Iodine → HCID 90412117, compound

HRID 1522014Notes

Reaction equation

HRID 1522014 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]([O:27][CH3:28])=[C:6]([C:8]2[CH:13]=[CH:12][N:11]=[C:10]3[N:14]([S:17]([C:20]4[CH:26]=[CH:25][C:23]([CH3:24])=[CH:22][CH:21]=4)(=[O:19])=[O:18])[CH:15]=[CH:16][C:9]=23)[CH:7]=1.C([N-]C(C)C)(C)C.[Li+].[I:37]I.[Cl-].[NH4+]>O1CCCC1>[F:1][C:2]1[CH:3]=[CH:4][C:5]([O:27][CH3:28])=[C:6]([C:8]2[CH:13]=[CH:12][N:11]=[C:10]3[N:14]([S:17]([C:20]4[CH:26]=[CH:25][C:23]([CH3:24])=[CH:22][CH:21]=4)(=[O:19])=[O:18])[C:15]([I:37])=[CH:16][C:9]=23)[CH:7]=1

Participants

6

Reactant 4

HCID 807IodineHCID 25517Ammonium ChlorideHCID 2724682Lithium diisopropylamideHCID 90412716HCID 90412716, compound

Product 1

HCID 90412117HCID 90412117, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of Example 258B (98 g, 247.2 mmol) in tetrahydrofuran (3528 mL) was added lithium diisopropylamide (1.8M in tetrahydrofuran/heptane/ethylbenzene, 233.4 mL, 420.2 mmol) at −78° C. The mixture was stirred for 20 minutes and a solution of iodine (116.07 g, 457.3 mmol) in tetrahydrofuran (392 mL) was added drop wise over 20 minutes, maintaining the temperature below −70° C. After 30 minutes, the mixture was poured into a saturated ammonium chloride (980 mL) and extracted with ethyl acetate (twice). The combined extracts were washed with saturated sodium thiosulfate (twice) and brine, dried over sodium sulfate, filtered, and concentrated. The residue was purified by flash chromatography on silica gel eluting with 0-11% ethyl acetate in 10% dichloromethane/petroleum ether to afford the title compound.

Workup

  1. temperaturemaintaining the temperature below −70° C
  2. waitAfter 30 minutes
  3. extractionextracted with ethyl acetate (twice)
  4. washThe combined extracts were washed with saturated sodium thiosulfate (twice) and brine
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by flash chromatography on silica gel eluting with 0-11% ethyl acetate in 10% dichloromethane/petroleum ether

Sources & evidence

ORD record
ord-c4f9b8ddfe3e49fea51dc4f4da37edbc
Source dataset
uspto-grants-2015_07
Patent number
US09073922B2

Reaction notes

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