Ferrocene dicarbonyl chloride

An explosion occurred immediately after pouring and capping of the chloride recovered from preparation of ferrocene-1,1-dicarbonyl chloride. The storage bottle contained phosphoryl chloride recovered from similar preparations and which had been stored for some 3 months. No explanation was apparent. 

FIGURE 3 MiV -Bis-[3-pyiTole-l-yl)propyl)ferrocene-l,r-dicarboxamide, as pictured above, was prepared by reacting iV-(3-aminopropyl)pyrrole in the presence of triethylamine with ferrocene-1,1 -dicarbonyl chloride. 

Khan et al. recently polymerized 1,1 -ferrocene dicarbonyl chloride with various aromatic diamines in solution at low temperatures.183 The resulting polyaramides, 100, possessed glass transition temperatures above 350°C in the range of 360°-390°C and 10% decomposition temperatures between 300 and 430°C (Scheme 2.30). 

Some uses of sugars in novel resolutions of enantiomers have been reported. The ferrocene derivative 225 could be isolated from reaction of a mixture of d,l-and meso-isomers of the corresponding ferrocene dicarbonyl chloride with methyl 4,6-0-benzylidene-a-D-glucopyranoside. This could then be converted by methanolysis into the enantiomerically-pure (R,/ )-ferrocene derivative 226. When the chiral pyridinium salt 227 was photolysed, equimolar amounts of the diastereomers 228 and 229 were obtained. Although no chirality transfer occurred, the two isomers could be separated after acetylation, and some further chemistry was performed on the fused aziridine ring of one of the dia-... 

Scheme 12.17 The synthesis of a series of novel ferrocene-oligomers 69-72 and polyferrocenyl peptide 73, after Boc-deprotection of l,n -bis(Boc-amino)ferrocene, it was coupled to ferrocene-1, /f -dicarbonyl chloride in THF, using the polycondensation protocol.

For the preparation of unsymmetrical ferrocenes, two ways by which only mono-substituted derivatives are produced have been suggested. One route starts from iron tetracarbonyl and a substituted cyclopenta-diene the other from monocyclopentadienyl iron dicarbonyl bromide, which on treatment with a substituted cyclopentadienyl lithium is finally converted into the corresponding mono-substituted ferrocene. Experience shows the first method to be more suitable for the preparation of aryl, and the latter method for the preparation of alkyl, derivatives (57). Corresponding work already carried out on substitution in Ru(C5H6)2 and Os CsH5)2 has also been fruitful. It is found that in the Friedel-Crafts reaction with acetyl or benzoyl chloride there is a distinct predominance of mono- over disubstitution as the atomic weight of the central atom increases (47, 72). 

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