- Nitroethane in polyphosphoric acid: A new reagent for acetamidation and amination of aromatic compounds
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A new method of acetamidation of aromatic compounds based on their reaction with nitroethane in polyphosphoric acid has been developed. Upon the hydrolysis of acetamides during the reaction mixture workup, the corresponding amines can be obtained. Georg Thieme Verlag Stuttgart New York.
- Aksenov, Alexander V.,Aksenov, Nicolai A.,Nadein, Oleg N.,Aksenova, Inna V.
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experimental part
p. 2628 - 2630
(2010/12/18)
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- The Multiplicity of Reaction Pathways of Cation Radicals Derived from Anthracene Derivatives in Solvents of Low Nucleophilicity
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In acetonitrile containing trifluoroacetic acid, the cation radicals of 9-substituted anthracenes either dimerize (a), react with acetonitrile (b) or react with trifluoroacetic acid (c) depending on the nature of 9-substituent.All three reaction pathways were demonstrated during kinetic and product studies.Pathway (a) is of importance when the intermediate dimeric dication, which has both the substituents and the charges in the 10,10'-positions, is stabilized by virtue of the electron donating properties of the substituent.This pathway was observed exclusively for 9-phenyl and 9-methoxy and to a lesser extent when the substituent was 9-chloro.Pathway (c) predominantes when the 9-substituent destabilizes the positive charge as is the case for 9-nitro.The intermediate case (b) is the predominant reaction pathway for the anthracene cation radical and is also observed when the substituent is 9-methyl.The feature of pathway (b) differs most from (c) is that the intermediate cation radical-nucleophile adduct in (b) is charged and if the substituent is electron withdrawing the oxidation of this species by cation radical is less favorable so that trifluoroacetylation (c) can then effectively complete.All three of the reaction pathways were observed to give rise to complex rate laws.
- Hammerich, Ole,Parker. Vernon D.
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p. 519 - 528
(2007/10/02)
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- Etudes sur les meso-aminoanthracenes. VIII. L'amino-10 anthracenecarboxylate-9 de methyle. Oxydation et diazotation
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Methyl 10-amino-9-anthracenecarboxylate, the preparation of which is described, hardly autoxydizes, and the corresponding 10-imino-9-hydroperoxyde is obtained more easily by photosensitized oxygenation.On the other hand, it is fairly sensitive to electron-abstracting oxydants like PbO2, giving its unsymmetrical dehydrodimer.It cannot be diazotized by the usual nitrosating agents, such as isoamyl nitrite, which lead mostly to 10-methoxycarbonyl-10-nitro-9-anthron.With nitric oxyde in ether, diazotization is also limited owing to an extensive competing reduction to methyl 9-anthroate.Yet, it is shown that a treatment of the amine in ethereal solution by N2O4 gives the corresponding diazonium salts in reasonable yields, the production of nitro-anthron being restricted in these conditions.
- Rigaudy, Jean,Ahond, Monique,Barcelo, Jacques,Valt-Taphanel, Marie-Helene
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p. 223 - 230
(2007/10/02)
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