hydroperoxycyclohexane

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

Procedure: Synthesize alkane oxidation catalyst in situ and oxidize alkane (cyclohexane) as follows. Add SiO2—C (3.3 mg, 0.6 groups/nm2) in acetonitrile (2 mL) and ([(C6H12N3R3)Mn2O3]Z2) (0.2 mM) to a container. The carboxylate group to Mn atom ratio is 0.50:1.0. Add o-dichlorobenzene (100 microliter (μL), 390 mmol) and cyclohexane (50 μL, 200 mmol) to the contents of container and maintain at 0° C. Add H2O2 (30 weight percent (wt %), 130 μL) to the contents of container. Seal the container and react to produce an alkane oxidation product (cyclohexanone (CyO), cyclohexanol (CyOH), and/or cyclohexyl hydroperoxide (Cy-OOH)). The concentrations of these species are determined as a function of time using gas chromatography and are shown in Table 1. Seal the container react

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

Procedure: reaction of the mixture obtained as fraction b4) and containing cyclohexyl hydroperoxide with cyclohexene in a mixture with cyclohexane at elevated temperature in the presence of transition-metal compounds from group 4 to 6 of the periodic table, to give an epoxidation mixture which essentially comprises cyclohexene oxide, cyclohexanol, cyclohexanone, cyclohexene, cyclohexane and catalyst and is separated by distillation in step b) together with the mixture from a). reaction of the mixture

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

Procedure: In step b), the cyclohexyl hydroperoxide-containing mixture from step a) and a cyclohexene oxide-containing epoxidation mixture which is produced in step c) and essentially comprises cyclohexanol, cyclohexanone, cyclohexene oxide, cyclohexene, cyclohexane and catalyst are jointly separated by distillation. The mixtures from step a) and step c) to be distilled are advantageously mixed before introduction into the column. On distillation, the following fractions are separated: containing epoxidation mixture which

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

Procedure: reaction of the mixture obtained as fraction b4) and containing cyclohexyl hydroperoxide with cyclohexene in a mixture with cyclohexane at elevated temperature in the presence of transition-metal compounds from group 4 to 6 of the periodic table, to give an epoxidation mixture which essentially comprises cyclohexene oxide, cyclohexanol, cyclohexanone, cyclohexene, cyclohexane and catalyst and is separated by distillation in step b) together with the mixture from a). reaction of the mixture

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

Procedure: A run was carried out in exactly the same manner as Run 10, except that the tertiary alcohol was cumenol and the tertiary hydroperoxide was cumene hydroperoxide. The mole ratio of cumenol to cyclohexane was 0.329:1 and the mole ratio of cumene hydroperoxide to cyclohexane was 0.086:1. A cyclohexyl hydroperoxide yield of 56 mole per cent, a cyclohexanol yield of 20 mole per cent, a cyclohexanone yield of 11 mole per cent and a residue of 13 mole per cent was obtained at a conversion level of 8.1 mole per cent and a per cent conversion rate of 5.8 per cent per hour. This run demonstrates that other tertiary alcohols and hydroperoxides are effective in the process of this invention.

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

Procedure: A run was carried out in exactly the same manner as Run 10, except that the tertiary alcohol was cumenol and the tertiary hydroperoxide was cumene hydroperoxide. The mole ratio of cumenol to cyclohexane was 0.329:1 and the mole ratio of cumene hydroperoxide to cyclohexane was 0.086:1. A cyclohexyl hydroperoxide yield of 56 mole percent, a cyclohexanol yield of 20 mole percent, a cyclohexanone yield of 11 mole percent and a residue of 13 mole percent was obtained at a conversion level of 8.1 mole percent and a percent conversion rate of 5.8 percent per hour. This run demonstrates that other tertiary alcohols and hydroperoxides are effective in the process of this invention.

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 350-ml autoclave made of stainless steel SUS 316 and equipped with a stirrer were placed 80 g (0.95 mol) of cyclohexane, 100 mg of N-hydroxyphthalimide, and 1.9 g of water (these formed a slurry at room temperature (25° C.)). The autoclave was hermetically sealed, pressurized to 3 MPa (gauge pressure) with a gaseous mixture of 50 percent by volume oxygen and 50 percent by volume nitrogen, and the mixture therein was stirred at 150° C. for 1 hour. As a result, 5.9 mmol of cyclohexane reacted (with a conversion of 0.7%) and thereby yielded 0.3 mmol of cyclohexanone (with a selectivity of 5.1%), 0.2 mmol of cyclohexanol (with a selectivity of 3.4%), and 3.8 mmol of cyclohexyl hydroperoxide (with a selectivity of 64.4%). The total yield of cyclohexanone, cyclohexanol, and cyclohexyl hydroperoxide was 0.45%. N-hydroxyphthalimide has a solubility in water (25° C.) of 0.01 g/100 g-H2O or less. equipped with a stirrer these formed a slurry at room temperature (25° C.)) The autoclave was hermetically sealed

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 350-ml autoclave made of stainless steel SUS 316 and equipped with a stirrer were placed 80 g (0.95 mol) of cyclohexane and 2 g of a 5 percent by weight N-hydroxysuccinimide aqueous solution which contained 100 mg of N-hydroxysuccinimide dissolved therein, at room temperature (25° C.). The autoclave was hermetically sealed, pressurized to 3 MPa (gauge pressure) with a gaseous mixture of 50 percent by volume oxygen and 50 percent by volume nitrogen, and the aqueous solution therein was stirred at 150° C. for 1 hour. As a result, 36 mmol of cyclohexane reacted (with a conversion of 3.8%) and thereby yielded 9.2 mmol of cyclohexanone (with a selectivity of 25.6%), 4.6 mmol of cyclohexanol (with a selectivity of 12.8%), and 12.3 mmol of cyclohexyl hydroperoxide (with a selectivity of 34.2%). The total yield of cyclohexanone, cyclohexanol, and cyclohexyl hydroperoxide was 2.7%. equipped with a stirrer dissolved at room temperature (25° C.) The autoclave was hermetically sealed

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

Procedure: Synthesize alkane oxidation catalyst in situ and oxidize alkane (cyclohexane) as follows. Add SiO2—C (3.3 mg, 0.6 groups/nm2) in acetonitrile (2 mL) and ([(C6H12N3R3)Mn2O3]Z2) (0.2 mM) to a container. The carboxylate group to Mn atom ratio is 0.50:1.0. Add o-dichlorobenzene (100 microliter (μL), 390 mmol) and cyclohexane (50 μL, 200 mmol) to the contents of container and maintain at 0° C. Add H2O2 (30 weight percent (wt %), 130 μL) to the contents of container. Seal the container and react to produce an alkane oxidation product (cyclohexanone (CyO), cyclohexanol (CyOH), and/or cyclohexyl hydroperoxide (Cy-OOH)). The concentrations of these species are determined as a function of time using gas chromatography and are shown in Table 1. Seal the container react