nonane

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

Procedure: 0.5M 9-Borobicyclo[3.3.1]nonane in THF (415 mL, 0.21 mol, 1.1 eq) was added under stirring in a stream of argon at room temperature to tert-butyl 6-[(cyclopropylmethoxy)methyl]-6-hydroxy-1,4-oxazepane-4-carboxylate (Preparation 80, 40 g, 0.19 mol, 1 eq). The reaction mixture was stirred at room temperature for 2 h. After this, the catalyst palladium (0) tetrakis(triphenylphosphine) (4 g, 0.003 mol, 0.02 eq) and 2-bromo-6-methylpyridine (36 g, 0.21 mmol, 1.1 eq) were added to the mixture, and the latter was stirred for 15 min. Then 3M potassium carbonate solution (125 mL, 0.38 mol, 2 eq) was added, and the reaction mixture was refluxed for 3 h. The mixture was cooled, diluted with hexane (300 mL) and DCM (100 mL). The organic layer was separated, washed with water (2×100 mL), and with the saturated sodium chloride solution. The combined aqueous layer was extracted with ethyl acetate/hexane (3:1) mixture (2×200 mL). The organic layers were sequentially filtered through silica (25 g; 63-100 μm) and sodium sulphate (50 g) and evaporated. The residue was subjected to chromatography (carbon tetrachloride/chloroform/isopropanol 100:0:0→90:10:0→70:30:0→50:50:0→30:70:0→0:100:0→0:99:1→0:98:2→0:97:3→0:95:5→0:93:7→0:92:8→0:90:10) on silica (500 g; 63-100 μm). The fractions, containing the product, were collected and evaporated to give title compound as a light oil in (42.5 g, 0.14 mol, 74%). the latter was stirred for 15 min the reaction mixture was refluxed for 3 h The mixture was cooled The organic layer was separated washed with water (2×100 mL) The combined aqueous layer was extracted with ethyl acetate/hexane (3:1) mixture (2×200 mL) The organic layers were sequentially filtered through silica (25 g; 63-100 μm) and sodium sulphate (50 g) evaporated The fractions, containing the product were collected evaporated

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

Procedure: A solution of (0.1 mmol) of 10, (0.12 mmol) of 14, 14 mg (0.13 mmol) of neopentyl glycol, 95 mg (0.3 mmol) of Ba(OH)2.8H2O, 80 μl (6.08 mmol, 5 mol %) of a 76 mM acetone solution of Pd(OAc)2 in 2 ml of 95% i-PrOH is stirred at 80° C. for 12 hours. The solvent is subsequently removed under reduced pressure. 2 ml of 2 M HCl are added to the residue, and the mixture is extracted with dichloromethane (3×2 ml). The combined organic phases are dried over MgSO4 and filtered through SiO2. The solvent is removed under reduced pressure, and the residue is purified by recrystallisation twice from nonane (yield: 68%). The solvent is subsequently removed under reduced pressure 2 ml of 2 M HCl are added to the residue the mixture is extracted with dichloromethane (3×2 ml) The combined organic phases are dried over MgSO4 filtered through SiO2 The solvent is removed under reduced pressure

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

Procedure: A solution of (0.1 mmol) of 10, (0.12 mmol) of 12, 14 mg (0.13 mmol) of neopentyl glycol, 95 mg (0.3 mmol) of Ba(OH)2.8H2O, 80 μl (6.08 mmol, 5 mol %) of a 76 mM acetone solution of Pd(OAc)2 in 2 ml of 95% i-PrOH is stirred at 80° C. for 12 hours. The solvent is subsequently removed under reduced pressure. 2 ml of 2 M HCl are added to the residue, and the mixture is extracted with dichloromethane (3×2 ml). The combined organic phases are dried over MgSO4 and filtered through SiO2. The solvent is removed under reduced pressure, and the residue is purified by recrystallisation twice from nonane (yield: 65%). The solvent is subsequently removed under reduced pressure 2 ml of 2 M HCl are added to the residue the mixture is extracted with dichloromethane (3×2 ml) The combined organic phases are dried over MgSO4 filtered through SiO2 The solvent is removed under reduced pressure

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

Procedure: A solution of (0.1 mmol) of 10, (0.12 mmol) of 4, 14 mg (0.13 mmol) of neopentyl glycol, 95 mg (0.3 mmol) of Ba(OH)2.8H2O, 80 μl (6.08 mmol, 5 mol %) of a 76 mM acetone solution of Pd(OAc)2 in 2 ml of 95% i-PrOH is stirred at 80° C. for 12 hours. The solvent is subsequently removed under reduced pressure. 2 ml of 2 M HCl are added to the residue, and the mixture is extracted with dichloromethane (3×2 ml). The combined organic phases are dried over MgSO4 and filtered through SiO2. The solvent is removed under reduced pressure, and the residue is purified by recrystallisation twice from nonane (yield: 60%). The solvent is subsequently removed under reduced pressure 2 ml of 2 M HCl are added to the residue the mixture is extracted with dichloromethane (3×2 ml) The combined organic phases are dried over MgSO4 filtered through SiO2 The solvent is removed under reduced pressure

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

Procedure: 10 mol of 2-nitrophenol was charged into a stirred, heated reactor, along with 800 ml of nonane and 5% N,N'-dimethylbenzoamidine, and the mixture was heated to 150° C. Then 12 mol of dimethyl carbonate was added portionwise over 5 hr. The methanol produced by the reaction was removed by distillation over a distillation column. After completion of the reaction, the reaction mixture was refined by distillation. 2-Nitroanisole was obtained in the amount of about 9 mol, corresponding to a yield of c. 90%, based on the starting amount of 2-nitrophenol. heated reactor was removed by distillation over a distillation column After completion of the reaction the reaction mixture was refined by distillation

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

Procedure: 10 mol of 2-nitrophenol was charged into a stirred, heated reactor, along with 800 ml of nonane and 5% N,N'-dimethylbenzoamidine, and the mixture was heated to 150° C. Then 12 mol of dimethyl carbonate was added portionwise over 5 hr. The methanol produced by the reaction was removed by distillation over a distillation column. After completion of the reaction, the reaction mixture was refined by distillation. 2-Nitroanisole was obtained in the amount of about 9 mol, corresponding to a yield of c. 90%, based on the starting amount of 2-nitrophenol. heated reactor was removed by distillation over a distillation column After completion of the reaction the reaction mixture was refined by distillation

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

Procedure: To a 33 ml solution of a 0.5M solution of 9-borabicyclo[3:3:1]nonane in tetrahydrofuran was added dropwise, under nitrogen, a solution of 6.0 g of 4-benzyloxy-1-heneicosene in 30 ml of dry tetrahydrofuran. After stirring at room temperature for 3 hours, the reaction was quenched by successive addition of 9 ml of ethanol, 3 ml of 6N sodium hydroxide and 6.5 ml 30% hydrogen peroxide. The reaction mixture was heated at 50° for 90 minutes and then allowed to stand at ambient temperature overnight. Upon standing, the reaction mixture separated into aqueous and organic phases. The aqueous phase was saturated with potassium carbonate, and the organic phase was separated, washed with 15 ml of 10% solution of sodium sulfite and 20 ml of saturated solution of sodium chloride, dried over potassium carbonate, and concentrated. The residue was taken up in a mixture of 20% diethyl ether/hexane, filtered and concentrated to an oil. Flash chromatography of the oil on silica gel using hexane/diethyl ether (2:1 by volume) as the eluent gave 4.88 g (78%) of 4-benzyloxyheneicosan-1-ol. the reaction was quenched by successive addition of 9 ml of ethanol, 3 ml of 6N sodium hydroxide and 6.5 ml 30% hydrogen peroxide The reaction mixture was heated at 50° for 90 minutes to stand at ambient temperature overnight the reaction mixture separated into aqueous and organic phases the organic phase was separated washed with 15 ml of 10% solution of sodium sulfite and 20 ml of saturated solution of sodium chloride dried over potassium carbonate concentrated The residue was taken up in a mixture of 20% diethyl ether/hexane filtered concentrated to an oil

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

Procedure: To a 33 ml solution of a 0.5M solution of 9-borabicyclo[3:3:1]nonane in tetrahydrofuran was added dropwise, under nitrogen, a solution of 6.0 g of 4-benzyloxy-1-heneicosene in 30 ml of dry tetrahydrofuran. After stirring at room temperature for 3 hours, the reaction was quenched by successive addition of 9 ml of ethanol, 3 ml of 6N sodium hydroxide and 6.5 ml 30% hydrogen peroxide. The reaction mixture was heated at 50° for 90 minutes and then allowed to stand at ambient temperature overnight. Upon standing, the reaction mixture separated into aqueous and organic phases. The aqueous phase was saturated with potassium carbonate, and the organic phase was separated, washed with 15 ml of 10% solution of sodium sulfite and 20 ml of saturated solution of sodium chloride, dried over potassium carbonate, and concentrated. The residue was taken up in a mixture of 20% diethyl ether/hexane, filtered and concentrated to an oil. Flash chromatography of the oil on silica gel using hexane/diethyl ether (2:1 by volume) as the eluent gave 4.88 g (78%) of 4-benzyloxyheneicosan-1-ol. the reaction was quenched by successive addition of 9 ml of ethanol, 3 ml of 6N sodium hydroxide and 6.5 ml 30% hydrogen peroxide The reaction mixture was heated at 50° for 90 minutes to stand at ambient temperature overnight the reaction mixture separated into aqueous and organic phases the organic phase was separated washed with 15 ml of 10% solution of sodium sulfite and 20 ml of saturated solution of sodium chloride dried over potassium carbonate concentrated The residue was taken up in a mixture of 20% diethyl ether/hexane filtered concentrated to an oil

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

Procedure: As directed by D. R. M. Walton and F. Waugh, J. Organomet. Chem. 37, 45 (1972), bis(trimethylsilyl)acetylene is acylated with cyclohexylacetic acid chloride and hydrolysed with aqueous/methanolic borax solution to 1-cyclohexyl-3-butyn-2-one. Reduction with (S)-B-(3-pinanyl)-9-borabiccyclo[3.3.1]nonane ((S)-Alpine-BoraneR, Aldrich, 88% ee) as directed by M. M. Midland et al., Tetrahedron 40, 1371 (1984) yields 1-cyclohexyl-3-butyn-2(S)-ol.

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

Procedure: This example demonstrates the utility of titanium-containing catalysts prepared in accordance with the present invention in an olefin epoxidation reaction using an organic hydroperoxide. In each run, catalyst (0.5 g) was added to a 4-neck round bottom flask equipped with a condenser, thermocouple, stir bar and a sampling port. A mixture containing 17.9 g 1-octene, 10 g of an ethylbenzene hydroperoxide solution obtained by air oxidation of ethyl benzene, and 1 g nonane (internal standard) was added to the flask under an inert atmosphere. A sample was taken after the reaction mixture was stirred thoroughly. The mixture was then heated to 90° C. and maintained at that temperature for 1 hour. The observed performance of each catalyst is summarized in the following table. containing catalysts equipped with a condenser

Conditions: temp:4.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 2-{2-[4-(2,6-dichloro-benzyloxy)-phenyl]-morpholin-4-yl}-ethanol (0.74 g; 1.94 mmol) in a mixture of THF (10 mL) and CH2Cl2 (10 mL) was added a tetrazole solution in CH3CN ((8.60 ml; 0.45 mol/1; 3.87 mmol) at RT. The resulting mixture was stirred for 30 minutes and subsequently di-tert-butyl N,N-diisopropylphosphoramidite (0.98 ml; 3.10 mmol) was added and stirred overnight at RT. Subsequently, the mixture was cooled to 4° C., and a solution of tert-butyl hydroperoxide in nonane (0.31 ml; ˜5.5 mol/L, 2.90 mmol) was added. Thereafter the mixture was stirred at RT for another 30 min. The reaction was quenched by the addition of an 5% aqueous NaHCO3 solution and extracted with EtOAc. The organic layer was dried (Na2SO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (SiO2, EtOAc) to afford phosphoric acid di-tert-butyl ester 2-{2-[4-(2,6-dichloro-benzyloxy)-phenyl]-morpholin-4-yl}-ethyl ester (0.66 g). stirred overnight at RT Thereafter the mixture was stirred at RT for another 30 min The reaction was quenched by the addition of an 5% aqueous NaHCO3 solution extracted with EtOAc The organic layer was dried (Na2SO4) filtered concentrated in vacuo The residue was purified by column chromatography (SiO2, EtOAc)

Conditions: temp:4.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 2-{2-[4-(2,6-dichloro-benzyloxy)-phenyl]-morpholin-4-yl}-ethanol (0.74 g; 1.94 mmol) in a mixture of THF (10 mL) and CH2Cl2 (10 mL) was added a tetrazole solution in CH3CN ((8.60 ml; 0.45 mol/1; 3.87 mmol) at RT. The resulting mixture was stirred for 30 minutes and subsequently di-tert-butyl N,N-diisopropylphosphoramidite (0.98 ml; 3.10 mmol) was added and stirred overnight at RT. Subsequently, the mixture was cooled to 4° C., and a solution of tert-butyl hydroperoxide in nonane (0.31 ml; ˜5.5 mol/L, 2.90 mmol) was added. Thereafter the mixture was stirred at RT for another 30 min. The reaction was quenched by the addition of an 5% aqueous NaHCO3 solution and extracted with EtOAc. The organic layer was dried (Na2SO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (SiO2, EtOAc) to afford phosphoric acid di-tert-butyl ester 2-{2-[4-(2,6-dichloro-benzyloxy)-phenyl]-morpholin-4-yl}-ethyl ester (0.66 g). stirred overnight at RT Thereafter the mixture was stirred at RT for another 30 min The reaction was quenched by the addition of an 5% aqueous NaHCO3 solution extracted with EtOAc The organic layer was dried (Na2SO4) filtered concentrated in vacuo The residue was purified by column chromatography (SiO2, EtOAc)