Manganese acetate, reaction with

Subsequent reaction of porphyrazines 170 and 171 with Cu(OAc)2 resulted in the selective metalation within the macrocyclic cavity to provide the corresponding copper complexes 166 (62%) and 172 (47%). Treatment of pz 170 with manganese acetate and iron sulfate in dimethyl sulfate gave the dmso adducts 173 (70%) and 174 (85%), respectively (168). Axial ligation was also observed when other metals were incorporated such as cobalt acetate, nickel acetate, and zinc acetate to give the metal complexes 175 (83%), 176 (70%), and 177 (90%) as the hydrates. The axial ligand of... 

Self condensation of phthalonitrile or o-cyanobenzamide in the presence of manganese metai gives a product which, on sublimation, yields pure [MnPc].510 Alternatively this product may be obtained by the reaction of phthalonitrile with manganese acetate. Although similarities exist, the chemistry of manganese phthalocyanine species show many differences to that of the corresponding porphyrins.6,510... 

Enantioselective epoxidation. This effective catalyst (1) is readily prepared in a 70-100 kg scale from the resolved diamine (with tartaric acid), the salicylaldehyde (from formylation of the phenol by Duff reaction), and manganese acetate, followed by anion exchange by treatment with aqueous NaCI. 

Dimethyl H-phosphonate reacts with calcium dichloride at 70 °C, with manganese acetate at 112 °C, and with calcium nitrate at 115 °C. Kinetic investigations [304] have shown that the reaction takes place as a bimolecular substitution of the second order. There is no difference in the reaction rate of the substitution of both alkyl groups. In general, it decreases with increase in the length of the carbon chain in the alkoxy group. 

De Klein WJ (1986) Reactions with manganese(III) acetate. In Mijs WJ, De Jonge CRHI (eds) Organic syntheses by oxidation with metal compounds. Prenum, New York, chap 4, p 261... 

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). 

Oxidation of parti-methoxyphenols.2 The last step in a synthesis of cyano-cycline A (1) requires oxidation of the para-methoxyphenol (2) to a quinone. This reaction is effected in highest yield (55%) with manganese(III) acetate (0.3%H2SO4-CH3CN). 

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. 

In 1995, Perkin-Ehner introduced a new enzyme rTth-DNA polymerase with a dual activity. It can perform both RT and PCR in the presence of manganese acetate buffer, sense and antisense primers, and nucleotides. This protocol is easier to perform and reduces total in situ RT-PCR reaction time (46). 

Reaction with acetic acid yields manganese(II) acetate and manganeseflll) oxide ... 

In order to shorten the reaction time, various heavy metal salts (zinc, lead, and manganese acetates) of weak organic acids, zinc or cobalt and tin chlorides are added to the reaction mixture [11]. For example, refluxing an uncatalyzed mixture of 3 moles of isobutyl alcohol and urea for 150 hr at 108°-126°C gives a 49% yield of the carbamate. Adding lead acetate or cobalt chloride to the same reaction lowers the reaction time to 75 hr, at which point an 88-92 % yield is obtained. In another example, ethylene glycol (1 mole) and urea (2 moles) are heated for 3 hr at 135°-155°C with Mn(OAc)2 to give a 78% yield of the diurethane [11]. The commercial production of butyl carbamate uses catalytic quantities of cupric acetate [12]. 

Figure 5. Effect of manganese acetate on the reaction of peracetic acid with acetaldehyde at 30°C.

With manganese and cobalt acetate the reaction of peracetic acid with acetaldehyde is very fast, and AMP is not detected. By comparing our rates with literature values of k17, k.17, and k18 we cannot propose a mechanism in which the only role of the metal ion is to catalyze the decomposition of AMP. The experimental rates in the presence of either manganese or cobalt acetates are much faster than the noncatalytic rate of formation of AMP. Thus, AMP per se is probably not an intermediate in the presence of these catalysts. 

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