3-(dibutylamino)propan-1-ol

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

実験手順: To 700 ml of chloroform is added 10.0 g (0.033 mole) of fluoranthene-3,8-dicarbonyl chloride and 12.4 g (0.066 mole) of 3-dibutylaminopropanol and the resulting solution is refluxed overnight. Upon cooling a solid forms which is crystallized from chloroform-ethyl acetate and twice from methanol-ethyl acetate. Further purification is achieved by dissolving the solid in water with subsequent conversion of the solid to the free base by the action of cold 3 N. aqueous potassium hydroxide, extraction of the free base with ether and after drying the ether solution converting the basic ester to the dihydrochloride salt with ethereal-hydrogen chloride. The product is crystallized from methanol-butanone-ether to give bis(3-dibutylaminopropyl)fluoranthene-3,8-dicarboxylate dihydrochloride hemidrate. M.P. 169°-173°C. the resulting solution is refluxed overnight Upon cooling a solid forms which is crystallized from chloroform-ethyl acetate and twice from methanol-ethyl acetate Further purification by dissolving the solid in water with subsequent conversion of the solid to the free base by the action of cold 3 N aqueous potassium hydroxide, extraction of the free base with ether after drying the ether solution The product is crystallized from methanol-butanone-ether

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

実験手順: To 700 ml of chloroform is added 10.0 g (0.033 mole) of fluoranthene-3,8-dicarbonyl chloride and 12.4 g (0.066 mole) of 3-dibutylaminopropanol and the resulting solution is refluxed overnight. Upon cooling a solid forms which is crystallized from chloroform-ethyl acetate and twice from methanol-ethyl acetate. Further purification is achieved by dissolving the solid in water with subsequent conversion of the solid to the free base by the action of cold 3 N. aqueous potassium hydroxide, extraction of the free base with ether and after drying the ether solution converting the basic ester to the dihydrochloride salt with ethereal-hydrogen chloride. The product is crystallized from methanol-butanone-ether to give bis(3-dibutylaminopropyl)fluoranthene-3,8-dicarboxylate dihydrochloride hemidrate. M.P. 169°-173°C. the resulting solution is refluxed overnight Upon cooling a solid forms which is crystallized from chloroform-ethyl acetate and twice from methanol-ethyl acetate Further purification by dissolving the solid in water with subsequent conversion of the solid to the free base by the action of cold 3 N aqueous potassium hydroxide, extraction of the free base with ether after drying the ether solution The product is crystallized from methanol-butanone-ether

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

実験手順: To 17.4 g (0.06 mole) of xanthene-2,7-dicarboxylic acid was added 100 ml (1.4 moles) of thionyl chloride and 4 drops of pyridine. The resulting solution was refluxed for four hours and solvent and excess thionyl chloride were removed. The intermediate diacid chloride in benzene-methylene chloride was reacted with 24 g (0.13 mole) of 3-di-n-butylamino-1-propanol by refluxing for three hours. Most of the solvent was removed and the residue allowed to stand for two days. The residue was diluted with methylene chloride and 10% hydrochloric acid. The organic layer and two methylene chloride washings of the aqueous layer were combined and dried over anhydrous magnesium sulfate. The solution was filtered and concentrated at reduced pressure to a solid residue. This was purified from isopropanol to give 12.9 g (29.6%) of bis(3-di-n-butylaminopropyl)xanthene-2,7-dicarboxylate dihydrochloride. M.P. 187.5°-190°C. The resulting solution was refluxed for four hours solvent and excess thionyl chloride were removed by refluxing for three hours Most of the solvent was removed The residue was diluted with methylene chloride and 10% hydrochloric acid dried over anhydrous magnesium sulfate The solution was filtered concentrated at reduced pressure to a solid residue This was purified from isopropanol

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

実験手順: To 700 ml of chloroform is added 10.0 g (0.033 mole) of fluoranthene-3,8-dicarbonyl chloride and 12.4 g (0.066 mole) of 3-dibutylaminopropanol and the resulting solution is refluxed overnight. Upon cooling a solid forms which is crystallized from chloroform-ethyl acetate and twice from methanol-ethyl acetate. Further purification is achieved by dissolving the solid in water with subsequent conversion of the solid to the free base by the action of cold 3 N. aqueous potassium hydroxide, extraction of the free base with ether and after drying the ether solution converting the basic ester to the dihydrochloride salt with ethereal-hydrogen chloride. The product is crystallized from methanol-butanone-ether to give bis(3-dibutylaminopropyl)fluoranthene-3,8-dicarboxylate dihydrochloride hemidrate. M.P. 169°-173°C. the resulting solution is refluxed overnight Upon cooling a solid forms which is crystallized from chloroform-ethyl acetate and twice from methanol-ethyl acetate Further purification by dissolving the solid in water with subsequent conversion of the solid to the free base by the action of cold 3 N aqueous potassium hydroxide, extraction of the free base with ether after drying the ether solution The product is crystallized from methanol-butanone-ether

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

実験手順: A suspension of 30.5 g (0.10 mole) of 9-oxo-fluorene-2,7-dicarbonyl chloride in 1 liter of dry chloroform (ethanol free) is stirred and treated all at once with 37.5 g (0.20 mole) of dry 3-dibutylamino-1-propanol causing a mildly exothermic reaction. The resulting mixture is stirred and refluxed for 2 hours, cooled to room temperature, filtered and the filtrate washed three times with 250 ml portions of a saturated sodium bicarbonate solution. The chloroform solution is washed with water and saturated sodium chloride solution, dried over anhydrous sodium sulfate and filtered. Most of the solvent is removed from the filtrate on the steam bath in vacuo and the remaining residue dissolved in butanone. This solution is made acid to Congo red with ethereal HCl causing the desired product to precipitate as a yellow crystalline solid. The bis [3-(dibutylamino)propyl]9-oxo-fluorene-2,7-dicarboxylate dihydrochloride so obtained is filtered, recrystallized from a butanone-methanol mixture and dried. The compound on standing in the atmosphere forms a monohydrate having a m.p. 178.5-179.5° C., λmaxH2O 276, and E 1cm1% 1,370. a mildly exothermic reaction The resulting mixture is stirred refluxed for 2 hours filtered the filtrate washed three times with 250 ml portions of a saturated sodium bicarbonate solution The chloroform solution is washed with water and saturated sodium chloride solution dried over anhydrous sodium sulfate filtered Most of the solvent is removed from the filtrate on the steam bath in vacuo the remaining residue dissolved in butanone to precipitate as a yellow crystalline solid

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

実験手順: A suspension of 30.5 g (0.10 mole) of 9-oxo-fluorene-2,7-dicarbonyl chloride in 1 liter of dry chloroform (ethanol free) is stirred and treated all at once with 37.5g (0.20 mole) of dry 3-dibutylamino-1-propanol causing a mildly exothermic reaction. The resulting mixture is stirred and refluxed for two hours, cooled to room temperature, filtered and the filtrate washed three times with 250 ml portions of a saturated sodium bicarbonate solution. The chloroform solution is washed with water and saturated sodium chloride solution, dried over anhydrous sodium sulfate and filtered. Most of the solvent is removed from the filtrate on the steam bath in vacuo and the remaining residue dissolved in butanone. This solution is made acid to Congo red with ethereal HCl causing the desired product to precipitate as a yellow crystalline solid. The bis [3-(dibutylamino)propyl]9-oxo-fluorene-2,7-dicarboxylate dihydrochloride so obtained is filtered, recrystallized from a butanone-methanol mixture and dried. The compound on standing in the atmosphere forms a monohydrate having a m.p. 178.5°-179.5°C., λmaxH2O 276, and E1cm1% 1,370. a mildly exothermic reaction The resulting mixture is stirred refluxed for two hours filtered the filtrate washed three times with 250 ml portions of a saturated sodium bicarbonate solution The chloroform solution is washed with water and saturated sodium chloride solution dried over anhydrous sodium sulfate filtered Most of the solvent is removed from the filtrate on the steam bath in vacuo the remaining residue dissolved in butanone to precipitate as a yellow crystalline solid

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

実験手順: To 17.4 g (0.06 mole) of xanthene-2,7-dicarboxylic acid was added 100 ml (1.4 moles) of thionyl chloride and 4 drops of pyridine. The resulting solution was refluxed for four hours and solvent and excess thionyl chloride were removed. The intermediate diacid chloride in benzene-methylene chloride was reacted with 24 g (0.13 mole) of 3-di-n-butylamino-1-propanol by refluxing for three hours. Most of the solvent was removed and the residue allowed to stand for two days. The residue was diluted with methylene chloride and 10% hydrochloric acid. The organic layer and two methylene chloride washings of the aqueous layer were combined and dried over anhydrous magnesium sulfate. The solution was filtered and concentrated at reduced pressure to a solid residue. This was purified from isopropanol to give 12.9 g (29.6%) of bis(3-di-n-butylaminopropyl)xanthene-2,7-dicarboxylate dihydrochloride. M.P. 187.5°-190°C. The resulting solution was refluxed for four hours solvent and excess thionyl chloride were removed by refluxing for three hours Most of the solvent was removed The residue was diluted with methylene chloride and 10% hydrochloric acid dried over anhydrous magnesium sulfate The solution was filtered concentrated at reduced pressure to a solid residue This was purified from isopropanol

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

実験手順: To 700 ml of chloroform is added 10.0 g (0.033 mole) of fluoranthene-3,8-dicarbonyl chloride and 12.4 g (0.066 mole) of 3-dibutylaminopropanol and the resulting solution is refluxed overnight. Upon cooling a solid forms which is crystallized from chloroform-ethyl acetate and twice from methanol-ethyl acetate. Further purification is achieved by dissolving the solid in water with subsequent conversion of the solid to the free base by the action of cold 3 N. aqueous potassium hydroxide, extraction of the free base with ether and after drying the ether solution converting the basic ester to the dihydrochloride salt with ethereal-hydrogen chloride. The product is crystallized from methanol-butanone-ether to give bis(3-dibutylaminopropyl)fluoranthene-3,8-dicarboxylate dihydrochloride hemidrate. M.P. 169°-173°C. the resulting solution is refluxed overnight Upon cooling a solid forms which is crystallized from chloroform-ethyl acetate and twice from methanol-ethyl acetate Further purification by dissolving the solid in water with subsequent conversion of the solid to the free base by the action of cold 3 N aqueous potassium hydroxide, extraction of the free base with ether after drying the ether solution The product is crystallized from methanol-butanone-ether