nonan-1-ol

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: To a solution of phosphorus oxychloride (1.53 g, 10.0 mmol) and triethylamine (3.5 mL, 25.0 mmol) in toluene (20 mL) at 0° C. is added dropwise a solution of 2,6 diisopropylphenol (1.78 g, 10.0 mmol) in toluene (5 mL). The mixture is allowed to warm slowly to room temperature and stirred for 2 hours. The mixture is cooled to 0° C., and a solution of 1-nonanol (1.44 g, 10.0 mmol) in toluene (5 mL) is added dropwise. The mixture is allowed to warm to room temperature and stirred for 2 hours. The mixture is filtered and the filtrate concentrated to afford 4.1 g of a crude oil, which is taken up in 1:1 EtOAc/hexane and filtered through a small pad of silica gel. The filtrate is concentrated to afford 3.7 g of a light yellow liquid; 1H NMR (200 MHz, CDCl3)δ7.17 (br s, 3 H), 4.30-4.10 (m, 2 H), 3.43 (m, 2 H), 1.85-1.65 (m, 4 H), 1.45-1.10 (m, 10 H), 1.25 (d, J=7 Hz, 12 H), 0.89 (t, J=7 Hz, 3 H). The mixture is cooled to 0° C. to warm to room temperature stirred for 2 hours The mixture is filtered the filtrate concentrated to afford 4.1 g of a crude oil, which filtered through a small pad of silica gel The filtrate is concentrated

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

Procedure: To a solution of phosphorus oxychloride (1.53 g, 10.0 mmol) and triethylamine (3.5 mL, 25.0 mmol) in toluene (20 mL) at 0° C. is added dropwise a solution of 2,6 diisopropylphenol (1.78 g, 10.0 mmol) in toluene (5 mL). The mixture is allowed to warm slowly to room temperature and stirred for 2 hours. The mixture is cooled to 0° C., and a solution of 1-nonanol (1.44 g, 10.0 mmol) in toluene (5 mL) is added dropwise. The mixture is allowed to warm to room temperature and stirred for 2 hours. The mixture is filtered and the filtrate concentrated to afford 4.1 g of a crude oil, which is taken up in 1:1 EtOAc/hexane and filtered through a small pad of silica gel. The filtrate is concentrated to afford 3.7 g of a light yellow liquid; 1H NMR (200 MHz, CDCl3)δ7.17 (br s, 3 H), 4.30-4.10 (m, 2 H), 3.43 (m, 2 H), 1.85-1.65 (m, 4 H), 1.45-1.10 (m, 10 H), 1.25 (d, J=7 Hz, 12 H), 0.89 (t, J=7 Hz, 3 H). The mixture is cooled to 0° C. to warm to room temperature stirred for 2 hours The mixture is filtered the filtrate concentrated to afford 4.1 g of a crude oil, which filtered through a small pad of silica gel The filtrate is concentrated

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

Procedure: To a solution of phenylphosphonic dichloride (3.0 g, 14.2 mmol) and triethylamine (2.4 mL, 17.1 mmol) in toluene (20 mL) at 0° C. is added dropwise a solution of 1-nonanol (2.05 g, 14.2 mmol) in toluene (5 mL). The mixture is allowed to warm slowly to room temperature and stirred for 2 hours. The mixture is filtered, and the filtrate is concentrated to afford 4.5 g of the title compound as a light yellow liquid; 1H NMR (200 MHz, CDCl3)δ7.40-7.15 (m, 5 H), 4.40-4.25 (m, 2 H), 1.90-1.65 (m, 2 H), 1.45-1.20 (m, 12 H), 0.89 (t, J=7 Hz, 3 H). The mixture is filtered the filtrate is concentrated

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

Procedure: To a solution of phenylphosphonic dichloride (3.0 g, 14.2 mmol) and triethylamine (2.4 mL, 17.1 mmol) in toluene (20 mL) at 0° C. is added dropwise a solution of 1-nonanol (2.05 g, 14.2 mmol) in toluene (5 mL). The mixture is allowed to warm slowly to room temperature and stirred for 2 hours. The mixture is filtered, and the filtrate is concentrated to afford 4.5 g of the title compound as a light yellow liquid; 1H NMR (200 MHz, CDCl3)δ7.40-7.15 (m, 5 H), 4.40-4.25 (m, 2 H), 1.90-1.65 (m, 2 H), 1.45-1.20 (m, 12 H), 0.89 (t, J=7 Hz, 3 H). The mixture is filtered the filtrate is concentrated

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

Procedure: To an ice-cooled solution of phenyl dichlorophosphate (2.83 g, 0.02 mol) in dry toluene (50 mL) is added triethylamine (2.02 g, 0.02 mol) followed by nonyl alcohol (2.89 g, 0.02 mol) in dry toluene (40 mL) dropwise. The reaction mixture is stirred in an ice bath for 2 hours and then filtered. To this filtrate are added triethylamine (2.02 g, 0.02 mol) and a solution of N-[2,6-bis(1-methylethyl)phenyl]-2-[phenylmethyl]amino-acetamide (Example V) (6.40 g, 0.02 mole) and the mixture is stirred at room temperature overnight. The reaction mixture is filtered and concentrated. Flash column chromatography and crystallization from ethyl acetate affords 3.8 g of the title compound; IR (KBr); 3285, 2961, 2925, 2858, 2367, 1684, and 1508. 1H NMR (250 MHz, DMSO)δ9.22 (1 H, s), 7.44-6.92 (13 H, m), 4.50-4.30 (2 H, m), 4.30-4.00 (2 H, m), 4.00-3.60 (2 H, m), 3.10-2.80 (2 H, m), 1.70-1.40 (2 H, m), 1.4-1.18 (12 H, m), 1.18-1.00 (12 H, d, J=7 Hz), 0.98-0.76 (3 H, m). filtered The reaction mixture is filtered concentrated Flash column chromatography and crystallization from ethyl acetate

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

Procedure: To an ice-cooled solution of phenyl dichlorophosphate (2.83 g, 0.02 mol) in dry toluene (50 mL) is added triethylamine (2.02 g, 0.02 mol) followed by nonyl alcohol (2.89 g, 0.02 mol) in dry toluene (40 mL) dropwise. The reaction mixture is stirred in an ice bath for 2 hours and then filtered. To this filtrate are added triethylamine (2.02 g, 0.02 mol) and a solution of N-[2,6-bis(1-methylethyl)phenyl]-2-[phenylmethyl]amino-acetamide (Example V) (6.40 g, 0.02 mole) and the mixture is stirred at room temperature overnight. The reaction mixture is filtered and concentrated. Flash column chromatography and crystallization from ethyl acetate affords 3.8 g of the title compound; IR (KBr); 3285, 2961, 2925, 2858, 2367, 1684, and 1508. 1H NMR (250 MHz, DMSO)δ9.22 (1 H, s), 7.44-6.92 (13 H, m), 4.50-4.30 (2 H, m), 4.30-4.00 (2 H, m), 4.00-3.60 (2 H, m), 3.10-2.80 (2 H, m), 1.70-1.40 (2 H, m), 1.4-1.18 (12 H, m), 1.18-1.00 (12 H, d, J=7 Hz), 0.98-0.76 (3 H, m). filtered The reaction mixture is filtered concentrated Flash column chromatography and crystallization from ethyl acetate

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

Procedure: 288 Parts of nonanol are reacted with phosgene in a similar way to the method described in Example 6 to give 342 parts of nonyl chloroformate as a colourless liquid b.p. 70° C. at 1 mm pressure.

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

Procedure: As an example, oleic acid can be oxidatively cleaved into nonanal (m.p. −18° C., b.p. 195° C.) and oxononanoic acid (m.p. 70° C., b.p. 181-182° C.) with oxygen, air or hydrogen peroxide. Nonanal can be utilized as is or converted to nonanol (m.p. −7° C., b.p. 215° C.) by catalytic hydrogenation. The nonanal can be distilled off and the high melting oxonanoic acid can be converted to an ester by reaction with bio-derived ethanol to produce ethyl 9-oxononanoate (m.p. 5° C.). The following represents the reaction scheme: The nonanal can be distilled off can be converted to an ester by reaction with bio-derived ethanol

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

Procedure: As an example, oleic acid can be oxidatively cleaved into nonanal (m.p. −18° C., b.p. 195° C.) and oxononanoic acid (m.p. 70° C., b.p. 181-182° C.) with oxygen, air or hydrogen peroxide. Nonanal can be utilized as is or converted to nonanol (m.p. −7° C., b.p. 215° C.) by catalytic hydrogenation. The nonanal can be distilled off and the high melting oxonanoic acid can be converted to an ester by reaction with bio-derived ethanol to produce ethyl 9-oxononanoate (m.p. 5° C.). The following represents the reaction scheme: The nonanal can be distilled off can be converted to an ester by reaction with bio-derived ethanol

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

Procedure: 396 Parts of nonyl alcohol are reacted with phosgene to give 558 parts of nonyl chloroformate as a colourless liquid b.p. 70°-72° C/1 mm.

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

Procedure: To a 3-neck 250 mL flask equipped with an argon inlet, stir bar and distillation apparatus was added 1-nonanol (19.99 g, 0.14 mol, obtained from Sigma-Aldrich), methyl 3,4-epoxycyclohexanecarboxylate (ERL-4140, 23.80 g, 0.15 mol, obtained from Dow Chemical Company), 1,4-diazabicyclo[2.2.2]octane (DABCO™, 3.96 g, 35 mmol, obtained from Sigma-Aldrich) and toluene (60 mL). The reaction mixture was refluxed until methanol ceased collecting in the receiving flask and the completion of the reaction was confirmed by 1H NMR spectroscopy. The still pot from the distillation was diluted with toluene (60 mL) and washed with brine (3×60 mL). The organic layer was separated, dried over MgSO4 and filtered. The solvent was removed in vacuo. The excess methyl 3,4-epoxycyclohexane carboxylate was removed via Kugelrohr distillation under reduced vacuum to give 33.39 g (90%) of a clear, colorless oil of nonyl-3,4-epoxycylohexanecarboxylate 1H NMR (CDCl3, δ): 4.06 (td, J=6.7, 1.9 Hz, 2H), 3.25-3.10 (m, 2H), 2.55-2.42 (m, 1H), 2.31-1.27 (m, 20H), 0.88 (t, J=6.7 Hz, 3H). To a 3-neck 250 mL flask equipped with an argon inlet distillation apparatus ceased collecting in the receiving flask The still pot from the distillation was diluted with toluene (60 mL) washed with brine (3×60 mL) The organic layer was separated dried over MgSO4 filtered The solvent was removed in vacuo The excess methyl 3,4-epoxycyclohexane carboxylate was removed via Kugelrohr distillation under reduced vacuum