Electrophilic oxidant produced in the photodeoxygenation of 1,2-benzodiphenylene sulfoxide.
نویسندگان
چکیده
We report that the photodeoxygenation of 1,2-benzodiphenylene sulfoxide, 1, generates an intermediate capable of oxidizing the solvent benzene to phenol. The reactivity of the intermediate was probed with various substrates (2-methylbutane, chloride ion, and para-substituted aryl sulfides). The intermediate produced in the sulfoxide photodeoxygenation displays an electrophilic oxidation chemistry. Our data on 1 contrast with the behavior of hydroxyl radical but resemble the chemistry observed for gas-phase atomic oxygen [O((3)P)] and for solution-phase photodeoxygenations of dibenzothiophene sulfoxide, 3, and pyridine N-oxide, 5. Correlations are made between the ionization potential of the acceptor molecules and the logarithm of the relative rate constants in order to advance the idea that the oxidizing agent of the title reaction may be solution-phase O((3)P).
منابع مشابه
Gauging the significance of atomic oxygen [O(3P)] in sulfoxide photochemistry. A method for hydrocarbon oxidation.
A liquid-phase photolysis of 1,2-benzodiphenylene sulfoxide, 1, and dibenzothiophene sulfoxide, 2, was used to generate atomic oxygen [O(3P)] or an equivalent active oxygen species. The reaction for sulfoxide photodeoxygenation was similar to a microwave discharge method for generating O(3P) atoms in the condensed phase (Zadok, E.; Rubinraut, S.; Mazur, Y. J. Org. Chem. 1987, 52, 385-90). Sulfo...
متن کاملMulti-wall Carbon Nanotubes Supported Molybdenum Acetylacetonate: Efficient and Highly Reusable Catalysts for Oxidation of Sulfides with Tert-butyl Hydroperoxide
In the present work, highly efficient oxidation of sulfides catalyzed by MoO2(acac)2 supported on multi-wall carbon nanotubes, MWCNTs, modified with 1,2-diaminobenzene (DAB) and 2-aminophenol (AP), at room temperature are reported. The effects of various parameters such as reaction time, solvent, catalyst amount, oxidant, etc, were studied. These heterogenized catalysts showed high activity in ...
متن کاملSulfoxide-mediated Umpolung of alkali halide salts.
A new protocol for the direct two-electron oxidative Umpolung of alkali halide salts is reported. This procedure, relying on the use of a commercially available sulfoxide as the oxidant, allows the electrophilic halogenation of carbonyl compounds as well as halolactonisation reactions to proceed from the corresponding sodium salts, at room temperature and under mild conditions.
متن کاملTRIPHENYLPHOSPHINE CATALYZED AROMATIC ELECTROPHILIC SUBSTITUTION OF 2-HYDROXYACETOPHENONE MEDIATED BY VINYLTRIPHENYLPHOSPHONIUM CATION
Protonation of the highly reactive 1:l intermediate produced in the reaction between triphenylphosphine and dimethyl acetylenedicarboxylate by 2- hydroxyacetophenone leads to vinyltriphenylphosphonium salt, which undergoes aromatic electrophilic substitution reaction with the conjugate base to produce compounds 4,5, and 6 in 1 : 1.2:0.5 ratios
متن کاملEfficient Oxidative Dehydrogenation of Dihydropyrimidinones and Thiocyanation of Aromatic Compounds Using 1,1,2,2-Tetrahydroperoxy-1,2-diphenylethane as the Oxidant
A new, efficient and mild approach for the oxidative dehydrogenation of dihydropyrimidinones and thiocyanation of aromatic compounds using 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane (THPDPE) as a terminal oxidant was developed. Initially, various substrates bearing different electron-donating and electron-releasing functionalities were synthesized and next under the optimized reaction conditio...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- The Journal of organic chemistry
دوره 66 13 شماره
صفحات -
تاریخ انتشار 2001