59239-07-5Relevant academic research and scientific papers
Safety assessment for the scale-up of an oxime reduction with melted sodium in standard pilot-plant equipment
Breitenmoser, Roland A.,Fink, Thomas,Abele, Stefan
, p. 2008 - 2014 (2013/03/13)
A pilot-plant process is described for the reduction of 2-allyl cyclohexanone oxime with melted sodium in xylenes, toluene, and 4-methyl-2-pentanol. The trans/cis ratio was 3-4:1. Safety data are presented from a range of thermokinetic experiments (heat flow calorimetry, differential scanning calorimetry, and accelerating rate calorimetry). The process has been designed and developed to enable an expedient and safe scale-up in a standard enameled 100-L steel reactor and has been reproduced six times on 209 mol scale (each 4.8 kg sodium). Crystallization of the product 2-allyl cyclohexylamine with oxalic acid from the reaction mixture in tert-butyl methyl ether successfully avoided the yield losses associated with the isolation of the volatile free 2-allyl cyclohexylamine.
The discovery of potent, selective, and orally bioavailable PDE9 inhibitors as potential hypoglycemic agents
DeNinno, Michael P.,Andrews, Melissa,Bell, Andrew S.,Chen, Yue,Eller-Zarbo, Cynthia,Eshelby, Nan,Etienne, John B.,Moore, Dianna E.,Palmer, Michael J.,Visser, Michael S.,Yu, Li J.,Zavadoski, William J.,Michael Gibbs
supporting information; experimental part, p. 2537 - 2541 (2009/12/25)
Starting from a non-selective pyrazolo-pyrimidone lead, the sequential use of parallel medicinal chemistry and directed synthesis led to the discovery of potent, highly selective, and orally bioavailable PDE9 inhibitors. The availability of these tools allowed for a thorough evaluation of the therapeutic potential of PDE9 inhibition.
Dioxime oxalates; new iminyl radical precursors for syntheses of N-heterocycles
Portela-Cubillo, Fernando,Lymer, James,Scanlan, Eoin M.,Scott, Jackie S.,Walton, John C.
supporting information; experimental part, p. 11908 - 11916 (2009/04/06)
Symmetrical and unsymmetrical dioxime oxalates were prepared by treatment of oximes with oxalyl chloride. UV photolysis of these precursors was found to be an atom-efficient way of generating iminyl radicals. The process was most efficient for dioxime oxalates having aryl substituents attached to their C{double bond, long}N bonds. The method was useful for EPR spectroscopic study of iminyl and iminoxyl radicals. Photolyses in toluene solution, of dioxime oxalates containing alkenyl acceptor groups, yielded unsaturated iminyl radicals that ring closed to afford 3,4-dihydro-2H-pyrroles in good yields. Dioxime oxalates with biphenyl substituents also released iminyl radicals that ring closed onto the aromatic acceptor groups and, in acetonitrile solution, this approach provided a useful and atom-efficient method of making substituted phenanthridines.
Stereoselective electrophile-induced mono- and bis-cyclisation-fragmentation reactions of alkenyl oxime O-allyl and O-benzyl ethers. Synthesis of dihydropinidine
Ali Dondas,Grigg, Ronald,Markandu, Jasothara,Perrior, Trevor,Suzuki, Tekka,Thibault, Sylvie,Anthony Thomas,Thornton-Pett, Mark
, p. 161 - 173 (2007/10/03)
Phenylseleny bromide-induced cyclisation of γ- and δ-unsaturated aldoxime and ketoxime O-allyl and O-benzyl ethers is followed by a slow fragmentation of the resultant oxyiminium ions furnishing cyclic iminium salts which are readily reduced to pyrrolidines, piperidines or tetrahydroisoquinolines by sodium borohydride; dialkenyl oximes yield indolizidines and quinolizidines by an analogous sequence terminating in a mercury(II)-induced cyclisation.
Iminyl, Amidyl, and Carbamyl Radicals from O-Benzoyl Oximes and O-Benzoyl Hydroxamic Acid Derivatives.
Boivin, Jean,Callier-Dublanchet, Anne-Claude,Quiclet-Sire, Beatrice,Schiano, Anne-Marie,Zard, Samir Z.
, p. 6517 - 6528 (2007/10/02)
Oxime benzoates and O-benzoyl hydroxamic acid derivatives react with tributylstannane in the presence of AIBN to give iminyl, amidyl, and carbamyl radicals which can be captured by an internal olefin.
N-hydroxypyridine-2-thione carbamates. V. Syntheses of alkaloid skeletons by aminium cation radical cyclizations
Newcomb, Martin,Marquardt, Donald J.,Deeb, Thomas M.
, p. 2329 - 2344 (2007/10/02)
The title radical precursors (PTOC carbamates) were employed as sources of a variety of 5,6-unsaturated aminium cation radicals. 5-Exo radical cyclization followed by trapping by t-BuSH or the PTOC carbamate gave a variety of aklaloid skeletons, typically in good to excellent yields, including pyrrolidines, perhydroindoles, pyrrolizidines, tropanes, 9-azabicyclo[4.2.1]nonanes, 6-azabicyclo [3.2.1]octanes. 6-Exo and 7-endo cyclizations competed in a 6,7-unsaturated system.
SYNTHESIS OF MONOCYCLIC ANALOGUES OF A POTENT THROMBOXANE RECEPTOR ANTAGONIST, (+/-)-(5Z)-7-BICYCLOHEPT-2-EXO-YL>HEPTENOIC ACID (S-145)
Kawada, Kenji,Tsushima, Tadahiko
, p. 573 - 578 (2007/10/02)
Several monocyclic analogues of the potent thromboxane-A2 receptor antagonist S-145, i.e. cyclohexane, cyclopentane, tetrahydrofuran, and pyrrolidine, as well as the biclooctane one were synthesized using allylation via oxime dianion and the Barton's method for oxime reduction in the key steps.
