1,1-diphenylurea

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: Freshly distilled acetaldehyde (0.22 mole) is added during 0.5 hr to a stirred solution of 0.1 mole each of 1,1-diphenylurea and triphenyl phosphite in 130g of benzene at 60° C. The solution is warmed at reflux (65°-70° with Dry Ice-cooled condenser) for 1.25 hr, giving a dark brown solution having a small 31P nmr peak at -126.2 ppm for unreacted phosphite and a large product peak at -18.4 ppm (~1:5 areas). The reaction mixture is stripped to 130°/3mm. The residue is diluted with 200 ml of acetonitrile and 10 g of H2O, and this solution is warmed at reflux for 3 hr. Solid that separates during warming is recrystallized from acetic acid-water to give a white solid; mp 186°-187° dec; P31 nmr -21.6 ppm; 1H nmr δ10.0 (s, 2, OH), 7.3 (m, 10, C 6 H5), 5.4 (d of d, 1, J = 9 and 5Hz, NH), 4.1 (m, 1, CH), 1.3 (d of d, 3, J = 16 and 7 Hz, CH3); acidity 2.00 equiv/mole, pK1 = 2.20, pK2 = 8.62. The solution is warmed at reflux giving a dark brown solution is stripped to 130° this solution is warmed at reflux for 3 hr Solid that separates during warming is recrystallized from acetic acid-water to give a white solid

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

実験手順: Freshly distilled acetaldehyde (0.22 mole) is added during 0.5 hr to a stirred solution of 0.1 mole each of 1,1-diphenylurea and triphenyl phosphite in 130g of benzene at 60° C. The solution is warmed at reflux (65°-70° with Dry Ice-cooled condenser) for 1.25 hr, giving a dark brown solution having a small 31P nmr peak at -126.2 ppm for unreacted phosphite and a large product peak at -18.4 ppm (~1:5 areas). The reaction mixture is stripped to 130°/3mm. The residue is diluted with 200 ml of acetonitrile and 10 g of H2O, and this solution is warmed at reflux for 3 hr. Solid that separates during warming is recrystallized from acetic acid-water to give a white solid; mp 186°-187° dec; P31 nmr -21.6 ppm; 1H nmr δ10.0 (s, 2, OH), 7.3 (m, 10, C 6 H5), 5.4 (d of d, 1, J = 9 and 5Hz, NH), 4.1 (m, 1, CH), 1.3 (d of d, 3, J = 16 and 7 Hz, CH3); acidity 2.00 equiv/mole, pK1 = 2.20, pK2 = 8.62. The solution is warmed at reflux giving a dark brown solution is stripped to 130° this solution is warmed at reflux for 3 hr Solid that separates during warming is recrystallized from acetic acid-water to give a white solid

反応条件: temp:87.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 21.2g (0.1 mole) of 1,1-diphenylurea, 15.1g (0.1 mole) of 4-nitrobenzaldehyde, and 31.0g (0.1 mole) of triphenyl phosphite in 50g of benzene is stirred under nitrogen and warmed at reflux (87° C.) for 2 hours to give a light yellow solution: 31P nmr -13.2 (d, J = 23Hz), -127.8 ppm (area ratio 5:1). Most of the benzene is removed at reduced pressure, and ether is stirred into the yellow oil remaining, causing 32g of solid to separate after a few minutes. A portion is recrystallized from acetonitrile to give a white solid: mp 157°-162°; 31P nmr -13.2 ppm (d, J = 24Hz); molecular weight (CHCl3) 565 (calcd 579). warmed to give a light yellow solution Most of the benzene is removed at reduced pressure, and ether is stirred into the yellow oil to separate after a few minutes A portion is recrystallized from acetonitrile to give a white solid

反応条件: temp:87.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 21.2g (0.1 mole) of 1,1-diphenylurea, 15.1g (0.1 mole) of 4-nitrobenzaldehyde, and 31.0g (0.1 mole) of triphenyl phosphite in 50g of benzene is stirred under nitrogen and warmed at reflux (87° C.) for 2 hours to give a light yellow solution: 31P nmr -13.2 (d, J = 23Hz), -127.8 ppm (area ratio 5:1). Most of the benzene is removed at reduced pressure, and ether is stirred into the yellow oil remaining, causing 32g of solid to separate after a few minutes. A portion is recrystallized from acetonitrile to give a white solid: mp 157°-162°; 31P nmr -13.2 ppm (d, J = 24Hz); molecular weight (CHCl3) 565 (calcd 579). warmed to give a light yellow solution Most of the benzene is removed at reduced pressure, and ether is stirred into the yellow oil to separate after a few minutes A portion is recrystallized from acetonitrile to give a white solid

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

実験手順: Freshly distilled acetaldehyde (0.22 mole) is added during 0.5 hr to a stirred solution of 0.1 mole each of 1,1-diphenylurea and triphenyl phosphite in 130g of benzene at 60°C. The solution is warmed at reflux (65°-70° with Dry Ice-cooled condenser) for 1.25 hr, giving a dark brown solution having a small 31P nmr peak at -126.2 ppm for unreacted phosphite and a large product peak at -18.4 ppm (~1:5 areas). The reaction mixture is stripped to 130°/3mm. The residue is diluted with 200 ml of acetonitrile and 10g of H2O, and this solution is warmed at reflux for 3 hr. Solid that separates during warming is recrystallized from acetic acid-water to give a white solid: mp 186°-187° dec; p31 nmr -21.6 ppm; 1H nmr δ10.0 (s, 2, OH), 7.3 (m, 10, C6H5 ), 5.4 (d of d, 1, J = 9 and 5Hz, NH), 4.1 (m, 1, CH), 1.3 (d of d, 3, J = 16 and 7 Hz, CH3); acidity 2.00 equiv/ mole, pK1 = 2.20, pK2 = 8.62. The solution is warmed at reflux giving a dark brown solution is stripped to 130° this solution is warmed at reflux for 3 hr Solid that separates during warming is recrystallized from acetic acid-water to give a white solid

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

実験手順: Freshly distilled acetaldehyde (0.22 mole) is added during 0.5 hr to a stirred solution of 0.1 mole each of 1,1-diphenylurea and triphenyl phosphite in 130g of benzene at 60°C. The solution is warmed at reflux (65°-70° with Dry Ice-cooled condenser) for 1.25 hr, giving a dark brown solution having a small 31P nmr peak at -126.2 ppm for unreacted phosphite and a large product peak at -18.4 ppm (~1:5 areas). The reaction mixture is stripped to 130°/3mm. The residue is diluted with 200 ml of acetonitrile and 10g of H2O, and this solution is warmed at reflux for 3 hr. Solid that separates during warming is recrystallized from acetic acid-water to give a white solid: mp 186°-187° dec; p31 nmr -21.6 ppm; 1H nmr δ10.0 (s, 2, OH), 7.3 (m, 10, C6H5 ), 5.4 (d of d, 1, J = 9 and 5Hz, NH), 4.1 (m, 1, CH), 1.3 (d of d, 3, J = 16 and 7 Hz, CH3); acidity 2.00 equiv/ mole, pK1 = 2.20, pK2 = 8.62. The solution is warmed at reflux giving a dark brown solution is stripped to 130° this solution is warmed at reflux for 3 hr Solid that separates during warming is recrystallized from acetic acid-water to give a white solid

反応条件: temp:87.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 21.2g (0.1 mole) of 1,1-diphenylurea. 15.1g (0.1 mole) of 4-nitrobenzaldehyde, and 31.0g (0.1 mole) of triphenyl phosphite in 50g of benzene is stirred under nitrogen and warmed at reflux (87°C) for 2 hours to give a light yellow solution: 31P nmr -13.2 (d, J = 23Hz), -127.8 ppm (area ratio 5:1). Most of the benzene is removed at reduced pressure, and ether is stirred into the yellow oil remaining, causing 32g of solid to separate after a few minutes. A portion is recrystallized from acetonitrile to give a white solid: mp 157°-162°; 31P nmr -13.2 ppm (d, J = 24Hz); molecular weight (CHCl3) 565 (calcd 579). warmed to give a light yellow solution Most of the benzene is removed at reduced pressure, and ether to separate after a few minutes A portion is recrystallized from acetonitrile to give a white solid

反応条件: temp:87.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 21.2g (0.1 mole) of 1,1diphenylurea, 15.1g (0.1 mole) of 4-nitrobenzaldehyde, and 31.0g (0.1 mole) of triphenyl phosphite in 50g of benzene is stirred under nitrogen and warmed at reflux (87° C) for 2 hours to give a light yellow solution: 31P nmr -13.2 (d, J = 23Hz), 127.8 ppm (area ratio 5:1). Most of the benzene is removed at reduced pressure, and ether is stirred into the yellow oil remaining, causing 32g of solid to separate after a few minutes. A portion is recrystallized from acetonitrile to give a white solid: mp 157°-162°; 31P nmr -13.2 ppm (d, J = 24Hz); molecular weight (CHCl3) 565 (calcd 579). warmed to give a light yellow solution Most of the benzene is removed at reduced pressure, and ether is stirred into the yellow oil to separate after a few minutes A portion is recrystallized from acetonitrile to give a white solid

反応条件: temp:87.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 21.2g (0.1 mole) of 1,1diphenylurea, 15.1g (0.1 mole) of 4-nitrobenzaldehyde, and 31.0g (0.1 mole) of triphenyl phosphite in 50g of benzene is stirred under nitrogen and warmed at reflux (87° C) for 2 hours to give a light yellow solution: 31P nmr -13.2 (d, J = 23Hz), 127.8 ppm (area ratio 5:1). Most of the benzene is removed at reduced pressure, and ether is stirred into the yellow oil remaining, causing 32g of solid to separate after a few minutes. A portion is recrystallized from acetonitrile to give a white solid: mp 157°-162°; 31P nmr -13.2 ppm (d, J = 24Hz); molecular weight (CHCl3) 565 (calcd 579). warmed to give a light yellow solution Most of the benzene is removed at reduced pressure, and ether is stirred into the yellow oil to separate after a few minutes A portion is recrystallized from acetonitrile to give a white solid

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

実験手順: Freshly distilled acetaldehyde (0.22 mole) is added during 0.5 hr to a stirred solution of 0.1 mole each of 1,1-diphenylurea and triphenyl phosphite in 130g of benzene at 60° C. The solution is warmed at reflux (65°-70° with Dry Ice-cooled condenser) for 1.25 hr, giving a dark brown solution having a small 31P nmr peak at -126.2 ppm for unreacted phosphite and a large product peak at -18.4 ppm (~1:5 areas). The reaction mixture is stripped to 130°/3mm. The residue is diluted with 200 ml of acetonitrile and 10 g of H2O, and this solution is warmed at reflux for 3 hr. Solid that separates during warming is recrystallized from acetic acid-water to give a white solid; mp 186°-187° dec; P31 nmr -21.6 ppm; 1H nmr δ10.0 (s, 2, OH), 7.3 (m, 10, C 6 H5), 5.4 (d of d, 1, J = 9 and 5Hz, NH), 4.1 (m, 1, CH), 1.3 (d of d, 3, J = 16 and 7 Hz, CH3); acidity 2.00 equiv/mole, pK1 = 2.20, pK2 = 8.62. The solution is warmed at reflux giving a dark brown solution is stripped to 130° this solution is warmed at reflux for 3 hr Solid that separates during warming is recrystallized from acetic acid-water to give a white solid

反応条件: temp:87.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 21.2g (0.1 mole) of 1,1-diphenylurea, 15.1g (0.1 mole) of 4-nitrobenzaldehyde, and 31.0g (0.1 mole) of triphenyl phosphite in 50g of benzene is stirred under nitrogen and warmed at reflux (87° C.) for 2 hours to give a light yellow solution: 31P nmr -13.2 (d, J = 23Hz), -127.8 ppm (area ratio 5:1). Most of the benzene is removed at reduced pressure, and ether is stirred into the yellow oil remaining, causing 32g of solid to separate after a few minutes. A portion is recrystallized from acetonitrile to give a white solid: mp 157°-162°; 31P nmr -13.2 ppm (d, J = 24Hz); molecular weight (CHCl3) 565 (calcd 579). warmed to give a light yellow solution Most of the benzene is removed at reduced pressure, and ether is stirred into the yellow oil to separate after a few minutes A portion is recrystallized from acetonitrile to give a white solid