Sodium hydride → HCID 75066176, compound

HRID 2238407Notes

Reaction equation

HRID 2238407 reaction equation
[Br:1][C:2]1[C:11]2[C:6](=[CH:7][C:8]([S:12]([CH3:15])(=[O:14])=[O:13])=[CH:9][CH:10]=2)[CH:5]=[CH:4][C:3]=1[NH:16][C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20].[H-].[Na+].[Cl:26][CH:27]=[CH:28][CH2:29]Cl>CN(C=O)C.[Na+].[Cl-]>[Br:1][C:2]1[C:11]2[C:6](=[CH:7][C:8]([S:12]([CH3:15])(=[O:14])=[O:13])=[CH:9][CH:10]=2)[CH:5]=[CH:4][C:3]=1[N:16]([CH2:29][CH:28]=[CH:27][Cl:26])[C:17](=[O:23])[O:18][C:19]([CH3:20])([CH3:22])[CH3:21]

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 248831,3-DichloropropeneHCID 44549796HCID 44549796, compound

Product 1

HCID 75066176HCID 75066176, compoundYield 970%

Reagents, catalysts & solvents 2

HCID 5234Sodium ChlorideSolventHCID 6228DimethylformamideSolvent

Procedure

A stirred suspension of 162 (4.70 g, 11.74 mmol) in dry DMF (40 mL) was treated portionwise at 0° C. with NaH (564 mg, 60% in oil, 14.10 mmol). The mixture was warmed to room temperature for 1 h then cooled to O—C and treated with 1,3-dichloropropene (3.4 mL, 37 mmol, mixed isomers). The mixture was stirred at room temperature for a further 6 h, then diluted with 10% aqueous NaCl and extracted with EtOAc (×2). The combined organic layers were washed with water (×2), dried, and concentrated to dryness under reduced pressure at 100° C. The residue was chromatographed on silica gel, eluting with CH2Cl2/EtOAc (9:1) to give tert-butyl 1-bromo-6-(methylsulfonyl)-2-naphthyl(3-chloro-2-propen-1-yl)carbamate (163) (5.41 g, 970%) as a foam; 1H NMR [(CD3)2SO] (mixture of rotamers and E and Z forms) δ 8.73-8.69 (m, 1H), 8.46 (d, J=9.0 Hz, 1H, 8.30, 8.29 (2 d, J=8.6 Hz, 1H), 8.14 (dd, J=9.0, 1.8 Hz, 1H), 7.71, 7.68 (2 d, J=8.6 Hz, 1H), 6.43-6.28 (m, 1H), 6.19-6.01 (m, 1 H), 4.59-4.48, 4.44-4.23, 4.19-4.05 (3 m, 2H), 327 (after D2O exchange, s, 3H), 1.50, 1.26 (2 s, 9H). HRMS (FAB) calcd. for C19H2279Br35ClNO4S (MH+) m/z 474.0141, found 474.0142.

Workup

  1. temperaturethen cooled to O—C
  2. extractionextracted with EtOAc (×2)
  3. washThe combined organic layers were washed with water (×2)
  4. customdried
  5. concentrationconcentrated to dryness under reduced pressure at 100° C
  6. customThe residue was chromatographed on silica gel
  7. washeluting with CH2Cl2/EtOAc (9:1)

Sources & evidence

ORD record
ord-fbe3b29cc16e4450808831a339c3f586
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

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