13080-96-1Relevant articles and documents
Redox-neutral palladium-catalyzed C-H functionalization to form isoindolinones with carboxylic acids or anhydrides as readily available starting materials
Liang, Hong-Wen,Ding, Wei,Jiang, Kun,Shuai, Li,Yuan, Yi,Wei, Ye,Chen, Ying-Chun
supporting information, p. 2764 - 2767 (2015/06/16)
An operationally simple, Pd-catalyzed C-H functionalization is described for the synthesis of important and useful isoindolinones from readily available carboxamides and carboxylic acids or anhydrides. The reactions proceed efficiently with a broad range
Chelate-Stabilized 1,3-Bis(acyloxy)-1,3-diethyldiboroxanes from Triethylboroxin and Carboxylic Acid Anhydrides
Koester, Roland,Sporzynski, Andrzej,Schuessler, Wilhelm,Blaeser, Dieter,Boese, Roland
, p. 1191 - 1200 (2007/10/02)
Triethylboroxin (A) reacts with carboxylic acid anhydrides (RCO)2O with various rates to give high yields of the 3,7-dialkyl-1,5-diethyl-4,8,9-trioxa-2,6-dioxonia-1,5-diboratabicyclonona-2,6-dienes (2) , presumably via the unstable compounds (3a, b, d, e).Compound 1c (R = CF3) reacts with A to form a mixture of 1,3-diethyl-1,3-bis(trifluoroacetoxy)diboroxane O=C(CF3)OB(Et)OB(Et)O(CF3)C=O (2c') and 2c (R = CF3) at room temperature.Whereas two compounds of the type 2 do not comproportionate, 1a-e spontaneously form the mixed substituted carboxylic acid anhydrides 1ab etc. on mixing at room temperature (GC, 13C NMR). - From the 17O-enriched A* and 1a-e the 17O-enriched compounds 2a*-e* with BO*B and groups are obtained.A* exchanges O atoms up to 200 deg C with succinic anhydride (1f) forming 1f* or with phthalic acid anhydride (1g) forming 1g* and 3g*. - The mixed carboxylic acid anhydrides 1xy are cleaved, and the mixtures of 1 are separated with A to yield the uniform 3,7-dialkyl-substituted compounds 2. - Key Words: Ethylboronic carboxylic acid anhydrides, comproportionation of / Bicyclononadienes, heteroatom-containing / Bicycloundecadienes, heteroatom-containing / 1,3,2-Diboroxanes / Oxygen atom exchange
On the Mechanism of Ester Aminolysis in the Presence of Alkylammonium Carboxylate Reversed Micelles
Seoud, Monica I. El,Vieira, Rita C.,Seoud, Omar A. El
, p. 5137 - 5141 (2007/10/02)
The mechanism of ester aminolysis by alkylammonium carboxylate reversed micelles was examined.There are two possible pathways, one involving the carboxylate group of the surfactant acting as a general base and another in which it is acting as a nucleophile.The latter mechanism involves the formation of a mixed anhydride (derived from the surfactant and the ester) leading, on aminolysis, to two amides.It was not possible to detect the formation of the intermediate anhydride.Careful analysis of the reaction products showed that only one amide, that derived from ester,is formed.Thus the second mechanism is in error.The nature of the slow step was explored by studying the aminolysis of a series of esters: p-X-phenyl acetates (where X = CH3O, CH3, H, Br, CN, and NO2) by dodecylammonium propionate (DAP) and by dodecylamine plus DAP in benzene and in cyclohexane.Excellent correlations between the logarithm of the rate constant and the Hammett (?-) values were obtained.This implies that the phenoxide ion is the leaving group and that the slow step probably involves the collapse of the tetrahedral intermediate formed by the attack of the amine on the ester.Thus it appears that ester aminolysis in the micellar pseudophase and that in aprotic solvents proceed with the same mechanism and rate-limiting step.
