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

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

In contemporary years, the liquid part oxidation of natural substrates utilizing transition steel compounds as catalysts has turn into a ecocnomic technique of acquiring industrially vital chemical substances. thousands of hundreds useful petrochemicals are produced during this demeanour each year [1]. usual examples of such methods are the construction of vinyl acetate or acetaldehyde through the Wacker approach, equations (1) and (2); the Mid­ Century approach for the oxidation of methyl aromatics, akin 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 + 0.5 O2 -H zero ~ CH3CHO 2 (2) Co(OAcjz ~ (3) (4) the majority of liquid part transition steel catalyzed oxidations of natural compounds fall into those 3 wide different types: (a) unfastened radical autoxidation reactions, (b) reactions regarding nucleophilic assault on coordinated substrate resembling the Wacker approach, or (c) steel catalyzed reactions of natural substrates with hydroperoxides. of those 3 sessions of oxidations in simple terms the 1st represents the particular interplay of dioxygen with an natural substrate. The functionality of oxygen within the Wacker procedure is just to re-oxidize the catalyst after every one cycle [2].

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Extra info for Aspects of Homogeneous Catalysis: A Series of Advances Volume 3

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2. The reaction products were separated by gel permeation chromatography with pyridine as the eluent. Elution of the product mixture results in two bands; the first XXI, is brown and catalytically active, and the ~econd, XXII, is green and inactive for the oxidative polymerization of phenols. The retention volume for the green component, XXII, was identical to that of [Cu(pY)2Ch]. The formation of this product was confirmed by quantitative ESR measurements which were consistent with the overall reaction shown in equation (115).

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].

6. Iron complexes The oxidation of triphenylphosphine has also been investigated using iron complexes as catalysts [133]. Kinetics of this reaction were studied using [Fe(mnt)2r and [Fe(mnt)3]2- where mne- is cis-l,2-dicyanoethylene-l,2-dithiolate. Approximately I mol of the iron(IV) complex catalyzed the oxidation of 15 mol of triphenylphosphine compared to about IOmol of triphenylphosphine for the iron(III) complex. The rate of oxygen uptake in the presence of either complex was found to be proportional to the concentrations of both triphenylphosphine and the iron complex but independent of oxygen pressure.

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