Read e-book online Aspects of Homogeneous Catalysis: A Series of Advances PDF

By James E. Lyons (auth.), Renato Ugo (eds.)

ISBN-10: 9401011990

ISBN-13: 9789401011990

ISBN-10: 9401012016

ISBN-13: 9789401012010

In fresh years, the liquid section oxidation of natural substrates utilizing transition steel compounds as catalysts has turn into a ecocnomic technique of acquiring industrially vital chemical substances. hundreds of thousands of lots of necessary petrochemicals are produced during this demeanour every year [1]. average examples of such approaches are the creation of vinyl acetate or acetaldehyde through the Wacker strategy, equations (1) and (2); the Mid­ Century procedure for the oxidation of methyl aromatics, equivalent to p-xylene to tereph­ thalic acid, equation (3); and the construction of propylene oxide from propylene utilizing alkyl hydroperoxides, equation (4). PdCI , CuCI 2 2 (1) CH2 = CH2 + half O2 -H zero ~ CH3CHO 2 (2) Co(OAcjz ~ (3) (4) nearly all of liquid section transition steel catalyzed oxidations of natural compounds fall into those 3 vast different types: (a) loose radical autoxidation reactions, (b) reactions related to nucleophilic assault on coordinated substrate corresponding to the Wacker strategy, or (c) steel catalyzed reactions of natural substrates with hydroperoxides. of those 3 sessions of oxidations basically the 1st represents the particular interplay of dioxygen with an natural substrate. The functionality of oxygen within the Wacker method is just to re-oxidize the catalyst after every one cycle [2].

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T-BuOOH (HO-CH 2CH 2hN .. I TI(/-OC 4 H 9 )4 (HOCH2CH2hN~O (127) The oxidation of nitrogen heterocycles by t-pentyl hydroperoxide in the presence 55 Table 10 MOL YBDENUM(V) - PROMOTED HYDROPEROXIDE OXIDATION OF NITROGEN HETEROCYCLES N-Dxides Yield % N-Oxides Yield % Pyridine 2-Picoline 3-Picoline 2,4,6-Collidine 4,4' -Bipyridyl (dioxide) 2-Phenylpyridine Methylnicotinate 4-Acetamidopyridine 100 100 100 95 80 90 90 40 Quinoline 2-Methylquinoline Methylquinaldinate Benzo( f )quinoline Acridine Phenazine (dioxide) 2,3,5,6-Tetramethylpyrazine (dioxide) Papavarine 100 95 90 95 100 90 80 70 of molybdenum pentachloride has been studied in some detail [184-186].

The chromium peroxo complex VI, selectively oxidizes tetraphenylcyclopentadienone, however, some disagreement exists concerning the nature of the organic product obtained [93, 94]. A number of logical explanations have been advanced for the enhancement of the reactivity of dioxygen upon coordination, yet each has its exceptions or drawbacks [3-7]. First, since coordinated dioxygen is usually diamagnetic, reactions with diamagnetic reactants to give diamagnetic products fulfill spin conservation requirements.

RuCI 2(PPh 3 h ~ RuCI 2(PPh 3 h + PPh 3 Ru(PPh 3 hCI 2 + O2 - - - RuCI 2(PPh 3 h(02) (73) (74) Another dioxygen complex, [RuCh(AsPPh 3 h], also appears to catalyze the oxidation of triphenylphosphine to triphenylphosphine oxide [81], however, a mechanism study has not yet been carried out. 3. Complexes of rhodium and iridium Rhodium complexes are also active catalysts for phosphine oxidation. 50 g) in refluxing toluene for 4 hr, a quantitative yield of triphenylphosphine oxide was obtained. Blank experiments carried out in the absence of the rhodium complex gave negative results.

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Aspects of Homogeneous Catalysis: A Series of Advances Volume 3 by James E. Lyons (auth.), Renato Ugo (eds.)

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