butyl formate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (The procedure described for the trans isomer in JCS Perkin I, 1999, 25, 3023 was used.) A mixture of cis-cyclohexane-1,4-dicarboxylic acid (TCI) (24.1 g, 140 mmol), butyl formate (700 ml, 623 g, 6.10 mol, 43.5 equiv.), and Dowex 50W×2 resin (50-100 mesh, 140 g) in octane (700 ml) was stirred under nitrogen in a 110° C. oil bath for 24 hours. The mixture was cooled to ambient temperature. The supernatant solution was decanted away from the resin. The resin was washed with ethyl acetate: hexane (1:1, five 150 ml portions), and the washings were added to the supernatant. The solution was evaporated under reduced pressure, the resulting residue diluted with toluene (25 ml), evaporated under reduced pressure, and dried to give crude cis-4-(butoxycarbonyl)cyclohexanecarboxylic acid (36.5 g) as a yellow oil: 1H NMR (CDCl3) 4.08 (2H, m), 2.53 (1H, m), 2.46 (1H, m), 1.92 (4H, m), 1.70 (4H, m), 1.61 (2H, m), 1.38 (2H, m), 0.93 (3H, t, J 7 Hz). The mixture was cooled to ambient temperature The supernatant solution was decanted away from the resin The resin was washed with ethyl acetate: hexane (1:1, five 150 ml portions) the washings were added to the supernatant The solution was evaporated under reduced pressure the resulting residue diluted with toluene (25 ml) evaporated under reduced pressure dried

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (The procedure described for the trans isomer in JCS Perkin I, 1999, 25, 3023 was used.) A mixture of cis-cyclohexane-1,4-dicarboxylic acid (TCI) (24.1 g, 140 mmol), butyl formate (700 ml, 623 g, 6.10 mol, 43.5 equiv.), and Dowex 50W×2 resin (50-100 mesh, 140 g) in octane (700 ml) was stirred under nitrogen in a 110° C. oil bath for 24 hours. The mixture was cooled to ambient temperature. The supernatant solution was decanted away from the resin. The resin was washed with ethyl acetate: hexane (1:1, five 150 ml portions), and the washings were added to the supernatant. The solution was evaporated under reduced pressure, the resulting residue diluted with toluene (25 ml), evaporated under reduced pressure, and dried to give crude cis-4-(butoxycarbonyl)cyclohexanecarboxylic acid (36.5 g) as a yellow oil: 1H NMR (CDCl3) 4.08 (2H, m), 2.53 (1H, m), 2.46 (1H, m), 1.92 (4H, m), 1.70 (4H, m), 1.61 (2H, m), 1.38 (2H, m), 0.93 (3H, t, J 7 Hz). The mixture was cooled to ambient temperature The supernatant solution was decanted away from the resin The resin was washed with ethyl acetate: hexane (1:1, five 150 ml portions) the washings were added to the supernatant The solution was evaporated under reduced pressure the resulting residue diluted with toluene (25 ml) evaporated under reduced pressure dried

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

Procedure: A mixture of palladium chloride [27 mg, 0.15 mmol] and CuCl2 [41 mg, 0.30 mmol] in dioxane (10 ml) was stirred under carbon monoxide for 5 minutes. Then n-butyl formate (4 ml), 1-decene [0.75 g, 5.35 mmol] and aqueous hydrochloric acid (0.1 ml) were added and CO/O2 (1:1) was bubbled through the solution at room temperature and atmospheric pressure for a period of 24 hours. Analysis of the product gave n-butyl 2-methyldecanoate and n-butyl undecanoate with respectively 87% and 13% selectivity with a 64% conversion of the formic acid ester. CO/O2 (1:1) was bubbled through the solution at room temperature atmospheric pressure for a period of 24 hours

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

Procedure: In a tubular reactor, there was packed 10 ml. of a 0.5 wt.% palladium chloride-on-alumina catalyst, followed by introduction of a gaseous mixture consisting of 30.0% by volume of carbon monoxide, 3.2% by volume of hydrogen, 1.8% by volume of n-butyl nitrite and 65.0% by volume of nitrogen at a rate of 38 l. per hour to subject the gaseous mixture to reaction at a reaction temperature of 120° C. under ambient pressure. According to a gas-chromatographic analysis of the reaction mixture, it was found that n-butyl formate was produced in a space time yield of 65 g./l.-catalyst.hr and small amounts of di-n-butyl oxalate and n-butanol were by-produced. In a tubular reactor, there was packed per hour to subject the gaseous mixture to reaction at a reaction temperature of 120° C. under ambient pressure was produced in a space time yield of 65 g

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

Procedure: Experiment was run in the same manner as in Example 4 except that the catalyst was replaced by 1.0 wt.% palladium-on-silicon-carbide. As the result, it was found that n-butyl formate was produced in a space time yield of 202 g./l.-catalyst.hr and small amounts of di-n-butyl oxalate and n-butanol were by-produced. was produced in a space time yield of 202 g

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

Procedure: Experiment was run in the same manner as in Example 4 except that the catalyst was replaced by 1.0 wt.% palladium-on-silicon-carbide. As the result, it was found that n-butyl formate was produced in a space time yield of 202 g./l.-catalyst.hr and small amounts of di-n-butyl oxalate and n-butanol were by-produced. was produced in a space time yield of 202 g

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

Procedure: Experiment was run in the same manner as in Example 2 except that the composition of the gaseous starting materials was replaced by 30.3% by volume of carbon monoxide, 2.6% by volume of hydrogen, 2.4% by volume of n-butyl nitrite and 65.5% by volume of nitrogen and that the catalyst was replaced by a 1.0 wt.% palladium-on-activated carbon catalyst. As the result, it was found that n-butyl formate was produced in a space time yield of 147 g./l.-catalyst.hr and small amounts of di-n-butyl oxalate and n-butanol were by-produced. was produced in a space time yield of 147 g

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

Procedure: Experiment was run in the same manner as in Example 2 except that the composition of the gaseous starting materials was replaced by 27.9% by volume of carbon monoxide, 6.2% by volume of hydrogen, 1.7% by volume of n-butyl nitrite and 64.2% by volume of nitrogen. As the result, it was found that n-butyl formate was produced in a space time yield of 109 g./l.-catalyst.hr, and small amounts of di-n-butyl oxalate and n-butanol were by-produced. was produced in a space time yield of 109 g