Diiodomethane → 5-Iodoquinoline

HRID 1955756Notes

Reaction equation

HRID 1955756 reaction equation
N[C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]=[N:7]2.C(ON=O)CC(C)C.[I:20]CI>>[I:20][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]=[N:7]2

Participants

4

Reactant 3

HCID 6346DiiodomethaneHCID 8053Isoamyl NitriteHCID 119115-Aminoquinoline

Product 1

HCID 220249805-Iodoquinoline

Conditions

Temperature
80 °C

Procedure

A suspension of 10 g (0.07 mol) of 5- aminoquinoline, 94 ml (0.7 mol) of isoamylnitrite and 100 ml of diiodomethane was heated at 80° C. for 2 hours. The reaction mixture was evaporated under reduced pressure at 60°-70° C. The residue was slurried with diethyl ether, decanted and the filtrate was evaporated under reduced pressure. The resulting residue was chromatographed on a silica gel column eluting with 3:1 hexane-ethyl acetate to yield 2.81 g of 5-iodoquinoline. 1H-NMR (CDC13, 300MHz) δ 7.42(d, 1H, J=7.7 Hz); 7.48 (dd, 1H, J=4.3 Hz); 8.1 (m, 2H,); 8.38 (d, 1H, J=8.5 Hz); 8.88 (m, 1H,). Mass spec. m/e=255=p. ##STR27## 2.18 g (0.022 mol) of triethylamine were added to a suspension of 2.75 g (0.011 mol) of 5-iodoquinoline in acetonitrile (24 ml) and the solution formed on warming. The solution was allowed to cool briefly. To the solution were added 50 mg of triphenylphosphine, 50 mg of palladium(II) acetate and 3.1 ml (0.022 mol) of 3,3- zdiethoxy-1-propyne (propiolaldehyde diethylacetal). The reaction was heated at 80° C. for 1.5 hours. The reaction was poured into water and extracted with hexane. The hexane was removed under reduced pressure and the residue was chromatographed on a silica gel column and eluted with 1% methanol-dichloromethane to yield 1.44 g of 5-quinoline-[l- propiolaldehyde diethyl acetal]. 1H-NMR (CDC13, 300MHz) 6 1.3 (t, 6H, J=7.2 Hz); 3.73 (m, 2H,); 3.88 (m, 2H); 5.62 (s, 1H,); 7.48 (dd, IH, J=8.5 and 4.2 Hz); 7.66 (d, 1H, J=7.4 Hz); 7.76 (d, 1H, J=7.2Hz); 8.1 (d, 1H, J=8.5Hz); 8.6 (d, 1H, J=8.5Hz); 8.94 (m, 1H). Mass spec. m/e=255=p. ##STR28##

Workup

  1. customThe reaction mixture was evaporated under reduced pressure at 60°-70° C
  2. customdecanted
  3. customthe filtrate was evaporated under reduced pressure
  4. customThe resulting residue was chromatographed on a silica gel column
  5. washeluting with 3:1 hexane-ethyl acetate

Sources & evidence

ORD record
ord-76218950f8d34629b75f29081617e2ee
Source dataset
uspto-grants-1998_07
Patent number
US05776939

Reaction notes

Loading…