ChemInform Abstract: CYANOACETYLENE AND ITS DERIVATIVES. VII. REACTION OF TERTIARY CYANOACETYLENIC C ALCOHOLS AND THEIR ACETALS WITH IMIDAZOLE

Abstract

Die Cyanacetylenalkohole (I) addieren Imidazol (II) unter Bildung der E‐Addukte (III).

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

“…The attempts to carry out the intramolecular cyclization of alkenonitrile IIa by treating with gaseous hydrogen chloride as it happened with 3-imidazolyl-2-alkenonitriles [4] were also unsuccessful.…”

“…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].…”

“…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].…”

“…cyano group in the diluted solution of compound IIa splits in two bands at 2222 and 2202 cm -1 belonging presumably to Ε-and Z-configurations respectively [4].…”

Cyanoacetylene and Its Derivatives: XXXIII. One-Pot Stereoselective Synthesis of Bis-iminodihydrofurans from 4-Hydroxy-4-methyl-2-pentynonitrile and Aromatic Amines

“…Systematic studies on the additions of a wide series of nitrogen-containing nucleophiles (ammonia [4,5], primary [6-8] and secondary amines [9], amino alcohols [10], azide ion [11], and some azoles [12][13][14]) to nitriles derived from α,β-acetylenic γ-hydroxy carboxylic acids led to the development of general procedures for the synthesis of 4-amino-2-iminodihydrofurans and aminoalkenonitriles, as well as of their azole analogs. We also reported [7, 8] on successive syntheses of mono-, bis-, tris-, and tetrakisiminodihydrofurans from methylamine and 4-hydroxy-4-methyl-2-pentynonitrile.…”