Synthesis and structure of new 6-substituted 5-methyl-5,6-dihydrocyclohepta[<Emphasis Type="Italic">b</Emphasis>]indole-9,10-dicarboxylic anhydrides

Reactions of (2-chloro-1-methyl-1H-indol-3-yl)-2-oxoacetyl chloride with alk-3-enoic acids gave the corresponding 6-substituted 5-methyl-5,6-dihydrocyclohepta[b]indole-9,10-dicarboxylic anhydrides which showed fluorescent properties.     

Spiropyrans and spirooxazines

The Duff formylation of 5-bromo- or 5-chloro-8-hydroxyquinoline leads to the corresponding 7-formyl derivatives, condensation of which with 2-methyleneindolines or 3H-indolium halides in the presence of a base afforded new photochromic 6′-halo-substituted spiro[indoline-2,2′-2H- pyrano[3,2-h]quinolines]. Thermal and photo-induced isomerization of compounds obtained have been investigated by 1H NMR and UV spectroscopy.     

Thermodynamic and kinetic analysis of metal ion complexation by photochromic spiropyrans

This review focuses on the results of the studies of metal ion complexation by spiropyrans published mostly in recent years. Introduction of ionophore substituents in the molecules of photochromic spiropyrans induces a reasonably strong bonding in the complexes of these compounds with metal ions. The degree of complexation depends on the state (open or closed) of the photochromic spiropyran fragment. Directed synthesis of structures able to form complexes with metal ion requires knowledge of structure-property relationships based, among other, on the studies of the compounds synthesized earlier. This requires accurate determination of thermodynamic and kinetic parameters of complex formation. Difficulties of such quantitative analysis due to the presence of several interrelated equilibria in the system are discussed.     

Spiropyrans and spirooxazines. 1. Synthesis and photochromic properties of 9"-hydroxy- and 9"-alkoxy-substituted spironaphthooxazines

A procedure was developed for phase-transfer catalyzed alkylation of 5-hydroxyindolenine and 9"-hydroxy-substituted spiro[indoline-2,3"-naphtho[2,1-b]oxazines] by alkyl halides. New 9"-hydroxy- and 9"-alkoxy-substituted spironaphthooxazines, spirooxazinyloxyacetic acids, and their esters containing substituents with different length of the carbon chain in the indoline moiety were synthesized. The influence of the substituents on the spectroscopic properties of the starting and colored forms and the kinetic characteristics of photochromic transformations of 9"-substituted spironaphthooxazines in solutions and polymeric films was investigated. The bipolar merocyanine forms of spirooxazines were found to produce H-aggregates.     

Photo- and thermochromic 2-amino-2H-chromenes

A number of N-aryl- and N-alkylimines of 2-hydroxy-5,6-benzocinnamaldehyde were synthesized. The cyclic 2-amino-2H-chromene structure in nonpolar solvents was established for them by IR, UV, and PMR spectroscopy. It is shown that the transition to polar solvents leads to the establishment of a tautomeric ring-chain equilibrium. The equilibrium thermal transformations and phototransformations of some N-aryl- and N-alkylimines were studied.Communication 12 from the series Photo- and Thermochromic Spirans. See [1] for Communication 11.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1035–1044, August, 1980.     

Energetics and structural mechanisms of photochemical processes in molecules of aldonitrone vinylogs

Depending on the multiplicity of the excited state, alternative photoreactions are realized in methoxy and acetoxy derivatives of aldonitrone vinylogs: diabatic nitrone-oxazypyridone rearrangement in the first excited singlet state and E-Z isomerization involving the C=N bond in the triplet state. In the case of aldonitrone vinylogs with an o-hydroxy group in the -aryl ring one observed adiabatic proton transfer from the hydroxy group to the azotoxido group with a subsequent diabatic reaction involving cyclization to the 2H-chromene structure. The same transfer is also realized in the triplet state. The quantum yields were determined, and the energies of activation of the photoreactions and the reverse thermal processes were evaluated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1373–1378, October, 1990.     

Kinetics of amine-inhibited naphthalene hydroxylation by rat liver microsomal cytochrome P-450

Inhibition constants for amine-inhibited naphthalene hydroxylation by rat liver microsomal cytochrome P-450 have been determined. Irrespective of the nature of the amine added, inhibition has a competitive character. The inhibition mechanism of cytochrome P-450 dependent hydroxylation is discussed.

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P-450 . , . - P-450- .

     

Ring-chain tautomerism and thermo- and photochromism of 3-(1-hydroxy-4-methyl-2-naphthyl)propenal imines

A series of previously undescribed 3-(1-hydroxy-4-methyl-2-naphthyl)propenal imines was synthesized. In the crystalline state all of the imines, except the N-(p-nitrophenyl)imine, have an open o-quinoid structure, whereas in solutions in nonpolar solvents they exist in the cyclic 2H-chromene form. In polar solvents the imines display ring-chain tautomeric equilibrium of the 2H-chromene and o-quinoid forms, the relative percentages of which are determined by the character of the substituent in the amino component of the molecule and by the polarity of the solvent. The N-(p-nitrophenyl)imine has-the 2H-chromene structure in the solid phase and in solvents.Communication 14 from the series Photochromic and thermochromic spirans. See [1] for communication 13.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1031–1039, August, 1983.