Ammonium Chloride → HCID 19918927, compound

HRID 2044125Notes

Reaction equation

HRID 2044125 reaction equation
[CH:1]([Mg]Br)=[CH2:2].[Br:5][C:6]1[CH:7]=[C:8]([N+:13]([O-])=O)[CH:9]=[CH:10][C:11]=1[Cl:12].[NH4+].[Cl-]>C1COCC1>[Br:5][C:6]1[C:11]([Cl:12])=[CH:10][CH:9]=[C:8]2[C:7]=1[CH:1]=[CH:2][NH:13]2.[Br:5][C:6]1[CH:7]=[C:8]2[C:9]([CH:1]=[CH:2][NH:13]2)=[CH:10][C:11]=1[Cl:12]

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 27355492-Bromo-1-chloro-4-nitrobenzeneHCID 178418507HCID 178418507, compound

Product 2

HCID 19918927HCID 19918927, compoundYield 9.7%HCID 534044606-Bromo-5-chloro-1H-indoleYield 7.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A 1.0 M solution of vinylmagnesium bromide in THF (0.13 L, 130 mmol) is added slowly to 10 g (43 mmol) of 3-bromo-4-chloro-nitrobenzene in 140 mL of THF at −40° C. The mixture is stirred at −40 C for an additional hour when aqueous NH4Cl is added. The mixture is allowed to warm to rt, and then is extracted with EtOAc. The extract is washed with brine, dried over MgSO4, filtered, concentrated, and purified twice by chromatography (33% EtOAc in hexanes) to provide 0.95 g (9.7%) of 4-bromo-5-chloro-1H-indole and 0.77 g (7.9%) of 6-bromo-5-chloro-1H-indole. Each of the indole products is separately treated with 1.1 equivalents of Boc2O and 0.2 equivalents of DMAP in MeCN. The mixtures are concentrated and the residues chromatographed (10% EtOAc in hexanes) to provide I-011 (32%) and I-012 (48%).

Workup

  1. additionis added
  2. extractionis extracted with EtOAc
  3. washThe extract is washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. custompurified twice by chromatography (33% EtOAc in hexanes)

Sources & evidence

ORD record
ord-43ee12ea5281407d9c8649597033b336
Source dataset
uspto-grants-2013_11
Patent number
US08586748B2

Reaction notes

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