Syntheses by Free-radical Reactions. VIII. Reactions of Amino Radicals with Olefins

Albisetti, C. J.; Coffman, D. D.; Hoover, F. W.; Jenner, E. L.; Mochel, W. E.

doi:10.1021/ja01515a052

Cited by 46 publications

(4 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The ultimate product of the oxidizing agent (hydroxylamine) was not established. The initial product of the one-electron reduction of hydroxylamine is the NH 2 • radical (and hydroxide). , No detectable amounts of ammonia were generated in the reaction, using the same procedure as was used with the iron reaction, indicating an alternate fate for this radical. Because the primary focus of this work was on the metalloporphyrin, the ultimate fate of the oxidizing agent was not investigated.…”

Section: Resultsmentioning

confidence: 99%

Reactions of Hydroxylamine with Metal Porphyrins

et al. 1997

View full text Add to dashboard Cite

The reaction of hydroxylamine with a series of metal porphyrins was examined in methanol/chloroform media. The reductive nitrosylation reaction was observed for the manganese and iron porphyrins, leading to a nitrosyl complex that precipitated out of the solution in good isolatable yield (80-90%). This reaction could be used synthetically for the generation of iron and manganese porphyrin nitrosyl complexes and was particularly useful for making isotopically labeled nitrosyl complexes. On the other hand, Co(II)(TPP) and Cr(TPP)(Cl) did not react with hydroxylamine under anaerobic conditions. With trace amounts of oxygen, the reaction of Co(II)(TPP) with hydroxylamine led to the formation of a stable cobalt(III)-bis(hydroxylamine) complex. The infrared, resonance Raman, and proton NMR spectra were consistent with a cobalt(III)-bis(hydroxylamine) complex. The cyclic voltammetry and visible spectroelectrochemistry of this complex were examined. The one-electron reduction of Co(III)(TPP)(NH(2)OH)(2)(+) formed Co(II)(TPP), for which there was no evidence for the coordination of hydroxylamine. Further reduction led to Co(I)(TPP)(-), which reacted with the halogenated solvent to form a cobalt-alkyl complex. The difference in the reactivity of these four metal porphyrins with hydroxylamine correlated well with their E(1/2) values. Iron(III) and manganese(III) porphyrins were relatively easy to reduce and readily underwent the reductive nitrosylation reaction, while cobalt(II) and chromium(III) porphyrins are unreactive. The one-electron oxidation of the hydroxylamine complex with a M(III) porphyrin would be expected to oxidize the N-atom in the coordinated hydroxylamine. The oxidation of M(III)(NH(2)OH) with the loss of a proton would form M(II)(N(I)H(2)O)(+) by an internal electron transfer, which will eventually lead to M(NO). The relationship between the reductive nitrosyl reaction and the enzymatic interconversion of NO and hydroxylamine was discussed.

show abstract

Section: Resultsmentioning

confidence: 99%

Reactions of Hydroxylamine with Metal Porphyrins

et al. 1997

View full text Add to dashboard Cite

show abstract

“…Additions with hydroxylamine-metal ion mixtures are carried out in solution ranging from neutral to concentrated H2S04 and the C-radical intermediate may undertake the alternative pathway of dimerization if there is no suitable radical donor.81 With vanadium ion as the catalyst, it is obvious that oxidation of the C-radical also occurs followed by carbonium ion reaction, to give an amino alcohol (eq 54). 68 The oxidation process appears to (54) depend on the ionization potentials and the nature of ligands.…”

Section: C02ck3mentioning

confidence: 99%

Nonaromatic aminium radicals

Chow¹,

Danen²,

Nelsen³

et al. 1978

Chem. Rev.

246

151

View full text Add to dashboard Cite

“…One of the earliest literature examples for the electrochemical incorporation of a primary amine was accomplished by the indirect reduction of hydroxylamine using a transition-metal electrochemical mediator . The reduction of hydroxylamine by transition metals (Ti(III), V(III), Cu(I), and Fe(II)) has been investigated extensively since the 1950s. − The mechanistic principle for the electrochemically mediated system is a three-step process. First, a transition-metal ion, M ( n +1) , is cathodically reduced to the M ( n ) state.…”

Section: Electrochemical Aminationmentioning

confidence: 99%

Electrochemical Synthesis of High-Nitrogen Materials and Energetic Materials

Yount

Piercey

2022

Chem. Rev.

View full text Add to dashboard Cite

Electrochemical synthesis is a valuable method for the preparation of molecules. It is innately eco-friendly, as potentially hazardous oxidation and reduction agents are replaced with electrochemical potentials. Electrochemistry is commonly applied globally in the synthesis of numerous chemicals, but the energetic materials field lags in this regard. In this review, we endeavor to cover the entire history of synthetic electrochemistry for the preparation of energetic materials and detail the electrochemical transformations of high-nitrogen materials that are relevant for the preparation of new energetic molecules. We hope this review serves as a starting point to inform those involved in synthetic energetic materials chemistry, and those interested in other applications of high-nitrogen molecules, about the environmentally friendly electrochemical methods available for such compounds.

show abstract

Syntheses by Free-radical Reactions. VIII. Reactions of Amino Radicals with Olefins

Cited by 46 publications

References 0 publications

Reactions of Hydroxylamine with Metal Porphyrins

Reactions of Hydroxylamine with Metal Porphyrins

Nonaromatic aminium radicals

Electrochemical Synthesis of High-Nitrogen Materials and Energetic Materials

Contact Info

Product

Resources

About