Matches in SemOpenAlex for { <https://semopenalex.org/work/W2043412480> ?p ?o ?g. }
- W2043412480 endingPage "1119" @default.
- W2043412480 startingPage "1115" @default.
- W2043412480 abstract "A kinetic study is reported for nucleophilic substitution reactions of benzyl 2-pyridyl thionocarbonate (5b) and t-butyl 2-pyridyl thionocarbonate (6b) with a series of alicyclic secondary amines in at . General-base catalysis, which has often been reported to occur for aminolysis of esters possessing a C=S electrophilic center, is absent for the reactions of 5b and 6b. The Brnsted-type plots for the reactions of 5b and 6b are linear with = 0.29 and 0.43, respectively, indicating that the reactions of 5b proceed through a stepwise mechanism with formation of a zwitterionic tetrahedral intermediate () being the rate-determining step while those of 6b proceed through a concerted mechanism. The reactivity of 5b and 6b is similar to that of their oxygen analogues (i.e., benzyl 2-pyridyl carbonate 5a and t-butyl 2-pyridyl carbonate 6a, respectively), indicating that the effect of modification of the electrophilic center from C=O to C=S (i.e., from 5a to 5b and from 6a to 6b) on reactivity is insignificant. In contrast, 6b is much less reactive than 5b, indicating that the replacement of the in 5b by the t-Bu in 6b results in a significant decrease in reactivity as well as a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway). It has been concluded that the contrasting reactivity and reaction mechanism for the reactions of 5b and 6b are not due to the electronic effects of and t-Bu but are caused by the large steric hindrance exerted by the bulky t-Bu in 6b." @default.
- W2043412480 created "2016-06-24" @default.
- W2043412480 creator A5034892664 @default.
- W2043412480 creator A5080068963 @default.
- W2043412480 creator A5088668565 @default.
- W2043412480 date "2013-04-20" @default.
- W2043412480 modified "2023-09-28" @default.
- W2043412480 title "Aminolysis of Benzyl 2-Pyridyl Thionocarbonate and t-Butyl 2-Pyridyl Thionocarbonate: Effects of Nonleaving Groups on Reactivity and Reaction Mechanism" @default.
- W2043412480 cites W1968240973 @default.
- W2043412480 cites W1976795194 @default.
- W2043412480 cites W1980494973 @default.
- W2043412480 cites W1984519656 @default.
- W2043412480 cites W1986320280 @default.
- W2043412480 cites W1995873709 @default.
- W2043412480 cites W1999343010 @default.
- W2043412480 cites W2011964071 @default.
- W2043412480 cites W2019724766 @default.
- W2043412480 cites W2022768037 @default.
- W2043412480 cites W2025321862 @default.
- W2043412480 cites W2028475408 @default.
- W2043412480 cites W2032131597 @default.
- W2043412480 cites W2032996016 @default.
- W2043412480 cites W2033373002 @default.
- W2043412480 cites W2034238766 @default.
- W2043412480 cites W2035679715 @default.
- W2043412480 cites W2036678803 @default.
- W2043412480 cites W2037853818 @default.
- W2043412480 cites W2042064626 @default.
- W2043412480 cites W2045420378 @default.
- W2043412480 cites W2045601230 @default.
- W2043412480 cites W2046461848 @default.
- W2043412480 cites W2048470083 @default.
- W2043412480 cites W2049325358 @default.
- W2043412480 cites W2050845368 @default.
- W2043412480 cites W2053177350 @default.
- W2043412480 cites W2059608682 @default.
- W2043412480 cites W2060428809 @default.
- W2043412480 cites W2065697489 @default.
- W2043412480 cites W2068593734 @default.
- W2043412480 cites W2069292034 @default.
- W2043412480 cites W2070065857 @default.
- W2043412480 cites W2074702049 @default.
- W2043412480 cites W2078179439 @default.
- W2043412480 cites W2080430037 @default.
- W2043412480 cites W2083164906 @default.
- W2043412480 cites W2083232589 @default.
- W2043412480 cites W2086565838 @default.
- W2043412480 cites W2090259345 @default.
- W2043412480 cites W2092431030 @default.
- W2043412480 cites W2095148353 @default.
- W2043412480 cites W2097097278 @default.
- W2043412480 cites W2145569370 @default.
- W2043412480 cites W2149070617 @default.
- W2043412480 cites W2169475757 @default.
- W2043412480 cites W2172810566 @default.
- W2043412480 cites W2325878024 @default.
- W2043412480 cites W2332281165 @default.
- W2043412480 cites W2952935415 @default.
- W2043412480 cites W4231070475 @default.
- W2043412480 cites W4240426390 @default.
- W2043412480 cites W4245546533 @default.
- W2043412480 doi "https://doi.org/10.5012/bkcs.2013.34.4.1115" @default.
- W2043412480 hasPublicationYear "2013" @default.
- W2043412480 type Work @default.
- W2043412480 sameAs 2043412480 @default.
- W2043412480 citedByCount "3" @default.
- W2043412480 countsByYear W20434124802013 @default.
- W2043412480 countsByYear W20434124802016 @default.
- W2043412480 crossrefType "journal-article" @default.
- W2043412480 hasAuthorship W2043412480A5034892664 @default.
- W2043412480 hasAuthorship W2043412480A5080068963 @default.
- W2043412480 hasAuthorship W2043412480A5088668565 @default.
- W2043412480 hasBestOaLocation W20434124801 @default.
- W2043412480 hasConcept C111472728 @default.
- W2043412480 hasConcept C138885662 @default.
- W2043412480 hasConcept C142724271 @default.
- W2043412480 hasConcept C155647269 @default.
- W2043412480 hasConcept C161790260 @default.
- W2043412480 hasConcept C178790620 @default.
- W2043412480 hasConcept C185592680 @default.
- W2043412480 hasConcept C204787440 @default.
- W2043412480 hasConcept C2776910235 @default.
- W2043412480 hasConcept C2777998946 @default.
- W2043412480 hasConcept C65024703 @default.
- W2043412480 hasConcept C71924100 @default.
- W2043412480 hasConcept C89611455 @default.
- W2043412480 hasConceptScore W2043412480C111472728 @default.
- W2043412480 hasConceptScore W2043412480C138885662 @default.
- W2043412480 hasConceptScore W2043412480C142724271 @default.
- W2043412480 hasConceptScore W2043412480C155647269 @default.
- W2043412480 hasConceptScore W2043412480C161790260 @default.
- W2043412480 hasConceptScore W2043412480C178790620 @default.
- W2043412480 hasConceptScore W2043412480C185592680 @default.
- W2043412480 hasConceptScore W2043412480C204787440 @default.
- W2043412480 hasConceptScore W2043412480C2776910235 @default.
- W2043412480 hasConceptScore W2043412480C2777998946 @default.
- W2043412480 hasConceptScore W2043412480C65024703 @default.
- W2043412480 hasConceptScore W2043412480C71924100 @default.