2-pentylidenecyclopentan-1-one

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

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

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

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

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

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 100 mL four-necked flask was charged with 16.6 g (0.92 mol) of water and 0.16 g (0.004 mol) of sodium hydroxide. After cooling the contents of the flask to 15° C. under stirring, a mixed solution containing 61.3 g (0.71 mol) of valeraldehyde (acid value: 1.5 mg-KOH/g) and 237.8 g (2.83 mol) of cyclopentanone, and 36.0 g of a sodium hydroxide aqueous solution (concentration of sodium hydroxide: 0.36% by mass) were added dropwise into the flask over 6 h. While dropping, the resulting reaction mixture was withdrawn from the flask at a rate 1.4 times the dropping rate, and introduced into a dropping funnel (separator) to separate the reaction mixture into an organic layer and a water layer. The water layer separated as a lower layer of the reaction mixture was returned to the flask. Whereas, the organic layer separated as an upper layer of the reaction mixture was collected every one hour, and each part of the organic layer collected every one hour was subjected to gas chromatography. After completion of the dropping, the reaction mixture in the flask was separated into the respective layers, and each of the thus separated organic and water layers was analyzed by gas chromatography. As a result, it was confirmed that the organic layer contained 3.06 g (0.036 mol) of valeraldehyde, 106.5 g (0.63 mol) of 2-(1-hydroxy-n-pentyl)cyclopentanone and 2.13 g (0.014 mol) of pentylidene cyclopentanone (conversion rate of valeraldehyde: 95.0%; yield: 89.9%). were added dropwise into the flask over 6 h the resulting reaction mixture was withdrawn from the flask at a rate 1.4 times the dropping rate introduced into a dropping funnel (separator) to separate the reaction mixture into an organic layer The water layer separated as a lower layer of the reaction mixture Whereas, the organic layer separated as an upper layer of the reaction mixture was collected every one hour each part of the organic layer collected every one hour After completion of the dropping, the reaction mixture in the flask was separated into the respective layers

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

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

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 100 ml-volume three-way-cocked eggplant type flask whose atmosphere had been displaced with nitrogen was charged 735 mg (0.66 mmole) of [RuI(p-cymene)((+]-BINAP)]I, and 2.5 g (16 mmole) of 2-pentylidenecyclopentanone and 50 ml of methylene chloride were added thereto to form a solution. The solution was put in a 100 ml autoclave having been displaced with nitrogen and stirred at 50° C. under a hydrogen pressure of 60 kg/cm2 for 113 hours to conduct a hydrogenation reaction. The solvent was removed from the reaction mixture by distillation, and the residue was purified by silica gel column chromatography using a mixed solvent of diethyl ether and hexane (1:4 by volume) as an eluent to obtain 1.7 g (percent yield 67%) of 2-pentylcyclopentanone. were added to form a solution a hydrogenation reaction The solvent was removed from the reaction mixture by distillation the residue was purified by silica gel column chromatography

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 100 ml-volume three-way-cocked eggplant type flask whose atmosphere had been displaced with nitrogen was charged 230 mg (0.14 mmole) of Ru2Cl4 ((+)-BINAP)2 (NEt3), and 5 g (32 mmole) of 2-pentylidenecyclopentanone and 50 ml of methanol were added thereto to form a solution. The solution was put in a 100 ml autoclave having been displaced with nitrogen and stirred at 50° C. under a hydrogen pressure of 90 kg/cm2 for 110 hours to conduct a hydrogenation reaction. The solvent was removed from the reaction mixture by distillation, and the residue was purified by silica gel column chromatography using a mixed solvent of diethyl ether and hexane (1:4 by volume) as an eluent to obtain 4.6 g (percent yield: 92%) of 2-pentylcyclopentanone. were added to form a solution a hydrogenation reaction The solvent was removed from the reaction mixture by distillation the residue was purified by silica gel column chromatography

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 100 ml-volume three-way-cocked eggplant type flask whose atmosphere had been displaced with nitrogen was charged 270 mg (0.16 mmole) of Ru2Cl4 ((+)-BINAP)2 (NEt3), and 5 g (32 mmole) of 2-pentylidenecyclopentanone and 50 ml of methylene chloride were added thereto to form a solution. The solution was put in a 100 ml autoclave having been displaced with nitrogen and stirred at 50° C. under a hydrogen pressure of 60 kg/cm2 for 20 hours to conduct a hydrogenation reaction. The solvent was removed from the reaction mixture by distillation, and the residue was purified by silica gel column chromatography using a mixed solvent of diethyl ether and hexane (1:4 by volume) as an eluent to obtain 5 g (percent yield: 100%) of 2-pentylcyclopentanone as a clear yellow liquid. were added to form a solution a hydrogenation reaction The solvent was removed from the reaction mixture by distillation the residue was purified by silica gel column chromatography

Conditions: temp:27.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 3-L reaction flask was charged with cyclopentanone (500 g, 6 mol), water (H2O) (500 mL) and sodium hydroxide (NaOH) (10 g, 0.25 mol). Valeraldehyde (430 g, 5 mol) was fed into the reaction flask over 3 hours while the temperature was maintained at 25-30° C. After the feeding was completed, the reaction was aged for 2 hours and neutralized with hydrochloric acid (HCl) (30 g, 0.3 mol) while the temperature was maintained at 25-30° C. The reaction mass was further aged for 2 hours. The organic layer was separated and washed with saturated aqueous sodium bicarbonate (NaHCO3) (200 mL). The obtained crude product was fractionated to provide 2-pentylidene-cyclopentanone (523 g) having a boiling point of 122° C. at 3 mmHg A 1-L zipper autoclave was charged with 2-pentylidine cyclopentanone (523 g) and palladium on carbon (Pd/C) (2 g). The autoclave was purged three times with nitrogen followed by three times with hydrogen. The autoclave agitator was then turned on to 1500 rpm and the pressure was set to 100 psi. The reaction was allowed to exotherm to about 120° C. and maintained at this temperature for 2 hours. The autoclave was cooled to an ambient temperature. The hydrogen was then vented and the autoclave was subsequently purged three times with nitrogen. The Pd/C was removed by filtration through Celite®. The crude product 2-pentyl-cyclopentanone (520 g) was obtained and used in following steps without further purification. was maintained at 25-30° C The reaction mass was further aged for 2 hours The organic layer was separated washed with saturated aqueous sodium bicarbonate (NaHCO3) (200 mL) The obtained crude product