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Novel preparations of dimethyl ferrocene-1 , 1'-dicarboxylate, 1,l '-bis-(dimethylaminomethyl) ferrocene, ferrocene-1 , 1'-dicarboxyaldehyde, and 1,l'dicyanoferrocene are described. Some reactions of ferrocene-mono-and -dicarboxyaldehyde are reported.

The rearrangement product of (ferrocenylmethyl) trimethylammonium iodide (I) is shown to be dimethyl 2-(ferroceny1)ethylamine (111). The corresponding primary amine (VIII; R = H) is converted by various routes into di-and tetra-hydropyridoferrocenes.THE preparation of (ferrocenylmethyl) trimethylammonium iodide (I) was first described by Hauser et aZ.l who also studied its rearrangement under the influence of amide ions. This reagent must cause initial hydrogen abstraction , yielding an equilibrium mixture of the zwitterions (IIa) and (IIb), in which the former may be presumed to predominate. These can then undergo a Stevens rearrangement to (IIIa or b) , respectively; alternatively the zwitterion (IIb) could rearrange by a cyclic mechanism to the amine (IV; R = CH,-NMe,). The last possibility, while analogous to the " ortho-rearrangement " of benzyltrimethylammonium salts, involves a much less favourable transition state for the ferrocene case, where there are two fused five-membered rings2 Hauser and his coworkers rejected this, their original formulation (IV; R = CH,*NMe,) for the product, Fc*CH,.NMe,+ I-(Fc = ferrocenyl) R Fc-CH Me*N Me,

Details of our synthesis of 5-aminomethyl-4,3'-dicarboxymethyl-3,4'-di-(2-carboxyethyl)-dipyrrylmethane (lb), as a stable potassium salt are now reported. This synthetic product had been shown to be an intermediate in the biosynthesis of uroporphinogen 1. The analogous tripyrrane, 15, should be available from the lactam of 2-(2-methoxycarbonylethyl)-3-methoxycarbonylmethyl-4,6-di-(2-ethoxycarbonylethyl)-5-ethoxycarbonylmethyl-7-carboxymethyl-8-aminomethyl-tripyrrane (22) which has also been synthesized. -F o r m y l -4 , 3 ' -d i -e t h o x y c a r b o n y l m e t h y l -3 , t lmethane (U), was obtained through the condensation of the bromomethyl pyrrole 2b with the hydrazone, 23, from a 2-formyl-5-free pyrrole and Girard's "T" reagent. This depends on the supression of the deactivating effect of the aldehyde group in a hydrazone from which the aldehyde is easily regenerated.