Acetaldehyde by oxidation

The synthesis of acetaldehyde by oxidation of ethylene, generally known as the Wacker process, was a major landmark in the application of homogeneous catalysis to industrial organic chemistry. It was also a major step in the displacement of acetylene (made from calcium carbide) as the feedstock for the manufacture of organic chemicals. Acetylene-based acetaldehyde was a major intermediate for production of acetic acid and butyraldehyde. However the cost was high because a large energy input is required to produce acetylene. The acetylene process still survives in a few East European countries and in Switzerland, where low cost acetylene is available. 

Some acetic acid still is derived from cthyiene-based acetaldehyde by oxidation with molecular oxygen, This is a free radical process and typically is manganese salt-... 

Ca.ta.lysis, The most important iadustrial use of a palladium catalyst is the Wacker process. The overall reaction, shown ia equations 7—9, iavolves oxidation of ethylene to acetaldehyde by Pd(II) followed by Cu(II)-cataly2ed reoxidation of the Pd(0) by oxygen (204). Regeneration of the catalyst can be carried out in situ or ia a separate reactor after removing acetaldehyde. The acetaldehyde must be distilled to remove chloriaated by-products. 

Acetic acid (qv) can be produced synthetically (methanol carbonylation, acetaldehyde oxidation, butane/naphtha oxidation) or from natural sources (5). Oxygen is added to propylene to make acrolein, which is further oxidized to acryHc acid (see Acrylic acid and derivatives). An alternative method adds carbon monoxide and/or water to acetylene (6). Benzoic acid (qv) is made by oxidizing toluene in the presence of a cobalt catalyst (7). 

Viayl acetate [108-05-4] is obtained by vapor-phase oxidation of ethylene with acetic acid. Acetic acid is obtained by oxidation of acetaldehyde. 

In recent years vinyl acetate has been prepared in large quantities by oxidation of ethylene. If ethylene is passed into a solution of palladium chloride in acetic acid containing sodium acetate, then vinyl acetate, ethylene diacetate and acetaldehyde are produced, the vinyl acetate being obtained in good yields by the reaction shown in Figure 14.3... 

Ethanol metabolism occurs mainly in the liver and proceeds by oxidation in two steps, first to acetaldehyde (CHjCHO) and then to acetic add (CH3CO2H)- When continuously present in the body, ethanol and acetaldehyde are toxic, leading to the devastating physical and metabolic deterioration... 

Approximately 2.5 million tons of acetic acid is produced each year in the United States for a variety of purposes, including preparation of the vinyl acetate polymer used in paints and adhesives. About 20% of the acetic acid synthesized industrially is obtained by oxidation of acetaldehyde. Much of the remaining 80% is prepared by the rhodium-catalyzed reaction of methanol with carbon monoxide. 

The one-pass yield of pyruvic acid reached 50 mol%. The main side reactions are the formation of acetaldehyde and CO2 by oxydative C-C bond fission of lactic acid and that of acetic acid and CO2 by oxidative C-C bond fission of the produced pyruvic acid. 

The oxidation of ethylene to acetaldehyde by palladium chloride in water has been known since the nineteenth century.80 However, the reaction requires the use of a stoichiometric amount of PdCl2, resulting in Pd(0) deposit. Anderson, in 1934, observed a similar reaction (but... 

Taurine is generally prepared from ox bile1 or the large muscle of the abalone.2 It has been synthesized from isethionic add through chloroethanesulfonic acid followed by the action of aqueous ammonia 3 from ethyleneimine and sulfur dioxide 4 from 2-mercaptothiazoline by oxidation with bromine water 5 from bromoethylamine and ammonium sulfite 6 and from acetaldehyde by a complex set of reactions involving sulfonation, formation of the aldehyde ammonia and the imido sulfonic add and finally reduction.7 The method given in the procedure has recently appeared in the literature.8 9... 

Glyoxal has been obtained by several methods, only a few of which are of preparative value. The most feasible are the oxidation of acetaldehyde by nitric3 4 5 or selenious6 acid the hydrolysis of dichlorodioxane 7 and the hydrolysis of the product resulting from the action of fuming sulfuric acid upon tetra-haloethanes.8... 

The oxidation of ethylene to acetaldehyde by dioxygen catalyzed by palladium and cupric salts found important technological application. The systematic study of this process was started by Smidt [245] and Moiseev [246]. The process includes the following stoichiometric stages [247,248] ... 

Daicel A process for making propylene oxide by oxidizing propylene with peroxyacetic acid. The peroxyacetic acid is made by reacting together ethyl acetate, acetaldehyde, a metal ion catalyst, and air. Developed by Daicel Chemical Industries, Japan from 1966 and commercialized from 1969 to 1980. See also Propylox. 

Rhone-Poulenc/Melle Bezons A process for making acetic acid by oxidizing acetaldehyde with oxygen in air. Removal of the nitrogen would incur a cost penalty. 

Sun, H., Blatter, F. and Frei, H. (1997). Oxidation of propane to acetone and of ethane to acetaldehyde by Oz in zeolites with complete selectivity. Catal. Lett. 44, 247-253... 

In the second procedure13 (see Scheme 3), D-glucitol (10) was converted into 5-O-benzoyl-1,3 2,4-di-O-ethyl idene-6-O-trityl-D-glucitol (17) by successive treatment with acetaldehyde to produce 15, with chlorotriphenylmethane to provide 16, and with benzoyl chloride to afford 17. Selective removal of the trityl protecting group from 17, to give 18, followed by oxidation of 18, provided 19 which, on hydrolysis, afforded L-gulose (9). 

Equation 11 occurs via 3-H abstraction by Pd(II) [33,40-42] Eq. 12 is related to the water-gas shift reaction (WGSR) [43-45] Eq. 13 and Eq. 14 are related to the oxidation of C2H4 to acetaldehyde by Pd(II) in the presence of H20 in the Wacker process [46]. Equation 15 has been shown to occur with octamethylferrocene-phosphine complexes [47]. Formic acid can also be a source of hydride species [48]. 

More recently, Pearce and Heydeman suggested non-oxidative removal of ethylene glycol units as acetaldehyde by a membrane-bound, oxygen-sensitive enzyme of a novel type, i.e., diethylene glycol lyase (18). Schoberl suggested that PEG was catabolized by Ci step, liberating formate which was metabolized by a serine pathway (19). 

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