29186-07-0

Upstream product

• 13150-73-7 3-chlorophenyl methyl sulfoxide 
• 30541-56-1 adamantylidene-adamantane 
• 934-73-6 methyl 4-chlorophenyl sulfoxide 
• 30541-56-1 adamantanylideneadamantane 
• 3517-99-5 1-methoxy-4-(methylsulfinyl)benzene 
• 934-72-5 Methyl p-tolyl sulfoxide 
• 1193-82-4 racemic methyl phenyl sulfoxide 
• 35544-39-9 dispiro(diadamantane-1,2-dioxetane) 

Relevant academic research and scientific papers

1,2-DIOXETANES AS CHEMILUMINESCENT INTERMEDIATES IN THE TRIPLET OXYGEN OXYGENATION OF OLEFINS.

Several enol ethers react in the dark at elevated temperatures with triplet oxygen, producing ketones and chemiluminescence.Other electron-rich olefins were investigated.

PHOTOADDITION OF ADAMANTYLIDENEADAMANTANE IN THE PRESENCE OF TETRACYANOETHYLENE. a NEW PHOTOEPOXIDATION PROCESS

Irradiation of a dichloromethane solution of adamantylideneadamantane in the presence of tetracyanoethylene with bubbling oxygen through a pyrex filter by a 650-W tungsten-halogen lamp gave a high yield (84percent) of the corresponding epoxide.A reasonable mechanism for the efficient epoxidation will be described.

THE REACTION OF ADAMANTYLIDENEADAMANTANE WITH SINGLET OXYGEN MEDIATED BY ROSE BENGAL AND CHARGE TRANSFER COMPLEXES

Chemically generated singlet oxygen reacts with adamantylideneadamantane (1) in acetone solution to give mainly the corresponding 1,2-dioxetane (2) together with traces of the epoxide 3.When rose bengal (RB) is added to the reaction mixture, epoxide 3 becomes the chief product at the expense of the dioxetane 2, even in the dark.Charge transfer complexes (CTCs) formed between N-ethylcarbazole and fluorene with 2,4,7-trinitrofluoren-9-one and pyromellitic dianhydride, as well as quinhydrone, behave like RB in that their addition to the reaction mixture favors epoxide formation.Their epoxidizing power is related to the energies of their CT bands.Free energies (ΔG) calculated for the interaction of the CTC with singlet oxygen ranged from -2.07 to 0.45 kcal/mol.CTCs having a ΔG greater than 0.5 kcal/mol are inefficient for the production of 3.The results are explained in terms of two different processes.The normal course is the reaction of singlet oxygen with 1 to give dioxetane.Addends such as CTCs and dimeric RB compete for singlet oxygen and convert it to superoxide radical ion, which in a secondary process is indirectly responsible for epoxidation.

MECHANISTIC CONSIDERATIONS ON PHOTOREACTION OF ORGANIC COMPOUNDS VIA EXCITATION OF CONTACT CHARGE TRANSFER COMPLEXES WITH OXYGEN

Reactions of various organic compounds induced by excitation of their contact charge transfer (CCT) pairs with oxygen were classified into three types of behaviour on the basis of reaction products.It is proposed that the excited state of the CCT pairs gives the products through the most isoenergetic course along the plausible exothermic pathway.

AUTOXIDATION OF ADAMANTYLIDENEADAMANTANE IN A PROTIC SOLVENT. FACILE PROTON-INDUCED ELECTRON TRANSFER FROM THE OLEFIN TO OXYGEN

Addition of trifluoroacetic acid to adamantylideneadamantane in dichloromethane solution under oxygen in the dark results in a rapid oxygenation of the olefin.The reaction is proposed to proceed through a mechanism involving proton-induced electon transfer from the olefin to oxygen giving its radical cation and a hydroperoxy radical followed by their subsequent reactions.

Chromyl Complexes in the Direct Epoxidation of Alkenes

Alkenes such as (E)- and (Z)-β-methylstyrene are converted stereospecifically by dinitratodioxochromium(VI), or chromyl nitrate, to the corresponding epoxide with high selectivities in aprotic media under rather mild conditions.The presence of the cosolvents, N,N-dimethylformamide (DMF), acetone, pyridine, etc., is critical for effective epoxidation with this reagent.In DMF and pyridine, the epoxide remains generally intact but in acetone it is transformed to the corresponding alkene ketal which can also be isolated in high yields.The rates of oxidation are evaluated by the competition method, and the relative reactivities of various alkenes toward chromyl nitrate are found to generally parallel those previously determined for other chromyl reagents such as chromic acid, chromyl acetate, and chromyl chloride.Under optimum conditions for epoxidation, chromyl nitrate effects exclusive oxidation of 1,2-diphenylethanol to deoxybenzoin, which is uncontaminated by the usual cleavage products benzaldehyde and benzyl alcohol.Since the latter is known to derive from chromium(IV) intermediates, we conclude that the active species in chromyl epoxidation is oxochromium(V) formed in situ by the prior one-electron oxidation of solvent.The latter is in accord with the efficient transfer of the oxygen atom from macrocyclic oxochromium(V) species previously observed by Grovers and co-workers.The ESR spectra of the transient chromium(V) intermediates derived from chromyl nitrate and chromyl acetate by reduction with cosolvent are reported.