2,6-dimethylhepta-2,5-dien-4-one

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

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

Procedure: Mesityl oxide isomer→MIBK→MIBC  (7)

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

Procedure: A flask was charged with 10.8 g of (2′,4′,6′-triisopropylbiphenyl-2-yl)phosphine (66% potent, 7.13 g, 22.8 mmol, 1.0 equiv) and 6.6 g of 2,6-dimethyl-2,5-heptadien-4-one (47.7 mmol, 2.1 equiv). The vessel was purged with argon gas and immersed in an oil bath at 170° C. with magnetic stirring. The flask was sealed with a Teflon stopcock and the reaction was allowed to proceed under a static argon atmosphere. The flask was removed from the oil bath after 14 h and the contents allowed to cool to room temperature under argon gas. Anhydrous ethanol (70 mL) was added to the unpurified solids and the solids were broken up manually. The slurry was warmed to 80° C., held for an hour, and cooled to room temperature. The product was isolated by filtration, washes with ethanol and dried in vacuo to give 7.82 g of 2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphinan-4-one (98 area % by HPLC, 74% yield). The vessel was purged with argon gas immersed in an oil bath at 170° C. with magnetic stirring The flask was sealed with a Teflon stopcock The flask was removed from the oil bath after 14 h Anhydrous ethanol (70 mL) was added to the unpurified solids The slurry was warmed to 80° C. held for an hour cooled to room temperature The product was isolated by filtration, washes with ethanol dried in vacuo

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

Procedure: This compound was prepared according to the method of Sandris and Ourisson, Bull. Soc. Chim. Fr. 25: 345 (1958), in which 25 gms (180 mmoles) of phorone and 180 mls of ammonium hydroxide are stirred at 35° C. for 12 hrs. The solution is then cooled in an ice bath and concentrated HCl is added until the pH of the solution is 1. This solution is then saturated with NaCl and extracted with ether. The pH of the remaining liquid is raised to 10 with ammonium hydroxide followed by ether extraction. The ether solution is then dried with anhydrous sodium sulfate and evaporated to dryness, in vacuo, giving 20 gms (78%) of the desired product, B. P. 80°-85° C. at 15 mm Hg. This compound was prepared The solution is then cooled in an ice bath saturated with NaCl and extracted with ether The pH of the remaining liquid is raised to 10 with ammonium hydroxide followed by ether extraction The ether solution is then dried with anhydrous sodium sulfate evaporated to dryness, in vacuo

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

Procedure: 47.1 g of bromobenzene and 37.8 g of phorone are stirred at room temperature for 48 hours in the presence of 40 g of aluminum trichloride in 600 ml of carbon disulfide. The reaction mixture is then poured on to ice, extracted with diethyl ether. The extract is washed with water, dried and evaporated. After chromatography on silica gel with petroleum ether (low-boiling) and ethyl acetate (9:1) and recrystallization from hexane, there is obtained 2-bromo-5,6,8,9-tetrahydro-5,5,9,9-tetramethyl-7H-benzocyclohepten-7-one of m.p. 104°-105°. The reaction mixture is then poured on to ice extracted with diethyl ether The extract is washed with water dried evaporated After chromatography on silica gel with petroleum ether (low-boiling) and ethyl acetate (9:1) and recrystallization from hexane

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

Procedure: 47.1 g of bromobenzene and 37.8 g of phorone are stirred at room temperature for 48 hours in the presence of 40 g of aluminum trichloride in 600 ml of carbon disulfide. The reaction mixture is then poured on to ice, extracted with diethyl ether. The extract is washed with water, dried and evaporated. After chromatography on silica gel with petroleum ether (low-boiling) and ethyl acetate (9:1) and recrystallization from hexane, there is obtained 2-bromo-5,6,8,9-tetrahydro-5,5,9,9-tetramethyl-7H-benzocyclohepten-7-one of m.p. 104°-105°. The reaction mixture is then poured on to ice extracted with diethyl ether The extract is washed with water dried evaporated After chromatography on silica gel with petroleum ether (low-boiling) and ethyl acetate (9:1) and recrystallization from hexane

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

Procedure: Heinz Annalen der Chemie 203 336 (1880) converts acetone to phorone in about 30% yield, and reacts phorone with ammonia to form triacetone amine in 70% yield.

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

Procedure: A flask was charged with 10.8 g of (2′,4′,6′-triisopropylbiphenyl-2-yl)phosphine (66% potent, 7.13 g, 22.8 mmol, 1.0 equiv) and 6.6 g of 2,6-dimethyl-2,5-heptadien-4-one (47.7 mmol, 2.1 equiv). The vessel was purged with argon gas and immersed in an oil bath at 170° C. with magnetic stirring. The flask was sealed with a Teflon stopcock and the reaction was allowed to proceed under a static argon atmosphere. The flask was removed from the oil bath after 14 h and the contents allowed to cool to room temperature under argon gas. Anhydrous ethanol (70 mL) was added to the unpurified solids and the solids were broken up manually. The slurry was warmed to 80° C., held for an hour, and cooled to room temperature. The product was isolated by filtration, washes with ethanol and dried in vacuo to give 7.82 g of 2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphinan-4-one (98 area % by HPLC, 74% yield). The vessel was purged with argon gas immersed in an oil bath at 170° C. with magnetic stirring The flask was sealed with a Teflon stopcock The flask was removed from the oil bath after 14 h Anhydrous ethanol (70 mL) was added to the unpurified solids The slurry was warmed to 80° C. held for an hour cooled to room temperature The product was isolated by filtration, washes with ethanol dried in vacuo

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

Procedure: Acetone, first percolated through a bed of alumina, was passed through a reactor containing 0.54 g of ZSM-5 zeolite having a silica-to-alumina ratio of 26,000 to 1 and an Na content of 1.48%. No condensation products were observed at reaction temperatures below 200° C. (392° F.). When the reactor containing zeolite was heated to 280° to 370° C. (536°-698° F.), about 10% of the acetone fed was converted to mesityl oxide. Some phorone was also formed. was passed through a reactor No condensation products were observed at reaction temperatures below 200° C. (392° F.)

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 6.9 g. (0.05 mole) of phorone and 23.2 g. (0.2 mole) of anhydrous 81% t-butyl hydroperoxide was diluted with 50 ml of pentane and the mixture stirred at 10° C., while 5.7 g. of 77% sulfuric acid solution was slowly added over a thirty minute time period. The mixture was then allowed to warm slowly to 25° C. and stirred for 72 hours. After the reaction mixture was washed with water and sodium bisulfite solution, it was dried over anhydrous magnesium sulfate, the drying agent separated and the pentane removed under reduced pressure. The product weighed 11.4 g. (71.7% of the calculated amount). The infrared spectrum showed a strong absorption in the 880 cm-1 region, usually associated with t-butylperoxy groups and no absorption in the regions ascribed to hydroxyl or olefin. A GLC scan showed one large major peak for the expected product. By active oxygen assay, the purity of the product was estimated at 93%. A mixture of 6.9 g to warm slowly to 25° C. stirred for 72 hours After the reaction mixture was washed with water and sodium bisulfite solution, it was dried over anhydrous magnesium sulfate the drying agent separated the pentane removed under reduced pressure a strong absorption in the 880 cm-1 region no absorption in the regions

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

Procedure: A mixture of 47.0 g. (0.34 mole) of phorone and 157 g (1.36 mole) of 78% t-butyl hydroperoxide was stirred with 34 g. of dry Amberlyst 15® sulfonic acid type ion exchange resin in a 500 ml flask equipped with a condenser and thermometer for forty-eight hours at 40° C. and one hour at 50° C. The ion exchange resin was separated by filtration and the product diluted with pentane. The pentane solution was washed with water, sodium bisulfite solution, 5% sodium hydroxide solution and water. After drying over anhydrous magnesium sulfate, the pentane was removed under reduced pressure. The recovered product weighed 74.2 g. (68.5% of the calculated amount). A GLC scan showed a large major peak for the expected product. In the infrared spectrum, small bands for hydroxyl and olefin were observed but the band in the 880 cm-1 region usually associated with t-butyl peroxy groups was strong. By active oxygen assay, the purity of the product was estimated at 83%. A mixture of 47.0 g The ion exchange resin was separated by filtration the product diluted with pentane The pentane solution was washed with water, sodium bisulfite solution, 5% sodium hydroxide solution and water After drying over anhydrous magnesium sulfate the pentane was removed under reduced pressure

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