A series of methyl aryl phosphorothiolate esters (SP) were synthesized and their reactions with pyridine derivatives were compared to those for methyl aryl phosphate esters (OP). Results show that SP esters react with pyridine nucleophiles via a concerted S(N)2(P) mechanism. Brønsted analysis suggests that reactions of both SP and OP esters proceed via transition states with dissociative character. The overall similarity of the transition state structures supports the use of phosphorothiolates as substrate analogues to probe mechanisms of enzyme-catalyzed phosphoryl transfer reactions.
Ethyl violet is added to carbon dioxide absorbents and normally serves as an indicator of absorbent exhaustion. During the course of several prior studies of anesthetic breakdown, we noted (but did not publish) that barium hydroxide lime (BL), but not soda lime, turns yellow upon desiccation. We hypothesize that ethyl violet undergoes chemical reaction to produce a yellow colorant in desiccated BL. We qualitatively studied the time course of yellow color development during desiccation of these absorbents with dry oxygen. The yellow colorant was extracted from desiccated absorbent with diethyl ether, separated with chromatography, and analyzed with proton nuclear magnetic resonance and combined gas chromatography and mass spectrometry. The yellow color develops after BL has reached nearly complete desiccation. We successfully identified that ethyl violet decomposes into the yellow colorant 4,4'-bis(diethylamino)benzophenone upon desiccation of BL. The color is not intense, is not useful for identifying low levels of absorbent desiccation, and may be difficult to see through tinted canisters. It may be possible for BL to be sufficiently desiccated to allow chemical breakdown of anesthetics, but not yet show yellow coloration. However, if yellow coloration exists, one should assume that it has become desiccated.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.