Methyl iodide → HCID 67552691, compound

HRID 2087003Notes

Reaction equation

HRID 2087003 reaction equation
[CH3:1][N:2]1[C:14]2[CH2:13][CH2:12][C@@H:11]([NH:15][C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[CH2:10][C:9]=2[C:8]2[C:3]1=[CH:4][CH:5]=[C:6]([S:23]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)(=[O:25])=[O:24])[CH:7]=2.[H-].[Na+].[CH3:34]I>CN(C=O)C>[CH3:34][N:15]([C@H:11]1[CH2:10][C:9]2[C:8]3[C:3](=[CH:4][CH:5]=[C:6]([S:23]([C:26]4[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=4)(=[O:25])=[O:24])[CH:7]=3)[N:2]([CH3:1])[C:14]=2[CH2:13][CH2:12]1)[C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:19])[CH3:20]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 86588260HCID 86588260, compound

Product 1

HCID 67552691HCID 67552691, compoundYield 76%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution of tert-butyl (3R)-9-methyl-6-(phenylsulfonyl)-2,3,4,9-tetrahydro-1H-carbazol-3-ylcarbamate (1.74 g, 3.95 mmol) in DMF (13.0 mL) was added to a 0° C. suspension of 60% sodium hydride (0.38 g, 9.62 mmol) in DMF (3.0 mL) and stirred at room temperature for 1.1 hours. Methyl iodide (0.30 mL, 4.81 mmol) was added, and the reaction was stirred at room temperature for 2.0 hours. The reaction was cooled to 0° C., quenched with water and filtered. The filtrate was concentrated in vacuo, combined with the previously filtered solid and partitioned between ethyl acetate and water. The organic layer was washed with brine, dried over MgSO4 and concentrated in vacuo to dryness, the residue was recrystallized from EtOAc/hexane to give 1.36 g (76%) of tert-butyl methyl[(3R)-9-methyl-6-(phenylsulfonyl)-2,3,4,9-tetrahydro-1H-carbazol-3-yl]carbamate as a colorless solid: mp 181.4-183.2° C.; [α]D=+103° (c 1.02, DMSO); 1H NMR (400 MHz, DMSO-d6) δ 8.06, 7.93-7.91, 7.62-7.53, 4.22, 3.64, 2.96-2.92, 2.84-2.79, 1.99-1.94, 1.42; 13C NMR (100 MHz, DMSO-d6) δ 155.6, 142.8, 138.7, 138.0, 132.7, 130.5, 129.3, 126.7, 125.9, 119.1, 118.0, 110.0, 108.6, 78.5, 29.3, 28.5, 28.0, 26.4, 23.5, 21.2; IR (diffuse reflectance) 1684, 1481, 1448, 1398, 1378, 1364, 1357, 1304, 1184, 1149 (s), 1103, 732, 690, 622, 612 cm−1; HRMS (FAB) calcd for C25H30N2O4S+H 455.2004, found 455.2027; Anal. Calcd for C25H30N2O4S: C, 66.05; H, 6.65; N, 6.16. Found: C, 65.99; H, 6.66; N, 6.19.

Workup

  1. stirringthe reaction was stirred at room temperature for 2.0 hours
  2. temperatureThe reaction was cooled to 0° C.
  3. customquenched with water
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated in vacuo
  6. custompartitioned between ethyl acetate and water
  7. washThe organic layer was washed with brine
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated in vacuo to dryness
  10. customthe residue was recrystallized from EtOAc/hexane

Sources & evidence

ORD record
ord-3d570d5738ff43308cac0e9c1582b3e6
Source dataset
uspto-grants-2004_04
Patent number
US06727274B2

Reaction notes

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