Triethylamine → HCID 86636562, compound

HRID 2370320Notes

Reaction equation

HRID 2370320 reaction equation
[CH:1]([C:3]1[C:11]2[C:10]([C:12]([O:14][CH3:15])=[O:13])=[CH:9][CH:8]=[CH:7][C:6]=2[NH:5][N:4]=1)=[O:2].[F:16][C:17]1[CH:22]=[CH:21][C:20](B(O)O)=[CH:19][CH:18]=1.C(N(CC)CC)C>C([O-])(=O)C.[Cu+2].C([O-])(=O)C.ClCCl>[F:16][C:17]1[CH:22]=[CH:21][C:20]([N:5]2[C:6]3[CH:7]=[CH:8][CH:9]=[C:10]([C:12]([O:14][CH3:15])=[O:13])[C:11]=3[C:3]([CH:1]=[O:2])=[N:4]2)=[CH:19][CH:18]=1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 2856454-Fluorophenylboronic acidHCID 178497600HCID 178497600, compound

Product 1

HCID 86636562HCID 86636562, compoundYield 9.5%

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent

Procedure

A mixture of methyl 3-formyl-1H-indazole-4-carboxylate (B1) (3.3 g, 16.1 mmol), 4-fluorophenylboronic acid (4.5 g, 32.3 mmol) and copper(II) acetate (3.99 g, 21.9 mmol) was degassed under nitrogen (3×). Anhydrous dichloromethane (240 ml) and triethylamine (4.5 ml, 13.5 mmol) were added. The mixture was degassed under nitrogen (2×) and stirred at ambient temperature for 21 h. The mixture was concentrated under reduced pressure and the residue was purified by column chromatography (silica gel, 0-30% ethyl acetate in hexanes) to afford methyl 1-(4-fluorophenyl)-3-formyl-1H-indazole-4-carboxylate (454 mg, 9%) as a brown solid. 1H NMR (500 MHz, CDCl3) δ 10.38 (s, 1H), 8.01 (d, J=8.3 Hz, 1H), 7.91-7.88 (m, 2H), 7.80 (d, J=7.1 Hz, 1H), 7.69 (dd, J=8.4, 7.3 Hz, 1H), 7.53 (t, J=8.7 Hz, 2H), 3.93 (s, 3H); MS (ESI+) m/z 299 (M+H).

Workup

  1. customwas degassed under nitrogen (3×)
  2. customThe mixture was degassed under nitrogen (2×)
  3. concentrationThe mixture was concentrated under reduced pressure
  4. customthe residue was purified by column chromatography (silica gel, 0-30% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-00e80ee0195e40c3ab6a30a602fc210d
Source dataset
uspto-grants-2014_04
Patent number
US08710047B2

Reaction notes

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