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Dimethylacetamide → 10-bromo-3-(2-chlorobenzyl)-6,7-dihydro-5H-5,7-methanobenzo[c]imidazo[1,2-a]azepine-2-carboxamide

HRID 575467
Notes
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Reaction equation

HRID 575467 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[CH:11]3[CH2:12][CH:9]([CH2:10]3)[N:8]3[C:13](I)=[C:14]([C:16](OC)=[O:17])[N:15]=[C:7]3[C:6]=2[CH:21]=1.[Br-].[Cl:23][C:24]1[CH:31]=[CH:30][CH:29]=[CH:28][C:25]=1[CH2:26][Zn+].CC([N:35](C)C)=O>[Zn]>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[CH:11]3[CH2:10][CH:9]([CH2:12]3)[N:8]3[C:13]([CH2:26][C:25]4[CH:28]=[CH:29][CH:30]=[CH:31][C:24]=4[Cl:23])=[C:14]([C:16]([NH2:35])=[O:17])[N:15]=[C:7]3[C:6]=2[CH:21]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 31374DimethylacetamideHCID 86693477Methyl 10-bromo-3-iodo-6,7-dihydro-5H-5,7-methanobenzo[c]imidazo[1,2-a]azepine-2-carboxylateHCID 178478033HCID 178478033, compound

Product 1

HCID 8669353210-bromo-3-(2-chlorobenzyl)-6,7-dihydro-5H-5,7-methanobenzo[c]imidazo[1,2-a]azepine-2-carboxamide

Reagents, catalysts & solvents 1

HCID 23994
Zinc
Catalyst

Conditions

Temperature
50 °C

Procedure

A solution of methyl 10-bromo-3-iodo-6,7-dihydro-5H-5,7-methanobenzo[c]imidazo[1,2-a]azepine-2-carboxylate (150 mg, 0.33 mmol) in dry dimethylacetamide (DMA, 1.0 mL) was sparged with nitrogen gas and treated with PdCl2-[P(o-Tol)3]2 (27 mg, 0.033 mmol). A degassed solution of 2-chlorobenzylzinc bromide (0.61 M, 0.96 mL, 0.59 mmol) was added over 5 min dropwise. The flask was sealed under nitrogen and heated at 50° C. An additional 0.5 mL, of the zinc reagent was added under nitrogen sparge. After 30 min, LCMS indicated complete consumption. The mixture was diluted with ammonium chloride and extracted with ethyl acetate. The combined organics were washed with brine, dried over sodium sulfate and concentrated by rotoevaporation. The crude residue was dissolved in DMF (2 mL) and treated with formamide (1 mL) then sodium methoxide (0.5 mL, 25 wt % in methanol). After 20 min at 50° C., complete conversion to the amide was evident by LCMS. The mixture was diluted with water and extracted with ethyl acetate. The combined organics were washed with brine, dried over sodium sulfate and concentrated by rotoevaporation. The amide was used in subsequent steps without further purification.

Workup

  1. customThe flask was sealed under nitrogen
  2. customsparge
  3. customconsumption
  4. additionThe mixture was diluted with ammonium chloride
  5. extractionextracted with ethyl acetate
  6. washThe combined organics were washed with brine
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated by rotoevaporation
  9. dissolutionThe crude residue was dissolved in DMF (2 mL)
  10. additiontreated with formamide (1 mL)
  11. waitAfter 20 min at 50° C.
  12. additionThe mixture was diluted with water
  13. extractionextracted with ethyl acetate
  14. washThe combined organics were washed with brine
  15. dry with materialdried over sodium sulfate
  16. concentrationconcentrated by rotoevaporation
  17. customThe amide was used in subsequent steps without further purification

Sources & evidence

ORD record
ord-d5de18719a03437aab172cfaaa81a7a3
Source dataset
uspto-grants-2015_05
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09034866B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes