5-propan-2-ylidenecyclopenta-1,3-diene

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

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

Procedure: Butyllithium (1.5 ml, 1.6M in hexane, 2.40 mmol) was added to 2,7-diphenyl-3,6-di-t-butyl-fluorene (0.95 g, 2.20 mmol) in THF (20 ml) at −78° C. The reaction mixture was allowed to warm to room temperature and stirred for 2.5 hours. The solvent was removed under vacuum. Ether (5 ml) was added and removed under vacuum. Ether (25 ml) was added and 6,6′-dimethylfulvene (0.23 g, 2.43 mmol) in ether (5 ml) was added to the reaction mixture at 0° C. The reaction was stirred at room temperature for 5 days. The reaction mixture was quenched with water, extracted with ether, dried over MgSO4, and evaporated under vacuum to afford the residue which was purified by column chromatography (silica gel, hexane/CH2Cl2=5/1) and crystallized from hot hexane. The yield was 0.40 g, 34%. 1H NMR (CDCl3): δ 7.91 and 7.30 (each s, 2H, 1,8- and 4,5-H (Flu), 7.35 (m, 10H, Ph), 6.76, 6.40 (m, 3H, Cp), 4.04 and 4.02 (s 2H, H9), 3.00 and 2.78 (br s, 2H, CH2 Cp), 1.31 (s, 18H, t-Bu), 1.11 and 1.09 (s, 6H, Me). 1H NMR (CD2Cl2): δ 7.91 and 7.29 (each s, 2H, 1,8- and 4,5-H (Flu), 7.2-7.4 (m, 10H, Ph), 6.8-6.7, 6.40 (m, 3H, Cp), 4.02 (brs, 2H, H9), 3.00 and 2.78 (br s, 2H, CH2 Cp), 1.28 (s, 18H, t-Bu), 1.07 and 1.04 (s, 6H, Me). HPLC: 10.38 and 10.65 min. The solvent was removed under vacuum Ether (5 ml) was added removed under vacuum Ether (25 ml) was added The reaction was stirred at room temperature for 5 days The reaction mixture was quenched with water extracted with ether dried over MgSO4 evaporated under vacuum to afford the residue which was purified by column chromatography (silica gel, hexane/CH2Cl2=5/1) crystallized from hot hexane 10.38 and 10.65 min.

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Potassium diphenylmethanide (5.72 g, 27.8 mmols) in about 50 mL of THF was slowly added to 6,6-dimethylfulvene (2.94 g, 27.8 mmols) in about 100 mL of THF at about 25 C. The reaction mixture was stirred at about 25° C. for about 16 hours. The solvent was removed under reduced pressure to give the desired product as a sticky, oily solid. The solvent was removed under reduced pressure

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

Procedure: To a solution of 3.0 g (10.8 mmol) of 3,6-di-tert-butylfluorene in 40 ml of THF, 7.0 ml (11.3 mmol) of a hexane solution of n-butyllithium was dropwise added in a nitrogen atmosphere with ice cooling, followed by stirring at room temperature for 6 hours. From the reaction mixture, the solvent was removed under reduced pressure, and the residue was washed with pentane and dried to obtain a white solid. To a solution of the solid in 30 ml of THF, a solution of 1.4 g (13.2 mmol) of 6,6-dimethylfulvene in 30 ml of THF was dropwise added in a nitrogen atmosphere with ice cooling, followed by stirring for 5 hours. Then, 30 ml of water-was added. The organic phase extracted with diethyl ether and separated was dried over magnesium sulfate and filtered. From the filtrate, the solvent was removed under reduced pressure to obtain a solid. The solid was recrystallized from methanol to obtain 2.9 g of a slightly yellow solid. The analyzed values are given below. From the reaction mixture, the solvent was removed under reduced pressure the residue was washed with pentane dried to obtain a white solid by stirring for 5 hours The organic phase extracted with diethyl ether separated was dried over magnesium sulfate filtered From the filtrate, the solvent was removed under reduced pressure to obtain a solid The solid was recrystallized from methanol to obtain 2.9 g of a slightly yellow solid

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

Procedure: To a solution of 3.0 g (10.8 mmol) of 3,6-di-tert-butylfluorene in 40 ml of THF, 7.0 ml (11.3 mmol) of a hexane solution of n-butyllithium was dropwise added in a nitrogen atmosphere with ice cooling, followed by stirring at room temperature for 6 hours. From the reaction mixture, the solvent was removed under reduced pressure, and the residue was washed with pentane and dried to obtain a white solid. To a solution of the solid in 30 ml of THF, a solution of 1.4 g (13.2 mmol) of 6,6-dimethylfulvene in 30 ml of THF was dropwise added in a nitrogen atmosphere with ice cooling, followed by stirring for 5 hours. Then, 30 ml of water-was added. The organic phase extracted with diethyl ether and separated was dried over magnesium sulfate and filtered. From the filtrate, the solvent was removed under reduced pressure to obtain a solid. The solid was recrystallized from methanol to obtain 2.9 g of a slightly yellow solid. The analyzed values are given below. From the reaction mixture, the solvent was removed under reduced pressure the residue was washed with pentane dried to obtain a white solid by stirring for 5 hours The organic phase extracted with diethyl ether separated was dried over magnesium sulfate filtered From the filtrate, the solvent was removed under reduced pressure to obtain a solid The solid was recrystallized from methanol to obtain 2.9 g of a slightly yellow solid

Conditions: temp:2.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 200 ml three-necked flask purged with nitrogen, 3.11 g (8.04 mmol, 1 eq) of 1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzo(b,h)-fluorene was placed at room temperature. Then, 40 ml of dehydrated THF was added, and the mixture was stirred by a magnetic stirrer to give a solution. The solution was cooled to 2° C. with an ice bath (light yellow solution). To the solution, 5.2 ml (8.48 mmol, 1.05 eq) of n-BuLi (hexane solution) was dropwise added over a period of 10 minutes, and 10 ml of dehydrated THF was further added. The ice bath was removed, and the mixture was stirred at room temperature for 22 hours (dark red slurry). After the slurry was cooled to 0° C. with an ice bath, a solution of 1.05 ml (8.54 mmol, 1.06 eq) of 6,6-dimethylfulvene in 10 ml of dehydrated THF was dropwise added over a period of 15 minutes (dark red solution). The ice bath was removed, and the solution was stirred at room temperature for 23 hours. The resulting dark red brown solution was poured into 100 ml of a diluted hydrochloric acid solution to perform quenching. After the organic phase was washed with 100 ml of a saturated saline solution, the soluble component was extracted from the aqueous layer with 50 ml of diethyl ether. The soluble component and the dispensed organic phase were together dried over MgSO4, then the MgSO4 was filtered off, and from the filtrate the solvent was vacuum distilled off by a rotary evaporator to obtain a yellowish orange solid. The solid was purified by silica gel column chromatography (developing solvent: hexane) to obtain a white powder (2.70 g, yield: 68%). was placed at room temperature to give a solution The ice bath was removed the mixture was stirred at room temperature for 22 hours (dark red slurry) After the slurry was cooled to 0° C. with an ice bath The ice bath was removed the solution was stirred at room temperature for 23 hours The resulting dark red brown solution was poured into 100 ml of a diluted hydrochloric acid solution to perform quenching After the organic phase was washed with 100 ml of a saturated saline solution the soluble component was extracted from the aqueous layer with 50 ml of diethyl ether The soluble component and the dispensed organic phase were together dried over MgSO4 the MgSO4 was filtered off distilled off by a rotary evaporator to obtain a yellowish orange solid The solid was purified by silica gel column chromatography (developing solvent: hexane)

Conditions: temp:2.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 200 ml three-necked flask purged with nitrogen, 3.11 g (8.04 mmol, 1 eq) of 1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzo(b,h)-fluorene was placed at room temperature. Then, 40 ml of dehydrated THF was added, and the mixture was stirred by a magnetic stirrer to give a solution. The solution was cooled to 2° C. with an ice bath (light yellow solution). To the solution, 5.2 ml (8.48 mmol, 1.05 eq) of n-BuLi (hexane solution) was dropwise added over a period of 10 minutes, and 10 ml of dehydrated THF was further added. The ice bath was removed, and the mixture was stirred at room temperature for 22 hours (dark red slurry). After the slurry was cooled to 0° C. with an ice bath, a solution of 1.05 ml (8.54 mmol, 1.06 eq) of 6,6-dimethylfulvene in 10 ml of dehydrated THF was dropwise added over a period of 15 minutes (dark red solution). The ice bath was removed, and the solution was stirred at room temperature for 23 hours. The resulting dark red brown solution was poured into 100 ml of a diluted hydrochloric acid solution to perform quenching. After the organic phase was washed with 100 ml of a saturated saline solution, the soluble component was extracted from the aqueous layer with 50 ml of diethyl ether. The soluble component and the dispensed organic phase were together dried over MgSO4, then the MgSO4 was filtered off, and from the filtrate the solvent was vacuum distilled off by a rotary evaporator to obtain a yellowish orange solid. The solid was purified by silica gel column chromatography (developing solvent: hexane) to obtain a white powder (2.70 g, yield: 68%). was placed at room temperature to give a solution The ice bath was removed the mixture was stirred at room temperature for 22 hours (dark red slurry) After the slurry was cooled to 0° C. with an ice bath The ice bath was removed the solution was stirred at room temperature for 23 hours The resulting dark red brown solution was poured into 100 ml of a diluted hydrochloric acid solution to perform quenching After the organic phase was washed with 100 ml of a saturated saline solution the soluble component was extracted from the aqueous layer with 50 ml of diethyl ether The soluble component and the dispensed organic phase were together dried over MgSO4 the MgSO4 was filtered off distilled off by a rotary evaporator to obtain a yellowish orange solid The solid was purified by silica gel column chromatography (developing solvent: hexane)

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

Procedure: To a solution of 4.18 g (39.4 mmol) 6,6-dimethylfulvene in 80 mL diethylether at 0° C. were added 22.9 mL of a 1.72M (39.4 mmol) methyl lithium solution in ether. The resulting slurry was stirred several days, then filtered, washed with pentane and dried under vacuum. filtered washed with pentane dried under vacuum

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

Procedure: To a solution of 4.18 g (39.4 mmol) 6,6-dimethylfulvene in 80 mL diethylether at 0° C. were added 22.9 mL of a 1.72M (39.4 mmol) methyl lithium solution in ether. The resulting slurry was stirred several days, then filtered, washed with pentane and dried under vacuum. filtered washed with pentane dried under vacuum

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

Procedure: A solution containing 6-nitroanthranilic acid (3) (19.65 g, 0.108 mol) and commercially available 6,6-dimethylfulvene (4) (17.2 g, 0.162 mol) in dimethoxyethane (DME, 125 mL) was added dropwise over 50 min to a stirred, 70° C. solution of tert-butylnitrite (90%, 17.3 g, 0.151 mol) in DME (350 mL). The mixture was stirred for 1 h and was cooled to room temperature. The reaction mixture was evaporated to yield a crude thick black oil which was directly subjected to silica gel chromatography eluting with ethyl acetate in petroleum ether (0-5% gradient) to afford 10 g of the crude product as a yellow oil, which partially crystallized on standing. Recrystallization from heptane gave the title compound (6.5 g, 26.5%) as a pale yellow solid: 1H NMR (300 MHz, DMSO) δ 7.70 (d, 1H), 7.42 (d, 1H), 7.09-7.01 (m, 1H), 7.00-6.92 (m, 2H), 5.33 (bs, 1H), 4.45 (bs, 1H), 1.55 (s, 6H); EIMS m/z 227. The reaction mixture was evaporated to yield a crude thick black oil which eluting with ethyl acetate in petroleum ether (0-5% gradient) to afford 10 g of the crude product as a yellow oil, which partially crystallized Recrystallization from heptane

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

Procedure: To a solution of 3.0 g(10.8 mmol) of 3,6-di-tert-butylfluorene in 40 ml of THF, 7.0 ml (11.3 mmol) of a hexane solution of n-butyllithium was dropwise added in a nitrogen atmosphere with ice cooling, followed by stirring at room temperature for 6 hours. From the reaction mixture, the solvent was removed under reduced pressure, and the residue was washed with pentane and dried to obtain a white solid. To a solution of the solid in 30 ml of THF, a solution of 1.4 g (13.2 mmol) of 6,6-dimethylfulvene in 30 ml of THF was dropwise added in a nitrogen atmosphere with ice cooling, followed by stirring for 5 hours. Then, 30 ml of water was added. The organic phase extracted with diethyl ether and separated was dried over magnesium sulfate and filtered. From the filtrate, the solvent was removed under reduced pressure to obtain a solid. The solid was recrystallized from methanol to obtain 2.9 g of a slightly yellow solid. The analyzed values are given below. From the reaction mixture, the solvent was removed under reduced pressure the residue was washed with pentane dried to obtain a white solid by stirring for 5 hours The organic phase extracted with diethyl ether separated was dried over magnesium sulfate filtered From the filtrate, the solvent was removed under reduced pressure to obtain a solid The solid was recrystallized from methanol to obtain 2.9 g of a slightly yellow solid

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

Procedure: In a 200 ml three-necked flask purged with nitrogen, 3.11 g (8.04 mmol, 1 eq) of 1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzo(b,h)-fluorene was placed at room temperature. Then, 40 ml of dehydrated THF was added, and the mixture was stirred by a magnetic stirrer to give a solution. The solution was cooled to 2° C. with an ice bath (light yellow solution) To the solution, 5.2 ml (8.48 mmol, 1.05 eq) of n-BuLi (hexane solution) was dropwise added over a period of 10 minutes, and 10 ml of dehydrated THF was further added. The ice bath was removed, and the mixture was stirred at room temperature for 22 hours (dark red slurry). After the slurry was cooled to 0° C. with an ice bath, a solution of 1.05 ml (8.54 mmol, 1.06 eq) of 6,6-dimethylfulvene in 10 ml of dehydrated THF was dropwise added over a period of 15 minutes (dark red solution). The ice bath was removed, and the solution was stirred at room temperature for 23 hours. The resulting dark red brown solution was poured into 100 ml of a diluted hydrochloride acid solution to perform quenching. After the organic phase was washed with 100 ml of a saturated saline solution, the soluble component was extracted from the aqueous layer with 50 ml of diethyl ether. The soluble component and the dispensed organic phase were together dried over MgSO4, then the MgSO4 was filtered off, and from the filtrate the solvent was vacuum distilled off by a rotary evaporator to obtain a yellowish orange solid. The solid was purified by silica gel column chromatography (developing solvent: hexane) to obtain a white powder (2.70 g, yield: 68%). was placed at room temperature to give a solution was dropwise added over a period of 10 minutes The ice bath was removed the mixture was stirred at room temperature for 22 hours (dark red slurry) The ice bath was removed the solution was stirred at room temperature for 23 hours The resulting dark red brown solution was poured into 100 ml of a diluted hydrochloride acid solution to perform quenching After the organic phase was washed with 100 ml of a saturated saline solution the soluble component was extracted from the aqueous layer with 50 ml of diethyl ether The soluble component and the dispensed organic phase were together dried over MgSO4 the MgSO4 was filtered off distilled off by a rotary evaporator to obtain a yellowish orange solid The solid was purified by silica gel column chromatography (developing solvent: hexane)