52134-09-5Relevant academic research and scientific papers
Zeolite matrix assisted decomposition of singlet oxygen sensitizers during photooxidation
Shailaja,Sivaguru,Ramamurthy
, p. 197 - 205 (2016/11/16)
Thiazine dyes such as thionine, methylene blue and methylene green were exchanged within monovalent cation exchanged Y zeolites. Depending on the water content the dye molecules exist as either monomer (‘dry’) or dimer (‘wet’). The monomeric dye is effect
SUBSTITUTED FLUOROETHYL UREAS AS ALPHA 2 ADRENERGIC AGENTS
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Page/Page column 45, (2008/12/04)
Therapeutic compounds, and methods, compositions, and medicaments related thereto are disclosed herein.
A radical cyclisation based cyclopentenone annulation of allyl alcohols
Srikrishna,Viswajanani,Sattigeri
, p. 2975 - 2983 (2007/10/03)
A four-step cyclopentenone annulation reaction of allylic alcohols employing a 5-exo-trig radical cyclisation reaction of mixed allyl methyl ketals of bromoacetone as the key step is described. The annulated product 12b obtained from 2,3-dimethylcyclohexenol has been further elaborated into (±)-epibakkenolides employing a 5-exo-dig radical cylisation reaction based α-spiro-β-methylene-γ-butyrolactone annulation methodology.
DICYANOANTHRACENE SENSITIZED PHOTO-OXYGENATION OF OLEFINS. ELECTRON TRANSFER AND SINGLET OXYGEN MECHANISMS
Foote, Christopher S.
, p. 2221 - 2228 (2007/10/02)
Cyanoaromatic sensitizers, in particular 9,10-dicyanoanthracene (DCA), sensitize the photooxygenation of olafins by two distinct mechanisms.In the case of aryl substituted olefins (OL), which react extremely slowly (if at all) with singlet oxygen, the reaction proceeds by way of electron transfer to produce discrete radical ions (DCA-. and OL+.).In the presence of oxygen, this ionic process results, ultimately, in the cleavage of the olefin to carbonyl compounds along with production of some epoxide and other minor byproducts.Aromatic ethers can interfere with this process by reducing the radical cation by electron transfer, resulting in net quenching of the reaction.With simple alkenes the DCA-sensitized reaction takes a different course, producing hydroperoxide products with distributions which are very similar to those obtained with the singlet oxygen ene reaction.Careful study has shown that this reaction does, indeed, proceed by way of singlet oxygen, which is produced by at least two mechanism: (1) enhanced intersystem crossing, in which 1DCA is quenched by interaction with the olefin, leading to a low yield of 3DCA, which subsequently reacts with oxygen to produce singlet oxygen; and (2) direct reaction of 1DCA with oxygen.At limiting high oxygen concentration, this process produces 2 mol of singlet oxygen for each mol of 1DCA quenched; the mechanism involves energy transfer to produce 3DCA and 1 mol of singlet oxygen; the 3DCA reacts again with oxygen to produce a second mol of singlet oxygen.The complex kinetic behaviour of simple olefins in the presence of DCA can be satisfactorily rationalized by these mechanisms.
MECHANISTIC STUDY ON THE PHOTO-OXIDATION OF α-DIKETONES. INTERACTION OF TRIPLET α-DIKETONES WITH OXYGEN
Sawaki, Yasuhiko
, p. 2199 - 2206 (2007/10/02)
The mechanism for photo-oxidation of α-diketones in the presence of olefins has been studied, focusing on the interaction of triplet diketones with O2.Two types of reactions occur competitively.One is the formation of 1O2 by energy transfer to O2 and the other is the addition of O2 to triplet diketone, which yields acylperoxy radicals leading to the radical epoxidation of olefins.Ratios of the two reactions were determined from the yields of 1O2 products and epoxides.For most diketones, quantum yields for 1O2 formation were considerably high, in the range 0.3-0.8; but the yields for epoxides were in a wider range of 0.001-0.5.While the ratios of 1O2 formation and O2 addition to triplet diketones ranged from 29:71 for biacetyl to 1:99 for mesitil, the ratios remained constant by changing solvents or temperature.The latter O2 addition reaction decreased in the order of MeCOCOMe > PhCOCOMe > PhCOCOPh but the effect of m- and p-substituents on benzils was not significant, indicating the addition of O2 as a neutral biradical.In exceptional cases, the O2 addition was not effective for sterically inaccessible mesitil and some cyclic α-diketones.The mechanism of 1O2 formation was discussed in comparison to other carbonyl compounds.
PHOTOCHEMICAL GENERATION OF SINGLET OXYGEN ON NON-TRANSITION-METAL OXIDE SURFACES
Gohre, Kirk,Miller, Glenn C.
, p. 793 - 800 (2007/10/02)
Irradiation of the non-transition-metal oxide powders silica gel, aluminium oxide and magnesium oxide in the presence of oxygen results in the formation of singlet oxygen (1O2).Two specific chemical traps were used to detect 1O2: 1,2-dimethylcyclohexene and geminally deuterated 2H6>-2,3-dimethylbut-2-ene.Both compounds gave product distributions characteristic of singlet-oxygen reactions when irradiated on the metal oxide surfaces.These results support previous suggestions that singlet oxygen is formed through an energy-transfer process involving oxygen and excitons on the metal oxide surface.Under the same reaction conditions TiO2 showed no production of 1O2.
Mechanism of the Reaction of Nitriles with Alkaline Hydrogen Peroxide. Reactivity of Peroxycarboximidic Acid and Application to Superoxide Ion Reaction
Sawaki, Yasuhiko,Ogata, Yoshiro
, p. 793 - 799 (2007/10/02)
Formation of peroxycarboximidic acid (1) is not rate-determining in the reaction of nitrile with alkaline hydrogen peroxide to form amide and oxygen; the yield of amide based on H2O2 varies from 20 to 60percent.When dimethyl sulfoxide (DMSO), a reactive substrate, is added, the rate is independent of and governed in turn by a rate-determining addition of HOO- to nitrile.This reaction gives a reliable α-value of kHOO-/kHO-, which is 10000 for benzonitrile.A facile conversion of nitrile to amide may be achieved by the reaction in the presence of DMSO, unacco mpanied by side reactions such as the epoxyamide formation from α,β-unsaturated nitrile.Kinetics and product analysis suggest that a predominant reaction is not a non-radical oxidation of H2O2 with 1 but a radical decomposition of H2O2 which is induced by the homolysis of anion of 1 (1A).No singlet oxygen could be trapped chemically.The reaction of superoxide ion, O2-., with acetonitrile is shown to be analogous to that of HOO-; the decomposition of O2-. is fast in the presence of MeCN and DMSO in benzene, affording acetamide and dimethyl sulfone.
