4-methylcyclohex-3-en-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:; See reaction.notes.procedure_details.

Procedure: To a 500 ml 3-neck, round-bottom flask were charged 37.5 g of 88% purity 4-methyl-3-cyclohexen-1-one, 100 ml of ether, 89.5 g of methyl iodide and 0.3 g of methyltrioctylammonium chloride. This mixture was stirred mechanically at ambient temperature and treated with 30 g of granular sodium hydroxide. After 20 minutes at gentle reflux (no cooling used), heat was applied to maintain the reflux for 2 hours longer. The cooled mixture was diluted with ether and treated with water to dissolve the suspended salts. The ether was separated and the aqueous layer was extracted with ether. The combined ether extracts were washed, dried, concentrated and Claisen-distilled to give 36.5 g of the desired product, b.p. 60° C. (10 mm). After 20 minutes at gentle reflux (no cooling heat to maintain the reflux for 2 hours longer to dissolve the suspended salts The ether was separated the aqueous layer was extracted with ether The combined ether extracts were washed dried concentrated Claisen-distilled

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

Procedure: To a 500 ml 3-neck, round-bottom flask were charged 37.5 g of 88% purity 4-methyl-3-cyclohexen-1-one, 100 ml of ether, 89.5 g of methyl iodide and 0.3 g of methyltrioctylammonium chloride. This mixture was stirred mechanically at ambient temperature and treated with 30 g of granular sodium hydroxide. After 20 minutes at gentle reflux (no cooling used), heat was applied to maintain the reflux for 2 hours longer. The cooled mixture was diluted with ether and treated with water to dissolve the suspended salts. The ether was separated and the aqueous layer was extracted with ether. The combined ether extracts were washed, dried, concentrated and Claisen-distilled to give 36.5 g of the desired product, b.p. 60° C. (10 mm). After 20 minutes at gentle reflux (no cooling heat to maintain the reflux for 2 hours longer to dissolve the suspended salts The ether was separated the aqueous layer was extracted with ether The combined ether extracts were washed dried concentrated Claisen-distilled

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

Procedure: To a stirred solution of the above (18) (6.1 g) in dry THF (100 mL) at -78° C. was added a solution of lithium bis-trimethylsilylamide (50 ml, 1N in THF). The solution was stirred for 20 min then benzylbromide (30 mL) was added in one portion. The reaction was stirred for 6 h at -78° C. then allowed to slowly warm to room temperature. After evaporation of the solvent, the remaining mixture was taken up in hexane, washed with saturated NaCl, dried over MgSO4 and evaporated. The product (19) was obtained by flash chromatography on silica gel eluted with 2.5% ethyl acetate in hexane. (4.15 g, 39%): GC RT 7.29 min. (HP 530 mμ×20 m methylsilicone column, He carrier flow rate 20 mL/min., 100° C., 1 min. , 100°-180° C. 10° C./min.; TLC Rf 0.31 (5% ethyl acetate, n-hexane); 1H NMR (CDCl3) δ1.73(3H, br s), 2.2-3.3(7H, m), 5.35(1H, br s), 7.28(5H, m). The reaction was stirred for 6 h at -78° C. After evaporation of the solvent washed with saturated NaCl dried over MgSO4 evaporated

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

Procedure: To a 500 ml 3-neck, round-bottom flask were charged 37.5 g of 88% purity 4-methyl-3-cyclohexen-1-one, 100 ml of ether, 89.5 g of methyl iodide and 0.3 g of methyltrioctylammonium chloride. This mixture was stirred mechanically at ambient temperature and treated with 30 g of granular sodium hydroxide. After 20 minutes at gentle reflux (no cooling used), heat was applied to maintain the reflux for 2 hours longer. The cooled mixture was diluted with ether and treated with water to dissolve the suspended salts. The ether was separated and the aqueous layer was extracted with ether. The combined ether extracts were washed, dried, concentrated and Claisen-distilled to give 36.5 g of the desired product, b.p. 60° C. (10 mm). After 20 minutes at gentle reflux (no cooling heat to maintain the reflux for 2 hours longer to dissolve the suspended salts The ether was separated the aqueous layer was extracted with ether The combined ether extracts were washed dried concentrated Claisen-distilled

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

Procedure: To a 500 ml 3-neck, round-bottom flask were charged 37.5 g of 88% purity 4-methyl-3-cyclohexen-1-one, 100 ml of ether, 89.5 g of methyl iodide and 0.3 g of methyltrioctylammonium chloride. This mixture was stirred mechanically at ambient temperature and treated with 30 g of granular sodium hydroxide. After 20 minutes at gentle reflux (no cooling used), heat was applied to maintain the reflux for 2 hours longer. The cooled mixture was diluted with ether and treated with water to dissolve the suspended salts. The ether was separated and the aqueous layer was extracted with ether. The combined ether extracts were washed, dried, concentrated and Claisen-distilled to give 36.5 g of the desired product, b.p. 60° C. (10 mm). After 20 minutes at gentle reflux (no cooling heat to maintain the reflux for 2 hours longer to dissolve the suspended salts The ether was separated the aqueous layer was extracted with ether The combined ether extracts were washed dried concentrated Claisen-distilled

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

Procedure: By procedures similar to those described in Embodiment 3, (+)-2-exo-hydroxy-1-methyl-7-oxabicyclo[2.2.1]heptane was prepared by treatment of 4-methyl-3-cyclohexen-1-one with sodium borohydride followed by epoxidation-cyclization and ether formation to yield the desired product, b.p. 100°-101° C. (0.2 mm).

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

Procedure: To a 500 ml 3-neck, round-bottom flask were charged 37.5 g of 88% purity 4-methyl-3-cyclohexen-1-one, 100 ml of ether, 89.5 g of methyl iodide and 0.3 g of methyltrioctylammonium chloride. This mixture was stirred mechanically at ambient temperature and treated with 30 g of granular sodium hydroxide. After 20 minutes at gentle reflux (no cooling used), heat was applied to maintain the reflux for 2 hours longer. The cooled mixture was diluted with ether and treated with water to dissolve the suspended salts. The ether was separated and the aqueous layer was extracted with ether. The combined ether extracts were washed, dried, concentrated and Claisen-distilled to give 36.5 g of the desired product, b.p. 60° C. (10 mm). After 20 minutes at gentle reflux (no cooling heat to maintain the reflux for 2 hours longer to dissolve the suspended salts The ether was separated the aqueous layer was extracted with ether The combined ether extracts were washed dried concentrated Claisen-distilled

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

Procedure: To a 500 ml 3-neck, round-bottom flask were charged 37.5 g of 88% purity 4-methyl-3-cyclohexen-1-one, 100 ml of ether, 89.5 g of methyl iodide and 0.3 g of "Aliquot 336" (methyltrioctylammonium chloride). This mixture was stirred mechanically at ambient temperature and treated with 30 g of granular sodium hydroxide. After 20 minutes at gentle reflux (no cooling used), heat was applied to maintain the reflux for 2 hours longer. The cooled mixture was diluted with ether and treated with water to dissolve the suspended salts. The ether was separated and the aqueous layer was extracted with ether. The combined ether extracts were washed, dried, concentrated and Claisen-distilled to give 36.5 g of the desired product, b.p. 60° C. (10 mm). After 20 minutes at gentle reflux (no cooling heat to maintain the reflux for 2 hours longer to dissolve the suspended salts The ether was separated the aqueous layer was extracted with ether The combined ether extracts were washed dried concentrated Claisen-distilled

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

Procedure: To a 500 ml 3-neck, round-bottom flask were charged 37.5 g of 88% purity 4-methyl-3-cyclohexen-1-one, 100 ml of ether, 89.5 g of methyl iodide and 0.3 g of methyltrioctylammonium chloride. This mixture was stirred mechanically at ambient temperature and treated with 30 g of granular sodium hydroxide. After 20 minutes at gentle reflux (no cooling used), heat was applied to maintain the reflux for 2 hours longer. The cooled mixture was diluted with ether and treated with water to dissolve the suspended salts. The ether was separated and the aqueous layer was extracted with ether. The combined ether extracts were washed, dried, concentrated and Claisen-distilled to give 36.5 g of the desired product, b.p. 60° C. (10 mm). After 20 minutes at gentle reflux (no cooling heat to maintain the reflux for 2 hours longer to dissolve the suspended salts The ether was separated the aqueous layer was extracted with ether The combined ether extracts were washed dried concentrated Claisen-distilled