Triethylamine → HCID 22609789, compound

HRID 2306689Notes

Reaction equation

HRID 2306689 reaction equation
S(Cl)(Cl)(=O)=O.[CH3:6][S:7][CH2:8][C:9]([O:11]CC)=O.[C:14]([C:16]1[CH:22]=[CH:21][C:19]([NH2:20])=[CH:18][CH:17]=1)#[N:15].CN(C)C1C2C(=CC=CC=2N(C)C)C=CC=1.C(N(CC)CC)C>ClCCl.C(O)(=O)C>[C:14]([C:16]1[CH:17]=[CH:18][C:19]2[C:21](=[C:8]([S:7][CH3:6])[C:9](=[O:11])[N:20]=2)[CH:22]=1)#[N:15]

Participants

8

Reactant 5

HCID 8471TriethylamineHCID 133964-AminobenzonitrileHCID 24648Sulfuryl chlorideHCID 78199Ethyl (methylthio)acetateHCID 88675Proton sponge

Product 1

HCID 22609789HCID 22609789, compoundYield 32.6%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

Sulphuryl chloride (3.4 ml , 5.71 g, 42.4 mmol) was added via syringe to a stirred solution of ethyl 2-(methylthio)acetate (5.4 ml, 5.63 g, 42.0 mmol) in dry dichloromethane (30 ml) cooled to −78° C., under a nitrogen atmosphere. After stirring for 15 min, a solution of 4-cyanoaniline (5.0 g, 42.3 mmol) and 1,8-bis(dimethylamino) naphthalene (9.0 g, 42.0 mmol) in dry dichloromethane (50 ml) was added maintaining the temperature at −78° C. Stirring was continued for 3 hours at −78° C., and then triethylamine (5.9 ml , 4.28 g, 42.3 mmol) was added at −78° C., and then the mixture was allowed to warm to room temperature. Stirring was continued under a nitrogen atmosphere for 3 days. Glacial acetic acid (5.0 ml, 5.25 g, 87.3 ml) was then added and the mixture was stirred for 1 hour. The reaction mixture was washed with 8%aq. NaHCO3 (50 ml) and water (2×100 ml), dried (Na2CO3), and concentrated in vacuo. Silica gel chromatography, eluting with 1:2 ethyl acetate/i-hexane, gave 5-cyano-3-methylthio-2-oxoindole as a yellow solid (2.8 g, 13.7 mmol, 32%); δH CDCl3 8.95 (1H, br s), 7.67 (1H, s). 7.60 (1H, d), 7.01 (1H, d), 4.30 (1H, s), 2.08 (3H, s).

Workup

  1. temperaturemaintaining the temperature at −78° C
  2. stirringStirring
  3. waitwas continued for 3 hours at −78° C.
  4. temperatureto warm to room temperature
  5. stirringStirring
  6. waitwas continued under a nitrogen atmosphere for 3 days
  7. stirringthe mixture was stirred for 1 hour
  8. washThe reaction mixture was washed with 8%aq
  9. dry with materialNaHCO3 (50 ml) and water (2×100 ml), dried (Na2CO3)
  10. concentrationconcentrated in vacuo
  11. washSilica gel chromatography, eluting with 1:2 ethyl acetate/i-hexane

Sources & evidence

ORD record
ord-7f53366e340d44de9623e6e6ad724554
Source dataset
uspto-grants-2004_12
Patent number
US06828320B2

Reaction notes

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