Iodoethane → HCID 49854629, compound

HRID 2368840Notes

Reaction equation

HRID 2368840 reaction equation
[C:1]([C:3]([C:11]1[C:19]2[C:14](=[CH:15][CH:16]=[C:17]([OH:20])[CH:18]=2)[N:13](C(OC(C)(C)C)=O)[CH:12]=1)=[CH:4][C:5]1[CH:6]=[N:7][CH:8]=[CH:9][CH:10]=1)#[N:2].[CH2:28](I)[CH3:29].C(=O)([O-])[O-].[K+].[K+].C[O-].[Na+]>CS(C)=O.C(OCC)C>[CH2:28]([O:20][C:17]1[CH:18]=[C:19]2[C:14](=[CH:15][CH:16]=1)[NH:13][CH:12]=[C:11]2/[C:3](=[CH:4]/[C:5]1[CH:6]=[N:7][CH:8]=[CH:9][CH:10]=1)/[C:1]#[N:2])[CH3:29]

Participants

7

Reactant 4

HCID 6340IodoethaneHCID 11430Potassium CarbonateHCID 10942334Sodium MethoxideHCID 67514100HCID 67514100, compound

Product 1

HCID 49854629HCID 49854629, compound

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 3283Diethyl EtherSolvent

Procedure

To a solution of tert-butyl 3-(1-cyano-2-(pyridin-3-yl)vinyl)-5-hydroxy-1H-indole-1-carboxylate (110 mg, 0.30 mmol, 1.0 eq.) and ethyl iodide (32 μL, 0.40 mmol, 1.3 eq.) in DMSO (8 mL) was added potassium carbonate (100 mg, 0.73 mmol, 2.4 eq.). The reaction apparatus was protected from light and the mixture was stirred at room temperature for 24 hours before sodium methanolate (41 mg, 0.75 mmol, 2.5 eq.) was added. The reaction was pursued at room temperature for 1 hour, and then quenched with a saturated aqueous ammonium chloride solution. The mixture was extracted with ethyl acetate and the organic layer was washed with brine, and then dried over MgSO4. The solvent was removed under reduced pressure, and the residue purified by silica gel flash-column chromatography (eluent: heptane/EtOAc, 60:40 to 40:60) to afford, after trituration with diethyl ether, the compound (22) as a yellow powder (60 mg, 69%). mp: 196° C.; IR νmax (cm-1): 2216 (νCN); 1H NMR (DMSO, 300 MHz): δ (ppm): 1.36 (3H, t, J9′-8′=7.0 Hz, 3H9′), 4.10 (2H, q, J8′-9′=7.0 Hz, 2H8′), 6.90 (1H, dd, J6′-7′=8.9 Hz, J6′-4′=2.1 Hz, H6′), 7.40 (1H, d, J7′-6′=8.9 Hz, H7′), 7.48 (1H, d, J4′-6′=2.1 Hz, H4′), 7.54 (1H, dd, J5″-4″=7.9 Hz, J5″-6″=4.7 Hz, H5″), 7.74 (1H, s, H3), 7.78 (1H, s, H2′), 8.32 (1H, d, J4″-5″=8.1 Hz, H4″), 8.58 (1H, dd, J6″-5″=4.8 Hz, J6″-4″=1.6 Hz, H6″), 8.98 (1H, d, J2″-4″=2.3 Hz, H2″), 11.65 (1H, s, indolic H); 13C NMR (DMSO, 75.5 MHz): δ (ppm): 15.3 (C9′), 64.1 (C8′), 103.3 (C4′), 108.7 (C2), 110.6 (C3′), 113.3 (C6′), 113.6 (C7′), 118.6 (C1), 124.1 (C5″), 124.5 (C3a′), 128.1 (C2′), 131.4 (C3″), 132.7 (C3 and C7a′), 135.1 (C4″), 150.0 (C6″), 150.4 (C2″), 154.2 (C5′); ESI-MS: m/z 290.1 ([M+H]+), 312.1 ([M+Na]+); HRESI-MS: m/z 290.1293 (calcd for C18H16N3O, 290.1293).

Workup

  1. additionwas added
  2. customquenched with a saturated aqueous ammonium chloride solution
  3. extractionThe mixture was extracted with ethyl acetate
  4. washthe organic layer was washed with brine
  5. dry with materialdried over MgSO4
  6. customThe solvent was removed under reduced pressure
  7. customthe residue purified by silica gel flash-column chromatography (eluent: heptane/EtOAc, 60:40 to 40:60)
  8. customto afford

Sources & evidence

ORD record
ord-3dba19a0712841f4a91efbf61ddeef39
Source dataset
uspto-grants-2014_04
Patent number
US08703808B2

Reaction notes

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