It was long supposed that the simplest ring obtainable contained six atoms of carbon, and the discovery of trimethylene in 1882 by August Freund by the action of sodium on trimethylene bromide, Br(CH 2) 3 Br, came somewhat as a surprise, especially in view of its behaviour with bromine and hydrogen bromide.
A similar behaviour has since been noticed in other trimethylene derivatives, but the fact that bromine, which usually acts so much more readily than hydrobromic acid on unsaturated compounds,, should be so inert when hydrobromic acid acts readily is one still.
Perkin, junr., in 1883, that ethylene and trimethylene bromides are capable of acting in such a way on sodium acetoacetic ester as to form triand tetramethylene rings.
It forms an addition product with acrylic ester, which on heating loses nitrogen and leaves trimethylene dicarboxylic ester.
When sodio-malonic ester is condensed with trimethylene bromide the chief product is ethyl pentane tetracarboxylate, tetramethylene dicarboxylic ester being also formed, and from this the free acid may be obtained on hydrolysis.