Photochemistry without light

White, Emil H.; Wiecko, Jacek; Roswell, David F.

doi:10.1021/ja01046a064

Cited by 60 publications

(26 citation statements)

References 1 publication

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“…The rate of thermal decomposition of 8 appears to be about three to four times that of 3. The decomposition is accompanied by luminescence whose intensity is greatly enhanced by the addition of 9,lO-dibromoanthracene (DBA) (17). Reduction of 8 using lithium aluminum hydride at -40" gave 1-(1-hydroxyethyl)cyclohexanol 10 in 87% yield.…”

Section: -Methyl-33-pentamethylene-12-dioxetane 86mentioning

confidence: 99%

Preparation and Thermolysis of Some 1,2-Dioxetanes

Kopecky¹,

Filby²,

Mumford³

et al. 1975

Can. J. Chem.

142

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DING. Can. J. Chem. 53,1103 (1975. Treatment of the bromohydroperoxides of 2-methyl-2-butene and ethylidenecyclohexane with cold methanolic base produces trimethyl-and 4-methyl-3,3-pentamethylene-1 ,2-dioxetane, 3 and 8. Under these conditions the bromo-and iodohydroperoxides of 2,3-dimethyl-2-butene A, 1,2-dimethylcyclohexene B, and AgJO-octalin C are converted rapidly to the corresponding allylic hydroperoxides. The reaction in methylene chloride between silver ion and the bromoand iodohydroperoxides of A and the iodohydroperoxides of B and C produces the corresponding dioxetanes in 20-30% yield: tetramethyl-1,Zdioxetane 11, 3,4-dimethyl-3,Cbutano-1,2-dioxetane 15, and 3,4:3,4-dibutano-1,2-dioxetane 23. About 50% of the corresponding allylic hydroperoxides also are formed as are pinacolone, -15%, l-acetyl-l-methylcyclopentane, ~2 0 % , and Ag.lO-octalin, -l%, from the appropriate halohydroperoxides.All the dioxetanes are yellow, thermolyze to give only carbonyl cleavage products, and are luminescent. Reduction of 3 with bisulfite ion produced trimethyloxacyclopropane and with iodide ion 2-methyl-2,3-butanediol. Reduction of 8,11,15, and 23 with lithium aluminum hydride at -78" gave good yields of the corresponding diols. Treatment with triphenylphosphine of 11 gave tetramethyloxacyclopropane, of 15, a 1 : 3 ratio of 2-methylene-1-methylcyclohexanol and 2,3-dimethylcyclohexen-3-01, and of 23, 10-hydroxy-A'~9-octalin.Activation parameters for thermolysis of the dioxetanes are (dioxetane, E,, kcal/mol, AS*, e.u.)3, 23.5 a 0.5, -5 f 2; 11, 25.8 f 0.5, -2 + 2; 15, 25.7 a 0.7, 2 f 2; 23, 22.7 f 0.9, -3 f 3. 3Holder of a Canadian Mortgage and Housing Corporation Fellowship, 1970 and a National Research Council of Canada Scholarship, 1971 4Holder of a National Research Council of Canada Scholarship, 1970Scholarship, -1973 Can. J. 53, 1975 20-30%: t6tramethyldioxetanne-1,2, 11, dimethyl-3,4 butano-3,4 dioxktanne-1,2, 15, et di-I butano-3,4:3,4 dioxetanne-1,2, 23. Dans ces reactions, il se forme environ 50% des hydroperoxydes allyliques correspondants et suivant les hydroperoxydes utilises de la pinacolone, 15% (approx), de I'acktyl-1 methyl-1 cyclopentane, 20% (approx), et de la A9*10-octaline, 1% (approx). Tous les dioxetannes sont des composks jaunes et luminescents, dont la thermolyse ne donne que les produits de fission carbonylique. La reduction de 3 avec le bisulphite donne le trim~thyloxacyclopropane alors que les ions iodures conduisent au methyl-2 butanediol-2,3. La reduction de 8,11,15 et 23 avec I'hydrure de lithium et aluminium ii -78" donne des bons rendements des diols correspondants. Le traitement de 11 avec de la triph6nylphosphine transforme 11 en t6tram6thyloxacyclopropane; 15 en methylene-2 methyl-1 cyclohexanol et en dimethyl-2,3 cyclohex8n-3-01 dans le rapport 1 : 3; et 23 en hydroxy-10 A1.9-octaline.Les parametres d'activation pour la thermolyse des dioxetannes sont (dioxktanne, E., kcal mol-l,AS* ~aldeg-~mol-');3,23.5 + 0.5, -5 + 2;11,25.8 + 0.5, -2 + 2;15,25.7 + 0.7, 2 + 2; 23, 22.7 + 0.9...

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Section: -Methyl-33-pentamethylene-12-dioxetane 86mentioning

confidence: 99%

Preparation and Thermolysis of Some 1,2-Dioxetanes

Kopecky¹,

Filby²,

Mumford³

et al. 1975

Can. J. Chem.

142

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“…IR spectra were recorded on Perkin-Elmer Spectrum BXseries FTIR, 1 H NMR spectra on Bruker Avance II 400 MHz NMR spectrometer using tetramethylsilane as internal standard and chemical shift values are reported in ä scale. Mass spectra were obtained on a Jeol JMSD-300 spectrometer at 70 ev.…”

Section: Methodsmentioning

confidence: 99%

Study of Photochemistry without Light of Substituted Benzylidine Acenaphthenones

Goel¹

2013

Orientjchem.

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“…The yield of acenaphthylene dimer, based on dioxetane used, was 2-3% from 2 and 3 and 1% from 4. In all these reactions the cis to trcins dimer ratio was -0.1, indicating that mainly triplet energy transfer to acenaphthalene was occurring (2).…”

Section: Karl R K~p E C K Ymentioning

confidence: 98%

“…This efficiency was assumed to be the same for all the carbonyl colnpounds produced from dioxetanes 1-4 and the value 0.2 determined for acetophenone (7) was used. The factor of 0.8 in [4] was used to correct for the fact that 20% of excited D P A molecules are quenched by oxygen in aerated solutions (8).…”

Section: Excited State Yields From Dioxetanesmentioning

confidence: 99%

Yields of excited states from thermolysis of some 1,2-dioxetanes

Kopecky¹,

Filby²

1979

Can. J. Chem.

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The singlet 1Φ and triplet 3Φ excited state product yields produced on thermolysis in toluene of trimethyl- (1), tetramethyl- (2), cis-3, 4-butano-3,4-dimethyl- (3), and 3,4:3,4-dibutano-1,2-dioxetane (4) were determined to be as follows (dioxetane, °C, 1Φ, 3Φ): 1, 40, 1.1 × 10−3, 0.15; 2, 45, 4.4 × 10−4, 0.31; 3, 26, 8.5 × 10−4, 0.23; 4, 24, 4.8 × 10−6, 0.011. The reason for the low yield of excited states obtained from 4 is not known. Thermochemical calculation indicate that as much energy is available from thermolysis of 4 as is available from 2.Dioxetane-energized dimerization of acenaphthylene, accompanied by an intense yellow luminescence, produced mainly the trans dimer in 1–3% yield. Dioxetane-energized cyclization of 1-(2,4-dimethylphenyl)-1,2-propanedione produced 2-hydroxy-2,5-dimethylindan-1-one in 0.5–6% yields.

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Photochemistry without light

Cited by 60 publications

References 1 publication

Preparation and Thermolysis of Some 1,2-Dioxetanes

Preparation and Thermolysis of Some 1,2-Dioxetanes

Study of Photochemistry without Light of Substituted Benzylidine Acenaphthenones

Yields of excited states from thermolysis of some 1,2-dioxetanes

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