Mechanistic aspects of the formation of aldehydes and nitriles in photosensitized reactions of aldoxime ethers

The photooxidation of a series of aldoxime ethers was studied by laser flash photolysis and steady-state (product studies) methods. Nanosecond laser flash photolysis studies have shown that chloranil (CA)-sensitized reactions of the O-methyl (1), O-ethyl (2), O-benzyl (3), and O-tert-butyl (4) benzaldehyde oximes result in the formation of the corresponding radical cations. In polar non-nucleophilic solvents such as acetonitrile, there are several follow-up pathways available depending on the structure of the aldoxime ether and the energetics of the reaction pathway. When the free energy of electron transfer (DeltaGET) becomes endothermic, syn-anti isomerization is the dominant pathway. This isomerization pathway is a result of triplet energy transfer from CA to the aldoxime ether. For substrates with alpha-protons (aldoxime ethers 1-3), the follow-up reactions involve deprotonation at the alpha-position followed by beta-scission to form the benziminyl radical (and an aldehyde). The benziminyl radical reacts to give benzaldehyde, the major product under these conditions. A small amount of benzonitrile is also observed. In the absence of alpha-hydrogens (aldoxime ether 4), the major product is benzonitrile, which is thought to occur via reaction of the excited (triplet) sensitizer with the aldoxime ether. Abstraction of the iminyl hydrogen yields an imidoyl radical, which undergoes a beta-scission to yield benzonitrile. An alternative pathway involving electron transfer followed by removal of the iminyl proton was not deemed viable based on charge densities obtained from DFT (B3LYP/6-31G*) calculations. Similarly, a rearrangement pathway involving an intramolecular hydrogen atom transfer process was ruled out through experiments with a deuterium-labeled benzaldehyde oxime ether. Studies involving nucleophilic solvents have shown that all aldoxime ethers reacted with MeOH by clean second-order kinetics with rate constants of 0.7 to 1.2 x 10(7) M(-1) s(-1), which suggests that there is only a small steric effect in these reactions. The steady-state experiments demonstrated that under these conditions no nitrile is formed. This is explained by a mechanistic scheme involving nucleophilic attack on the nitrogen of the aldoxime ether radical cation, followed by solvent-assisted [1,3]-proton transfer and elimination of an alcohol, similar to the results obtained for a series of acetophenone oxime ethers.     

Quinone-sensitized steady-state photolysis of acetophenone oximes under aerobic conditions: kinetics and product studies

Oxidation of oximes via photosensitized electron transfer (PET) results in the formation of the corresponding ketones as the major product via oxime radical cations and iminoxyl radicals. The influence of electron-releasing and electron-accepting substituents on these reactions was studied. The observed substituent effect strongly supports formation of iminoxyl radicals from the oximes via an electron transfer-proton transfer sequence rather than direct hydrogen atom abstraction. Correlation of the relative conversion of the oximes with Hammett parameters shows that radical effects dominate for the meta-substituted acetophenone oximes (rho(rad)/rho(pol) = 5.4; r2 = 0.93), whereas the para-substituted oximes are influenced almost equally by radical and ionic effects (rho(rad)/rho(pol) = -1.1; r2 = 0.98). From these data sets we conclude that the follow-up reactions proceed through a number of intermediates with both radical and ionic character. This was confirmed by product studies with the use of an isotopically labeled nucleophile. In addition to the major oxidation product (ketone), a chlorine-containing product was often identified as well. Studies on the formation of this product show that the most likely pathway is either via a direct nucleophilic addition in a complex formed between the oxime radical cation and the chloranil radical anion or via a radical substitution (SH2) mechanism. These studies show that with the increasing use of oximes as drugs and pesticides, intake of these chemicals followed by enzymatic oxidation may result in the formation of a variety of reactive intermediates, which may lead to cell and tissue damage.     

Photosensitized reactions of oxime ethers: a steady-state and laser flash photolysis study

The mechanistic aspects of the photosensitized reactions of a series of oxime ethers were studied by steady-state (product studies) and laser flash photolysis methods. Nanosecond laser flash photolysis studies have shown that chloranil-sensitized reactions of the oxime ethers result in the formation of the corresponding radical cations. The radical cation species react with nucleophiles such as MeOH by clean second-order kinetics with rate constants of (0.7-1.4) x 10(6) M(-1) s(-1). Only a small steric effect is observed in these reactions, which is taken as an indication that the reaction center is not the O-alkyl moiety, but rather somewhere else in the molecule. Product studies in a polar nonnucleophilic solvent (MeCN) revealed that in order for the oxime ether radical cation to react more readily, alpha-protons must be available on the alkyl group. The O-methyl (1), O-ethyl (2), and O-benzyl (3) acetophenone oximes all reacted readily to give acetophenone oxime as the major product (as well as an aldehyde derived from the O-alkyl group), whereas O-tert-butyl acetophenone oxime (4) did not. The product formation can be explained by a mechanism that involves electron transfer followed by proton transfer (alpha to the oxygen) and subsequent beta-cleavage. When using 3 in MeOH, a change in the product formation is observed, the most important difference being the presence of benzyl alcohol rather than benzaldehyde as the major product. On the basis of the data from LFP and steady-state experiments, it is suggested that the competing mechanism under these conditions involves electron transfer, followed by a nucleophilic attack on the nitrogen, a MeOH-assisted [1,3]-proton transfer, and subsequent loss of benzyl alcohol. This mechanism is supported by DFT (B3LYP/6-31G) and AM1 calculations.     

Photochemistry of thioxanthones—IV. Spectroscopic and flash photolysis study on novel n-propoxy and methyl,n-propoxy derivatives

The spectroscopic properties of seven oil soluble n-propoxy and methyl, n-propoxy substituted thioxanthone structures have been examined in various solvents and the data compared to their photopolymerization efficiencies, photochemical stabilities and flash photolysis behaviours in solution. Absorption maxima, extinction coefficients, fluorescence and phosphorescence spectra and quantum yields have been measured. Generally, all the compounds exhibit low fluorescence and high phosphorescence quantum yields but the ratio is solvent dependent. These observations are consistent with the high photoreactivity of the molecules operating in the lowest excited triplet state which is nπ* in character. Photopolymerization rates of n-butyl methacrylate with N-diethylmethylamine co-initiator correlate with the absorption maxima and extinction coefficients of the thioxanthones and also the degree of quenching of their fluorescence by the amine, indicating the importance of electron transfer. In the absence of a tertiary amine, transient formation on micro-second flash photolysis in 2-propanol is associated with the ketyl radical formed by the lowest excited triplet state abstracting a hydrogen atom from the solvent. In the presence of a tertiary amine, both ketyl radical and radical anion (at longer wavelengths) are observed, the latter being formed via abstraction of an electron from the amine. This is confirmed by a flash photolysis study using amines of various ionization potentials where a correlation is observed with radical anion absorbance. A pH study confirms the identity of the transient species. Activation of the thioxanthone molecule in the 3 and 4 positions with a methyl group enhances initiator activity whereas substitution in the t-position deactivates the molecule through intra-molecular hydrogen atom abstraction.     

Photoenolization of 2-(2-methyl benzoyl) benzoic acid, methyl ester: effect of E photoenol lifetime on the photochemistry

[reaction: see text] Photolysis of 3 in argon-saturated 2-propanol led to formation of 5 via intermolecular H-atom abstraction followed by lactonization. Irradiation of 4 in 2-propanol gave compounds 6 and 7 that also come from intermolecular H-atom abstraction. In contrast, photolysis of an oxygen-saturated solution of 3 in 2-propanol yields products 8, 9, and 10, which were all formed from intramolecular H-atom abstraction and trapping of the corresponding biradical with oxygen. Laser flash photolysis of 3 in methanol showed formation of biradical 3BR (lambda(max) 330 nm, and tau = 50 ns) via intramolecular H-atom abstraction as the main photoreactivity of 3. Biradical 3BR decayed into photoenols 3Z and 3E (lambda(max) 390 nm, tau = 6.5 micros and tau = 162 micros, respectively). In comparison, laser flash photolysis of 4 yielded photoenols 4Z and 4E (lambda(max) 390 nm, tau = 15 micros and tau = 3.6 ms, respectively). Thus photoenol 3E is unusually short-lived, and therefore it does not undergo the intramolecular lactonization as we have observed for the analogous photoenol 1E. Photoenol 3Z decays back to 3 via an intramolecular 1,5-H shift, whereas photoenol 3E reforms 3 efficiently via the solvent with the aid of the ortho ester group. The intramolecular lactonization of photoenols 1E and 3E must be a slow process, presumably because the photoenols are rigid and the hydroxyl group is inhibited, by intramolecular hydrogen bonding, from acquiring the correct geometry for lactonization. Thus only photoenols that are resistant to reformation of their ketone via the solvent are long-lived enough to undergo lactonization and release the alcohol moiety.     

Photodegradation of poly(vinyl esters)—III. Photolysis mechanism for both polymeric and low molecular mass esters

Acid, aldehyde and carbon dioxide were the major products of the vacuum photodegradations of poly(vinyl acetate) (PVAC), poly(vinyl propanoate) (PVPR) and poly(ethylene-co-vinyl acetate) (PEVAC). Aldehydes have not previously been reported as formed from the acid portions of esters undergoing photolysis. The generality of aldehyde formation has been demonstrated by the detection of the respective aldehydes in the liquid-phase photolysis of butane-1,3-diol diacetate (BDAC) and butane-1,3-diol dipropanoate (BDPR) in this study, which is the first to report the quantum yields for acid and aldehyde formation in low molecular mass esters. Two mechanisms, one involving hydrogen abstraction by the acyl radical formed in a Norrish Type I cleavage process and the other involving an intramolecular hydrogen abstraction by an excited carbonyl group followed by fragmentation, have been proposed to account for aldehyde formation. The absence of propanal from the product distribution in the photo-oxidation of PVPR could be explained by both mechanisms.     

表面活性剂TX-100与SDBS胶束中光解苯甲醛自由基的化学诱导动态电子极化

利用时间分辨ESR波谱仪，研究了苯甲醛在乙二醇和表面活性剂SDBS，TX-100 的胶束溶液中的激光光解化学诱导动态电子极化（CIDEP）现象。苯甲醛在激光照 射下可以从体系和自身中得到氢生成α-羟基苄自由基和苯酰自由基，在SDBS胶束 中是自由基对机理RPM极化，而在TX-100胶束中是三重态机理TM极化。计算机模拟 谱图进一步证实了自由基的产生和极化机理。     

Stereodifferentiation in the decay of triplets and biradicals involved in intramolecular hydrogen transfer from phenols or indoles to pi,pi aromatic ketones

Laser flash photolysis studies on (R,S) and (S,S) diastereoisomers of the bichromophoric compounds 1-6 have been used to investigate the possible chiral discrimination in the quenching of triplet excited ketones, resulting in formal hydrogen abstraction. Deuterium isotopic effects show that triplet deactivation in these bichromophores is dominated by hydrogen atom transfer. A remarkable stereodifferentiation is found in the intramolecular quenching of the ketone triplets of 1-3 and 5 by the phenolic or indolic moieties, either in methanol or acetonitrile as solvents. This indicates the existence of specific structural requirements for hydrogen transfer. On the other hand, the lifetimes of the generated biradicals show large solvent dependence; solvation appears to slow their reversion to the starting ketone. The considerable stereodifferentiation observed for the biradical lifetimes suggests that the kinetics of biradical decay is faster when the approach of the two radical termini becomes easier.     

油溶和水溶性羰基引发剂的光化学

本文回顾了在羰基引发剂的作用下烯烃单体光引发聚合的最新机理。报道了有关多种当前通用的新型羰基引发剂的光物理和光化学的近期工作,其中包括 UV 吸收,发光光谱和闪光光解的研究。还报道了油溶性引发剂对丙烯酸丁酯的光聚合效应。证明油溶性引发剂实质上是经过三重态来起作用,其中包含一个从溶剂中攫取氢的引发步骤。对于硫杂蒽酮衍生物来说,它们从叔胺接受电子的能力及其光聚合效应之间有一定的关系。从闪光光解获得的证据说明在这种情况下存在着自由基阴离子,但是基于二苯酮和苯基酮的引发剂则没有。预料后者直接从胺攫氢是通过三重态羰基或是引发剂的自由基。有证据表明联苯甲酰主要是通过光裂解来起作用。水溶性硫杂蒽酮引发剂的作用主要是经过单重态,其中包含引发时攫氢一步。在这种情况下,自由基的形成不受氧的影响。     

Intramolecular hydrogen abstraction promoted by amidyl radicals. Evidence for electronic factors in the nucleophilic cyclization of ambident amides to oxocarbenium ions

A tandem 1,5-hydrogen atom transfer/radical oxidation/nucleophilic cyclization mechanism is proposed for the intramolecular hydrogen abstraction reaction promoted for primary carboxamidyl radicals. The electron-withdrawing capacity of the C-5 substituent can switch the reaction to give exclusively bicyclic spirolactams (6-oxa-1-azaspiro[4.5]decan-2-one) when R(1) = H or spirolactones (1,6-dioxaspiro[4.5]decan-2-one) when R(1) = OAc. With a substituent of medium polarity (R(1) = OMe), a mixture of lactones and lactams is formed.     

Photophysical and photochemical processes of riboflavin (vitamin B_2) by means of the transient absorption spectra in aqueous solution

Using time-resolved techniques of 337 and 248 nm laser flash photolysis, the photo-physical and photochemical processes of riboflavin (RF, vitamin B2) were studied in detail in aqueous solution. The excited triplet state of riboflavin (3RF*) was produced with 337 nm laser, while under 248 nm irradiation, both 3RF* and hydrated electron (eaq) formed from photoionizationcould be detected. Photobiological implications have been inferred on the basis of reactivity of 3RF* including energy transfer, electron transfer and hydrogen abstraction. The RF.+ was generated by oxidation of SO4.- radical with the aim of confirming the results of photolysis.     

Independent generation and study of 5,6-Dihydro-2'-deoxyuridin-6-yl,a member of the major family of reactive intermediates formed in DNA from the effects of gamma-radiolysis

Nucleobase radicals are the major family of reactive intermediates formed when nucleic acids are exposed to gamma-radiolysis. Elucidation of their reactivity is complicated by the formation of multiple species randomly throughout the biopolymers. 5,6-Dihydro-2'-deoxyuridin-6-yl (1) was generated upon photolysis (350 nm) of the respective tert-butyl ketone (2). The radical abstracts hydrogen atoms from beta-mercaptoethanol (k = 8.8 +/- 0.5 x 10(6) M(-)(1) s(-)(1)) and 2,5-dimethyltetrahydrofuran (k = 31 +/- 2.5 M(-)(1) s(-)(1)). The latter was used as a model for the 2-deoxyribose component of DNA. The major product formed in the presence of O(2) was 6-hydroxy-5,6-dihydro-2'-deoxyuridine (11), which is believed to be formed directly from the peroxy precursor and not via elimination of superoxide. Small amounts of 2-deoxyribonolactone (13) were also formed under aerobic conditions. This product is believed to result from intramolecular hydrogen atom abstraction by the C6-peroxyl radical (14) and suggests that gamma-radiolysis may indirectly result in oxidation of the C1'-position of nucleotides, despite the inaccessibility of this hydrogen in duplex DNA.     

Mechanism of the hydrogen transfer from the OH group to oxygen-centered radicals: proton-coupled electron-transfer versus radical hydrogen abstraction

High-level ab initio electronic structure calculations have been carried out with respect to the intermolecular hydrogen-transfer reaction HCOOH+.OH-->HCOO.+H(2)O and the intramolecular hydrogen-transfer reaction .OOCH2OH-->HOOCH(2)O.. In both cases we found that the hydrogen atom transfer can take place via two different transition structures. The lowest energy transition structure involves a proton transfer coupled to an electron transfer from the ROH species to the radical, whereas the higher energy transition structure corresponds to the conventional radical hydrogen atom abstraction. An analysis of the atomic spin population, computed within the framework of the topological theory of atoms in molecules, suggests that the triplet repulsion between the unpaired electrons located on the oxygen atoms that undergo hydrogen exchange must be much higher in the transition structure for the radical hydrogen abstraction than that for the proton-coupled electron-transfer mechanism. It is suggested that, in the gas phase, hydrogen atom transfer from the OH group to oxygen-centered radicals occurs by the proton-coupled electron-transfer mechanism when this pathway is accessible.     

Triplet reactivity and regio-/stereoselectivity in the macrocyclization of diastereomeric ketoprofen-quencher conjugates via remote hydrogen abstractions

Intramolecular excited triplet state interactions in diastereomeric compounds composed of a benzophenone chromophore (ketoprofen) and various hydrogen donor moieties (tetrahydrofuran, isopropylbenzene) have been investigated by laser flash photolysis. The rate constants for hydrogen abstraction by excited triplet benzophenone are in the order of 10(4)-10(5) s(-1), with the highest reactivity for the tetrahydrofuran residue. A remarkable diastereodifferentiation, expressed in the triplet lifetimes of the carbonyl chromophore (e.g., 1.6 versus 2.7 micros), has been found for these compounds. With an alkylaromatic moiety as donor, related effects have been observed, albeit strongly dependent on the length of the spacer. The reactivity trend for the initial hydrogen transfer step is paralleled by the quantum yields of the overall photoreaction. The biradicals, formed via remote hydrogen abstraction, undergo intramolecular recombination to macrocyclic ring systems. The new photoproducts have been isolated and characterized by NMR spectroscopy. The stereochemistry of the macrocycles, which contain up to four asymmetric carbons, has been unambiguously assigned on the basis of single-crystal structures and/or NOE effects. Interestingly, a highly regio- and stereoselective macrocyclization has been found for the ketoprofen-tetrahydrofuran conjugates, where hydrogen abstraction from the less substituted carbon is exclusive; cisoid ring junction is always preferred over the transoid junction. The photoreaction is less regioselective for compounds with an isopropylbenzene residue. The reactivity and selectivity trends have been rationalized by DFT (B3LYP/6-31G*) calculations.     

取代苯甲醛肟和取代苯乙酮肟电化学氧化机理的研究

研究了１０种取代苯甲醛肟和５种取代苯乙酮肟的电化学氧化机理。这二类肟的氧化电位随取代基吸电子能力的增大而增高，并与它们相应的Ｈａｍｍｅｔｔ常数有线性关系。它们在电化学氧化过程中均有ｉｍｉｎｏｘｙ自由基生成，但最后产物各不相同。用控制电位电解和紫外吸收光谱检法验证了部分电化学氧化产物。因此，电化学氧化法可作为由肟类产生ｉｍｉｎｏｘｙ自由基的一种方法。     

THE PHOTOREDUCTION OF FLAVINS BY AMINO ACIDS AND EDTA. A CONTINUOUS AND FLASH PHOTOLYSIS STUDY

Abstract— Primary and secondary photochemical processes in oxygen-free aqueous solution have been characterised for FMN alone and in the presence of EDTA and four amino acids using nanosecond and microsecond flash photolysis and continuous photolysis techniques. The relative contributions of oneelectron and two-electron (group or hydride transfer) reactions to the deactivation of the triplet has been determined by comparing the radical concentration (560 nm) with the bleaching of the ground state (446 nm). It was concluded that one-electron reactions (hydrogen atom or electron abstraction) are the major mode of reactivity of the flavin triplet state with all the suhstrates studied.
The nature of the reactions of the flavin semiquinone radical have been studied quantitatively by microsecond flash photolysis. These secondary reactions consist of either a 'back reaction' between the flavin and substrate radicals (tryptophan or glycyl-tyrosine) or the transfer of a second electron (or hydrogen atom) from the substrate radical to the flavin radical (EDTA, methionine and possibly cysteine) to form reduced flavin and oxidised substrate. From a comparison of the quantum yields of formation of reduced flavin using 'flash' and continuous irradiation, an additional pathway for the decay of the flavin radical is suggested to occur at low light intensities in the presence of glycyl-tyrosine or histidine.     

Physico-chemical aspects of polyethylene processing in an open mixer. Part 19: Mechanisms and kinetics of vinyl and vinylidene group formation

Vinyl and vinylidene group formation is detected in the initial stages of polyethylene processing. In the high temperature range (170-200 °C) the amount formed is small but significant. Formation of these double bonds is usually obscured by their rapid consumption. Bimolecular hydroperoxide decomposition does not seem to be an important source for these products in the early stages of processing. Vinyl and vinylidene group formation can be attributed mainly to intramolecular decomposition of special hydroperoxide groups. The data suggest vinyl groups to arise from secondary hydroperoxide groups formed in α-position to methyl branching. Intramolecular hydroperoxide decomposition involving a primary hydrogen atom from the methyl group yields a vinyl group and an aldehyde. Vinylidene groups seem to arise from secondary hydroperoxide groups formed in α-position to quaternary structures that necessarily include one methyl group. Intramolecular hydrogen abstraction of a primary hydrogen atom from the methyl group yields a vinylidene group and an aldehyde. The calculated rate parameters are in agreement with the thermochemical estimations relative to intramolecular abstraction of primary hydrogen atoms for both reactions. Vinyl groups are also formed on bimolecular hydroperoxide decomposition. The yield of vinylidene groups from the last reaction is negligible.     

Photochemistry of thioxanthones—III. Spectroscopic and flash photolysis study on hydroxy and methoxy derivatives

The spectroscopic properties of 9 oil soluble hydroxy and methoxy thioxanthone derivatives have been examined in various solvents and the data compared to their photopolymerization efficiency and flash photolysis behaviour in solution. Absorption maxima, extinction coefficients, fluorescence and phosphorescence spectra and quantum yields have been measured. Generally, most of the compounds exhibit low fluorescence and high phosphorescence quantum yields except 1-substituted derivatives where intra-molecular hydrogen bonding is involved. These observations are consistent with the high photoreactivity of the molecules occurring via the lowest excited triplet state. Photopolymerization rates of n-butyl methacrylate, using N-diethylmethylamine as co-initiator, correlate to some extent with the absorption maxima and extinction coefficients of the thioxanthones. Transient formation on micro-second flash photolysis is associated with the ketyl radical formed by the lowest excited triplet state of the thioxanthones abstracting a hydrogen atom from the solvent. In the presence of a tertiary amine, a new longer wavelength transient absorption is produced and is assigned to a radical-anion formed by the lowest excited triplet state of the thioxanthones abstracting an electron from the amine. A correlation was observed between the transient absorption due to the radical-anion and the ionisation potential of various amines. Flash photolysis studies in acid and base media confirmed the identity of the radical and radical-ion species. Intra-molecular hydrogen bonding in the α-position to the carbonyl group deactivates both the lowest excited singlet and triplet states of thioxanthone but has little effect on polymerization efficiency. The latter is associated with competition of the carbonyl group with the amine co-initiator for hydrogen bonding and consequent electron abstraction to give an active radical-anion. This is confirmed using micro-second flash photolysis.     

Excited-state behavior and photoionization of 1,8-acridinedione dyes in micelles--comparison with NADH oxidation

The photophysics and photochemistry of 1,8-acridinedione dyes, which are analogues of reduced nicotinamide adenine dinucleotide (NADH), are studied in anionic and cationic micelles. Acridinedione dyes (ADDs) are solubilized in micelles at the micelle-water interface and are in equilibrium between the aqueous and micellar phase. The binding of the ADDs with micelles is attributed to hydrophobic interactions and the binding constants are determined with steady-state and time-resolved techniques. Nanosecond laser flash photolysis studies are carried out in aqueous, anionic, and cationic micellar solutions. The ADD undergoes photoionization in the excited state to give a solvated electron. The solvated electron reacts with the ADD to give an anion radical. In anionic micelles, the yield of the solvated electron increases because of the efficient separation of the cation radical and the electron. Cation radicals derived from the photooxidation of ADDs are involved in keto-enol tautomerization. Under acidic conditions, an enol radical cation of the acridinedione dye is formed from the keto form of the cation radical by intramolecular hydrogen atom transfer. In cationic micelles, due to electrostatic attraction, the electron cannot escape from the micelle and recombination of the cation radical and the electron results in the formation of a triplet state. For the first time, a solvated electron is observed in the laser flash photolysis of ADDs in anionic micelles. The photoionization of ADDs depends on the excitation wavelength and is biphotonic at 355 nm and monophotonic at 248 nm. From the results with this NADH model compound, the sequential electron-proton-electron transfer oxidation of NADH is confirmed and the nature of the intermediates involved in the oxidation is unraveled; these intermediates are found to depend on the pH value of the medium.     

Photoenolization as a means to release alcohols

We have designed molecules which release alcohols upon exposure to UV light independent of the reaction media, making it possible to liberate alcohols in a controlled manner in applications. Photolysis of 2-(2-isopropylbenzoyl)benzoate ester derivatives 4 in various solvents and in thin films results in the liberation of the alcohol moiety from the ester. The reaction mechanism for the release of the alcohol has been elucidated by time-resolved laser flash photolysis. Upon irradiation the triplet excited state of ketone, 4 is formed, and its lifetime can be estimated to be between 0.08 and 0.8 ns. The triplet excited state decays by efficient intramolecular H-atom abstraction to form a 1,4-biradical, 8, that has a lifetime of less than 17 ns and is trapped by molecular oxygen. In the absence of oxygen, biradical 8 intersystem crosses to form photoenols (Z)-9 and (E)-10 in a ratio of 5:2, respectively. Photoenol (Z)-9 has a lifetime of approximately 3000 ns in protic solvents and returns to the starting material through 1,5 intramolecular hydrogen transfer. The other isomer, (E)-10, is much longer lived (>1 ms) and releases the alcohol moiety through an intramolecular lactonization.