Facile and effective preparation of substituted phenylferrocene under phase transfer catalysis

Abstract

Procedures have been reported for the synthesis of phenylferrocene via diazo-salt reactions, 1 but the methods were tedious and the yields were usually low. Phase transfer catalysis (PTC) is one of the most attractive techniques in organic synthesis and the use of it for nucleophillic substitution reactions is well documented. 2 We know phase-transferring agents can activate oxidation 3 and other reaction such as synthesis of chiral complexes, 4 and of coordination compounds 5 etc. However, to the best of our knowledge, the application of phase-transfer catalyst as a preparative method in the reaction of synthesis of substituted phenylferrocene is little described so far. 6 We are interested in developing new methods of simplicity, convenience and efficency to synthesize a variety of substituted phenylferrocene compounds using diazoniumsalts of aromatic amines under PTC[C 16 H 33 N(CH 3 ) 3 Br] for our further work. 7 The procedure of synthesis is shown in Scheme 1.

Synthesis, spectral characterization and electrochemical properties of 1H-3-(o-, m- and p-ferrocenylphenyl)-1-phenylpyrazole-4-carboxaldehydes

“…In the first step of this synthesis (Scheme 2), we prepared ferrocenylacetophenones 3a-c by coupling of ferrocene with the appropriate diazonium salts 2a-c, obtained by diazotation of the corresponding aminoacetophenones 1a-c, as described elsewhere [21][22][23]. Methylketones 3a-c were treated with phenylhydrazine to give the corresponding hydrazones 4a-c.…”

A cytotoxic bis(carbene)gold(i) complex of ferrocenyl complexes: synthesis and structural characterisation

“…[16][17][18][19][20] Further examples of phosphine-free, ferrocene-containing complexes were described by Gimeno et al, 21 who studied the gold(I) complexes [Fe(C 5 H 4 S 2 -CNEt 2 ) 2 (AuCl) 2 ] 22 and [AuX(pzCH 2 Fc)] (X = Cl or C 6 F 5 ; pzCH 2 Fc = ferrocenylmethylpyrazole), 23 and one gold(III) complex: [Au(C 6 F 5 ) 3 (pzCH 2 Fc)]. 23 One of the most general strategies for introducing a large diversity of arene-spacered functionalities onto ferrocene is the Gomberg-Bachmann-Hey arylation, as previously described for carboxylic acids, [24][25][26] carboxylic acid esters, 27 nitrophenyls, 28 halophenyls, 24-25,29 mercaptophenyls 30 and terminal phenylacetylenes. 31 The same concept can also be applied to the conjugative attachment of imidazoles in order to access electrophoric NHC complexes, which have received attention as redox responsive model systems.…”

Redox‐Switchable Phase Tags – Facile Mitsunobu Reactions using Ferrocenyl‐Tagged Triphenylphosphine

“…Following the diazotation of 4-bromoaniline, the reaction of the diazonium salt with ferrocene was performed under phase-transfer conditions, [14] to easily yield deca-gram amounts of 4-bromophenylferrocene (1) in 74 % yield. Next, the Grignard reagent generated from 1 is reacted with diphenylchlorophosphine to result in the formation of the ferrocenyl-tagged triphenylphosphine (2) in 83 % yield.…”