cyclohexane-1,4-dione

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

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

Procedure: A mixture of 4,4′-dibromodiphenylamine (7.3 g. 22 mmol), cyclohexane-1,4-dione (2.5 g., 23.3 mole), para-toluenesulfonic acid (0.1 g.) and toluene (100 ml) was kept at reflux with a Dean-Stark phase separator containing 4A molecular sieves. After 18 hours at reflux, the reaction was diluted with toluene, and the toluene solution was washed with water, dried and concentrated. The residue was dissolved in hexanes, and the hexanes solution was passed through a column of silica gel to afford 4,4′-dibromotriphenylamine as a colorless glass, 5.04 g., 67% yield. Mass Spec (m/z): 401, 403, 405 (M+). at reflux with a Dean-Stark phase separator After 18 hours at reflux the toluene solution was washed with water dried concentrated The residue was dissolved in hexanes

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

Procedure: 30 g (0.27 mmol) of cyclohexane-1,4-dione, 35.4 g (0.27 mol) of 2,2-diethylpropane-1,3-diol and 360 mg of para-toluenesulfonic acid were heated in 200 ml of toluene on a water separator. After the mixture had been cooled to room temperature and the water of reaction separated off, the organic phase was washed with a semisaturated sodium hydrogen carbonate solution and dried over magnesium sulfate. After the solvent had been evaporated, 65 g of crude product were obtained which was purified by flash chromatography (ethyl acetate/petroleum ether=1:4). The first fraction contained the 1,4-diketal which was formed as secondary product (10 g). The main fraction contained 28.5 g (47%) of a yellow oil. separated off the organic phase was washed with a semisaturated sodium hydrogen carbonate solution dried over magnesium sulfate After the solvent had been evaporated 65 g of crude product were obtained which was purified by flash chromatography (ethyl acetate/petroleum ether=1:4)

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

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

Procedure: 5,11-Dihydridoindolo[3,2-b]carbazole was synthesized by double Fischer indolization starting from phenylhydrazine and 1,4-cyclohexanedione according to the method described in B. Robinson, J. Chem. Soc. 1963, 3097-3099.

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

Procedure: 5,11-Dihydridoindolo[3,2-b]carbazole was synthesized by double Fischer indolization starting from phenylhydrazine and 1,4-cyclohexanedione according to the method described in B. Robinson, J. Chem. Soc. 1963, 3097-3099.

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

Procedure: Compound [I-c] was synthesized in the same manner as in Synthesis Example (5) except that 1,4-cyclohexanedione was replaced by 27.6 g (0.2 mole) of bicyclo[3.3.0]octane-3,7-dione (m.p. 85° C.).

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

Procedure: Into a molten mixture of 300 g (3.2 mole) of phenol and 22.4 g (0.2 mole) of 1,4-cyclohexanedione (m.p. 78° C.) was introduced hydrochloric acid gas at a temperature of 50° C. to saturation.

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

Procedure: A solution of 1,4-cyclohexanedione monoethyleneketa (50.0 g), 1-(2-pyridyl)piperazine (52.16 g), and p-toluenesulfonic acid (0.5 g) in 500 ml of toluene is refluxed with a Dean-Stark trap until the theoretical amount of water is collected (about four hours). The solvent is evaporated in vacuo and the residue is dissolved in 750 ml of methanol. This solution is cooled in an ice bath and sodium cyanoborohydride (30.1 g) is added in small portions over a two-minute period. The resulting suspension is stirred mechanically and over the next 30 minutes enough concentrated hydrochloric acid solution is added dropwise to the reaction mixture to maintain a pH of about 4. The solvent is removed in vacuo to leave a semisolid residue which is dissolved in 300 ml of a 10% solution of hydrochloric acid in a well ventilated fume hood. This solution is diluted with an equal volume of acetone and refluxed for two hours. The volatile components of the mixture are removed in vacuo and the residue is cooled in an ice bath and made basic with concentrated ammonium hydroxide. The white solid which forms is recrystallized from ethyl acetate-heptane to give 52.4 g of the title compound; mp 142°-144° C. is collected (about four hours) The solvent is evaporated in vacuo the residue is dissolved in 750 ml of methanol This solution is cooled in an ice bath sodium cyanoborohydride (30.1 g) is added in small portions over a two-minute period is added dropwise to the reaction mixture to maintain a pH of about 4 The solvent is removed in vacuo to leave a semisolid residue which refluxed for two hours The volatile components of the mixture are removed in vacuo the residue is cooled in an ice bath The white solid which forms is recrystallized from ethyl acetate-heptane

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

Procedure: To a solution of 1,4-cyclohexanedione (6.72 g, 60 mmol) in THF (100 mL) cooled in an ice bath was added a 1 M solution of phenyl magnesium bromide in THF (20 mL, 20 mmol). The mixture was stirred at room temperature for 3 hours and quenched with an NH4Cl solution. The resulting solution was extracted with EtOAc three times. The combined organic phase was washed with brine, dried over MgSO4 and concentrated. Purification on silica gel eluting with 1:1 EtOAc/hexanes yielded 0.83 g (22%) of the title compound. MS calculated (M+H)+ 190, found 173 (M+H−H2O)+. quenched with an NH4Cl solution The resulting solution was extracted with EtOAc three times The combined organic phase was washed with brine dried over MgSO4 concentrated Purification on silica gel eluting with 1:1 EtOAc/hexanes

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

Procedure: To a solution of 1,4-cyclohexanedione (6.72 g, 60 mmol) in THF (100 mL) cooled in an ice bath was added a 1 M solution of phenyl magnesium bromide in THF (20 mL, 20 mmol). The mixture was stirred at room temperature for 3 hours and quenched with an NH4Cl solution. The resulting solution was extracted with EtOAc three times. The combined organic phase was washed with brine, dried over MgSO4 and concentrated. Purification on silica gel eluting with 1:1 EtOAc/hexanes yielded 0.83 g (22%) of the title compound. MS calculated (M+H)+ 190. found 173 (M+H−H2O)+. quenched with an NH4Cl solution The resulting solution was extracted with EtOAc three times The combined organic phase was washed with brine dried over MgSO4 concentrated Purification on silica gel eluting with 1:1 EtOAc/hexanes

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 5-Iodo-2,3-thiophenedicarboxaldehyde (20.00 g, 75.15 mmol) and 1,4-cyclohexandione (4.25 g, 37.12 mmol) were dissoved in IMS (industrial methylated spirits) (600 cm3) by warming and stirring, and then cooled to 20° C. with a water bath. 5% KOH solution (7.5 cm3) was added in one portion under nitrogen with vigorous stirring. The reaction mixture was stirred at 20° C. for 30 minutes and the precipitate formed was collected by suction filtration, washed with IMS, water, IMS, then acetone, and dried in the vacuum oven at 40° C. overnight to yield 2,8-diiodo-anthra[2,3-b:7,6-b′]dithiophene-5,11-dione (18.39 g, 87%). The solid was directly used for the following reactions without further purification. by warming The reaction mixture was stirred at 20° C. for 30 minutes the precipitate formed was collected by suction filtration washed with IMS, water, IMS acetone, and dried in the vacuum oven at 40° C. overnight