Generation and trapping of cyclopropene-3-carboxaldehyde and 2,3-butadienal in liquid furan photolysis

Rendall, W. A.; Torres, M. A. P.; Strausz, O. P.

doi:10.1021/jo00217a002

Cited by 21 publications

(6 citation statements)

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“…Such processes are probably concerted and all of them imply both a hydrogen atom migration from the CH 2 OH moiety to the furyl group and the cleavage of the C1–O5 bond. The formation of CPC consists then in a ring contraction similar to that reported previously for furan and both furan-2- and furan-3- carboxaldehydes. ,,, As mentioned before, this reaction was found to be the favored one when irradiation of matrix-isolated FFA took place at λ = 229 nm. The formation of all the remaining observed C 4 H 4 O isomeric forms requires an additional H atom migration within the C 4 H 4 O moiety.…”

Section: Resultssupporting

confidence: 80%

“…The formation of CPC consists then in a ring contraction similar to that reported previously for furan and both furan-2-and furan-3-carboxaldehydes. 14,33,43,44 As mentioned before, this reaction was found to be the favored one when irradiation of matrix-isolated FFA took place at λ = 229 nm. The formation of all the remaining observed C 4 H 4 O isomeric forms requires Finally, it is also interesting to note that the alternative radicalar mechanism involving formation of CH 2 OH and furyl radicals seems to be improbable in the light of the present experiments, since its expected main product, furan, could not be observed.…”

Section: The Journal Of Physical Chemistry Asupporting

confidence: 55%

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Conformers, Infrared Spectrum and UV-Induced Photochemistry of Matrix-Isolated Furfuryl Alcohol

et al. 2012

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The infrared spectra of furfuryl alcohol (2-furanmethanol, FFA) were investigated for FFA monomers isolated in low-temperature argon matrices. The structural interpretation of the obtained experimental spectra was assisted by analysis of the molecule's conformational landscape. According to the DFT(B3LYP)/6-311++G(d,p) calculations, five different minimum energy structures were found on the potential energy surface of the molecule. They can be defined by the orientation of the OCCO and CCOH dihedral angles: GG', GG, TG, TT, GT (G = +gauche, G' = -gauche, T = trans) and have a symmetry equivalent configuration: GG' = G'G, GG = G'G', TG = TG', GT = G'T. When zero-point energies are taken into account, only three (GG', GG, and TT) out of the five unique minima correspond to stable structures. The most stable conformer GG' (OCCO, 72.7°; CCOH, -59.3°), which in gas phase at room temperature accounts for ∼65% of the total population, was the only form isolated in the argon matrices at 14 K. The other two relevant forms convert into conformer GG' during matrix deposition. The low temperature glassy and crystalline states of FFA were also obtained and their infrared spectra assigned, suggesting the sole existence of the GG' conformer also in these phases. The photochemical behavior of FFA induced in situ, by tunable UV-laser, was also studied. The longest wavelength resulting in photochemical changes in the structure of the irradiated sample was found to be λ = 229 nm. Such UV irradiation of the matrix-isolated FFA led to production of formaldehyde and different isomeric C(4)H(4)O species. Cycloprop-2-ene-1-carbaldehyde and buta-2,3-dienal (two conformers) are the main initial C(4)H(4)O photoproducts formed upon short-time excitation at λ = 229 nm. But-3-ynal (two conformers) was the principal photoproduct resulting from prolonged excitation at λ= 229 nm, being consumed upon irradiation at shorter wavelengths (λ < 227.5 nm). Vinyl ketene is produced from FFA in the trans conformation and undergoes isomerization to the cis form upon irradiation at λ < 227.5 nm. Cyclopropene, propyne, allene, and CO were also identified in the irradiated matrices (in particular at the later stages of irradiation), suggesting that the photoproduced aldehydes partially decarbonylate during the performed photochemical experiments.

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Section: Resultssupporting

confidence: 80%

Section: The Journal Of Physical Chemistry Asupporting

confidence: 55%

Conformers, Infrared Spectrum and UV-Induced Photochemistry of Matrix-Isolated Furfuryl Alcohol

et al. 2012

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“…Liquid-phase photolysis of furan is in agreement with the formation of cyclopropene-3-carbaldehyde . The direct flash photolysis of furan gave, on the contrary, a different behavior.…”

Section: Resultssupporting

confidence: 62%

“…6,7 Liquid-phase photolysis of furan is in agreement with the formation of cyclopropene-3-carbaldehyde. 8 The direct flash photolysis of furan gave, on the contrary, a different behavior. Mass fragments corresponding to C 4 H + , C 4 H 2 + , C 4 H 3 + , and C 4 H 4 + were observed together with the formation of cyclopropene-3-carbaldehyde.…”

Section: Resultsmentioning

confidence: 99%

Ab Initio Study on the Photochemical Isomerization of Furan Derivatives

D’Auria

2000

J. Org. Chem.

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The photochemical isomerization reactions of furan, 2-methylfuran, 2-trimethylsilylfuran, and furan-2-carbonitrile were studied using ab initio methods. The results are in agreement with the previously reported data obtained through semiempirical methods. In particular, the sensitized irradiation of furan derivatives populates the first excited triplet state of the furan, and this triplet state can evolve only through O-Ca cleavage. The selection of the bond to be broken can depend on energetic factors (furan-2-carbonitrile) or on kinetic factors (2-methylfuran, 2-trimethylsilylfuran). The direct irradiation of furan derivatives populates the singlet excited state and leads to a conversion into the Dewar isomer or into the corresponding triplet state through the usual intersystem crossing procedure. The efficiency of these processes determines the presence or the absence of isomerized furan derivatives in the reaction mixtures.

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“…The proposed mechanism shown in Scheme can account for the transformation. Cyclopropene intermediate 8 19a,19b is generated via diradical 7 by photolysis of 3b . Deuterium exchange of 8 with D 2 O to generate 10 via oxonium ion 9 could result from the electron-donating capability of the vinylic methoxy group.…”

Section: Resultsmentioning

confidence: 99%

Self-Sensitized Photooxygenation of 3,4-Dialkoxyfurans to Vitamin C or Its Derivatives

Hakimelahi

Jain

et al. 2001

J. Org. Chem.

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Self-sensitized photooxygenation of 3,4-dialkoxyfurans 3a-d with molecular oxygen and UV- or sunlight at room temperature gave vitamin C derivatives 2a-d in good to excellent yields. Furan 3c, having photodegradable protecting groups, was also photooxygenated to give L-ascorbic acid (1) in a "one-pot" reaction. Furthermore, a novel photolytic transformation was developed for deuteration of furan 3b at the C-2 position with D(2)O to give furan 3d in 95% yield. Toxicity of furans 3a-c and butenolides 2a-c against human embryonic cell, murine embryo fibroblasts, normal fibroblasts, HeLa, and Vero cell lines in the presence of oxygen and indirect solar light was found to be much less than those of the antipsoriasis drugs anthralin and 8-methoxypsoralen.

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Generation and trapping of cyclopropene-3-carboxaldehyde and 2,3-butadienal in liquid furan photolysis

Cited by 21 publications

References 1 publication

Conformers, Infrared Spectrum and UV-Induced Photochemistry of Matrix-Isolated Furfuryl Alcohol

Conformers, Infrared Spectrum and UV-Induced Photochemistry of Matrix-Isolated Furfuryl Alcohol

Ab Initio Study on the Photochemical Isomerization of Furan Derivatives

Self-Sensitized Photooxygenation of 3,4-Dialkoxyfurans to Vitamin C or Its Derivatives

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