1971
DOI: 10.1021/ja00749a037
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Photolysis of matrix isolated 1,3-cyclohexadiene, cis-1,3,5-hexatriene, and trans-1,3,5-hexatriene

Abstract: Ultraviolet and infrared spectroscopy have been used to study the photochemistry of 1,3-cyclohexadiene (I), cis-l,3,5-hexatriene (II), and transA,3,5-hexatriene (III) suspended in argon matrices at 20°K. It was found that I photolyzed rapidly and irreversibly to II, which photolyzed slowly and irreversibly to III and several thermally unstable photo products. Various possibilities are considered for the latter and 1,2,4-hexatriene (IV) and exo-2vinylbicyclo[1.1.0]butane (XI) are suggested as likely candidates.… Show more

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Cited by 22 publications
(9 citation statements)
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“…Therefore, only the Z-type of ketene isomers (note the Z-orientations around the green double bonds in Scheme ) was here considered as candidates for photoproducts 5a and 5b . There is experimental evidence that 1,3-CHD converts rapidly to Z-1,3,5-HT and slowly to E-1,3,5-HT. , Apparently, a slow accumulation of the E-isomer of open-ring carvacrol is not competitive with other observed UV-induced isomerizations and other exit channels (decarbonylation, see below).…”
Section: Resultsmentioning
confidence: 99%
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“…Therefore, only the Z-type of ketene isomers (note the Z-orientations around the green double bonds in Scheme ) was here considered as candidates for photoproducts 5a and 5b . There is experimental evidence that 1,3-CHD converts rapidly to Z-1,3,5-HT and slowly to E-1,3,5-HT. , Apparently, a slow accumulation of the E-isomer of open-ring carvacrol is not competitive with other observed UV-induced isomerizations and other exit channels (decarbonylation, see below).…”
Section: Resultsmentioning
confidence: 99%
“…There is experimental evidence that 1,3-CHD converts rapidly to Z-1,3,5-HT and slowly to E-1,3,5-HT. 33,34 Apparently, a slow accumulation of the E-isomer of open-ring carvacrol is not competitive with other observed a Note that the substituents of the starting form (top-left) have indexes 3 and 5 corresponding to the ring positions where they occur. In the entire scheme, these indexes (R 3 , R 5 ) are kept the same.…”
Section: Ring Contraction To the Dewar Isomermentioning
confidence: 99%
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“…The rate indicated for E-hexatriene is from a measurement at high excess energy [23]. The barrier was drawn higher for this molecule than for the Z isomer, since for the former the photoisomerization in a cold matrix does take place, whereas for the latter it is frozen [24]. Table 1 compares the 1 B and 2A lifetimes for the different molecules.…”
Section: Hexatriene: Several Separate 2 a Minima And Conical Intersecmentioning
confidence: 99%
“…37,40 That explanation did not consider the efficient regioselective cis → trans photoisomerization at C 1 C 2 of 1-cis-deuterio-trans-1,3-pentadiene, 41 which Squillacote attributed to an allyl cation-methylene anion intermediate following Dauben's lead 42 and Salem's sudden polarization theoretical prediction. 43, 44 1,3-Bond formation was proposed to yield an unstable product on irradiation of c-Ht at 20 K in an argon matrix 45 whose formation via the calculated "kink" CI 21,22 is plausible. It was suggested 34,35 that, following S 2 (1 B) → S 1 (2 A) decay in the femtosecond time scale, S 1 → S 0 radiationless decay to the original ground state occurs very fast via a barrierless process involving a "non-totally symmetric deformation of the molecular backbone" that provides access to the "kink" CI.…”
Section: ■ Introductionmentioning
confidence: 99%