3-amino-5,5-dimethylcyclohex-2-en-1-one

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

Procedure: Prepared analogously to Example G from 1-amino- 5,5-dimethyl-cyclohexen-3-one and acrylic acid at 140° C. for 3 hours.

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

Procedure: Prepared analogously to Example G from 1-amino- 5,5-dimethylcyclohexen-3-one and methacrylic acid in an autoclave at 180° C. over a period of one hour.

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

Procedure: Prepared analogously to Example G from 1-amino- 5,5-dimethylcyclohexen-3-one and methacrylic acid in an autoclave at 180° C. over a period of one hour.

Conditions: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 10 g Ethyl 2-oxo-1,8-dioxaspiro[4.5]dec-3-ene-3-carboxylate and 6.15 g 3-amino-5,5-dimethylcyclohex-2-enone are mixed and heated to 200° C. for 20 minutes under a vacuo of 20 mbar. The mixture is cooled to room temperature and dissolved in 100 ml ethylacetate. 10 g 2,3-dichloro-5,6-dicyano-p-benzoquinone are added and the mixture is stirred for 4 hours at 50° C. and for 18 hours at room temperature. The product is isolated by filtration and washed with ethylacetate. The mixture is cooled to room temperature The product is isolated by filtration washed with ethylacetate

Conditions: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3.12 g 3-Isobutyryl-1,8-dioxaspiro[4.5]dec-3-en-2-one and 2.13 g 3-amino-5,5-dimethylcyclohex-2-enone are mixed and heated to 200° C. for 10 minutes under a vacuo of 20 mbar. The mixture is cooled to room temperature, 15 ml ethylacetate are added and the mixture is stirred for 30 minutes. Then 15 ml petrole ether are added and the precipitate is isolated by filtration. The crude product is dissolved in 350 ml dichloromethane, treated with 2.46 g 2,3dichloro-5,6-dicyano-p-benzoquinone and stirred for 18 hours. 2 g Ascorbic acid are added and the mixture is stirred for 10 minutes. The it is washed for three times with water. The organic phase is dried with sodium sulphate and the solvents are evaporated in vacuo. The residue is chromatographed on silica gel (petrole ether/ethylacetate 100:0 to 50:50). The mixture is cooled to room temperature the precipitate is isolated by filtration stirred for 18 hours the mixture is stirred for 10 minutes The it is washed for three times with water The organic phase is dried with sodium sulphate the solvents are evaporated in vacuo The residue is chromatographed on silica gel (petrole ether/ethylacetate 100:0 to 50:50)

Conditions: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3.12 g 3-Isobutyryl-1,8-dioxaspiro[4.5]dec-3-en-2-one and 2.13 g 3-amino-5,5-dimethylcyclohex-2-enone are mixed and heated to 200° C. for 10 minutes under a vacuo of 20 mbar. The mixture is cooled to room temperature, 15 ml ethylacetate are added and the mixture is stirred for 30 minutes. Then 15 ml petrole ether are added and the precipitate is isolated by filtration. The crude product is dissolved in 350 ml dichloromethane, treated with 2.46 g 2,3dichloro-5,6-dicyano-p-benzoquinone and stirred for 18 hours. 2 g Ascorbic acid are added and the mixture is stirred for 10 minutes. The it is washed for three times with water. The organic phase is dried with sodium sulphate and the solvents are evaporated in vacuo. The residue is chromatographed on silica gel (petrole ether/ethylacetate 100:0 to 50:50). The mixture is cooled to room temperature the precipitate is isolated by filtration stirred for 18 hours the mixture is stirred for 10 minutes The it is washed for three times with water The organic phase is dried with sodium sulphate the solvents are evaporated in vacuo The residue is chromatographed on silica gel (petrole ether/ethylacetate 100:0 to 50:50)

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

Procedure: 13.3 g 2-Cyano-3-cyclopentyl-acrylic acid methyl ester and 5.8 ml trifluoroacetic acid are dissolved in 70 ml acetonitrile and heated for 7 days to reflux. During the first 5 days 3-amino-5,5-dimethyl-cyclohex-2-enone is added in daily portions (12 g in total). Afterwards the reaction mixture is cooled to 0° C., the precipitate is isolated by filtration, washed 2 times with cold acetonitrile and dried in vacuo. The product is obtained as a mixture of diastereomers. heated for 7 days to reflux the precipitate is isolated by filtration washed 2 times with cold acetonitrile dried in vacuo The product is obtained as a mixture of diastereomers

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

Procedure: 13.3 g 2-Cyano-3-cyclopentyl-acrylic acid methyl ester and 5.8 ml trifluoroacetic acid are dissolved in 70 ml acetonitrile and heated for 7 days to reflux. During the first 5 days 3-amino-5,5-dimethyl-cyclohex-2-enone is added in daily portions (12 g in total). Afterwards the reaction mixture is cooled to 0° C., the precipitate is isolated by filtration, washed 2 times with cold acetonitrile and dried in vacuo. The product is obtained as a mixture of diastereomers. heated for 7 days to reflux the precipitate is isolated by filtration washed 2 times with cold acetonitrile dried in vacuo The product is obtained as a mixture of diastereomers

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

Procedure: In analogy to (Pettit, G. R.; Fleming, W. C.; Paull, K. D. J. Org. Chem. 1968, 33 (3) 1089-1092.), 3-amino-5,5-dimethylcyclohex-2-en-1-one was reacted with ethyl propio-late to give the title compound as a light brown solid in 78.5% yield.

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

Procedure: A mixture of 3-amino-5,5-dimethylcyclohex-2-enone (27.8g., 0.2 mol.) and 2-methyl-3-ethoxyacrolein (22.8 g., 0.2 mol.), in an apparatus equipped for downward distillation, was heated in an oil bath at 120° until the theoretical quantity of distillate was collected (13 ml.) The cooled residue was diluted with 2N HCl (50 ml.), extracted with ethyl acetate (3 × 50 ml.) and the combined extracts discarded. The aqueous solution was adjusted to pH 9.0 with sodium carbonate and extracted with ethyl acetate (3 × 50 ml.). The combined extracts were dried (MgSO4) and the solvent removed in vacuo and the residual oil distilled to give the title compound as a colourless oil (23 g., 53%) b.p. 83°/0.2 mm Hg. (RT = 2 min., 2% OV17, T=150° C). in an apparatus equipped for downward distillation was heated in an oil bath at 120° until the theoretical quantity of distillate was collected (13 ml.) The cooled residue was diluted with 2N HCl (50 ml.) extracted with ethyl acetate (3 × 50 ml.) extracted with ethyl acetate (3 × 50 ml.) The combined extracts were dried (MgSO4) the solvent removed in vacuo the residual oil distilled

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

Procedure: In analogy to (Pettit, G. R.; Fleming, W. C.; Paull, K. D. J. Org. Chem. 1968, 33 (3) 1089-1092), 3-amino-5,5-dimethylcyclohex-2-en-1-one was reacted with ethyl propio-late to give the title compound as a light brown solid in 78.5% yield.

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

Procedure: A solution of 1.39 g of 3-amino-5,5-dimethyl-2-cyclohexen-1-one, 1.26 g of 5-methyl-cyclohexane-1,3-dione and 1.51 g of 4-bromobenzaldehyde in 18 ml of absolute ethanol and 6 ml of glacial acetic acid was heated under reflux under a nitrogen atmosphere for 12 hours. The mixture was then cooled to room temperature and about 10 ml of water was added until the product precipitated. The product was filtered off and washed with three 50 ml portions of cold diethyl ether to give 9-(4-bromophenyl)-3,4,6,7,9,10-hexahydro-3,3,6(RS)-trimethyl-1,8(2H,5H)-acridinedione as a pale yellow solid. The product was shown to be a 9:1 mixture of diastereoisomers by HPLC and gave a mass ion of 414 (FAB, [M+H]+). under reflux under a nitrogen atmosphere for 12 hours precipitated The product was filtered off washed with three 50 ml portions of cold diethyl ether