3-Nitrophenylboronic Acid → HCID 58020025, compound

HRID 1632054Notes

Reaction equation

HRID 1632054 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:15]=[CH:16][C:17]=1[O:18][CH3:19])[CH2:5][N:6]1[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=2[N:8]=[N:7]1.[N+:20]([C:23]1[CH:24]=[C:25](B(O)O)[CH:26]=[CH:27][CH:28]=1)([O-:22])=[O:21].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Na+].[Na+]>CN(C)C=O.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.[Pd]>[CH3:19][O:18][C:17]1[C:2]([C:27]2[CH:26]=[CH:25][CH:24]=[C:23]([N+:20]([O-:22])=[O:21])[CH:28]=2)=[CH:3][C:4]([CH2:5][N:6]2[C:10]3[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=3[N:8]=[N:7]2)=[CH:15][CH:16]=1

Participants

7

Reactant 4

HCID 16773-Nitrophenylboronic AcidHCID 10340Sodium CarbonateHCID 11776TriphenylphosphineHCID 58020140HCID 58020140, compound

Product 1

HCID 58020025HCID 58020025, compoundYield 39%

Reagents, catalysts & solvents 2

HCID 1542701,5-Diphenylpenta-1,4-dien-3-one;palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
85 °C

Procedure

A suspension of 1-(3-Bromo-4-methoxy-benzyl)-1H-benzotriazole (I-106) (477 mg, 1.50 mmol), 3-nitrophenylboronic acid (250 mg, 1.50 mmol), palladium(0) bis(dibenzylideneacetone) (43 mg, 0.075 mmol), and triphenyl phosphine (39 mg, 0.15 mmol) in dimethylformamide (10 mL) and 1 M aqueous sodium carbonate (4.5 mL, 4.5 mmol) was heated to 85° C. with stirring overnight. The solvent was removed under vacuum and the residue suspended in ethyl acetate (20 mL). The organic suspension was washed with water (3×20 mL) and brine, dried over sodium sulfate, decolorized over activated carbon, and the solvent removed under vacuum to give crude material. The residue was purified dissolving in ethyl acetate (5 mL) and adding hexanes (25 mL) until a solid formed. This was repeated 3 times to give P-482 (210 mg, 39% yield). 1H NMR (400 MHz, CDCl3) 1H NMR (400 MHz, CDCl3): 3.82 (s, 3H), 5.86 (s, 2H), 6.98 (d, J=8.2 Hz, 1H), 7.30-7.37 (m, 2H), 7.37-7.52 (m, 3H), 7.52-7.59 (m, 1H), 7.75 (d, J=7.8 Hz, 1H), 8.12 (d, J=8.3 Hz, 1H), 8.18 (dd, J=8.2, 1.2 Hz, 1H), 8.35 (d, J=1.6 Hz, 1H) ppm. LCMS=93.9% purity.

Workup

  1. customThe solvent was removed under vacuum
  2. washThe organic suspension was washed with water (3×20 mL) and brine
  3. dry with materialdried over sodium sulfate
  4. customthe solvent removed under vacuum
  5. customto give crude material
  6. customThe residue was purified
  7. dissolutiondissolving in ethyl acetate (5 mL)
  8. additionadding hexanes (25 mL) until a solid
  9. customformed
  10. customto give P-482 (210 mg, 39% yield)

Sources & evidence

ORD record
ord-450e71966e6a4847a2f045f5528f7b40
Source dataset
uspto-grants-2014_07
Patent number
US08791267B2

Reaction notes

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