cobalt(2+);diacetate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The C12–C14 α-olefin mixture from Example 1 with the composition shown in Table I was hydroformylated in the manner indicated in Example 1. Unlike Example 1, instead of the rhodium catalyst and the polyethyleneimine ligand, the hydroformylation catalyst used was dicobaltoctacarbonyl without any other ligand, the amount being 2 g of cobalt based on 1000 g of reactor contents. In order that the olefin conversion obtained was from 98 to 99%, as in Example 1, using the same olefin feed, a reactor temperature of 140° C. was required in both reactors. The (aldehyde+alcohol) selectivity was 94%, the paraffin selectivity was 3%, and the selectivity to give higher-boiling aldehyde condensation products was 3%. Once the pressure in the reactors had been released, the discharge was treated with aqueous acetic acid solution while introducing atmospheric oxygen, until the cobalt carbonyl had been oxidized to give cobalt acetate. The aqueous, cobalt-containing phase was separated off in a phase separator, and the organic phase, as in Example 1, hydrogenated and distilled. Table III gives the composition of the C13–C15 alcohol mixture. the selectivity to give higher-boiling

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Experiments conducted at 120° C. using just Cobalt (III) acetate without any promoters in air and using acetic acid as solvent resulted in much quicker oxidation than Cobalt (II) acetate with the promoters as described above, leading to rapid consumption of xylenes, as indicated by the green solution turning pink-purple after approximately an hour. Under identical reaction conditions using Co(II) there was a long induction period before any early phase oxidation. conducted at 120° C.

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 24.9 g (0.1 mol) of cobalt acetate was added to 500 ml of dimethylformamide and completely dissolved. The solution was heated to 50° C., and 42.6 g (0.2 mol) of N-phenylanthranilic acid was gradually added thereto. The mixture was allowed to react for 3 hours at about 145° C. under refluxing, and the heating was terminated. The mixture, when cooled down to 100° C., was dispersed in 2 liters of water and, after 1 hour, subjected to filtration. The precipitate was washed with water until neutrality and then dried at 90° C., whereby about 40 g of pale reddish grey powder. completely dissolved to react for 3 hours at about 145° C. under refluxing the heating was terminated The mixture, when cooled down to 100° C. was dispersed in 2 liters of water and, after 1 hour subjected to filtration The precipitate was washed with water until neutrality dried at 90° C.

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 24.9 g (0.1 mol) of cobalt acetate was added to 500 ml of dimethylformamide and completely dissolved. The solution was heated to 50° C., and 42.6 g (0.2 mol) of N-phenylanthranilic acid was gradually added thereto. The mixture was allowed to react for 3 hours at about 145° C. under refluxing, and the heating was terminated. The mixture, when cooled down to 100° C., was dispersed in 2 liters of water and, after 1 hour, subjected to filtration. The precipitate was washed with water until neutrality and then dried at 90° C., whereby about 40 g of pale reddish grey powder. completely dissolved to react for 3 hours at about 145° C. under refluxing the heating was terminated The mixture, when cooled down to 100° C. was dispersed in 2 liters of water and, after 1 hour subjected to filtration The precipitate was washed with water until neutrality dried at 90° C.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Indicator compositions were prepared as for Example 11. The colorants used are listed in Table 13. The second solution (Indicator Composition 13) was prepared by adding 1.0 g of cobalt(II) acetate tetrahydrate {Co(C2H3O2)2.4H2O} (available from Sigma-Aldrich Fine Chemicals, St. Louis, Mo.) to 13 ml of water. Devices were prepared and tested as described in Example 11. The results are recorded in Table 13. Indicator compositions were prepared as for Example 11 The second solution (Indicator Composition 13) was prepared Devices were prepared

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Indicator compositions were prepared as for Example 11. The colorants used are listed in Table 13. The second solution (Indicator Composition 13) was prepared by adding 1.0 g of cobalt(II) acetate tetrahydrate {Co(C2H3O2)2.4H2O} (available from Sigma-Aldrich Fine Chemicals, St. Louis, Mo.) to 13 ml of water. Devices were prepared and tested as described in Example 11. The results are recorded in Table 13. Indicator compositions were prepared as for Example 11 The second solution (Indicator Composition 13) was prepared Devices were prepared

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Indicator compositions were prepared as for Example 11. The colorants used are listed in Table 13. The second solution (Indicator Composition 13) was prepared by adding 1.0 g of cobalt(II) acetate tetrahydrate {Co(C2H3O2)2.4H2O} (available from Sigma-Aldrich Fine Chemicals, St. Louis, Mo.) to 13 ml of water. Devices were prepared and tested as described in Example 11. The results are recorded in Table 13. Indicator compositions were prepared as for Example 11 The second solution (Indicator Composition 13) was prepared Devices were prepared

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The C12–C14 α-olefin mixture from Example 1 with the composition shown in Table I was hydroformylated in the manner indicated in Example 1. Unlike Example 1, instead of the rhodium catalyst and the polyethyleneimine ligand, the hydroformylation catalyst used was dicobaltoctacarbonyl without any other ligand, the amount being 2 g of cobalt based on 1000 g of reactor contents. In order that the olefin conversion obtained was from 98 to 99%, as in Example 1, using the same olefin feed, a reactor temperature of 140° C. was required in both reactors. The (aldehyde+alcohol) selectivity was 94%, the paraffin selectivity was 3%, and the selectivity to give higher-boiling aldehyde condensation products was 3%. Once the pressure in the reactors had been released, the discharge was treated with aqueous acetic acid solution while introducing atmospheric oxygen, until the cobalt carbonyl had been oxidized to give cobalt acetate. The aqueous, cobalt-containing phase was separated off in a phase separator, and the organic phase, as in Example 1, hydrogenated and distilled. Table III gives the composition of the C13–C15 alcohol mixture. the selectivity to give higher-boiling

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The C12–C14 α-olefin mixture from Example 1 with the composition shown in Table I was hydroformylated in the manner indicated in Example 1. Unlike Example 1, instead of the rhodium catalyst and the polyethyleneimine ligand, the hydroformylation catalyst used was dicobaltoctacarbonyl without any other ligand, the amount being 2 g of cobalt based on 1000 g of reactor contents. In order that the olefin conversion obtained was from 98 to 99%, as in Example 1, using the same olefin feed, a reactor temperature of 140° C. was required in both reactors. The (aldehyde+alcohol) selectivity was 94%, the paraffin selectivity was 3%, and the selectivity to give higher-boiling aldehyde condensation products was 3%. Once the pressure in the reactors had been released, the discharge was treated with aqueous acetic acid solution while introducing atmospheric oxygen, until the cobalt carbonyl had been oxidized to give cobalt acetate. The aqueous, cobalt-containing phase was separated off in a phase separator, and the organic phase, as in Example 1, hydrogenated and distilled. Table III gives the composition of the C13–C15 alcohol mixture. the selectivity to give higher-boiling

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Experiments conducted at 120° C. using just Cobalt (III) acetate without any promoters in air and using acetic acid as solvent resulted in much quicker oxidation than Cobalt (II) acetate with the promoters as described above, leading to rapid consumption of xylenes, as indicated by the green solution turning pink-purple after approximately an hour. Under identical reaction conditions using Co(II) there was a long induction period before any early phase oxidation. conducted at 120° C.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The reaction was carried out in a glove box and solvents were degassed prior to use. The polymer 4 (95 mg, 0.16 mmol) was dissolved in dichloromethane (2 mL) in a vial charged with a stir bar. A solution of cobalt acetate tetrahydrate (49.8 mg, 0.20 mmol) in methanol (2 mL) was added slowly to the vial, resulting in precipitation of a red-brown powder. After the suspension was stirred at rt for 3 h, additional methanol (6 mL) was added to precipitate more solid. The solid was collected by filtration, washed with 1/10 dichloromethane/methanol (2×10 mL) and methanol (10 mL), and dried under high vacuum to give the desired product Co(II)(4) (99 mg, 95%). Using a similar procedure, Co(II)(2), Co(II)(3), Co(II)(5), Co(II)(6), and Co(II)(7) were synthesized. The reaction was carried out in a glove box solvents were degassed a vial charged with a stir bar resulting in precipitation of a red-brown powder to precipitate more solid The solid was collected by filtration washed with 1/10 dichloromethane/methanol (2×10 mL) and methanol (10 mL) dried under high vacuum

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A high pressure tube (stage a)) filled with 600 ml of active charcoal (from Norit, particle size 3-5 mm) is charged with 180 ml/hour of an aqueous cobalt acetate solution which contains 2.5% by weight of Co2+. In addition, 50 liters (STP)/hour of an equimolar mixture of carbon monoxide and hydrogen are introduced. A temperature of 120° C. and a pressure of 300 bar are maintained. The solution taken off at the other end of the tube contains 0.65% by weight of Co2+ and 1.85% by weight of cobalt as cobalt carbonyl hydride, as well as the corresponding amount of acetic acid. This solution is let down to 20 bar and then thoroughly mixed, at room temperature, with 310 ml of a C4 -cut which contains 43% by weight of butadiene (1.57 moles) (stage b)). After phase separation, the C4 -cut contains 3.7 g of cobalt in the form of cobalt carbonyl compounds. The aqueous phase separated off, which is subsequently used to remove cobalt from the reaction mixture, contains 0.65% by weight of Co2+ and 1.3% by weight of acetic acid. This cobalt-containing C4 -cut is then fed to a high-pressure vessel (stage c)) of 1.9 liters capacity, and furthermore 127 ml (1.57 moles) of pyridine, 127 ml (3.14 moles) of methanol and 60 liters (STP) of carbon monoxide are added per hour. The carbonylation takes place at 130° C. and 600 bar. The product taken off at the top of the high-pressure vessel is let down, so that in addition to excess carbon monoxide excess C4 -hydrocarbons are separated off; the latter contain virtually no butadiene and the conversion is thus quantitative. Per hour, about 52 g of methanol and 100 g of pyridine are distilled from the material discharged (stage d)), the distillation being carried out under reduced pressure so as not to damage the catalyst. The temperature of the material in the distillation vessel is not allowed to exceed 65° C. This material, which contains 3.7 g of cobalt as carbonyl complex and 165 g (1.44 moles) of pentenoic acid ester is continuously fed, together with 117 ml (2.88 moles) of methanol and 55 liters (STP) of carbon monoxide, containing 2% by volume of hydrogen, into the bottom of a further high-pressure vessel of 1.7 liters capacity. The carbonylation is carried out at 170° C. and under a pressure of 150 bar. The excess methanol and the free pyridine are distilled from the material discharged (328 g) in a further column, whilst introducing about 50 liters (STP) of carbon monoxide per hour. The material from the bottom of the distillation column (265 g/hour) is thoroughly mixed with 200 ml/hour of the aqueous acetic acid solution obtained from the cobalt carbonyl extraction stage, at 100° C. in a tube packed with Raschig rings, whilst about 50 liters (STP) of air are being passed through (stage (e)). After separation, 200 ml of aqueous cobalt acetate solution containing 2.45% by weight of cobalt2+ are obtained; after extraction with cyclohexane, this solution is fed to the cobalt carbonyl formation stage (a). The organic phase is separated by fractional distillation into pyridine (about 5 g), valeric acid esters (6.5 g), pentenoic acid esters (11.5 g) and dimethyl butanedicarboxylates (220 g). The latter constituent contains 181 g of dimethyl adipate. are introduced thoroughly mixed, at room temperature, with 310 ml of a C4 -cut which After phase separation The aqueous phase separated off to remove cobalt from the reaction mixture This cobalt-containing C4 -cut is then fed to a high-pressure vessel at 130° C. are separated off Per hour, about 52 g of methanol and 100 g of pyridine are distilled from the material the distillation to exceed 65° C is carried out at 170° C. and under a pressure of 150 bar The excess methanol and the free pyridine are distilled from the material whilst introducing about 50 liters (STP) of carbon monoxide per hour The material from the bottom of the distillation column (265 g/hour) is thoroughly mixed with 200 ml/hour of the aqueous acetic acid solution