Manganese acetate oxidation with

Oxidation. Acetaldehyde is readily oxidised with oxygen or air to acetic acid, acetic anhydride, and peracetic acid (see Acetic acid and derivatives). The principal product depends on the reaction conditions. Acetic acid [64-19-7] may be produced commercially by the Hquid-phase oxidation of acetaldehyde at 65°C using cobalt or manganese acetate dissolved in acetic acid as a catalyst (34). Liquid-phase oxidation in the presence of mixed acetates of copper and cobalt yields acetic anhydride [108-24-7] (35). Peroxyacetic acid or a perester is beheved to be the precursor in both syntheses. There are two commercial processes for the production of peracetic acid [79-21 -0]. Low temperature oxidation of acetaldehyde in the presence of metal salts, ultraviolet irradiation, or osone yields acetaldehyde monoperacetate, which can be decomposed to peracetic acid and acetaldehyde (36). Peracetic acid can also be formed directiy by Hquid-phase oxidation at 5—50°C with a cobalt salt catalyst (37) (see Peroxides and peroxy compounds). Nitric acid oxidation of acetaldehyde yields glyoxal [107-22-2] (38,39). Oxidations of /)-xylene to terephthaHc acid [100-21-0] and of ethanol to acetic acid are activated by acetaldehyde (40,41). 

The use of the Hquid-phase process in acetic acid with the cobalt— manganese—bromine system as explained in the tetephthaUc acid section is also possible (149). This process has been used by Amoco Chemical to produce pyromellitic acid, and facUities remain in place to do so again in the future. As with all hquid-phase oxidations of this type, yields ate high. A separate dehydration step would be needed to yield the dianhydtide. 

Although an inherently more efficient process, the direct chemical oxidation of 3-methylpyridine does not have the same commercial significance as the oxidation of 2-methyl-5-ethylpyridine. Liquid-phase oxidation procedures are typically used (5). A Japanese patent describes a procedure that uses no solvent and avoids the use of acetic acid (6). In this procedure, 3-methylpyridine is combined with cobalt acetate, manganese acetate and aqueous hydrobromic acid in an autoclave. The mixture is pressurized to 101.3 kPa (100 atm) with air and allowed to react at 210°C. At a 32% conversion of the picoline, 19% of the acid was obtained. Electrochemical methods have also been described (7). 

Terephthalic acid is made by air oxidation of /i-xylene in acetic acid with cobalt and manganese salts of metal bromide at 200 °C and 400 tit. 

Ogawa and co-workers37 have reported the synthesis of 6,7-benzo-4,9-epoxy[ 11]-annulenone 60. Manganese dioxide oxidation of the bis(hydroxymethylene)benzo-xepin 57 gave the dialdehyde 58 which on condensation with dimethyl acetonedicarb-oxylate 23 in chloroform in presence of piperidinium acetate gave the diester 59. This on hydrolysis followed by decarboxylation gave the annulenone 60. The NMR spec-... 

Amoco Amoco Chemicals Company, a subsidiary of Amoco Corporation, formerly Standard Oil Company (IN), is best known in the chemicals industry for its modification of the Mid-Century process for making pure terephthalic acid. /7-Xylene in acetic acid solution is oxidized with air at high temperature and pressure. Small amounts of manganese, cobalt, and bromide are used as catalysts. The modification allows the use of terephthalic acid, rather than dimethyl terephthalate, for making fiber. The process can also be used for oxidizing other methylbenzenes and methylnaphthalenes to aromatic carboxylic acids. See also Maruzen. 

The TPA process. The technology involves the oxidation of p-xylene, as shown already in Figure 18—2. The reaction takes place in the liquid phase in an acetic acid solvent at 400°F and 200 psi, with a cobalt acetate/ manganese acetate catalyst and sodium bromide promoter. Excess air is present to ensure the p-xylene is fully oxidized and to minimize by-products. The reaction time is about one hour. Yields are 90—95% based on the amount of p-xylene that ends up as TPA. Solid TPA has only limited solubility in acetic acid, so happily the TPA crystals drop out of solution as they form. They are continuously removed by filtration of a slipstream from the bottom of the reactor. The crude TPA is purified by aqueous methanol extraction that gives 99 % pure flakes. 

A second manufacturing method for acetic acid utilizes butane from the C4 petroleum stream rather than ethylene. It is a very complex oxidation with a variety of products formed, but conditions can be controlled to allow a large percentage of acetic acid to be formed. Cobalt (best), manganese, or chromium acetates are catalysts with temperatures of 50-250 °C and a pressure of 800 psi. 

Manganese(lll) acetate oxidation of (+)-p-menth-l-ene yields the two lactones (165 X=0, Y = CH2) and (165 X = CH2, Y = O) as major products together with anticipated acetates similar oxidation of (+)-pulegone yields the C-2 acetates in low yield and oxidation of isomenthone in the presence of isopropenyl acetate results in acetonylation at C-2 and C-4. Further examples of the rearrangement of epoxides with KOBu -aprotic solvents (pyridine is favoured) have been reported (c/. Vol. 6, p. 44), e.g. (166) to (167), although with the corresponding 1,2-epoxy-... 

Manganese(lil) acetate oxidation of a-pinene yields two lactones analogous to those reported earlier with (+)-p-menth-l-ene however, the major product consists of derived acetates [of a-terpineol, c/5-pin-3-en-2-ol, and myrtenol (224 ... 

Of the numerous combinations of manganese with the halogens, and of the oxides with acids, the acetate, protochloride, and the sulphate of the protoxide are the only compounds which aro manufactured on the large scale or applied to economic purposes, and are, consequently, sufficiently important to claim consideration in a work on technology. 

Oxidation of Acetaldehyde. When using cobalt or manganese acetate the main role of the metal ion (beside the initiation) is to catalyze the reaction of peracetic acid with acetaldehyde so effectively that it becomes the main route to acetic acid and can also account for the majority of by-products. Small discrepancies between acetic acid efficiencies in this reaction and those obtained in acetaldehyde oxidation can be attributed to the degradation of peracetoxy radicals—a peracetic acid precursor— by Reactions 14 and 16. The catalytic decomposition of peracetic acid is too slow (relative to the reaction of acetaldehyde with peracetic acid) to be significant. The oxidation of acetyl radical by the metal ion in the 3+ oxidation state as in Reaction 24 is a possible side reaction. Its importance will depend on the competition between the metal ion and oxygen for the acetyl radical. 

We have not been able to unscramble the complex kinetics of p-xylene oxidation. Ravens studied the second stage of oxidation, that of p-toluic acid in acetic acid with cobalt and manganese acetates and sodium bromide (25), and established the rate equation... 

Homolytic liquid-phase processes are generally well suited to the synthesis of carboxylic acids, viz. acetic, benzoic or terephthalic acids which are resistant to further oxidation. These processes operate at high temperature (150-250°C) and generally use soluble cobalt or manganese salts as the main catalyst components. High conversions and selectivities are usually obtained with methyl-substituted aromatic hydrocarbons such as toluene and xylenes.95,96 The cobalt-catalyzed oxidation of cyclohexane by air to a cyclohexanol-cyclohexanone mixture is a very important industrial process since these products are intermediates in the manufacture of adipic acid (for nylon 6,6) and caprolactam (nylon 6). However, the conversion is limited to ca. 10% in order to prevent consecutive oxidations, with roughly 70% selectivity.97... 

In the Amoco process, p-xylene is oxidized at 200 °C under 15-20 atm in acetic acid and in the presence of a catalyst consisting of a mixture of cobalt acetate (5% weight of the solution), manganese acetate (1%) and ammonium bromide. Owing to the highly corrosive nature of the reaction mixture, special titanium reactor vessels are required. One of the main difficulties of this process is to remove the intermediate oxidation products such as p-toluic acid or p-carboxybenzal-dehyde which contaminate TPA obtained by precipitation from the reaction medium. A series of recrystallization and solvent extraction apparatus is required to obtain fiber grade TPA with 99.95% purity. The overall yield in TPA is ca. 90% for a 95% conversion of p-xylene. 

L-Gulono-l,4-]actone (21) was converted383 into 1 by the procedure shown in Scheme 11. When 21 was treated with benzaldehyde-hy-drogen chloride, 74 was isolated in >65% yield.384 On oxidation with manganese dioxide, compound 74 gave 75 in 70-90% yield on hydrolysis with 70% acetic acid-water, 75 afforded 1 in 70% yield. That this is one of the few syntheses of 1 which does not have the cycliza-tion of 28 or 29 as its last step is noteworthy. Under different conditions of lysis, (methanolic hydrogen chloride), 75 is converted into 29, not 1. 

---