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...
. Can. J. Chem. 59,851 (1981). The title compounds have been isolated in crystalline form by cyclization of the corresponding bromo-or iodohydroperoxides.The activation parameters for thermolysis are, respectively (E,, kcallmol, AS*, eu): 25.6 f. 0.6,4 f. 2; 29.8 f. 0.4,4 f. 2; 26.3 f 0.5, 1 f 2. Thesinglet '4 and triplet '4 excited state product yieldsproduced on thermolysisofthese compounds are, respectively: 0.01 1, 0.10; 0.0019,O. 18; 0.0013,O. 11. These yields are relative to a value of0.31 for '4 oftetramethyl-1,2-dioxetane. 'The cyclic 1,5-diones from thermolysis of the last two title compounds cyclized before isolation to give the bicyclic hydroxyketones. Thermolysis of 1 ,2-dioxetanes results in the for-3,4-propano-1,2-dioxetane 6, and 3,4-pentanomation of carbonyl cleavage products in quantita-3,4-propano-1 ,Zdioxetane 7 in a test to determine tive yield and in light emission (I), eq. [I]. Both whether the behaviour of 1 is general for dioxetanes n of this structural type. singlet and triplet excited states are formed directly in the primary step of the reaction and the triplet almost always predominates by a large factor in the examples studied to date; for reviews see ref.2. The factors which affect the yield of excited states and the triplet-singlet ratio are the subject of considerable investigation (3). The tricyclic dioxetane 3,4:3,4-dibutano-1 ,Zdioxetane 1, prepared in order to study the effect of the rigidity of its structure on the rate of its thermolysis and the yield of excited states produced, was found to produce much smaller amounts of excited state products than were formed from the mono-and bicyclic dioxetanes trimethyl-, 2, tetramethyl-, 3, and cis-3,4-butano-3,Cdimethyl-1 ,Zdioxetane, 4 (4).The present paper reports the preparation and thermolysis of three other tricyclic dioxetanes, 3,4: 3,Cdipropano-1 ,Zdioxetane 5, 3,4-butano-
Addition of acetic acid-0-d to bicyclo [2.1.0] pentane and subsequent cleavage of the resulting acetate by LiAlH, gave cyclopentanol-dv The alcohol was oxidized and the resulting cyclopentanone was treated with base to effect «-deuterium exchange. Mass spectral isotopic distributions were determined for cyclopentanol-di and cyclopentanone-di before and after exchange. No label was lost on oxidation but 33-36% of the label was lost in exchange. Similar experiments were carried out with bicyclo [3.1.0] hexane. Again no oxidation loss was observed. Exchange losses were less than in the bicyclopentane system. That hydride migration occurs chiefly from Ce was demonstrated from the degree of shift of m/e 55, the base peak in the mass spectrum of the labeled cyclohexanone. Neither oxidative nor exchange losses were observed for methylcyclopentyl acetates, produced along with cyclohexyl acetates, in the addition of acetic acid to bicyclo [2.1.0] hexane.
Die Bicycloalkane (Ia) und (Ib) werden mit Eisessig unter Verwendung deuterierter Komponenten in die Acetate (II) übergeführt, die nach Hydrolyse zu den entsprechenden Ketonen oxidiert werden.
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