5-methylcyclohexane-1,3-dione

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: By the procedure of Example 29, allyl bromide is reacted with 5-methyl-1,3-cyclohexanedione to produce 2-allyl-5-methyl-1,3-cyclohexanedione.

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5-Methyl-1,3-cyclohexanedione (40 g, 0.32 mol) was dissolved in 500 ml of benzene at 70° C. The solution was heated at reflux for 2 hours, during which NH3 was bubbled through the reaction mixture and formed H2O was collected in a Dean-Stark trap. The mixture was then cooled to 0° C. and title product recovered by filtration, 39.8 g, m.p. 165°-169° C. 1H-NMR(DMSO-d6)delta(ppm): 0.98 (s, 3H), 1.6-1.88 (2H), 2.14-2.38 (2H), 3.14-3.6 (1H), 4.93 (s, 1H), 6.2-7.2 (m, 2H). The solution was heated was bubbled through the reaction mixture formed H2O was collected in a Dean-Stark trap title product recovered by filtration, 39.8 g, m.p. 165°-169° C

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 30.2 g (0.2 mole) of 2-nitrobezaldehyde and 25.2 g (0.2 mole) of 5-methyl-1,3-cyclohexane-dione were dissolved in 300 ml of tetrahydrofurane, the solution was saturated at 18° C with hydrogen chloride and allowed to stand for 4 days at room temperature. Water was added, the oily layer was separated and stirred with methanol. The crystals that had formed were filtered off, washed with methanol and dissolved and recrystallized from glacial acetic acid. 9.5 g (17 % of the theory) of 7-chloro-3-methyl-10-hydroxy-1-oxo-1,2,3,4-tetrahydro-9(10H)-acridone having a decomposition point of 255° C were obtained. the oily layer was separated The crystals that had formed were filtered off washed with methanol dissolved recrystallized from glacial acetic acid

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 30.2 g (0.2 mole) of 2-nitrobezaldehyde and 25.2 g (0.2 mole) of 5-methyl-1,3-cyclohexane-dione were dissolved in 300 ml of tetrahydrofurane, the solution was saturated at 18° C with hydrogen chloride and allowed to stand for 4 days at room temperature. Water was added, the oily layer was separated and stirred with methanol. The crystals that had formed were filtered off, washed with methanol and dissolved and recrystallized from glacial acetic acid. 9.5 g (17 % of the theory) of 7-chloro-3-methyl-10-hydroxy-1-oxo-1,2,3,4-tetrahydro-9(10H)-acridone having a decomposition point of 255° C were obtained. the oily layer was separated The crystals that had formed were filtered off washed with methanol dissolved recrystallized from glacial acetic acid

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: By the procedure of Example 29, allyl bromide is reacted with 5-methyl-1,3-cyclohexanedione to produce 2-allyl-5-methyl-1,3-cyclohexanedione.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: By the procedure of Example 29, allyl bromide is reacted with 5-methyl-1,3-cyclohexanedione to produce 2-allyl-5-methyl-1,3-cyclohexanedione.

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 150 g 5-methylcyclohexane-1,3-dione was dissolved in 1.4 L methanol and 82.5 g hydroxylamine hydrochloride was added. The mixture was stirred for 1.5 h under reflux. The solvent was removed in vacuo and the residue was dissolved in 1 L acetonitrile and was cooled to 0° C. Triethylamine was added followed by addition of a solution of 4-toluenesulfonyl chloride in 1.1 L acetonitrile. The mixture was stirred for 1 h at RT, 6.7 mL of water was added and the mixture was stirred for additional 1 h while gently warming the mixture to 55° C. The volatiles were removed in vacuo. 250 mL water was added to the residue and the pH was adjusted to 5 with 5 N aq. NaOH and the volatiles were removed in vacuo. The solids were extracted with acetone and after concentration in vacuo the residue was purified by column chromatography on silica gel with ethyl acetate to yield 82.6 g of the desired compound. under reflux The solvent was removed in vacuo the residue was dissolved in 1 L acetonitrile Triethylamine was added followed by addition of a solution of 4-toluenesulfonyl chloride in 1.1 L acetonitrile The mixture was stirred for 1 h at RT 6.7 mL of water was added the mixture was stirred for additional 1 h while gently warming the mixture to 55° C The volatiles were removed in vacuo 250 mL water was added to the residue the volatiles were removed in vacuo The solids were extracted with acetone after concentration in vacuo the residue was purified by column chromatography on silica gel with ethyl acetate

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: By the procedure of Example 29, allyl bromide is reacted with 5-methyl-1,3-cyclohexanedione to produce 2-allyl-5-methyl-1,3-cyclohexanedione.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 5-methyl-1,3-cyclohexanedione (23) (45.4 g, 360 mmol) in acetic acid (540 mL) was added bromine (19.4 mL, 378 mmol) over 5 min. After 30 min of stirring (with mechanical stirrer), the reaction mixture was filtered. The solid was left under high vacuum overnight and used in the subsequent step without further purification. the reaction mixture was filtered The solid was left under high vacuum overnight used in the subsequent step without further purification