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• 110-91-8 morpholine 
• 1005-56-7 phenylcarbonochloridothioate 
• 13509-34-7 diphenylthiocarbonate 
• 109-02-4 4-methyl-morpholine 
• 149775-78-0 O-phenyl 4-nitrophenyl dithiocarbonate 

Relevant academic research and scientific papers

Kinetics and mechanism of the aminolysis of O-phenyl 4-nitrophenyl dithiocarbonate in aqueous ethanol

The reactions of the title substrate (1) with a series of secondary alicyclic amines are subjected to a kinetic investigation in 44 wt% ethanol-water, at 25.0 °C, ionic strength 0.2 M (KCl). Under amine excess over the substrate, pseudo-first-order rate coefficients (kobs) are obtained. Plots of kobs against [NH], where NH is the free amine, are nonlinear upwards, except the reactions of piperidine, which show linear plots. According to the kinetic results and the analysis of products, a reaction scheme is proposed with two tetrahedral intermediates, one zwitterionic (T±) and another anionic (T-), with a kinetically significant proton transfer from T± to an amine to yield T- (k3 step). By nonlinear least-squares fitting of an equation derived from the scheme to the experimental points, the rate microcoefficients involved in the reactions are determined. Comparison of the kinetics of the title reactions with the linear kobs vs. [NH] plots found in the same aminolysis of O-ethyl 4-nitrophenyl dithiocarbonate (2) in the same solvent shows that the rate coefficient for leaving group expulsion from T± (k2) is larger for 2 due to a stronger push by EtO than PhO. The k3 value is the same for both reactions since both proton transfers are diffusion controlled. Comparison of the title reactions with the same aminolysis of phenyl 4-nitrophenyl thionocarbonate (3) in water indicates that (i) the k2 value is larger for the aminolysis of 1 due to the less basic nucleofuge involved and the small solvent effect on k2, (ii) the k3 value is smaller for the reactions of 1 due to the more viscous solvent, (iii) the rate coefficient for amine expulsion from T± (k-1) is larger for the aminolysis of 1 than that of 3 due to a solvent effect, and (iv) the value of the rate coefficient for amine attack (k1) is smaller for the aminolysis of 1 in aqueous ethanol, which can be explained by a predominant solvent effect relative to the electron-withdrawing effect from the nucleofuge.

Phenyl chloro(thionoformate): A new dealkylating agent of tertiary amines

Phenyl chloro(thionoformate) reacts rapidly with unhindered tertiary aliphatic amines at 20° to give a thiocarbamate and an alkyl chloride. Dialkylcyclohexylamines react surprisingly rapidly to form predominantly cyclohexene. The thiocarbamates are converted into the secondary amine salt by treatment with dimethyl sulfate, followed by hydrolysis with water. Rates of reaction and alkyl group cleavage selectivity in amines were found to be superior or comparable to those previously reported with chloroformates.

The dealkylation of tertiary aliphatic amines with phenyl chlorothionoformate

Phenyl chlorothionoformate reacts reacts rapidly with aliphatic amines at 20°C to give a thiourethane and an alkyl chloride. The urethanes are readily converted to the secondary amine salt by reaction with dimethyl sulfate, followed by hydrolysis with wat

Structure-Reactivity Correlations in the Aminolysis and Pyridinolysis of Bis(phenyl) and Bis(4-nitrophenyl) Thionocarbonates

The reactions of a series of secondary alicyclic amines with bis(phenyl) and bis(4-nitrophenyl) thionocarbonates (BPTOC and BNPTOC, respectively), and a series of pyridines with the latter substrate, are subjected to a kinetic investigation in water, 25.0

Kinetics and Mechanism of the Aminolysis of Phenyl and 4-Nitrophenyl Chlorothionoformates

The reactions of a series of secondary alicyclic amines with the title substrates are subjected to a kinetic investigation in aqueous solution, 25 °C, ionic strength 0.2 M (maintained with KCl). Under amine excess pseudo-first-order rate coefficients (kobsd) are found. The plots of kobsd against concentration of free amine at constant pH are linear, with the slopes (kN) independent of pH. The Broensted-type plots obtained (log kN vs amine pKa) for the aminolysis of both substrates are linear with the same slope, β = 0.26. From this value, the kinetic law, and the analysis of products, it is deduced that these reactions proceed through a zwitterionic tetrahedral addition intermediate (T±) on the reaction path, and its formation is the rate-determining step. From a comparison of the present reactions with the concerted aminolysis of substituted phenyl chloroformates in acetonitrile it is inferred that the change of S- by O- in T± and that of water by acetonitrile as solvent destabilizes T± in such a way that the stepwise reaction becomes enforced concerted.

Cyanic Acid Esters. 29. Bezoxazoline-thione-N-imid Esters and Their Consecutive Reactions

Oxazoline-thiones-(2) and aryl cyanates react to form the corresponding isoureas 4.These compounds are remarkably stable against electrophilic reagents.The aminolysis of 4 proceeds two pathwais: a transformation of the imid ester residue to the amin and a ring opening reaction by attack of the amin to the C=S-bond.The hydrazinolysis causes a ring-transformation of the oxazoline- to the 1,3,4-triazole systems.