Matches in SemOpenAlex for { <https://semopenalex.org/work/W2078583998> ?p ?o ?g. }
Showing items 1 to 95 of
95
with 100 items per page.
- W2078583998 endingPage "271" @default.
- W2078583998 startingPage "266" @default.
- W2078583998 abstract "The rate constants for reaction of PhMe2SiCHCO (6) with amines to form amides in CH3CN are best fitted with a mixed second- and third-order dependence on [amine], in stark contrast to previous studies of Ph2CCO and other reactive ketenes in which only a first-order dependence on [amine] was observed in H2O or in CH3CN. Derived third-order rate constants for 6 depend on the amine basicity, with a 1.7 × 107 greater reactivity for n-BuNH2 compared to CF3CH2NH2. These kinetic results are consistent with recently reported theoretical studies for reaction of CH2CO with NH3. For 6 the relative reactivity k(n-BuNH2)/k(H2O) is estimated to be 1013 in CH3CN. The crowded ketene t-Bu2CCO (10) is enormously deactivated toward amination and reacts in neat n-BuNH2 with rates 1012 and 2 × 105 times slower than those for t-BuCHCO and t-BuC(i-Pr)CO (11), respectively. The observed rate constants for 11 also show a higher than first-order dependence on [n-BuNH2]. The absence of higher order kinetic terms in [amine] for more reactive ketenes is attributed to irreversibility of addition of an initial amine to the ketene, while with more stable ketenes the initial step is reversible and later steps involving additional amine molecules are kinetically significant. The general acid CF3CH2NH3+ catalyses the addition of CF3CH2NH2 to 6 in a process independent of [CF3CH2NH2]. The reactivity of 6 with n-BuNH2 is 370 times greater in CH3CN compared to isooctane, a result attributed to the polar nature of the transition state and possible catalysis of the addition by CH3CN." @default.
- W2078583998 created "2016-06-24" @default.
- W2078583998 creator A5028532429 @default.
- W2078583998 creator A5037323790 @default.
- W2078583998 date "1998-12-17" @default.
- W2078583998 modified "2023-10-16" @default.
- W2078583998 title "Amination of Ketenes: Kinetic and Mechanistic Studies" @default.
- W2078583998 cites W1975015941 @default.
- W2078583998 cites W1985414337 @default.
- W2078583998 cites W1985528718 @default.
- W2078583998 cites W1995841143 @default.
- W2078583998 cites W2018631815 @default.
- W2078583998 cites W2051265226 @default.
- W2078583998 cites W2056271200 @default.
- W2078583998 cites W2085181434 @default.
- W2078583998 cites W2125378967 @default.
- W2078583998 cites W2163796832 @default.
- W2078583998 cites W2949178645 @default.
- W2078583998 cites W2949549598 @default.
- W2078583998 cites W2949688130 @default.
- W2078583998 cites W2950951766 @default.
- W2078583998 cites W3005269541 @default.
- W2078583998 cites W4233751020 @default.
- W2078583998 doi "https://doi.org/10.1021/jo982054l" @default.
- W2078583998 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/11674111" @default.
- W2078583998 hasPublicationYear "1998" @default.
- W2078583998 type Work @default.
- W2078583998 sameAs 2078583998 @default.
- W2078583998 citedByCount "25" @default.
- W2078583998 countsByYear W20785839982012 @default.
- W2078583998 countsByYear W20785839982013 @default.
- W2078583998 countsByYear W20785839982014 @default.
- W2078583998 countsByYear W20785839982017 @default.
- W2078583998 countsByYear W20785839982018 @default.
- W2078583998 countsByYear W20785839982020 @default.
- W2078583998 countsByYear W20785839982022 @default.
- W2078583998 crossrefType "journal-article" @default.
- W2078583998 hasAuthorship W2078583998A5028532429 @default.
- W2078583998 hasAuthorship W2078583998A5037323790 @default.
- W2078583998 hasConcept C121332964 @default.
- W2078583998 hasConcept C131779359 @default.
- W2078583998 hasConcept C142724271 @default.
- W2078583998 hasConcept C147597530 @default.
- W2078583998 hasConcept C148898269 @default.
- W2078583998 hasConcept C155647269 @default.
- W2078583998 hasConcept C161790260 @default.
- W2078583998 hasConcept C178790620 @default.
- W2078583998 hasConcept C185592680 @default.
- W2078583998 hasConcept C198503264 @default.
- W2078583998 hasConcept C204787440 @default.
- W2078583998 hasConcept C2776910235 @default.
- W2078583998 hasConcept C2778874822 @default.
- W2078583998 hasConcept C62520636 @default.
- W2078583998 hasConcept C71924100 @default.
- W2078583998 hasConcept C75473681 @default.
- W2078583998 hasConcept C93391505 @default.
- W2078583998 hasConceptScore W2078583998C121332964 @default.
- W2078583998 hasConceptScore W2078583998C131779359 @default.
- W2078583998 hasConceptScore W2078583998C142724271 @default.
- W2078583998 hasConceptScore W2078583998C147597530 @default.
- W2078583998 hasConceptScore W2078583998C148898269 @default.
- W2078583998 hasConceptScore W2078583998C155647269 @default.
- W2078583998 hasConceptScore W2078583998C161790260 @default.
- W2078583998 hasConceptScore W2078583998C178790620 @default.
- W2078583998 hasConceptScore W2078583998C185592680 @default.
- W2078583998 hasConceptScore W2078583998C198503264 @default.
- W2078583998 hasConceptScore W2078583998C204787440 @default.
- W2078583998 hasConceptScore W2078583998C2776910235 @default.
- W2078583998 hasConceptScore W2078583998C2778874822 @default.
- W2078583998 hasConceptScore W2078583998C62520636 @default.
- W2078583998 hasConceptScore W2078583998C71924100 @default.
- W2078583998 hasConceptScore W2078583998C75473681 @default.
- W2078583998 hasConceptScore W2078583998C93391505 @default.
- W2078583998 hasIssue "1" @default.
- W2078583998 hasLocation W20785839981 @default.
- W2078583998 hasLocation W20785839982 @default.
- W2078583998 hasOpenAccess W2078583998 @default.
- W2078583998 hasPrimaryLocation W20785839981 @default.
- W2078583998 hasRelatedWork W2000857219 @default.
- W2078583998 hasRelatedWork W2001212443 @default.
- W2078583998 hasRelatedWork W2027916341 @default.
- W2078583998 hasRelatedWork W2078257228 @default.
- W2078583998 hasRelatedWork W2078583998 @default.
- W2078583998 hasRelatedWork W2083530323 @default.
- W2078583998 hasRelatedWork W2100531297 @default.
- W2078583998 hasRelatedWork W2950666266 @default.
- W2078583998 hasRelatedWork W3034897343 @default.
- W2078583998 hasRelatedWork W3213630657 @default.
- W2078583998 hasVolume "64" @default.
- W2078583998 isParatext "false" @default.
- W2078583998 isRetracted "false" @default.
- W2078583998 magId "2078583998" @default.
- W2078583998 workType "article" @default.