- Redox-neutral palladium-catalyzed C-H functionalization to form isoindolinones with carboxylic acids or anhydrides as readily available starting materials
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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
- Liang, Hong-Wen,Ding, Wei,Jiang, Kun,Shuai, Li,Yuan, Yi,Wei, Ye,Chen, Ying-Chun
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supporting information
p. 2764 - 2767
(2015/06/16)
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- FTIR spectroscopic study of the OH-induced oxidation of two linear acetates: Ethyl and n-propyl acetates
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OH-induced oxidation mechanisms of ethyl and n-propyl acetates have been investigated at room temperature (298 ± 5 K) and atmospheric pressure by photolysing CH3ONO/acetate/NO mixtures with FTIR spectroscopy as analytical device. The main oxidation products and their yields were as follows: from ethyl acetate, acetic acid (0.75 ± 0.13), acetoxyacetaldehyde (0.15 ± 0.05), acetic anhydride (0.02 ± 0.01), formic acetic anhydride (0.02 ± 0.01) and peroxyacetyl nitrate (PAN); from n-propyl acetate, acetoxyacetaldehyde (0.22 ± 0.06), formic acetic anhydride (0.28 ± 0.03), acetic acid (0.15 ± 0.02), acetaldehyde (0.35 ± 0.10), peroxypropionyl nitrate (PPN) and probably acetoxypropionaldehyde (0.30 ± 0.10). From these data, oxidation schemes of these two acetates were elucidated. This study reveals in particular the specifc reactivity of acetates by confirming the novel α-ester rearrangement proposed recently by Tuazon et al. (J. Phys. Chem. A, 1998, 102, 2316) and then by showing that oxygenated alkoxyl radicals may not follow the same rules of reactivity as other alkoxyl radicals. This last observation shows the necessity for further experiments to understand the influence of the oxygenated function on alkoxyl reactivity.
- Picquet-Varrault,Doussin,Durand-Jolibois,Carlier
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p. 2595 - 2606
(2007/10/03)
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- Chelate-Stabilized 1,3-Bis(acyloxy)-1,3-diethyldiboroxanes from Triethylboroxin and Carboxylic Acid Anhydrides
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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
- Koester, Roland,Sporzynski, Andrzej,Schuessler, Wilhelm,Blaeser, Dieter,Boese, Roland
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p. 1191 - 1200
(2007/10/02)
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- On the Mechanism of Ester Aminolysis in the Presence of Alkylammonium Carboxylate Reversed Micelles
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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.
- Seoud, Monica I. El,Vieira, Rita C.,Seoud, Omar A. El
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p. 5137 - 5141
(2007/10/02)
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- The Reactivity of p-Nitrophenyl Esters with Surfactants in Nonaqueous Solvents. I p-Nitrophenyl Acetate in Benzene Solutions of Dodecylammonium Propionate
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The rate of decomposition of p-nitrophenyl acetate, pnpa, in benzene in the presence of dodecylammonium propionate, dap, has been measured at temperatures between 288 and 308 K.The proposed rate equation consists of a term arising from micellar catalysis
- O'Connor, Charmian J.,Ramage, Robyn E.
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p. 757 - 770
(2007/10/02)
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