1-methoxycyclohexene

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: The compound 14 (166 mg, 0.5 mmol), 1-methoxycyclohexene (280 mg, 2.50 mmol) and p-toluenesulfonic acid pyridinium (132 mg, 0.505 mmol) was dissolved in toluene (4 mL). The reaction mixture was stirred at room temperature for 20 hours. Benzene (60 mL) was added thereto, the reaction mixture was heated under reflux over 45 minutes and concentrated to a small amount. A drop of triethylamine was added to the reaction mixture, and the mixture was filtered to remove the insoluble matter. The filtrate was concentrated under reduced pressure. The residue was extracted with hexane, and filtered off the insoluble matter. The filtrate was purified by chromatography on an alumina column (eluate: toluene) to give the compound 17 (61 mg, 30%) as crystals. Mp 69-71° C. Rf 0.57 (Al2O3 60, Type E, toluene). the reaction mixture was heated under reflux over 45 minutes concentrated to a small amount A drop of triethylamine was added to the reaction mixture the mixture was filtered to remove the insoluble matter The filtrate was concentrated under reduced pressure The residue was extracted with hexane filtered off the insoluble matter The filtrate was purified by chromatography on an alumina column (eluate: toluene)

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

Procedure: To a solution of 5-(3,5-dichlorophenylthio)-4-isopropyl-1-methyl-2-hydroxymethyl-1H-imidazole (14) (33 mg, 0.1 mmol) prepared in accordance with the method as described in WO 96/10019 and p-toluenesulfonic acid pyridinium (27.6 mg, 0.11 mmol) in toluene (1.5 mL) was added 1-methoxycyclohexene (112 mg, 1.00 mmol) under ice-cooling, and stirred at room temperature for 6 hours. A drop of triethylamine was added to the reaction mixture, and the mixture was filtered to remove the insoluble matter. The filtrate was concentrated under reduced pressure. The residue was purified by chromatography on an alumina column (eluate: toluene) to give the compound 15 (37.0 mg, 70%) as oil. Rf 0.16 (Al2O3 60, Type E, toluene). cooling the mixture was filtered to remove the insoluble matter The filtrate was concentrated under reduced pressure The residue was purified by chromatography on an alumina column (eluate: toluene)

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

Procedure: A solution of the compound 1 (33.4 mg, 0.1 mmol) and p-toluenesulfonic acid hydrate (20.0 mg, 0.105 mmol) in a mixture of methylene chloride (1 mL) - toluene (0.1 mL) was concentrated under reduced pressure. The residue was dissolved in a mixture of dioxane (2 mL) - benzene (0.5 mL), to which was added 1-methoxycyclohexene (112 mg, 1.00 mmol). The reaction mixture was heated under reflux, and concentrated to a small volume over 1 hour. A drop of triethylamine was added to the reaction mixture, and the mixture was concentrated under reduced pressure. Hexane was added to the residue, the mixture was filtered to remove the insoluble matter, and the filtrate was purified by chromatography on an alumina column (eluate: hexane - ethyl acetate (2:1)) to give the same compound 6 (31 mg, 75%) as oil. Rf 0.62 (Al2O3 60, Type E, 2:1 hexane -EtOAc). was concentrated under reduced pressure The residue was dissolved in a mixture of dioxane (2 mL) - benzene (0.5 mL), to which The reaction mixture was heated under reflux concentrated to a small volume over 1 hour A drop of triethylamine was added to the reaction mixture the mixture was concentrated under reduced pressure Hexane was added to the residue the mixture was filtered to remove the insoluble matter the filtrate was purified by chromatography on an alumina column (eluate: hexane - ethyl acetate (2:1))

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

Procedure: The compound 1 (502 mg, 1.50 mmol) was converted to the acetal with 1-methoxycyclohexene (1.68 g, 15.0 mmol) in the same manner as the example 2 to give the compound 3 (502 mg, 72%).

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

Procedure: 1,1-Dimethoxy-2-nitrosocyclohexane dimer was prepared as described in Example 1 from 1-methoxycyclohexene (46.8 g., 0.417 mole), methyl nitrite (30.6 g., 0.501 mole) and boron trifluoride-etherate (0.25 ml., 0.28 g., 2.0 × 10-3 mole) in 250 ml. of sulfur dioxide. The crude nitroso dimer, 76.0 g. of a gummy yellow-green solid still containing traces of sulfur dioxide, was obtained by the method described earlier. Without purification, the dimer was subjected to isomerizing conditions in methanol/sodium methoxide solution. Filtration through celite (to remove colloidal solids that had formed) and evaporation afforded 66.0 g. of an off-white slightly moist solid. Recrystallization from 180 ml. of ether at -70° C. gave 26.8 g. (37.2%) of 1,1-dimethoxy-2-oximinocyclohexane as colorless fine needles, m.p. 112°-116° C. An additional 2.9 g. (4.0%) of slightly impure oxime was obtained from the mother liquor as a white powder, m.p. 105°-112° C.

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: 1.4 g of the above obtained polymer was dissolved in 18.9 g of PGMEA in a round bottom flask. To the polymer solution approximately 40 mg of p-toluenesulfonic acid was added. After the acid was dissolved, 1.7 g of 1-methoxycyclohexene, 1.1 g of 2-methoxypropene and 0.5 g of dihydropyrane were added to the solution. The reaction was carried out at room temperature for a few days until the solution was clear. The reaction was then quenched with 5 g of basic active aluminum oxide. The quenched solution was filtered through 0.2 μm filter into a glass bottle. After the acid was dissolved The reaction was carried out at room temperature for a few days until the solution The reaction was then quenched with 5 g of basic active aluminum oxide The quenched solution was filtered through 0.2 μm filter into a glass bottle

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

Procedure: 1,1-Dimethoxy-2-nitrosocyclohexane dimer was prepared as described in Example 1 from 1-methoxycyclohexene (46.8 g., 0.417 mole), methyl nitrite (30.6 g., 0.501 mole) and boron trifluoride-etherate (0.25 ml., 0.28 g., 2.0×10-3 mole) in 250 ml. of sulfur dioxide. The crude nitroso dimer, 76.0 g. of a gummy yellow-green solid still containing traces of sulfur dioxide, was obtained by the method described earlier. Without purification, the dimer was subjected to isomerizing conditions in methanol/sodium methoxide solution. Filtration through celite (to remove colloidal solids that had formed) and evaporation afforded 66.0 g. of an off-white slightly moist solid. Recrystallization from 180 ml. of ether at -70° C. gave 26.8 g. (37.2%) of 1,1-dimethoxy-2-oximinocyclohexane as colorless fine needles, m.p. 112°-116° C. An additional 2.9 g. (4.0%) of slightly impure oxime was obtained from the mother liquor as a white powder, m.p. 105°-112° C.

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

Procedure: The compound 14 (166 mg, 0.5 mmol), 1-methoxycyclohexene (280 mg, 2.50 mmol) and p-toluenesulfonic acid pyridinium (132 mg, 0.505 mmol) was dissolved in toluene (4 mL). The reaction mixture was stirred at room temperature for 20 hours. Benzene (60 mL) was added thereto, the reaction mixture was heated under reflux over 45 minutes and concentrated to a small amount. A drop of triethylamine was added to the reaction mixture, and the mixture was filtered to remove the insoluble matter. The filtrate was concentrated under reduced pressure. The residue was extracted with hexane, and filtered off the insoluble matter. The filtrate was purified by chromatography on an alumina column (eluate: toluene) to give the compound 17 (61 mg, 30%) as crystals. Mp 69-71° C. Rf 0.57 (Al2O3 60, Type E, toluene). the reaction mixture was heated under reflux over 45 minutes concentrated to a small amount A drop of triethylamine was added to the reaction mixture the mixture was filtered to remove the insoluble matter The filtrate was concentrated under reduced pressure The residue was extracted with hexane filtered off the insoluble matter The filtrate was purified by chromatography on an alumina column (eluate: toluene)