Methyl iodide → Methyl 3-methyl-5-nitrobenzoate

HRID 1515555Notes

Reaction equation

HRID 1515555 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7](B(O)O)[CH:8]=[C:9]([N+:11]([O-:13])=[O:12])[CH:10]=1)=[O:4].[C:17]1(P(C2C3C(=CC=CC=3)C=CC=2)C2C3C(=CC=CC=3)C=CC=2)C2C(=CC=CC=2)C=CC=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].CI>O1CCCC1.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:17][C:7]1[CH:6]=[C:5]([CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[CH:8]=1)[C:3]([O:2][CH3:1])=[O:4]

Participants

8

Reactant 4

HCID 6328Methyl iodideHCID 62657Potassium Phosphate, TribasicHCID 271443Tri(naphthalen-1-yl)phosphaneHCID 27734923-(Methoxycarbonyl)-5-nitrophenylboronic Acid (contains varying amounts of Anhydride)

Product 1

HCID 21129904Methyl 3-methyl-5-nitrobenzoateYield 683.2%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

Following a general procedure from Applied Organometallic Chemistry 2004, 18, 602-604, a solution of 3-(methoxycarbonyl)-5-nitrophenylboronic acid (900 mg, 4.0 mmol) in tetrahydrofuran (16 mL) was added to a round bottom flask charged with palladium acetate (27 mg, 0.12 mmol), tri-1-napthylphosphine (112 mg, 0.27 mmol), potassium phosphate (1.70 g, 8.00 mmol), and methyl iodide (0.370 mL, 5.9 mmol) under nitrogen atmosphere. Water (0.14 mL, 7.8 mmol) was added and the mixture was stirred overnight at rt. The reaction mixture was diluted with water and extracted with ethyl acetate (3×). The combined organics were washed with water and brine, dried, and concentrated in vacuo. The residue was purified by silica gel chromatography (gradient from 0 to 40% ethyl acetate in hexanes) to give 89A (0.36 g, 46%) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 2.54 (s, 3H) 3.98 (s, 3H) 8.19 (s, 1H) 8.23 (s, 1H) 8.67 (s, 1H).

Workup

  1. extractionextracted with ethyl acetate (3×)
  2. washThe combined organics were washed with water and brine
  3. customdried
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by silica gel chromatography (gradient from 0 to 40% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-2034ca627ae648ab86bbd90f0d7284e3
Source dataset
uspto-grants-2012_07
Patent number
US08222453B2

Reaction notes

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