Crystal structure of 2,6-dimethyl-4-chloromethylpyrylium perchlorate

P. I. Lebedev-Polyanskii Vladimir State Pedagogic Institute. A. N. Nesmeyanov Institute of Heteroorganic Compounds, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 3, pp. 164–166, May–June, 1989.     

New rearrangement in the 3-indolinone series

In an aqueous alcohol solution of hydrogen chloride 1-(2-propionylphenyl)amino-2-alkoxy-2-methyl-3-indolinone undergoes rearrangement to 2-(2-acetylcarbonyl)phenyl-3-ethylindazole. The structure of the rearrangement product was investigated by x-ray diffraction analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 929–932, July, 1991.     

Ethynyl carbonium ions. 1. Reaction of 2.6-diaryl-4-phenylethynylpyrulium perchlorates with oxygen-containing nucleophiles

When 2,6-diaryl-4-phenylethynylpyrylium perchlorates are refluxed in water, methanol, or ethanol, they are converted to monomethinecyanines, the formation of which is explained by hydration of the phenylethynyl group and subsequent [2+2]-cycloaddition of the resulting 2,6-diaryl-4-benzoylmethylenepyrans to the starting pyrylium salt. The corresponding pyridine derivatives were obtained by the action of ammonia and aniline on the monomethinecyanines. The IR and PMR spectra of the compounds and the results of x-ray diffraction analysis of 2,6-diphenyl-4-[1-(2,6-diphenyl-4-pyranylidene)-2-phenyl-3-benzoylallyl]pyridine are presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 885–890, July, 1988.     

Structure of the trimer of acrolein diethyl acetal

Summary The product formed by the condensation of acrolein diethyl acetal under the influence of BF₃ etherate is a trimer of composition C₂₁H₄₂O₆ and is 2-ethoxy-4-(1-ethoxyallyl)glutaraldehyde diethyl acetal. A mechanism is proposed for its formation via a quasi-aromatic complex with subsequent cyclic electron transfer.     

Synthesis of 4-trifluoromethyl-7-hydroxycoumarin derivatives. Structure of 3-cyano-4-trifluoromethyl-7-acetoxycoumarin

A method was developed for the production of derivatives of 4-trifluoromethyl-7-hydroxycoumarin with electron-withdrawing groups (CN, CF₃CO) at position 3. The structure of 3-cyano-4-trifluoromethyl-7-acetoxycoumarin was proved by x-ray crystallographic investigation. The effect of the substituents on the geometry of the molecule is discussed.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Institute of Biochemistry, Academy of Sciences of Armenia, 375044 Erevan. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1371–1375, June, 1992.     

The first enantiomerically pure [n]triangulanes and analogues: sigma-[n]helicenes with remarkable features

(M)-(-)- and (P)-(+)-Trispiro[2.0.0.2.1.1]nonanes [(M)- and (P)-3] as well as (M)-(-)- and (P)-(+)-tetraspiro[2.0.0.0.2.1.1.1]undecanes [(M)- and (P)-4]-enantiomerically pure unbranched [4]- and [5]triangulanes-have been prepared starting from racemic bicyclopropylidenecarboxylic [(1RS)-12] and exo-dispiro[2.0.2.1]heptane-1-carboxylic [(1RS,3SR)-13] acids. The optical resolutions of rac-12 and rac-13 furnished enantiomerically pure acids (S)-(+)-12, (R)-(-)-12, (1R,3S)-(-)-13, and (1S,3R)-(+)-13. The ethyl ester (R)-25 of the acid (R)-(-)-12 was cyclopropanated to give carboxylates (1R,3R)-26 and (1R,3S)-26. The ester (1R,3S)-26 and acids (1R,3S)-13 and (1S,3R)-13 were converted into enantiomerically pure methylene[3]triangulanes (S)-(-)- and (R)-(+)-28. An alternative approach consisted of an enzymatic deracemization of endo-[(1SR,3SR)-dispiro[2.0.2.1]heptyl]methanol (rac-20) or anti-[(1SR,3RS)-4-methylenespiropentyl]methanol (rac-18). This afforded (S)-(-)- and (R)-(+)-28 (starting from rac-20), as well as enantiomerically pure (M)-(-)- and (P)-(+)-1,4-dimethylenespiropentanes [(M)- and (P)-23] starting from rac-18. The methylenetriangulanes (S)-(-)- and (R)-(+)-28 were cyclopropanated furnishing (M)- and (P)-3. The rhodium-catalyzed cycloaddition of ethyl diazoacetate onto (S)-(-)- and (R)-(+)-28 yielded four diastereomeric ethyl trispiro[2.0.0.2.1.1]nonane-1-carboxylates in approximately equal proportions. The enantiomerically pure esters (1R,3S,4S)- and (1S,3R,4R)-30 were isolated by careful distillation and then transformed into [5]triangulanes (M)- and (P)-4 using the same sequence of reactions as applied for (M)- and (P)-3. The structures of the key intermediates (R)-12 and rac-31 were confirmed by X-ray analyses. Although [4]- and [5]triangulanes have no chromophore which would lead to any significant absorption above 200 nm, they have remarkably high specific rotations even at 589 nm with [alpha](20)D=-192.7 [(M)-3, c=1.18, CHCl(3))] or +373.0 [(P)-4, c=1.18, CHCl(3))]. This remarkable optical rotatation is in line with their helical arrangement of sigma bonds, as confirmed by a full valence space single excitation configuration interaction treatment (SCI) in conjunction with DFT computations at the B3LYP/TZVP//B3LYP/6-31+G(d,p) level of theory which reproduce the ORD very well. Thus, it is appropriate to call the helically shaped unbranched [n]triangulanes the "sigma-[n]helicenes", representing the sigma-bond analogues of the aromatic [n]helicenes.     

Cubane derivatives

A precision X-ray structural investigation of 1,4-dimethoxycarbonylcubane at 218 K was carried out. Analysis of the experimental maps of deformational electron density indicates the existence of partial electron density transfer from the cage bonds to the C_cubane-COOR bonds and the shift of the electron density to the symmetrical (relative to the COOMe planes) cube faces.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1210–1213, July, 1993.     

Molecular structure of 3-aceto-5-cyano-6-dimethylaminohexa 3.5-dien-2-one and z-7-dimethylamino-2-aceto-4-methylhepta-2,4,6-trienecarboxylic acid methyl ester

X-ray structural analyses have been carried out for 3-aceto-5-cyano-6-dimethyl-aminohexa-3, 5-dien-2-one (I) and Z-7-dimethylamino-2-aceto-4-methylhepta-2,4,6-trienecarboxylic acid methyl ester (II). Introduction of an electron-withdrawing CN-group in the middle of the polyene chain in molecule (I) has been shown to reduce the degree of double bond delocalization. CNDO/2 calculations have also been performed for compound (I) and the resulting atomic charge distribution data are discussed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 396–402, February, 1991.The authors acknowledge the generosity of Zh. A. Krasnaya and T. S. Stytsenko for providing samples and for valuable discussons of the results.