Functional Group Migration in Reactions of 1,2‐Diferrocenyl‐3‐(methylthio)cyclopropenylium Iodide with CH Acids

Abstract

1,2‐Diferrocenyl‐3‐(methylthio)cyclopropenylium iodide reacts with malonic acid derivatives (diethyl malonate and malononitrile as the active methylene compounds) to give mainly the corresponding 3,4‐diferrocenyl‐2‐(methylthio)hexa‐2,4‐dienedioic acid and 2,3‐diferrocenyl‐4‐(methylthio)buta‐1,3‐diene‐1,1‐dicarboxylic acid derivatives as well as ethyl 2,3‐diferrocenyl‐4‐(methylthio)‐5‐oxocyclo‐1,3‐pentadiene‐1‐carboxylate or 2‐cyano‐3,4‐diferrocenyl‐5‐(methylthio)‐2,4‐cyclopentadien‐1‐imine. X‐ray diffraction data for diethyl (2Z,4E)‐3,4‐diferrocenyl‐2‐(methylthio)hexa‐2,4‐dienedioate and 2,3‐diferrocenyl‐4‐(methylthio)buta‐1,3‐diene‐1,1‐dicarbonitrile are presented. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Synthesis of 1,2-diferrocenyl-3-(diacylmethylidene)cyclopropenes and 1,1-diacyl-2,3-diferrocenyl-4-methylsulfanylbuta-1,3-dienes, their structures and electrochemical properties

“…The transformations of vinylcarbenes (12a-c) with intramolecular proton shift affords ultimately the linear products 10a-c. The intramolecular character of the transformation of analogous vinylcarbenes was proved earlier for the reaction of the cation 5c with diethyl [D 2 ]malonate [15].…”

A Novel Synthesis of Ferrocenylpyridazines

“…1,3-Dicarbonyl compounds (1a-f) react with 1-morpholino-(or 1-piperidino-)-2,3-diferrocenylcyclopropenilyum terafluoroborates as described earlier [14,15] to afford 3-[acyl-(ethoxycarbonyl)]methylidene-1,2-diferrocenylcyclopropenes and 3-diacylmethylidene-1,2-diferrocenylcyclopropenes (2a-f) in 55-65 % yield; these compounds are used as starting compounds (Scheme 2). Scheme 2. We found that diferrocenylcyclopropene 2a reacts with hydrazine in boiling ethanol to afford regioselectively only one reaction product, methylpyridazine 3a (Scheme 3).…”

Cover Picture: Isolatable Organophosphorus(III)–Tellurium Heterocycles (Chem. Eur. J. 3/2014)

“…90%. Ethyl ( E ) ‐ 2‐ferrocenylmethylidene(benzoyl)acetate ( 1 ) and ‐( p ‐nitrobenzoyl)acetate ( 2 ), ethyl E‐ and Z ‐ 2‐ferrocenylmethylideneacetoacetates ( 3a ) and ( 3b ) were prepared by condensation of ferrocenecarbaldehyde with ethyl benzoyl‐, p ‐nitrobenzoyl‐, and acetoacetates 4a , 4b , 4c , respectively, in benzene in the presence of piperidinium acetate [20, 21, 26, 27]. The physical and 1 H‐NMR spectroscopic characteristics of compounds 1 , 3a , and 3b were in accord with the literature data [20, 21, 26, 27].…”