- Scrabbling around in Synthetic Nuances Managing Sodium Compounds: Bisphenol/Bisnaphthol Synthesis by Hydroxyl Group Masking
-
A unique method of bisphenol/bisnaphthol synthesis is being proposed, serendipitously discovered in the course of the careful analysis of an aminophenol methylation reaction. The insightful exploration of the synthesis of N- or O-methylated species, originating from functionalized phenols obtained by a conventional strategy, provided the opportunity to discover an unexpected reaction pathway yielding various bisphenols. Sodium complexes were found to be crucial intermediates in the synthetic scenario. Their formation, which is usually an imperceptive step, was substantial for the productive outcome of functional group protection. Thorough exploration revealed an essential structural motif of aminophenolate, necessary for the successful outcome of the reaction, and also enabled establishing the limitations of the new method. The work demonstrated that a slight change in the perspective and close inspection of the synthetic nuances can answer the important question concerning what a specific target-oriented synthesis strategy is lacking.
- Ejfler, Jolanta,J?drzkiewicz, Dawid,Marsza?ek-Harych, Aleksandra,Trybu?a, Danuta
-
-
- Oxidative ortho-amino-methylation of phenols via C-H and C-C bond cleavage
-
Initiated by CCl3Br, phenols undergo efficient ortho-selective oxidative cross dehydrogenative coupling (CDC) with trimethylamine. When tetramethylethylenediamine (TMEDA) is used instead of trimethylamine, oxidative carbon-carbon activation coupling (CAC) could occur to give the same salicylamines together with CDC by-products. These reactions are accelerated by a gold salt.
- Sun, Wenbo,Lin, Huacan,Zhou, Wenyu,Li, Zigang
-
p. 7491 - 7494
(2014/02/14)
-
- Synthesis and study of the antiradical activity of substituted hydroxybenzylamines and their hydrogen chloride salts
-
Different alkylated hydroxybenzylamines and their hydrogen chloride salts were synthesized. The rate constants of their reactions with peroxide radicals k1 and the stoichiometric factors of inhibition f were measured in the initiated oxidation of cumene and methyl oleate. Copyright
- Dyubchenko,Nikulina,Terakh,Kandalintseva,Markov,Grigor'Ev,Prosenko
-
p. 330 - 334
(2007/10/03)
-
- New opportunities for duff reaction
-
Reaction of 2,4-di-tert-butylphenol with urotropin in conditions of Duff reaction takes an abnormal route and instead of the expected di-tert-butylsalicylaldehyde provides a mixture of N-substituted 3,5-di-tert-butyl-2-hydroxybenzylamines and redox conjugate benzoxazines containing mostly 6,8-di-tert-butyl-3-(3,5-di-tert-butyl-2-hydroxybenzyl)-2H-3, 4-dihydrobenz[e][1,3]oxazine. A solvolysis of an individual benzoxazine in the system HO(CH2)2OH-H2O-HCl affords di(3,5-di-tert-butyl-2-hydroxybenzyl)amine, and in AcOH 3,5-di-tert- butylsalicilaldehyde. A mechanism of Duff reaction was suggested involving the formation of a benzoxazine intermediate. 2005 Pleiades Publishing, Inc.
- Belostotskaya,Komissarova,Prokof'Eva,Kurkovskaya,Vol'Eva
-
p. 703 - 706
(2007/10/03)
-
- Oxidation of 2-dialkylaminomethyl-4,6-di-tert-butylphenols
-
Oxidative transformations of 2-dialkylaminomethyl-4,6-di-tert-butylphenols depend on the nature of the oxidant, the character of the substituents at the nitrogen atom, and the medium. A mechanism of the oxidation of these compounds is suggested. The molecular structure of the compound obtained as a result of oxidative trimerization of 2-dimethylaminomethyl-4,6-di-tert-butylphenol was established by X-ray structural analysis.
- Belostotskaya,Vol'eva,Komissarova,Dekaprilevich,Khrustalev,Karmilov,Ershov
-
p. 1272 - 1280
(2007/10/03)
-
- Heterocyclic Spirocyclohexadienones from Substituted Phenols
-
Mannich bases were prepared from substituted phenols with aliphatic amines and formaldehyde.Amine exchange with N-methyl-2-naphthylamine followed by a Hofmann Martius rearrangement gave rise to o,o'-amino-hydroxy-diphenylmethane derivatives.Under cyclization conditions some of these compounds produced spirocyclohexadienones, which are the ipso analogs to the hypothetic intermediates postulated in the aminomethylation mechanism of phenols. - Keywords: Mannich Reaction; Phenol Dienone Tautomerism; Hofmann Martius Rearrangement
- Moehrle, H.,Schake, D.
-
p. 1859 - 1868
(2007/10/03)
-