Phenylboronic Acid → HCID 66580952, compound

HRID 1521841Notes

Reaction equation

HRID 1521841 reaction equation
[N+:1]([C:4]1[C:5]([C:9]([N:11]2[CH2:16][CH2:15][O:14][CH2:13][CH2:12]2)=[O:10])=[N:6][NH:7][CH:8]=1)([O-:3])=[O:2].[C:17]1(B(O)O)[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.C([O-])(O)=O.[Na+]>C(Cl)Cl.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[N+:1]([C:4]1[C:5]([C:9]([N:11]2[CH2:16][CH2:15][O:14][CH2:13][CH2:12]2)=[O:10])=[N:6][N:7]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:8]=1)([O-:3])=[O:2]

Participants

6

Reactant 3

HCID 66827Phenylboronic AcidHCID 516892Sodium BicarbonateHCID 178520059HCID 178520059, compound

Product 1

HCID 66580952HCID 66580952, compoundYield 3%

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent2×

Procedure

A solution of 4-[(4-nitro-1H-pyrazol-3-yl)carbonyl]morpholine (1.50 g; 6.63 mmol; 1.00 eq.) and copper acetate (1 204.49 mg; 6.63 mmol; 1.00 eq.) in DCM (5 mL) is stirred at rt for 18 h after which phenylboronic acid (808.58 mg; 6.63 mmol; 1.00 eq.) and TEA (1.83 mL) are added and the mixture is stirred at room temperature for 18 h. After this time, reaction mixture is diluted with DCM, ished with sat. aq. NaHCO3 then brine, dried over MgSO4, filtered through a short plug of silica and concentrated in vacuo to give as a pale yellow oil. Purification by column chromatography (DCM to 15% ethyl acetate in DCM) followed by crystallization from MTBE afford 60 mg of the title compound as a white solid. 1H NMR (DMSO) 9.76 (s, 1H), 8.00-7.91 (m, 2H), 7.65-7.54 (m, 2H), 7.53-7.43 (m, 1H), 3.70 (s, 4H), 3.60-3.48 (m, 2H), 3.41-3.32 (m, 2H). MS (ESI+): 303.0.

Workup

  1. additionare added
  2. customAfter this time, reaction mixture
  3. dry with materialbrine, dried over MgSO4
  4. filtrationfiltered through a short plug of silica
  5. concentrationconcentrated in vacuo
  6. customto give as a pale yellow oil
  7. customPurification by column chromatography (DCM to 15% ethyl acetate in DCM)
  8. customfollowed by crystallization from MTBE

Sources & evidence

ORD record
ord-0d4a7789cb5c40b186dea974f68156fa
Source dataset
uspto-grants-2015_07
Patent number
US09073940B2

Reaction notes

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