[(Z)-4-acetyloxybut-2-enyl] acetate

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

Procedure: A solution of dibenzylamine (40 g, 0.2 mol) and 2-butene-1,4-diol diacetate (105 g, 0.61 mol) dissolved in 150 ml of tetrahydrofuran (THF) is treated with tetrakis(triphenylphosphine)palladium(0) (1.0 g, 0.9 mmol) and stirred at room temperature overnight. The reaction mixture is concentrated in vacuo and the excess 2-butene-1,4-diol diacetate is removed by bulb-to-bulb distillation at 80°-90° C./1 mm. The residue is purified by eluting through a short plug of silica gel (1:1 ethyl acetate:hexanes). 1-Acetoxy-4-dibenzylamino-2-butene is obtained in a yield of 59.2 g (95%). The reaction mixture is concentrated in vacuo the excess 2-butene-1,4-diol diacetate is removed by bulb-to-bulb distillation at 80°-90° C./1 mm The residue is purified by eluting through a short plug of silica gel (1:1 ethyl acetate:hexanes)

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

Procedure: A solution of dibenzylamine (40 g, 0.2 mol) and 2-butene-1,4-diol diacetate (105 g, 0.61 mol) dissolved in 150 ml of tetrahydrofuran (THF) is treated with tetrakis(triphenylphosphine)palladium(0) (1.0 g, 0.9 mmol) and stirred at room temperature overnight. The reaction mixture is concentrated in vacuo and the excess 2-butene-1,4-diol diacetate is removed by bulb-to-bulb distillation at 80°-90° C./1 mm. The residue is purified by eluting through a short plug of silica gel (1:1 ethyl acetate:hexanes). 1-Acetoxy-4-dibenzylamino-2-butene is obtained in a yield of 59.2 g (95%). The reaction mixture is concentrated in vacuo the excess 2-butene-1,4-diol diacetate is removed by bulb-to-bulb distillation at 80°-90° C./1 mm The residue is purified by eluting through a short plug of silica gel (1:1 ethyl acetate:hexanes)

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

Procedure: A solution of di-n-decylamine (10.9 g, 36.6 mmol) and 2-butene-1,4-diol diacetate (3.15 g, 18.3 mmol) in tetrahydrofuran (THF) (150 ml) is treated with tetrakis(triphenylphosphine)palladium(0) (1.0 g, 0.9 mmol) and stirred at room temperature overnight. The reaction mixture is concentrated in vacuo to a oil that is redissolved in THF (500 ml) and treated with 20% aqueous sodium hydroxide (250 ml). The mixture is stirred for one hour, concentrated, and extracted with ether. The ether extracts are dried and concentrated giving an orange oil which is purified by medium pressure chromatography (silica gel; 25% ethyl acetate in hexanes). The title compound is isolated as 5.8 g (49% yield) of a clear oil. The reaction mixture is concentrated in vacuo to a oil that is redissolved in THF (500 ml) treated with 20% aqueous sodium hydroxide (250 ml) The mixture is stirred for one hour concentrated extracted with ether The ether extracts are dried concentrated giving an orange oil which is purified by medium pressure chromatography (silica gel; 25% ethyl acetate in hexanes)

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

Procedure: A solution of di-n-decylamine (10.9 g, 36.6 mmol) and 2-butene-1,4-diol diacetate (3.15 g, 18.3 mmol) in tetrahydrofuran (THF) (150 ml) is treated with tetrakis(triphenylphosphine)palladium(0) (1.0 g, 0.9 mmol) and stirred at room temperature overnight. The reaction mixture is concentrated in vacuo to a oil that is redissolved in THF (500 ml) and treated with 20% aqueous sodium hydroxide (250 ml). The mixture is stirred for one hour, concentrated, and extracted with ether. The ether extracts are dried and concentrated giving an orange oil which is purified by medium pressure chromatography (silica gel; 25% ethyl acetate in hexanes). The title compound is isolated as 5.8 g (49% yield) of a clear oil. The reaction mixture is concentrated in vacuo to a oil that is redissolved in THF (500 ml) treated with 20% aqueous sodium hydroxide (250 ml) The mixture is stirred for one hour concentrated extracted with ether The ether extracts are dried concentrated giving an orange oil which is purified by medium pressure chromatography (silica gel; 25% ethyl acetate in hexanes)

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

Procedure: Another run was conducted employing the same apparatus as that used in Example I but in this run there was no source of halide in the catalyst system. The reactor was charged with 3.4 grams (20 millimoles) of ceric oxide, 7.6 grams (75 millimoles) of lithium acetate dihydrate, 50 ml of acetic acid, 25 ml of acetic anhydride, and 10.0 grams (185.2 millimoles) of butadiene charged from the vapor phase. The reactor was placed in an oil bath, pressured to 30 psig with oxygen and heated to 140° C. About one hour was required for the oil bath temperature to reach the reaction temperature desired, after which a reaction period of 5.3 hours was employed. During the reaction the reactor was pressured to 120 psig with oxygen intermittently. At the end of the reaction period (5.3 hours) the reactor was vented and 1.8 grams of unreacted butadiene was recovered in a cold trap. The reaction mixture was diluted with ether and 2.67 grams of a solid pecipitate was collected by filtration and dried. The ether solution filtrate was washed with water, neutralized with sodium carbonate solution, dried over magnesium sulfate, filtered, and the ether then removed by distillation. The distillation residue (21.3 g) was a pale brown oil. It was analyzed by gas-liquid chromatography which showed that the residue was 86 per cent. ether with the remainder being the diacetoxy butenes. Specifically, there was produced 11 millimoles of 1,2-diacetoxy-3-butene and 3 millimoles of 1,4-diacetoxy-2 -butene for a total yield of 14 millimoles of diacetoxy butenes which represents a yield of 7 per cent bases on the butadiene charged. charged from the vapor phase The reactor was placed in an oil bath after which a reaction period of 5.3 hours During the reaction the reactor At the end of the reaction period (5.3 hours) the reactor 1.8 grams of unreacted butadiene was recovered in a cold trap The reaction mixture was diluted with ether and 2.67 grams of a solid pecipitate was collected by filtration dried The ether solution filtrate was washed with water dried over magnesium sulfate filtered the ether then removed by distillation

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

Procedure: Another run was conducted employing the same apparatus as that used in Example I but in this run there was no source of halide in the catalyst system. The reactor was charged with 3.4 grams (20 millimoles) of ceric oxide, 7.6 grams (75 millimoles) of lithium acetate dihydrate, 50 ml of acetic acid, 25 ml of acetic anhydride, and 10.0 grams (185.2 millimoles) of butadiene charged from the vapor phase. The reactor was placed in an oil bath, pressured to 30 psig with oxygen and heated to 140° C. About one hour was required for the oil bath temperature to reach the reaction temperature desired, after which a reaction period of 5.3 hours was employed. During the reaction the reactor was pressured to 120 psig with oxygen intermittently. At the end of the reaction period (5.3 hours) the reactor was vented and 1.8 grams of unreacted butadiene was recovered in a cold trap. The reaction mixture was diluted with ether and 2.67 grams of a solid pecipitate was collected by filtration and dried. The ether solution filtrate was washed with water, neutralized with sodium carbonate solution, dried over magnesium sulfate, filtered, and the ether then removed by distillation. The distillation residue (21.3 g) was a pale brown oil. It was analyzed by gas-liquid chromatography which showed that the residue was 86 per cent. ether with the remainder being the diacetoxy butenes. Specifically, there was produced 11 millimoles of 1,2-diacetoxy-3-butene and 3 millimoles of 1,4-diacetoxy-2 -butene for a total yield of 14 millimoles of diacetoxy butenes which represents a yield of 7 per cent bases on the butadiene charged. charged from the vapor phase The reactor was placed in an oil bath after which a reaction period of 5.3 hours During the reaction the reactor At the end of the reaction period (5.3 hours) the reactor 1.8 grams of unreacted butadiene was recovered in a cold trap The reaction mixture was diluted with ether and 2.67 grams of a solid pecipitate was collected by filtration dried The ether solution filtrate was washed with water dried over magnesium sulfate filtered the ether then removed by distillation

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

Procedure: Another control run was carried out, employing the same reaction vessel as that utilized in Examples I and II above. In this run, the reactor was charged with 3.9 grams (50 mmoles) of lithium nitrate, 50 ml of acetic acid, 25 ml of acetic anhydride, and 11.0 grams (204 mmoles) of butadiene charged from the vapor phase. The reactor was placed in an oil bath and pressured to 30 psig with oxygen, and heated to 140° C. for 3 hours. Oxygen was added to the reactor intermittently in the same manner as in Example I. At the end of the reaction period, the reactor was vented and the contents fractionally distilled through an 18" Vigreaux column, fraction 1 boiling at 46-51° C. at 55 mm Hg, weighed 88.4 grams while fraction 2 boiling at 74-78° C. at 6 mm Hg, weighed 2.1 grams and the distillation residue fraction 3 weighed 17.7 grams and was a thick black tar. Fractions 1 and 2 were analyzed by gas-liquid phase chromatography, which indicated that there was obtained 1.16 grams (6.7 mmoles) of 1,2-diacetoxy-3-butene and 0.43 grams (2.5 mmoles) of 1,4-diacetoxy-2-butene for a total yield of 9.2 mmoles of the diacetoxy butenes. This represents a yield of 4.5% based on the butadiene charged. This result shows that a much lower yield of diacetoxy butenes was obtained when the bismuth catalyst component is omitted from the reaction mixture. charged from the vapor phase The reactor was placed in an oil bath At the end of the reaction period the contents fractionally distilled through an 18" Vigreaux column, fraction 1 boiling at 46-51° C. at 55 mm Hg

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

Procedure: Another control run was carried out, employing the same reaction vessel as that utilized in Examples I and II above. In this run, the reactor was charged with 3.9 grams (50 mmoles) of lithium nitrate, 50 ml of acetic acid, 25 ml of acetic anhydride, and 11.0 grams (204 mmoles) of butadiene charged from the vapor phase. The reactor was placed in an oil bath and pressured to 30 psig with oxygen, and heated to 140° C. for 3 hours. Oxygen was added to the reactor intermittently in the same manner as in Example I. At the end of the reaction period, the reactor was vented and the contents fractionally distilled through an 18" Vigreaux column, fraction 1 boiling at 46-51° C. at 55 mm Hg, weighed 88.4 grams while fraction 2 boiling at 74-78° C. at 6 mm Hg, weighed 2.1 grams and the distillation residue fraction 3 weighed 17.7 grams and was a thick black tar. Fractions 1 and 2 were analyzed by gas-liquid phase chromatography, which indicated that there was obtained 1.16 grams (6.7 mmoles) of 1,2-diacetoxy-3-butene and 0.43 grams (2.5 mmoles) of 1,4-diacetoxy-2-butene for a total yield of 9.2 mmoles of the diacetoxy butenes. This represents a yield of 4.5% based on the butadiene charged. This result shows that a much lower yield of diacetoxy butenes was obtained when the bismuth catalyst component is omitted from the reaction mixture. charged from the vapor phase The reactor was placed in an oil bath At the end of the reaction period the contents fractionally distilled through an 18" Vigreaux column, fraction 1 boiling at 46-51° C. at 55 mm Hg

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

Procedure: A run was carried out according to the process of this invention by charging a 250 ml Fisher-Porter aerosol compatibility bottle equipped with a magnetic stirrer with 4.6 grams (21.5 mmoles) of 1,4-dibromo-2-butene, 3.9 grams (50 mmoles) of lithium nitrate, 4.7 grams (10 mmoles) of bismuth trioxide, 50 ml of acetic acid and 25 ml of acetic anhydride and 10.5 grams (194 mmoles) of butadiene charged in the vapor phase. The reaction vessel was pressured to 30 psig with oxygen, placed in an oil bath and heated to 140° C. About 1 hour was required for the reaction vessel to reach 140° C. reaction temperature. Subsequently the reaction was carried out for 5.8 hours during which oxygen was added to the reactor intermittently by pressuring the reactor to 120 psig at about 20 minute intervals. At the end of the reaction period, the reactor was vented, and a black solid material filtered from the reaction mixture. The filtrate was distilled through an 18" Vigreaux column to remove acetic acid. The distillation residue was mixed with water and ether, and the aqueous layer extracted several times with ether. The combined ether extracts were washed with water, a sodium carbonate solution, dried over magnesium sulfate, filtered, and the ether removed on a rotary evaporator. The residue remaining weighed 10.0 grams. This residue was analyzed by gas-liquid phase chromatography which indicated that there was obtained 3.14 grams (18.3 mmoles) of 1,2-diacetoxy-3-butene and 3.97 grams (23.1 mmoles) of 1,4-diacetoxy-2-butene for a combined yield of the diacetoxy butenes of 21% based on the butadiene charged. This result demonstrates the operability of the catalyst system of this invention for producing diacyloxy olefins from conjugated diolefin reactants. charged in the vapor phase placed in an oil bath to reach 140° C. reaction temperature was added to the reactor intermittently at about 20 minute At the end of the reaction period a black solid material filtered from the reaction mixture The filtrate was distilled through an 18" Vigreaux column to remove acetic acid The distillation residue was mixed with water and ether the aqueous layer extracted several times with ether The combined ether extracts were washed with water a sodium carbonate solution, dried over magnesium sulfate filtered the ether removed on a rotary evaporator

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

Procedure: Another control run was carried out, employing the same reaction vessel as that utilized in Examples I and II above. In this run, the reactor was charged with 3.9 grams (50 mmoles) of lithium nitrate, 50 ml of acetic acid, 25 ml of acetic anhydride, and 11.0 grams (204 mmoles) of butadiene charged from the vapor phase. The reactor was placed in an oil bath and pressured to 30 psig with oxygen, and heated to 140° C for 3 hours. Oxygen was added to the reactor intermittently in the same manner as in Example I. At the end of the reaction period, the reactor was vented and the contents fractionally distilled through an 18 inch Vigreaux column, fraction 1 boiling at 46° - 51° C at 55 mm Hg, weighed 88.4 grams while fraction 2 boiling at 74° - 78° C at 6 mm Hg, weighed 2.1 grams and the distillation residue fraction 3 weighed 17.7 grams and was a thick black tar. Fractions 1 and 2 were analyzed by gas-liquid phase chromatography, which indicated that there was obtained 1.16 grams (6.7 mmoles) of 1,2-diacetoxy-3-butene and 0.43 grams (2.5 mmoles) of 1,4-diacetoxy-2-butene for a total yield of 9.2 mmoles of the diacetoxy butenes. This represents a yield of 4.5% based on the butadiene charged. This result shows that a much lower yield of diacetoxy butenes was obtained when the bismuth catalyst component is omitted from the reaction mixture. charged from the vapor phase The reactor was placed in an oil bath At the end of the reaction period the contents fractionally distilled through an 18 inch Vigreaux column, fraction 1 boiling at 46° - 51° C at 55 mm Hg

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

Procedure: Another control run was carried out, employing the same reaction vessel as that utilized in Examples I and II above. In this run, the reactor was charged with 3.9 grams (50 mmoles) of lithium nitrate, 50 ml of acetic acid, 25 ml of acetic anhydride, and 11.0 grams (204 mmoles) of butadiene charged from the vapor phase. The reactor was placed in an oil bath and pressured to 30 psig with oxygen, and heated to 140° C for 3 hours. Oxygen was added to the reactor intermittently in the same manner as in Example I. At the end of the reaction period, the reactor was vented and the contents fractionally distilled through an 18 inch Vigreaux column, fraction 1 boiling at 46° - 51° C at 55 mm Hg, weighed 88.4 grams while fraction 2 boiling at 74° - 78° C at 6 mm Hg, weighed 2.1 grams and the distillation residue fraction 3 weighed 17.7 grams and was a thick black tar. Fractions 1 and 2 were analyzed by gas-liquid phase chromatography, which indicated that there was obtained 1.16 grams (6.7 mmoles) of 1,2-diacetoxy-3-butene and 0.43 grams (2.5 mmoles) of 1,4-diacetoxy-2-butene for a total yield of 9.2 mmoles of the diacetoxy butenes. This represents a yield of 4.5% based on the butadiene charged. This result shows that a much lower yield of diacetoxy butenes was obtained when the bismuth catalyst component is omitted from the reaction mixture. charged from the vapor phase The reactor was placed in an oil bath At the end of the reaction period the contents fractionally distilled through an 18 inch Vigreaux column, fraction 1 boiling at 46° - 51° C at 55 mm Hg

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

Procedure: A run was carried out according to the process of this invention by charging a 250 ml Fisher-Porter aerosol compatibility bottle equipped with a magnetic stirred with 4.6 grams (21.5 mmoles) of 1,4-dibromo-2-butene, 3.9 grams (50 mmoles) of lithium nitrate, 4.7 grams (10 mmoles) of bismuth trioxide, 50 ml of acetic acid and 25 ml of acetic anhydride and 10.5 grams (194 mmoles) of butadiene charged in the vapor phase. The reaction vessel was pressured to 30 psig with oxygen, placed in an oil bath and heated to 140° C. About 1 hour was required for the reaction vessel to reach 140° C reaction temperature. Subsequently the reaction was carried out for 5.8 hours during which oxygen was added to the reactor intermittently by pressuring the reactor to 120 psig at about 20 minute intervals. At the end of the reaction period, the reactor was vented, and a black solid material filtered from the reaction mixture. The filtrate was distilled through an 18 inch Vigreaux column to remove acetic acid. The distillation residue was mixed with water and ether, and the aqueous layer extracted several times with ether. The combined ether extracts were washed with water, a sodium carbonate solution, dried over magnesium sulfate, filtered, and the ether removed on a rotary evaporator. The residue remaining weighed 10.0 grams. This residue was analyzed by gas-liquid phase chromatography which indicated that there was obtained 3.14 grams (18.3 mmoles) of 1,2-diacetoxy-3-butene and 3.97 grams (23.1 mmoles) of 1,4-diacetoxy-2-butene for a combined yield of the diacetoxy butenes of 21% based on the butadiene charged. This result demonstrates the operability of the catalyst system of this invention for producing diacyloxy olefins from conjugated diolefin reactants. equipped with charged in the vapor phase placed in an oil bath to reach 140° C reaction temperature was added to the reactor intermittently at about 20 minute At the end of the reaction period a black solid material filtered from the reaction mixture The filtrate was distilled through an 18 inch Vigreaux column to remove acetic acid The distillation residue was mixed with water and ether the aqueous layer extracted several times with ether The combined ether extracts were washed with water a sodium carbonate solution, dried over magnesium sulfate filtered the ether removed on a rotary evaporator