Photolysis of 2,4,6-Tri-<i>t</i>-butylnitrobenzene

Barclay, L. R. C.; MCMASTER, I. T.

doi:10.1139/v71-113

Cited by 9 publications

(2 citation statements)

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“…It was a colorless crystalline compound, mp 105-106°C. The nmr and ir spectra established this compound to be identical to 7 obtained earlier (13) (2H, nonequivalent olefinic Hi of ' c=cH,), a singlet at / 3.80 (2H exchangeable, -NH,), and doublets at 7.11 and 7.37 6 ( J --3 Hz) ( I H each, meta aryl hydrogens). The ir spectrum showed bands at 3520 and 3420 cm-' attributed to N-H stretching absorption of a primary amine and a band at 3090 cm-' to the C-H stretching \ absorption of the 'C=CH, group.…”

supporting

confidence: 79%

“…However, the product mixture was not so complex as in the reduction of 1 (compare Scheme 2 and Table 2), in that reduction of 2 gave a high yield of 3,3-dimethyl-5,7-di-tertbutyl-2,3-dihydroindole (7). The cyclic amine 7 was identified by its spectroscopic properties and by preparing it through hydride reduction of $7-di-tert-butyl-3,3-dimethyloxindole (101, a known photolysis product from 2,4,6-tri-tertbutylnitrobenzene (13).…”

Section: Introductionmentioning

confidence: 99%

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Sterically hindered aromatic compounds. VII. Deoxygenation of 2,5-di-tert-butyl- and 2,4,6-tri-tert-butylnitrosobenzene

Barclay¹,

Khazanie²,

Adams³

et al. 1977

Can. J. Chem.

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. Deoxygenation of 2,5-di-tert-butylnitrosobenzene (1) by triethylphosphite gave a complex mixture containing 2,5-di-tert-butylaniline, 2,5,2',5'-tetra-tert-butylazobenzene, N-(2,5-ditert-butylphenyl)-~ert-butyl-a-2-(5-tert-butypyridyl)nitrone, and diethyl N-(2,5-di-tert-butylphenyl)phosphoramidate. In contrast deoxygenation of 2,4,6-tri-tert-butylnitrosobenzene (2) yielded mainly 3,3-dimethyl-5,7-di-tert-butyl-2,3-dihydrondoe (80%), together with small amounts of 2,4,6-tri-tert-butylaniline and a product of side chain rearrangement, 2-(2-methyl-3-propeny1)-4,6-di-tert-butylaniline. Reaction pathways involving nitrenoid intermediates account for the various products. The different types of products from 1 and 2 are explained in terms of differential steric and conformational effects.L. Ross C. BARCLAY, PRABHAKER G. KHAZANIE, KENNETH A. H. ADAMS et ELAINE REID. Can. J. Chem. 55,3273 (1977).La deoxygination du di-tert-butyl-2.5 nitrosobenzene (1) par la triethylphosphite donne un melange complexe de di-tert-butyl-2,5 aniline, tetra-tert-butyl-2,5,2',5' azobenzene, N-(di-tertbutyl-2,5 phCny1)-cr tert-butyl-cr (tert-butyl-5 pyridy1)-2 nitrone et N-(di-tert-butyl-2,5 phenyl) phosphoramidate de diethyle. Par contre, la deoxygenation du trl-tert-butyl-2,4,6 nitrosobenzene (2) conduit principalement au dimethyl-3,3 di-tert-butyl-5,7 dihydro-2,3 indole (80%), avec un faible pourcentage de tri-tert-butyl-2,4,6 aniline contenant un produit de rearrangement de la chaine laterale, le (methyl-2 propenyl-3)-2 di-tert-butyl-4,6 aniline. Les sentiers reactionnels impliquant des intermediaires nitrknoi'de sont responsables des composes divers. Les

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supporting

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Sterically hindered aromatic compounds. VII. Deoxygenation of 2,5-di-tert-butyl- and 2,4,6-tri-tert-butylnitrosobenzene

Barclay¹,

Khazanie²,

Adams³

et al. 1977

Can. J. Chem.

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Hydroxyindoles, Indole Alcohols, and Indolethiols

Spande

1979

Chemistry of Heterocyclic Compounds: A Series of Monographs

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Photochemie aromatischer Nitroverbindungen, IX. Photolyseprodukte des 1,3,5‐Tri‐ tert ‐butyl‐2‐nitrobenzols

Döpp

Sailer

1975

Chem. Ber.

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Bei der Bestrahlung in Eisessig, Methanol, Aceton, Dioxan, Benzol und Cyclohexan sowie als kristallines Pulver geht 1,3,5-Tri-rert-butyl-2-nitrobeml (1) in 5,7-Di-tert-butyl-3.3dimethyl-3H-indol-l-oxid (5) uber, welches je nach den Reaktionsbedingungen als solches isoliert werden kann oder zu verschiedenen Produkten photoisomerisiert bzw. zu 5,7-Di-tertbutyl-I -hydroxy-3,3-dimethyI-2-indolinon (44 oxidiert wird. In Di-bzw. Triathylamin findet glatte Photoreduktion der Nitrogruppe. ohne Beteiligung der ortho-tert-Butylgruppcn statt, man isoliert Produkte, die sich dmtlich vom I ,3,5-Tri-tert-butyl-2-(hydroxylamino)benzol ableiten. Pbotocbemistry of Aromatic Nitro Compounds, M*.) Products from Photdysis of 1 f,STri-rert-butyl-2-dtmbenmw Ib)Upon irradiation in acetic acid, methanol, acetone, dioxane, benzene, and cyclohexane solution or as powdered crystals 1,3,5-tri-terr-butyl-2-nitrobenz.ene (1) is converted to 5,7-di-tertbutyl-3,3-dimethyl-3H-indole-l-oxide (5). which may be isolated. Alternatively, depending on the reaction conditions, 5 may be photoisomerized to various products or oxidized to 5,7di-tertrr-butyl-l-hydroxy-3,3-dimethyl-2-indolinone (44. In di-or triethylamine solution. smooth photoreduction of the nitro group of 1 without interference by the ortho tert-butyl groups is observed; all products isolated are derived from 1,3,5-tri-tert-butyl-2-(hydroxylamino)benzene.Die Photochemie sterisch gehinderter aromatischer Nitroverbindungen fand in neuerer Zeit das Intemse mehrerer ArbeitskreiseJ-6). Zur Photolyse des hoch gehinderten 1,3,5-Tri-rert-butyl-2-nitrobenzols (1) wurden in Kurzform5-~ und im Rahnien einer Arbeit4) iiber die Photochemie verschiedener gehinderter Nitroaromaten unterschiedliche Ergebnisse mitgeteilt. So sol1 die Belichtung von 1 in Cyclohexan mit 1) la) VIII. Mitteil.: D. Dopp, D. Muller und K.-H. Suiler, Tetrahedron Lett. 1974, 2137. -2) Anfragen an diese Adresse. 3) J. A. Barltrop und N .

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Photolysis of 2,4,6-Tri-t-butylnitrobenzene

Cited by 9 publications

References 1 publication

Sterically hindered aromatic compounds. VII. Deoxygenation of 2,5-di-tert-butyl- and 2,4,6-tri-tert-butylnitrosobenzene

Sterically hindered aromatic compounds. VII. Deoxygenation of 2,5-di-tert-butyl- and 2,4,6-tri-tert-butylnitrosobenzene

Hydroxyindoles, Indole Alcohols, and Indolethiols

Photochemie aromatischer Nitroverbindungen, IX. Photolyseprodukte des 1,3,5‐Tri‐ tert ‐butyl‐2‐nitrobenzols

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