methyl hexanoate

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 100 g. of dimethyl methylphosphonate in 670 ml. of anhydrous tetrahydrofuran is cooled to -78°C. under an argon atmosphere. To the cold solution are added dropwise under stirring and under argon atmosphere, 495 ml. of a 0.1M solution of n-butyllithium in tetrahydrofuran, maintaining the temperature at -70°C. When the addition is complete the reaction mixture is maintained under the same conditions for 10 additional minutes, a solution of 58 ml. of methyl caproate dissolved in 187 ml. of tetrahydrofuran is then carefully added, maintaining the temperature at -78°C. The reaction mixture is stirred at -78°C. for 2 hours followed by stirring for 4 hours at room temperature. The excess base is neutralized with acetic acid and the solvent is evaporated under high vacuo. The residue is dissolved in ether-water (1:1, 950 ml. each), the ethereal phase is separated, washed with water and dried over magnesium sulfate. The ether is evaporated and the residue is purified by vacuum distillation, thus obtaining the pure dimethyl 2-oxoheptylphosphonate. To the cold solution are added dropwise When the addition is maintained under the same conditions for 10 additional minutes The reaction mixture is stirred at -78°C. for 2 hours by stirring for 4 hours at room temperature the solvent is evaporated under high vacuo The residue is dissolved in ether-water (1:1, 950 ml each), the ethereal phase is separated washed with water dried over magnesium sulfate The ether is evaporated the residue is purified by vacuum distillation

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

Procedure: Under nitroqen, a solution of 262 g (8 2 mol) of anhydrous hydrazine in 1300 mL of methanol was cooled to 0° C. and treated with 885 g (6.8 mol) of methyl caproate. The reaction was allowed to warm to ambient temperature and stir overnight prior to stirring at reflux for 7 h. The reaction was concentrated in vacuo; recrystallization from toluene gave 707 g (80%) of caproic acid hydrazide as a colorless solid: mp 72.5°-73.9° C.; NMR (CDCl3) δ 0.82 (t, J=7 Hz, 3H), 1.15-1.33 (m, 4H), 1.51-1.64 (m, 2H), 2.10 (t, J=7 Hz, 2H), 3.91 (br s, 2H), 7.56 (br s, 1H). A 5.0 g (39 mmol) sample of the hydrazide was dissolved in 40 mL of methanol and treated with 11.2 g (78 mmol) of ethyl iminocaproate [P. Reynaud and R. C. Moreau, Bull. Soc., Chim. France, 2997 (1964)-which. was only about 50% pure by NMR] under nitrogen. The reaction was stirred at reflux for 2 days and concentrated in vacuo. Purification by silica gel chromatography (Waters Prep-500A) using ethyl acetate/hexane (48:52) gave 7.56 g (92%) of 3,5-dipentyl-1H-1,2,4-triazole as a colorless solid: mp 66°-68° C.; NMR (CDCl3) δ 0.88 (t, J=7 Hz, 6H), 1.24-1.41 (m, 8H), 1.66- 1.81 (m, 4H), 2.72 (t, J=7 Hz, 4H); MS (FAB) m/e (rel intensity) 210 (100), 166 (14); HRMS. Calcd for M+H: 210.1970. Found: 210.1964. to stirring at reflux for 7 h The reaction was concentrated in vacuo recrystallization from toluene

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

Procedure: Under nitroqen, a solution of 262 g (8 2 mol) of anhydrous hydrazine in 1300 mL of methanol was cooled to 0° C. and treated with 885 g (6.8 mol) of methyl caproate. The reaction was allowed to warm to ambient temperature and stir overnight prior to stirring at reflux for 7 h. The reaction was concentrated in vacuo; recrystallization from toluene gave 707 g (80%) of caproic acid hydrazide as a colorless solid: mp 72.5°-73.9° C.; NMR (CDCl3) δ 0.82 (t, J=7 Hz, 3H), 1.15-1.33 (m, 4H), 1.51-1.64 (m, 2H), 2.10 (t, J=7 Hz, 2H), 3.91 (br s, 2H), 7.56 (br s, 1H). A 5.0 g (39 mmol) sample of the hydrazide was dissolved in 40 mL of methanol and treated with 11.2 g (78 mmol) of ethyl iminocaproate [P. Reynaud and R. C. Moreau, Bull. Soc., Chim. France, 2997 (1964)-which. was only about 50% pure by NMR] under nitrogen. The reaction was stirred at reflux for 2 days and concentrated in vacuo. Purification by silica gel chromatography (Waters Prep-500A) using ethyl acetate/hexane (48:52) gave 7.56 g (92%) of 3,5-dipentyl-1H-1,2,4-triazole as a colorless solid: mp 66°-68° C.; NMR (CDCl3) δ 0.88 (t, J=7 Hz, 6H), 1.24-1.41 (m, 8H), 1.66- 1.81 (m, 4H), 2.72 (t, J=7 Hz, 4H); MS (FAB) m/e (rel intensity) 210 (100), 166 (14); HRMS. Calcd for M+H: 210.1970. Found: 210.1964. to stirring at reflux for 7 h The reaction was concentrated in vacuo recrystallization from toluene

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In 12 ml of anhydrous tetrahydrofuran (THF) was dissolved 1.02 ml of diisopropylamine, and 4.8 ml of a 1.58M solution of n-butyl lithium in hexane was added to the solution at -40° C. in an argon atmosphere, and the mixture was stirred for 20 minutes and cooled to -78° C. A solution of 0.92 g of methyl hexanoate in 12 ml of anhydrous THF was added dropwise into the mixture over a period of 1 hour. The mixture was stirred for 20 minutes, and about 3 ml of a solution of 1.0 g of (S)-4-iodobutane-1,2-glycolactonide synthesized from (S)-1,2,4-butanetriol and 1.3 g of hexamethylphosphoramide in THF was added to the mixture. Then, the mixture was stirred at -40° C. for 3 hours, a saturated aqueous solution of ammonium chloride was added to the mixture, the mixture was extracted with ether, and the ether extract was washed with water and dried over magnesium sulfate. The solvent was removed by distillation and the obtained crude product was purified by the silica gel column chromatography to obtain 0.9 g of methyl 2-butyl-5,6-dihydroxyhexanoate acetonide. The obtained compound was treated with 4N hydrochloric acid in a 1/1 mixed solvent of methanol/water and hydrolyzed with an equivalent amount of potassium hydroxide. The majority of methanol was removed by distillation, and the residual mixture was made acidic and extracted with chloroform. The chloroform extract was washed with water and dried over magnesium sulfate. The solvent was removed by distillation, the obtained crude product was dissolved in benzene, and a catalytic amount of p-TsOH was added to the solution. The solution was refluxed for 3 hours and cooled. Then, the benzene solution was washed with an aqueous solution of sodium hydrogen carbonate and a saturated aqueous solution of sodium chloride and dried, the solvent was removed by distillation, and the obtained crude product was purified by the silica gel column chromatography to obtain 0.4 g of (S)-2-butyl-5-hydroxymethyl-δ-valerolactone. The obtained compound was dissolved in 20 ml of benzene, 0.8 g of 4-(4'-octyloxy)biphenol was added to the solution, and 1 g of triphenylphosphine and 0.9 g of diethyl azodicarboxylate were further added. Reaction was carried out at room temperature overnight. The reaction product was concentrated under a reduced pressure and purified by the silica gel column chromatography to obtain 0.6 g of (2R,5S)-2-butyl-5-(4'-octyloxybiphenyloxymethyl)-δ-valerolactone. The obtained compound was fractionated and purified by HPLC to obtain 0.2 g of (2R,5S)-2-butyl-5-(4'-oxtyloxybiphenyloxymethyl)-δ-valerolactone and 0.2 g of (2S,5S)-2-butyl-5-(4'-octyloxybiphenyloxymethyl)-δ-valerolactone. These compounds showed the following phase transitions. ##STR36## was added to the solution at -40° C. in an argon atmosphere The mixture was stirred for 20 minutes was added to the mixture Then, the mixture was stirred at -40° C. for 3 hours the mixture was extracted with ether the ether extract was washed with water dried over magnesium sulfate The solvent was removed by distillation the obtained crude product was purified by the silica gel column chromatography

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

Procedure: A stirred autoclave was charged, at room temperature, with 65.61 g (712 mmol) of glycerol, 2.29 g (17.6 mmol) of methyl caproate, 0.23 g (10 wt %) of AMBERLYST® (a polymer based catalyst) 15 resin and 0.23 g (1 mol %) of Pd/C at 5%. The autoclave was then pressurized at 50 bar of dihydrogen gas H2, and then it was heated at 140° C. for 16 h, stirring vigorously. After 16 h of reaction, the reaction mixture was brought back to room temperature. The catalyst was then filtered on a MILLIPORE® filter (a membrane filter) (0.45 pm) and was rinsed with absolute ethanol. The solvents were then evaporated and the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml). The organic phase was washed with water (2×20 ml) and the CH2Cl2 was then evaporated at reduced pressure. The crude reaction product was analyzed by GC/MS. 1-O-hexyl-glycerol ether was obtained at 62% GC yield. After 16 h of reaction was brought back to room temperature The catalyst was then filtered on a MILLIPORE® filter (a membrane filter) (0.45 pm) was rinsed with absolute ethanol The solvents were then evaporated the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml) The organic phase was washed with water (2×20 ml) the CH2Cl2 was then evaporated at reduced pressure The crude reaction product

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A stirred autoclave was charged, at room temperature, with 65.84 g (715 mmol) of glycerol, 2.29 g (17.6 mmol) of methyl caproate, 0.23 g (10 wt %) of camphosulfonic acid and 0.39 g (1 mol %) of Pd/C at 5%. The autoclave was then pressurized at 50 bar of dihydrogen gas H2, and then it was heated at 120° C. for 16 h, stirring vigorously. After 16 h of reaction, the reaction mixture was brought back to room temperature. The catalyst was then filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) and was rinsed with absolute ethanol. The solvents were then evaporated and the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml). The organic phase was washed with water (2×20 ml) and the CH2Cl2 was then evaporated at reduced pressure. The crude reaction product was analyzed by GC/MS. 1-O-hexyl-glycerol ether was obtained at 59% GC yield. After 16 h of reaction was brought back to room temperature The catalyst was then filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) was rinsed with absolute ethanol The solvents were then evaporated the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml) The organic phase was washed with water (2×20 ml) the CH2Cl2 was then evaporated at reduced pressure The crude reaction product

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

Procedure: A stirred autoclave was charged, at room temperature, with 65.50 g (711 mmol) of glycerol, 2.29 g (17.6 mmol) of methyl caproate, 0.23 g (10 wt %) of camphosulfonic acid and 0.39 g (1 mol %) of Pd/C at 5%. The autoclave was then pressurized at 50 bar of dihydrogen gas H2, and then it was heated at 140° C. for 16 h, stirring vigorously. After 16 h of reaction, the reaction mixture was brought back to room temperature. The catalyst was then filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) and was rinsed with absolute ethanol. The solvents were then evaporated and the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml). The organic phase was washed with water (2×20 ml) and the CH2Cl2 was then evaporated at reduced pressure. The crude reaction product was analyzed by GC/MS. 1-O-hexyl-glycerol ether was obtained at 83% GC yield. After 16 h of reaction was brought back to room temperature The catalyst was then filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) was rinsed with absolute ethanol The solvents were then evaporated the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml) The organic phase was washed with water (2×20 ml) the CH2Cl2 was then evaporated at reduced pressure The crude reaction product

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

Procedure: A stirred autoclave was charged, at room temperature, with 55.2 g (600 mmol) of glycerol, 3.9 g (30 mmol) of methyl caproate, 0.4 g (10 wt %) of camphosulfonic acid and 0.6 g (1 mol %) of Pd/C at 5%. The autoclave was then pressurized at 50 bar of dihydrogen gas H2, and then it was heated at 140° C. for 24 h, stirring vigorously. After 24 h of reaction, the reaction mixture was brought back to room temperature. The catalyst was then filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) and was rinsed with absolute ethanol. The solvents were then evaporated and the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml). The organic phase was washed with water (2×20 ml) and the CH2Cl2 was then evaporated at reduced pressure. The crude reaction product was analyzed by GC/MS. 1-O-hexyl-glycerol ether was obtained at 58% GC yield. After 24 h of reaction was brought back to room temperature The catalyst was then filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) was rinsed with absolute ethanol The solvents were then evaporated the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml) The organic phase was washed with water (2×20 ml) the CH2Cl2 was then evaporated at reduced pressure The crude reaction product

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

Procedure: A stirred autoclave was charged, at room temperature, with 55.2 g (600 mmol) of glycerol, 3.9 g (30 mmol) of methyl caproate, 0.4 g (10 wt %) of camphosulfonic acid and 0.3 g (0.5 mol %) of Pd/C at 5%. The autoclave was then pressurized at 40 bar of dihydrogen gas H2, and then it was heated at 140° C. for 24 h, stirring vigorously. After 24 h of reaction, the reaction mixture was brought back to room temperature. The catalyst was then filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) and was rinsed with absolute ethanol. The solvents were then evaporated and the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml). The organic phase was washed with water (2×20 ml) and the CH2Cl2 was then evaporated at reduced pressure. The crude reaction product was analyzed by GC/MS. 1-O-hexyl-glycerol ether was obtained at 55% GC yield. After 24 h of reaction was brought back to room temperature The catalyst was then filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) was rinsed with absolute ethanol The solvents were then evaporated the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml) The organic phase was washed with water (2×20 ml) the CH2Cl2 was then evaporated at reduced pressure The crude reaction product

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

Procedure: A stirred autoclave was charged, at room temperature, with 55.2 g (600 mmol) of glycerol, 3.9 g (30 mmol) of methyl caproate, 0.4 g (10 wt %) of camphosulfonic acid and 0.3 g (0.5 mol %) of Pd/C at 5%. The autoclave was then pressurized at 30 bar of dihydrogen gas H2, and then it was heated at 140° C. for 24 h, stirring vigorously. After 24 h of reaction, the reaction mixture was brought back to room temperature. The catalyst was then filtered on a MILLIPORE® filter (a membrane filter)(0.45 μm) and was rinsed with absolute ethanol. The solvents were then evaporated and the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml). The organic phase was washed with water (2×20 ml) and the CH2Cl2 was then evaporated at reduced pressure. The crude reaction product was analyzed by GC/MS. 1-O-hexyl-glycerol ether was obtained at 50% GC yield. After 24 h of reaction was brought back to room temperature The catalyst was then filtered on a MILLIPORE® filter (a membrane filter)(0.45 μm) was rinsed with absolute ethanol The solvents were then evaporated the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml) The organic phase was washed with water (2×20 ml) the CH2Cl2 was then evaporated at reduced pressure The crude reaction product

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

Procedure: A stirred autoclave was charged, at room temperature, with 55.2 g (600 mmol) of glycerol, 3.9 g (30 mmol) of methyl caproate, 0.4 g (10 wt %) of camphosulfonic acid and 0.3 g (0.5 mol %) of Pd/C at 5%. The autoclave was then pressurized at 20 bar of dihydrogen gas H2, and then it was heated at 140° C. for 24 h, stirring vigorously. After 24 h of reaction, the reaction mixture was brought back to room temperature. The catalyst was filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) and was rinsed with absolute ethanol. The solvents were then evaporated and the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml). The organic phase was washed with water (2×30 ml) and the CH2Cl2 was then evaporated at reduced pressure. The crude reaction product was analyzed by GC/MS. 1-O-hexyl-glycerol ether was obtained at 30% GC yield. After 24 h of reaction was brought back to room temperature The catalyst was filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) was rinsed with absolute ethanol The solvents were then evaporated the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml) The organic phase was washed with water (2×30 ml) the CH2Cl2 was then evaporated at reduced pressure The crude reaction product

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

Procedure: A stirred autoclave was charged, at room temperature, with 55.2 g (600 mmol) of glycerol, 3.9 g (30 mmol) of methyl caproate, 0.39 g (10 wt %) of camphosulfonic acid and 0.3 g (0.5 mol %) of Pd/C at 5%. The autoclave was then pressurized at 10 bar of dihydrogen gas H2, and then it was heated at 140° C. for 24 h, stirring vigorously. After 24 h of reaction, the reaction mixture was brought back to room temperature. The catalyst was filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) and was rinsed with absolute ethanol. The solvents were evaporated and the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml). The organic phase was washed with water (2×30 ml) and the CH2Cl2 was then evaporated at reduced pressure. The crude reaction product was analyzed by GC/MS. 1-O-hexyl-glycerol ether was obtained at 22% GC yield. After 24 h of reaction was brought back to room temperature The catalyst was filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) was rinsed with absolute ethanol The solvents were evaporated the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml) The organic phase was washed with water (2×30 ml) the CH2Cl2 was then evaporated at reduced pressure The crude reaction product