Acylation of 3,4-Dihydropyrrolo[1,2-a]pyrazines

The direction of trifluoroacetylation with trifluoroacetic anhydride of 3,4-dihydropyrrolo[1,2-a]pyrazines containing an alkyl or aralkyl substituent in position 1 depends on both the structure of the 3,4-dihydropyrrolo[1,2-a]pyrazine starting materials and on the ratio of reagent:substrate. It may lead to both mono- and disubstituted products. Trifluoroacetylation of 1-methyl-3,4-dihydropyrrolo[1,2-a]pyrazines occurs at the methyl group. Acetylation of 3,4-dihydropyrrolo[1,2-a]pyrazines leads only to N-acetyl-substituted reaction products.     

Formylation of Furyl-substituted Imidazo[1,2-a]pyridine, Imidazo[1,2-a]pyrimidine and Imidazo[2,1-b]thiazole

Vilsmeier formylation of 2-(2-furyl)-substituted imidazo[1,2-a]pyridine and imidazo[1,2-a]pyrimidine, and also 6-(2-furyl)imidazo[2,1-b]thiazole with 1 mole of reagent occurs at the free position of the imidazole ring, while with an excess of the reagent it also occurs at the position 5 of the furyl group.     

Formylation of pyrrolo-[1,2-<Emphasis Type="Italic">a</Emphasis>]pyrazines

The formylation of pyrrolo[1,2-a]pyrazines containing alkyl, aryl, or hetaryl substituents in positions 1 and 6 of the heterocycle has been studied. It has been shown that formylation of 1-phenyl-and 1-(2 thienyl)pyrrolo[1,2-a]pyrazine occurs selectively at the α-position of the pyrrole ring. In all of the remaining examples the reaction course depends on substituent, reagent ratio, and reaction time. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 88–93, January, 2008.     

Acylation of pyrrolo[1,2-a]pyrazines

The acylation of pyrrolo[1,2-a]pyrazines with acetic anhydride and the acid chlorides of various carboxylic acids has been studied. It has been shown that pyrrole[1,2-a]pyrazines are selectively acylated at the α-position of the pyrrole ring when it is free. Products of the condensation of 1-methylsubstituted pyrrolo[1,2-a]pyrazines have been obtained for the first time in the process of acetylation. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, 263–272, February, 2008.     

Dipyrrolo[1,2-a;2':,1'-c]pyrazines. 7. Electrophilic Substitution of Dipyrrolo[1,2-a;2',1'-c]pyrazines and 5,6-Dihydrodipyrrolo[1,2-a;2',1'-c]pyrazines via Formylation of Dipyrrolo[1,2-a;2':,1'-c]pyrazines

A series of previously unreported aldehydes has been prepared by the formylation reaction of dipyrrolo[1,2-a;2':,1'-c]pyrazines and their 5,6-dihydro analogs by DMF and phosphorus oxychloride.     

Dipyrrolo[1,2-a;2',1'-c]pyrazines. 6. Electrophilic Substitution in a Series of Dipyrrolo[1,2-a;2',1'-c]pyrazine and 5,6-Dihydrodipyrrolo[1,2-a;2',1'-c]pyrazine Derivatives. Phosphorylation of Dipyrrolo[1,2-a;2',1'-c]pyrazines

We have studied the behavior of asymmetrically substituted dipyrrolo[1,2-a;2',1'-c]pyrazines and their 5,6-dihydro analogs under phosphorylation reaction conditions.     

Dipyrrolo[1,2-a:2',1'-c]pyrazines. 8. Electrophilic Substitution in Dipyrrolo[1,2-a:2',1'-c]pyrazines and 5,6-Dihydrodipyrrolo[1,2-a:2',1'-c]pyrazines. Acylation of Dipyrrolo[1,2-a:2',1'-c]pyrazines

Esters, nitriles, and amides of dipyrrolo[1,2-a:2',1'-c]pyrazines have been synthesized by the acylation of dipyrrolo[1,2-a:2',1'-c]pyrazines and 5,6-dihydrodipyrrolo[1,2-a:2',1'-c]pyrazines with trichloroacetic acid chloride, p-tosyl isocyanate, and isocyanatophosphoric acid dichloride (Kirsanov isocyanate).     

Effect of the trifluoroacetyl group on the direction of the recyclization of the pyrazine ring in 6-trifluoroacetylpyrrolo[1,2-a]pyrazinium salts

A cyclotransformation of 6-trifluoroacetylpyrrolo[1,2-a]pyrazinium salts involving the trifluoroacetyl group carbon atom was discovered and investigated. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1714–1719, November, 2007.     

Trifluoroacetylation of pyrrolo[1,2-<Emphasis Type="Italic">a</Emphasis>]pyrazines

A study was carried out on the reaction of pyrrolo[1,2-a]pyrazines containing an alkyl, aryl, or aralkyl substituent at C-1 with trifluoroacetic anhydride. Trifluoroacetylation products may be formed either by reaction in the pyrrole ring or at the aryl or aralkyl groups at C-1. Products of electrophilic substitution at C-6 are formed in the trifluoroacetylation of pyrrolo[1,2-a]pyrazines containing at C-1 a substituent bulkier than a methyl group but lacking substituents at C-6 (the α-position of the pyrrole ring). __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1226–1233, August, 2007.     

Synthesis of 5-Phenyl-7-trifluoromethyl-2,3-dihydroimidazo[1,2-a]pyridines

Syntheses are reported for a series of 2-alkylamino-6-phenyl-4-trifluoromethylpyridines. The reaction of 3-cyano-2-(hydroxyalkylamino)-6-phenyl-4-trifluoromethylpyridines with thionyl chloride gave the corresponding 2-(chloroalkylamino)pyridines, 8-cyano-5-phenyl-7-trifluoromethyl-2,3-dihydro-imidazo[1,2-a]pyridines, and 9-cyano-6-phenyl-8-trifluoromethyl-2,3,4-trihydropyrido[1,2-a]-pyrimidines. X-ray diffraction structural analysis was used to study 8-cyano-5-phenyl-7-trifluoromethyl-2,3-dihydroimidazo[1,2-a]pyridine.     

Reactions of 1-Substituted Benzo[4,5]imidazo[1,2-a]pyridines

Bromination of 1-oxo(imino, amino)benzo[4,5]imidazo[1,2-a]pyridines gave the corresponding 2-bromo derivatives. Acylation using the Vilsmeier complex in acetic anhydride gave the N-formyl and N-acetyl derivatives. The reaction of the amine with the Vilsmeier complex, acetyl acetone, ethyl acetoacetate, and 2,5-dimethoxytetrahydrofuran occurs at the amino group.     

Synthesis and properties of 1,2,4-triazolo[4,3-d]-1,2,4-triazolo-[3,4-f]furazano[3,4-b]pyrazines

New methods for the synthesis of 1,2,4-triazolo[4,3-d]-1,2,4-triazolo[3,4-f]furazano[3,4-b]pyrazines with functional substituents of various types are proposed and some properties of these compounds are studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1776–1778, October, 1993.     

Imidazo[1,5-a]- and Thiazolo[3,4-a]quinoxalines Based on 3-(a-Thiocyanobenzyl)quinoxalin-2(1H)-one

When 3-(a-thiocyanobenzyl-2(1H)-one is heated, competing processes of [a]-annelation of the imidazole or thiazole rings occurs with formation of imidazo[1,5-a]- and thiazolo[3,4-a]quinoxalin-4(5H)-ones.     

Properties of 8-Cyano-5-phenyl-7-trifluoromethyl-2,3-dihydroimidazo[1,2-a]pyridines

The alkylation, acylation, halogenation, nitration, oxidation, and hydrolysis reactions of 8-cyano-5-phenyl-7-trifluoromethyl-2,3-dihydroimidazo[1,2-a]pyridine have been studied. It was found that the 6-halo derivatives add alcohol to give covalent solvates. X-ray analysis has been carried out on one of the solvates (6-chloro-8-cyano-7-ethoxy-5-phenyl-7-trifluoromethyl-1,2,3,7-tetrahydroimidazo[1,2-a]pyridine) as well as on 8-cyano-5-phenyl-7-trifluoromethyl-2,3-dihydroimidazo[1,2-a]pyridine trifluoroacetate.     

Spatial Configuration of Derivatives of 5,5a,6,7-Tetrahydropyrido[1,2-a]benzimidazole and 6,7-Dihydro-5aH-pyrido[1,2-b]benzoxazole

The spatial configurations of 7,9-diphenyl-5a,6-tetramethylene-5,5a,6,7-tetrahydropyrido[1,2-a]benzimidazole and 7,9-diphenyl-5a,6-tetramethylene-2,5a,6,7-tetrahydropyrido[1,2-a]benzimidazol-2-one have been established by X-ray crystallography. Analogous configurations are proposed for a series of other derivatives of 5,5a,6,7-tetrahydropyrido[1,2-a]benzimidazoles and some derivatives of 6,7-dihydro-5aH-pyrido[1,2-b]benzoxazoles on the basis of ¹H NMR spectroscopic data and the results of quantum chemical calculations using the MNDO, AM1, and PM3 methods.