The kinetics of the oxidation of a substituted thiourea, trimethylthiourea (TMTU), by chlorite have been studied in slightly acidic media. The reaction is much faster than the comparable oxidation of the unsubstituted thiourea by chlorite. The stoichiometry of the reaction was experimentally deduced to be 2ClO2- + Me2N(NHMe)C=S + H2O --> 2Cl- + Me2N(NHMe)C=O + SO4(2-) + 2H+. In excess chlorite conditions, chlorine dioxide is formed after a short induction period. The oxidation of TMTU occurs in two phases. It starts initially with S-oxygenation of the sulfur center to yield the sulfinic acid, which then reacts in the second phase predominantly through an initial hydrolysis to produce trimethylurea and the sulfoxylate anion. The sulfoxylate anion is a highly reducing species which is rapidly oxidized to sulfate. The sulfinic and sulfonic acids of TMTU exists in the form of zwitterionic species that are stable in acidic environments and rapidly decompose in basic environments. The rate of oxidation of the sulfonic acid is determined by its rate of hydrolysis, which is inhibited by acid. The direct reaction of chlorine dioxide and TMTU is autocatalytic and also inhibited by acid. It commences with the initial formation of an adduct of the radical chlorine dioxide species with the electron-rich sulfur center of the thiocarbamide followed by reaction of the adduct with another chlorine dioxide molecule and subsequent hydrolysis to yield chlorite and a sulfenic acid. The bimolecular rate constant for the reaction of chlorine dioxide and TMTU was experimentally determined as 16 +/- 3.0 M(-1) s(-1) at pH 1.00.

The reaction between tetramethylthiourea (TTTU) and slightly acidic chlorite has been studied. The reaction is much faster than comparable oxidations of the parent thiourea compound as well as other substituted thioureas. The stoichiometry of the reaction in excess oxidant showed a complete desulfurization of the thiocarbamide to yield the corresponding urea and sulfate: 2ClO2(-) + (Me2N)2C ═ S + H2O → (Me2N)2C ═ O + SO4(2-) + 2Cl(-) + 2H(+). The reaction mechanism is unique in that the most stable metabolite before formation of the corresponding urea is the S-oxide. This is one of the rare occasions in which a low-molecular-weight S-oxide has been stabilized without the aid of large steric groups. ESI-MS data show almost quantitative formation of the S-oxide and negligible formation of the sulfinic and sulfonic acids. TTTU, in contrast to other substituted thioureas, can only stabilize intermediate oxoacids, before formation of sulfate, in the form of zwitterions. With a stoichiometric excess of TTTU over oxidant, the TTTU dimer is the predominant product. Chlorine dioxide, which is formed from the reaction of excess chlorite and HOCl, is a very important reactant in the overall mechanism. It reacts rapidly with TTTU to reform ClO2(-). Oxidation of TTTU by chlorite has a complex dependence on acid as a result of chlorous acid dissociation and protonation of the thiol group on TTTU in high-acid conditions, which renders the thiol center a less effective nucleophile.

The oxidation of trimethylthiourea (TMTU) by acidic bromate has been studied. The reaction mimics the dynamics observed in the oxidation of unsubstituted thiourea by bromate with an induction period before formation of bromine. The stoichiometry of the reaction was determined to be 4:3, thus 4BrO(3)- + 3R(1)R(2)C=S+ 3H(2)O --> 4Br- + 3R(1)R(2)C=O + 3SO(4)(2-) + 6H+. This substituted thiourea is oxidized at a much faster rate than the unsubstituted thiourea. The oxidation mechanism of TMTU involves initial oxidations through sulfenic and sulfinic acids. At the sulfinic acid stage, the major oxidation pathway is through the cleavage of the C-S bond to form a reducing sulfur leaving group, which is easily oxidized to sulfate. The minor pathway through the sulfonic acid produces a very stable intermediate that is oxidized only very slowly to urea and sulfate. The direct reaction of aqueous bromine with TMTU was faster than reactions that form bromine, with a bimolecular rate constant of (1.50 +/- 0.04) x 10(2) M(-1) s(-1). This rapid reaction ensured that no oligooscillatory bromine formation was observed. The oxidation of TMTU was modeled by a simple reaction scheme containing 20 reactions.

H ] 2SO 4 ~2 ] 3Cl~] 4H`. taurine and dichlorotaurine, monochlorotaurine was the dominant species at pH 1È3. This Bunte salt showed a facile SÈS bond cleavage after a single S-oxygenation step on the inner sulfur atom. The sulfoxide is quite stable but there was no experimental evidence for the existence of the sulfone-sulfonic acid. Sulfate production was almost quantitative for the oxidation of only one of the sulfur atoms. Further reaction of the taurine occurred only on the nitrogen atom with no cleavage of the CÈS bond. A 21-reaction kinetics scheme model gave reasonable agreement with experiment.

The oxidation of 1-phenyl-2-thiourea (PTU) by chlorite was studied in aqueous acidic media. The reaction is extremely complex with reaction dynamics strongly influenced by the pH of reaction medium. In excess chlorite concentrations the reaction stoichiometry involves the complete desulfurization of PTU to yield a urea residue and sulfate: 2ClO2- + PhN(H)CSNH2 + H2O --> SO4(2-) + PhN(H)CONH2 + 2Cl- + 2H+. In excess PTU, mixtures of sulfinic and sulfonic acids are formed. The reaction was followed spectrophotometrically by observing the formation of chlorine dioxide which is formed from the reaction of the reactive intermediate HOCl and chlorite: 2ClO2- + HOCl + H+ --> 2ClO2(aq) + Cl- + H2O. The complexity of the ClO2- - PTU reaction arises from the fact that the reaction of ClO2 with PTU is slow enough to allow the accumulation of ClO2 in the presence of PTU. Hence the formation of ClO2 was observed to be oligooscillatory with transient formation of ClO2 even in conditions of excess oxidant. The reaction showed complex acid dependence with acid catalysis in pH conditions higher than pKa of HClO2 and acid retardation in pH conditions of less than 2.0. The rate of oxidation of PTU was given by -d[PTU]/dt = k1[ClO2-][PTU] + k2[HClO2][PTU] with the rate law: -d[PTU]/dt = [Cl(III)](T)[PTU]0/K(a1) + [H+] [k1K(a1) + k2[H+]]; where [Cl(III)]T is the sum of chlorite and chlorous acid and K(a1) is the acid dissociation constant for chlorous acid. The following bimolecular rate constants were evaluated; k1 = 31.5+/-2.3 M(-1) s(-1) and k2 = 114+/-7 M(-1) s(-1). The direct reaction of ClO2 with PTU was autocatalytic in low acid concentrations with a stoichiometric ratio of 8:5; 8ClO2 + 5PhN(H)CSNH2 + 9H2O --> 5SO4(2-) + 5PhN(H)CONH2 + 8Cl- + 18H+. The proposed mechanism implicates HOCl as a major intermediate whose autocatalytic production determined the observed global dynamics of the reaction. A comprehensive 29-reaction scheme is evoked to describe the complex reaction dynamics.