Structure of a product obtained on treatment of 1-thioacetoacetanilide with sulfuryl chloride

Abstract

large chain lengths, first order in H20,. Table 1 and Fig. 4 demonstrate that these are experimentally realized. The apparent first-order rate constant includes a square-root dependence on dose rate which is again in agreement with the experimental results. Ass~lming a value of 2/c1, = 2.4 x lo9 (12) for the bimolecular termination reaction, a rate constant for the chain propagating ~.eaction may be estimated as k,, = (4.0 f 0.4) x lo4 M-' s-'. This is somewhat less than the rate constant found by Seddon and Allen (4) for the propagating reaction in the ethano1/H20, chain reaction. It Inay be noted that the rate co~lstant for reduction of ferricyanide by CH,OH is slightly less than that for reduction by CH,CHOH (8).The small yield of ethylene glycol found,of the termination reaction. In the photolysis of n~ethanol-water solutions (13), the major product of radical combination was said to be ethylene glycol. At high concentrations of either alcohol the yield of the chain reaction is decreased. This phenomenon has previously been reported for the photo-induced reaction in mixed wateralcohol systems (5) and in the radiation-induced oxidation of 2-propanol (1). I11 the latter case the decreased yield was attributed to a decrease in the rate of reaction [7], as a res~ilt of the decreasing dielectric constant of the medium at alcohol concentrations s~~fficiently high to make reaction [7] rather than reaction [8] the ratedetermining propagation step. SummaryThe principal n~~merical results are summarized in Table 2. We have demonstrated that the two-radical model for the chain oxidation of alcohols by H,O,, as developed for 2-propanol, is applicable also to ethanol but that a oneradical model accounts satisfactorilv for the features of the oxidation of ~nethanol. Treatment of 1-thioacetoacetanilide with sulfuryl chloride or thionyl chloride produced a crystalline compound identified as 3.5-diacetonylidene-4-phenyl-l,2,4-ditliiazolidine. The absence of carbonyl absorption in the infrared spectrum of the conipo~~nd indicated that it s h o~~l d be represented by a resonance structLlrc (2) involving non-carbonyl components.Canadian Journal o r Chemistry. 48, 2632 (1970) In connection with our synthetic work on instead of the desired product, a chlorine-free pesticides, the preparation of 2-chloro-I-thio-crystalli~le compound (1n.p. 195-195.5') was acetoacetanilide was required. Accordingly I -obtained. thioacetoacetanilide (1) was treated at roomIn the present p~~blication we provide evidence temperature with ail equinlolar quantity of establishing the structure of this compound. sulfi~ryl chloride. Reaction occurred readily; butThe n~o l e c~~l a r formula Cl,Hl,NO,S,, estabCan. J. Chem. Downloaded from www.nrcresearchpress.com by 34.218.44.141 on 05/11/18For personal use only.