The Photochemistry of Dienes and Polyenes: Application to the Synthesis of Complex Molecules

Nuss, John M.; West, F. G.

doi:10.1002/9780470682531.pat0103

Cited by 2 publications

(2 citation statements)

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“…On preparative irradiation of 2-methyl-1-(o-vinylphenyl)-4-phenylbutadiene derivative (4) at 350 nm, cyclohexadiene derivative 8 was found and isolated as the main photoproduct as a result of an electrocyclic ring-closure process characteristic for 1,3,5-hexatriene (Scheme 3). 3,46 The proposed reaction mechanism for transformation of the o-vinyl derivative 4 involves a six-membered ring closure followed by a sigmatropic 1,5-H shift to give 8. A primary photochemical process observed after very short irradiation time is cisÀtrans isomerization giving preferably the trans-4 isomer (existing in different conformations; Scheme 1 and 4) followed by competitive processes from two different conformations of trans-4 (Scheme 4).…”

Section: ' Results and Discussionmentioning

confidence: 99%

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Synthesis, Photochemistry, and Photophysics of Butadiene Derivatives: Influence of the Methyl Group on the Molecular Structure and Photoinduced Behavior

et al. 2011

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Novel butadiene derivatives display diverse photochemistry and photophysics. Excitation of 2-methyl-1-(o-vinylphenyl)-4-phenylbutadiene leads to the dihydronaphthalene derivative, whereas photolysis of the corresponding model o-methyl analogue results in the formation of the naphthalene-like derivative, deviating from the nonmethylated analogue of the prior starting compound and producing benzobi- and -tricyclic compounds. The effect of the methyl substituents is even more dramatic in the case of the dibutadienes. The parent unsubstituted compound undergoes photoinduced intramolecular cycloaddition giving benzobicyclo[3.2.1]octadiene, whereas the photochemical reaction of the corresponding dimethylated derivative shows only geometrical isomerization due to the steric effect of the substituents. Methyl groups on the butadiene backbones reduce the extent of conjugation, causing a blue-shift of the characteristic absorption band. The fluorescence efficiency is dramatically decreased, as a consequence of nonplanarity and reduced rigidity of the molecules due to the crowding by the methyl and phenyl groups together. Four molecules of very similar structures show dramatically different photoinduced behavior, revealing how changes of the nature and position of the substituents are valuable in understanding the photophysics and photochemistry of these types of compounds.

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Section: ' Results and Discussionmentioning

confidence: 99%

“…cis,cis-5: white crystals; mp 65À67 °C; UV (n-hexane) λ max /nm (ε/dm 3 1-Methyl-2-(3-methyl-4-phenylbuta-1,3-dienyl)benzene (7).…”

Section: -(3-methyl-4-phenylbuta-13-dienyl)-2-vinylbenzene (4)mentioning

confidence: 99%

Synthesis, Photochemistry, and Photophysics of Butadiene Derivatives: Influence of the Methyl Group on the Molecular Structure and Photoinduced Behavior

et al. 2011

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Synthesis and photochemical transformations of new butadiene chromophores: The influence of the nature and position of chlorine substituent on the photoinduced behaviour

Vuk

Potroško

Šindler‐Kulyk

et al. 2013

Journal of Molecular Structure

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The Photochemistry of Dienes and Polyenes: Application to the Synthesis of Complex Molecules

Abstract: Introduction Photorearrangements of Dienes and Polyenes Photocycloadditions Involving Dienes and Polyenes Concluding Remarks

Cited by 2 publications

References 183 publications

Synthesis, Photochemistry, and Photophysics of Butadiene Derivatives: Influence of the Methyl Group on the Molecular Structure and Photoinduced Behavior

Synthesis, Photochemistry, and Photophysics of Butadiene Derivatives: Influence of the Methyl Group on the Molecular Structure and Photoinduced Behavior

Synthesis and photochemical transformations of new butadiene chromophores: The influence of the nature and position of chlorine substituent on the photoinduced behaviour

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