Sodium hydride → HCID 75066242, compound

HRID 2238432Notes

Reaction equation

HRID 2238432 reaction equation
[Br:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([S:12]([CH3:15])(=[O:14])=[O:13])[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][CH:8]=[C:9]([S:12]([CH3:15])(=[O:14])=[O:13])[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 44549921HCID 44549921, compound

Product 1

HCID 75066242HCID 75066242, compoundYield 97%

Reagents, catalysts & solvents 2

HCID 5234Sodium ChlorideSolventHCID 6228DimethylformamideSolvent

Procedure

A stirred solution of 203 (2.29 g, 5.72 mmol) in dry DMF (20 mL) was treated portionwise at 0° C. with NaH (275 mg, 60% in oil, 6.88 mmol). The mixture was warmed to room temperature for 30 min, then cooled to 0° C. and treated with 1,3-dichloropropene (1.66 mL, 18 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 (19:1) to give crude tert-butyl 1-bromo-7-(methylsulfonyl)-2-naphthyl(3-chloro-2-propen-1-yl)carbamate (204) (2.63 g, 97%) as a foam: 1H NMR [(CD3)2SO] (mixture of rotamers and B and Z forms) δ 8.78 (s, 1H), 8.32 (dd, J=8.6, 2.2 Hz, 1H), 8.18, 8.17 (2 d, J=8.7 Hz, 1H), 8.13-8.06 (1, 1H), 7.75, 7.70 (2 d, J=8.7 Hz, 1H), 6.44-6.29 (m, 1H), 6.20-6.01 (m, 1H), 4.58-4.48, 4.43-4.22, 4.16-4.05 (3 m, 21H), 3.35 (s, 3H), 1.50, 1.27 (2 s, 9H). HRMS (FAB) calcd. for C19H2279Br35ClCNO4S (m/z 474.0141, found 474.0143.

Workup

  1. temperaturecooled to 0° 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 (19:1)

Sources & evidence

ORD record
ord-abd1071b91c948d4b1148d925f0a37ee
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

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