| 80% |
With sulfuric acid; In toluene; for 5.0h;Heating / reflux; |
This example describes the preparation of (4-n-butoxycarbonyl-9-fluorenylidene) malononitrile, for convenience to be designated ETM-2. [0094] A 460 g quantity of concentrated sulfuric acid (4.7 moles, analytical grade, commercially obtained from Sigma-Aldrich, Milwaukee, Wis.) and 100 g of diphenic acid (0.41 mole, commercially obtained from Acros Fisher Scientific Company Inc., Hanover Park, Ill.) were added to a 1-liter 3-neck round bottom flask, equipped with a thermometer, mechanical stirrer and a reflux condenser. Using a heating mantle, the flask was heated to 135-145 C. for 12 minutes, and then cooled to room temperature. After cooling to room temperature, the solution was added to a 4-liter Erlenmeyer flask containing 3 liter of water. The mixture was stirred mechanically and was boiled gently for one hour. A yellow solid was filtered out hot, washed with hot water until the pH of the wash-water was neutral, and was air-dried overnight. The yellow solid was fluorenone-4-carboxylic acid. The yield was 75 g (80%). The product was then characterized. The melting point (m.p.) was found to be 223-224 C. A 1H-NMR spectrum of fluorenone-4-carboxylic acid was obtained in d6-DMSO solvent with a 300 MHz NMR from Bruker Instrument. The peaks were found at (ppm) delta=7.39-7.50 (m, 2H); delta=7.79-7.70 (q, 2H); delta=7.74-7.85 (d, 1H); delta=7.88-8.00 (d, 1H); and delta=8.18-8.30 (d, 1H), where d is doublet, t is triplet, m is multiplet; dd is double doublet, q is quintet. [0095] A 70 g (0.312 mole) quantity of fluorenone-4-carboxylic acid, 480 g (6.5 mole) of n-butanol (commercially obtained from Fisher Scientific Company Inc., Hanover Park, Ill.), 1000 ml of Toluene and 4 ml of concentrated sulfuric acid were added to a 2-liter round bottom flask equipped with a mechanical stirrer and a reflux condenser with a Dean Stark apparatus. With aggressive agitation and refluxing, the solution was refluxed for 5 hours, during which 6 g of water were collected in the Dean Stark apparatus. The flask was cooled to room temperature. The solvents were evaporated and the residue was added, with agitation, to 4-liter of a 3% sodium bicarbonate aqueous solution. The solid was filtered off, washed with water until the pH of the wash-water was neutral, and dried in the hood overnight. The product was n-butyl fluorenone-4-carboxylate ester. The yield was 70 g (80%). A 1H-NMR spectrum of n-butyl fluorenone-4-carboxylate ester was obtained in CDCl3 with a 300 MHz NMR from Bruker Instrument. The peaks were found at (ppm) delta=0.87-1.09 (t, 3H); delta=1.42-1.70 (m, 2H); delta=1.75-1.88 (q, 2H); delta=4.26-4.64 (t, 2H); delta=7.29-7.45 (m, 2H); delta=7.46-7.58 (m, 1H); delta=7.60-7.68 (dd, 1H); delta=7.75-7.82 (dd, 1H); delta=7.90-8.00 (dd, 1H); delta=8.25-8.35 (dd, 1H). [0096] A 70 g (0.25 mole) quantity of n-butyl fluorenone-4-carboxylate ester, 750 ml of absolute methanol, 37 g (0.55 mole) of malononitrile (commercially obtained from Sigma-Aldrich, Milwaukee, Wis.), 20 drops of piperidine (commercially obtained from Sigma-Aldrich, Milwaukee, Wis.) were added to a 2-liter, 3-neck round bottom flask equipped with a mechanical stirrer and a reflux condenser. The solution was refluxed for 8 hours and the flask was cooled to room temperature. The orange crude product was filtered, washed twice with 70 ml of methanol and once with 150 ml of water, and dried overnight in the hood. This orange crude product was recrystalized from a mixture of 600 ml of acetone and 300 ml of methanol using activated charcoal. The flask was placed at 0 C. for 16 hours. The crystals were filtered and dried in a vacuum oven at 50 C. for 6 hours to obtain 60 g of pure (4-n-butoxycarbonyl-9-fluorenylidene) malononitrile. The melting point (m.p.) of the solid was found to be 99-100 C. A 1H-NMR spectrum of (4-n-butoxycarbonyl-9-fluorenylidene) malononitrile was obtained in CDCl3 with a 300 MHz NMR from Bruker Instrument. The peaks were found at (ppm) delta=0.74-1.16 (t, 3H); delta=1.38-1.72 (m, 2H); delta=1.70-1.90 (q, 2H); delta=4.29-4.55 (t, 2H); delta=7.31-7.43 (m, 2H); delta=7.45-7.58 (m, 1H); delta=7.81-7.91 (dd, 1H); delta=8.15-8.25 (dd, 1H); delta=8.42-8.52 (dd, 1H); delta=8.56-8.66 (dd, 1H) |
| 80% |
With sulfuric acid; In toluene; for 5.0h;Heating / reflux; |
A 460 g quantity of concentrated sulfuric acid (4.7 moles, analytical grade, commercially obtained from Sigma-Aldrich, Milwaukee, Wis.) and 100 g of diphenic acid (0.41 mole, commercially obtained from Acros Fisher Scientific Company Inc., Hanover Park, Ill.) were added to a 1-liter 3-neck round bottom flask, equipped with a thermometer, mechanical stirrer and a reflux condenser. Using a heating mantle, the flask was heated to 135-145 C. for 12 minutes, and then cooled to room temperature. After cooling to room temperature, the solution was added to a 4-liter Erlenmeyer flask containing 3 liter of water. The mixture was stirred mechanically and was boiled gently for one hour. A yellow solid was filtered out hot, washed with hot water until the pH of the wash-water was neutral, and was air-dried overnight. The yellow solid was fluorenone-4-carboxylic acid. The yield was 75 g (80%). The product was then characterized. The melting point (m.p.) was found to be 223-224 C. A 1H-NMR spectrum of fluorenone-4-carboxylic acid was obtained in d6-DMSO solvent with a 300 MHz NMR from Bruker Instrument. The peaks were found at (ppm) delta=7.39-7.50 (m, 2H); delta=7.79-7.70 (q, 2H); delta=7.74-7.85 (d, 1H); delta=7.88-8.00 (d, 1H); and delta=8.18-8.30 (d, 1H), where d is doublet, t is triplet, m is multiplet; dd is double doublet, q is quintet. [0089] A 70 g (0.312 mole) quantity of fluorenone-4-carboxylic acid, 480 g (6.5 mole) of n-butanol (commercially obtained from Fisher Scientific Company Inc., Hanover Park, Ill.), 1000 ml of toluene and 4 ml of concentrated sulfuric acid were added to a 2-liter round bottom flask equipped with a mechanical stirrer and a reflux condenser with a Dean Stark apparatus. With aggressive agitation and refluxing, the solution was refluxed for 5 hours, during which 6 g of water were collected in the Dean Stark apparatus. The flask was cooled to room temperature. The solvents were evaporated and the residue was added, with agitation, to 4-liter of a 3% sodium bicarbonate aqueous solution. The solid was filtered off, washed with water until the pH of the wash-water was neutral, and dried in the hood overnight. The product was n-butyl fluorenone-4-carboxylate ester. The yield was 70 g (80%). A 1H-NMR spectrum of n-butyl fluorenone-4-carboxylate ester was obtained in CDCl3 with a 300 MHz NMR from Bruker Instrument. The peaks were found at (ppm) delta=0.87-1.09 (t, 3H); delta=1.42-1.70 (m, 2H); delta=1.75-1.88 (q, 2H); delta=4.26-4.64 (t, 2H); delta=7.29-7.45 (m, 2H); delta=7.46-7.58 (m, 1H); delta=7.60-7.68 (dd, 1H); delta=7.75-7.82 (dd, 1H); delta=7.90-8.00 (dd, 1H); delta=8.25-8.35 (dd, 1H). [0090] A 70 g (0.25 mole) quantity of n-butyl fluorenone-4-carboxylate ester, 750 ml of absolute methanol, 37 g (0.55 mole) of malononitrile (commercially obtained from Sigma-Aldrich, Milwaukee, Wis.), 20 drops of piperidine (commercially obtained from Sigma-Aldrich, Milwaukee, Wis.) were added to a 2-liter, 3-neck round bottom flask equipped with a mechanical stirrer and a reflux condenser. The solution was refluxed for 8 hours and the flask was cooled to room temperature. The orange crude product was filtered, washed twice with 70 ml of methanol and once with 150 ml of water, and dried overnight in the hood. This orange crude product was recrystalized from a mixture of 600 ml of acetone and 300 ml of methanol using activated charcoal. The flask was placed at 0 C. for 16 hours. The crystals were filtered and dried in a vacuum oven at 50 C. for 6 hours to obtain 60 g of pure (4-n-butoxycarbonyl-9-fluorenylidene) malononitrile. The melting point (m.p.) of the solid was found to be 99-100 C. A 1H-NMR spectrum of (4-n-butoxycarbonyl-9-fluorenylidene) malononitrile was obtained in CDCl3 with a 300 MHz NMR from Bruker Instrument. The peaks were found at (ppm) delta=0.74-1.16 (t, 3H); delta=1.38-1.72 (m, 2H); delta=1.70-1.90 (q, 2H); delta=4.29-4.55 (t, 2H); delta=7.31-7.43 (m, 2H); delta=7.45-7.58 (m, 1H); delta=7.81-7.91 (dd, 1H); delta=8.15-8.25 (dd, 1H); delta=8.42-8.52 (dd, 1H); delta=8.56-8.66 (dd, 1H). |
|
With sulfuric acid; sodium hydrogencarbonate; In water; toluene; |
A mixture of <strong>[6223-83-2]9-fluorenone-4-carboxylic acid</strong> (70 g, 0.312 mole, from Sigma-Aldrich, Milwaukee, WI), n-butanol (480 g, 6.5 mole, from Fisher Scientific Company Inc., Hanover Park, IL), toluene (1000 ml), and concentrated sulfuric acid (4 ml) was added to a 2-liter round bottom flask equipped with a mechanical stirrer and a reflux condenser with a Dean Stark apparatus. With aggressive agitation, the solution was refluxed for 5 hours, during which time ~ 6 g of water were collected in the Dean Stark apparatus. After refluxing, the flask was cooled to room temperature. The solvents were evaporated and the residue was added with agitation to 4-liter of a 3% aqueous solution of sodium bicarbonate. The solid was filtered off, washed with water until the pH of the washed water was neutral, and dried in the hood overnight. The product was n-butyl fluorenone-4-carboxylate ester. The yield was 70 g (80%). A 1H-NMR spectrum of n-butyl fluorenone-4-carboxylate ester was obtained in CDCl3 with a 300 MHz NMR from Bruker Instrument. The 1H NMR spectrum was characterized by the following chemical shifts (delta, ppm): 0.87 -1.09 (t, 3H); 1.42 - 1.70 (m, 2H); 1.75 - 1.88 (q, 2H); 4.26 -4.64 (t, 2H); 7.29 -7.45 (m, 2H); 7.46 -7.58 (m, 1H); 7.60 - 7.68 (dd, 1H); 7.75 - 7.82 (dd, 1H); 7.90 - 8.00 (dd, 1H); and 8.25 - 8.35 (dd, 1H). |
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