Carboxymethylene triphenylphosphorane → 5,7-diethyl-[1,6]naphthyridin-2(1H)-one

HRID 487380

反応式

HRID 487380 の反応式
[NH2:1][C:2]1[CH:7]=[C:6]([CH2:8][CH3:9])[N:5]=[C:4]([CH2:10][CH3:11])[C:3]=1[CH:12]=O.[C:14]([CH:17]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)(O)=[O:15]>C1(C)C=CC=CC=1>[CH2:10]([C:4]1[N:5]=[C:6]([CH2:8][CH3:9])[CH:7]=[C:2]2[C:3]=1[CH:12]=[CH:17][C:14](=[O:15])[NH:1]2)[CH3:11]

参加物

4

反応物 2

HCID 10870911Carboxymethylene triphenylphosphoraneHCID 190937814-Amino-2,6-diethyl-pyridine-3-carbaldehyde

生成物 1

HCID 200942525,7-diethyl-[1,6]naphthyridin-2(1H)-one収率 76.2%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

A mixture of 4-amino-2,6-diethylpyridine-3-carbaldehyde (40 g) and (carboxymethylene)triphenylphosphorane (82.5 g) in toluene (1 l) was stirred and heated at reflux for 3 hours. The solution was cooled and the solvent was removed by evaporation. A solution of sodium (20 g) in methanol (800 ml) was added to the residue and the resulting solution was heated at reflux for 4 hours. Methanol was removed by evaporation and water (500 ml) was added. The mixture was acidified to pH 1-2 by addition of concentrated hydrochloric acid. The mixture was then extracted with ethyl acetate (2×500 ml) and ether (1×500) and the extracts were discarded. The aqueous phase was then basified by addition of solid potassium carbonate and the solid which crystallised was collected by filtration and washed with water. The solid was recrystallised from acetone to give 5,7-diethyl-1,6-naphthyridin-2(1H)-one (34.6 g), m.p. 168°-169° C.; NMR (d6 -DMSO): 1.24(dt, 6H), 2.72(q, 2H), 3.0(q, 2H), 6.46(d, 1H), 6.9(s, 1H), 8.07(d, 1H); mass spectrum (CI): 203 (M+H)+ ; microanalysis, found: C, 70.9; H, 6.9; N, 13.8%; C12H14N2O requires: C, 71.3; H, 6.98; N, 13.9%.

後処理

  1. temperatureheated
  2. temperatureat reflux for 3 hours
  3. temperatureThe solution was cooled
  4. customthe solvent was removed by evaporation
  5. additionA solution of sodium (20 g) in methanol (800 ml) was added to the residue
  6. temperaturethe resulting solution was heated
  7. temperatureat reflux for 4 hours
  8. customMethanol was removed by evaporation and water (500 ml)
  9. additionwas added
  10. additionThe mixture was acidified to pH 1-2 by addition of concentrated hydrochloric acid
  11. extractionThe mixture was then extracted with ethyl acetate (2×500 ml) and ether (1×500)
  12. additionThe aqueous phase was then basified by addition of solid potassium carbonate
  13. customthe solid which crystallised
  14. filtrationwas collected by filtration
  15. washwashed with water
  16. customThe solid was recrystallised from acetone

出典と根拠

ORDレコード
ord-c52a70687fc848fda67ac0410333c51d
出典データセット
uspto-grants-1994_03
特許番号
US05294620

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