Generation, Spectroscopic Characterization, and Reactions of 3,4-Benzotropone. Distinctive Photochemical Behavior of 6,7-Benzobicyclo[3.2.0]hepta-3,6-dien-2-one in Rigid Glass at Low Temperature and in Fluid Solution
Abstract:Irradiation of 6,7-benzobicyclo[3.2.0]hepta-3,6-dien-2-one (2) in a rigid glass at -196°C leads to the formation of 3,4-benzotropone (1), which exhibits a characteristic UV-vis absorption extending to 535 nm and dimerizes to give syn-and anti-[π8 + π10] dimers 7 and 8 upon thawing the glass. The rate constant of the thermal dimerization of 1 is 12 ( 3 M -1 s -1 at -78°C. Photochemically, 1 is stable under matrix isolation, but undergoes [π10 + π10] dimerization in solution. Compound 1 in a CFCl 3 -CF 2 BrCF 2 … Show more
“…The aromaticity of 3,4-benzotropone ( 13A ) is considered to depend on the contribution of electronically polarized form 13B such as tropone 1A ( Fig. 8 ) [ 153 – 154 ]. Kurihara’s group reported the calculated resonance energies and bond currents for benzotropones and troponoid compounds [ 155 ].…”
Section: Reviewmentioning
confidence: 99%
“…9 ) [ 153 ]. In a subsequent study, Tsuji’s group described details of the spectral and chemical properties of 13 [ 154 ]. The IR spectroscopic results showed a substantial contribution of 13B to 13A in the ground state.…”
Section: Reviewmentioning
confidence: 99%
“…Moreover, it was found that the photochemical behavior of 230 depended on the state of the irradiation medium. For example, the smooth [π10 + π10] dimerization of 13 to give dimeric product 233 was realized with the irradiation (>420 nm) of 13 in a fluid EPA solution below −100 °C [ 154 ]. Furthermore, the IR spectra of 3,4-benzotropone ( 13 ) generated in matrices at 13 K by the photoisomerization of 230 were directly observed [ 156 ].…”
Section: Reviewmentioning
confidence: 99%
“…Furthermore, the IR spectra of 3,4-benzotropone ( 13 ) generated in matrices at 13 K by the photoisomerization of 230 were directly observed [ 156 ]. In addition, the thermal generation of 13 from 230 was investigated [ 153 – 154 ]. When 230 with 10 equiv of maleic anhydride in benzene at 220 °C was reacted, [π2 + π8] cyclo-adduct 234 as a single product was isolated in 52% yield ( Fig.…”
Section: Reviewmentioning
confidence: 99%
“…When 230 with 10 equiv of maleic anhydride in benzene at 220 °C was reacted, [π2 + π8] cyclo-adduct 234 as a single product was isolated in 52% yield ( Fig. 9 ) [ 153 – 154 ]. The thermolysis of 230 in the presence of ethyl vinyl ether gave three volatile products 235 – 237 in GLC yields of 10%, 7%, and 15%, respectively ( Fig.…”
This review focuses on the chemistry of benzo-annulated tropones and tropolones reported since the beginning of the 20th century, which are currently used as tools by the synthetic and biological communities.
“…The aromaticity of 3,4-benzotropone ( 13A ) is considered to depend on the contribution of electronically polarized form 13B such as tropone 1A ( Fig. 8 ) [ 153 – 154 ]. Kurihara’s group reported the calculated resonance energies and bond currents for benzotropones and troponoid compounds [ 155 ].…”
Section: Reviewmentioning
confidence: 99%
“…9 ) [ 153 ]. In a subsequent study, Tsuji’s group described details of the spectral and chemical properties of 13 [ 154 ]. The IR spectroscopic results showed a substantial contribution of 13B to 13A in the ground state.…”
Section: Reviewmentioning
confidence: 99%
“…Moreover, it was found that the photochemical behavior of 230 depended on the state of the irradiation medium. For example, the smooth [π10 + π10] dimerization of 13 to give dimeric product 233 was realized with the irradiation (>420 nm) of 13 in a fluid EPA solution below −100 °C [ 154 ]. Furthermore, the IR spectra of 3,4-benzotropone ( 13 ) generated in matrices at 13 K by the photoisomerization of 230 were directly observed [ 156 ].…”
Section: Reviewmentioning
confidence: 99%
“…Furthermore, the IR spectra of 3,4-benzotropone ( 13 ) generated in matrices at 13 K by the photoisomerization of 230 were directly observed [ 156 ]. In addition, the thermal generation of 13 from 230 was investigated [ 153 – 154 ]. When 230 with 10 equiv of maleic anhydride in benzene at 220 °C was reacted, [π2 + π8] cyclo-adduct 234 as a single product was isolated in 52% yield ( Fig.…”
Section: Reviewmentioning
confidence: 99%
“…When 230 with 10 equiv of maleic anhydride in benzene at 220 °C was reacted, [π2 + π8] cyclo-adduct 234 as a single product was isolated in 52% yield ( Fig. 9 ) [ 153 – 154 ]. The thermolysis of 230 in the presence of ethyl vinyl ether gave three volatile products 235 – 237 in GLC yields of 10%, 7%, and 15%, respectively ( Fig.…”
This review focuses on the chemistry of benzo-annulated tropones and tropolones reported since the beginning of the 20th century, which are currently used as tools by the synthetic and biological communities.
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