2-phenylethyl benzoate

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

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2-L, 4-neck round bottom flask, fitted with a thermometer, mechanical stirrer, nitrogen inlet tube and Liebig condenser/receiving flask, was charged with 671.7 g (5.50 mol, 1.00 equiv) of benzoic acid, 806.3 g (6.60 mol, 1.20 equiv) of 2-phenylethyl alcohol, 5.30 g (0.43% w/w, 1.0 mol %) of methanesulfonic acid (MSA) and 1.25 g (0.1% w/w) of triisodecylphosphite (TDP). The system was heated gently with slow stirring (<50 rpm) until the benzoic acid dissolved. The air was removed with three cycles of evacuation/nitrogen fill using a mechanical vacuum pump (50-100 torr). The rate of stirring was increased to ca. 200 rpm, the nitrogen sparge was set at 0.2 scfh, and the reaction mixture was heated to 140° C. After a 1-h hold, the temperature was increased to 150° C, and held for 1 h. The temperature was increased to 160° C. and the nitrogen sparge was increased to 0.5 scfh. After a 1-h hold, the reaction mixture was cooled to room temperature and sampled for analysis. The acid number was 8.1 mg KOH/g (97.3% conversion of benzoic acid, corrected for MSA), the APHA color was 66, and the excess 2-phenylethyl alcohol was 7.9% by GLC. To the reaction mixture at 25° C. was added 213 g of 10% w/w aqueous sodium carbonate solution. The batch was heated to 50° C. and stirred for 15 min. The stirring was stopped and the batch was allowed to settle for 30 min. The bottom aqueous layer was removed from the flask with a pipette, and 2-phenylethyl alcohol was removed by vacuum distillation at 180-190° C. (20 torr) for 1 h with a nitrogen sweep of 0.5 scfh. The reaction mixture was cooled to ca. 70° C. and sampled for analysis. The residual 2-phenylethyl alcohol was 0.17% by GLC, the acid number was 0.10 mg KOH/g, and the APHA color was 95. Treatment with activated carbon and filtration as usual (see Example 1) gave 1100 g (88%) of 2-phenylethyl benzoate. The APHA color was 72, the acid number was 0.11 mg KOH/g, the saponification number was 242 mg KOH/g, the residual sulfur was <10 ppm, and the residual phosphorous was <10 ppm. The system was heated gently dissolved The air was removed with three cycles of evacuation/nitrogen was increased to ca. 200 rpm the nitrogen sparge After a 1-h hold, the temperature was increased to 150° C The temperature was increased to 160° C. the nitrogen sparge was increased to 0.5 scfh After a 1-h hold, the reaction mixture was cooled to room temperature sampled for analysis To the reaction mixture at 25° C. was added 213 g of 10% w/w aqueous sodium carbonate solution The batch was heated to 50° C. stirred for 15 min to settle for 30 min The bottom aqueous layer was removed from the flask with a pipette, and 2-phenylethyl alcohol was removed by vacuum distillation at 180-190° C. (20 torr) for 1 h with a nitrogen sweep of 0.5 scfh The reaction mixture was cooled to ca. 70° C. sampled for analysis Treatment with activated carbon and filtration as usual (see Example 1)

Conditions: temp:210.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The reaction was set up as in Example 2 except that methyl benzoate (748.8 g, 5.50 mol) was used instead of benzoic acid and 671.9 g (5.50 mol) of 2-phenylethyl alcohol was used. After 4 h at 190° C., 230 g of distillate was collected and the reaction mixture was 51% product by GLC. The methanol was stripped from the distillate on a Buchi rotary evaporator and the residue was returned to the reaction flask. The batch was heated for 2 h at 200° C. and 2 h at 210° C., whereupon 170 g of distillate was collected and the reaction mixture was 80% product by GLC. The methanol was stripped from the distillate as before, and the residue was returned to the reaction flask. The batch was heated for 2 h at 210° C. and 2 h at 220° C., whereupon 40 g of distillate was collected and the reaction mixture was 94% product by GLC. The excess 2-phenylethyl alcohol (3.5% by GLC) and methyl benzoate (2.7% by GLC) were removed by vacuum distillation as usual and the product was treated with activated carbon as usual to afford 1000 g (81%) of 2-phenylethyl benzoate. The residual 2-phenylethyl alcohol was 0.30, the APHA color was 40, the acid number was 0.13 mg KOH/g, the saponification number was 245 mg KOH/g, and the residual tin was <10 ppm. 230 g of distillate was collected The methanol was stripped from the distillate on a Buchi rotary evaporator was collected The batch was heated for 2 h at 210° C. and 2 h at 220° C., whereupon 40 g of distillate was collected The excess 2-phenylethyl alcohol (3.5% by GLC) and methyl benzoate (2.7% by GLC) were removed by vacuum distillation as usual and the product was treated with activated carbon as usual

Conditions: temp:210.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The reaction was set up as in Example 2 except that methyl benzoate (748.8 g, 5.50 mol) was used instead of benzoic acid and 671.9 g (5.50 mol) of 2-phenylethyl alcohol was used. After 4 h at 190° C., 230 g of distillate was collected and the reaction mixture was 51% product by GLC. The methanol was stripped from the distillate on a Buchi rotary evaporator and the residue was returned to the reaction flask. The batch was heated for 2 h at 200° C. and 2 h at 210° C., whereupon 170 g of distillate was collected and the reaction mixture was 80% product by GLC. The methanol was stripped from the distillate as before, and the residue was returned to the reaction flask. The batch was heated for 2 h at 210° C. and 2 h at 220° C., whereupon 40 g of distillate was collected and the reaction mixture was 94% product by GLC. The excess 2-phenylethyl alcohol (3.5% by GLC) and methyl benzoate (2.7% by GLC) were removed by vacuum distillation as usual and the product was treated with activated carbon as usual to afford 1000 g (81%) of 2-phenylethyl benzoate. The residual 2-phenylethyl alcohol was 0.30, the APHA color was 40, the acid number was 0.13 mg KOH/g, the saponification number was 245 mg KOH/g, and the residual tin was <10 ppm. 230 g of distillate was collected The methanol was stripped from the distillate on a Buchi rotary evaporator was collected The batch was heated for 2 h at 210° C. and 2 h at 220° C., whereupon 40 g of distillate was collected The excess 2-phenylethyl alcohol (3.5% by GLC) and methyl benzoate (2.7% by GLC) were removed by vacuum distillation as usual and the product was treated with activated carbon as usual

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

Procedure: The reaction was run as described in Example 2 except that the initial excess of 2-phenylethyl alcohol was 10% rather than 20%, and the organic layer that co-distilled with the water of reaction was returned to the batch at the end of each hold but the last one. After 4 h at 180-210° C., the reaction mixture was cooled to room temperature, where the acid number was 5.50 (97.8% conversion), the APHA color was 114, and the excess 2-phenylethyl alcohol was 4.8% by GLC. A 9.94-g aliquot of 50% w/w aqueous hypophosphorous acid (HPA, 0.40% w/w based on H3PO2) was added. The excess 2-phenylethyl alcohol was removed by vacuum distillation as usual. The APHA color was 39 and the residual 2-phenylethyl alcohol was 0.19% by GLC. Treatment with activated carbon as usual afforded 1100 g (88%) of 2-phenylethyl benzoate. The APHA color was 36, the acid number was 2.10 mg KOH/g, the saponification number was 244 mg KOH/g, the residual tin was 270 ppm, and the residual phosphorous was 1300 ppm. The excess 2-phenylethyl alcohol was removed by vacuum distillation as usual

Conditions: temp:180.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2-L, 4-neck round bottom flask, fitted with a thermometer, mechanical stirrer, nitrogen inlet tube and Liebig condenser/receiving flask, was charged with 671.7 g (5.50 mol, 1.00 equiv) of benzoic acid, 806.3 g (6.60 mol, 1.20 equiv) of 2-phenylethyl alcohol, and 1.25 g (0.1% w/w) of Fascat 2001®. The system was heated gently with slow stirring (<50 rpm) until the benzoic acid dissolved. The air was removed with three cycles of evacuation/nitrogen fill using a mechanical vacuum pump (50-100 torr). The rate of stirring was increased to ca. 200 rpm, the nitrogen sparge was set at 0.2 scfh, and the reaction mixture was heated to 180° C. After a 1-h hold, the temperature was increased to 190° C. for 1 h and then to 200° C. for 1 h. The temperature was increased to 210° C. and the nitrogen sparge was increased to 0.5 scfh. After a 1-h hold, the temperature was further increased to 220° C. for 1 h. The total amount of distillate was 159.2 g, from which 94.4 g of water (theor. 99.1 g) was separated as the top layer. The reaction mixture was cooled to room temperature and sampled for analysis. The acid number was 1.10 mg KOH/g (99.7% conversion) and the APHA color was 115. The excess 2-phenylethyl alcohol (5.5% by GLC) was removed by vacuum distillation. Thus, after 1 h at 180-190° C. and 20 torr (0.5 scfh nitrogen sweep), the residual 2-phenylethyl alcohol was <0.05% by GLC and the APHA color was 222. Activated carbon (37.3 g, 3% w/w) was added, and the mixture was heated at 75-80° C. under vacuum (50-70 torr) for 1 h. After cooling to room temperature, filtration through Celite® gave 1100 g (90%) of 2-phenylethyl benzoate. The APHA color was 20, the acid number was 0.14 mg KOH/g, the saponification number was 246 mg KOH/g (theor. 248), and the residual tin was <10 ppm. The system was heated gently dissolved The air was removed with three cycles of evacuation/nitrogen was increased to ca. 200 rpm the nitrogen sparge After a 1-h hold, the temperature was increased to 190° C. for 1 h The temperature was increased to 210° C. the nitrogen sparge was increased to 0.5 scfh After a 1-h hold, the temperature was further increased to 220° C. for 1 h from which 94.4 g of water (theor. 99.1 g) was separated as the top layer The reaction mixture was cooled to room temperature sampled for analysis The excess 2-phenylethyl alcohol (5.5% by GLC) was removed by vacuum distillation Thus, after 1 h at 180-190° C. Activated carbon (37.3 g, 3% w/w) was added the mixture was heated at 75-80° C. under vacuum (50-70 torr) for 1 h After cooling to room temperature filtration through Celite®

Conditions: temp:180.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2-L, 4-neck round bottom flask, fitted with a thermometer, mechanical stirrer, nitrogen inlet tube and Liebig condenser/receiving flask, was charged with 671.7 g (5.50 mol, 1.00 equiv) of benzoic acid, 806.3 g (6.60 mol, 1.20 equiv) of 2-phenylethyl alcohol, and 1.25 g (0.1% w/w) of Fascat 2001®. The system was heated gently with slow stirring (<50 rpm) until the benzoic acid dissolved. The air was removed with three cycles of evacuation/nitrogen fill using a mechanical vacuum pump (50-100 torr). The rate of stirring was increased to ca. 200 rpm, the nitrogen sparge was set at 0.2 scfh, and the reaction mixture was heated to 180° C. After a 1-h hold, the temperature was increased to 190° C. for 1 h and then to 200° C. for 1 h. The temperature was increased to 210° C. and the nitrogen sparge was increased to 0.5 scfh. After a 1-h hold, the temperature was further increased to 220° C. for 1 h. The total amount of distillate was 159.2 g, from which 94.4 g of water (theor. 99.1 g) was separated as the top layer. The reaction mixture was cooled to room temperature and sampled for analysis. The acid number was 1.10 mg KOH/g (99.7% conversion) and the APHA color was 115. The excess 2-phenylethyl alcohol (5.5% by GLC) was removed by vacuum distillation. Thus, after 1 h at 180-190° C. and 20 torr (0.5 scfh nitrogen sweep), the residual 2-phenylethyl alcohol was <0.05% by GLC and the APHA color was 222. Activated carbon (37.3 g, 3% w/w) was added, and the mixture was heated at 75-80° C. under vacuum (50-70 torr) for 1 h. After cooling to room temperature, filtration through Celite® gave 1100 g (90%) of 2-phenylethyl benzoate. The APHA color was 20, the acid number was 0.14 mg KOH/g, the saponification number was 246 mg KOH/g (theor. 248), and the residual tin was <10 ppm. The system was heated gently dissolved The air was removed with three cycles of evacuation/nitrogen was increased to ca. 200 rpm the nitrogen sparge After a 1-h hold, the temperature was increased to 190° C. for 1 h The temperature was increased to 210° C. the nitrogen sparge was increased to 0.5 scfh After a 1-h hold, the temperature was further increased to 220° C. for 1 h from which 94.4 g of water (theor. 99.1 g) was separated as the top layer The reaction mixture was cooled to room temperature sampled for analysis The excess 2-phenylethyl alcohol (5.5% by GLC) was removed by vacuum distillation Thus, after 1 h at 180-190° C. Activated carbon (37.3 g, 3% w/w) was added the mixture was heated at 75-80° C. under vacuum (50-70 torr) for 1 h After cooling to room temperature filtration through Celite®

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

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2-L, 4-neck round bottom flask, fitted with a thermometer, mechanical stirrer, nitrogen inlet tube and Liebig condenser/receiving flask, was charged with 671.7 g (5.50 mol, 1.00 equiv) of benzoic acid, 806.3 g (6.60 mol, 1.20 equiv) of 2-phenylethyl alcohol, 5.30 g (0.43% w/w, 1.0 mol %) of methanesulfonic acid (MSA) and 1.25 g (0.1% w/w) of triisodecylphosphite (TDP). The system was heated gently with slow stirring (<50 rpm) until the benzoic acid dissolved. The air was removed with three cycles of evacuation/nitrogen fill using a mechanical vacuum pump (50–100 torr). The rate of stirring was increased to ca. 200 rpm, the nitrogen sparge was set at 0.2 scfh, and the reaction mixture was heated to 140° C. After a 1-h hold, the temperature was increased to 150° C. and held for 1 h. The temperature was increased to 160° C. and the nitrogen sparge was increased to 0.5 scfh. After a 1-h hold, the reaction mixture was cooled to room temperature and sampled for analysis. The acid number was 8.1 mg KOH/g (97.3% conversion of benzoic acid, corrected for MSA), the APHA color was 66, and the excess 2-phenylethyl alcohol was 7.9% by GLC. To the reaction mixture at 25° C. was added 213 g of 10% w/w aqueous sodium carbonate solution. The batch was heated to 50° C. and stirred for 15 min. The stirring was stopped and the batch was allowed to settle for 30 min. The bottom aqueous layer was removed from the flask with a pipette, and 2-phenylethyl alcohol was removed by vacuum distillation at 180–190° C. (20 torr) for 1 h with a nitrogen sweep of 0.5 scfh. The reaction mixture was cooled to ca. 70° C. and sampled for analysis. The residual 2-phenylethyl alcohol was 0.17% by GLC, the acid number was 0.10 mg KOH/g, and the APHA color was 95. Treatment with activated carbon and filtration as usual (see Example 1) gave 1100 g (88%) of 2-phenylethyl benzoate. The APHA color was 72, the acid number was 0.11 mg KOH/g, the saponification number was 242 mg KOH/g, the residual sulfur was <10 ppm, and the residual phosphorous was <10 ppm. The system was heated gently dissolved The air was removed with three cycles of evacuation/nitrogen was increased to ca. 200 rpm the nitrogen sparge After a 1-h hold, the temperature was increased to 150° C. The temperature was increased to 160° C. the nitrogen sparge was increased to 0.5 scfh After a 1-h hold, the reaction mixture was cooled to room temperature sampled for analysis To the reaction mixture at 25° C. was added 213 g of 10% w/w aqueous sodium carbonate solution The batch was heated to 50° C. stirred for 15 min to settle for 30 min The bottom aqueous layer was removed from the flask with a pipette, and 2-phenylethyl alcohol was removed by vacuum distillation at 180–190° C. (20 torr) for 1 h with a nitrogen sweep of 0.5 scfh The reaction mixture was cooled to ca. 70° C. sampled for analysis Treatment with activated carbon and filtration as usual (see Example 1)

Conditions: temp:210.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The reaction was set up as in Example 2 except that methyl benzoate (748.8 g, 5.50 mol) was used instead of benzoic acid and 671.9 g (5.50 mol) of 2-phenylethyl alcohol was used. After 4 h at 190° C., 230 g of distillate was collected and the reaction mixture was 51% product by GLC. The methanol was stripped from the distillate on a Buchi rotary evaporator and the residue was returned to the reaction flask. The batch was heated for 2 h at 200° C. and 2 h at 210° C., whereupon 170 g of distillate was collected and the reaction mixture was 80% product by GLC. The methanol was stripped from the distillate as before, and the residue was returned to the reaction flask. The batch was heated for 2 h at 210° C. and 2 h at 220° C., whereupon 40 g of distillate was collected and the reaction mixture was 94% product by GLC. The excess 2-phenylethyl alcohol (3.5% by GLC) and methyl benzoate (2.7% by GLC) were removed by vacuum distillation as usual and the product was treated with activated carbon as usual to afford 1000 g (81%) of 2-phenylethyl benzoate. The residual 2-phenylethyl alcohol was 0.30, the APHA color was 40, the acid number was 0.13 mg KOH/g, the saponification number was 245 mg KOH/g, and the residual tin was <10 ppm. 230 g of distillate was collected The methanol was stripped from the distillate on a Buchi rotary evaporator was collected The batch was heated for 2 h at 210° C. and 2 h at 220° C., whereupon 40 g of distillate was collected The excess 2-phenylethyl alcohol (3.5% by GLC) and methyl benzoate (2.7% by GLC) were removed by vacuum distillation as usual and the product was treated with activated carbon as usual

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

Procedure: The reaction was run as described in Example 2 except that the initial excess of 2-phenylethyl alcohol was 10% rather than 20%, and the organic layer that co-distilled with the water of reaction was returned to the batch at the end of each hold but the last one. After 4 h at 18014 210° C., the reaction mixture was cooled to room temperature, where the acid number was 5.50 (97.8% conversion), the APHA color was 114, and the excess 2-phenylethyl alcohol was 4.8% by GLC. A 9.94-g aliquot of 50% w/w aqueous hypophosphorous acid (H PA, 0.40% w/w based on H3PO2) was added. The excess 2-phenylethyl alcohol was removed by vacuum distillation as usual. The APHA color was 39 and the residual 2-phenylethyl alcohol was 0.19% by GLC. Treatment with activated carbon as usual afforded 1100 g (88%) of 2-phenylethyl benzoate. The APHA color was 36, the acid number was 2.10 mg KOH/g, the saponification number was 244 mg KOH/g, the residual tin was 270 ppm, and the residual phosphorous was 1300 ppm. The excess 2-phenylethyl alcohol was removed by vacuum distillation as usual

Conditions: temp:180.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2-L, 4-neck round bottom flask, fitted with a thermometer, mechanical stirrer, nitrogen inlet tube and Liebig condenser/receiving flask, was charged with 671.7 g (5.50 mol, 1.00 equiv) of benzoic acid, 806.3 g (6.60 mol, 1.20 equiv) of 2-phenylethyl alcohol, and 1.25 g (0.1% w/w) of Fascat 2001®. The system was heated gently with slow stirring (<50 rpm) until the benzoic acid dissolved. The air was removed with three cycles of evacuation/nitrogen fill using a mechanical vacuum pump (50–100 torr). The rate of stirring was increased to ca. 200 rpm, the nitrogen sparge was set at 0.2 scfh, and the reaction mixture was heated to 180° C. After a 1 -h hold, the temperature was increased to 190° C. for 1 h and then to 200° C. for 1 h. The temperature was increased to 210° C. and the nitrogen sparge was increased to 0.5 scfh. After a 1-h hold, the temperature was further increased to 220° C. for 1 h. The total amount of distillate was 159.2 g, from which 94.4 g of water (theor. 99.1 g) was separated as the top layer. The reaction mixture was cooled to room temperature and sampled for analysis. The acid number was 1.10 mg KOH/g (99.7% conversion) and the APHA color was 115. The excess 2-phenylethyl alcohol (5.5% by GLC) was removed by vacuum distillation. Thus, after 1 h at 180–190° C. and 20 torr (0.5 scfh nitrogen sweep), the residual 2-phenylethyl alcohol was <0.05% by GLC and the APHA color was 222. Activated carbon (37.3 g, 3% w/w) was added, and the mixture was heated at 75–80° C. under vacuum (50–70 torr) for 1 h. After cooling to room temperature, filtration through Celite® gave 1100 g (90%) of 2-phenylethyl benzoate. The APHA color was 20, the acid number was 0.14 mg KOH/g, the saponification number was 246 mg KOH/g (theor. 248), and the residual tin was <10 ppm. The system was heated gently dissolved The air was removed with three cycles of evacuation/nitrogen was increased to ca. 200 rpm the nitrogen sparge After a 1 -h hold, the temperature was increased to 190° C. for 1 h The temperature was increased to 210° C. the nitrogen sparge was increased to 0.5 scfh After a 1-h hold, the temperature was further increased to 220° C. for 1 h from which 94.4 g of water (theor. 99.1 g) was separated as the top layer The reaction mixture was cooled to room temperature sampled for analysis The excess 2-phenylethyl alcohol (5.5% by GLC) was removed by vacuum distillation Thus, after 1 h at 180–190° C. Activated carbon (37.3 g, 3% w/w) was added the mixture was heated at 75–80° C. under vacuum (50–70 torr) for 1 h After cooling to room temperature filtration through Celite®