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

HRID 1108014Notes

Reaction equation

HRID 1108014 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-methoxynicotinaldehyde2×

Product 1

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

Conditions

Temperature
22 °C

Procedure

A 500 mL 3-necked round-bottom flask is equipped with an overhead mechanical stirrer under nitrogen, the flask is charged with 4-iodo-2-methoxy-pyridine-3-carbaldehyde (Intermediate 1, 75.0 g, 0.29 mol), 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 hours. 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 (about 0.4 mm Hg, about 120-130° C.) yields 3-(but-2-enyloxymethyl)-4-iodo-2-methoxypyridine as a pale yellow oil: 1H-NMR (400 MHz, CDCl3) d 7.69 (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 is equipped with an overhead mechanical stirrer 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 (about 0.4 mm Hg, about 120-130° C.)

Sources & evidence

ORD record
ord-5db1c9a2191f49ef8e00bf8575d3b4de
Source dataset
uspto-grants-2000_05
Patent number
US06063923

Reaction notes

Loading…