- Utility of Nitrogen Extrusion of Azido Complexes for the Synthesis of Nitriles, Benzoxazoles, and Benzisoxazoles
-
The utility of the nitrogen extrusion reaction of azido complexes, generated in situ from the corresponding aldehydes or ketones with TMSN3 in the presence of ZrCl4 or TfOH, has been described. These azido complexes could undergo three different pathways, depending on the substrates. First, azido methanolate complexes or imine diazonium ions could lead to benzisoxazole products via an intramolecular nucleophilic substitution. Second, imine diazonium ions could also undergo either the elimination of proton to provide nitrile products in good to excellent yields or an aryl migration, followed by an intramolecular nucleophilic addition, to give benzoxazole products in good yields.
- Nimnual, Phongprapan,Tummatorn, Jumreang,Thongsornkleeb, Charnsak,Ruchirawat, Somsak
-
p. 8657 - 8667
(2015/09/15)
-
- Facile one-pot transformation of phenols into o-cyanophenols
-
The treatment of phenols with paraformaldehyde in the presence of MgCl2 and Et3N in THF at 80 C, followed by reaction with molecular iodine and aq. ammonia at room temperature provided the corresponding o-cyanophenols in moderate to good yields. The present reaction is a one-pot transformation of phenols into o-cyanophenols using much less expensive reagents than are typically used; the reaction is free of both transition-metals and cyanide. The utility of this reaction was highlighted during our preparation of Febuxostat from p-bromophenol.
- Nakai, Yuhta,Moriyama, Katsuhiko,Togo, Hideo
-
p. 6077 - 6083
(2015/03/30)
-
- NON-METALLOCENE CATALYSTS HAVING TETRAZOL GROUP FOR OLEFIN POLYMERIZATION AND POLYMERIZING METHOD OF OLEFIN USING THE SAME
-
The present invention provides a non-metallocene transition metal compound that is easily produced, includes a tetrazol group having the high polymerization activity and high temperature stability in the polymerization of olefins, and a catalytic composit
- -
-
-
- A one-pot synthesis of substituted salicylnitriles
-
Phenols were converted to salicylaldehydes with paraformaldehyde, MgCl2-Et3N in THF, and subsequent treatment with aqueous ammonia gave the corresponding imines which were oxidized with IBX to the desired salicylnitriles. The sequence of reactions was conveniently carried out as a one-pot procedure under mild conditions.
- Anwar, Hany F.,Hansen, Trond Vidar
-
p. 4443 - 4445
(2008/12/21)
-
- Urotropin synthesis of 3,5-di-tert-butylsalicylic acid derivatives
-
The stability of 3,5-di-tert-butylsalicylic aldehyde against oxidation is due to autoinhibiting of the chain process. However its oxidation into 3,5-di-tert-butylsalicylic acid was performed at the use of acetyl protection of the hydroxy group. In reaction of 6-bromo-2,4-di-tert-butylphenol with urotropin the formation was discovered of 3,5-di-tert-butylsalicylic acid, its nitrile and amide.
- Vol'eva,Belostotskaya,Komissarova,Kurkovskaya,Pleshakova,Prokofeva
-
p. 1488 - 1491
(2008/09/16)
-
- A practical route to regiospecifically substituted (R)- and (S)-oxazolylphenols
-
New, diversely substituted phenolic oxazolines 14a-d and 15a-d were prepared by two complementary routes A and B, starting from salicylic derivatives 4-7 and various enantiomerically pure 1,2-amino alcohols 13a-d. In route A, the 1,2amino alcohols 13a-d were directly condensed with the salicylic acids 5 and 7, using the Appel reaction, whereas in route B the amino alcohols 13b-d were treated with the 2-hydroxybenzonitriles 4 and 6, under Witte-Seeliger conditions. The latter route was advantageous for L-valinol 13b and L-tert-leucinol 13c, while route A was the method of choice for the new, sterically demanding amino alcohol 13a, prepared from D- and L-serine. The nitro group in the salicylic derivatives 5 and 6 was introduced by means of a regiospecific ipso substitution of a tert-butyl group by nitric acid. The structure of the nitro product 5 was unambiguously assigned by NOE spectroscopy on the basis of the recently developed DPFGSE-ROE pulse sequence.
- Scheurer, Andreas,Mosset, Paul,Bauer, Walter,Saalfrank, Rolf W.
-
p. 3067 - 3074
(2007/10/03)
-
- Oxygenation of tert-Butylphenols with an Unsaturated Side Chain
-
Base- and Co(Salpr)-promoted oxygenations of title compounds have been investigated with a view to obtaining further details concerning controlling factors in regioselective O2 incorporation into phenols.In the oxygenation of 4-alkenyl-2,6-di-tert-butyl- and 2-alkenyl-4,6-di-tert-butylphenols (1 and 12), the reactivity of the substrates and regioselectivity in the O2 incorporation may be interpreted in terms of electronic and steric effects of the alkenyl group as well as association effect of the countercation K+ on the transition-state 26 involving a charge transfer from the substrate anion to O2.With 4-alkynyl-2,6-di-tert-butylphenols (21), dioxygen was incorporated exclusively into the ortho position only when the phenolate anion was associated with K+.On the contrary, in the oxygenation of 1 and 12 with Co(Salpr), O2 was incorporated exclusively into the alkynyl side chain, regardless of the nature of the substituent, whereas with 21, O2 incorporation was distributed to both the ortho and the alkenyl side chain.The substituent-dependent regioselectivity in the oxygenation of phenols with Co(Salpr) is because the reactive phenolate-COIII species undergo homolysis to form phenoxy radical-CoII species reversibly, whose oxygenations compete with each other.When the oxygenation of the anionic species predominates, O2 is incorporated into the ortho position, whereas with the radical species the para and side chain oxydations predominate.
- Nishinaga, Akira,Iwasaki, Hitoshi,Shimizu, Tadashi,Toyoda, Yasushi,Matsuura, Teru
-
p. 2257 - 2266
(2007/10/02)
-