methyl tetradecanoate

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

Procedure: 98 mg(3.3 mmol)Sodium hydride(80% in mineral oil)was added to a solution of 764 mg (2.96 mmol) methyl(R)-3-hydroxytetradecanoate in 20.0 mL tetrahydrofuran. After 25 minutes, a solution of 732 mg (3.03 mmol) 2-bromooctanoyl chloride in 10.0 mL tetrahydrofuran was added dropwise via syringe to the cloudy offwhite mixture. After 10 minutes at 0° C., the reaction flask was removed from the cold bath for 24 hours. The mixture was poured into 100 mL 10% NaHCO3 and extraction with ether (3×50 mL) was performed. Drying over MgSO4 and removal of the solvent by rotary evaporation gave yellow oil. Purification by flash chromatography (3×24 cm column, 50% CH2Cl2 /hexane) gave 407 mg (30% yield based on methyl (R)-3-hydroxytetradecanoate)(R)-3-[2-bromo-1-oxooctyl)oxy]tetradecanoic acid methyl ester. After 10 minutes at 0° C. the reaction flask was removed from the cold bath for 24 hours The mixture was poured into 100 mL 10% NaHCO3 and extraction with ether (3×50 mL) Drying over MgSO4 and removal of the solvent by rotary evaporation gave yellow oil Purification by flash chromatography (3×24 cm column, 50% CH2Cl2 /hexane)

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

Procedure: Mixture of methyl esters, namely methyl myristate (0.5%), methyl palmitate (4.9%), methyl oleate (83.6%) and methyl linoleate (11.0%) exhibit low pour point of −21° C. This methyl esters mixture was obtained via acid-catalysed direct esterification of technical grade of oleic acid (with purity ≈80%) with methanol. pour point of −21° C

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

Procedure: Mixture of methyl esters, namely methyl myristate (0.5%), methyl palmitate (4.9%), methyl oleate (83.6%) and methyl linoleate (11.0%) exhibit low pour point of −21° C. This methyl esters mixture was obtained via acid-catalysed direct esterification of technical grade of oleic acid (with purity ≈80%) with methanol. pour point of −21° C

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

Procedure: 98 mg(3.3 mmol)Sodium hydride(80% in mineral oil)was added to a solution of 764 mg (2.96 mmol) methyl(R)-3-hydroxytetradecanoate in 20.0 mL tetrahydrofuran. After 25 minutes, a solution of 732 mg (3.03 mmol) 2-bromooctanoyl chloride in 10.0 mL tetrahydrofuran was added dropwise via syringe to the cloudy offwhite mixture. After 10 minutes at 0° C., the reaction flask was removed from the cold bath for 24 hours. The mixture was poured into 100 mL 10% NaHCO3 and extraction with ether (3×50 mL) was performed. Drying over MgSO4 and removal of the solvent by rotary evaporation gave yellow oil. Purification by flash chromatography (3×24 cm column, 50% CH2Cl2 /hexane) gave 407 mg (30% yield based on methyl (R)-3-hydroxytetradecanoate)(R)-3-[2-bromo-1-oxooctyl)oxy]tetradecanoic acid methyl ester. After 10 minutes at 0° C. the reaction flask was removed from the cold bath for 24 hours The mixture was poured into 100 mL 10% NaHCO3 and extraction with ether (3×50 mL) Drying over MgSO4 and removal of the solvent by rotary evaporation gave yellow oil Purification by flash chromatography (3×24 cm column, 50% CH2Cl2 /hexane)

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

Procedure: 98 mg(3.3 mmol)Sodium hydride(80% in mineral oil)was added to a solution of 764 mg (2.96 mmol) methyl(R)-3-hydroxytetradecanoate in 20.0 mL tetrahydrofuran. After 25 minutes, a solution of 732 mg (3.03 mmol) 2-bromooctanoyl chloride in 10.0 mL tetrahydrofuran was added dropwise via syringe to the cloudy offwhite mixture. After 10 minutes at 0° C., the reaction flask was removed from the cold bath for 24 hours. The mixture was poured into 100 mL 10% NaHCO3 and extraction with ether (3×50 mL) was performed. Drying over MgSO4 and removal of the solvent by rotary evaporation gave yellow oil. Purification by flash chromatography (3×24 cm column, 50% CH2Cl2 /hexane) gave 407 mg (30% yield based on methyl (R)-3-hydroxytetradecanoate)(R)-3-[2-bromo-1-oxooctyl)oxy]tetradecanoic acid methyl ester. After 10 minutes at 0° C. the reaction flask was removed from the cold bath for 24 hours The mixture was poured into 100 mL 10% NaHCO3 and extraction with ether (3×50 mL) Drying over MgSO4 and removal of the solvent by rotary evaporation gave yellow oil Purification by flash chromatography (3×24 cm column, 50% CH2Cl2 /hexane)

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

Procedure: 98 mg (3.3 mmol) Sodium hydride (80% in mineral oil) was added to a solution of 764 mg (2.96 mmol) methyl(R)-3-hydroxytetradecanoate in 20.0 mL tetrahydrofuran. After 25 minutes, a solution of 732 mg (3.03 mmol) 2-bromooctanoyl chloride in 10.0 mL tetrahydrofuran was added dropwise via syringe to the cloudy off-white mixture. After 10 minutes at 0° C., the reaction flask was removed from the cold bath for 24 hours. The mixture was poured into 100 mL 10% NaHCO3 and extraction with ether (3×50 mL) was performed. Drying over MgSO4 and removal of the solvent by rotary evaporation gave yellow oil. Purification by flash chromatography (3×24 cm column, 50% CH2Cl2 /hexane) gave 407 mg (30% yield based on methyl (R)-3-hydroxytetradecanoate) (R)-3-[2-bromo-1-oxooctyl)oxy]tetradecanoic acid methyl ester. After 10 minutes at 0° C. the reaction flask was removed from the cold bath for 24 hours The mixture was poured into 100 mL 10% NaHCO3 and extraction with ether (3×50 mL) Drying over MgSO4 and removal of the solvent by rotary evaporation gave yellow oil Purification by flash chromatography (3×24 cm column, 50% CH2Cl2 /hexane)

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

Procedure: 98 mg (3.3 mmol) Sodium hydride (80% in mineral oil) was added to a solution of 764 mg (2.96 mmol) methyl(R)-3-hydroxytetradecanoate in 20.0 mL tetrahydrofuran. After 25 minutes, a solution of 732 mg (3.03 mmol) 2-bromooctanoyl chloride in 10.0 mL tetrahydrofuran was added dropwise via syringe to the cloudy off-white mixture. After 10 minutes at 0° C., the reaction flask was removed from the cold bath for 24 hours. The mixture was poured into 100 mL 10% NaHCO3 and extraction with ether (3×50 mL) was performed. Drying over MgSO4 and removal of the solvent by rotary evaporation gave yellow oil. Purification by flash chromatography (3×24 cm column, 50% CH2Cl2 /hexane) gave 407 mg (30% yield based on methyl (R)-3-hydroxytetradecanoate) (R)-3-[2-bromo-1-oxooctyl)oxy]tetradecanoic acid methyl ester. After 10 minutes at 0° C. the reaction flask was removed from the cold bath for 24 hours The mixture was poured into 100 mL 10% NaHCO3 and extraction with ether (3×50 mL) Drying over MgSO4 and removal of the solvent by rotary evaporation gave yellow oil Purification by flash chromatography (3×24 cm column, 50% CH2Cl2 /hexane)

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

Procedure: We compared the production of ω-hydroxy myristic acid and α,ω-tetradecanoic acid by a Candida tropicalis strain lacking CYP52A13, CYP52A14, CYP52A17, CYP52A18, FAO1, FAO1B, FAO2A, FAO2B, CYP52A12, CYP52A12B, ADH-A4, ADH-A4B, ADH-B4, ADH-B4B, ADH-A10 and ADH-B11 and with CYP52A17 added back under control of the isocitrate lyase promoter (DP428).

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

Procedure: Sodium metal (1.6 g, 0.068 mol) was added to 4 Å molecular sieves (12 g) and ethanol (200 mL) under nitrogen. The mixture was stirred for 15 minutes, then hydroxyguanidine sulfate (9.32 g, 0.035 mol) added and the mixture stirred for 30 minutes. Methyltetradecanoate (1.43 g, 0.006 mol) was then added and the mixture refluxed for 1.5 hours, allowed to cool, filtered, and concentrated. The concentrate was partitioned between CH2Cl2 and water. The organic layer was washed with water and brine, dried with Na2SO4, filtered, concentrated, and triturated with hexane. The resulting solid was filtered, washed with hexane, and dried in vacuo to yield 0.23 g, m.p. 90°-91° C. the mixture stirred for 30 minutes the mixture refluxed for 1.5 hours to cool filtered concentrated The concentrate was partitioned between CH2Cl2 and water The organic layer was washed with water and brine dried with Na2SO4 filtered concentrated triturated with hexane The resulting solid was filtered washed with hexane dried in vacuo to yield 0.23 g, m.p. 90°-91° C.

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

Procedure: Hydrazine (1.9 mL, 0.058 mol) was added to a solution of methyl tetradecanoate (13.96 g, 0.058 mol) in methanol (300 mL) and the solution refluxed for 3 days. The mixture was allowed to cool and filtered to yield 6.17 g of a crystalline solid, m.p. 107°-111° C. the solution refluxed for 3 days to cool filtered

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

Procedure: We compared the production of ω-hydroxy myristic acid and α,ω-tetradecanoic acid by a Candida tropicalis strain lacking CYP52A13, CYP52A14, CYP52A17, CYP52A18, FAO1, FAO1B, FAO2A, FAO2B, CYP52A12, CYP52A12B, ADH-A4, ADH-A4B, ADH-B4, ADH-B4B, ADH-A10 and ADH-B11 and with CYP52A17 added back under control of the isocitrate lyase promoter (DP428).

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Oxetane 2 (5 g, 41 mmol) was dried in vacuo at 100° C. for 1 h and then dissolved in THF (120 mL). To the solution at room temperature was added freshly distilled triethylamine (10 mL, 72 mmol) and N,N-(dimethylamino)pyridine (400 mg, 3.3 mmol) and the reaction was cooled to 0° C. Myristoyl chloride (8.9 mL, 33 mmol) was added via cannula to the reaction mixture, and the resulting yellowish solution was stirred at 0° C. for 4 h and then warmed to room temperature and stirred an additional 4 h. The reaction was quenched by addition of diethyl ether and washing with sat'd aq. NaHCO3, followed by washing with brine. The organic layer was separated and dried (Na2SO4). The solvents were removed by rotary evaporation, and the crude product was purified by silica gel column chromatography to yield 8 g (74%) of the ester 3 as white powder. warmed to room temperature stirred an additional 4 h The reaction was quenched by addition of diethyl ether washing with sat'd aq. NaHCO3 by washing with brine The organic layer was separated dried (Na2SO4) The solvents were removed by rotary evaporation the crude product was purified by silica gel column chromatography