pentyl acetate

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

Procedure: A 100 milligram quantity of the hydroxy ester described in Example III is pyrolyzed in a sealed tube at 400° C. for 3 minutes. Analysis of the pyrolysis mixture by gas chromatography indicates the presence of about 30% of a mixture in a 1:1 ratio of amyl acetate and 4-acetylpyridine. The remainder of the mixture contains unreacted starting material.

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

Procedure: One of the commercially important ways to manufacture n-amyl acetate is by the catalytic esterification of n-amyl alcohol with acetic acid. n-Amyl acetate (b.p.=148.4° C.), n-amyl alcohol (b.p.=138.1° C.) and water (b.p.=100° C.) form a minimum ternary azeotrope boiling at 94.8° C. and containing 10.5 weight percent n-amyl acetate, 33.3 wt. % n-amyl alcohol and 56.2 wt. % water. n-Amyl acetate forms a binary azeotrope with water boiling at 95.2° C. containing 59 wt. % n-amyl acetate. n-Amyl alcohol also forms a binary minimum azeotrope with water which boils at 95.8° C. and contains 45.6 wt. % n-amyl alcohol. Thus in the esterification of n-amyl alcohol with acetic acid to form n-amyl acetate and water, the rectification of this mixture has two binary and a ternary azeotrope to contend with, and yields the lowest boiling constituent, namely the n-amyl acetate - n-amyl alcohol - water ternary azeotrope. It is therefore impossible to produce n-amyl acetate from n-amyl alcohol and water mixtures by rectification because the lower boiling ternary azeotrope will always come off overhead as the initial product. Any mixture of n-amyl acetate, n-amyl alcohol and water subjected to rectification at one atmosphere pressure will produce an overhead product boiling at 94.8° C. and containing 10.5 wt. % n-amyl acetate, 33.3 wt. % n-amyl alcohol and 56.2 wt. % water. Extractive distillation would be an attractive method of effecting the separation of n-amyl acetate from n-amyl alcohol if agents can be found that (1) will break the n-amyl acetate - n-amyl alcohol - water azeotrope and (2) are easy to recover from the n-amyl alcohol, that is, form no azeotrope with n-amyl alcohol and boil sufficiently above n-amyl alcohol to make the separation by rectification possible with only a few theoretical plates. yields the lowest boiling constituent

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

Procedure: One of the commercially important ways to manufacture n-amyl acetate is by the catalytic esterification of n-amyl alcohol with acetic acid. n-Amyl acetate (b.p.=148.4° C.), n-amyl alcohol (b.p.=138.1° C.) and water (b.p.=100° C.) form a minimum ternary azeotrope boiling at 94.8° C. and containing 10.5 weight percent n-amyl acetate, 33.3 wt. % n-amyl alcohol and 56.2 wt. % water. n-Amyl acetate forms a binary azeotrope with water boiling at 95.2° C. containing 59 wt. % n-amyl acetate. n-Amyl alcohol also forms a binary minimum azeotrope with water which boils at 95.8° C. and contains 45.6 wt. % n-amyl alcohol. Thus in the esterification of n-amyl alcohol with acetic acid to form n-amyl acetate and water, the rectification of this mixture has two binary and a ternary azeotrope to contend with, and yields the lowest boiling constituent, namely the n-amyl acetate - n-amyl alcohol - water ternary azeotrope. It is therefore impossible to produce n-amyl acetate from n-amyl alcohol and water mixtures by rectification because the lower boiling ternary azeotrope will always come off overhead as the initial product. Any mixture of n-amyl acetate, n-amyl alcohol and water subjected to rectification at one atmosphere pressure will produce an overhead product boiling at 94.8° C. and containing 10.5 wt. % n-amyl acetate, 33.3 wt. % n-amyl alcohol and 56.2 wt. % water. Extractive distillation would be an attractive method of effecting the separation of n-amyl acetate from n-amyl alcohol if agents can be found that (1) will break the n-amyl acetate - n-amyl alcohol - water azeotrope and (2) are easy to recover from the n-amyl alcohol, that is, form no azeotrope with n-amyl alcohol and boil sufficiently above n-amyl alcohol to make the separation by rectification possible with only a few theoretical plates. yields the lowest boiling constituent

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To two 125 mL 3 neck flasks with mechanical stirring, condensers, and a heating apparatus consisting of an RTD probe in the flask hooked via a temperature controller to a heating mantle the following were added: 7.61 g of methyl 4-hydroxybenzoate, 11.05 g of β-chloroethylpiperidine hydrochloride, 16.59 g of powdered potassium carbonate, and 60 mL of amyl acetate. The flasks were placed in an ambient oil bath and heated under nitrogen to 95° C.-100° C. The reaction was allowed to proceed until HPLC indicated 8% unreacted methyl 4-hydroxybenzoate in A, 12% unreacted in B. The flasks were then cooled to less than 50° C. 40 mL deionized water was added with stirring to dissolve solids. The aqueous layer was separated and discarded. The water wash was repeated and the aqueous layer was separated and discarded. HPLC of organic layers showed 6% 4-hydroxybenzoate remains in A, 3% in B. 25 mL of 8N hydrochloric acid was added with stirring to extract the intermediate. The layers were separated and the acid layers returned to reaction flasks. The acid solutions were heated at about 95° C. for about 4 hours. The flasks were then cooled to less than 40° C. and 25 mL of acetone was added. The mixture was then cooled to 0° C.-5° C. for 1 hour. The mixture was filtered and the cakes rinsed with approximately 25 mL of acetone and dried. A=11.50 g (80.5%), B=10.5 g (73.8%) were added The flasks were placed in an ambient oil bath heated under nitrogen to 95° C.-100° C The flasks were then cooled to less than 50° C was added to dissolve solids The aqueous layer was separated The water wash the aqueous layer was separated 25 mL of 8N hydrochloric acid was added with stirring to extract the intermediate The layers were separated the acid layers returned to reaction flasks The flasks were then cooled to less than 40° C. The mixture was then cooled to 0° C.-5° C. for 1 hour The mixture was filtered the cakes rinsed with approximately 25 mL of acetone dried

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

Procedure: A 100 milligram quantity of the hydroxy ester described in Example III is pyrolyzed in a sealed tube at 400° C. for 3 minutes. Analysis of the pyrolysis mixture by gas chromatography indicates the presence of about 30% of a mixture in a 1:1 ratio of amyl acetate and 4-acetylpyridine. The remainder of the mixture contains unreacted starting material.

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To two 125 mL 3 neck flasks with mechanical stirring, condensers, and a heating apparatus consisting of an RTD probe in the flask hooked via a temperature controller to a heating mantle the following were added: 7.61 g of methyl 4-hydroxybenzoate, 11.05 g of β-chloroethylpiperidine hydrochloride, 16.59 g of powdered potassium carbonate, and 60 mL of amyl acetate. The flasks were placed in an ambient oil bath and heated under nitrogen to 95° C.-100° C. The reaction was allowed to proceed until HPLC indicated 8% unreacted methyl 4-hydroxybenzoate in A, 12% unreacted in B. The flasks were then cooled to less than 50° C. 40 mL deionized water was added with stirring to dissolve solids. The aqueous layer was separated and discarded. The water wash was repeated and the aqueous layer was separated and discarded. HPLC of organic layers showed 6% 4-hydroxybenzoate remains in A, 3% in B. 25 mL of 8N hydrochloric acid was added with stirring to extract the intermediate. The layers were separated and the acid layers returned to reaction flasks. The acid solutions were heated at about 95° C. for about 4 hours. The flasks were then cooled to less than 40° C. and 25 mL of acetone was added. The mixture was then cooled to 0° C.-5° C. for 1 hour. The mixture was filtered and the cakes rinsed with approximately 25 mL of acetone and dried. A=11.50 g (80.5%), B=10.5 g (73.8%) were added The flasks were placed in an ambient oil bath heated under nitrogen to 95° C.-100° C The flasks were then cooled to less than 50° C was added to dissolve solids The aqueous layer was separated The water wash the aqueous layer was separated 25 mL of 8N hydrochloric acid was added with stirring to extract the intermediate The layers were separated the acid layers returned to reaction flasks The flasks were then cooled to less than 40° C. The mixture was then cooled to 0° C.-5° C. for 1 hour The mixture was filtered the cakes rinsed with approximately 25 mL of acetone dried

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

Procedure: A 100 milligram quantity of the hydroxy ester described in Example III is pyrolyzed in a sealed tube at 400° C. for 3 minutes. Analysis of the pyrolysis mixture by gas chromatography indicates the presence of about 30% of a mixture in a 1:1 ratio of amyl acetate and 4-acetylpyridine. The remainder of the mixture contains unreacted starting material.

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

Procedure: Thus in the esterification of n-amyl alcohol with acetic acid to form n-amyl acetate and water, the rectification of this mixture has two binary and a ternary azeotrope to contend with, and yields the lowest boiling constituent, namely the n-amyl acetate - n-amyl alcohol - water ternary azeotrope. It is therefore impossible to produce n-amyl acetate from n-amyl alcohol and water mixtures by rectification because the lower boiling ternary azeotrope will always come off overhead as the initial product. Any mixture of n-amyl acetate, n-amyl alcohol and water subjected to rectification at one atmosphere pressure will produce an overhead product boiling at 94.8° C. and containing 10.5 wt. % n-amyl acetate, 33.3 wt. % n-amyl alcohol and 56.2 wt. % water. Extractive distillation would be an attractive method of effecting the separation of n-amyl acetate from n-amyl alcohol if agents can be found that (1) will break the n-amyl acetate - n-amyl alcohol - water azeotrope and (2) are easy to recover from the n-amyl alcohol, that is, form no azeotrope with n-amyl alcohol and boil sufficiently above n-amyl alcohol to make the separation by rectification possible with only a few theoretical plates. yields the lowest boiling constituent

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

Procedure: Thus in the esterification of n-amyl alcohol with acetic acid to form n-amyl acetate and water, the rectification of this mixture has two binary and a ternary azeotrope to contend with, and yields the lowest boiling constituent, namely the n-amyl acetate - n-amyl alcohol - water ternary azeotrope. It is therefore impossible to produce n-amyl acetate from n-amyl alcohol and water mixtures by rectification because the lower boiling ternary azeotrope will always come off overhead as the initial product. Any mixture of n-amyl acetate, n-amyl alcohol and water subjected to rectification at one atmosphere pressure will produce an overhead product boiling at 94.8° C. and containing 10.5 wt. % n-amyl acetate, 33.3 wt. % n-amyl alcohol and 56.2 wt. % water. Extractive distillation would be an attractive method of effecting the separation of n-amyl acetate from n-amyl alcohol if agents can be found that (1) will break the n-amyl acetate - n-amyl alcohol - water azeotrope and (2) are easy to recover from the n-amyl alcohol, that is, form no azeotrope with n-amyl alcohol and boil sufficiently above n-amyl alcohol to make the separation by rectification possible with only a few theoretical plates. yields the lowest boiling constituent

Conditions: temp:97.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 125 mL 3 neck flask with mechanical stirring, condensers, and a heating apparatus consisting of an RTD probe in the flask hooked via a temperature controller to a heating mantle, the following were added: 7.61 g methyl 4-hydroxybenzoate, 11.05 g -chloroethylpiperidine hydrochloride, 16.59 g powdered potassium carbonate, and 60 mL amyl acetate. The mixture was slowly heated under nitrogen in an oil bath to 97° C. The reaction was allowed to proceed overnight. The mixture was cooled to ambient temperature and 40 mL deionized water was added to dissolve the solids. The aqueous layer was separated and discarded and the water wash repeated. 25 mL of 8N hydrochloric acid were added in a single aliquot to extract the intermediate. The layers were separated and the acidic aqueous layer returned to the reaction flask. The aqueous layer was heated to 95° C. and the reaction was allowed to proceed for 24 hours as a stress test. After 6 hours, 0.3% of ester remained. The mixture was cooled to 40° C. and 25 mL acetone was added. The mixture was cooled to 0° C.-5° C. for 1 hour. The filter cakes were rinsed with approx. 25 mL acetone and dried. HPLC revealed 0.2 g of product in filtrate. Yield (crystalline) 13.38 g (95.1% of theoretical). the following were added The mixture was cooled to ambient temperature was added to dissolve the solids The aqueous layer was separated the water wash 25 mL of 8N hydrochloric acid were added in a single aliquot to extract the intermediate The layers were separated The aqueous layer was heated to 95° C. to proceed for 24 hours as a stress test After 6 hours The mixture was cooled to 40° C. 25 mL acetone was added The mixture was cooled to 0° C.-5° C. for 1 hour The filter cakes were rinsed with approx. 25 mL acetone dried Yield (crystalline) 13.38 g (95.1% of theoretical)

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

Procedure: To a 125 mL 3 neck flask with mechanical stirring, condenser, and a heating apparatus consisting of an RTD probe hooked via a temperature controller to a heating mantle, the following were added: 7.61 g methyl 4-hydroxybenzoate, 11.05 g β-chloroethylpiperidine hydrochloride, 16.59 g powdered potassium carbonate, and 60 mL amyl acetate. The mixture was heated in an oil bath under nitrogen to 115° C.-120° C. for 4 hour. HPLC indicated that the reaction was complete. The mixture was then cooled to ambient temperature and 40 mL of deionized water were added to dissolve solids. The aqueous layer was separated and discarded and the water wash was repeated. 5 mL of the organic phase was removed as an analytical standard. 25 mL 8N hydrochloric acid was added to remaining organic phase to extract the intermediate. The layers were separated and the acidified aqueous layers returned to the reaction flasks. The organic phase was discarded. The aqueous phase was heated to 95° C. until HPLC indicated complete hydrolysis of the ester (about 4 hours). The mixtures were cooled to 0° C.-5° C. for 1 hour and filtered. The filter cakes were rinsed with acetone (approx. 25 mL) and dried. Yield 12.61 g (83.6% theoretical). the following were added The mixture was heated in an oil bath under nitrogen to 115° C.-120° C. for 4 hour to dissolve solids The aqueous layer was separated the water wash 5 mL of the organic phase was removed as an analytical standard 25 mL 8N hydrochloric acid was added to extract the intermediate The layers were separated The aqueous phase was heated to 95° C. until HPLC hydrolysis of the ester (about 4 hours) The mixtures were cooled to 0° C.-5° C. for 1 hour filtered The filter cakes were rinsed with acetone (approx. 25 mL) dried

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

Procedure: To a 2000 gallon reaction tank were added: 1320L of amyl acetate, 167.42 kg of methyl 4-hydroxybenzoate, 408.6 kg of anhydrous potassium carbonate, and 283.5 kg of β-chloroethylpiperidine hydrochloride. The mixture was heated to 120° C.–125° C. for 5 hours, at which time HPLC analysis indicated complete consumption of the methyl 4-hydroxybenzoate. The tank was cooled to less than 50° C. 880L of deionized water were added to the tank. The layers were separated and the aqueous layer was discarded. In a glass-lined tank was mixed 367 liters of food grade hydrochloric acid and 184L of deionized water. The acid mixture was combined with the organic layer. The layers were separated and the organic layer was discarded. The mixture of the intermediate ester in aqueous acid heated to reflux until HPLC suggested no further consumption of the ester (13 hours). The mixture was cooled to less than 40° C., 550 liters of acetone was added to the mixture and the mixture was cooled to 0° C.–5° C. and stirred for 1 hour. The product was collected by filtration on a centrifuge. The wet cake was rinsed on the centrifuge with 400L of acetone. The product was dried in a rotary vacuum (double cone) dryer at less than 50° C. and 25–27 inches in mercury. Yield was 91% of theoretical. To a 2000 gallon reaction tank were added The mixture was heated to 120° C.–125° C. for 5 hours, at which time HPLC analysis consumption of the methyl 4-hydroxybenzoate The tank was cooled to less than 50° C 880L of deionized water were added to the tank The layers were separated In a glass-lined tank was mixed 367 liters of food grade hydrochloric acid and 184L of deionized water The layers were separated The mixture of the intermediate ester in aqueous acid heated to reflux until HPLC no further consumption of the ester (13 hours) The mixture was cooled to less than 40° C. 550 liters of acetone was added to the mixture the mixture was cooled to 0° C.–5° C. The product was collected by filtration on a centrifuge The wet cake was rinsed on the centrifuge with 400L of acetone The product was dried in a rotary vacuum (double cone) dryer at less than 50° C.