Novel preparation of 3-oxazoline-2(1H)-2-thiones involving a benzilic acid-type rearrangement

1971 ◽  
Vol 36 (19) ◽  
pp. 2886-2887 ◽  
Author(s):  
David N. Harpp ◽  
P. Mathiaparanam
Keyword(s):  
Acid Type ◽  
Benzilic Acid

scholarly journals C18FATTY ACIDS. IV. A REARRANGEMENT OF THE BENZILIC ACID TYPE IN THE ALIPHATIC SERIES

1922 ◽  
Vol 44 (5) ◽  
pp. 1136-1141 ◽  
Author(s):  
Ben H. Nicolet ◽  
Alfred E. Jurist
Keyword(s):  
Acid Type ◽  
Benzilic Acid

Mechanism Study of a Benzilic Acid-Type Rearrangement1

1963 ◽  
Vol 28 (8) ◽  
pp. 2152-2153 ◽  
Author(s):  
Kenneth S. Warren ◽  
O. K. Neville ◽  
Edward C. Hendley
Keyword(s):  
Mechanism Study ◽  
Acid Type ◽  
Benzilic Acid

scholarly journals Formation of carboxylic acids during degradation of monosaccharides

2008 ◽  
Vol 26 (No. 2) ◽  
pp. 113-131 ◽  
Author(s):  
O. Novotný ◽  
K. Cejpek ◽  
J. Velíšek
Keyword(s):  
Free Radicals ◽  
Aqueous Solutions ◽  
Carboxylic Acids ◽  
Sodium Hydroxide Solution ◽  
Model Systems ◽  
Alkaline Solutions ◽  
Hydroxycarboxylic Acids ◽  
Acid Type ◽  
Cannizzaro Reaction ◽  
Benzilic Acid

The formation of low molecular carboxylic and hydroxycarboxylic acids as well as sugar and deoxysugar acids from monosaccharides (D-glucose, D-fructose, D-arabinose, DL-glyceraldehyde, and 1,3-dihydroxyacetone) was studied in three different model systems: aqueous and alkaline solutions of potassium peroxodisulfate (K<sub>2</sub>S<sub>2</sub>O<sub>8</sub>), and sodium hydroxide solution. In total, 3 low molecular carboxylic acids (formic, acetic and propionic), 24 hydroxycarboxylic acids, and 12 corresponding lactones were identified and quantified by GC/MS. Formic, acetic, and propionic acids were isolated by extraction with diethyl ether and directly analysed by GC/MS; hydroxycarboxylic acids and their lactones were monitored as their trimethylsilylated derivatives using the same method. Formic, acetic, L-lactic, glycollic, DL-2,4-dihydroxybutanoic acids and aldonic acids derived from the parent sugars were the most abundant compounds in all model systems. Within the models investigated, the yield of carboxylic acids and hydroxycarboxylic acids (together with their lactones) ranged between 9.3–22.2% (n/n) and between 3.6–116.9% (n/n), respectively. The amount of acids was significantly lower in aqueous solutions of K<sub>2</sub>S<sub>2</sub>O<sub>8</sub> than in the alkaline solutions. The data obtained indicate that lower carboxylic acids are formed by both subsequent reactions (oxidation and/or intramolecular Cannizzaro reaction) of the sugar fragmentation products and direct decomposition of some intermediates such as uloses or hydroperoxides derived from the parent sugars. The acids possessing the original sugar skeleton are formed as a result of sugar oxidation or benzilic acid type rearrangement of deoxyuloses. Lower acids may also be formed by a recombination of free radicals.

Enantioselective Total Synthesis of (+)-Stephadiamine through Bioinspired Aza-Benzilic Acid Type Rearrangement

2021 ◽  
Vol 143 (7) ◽  
pp. 2699-2704
Author(s):  
Minami Odagi ◽  
Taisei Matoba ◽  
Keisuke Hosoya ◽  
Kazuo Nagasawa
Keyword(s):  
Total Synthesis ◽  
Enantioselective Total Synthesis ◽  
Acid Type ◽  
Benzilic Acid

Nucleophilic 1,2-Shifts of Carboxamide Groups in the Benzil-Benzilic Acid Type Rearrangement of 4-Aryl-2,3-dioxobutyramides and of Quinisatine

1985 ◽  
Vol 68 (8) ◽  
pp. 2132-2139 ◽  
Author(s):  
Heike Gowal ◽  
Anita Spiess ◽  
Marc Ballenegger ◽  
Laurent Due ◽  
Hans Moll ◽  
...  
Keyword(s):  
Acid Type ◽  
Benzilic Acid

scholarly journals A computational study of base-catalyzed reactions of cyclic 1,2-diones: cyclobutane-1,2-dione

2013 ◽  
Vol 9 ◽  
pp. 594-601 ◽  
Author(s):  
Nargis Sultana ◽  
Walter M F Fabian
Keyword(s):  
Ab Initio ◽  
Density Functional ◽  
Computational Study ◽  
Free Energies ◽  
Reaction Paths ◽  
Acid Type ◽  
Benzilic Acid ◽  
Catalyzed Reactions

The reaction of cyclobutane-1,2-dione with hydroxide was studied by a variety of ab initio (MP2, SCS-MP2, CCSD(T), CEPA/1) and density functional (M06-2X) methods. Three possible reaction paths of the initially formed tetrahedral adduct leading to either 1-hydroxycyclopropane-1-carboxylate (benzilic acid type rearrangement, path A), α-oxobutanoate (path B) or γ-oxobutanoate (path C) were considered. Although the latter two products show similar or even more negative Gibbs free energies of reaction than calculated for the benzilic acid type rearrangement, the Gibbs free energies of activation are substantially higher. According to the calculations, the only feasible reaction appears to be the formation of 1-hydroxycyclopropane-1-carboxylate, which is corroborated by previous experimental observations.

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