Cobalt - , hydrate, methanolate

Cobalt(II), [triaconta-/i-cyano octakis-(trimethanolcobalt(II)) hexakis-(hexacyanomolybdate(V)) -], hydrate, methanolate, 34 159... 

Meanwhile, Wacker Chemie developed the palladium-copper-catalyzed oxidative hydration of ethylene to acetaldehyde. In 1965 BASF described a high-pressure process for the carbonylation of methanol to acetic acid using an iodide-promoted cobalt catalyst (/, 2), and then in 1968, Paulik and Roth of Monsanto Company announced the discovery of a low-pressure carbonylation of methanol using an iodide-promoted rhodium or iridium catalyst (J). In 1970 Monsanto started up a large plant based on the rhodium catalyst. 

Cobalt(II) chloride-6-hydrate (1.0 g, 4 mmole) and a slight excess of [13]aneN4 (0.8 g, 4.3 mmole) are warmed ( 60°) in 100 mL of methanol for 15 minutes. Concentrated HCl is then added dropwise to the solution until the red-brown solution turns green-brown (about 1 mL). Air is bubbled through the solution for 2 hours and its volume is reduced. At this point, red crystals of the cw-isomer separate (yield 15%). Reduction of the volume of the filtrate results in isolation... 

A mixture of 20.0 g. (0.08 mol) of cobalt(II) acetate 4-hydrate, 50.0 g. (0.27 mol) of potassium oxalate 1-hydrate, and 0.5 ml. of glacial acetic acid in 150 ml. of water is placed in a beaker protected from light and is stirred mechanically and heated to 55°, whereupon a clear solution results. Sixty milliliters of 6% hydrogen peroxide is added dropwise from a buret over a 15-minute interval. The temperature is kept at 55 to 56° by the addition of small pieces of ice as the reaction proceeds. The dark green product is filtered off at room temperature, washed well with ice water, methanol, and finally acetone, and dried in the dark at 40° yield, 27.1 g. (94%). Anal. Calcd. for K4[Co2(C204)4(OH)2]-3H20 C, 13.45 H, 1.12. Found C, 13.44 H, 1.05. 

A suspension of 172 g. (1.5 moles) of dimethylglyoxime and 178 g. (0.75 mole) of cobalt(II) chloride 6-hydrate in 2 1. of methanol is stirred under nitrogen in a 3-1. Erlenmeyer flask until the cobalt(II) salt dissolves (complete dissolution of the dimethylglyoxime is not necessary). There is then added 60 g. (1.5 moles) of sodium hydroxide (in the form of a 50% by weight aqueous solution), plus 60 g. (0.75 mole) of pyridine. A dark... 

A solution of 47.6 g. (0.2 mole) of cobalt(II) chloride 6-hydrate in 270 ml. of methanol is added drop by drop with vigorous stirring over a 25-minute period to a solution of 24 g. (0.6 mole) of sodium hydroxide and 60 g. (0.6 mole) of 2,4-pentanedione in... 

Aqueous hydrobromic acid (32.6 g, 0.2 mole of 48% HBr) is added slowly from a dropping funnel to a solution of 1,3-propanediamine (15 g, 0.2 mole) in 600 mL of degassed methanol. 2,3-Butanedione (biacetyl, 17.2 g, 0.2 mole) is added under nitrogen from a dropping funnel over a 30-minute period in a well-ventilated hood and the mixture is stirred. The solution slowly changes color from yellow to orange-red. After addition of the 2,3-butanedione is completed, hydrated cobalt(II) acetate (24.9 g, 0.1 mole) is added, and the solution is stirred under nitrogen for 3 hours at room temperature. To the resultant deep-purple solution is added about 70 mL of 48% aqueous hydrobromic acid, and air... 

Cobalt(II) chloride is a blue, crystalline solid, which gives the red hexa-hydrate on exposure to moist air. The compound melts at 724° and boils at 1049°. It dissolves readily in water, methanol, and ethanol but is sparingly soluble in most organic solvents. 

Pyridil allowed to react with hydrated Ni-acetate in methanol 2,2 -pyridilic acid Ni-complex. Y almost 100%. - This extremely mild rearrangement is dependent on chelation. Also with cobaltous acetate and limitations s. D. S. C. Black, Chem. Gommun. 1967, 311. 

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