Heterocyclic analogs of pleiadiene. 67. Formylation of perimidones, 2,3-dihydroperimidines, and perimidines

Vilsmeier formylation of 1,3-dialkylperimidones, 1,3-dialkyl-2,3-dihydroperimidines, and 2-trifluoromethyl-perimidines is performed. The¹H NMR spectra of the resulting mono- and dialdehydes are discussed.For No. 66, see [1].Rostov State University, Rostov-on-Don 344006Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 365–374, March, 1999.     

Heterocyclic analogs of pleiadiene. 50. Sulfonation of perimidines,perimidones, and 2,3-dihydroperimidines

The action of concentrated sulfuric acid on perimidine and 2-substituted perimidines, 1,3-dimethylperimidinium perchlorate, and the 1,3-dimethyl derivatives of perimidone and 2,3-dihydroperimidine gave the 6(7)-sulfonic acids of these compounds.See [1] for communication 49.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 691–696, May, 1980.     

Heterocyclic analogs of pleiadiene. 49. Mass spectra of some N-substituted perimidines and 2,3-dihydroperimidines

The mass spectra of nine compounds of the perimidine series, as well as 1,3-dimethyl derivatives of 2,3-dihydroperimidine, perimidone, and thioperimidone, were obtained and are discussed. The perimidines are distinguished by their high resistance to electron impact. The initial fragmentation of their molecular ions is characterized by detachment of the substituent attached to nitrogen, as well as by detachment of a hydrogen atom from the N-methyl group. It is proposed that the intensities of the doubly charged M²⁺ ions be used to estimate the -donor properties of heterocyclic compounds.See [1] for communication 48.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 684–690, May, 1980.     

Heterocyclic analogs of pleiadiene. 70. Synthesis of 6-hydroxy-1,3-diazapyrenes

The regioselectivity of the reactions of perimidine with cinnamic acids in polyphosphoric acid (PPA) depends on the P₂O₅ content. Procedures were developed for the synthesis of 4(9)- and 6(7)-cinnamoylperimidines. Cyclization of the latter under the action of an excess of AlBr₃ was accompanied by dearylation to form 6-hydroxy-1,3-diazapyrene.     

Heterocyclic analogs of pleiadiene. 42. Acylation of perimidines and 2,3-dihydroperimidines with derivatives of perfluorocarboxylic acids

2-Perfluoroalkylperimidines, 2,3-dihydroperimidines, perimidones, and thioxoperimidines are acylated by anhydrides and chlorides of perfluorinated acids without catalysts. It was established that this reaction proceeds considerably more readily than in the case of perimidine and its alkyl-substituted derivatives, since 2-perfluoroalkylperimidines, 2,3-dihydroperimidines, perimidones, and thioxoperimidines, because of their low basicities, are acylated in the form of neutral molecules, whereas simple perimidines form cations with low reactivities under the same conditions.See [1] for communication 41.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 418–421, March, 1979.     

Heterocyclic analogs of pleiadiene. XVII. Nitration of perimidines with nitrous acid and nitrogen dioxide

The corresponding nitroperimidines are formed instead of the expected nitroso compounds in the reaction of nitrous acid with perimidine and aceperimidine derivatives. Nitrogen oxides formed during the decomposition of nitrous acid are apparently the nitrating agent. In fact, nitrogen dioxide very readily nitrates perimidines and aceperimidines.     

Heterocyclic analogs of pleiadiene 76. Synthesis and tautomeric conversions of mono- and disubstituted perimidines with electron-withdrawing substituents in the naphthalene fragment

A series of new mono- and disubstituted perimidines with electron-withdrawing substituents in the naphthalene fragment has been synthesized. Their prototropic annular tautomerism has been investigated by ¹H NMR spectroscopy.     

Heterocyclic Analogs of Pleiadiene. 72. Sulfones of Perimidine and 2,3-Dihydroperimidine. Synthesis and Some Properties

The arenesulfonation of perimidines has been carried out in polyphosphoric acid and found to occur at the 6(7) and 4(9) positions. Reduction then gave the first representatives of 2,3-dihydroperimidine sulfones. We report a comparative ¹H NMR spectroscopic analysis of the arenesulfonyl- and acylperimidines together with their annular prototropic tautomerism.     

Heterocyclic analogs of pleiadiene 61. 2-cyano- and 2-carbamoylperimidines

Treatment of 1-R-2 chloroperimidines with potassium or sodium cyanides in DMSO solution leads to facile substitution of the chlorine atom by the CN group and formation of previously unknown 1-R-2-cyanoperimidines. The latter upon heating in polyphosphoric acid are converted to 1-R-2-carbomoylperimidines in good yield.For Communication 60, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 804–806, June, 1993.     

Heterocyclic analogs of pleiadiene. 63. Synthesis and crystal structure of 1-aminoperimidines

By action of O-picrylhydroxylamine on perimidine and 2-methylperimidine, we have synthesized their 1-amino derivatives. An x-ray diffraction investigated of 1-aminoperimidine showed that the amino group in them is found in a pyramidal configuration with the axis of the unshared electron pair lying in the plane of the heterocyclic ring, oriented toward the -carbon atom.     

Twice as Nice: The Duff Formylation of Umbelliferone Revised

More efficient and preferably more convenient and greener synthetic solutions in coumarin scaffold functionalization are in steady demand. The Duff ortho-formylation of unsubstituted umbelliferone was revised in this study. The reaction conditions were optimized based upon data from the literature analysis and resulted in unexpectedly rapid ortho-formylation of umbelliferone, yielding a mixture of ortho-formyl position isomers. Thorough studies on the separation of ortho-formylated umbelliferones using chromatographic and recrystallization methods as well as the evaluation of their solubility in common organic solvents led to complete resolution of 8-formyl- and 6-formylumbelliferones. The precise protocol for simultaneous preparation, extraction, and purification of 8-formyl- and 6-formylumbelliferones is provided, and the prospective studies of biological and pharmacological activities of these compounds are synopsized.     

Heterocyclic analogs of pleiadiene 60. Synthesis and properties of 1-methyl-2-chloromethylperimidine

The previously unknown 1-methyl-2-chloromethylperimidine was synthesized. The chlorine atom in it has high lability and is readily exchanged under the influence of S, O, N, and C nucleophiles. It is shown that 1-methyl-2-cyanomethylperimidine exists in the methylidene form.See [1] for Communication 59.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 827–830, Junek 1988.     

Heterocyclic analogs of pleiadiene. XV. Direct acylation of perimidines in the naphthalene ring. Synthesis of 4 (9)- and 6 (7)-acylperimidines

It is shown that perimidines and aceperimidines are acylated by carboxylic acid or their anhydrides in polyphosphoric acid to give 6(7)-acylperimidines at 70–80° (kinetic control) and 4(9)-acylperimidines at 120–150° (thermodynamic control). Acetylation of the perimidines with acetic anhydride also takes place in the presence of perchloric acid.     

Heterocyclic analogs of pleiadiene. 51. N-acylperimidines: Ring opening instead of deacylation under the influence of nucleophiles

N-Acetyl- and N-benzoylperimidines, as well as quaternary salts based on them, were synthesized. It is shown that the heteroring is opened to give N-acyl derivatives of 1,8-naphthalenediamine by the action of nucleophiles on N-acyl-perimidines and N-benzoylperimidine salts.See [1] for Communication 50.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1398–1403, October, 1980.     

Heterocyclic analogs of pleiadiene. 52. Intramolecular C-acylation of perimidines and perimidones. synthesis of a new heterocyclic system — 3,4,5,6-tetrahydropyrido [3,2,1-k,l]perimidine

Intramolecular C-acylation in the 9 position of -(1-perimidinyl)- and -(1-perimidonyl)propionic acids and cyanoethylation of perimidines and perimidones were studied. Derivatives of a new bridged system, viz., 3,4,5,6-tetrahydropyrido [3,2,1-k,l]perimidine, were synthesized for the first time.See [1] for communication 51.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 973–979, July, 1981.     

Heterocyclic Analogs of Pleiadene. 73. Intramolecular Cyclization of Cinnamoyl- and o-Chlorobenzoylperimidines

We have carried out the intramolecular cyclization of the anions of 4(9)- and 6(7)-cinnamoylperimidines and also of 4(9)-o-chlorobenzoylperimidine. These partially hydrogenated pyrido- and quino[1,2,3-cd]perimidines were obtained for the first time. Their ¹H NMR spectroscopic features are discussed.     

Heterocyclic analogs of pleiadiene. 69. Synthesis and oxidative hydroxylation of 1-alkyl-1,3-diazapyrenium salts

1-Alkyl-1,3-diazapyrenium salts were prepared according to two procedures. Oxidative hydroxylation of these salts afforded 1-alkyl-1,3-diazapyren-2-ones. The spectral characteristics of the resulting compounds are discussed.     

Domino synthesis of indenols and alkyl-indene ethers under modified Vilsmeier conditions

Indenols are produced in high yields through domino reactions, when electron-rich trans-stilbenes and other trans aryl-alkyl olefins were subjected to Vilsmeier formylation in the presence of excess POCl₃ in a one-pot procedure. The method is even suitable for converting aryl-alkyl carbinols (precursors for olefins) directly into indenols. The corresponding indene ethers could be prepared in high yields directly when less reactive α,β-unsaturated aldehydes were subjected to cyclization in alcoholic HCl.     

Heterocyclic analogs of pleiadiene. XVI. Nitration of perimidine and its 1- and 2-methyl derivatives

Perimidine and 2-methylperimidine are nitrated by 1 mole of nitric acid in acetic acid to give a mixture of 4(9)- and 6(7)-mononitro derivatives. Renitration gives a mixture of 6,9- and 6,7-dinitroperimidines. Depending on the conditions, 6,7,9-trinitroperimidines and 4,6,7,9-tetranitroperimidines are formed when a large excess of nitric acid is present. 1-Methylperimidine is nitrated by 1 mole of nitric acid to give a mixture of 4-, 6-, and 7-mononitro derivatives.     

Heterocyclic analogs of pleiadiene. 59. Reaction of 1-acetonyl- and 1-phenacylperimidinium salts with hydrazine and ammonium acetate

1-Acetonyl-3-methyl- and 1-methyl-3-phenacylperimidinium salts react with hydrazine hydrate to give tetrahydro-derivatives of the hitherto unknown heterocyclic system 1,2,4-triazino[4,3-a]perimidine. On boiling in acetic acid with ammonium acetate, 3-phenacyl- and 3-(2,4-dimethyl)phenacyl-1-methylperidinium salts are converted into 1-methylamino-8-(4-phenylimidazol-1-y1)naphthalenes, with small amounts of 11-methylimidazo[1,2-a]perimidines also being formed.For No. 58, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1389–1395, October, 1986.The author thank V. A. Anisimova for discussions, and N. A. Klyuev and A. I. Chernyshev for obtaining the PMR and mass spectra.