Azobenzol‐Keten‐Addukt

Schenck, Günther O.; Engelhard, Norbert

doi:10.1002/ange.19560680214

Cited by 27 publications

(5 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The yellow color of these 1,2-dioxetanes is neither a universal nor a unique characteristic of this class of peroxide. At least some 1,2-dioxetanes are reported to be white (4a, 4f) and the endoperoxides, 2,3-dioxabicyclo[2.2.2]oct-5-ene (26) and 2,3-dioxabicyclo[2.2.2]hept-5-ene (27), are yellow. The spectrum of cis-3,4-diethoxy-l,2-dioxetane does not show a maximum (28) as exhibited in Fig.…”

Section: The Iodohydroperoxide Was Prepared After It Wasmentioning

confidence: 99%

Preparation and Thermolysis of Some 1,2-Dioxetanes

Kopecky¹,

Filby²,

Mumford³

et al. 1975

Can. J. Chem.

142

View full text Add to dashboard Cite

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...

show abstract

Section: The Iodohydroperoxide Was Prepared After It Wasmentioning

confidence: 99%

Preparation and Thermolysis of Some 1,2-Dioxetanes

Kopecky¹,

Filby²,

Mumford³

et al. 1975

Can. J. Chem.

142

View full text Add to dashboard Cite

show abstract

“…[26][27][28][29][30][31][32][33][34][35], olefins with isolated double bonds and allylic hydrogen atoms36-so, furans51-55, sulphides56, and sulphoxides 5 7. These compounds are oxidized to endoperoxides, allylic hydroperoxides, ozonides of the yet unknown cyclobutadienes (which in polar solvents such as alcohols react spontaneously to alkoxyhydroperoxides) 55, sulphoxides, and sulphones, respectively. Acenes are able to act as sensitizers as weil as substrates.…”

Section: Introductionmentioning

confidence: 99%

Mechanism and stereoselectivity of photosensitized oxygen transfer reactions

Gollnick¹,

Schenck²

1964

Pure and Applied Chemistry

Self Cite

291

View full text Add to dashboard Cite

show abstract

“…cis -Azoarenes have been reported to engage in net-cycloaddition reactions faster than their trans -counterparts. 19–23…”

Section: Resultsmentioning

confidence: 99%

“…cis-Azoarenes have been reported to engage in net-cycloaddition reactions faster than their transcounterparts. [19][20][21][22][23] The computed PES for the reaction between cis-1a and obenzyne is shown in Fig. 3c.…”

Section: Resultsmentioning

confidence: 99%