1-methylcyclopentene

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

Procedure: To a magnetically stirred solution of 22.3 g (0.1 mol) N-Cbz-D-alanine in 50 mls of dry dichloromethane containing 0.5 mls of concentrated sulfuric acid at 0° C., was added dropwise a 10 g (0.1 mol) sample of 1-methylcyclopentene in 50 mls of dichloromethane. After 5 days of stirring at room temperature, the mixture was heated to reflux for 4 hours, after which the reaction was cooled to room temperature, washed with 100 mls of saturated NaHCO3, 100 mls of water and dried over MgSO4. Filtration followed by evaporation of the solvent yielded 1.81 g of the product. NMR(CDCl3): δ1.3-1.4 (d, 3H), 1.5 (s, 3H), 1.5-1.7 (m, 8H), 4.2 (m, 1H), 5.05 (s, 2H), 5.25 (m, 1H), 7.3 (s, 5H). the mixture was heated to reflux for 4 hours after which the reaction was cooled to room temperature washed with 100 mls of saturated NaHCO3, 100 mls of water dried over MgSO4 Filtration followed by evaporation of the solvent

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

Procedure: To a magnetically stirred solution of 22.3 g (0.1 mol) N-Cbz-D-alanine in 50 mls of dry dichloromethane containing 0.5 mls of concentrated sulfuric acid at 0° C., was added dropwise a 10 g (0.1 mol) sample of 1-methylcyclopentene in 50 mls of dichloromethane. After 5 days of stirring at room temperature, the mixture was heated to reflux for 4 hours, after which the reaction was cooled to room temperature, washed with 100 mls of saturated NaHCO3, 100 mls of water and dried over MgSO4. Filtration followed by evaporation of the solvent yielded 1.81 g of the product. NMR(CDCl3): δ1.3-1.4(d, 3H), 1.5(s, 3H), 1.5-1.7 (m, 8H), 4.2 (m, 1H), 5.05 (s, 2H), 5.25 (m, 1H), 7.3 (s, 5H). the mixture was heated to reflux for 4 hours after which the reaction was cooled to room temperature washed with 100 mls of saturated NaHCO3, 100 mls of water dried over MgSO4 Filtration followed by evaporation of the solvent

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

Procedure: With respect to the manner of the hydration reaction, there is no particular limitation; the reaction can be performed in either of continuous and batchwise manners. The hydration reaction is generally performed as follows. Cyclohexene is added to a catalyst slurry comprising a hydration catalyst and water to effect hydration of cyclohexene in a suspension state to obtain a reaction mixture comprising an aqueous phase comprised of the catalyst slurry and an oil phase comprised of cyclohexanol produced and the cyclohexene remaining unreacted. The oil phase is phase-separated from the aqueous phase, and provided to a separation step. The aqueous phase containing the hydration catalyst can be recycled as the catalyst slurry to the reactor. In the hydration reaction, a small amount of methylcyclopentene is generally formed as a by-product as well as cyclohexanol as the desired intermediate. The oil phase, which contains the cyclohexanol, the methylcyclopentene and the cyclohexene, is separated into a high boiling point component containing cyclohexanol and a low boiling point component containing cyclohexene by a customary method, such as distillation. If desired, the separated cyclohexanol can be further subjected to treatment for isolation, thereby obtaining a cyclohexanol having a desired purity. In such a case, it is preferred that the obtained cyclohexanol has a purity of 99% or more. In general, it is preferred that the unreacted cyclohexene which is separated from cyclohexanol is subjected to treatment for isolation so as to obtain cyclohexene having a desired purity, followed by recycling thereof to the reactor. With respect to the manner of the hydration reaction, there the reaction The hydration reaction to obtain a reaction mixture produced The oil phase is phase-separated from the aqueous phase provided to a separation step The aqueous phase containing the hydration catalyst In the hydration reaction

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

Procedure: To a magnetically stirred solution of 22.3 g (0.1 mol) N-Cbz-D-alanine in 50 mls of dry dichloromethane containing 0.5 mls of concentrated sulfuric acid at 0° C., was added dropwise a 10 g (0.1 mol) sample of 1-methylcyclopentene in 50 mls of dichloromethane. After 5 days of stirring at room temperature, the mixture was heated to reflux for 4 hours, after which the reaction was cooled to room temperature, washed with 100 mls of saturated NaHCO3, 100 mls of water and dried over MgSO4. Filtration followed by evaporation of the solvent yielded 1.81 g of the product. NMR(CDCl3): δ1.3-1.4(d, 3H), 1.5(s, 3H), 1.5-1.7 (m, 8H), 4.2 (m, 1H), 5.05 (s, 2H), 5.25 (m, 1H), 7.3 (s, 5H). the mixture was heated to reflux for 4 hours after which the reaction was cooled to room temperature washed with 100 mls of saturated NaHCO3, 100 mls of water dried over MgSO4 Filtration followed by evaporation of the solvent

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

Procedure: With respect to the manner of the hydration reaction, there is no particular limitation; the reaction can be performed in either of continuous and batchwise manners. The hydration reaction is generally performed as follows. Cyclohexene is added to a catalyst slurry comprising a hydration catalyst and water to effect hydration of cyclohexene in a suspension state to obtain a reaction mixture comprising an aqueous phase comprised of the catalyst slurry and an oil phase comprised of cyclohexanol produced and the cyclohexene remaining unreacted. The oil phase is phase-separated from the aqueous phase, and provided to a separation step. The aqueous phase containing the hydration catalyst can be recycled as the catalyst slurry to the reactor. In the hydration reaction, a small amount of methylcyclopentene is generally formed as a by-product as well as cyclohexanol as the desired intermediate. The oil phase, which contains the cyclohexanol, the methylcyclopentene and the cyclohexene, is separated into a high boiling point component containing cyclohexanol and a low boiling point component containing cyclohexene by a customary method, such as distillation. If desired, the separated cyclohexanol can be further subjected to treatment for isolation, thereby obtaining a cyclohexanol having a desired purity. In such a case, it is preferred that the obtained cyclohexanol has a purity of 99% or more. In general, it is preferred that the unreacted cyclohexene which is separated from cyclohexanol is subjected to treatment for isolation so as to obtain cyclohexene having a desired purity, followed by recycling thereof to the reactor. With respect to the manner of the hydration reaction, there the reaction The hydration reaction to obtain a reaction mixture produced The oil phase is phase-separated from the aqueous phase provided to a separation step The aqueous phase containing the hydration catalyst In the hydration reaction

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This reaction was performed with a solution of 0.1191 g (1.03 mmol) of N-hydroxysuccinimide, 2.0 g (24.3 mmol) of 1-methylcyclopentene and 0.1330 g (0.53 mmol) of cobalt acetate tetrahydrate in 40 ml of acetic acid was heated to 100° C. in a Parr Hastelloy reactor with temperature and pressure transducer. After the temperature reached 100° C., 745 psi of CO2 was introduced into the reactor, then 120 psi of O2 was added slowly to the reactor. The mixture was stirred under pressure for one hour at 100° C., then the pressure was released, and the mixture was cooled to room temperature. The solution was extracted with ethyl acetate then with a saturated NaCl solution in water and, dried over Na2SO4 to give, as the major 60% 5-ketohexanoic acid. reached 100° C. the mixture was cooled to room temperature The solution was extracted with ethyl acetate with a saturated NaCl solution in water and, dried over Na2SO4

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

Procedure: To a magnetically stirred solution of 22.3 g (0.1 mol) N-Cbz-D-alanine in 50 mls of dry dichloromethane containing 0.5 mls of concentrated sulfuric acid at 0° C., was added dropwise a 10 g (0.1 mol) sample of 1-methylcyclopentene in 50 mls of dichloromethane. After 5 days of stirring at room temperature, the mixture was heated to reflux for 4 hours, after which the reaction was cooled to room temperature, washed with 100 mls of saturated NaHCO3, 100 mls of water and dried over MgSO4. Filtration followed by evaporation of the solvent yielded 1.81 g of the product. the mixture was heated to reflux for 4 hours after which the reaction was cooled to room temperature washed with 100 mls of saturated NaHCO3, 100 mls of water dried over MgSO4 Filtration followed by evaporation of the solvent

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

Procedure: To a magnetically stirred solution of 22.3 g (0.1 mol) N-Cbz-D-alanine in 50 mls of dry dichloromethane containing 0.5 mls of concentrated sulfuric acid at 0° C., was added dropwise a 10 g (0.1 mol) sample of 1-methylcyclopentene in 50 mls of dichloromethane. After 5 days of stirring at room temperature, the mixture was heated to reflux for 4 hours, after which the reaction was cooled to room temperature, washed with 100 mls of saturated NaHCO3, 100 mls of water and dried over MgSO4. Filtration followed by evaporation of the solvent yielded 1.81 g of the product. the mixture was heated to reflux for 4 hours after which the reaction was cooled to room temperature washed with 100 mls of saturated NaHCO3, 100 mls of water dried over MgSO4 Filtration followed by evaporation of the solvent

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

Procedure: To a magnetically stirred solution of 22.3 g (0.1 mol) N-Cbz-D-alanine in 50 mls of dry dichloromethane containing 0.5 mls of concentrated sulfuric acid at 0° C., was added dropwise a 10 g (0.1 mol) sample of 1-methylcyclopentene in 50 mls of dichloromethane. After 5 days of stirring at room temperature, the mixture was heated to reflux for 4 hours, after which the reaction was cooled to room temperature, washed with 100 mls of saturated NaHCO3, 100 mls of water and dried over MgSO4. Filtration followed by evaporation of the solvent yielded 1.81 g of the product. the mixture was heated to reflux for 4 hours after which the reaction was cooled to room temperature washed with 100 mls of saturated NaHCO3, 100 mls of water dried over MgSO4 Filtration followed by evaporation of the solvent

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

Procedure: To a magnetically stirred solution of 22.3 g (0.1 mol) N-Cbz-D-alanine in 50 mls of dry dichloromethane containing 0.5 mls of concentrated sulfuric acid at 0° C., was added dropwise a 10 g (0.1 mol) sample of 1-methylcyclopentene in 50 mls of dichloromethane. After 5 days of stirring at room temperature, the mixture was heated to reflux for 4 hours, after which the reaction was cooled to room temperature, washed with 100 mls of saturated NaHCO3, 100 mls of water and dried over MgSO4. Filtration followed by evaporation of the solvent yielded 1.81 g of the product. the mixture was heated to reflux for 4 hours after which the reaction was cooled to room temperature washed with 100 mls of saturated NaHCO3, 100 mls of water dried over MgSO4 Filtration followed by evaporation of the solvent

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

Procedure: To a solution of 1-methylcyclopent-1-ene (CAS number 693-89-0; 38.5 mL, 365 mmol) in diethyl ether (220 ml) at 0° C. was added drop wise [(chlorosulfonyl)imino]methanone (CAS number 1189-71-5; 33.3 ml, 383 mmol). The reaction was then allowed to warm to room temperature and then heated to 36° C. for 72 hours. The reaction was then cooled to room temperature and a solution of sodium sulfite (73.5 g) in water (400 ml) was added drop wise, followed by the addition of 15% w/v potassium hydroxide (500 ml) to obtain pH 7-8. The phases were separated and aqueous phase was extracted with diethyl ether (2×200 ml). The combined organics were dried over magnesium sulfate and concentrated in vacuo to afford the title compound. heated to 36° C. for 72 hours The reaction was then cooled to room temperature followed by the addition of 15% to obtain pH 7-8 The phases were separated aqueous phase was extracted with diethyl ether (2×200 ml) The combined organics were dried over magnesium sulfate concentrated in vacuo

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 1-methylcyclopent-1-ene (CAS number 693-89-0; 50.0 g, 609.75 mmol) iii and sodium chloro(4-methylbenzenesulfonyl)azanide (CAS number 127-65-1; 192 g, 680.85 mmol) in THF (2500 ml) was added trimethylphenylammonium tribromide (13.3 g, 61.57 mmol). The reaction was stirred vigorously at 25° C. for 12 hours. The reaction mixture was poured into water (1500 ml) and the organics were extracted with ethyl acetate (3×1000 ml). The combined organics were washed with water (500 ml), brine (500 ml), dried over sodium sulfate and concentrated in vacuo. This was then purified by column chromatography (silica, 0-2.5% ethyl acetate/n-hexane) to afford the title compound. the organics were extracted with ethyl acetate (3×1000 ml) The combined organics were washed with water (500 ml), brine (500 ml) dried over sodium sulfate concentrated in vacuo This was then purified by column chromatography (silica, 0-2.5% ethyl acetate/n-hexane)