converted into the corresponding carboximide which was epoxidized by performic acid.     

Exchange reactions of copper complexes with amines

Square planar mixed ligand complexes of the type [CuLL′] where L = 5-chlorosalicylaldehyde and L′ = acetoacetanilide, have been synthesized on treatment with ammonia. Amine exchange of the above Schiff base complexes has been carried out on treatment with different amines. The reaction with ethanol amine is quite interesting compared to other amines. It reacts with 5-chlorosalicylaldehyde to form a Schiff base, while the β-diketone part is removed in the complex formation. All the complexes were characterized by elemental analysis, spectral studies, magnetic measurement, TLC, and conductane.     

Features of reactions of phthalic anhydride with polyfluorinated alcohols

Polyifluoroalkyl mono- and diesters of phthalic acid were obtained by the reaction of phthalic anhydride with polyfluorinated alcohols. The structure of the polyfluoroalkyl phthalates was studied using IR and ¹H, ¹³C NMR spectroscopy. The nature of the associative interactions between cyclohexanone and polyfluorinated alcohols was revealed.     

Pyridoxal reactions with amines and aliphatic diamines

Interaction of pyridoxal (3-hydroxy-5-hydroxymethyl-2-methylisonicotinaldehyde) with amines, mono- and disubstituted diamines led to the formation of compounds having in their structure imine, imidazolidine, and pyrimidine moieties. Structure of the obtained compounds was proved by IR data, ¹H NMR spectroscopy, mass spectrometry, and X-ray diffraction analysis.     

Hydrogen transfer from tertiary amines to trifluoroacetic anhydride

Tertiary amines are found to be oxidized by trifluoroacetic anhydride (TFAA). A discussion of the mechanism is given.     

Reactions of Bi-, Tri-, and tetracyclic amines with succinic anhydride

Succinic anhydride reacted with cage-like amines {bicyclo[2.2.1]hept-5-en-exo-and-endo-2-yl-methanamines, 2-(bicyclo[2.2.1]hept-5-en-endo-2-yl)ethanamine, exo-5,6-epoxybicyclo[2.2.1]heptan-exo-2-yl-methanamine, tetracyclo[6.2.1.1^3,6.0^2,7]dodec-9-en-endo-4-ylmethanamine, 1-(bicyclo[2.2.1]heptan-2-yl)ethanamine, and 4-azatricyclo[5.2.1.0^2,6]dec-8-ene} to give the corresponding amido acids having a cage-like fragment. The latter were converted into carboximides by the action of hexamethyldisilazane in boiling benzene in the presence of zinc(II) chloride and then into epoxy derivatives. The structure of the newly synthesized compounds was confirmed by IR and NMR spectroscopy.     

Electron-transfer reactions of amines with α-ferrocenylcarbonium ions

The production observed in the reactions of α-ferrocenylcarbonium ions with tertiary amines do not originate from ferrocenylcarbene intermediates. Evidence is presented in support of an electron-transfer mechanism leading to α-ferrocenylcarbinyl radicals as reaction intermediates.     

Ambiguous reactivity of hydroxyperoxide radicals in reactions with aromatic amines

Conclusions It was experimentally shown that hydroxyperoxide radicals reduce diphenyl nitrogenous radicals to diphenylamlne. An explanation of the phenomenon of multiple chain terminations by aromatic amine molecules in the alcohols which are being oxidized was given.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2764–2766, December, 1967.     

α-Acetylenic ethyleneimides and their reactions with amines

The reaction of aziridines with phenyl and p-chlorophenylpropiolyl chlorides at —30 to 60°C leads only to 1,2-addition products, viz., -acetylenic ethyleneimides, or their isoraerization products, viz., 2-ethynyl-substituted 2-oxazolines. Reactions with amines showed that the p-chlorophenylpropiolic acid ethyleneimides obtained are mild N-acylating agents.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1064–1067, August, 1980.     

Manganese-catalyzed cross-coupling reactions of aliphatic amines with aryl halides

An efficient and convenient protocol has been developed for the N-arylation of aliphatic amines with differently substituted aryl halides using a MnCl₂·4H₂O/l-proline catalyst and NaOt-Bu as the base in DMSO.     

1-(Phenylethynyl)aziridine in reactions with amines

The reaction of 1-(phenylethynyl)aziridine with a primary or secondary amine gave 2-benzylimidazoline-2 or N-aminoethyl substituted phenylacetamidine via nucleophilic attack on the aziridine ring. The mechanism of aziridine ring opening by an amine was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 600–603, May, 1989.