(E)-5-phenylpent-4-en-1-ol

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of 4 g of benzyltriphenylphosphonium chloride in 20 ml of tetrahydrofuran was added 7.07 ml of 1.6M hexane solution of n-butyl lithium under cooling at 0° C. After stirring at room temperature for 30 minutes, 1 g of 2-hydroxytetrahydrofuran was added, followed by stirring at room temperature for 16 hours. Subsequently, after refluxing for 2 hours, insolubles were filtered off and the solvent was distilled off. The residue was purified by silica gel column chromatography (solvent: hexane-ethyl acetate=2:1) to give 2 g of (E)-5-phenyl-4-penten-1-ol as a colorless oily substance. by stirring at room temperature for 16 hours Subsequently, after refluxing for 2 hours insolubles were filtered off the solvent was distilled off The residue was purified by silica gel column chromatography (solvent: hexane-ethyl acetate=2:1)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of 4 g of benzyltriphenylphosphonium chloride in 20 ml of tetrahydrofuran was added 7.07 ml of 1.6M hexane solution of n-butyl lithium under cooling at 0° C. After stirring at room temperature for 30 minutes, 1 g of 2-hydroxytetrahydrofuran was added, followed by stirring at room temperature for 16 hours. Subsequently, after refluxing for 2 hours, insolubles were filtered off and the solvent was distilled off. The residue was purified by silica gel column chromatography (solvent: hexane-ethyl acetate=2:1) to give 2 g of (E)-5-phenyl-4-penten-1-ol as a colorless oily substance. by stirring at room temperature for 16 hours Subsequently, after refluxing for 2 hours insolubles were filtered off the solvent was distilled off The residue was purified by silica gel column chromatography (solvent: hexane-ethyl acetate=2:1)

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

Procedure: Magnesium (a) (12.5 g) was flame dried in a 250 ml 3-necked flask equipped with mechanical stirrer, reflux condenser, and addition funnel. The magnesium was covered with 52 ml of dry tetrahydrofuran (b) and reaction was initiated by the addition of ca. 0.5 ml of ethylene dibromide under a nitrogen atomosphere. To the stirred mixture was added 30.9 g of 2-bromopropene (c) dropwise at a rate which maintained reflux without external heating. After the addition, the Grignard solution was stirred until it had cooled to room temperature (0.5-1 hour) and then cooled to -15°. Then 27.35 g of trans-5-phenyl-4-pentenal (d) was added dropwise over 15 minutes. After the resultant green mixture was stirred at room temperature for 2 hours, 130 ml of a saturated solution of ammonium chloride was added followed by 200 ml of water. The layers were separated and the aqueous portion extracted with ether (3×200 ml). The organic layer were worked up in the usual manner to give after evaporation, the alcohol as an orange liquid (33 g). TLC; silica gel HF254 ; ethyl acetate/benzene 2:8 Rf 0.45. dried in a 250 ml 3-necked flask equipped with mechanical stirrer reflux condenser, and addition funnel The magnesium was covered with 52 ml of dry tetrahydrofuran (b) and reaction maintained reflux without external heating After the addition cooled to -15° After the resultant green mixture was stirred at room temperature for 2 hours The layers were separated the aqueous portion extracted with ether (3×200 ml) to give after evaporation

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

Procedure: To a dry 3 liter 3-necked flask equipped with mechanical stirrer, thermometer and nitrogen inlet was added 1.5 liter of dry dichloromethane (a) and 95 g of dry pyridine (b). The stirred solution was cooled ot an internal temperature of 5° and 60 g of chromium trioxide (c) was added in one portion. The mixture was stirred an additional 5 minutes and then allowed to warm to 20° over 60 minutes, giving a solution of Collins reagent. A solution of 16.2 g of trans-5-phenyl-4-penten-1-ol (d) in 100 ml of dry dichloromethane (e) was then added rapidly. The mixture was stirred an additional 15 minutes and then decanted from the residue. The residue, a black tar, was washed with ether (3×500 ml) and the combined organic solution was worked up in the usual manner. Evaporation of the solvent gave the aldehyde (15 g) as a pale yellow liquid. TLC; silica gel HF254 ; ethyl acetate/benzene 1:9 Rf 0.50. decanted from the residue The residue, a black tar, was washed with ether (3×500 ml) Evaporation of the solvent

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

Procedure: Into a flask fitted with dropping funnel, mechanical stirrer and reflux condenser with nitrogen inlet was introduced 2 ml of dry xylene (a) and 69 g (3.0 g-atom) of sodium (b). The xylene was heated until the metal softened, the heating mantel removed, the flask briskly shaken to divide the sodium into sand-like particles and the flask allowed to cool. The xylene was removed and the sodium sand washed with dry ether (3×100 ml) and the finely divided metal residue covered with 1.2 liters of dry ether (c). To the rapidly stirred suspension was added 256 g (1.3 mole) of 3-chloro-2-phenyltetrahydropyran (e) in 20 ml of ether (f). The addition was dropwise until the reaction began, as evidenced by a blue color and the remainder of the halide was added over 90 minutes. The resulting gray slurry was stirred, refluxed after one hour of addition, with the color changing to cream color and the reaction vessel then cooled in an ice bath and with rapid stirred 40 ml of ethanol followed by 9 ml of water were added cautiously. After separation of the layers, the aqueous phase was extracted with ether (3×200 ml), the combined ethereal fractions washed with brine (200 ml) and dried over potassium carbonate. In vacuo removal of solvent left 219 g of a red liquid which was fractionally distilled and the fraction boiling at 94°-95°/0.18 mm Hg collected providing 61.5 g (29% yield). Into a flask fitted reflux condenser with nitrogen inlet the heating mantel removed to cool The xylene was removed the sodium sand washed with dry ether (3×100 ml) The addition The resulting gray slurry was stirred refluxed after one hour of addition, with the color the reaction vessel then cooled in an ice bath were added cautiously After separation of the layers the aqueous phase was extracted with ether (3×200 ml) the combined ethereal fractions washed with brine (200 ml) dried over potassium carbonate In vacuo removal of solvent left 219 g of a red liquid which was fractionally distilled the fraction boiling at 94°-95°/0.18 mm Hg collected providing 61.5 g (29% yield)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of 4 g of benzyltriphenylphosphonium chloride in 20 ml of tetrahydrofuran was added 7.07 ml of 1.6M hexane solution of n-butyl lithium under cooling at 0° C. After stirring at room temperature for 30 minutes, 1 g of 2-hydroxytetrahydrofuran was added, followed by stirring at room temperature for 16 hours. Subsequently, after refluxing for 2 hours, insolubles were filtered off and the solvent was distilled off. The residue was purified by silica gel column chromatography (solvent: hexane-ethyl acetate=2:1) to give 2 g of (E)-5-phenyl-4-penten-1-ol as a colorless oily substance. by stirring at room temperature for 16 hours Subsequently, after refluxing for 2 hours insolubles were filtered off the solvent was distilled off The residue was purified by silica gel column chromatography (solvent: hexane-ethyl acetate=2:1)