Phosphorus trichloride → HCID 136338372, compound

HRID 2245553Notes

Reaction equation

HRID 2245553 reaction equation
[H-].[Na+].[O:3]=[C:4]1[CH2:12][C:11]2[C:6](=[CH:7][C:8]([C:13]#[N:14])=[CH:9][CH:10]=2)[NH:5]1.Cl[C:16]1[CH:26]=[CH:25][C:19]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:18][N+:17]=1[O-].P(Cl)(Cl)Cl>C(=O)([O-])O.[Na+].CN(C)C=O>[C:13]([C:8]1[CH:7]=[C:6]2[C:11]([C:12]([C:16]3[CH:26]=[CH:25][C:19]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:18][N:17]=3)=[C:4]([OH:3])[NH:5]2)=[CH:10][CH:9]=1)#[N:14]

Participants

7

Reactant 4

HCID 24387Phosphorus trichlorideHCID 24758Sodium hydrideHCID 27733482-Oxindole-6-carbonitrileHCID 11252660HCID 11252660, compound

Product 1

HCID 136338372HCID 136338372, compoundYield 60%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 516892Sodium BicarbonateSolvent2×

Procedure

To a N,N-dimethylformamide (6 mL) suspension of sodium hydride (97%, 0.144 g, 6.0 mmol) was added 2-oxoindoline-6-carbonitrile (0.712 g, 4.5 mmol). The formed mixture was stirred for 10 min at room temperature followed by the addition of ethyl 6-chloronicotinate 1-oxide (0.605 g, 3.0 mmol). The resulting reaction mixture was set under N2 atmosphere and stirred for 2 h at room temperature. The N,N-dimethylformamide reaction solution was diluted with a saturated aqueous sodium hydrogen carbonate solution and extracted with chloroform and ethyl acetate. The combined organic layers were dried (Na2SO4) and concentrated in vacuo. The remaining N,N-dimethylformamide was removed by co-evaporation with toluene. The residue was dissolved in chloroform (10 mL) and phosphorus trichloride (1.65 g, 12.0 mmol) was added. The reaction mixture was stirred for 30 min at 60° C. and then cooled to room temperature. The mixture was poured into a saturated aqueous sodium hydrogen carbonate solution. The resulting brown precipitate was filtered off and the mother liquor was extracted with chloroform (4×). The organic layers were concentrated in vacuo and the residue was combined with the filtrate and was washed with ethyl acetate and diethyl ether to afford 0.55 g (60% yield) of the title compound as a yellow-brown solid: 1H NMR (DMSO-d6, 400 MHz) δ 8.85 (s, 1H), 8.06 (s, 1H), 8.00 (d, J=8.8 Hz, 1H), 7.75 (d, J=8.0 Hz, 1H), 7.69 (d, J=8.0 Hz, 1H), 7.45 (s, 1H), 7.29 (d, J=8.8 Hz, 1H), 4.33 (m, 2H), 1.35 (t, J=7.2 Hz, 3H); MS (EI) m/z 308 (M++1).

Workup

  1. customThe resulting reaction mixture
  2. stirringstirred for 2 h at room temperature
  3. extractionextracted with chloroform and ethyl acetate
  4. dry with materialThe combined organic layers were dried (Na2SO4)
  5. concentrationconcentrated in vacuo
  6. customThe remaining N,N-dimethylformamide was removed by co-evaporation with toluene
  7. dissolutionThe residue was dissolved in chloroform (10 mL)
  8. stirringThe reaction mixture was stirred for 30 min at 60° C.
  9. temperaturecooled to room temperature
  10. filtrationThe resulting brown precipitate was filtered off
  11. extractionthe mother liquor was extracted with chloroform (4×)
  12. concentrationThe organic layers were concentrated in vacuo
  13. washwas washed with ethyl acetate and diethyl ether

Sources & evidence

ORD record
ord-9adede50055b41b8a4520e7c1570a6af
Source dataset
uspto-grants-2010_03
Patent number
US07683067B2

Reaction notes

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