Cobalt acetates

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. 

Copper acetate, ferrous acetate, silver acetate [563-63-3] basic aluminum acetate, nickel acetate [373-02-4] cobalt acetate, and other acetate salts have been reported to furnish anhydride when heated. In principle, these acetates could be obtained from low concentration acetic acid. CompHcations of soHds processing and the scarcity of knowledge about these thermolyses make industrial development of this process expensive. In the eady 1930s, Soviet investigators discovered the reaction of dinitrogen tetroxide [10544-72-6] and sodium acetate [127-09-3] to form anhydride ... 

Other apphcations of sodium bromide iaclude use ia the photographic iadustry both to make light-sensitive silver bromide [7785-23-1] emulsions and to lower the solubiUty of silver bromides during the developing process use as a wood (qv) preservative in conjunction with hydrogen peroxide (14) as a cocatalyst along with cobalt acetate [917-69-1] for the partial oxidation of alkyl side chains on polystyrene polymers (15) and as a sedative, hypnotic, and anticonvulsant. The FDA has, however, indicated that sodium bromide is ineffective as an over-the-counter sleeping aid for which it has been utilized (16). 

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). 

A number of different cobalt salts have been used in the oxidation of toluene, the most common being cobalt acetate [71-48-7] cobalt naphthenate, and cobalt octoate [1588-79-0],... 

Physical and Chemical Properties. The (F)- and (Z)-isomers of cinnamaldehyde are both known. (F)-Cinnamaldehyde [14371-10-9] is generally produced commercially and its properties are given in Table 2. Cinnamaldehyde undergoes reactions that are typical of an a,P-unsaturated aromatic aldehyde. Slow oxidation to cinnamic acid is observed upon exposure to air. This process can be accelerated in the presence of transition-metal catalysts such as cobalt acetate (28). Under more vigorous conditions with either nitric or chromic acid, cleavage at the double bond occurs to afford benzoic acid. Epoxidation of cinnamaldehyde via a conjugate addition mechanism is observed upon treatment with a salt of /-butyl hydroperoxide (29). 

Cobaltous acetate (4H2O) [6147-53-1] M 249.1, pKj 9.85 (for Co " "). Crystd several times as the tetrahydrate from 50% aqueous acetic acid. Converted to the anhydrous salt by drying at 80°/1mm for 60h. 

In the case of ester exchange for the manufacture of poly(ethylene terephthalate), a low molecular weight diester, known as the monomer , is first prepared by reacting 1 mol of dimethyl terephthalate with about 2.1-2.2 mol ethylene glycol at about 150°C in the presence of catalysts such as antimony trioxide and cobaltous acetate ... 

Chemical Designations - Synonyms Cobalt (II) Acetate Cobalt Acetate Tetrahydrate Cobaltous Acetate Chemical Formula Co(C2H302)2 4H20. 

Cyclohexane is also a precursor for adipic acid. Oxidizing cyclohexane in the liquid-phase at lower temperatures and for longer residence times (than for KA oil) with a cobalt acetate catalyst produces adipic acid ... 

The catalyzed oxidation of p-xylene produces terephthalic acid (TPA). Cobalt acetate promoted with either NaBr or HBr is used as a catalyst in an acetic acid medium. Reaction conditions are approximately 200°C and 15 atmospheres. The yield is about 95% ... 

Although the enantioselective intermolecular addition of aliphatic alcohols to meso-epoxides with (salen)metal systems has not been reported, intramolecular asymmetric ring-opening of meso-epoxy alcohols has been demonstrated. By use of monomeric cobalt acetate catalyst 8, several complex cyclic and bicydic products can be accessed in highly enantioenriched form from the readily available meso-epoxy alcohols (Scheme 7.17) [32]. 

An impressive application of the (salen) Co-catalyzed intramolecular ARO of meso-epoxy alcohols in the context of total synthesis was reported recently by Danishefsky [33], Enantioselective desymmetrization of intermediate 9 by use of the cobalt acetate catalyst 8 at low temperatures afforded compound 10, which was obtained in 86% ee and >86% yield (Scheme 7.18). Straightforward manipulation of 10 eventually produced an intermediate that intersected Danishefsky s previ-... 

PET methanolysis involves the reaction of PET with methanol at high temperatures and pressures in the presence of transesterification catalysts such as magnesium acetate, cobalt acetate, and lead dioxide. 

Little information exists on low-T precipitation of borides from solution. Chromium, cobalt and platinum borides are the only ones claimed to have been obtained from aqueous solution ". Ni2B and C02B are precipitated from a solution of nickel or cobalt acetates by adding a solution of sodium tetrahydroborate ". The formation of these borides at RT gives amorphous products. Hence, heat treatment at 300-700°C leads to crystalline NijB as the main constituent, although the average composition of the precipitate corresponds to NijB . 

Patil, V.a, Sevalkar, M.T.. Fidalikar, SV. "rhiii-layer Chiomatognphic Detection of Eo-doml n and Photphamidon by Use of Cobalt Acetate and o-lblidine , 1 C/mMnafdgr. 1990, 519. 268-270. 

Quite different kinetics are exhibited by the anaerobic oxidation of alkyl-benzenes by cobaltic acetate in a 95 % acetic acid medium , viz. 

Cobaltic acetate oxidises /er/-butyl hydroperoxide to a mixture of /err-butanol, di- er/-butyl peroxide and oxygen with essentially second-order kinetics . The reaction does not involve 0-0 fission, the mechanism suggested being... 

The cobaltous acetate reduction of tert-butyl hydroperoxide in acetic acid yields mainly ter/-butanol and oxygen the metal ion stays in the +2 oxidation state because of the reactivity of Co(III) towards hydroperoxides (p. 378) °. The rate law is... 

Oxidising acetaldehyde in air when cobalt acetate at -20°C is present gives rise to a detonation, if the medium is stirred. It has been put down to the formation of a very sensitive peroxidic compound. On the other hand, the presence of a halogen derivative inhibits this oxidation. 

Synthesis of Tetrakis(polyethyleneoxy)phthalocyanine cobalt (II) (9). The polyethylene-tethered phthalonitrile (0.827 g, 1.0 mmol), 1,5-diazabicyclo [4.3.0] non-5-ene (0.062 g, 0.50 mmol) and cobalt acetate (0.044 g, 0.25 mmol) were added to a reaction vial equipped with a magnetic stir bar. The reaction was then heated to 175°C for 2 hours before reducing the temperature to 95°C and adding toluene. The reaction mixture was then poured into methanol, filtered, and the sohd washed further with methanol. The collected product was then dried under vacuum to yield... 

Later, Chung et al. successfully developed an intramolecular Pauson-Khand reaction in water without any cosolvent by using aqueous colloidal cobalt nanoparticles as catalysts. The catalyst was prepared by reducing an aqueous solution of cobalt acetate containing sodium dode-cyl sulfate (SDS) surfactant. The cobalt nanoparticle could be reused eight times without any loss of catalytic activity (Eq. 4.57).107... 

Bloomfield, G. F. et al., J. Soc. Chem. Ind., 1935, 54, 129T Oxygenation of acetaldehyde in presence of cobalt acetate at — 20°C caused precipitation of 1-hydroxyethyl peroxyacetate (acetaldehyde hemi-peracetate), which exploded violently on stirring [1], Ozone or UV light also catalyses the autox-idation [2],... 

One of the most selective hydroformylation catalysts was obtained when cobalt acetate was irradiated in the presence of an excess of a phosphine, with synthesis gas at 80 atm, in methanol as the solvent. Propylene was hydroformylated with this catalyst to give butyraldehyde with an n/i ratio of more than 99/1 /10/. In the absence of phosphine, the cobalt acetate forms a more active catalyst which is, however, less selective for straight chain products /23/. 

The mechanism of this reaction was studied in detail, using high-pressure UV and IR spectroscopy. The first step is a fast thermal reaction of cobalt acetate with syn-gas and phosphine to from the ionic complex 7. The yellow cation is the photoactive species. 

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