Sodium hydride → HCID 69306640, compound

HRID 2217266Notes

Reaction equation

HRID 2217266 reaction equation
[H-].[Na+].[I-].[CH3:4][S+](C)(C)=O.[NH2:9][C:10]1[C:15]([Br:16])=[CH:14][C:13]([C:17](=[O:24])/[CH:18]=[CH:19]/[C:20]([O:22][CH3:23])=[O:21])=[CH:12][C:11]=1[Br:25]>CS(C)=O>[NH2:9][C:10]1[C:11]([Br:25])=[CH:12][C:13]([C:17]([C@@H:18]2[CH2:4][C@H:19]2[C:20]([O:22][CH3:23])=[O:21])=[O:24])=[CH:14][C:15]=1[Br:16]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 17958699HCID 17958699, compound

Product 1

HCID 69306640HCID 69306640, compound

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent2×

Procedure

0.45 g (0.01781 mol) of 95% sodium hydride was added in small amounts to a solution of 3.9 g (0.02074 mol) of trimethyl-oxosulfonium iodide in 50 mL anhydrous dimethylsulfoxide at ambient temperature, with stirring. The mixture was stirred for another 30 minutes at ambient temperature and then a solution of 5.8 g (0.01598 mol) of methyl trans-4-(4-amino-3,5-dibromophenyl)-4-oxobutenoate in 50 mL of dimethylsulfoxide was added dropwise without external heating, whereupon the temperature of the mixture rose to 35° C., and stirring was continued for another hour at ambient temperature. The mixture was stirred into in 500 mL of saturated aqueous saline solution, then extracted exhaustively with ethyl acetate. The combined ethyl acetate extracts were dried over sodium sulfate and evaporated down in vacuo. The residue yielded 2.6 g (43% of theoretical) of a colorless oil after purification by column chromatography on silica gel (30 to 60 μm) using EE/cyclohexane (1/1 v/v) as eluant. IR (KBr): 3475, 3363 (NH2); 1728, 1662 (C═O) cm−1; MS: M+=375/377/379 (Br2).

Workup

  1. stirringThe mixture was stirred for another 30 minutes at ambient temperature
  2. customrose to 35° C.
  3. stirringstirring
  4. waitwas continued for another hour at ambient temperature
  5. extractionextracted exhaustively with ethyl acetate
  6. dry with materialThe combined ethyl acetate extracts were dried over sodium sulfate
  7. customevaporated down in vacuo
  8. customThe residue yielded 2.6 g (43% of theoretical) of a colorless oil
  9. customafter purification by column chromatography on silica gel (30 to 60 μm)

Sources & evidence

ORD record
ord-ef5d8f39081542cc9afe05a6365ce1f3
Source dataset
uspto-grants-2008_08
Patent number
US07407963B2

Reaction notes

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