Reaction of Stabilised Phosphorus Ylides with Nitrogen Dioxide

Aitken, R. A.; Karodia, Nazira

doi:10.1002/(sici)1099-0690(199901)1999:1<251::aid-ejoc251>3.0.co;2-m

Cited by 6 publications

(4 citation statements)

References 18 publications

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“…Solvents were dried by standard methods and purified by distillation before use. All oxidation products 11a , 11b − d , 11f , 11g , 13a − c , f 32 13d , 13e , 13g , 15a , and 15b are known and gave the reported spectral data.…”

Section: Methodsmentioning

confidence: 79%

Chemoselective Electrophilic Oxidation of Heteroatoms by Hydroperoxy Sultams

Gelalcha

Schulze

2002

J. Org. Chem.

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The synthesis of novel hydroperoxy sultams 1b-d and their potential as renewable chemoselective electrophilic oxidants for a wide range of nitrogen, sulfur, and phosphorus heteroatoms in nonaqueous media is described. Reactions of 1b,c with secondary amines 10f,g yielded the hydroxysultams 2b,c and nitrone 11f or radical 11g depending on the substrate and stoichiometry, while tertiary amines 10a-d gave amine oxides 11a-d. Compounds 1c,d oxidized various thioethers 12a-g to sulfoxides 13a-g smoothly that were isolated by chromatography in nearly quantitative yields. 1c was regenerated from 2c by treatment of the latter with acidified H2O2. Kinetic studies of the reaction of 1c with 1,4-thioxane 12f suggest that the reaction follows the second-order kinetics, first order in substrate and first order in oxidant with the second-order rate constant several orders of magnitude larger than that of the corresponding reaction with hydrogen peroxide and tert-butyl hydroperoxide without the need for any acid or heavy metal catalysts. The phosphines 14a,b were also oxidized by 1c to the respective phosphine oxides 15a,b readily in quantitative yields. The reactions may be conducted at ambient temperature or lower and appear to proceed via a nonradical mechanism. Reactions are sensitive to steric as well as electronic factors.

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Section: Methodsmentioning

confidence: 79%

Chemoselective Electrophilic Oxidation of Heteroatoms by Hydroperoxy Sultams

Gelalcha

Schulze

2002

J. Org. Chem.

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“…The analysis showed the presence of the nitrocompounds: 16, 18 – 28 . The products were analysed by GC/MS, 1 H NMR and cyclic voltammetry and identified by comparison of their spectroscopic behaviour with the reported in the literature in each case ( 16 ,33 18 ,34 23 ,35 24 ,36 25 ,37 26 ,38 28 ,39 20 40). Compounds 19 and 21 gave the same voltammetric behaviour as 20 .…”

Section: Methodsmentioning

confidence: 99%

“…[22] 2,4-Dinitro-1-naphthalenamine (28): Table 1, Entry 6. MS (70 eV): m/z (%) ϭ 233 (100) [M] ϩ , 234 (12), 203 (24), 157 (19), 141 (42), 140 (42), 129 (33), 128 (10), 114 (57), 113 (22), 88 (12), 63 (15).…”

Section: Full Papermentioning

confidence: 99%

Nucleophilic Aromatic Substitution of Hydrogen: A Novel Electrochemical Approach to the Cyanation of Nitroarenes

2001

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The nucleophilic aromatic substitution of hydrogen through electrochemical oxidation of the intermediate sigma complexes (Meisenheimer complexes) in simple nitroaromatic compounds is reported for the first time. The studies have been carried out with hydride and cyanide anions as the nucleophiles using cyclic voltammetry (CV) and preparative electrolysis. The cyclic voltammetry experiments allow for the detection and characterization of the sigma complexes and led us to a proposal for the mechanism of the oxidation step. Furthermore, the power of the CV technique in the analysis of the reaction mixture throughout the whole chemical and electrochemical process is described.

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“…88 Tricarbonyl compounds, viz., esters of 2,3-dioxo carboxylic acids 42, were obtained by oxidation of acylated alkylidene-phosphoranes 18 with ozone, 90 magnesium monoperoxyphthalate 91 or dimethyldioxirane. 92 It is unlikely that nitrogen dioxide tested as an oxidant for alkylidenephosphoranes 93,94 will find preparative use because even small variations in the phosphorane structure result in different product mixtures.…”

Section: Ch C(o)armentioning

confidence: 99%