cyclooctane

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: An 11.0-g (0.1 mol) sample of cyclooctane was added dropwise at 0°C. to a solution of 0.1 mol N-chlorothio-N-methyl-N'-(3,4-dichlorophenyl) urea, prepared by a procedure similar to that of Example 3, in methylene dichloride. After the addition was completed, the reaction mixture was washed successively with water, aqueous sodium bicarbonate solution and water, dried over magnesium sulfate and evaporated to give a solid residue. The solid was recrystallized from isopropyl alcohol and washed with hexane to give 15 g of product, m.p. 90°-91°C. Elemental analysis for C16H21Cl3N2OS showed: %S, calc. 8.1, found 8.2; %Cl, calc. 26.9, found 27.4. prepared by a procedure similar to that of Example 3 After the addition the reaction mixture was washed successively with water, aqueous sodium bicarbonate solution and water dried over magnesium sulfate evaporated to give a solid residue The solid was recrystallized from isopropyl alcohol washed with hexane

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

Procedure: An 11.0-g (0.1 mol) sample of cyclooctane was added dropwise at 0°C. to a solution of 0.1 mol N-chlorothio-N-methyl-N'-(3,4-dichlorophenyl) urea, prepared by a procedure similar to that of Example 3, in methylene dichloride. After the addition was completed, the reaction mixture was washed successively with water, aqueous sodium bicarbonate solution and water, dried over magnesium sulfate and evaporated to give a solid residue. The solid was recrystallized from isopropyl alcohol and washed with hexane to give 15 g of product, m.p. 90°-91°C. Elemental analysis for C16H21Cl3N2OS showed: %S, calc. 8.1, found 8.2; %Cl, calc. 26.9, found 27.4. prepared by a procedure similar to that of Example 3 After the addition the reaction mixture was washed successively with water, aqueous sodium bicarbonate solution and water dried over magnesium sulfate evaporated to give a solid residue The solid was recrystallized from isopropyl alcohol washed with hexane

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

Procedure: The experimental procedure was substantially the same as in Example 1 except that the amount of benzene as the starting hydrocarbon compound was decreased to 12 ml while 13.8 ml of isopropyl alcohol were replaced with 18 ml of cyclooctane as the hydrogen donor compound. The result of the analysis of the reaction mixture after completion of the reaction was that the molar yields of benzyl alcohol, benzaldehyde and biphenyl were 6624%, 350% and 8%, respectively, based on the molar amount of the rhodium complex used as the catalyst. Small amounts of cyclooctane carbaldehyde and cyclooctanemethanol were detected in the reaction mixture. The result of the analysis of the reaction mixture after completion of the reaction

Conditions: temp:-15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 1 L flask is charged with 2-(5-bromo-3-hydroxy-2-oxo-2,3-dihydro-1H-indol-3-yl)-N,N-dimethyl-acetamide (Reference Example 1) (31.2 g, 0.1 mol), sodium borohydride (11.8 g 96%, 0.3 mol), and 250 mL of dimethoxyethanol (DME). The mixture is cooled to −15° C., and to the stirred suspension, BF3-etherate (56.6 g, 0.4 mol) is added dropwise. The temperature is maintained between −15 and −10° C. during the exothermic addition. The mixture is then allowed to warm slowly to ambient temperature (25-27° C.), and left stirring over night. The mixture is cooled with an ice bath and quenched by the addition of 4N NaOH (200 mL). The formed viscous emulsion is heated to 80° C. for 30 minutes, then diazabicyclo[2.2.2]cyclooctane (DABCO) (12.7 g 97%, 0.11 mol) is added, and then the mixture is heated for two additional hours under reflux. After cooling to ambient temperature, the aqueous layer is removed and the organic layer is extracted twice with each 50 mL of a 4 N NaOH.solution. After re-extraction of the combined inorganic layers with toluene (150 mL), the aqueous phase is disposed off, and the toluene layer is added back into the reaction vessel. To the vessel, additional toluene (150 mL) is added and the mixture is then extracted with water (200 mL). The aqueous layer is separated, and extracted twice with each 150 mL of toluene. After disposal of the inorganic the combined toluene layers are extracted for three times with water (300 mL, 2×150 mL), and the aqueous layer is again discarded. The toluene layer is then extracted twice with 4N HCl (100 mL and 50 mL). Using the combined acidic extracts, the pH is then adjusted to 14 by the addition of 4 N NaOH. Then the aqueous layer is extracted twice with tert-butyl methyl ether TBME (150 mL and 50 mL), and the combined extracts are washed with brine (50 mL) and then transferred into a 500 mL flask. To the stirred TBME solution, MnO2 (34.8 g, 0.4 mol) is then added, and temporarily the temperature rises to 40° C. After one hour the aniline by-product has been converted completely, and then the MnO2 is filtered off. Removal of the solvent from the filtrate gives the title product as a colourless viscous oil which crystallizes (23.85 g, 85%), mp=95-96° C. The temperature is maintained between −15 and −10° C. during the exothermic addition to warm slowly to ambient temperature (25-27° C.) left The mixture is cooled with an ice bath quenched by the addition of 4N NaOH (200 mL) The formed viscous emulsion is heated to 80° C. for 30 minutes the mixture is heated for two additional hours under reflux After cooling to ambient temperature the aqueous layer is removed the organic layer is extracted twice with each 50 mL of a 4 N NaOH After re-extraction of the combined inorganic layers with toluene (150 mL) the toluene layer is added back into the reaction vessel To the vessel, additional toluene (150 mL) is added the mixture is then extracted with water (200 mL) The aqueous layer is separated extracted twice with each 150 mL of toluene After disposal of the inorganic the combined toluene layers are extracted for three times with water (300 mL, 2×150 mL) The toluene layer is then extracted twice with 4N HCl (100 mL and 50 mL) the pH is then adjusted to 14 by the addition of 4 N NaOH Then the aqueous layer is extracted twice with tert-butyl methyl ether TBME (150 mL and 50 mL) the combined extracts are washed with brine (50 mL) transferred into a 500 mL flask rises to 40° C the MnO2 is filtered off Removal of the solvent from the filtrate

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

Procedure: An 11.0-g (0.1 mol) sample of cyclooctane was added dropwise at 0°C. to a solution of 0.1 mol N-chlorothio-N-methyl-N'-(3,4-dichlorophenyl) urea, prepared by a procedure similar to that of Example 3, in methylene dichloride. After the addition was completed, the reaction mixture was washed successively with water, aqueous sodium bicarbonate solution and water, dried over magnesium sulfate and evaporated to give a solid residue. The solid was recrystallized from isopropyl alcohol and washed with hexane to give 15 g of product, m.p. 90°-91°C. Elemental analysis for C16H21Cl3N2OS showed: %S, calc. 8.1, found 8.2; %Cl, calc. 26.9, found 27.4. prepared by a procedure similar to that of Example 3 After the addition the reaction mixture was washed successively with water, aqueous sodium bicarbonate solution and water dried over magnesium sulfate evaporated to give a solid residue The solid was recrystallized from isopropyl alcohol washed with hexane

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

Procedure: The title compound is prepared from 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol and cyclooctane following a procedure to that of Example 5.

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

Procedure: 2 mmol of N-hydroxyphthalimide and 4 mmol of di-tert-butyl peroxide are added at a temperature of 130° C. to 200 mmol of cyclooctane in a round-bottomed flask having an attached reflux condenser. Air at approximately 15 l/h is passed through the reaction mixture for 8 hours at said temperature. Cyclooctanol is obtained at a selectivity of 15% and cyclooctanone at a selectivity of 43%, at a cyclooctane conversion rate of 51%. an attached reflux condenser

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

Procedure: 2 mmol of N-hydroxyphthalimide and 4 mmol of cumene hydroperoxide are added at a temperature of 130° C. to 200 mmol of cyclooctane in a round-bottomed flask having an attached reflux condenser. Oxygen at approximately 15 l/h is passed through the reaction mixture for 8 hours at said temperature. Cyclooctanol is obtained at a selectivity of 17% and cyclooctanone at a selectivity of 46%, at a cyclooctcane conversion rate of 53%. an attached reflux condenser

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: The title compound is prepared from 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol and cyclooctane following a procedure to that of Example 5.

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

Procedure: 2 mmol of N-hydroxyphthalimide and 4 mmol of di-tert-butyl peroxide are added at a temperature of 130° C. to 200 mmol of cyclooctane in a round-bottomed flask having an attached reflux condenser. Air at approximately 15 l/h is passed through the reaction mixture for 8 hours at said temperature. Cyclooctanol is obtained at a selectivity of 15% and cyclooctanone at a selectivity of 43%, at a cyclooctane conversion rate of 51%. an attached reflux condenser