共查询到20条相似文献,搜索用时 15 毫秒
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The 3-alkyl-2,2-dimethyl-4-(tert-butyl)-2H-thietes 9a–c were obtained in several steps from the corresponding, newly synthesized, 3-alkyl-2-(tert-butyl)thiophenes 5a–c. Irradiation (254nm) of these tetraalkylated four membered S-heterocycles leads to a photostationary equilibrium with enethiones 10a–c (thiete/enethione 3:1). 相似文献
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The 6-chloro-2-cyclohexenones 3, 6 and 11 , and the 5-chloro-2-cyclopentenone 15 were newly synthesized. The results obtained with compounds 3 and 15 in photocycloadditions to olefins show that the oxetane vs. cyclobutane product ratio is reduced by the substitution of florine by chlorine in the α′ -position of the enone. No oxetanes are formed in the intramolecular photocycloaddition of 6. Compound 11 does not photoadd to olefins. The newly synthesized 2-chloro-3-cyclohexenones 8 and 9 are also photostable towards light of λ=366 nm, but π-π*-excitation (λ=254 nm) in pentane leads to the formation of 4,4-dimethylcyclohexanone (29) . 相似文献
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Upon irradiation in 2-propanol, p-nitroacetophenone 1 was reduced via the triplet state to p-hydroxyaminoacetophenone 5 which was further reduced to p-aminoacelophenone 2 and 4,4′-diacetylazobenzene 4 . Similar irradiation of 5 also gave 2 and 4 , and its oxidation by oxygen gave 4,4′-diacetylazoxybenzene 3 . Photolysis of monomeric p-nitrosoacetophenone 6 afforded acetophenone and 3 that were not produced during the irradiation of 1 . Possible photoreaction pathways were discussed on the basis of published mechanisms. 相似文献
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《Journal of fluorine chemistry》1986,34(1):105-115
The photochemical behaviour of the title compound, newly synthesized from 2-trifluoromethylcyclohexanone by a bromination/dehydrobromination sequence, is compared to that of 6-methyl-2-cyclohexenone. Both compounds behave similarly regarding photocyclodimerization and addition to 2-methylpropene. Higher yields of reduction (electron transfer) products from the trifluorometahyl- vs. the methyl enone are obtained in the irradiations in the presence of 2,3-dimethyl-2-butene or in 2-propanol, respectively. 相似文献
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Kehrloesser D Baumann RP Kim HC Hampp N 《Langmuir : the ACS journal of surfaces and colloids》2011,27(7):4149-4155
We describe the synthesis and photochemistry of coumarin-functionalized silica nanoparticles, which were prepared utilizing 7-[3-(triethoxysilyl)propanyloxy]coumarin (TPC) to attach coumarin as a photoactive group to the silica nanoparticle surface. The nanoparticle size and morphology were investigated by scanning electron microscopy, atomic force microscopy, and dynamic light scattering. The diameter of the spherical nanoparticles was determined by all three methods to be about 40 nm. The surface functionalization was characterized in the bulk by ζ-potential measurements and on the single-nanoparticle level by electrostatic force microscopy, where the difference in surface potential between TPC-modified and unmodified silica nanoparticles is measured. The degree of surface functionalization was determined by thermogravimetric analysis (TGA), and a theoretical limit of about 23,000 coumarin entities per nanoparticle was calculated. The photochemistry, and its reversibility, of the nanoparticle-attached coumarin entities was found to be quite different from the coumarin photochemistry in solution or on flat surfaces. Photodimerization with light of 355 nm and photocleavage with light of 254, 266, and 280 nm were analyzed by absorption and fluorescence spectroscopy. Following several cycles of photodimerization and photocleavage showed that the absorption change at 320 nm decreases from cycle to cycle. The coumarin layer on the nanoparticles was proven to be unchanged by TGA. The apparent loss of absorption change is due to the formation of interlinked nanoparticles during the dimerization-cleavage cycles. Because the coumarin groups on the inside of the obtained nanoparticle clusters are inaccessible to light, the amount of "uncleavable" dicoumarins increases, thus lowering the obtainable absorption change from cycle to cycle. 相似文献
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Methyl 2-allyl-3-oxo-2,3-dihydrothiophene-2-carboxylate ( 2 ) photocyclizes selectively to methyl 2-oxo-7-thiatricyclo[3.2.1.03,6]octane-1-carboxylate ( 4 ). In contrast, 4-thia-2-cyclohexenone 3 , on irradiation, affords only low yields of dimers, cycloadducts (2-methylpropene) or RH reduction products (i-ProH). 相似文献
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《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》1987,43(8):1087-1098
A new technique—photoacoustic spectroscopy—has been used for the first time to record the u.v.-vis spectra of three substituted toluenes, namely 2-amino-6-nitrotoluene, 4-amino-3-bromotoluene and 5-amino-2-bromotoluene. The π-π* electronic transitions analogous to the benzene first primary and secondary transitions could be detected from the PAS spectra in comparison with the u.v. solution and vapour spectra recorded by conventional methods. Detection of singlet → triplet absorptions from the PAS spectra, with significant intensity, is considered to be an important feature which transitions are in general either not observed or observed with only very weak intensity, in solution or vapour, by conventional methods. The analysis shows that a few excited state combinations observed in the u.v. PAS spectra of the molecules presently studied are well comparable with such combinations in ground state observed in the near i.r. PAS spectra. 相似文献
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Hans-Ulrich Gonzenbach Inga-Mai Tegmo-Larsson Jean-Pierre Grosclaude Kurt Schaffner 《Helvetica chimica acta》1977,60(3):1091-1123
2-Cyclopentenyl and 3-phenyl-2-cyclopentenyl methyl ketones (15–18, 30, 31) undergo a 1,3-acetyl shift on direct irradiation, and the oxa-di-π-methane rearrangement to photochemically non-interconverting endo and exo bicyclo-[2.1.0]pentyl methyl ketones on triplet sensitization. Exceptions include the 2-methyl-3-phenyl-2-cyclopentenyl methyl ketone 32 and the 1-phenyl-2-cyclo-pentenyl methyl ketone 44 which are unreactive on direct irradiation and on triplet sensitization, respectively, and the 2-phenyl-2-cyclopentenyl methyl ketones 42 and 43 which do not react under either condition. The reactive triplet of the 3-phenyl-2-cyclopentenyl methyl ketone 30 has been identified as the localized styrene π,π*-state of ET=59 kcal/mol by comparison of its phosphorescence at 77K in rigid glasses with that of 1-phenyl-cyclopentene, and by the independence of the quantum yield on sensitizer energy in the range of 61–74 kcal/mol. 相似文献
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《Tetrahedron letters》1986,27(39):4675-4678
Photolysis of the title compounds (n=10, 11, 12, 15) yields mainly cyclophanes. The product distribution depends on temperature and solvent. 相似文献
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