ChemInform Abstract: CYANOACETYLENE AND ITS DERIVATIVES. VI. REACTION OF TERTIARY CYANOACETYLENIC ALCOHOLS WITH BENZIMIDAZOLE

Skvortsov, Yu. M.; Малькина, А. Г.; Трофимов, Б. А.; Volkov, A. N.; Glazkova, N. P.; Proidakov, A. G.; Modonov, V. B.

doi:10.1002/chin.198238214

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“…As reported before among the azole 2-alkenonitrile analogs of compounds IIa-IId only 3-imidazolyl-2- [4] and 3-pyrazolyl-2-alkenonitriles [5] underwent intramolecular cyclization into 2-iminodihydrofurans [5-10% MOH (M = Na, K), dioxane], and at the attempt to carry out cyclization of 3-benzimidazolyl-2-alkenonitriles (triethylamine, 78°C, ethanol) the elimination of benzimidazole was observed [3].…”

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“…The nucleophilic addition of a number of azoles (imidazole, 2-methylimidazole, benzimidazole, 2-ethyl-benzimidazole, pyrazole, 3,5-dimethylpyrazole, 1,2,4-triazole, 5-methyl-3-chloro-1,2,4-triazole) to cyanoacetylene alcohols and to 3-phenyl-2-propynonitrile occurs regioand stereoselectively and furnishes the corresponding alkenes of a Z-configuration, 3-azolyl-2-alkenonitriles, in a quantitative yield [2][3][4][5]. The reaction of 3-phenyl-2-propynonitrile with pyrrole, 2-phenylpyrrole, and 4,5,6,7-tetrahydroindole (KOH, 20°C, 3 h, DMSO) gave rise to a mixture of E-and Z-isomers of N-adducts in a 43-88% yield [6].…”

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Cyanoacetylene and Its Derivatives: XXXIV. Nucleophilic Addition of Tetrazole to Cyanoacetylenes

et al. 2005

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Nucleophilic addition of tetrazole to 4-hydroxy-4-alkyl-2-alkynonitriles and to 3-phenyl-2-propynonitrile occurred regiospecifically and afforded E-, Z-4-hydroxy-4-methyl-3-tetrazolyl-2-alkenonitriles and 3-tetrazolyl-3-phenyl-2-propenonitrile [20-40°C, 13-50 h, 4-15 wt% MOH (M = Na, K), THF (or DMSO)] in up to 69% yield. The attempt to perform cyclization of the hydroxy-containing adducts into iminodihydrofurans (KOH, ethanol, 23-25°C) resulted in vinyl nucleophilic substitution of the tetrazole moiety by an ethoxy group. * For communication XXXIII, see [1].

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Cyanoacetylene and Its Derivatives: XXXIV. Nucleophilic Addition of Tetrazole to Cyanoacetylenes

et al. 2005

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“…An unsubstituted benzimidazole (R 1 = H) with acetylenes (5, 6) is known to yield the expected addition products across the triple bond, no annelation being absorb, [15] whereas the simple substituted imidazoles under the same conditions and with the same acetylenes undergo another reaction, which will be reported elsewhere.…”

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Annelation of Benzimidazoles with α,β‐Acetylenic γ‐Hydroxyacid Nitriles and Hydrolytic Rearrangement of the Cycloadducts on Alumina

et al. 2007

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Abstract1‐Substituted benzimidazoles are readily annelated regio‐ and stereoselectively with α,β‐acetylenic γ‐hydroxyacidnitriles under mild conditions (20–25 °C, no catalyst, no solvent) to form new polyfunctional condensed systems, 4‐cyanomethylene‐1,3‐oxazolobenzimidazoles (30–88 % yield). Unexpectedly, the latter, when chromatographed on neutral Al2O3 at room temperature, undergo a complex multi‐position hydrolytic rearrangement involving the cleavage of the imidazole ring to aminophenyl N‐substituted formamides with an aminodihydrofuran moiety in the aminophenylsubstituent, N‐(2‐{[5‐amino‐2,2‐dialkyl‐3(2H)‐furanylidene]amino}phenyl)‐N‐substituted formamides, a novel class of highly functionalized pharmacophoric compounds. The results contribute to the basic benzimidazole chemistry and provide for prospective families of drug candidates.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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“…When dioxane (which is successfully used for the synthesis of some azolylalkenonitriles) 13 is utilized as a solvent, the reaction fails to take place at all. Replacement of KOH with LiOH, which proved to be active in the reaction of azoles with tertiary cyanoacetylenic alcohols, 14 affords the adduct 5b in as low as 5% yield. Only a two-fold molar excess of acetylene 2 in the KOH-DMSO system allowed us to obtain pyrrole 5b in 89% yield.…”

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N-andC-Vinylation of Pyrroles with DisubstitutedActivated Acetylenes

2003

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Addition of pyrrole and 2-phenylpyrrole to 2-acyl-and 2-cyano-1-phenylacetylenes in the KOH-DMSO system affords chemo-and regioselectively N-adducts: 1-(2-acyl-and 1-(2-cyano-1-phenylethenyl)pyrroles in 32-89% yield. 4,5,6,7-Tetrahydroindole reacts with 2-cyano-1-phenylacetylene analogously. Unexpectedly, with 2-benzoyl-1-phenylacetylene, the reaction follows mainly the C-vinylation route to give (E,Z)-2-(2-benzoyl-1-phenylethenyl)-4,5,6,7-tetrahydroindole and cyclo-bis-adduct, 2-(2benzoyl-1, 3-diphenyl-1,4,5,6,7,8-hexahydrocyclopenta[b]indol-1yl)-1-phenylethanone, a product of intramolecular cyclization of 2,3-di(2-benzoyl-1-phenylethenyl)-4,5,6,7-tetrahydroindole.At the same time, the reaction smoothly and selectively proceeds (r.t., 3 h) in the KOH-DMSO system to furnish either predominantly (in the case of pyrrole 1a) or exclusively (in the case of pyrroles 1b,c) (Z)-1-(2-cyano-1-phenylethenyl)pyrroles 5a-c in 43-88% yield (Scheme 1). The content of the E-isomer increases along with concentration of KOH and process duration, presumably, due to the subsequent Z®E isomerization.Unlike pyrroles 1a and 1c, which add in full to the acetylene 2 (yields of adducts 5a and 5c are 85% and 88%, re-Scheme 1

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ChemInform Abstract: CYANOACETYLENE AND ITS DERIVATIVES. VI. REACTION OF TERTIARY CYANOACETYLENIC ALCOHOLS WITH BENZIMIDAZOLE

Abstract: Die basenkatalysierte nucleophile Umsetzung der Alkohole (I) von denen (Ic) erstmals dargestellt wird, mit Benzimidazol (II) verläuft regio‐ und stereospezifisch unter Bildung der Z‐Alkene (III).

Cited by 3 publications

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Cyanoacetylene and Its Derivatives: XXXIV. Nucleophilic Addition of Tetrazole to Cyanoacetylenes

Cyanoacetylene and Its Derivatives: XXXIV. Nucleophilic Addition of Tetrazole to Cyanoacetylenes

Annelation of Benzimidazoles with α,β‐Acetylenic γ‐Hydroxyacid Nitriles and Hydrolytic Rearrangement of the Cycloadducts on Alumina

N-andC-Vinylation of Pyrroles with DisubstitutedActivated Acetylenes

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