Photorearrangement of vinylidenecyclopropanes to 1,2,3-butatriene derivatives

[reaction: see text] Photoirradiation of benzene solutions containing 1-diarylvinylidene-2,2,3,3-tetramethylcyclopropanes (2a--d) afforded rearranged products 1,2,3-butatrienes (3a-d) in good to high yields. Photorearrangement from 2,2,3-trimethyl and 2,2- and 2,3-dimethyl derivatives 2e--g also proceeded, but the rates of the rearrangement were lower than those of 2a--d. A singlet mechanism is proposed for this photorearrangement, where alkyl migration occurs from 1,3-biradical intermediates generated via the homolysis of the C1-C2 bond. Generation of diarylvinylidene carbenes from 1,3-biradicals might be competitive with the formation of 3.     

Photoinduced reactions—LXXI: Photorearrangement of 3-hydroxyflavones to 3-aryl-3-hydroxy-1,2-indandiones

3-Hydroxyflavones (1) were found to undergo a novel photorearrangement to 3-aryl-3-hydroxy-1,2-indandiones (2) which were characterized as o-phenylenediamine adducts, 1-aryl-1-hydroxy-11H-indeno[1,2-b]quinoxalines (3). To the contrary, 3-methoxyflavone underwent photochemical intramolecular hydrogen transfer. Photochemical reactivities of several other flavonoids were examined. It appears that the 5-hydroxyl H-bonded to the 4-carbonyl causes photoresistance in flavonoids.     

Photorearrangement of phenyl selenide derivatives. Access to selenium substituted C-nucleosides

The photorearrangements of benzyl phenyl selenide and phenyl ribosyl selenide derivatives afford 2-benzyl phenylselenol and 2-ribosyl phenylselenol, respectively which can be isolated as their methyl derivatives.     

Photocyclization of enol acetates of o-acetoxyacetophenones to chromones

Enol acetates of o-acetoxyacetophenones give chromones upon irradiation with uv-light.     

Photorearrangement of Aryl Esters in Micellar Medium

Effect of a micelle (SDS) on the photorearrangement of aryl esters have been investigated. Thus, phenyl, p- and m-cresyl, and 2-naphthyl benzoates yielded the corresponding o-hydroxybenzophenones as a major product in high yield. Phenyl cinnamate gave 2-hydroxychalcone. 2,4,6-Tri-butylphenylbenzoate, however, underwent decarboxylation yielding 2,4,6-tri-t-butyl biphenyl in quantitative yield.     

Photorearrangement of phenyl cinnamates under micellar environment

Photolysis of phenyl cinnamates in aqueous SDS medium results in an efficient and high yield synthesis of the corresponding 2′-hydroxychalcones.     

Photocyclization of 2-[1]benzothien-3-yl)-3-phenylpropenoic acids

Photocyclization of the substituted 2-([1]benzothien-3-yl)-3-phenylpropenoic acids 3a-c in the presence of iodine and air in a benzene-cyclohexane mixture afforded a separable mixture of three compounds, benzo[b]naphtho[2,1-d]thiophene-6-carboxylic acids 4a-c , 6H-benzo[b]naphtho[2,3-d]thiopyran-6-ones 5a-c , and 10-methoxy-2-methyl-6H-benzo[b]naphtho[2,3-d]pyran-6-one ( 6 ).     

Photocyclization of 2-chloro-substituted 1,3-diarylpropan-1,3-diones to flavones

The photochemical behavior of 2-halo-substituted 1,3-diarylpropan-1,3-dione strongly depends on the nature of the halogen atom bonded and the presence of electron-donor groups on the phenyl ring. In the case of 2-chloro-1,3-diphenylpropan-1,3-dione and 1-(3,5-dimethoxyphenyl)-3-phenylpropan-1,3-dione, cyclization to flavones was the sole reaction pathway, whereas in the case of 2-chloro-1,3-di(4-methoxyphenyl)propan-1,3-dione, only products derived from alpha-cleavage were observed. 2-Fluoro derivatives of 1,3-diarylpropan-1,3-diones were photostable; on the other hand, 2-chloro-2-fluoro derivates resulted in 3-fluoroflavones.     

联苯基团引起的激发三重态重排活性增长

双发色团分子光化学研究兴趣与日俱增。我们在以前报道一个有趣的现象:基态发色团间的分子轨道交叠左右光反应机理。3-甲基-3-联苯基-1-丁烯(1),是有特殊意义的分子。与激发能高达(143 kcal/mol)的孤立双键相比,联苯基的激发能特别低(69 kcal/mool)。如此大的激发能差使乙烯基与联苯 p电子间的交叠通道更加畅通,基态1的稳定构象是 endo 型,1的光化学行为将不同于无环双π甲烷分子。1000 W 高压汞灯照射1的正已烷溶液,     

Photorearrangement of photocycloadducts from arenes and 1,3-cyclohexadiene

The 4π_s+π_s photoadduct from an arene and 1,3-cyclohexadiene may undergo a photochemical rearrangement to the 4π_s+π_s adduct.     

Photocyclization of 2,4,6-triethylbenzophenones in the solid state

Photocyclization of 2,4,6-triethylbenzophenones (TEBPs) into (E)- or (Z)-benzocyclobutenols ((E)- or (Z)-CBs) is E-selective in solution. By contrast, upon solid-state photolysis, TEBP-3,4-diCl and especially TEBP-4-t-Bu gave (Z)-CB relative to (E)-CB with a much higher proportion than that in solution. For TEBP-4-t-Bu, the most major product in the solid state is an indanol derivative (Inol) (E/Z/Inol=1:3.9:10.3 at 9% conversion). On the basis of the X-ray crystallographic analysis, Inol and (Z)-CB are both topochemical products. Notably, the relative proportion of (E)-CB increased with increased conversion, namely with increased disruption of the crystal lattice. The DFT calculation of highly hindered 2,6-diisopropylbenzophenone (DIBP) was also conducted. These results in conjunction with the previous results on 2,4,6-triisopropylbenzophenones (TIBPs) indicate that CB is formed either via trans-enol followed by its conrotatory ring-closure (paths a and d) or through direct cyclization of biradical (BR) (path b) as shown in Scheme 1. Normally the former route is faster. However, in the crystalline state or in the case of sterically hindered phenyl ketones, path b tends to be adopted.     

Photorearrangement of ylidene tautomers of azinyl(o-nitrophenyl)-carbomethoxymethanes

The photochemical properties of ylidene tautomers of azinyl (o-nitrophenyl) carbomethoxy-methanes have been examined. Photolysis at the absorption wavelength of the ylidene tautomer results in selective rearrangement of a type hitherto unknown in o-nitro-styrenes, involving transfer of an oxygen atom to exocyclic carbon, and reduction of the nitro group to nitroso.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2323–2327, October, 1989.