20153-15-5

Upstream product

• 20153-17-7 1,4-dimethyl-9,10-diphenylanthracene 1,4-endoperoxide 
• 20153-16-6 1,4-dimethyl-9,10-diphenyl-9,10-dihydro-9,10-epidioxido-anthracene 
• 32314-49-1 1,4-epidioxy-1,4-dimethyl-9,10-diphenyl-1,2,3,4-tetrahydroanthracene 
• 40732-11-4 C₂₉H₂₅N 
• 32456-88-5 (1S,4R)-1,4-Dimethyl-9,10-diphenyl-1,2,3,4-tetrahydro-anthracene-1,4-diol 

Downstream Products

• 20153-17-7 1,4-dimethyl-9,10-diphenylanthracene 1,4-endoperoxide 
• 20153-16-6 1,4-dimethyl-9,10-diphenyl-9,10-dihydro-9,10-epidioxido-anthracene 

Relevant academic research and scientific papers

Mechanism of Thermolysis of Endoperoxides of Aromatic Compounds. Activation Parameters, Magnetic Field, and Magnetic Isotope Effecs

A mechanistic investigation has been made of the thermolysis of several endoperoxides of anthracenes and naphthalenes which produce molecular oxygen and the parent aromatic species quantitatively.Qualitative thermochemical measurements in the solid state indicate that in all cases studied, the reactions were endothermic.This situation appears to be valid in solution also.Clean first-order kinetics were observed for these thermolyses.Activation parameters were derived from the temparature dependence of the first-order rate constants.The primary yields of singlet oxygen (1O2) from the several endoperoxides were determined, and a correlation was discovered between the A factors (ΔS values) for thermolysis and the yield of 1O2.It was found that high A factors (positive ΔS values) correlated with relatively low yields of 1O2 and that low A factors (slightly negative or near zero ΔS values) correlated with nearly quantitative yields of 1O2.These two results are interpreted in terms of a diradical mechanism which leads to low yield of 1O2 and a concerted mechanism which leads to quantitative yields of 1O2.This interpretation is consistent with the observation of a magnetic field effect on the yield of 1O2 from endoperoxides whose thermolyses proceed with positive ΔS values and the absence of a magnetic field effect on the yield of 1Oi endoperoxides whose thermolyses proceed with near zero ΔS values.Further support for the occurrence of a diradical mechanism is available from the demonstration of a special 17O isotope effect on the thermolysis of an endoperoxide which is postulated to undergo thermolysis principally via a diradical intermediate.The thermolysis of endoperoxides which decompose mainly by a diradical mechanism yields triplet molecular oxygen that is selectively enriched in 17O.

Photolysis of endoperoxides in the presence of nitroxides: A laser flash photolysis study with optical and ESR detection

Time-resolved electron paramagnetic resonance spectroscopy, transient absorption, and phosphorescence spectroscopy were used to investigate the spin polarization of a nitroxide free radical induced by interaction with singlet oxygen (1O2). The latter was generated by photolysis of endoperoxides of two anthracene derivatives. Although both anthracene endoperoxides are structurally similar, opposite spin polarization of the nitroxide was observed. Photolysis of one endoperoxide leads to absorptive nitroxide spin polarization due to interaction with the generated 1O2. Photolysis of the other endoperoxide generated emissive nitroxide spin polarization, probably due to interaction of the endoperoxide triplet states with nitroxides. The Royal Society of Chemistry and Owner Societies.

Chemical syntheses of syn- and anti-1,2;3,4-diepoxides derived from 1,4-dimethyl-and 1,2,3,4-tetramethylanthracenes and naphthalenes

Chemical isomerization of 1,4-endoperoxides 1a,b,n derived from meso-unsubstituted 1,4-dimethyl- or 1,2,3,4-tetramethylanthracenes (and naphthalenes) to syn-1,2;3,4-diepoxides 2a,b,n has been achieved by treatment at room temperature with FeSO4 in CH3CN containing pyridine. With analogous 9,10-diphenyl derivatives 1c,d, heating appears necessary and the same isomerization is then superseded by another type of rearrangement leading to dihydronaphthoxanthenols 4c,d. An electron-exchange mechanism may explain the difference between both series. In contrast, the isomeric anti-1,2;3,4-diepoxides 19b,c,d,n have been prepared by direct epoxidation of the hydrocarbons 18a-d,n with dimethyldioxirane generated in situ. In this case, the reaction is more efficient for 9,10-diphenyl derivatives 18c,d than for meso-unsubstituted ones 18a,b as the latter can undergo competitive oxidations at meso-positions leading to 10-hydroxy-9-anthrones 22a,b at the same time as anthraquinones 23a,b. Elsevier.

State-Selective Photochemistry of Singlet Oxygen Precursors: Kinetics and Wavelength Dependence of the Photodissociation of Anthracene Endoperoxides

The photochemical behavior of the two isomeric endoperoxides (9,10-PMO2 and 1,4-PMO2) of 1,4-dimethyl-9,10-diphenylanthracene was found to differ in their kinetics and reaction efficiencies.Consistent with the work of Rigaudy et al. and Brauer et al. on a related endoperoxide we find that the generation of 1O2 is wavelength dependent, occuring from upper excited singlet states of the endoperoxide, whereas bond cleavage of the O-O endoperoxide bond occurs principally from the lowest excited singlet and triplet states.Results of picosecond kinetics and absolute quantum yield measurements are discussed in terms of various concerted and nonconcerted mechanisms for the formation of 1O2 and the anthracene fragment.

THE ROLE OF INTERSYSTEM CROSSING STEPS IN SINGLET OXYGEN CHEMISTRY AND PHOTO-OXIDATIONS

Singlet oxygen chemistry and photo-oxidation reactions, in general, often require one or more critical reaction steps that involve an intersystem crossing from a singlet state to a triplet state or vice versa.This paper considers two important intersystem crossing mechanisms, electron spin-electron orbit (spin-orbit) coupling and electron spin-nuclear spin (spin-spin) coupling, and how they may be involved: (1) in the deactivation of 1O2 to 3O2; (2) in the thermal catalytic conversion of 3O2 to 1O2; and (3) in the fragmentation of aromatic endoperoxides to yield O2 and an aromatic substrate.

Transformations photochimiques d'endoperoxydes derives d'hydrocarbures aromatiques polycycliques IV. Effet de phenyles en peri sur la photo-isomerisation des endoperoxydes-1,4 tetrahydroaromatiques

Photolysis in benzene at long wavelengths of 1,4-epidioxy-1,4-dimethyl-9,10-diphenyl-1,2,3,4-tetrahydroanthracene 1a affords essentially two products: 2,5-epoxy-2,5-dimethyl-6,11-diphenyl-2,3,4,5-tetrahydronaphthooxepine 8a and 5a,8-dimethyl-9-phen