2,5-dimethylhexane-2,5-diol

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

Procedure: 2-Methyl-3-buten-2-ol, 2-propanol and tert.-butyl peroxy pivalate (75% solution in aliphates) are reacted in a molar ratio of 1:15:0.3 at 90° C. and a pressure of 500 kPa as described in example 1. After a contact period of 20 minutes of the reaction mixture in a tube reactor 95% of the olefin used has been converted. 2,5-dimethylhexane-2,5-diol is formed with a selectivity of 76%.

Conditions: temp:-8.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 500 ml three-necked flask purged with nitrogen, 9.72 g (58.6 mmol, 1 eq) of fluorene and 19.61 g (134 mmol, 2.3 eq) of 2,5-dimethyl-2,5-hexanediol were placed at room temperature. Then, 85 ml of dehydrated dichloromethane was added. After stirring by a magnetic stirrer, the mixture was cooled to −8° C. with an ice bath (light brown slurry). To the slurry, 38.9 g (292 mmol, 5.0 eq) of pulverized anhydrous aluminum chloride was added over a period of 70 minutes, followed by stirring at 0° C. for 2 hours. The ice bath was removed, and the solution was stirred at room temperature for 19 hours (dark brown solution). After disappearance of fluorene was confirmed by gas chromatography, the dark brown solution was poured into 150 ml of ice water to perform quenching (yellowish brown slurry) After the soluble component was extracted with 500 ml of diethyl ether, the organic phase was neutralized with a saturated sodium hydrogencarbonate aqueous solution and washed with water. The dispensed organic phase was dried over MgSO4, then the MgSO4 was filtered off, and from the filtrate the solvent was vacuum distilled off by a rotary evaporator. The residue was transferred onto a Kiriyama funnel, washed 6 times with 10 ml of hexane and vacuum dried to obtain a white powder (12.0 g, yield: 53%) were placed at room temperature by stirring at 0° C. for 2 hours The ice bath was removed the solution was stirred at room temperature for 19 hours (dark brown solution) the dark brown solution was poured into 150 ml of ice water to perform quenching (yellowish brown slurry) After the soluble component was extracted with 500 ml of diethyl ether washed with water The dispensed organic phase was dried over MgSO4 the MgSO4 was filtered off distilled off by a rotary evaporator washed 6 times with 10 ml of hexane and vacuum dried

Conditions: temp:-8.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 500 ml three-necked flask purged with nitrogen, 9.72 g (58.6 mmol, 1 eq) of fluorene and 19.61 g (134 mmol, 2.3 eq) of 2,5-dimethyl-2,5-hexanediol were placed at room temperature. Then, 85 ml of dehydrated dichloromethane was added. After stirring by a magnetic stirrer, the mixture was cooled to −8° C. with an ice bath (light brown slurry). To the slurry, 38.9 g (292 mmol, 5.0 eq) of pulverized anhydrous aluminum chloride was added over a period of 70 minutes, followed by stirring at 0° C. for 2 hours. The ice bath was removed, and the solution was stirred at room temperature for 19 hours (dark brown solution). After disappearance of fluorene was confirmed by gas chromatography, the dark brown solution was poured into 150 ml of ice water to perform quenching (yellowish brown slurry) After the soluble component was extracted with 500 ml of diethyl ether, the organic phase was neutralized with a saturated sodium hydrogencarbonate aqueous solution and washed with water. The dispensed organic phase was dried over MgSO4, then the MgSO4 was filtered off, and from the filtrate the solvent was vacuum distilled off by a rotary evaporator. The residue was transferred onto a Kiriyama funnel, washed 6 times with 10 ml of hexane and vacuum dried to obtain a white powder (12.0 g, yield: 53%) were placed at room temperature by stirring at 0° C. for 2 hours The ice bath was removed the solution was stirred at room temperature for 19 hours (dark brown solution) the dark brown solution was poured into 150 ml of ice water to perform quenching (yellowish brown slurry) After the soluble component was extracted with 500 ml of diethyl ether washed with water The dispensed organic phase was dried over MgSO4 the MgSO4 was filtered off distilled off by a rotary evaporator washed 6 times with 10 ml of hexane and vacuum dried

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

Procedure: A mixture of 730 g (5 mol) of 2,5-dimethylhexane-2,5-diol, 3 g of p-toluenesulfonic acid, 430 g (5 mol) of pivalaldehyde and 1 l of toluene was refluxed for 4 hours (h) during which the water of reaction produced (90 ml) was removed. The reaction mixture was then cooled down to room temperature (RT) and stirred up with 10 ml of 25% strength aqueous sodium hydroxide solution, the phases were separated, the organic phase was washed with a little water until neutral, and the toluene was then removed at 50°-60° C. The residue obtained was fractionated under reduced pressure affording 909 g (4.25 mol) of 2-tert.-butyl-4,4,7,7,-tetramethyl-1,3-dioxacycloheptane (boiling point 54° C./0.2 mbar). This corresponds to a yield of 85% of theory. was refluxed for 4 hours (h) during which produced (90 ml) was removed the phases were separated the organic phase was washed with a little water until neutral, and the toluene was then removed at 50°-60° C The residue obtained

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

Procedure: A mixture of 730 g (5 mol) of 2,5-dimethylhexane-2,5-diol, 3 g of p-toluenesulfonic acid, 430 g (5 mol) of pivalaldehyde and 1 l of toluene was refluxed for 4 hours (h) during which the water of reaction produced (90 ml) was removed. The reaction mixture was then cooled down to room temperature (RT) and stirred up with 10 ml of 25% strength aqueous sodium hydroxide solution, the phases were separated, the organic phase was washed with a little water until neutral, and the toluene was then removed at 50°-60° C. The residue obtained was fractionated under reduced pressure affording 909 g (4.25 mol) of 2-tert.-butyl-4,4,7,7,-tetramethyl-1,3-dioxacycloheptane (boiling point 54° C./0.2 mbar). This corresponds to a yield of 85% of theory. was refluxed for 4 hours (h) during which produced (90 ml) was removed the phases were separated the organic phase was washed with a little water until neutral, and the toluene was then removed at 50°-60° C The residue obtained

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

Procedure: A reactor corresponding to FIG. 1 was initially charged with a mixture of 550 kg of 70% by weight hydrogen peroxide and 366 kg of 80% by weight sulphuric acid. With stirring and cooling of the reactor through the jacket, 250 kg of 2,5-dimethyl-2,5-hexanediol were metered in within 60 min, in the course of which the temperature rose from 20° C. to 30-32° C. The reaction mixture was stirred at 30° C. for another 90 min and then admixed with 200 kg of water. The stirrer was then switched off and the suspension formed was filtered within 10 min by applying reduced pressure to the filtration devices (5), in the course of which the liquid phase was sucked into the collecting vessel (7) and the precipitated 2,5-dimethylhexane-2,5-dihydroperoxide was retained in the vessel (2). The solid product retained in the reactor was washed by adding 500 kg of water, stirring the suspension for 3 min and filtering again by applying reduced pressure to the filtration devices (5). This washing operation was repeated once more. Thereafter, 481 kg of tert-butanol were added and the solid was dissolved therein by stirring and heating. 500 kg of 80% by weight sulphuric acid were metered into the resulting solution within 60 min with stirring and cooling of the reactor through the jacket, in the course of which the temperature rose to from 40 to 45° C. The reaction mixture was stirred at this temperature for a further 60 min and then admixed with 50 kg of water. The lower aqueous phase was removed and the liquid product was washed successively with 150 kg of water, 150 kg of 1% by weight sodium hydroxide solution and 150 kg of water, by stirring the phases and then removing the lower aqueous phase. After removal of residual water and volatile by-products by stripping under reduced pressure in a stripping column, 405 kg (90%) of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane were obtained. were metered in within 60 min, in the course of which rose from 20° C. to 30-32° C The reaction mixture was stirred at 30° C. for another 90 min the suspension formed was filtered within 10 min to the filtration devices (5) was washed by adding 500 kg of water stirring the suspension for 3 min filtering again to the filtration devices (5) Thereafter, 481 kg of tert-butanol were added the solid was dissolved by stirring heating with stirring cooling of the reactor through the jacket, in the course of which the temperature rose to from 40 to 45° C The reaction mixture was stirred at this temperature for a further 60 min The lower aqueous phase was removed the liquid product was washed successively with 150 kg of water, 150 kg of 1% by weight sodium hydroxide solution and 150 kg of water by stirring the phases removing the lower aqueous phase After removal of residual water and volatile by-products

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2 L three neck round bottom flask fit with an overhead stirrer, thermometer, and nitrogen inlet was charged with 1.2 L concentrated HCl. The HCl was stirred land chilled in an ice/salt bath to 0° C. Gradually, 150 g of 2,5-dimethyl-2,5-hexanediol (Aldrich) was added to the HCl. The reaction mixture was initially a milky white slurry which gradually thickened and the ice bath was removed to allow the reaction to warm to 10 C. The solids were isolated by filtration, dissolved in methylene chloride (500 mL) and washed repeatedly with water until neutral to pH paper. The organics were dried over anhydrous magnesium sulfate and left in the refrigerator overnight. The resulting mixture stripped on the rotary evaporator to yield)of white crystalline 2,5-dichloro-2,5-dimethylhexane (152 g, 94% pure by GC). 1HNMR (CDCl3, 500 MHz) δ1.95 (s, 4H); 1.60 (s, 12H). the ice bath was removed the reaction to warm to 10 C The solids were isolated by filtration washed repeatedly with water until neutral The organics were dried over anhydrous magnesium sulfate The resulting mixture stripped on the rotary evaporator

Conditions: temp:-8.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 500 ml three-necked flask purged with nitrogen, 9.72 g (58.6 mmol, 1 eq) of fluorene and 19.61 g (134 mmol, 2.3 eq) of 2,5-dimethyl-2,5-hexanediol were placed at room temperature. Then, 85 ml of dehydrated dichloromethane was added. After stirring by a magnetic stirrer, the mixture was cooled to −8° C. with an ice bath (light brown slurry). To the slurry, 38.9 g (292 mmol, 5.0 eq) of pulverized anhydrous aluminum chloride was added over a period of 70 minutes, followed by stirring at 0° C. for 2 hours. The ice bath was removed, and the solution was stirred at room temperature for 19 hours (dark brown solution). After disappearance of fluorene was confirmed by gas chromatography, the dark brown solution was poured into 150 ml of ice water to perform quenching (yellowish brown slurry). After the soluble component was extracted with 500 ml of diethyl ether, the organic phase was neutralized with a saturated sodium hydrogencarbonate aqueous solution and washed with water. The dispensed organic phase was dried over MgSO4, then the MgSO4 was filtered off, and from the filtrate the solvent was vacuum distilled off by a rotary evaporator. The residue was transferred onto a Kiriyama funnel, washed 6 times with 10 ml of hexane and vacuum dried to obtain a white powder (12.0 g, yield: 53%) were placed at room temperature by stirring at 0° C. for 2 hours The ice bath was removed the solution was stirred at room temperature for 19 hours (dark brown solution) the dark brown solution was poured into 150 ml of ice water to perform quenching (yellowish brown slurry) After the soluble component was extracted with 500 ml of diethyl ether washed with water The dispensed organic phase was dried over MgSO4 the MgSO4 was filtered off distilled off by a rotary evaporator washed 6 times with 10 ml of hexane and vacuum dried

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

Procedure: To 2,5-dimethyl-2,5-hexanediol (10 g, 68.5 mmol) in a 500 mL flask was added reagent grade concentrated HCl (150 mL) and the solution was stirred at ambient temperature for 1 h. Water (100 mL) and CH2Cl2 (100 mL) were then added slowly and the layers were separated. The aqueous layer was washed with additional CH2Cl2 (100 mL). The combined organic layers were dried over MgSO4 and filtered thru silica gel pad. The solvent was removed to yield 10.9 g (87%) of 2,5-dichloro-2,5-dimethylhexane. The dichloride was dissolved in 150 mL of CH2Cl2 and 9.6 mL of toluene (90 mmol) was added. AlCl3 (390 mg, 2.9 mol) was added in portions over 5 min at ambient temperature. HCl is evolved and the solution tums dark red. The reaction was placed in an ice-bath and quenched with deionized water (120 mL). Hexane (150 mL) was added and the organic layer was removed. The aqueous layer was washed with additional hexane (150 mL). The combined organic layers were washed with water (200 mL) and brine (100 mL) and dried over MgSO4. The solvent was removed in vacuo to give 1,1,4,4,6-pentamethyl-1,2,3,4-tetrahydronaphthalene as a colorless oil that crystallized after storage at −20° C. the layers were separated The aqueous layer was washed with additional CH2Cl2 (100 mL) The combined organic layers were dried over MgSO4 filtered The solvent was removed

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

Procedure: 2-Methyl-3-buten-2-ol, 2-propanol and tert.-butyl peroxy pivalate (75% solution in aliphates) are reacted in a molar ratio of 1:15:0.3 at 90° C. and a pressure of 500 kPa as described in example 1. After a contact period of 20 minutes of the reaction mixture in a tube reactor 95% of the olefin used has been converted. 2,5-dimethylhexane-2,5-diol is formed with a selectivity of 76%.

Conditions: temp:-8.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 500 ml three-necked flask purged with nitrogen, 9.72 g (58.6 mmol, 1 eq) of fluorene and 19.61 g (134 mmol, 2.3 eq) of 2,5-dimethyl-2,5-hexanediol were placed at room temperature. Then, 85 ml of dehydrated dichloromethane was added. After stirring by a magnetic stirrer, the mixture was cooled to −8° C. with an ice bath (light brown slurry). To the slurry, 38.9 g (292 mmol, 5.0 eq) of pulverized anhydrous aluminum chloride was added over a period of 70 minutes, followed by stirring at 0° C. for 2 hours. The ice bath was removed, and the solution was stirred at room temperature for 19 hours (dark brown solution). After disappearance of fluorene was confirmed by gas chromatography, the dark brown solution was poured into 150 ml of ice water to perform quenching (yellowish brown slurry) After the soluble component was extracted with 500 ml of diethyl ether, the organic phase was neutralized with a saturated sodium hydrogencarbonate aqueous solution and washed with water. The dispensed organic phase was dried over MgSO4, then the MgSO4 was filtered off, and from the filtrate the solvent was vacuum distilled off by a rotary evaporator. The residue was transferred onto a Kiriyama funnel, washed 6 times with 10 ml of hexane and vacuum dried to obtain a white powder (12.0 g, yield: 53%) were placed at room temperature by stirring at 0° C. for 2 hours The ice bath was removed the solution was stirred at room temperature for 19 hours (dark brown solution) the dark brown solution was poured into 150 ml of ice water to perform quenching (yellowish brown slurry) After the soluble component was extracted with 500 ml of diethyl ether washed with water The dispensed organic phase was dried over MgSO4 the MgSO4 was filtered off distilled off by a rotary evaporator washed 6 times with 10 ml of hexane and vacuum dried

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

Procedure: A mixture of 730 g (5 mol) of 2,5-dimethylhexane-2,5-diol, 3 g of p-toluenesulfonic acid, 430 g (5 mol) of pivalaldehyde and 1 l of toluene was refluxed for 4 hours (h) during which the water of reaction produced (90 ml) was removed. The reaction mixture was then cooled down to room temperature (RT) and stirred up with 10 ml of 25% strength aqueous sodium hydroxide solution, the phases were separated, the organic phase was washed with a little water until neutral, and the toluene was then removed at 50°-60° C. The residue obtained was fractionated under reduced pressure affording 909 g (4.25 mol) of 2-tert.-butyl-4,4,7,7,-tetramethyl-1,3-dioxacycloheptane (boiling point 54° C./0.2 mbar). This corresponds to a yield of 85% of theory. was refluxed for 4 hours (h) during which produced (90 ml) was removed the phases were separated the organic phase was washed with a little water until neutral, and the toluene was then removed at 50°-60° C The residue obtained