Tricyclohexylphosphine → 1-o-Tolylphthalazin-6-ylboronic acid

HRID 2357525Notes

Reaction equation

HRID 2357525 reaction equation
Cl[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[CH3:18])=[N:7][N:6]=[CH:5]2.[B:19]1(B2OC(C)(C)C(C)(C)O2)[O:23]C(C)(C)C(C)(C)[O:20]1.C([O-])(=O)C.[K+].C1(P(C2CCCCC2)C2CCCCC2)CCCCC1>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:13]1([CH3:18])[CH:14]=[CH:15][CH:16]=[CH:17][C:12]=1[C:8]1[C:9]2[C:4](=[CH:3][C:2]([B:19]([OH:23])[OH:20])=[CH:11][CH:10]=2)[CH:5]=[N:6][N:7]=1

Participants

7

Reactant 4

HCID 75806TricyclohexylphosphineHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 684526856-Chloro-1-o-tolylphthalazine

Product 1

HCID 684524221-o-Tolylphthalazin-6-ylboronic acid

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
125 °C

Procedure

In a sealed glass tube, a mixture of 6-chloro-1-o-tolylphthalazine (127 mg, 0.50 mmol), bis(pinacolato)diboron (146 mg, 0.57 mmol), potassium acetate (98 mg, 1.0 mmol), tris(dibenzylideneacetone)dipalladium (18 mg, 20 μmol) and tricyclohexylphosphine (11 mg, 40 μmol) in 1,4-dioxane (2 mL) was heated in a Personal Chemistry microwave at 125° C. for 30 min. The reaction mixture was filtered through a pad of Celite, and rinsed with ethyl acetate (5 mL). The filtrate was concentrated, then treated with 2 N aq. HCl (2 mL), and extracted with hexanes (5 mL). The acidic layer was diluted with 1 mL of DMSO and put on a reversed phase HPLC (5-90% [0.1% TFA in acetonitrile] in [0.1% TFA in water]) to provide 1-o-tolylphthalazin-6-ylboronic acid as a white fluffy solid. MS (ESI, pos. ion.) m/z: 255 (M+1).

Workup

  1. filtrationThe reaction mixture was filtered through a pad of Celite
  2. washrinsed with ethyl acetate (5 mL)
  3. concentrationThe filtrate was concentrated
  4. additiontreated with 2 N aq. HCl (2 mL)
  5. extractionextracted with hexanes (5 mL)
  6. additionThe acidic layer was diluted with 1 mL of DMSO

Sources & evidence

ORD record
ord-dc880b97b32f4b60bce7bdd5dd9d445a
Source dataset
uspto-grants-2010_07
Patent number
US07759337B2

Reaction notes

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