A novel aza-di-Π-methane rearrangement the photoreaction of 4,4-dimethyl-1,6,6-triphenyl-2-aza-hexa-2,5-diene

Armesto, Diego; Martin, Juan Antonio F.; Perez‐Ossorio, R.; Horspool, W. M.

doi:10.1016/s0040-4039(00)87285-8

Cited by 29 publications

(12 citation statements)

References 9 publications

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“…downfield from internal Me,%. (8).--Tmine (8a) was synthesized by the previously reported route.' 2,2-Dimethyl-4,4-diphenylbut-3-enal(5a) was synthesized by the method of Zimmerman and Pratt."…”

Section: Methodsmentioning

confidence: 99%

Substitution effects on the aza-di-π-methane rearrangement of imines

Armesto¹,

Horspool²,

Langa³

et al. 1987

J. Chem. Soc., Perkin Trans. 2

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Section: Methodsmentioning

confidence: 99%

Substitution effects on the aza-di-π-methane rearrangement of imines

Armesto¹,

Horspool²,

Langa³

et al. 1987

J. Chem. Soc., Perkin Trans. 2

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“…The formation of a quinoline derivative (12) by photochemical cyclization of a diene (5) does have literature precedent in that Glinka" reported with little comment that the oxime (13) is transformed photochemically into the quinoline (14). The cyclization in this example and those reported by us can be rationalized readily in terms of a six-electron process involving the atoms of the diene skeleton and the 4-aryl group.…”

Section: Resrilts and Discussionmentioning

confidence: 99%

Photochemical synthesis of quinoline derivatives by cyclization of 4-aryl-N-benzoyloxy-2,3-diphenyl-1-azabuta-1,3-dienes

Armesto¹,

Gallego²,

Horspool³

1989

J. Chem. Soc., Perkin Trans. 1

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“…Flash chromatography of the residue using hexane-ethyl acetate (8 : 2) as eluent afforded the desired tosylhydrazone 8a (0.37 g, 78%) as a white solid, mp 176-177 ЊC (from EtOH); ν max /cm Ϫ1 3090 (NH), 1630 (C᎐ ᎐ N); λ max /nm 230 (24 000); δ H (300 MHz) 1.2 (6 H, s, 2Me), 1.3 (3 H, s, MeCN), 2.4 (3 H, s, ArMe), 5.9 (1 H,s,m,aryl H and NH); δ C (75 MHz) 13.7 (MeCN), 21.5 (ArMe), 27.8 (2Me), 45.1 (quaternary C), 127. 0-143.7 (aryl and vinyl C) and 161.8 (C᎐ ᎐ N); m/z 432 (M ϩ , 1), 265 (100), 167 (19), 155 (38) and 91 (65) (Found: C, 72.2; H, 6.34; N, 6.5; S, 7.0. C 26 H 28 C, 72.23; H, 6.48; N, 6.48; S, 7.41%).…”

Section: Synthesis Of 33-dimethyl-55-diphenylpent-4-en-2-one Tosylhmentioning

confidence: 99%

Novel photochemical behaviour of the oximes and hydrazones of β,γ-unsaturated carbonyl compounds

Armesto¹,

Ramos²,

Ortiz³

et al. 1997

J. Chem. Soc., Perkin Trans. 1

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A study of the photochemical reactivity of a series of , -unsaturated oximes and hydrazone derivatives under triplet sensitized conditions has been carried out. The oximes 3c, 4a and 4c cyclize to the corresponding dihydroisoxazoles 5c, 6a and 6c while the tosyl hydrazone 8a affords the dihydropyrazole 9a. An intramolecular single electron-transfer mechanism from the alkene moiety to the oximino group, in the case of the oximes 3c, 4a and 4c, and to the tosyl group for the tosyl hydrazone 8a, is proposed to account for these results. Oximes and hydrazine derivatives from aldehydes behave differently. Thus, the oxime 3d yields the cyclopropyl oxime 10 by an aza di--methane (ADPM) rearrangement while the aldoxime 3e gives a mixture of the corresponding dihydroisoxazole 5d and cyclopropane 11a resulting from an ADPM process. Irradiation of the hydrazine derivatives 8b, 8c and 8d gives a mixture of the corresponding dihydropyrazoles 9b, 9c and 9d and the cyclopropanes 11b, 11c and 11d, respectively. However, under the same experimental conditions, dihydronaphthalene derivatives such as the oxime 12a and the tosyl hydrazone 12b undergo ADPM rearrangements exclusively, affording the cyclopropanes 13a and 13b, respectively. Sensitized irradiation of the tosyl hydrazone 12c yields the cyclopropane 13c, as the major product. In this instance a small amount of the hexahydrophenanthroline 14, resulting from an endo cyclization is also formed. The influence of substitution on the outcome of the reaction is discussed.

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A novel aza-di-Π-methane rearrangement the photoreaction of 4,4-dimethyl-1,6,6-triphenyl-2-aza-hexa-2,5-diene

Cited by 29 publications

References 9 publications

Substitution effects on the aza-di-π-methane rearrangement of imines

Substitution effects on the aza-di-π-methane rearrangement of imines

Photochemical synthesis of quinoline derivatives by cyclization of 4-aryl-N-benzoyloxy-2,3-diphenyl-1-azabuta-1,3-dienes

Novel photochemical behaviour of the oximes and hydrazones of β,γ-unsaturated carbonyl compounds

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