Zh. I. Orlova

Formation of π-allyl ligand from pyrylium salts, synthesis and structure of novel π-allyl complexes of palladium(II)

Abstract 2.6-Disubstituted pyrylium salts are found to react with PdCl 2 in an unexpected manner with the ring opening and the formation of novel complexes of the π-allyl type. The structure of the complex with t-butyl substituents is elucidated by X-ray analysis. Crystals are monoclinic, a = 12.310, b = 10.932, c = 12.357 A, α = 112.71°, Z = 4, space group P 2 1 / b . The structure is refined with 2595 reflections to R = 0.034

Dehydration Rearrangements of Derivatives of Methylenedihydrobenzofuran - a New Path to Substituted Benzofurans

When heated with acidic agents derivatives of 3-amino-2-(hydroxydialkylmethyl)methylene-2,3-dihydrobenzofuran undergo rapid dehydration and rearrangement to substituted 2-alkenyl-3-aminobenzofurans.

Reactions ofo-tosylaminobenzaldehyde withp-aminobenzenesulfonamides. Synthesis and structures of 13-(4-aminosulfonylphenyl)-6,12-epimino-5,11-ditosyl-5,6,11,12-tetrahydrodibenzo[b,f]-1,5-diazocine and itsN-substituted derivatives

The reactions ofo-tosylaminobenzaldehyde (1) withp-aminobenzenesulfonamides (2a-c) yielded 13-(p-RNHSO2C6H4)-6,12-epimino-5,11-ditosyl-5,6,11,12-tetrahydrodibenzo[b f]-1,5-diazocines (3a-c) (R=H (a); 2-thiazolyl (b); or 2,6-dimethoxy-4-pyrimidinyl 2,6-dimethoxy-4-pyrimidinyl (c). The structure of compound3c was confirmed by X-ray diffurction study.

Synthesis, structure, and properties of new spirooxindolodibenzodiazepine derivatives

An acid-catalyzed reaction of 3-(2-aminophenylamino)-5,5-dimethylcyclohexen-1-one with isatines leads to the formation of the earlier undescribed 3,3-dimethyl-2,3,4,5,10,11-hexahydrospiro[1H-dibenzo[b,e][1,4]diazepine-11,3′-2H-indole]-1,2′-dione derivatives (6). Spiranes 6 upon heating undergo auto-redox rearrangement with disintegration to 3,3-dimethyl-1,2,3,4-tetrahydrophenazine and the corresponding oxindole. Crystals of four derivatives of compound 6 were studied by X-ray diffraction method.

Reaction of copper acetylides with tetracyanoquinodimethane and tetracyanoethylene

1. Tetracyanoquinodimethane (TCQ) reacts with copper phenylacetylide to form a complex of copper with TCQ and diphenylbutadiyne. 2. The reaction between copper phenylacetylide and tetracyanoethylene (TCE) leads to the replacement of one of the nitrile groups in TCE by a phenylethinyl group.

Reactions of 4-morpholino-1,2-naphthoquinone with enamines ando-phenylenediamine

The reactions of 4-morpholino-1,2-naphthoquinone with enamines, cyclohexanone derivatives, afford 7a-amino-5-morpholinohexahydrobenzo[b]naphtho[1,2][1,4]dioxines, while the reaction witho-phenylenediamine yields 5-morpholinobenzo[a]phenazine.

Formation of benzofuran and 2H-chromene structures in one reaction. A novel synthesis of 2H-chromene derivatives

Heating the morpholinal of nitrosalicylic aldehyde with methyl propiolate in acetonitrile in the presence of Cul affords an equimolar mixture of 2-methoxycarbonylmethyl-3-morpholino-5-nitrobenzofuran and 3-methoxycarbonyl-2-morpholino-6-nitro-2H-chromene, the structures of which were determined by X-ray analysis. Only the 2H-chromene mentioned above was obtained in the absence of Cul and solvent.

Formation of H-bonded ionic associates in reactions of 5-nitrosalicylaldehyde with secondary amines

Abstract5-Nitrosalicylaldehyde reacts with highly basic secondary aliphatic amines to form molecular complexes of 1 ∶ 1 composition. The complexes with piperidine, diethylamine, dipentylamine, and dibenzylamine (1–4, respectively) have been obtained in the crystalline state and characterized. The X-ray diffraction structural analysis of complex1 demonstrated that it exists in a crystal as an H-bonded dimeric ionic associate [C5H12N+ · C7H4NO4−]2 formed as a result of the transfer of the phenyl proton of the aldehyde to the piperidine N atom. According to the results of IR spectroscopy, the other complexes obtained have similar structures.

Synthesis of 1-morpholino-1-(phenylethynyl)cycloalkanes from enamines and phenylacetylene in the presence of Cu(I) halides

Abstract1-Morpholino-1-(phenylethynyl)cyclopentane and 1-morpholino-1-(phenylethynyl)cyclohexane were obtained by reactions of enamines, derivatives of cyclic ketones, with phenylacetylene in the presence of CuI. A scheme for catalysis by Cu(I) compounds with the intermediate formation of copper phenylacetylide and iminium salts was suggested.

Synthesis of substituted propargylamines from Cu(I) and Ag(I) acetylides and iminium salts

The authors have found that iminium salts react with copper and silver organoacetylides in refluxing acetonitrile to form propargylamines. The precursor salts were prepared by quaternization of the appropriate azomethines with excess methyl iodide. The carbon 13 NMR spectra indicate the presence of the propargyl fragment. Treatment with methyl iodide resulted in the conversion to the crystalline methyl iodide derivative.