51570-52-6Relevant articles and documents
Radical and ionic mechanisms in rearrangements of o-tolyl aryl ethers and amines initiated by the Grubbs-stoltz reagent, et3SiH/KOtbu
Kolodziejczak, Krystian,Murphy, John A.,Stewart, Alexander J.,Tuttle, Tell
, (2021/12/04)
Rearrangements of o-tolyl aryl ethers, amines, and sulfides with the Grubbs-Stoltz reagent (Et3SiH + KOtBu) were recently announced, in which the ethers were converted to o-hydroxydiarylmethanes, while the (o-tol)(Ar)NH amines were transformed into dihydroacridines. Radical mechanisms were proposed, based on prior evidence for triethylsilyl radicals in this reagent system. A detailed computational investigation of the rearrangements of the aryl tolyl ethers now instead supports an anionic Truce-Smiles rearrangement, where the initial benzyl anion can be formed by either of two pathways: (i) direct deprotonation of the tolyl methyl group under basic conditions or (ii) electron transfer to an initially formed benzyl radical. By contrast, the rearrangements of o-tolyl aryl amines depend on the nature of the amine. Secondary amines undergo deprotonation of the N-H followed by a radical rearrangement, to form dihydroacridines, while tertiary amines form both dihydroacridines and diarylmethanes through radical and/or anionic pathways. Overall, this study highlights the competition between the reactive intermediates formed by the Et3SiH/KOtBu system.
Thermal reactions of N-Alkyl-2-benzylaniline and N-Alkyl-N′-phenyl-o- phenylenediamine: An unusual route to 2-phenylindole and 2-phenylbenzimidazole
Creencia, Evelyn Cuevas,Taguchi, Kei,Horaguchi, Takaaki
, p. 837 - 843 (2008/09/21)
(Chemical Equation Presented) Thermal cyclization reactions of N-alkyl-2-benzylaniline 1a-d and N-alkyl-N′-phenyl-o-phenylenediamine 2a-b were carried out expecting to get seven-membered heterocyclic compounds. However, the results show that aside from th
A SYNTHETIC EQUIVALENT FOR ORTHO-LITHIO-N-METHYLANILINE
Sisko, Joseph,Weinreb, Steven M.
, p. 1035 - 1042 (2007/10/02)
o-Bromo-N-methyl-N-n-propoxyaniline undergoes halogen-metal exchange with butyllithium and the resulting lithio species reacts cleanly with a variety of electrophiles.The N-O bond of these products can be reduced with Raney nickel to afford ortho-substituted-N-methylanilines.
MOLECULAR REARRANGEMENTS, XVIII. PHOTOLYSIS OF N-ALKYL-ARYLAMINES
Aly, Morsy M.,Badr, Mahmoud Zarif A.,Fahmy, Attiat M.,Mahgoub, Safaa A.
, p. 15 - 22 (2007/10/02)
The direct photolysis of N-benzyl-N-methyl-aniline in isopropanol at 25 deg C for 15 hours in air gives benzaldehyde, toluene, bibenzyl, N-methylaniline and a mixture of o- and p-benzyl-N-methylaniline.Analogous products are also obtained from the photolysis of N-α- or -β-phenethyl-N-methyl-aniline in addition to trans-2,3-diphenylbutene-2 and 9,10-dimethyl-phenanthrene.The results are interpreted in terms of an intramolecular free radical mechanism starting by homolysis of the N-aralkyl bond into N-methyl-anilino and aralkyl free radicals that subsequently contribute to the formation of the identified products.
Recyclization of 2-(2-Phenylethyl)pyridinium Salts
Yudin, L. G.,Rumyantsev, A. N.,Sagitullin, R. S.,Kost, A. N.
, p. 57 - 59 (2007/10/02)
Under the influence of aqueous solutions of alkylammonium sulfites 2-(2-phenylethyl)pyridinium salts undergo recyclization to 2-benzyl-N-alkylanilines.The effect of structural factors on the transamination, which takes place when a reagent with an alkyl g