(3,7-dimethyl-8-oxoocta-2,6-dienyl) acetate

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 aldehyde 230a (19.5 g, 92.7 mmol) in 300 mL of tert-butyl alcohol was added 2-methyl-2-butene (98.0 mL, 925 mmol). To this was added a solution of sodium dihydrogen phosphate (44.5 g, 371 mmol) in 300 mL of water. Sodium chlorite (33.6 g, 371 mmol) was added in several portions. The resulting mixture was rapidly stirred overnight at room temperature. Ethyl acetate was added and the aqueous layer was acidified to pH 3 by addition of 1 M HCl. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate (3×200 mL). The combined organic extracts were washed with brine, dried over MgSO4, and reduced to dryness in vacuo. The crude product (27.4 g, 121 mmol, >100% yield) was used in the next step without further purification: The organic layer was separated the aqueous layer was extracted with ethyl acetate (3×200 mL) The combined organic extracts were washed with brine dried over MgSO4

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

Procedure: To a solution of aldehyde 230a (19.5 g, 92.7 mmol) in 300 mL of tert-butyl alcohol was added 2-methyl-2-butene (98.0 mL, 925 mmol). To this was added a solution of sodium dihydrogen phosphate (44.5 g, 371 mmol) in 300 mL of water. Sodium chlorite (33.6 g, 371 mmol) was added in several portions. The resulting mixture was rapidly stirred overnight at room temperature. Ethyl acetate was added and the aqueous layer was acidified to pH 3 by addition of 1 M HCl. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate (3×200 mL). The combined organic extracts were washed with brine, dried over MgSO4, and reduced to dryness in vacuo. The crude product (27.4 g, 121 mmol, >100% yield) was used in the next step without further purification: 1H NMR (500 MHz, CDCl3) δ: 6.84(t of q, J=7.25 Hz, J=1.50 Hz, 1H, ═CH), 5.34 (t of q, J=7.00 Hz, J=1.50 Hz, 1H, ═CH), 4.56 (d, J=7.00 Hz, 2H, —CH2O—), 2.31 (q, J=7.50 Hz, 2H, —CH2—), 2.15 (t, J=7.50 Hz, 2H, —CH2—), 2.03 (s, 3H, —CH3), 1.81 (s, 3H, —CH3), 1.70 (s, 3H, —CH3). LC/MS (ESI): m/z 249 [M+Na]+. The organic layer was separated the aqueous layer was extracted with ethyl acetate (3×200 mL) The combined organic extracts were washed with brine dried over MgSO4

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

Procedure: 2.36 g (9.41 mmols) of 6-chloro-3,7-dimethyl-2,7-octadienyl acetate (purity: 92%), 92 mg (0.93 mmols) of copper(I) chloride and 3.65 g (29.6 mmols) of triethylamine N-oxide (purity: 95%) were placed in a flask, to which 5 ml of dioxane was added, followed by agitation of the mixture at 50° C. for 10 hours. 40 ml of water was added to the reaction mixture, after which it was extracted twice each with 70 ml of diethyl ether. The resultant extract was successively washed with each 20 ml of 3% sulfuric acid, a saturated sodium hydrogen carbonate aqueous solution and a saturated ammonium chloride aqueous solution, and dried with magnesium sulfate. The solvent was distilled off from the solution and the resultant residue was purified by column chromatography using silica gel [eluent: ethyl acetate/hexane (ratio by volume)=1/9-1/3], thereby obtaining 1.21 g of 8-acetoxy-2,6-dimethyl-2,6-octadienal. Yield: 61%. The results of the instrumental analysis were found to be substantially coincident with those obtained in Example 9(b). was added after which it was extracted twice each with 70 ml of diethyl ether The resultant extract was successively washed with each 20 ml of 3% sulfuric acid a saturated sodium hydrogen carbonate aqueous solution and a saturated ammonium chloride aqueous solution, and dried with magnesium sulfate The solvent was distilled off from the solution the resultant residue was purified by column chromatography

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

Procedure: 1.15 g (3.99 mmols) of 6-chloro-3,7-dimethyl-2,7-octadienyl acetate (purity: 80%), 0.91 g (6 mmols) of sodium iodide and 1.36 g (10 mmols) of N-methylmorpholine N-oxide (monohydrate) were placed in a flask, to which was added 5 ml of N,N-dimethylformamide. The mixture was agitated at 50° C. for 4 hours. After completion of the reaction, 10 ml of water was added to the reaction mixture, followed by extraction twice each with 70 ml of diethyl ether. The resulting extract was washed with each 20 ml of 3% sulfuric acid, a saturated sodium hydrogen carbonate aqueous solution and a 10% sodium sulfite aqueous solution, and dried with magnesium sulfate. After drying, the solvent was removed by distillation from the solution and the resulting residue was purified by column chromatography using silica gel [eluent: ethyl acetate/hexane (volume by ratio)=1/9-1/3], thereby obtaining 0.627 g of 8-acetoxy-2,6-dimethyl-2,6-octadienal. Yield: 75%. The results of an instrumental analysis of the 8-acetoxy-2,6-dimethyl-2,6-octadienal are as follows. was added to the reaction mixture followed by extraction twice each with 70 ml of diethyl ether The resulting extract was washed with each 20 ml of 3% sulfuric acid a saturated sodium hydrogen carbonate aqueous solution and a 10% sodium sulfite aqueous solution, and dried with magnesium sulfate After drying the solvent was removed by distillation from the solution the resulting residue was purified by column chromatography