Cesium carbonate → HCID 23405921, compound

HRID 489116Notes

Reaction equation

HRID 489116 reaction equation
[Br:1][C:2]1[CH:23]=[CH:22][CH:21]=[CH:20][C:3]=1[CH2:4][N:5]1[C:13]2[C:8](=[C:9]([O:17][CH3:18])[CH:10]=[C:11]3[CH2:16][CH2:15][CH2:14][C:12]3=2)[CH:7]=[C:6]1[CH3:19].B(Br)(Br)Br.C(=O)([O-])[O-].[Cs+].[Cs+].BrC[C:36]([O:38][CH3:39])=[O:37]>C(Cl)Cl.CO.C(=O)(O)[O-].[Na+]>[CH3:39][O:38][C:36](=[O:37])[CH2:18][O:17][C:9]1[CH:10]=[C:11]2[CH2:16][CH2:15][CH2:14][C:12]2=[C:13]2[C:8]=1[CH:7]=[C:6]([CH3:19])[N:5]2[CH2:4][C:3]1[CH:20]=[CH:21][CH:22]=[CH:23][C:2]=1[Br:1]

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 25134Boron tribromideHCID 60984Methyl bromoacetateHCID 22268701HCID 22268701, compound

Product 1

HCID 23405921HCID 23405921, compoundYield 84%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 6344DichloromethaneSolventHCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
-10 °C

Procedure

A solution of 1-(2-bromobenzyl)-2-methyl-4-methoxy-1,6,7,8-tetrahydrocyclopent[g]indole (1.28 g, 3.40 mmol) in methylene chloride (20 mL) was cooled in an ice/methanol bath and treated with boron tribromide (0.65 mL, 6.9 mmol). The mixture was warmed to −10° C. over 1.5 h then diluted with methanol (2 mL) and excess saturated aqueous sodium bicarbonate solution. The aqueous layer was separated and extracted with a fresh portion of methylene chloride. The combined methylene chloride layers were washed once with water, dried (magnesium sulfate), filtered, and concentrated in vacuo. The residue was dissolved in methylene chloride and filtered through a pad of silica gel. The filtrate was concentrated in vacuo and the residue dissolved in N,N-dimethylformamide (5 mL) and treated with cesium carbonate (1.00 g, 3.06 mmol) and methyl bromoacetate (0.29 mL, 3.1 mmol) at room temperature for 20 h. The mixture was concentrated in vacuo via vacuum transfer and the residue dissolved in methylene chloride and filtered through a pad of silica gel. The filtrate was concentrated in vacuo. Chromatography (silica gel, methylene chloride/hexanes) of the residue provided 1.10 g (84%) of the title compound. 1H NMR (CDCl3) δ 7.59 (m, 1H), 7.07 (m, 2H), 6.47 (s, 1H), 6.33 (s, 1H), 6.18 (m, 1H), 5.35 (bs, 2H), 4.74 (s, 3H), 3.80 (s, 3H), 2.86 (m, 4H), 2.26 (s, 3H), 1.99 (quintet, J=7.3 Hz, 2H); MS ES+ m/e 428, 430 (p+1).

Workup

  1. customThe aqueous layer was separated
  2. extractionextracted with a fresh portion of methylene chloride
  3. washThe combined methylene chloride layers were washed once with water
  4. dry with materialdried (magnesium sulfate)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. dissolutionThe residue was dissolved in methylene chloride
  8. filtrationfiltered through a pad of silica gel
  9. concentrationThe filtrate was concentrated in vacuo
  10. dissolutionthe residue dissolved in N,N-dimethylformamide (5 mL)
  11. concentrationThe mixture was concentrated in vacuo via vacuum transfer
  12. dissolutionthe residue dissolved in methylene chloride
  13. filtrationfiltered through a pad of silica gel
  14. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-286d3da580b24691a4ebaafb62f25e81
Source dataset
uspto-grants-2005_12
Patent number
US06974831B2

Reaction notes

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