Methyl iodide → HCID 58403394, compound

HRID 1897541Notes

Reaction equation

HRID 1897541 reaction equation
[CH3:1][O:2][C:3]1[CH:18]=[C:17]2[C:6]([CH2:7][C:8]3[C:16]4[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=4[NH:10][C:9]=32)=[CH:5][CH:4]=1.[OH-].[Na+].I[CH3:22]>C1C=CC=CC=1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[CH3:1][O:2][C:3]1[CH:18]=[C:17]2[C:6]([CH2:7][C:8]3[C:16]4[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=4[N:10]([CH3:22])[C:9]=32)=[CH:5][CH:4]=1

Participants

7

Reactant 3

HCID 6328Methyl iodideHCID 14798Sodium HydroxideHCID 11183936HCID 11183936, compound

Product 1

HCID 58403394HCID 58403394, compoundYield 87%

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 241BenzeneSolvent2×HCID 962WaterSolvent

Conditions

Temperature
40 °C

Procedure

To a solution of 37a (592 mg, 2.52 mmol) in benzene (8 mL) was added aqueous sodium hydroxide (50% by mass, 4 mL), tetrabutylammonium iodide (82.7 mg, 0.22 mmol), and iodomethane (1.25 mL, 20.13 mmol). The reaction mixture was stirred vigorously at 40° C. for 16 hours and then at 55° C. for 2 additional hours. Upon cooling to room temperature, the mixture was diluted with benzene (20 mL) and H2O (20 mL), and the aqueous layer was extracted 2×15 mL ethyl acetate. Organic layers were combined, washed 1×25 mL H2O, dried over anhydrous magnesium sulfate and concentrated to yield a brown solid. Crude product was purified by flash column chromatography (20:1 to 10:1 hexanes-ethyl acetate) to give a tan brown solid in 87% yield (545 mg, 2.19 mmol). 1H NMR (600 MHz, CDCl3): δ 7.65 (d, 1H, J=7.8 Hz), 7.42 (d, 1H, J=8.4 Hz), 7.38 (d, 1H, J=7.8 Hz), 7.25-7.27 (t, 1H, J=7.8 Hz), 7.18-7.21 (m, 2H), 6.78-6.79 (dd, 1H, J=8.4 Hz, 2.4 Hz), 3.99 (s, 3H), 3.92 (s, 3H), 3.63 (s, 2H). 13C NMR (150 MHz, CDCl3): δ 158.74, 144.24, 141.77, 140.11, 136.45, 125.63, 123.98, 121.54, 121.16, 119.45, 118.95, 109.63, 109.01, 104.58, 55.50, 30.83, 29.19. FTIR: cm−1 3049, 2900, 1606, 1526, 1469, 1250, 1197, 1037, 742.

Workup

  1. customat 55° C.
  2. temperatureUpon cooling to room temperature
  3. extractionthe aqueous layer was extracted 2×15 mL ethyl acetate
  4. washwashed 1×25 mL H2O
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated
  7. customto yield a brown solid
  8. customCrude product was purified by flash column chromatography (20:1 to 10:1 hexanes-ethyl acetate)
  9. customto give a tan brown solid in 87% yield (545 mg, 2.19 mmol)

Sources & evidence

ORD record
ord-b0f3189db91f4246915029f561f37dc2
Source dataset
uspto-grants-2013_08
Patent number
US08519122B2

Reaction notes

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