benzyl formate

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

Procedure: The same autoclave as used in Example 17 is charged with 20 grams of benzyl formate, and 20 grams of N-methyl-2-pyrrolidone and 1.4 grams of mercurous iodide are added thereto. Carbon monoxide is introduced into the autoclave under pressure and the reaction is conducted at a pressure of 300 kg./cm.2 gauge and a temperature of 210° C. for 2 hours. As a result there is obtained phenyl acetic acid in a yield of 12.6 grams, which corresponds to a conversion of 63% based on the starting benzyl formate. are added As a result there

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

Procedure: The same autoclave as used in Example 17 is charged with 20 grams of benzyl formate, and 20 grams of N-methyl-2-pyrrolidone and 1.4 grams of mercurous iodide are added thereto. Carbon monoxide is introduced into the autoclave under pressure and the reaction is conducted at a pressure of 300 kg./cm.2 gauge and a temperature of 210° C. for 2 hours. As a result there is obtained phenyl acetic acid in a yield of 12.6 grams, which corresponds to a conversion of 63% based on the starting benzyl formate. are added As a result there

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

Procedure: In a dry argon-purged flask, 2,7-fluorenedicarboxylic acid dibenzyl ester (3.0 g, 0.0065 mol) was dissolved in anh. THF (60 mL) at room temperature. Benzyl formate (4.2 mL, 0.035 mol, stored over anhydrous K2CO3) was added followed by addition of potassium tert-butoxide 95% (2.7 g, 0.023 mol). The reaction was stirred for three hours then the reaction was quenched with the addition of water and acidified with HCl to pH 2. The organic solvent was partially evaporated at reduced pressure. The product was twice extracted with ethyl acetate (600 mL then 200 mL). The combined organic layers were washed three times with brine, dried over sodium sulfate, filtered and evaporated to dryness. The crude product was washed with hexanes and methanol (1.9 g, 60%). 1H-NMR (d6-DMSO): δ (ppm) 11.9 (s, ˜1H, formyl); 8.8 (s, 1H, Ar); 8.5 (s, 1H, Ar); 8.4 (s, 1H, Ar); 8.2 (m, 2H, Ar); 7.9 (m, 2H, Ar); 7.5-7.4 (m, 10H, Bz); 5.4 (s, 4H, Ar). In a dry argon-purged flask the reaction was quenched with the addition of water The organic solvent was partially evaporated at reduced pressure The product was twice extracted with ethyl acetate (600 mL The combined organic layers were washed three times with brine dried over sodium sulfate filtered evaporated to dryness The crude product was washed with hexanes and methanol (1.9 g, 60%)

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

Procedure: In a dry argon-purged flask, 2,7-fluorenedicarboxylic acid dibenzyl ester (3.0 g, 0.0065 mol) was dissolved in anh. THF (60 mL) at room temperature. Benzyl formate (4.2 mL, 0.035 mol, stored over anhydrous K2CO3) was added followed by addition of potassium tert-butoxide 95% (2.7 g, 0.023 mol). The reaction was stirred for three hours then the reaction was quenched with the addition of water and acidified with HCl to pH 2. The organic solvent was partially evaporated at reduced pressure. The product was twice extracted with ethyl acetate (600 mL then 200 mL). The combined organic layers were washed three times with brine, dried over sodium sulfate, filtered and evaporated to dryness. The crude product was washed with hexanes and methanol (1.9 g, 60%). 1H-NMR (d6-DMSO): δ (ppm) 11.9 (s, ˜1H, formyl); 8.8 (s, 1H, Ar); 8.5 (s, 1H, Ar); 8.4 (s, 1H, Ar); 8.2 (m, 2H, Ar); 7.9 (m, 2H, Ar); 7.5-7.4 (m, 10H, Bz); 5.4 (s, 4H, Ar). In a dry argon-purged flask the reaction was quenched with the addition of water The organic solvent was partially evaporated at reduced pressure The product was twice extracted with ethyl acetate (600 mL The combined organic layers were washed three times with brine dried over sodium sulfate filtered evaporated to dryness The crude product was washed with hexanes and methanol (1.9 g, 60%)

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Hexadecanedioic acid (20.0 g, 69.8 mmol) and Dowex® were suspended in n-octane and heated to reflux. Benzyl formate (22.0 g, 162 mmol) was added. After 6 hours additional benzyl formate (22.0 g, 162 mmol) was added. The heating was continued for 50 hours. The reaction mixture was filtered at 80° C. The filtrate was cooled to 20° C., and the precipitate was collected by filtration. The crude product (20.2 g) was suspended in dichloromethane (220 ml) at 20° C. for 4 hours. The suspension was filtered, and the filtrate was evacuated to dryness at 20-30° C. The resulting solid (13.9 g) was recrystallised from 2-propanol (140 ml). The product was isolated by filtration, and dried to constant weight under reduced pressure at 30-40° C. Yield: 10.2 g (39%) of white material. heated to reflux The reaction mixture was filtered at 80° C the precipitate was collected by filtration The crude product (20.2 g) was suspended in dichloromethane (220 ml) at 20° C. for 4 hours The suspension was filtered the filtrate was evacuated to dryness at 20-30° C The resulting solid (13.9 g) was recrystallised from 2-propanol (140 ml) The product was isolated by filtration dried to constant weight under reduced pressure at 30-40° C

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Hexadecanedioic acid (20.0 g, 69.8 mmol) and Dowex® were suspended in n-octane and heated to reflux. Benzyl formate (22.0 g, 162 mmol) was added. After 6 hours additional benzyl formate (22.0 g, 162 mmol) was added. The heating was continued for 50 hours. The reaction mixture was filtered at 80° C. The filtrate was cooled to 20° C., and the precipitate was collected by filtration. The crude product (20.2 g) was suspended in dichloromethane (220 ml) at 20° C. for 4 hours. The suspension was filtered, and the filtrate was evacuated to dryness at 20-30° C. The resulting solid (13.9 g) was recrystallised from 2-propanol (140 ml). The product was isolated by filtration, and dried to constant weight under reduced pressure at 30-40° C. Yield: 10.2 g (39%) of white material. heated to reflux The reaction mixture was filtered at 80° C the precipitate was collected by filtration The crude product (20.2 g) was suspended in dichloromethane (220 ml) at 20° C. for 4 hours The suspension was filtered the filtrate was evacuated to dryness at 20-30° C The resulting solid (13.9 g) was recrystallised from 2-propanol (140 ml) The product was isolated by filtration dried to constant weight under reduced pressure at 30-40° C

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

Procedure: The same autoclave as used in Example 17 is charged with 20 grams of benzyl formate, and 20 grams of N-methyl-2-pyrrolidone and 1.4 grams of mercurous iodide are added thereto. Carbon monoxide is introduced into the autoclave under pressure and the reaction is conducted at a pressure of 300 kg./cm.2 gauge and a temperature of 210° C. for 2 hours. As a result there is obtained phenyl acetic acid in a yield of 12.6 grams, which corresponds to a conversion of 63% based on the starting benzyl formate. are added As a result there

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

Procedure: A mixture of water (10.0061 g) and benzyl formate (E, 10.7949 g) was in each case introduced into a thermostated glass vessel and stirred at 20.0 (±0.2)° C. In each case, a small amount of formic acid was added to this mixture. After vigorous mixing, the stirrer was stopped and phase separation was awaited. Samples were in each case taken from the water phase and the benzyl formate phase and their formic acid content analyzed. The values determined are given in Table 5. introduced into a thermostated glass vessel phase separation

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

Procedure: A mixture of water (10.0061 g) and benzyl formate (E, 10.7949 g) was in each case introduced into a thermostated glass vessel and stirred at 20.0 (±0.2)° C. In each case, a small amount of formic acid was added to this mixture. After vigorous mixing, the stirrer was stopped and phase separation was awaited. Samples were in each case taken from the water phase and the benzyl formate phase and their formic acid content analyzed. The values determined are given in Table 5. introduced into a thermostated glass vessel phase separation

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

Procedure: In a dry argon-purged flask, 2,7-fluorenedicarboxylic acid dibenzyl ester (3.0 g, 0.0065 mol) was dissolved in anh. THF (60 mL) at room temperature. Benzyl formate (4.2 mL, 0.035 mol, stored over anhydrous K2CO3) was added followed by addition of potassium tert-butoxide 95% (2.7 g, 0.023 mol). The reaction was stirred for three hours then the reaction was quenched with the addition of water and acidified with HCl to pH 2. The organic solvent was partially evaporated at reduced pressure. The product was twice extracted with ethyl acetate (600 mL then 200 mL). The combined organic layers were washed three times with brine, dried over sodium sulfate, filtered and evaporated to dryness. The crude product was washed with hexanes and methanol (1.9 g, 60%). 1H-NMR (d6-DMSO): δ (ppm) 11.9 (s, ˜1H, formyl); 8.8 (s, 1H, Ar); 8.5 (s, 1H, Ar); 8.4 (s, 1H, Ar); 8.2 (m, 2H, Ar); 7.9 (m, 2H, Ar); 7.5-7.4 (m, 10H, Bz); 5.4 (s, 4H, Ar). In a dry argon-purged flask the reaction was quenched with the addition of water The organic solvent was partially evaporated at reduced pressure The product was twice extracted with ethyl acetate (600 mL The combined organic layers were washed three times with brine dried over sodium sulfate filtered evaporated to dryness The crude product was washed with hexanes and methanol (1.9 g, 60%)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: DOWEX® 50W-X2 (2 g), benzyl formate (10 mL, mol), and adipic acid (2 g, mol) were added to octane (10 mL). The mixture was refluxed for 4 hours at 100° C., and the crude product was purified via silica chromatography to yield a clear, colorless liquid (87% yield). 1H NMR (CDCl3) 1.59-1.78 (m, 4H, CH2CH2), 2.33-2.39 (m, 4H, CH2COOH), 5.09 (s, 2H, PhCH2), 7.25-7.30 (m, 5H, aromatic). the crude product was purified via silica chromatography

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: DOWEX® 50W-X2 (2 g), benzyl formate (10 mL, mol), and adipic acid (2 g, mol) were added to octane (10 mL). The mixture was refluxed for 4 hours at 100° C., and the crude product was purified via silica chromatography to yield a clear, colorless liquid (87% yield). 1H NMR (CDCl3) 1.59-1.78 (m, 4H, CH2CH2), 2.33-2.39 (m, 4H, CH2COOH), 5.09 (s, 2H, PhCH2), 7.25-7.30 (m, 5H, aromatic). the crude product was purified via silica chromatography