20464-87-3Relevant academic research and scientific papers
Exploration of chiral Lewis acid Mg2+ catalysts in the synthesis of aryl organophosphate triesters from phosphorus oxychloride through a three-step, two-pot substitution sequence
Granger, Emily,Solomianko, Katarzyna,Young, Cori,Erb, Jeremy
, p. 1404 - 1408 (2018)
A variety of nucleophilic and Lewis acid catalysts were examined for use in promoting the synthesis of organophosphate triesters. Eight novel organophosphate triesters are reported here for the first time. MgSO4 was discovered as an inexpensive catalyst capable of improving the synthesis of a variety of aryl organophosphate triesters from the readily available and low cost precursor phosphorus oxychloride in a three-step, two-pot sequence. Yields for this method improve upon the uncatalyzed method by 8–36%. Several chiral catalysts were tested, but none were able to induce enantioselectivity in the reaction.
Kinetics and mechanism of the aminolysis of phenyl substituted phenyl chlorophosphates with anilines in acetonitrile
Guha, Arun Kanti,Lee, Hai Whang,Lee, Ikchoon
, p. 765 - 769 (2007/10/03)
The kinetics and mechanism of the aminolysis of phenyl substituted phenyl chlorophosphates with anilines are investigated in acetonitrile at 55.0°C. Very sensitive variation of ρY (δρY ? 0) with the change of substituent on the nucleophile (δσX) leads to a large negative cross-interaction constant, ρXY = (δρY)/(δσX) = -1.31. The secondary kinetic isotope effects observed with deuterated aniline nucleophiles are of the inverse type (kH/kD = 0.61-0.87), and small ΔH? (1.6-9.7 kcal mol-1) and large negative ΔS? (-43 to -65 e.u.) values are obtained. These results are consistent with a concerted process with a late, product-like transition state in which both bond making and leaving group departure are extensive.
