100-02-7 CERIUM(IV) INDUCED HYDROXYLATION OF C-ALKYLATED HYDROCARBONS AND PHENOLS

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Hydroxylation of C-alkylated phenols has benn achieved by employing cerium(IV) ammonium nitrate and hydrogen peroxyde in acetic acid medium.The yield of hydroxylation products increases markedly when 3*E-3 M solution of sodium dodecyl sulphate is added to the oxidation system.The plausible mechanism of the reaction seems to involve free radical intermediates and is influenced by hydrophobic environment.The finding are also of significance from the view point of oxidative coupling of phenols. https://www.lookchem.com/CASDataBase_100-02-7.htm

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1023-17-2 Syntheses, structures, and catalytic activity in Friedel–Crafts acylations of substituted tetramethylcyclopentadienyl molybdenum carbonyl complexes

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Reactions of the substituted tetramethylcyclopentadienes [C 5 HMe 4 R] [R?=? t Bu, Ph, CH 2 CH 2 C(CH 3 ) 3 ] with Mo(CO) 3 (CH 3 CN) 3 in refluxing xylene gave a series of dinuclear molybdenum carbonyl complexes [(η 5 -C 5 Me 4 R)Mo(CO) 3 ] 2 [R?=? t Bu (1), Ph (2), CH 2 CH 2 C(CH 3 ) 3 (3)], [(η 5 -C 5 Me t Bu)Mo(μ-CO) 2 ] 2 (4)], and [(η 5 -C 5 Me 4 ) t Bu] 2 Mo 2 O 4 (μ-O) (5)], respectively. Complexes 1–5 were characterized by elemental analysis, IR, 1 H NMR, and 13 C NMR spectroscopy. In addition, their crystal structures were determined by X-ray crystal diffraction analysis. The catalytic activities of complexes 1–3 in Friedel–Crafts acylation in the presence of o-chloranil has also been investigated; the reactions were achieved under mild conditions to give the corresponding products in moderate yields. https://www.lookchem.com/CASDataBase_1023-17-2.htm
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75-01-4 Nickel(I) Octaethylisobacteriochlorin Anion. An Exceptional Nucleophile. Reduction and Coupling of Alkyl Halides by Anionic and Radical Processes. A Model for Factor F-430

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Nickel(I)octaethylisobacteriochlorin anion (Ni(I)OEiBC - ) reacts extremely rapidly with aliphatic halides and methyl tosylate in homogeneous DMF solution.The reactivity sequence, CH3 > primary > secondary tertiary, and the rate law accord with an S N 2-like process for the carbon-halogen bond scission.However, the main products of the reactions derive from free radicals.The rate for methyl chloride is 2000 times faster than the corresponding reaction with the super nucleophile Co(I)B12 s -1 and the rate constant for isopropyl bromide is 350 times greater than that observed with CpFe(CO)2 - .The results indicate NiOEiBC - is the fastest nucleophile on record.Studies of the influence of solvent and reactant deuteration and the influence of anion and radical scavengers upon the product distribution suggest the intermediacy of at least one and possibly two nickel alkyls of fleeting lifetime.A novel explanation for the unusual speed of these reactions is put forward.It entails the...
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100-64-1 On the Oxidation of Hydroxylamines with o -Iodoxybenzoic Acid (IBX)

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o -Iodoxybenzoic acid (IBX) is confirmed as a powerful tool for the oxidation of hydroxylamines. The synthetic route is demonstrated as efficient and user friendly, and is exploited on various carbohydrate-derived N,N-disubstituted hydroxylamines (cyclic, acyclic, and functionalized ones), affording the corresponding nitrones in good yields and regioselectivity. N-Monosubstituted hydroxylamines revealed an interesting divergent behavior depending on the reaction conditions. While IBX oxidation in dimethyl sulfoxide at 45 °C furnished oximes as reported, the oxidation in dichloromethane at room temperature afforded efficiently the unusual corresponding nitroso dimers. https://www.lookchem.com/CASDataBase_100-64-1.htm
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