| pubmed-article:16526777 | rdf:type | pubmed:Citation | lld:pubmed |
| pubmed-article:16526777 | lifeskim:mentions | umls-concept:C1280500 | lld:lifeskim |
| pubmed-article:16526777 | lifeskim:mentions | umls-concept:C0392747 | lld:lifeskim |
| pubmed-article:16526777 | lifeskim:mentions | umls-concept:C0205099 | lld:lifeskim |
| pubmed-article:16526777 | lifeskim:mentions | umls-concept:C1554963 | lld:lifeskim |
| pubmed-article:16526777 | lifeskim:mentions | umls-concept:C0441712 | lld:lifeskim |
| pubmed-article:16526777 | lifeskim:mentions | umls-concept:C1871730 | lld:lifeskim |
| pubmed-article:16526777 | pubmed:issue | 6 | lld:pubmed |
| pubmed-article:16526777 | pubmed:dateCreated | 2006-3-10 | lld:pubmed |
| pubmed-article:16526777 | pubmed:abstractText | A kinetic study is reported for nucleophilic substitution reactions of 4-nitrophenyl phenyl carbonate (5) and 4-nitrophenyl phenyl thionocarbonate (6) with a series of primary amines. The thiono compound 6 is less reactive than its oxygen analogue 5 toward strongly basic amines but is more reactive toward weakly basic CF3CH2NH2. The Brønsted-type plots obtained from the aminolyses of 5 and 6 are curved downwardly. The reactions are proposed to proceed through a stepwise mechanism with a change in the RDS on the basis of the curved Brønsted-type plots. The microscopic rate constants (k(1) and k(2)/k(-1) ratio) associated with the current aminolyses are consistent with the proposed reaction mechanism. The replacement of the C=O bond in 5 by a polarizable C=S group results in a decrease in the k(1) value but an increase in the k(2)/k(-1) ratio. Besides, such a modification of the electrophilic center causes a decrease in pKa degrees , defined as the pK(a) at the curvature center of curved Brønsted-type plots, but does not alter the reaction mechanism. The larger k(2)/k(-1) ratio for the reactions of 6 compared to those of 5 is proposed to be responsible for the decreased pK(a) degrees value. | lld:pubmed |
| pubmed-article:16526777 | pubmed:language | eng | lld:pubmed |
| pubmed-article:16526777 | pubmed:journal | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16526777 | pubmed:citationSubset | IM | lld:pubmed |
| pubmed-article:16526777 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16526777 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16526777 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16526777 | pubmed:status | MEDLINE | lld:pubmed |
| pubmed-article:16526777 | pubmed:month | Mar | lld:pubmed |
| pubmed-article:16526777 | pubmed:issn | 0022-3263 | lld:pubmed |
| pubmed-article:16526777 | pubmed:author | pubmed-author:KimEun... | lld:pubmed |
| pubmed-article:16526777 | pubmed:author | pubmed-author:UmIk-HwanIH | lld:pubmed |
| pubmed-article:16526777 | pubmed:author | pubmed-author:JeonSang-EunS... | lld:pubmed |
| pubmed-article:16526777 | pubmed:author | pubmed-author:ParkHye-RanHR | lld:pubmed |
| pubmed-article:16526777 | pubmed:issnType | Print | lld:pubmed |
| pubmed-article:16526777 | pubmed:day | 17 | lld:pubmed |
| pubmed-article:16526777 | pubmed:volume | 71 | lld:pubmed |
| pubmed-article:16526777 | pubmed:owner | NLM | lld:pubmed |
| pubmed-article:16526777 | pubmed:authorsComplete | Y | lld:pubmed |
| pubmed-article:16526777 | pubmed:pagination | 2302-6 | lld:pubmed |
| pubmed-article:16526777 | pubmed:meshHeading | pubmed-meshheading:16526777... | lld:pubmed |
| pubmed-article:16526777 | pubmed:meshHeading | pubmed-meshheading:16526777... | lld:pubmed |
| pubmed-article:16526777 | pubmed:meshHeading | pubmed-meshheading:16526777... | lld:pubmed |
| pubmed-article:16526777 | pubmed:meshHeading | pubmed-meshheading:16526777... | lld:pubmed |
| pubmed-article:16526777 | pubmed:meshHeading | pubmed-meshheading:16526777... | lld:pubmed |
| pubmed-article:16526777 | pubmed:year | 2006 | lld:pubmed |
| pubmed-article:16526777 | pubmed:articleTitle | Aminolyses of 4-nitrophenyl phenyl carbonate and thionocarbonate: effect of modification of electrophilic center from C=O to C=S on reactivity and mechanism. | lld:pubmed |
| pubmed-article:16526777 | pubmed:affiliation | Department of Chemistry, Ewha Womans University, Seoul 120-750, Korea. ihum@mm.ewha.ac.kr | lld:pubmed |
| pubmed-article:16526777 | pubmed:publicationType | Journal Article | lld:pubmed |
| pubmed-article:16526777 | pubmed:publicationType | Research Support, Non-U.S. Gov't | lld:pubmed |
