A New Chemical Reaction with the Nitrosyl Radical NOH

Baudisch, Oskar

doi:10.1126/science.92.2389.336

Cited by 32 publications

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“…The order of reagent addition in Baudisch’s reported reactions (Scheme 1) implies he believed the mechanism proceeded through nitrosation, followed by secondary phenolation. Baudisch stated that the ‘nitrosyl radical’ could be generated in 3 different ways: (1) via oxidation of NH 2 OH with Cu(II), (2) reduction of HNO 2 with Cu(I), and (3) release from benzenesulfohydroxamic acid by copper ions and H 2 O 2 [20]. While no radicals of a type corresponding to NOH are known to exist, the nitric oxide (·N=O) radical can be observed under nitrosation conditions, but is rapidly oxidised in the presence of oxygen to the active nitrosation species (nitrosonium, NO + ) and can itself only form C -nitroso compounds by reacting with a carbon centred radical under an inert atmosphere [29].…”

Section: History and Development Of The Complex Formationmentioning

confidence: 99%

“…As discussed, the title compounds have found uses in the determination of metal ion concentrations, epoxidation and redox catalysts, as well as being good reagents for the synthesis of four distinct heterocyclic systems from simple aromatic starting materials. Despite its ‘amazingly simple’ [20] functionalisation of aromatic (particularly phenolic) substrates and well-defined regiochemistry, these processes do not appear to have been investigated further, at the time of writing. This may be attributed to a lack of general understanding in the formation of the copper complexes and their nitrosophenol ligands.…”

Section: Future Applications Of Copper-nitrosophenolato Complexesmentioning

confidence: 99%

“…The next big development in the preparation of metal-nitrosophenolato compounds was realized by the Austrian chemist, Oskar Baudisch, during the early part of last century [20,21]. The developed synthesis represents a very interesting and novel functionalisation of an aromatic ring (such as benzene), where a hydroxy and nitroso moiety are added with defined ortho -regioselectivity.…”

Section: Introduction To Metal-nitrosophenolato Complexesmentioning

confidence: 99%

“…While not being a commonly encountered or formally recognised named reaction, the term ‘Baudisch reaction’ has become synonymous with specific processes that synthesise metal-nitrosophenolato compounds. In the original reported work, Baudisch employed a range of copper(I) and (II) sources and ‘Merck’s Superoxol’ (historic, commercial name for aqueous hydrogen peroxide) with benzene [20,21]. In addition, either hydroxylamine or a nitrous acid source was further supplied to introduce the corresponding nitroso moiety, hence forming complexes as the end product (Scheme 1 and Scheme 2).…”

Section: Introduction To Metal-nitrosophenolato Complexesmentioning

confidence: 99%

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The Synthesis and Utility of Metal-Nitrosophenolato Compounds—Highlighting the Baudisch Reaction

2019

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The syntheses of the title compounds demonstrate a privileged introduction of a nitroso (and a hydroxyl via the Baudisch reaction) group to an aromatic ring. These complexes first appeared in the literature as early as 1939, and a range of applications has subsequently been published. However, optimisations of the preparative sequences were not considered, and as such, the reactions have seldom been utilised in recent years; indeed, there remains confusion in the literature as to how such complexes form. In this review, we aim to demystify the misunderstanding surrounding these remarkable complexes and consider their renewed application in the 21st century.

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Section: History and Development Of The Complex Formationmentioning

confidence: 99%

Section: Future Applications Of Copper-nitrosophenolato Complexesmentioning

confidence: 99%

Section: Introduction To Metal-nitrosophenolato Complexesmentioning

confidence: 99%

Section: Introduction To Metal-nitrosophenolato Complexesmentioning

confidence: 99%

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The Synthesis and Utility of Metal-Nitrosophenolato Compounds—Highlighting the Baudisch Reaction

2019

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“…An intriguing method for preparing phenolic nitroso compounds was dis covered by Baudisch [95]. Interestingly enough, the product mixture from the reaction appears to be primarily the ortho-substituted phenol, a class of com pounds of which very few examples seem to have been described.…”

Section: G the Baudisch Reactionmentioning

confidence: 99%

C-Nitroso Compounds

1971

Organic Chemistry: A Series of Monographs

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The Importance of Trace Elements in Biologic Activity

Baudisch¹

1943

JAMA

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of the infection and his temperature dropped to normal within three days. The lesions on his skin healed slowly, however.Because the patient was going into a combat zone, it was thought important to establish his sensitivity to sulfathiazole. Accordingly, six weeks later 5 per cent sulfathiazole ointment was applied to the back of one hand and a similar amount of 5 per cent boric acid ointment to the back of the other as a control. A few small vesicles appeared tinder the sulfathiazole ointment within twenty-four hours. The next day the patient was given sulfathiazole by mouth, 0.5 Gm. for three doses. During the night his face became flushed, and by morning the cutaneous areas of his face, ears and neck were red, weeping and crusted, exactly as they had been on admission. These tests left little doubt that the condition of the patient's skin was the result of sensitivity to sulfathiazole.Ten weeks after admission he was sent back to his unit. The first morning after his return, his face, ears and neck were again covered by a red vesicular eruption, with oozing and crusting. His hands were not involved this time. The explanation for this flare-up was obscure, though it seemed probable that some sulfathiazole ointment had got onto his blankets at the time it was first applied to his face for impetigo and that contact with the ointment on these blankets had caused this latest flare-up. On final discharge he was issued new blankets.When seen one month later he had suffered no recurrences.Because he reacted so violently to sulfathiazole, a notice was attached to his identification tags stating that he was extremely sensitive to this drug. C0MMENT The distribution of the cutaneous lesions in this case was so definitely limited to the areas exposed to the sun that it was thought there must have been a relationship between the reaction of these portions of the skin to sulfathiazole and the effect of sunlight on the same areas. Photosensitivity of the skin and eyes after the taking of sulfathiazole has been mentioned in the literature.2 In this case the dermatitis was not precipitated by exposure to sunlight but by the sulfathiazole itself. The first s'ulfathiazole given to the patient was in an ointment applied to the skin. The patient was ambulatory at this time and thus exposed to strong sunlight most of every day. The dermatitis appeared ten days later, shortly after the administration of the drug by mouth. Therefore it seems probable that sunlight conditioned the skin to a sensitivity to sulfathiazole but did not itself cause the reaction. Sensitivity in this case was undoubtedly induced by the application of sulfathiazole ointment when the patient was first treated for impetigo contagiosa. He had never taken the drug before. Livingood and Pillsbury,3 Cohen, Thomas and Kalisch,4 and Weiner5 have recently reported similar cases in which sensitivity to sulfathiazole was produced by topical application of that drug. These illustrate the danger of using sulfathiazole ointments without due regard for the onset of reac...

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A New Chemical Reaction with the Nitrosyl Radical NOH

Cited by 32 publications

References 2 publications

The Synthesis and Utility of Metal-Nitrosophenolato Compounds—Highlighting the Baudisch Reaction

The Synthesis and Utility of Metal-Nitrosophenolato Compounds—Highlighting the Baudisch Reaction

C-Nitroso Compounds

The Importance of Trace Elements in Biologic Activity

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