FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2012183926> ?p ?o ?g. }

• W2012183926 endingPage "1530" @default.
• W2012183926 startingPage "1522" @default.
• W2012183926 abstract "Fundamental reaction pathways for the alkaline hydrolysis of carboxylic acid esters, RCOOR‘, were examined through a series of first-principle calculations. The reactions of six representative esters with hydroxide ion were studied in the gas phase. A total of three competing reaction pathways were found and theoretically confirmed for each of the esters examined: bimolecular base-catalyzed acyl-oxygen cleavage (BAC2), bimolecular base-catalyzed alkyl-oxygen cleavage (BAL2), and carbonyl oxygen exchange with hydroxide. For the two-step BAC2 process, this is the first theoretical study to consider the individual sub-steps of the reaction process and to consider substituent effects. For the carbonyl oxygen exchange with hydroxide and for the one-step BAL2 process, we report here the first quantitative theoretical results for the reaction pathways and for the energy barriers. The energy barrier calculated for the second step of the BAC2 process, that is, the decomposition of the tetrahedral intermediate, is larger in the gas phase than that of the first step, that is, the formation of the tetrahedral intermediate, for all but one of the esters examined. The exception, CH3COOC(CH3)3, does not have an α hydrogen in the leaving group. The highest energy barrier calculated for the BAC2 process is always lower than the barriers for the oxygen exchange and for the BAL2 process. The difference between the barrier for the BAL2 process and the highest barrier for the BAC2 process is only ∼1−3 kcal/mol for the methyl esters, but becomes much larger for the others. Substitution of an α hydrogen in R‘ with a methyl group considerably increases the energy barrier for the BAL2 process, and significantly decreases the energy barrier for the second step of the BAC2 process. The calculated substituent shifts of the energy barrier for the first step of the BAC2 process in gas phase are in good agreement with the observed substituent shifts for the base-catalyzed hydrolysis of alkyl acetates in aqueous solution. All of the calculated results are consistent with the available experimental results and lead to a deeper understanding of previously reported gas-phase experimental observations." @default.
• W2012183926 created "2016-06-24" @default.
• W2012183926 creator A5037378495 @default.
• W2012183926 creator A5054898557 @default.
• W2012183926 creator A5069223890 @default.
• W2012183926 date "2000-02-01" @default.
• W2012183926 modified "2023-10-16" @default.
• W2012183926 title "Theoretical Studies of Fundamental Pathways for Alkaline Hydrolysis of Carboxylic Acid Esters in Gas Phase" @default.
• W2012183926 cites W1607280480 @default.
• W2012183926 cites W1964820261 @default.
• W2012183926 cites W1973280220 @default.
• W2012183926 cites W1973659809 @default.
• W2012183926 cites W1974616802 @default.
• W2012183926 cites W1974959797 @default.
• W2012183926 cites W1977572193 @default.
• W2012183926 cites W1979287993 @default.
• W2012183926 cites W1980228534 @default.
• W2012183926 cites W1984120373 @default.
• W2012183926 cites W1984122379 @default.
• W2012183926 cites W1986531716 @default.
• W2012183926 cites W1990417626 @default.
• W2012183926 cites W2002261101 @default.
• W2012183926 cites W2002558252 @default.
• W2012183926 cites W2011400372 @default.
• W2012183926 cites W2014767176 @default.
• W2012183926 cites W2017814150 @default.
• W2012183926 cites W2018876486 @default.
• W2012183926 cites W2023271753 @default.
• W2012183926 cites W2028462745 @default.
• W2012183926 cites W2033188858 @default.
• W2012183926 cites W2036174404 @default.
• W2012183926 cites W2046270371 @default.
• W2012183926 cites W2047393182 @default.
• W2012183926 cites W2049731349 @default.
• W2012183926 cites W2054440002 @default.
• W2012183926 cites W2061239731 @default.
• W2012183926 cites W2062762024 @default.
• W2012183926 cites W2065014576 @default.
• W2012183926 cites W2065172506 @default.
• W2012183926 cites W2079458939 @default.
• W2012183926 cites W2086464420 @default.
• W2012183926 cites W2089522823 @default.
• W2012183926 cites W2127021519 @default.
• W2012183926 cites W2143981217 @default.
• W2012183926 cites W2149020264 @default.
• W2012183926 cites W2166900726 @default.
• W2012183926 cites W2169166387 @default.
• W2012183926 cites W2321559493 @default.
• W2012183926 cites W2330452086 @default.
• W2012183926 cites W2332265818 @default.
• W2012183926 cites W2334811087 @default.
• W2012183926 cites W2949387607 @default.
• W2012183926 cites W2950807065 @default.
• W2012183926 cites W2950925387 @default.
• W2012183926 cites W2951311229 @default.
• W2012183926 cites W2951648924 @default.
• W2012183926 cites W2951914890 @default.
• W2012183926 cites W2952371931 @default.
• W2012183926 cites W2952764481 @default.
• W2012183926 cites W2952920474 @default.
• W2012183926 cites W3004797657 @default.
• W2012183926 cites W3005153516 @default.
• W2012183926 doi "https://doi.org/10.1021/ja993311m" @default.
• W2012183926 hasPublicationYear "2000" @default.
• W2012183926 type Work @default.
• W2012183926 sameAs 2012183926 @default.
• W2012183926 citedByCount "57" @default.
• W2012183926 countsByYear W20121839262012 @default.
• W2012183926 countsByYear W20121839262013 @default.
• W2012183926 countsByYear W20121839262014 @default.
• W2012183926 countsByYear W20121839262015 @default.
• W2012183926 countsByYear W20121839262016 @default.
• W2012183926 countsByYear W20121839262022 @default.
• W2012183926 countsByYear W20121839262023 @default.
• W2012183926 crossrefType "journal-article" @default.
• W2012183926 hasAuthorship W2012183926A5037378495 @default.
• W2012183926 hasAuthorship W2012183926A5054898557 @default.
• W2012183926 hasAuthorship W2012183926A5069223890 @default.
• W2012183926 hasConcept C161790260 @default.
• W2012183926 hasConcept C178790620 @default.
• W2012183926 hasConcept C178907741 @default.
• W2012183926 hasConcept C179104552 @default.
• W2012183926 hasConcept C185592680 @default.
• W2012183926 hasConcept C192604958 @default.
• W2012183926 hasConcept C2775896084 @default.
• W2012183926 hasConcept C2778689049 @default.
• W2012183926 hasConcept C2779074116 @default.
• W2012183926 hasConcept C2780263894 @default.
• W2012183926 hasConcept C512968161 @default.
• W2012183926 hasConcept C540031477 @default.
• W2012183926 hasConcept C90932021 @default.
• W2012183926 hasConcept C94412978 @default.
• W2012183926 hasConceptScore W2012183926C161790260 @default.
• W2012183926 hasConceptScore W2012183926C178790620 @default.
• W2012183926 hasConceptScore W2012183926C178907741 @default.
• W2012183926 hasConceptScore W2012183926C179104552 @default.
• W2012183926 hasConceptScore W2012183926C185592680 @default.
• W2012183926 hasConceptScore W2012183926C192604958 @default.

• next