Iodine → HCID 22615147, compound

HRID 842639Notes

Reaction equation

HRID 842639 reaction equation
C(NC(C)C)(C)C.[F:8][C:9]1[C:10]([CH:15]([N:17]2[C:21]([CH3:22])=[CH:20][CH:19]=[C:18]2[CH3:23])[CH3:16])=[N:11][CH:12]=[CH:13][CH:14]=1.[I:24]I>O1CCCC1>[F:8][C:9]1[C:10]([CH:15]([N:17]2[C:18]([CH3:23])=[CH:19][CH:20]=[C:21]2[CH3:22])[CH3:16])=[N:11][CH:12]=[CH:13][C:14]=1[I:24]

Participants

5

Reactant 3

HCID 807IodineHCID 7912DiisopropylamineHCID 22615127HCID 22615127, compound

Product 1

HCID 22615147HCID 22615147, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

A dry 250 ml 3-neck roundbottom flask equipped with a thermometer, rubber septum, magnetic stirrer, and nitrogen inlet was charged with 30 ml of anhydrous tetrahydrofuran and 2.1 ml (14.67 mmole) of dry diisopropylamine. The stirring solution was cooled to −78° C. After which 9.5 ml (15.11 mmole) of 1,6 n-butyllithium in hexanes was added over 10 minutes by syringe. The solution was stirred 30 minutes longer and 3.2 g (14.67 mmole) of N-[(3-Fluoropyrid-2-yl)eth-2-yl]-2,5-dimethylpyrrole in 30 ml of dry tetrahydrofuran was added dropwise via syringe over 30 minutes, keeping the internal temperature below −65° C. After stirring 30 minutes longer, a solution of 4.0 g (15.80 mmole) of iodine in 30 ml of dry tetrahydrofuran was added by canula over 10 minutes. The mixture was warmed to room temperature (a color change, quenching, occurred at −30° C.) and stirred overnight under nitrogen. The solution was diluted to 200 ml with ethyl ether, extracted with aqueous saturated sodium bicarbonate (IX), brine (IX), and dried over sodium sulfate. Filtration and concentration gave a dark solid which was purified by flash silica gel chromatography (20% ethyl acetate in hexanes) to give the titled compound as a white solid, 3,9 g (77%): mp 156-158° C.; IR (KBr, cm−1) 3000, 2950, 1574, 1408, 752; 1H NMR (300 MHz, DMSO-d6) δ 8.05 (d, 1H) 7.85 (t, 1H), 5.60 (s, 2H), 4.05 (t, 2H), 3.00 (dt, 2H), 2.10 (s, 6H); MS (FD) m/e 344 (Mt). Anal. Calc'd. for C13H14FIN2: C, 45.37; H, 4.10; N, 8.14. Found: C, 45.07; H, 4.03; N, 8.06.

Workup

  1. customA dry 250 ml 3-neck roundbottom flask equipped with a thermometer, rubber septum, magnetic stirrer, and nitrogen inlet
  2. customthe internal temperature below −65° C
  3. stirringAfter stirring 30 minutes longer
  4. temperatureThe mixture was warmed to room temperature (a color change
  5. customquenching
  6. customoccurred at −30° C.
  7. stirringstirred overnight under nitrogen
  8. additionThe solution was diluted to 200 ml with ethyl ether
  9. extractionextracted with aqueous saturated sodium bicarbonate (IX), brine (IX)
  10. dry with materialdried over sodium sulfate
  11. filtrationFiltration and concentration
  12. customgave a dark solid which
  13. customwas purified by flash silica gel chromatography (20% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-939dcd3cd3cc467ca1a99ec73ee05c0e
Source dataset
uspto-grants-2002_04
Patent number
US06376492B1

Reaction notes

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