undecan-6-one

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 5.11 g of 6-undecanone in 20 ml of ethanol were successively added a solution of 3.47 g of hydroxylamine hydrochloride in 6 ml of water and a solution of 4.77 g of potassium hydroxide in 6 ml of water. The resulting mixture was heated under reflux for 3 hours. The reaction mixture was then poured into 150 ml of ice-containing water. The resulting aqueous mixture was made acidic by addition of 2N hydrochloric acid, and extracted with benzene. The organic layer was washed with saturated aqueous sodium chloride and evaporated under reduced pressure to remove the solvent. There was obtained 5.57 g (corresponding to theoretical amount) of 6-undecanone oxime as a pale yellow solid, The resulting mixture was heated under reflux for 3 hours extracted with benzene The organic layer was washed with saturated aqueous sodium chloride evaporated under reduced pressure to remove the solvent

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

Procedure: Diamylketone (12 g) was hydrogenated at 50 psi in the presence of 10% Pd/C (1.5 g) and benzylamine (8.31 g) at room temperature for 6 hours. Further catalyst (1.5 g) was added and the mixture was hydrogenated at 40° for 5 hours. The reaction mixture was filtered and evaporated to dryness (combined with the product from a previous 12 g hydrogenation). The oil was purified by column chromatography to give 6-undecylamine as an oil (9.1 g, 38%). The reaction mixture was filtered evaporated to dryness ( The oil was purified by column chromatography

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

Procedure: Diamylketone (12 g) was hydrogenated at 50 psi in the presence of 10% Pd/C (1.5 g) and benzylamine (8.31 g) at room temperature for 6 hours. Further catalyst (1.5 g) was added and the mixture was hydrogenated at 40° for 5 hours. The reaction mixture was filtered and evaporated to dryness (combined with the product from a previous 12 g hydrogenation). The oil was purified by column chromatography to give 6-undecylamine as an oil (9.1 g, 38%). The reaction mixture was filtered evaporated to dryness ( The oil was purified by column chromatography

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

Procedure: Sodium borohydride (0.55 g, 14.6 mmol) was added to a solution of 6-undecanone (1.66 g, 9.8 mmol) in 50 ml methanol, and the mixture was stirred at room temperature 2 hours. Solvent was evaporated and water was added to the residue which was extracted with CH2Cl2. The extracts were dried over anhydrous potassium carbonate, filtered, and the solvent was evaporated to leave crude 6-undecanol. The procedure of example 13 a. was followed but the crude 6-undecanol was substituted in place of 9-dodecyn-1-ol to obtain crude 6-undecanyl methanesulfonate. The crude 6-undecanyl methanesulfonate was dissolved in 20 ml acetonitrile and 1 g potassium cyanide were added, as well as 50 mg 18-crown-6, and 100 mg Et4NCN. The mixture was stirred and heated at reflux for 4 days. The mixture was cooled, poured into 5% aqueous NaOH, and extracted with CH2Cl2. The extracts were dried over Na 2 SO4. The extracts were filtered, and the solvent was evaporated. The residue was chromatographed on silica gel eluting with EtOAc-hexanes (2:98) to obtain crude 3-pentylheptanenitrile in low yield. This nitrile was dissolved in 30 ml THF, 1 ml 1M BH3 -THF solution was added, and the mixture was stirred at reflux for 4 hours. Water and 1N NaOH were added. The mixture was concentrated and water was added. The mixture was extracted with CH2Cl2. The extracts were dried over Na2SO4, filtered, and the solvent was evaporated to leave the title compound as an oil (57 mg, 3% yield overall): C12H27N (185.36); 1H-NMR (CDCl3) δ2.64 (d,2), 1.28 (m,17), 0.89 (t,6). Solvent was evaporated water was added to the residue which was extracted with CH2Cl2 The extracts were dried over anhydrous potassium carbonate filtered the solvent was evaporated

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

Procedure: Sodium borohydride (0.55 g, 14.6 mmol) was added to a solution of 6-undecanone (1.66 g, 9.8 mmol) in 50 ml methanol, and the mixture was stirred at room temperature 2 hours. Solvent was evaporated and water was added to the residue which was extracted with CH2Cl2. The extracts were dried over anhydrous potassium carbonate, filtered, and the solvent was evaporated to leave crude 6-undecanol. The procedure of example 13 a. was followed but the crude 6-undecanol was substituted in place of 9-dodecyn-1-ol to obtain crude 6-undecanyl methanesulfonate. The crude 6-undecanyl methanesulfonate was dissolved in 20 ml acetonitrile and 1 g potassium cyanide were added, as well as 50 mg 18-crown-6, and 100 mg Et4NCN. The mixture was stirred and heated at reflux for 4 days. The mixture was cooled, poured into 5% aqueous NaOH, and extracted with CH2Cl2. The extracts were dried over Na 2 SO4. The extracts were filtered, and the solvent was evaporated. The residue was chromatographed on silica gel eluting with EtOAc-hexanes (2:98) to obtain crude 3-pentylheptanenitrile in low yield. This nitrile was dissolved in 30 ml THF, 1 ml 1M BH3 -THF solution was added, and the mixture was stirred at reflux for 4 hours. Water and 1N NaOH were added. The mixture was concentrated and water was added. The mixture was extracted with CH2Cl2. The extracts were dried over Na2SO4, filtered, and the solvent was evaporated to leave the title compound as an oil (57 mg, 3% yield overall): C12H27N (185.36); 1H-NMR (CDCl3) δ2.64 (d,2), 1.28 (m,17), 0.89 (t,6). Solvent was evaporated water was added to the residue which was extracted with CH2Cl2 The extracts were dried over anhydrous potassium carbonate filtered the solvent was evaporated

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

Procedure: Sodium borohydride (0.55 g, 14.6 mmol) was added to a solution of 6-undecanone (1.66 g, 9.8 mmol) in 50 ml methanol, and the mixture was stirred at room temperature 2 hours. Solvent was evaporated and water was added to the residue which was extracted with CH2Cl2. The extracts were dried over anhydrous potassium carbonate, filtered, and the solvent was evaporated to leave crude 6-undecanol. The procedure of example 13 a. was followed but the crude 6-undecanol was substituted in place of 9-dodecyn-1-ol to obtain crude 6-undecanyl methanesulfonate. The crude 6-undecanyl methanesulfonate was dissolved in 20 ml acetonitrile and 1 g potassium cyanide were added, as well as 50 mg 18-crown-6, and 100 mg Et4NCN. The mixture was stirred and heated at reflux for 4 days. The mixture was cooled, poured into 5% aqueous NaOH, and extracted with CH2Cl2. The extracts were dried over Na 2 SO4. The extracts were filtered, and the solvent was evaporated. The residue was chromatographed on silica gel eluting with EtOAc-hexanes (2:98) to obtain crude 3-pentylheptanenitrile in low yield. This nitrile was dissolved in 30 ml THF, 1 ml 1M BH3 -THF solution was added, and the mixture was stirred at reflux for 4 hours. Water and 1N NaOH were added. The mixture was concentrated and water was added. The mixture was extracted with CH2Cl2. The extracts were dried over Na2SO4, filtered, and the solvent was evaporated to leave the title compound as an oil (57 mg, 3% yield overall): C12H27N (185.36); 1H-NMR (CDCl3) δ2.64 (d,2), 1.28 (m,17), 0.89 (t,6). Solvent was evaporated water was added to the residue which was extracted with CH2Cl2 The extracts were dried over anhydrous potassium carbonate filtered the solvent was evaporated

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

Procedure: The compound was prepared according to the procedure described in Example 84 except that the reaction was worked up after 3 days. The following reagents were used: 6-undecanone (17 g), diisopropylamine (32.2 mL), 1.6M n-butyl lithium in hexane (143 mL), acetaldehyde N-tert-butylimine (14.75 mL), diethyl chlorophosphonate (16.6 mL) and tetrahydrofuran (200 mL). The work up, varied only in that the oxalic acid catalyzed hydrolysis was run overnight at room temperature, gave the crude aldehyde which was purified by HPLC (ether-hexane; 1:16.6) to yield 15.5 g of 3-pentyl-2-octenal as an oil. The compound was prepared hydrolysis was run overnight at room temperature gave the crude aldehyde which was purified by HPLC (ether-hexane; 1:16.6)

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

Procedure: 3-Bromo-2,2′-bithiophene (IIIa) (0.500 g, 2.04 mmol) in dry diethylether (20 mL) was added slowly to a solution of n-butyllithium (1.6 M in hexane, 1.25 mL, 2.04 mmol) in dry diethylether (20 mL) at −78° C. over 2 h under N2. The mixture was stirred for 15 minutes at the same temperature. Freshly distilled 6-undecanone (0.42 mL, 2.04 mmol) was added via a syringe to the mixture at −78° C., followed by stirring overnight at room temperature. The reaction was quenched with an aqueous NH4Cl-solution (2.5 M, 10 mL) and water (10 mL) at 0° C. The organic phase was separated and the aqueous phase was extracted with diethylether. The combined organic phases were washed with brine, dried over MgSO4 and evaporated under reduced pressure to give a crude oil. The oily residue was purified by column chromatography (eluent hexane/EtOAc 90:10) to afford the title compound (IIu) as a yellow oil (0.425 g, 62.0%). 1H-NMR (CDCl3): δ=7.35 (dd, J=1.3 Hz, J=5.3 Hz, 1H), 7.23 (d, J=5.4 Hz, 1H), 7.09 (dd, J=1.3 Hz, J=3.5 Hz, 1H), 7.01 (dd, J=5.3, J=3.5 Hz, 1H), 6.98 (d, J=5.4 Hz, 1H), 2.02 (s, 1H), 1.83-1.60 (m, 4H), 1.42-1.05 (m, 12H), 0.84 (t, J=6.7 Hz, 6H). 13C-NMR (CDCl3): δ=146.06, 136.07, 129.93, 129.19, 128.92, 127.78, 127.31, 125.41, 78.68, 43.60, 32.75, 24.00, 23.21, 14.70. by stirring overnight at room temperature The reaction was quenched with an aqueous NH4Cl-solution (2.5 M, 10 mL) and water (10 mL) at 0° C The organic phase was separated the aqueous phase was extracted with diethylether The combined organic phases were washed with brine dried over MgSO4 evaporated under reduced pressure to give a crude oil The oily residue was purified by column chromatography (eluent hexane/EtOAc 90:10)

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

Procedure: The same procedures as in Production Example 3 are carried out except that glycerol is replaced with 292.1 g (2.18 mol) of trimethylolpropane, 6-undecanone is replaced with 474.0 g (8.17 mol) of acetone, and the amount of paratoluenesulfonic acid monohydrate is changed to 6.0 g (0.0315 mol) and the amount of hexane is changed to 900 ml to give 5-hydroxymethyl-5-ethyl-2,2-dimethyl-1,3-dioxane.

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

Procedure: Using the general procedure described in Sedgwick, Organic Chemistry of Nitrogen, pages 169-175 (1937 Edition), 1.2 moles of 6-undecanone is reacted with an alcohol solution of 1 mole of hydroxylamine at room temperature to produce 0.8 moles of 6-undecanone oxime, ##EQU1## contaminated with 3.5% 6-undecanone.

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

Procedure: To a solution of 5.11 g of 6-undecanone in 20 ml of ethanol were successively added a solution of 3.47 g of hydroxylamine hydrochloride in 6 ml of water and a solution of 4.77 g of potassium hydroxide in 6 ml of water. The resulting mixture was heated under reflux for 3 hours. The reaction mixture was then poured into 150 ml of ice-containing water. The resulting aqueous mixture was made acidic by addition of 2 N hydrochloric acid, and extracted with benzene. The organic layer was washed with saturated aqueous sodium chloride and evaporated under reduced pressure to remove the solvent. There was obtained 5.57 g (corresponding to theoretical amount) of 6-undecanone oxime as a pale yellow solid, The resulting mixture was heated under reflux for 3 hours extracted with benzene The organic layer was washed with saturated aqueous sodium chloride evaporated under reduced pressure to remove the solvent