Molecular Complexes of Phenols with Dicyclohexylamine

The Mannich reaction of 2,4-di-tert-butylphenol with dicyclohexylamine was found to involve formation of a stable 1:1 molecular complex between the phenol and amine. The complex does not change on melting, sublimation, and chromatography on silica gel. Its structure was determined by X-ray analysis. Stable 1:1 complexes of dicyclohexylamine with a series of substituted phenols were synthesized; exceptions were 2,6-disubstituted phenols with bulky substituents.     

Bisindoles. 18. Some electrophilic substitution reactions in the 1,2-di(indol-5-yl)ethane series

A quantum-chemical calculation has been made and the laws of the electron-density distribution in the molecule of 1,2-di(indol-5-yl)ethane have been determined. The electrophilic substitution reactions most characteristic for it have been studied.For communications 15–17, see [1–3].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 73–77, January, 1984.     

Pyrroloindoles. 6. New synthesis of 1H, 5H-pyrrolo[2,3-f]indole and 3H,6H-pyrrolo[3,2-e]indole

Ethyl pyruvate 1-acetyl-5-indolinylhydrazone was obtained by diazotization of 1-acetyl-5-aminoindoline with subsequent reduction of the diazonium salt and condensation of the hydrazine with ethyl pyruvate. A mixture of hydrogenated derivatives of linear and angular pyrroloindoles is formed as a result of cyclization of the hydrazone in polyphosphoric acid esters. Subsequent hydrolysis, decarboxylation, and dehydrogenation lead to 1H,5H-pyrrolo[2,3-f]indole and 3H,6H-pyrrolo-[3,2-e]indole.See [1] for Communication 5.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 504–507, April, 1982.     

Synthesis of isomeric indolobenzo[b]thiophenes

Indolo[6,5-d]benzo[b]thiophene, indolo[4,5-d]benzo[b]thiophene, indolo[5,6-d]benzo-[b]thiophene, and indolo[5,4-d]benzo[b]thiophene were obtained from the 2- and 3-dibenzothienylhydrazones by means of the Fischer reaction. The structures of the compounds obtained were proved by their PMR, IR, UV, and mass spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 203–208, February, 1980.     

Pyrroloindoles. 16. Some electrophilic substitution reactions of 2,7-dicarbethoxy-1H,6H-pyrrolo[2,3-e]indoles

Electrophilic substitutions of 2,7-dicarbethoy-1H,6H-pyrrolo[2,3-e]indole (Friedel-Crafts acylation, nitration, bromination) take place both at position 3 of the indole ring and at positions 5 and 8 in the benzene ring.For communication 15 see [1].Iv. Dzhavakhishvili State University, Tbilisi 380028. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1197–1201, September, 1994. Original article submitted July 5, 1994.     

Protonation of isomeric angular pyrroloquinolines

The protonation (deuteration) rate, K_D, for the β-position of the pyrrole ring has been measured for several angular pyrroloquinolines. A relationship has been found between the K_D values and the PMR spectral parameters characterizing the structural features of the isomers, enabling the relative reactivities of the latter towards electrophilic substitution reactions to be determined.