Cobalt acetate, hydrolysis

High purity acetaldehyde is desirable for oxidation. The aldehyde is diluted with solvent to moderate oxidation and to permit safer operation. In the hquid take-off process, acetaldehyde is maintained at 30—40 wt % and when a vapor product is taken, no more than 6 wt % aldehyde is in the reactor solvent. A considerable recycle stream is returned to the oxidation reactor to increase selectivity. Recycle air, chiefly nitrogen, is added to the air introducted to the reactor at 4000—4500 times the reactor volume per hour. The customary catalyst is a mixture of three parts copper acetate to one part cobalt acetate by weight. Either salt alone is less effective than the mixture. Copper acetate may be as high as 2 wt % in the reaction solvent, but cobalt acetate ought not rise above 0.5 wt %. The reaction is carried out at 45—60°C under 100—300 kPa (15—44 psi). The reaction solvent is far above the boiling point of acetaldehyde, but the reaction is so fast that Httle escapes unoxidized. This temperature helps oxygen absorption, reduces acetaldehyde losses, and inhibits anhydride hydrolysis. 

In contrast to aqueous methods, the polyol approach resulted in the synthesis of metallic nanoparticles protected by surface-adsorbed glycol, thus minimizing the oxidation problem The use of polyol solvent also reduces the hydrolysis problem of ultrafine metal particles, which often occurs in aqueous systems. Oxide nanoparticles can be prepared, however, with the addition of water, which makes the polyol method act more like a sol—gel reaction (forced hydrolysis). For example, 5.5-nm CoFe204 has been prepared by the reaction of ferric chloride and cobalt acetate in 1,2- propanediol with the addition of water and sodium acetate. 

Examples include acetal hydrolysis, base-catalyzed aldol condensation, olefin hydroformylation catalyzed by phosphine-substituted cobalt hydrocarbonyls, phosphate transfer in biological systems, enzymatic transamination, adiponitrile synthesis via hydrocyanation, olefin hydrogenation with Wilkinson s catalyst, and osmium tetroxide-catalyzed asymmetric dihydroxylation of olefins. 

Jacobsen and co-workers have used similar catalysts in the enantioselective opening of epoxide rings. Stereospecific hydrolysis with a cobalt acetate chelate can be used to resolve racemic epoxides.97 Propylene oxide was opened with trimethylsilylazide in the presence of a 7 7 chromium azide chelate catalyst to produce (5)-l-azido-2-trimethyl-siloxypropane in quantitative yield with 97% ee.98 Cyclohexene oxide was opened with benzoic acid in the presence of 1 mol% cobalt chelate catalyst to give the hydroxyben-zoate in 98% yield with 77% ee.99... 

Acetal hydrolysis has also been successfully used to affect such organic ligand modifications. Thus Silverman and Dolphin [111] obtained both formylmethylco-baloxime and formylmethylcobalamin by hydrolysis of both the 2,2-diethoxyethyl-and 1,3-dioxa-2-cyclopentylmethyl-cobalt complexes (Eqn. 65). 

The starting materials were soluble salts, cobalt acetate (Co(C2H302)2 H2O) and iron nitrate (Fe(N03)2 9H2O). These salts produce hydroxides (M(OH)2), oxyhydroxides (MOOH) or hydrated oxides in water, where M is Co or Fe. These solutions were reacted with lithium hydroxide. Diluted ammonium hydroxide (3M) was added to form stable colloids (Barboux, 1991). Lithium hydroxide and cobalt acetate were dissolved separately in distilled water. These two solutions were then mixed together and stirred vigorously. The hydrolysis of the mixture was promoted by slow addition of 3M ammonium hydroxide. Similarly, sols with ferric nitrate, or ferric nitrate plus cobalt acetate, were prepared. The sols used for coating were diluted to give a 2 1 ratio of moles water to moles oxide. 

The TCBOC group is stable to the alkaline hydrolysis of methyl esters and to the acidic hydrolysis of r-butyl esters. It is rapidly cleaved by the supemucleophile lithium cobalt(I)phthalocyanine, by zinc in acetic acid, and by cobalt phthalocy-anine (0.1 eq., NaBH4, EtOH, 77-90% yield). 

The first examples of a homogeneous reduction of this type were reported in 1971. Cobalt carbonyl was found to reduce anhydrides such as acetic anhydride, succinic anhydride and propionic anhydride to mixtures of aldehydes and acids. However, scant experimental details were recorded [94]. In 1975, Lyons reported that [Ru(PPh3)3Cl2] catalyzes the reduction of succinic and phthalic anhydrides to the lactones y-bulyrolaclone and phthalide, respectively [95], The proposed reaction sequence for phthalic anhydride is shown in Scheme 15.15. Conversion of phthalic anhydride was complete in 21 h at 90 °C, but yielded an equal mixture of the lactone, phthalide (TON = 100 TOF 5) and o-phthalic acid, which is presumably formed by hydrolysis of the anhydride by water during lactoniza-tion. Neither acid or lactone were further hydrogenated to any extent using this catalyst system, under these conditions. 

Potassium nitrosodisulfonate, 258 Trimethylsilyl chlorochromate, 327 By hydrolysis of acetals or thioacetals Amberlyst ion-exchange resin, 152 Methylthiomethyl p-tolyl sulfone, 192 By isomerization of allylic alcohols N-Lithioethylenediamine, 157 By oxidation of aromatic side chains Trimethylsilyl chlorochromate, 327 From oxidative cleavage of alkenes [Bis(salicylidene-7-iminopropyl)-methylamine]cobalt(II)... 

Base hydrolysis of cis-[Co(en)2X(NH2CH2CH2OCOMe)]2+ (X = C1 or Br) in which the ester of an amino-alcohol is employed as the ligand has also been studied.151 A two-step hydrolysis is observed, the first involving CP or Br- loss and the second ester hydrolysis. It is noteworthy that N-coordination to cobalt prevents the rapid base-catalyzed isomerization of 2-aminoethyl acetate to 2-acetylaminoethanol. 

Mankind has produced acetic acid for many thousand years but the traditional and green fermentation methods cannot provide the large amounts of acetic acid that are required by today s society. As early as 1960 a 100% atom efficient cobalt-catalyzed industrial synthesis of acetic acid was introduced by BASF, shortly afterwards followed by the Monsanto rhodium-catalyzed low-pressure acetic acid process (Scheme 5.36) the name explains one of the advantages of the rhodium-catalyzed process over the cobalt-catalyzed one [61, 67]. These processes are rather similar and consist of two catalytic cycles. An activation of methanol as methyl iodide, which is catalytic, since the HI is recaptured by hydrolysis of acetyl iodide to the final product after its release from the transition metal catalyst, starts the process. The transition metal catalyst reacts with methyl iodide in an oxidative addition, then catalyzes the carbonylation via a migration of the methyl group, the "insertion reaction". Subsequent reductive elimination releases the acetyl iodide. While both processes are, on paper, 100%... 

Commercial methanol carbonylation processes have employed each of the group 9 metals, cobalt, rhodium and iridium as catalysts. In each case acid and an iodide co-catalyst are required to activate the methanol by converting it into iodomethane (CH3OH + HI CH3I + H2O) catalytic carbonylation of iodomethane into acetyl iodide is followed by hydrolysis to acetic acid. A problem common to all these processes arises because the mixture of HI and acetic acid is highly corrosive this necessitates special techniques for plant construction involving the use of expensive steels. We discuss each catalyst system in turn below. 

Catalysts of this type can be used not only for the enantioseleetive generation of epoxides from alkenes, but also for the hydrolytic kinetic resolution (HKR) of racemic epoxides, particularly the terminal variety. For example, the cobalt(III)salen complex 2 catalyzed the enantioseleetive hydrolysis of racemic hexene oxide 3 in the presence of 0.5 equivalents of water to provide the f/ j-enantiomer in 99% ee. Here, the inorganic ligand was found to be important for catalyst activity and selectivity, with the conventional acetate ligand giving inferior results <03TL5005>. 

Benzoic acid is prepared industrially by the oxidation of toluene using air at 170 °C over a catalyst of cobalt and manganese acetate. An alternative route involves the hydrolysis of (trichloromethyl)benzene using aqueous calcium hydroxide in the presence of iron powder as catalyst PhCCl3 is prepared by chlorination of toluene in the presence of light. 

Di-/Li-hydroxo-bis[bis(ethylenediamine)cobalt(III)] dithionate may be obtained analogously to the chromium(III) salt from cis- [aquabis(ethylenediamine)hydrox-ocobalt(III)] dithionate, either by heating at 110° or by refluxing in acetic anhydride. The formation of the bridged cation of cobalt(III) is much slower than that of chromium(III). In contrast to the chromium(III) complex there is no evidence that the bridged cobalt(III) complex can be formed by aqueous hydrolysis. 

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