methyl dodec-9-enoate

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

Procedure: Methyl 9-dodecenoate (1273 g, 6.00 mol), water (540 mL), and isopropanol (300 mL) were added to a 5 L, 4-neck round-bottom flask at room-temperature. The flask was fitted with an over-head stirrer, condenser, a thermocouple, and an addition flask. Nitrogen was passed through the headspace for thirty-minutes while stirring. Potassium hydroxide (10 M, 660 mL, 6.60 mol) was added drop-wise over thirty-minutes. After stirring for about 45 minutes, an exotherm was observed and the mixture became homogenous. Within the next hour, stirring became impeded by formation of a gel. To re-enable stirring, an additional 300 mL of isopropanol was kneaded into the mixture with a metal spatula. The reaction was monitored by thin layer chromatography (10% EtOAc in hexanes eluent, iodine stain); reaction aliquots were quenched with aqueous hydrochloric acid, washed with water, then taken up in iPrOH. When all starting material had been consumed, the reaction was placed in an ice bath and acidified with 37% aqueous HCl (600 mL) while maintaining a temperature below 40° C. The reaction mixture was transferred into a large separatory funnel and washed with brine (3×250 mL), dried with magnesium sulfate, filtered, and dried in vacuo. The reaction was purified by vacuum distillation to give 9-dodecenoic acid (1054 g, 5.3 mol, 89% yield). The flask was fitted with an over-head stirrer, condenser Nitrogen was passed through the headspace for thirty-minutes After stirring for about 45 minutes Within the next hour, stirring To re-enable stirring reaction aliquots were quenched with aqueous hydrochloric acid washed with water When all starting material had been consumed the reaction was placed in an ice bath while maintaining a temperature below 40° C The reaction mixture was transferred into a large separatory funnel washed with brine (3×250 mL) dried with magnesium sulfate filtered dried in vacuo The reaction was purified by vacuum distillation

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A dibasic ester composition is produced in accordance with the exemplary procedure below, including a cross-metathesis reaction between methyl 9-decenoate (9-decenoic acid methyl ester, 9-DAME) and methyl 9-dodecenoate (9-dodecenoic acid methyl ester, 9-DDAME). A 1.0:1.0 mole ratio mixture of 9-DAME and 9-DDAME (332 g) is charged to a 1 L round bottom flask and heated to 60° C. Pressure is adjusted to 100 mg Hg with ChemGlass diaphragm vacuum pump model CG-4812-30/and J-Kem Scientific Digital Vacuum Regulator Model 200 and stirring is initiated with a magnetic stir bar. After the system stabilizes at desired conditions, 80 ppm of C-827 (as toluene solution) is added (t=0 min). At approximately 15-20 min, the reaction starts bubbling vigorously and the pressure rises to approximately 500 mm Hg. Pressure restabilizes at 100 mm Hg after approximately 5-10 more minutes. At 180 min, an additional 40 ppm of the catalyst C-827 (as toluene solution) is added. Subsequently, the catalyst is deactivated with 25 equivalents tris hydroxymethyl phosphine (THMP) to C-827 at 80° C. for 120 min, THMP. The catalyst is then removed by water extraction (5:1 oil to water). The composition is dried with MgSO4. Then, light FAME stripping is conducted at 1 mm Hg and approximately 100° C. The products from this reaction include a large fraction of 18:1 dibasic ester. is charged to a 1 L round bottom flask is initiated with a magnetic stir bar is added (t=0 min) the reaction starts bubbling vigorously At 180 min an additional 40 ppm of the catalyst C-827 (as toluene solution) is added The catalyst is then removed by water extraction (5:1 oil to water) The composition is dried with MgSO4 is conducted at 1 mm Hg and approximately 100° C

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

Procedure: The 9-dodecenoic acid methyl ester is then hydrolyzed under basic conditions (reflux with an excess of dilute aqueous NaOH), followed by removal of methanol. The resulting aqueous solution is then treated with an excess of dilute HCl, and the solution is distilled to provide 9-dodecenoic acid. Estolides are then prepared according to the methods set forth in Examples 1 and 2, wherein the oleic acid is replaced with 9-dodecenoic acid. followed by removal of methanol The resulting aqueous solution is then treated with an excess of dilute HCl the solution is distilled

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl oleate (20 mol) and a second-generation Grubbs' catalyst (e.g., C827, 25 ppm) are added to a Parr Reactor and degassed with argon for 1 hr. 1-Butene is added while heating to 60° C. while keeping the pressure of the reaction between about 25 to about 60 psi. The 1-butene is added using a one-way check valve to prevent backflow into the 1-butene cylinder. After 4 hrs, the pressure is released and vented into the fume hood. After allowing the reactor to cool to room temperature, a 50 ml 1M tris-hydroxymethylphosphine (THMP) solution in isopropanol (IPA) (50 mol equiv.) is added, and the reactor is degassed with argon and heated to 60° C. for 18 hrs. The reactor is then again allowed to cool to room temperature. The crude reaction product is then washed with water and brine. The washed reaction product is them dried over sodium sulfate, filtered, and distilled to provide 1-decene, 3-dodecene, 9-decenoic acid methyl ester, and 9-dodecenoic acid methyl ester. degassed with argon for 1 hr 1-Butene is added the pressure of the reaction between about 25 to about 60 psi to cool to room temperature the reactor is degassed with argon heated to 60° C. for 18 hrs to cool to room temperature The crude reaction product is then washed with water and brine The washed reaction product dried over sodium sulfate filtered distilled

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

Procedure: To a dry 2 L 3-neck round bottom flask fitted with a nitrogen inlet and outlet, thermocouple, condenser, mechanical stirrer and pressure-equalizing dropping funnel was added lithium aluminum hydride (30.10 g, 0.754 mol, 95% technical grade solid) in one portion, under a positive pressure of nitrogen. The metal hydride was suspended in anhydrous tetrahydrofuran (500 mL) and the mixture cooled on an ice bath. Methyl 9-dodecenoate (200 g, 0.942 mol) was added dropwise via addition funnel to the stirred lithium aluminum hydride suspension over 1 h at such a rate as to maintain the internal temperature below 50° C. When the reaction exotherm subsided, the external cooling bath was removed and the resulting viscous mixture was stirred for a further 8 h at ambient temperature. Complete consumption of starting material was confirmed by thin layer chromatography and by FTIR. The reaction was quenched by the careful addition of the reactor contents to a 4 L Erlenmeyer flask containing chilled concentrated aqueous sodium chloride (300 mL). The reactor was rinsed with ethyl acetate (100 mL) then 10% (v/v) aqueous sulfuric acid (100 mL); both rinse aliquots were combined with the reaction neutralization mixture. An additional aliquot of 10% (v/v) aqueous sulfuric acid was added to neutralize the aqueous phase then the biphasic neutralization mixture was transferred to a separatory funnel. The aqueous phase was partitioned and washed with ethyl acetate (100 mL×2). The combined organic phases were successively washed with concentrated aqueous sodium bicarbonate (100 mL), brine (100 mL), dried (MgSO4) then filtered. The organic phase was concentrated in vacuo, giving 9-dodecen-1-ol (165 g, 95%) as clear, colorless oil. To a dry 2 L 3-neck round bottom flask fitted with a nitrogen inlet and outlet thermocouple, condenser, mechanical stirrer and pressure-equalizing dropping the mixture cooled on an ice bath to maintain the internal temperature below 50° C the external cooling bath was removed consumption of starting material The reaction was quenched by the careful addition of the reactor contents to a 4 L Erlenmeyer flask containing chilled concentrated aqueous sodium chloride (300 mL) The reactor was rinsed with ethyl acetate (100 mL) An additional aliquot of 10% (v/v) aqueous sulfuric acid was added the biphasic neutralization mixture was transferred to a separatory funnel The aqueous phase was partitioned washed with ethyl acetate (100 mL×2) The combined organic phases were successively washed with concentrated aqueous sodium bicarbonate (100 mL), brine (100 mL) dried (MgSO4) then filtered The organic phase was concentrated in vacuo

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

Procedure: The 9-dodecenoic acid methyl ester is then hydrolyzed under basic conditions (reflux with an excess of dilute aqueous NaOH), followed by removal of methanol. The resulting aqueous solution is then treated with an excess of dilute HCl, and the solution is distilled to provide 9-dodecenoic acid. Estolides are then prepared according to the methods set forth in Examples 1 and 2, wherein the oleic acid is replaced with 9-dodecenoic acid. followed by removal of methanol The resulting aqueous solution is then treated with an excess of dilute HCl the solution is distilled

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl oleate (20 mol) and a second-generation Grubbs' catalyst (e.g., C827, 25 ppm) are added to a Parr Reactor and degassed with argon for 1 hr. 1-Butene is added while heating to 60° C. while keeping the pressure of the reaction between about 25 to about 60 psi. The 1-butene is added using a one-way check valve to prevent backflow into the 1-butene cylinder. After 4 hrs, the pressure is released and vented into the fume hood. After allowing the reactor to cool to room temperature, a 50 ml 1M tris-hydroxymethylphosphine (THMP) solution in isopropanol (IPA) (50 mol equiv.) is added, and the reactor is degassed with argon and heated to 60° C. for 18 hrs. The reactor is then again allowed to cool to room temperature. The crude reaction product is then washed with water and brine. The washed reaction product is them dried over sodium sulfate, filtered, and distilled to provide 1-decene, 3-dodecene, 9-decenoic acid methyl ester, and 9-dodecenoic acid methyl ester. degassed with argon for 1 hr 1-Butene is added the pressure of the reaction between about 25 to about 60 psi to cool to room temperature the reactor is degassed with argon heated to 60° C. for 18 hrs to cool to room temperature The crude reaction product is then washed with water and brine The washed reaction product dried over sodium sulfate filtered distilled

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

Procedure: The 9-dodecenoic acid methyl ester is then hydrolyzed under basic conditions (reflux with an excess of dilute aqueous NaOH), followed by removal of methanol. The resulting aqueous solution is then treated with an excess of dilute HCl, and the solution is distilled to provide 9-dodecenoic acid. Estolides are then prepared according to the methods set forth in Examples 1 and 2, wherein the oleic acid is replaced with 9-dodecenoic acid. followed by removal of methanol The resulting aqueous solution is then treated with an excess of dilute HCl the solution is distilled

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl oleate (20 mol) and a second-generation Grubbs' catalyst (e.g., C827, 25 ppm) are added to a Parr Reactor and degassed with argon for 1 hr. 1-Butene is added while heating to 60° C. while keeping the pressure of the reaction between about 25 to about 60 psi. The 1-butene is added using a one-way check valve to prevent backflow into the 1-butene cylinder. After 4 hrs, the pressure is released and vented into the fume hood. After allowing the reactor to cool to room temperature, a 50 ml 1M tris-hydroxymethylphosphine (THMP) solution in isopropanol (IPA) (50 mol equiv.) is added, and the reactor is degassed with argon and heated to 60° C. for 18 hrs. The reactor is then again allowed to cool to room temperature. The crude reaction product is then washed with water and brine. The washed reaction product is them dried over sodium sulfate, filtered, and distilled to provide 1-decene, 3-dodecene, 9-decenoic acid methyl ester, and 9-dodecenoic acid methyl ester. degassed with argon for 1 hr 1-Butene is added the pressure of the reaction between about 25 to about 60 psi to cool to room temperature the reactor is degassed with argon heated to 60° C. for 18 hrs to cool to room temperature The crude reaction product is then washed with water and brine The washed reaction product dried over sodium sulfate filtered distilled