Matches in SemOpenAlex for { <https://semopenalex.org/work/W1758090160> ?p ?o ?g. }
- W1758090160 endingPage "1556" @default.
- W1758090160 startingPage "1551" @default.
- W1758090160 abstract "Second‐order rate constants ( k quin ) have been measured spectrophotometrically for the reactions of O ‐3,4‐dinitrophenyl thionobenzoate ( 1a ) with a series of quinuclidine derivatives and of O ‐4‐nitrophenyl X‐substituted thionobenzoates ( 2a–2f ) with quinuclidine in 80 mol% H 2 O /20 mol% DMSO at 25.0 ± 0.1 °C. Quinuclidine is less reactive toward the thione esters than less basic benzylamine. Steric hindrance exerted by the tertiary amine is responsible for the decreased reactivity. The Hammett plot for the reactions of 2a–2f with quinuclidine consists of two intersecting straight lines, while the Yukawa–Tsuno plot for the same reactions exhibits an excellent linear correlation with ρ X = 1.10 and r = 0.71. This indicates that the nonlinear Hammett plot is not due to a change in the rate‐determining step but is caused by ground‐state stabilization of substrates possessing an electron‐donating group in the thionobenzoyl moiety through resonance interactions. Brønsted‐type plot for the reactions of 1a with quinuclidines is linear with β nuc = 0.89, which is typical for reactions reported to proceed through a stepwise mechanism. However, the reactions have been concluded to proceed through a forced concerted mechanism. Instability of a plausible intermediate T ± forces the reactions to proceed through such a mechanism." @default.
- W1758090160 created "2016-06-24" @default.
- W1758090160 creator A5006996627 @default.
- W1758090160 creator A5034892664 @default.
- W1758090160 creator A5088668565 @default.
- W1758090160 date "2015-05-26" @default.
- W1758090160 modified "2023-10-16" @default.
- W1758090160 title "Kinetic Study on Quinuclidinolysis ofO-4-Nitrophenyl X-substituted Thionobenzoates andO-3,4-Dinitrophenyl Thionobenzoate: Effect of Amine Nature on Reactivity and Reaction Mechanism" @default.
- W1758090160 cites W1825697289 @default.
- W1758090160 cites W1968055794 @default.
- W1758090160 cites W1976795194 @default.
- W1758090160 cites W1980494973 @default.
- W1758090160 cites W1988234478 @default.
- W1758090160 cites W1996211420 @default.
- W1758090160 cites W1999343010 @default.
- W1758090160 cites W2004191704 @default.
- W1758090160 cites W2004947786 @default.
- W1758090160 cites W2007198693 @default.
- W1758090160 cites W2009204807 @default.
- W1758090160 cites W2009575359 @default.
- W1758090160 cites W2010677108 @default.
- W1758090160 cites W2012999542 @default.
- W1758090160 cites W2016921009 @default.
- W1758090160 cites W2019724766 @default.
- W1758090160 cites W2022768037 @default.
- W1758090160 cites W2024531292 @default.
- W1758090160 cites W2028700934 @default.
- W1758090160 cites W2035679715 @default.
- W1758090160 cites W2036678803 @default.
- W1758090160 cites W2042064626 @default.
- W1758090160 cites W2045601230 @default.
- W1758090160 cites W2048657182 @default.
- W1758090160 cites W2049325358 @default.
- W1758090160 cites W2050845368 @default.
- W1758090160 cites W2051589826 @default.
- W1758090160 cites W2053177350 @default.
- W1758090160 cites W2059608682 @default.
- W1758090160 cites W2060428809 @default.
- W1758090160 cites W2070065857 @default.
- W1758090160 cites W2073089890 @default.
- W1758090160 cites W2074170669 @default.
- W1758090160 cites W2074702049 @default.
- W1758090160 cites W2078179439 @default.
- W1758090160 cites W2086565838 @default.
- W1758090160 cites W2090259345 @default.
- W1758090160 cites W2134431552 @default.
- W1758090160 cites W2139831452 @default.
- W1758090160 cites W2169475757 @default.
- W1758090160 cites W2172810566 @default.
- W1758090160 cites W2314492519 @default.
- W1758090160 cites W2316887560 @default.
- W1758090160 cites W2322419368 @default.
- W1758090160 cites W2325878024 @default.
- W1758090160 cites W2332281165 @default.
- W1758090160 cites W2521111050 @default.
- W1758090160 cites W2525251073 @default.
- W1758090160 cites W2526790498 @default.
- W1758090160 cites W2549362282 @default.
- W1758090160 cites W2554982062 @default.
- W1758090160 cites W2949387607 @default.
- W1758090160 cites W2951594778 @default.
- W1758090160 cites W2952690501 @default.
- W1758090160 cites W2953258647 @default.
- W1758090160 cites W3022385589 @default.
- W1758090160 cites W4240426390 @default.
- W1758090160 doi "https://doi.org/10.1002/bkcs.10293" @default.
- W1758090160 hasPublicationYear "2015" @default.
- W1758090160 type Work @default.
- W1758090160 sameAs 1758090160 @default.
- W1758090160 citedByCount "2" @default.
- W1758090160 countsByYear W17580901602017 @default.
- W1758090160 countsByYear W17580901602019 @default.
- W1758090160 crossrefType "journal-article" @default.
- W1758090160 hasAuthorship W1758090160A5006996627 @default.
- W1758090160 hasAuthorship W1758090160A5034892664 @default.
- W1758090160 hasAuthorship W1758090160A5088668565 @default.
- W1758090160 hasConcept C121332964 @default.
- W1758090160 hasConcept C131779359 @default.
- W1758090160 hasConcept C142724271 @default.
- W1758090160 hasConcept C147597530 @default.
- W1758090160 hasConcept C148898269 @default.
- W1758090160 hasConcept C155647269 @default.
- W1758090160 hasConcept C161790260 @default.
- W1758090160 hasConcept C178790620 @default.
- W1758090160 hasConcept C185592680 @default.
- W1758090160 hasConcept C201194858 @default.
- W1758090160 hasConcept C204787440 @default.
- W1758090160 hasConcept C2775995839 @default.
- W1758090160 hasConcept C2776276205 @default.
- W1758090160 hasConcept C2776910235 @default.
- W1758090160 hasConcept C2780051471 @default.
- W1758090160 hasConcept C62520636 @default.
- W1758090160 hasConcept C65024703 @default.
- W1758090160 hasConcept C71240020 @default.
- W1758090160 hasConcept C71924100 @default.
- W1758090160 hasConcept C75473681 @default.
- W1758090160 hasConcept C8503813 @default.
- W1758090160 hasConcept C93391505 @default.