Chlorosulfonyl isocyanate (CSI) may play an antarafacial role as the 2 component in concerted reactions with T2a systems. It does so in additions at low temperature to such conjugated dienes as 1,3-butadiene, isoprene, 2,3-dimethyl-l,3-butadiene, the cis,irons-1,3-pentadiene mixture, and irons-1,3-and trans,trans-2,4hexadiene. The /3-lactam products are Markovnikov-oriented 1,2-cycloadducts in which CSI has added to the terminal double bond. In no instance was the symmetry-allowed T4S + T2a reaction observed. These initially formed N-chlorosulfonyl-^-lactams thermally rearrange to Nand 0-1,4 cycloadducts. Alternative stepwise and concerted mechanisms are proffered. Alkaline hydrolysis of the N-chlorosulfonyl-/3-lactams in acetonewater conventionally afford NH 2-azetidinones. In methanol, solvent participation in the alkaline hydrolysis led to ring cleavage and the formation of bis esters of /3-amino(A7-sulfonic acid)carboxylie acids. Since both hydrolytic processes probably commence by displacement of Clby OH-, the intermediate sulfonic acid must be trapped by the methanol as the sulfonate ester. In the nmr spectra of 2-azetidinones, four-bond coupling was

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Synopsis2-Chloromethylbutadiene has been converted to quaternary ammonium and sulfonium monomers which have been polymerized at room temperature. They show a very great tendency to dimerise on heating in water solution. The aqueous quaternary monomer dimerized 2.5 times as fast as the aqueous sulfonium monomer and nearly 106 times as fast as neat isoprene at 50°C. The quaternary monomer dimerized with itself in a water solution to which Zhydroxymethylbutadiene has been added as an example of a nonionic diene. The latter monomer did not dimerize rapidly in water, nor did 2-aminomethylbutadiene. The hydrochlorides of 2-aminomethylbutadiene and 2-dimethylaminomethylbutadiene dimerized at rates comparable to that of the sulfonium monomer. Poly 2-chloromethylbutadiene contains reactive chlorine except for the structure resulting from the minor extent of 1,2 addition. Water-soluble derivatives have been made from it with nucleophilic tertiary amines and sulfides. Cationic polymers are substantive to paper pulp, and the sulfonium polymers can be cured in paper to give improved wet strength.N-methylmorpholine could be crystallized as chlorides. All had the charac-* In honor of C. S. Marvel on the occasion of his 75th birthday. 2123 a 0 1.95 7.5 9 . 3 3 9 6 b l . 4 1 55 ~O U M 4 9 . 1* The rate of dimerization of neat isoprene is given12 as 4.57 X 10-0 l./mole-sec at 6OoC and 2.12 X 10-8 at 75OC with k = 7.9 X 107 exp { 24900/RT).

Die Reaktion von Chlorsulfonylisocyanat (II) mit den Polyenen (Ia)‐(Ig) bzw. den Olefinen (V) zu den β‐Lactamen (III) bzw. (VI) wird untersucht.