86317-34-2

Upstream product

• 937-63-3 p-Tolyl chlorothionoformate 
• 62-53-3 aniline 
• 106-44-5 p-cresol 
• 103-72-0 phenyl isothiocyanate 

Downstream Products

• 86884-98-2 N-(4-methoxybenzyl)-N'-phenylthiourea 
• 57294-98-1 N-(4-chlorobenzyl)-N'-phenylthiourea 
• 103-72-0 phenyl isothiocyanate 

Relevant academic research and scientific papers

Kinetics and mechanism of the reactions of O-aryl S-(4-nitrophenyl) dithiocarbonates with anilines in aqueous ethanol

The reactions of O-(4-methylphenyl) S-(4-nitrophenyl) dithiocarbonate and O-(4-chlorophenyl) S-(4-nitrophenyl) dithiocarbonate with a series of anilines are subjected to a kinetic investigation in 44wt% ethanol-water, at 25.0 °C and an ionic strength of 0.2 M. The reactions are followed spectrophotometrically at 420nm (appearance of 4-nitrobenzenethiolate anion). Under excess amine, pseudo-first-order rate coefficients (kobs) are found. For the reactions of both substrates with anilines, plots of k obs versus free amine concentration at constant pH are nonlinear upwards, according to a second-order polynomial equation. This kinetic behavior is in agreement with a stepwise mechanism consisting of two tetrahedral intermediates, one zwitterionic (T±) and the other anionic (T-), with a kinetically significant proton transfer from T ± to an aniline to yield T-. The rate equation was derived from the proposed mechanism. By nonlinear least-squares fitting of the rate equation to the experimental data, values of the rate micro-coefficients involved in both steps were determined. Copyright

Aminolysis of aryl chlorothionoformates with anilines in acetonitrile: Effects of amine nature and solvent on the mechanism

The aminolysis of aryl chlorothionoformates (7, YC6H 4OC(=S)Cl) with anilines (XC6H4NH2) in acetonitrile at 5.0 °C has been investigated. The rates are slower than those for the corresponding reactions of aryl chloroformates (6, YC 6H4OC(=O)Cl). This rate sequence is a reverse of that for alkyl chloroformates (1 4) in water, for which rate-limiting formation of a tetrahedral intermediate, T±, is predicted. On the basis of the large negative cross-interaction constant, ρXY = -0.77, failure of the reactivity-selectivity principle, normal kH/k D values involving deuterated nucleophiles (XC6H 4ND2), and low ΔH≠ with large negative ΔS≠ values, a concerted mechanism with a four-membered hydrogen bonded cyclic transition state (11) is proposed for the title reaction series. It has been shown that the solvent change from water to acetonitrile for the aminolysis of 6 and 7 causes a mechanistic change from stepwise to concerted.

An efficient organotin (IV) catalyst towards the syntheses of thiourethanes

Dibenzyltin(IV) diacetate catalyses the reactions of phenyl isothiocyanate and various alcohols in refluxing benzene giving rise to the corresponding thiourethanes in excellent yields.