Aryl radical formation during the thermal decomposition of aryldizao alkyl ethers

Paton, R. M.; Weber, Rudolf U.

doi:10.1039/c39770000769

Cited by 6 publications

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“…6-8) gave benzene as the only detectable polarized species by our method. Polarized benzene and substituted benzenes have been found in CIDNP studies of various dediazoniations (29-33), including pyrolysis of NNA in acetonitrile at low field (34), whereas spin polarized biphenyl from these systems is unusual and was not reported in CIDNP studies even when biaryls were formed in significant yields (33). Both polarized benzene and biphenyl were reported in 13C CIDNP studies of the decomposition of diazoaminobenzene where the enhanced absorption of two carbons of biphenyl was assigned to cage recombination of two phenyl radicals (35).…”

Section: Electron Spin Resonancementioning

confidence: 99%

Sterically hindered aromatic compounds. XI. Spectral and product studies of the decomposition of N-nitrosoacetanilides

Barclay¹,

Dust²

1982

Can. J. Chem.

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DUST. Can. J. Chem. 60,607 (1982). Decomposition of N-nitroso-2,4,6-tri-?err-butylacetanilide (1) in benzene forms products 2,4,6-tri-rert-butylphenyl acetate ( 3 , 3-(3,5-di-tert-butyIphenyl)-2-acetoxy-2-methypropane (4), and hydrocarbons 3-(3,s-di-terr-butylpheny1)-and I-(3,5-di-terr-butylphenyl)-2-methylpropene (5 and 6) explained by a reactive aryl cation (21, the rearranged products (4, 5, 6) originating from a 1,5-hydride shift from an ortho tert-butyl group in 2. In contrast, decomposition of 1 in triethylamine forms products 1,3,5-tri-rerr-butylbenzene (lo), 2,4,6-tri-tert-butylacetanilide (151, and 2-(3,5-di-terr-butylpheny1)-2-methylpropan oxime (13), expected of a free radical pathway. Electron spin resonance evidence is given for intermediates formed by rearrangement of the 2,4,6-tri-tert-butylphenyl radical and spin trapped by the nitroso group of 1. CIDNP and esr studies on the dediazoniation of N-nitrosoacetanilide and aniline in the presence of tertiary amines support the proposed electron transfer mechanism. The results are briefly discussed in terms of the role of steric effects and electron transfer in the dediazoniation of nitrosoacetanilides and diazonium salts.L. Ross C. BARCLAY et JULIAN M. DUST. Can. J. Chem. 60,607 (1982). La decomposition du N-nitroso tri-tert-butyl-2,4,6 acetanilide (1) dans le benzene conduit a la formation de I'acttate de tri-rert-butyl-2,4,6 phenyle (3), de (di-tert-butyl-3,5 phenyl)-3 acetoxy-2 methyl-2 propane (4) et des (di-terr-butyl-3,5 phCny1)-3 et (di-tert-butyl-3,5 ph6nyl)-1 methyl-2 propenes (5 et 6) dont on explique la formation a I'aide d'un cation aryle reactif (2), les produits de transposition ( 4 , s et 6) proviennent d'un deplacement-1,5 d'un hydmre provenant d'un groupement tert-butyle ortho dans 2. Par opposition, la decomposition de 1 dans la triethylamine conduit a la formation de tri-tert-butyl-1,3,5 benzene (lo), de tri-terr-butyl-2,4,6 acetanilide (15) et de l'oxime du (di-tert-butyl-3,5 phenyl)-2 methyl-2 propanal (13) dont la formation est prevue pour un processus radicalaire. Les donnees de la rpe suggerent la presence d'intermediaires formes par une transposition du radical tri-tert-butyl-2,4,6 phenyle qui est piege par le nitroso de 1. Des etudes de CIDNP et rpe sur la dediazotation du N-nitrosoacetanilide et de I'aniline en presence d'amines tertiaires est en accord avec le mecanisme de transfert d'electron propose. On discute brievement des resultats obtenus en termes du r81e des effets steriques et des transferts d'electrons lors de la dediazotation des nitrosoacetanilides et des sels de diazonium.[Traduit par le journal]

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Section: Electron Spin Resonancementioning

confidence: 99%

Sterically hindered aromatic compounds. XI. Spectral and product studies of the decomposition of N-nitrosoacetanilides

Barclay¹,

Dust²

1982

Can. J. Chem.

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Catalytic Cross‐Coupling of Vinyl Golds with Diazonium Salts under Photoredox and Thermal Conditions

2015

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Catalytically generated vinyl gold complexes from tert‐butyl allenoates were found to undergo an efficient cross‐coupling with arenediazonium salts. The gold(I)‐gold(III) redox cycle can be accessed under two different conditions, i.e., visible‐light photoredox as well as a thermally induced radical chain pathway. The current C(sp2)C(sp2) cross‐coupling protocol that is catalytic in gold, would make available desirable structural diversity to the traditional cross‐coupling chemistry.magnified image

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ChemInform Abstract: ARYL RADICAL FORMATION DURING THE THERMAL DECOMPOSITION OF ARYLDIAZO ALKYL ETHERS

Paton¹,

Weber²

1978

Chemischer Informationsdienst

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Aryl radical formation during the thermal decomposition of aryldizao alkyl ethers

Cited by 6 publications

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Sterically hindered aromatic compounds. XI. Spectral and product studies of the decomposition of N-nitrosoacetanilides

Sterically hindered aromatic compounds. XI. Spectral and product studies of the decomposition of N-nitrosoacetanilides

Catalytic Cross‐Coupling of Vinyl Golds with Diazonium Salts under Photoredox and Thermal Conditions

ChemInform Abstract: ARYL RADICAL FORMATION DURING THE THERMAL DECOMPOSITION OF ARYLDIAZO ALKYL ETHERS

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