Bromine → 5-Bromo-2,3-dihydro-7-azaindole

HRID 1994185Notes

Reaction equation

HRID 1994185 reaction equation
[Br:1]Br.[NH:3]1[C:7]2=[N:8][CH:9]=[CH:10][CH:11]=[C:6]2[CH2:5][CH2:4]1.C([O-])(O)=O.[Na+].[O-]S([O-])(=S)=O.[Na+].[Na+]>C(Cl)Cl.CO.N1C=CC=CC=1>[Br:1][C:10]1[CH:11]=[C:6]2[CH2:5][CH2:4][NH:3][C:7]2=[N:8][CH:9]=1

Participants

8

Reactant 4

HCID 24408BromineHCID 24477Sodium ThiosulfateHCID 516892Sodium BicarbonateHCID 100118891H,2H,3H-pyrrolo(2,3-b)pyridine

Product 1

HCID 219640795-Bromo-2,3-dihydro-7-azaindoleYield 85%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 1049PyridineSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of Br2 (18.1 mL, 56.2 g, 0.351 mol) in dry CH2Cl2 (250 mL) was added dropwise over a period of 1 h 45 min to a stirred and cooled (−5° C.) solution of 2 (42.22 g, 0.351 mol) in dry CH2Cl2 (410 mL)-pyridine (40 mL). The yellow suspension was stirred at 0° C. for 45 min and poured into a mixture of saturated aqueous NaHCO3 (800 mL) and saturated aqueous Na2S2O3 (100 mL). Methanol (10 mL) was added and the lower organic layer was separated and dried over MgSO4. The aqueous layer was extracted with AcOEt:MeOH=99:1 (7×1000 mL). These extracts were also dried with MgSO4. The organic solutions were combined and concentrated to afford 5 (59.17 g, 85%), which was used in the next step without further purification. 1H NMR (400 MHz, CDCl3) δ 3.07 (tt, J=8.4, 1.1 Hz, 2H), 3.64 (t, J=8.4 Hz, 2H), 4.47 (bs, 1H), 7.31 (m, 1H), 7.85 (dt, J=2.1, 0.9 Hz, 1H).

Workup

  1. stirringThe yellow suspension was stirred at 0° C. for 45 min
  2. customthe lower organic layer was separated
  3. dry with materialdried over MgSO4
  4. extractionThe aqueous layer was extracted with AcOEt
  5. dry with materialThese extracts were also dried with MgSO4
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-91fda395bed54d67b137117b4a13a5d6
Source dataset
uspto-grants-2010_01
Patent number
US07652137B2

Reaction notes

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