Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester → HCID 19093694, compound

HRID 487402Notes

Reaction equation

HRID 487402 reaction equation
[C:1]([C:9]1[C:10]([CH3:28])=[N:11][C:12]([CH2:26][CH3:27])=[CH:13][C:14]=1[NH:15]S(C1C=CC(C)=CC=1)(=O)=O)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(C=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)(OCC)=O>C1(C)C(C)=CC=CC=1>[NH2:15][C:14]1[CH:13]=[C:12]([CH2:26][CH3:27])[N:11]=[C:10]([CH3:28])[C:9]=1[C:1](=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 19093722HCID 19093722, compound

Product 1

HCID 19093694HCID 19093694, compoundYield 46.3%

Reagents, catalysts & solvents 1

HCID 7237O-XyleneSolvent

Procedure

A mixture of compound C (1.1 g) and (carbethoxymethylene)triphenylphosphorane (6 g) in xylene (200 ml) was stirred and heated at reflux for 4 hours. The solution was then concentrated by evaporation and a solution of sodium (2.6 g) in methanol (200 ml) was added. The mixture was stirred and heated at reflux for 4 hours. Volatile material was removed by evaporation and water was added to the residue. The mixture was then acidified by the addition of concentrated hydrochloric acid and extracted twice with ether. The ether extracts were discarded. The aqueous phase was basified with solid potassium carbonate and extracted twice with ethyl acetate. The combined extracts were washed with water, saturated sodium chloride solution and dried (MgSO4). Solvent was removed by evaporation to leave a residue which was recrystallised from acetone to give 5,7-diethyl-4-methyl-1,6-naphthyridin-2(1H)-one (D) (0.31 g) as a solid, m.p. 220°-223° C.; NMR (d6 -DMSO): 1.22(t, 3H), 1.24(t, 3H), 2.62(s, 3H), 2.69(q, 2H), 3.16(q, 2H), 6.33(s, 1H), 6.91(s, 1H), 11.68(s, 1H); mass spectrum (CI, ammonia): 217 (M+H)+ ; microanalysis, found: C, 71.5; H, 7.1; N, 12.9%; C13H16N2O requires: C, 72.2; H, 7.5; N, 13.0%.

Workup

  1. temperatureheated
  2. temperatureat reflux for 4 hours
  3. concentrationThe solution was then concentrated by evaporation
  4. additiona solution of sodium (2.6 g) in methanol (200 ml) was added
  5. stirringThe mixture was stirred
  6. temperatureheated
  7. temperatureat reflux for 4 hours
  8. customVolatile material was removed by evaporation and water
  9. additionwas added to the residue
  10. additionThe mixture was then acidified by the addition of concentrated hydrochloric acid
  11. extractionextracted twice with ether
  12. extractionextracted twice with ethyl acetate
  13. washThe combined extracts were washed with water, saturated sodium chloride solution
  14. dry with materialdried (MgSO4)
  15. customSolvent was removed by evaporation
  16. customto leave a residue which
  17. customwas recrystallised from acetone

Sources & evidence

ORD record
ord-9cf166ad5ef24f4daa7939b1c8f3b75a
Source dataset
uspto-grants-1994_03
Patent number
US05294620

Reaction notes

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