Methyl 3-(bromomethyl)benzoate → Methyl 3-((3-iodo-4-nitro-1H-indazol-1-yl)methyl)benzoate

HRID 706674Notes

Reaction equation

HRID 706674 reaction equation
[I:1][C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][C:9]=2[N+:11]([O-:13])=[O:12])[NH:4][N:3]=1.Br[CH2:15][C:16]1[CH:17]=[C:18]([CH:23]=[CH:24][CH:25]=1)[C:19]([O:21][CH3:22])=[O:20].C(N=C(N(C)C)N(C)C)(C)(C)C>CC#N>[I:1][C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][C:9]=2[N+:11]([O-:13])=[O:12])[N:4]([CH2:15][C:16]2[CH:17]=[C:18]([CH:23]=[CH:24][CH:25]=2)[C:19]([O:21][CH3:22])=[O:20])[N:3]=1

Participants

5

Reactant 3

HCID 517981Methyl 3-(bromomethyl)benzoateHCID 35715812-tert-Butyl-1,1,3,3-tetramethylguanidineHCID 178526562HCID 178526562, compound

Product 1

HCID 67976101Methyl 3-((3-iodo-4-nitro-1H-indazol-1-yl)methyl)benzoateYield 68.8%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a slurry of 3-iodo-4-nitro-1H-indazole (1.0 g, 3.46 mmol) and methyl 3-(bromomethyl)benzoate (1.59 g, 6.92 mmol) and CH3CN (12 mL) was added 2-tert-butyl-1,1,3,3-tetramethylguanidine (0.697 mL, 3.46 mmol) dropwise and the mixture was allowed to stir overnight at ambient temperature. The mixture was concentrated and diluted with saturated aqueous NH4Cl (40 mL) and EtOAc (70 mL). The layers were mixed and separated and the aqueous phase was extracted with EtOAc (25 mL). The combined organic extracts were washed with brine, dried over Na2SO4, filtered and concentrated. The crude product was purified by column chromatography (50% EtOAc/hexane) to provide 1.04 g (68%) of the product as a yellow/orange solid.

Workup

  1. concentrationThe mixture was concentrated
  2. additiondiluted with saturated aqueous NH4Cl (40 mL) and EtOAc (70 mL)
  3. additionThe layers were mixed
  4. customseparated
  5. extractionthe aqueous phase was extracted with EtOAc (25 mL)
  6. washThe combined organic extracts were washed with brine
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude product was purified by column chromatography (50% EtOAc/hexane)

Sources & evidence

ORD record
ord-01fb6d1daea841848b4a5b76a529849d
Source dataset
uspto-grants-2015_11
Patent number
US09174981B2

Reaction notes

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