Hydrochloric Acid → HCID 67981372, compound

HRID 1520023Notes

Reaction equation

HRID 1520023 reaction equation
[C:1]([O:5][C:6]([N:8]1[C:16]2[C:11](=[CH:12][C:13]([CH3:17])=[CH:14][CH:15]=2)[C:10]([C:18]#[CH:19])=[N:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[N:20]([C:23]1[CH:32]=[CH:31][C:26]([C:27]([O:29][CH3:30])=[O:28])=[CH:25][CH:24]=1)=[N+:21]=[N-:22].Cl>CN(C=O)C.O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Cu+2]>[CH3:30][O:29][C:27]([C:26]1[CH:25]=[CH:24][C:23]([N:20]2[CH:19]=[C:18]([C:10]3[C:11]4[C:16](=[CH:15][CH:14]=[C:13]([CH3:17])[CH:12]=4)[N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[N:9]=3)[N:22]=[N:21]2)=[CH:32][CH:31]=1)=[O:28]

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 146531Benzoic acid, 4-azido-, methyl esterHCID 77230607tert-butyl-3-ethynyl-5-methyl-1H-indazole-1-carboxylate

Product 1

HCID 67981372HCID 67981372, compound

Reagents, catalysts & solvents 3

HCID 24463Copper sulfate pentahydrateCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

Copper sulfate pentahydrate (0.08 g; 0.33 mmol; 0.06 eq.) was added to a solution of tert-butyl-3-ethynyl-5-methyl-1H-indazole-1-carboxylate (1.55 g; 6.03 mmol; 1.0 eq.), methyl 4-azidobenzoate (prepared as described in JOC (2006), 71(15), 5822-5825; 1.20 g; 6.77 mmol; 1.1 eq.) and D-(−)-isoascorbic acid sodium salt (0.24 g; 1.22 mmol; 0.20 eq.) in DMF (15 mL) and water (0.50 mL). The reaction suspension was heated in MW at 80° C. for 45 min then poured into HCl (0.1 N solution) and extracted with EtOAc. Combined organic phases were washed with brine, dried over magnesium sulfate, filtered and concentrated. The crude was purified by flash chromatography on silica (n-heptane/EtOAc, gradient from 90:10 to 60:40) to give the title compound as a yellow solid. 1H NMR (300 MHz, DMSO) δ 9.66 (s, 1H), 8.35-8.25 (m, 3H), 8.20 (d, J=8.8 Hz, 2H), 8.05 (d, J=8.7 Hz, 1H), 7.54 (dd, J=1.5, 8.7 Hz, 1H), 3.91 (s, 3H), 2.53 (s, 3H), 1.69 (s, 9H). HPLC (Condition A): Rt 5.07 min (purity 96.8%). MS (ESI+): 434.4.

Workup

  1. extractionextracted with EtOAc
  2. washCombined organic phases were washed with brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe crude was purified by flash chromatography on silica (n-heptane/EtOAc, gradient from 90:10 to 60:40)

Sources & evidence

ORD record
ord-4dee0ba0ddd04d238c3f8678b2f75b10
Source dataset
uspto-grants-2015_07
Patent number
US09073892B2

Reaction notes

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