67803-58-1

Upstream product

• 463-71-8 thiophosgene 
• 106-48-9 4-chloro-phenol 
• 937-64-4 4-chlorophenyl chlorothionoformate 
• 571-22-2 5β-androstan-17β-ol-3-one 
• 5070-14-4 bis(4-nitrophenyl) thionocarbonate 
• 1443430-40-7 3-nitrophenyl 4-cyanophenyl thionocarbonate 
• 24573-38-4 4-chlorophenolate 

Downstream Products

• 17999-21-2 thiocarbonic acid O,S-bis-(4-chloro-phenyl ester) 
• 2167-53-5 bis(4-chlorophenyl) carbonate 

Relevant academic research and scientific papers

Kinetic and theoretical study on nucleofugality in the phenolysis of 3-nitrophenyl and 4-nitrophenyl 4-cyanophenyl thionocarbonates

The phenolysis of 3-nitrophenyl 4-cyanophenyl thionocarbonate (1) and 4-nitrophenyl 4-cyanophenyl thionocarbonate (2) are subjected to a kinetic investigation in order to evaluate the nucleofugality of the corresponding leaving groups. For the reaction of 2 only 4-nitrophenoxide is obtained as leaving group. For the reaction of 1 the nucleofugality ratio 3-nitrophenoxide/4-cyanophenoxide is 1/3 from the corresponding T- intermediate. Theoretical calculations confirm the experimental results. From these results it can be concluded that the non-leaving group affects the nucleofugality ratio.

Kinetic study of the phenolysis of bis(4-nitrophenyl) carbonate, bis(4-nitrophenyl) thionocarbonate, and methyl 4-nitrophenyl thionocarbonate

The reactions of a homogeneous series of phenols with bis(4-nitrophenyl) carbonate (BNPC), bis-(4-nitrophenyl) thionocarbonate (BNPTOC), and methyl 4-nitrophenyl thionocarbonate (MNPTOC) are subjected to a kinetic investigation in water, at 25.0 °C and ionic strength of 0.2 M (KCl). Under excess of phenol over the substrate, all the reactions obey pseudo-first-order kinetics and are first order in phenoxide anion. The reactions of BNPC show a linear Broensted-type plot with slope β=0.66, consistent with a concerted mechanism (one step). In contrast, those of BNPTOC and MNPTOC show biphasic Broensted-type plots with slopes β=0.30 and 0.44, respectively, at high pKa, and β=1.25 and 1.60, respectively, at low pKa, consistent with stepwise mechanisms. For the reactions of both thionocarbonates, the pKa value at the center of the BrSnsted plot (pKa0) is 7.1, which corresponds to the pKa of 4-nitrophenol. This confirms that the phenolyses of the thionocarbonates are stepwise processes, with the formation of an anionic tetrahedral intermediate. By the comparison of the kinetics and mechanisms of the title reactions with similar reactions, the following conclusions can be drawn: (i) Substitution of S- by O- in an anionic tetrahedral intermediate (T-) destabilizes it. (ii) The change of MeO by 4-nitrophenoxy in T- results in an increase of both the rate constant and equilibrium constant, for the formation ofT-, and also in an enlargement of the rate coefficient for the expulsion of 4-nitrophenoxide from T-. (iii) Substitution of an amino group in a tetrahedral intermediate by ArO destabilizes it. (iv) Secondary alicyclic amines and other amines show greater reactivity toward MNPTOC than isobasic phenoxide anions.

The invention of radical reactions. Part XXIV. Relative rates of acylation and radical deoxygenation of secondary alcohols

Secondary alcohols were transformed into various thiocarbonyl derivatives. Reduction of these compounds using tributyltin hydride and an initiator afforded the corresponding deoxy-compounds. Half-life and competitive measurements showed that all these reactions were fast and could be run to completion.

Synthesis of Samanine

The salamander alkaloid samanine (3-aza-A-homo-5β-androstan-16β-ol) has been synthesized in 10 steps from testosterone acetate in 17percent overall yield, the transposition of the oxygen functionality from C-17 to C-16 being achieved by an elimination-hyd