56756-91-3Relevant articles and documents
Copper-mediated direct aryl C-H cyanation with azobisisobutyronitrile via a free-radical pathway
Xu, Hao,Liu, Peng-Tang,Li, Yun-Hui,Han, Fu-She
supporting information, p. 3354 - 3357 (2013/07/26)
An unprecedented protocol for the copper-mediated direct cyanation of aryl C-H by employing 2,2′-azobisisobutyronitrile (AIBN) as a free radical "CN" source is presented. The protocol not only provides a more efficient pathway for the synthesis of aryl nitriles in terms of the yields and the loading amount of copper salts but also, more importantly, represents a novel strategy for aryl C-H cyanation via a CN free-radical mechanism as compared to the CN anion-participating protocols often reported.
TRANSNITRILATION OF ACETONE CYANOHYDRIN WITH ACETIC ACID
Kobyakova, N. K.,Sivenkov, E. A.,Fomin, V. A.
, p. 2107 - 2111 (2007/10/02)
This work is dedicated to a search for new methods for obtaining methacrylic acid, namely, by transnitrilation of acetone cyanohydrin with acetic acid in the presence of various catalysts: chlorides of zinc, copper, and nickel.
NEW SYNTHETIC METHODS FOR 4-AMINO-2(5H)-FURANONES
Hiyama, Tamejiro,Oishi, Haruhito,Saimoto, Hiroyuki
, p. 2459 - 2462 (2007/10/02)
Two new efficient methods are disclosed for the synthesis of the title compounds: (1) base-promoted ring closure of 2-acyloxy alkanenitrile and (2) acid-mediated lactonization of t-butyl-4-alkoxy-3-amino-2-alkenoates.
Thermolytic reactions of esters. Part XIII. The effect of electron-attracting α-substituents in alkyl acetates
Louw, Robert,Tinkelenberg, Arie,Werner, Erik S. E.
, p. 519 - 522 (2007/10/02)
α-Alkylation of esters, e.g.AcO-iPr -> AcO-tBu, results in a large rate increase for β-elimination of acetic acid, indicating that in the transition state Cα is positively charged.Replacement of α-H by electron-attracting groups Z, such as COOMe, also enhances the rate of formation of alkene.Neither differences in product stability nor steric acceleration appear to play a significant role.A major factor is dipolar destabilization of starting compounds containing two electronegative groups, such as AcOCMeZ compared with AcO-tBu.The free energies of the transition states are found to parallel those of the fully ionized species, AcO(-) + R(+).At elevated temperatures, esters such as AcOCMe(CN)Ph will give rise to O-C bond homolysis rather than to molecular elimination of acetic acid.
Gas-Phase Pyrolysis Kinetics of 2-Substituted-2-Propyl Acetates. Effect of Substituents on the α-Carbon of Tertiary Acetates
Martin, Ignacio,Chuchani, Gabriel,Avila, Irama,Rotinov, Alexandra,Olmos, Rolando
, p. 9 - 11 (2007/10/02)
Three 2-substituted-2-propyl acetates undergo a homogeneous, first-order, unimolecular elimination in the gas phase at temperatures from 230 to 340 deg C and pressures from 56 to 210 mmHg.The rate constants are expressible by the Arrhenius equation: for 2,3,3-trimethyl-2-butyl acetate, log k (s-1) = (14.40 +/- 0.49) - (171.5 +/- 4.6) kJ mol-1 (2.303RT)-1; for α-acetoxyisobutyronitrile, log k (s-1) = (14.45 +/- 0.82) - (198.7 +/- 8.8) kJ mol-1 (2.303RT)-1; for methyl α-acetoxyisobutyrate, log k (s-1) = (12.53 +/- 0.32) - (176.1 +/- 3.6) kJ mol-1 (2.303RT)-1.The Taft correlation for the pyrolyses of tertiary esters with substituents on the α-carbon is projected and discussed.Many of these substituents enhance the elimination by steric accelaration.
