Methyl iodide → HCID 22277794, compound

HRID 1064009Notes

Reaction equation

HRID 1064009 reaction equation
Br[C:2]1[C:3]([NH:17][C:18](=[O:23])[C:19]([CH3:22])([CH3:21])[CH3:20])=[CH:4][C:5]2[C:9]3[CH:10]=[CH:11][CH:12]=[CH:13][C:8]=3[S:7](=[O:15])(=[O:14])[C:6]=2[CH:16]=1.[C:24]([Li])(C)(C)C.CCCCC.IC.C([O-])(=O)C.[NH4+]>C1COCC1.C(Cl)Cl>[CH3:24][C:2]1[C:3]([NH:17][C:18](=[O:23])[C:19]([CH3:22])([CH3:21])[CH3:20])=[CH:4][C:5]2[C:9]3[CH:10]=[CH:11][CH:12]=[CH:13][C:8]=3[S:7](=[O:15])(=[O:14])[C:6]=2[CH:16]=1

Participants

8

Reactant 5

HCID 6328Methyl iodideHCID 8003PentaneHCID 517165Ammonium AcetateHCID 22277833HCID 22277833, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 22277794HCID 22277794, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

3-Bromo-5,5-dioxo-2-pivaloylaminodibenzothiophene (Example 70; 0.1 g, 0.254 mmol) was suspended in dry THF (2 ml) under argon, cooled to −70° C. and 1.7 M tert-butyllithium in pentane (0.49 ml, 0.838 mmol) was added dropwise over 5 minutes. The mixture was allowed to warm to −30° C. and the suspension slowly dissolved as the solution darkened. The mixture was then re-cooled to −70° C. and iodomethane (0.17 ml, 0.279 mmol) added and stirred for 30 minutes. Saturated ammonium acetate (5 ml) and DCM (25 ml) were added and the organic phase washed with water and dried. The mixture was evaporated in vacuo and the residue purified by preparative HPLC (Dynamax C-18 60A column eluted with 30-90% acetonitrile in water plus 0.1% trifluoroacetic acid) to give the product as a colourless solid. NMR: 9.16 (s, 1H), 8.13 (d, 1H), 7.99 (s, 1H), 7.92 (d, 1H), 7.86 (s, 1H), 7.76 (t, 1H), 7.61 (t, 1H), 2.28 (s, 3H), 1.26 (s, 9H); m/z 330.

Workup

  1. temperatureto warm to −30° C.
  2. dissolutionthe suspension slowly dissolved as the solution
  3. temperatureThe mixture was then re-cooled to −70° C.
  4. washthe organic phase washed with water
  5. customdried
  6. customThe mixture was evaporated in vacuo
  7. customthe residue purified by preparative HPLC (Dynamax C-18 60A column eluted with 30-90% acetonitrile in water plus 0.1% trifluoroacetic acid)

Sources & evidence

ORD record
ord-36b79c1520034a488ac981a2f0f0f080
Source dataset
uspto-grants-2005_11
Patent number
US06967216B2

Reaction notes

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