Methyl iodide → HCID 58403389, compound

HRID 1897543Notes

Reaction equation

HRID 1897543 reaction equation
[F:1][C:2]1[CH:17]=[C:16]2[C:5]([CH2:6][C:7]3[C:15]4[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=4[NH:9][C:8]=32)=[CH:4][CH:3]=1.[OH-].[Na+].I[CH3:21]>C1C=CC=CC=1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[F:1][C:2]1[CH:17]=[C:16]2[C:5]([CH2:6][C:7]3[C:15]4[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=4[N:9]([CH3:21])[C:8]=32)=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 6328Methyl iodideHCID 14798Sodium HydroxideHCID 58403372HCID 58403372, compound

Product 1

HCID 58403389HCID 58403389, compoundYield 71%

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 241BenzeneSolvent2×HCID 962WaterSolvent

Conditions

Temperature
40 °C

Procedure

To a solution of 37b (1.38 g, 6.17 mmol) in benzene (12 mL) was added aqueous sodium hydroxide (33% by mass, 3.2 mL), tetrabutylammonium iodide (122.5 mg, 0.33 mmol), and iodomethane (3.04 mL, 48.78 mmol). The reaction mixture was stirred vigorously at 40° C. for 19 hours and then cooled 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 an orange/brown solid. Crude product was purified by flash column chromatography (10:1 to 4:1 hexanes-ethyl acetate) to give a 38b as a white solid in 71% yield (976 mg, 4.37 mmol). 1H NMR (600 MHz, CDCl3): δ 7.64 (d, 1H, J=7.8 Hz), 7.39-7.41 (dd, 1H, J=7.8, 4.8 Hz), 7.49 (d, 1H, J=8.4 Hz), 7.25-7.30 (m, 2H), 7.20-7.23 (t, 1H, J=7.8 Hz), 6.90-6.94 (m, 1H), 3.88 (s, 3H), 3.55 (s, 2H). 13C NMR (150 MHz, CDCl3): δ 162.1 (d, J=240 Hz), 143.5 (d, J=3 Hz), 143.1 (d, J=2.6 Hz), 141.8, 136.7 (d, J=9.5 Hz), 125.9 (d, J=9.2Hz), 123.8, 122.1, 121.6, 119.6, 119.1, 110.6 (d, J=22.5 Hz), 109.7, 104.9 (d, J=24.6 Hz), 30.7 (d, J=1.7 Hz), 29.3.

Workup

  1. temperaturecooled to room temperature
  2. extractionthe aqueous layer was extracted 2×15 mL ethyl acetate
  3. washwashed 1×25 mL H2O
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated
  6. customto yield an orange/brown solid
  7. customCrude product was purified by flash column chromatography (10:1 to 4:1 hexanes-ethyl acetate)

Sources & evidence

ORD record
ord-fabcda5ad3054951920bf46689418898
Source dataset
uspto-grants-2013_08
Patent number
US08519122B2

Reaction notes

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