3-(diethylamino)-2,2-dimethylpropan-1-ol

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

Procedure: P-Chlorocinnamic acid (27.5 g, 0.15 mole) was added with rapid stirring to thionyl chloride (52.5 ml) and refluxed for 31/2 hours. The mixture was stripped of excess thionyl chloride under reduced pressure, benzene (100 ml) was added and the mixture was again stripped of solvent. The residue was treated with a solution of 3-diethylamino-2,2-dimethylpropanol (24.2 g, 0.15 mole) in benzene (500 ml), refluxed for 3 hours, cooled, diluted with petroleum ether (500 ml), and stored overnight at room temperature. The benzene-petroleum ether solution was decanted, the residue dissolved in H2O (700 ml) and the solution adjusted to pH 10 with saturated aqueous K2CO3 (60 ml). The product was extracted from the aqueous phase with benzene (800 ml) in portions and the extract dried overnight over MgSO4 and Darco. The solution was filtered and the filtrate adjusted to pH 2 with a solution of dry HCl in ether (cooled in an ice bath). Petroleum ether (500 ml) was added and the product oiled out of solution. The benzene-petroleum ether solution was decanted and the product was recrystallized from ethyl acetate (600 ml), yield: 33 g (61%). A sample was recrystallized from ethyl acetate, m.p. 132°-134°. refluxed for 31/2 hours was added refluxed for 3 hours cooled The benzene-petroleum ether solution was decanted the residue dissolved in H2O (700 ml) The product was extracted from the aqueous phase with benzene (800 ml) in portions the extract dried overnight over MgSO4 and Darco The solution was filtered Petroleum ether (500 ml) was added The benzene-petroleum ether solution was decanted the product was recrystallized from ethyl acetate (600 ml), yield: 33 g (61%) A sample was recrystallized from ethyl acetate, m.p. 132°-134°

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

Procedure: P-Chlorocinnamic acid (27.5 g, 0.15 mole) was added with rapid stirring to thionyl chloride (52.5 ml) and refluxed for 31/2 hours. The mixture was stripped of excess thionyl chloride under reduced pressure, benzene (100 ml) was added and the mixture was again stripped of solvent. The residue was treated with a solution of 3-diethylamino-2,2-dimethylpropanol (24.2 g, 0.15 mole) in benzene (500 ml), refluxed for 3 hours, cooled, diluted with petroleum ether (500 ml), and stored overnight at room temperature. The benzene-petroleum ether solution was decanted, the residue dissolved in H2O (700 ml) and the solution adjusted to pH 10 with saturated aqueous K2CO3 (60 ml). The product was extracted from the aqueous phase with benzene (800 ml) in portions and the extract dried overnight over MgSO4 and Darco. The solution was filtered and the filtrate adjusted to pH 2 with a solution of dry HCl in ether (cooled in an ice bath). Petroleum ether (500 ml) was added and the product oiled out of solution. The benzene-petroleum ether solution was decanted and the product was recrystallized from ethyl acetate (600 ml), yield: 33 g (61%). A sample was recrystallized from ethyl acetate, m.p. 132°-134°. refluxed for 31/2 hours was added refluxed for 3 hours cooled The benzene-petroleum ether solution was decanted the residue dissolved in H2O (700 ml) The product was extracted from the aqueous phase with benzene (800 ml) in portions the extract dried overnight over MgSO4 and Darco The solution was filtered Petroleum ether (500 ml) was added The benzene-petroleum ether solution was decanted the product was recrystallized from ethyl acetate (600 ml), yield: 33 g (61%) A sample was recrystallized from ethyl acetate, m.p. 132°-134°

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

Procedure: 3,4-METHYLENEDIOXYCINNAMIC ACID (15 G, 0.08 MOLE) WAS ADDED TO THIONYL CHLORIDE (30 ML) WITH RAPID STIRRING AND THEN REFLUXED FOR 3 HOURS. The mixture was stripped of excess thionyl chloride, benzene (100 ml) was added, and the mixture was again stripped of solvent. The residue was treated with a solution of 3-diethylamino-2,2-dimethylpropanol (12.8 g, 0.08 mole) in benzene (400 ml), refluxed for 3 hours, cooled, diluted with petroleum ether (500 ml) and stored overnight at room temperature. The benzene-petroleum ether solution was decanted, the residue dissolved in H2O (500 ml), adjusted to pH 10 with saturated aqueous K2CO3, and the product was extracted with CHCl3 (600 ml). The CHCl3 extract was dried overnight over MgSO4 and Darco, filtered, and the filtrate was stripped of solvent under reduced pressure. The product was dissolved in ether (800 ml) and the solution was adjusted to pH 2 with a solution of dry HCl in ether. The product crystallized with scratching and was collected by filtration. Yield: 18 g (61%). A sample was recrystallized from ethyl acetate, m.p. 152°-154°. REFLUXED FOR 3 HOURS was added refluxed for 3 hours cooled The benzene-petroleum ether solution was decanted the residue dissolved in H2O (500 ml) the product was extracted with CHCl3 (600 ml) The CHCl3 extract was dried overnight over MgSO4 and Darco filtered The product was dissolved in ether (800 ml) The product crystallized was collected by filtration A sample was recrystallized from ethyl acetate, m.p. 152°-154°

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

Procedure: 3,4-METHYLENEDIOXYCINNAMIC ACID (15 G, 0.08 MOLE) WAS ADDED TO THIONYL CHLORIDE (30 ML) WITH RAPID STIRRING AND THEN REFLUXED FOR 3 HOURS. The mixture was stripped of excess thionyl chloride, benzene (100 ml) was added, and the mixture was again stripped of solvent. The residue was treated with a solution of 3-diethylamino-2,2-dimethylpropanol (12.8 g, 0.08 mole) in benzene (400 ml), refluxed for 3 hours, cooled, diluted with petroleum ether (500 ml) and stored overnight at room temperature. The benzene-petroleum ether solution was decanted, the residue dissolved in H2O (500 ml), adjusted to pH 10 with saturated aqueous K2CO3, and the product was extracted with CHCl3 (600 ml). The CHCl3 extract was dried overnight over MgSO4 and Darco, filtered, and the filtrate was stripped of solvent under reduced pressure. The product was dissolved in ether (800 ml) and the solution was adjusted to pH 2 with a solution of dry HCl in ether. The product crystallized with scratching and was collected by filtration. Yield: 18 g (61%). A sample was recrystallized from ethyl acetate, m.p. 152°-154°. REFLUXED FOR 3 HOURS was added refluxed for 3 hours cooled The benzene-petroleum ether solution was decanted the residue dissolved in H2O (500 ml) the product was extracted with CHCl3 (600 ml) The CHCl3 extract was dried overnight over MgSO4 and Darco filtered The product was dissolved in ether (800 ml) The product crystallized was collected by filtration A sample was recrystallized from ethyl acetate, m.p. 152°-154°

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

Procedure: 5-(p-Chlorophenyl)-2-furoic acid (33.5 g., 0.15 mole) is added with rapid stirring to thionyl chloride (58 ml.) at room temperature, heated until solution occurs (about 20 min.) and then refluxed for 2 hr. The mixture is stripped of excess thionyl chloride in vacuo, benzene (100 ml.) is added, and again stripped of solvent. The residue is treated with a solution of 3-diethylamino-2,2 dimethylpropanol (24.1 g., 0.15 mole) in benzene (700 ml.), refluxed for 4 hr., cooled, diluted with petroleum ether (450 ml.) and stored for 18 hours at room temperature. The benzene-petroleum ether solution is decanted, the residue is dissolved in H2O (1000 ml.), and the solution is adjusted to pH 8 with saturated aqueous Na2CO3 (70 ml.). The product is extracted from the aqueous phase with benzene (1000 ml.) in portions and the extract is dried overnight with MgSO4 and activated charcoal. The solution is filtered and the filtrate is adjusted to pH 3 with ether-HCl (cooled in ice bath). Petroleum ether (300 ml.) is added and the product oiled out of solution. The benzene-petroleum ether solution is decanted and the product is washed twice with anhydrous ether (scratching induced crystallization). The solid is recrystallized from ethanol (200 ml.) to yield: 32 g. (53%). A sample is recrystallized twice from isopropanol, m.p. 139°-143°. heated until solution (about 20 min.) refluxed for 2 hr is added refluxed for 4 hr , cooled The benzene-petroleum ether solution is decanted the residue is dissolved in H2O (1000 ml.) The product is extracted from the aqueous phase with benzene (1000 ml.) in portions the extract is dried overnight with MgSO4 and activated charcoal The solution is filtered Petroleum ether (300 ml.) is added The benzene-petroleum ether solution is decanted the product is washed twice with anhydrous ether (scratching induced crystallization) The solid is recrystallized from ethanol (200 ml.) to yield: 32 g A sample is recrystallized twice from isopropanol, m.p. 139°-143°

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

Procedure: 5-(p-Chlorophenyl)-2-furoic acid (33.5 g., 0.15 mole) is added with rapid stirring to thionyl chloride (58 ml.) at room temperature, heated until solution occurs (about 20 min.) and then refluxed for 2 hr. The mixture is stripped of excess thionyl chloride in vacuo, benzene (100 ml.) is added, and again stripped of solvent. The residue is treated with a solution of 3-diethylamino-2,2 dimethylpropanol (24.1 g., 0.15 mole) in benzene (700 ml.), refluxed for 4 hr., cooled, diluted with petroleum ether (450 ml.) and stored for 18 hours at room temperature. The benzene-petroleum ether solution is decanted, the residue is dissolved in H2O (1000 ml.), and the solution is adjusted to pH 8 with saturated aqueous Na2CO3 (70 ml.). The product is extracted from the aqueous phase with benzene (1000 ml.) in portions and the extract is dried overnight with MgSO4 and activated charcoal. The solution is filtered and the filtrate is adjusted to pH 3 with ether-HCl (cooled in ice bath). Petroleum ether (300 ml.) is added and the product oiled out of solution. The benzene-petroleum ether solution is decanted and the product is washed twice with anhydrous ether (scratching induced crystallization). The solid is recrystallized from ethanol (200 ml.) to yield: 32 g. (53%). A sample is recrystallized twice from isopropanol, m.p. 139°-143°. heated until solution (about 20 min.) refluxed for 2 hr is added refluxed for 4 hr , cooled The benzene-petroleum ether solution is decanted the residue is dissolved in H2O (1000 ml.) The product is extracted from the aqueous phase with benzene (1000 ml.) in portions the extract is dried overnight with MgSO4 and activated charcoal The solution is filtered Petroleum ether (300 ml.) is added The benzene-petroleum ether solution is decanted the product is washed twice with anhydrous ether (scratching induced crystallization) The solid is recrystallized from ethanol (200 ml.) to yield: 32 g A sample is recrystallized twice from isopropanol, m.p. 139°-143°

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

Procedure: 5-(p-Fluorophenyl)-2-furoic acid (18.6 g., 0.09 mole) is added with rapid stirring to thionyl chloride (31.5 ml.) at room temperature, heated until solution occurs (about 1/4 hr.) and then is refluxed for 2 hr. The mixture is stripped of excess thionyl chloride in vacuo, benzene (100 ml.) is added, and again stripped of solvent. The reside is treated with a solution of 3-diethylamino-2,2-dimethylpropanol (14.5 g. 0.09 mole) in benzene (490 ml.) is refluxed for 3 hr., cooled, is diluted with petroleum ether (300 ml.), and is stored for 2 days at room temperature. The benzene-petroleum ether solution is decanted, the residue dissolved in H2O (750 ml.) and the solution adjusted to pH 8 with saturated aqueous Na2CO3 (75 ml.). The product is extracted from the aqueous phase with benzene (860 ml.) in portions and the extract dried for hours over MgSO4 and activated charcoal. The solution is filtered and the filtrate adjusted to pH 3 with ether-HCl (cooled in ice bath). Petroleum ether (400 ml.) is added and the product oiled out of solution. The benzene-petroleum ether solution is decanted and the product washed twice with anhydrous ether (scratching induced crystallization). The solid is recrystallized from isopropanol (200 ml.) to yield 16.9 g. (49%). A sample is recrystallized from isopropanol, m.p. 134°-138°. heated until solution (about 1/4 hr.) is refluxed for 2 hr is added is refluxed for 3 hr , cooled The benzene-petroleum ether solution is decanted the residue dissolved in H2O (750 ml.) The product is extracted from the aqueous phase with benzene (860 ml.) in portions the extract dried for hours over MgSO4 and activated charcoal The solution is filtered Petroleum ether (400 ml.) is added The benzene-petroleum ether solution is decanted the product washed twice with anhydrous ether (scratching induced crystallization) The solid is recrystallized from isopropanol (200 ml.) to yield 16.9 g A sample is recrystallized from isopropanol, m.p. 134°-138°

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

Procedure: P-Chlorocinnamic acid (27.5 g, 0.15 mole) was added with rapid stirring to thionyl chloride (52.5 ml) and refluxed for 31/2 hours. The mixture was stripped of excess thionyl chloride under reduced pressure, benzene (100 ml) was added and the mixture was again stripped of solvent. The residue was treated with a solution of 3-diethylamino-2,2-dimethylpropanol (24.2 g, 0.15 mole) in benzene (500 ml), refluxed for 3 hours, cooled, diluted with petroleum ether (500 ml), and stored overnight at room temperature. The benzene-petroleum ether solution was decanted, the residue dissolved in H2O (700 ml) and the solution adjusted to pH 10 with saturated aqueous K2CO3 (60 ml). The product was extracted from the aqueous phase with benzene (800 ml) in portions and the extract dried overnight over MgSO4 and Darco. The solution was filtered and the filtrate adjusted to pH 2 with a solution of dry HCl in ether (cooled in an ice bath). Petroleum ether (500 ml) was added and the product oiled out of solution. The benzene-petroleum ether solution was decanted and the product was recrystallized from ethyl acetate (600 ml), yield: 33 g (61%). A sample was recrystallized from ethyl acetate, m.p. 132°-134°. refluxed for 31/2 hours was added refluxed for 3 hours cooled The benzene-petroleum ether solution was decanted the residue dissolved in H2O (700 ml) The product was extracted from the aqueous phase with benzene (800 ml) in portions the extract dried overnight over MgSO4 and Darco The solution was filtered Petroleum ether (500 ml) was added The benzene-petroleum ether solution was decanted the product was recrystallized from ethyl acetate (600 ml), yield: 33 g (61%) A sample was recrystallized from ethyl acetate, m.p. 132°-134°

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

Procedure: 3,4-METHYLENEDIOXYCINNAMIC ACID (15 G, 0.08 MOLE) WAS ADDED TO THIONYL CHLORIDE (30 ML) WITH RAPID STIRRING AND THEN REFLUXED FOR 3 HOURS. The mixture was stripped of excess thionyl chloride, benzene (100 ml) was added, and the mixture was again stripped of solvent. The residue was treated with a solution of 3-diethylamino-2,2-dimethylpropanol (12.8 g, 0.08 mole) in benzene (400 ml), refluxed for 3 hours, cooled, diluted with petroleum ether (500 ml) and stored overnight at room temperature. The benzene-petroleum ether solution was decanted, the residue dissolved in H2O (500 ml), adjusted to pH 10 with saturated aqueous K2CO3, and the product was extracted with CHCl3 (600 ml). The CHCl3 extract was dried overnight over MgSO4 and Darco, filtered, and the filtrate was stripped of solvent under reduced pressure. The product was dissolved in ether (800 ml) and the solution was adjusted to pH 2 with a solution of dry HCl in ether. The product crystallized with scratching and was collected by filtration. Yield: 18 g (61%). A sample was recrystallized from ethyl acetate, m.p. 152°-154°. REFLUXED FOR 3 HOURS was added refluxed for 3 hours cooled The benzene-petroleum ether solution was decanted the residue dissolved in H2O (500 ml) the product was extracted with CHCl3 (600 ml) The CHCl3 extract was dried overnight over MgSO4 and Darco filtered The product was dissolved in ether (800 ml) The product crystallized was collected by filtration A sample was recrystallized from ethyl acetate, m.p. 152°-154°

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

Procedure: 5-(p-Chlorophenyl)-2-furoic acid (33.5 g., 0.15 mole) is added with rapid stirring to thionyl chloride (58 ml.) at room temperature, heated until solution occurs (about 20 min.) and then refluxed for 2 hr. The mixture is stripped of excess thionyl chloride in vacuo, benzene (100 ml.) is added, and again stripped of solvent. The residue is treated with a solution of 3-diethylamino-2,2-dimethylpropanol (24.1 g., 0.15 mole) in benzene (700 ml.), refluxed for 4 hr., cooled, diluted with petroleum ether (450 ml.) and stored for 18 hours at room temperature. The benzene-petroleum ether solution is decanted, the residue is dissolved in H2O (1000 ml.), and the solution is adjusted to pH 8 with saturated aqueous Na2CO3 (70 ml.). The product is extracted from the aqueous phase with benzene (1000 ml.) in portions and the extract is dried overnight with MgSO4 and activated charcoal. The solution is filtered and the filtrate is adjusted to pH 3 with ether-HCl (cooled in ice bath). Petroleum ether (300 ml.) is added and the product oiled out of solution. The benzene-petroleum ether solution is decanted and the product is washed twice with anhydrous ether (scratching induced crystallization). The solid is recrystallized from ethanol (200 ml.) to yield: 32 g. (53%). A sample is recrystallized twice from isopropanol, m.p. 139°-143°. heated until solution (about 20 min.) refluxed for 2 hr is added refluxed for 4 hr , cooled The benzene-petroleum ether solution is decanted the residue is dissolved in H2O (1000 ml.) The product is extracted from the aqueous phase with benzene (1000 ml.) in portions the extract is dried overnight with MgSO4 and activated charcoal The solution is filtered Petroleum ether (300 ml.) is added The benzene-petroleum ether solution is decanted the product is washed twice with anhydrous ether (scratching induced crystallization) The solid is recrystallized from ethanol (200 ml.) to yield: 32 g A sample is recrystallized twice from isopropanol, m.p. 139°-143°

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

Procedure: 5-(p-Fluorophenyl)-2-furoic acid (18.6 g., 0.09 mole) is added with rapid stirring to thionyl chloride (31.5 ml.) at room temperature, heated until solution occurs (about 1/4 hr.) and then is refluxed for 2 hr. The mixture is stripped of excess thionyl chloride in vacuo, benzene (100 ml.) is added, and again stripped of solvent. The residue is treated with a solution of 3-diethylamino-2,2-dimethylpropanol (14.5 g. 0.09 mole) in benzene (490 ml.), is refluxed for 3 hr., cooled, is diluted with petroleum ether (300 ml.), and is stored for 2 days at room temperature. The benzene- petroleum ether solution is decanted, the residue dissolved in H2O (750 ml.) and the solution adjusted to pH 8 with saturated aqueous Na2CO3 (75 ml.). The product is extracted from the aqueous phase with benzene (860 ml.) in portions and the extract dried for 18 hours over MgSO4 and activated charcoal. The solution is filtered and the filtrate adjusted to pH 3 with ether-HCl (cooled in ice bath). Petroleum ether (400 ml.) is added and the product oiled out of solution. The benzene-petroleum ether solution is decanted and the product washed twice with anhydrous ether (scratching induced crystallization). The solid is recrystallized from isopropanol (200 ml.) to yield 16.9 g. (49%). A sample is recrystallized from isopropanol, m.p. 134°-138°. heated until solution (about 1/4 hr.) is refluxed for 2 hr is added is refluxed for 3 hr , cooled The benzene- petroleum ether solution is decanted the residue dissolved in H2O (750 ml.) The product is extracted from the aqueous phase with benzene (860 ml.) in portions the extract dried for 18 hours over MgSO4 and activated charcoal The solution is filtered Petroleum ether (400 ml.) is added The benzene-petroleum ether solution is decanted the product washed twice with anhydrous ether (scratching induced crystallization) The solid is recrystallized from isopropanol (200 ml.) to yield 16.9 g A sample is recrystallized from isopropanol, m.p. 134°-138°

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

Procedure: 5-(p-Chlorophenyl)-2-furoic acid (33.5 g., 0.15 mole) is added with rapid stirring to thionyl chloride (58 ml.) at room temperature, heated until solution occurs (about 20 min.) and then refluxed for 2 hr. The mixture is stripped of excess thionyl chloride in vacuo, benzene (100 ml.) is added, and again stripped of solvent. The residue is treated with a solution of 3-diethylamino-2,2 dimethylpropanol (24.1 g., 0.15 mole) in benzene (700 ml.), refluxed for 4 hr., cooled, diluted with petroleum ether (450 ml.) and stored for 18 hours at room temperature. The benzene-petroleum ether solution is decanted, the residue is dissolved in H2O (1000 ml.), and the solution is adjusted to pH 8 with saturated aqueous Na2CO3 (70 ml.). The product is extracted from the aqueous phase with benzene (1000 ml.) in portions and the extract is dried overnight with MgSO4 and activated charcoal. The solution is filtered and the filtrate is adjusted to pH 3 with ether-HCl (cooled in ice bath). Petroleum ether (300 ml.) is added and the product oiled out of solution. The benzene-petroleum ether solution is decanted and the product is washed twice with anhydrous ether (scratching induced crystallization). The solid is recrystallized from ethanol (200 ml.) to yield: 32 g. (53%). A sample is recrystallized twice from isopropanol, m.p. 139°-143°. heated until solution (about 20 min.) refluxed for 2 hr is added refluxed for 4 hr , cooled The benzene-petroleum ether solution is decanted the residue is dissolved in H2O (1000 ml.) The product is extracted from the aqueous phase with benzene (1000 ml.) in portions the extract is dried overnight with MgSO4 and activated charcoal The solution is filtered Petroleum ether (300 ml.) is added The benzene-petroleum ether solution is decanted the product is washed twice with anhydrous ether (scratching induced crystallization) The solid is recrystallized from ethanol (200 ml.) to yield: 32 g A sample is recrystallized twice from isopropanol, m.p. 139°-143°