Benzyl Bromide → HCID 69231351, compound

HRID 915349Notes

Reaction equation

HRID 915349 reaction equation
[Br:1]N1C(=O)CCC1=O.[N+:9]([C:12]1[CH:13]=[C:14]2[C:18](=[CH:19][CH:20]=1)[NH:17][C:16]([C:21]([O:23][CH2:24][CH3:25])=[O:22])=[CH:15]2)([O-:11])=[O:10].[CH2:26](Br)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1.C([O-])([O-])=O.[Cs+].[Cs+]>CN(C=O)C.O>[CH2:26]([N:17]1[C:18]2[C:14](=[CH:13][C:12]([N+:9]([O-:11])=[O:10])=[CH:20][CH:19]=2)[C:15]([Br:1])=[C:16]1[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

7

Reactant 4

HCID 7498Benzyl BromideHCID 10796Cesium carbonateHCID 67184N-bromobutanimideHCID 280312Ethyl 5-nitro-1H-indole-2-carboxylate

Product 1

HCID 69231351HCID 69231351, compoundYield 61.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Procedure

A solution of N-bromosuccinimide (0.83 g, 4.7 mmol) in DMF (5 mL) was added dropwise to a stirred solution of ethyl 5-nitro-1H-indole-2-carboxylate (1.0 g, 4.27 mmol) in DMF (5 mL) at 0˜5° C. After the addition was completed, the reaction was warmed to room temperature and stirring was continued for an additional 1.5 h. The reaction mixture was poured over ice water and the resulting precipitate was collected and dried. The dried solid was re-dissolved in DMF (10 mL) and benzyl bromide (0.68 g, 4.0 mmol) and Cs2CO3 (6.56 g, 20 mmol) were added successively. The reaction was stirred for overnight and then diluted with water. The product was extracted with ethyl acetate, dried over magnesium sulfate. Recrystalization from ethyl acetate and hexane gave 0.99 g (57%) of ethyl 1-benzyl-3-bromo-5-nitro-1H-indole-2-carboxylate as an off-white solid: 1H NMR (DMSO-d6) δ 1.28 (t, J=7.0 Hz, 3 H), 4.35 (q, J=7.0 Hz, 2 H), 5.90 (s, 2 H), 7.00-7.10 (m, 2 H), 7.20-7.35 (m, 3 H), 7.95 (d, J=9.3 Hz, 1 H), 8.25 (dd, J=9.3, 2.0 Hz, 1 H), 8.48 (d, J=2.0 Hz, 1 H); MS (ESI) m/z 403/405 (MH+).

Workup

  1. additionAfter the addition
  2. customthe resulting precipitate was collected
  3. customdried
  4. dissolutionThe dried solid was re-dissolved in DMF (10 mL)
  5. stirringThe reaction was stirred for overnight
  6. extractionThe product was extracted with ethyl acetate
  7. dry with materialdried over magnesium sulfate
  8. customRecrystalization from ethyl acetate and hexane

Sources & evidence

ORD record
ord-d5cc4784d370466bb8cb20feed3860dd
Source dataset
uspto-grants-2007_09
Patent number
US07265148B2

Reaction notes

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