Methyl iodide → HCID 25140995, compound

HRID 2272771Notes

Reaction equation

HRID 2272771 reaction equation
[CH3:1][O:2][CH2:3][O:4][C:5]1[CH:10]=[C:9]([O:11][CH2:12][O:13][CH3:14])[CH:8]=[CH:7][C:6]=1[O:15][CH2:16][CH2:17][CH3:18].[Li][CH2:20]CCC.CI>C1COCC1>[CH3:14][O:13][CH2:12][O:11][C:9]1[CH:8]=[CH:7][C:6]([O:15][CH2:16][CH2:17][CH3:18])=[C:5]([O:4][CH2:3][O:2][CH3:1])[C:10]=1[CH3:20]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 25140254HCID 25140254, compoundHCID 178418339Butyllithium

Product 1

HCID 25140995HCID 25140995, compoundYield 96%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A solution of 4b (165 mg, 0.64 mmol) in anhydrous THF (520 μL) was added dropwise to a solution of nBuLi (2.5 M in hexanes, 390 μL, 0.97 mmol) in anhydrous THF (420 μL) at room temperature. After 1 hour, the solution was cooled to −78° C. and methyl iodide (160 μL, 2.58 mmol) was added. The resulting solution was warmed to room temperature over 12 hours, and the reaction was quenched by the addition of saturated aqueous NH4Cl. Water (5 mL) was added and the solution was extracted with CH2Cl2 (3×10 mL). Combined organic fractions were dried (Na2SO4), filtered, and concentrated. The residue was purified via column chromatography (SiO2, 6:1 Hexane:EtOAc) to afford 5b as a yellow oil (166 mg, 95%): 1H NMR (CDCl3, 500 MHz) δ 6.66 (d, J=9.0 Hz, 1H), 6.60 (d, J=9.0 Hz, 1H), 5.02 (s, 2H), 5.00 (s, 2H), 3.80-3.77 (m, 2H), 3.49 (s, 3H), 3.47 (s, 3H), 2.14 (d, J=7.1 Hz, 3H), 1.73-1.69 (m, 2H), 0.94 (t, J=7.5 Hz, 3H); 13C NMR (CDCl3, 125 MHz) δ 148.5, 148.5, 147.3, 145.6, 126.7, 123.0, 112.8, 110.8, 110.4, 99.2, 57.7, 57.6, 21.2, 10.9, 10.0; IR (film) νmax 2957, 2924, 2853, 1738, 1597, 1487, 1468, 1391, 1335, 1231, 1157, 974, 798 cm−1; HRMS (ESI+) m/z: [M+H]+ calcd for C14H22O5, 271.1545. found, 271.1558.

Workup

  1. temperatureThe resulting solution was warmed to room temperature over 12 hours
  2. customthe reaction was quenched by the addition of saturated aqueous NH4Cl
  3. additionWater (5 mL) was added
  4. extractionthe solution was extracted with CH2Cl2 (3×10 mL)
  5. dry with materialCombined organic fractions were dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified via column chromatography (SiO2, 6:1 Hexane:EtOAc)

Sources & evidence

ORD record
ord-67b355849f944609a57ed8cd3079534a
Source dataset
uspto-grants-2015_09
Patent number
US09120774B2

Reaction notes

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