Iodine → HCID 22615147, compound

HRID 1457833Notes

Reaction equation

HRID 1457833 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×

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. afterwhich 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 (1×), brine (1×), 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. additionwas added over 10 minutes by syringe
  3. customthe internal temperature below -65° C
  4. stirringAfter stirring 30 minutes longer
  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 (1×), brine (1×)
  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-45182c4fea4f4ef4b8eb088a8e899458
Source dataset
uspto-grants-1998_12
Patent number
US05849769

Reaction notes

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