1,2-Hexadecanediol

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Approximately 360 g of the 1,2-mixed pentadecanedioloctadecanediol (obtained from Viking Chemical Co. as Vikol 158 containing about 28% 1,2-pentadecanediol, about 28% 1,2-hexadecanediol, about 28% 1,2-heptadecanediol and about 16% 1,2-octadecanediol) were charged to a glass reactor equipped with heater, agitator, Dean-Stark tube with condenser and provision for blanketing the vapor space with nitrogen. The contents were heated to 70° C. to liquify and 55 g of dimethyl hydrogen phosphite were slowly added. The reaction mixture was heated to 110° C. and held for 2 hours, held at 120° C. for 1 hour, and held at 130° C. for 1 hour. During this reaction period, methanol distilled over and condensed into the trap. The crude product was vacuum stripped at 150° C. to remove volatile materials. 379 g of finished additive were produced. The product was an amber fluid which became waxy on cooling. equipped with heater, agitator, Dean-Stark tube with condenser The reaction mixture was heated to 110° C. held at 120° C. for 1 hour held at 130° C. for 1 hour distilled over and condensed into the trap stripped at 150° C. to remove volatile materials 379 g of finished additive were produced on cooling

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

Procedure: The bioconversion of 1,2-hexadecanediol was tested following the procedures set forth in Example 24. This substrate was tested to demonstrate the ability to form a (ω,ω-1)-dihydroxy fatty acid. Recovery was 0.138 g from 0.253 g starting material (54.5% recovery). NMR shows the 1,2-diol to be unchanged, as expected from olefin studies. But, interestingly, CH3 oxidation to the 15,16-dihydroxyhexadecanoic acid was lower than seen with octadecene, because the starting material was solid. Conversion was only about 30%. Some fatty unsaturation and minor polypropylene glycol were also seen. Since the NMR results were fairly convincing, no GC/MS analysis was performed. Since the NMR results

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Approximately 360 g of the 1,2-mixed pentadecanedioloctadecanediol (obtained from Viking Chemical Co. as Vikol 158 containing about 28% 1,2-pentadecanediol, about 28% 1,2-hexadecanediol, about 28% 1,2-heptadecanediol and about 16% 1,2-octadecanediol) were charged to a glass reactor equipped with heater, agitator, Dean-Stark tube with condenser and provision for blanketing the vapor space with nitrogen. The contents were heated to 70° C. to liquify and 55 g of dimethyl hydrogen phosphite were slowly added. The reaction mixture was heated to 110° C. and held for 2 hours, held at 120° C. for 1 hour, and held at 130° C. for 1 hour. During this reaction period, methanol distilled over and condensed into the trap. The crude product was vacuum stripped at 150° C. to remove volatile materials. 379 g of finished additive were produced. The product was an amber fluid which became waxy on cooling. equipped with heater, agitator, Dean-Stark tube with condenser The reaction mixture was heated to 110° C. held at 120° C. for 1 hour held at 130° C. for 1 hour distilled over and condensed into the trap stripped at 150° C. to remove volatile materials 379 g of finished additive were produced on cooling

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Approximately 360 g of the 1,2-mixed pentadecanedioloctadecanediol (obtained from Viking Chemical Co. as Vikol 158 containing about 28% 1,2-pentadecanediol, about 28% 1,2-hexadecanediol, about 28% 1,2-heptadecanediol and about 16% 1,2-octadecanediol) were charged to a glass reactor equipped with heater, agitator, Dean-Stark tube with condenser and provision for blanketing the vapor space with nitrogen. The contents were heated to 70° C. to liquify and 55 g of dimethyl hydrogen phosphite were slowly added. The reaction mixture was heated to 110° C. and held for 2 hours, held at 120° C. for 1 hour, and held at 130° C. for 1 hour. During this reaction period, methanol distilled over and condensed into the trap. The crude product was vacuum stripped at 150° C. to remove volatile materials. 379 g of finished additive were produced. The product was an amber fluid which became waxy on cooling. equipped with heater, agitator, Dean-Stark tube with condenser The reaction mixture was heated to 110° C. held at 120° C. for 1 hour held at 130° C. for 1 hour distilled over and condensed into the trap stripped at 150° C. to remove volatile materials 379 g of finished additive were produced on cooling

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

Procedure: Approximately 92 g of glycerol monooleate (commercially available as 60/40 mixture of glycerol monoleate/glycerol diooleate), 52 g of 1,2-hexadecanediol and 100 g of toluene were charged to a reactor equipped as described in Example 1. The contents were heated to liquify and 11 g of boric acid were added. The mixture was further heated up to 150° C. over a period of 6 hours until water evolution stopped. Approximately 9 ml. of water collected. The solvent was removed by vacuum distillation at 150° C. and the product was filtered at about 100° C. through diatomaceous earth. The product became a waxy solid after cooling. were charged to a reactor equipped The contents were heated of water collected The solvent was removed by vacuum distillation at 150° C. the product was filtered at about 100° C. through diatomaceous earth after cooling

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Approximately 54 g of oleyl alcohol, 51 g of 1,2-hexadecanediol and 100 g of toluene were reacted in a 1 liter reaction equipped as described in Example 1. The contents were heated to about 65° C. and 13 g of boric acid were added. The mixture was further heated up to 155° C. over a period of 4 hours until water evolution stopped. Approximately 11 ml. of water were collected by azeotropic distillation. The solvent was removed by vacuum distillation at 155° C. and the product was filtered at 90°-100° C. through diatomaceous earth. equipped of water were collected by azeotropic distillation The solvent was removed by vacuum distillation at 155° C. the product was filtered at 90°-100° C. through diatomaceous earth

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

Procedure: Approximately 86 g of 1,2-hexadecanediol and approximatel 200 g toluene solvent was charged to a 1 liter reactor equipped with agitator, heater and Dean-Stark tube with condenser. The contents wee heated up to ~80°-90° C. to dissolve the diol and approximately 11 g boric acid was added. The mixture was heated up to 155° C. until water evolution stopped over a period of ~4 hours. Approximately 9 ml water was removed by azeotropic distillation. The solvent was removed by vacuum distillation and the product was filtered at 100° C. through diatomaceous earth. The product became waxy after cooling. equipped with agitator, heater and Dean-Stark tube with condenser The contents wee heated up to ~80°-90° C. was added stopped over a period of ~4 hours Approximately 9 ml water was removed by azeotropic distillation The solvent was removed by vacuum distillation the product was filtered at 100° C. through diatomaceous earth after cooling

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

Procedure: Approximately 86 g of 1,2-hexadecanediol and approximatel 200 g toluene solvent was charged to a 1 liter reactor equipped with agitator, heater and Dean-Stark tube with condenser. The contents wee heated up to ~80°-90° C. to dissolve the diol and approximately 11 g boric acid was added. The mixture was heated up to 155° C. until water evolution stopped over a period of ~4 hours. Approximately 9 ml water was removed by azeotropic distillation. The solvent was removed by vacuum distillation and the product was filtered at 100° C. through diatomaceous earth. The product became waxy after cooling. equipped with agitator, heater and Dean-Stark tube with condenser The contents wee heated up to ~80°-90° C. was added stopped over a period of ~4 hours Approximately 9 ml water was removed by azeotropic distillation The solvent was removed by vacuum distillation the product was filtered at 100° C. through diatomaceous earth after cooling

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

Procedure: A solution of 14.6 g (58.0 mmol) of 2,6-diphenyl-4-piperidone and 12.2 g (64 mmol) of p-toluenesulfonic acid monohydrate in 500 mL of toluene is refluxed and the azeotroping water is collected in a Dean Stark trap. When 1 mL of water is collected, 15.0 g (58.0 mmol) of 1,2-hexadecanediol (Aldrich) is added and the reaction is refluxed until another 1 mL of water is collected. The reaction mixture is cooled to room temperature and made basic with 50% aqueous sodium hydroxide solution. The organic layer is separated and the aqueous phase is extracted with toluene (2×100 mL). The combined organic phases are dried over anhydrous magnesium sulfate and the solvent is removed under reduced pressure. 11.0 g (38% yield) of the title compound is isolated after purification by liquid chromatography (LC) (silica gel, ethyl acetate/hexane) followed by recrystallization from ethanol: mp 63°-70° C. the azeotroping water is collected in a Dean Stark trap When 1 mL of water is collected is collected The organic layer is separated the aqueous phase is extracted with toluene (2×100 mL) The combined organic phases are dried over anhydrous magnesium sulfate the solvent is removed under reduced pressure

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

Procedure: A solution of 14.6 g (58.0 mmol) of 2,6-diphenyl-4-piperidone and 12.2 g (64 mmol) of p-toluenesulfonic acid monohydrate in 500 mL of toluene is refluxed and the azeotroping water is collected in a Dean Stark trap. When 1 mL of water is collected, 15.0 g (58.0 mmol) of 1,2-hexadecanediol (Aldrich) is added and the reaction is refluxed until another 1 mL of water is collected. The reaction mixture is cooled to room temperature and made basic with 50% aqueous sodium hydroxide solution. The organic layer is separated and the aqueous phase is extracted with toluene (2×100 mL). The combined organic phases are dried over anhydrous magnesium sulfate and the solvent is removed under reduced pressure. 11.0 g (38% yield) of the title compound is isolated after purification by liquid chromatography (LC) (silica gel, ethyl acetate/hexane) followed by recrystallization from ethanol: mp 63°-70° C. the azeotroping water is collected in a Dean Stark trap When 1 mL of water is collected is collected The organic layer is separated the aqueous phase is extracted with toluene (2×100 mL) The combined organic phases are dried over anhydrous magnesium sulfate the solvent is removed under reduced pressure

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

Procedure: Approximately 86 g of 1,2-hexadecanediol and approximatel 200 g toluene solvent was charged to a 1 liter reactor equipped with agitator, heater and Dean- Stark tube with condenser. The contents were heated up to 80°-90° C. to dissolve the diol and approximately 11 g boric acid was added. The mixture was heated up to 155° C. until water evolution stopped over a period of 4 hours. Approximately 9 ml water was removed by azeotropic distillation. The solvent was removed by vacuum distillation and the product was filtered at 100° C. through diatomaceous earth. The product became waxy after cooling. equipped with agitator, heater and Dean- Stark tube with condenser The contents were heated up to 80°-90° C. was added Approximately 9 ml water was removed by azeotropic distillation The solvent was removed by vacuum distillation the product was filtered at 100° C. through diatomaceous earth after cooling

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

Procedure: Approximately 86 g of 1,2-hexadecanediol and approximatel 200 g toluene solvent was charged to a 1 liter reactor equipped with agitator, heater and Dean- Stark tube with condenser. The contents were heated up to 80°-90° C. to dissolve the diol and approximately 11 g boric acid was added. The mixture was heated up to 155° C. until water evolution stopped over a period of 4 hours. Approximately 9 ml water was removed by azeotropic distillation. The solvent was removed by vacuum distillation and the product was filtered at 100° C. through diatomaceous earth. The product became waxy after cooling. equipped with agitator, heater and Dean- Stark tube with condenser The contents were heated up to 80°-90° C. was added Approximately 9 ml water was removed by azeotropic distillation The solvent was removed by vacuum distillation the product was filtered at 100° C. through diatomaceous earth after cooling