Configurational stereoselectivity in the nucleophilic substitution of poly(vinyl chloride) with sodium thiophenate: NMR study and Monte‐Carlo simulation of the reaction

The nucleophilic substitution of the chlorine atoms of poly(vinyl chloride) with sodium thiophenate is assumed to obey an SN2 mechanism with inversion of configuration and a steric control according to which reactivities R of the triads follow the order Rmm > Rmr ≫ Rrr. Such a reaction cannot be described by simple differential equations, but a Monte Carlo simulation, first generating a random Bernouillian chain and then simulating random attack of the chain by the reactant according to the triad reactivities, allows a good agreement with the experimental results of both the kinetics of a reaction carried out in cyclohexanone solution at 40°C and the evolution of the 13C and 1H NMR spectra of the tertiary carbon atoms, assuming the following parameters: Bernouillian probability for a meso placement in the initial chain: 0.431; relative reactivities of the mm, mr and rm, rr triads: 1, 0.5, and 0., respectively. The agreement is excellent until the reaction is about three‐quarters complete; this shows a limiting level of about 60% substitution. Better agreement can be obtained up to the limit, if a secondary process of steric control by the substituant in a partially substituted mr triad is assumed. Other possibilities for that secondary process are discussed.