Trifluoroacetic acid → 3-(But-2-enyloxymethyl)-4-iodo-2-methoxypyridine

HRID 2396388Notes

Reaction equation

HRID 2396388 reaction equation
[I:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([O:8][CH3:9])[C:3]=1[CH:10]=[O:11].[CH2:12](O)[CH:13]=[CH:14][CH3:15].C([SiH](CC)CC)C.FC(F)(F)C(O)=O.C(=O)(O)[O-].[Na+]>>[CH2:12]([O:11][CH2:10][C:3]1[C:4]([O:8][CH3:9])=[N:5][CH:6]=[CH:7][C:2]=1[I:1])[CH:13]=[CH:14][CH3:15]

Participants

6

Reactant 5

HCID 6422Trifluoroacetic acidHCID 12052TriethylsilaneHCID 200242-Buten-1-olHCID 516892Sodium BicarbonateHCID 100383814-Iodo-2-methoxynicotinaldehyde

Product 1

HCID 544155093-(But-2-enyloxymethyl)-4-iodo-2-methoxypyridine

Conditions

Temperature
22 °C

Procedure

A 500 mL 3-necked round-bottom flask equipped with an overhead mechanical stirrer and under nitrogen, is charged with 4-iodo-2-methoxy-pyridine-3-carbaldehyde (75.0 g, 0.29 mol) as prepared in example 1, crotyl alcohol (75 mL, 0.88 mol), and triethylsilane (70 mL, 0.44 mol). To the stirred suspension at 0° C. is added trifluoroacetic acid (175 mL, 2.27 mol) dropwise via an addition funnel. The resulting solution is stirred at about 22° C. for approximately 12 hr. The reaction mixture is slowly poured into a rapidly stirring saturated sodium bicarbonate solution (2 L). The mixture is extracted with 3×500 mL of hexane. The combined organic layers are dried over sodium sulfate, filtered, and concentrated in vacuo to give an oil. Purification of this oil by vacuum distillation (ca. 0.4 mm Hg, ca. 120°-130° C.) yields 3-(but-2-enyloxymethyl)-4-iodo-2-methoxy-pyridine as a pale yellow oil: 1H-NMR (400 MHz, CDCl3) δ7.69 (d, J=5 Hz, 1H), 7.34 (d, J=5 Hz, 1H), 5.71 (m, 2H), 4.58 (s, 2H), 4.02 (d, J=1 Hz, 2H), 3.94 (s, 3H), 1.72(d, J=6 Hz, 3H); IR (neat) 2948, 2859, 1561, 1459, 1381, 1361, 1301, 1233, 1169, 1094, 1052 cm-1 ; Elemental analysis: calculated for C11H14NO2I: C 41.40, H 4.42, N 4.39, I 39.76; Found: C 41.31, H 4.45, N 4.37, I 39.71.

Workup

  1. customA 500 mL 3-necked round-bottom flask equipped with an overhead mechanical stirrer and under nitrogen
  2. extractionThe mixture is extracted with 3×500 mL of hexane
  3. dry with materialThe combined organic layers are dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customto give an oil
  7. customPurification of this oil
  8. distillationby vacuum distillation (ca. 0.4 mm Hg, ca. 120°-130° C.)

Sources & evidence

ORD record
ord-2eaf4596219f45f4a206c31adc8c2c71
Source dataset
uspto-grants-1996_02
Patent number
US05491237

Reaction notes

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