Water → HCID 19756351, compound

HRID 1587826Notes

Reaction equation

HRID 1587826 reaction equation
[NH2:1][C:2]1[CH:3]=[CH:4][C:5]([O:8][CH2:9][CH2:10][O:11][Si:12]([C:25]([CH3:28])([CH3:27])[CH3:26])([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[N:6][CH:7]=1.[C:29]([CH2:33][C:34](OC)=[O:35])(=O)[CH2:30][CH3:31].O>C1CCCCC1.C1(C)C=CC(S(O)(=O)=O)=CC=1>[Si:12]([O:11][CH2:10][CH2:9][O:8][C:5]1[N:6]=[C:7]2[C:2](=[CH:3][CH:4]=1)[NH:1][C:29]([CH2:30][CH3:31])=[CH:33][C:34]2=[O:35])([C:25]([CH3:28])([CH3:27])[CH3:26])([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

6

Reactant 3

HCID 962WaterHCID 121699Methyl 3-oxovalerateHCID 19756412HCID 19756412, compound

Product 1

HCID 19756351HCID 19756351, compoundYield 51.4%

Reagents, catalysts & solvents 2

HCID 6101p-Toluenesulfonic acidCatalystHCID 8078CyclohexaneSolvent

Conditions

Temperature
260 °C

Procedure

A solution of compound C (89.5 g), methyl propionylacetate (32.8 g) and p-toluenesulphonic acid (1.0 g) in cyclohexane (900 ml) was heated under reflux with azeotropic removal of water for 20 hours. Volatile material was then removed from the reaction mixture by evaporation and the residue was dissolved in ethyl acetate (1 l). The solution was washed with saturated sodium hydrogen carbonate solution (500 ml), water (500 ml), saturated sodium chloride solution (500 ml), and then dried (MgSO4). The solvent was removed by evaporation and the residue dissolved in a eutectic mixture of 26.5% v/v diphenyl and 73.5% v/v diphenyl oxide (750 ml). The solution was heated to 260° C. and the temperature maintained for 30 minutes. The solution was cooled and diluted with hexane (1 l) to give 6-[2-(t-butyldiphenylsilyl)oxyethoxy]-2-ethyl-1,5-naphthyridin-4(1H)-one (D) (55.4 g), as a white solid, m.p. 209°-210° C.; NMR (d6 -DMSO): 1.1(s,9H), 1.35(t,3H), 2.8(q,2H), 4.15(t,2H), 4.65(t,2H), 6.3(br s,1H), 7.25(d,1H), 7.5-7.6(m,7H), 7.65-7.8(m,4H), 8.1(d,1H).

Workup

  1. customVolatile material was then removed from the reaction mixture by evaporation
  2. dissolutionthe residue was dissolved in ethyl acetate (1 l)
  3. washThe solution was washed with saturated sodium hydrogen carbonate solution (500 ml), water (500 ml), saturated sodium chloride solution (500 ml)
  4. dry with materialdried (MgSO4)
  5. customThe solvent was removed by evaporation
  6. dissolutionthe residue dissolved in a eutectic mixture of 26.5% v/v diphenyl and 73.5% v/v diphenyl oxide (750 ml)
  7. temperaturethe temperature maintained for 30 minutes
  8. temperatureThe solution was cooled
  9. additiondiluted with hexane (1 l)

Sources & evidence

ORD record
ord-c6a335c15aa345fbbb468bf74837cc62
Source dataset
uspto-grants-1993_06
Patent number
US05219863

Reaction notes

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