Abstract:The radical scavenging properties of nitroso compounds were discovered accidentally during investigations of photochemical nitrosation of hydrocarbons with alkyl nitrites. Depending on the nature of substrates and nitrosating agent, various nitroxides can be generated. Identification of these nitroxides by their esr spectra has triggered the development of the spin-trapping technique which has been useful in the elucidation of many organic radical reaction mechanisms. Recent studies have shown that the behavio… Show more
“…Gingras and Waters observed this reaction when nitrosobenzene was reacted with an excess of AIBN (Scheme ). That this reaction pathway is general was assessed by spin-trapping experiments with different nitroso compounds. ,− 30 …”
Section: Nitroso Compoundsmentioning
confidence: 99%
“…That this reaction pathway is general was assessed by spin-trapping experiments with different nitroso compounds. 113,[174][175][176][177][178][179][180][181][182] Some nitroso compounds are commercially available or quite easily prepared 179,[183][184][185] by oxidation of amines and hydroxylamines, by reduction of nitro compounds, 179,[183][184][185][186] from alkyl nitrites, 184,185,187 and by free radical addition onto nitric oxides. 173,177,[188][189][190][191][192] For more details, the reader is referred to a recent review by Gowenlock and Richter-Addo.…”
Section: Reaction Of C-nitroso Compounds With Free Radicalsmentioning
Introduction 1104 2. Common Radical Synthesis of Alkoxyamines Active in NMP 1106 3. Nitrones: Precursors of Nitroxides for the Synthesis of Alkoxyamines and in-Situ NMP 1107 3.1. Nitrones as Precursors of Nitroxides 1107 3.2. Contributions of Nitrones to the in-Situ NMP 1107 3.3. Cyclic Oxazolidine as Initiator and Regulator for the Radical Polymerization of Vinyl Monomers 1111 3.4. Advantages and Drawbacks of the Nitrone Systems 1112 4. Nitroso Compounds 1112 4.1. Reaction of C-Nitroso Compounds with Free Radicals 1112 4.2. Use of C-Nitroso Compounds in Controlled Radical Polymerization 1113 4.3. Limitations of C-Nitroso Compounds 1116 5. Sodium Nitrite and NO/NO 2 Mixtures for the in-Situ NMP 1116 5.1. Preliminary Results and Mechanistic Considerations 1116 5.2. Controlled Radical Polymerization of Alkyl Methacrylates in the Presence of the in-Situ-Formed R-Nitro-ω-nitroso Adducts 1117 5.3. NO/NO 2 Mixtures: An Alternative Way to the Nitroso Compounds as Precursors of Nitroxides 1118 5.4. Advantages and Limitations of the Sodium Nitrite and NO/NO 2 Systems 1118 6. Hindered Secondary Amines and the in-Situ NMP 1118 6.1. Oxidation of Secondary Amines into Nitroxides 1118 6.2. One-Pot Processes for the Preparation of Alkoxyamines Active in NMP 1118 6.3. In-Situ NMP Using Hindered Secondary Amines and Oligomeric Secondary Amines 1120 6.4. Advantages and Limitations 1120 7. Hydroxylamines and the in-Situ NMP 1120 7.1. Oxidation of Hydroxylamines into Nitroxides 1120 7.2. Hydroxylamines and the in-Situ NMP 1120 7.3. High Molecular Weight Hydroxylamines for the Polymerization of Vinyl Monomers and Synthesis of Block Copolymers 1122 7.4. Advantages and Limitations 1122 8. Conclusions 1122 9. Acknowledgments 1123 10. References 1123
“…Gingras and Waters observed this reaction when nitrosobenzene was reacted with an excess of AIBN (Scheme ). That this reaction pathway is general was assessed by spin-trapping experiments with different nitroso compounds. ,− 30 …”
Section: Nitroso Compoundsmentioning
confidence: 99%
“…That this reaction pathway is general was assessed by spin-trapping experiments with different nitroso compounds. 113,[174][175][176][177][178][179][180][181][182] Some nitroso compounds are commercially available or quite easily prepared 179,[183][184][185] by oxidation of amines and hydroxylamines, by reduction of nitro compounds, 179,[183][184][185][186] from alkyl nitrites, 184,185,187 and by free radical addition onto nitric oxides. 173,177,[188][189][190][191][192] For more details, the reader is referred to a recent review by Gowenlock and Richter-Addo.…”
Section: Reaction Of C-nitroso Compounds With Free Radicalsmentioning
Introduction 1104 2. Common Radical Synthesis of Alkoxyamines Active in NMP 1106 3. Nitrones: Precursors of Nitroxides for the Synthesis of Alkoxyamines and in-Situ NMP 1107 3.1. Nitrones as Precursors of Nitroxides 1107 3.2. Contributions of Nitrones to the in-Situ NMP 1107 3.3. Cyclic Oxazolidine as Initiator and Regulator for the Radical Polymerization of Vinyl Monomers 1111 3.4. Advantages and Drawbacks of the Nitrone Systems 1112 4. Nitroso Compounds 1112 4.1. Reaction of C-Nitroso Compounds with Free Radicals 1112 4.2. Use of C-Nitroso Compounds in Controlled Radical Polymerization 1113 4.3. Limitations of C-Nitroso Compounds 1116 5. Sodium Nitrite and NO/NO 2 Mixtures for the in-Situ NMP 1116 5.1. Preliminary Results and Mechanistic Considerations 1116 5.2. Controlled Radical Polymerization of Alkyl Methacrylates in the Presence of the in-Situ-Formed R-Nitro-ω-nitroso Adducts 1117 5.3. NO/NO 2 Mixtures: An Alternative Way to the Nitroso Compounds as Precursors of Nitroxides 1118 5.4. Advantages and Limitations of the Sodium Nitrite and NO/NO 2 Systems 1118 6. Hindered Secondary Amines and the in-Situ NMP 1118 6.1. Oxidation of Secondary Amines into Nitroxides 1118 6.2. One-Pot Processes for the Preparation of Alkoxyamines Active in NMP 1118 6.3. In-Situ NMP Using Hindered Secondary Amines and Oligomeric Secondary Amines 1120 6.4. Advantages and Limitations 1120 7. Hydroxylamines and the in-Situ NMP 1120 7.1. Oxidation of Hydroxylamines into Nitroxides 1120 7.2. Hydroxylamines and the in-Situ NMP 1120 7.3. High Molecular Weight Hydroxylamines for the Polymerization of Vinyl Monomers and Synthesis of Block Copolymers 1122 7.4. Advantages and Limitations 1122 8. Conclusions 1122 9. Acknowledgments 1123 10. References 1123
“…While less common than TEMPO, nitroso compounds exert radical scavenging properties. 38 As such, we rationalized that 2-nitroso-1-naphthol ( 21 ) could potentially differentiate radical and polar pathways. The donating capacity of the phenolic group could render the nitroso functionality reactive towards polar electrophiles to give oxime ether 22 .…”
Dual Brønsted/Lewis acid catalysis involving environmentally benign, readily accessible protic acid and iron promotes site-selective tert-alkylation of arenes using di-tert-butylperoxide and tertiary alcohols.
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