Triethylamine → HCID 69076751, compound

HRID 2404981Notes

Reaction equation

HRID 2404981 reaction equation
[I:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.C(N(CC)CC)C.[CH2:17]([C:19]1[N:20]([CH2:33][C:34]#[CH:35])[C:21]2[C:30]3[CH:29]=[CH:28][CH:27]=[CH:26][C:25]=3[N:24]=[C:23]([NH2:31])[C:22]=2[N:32]=1)[CH3:18]>CN(C=O)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C(Cl)(Cl)Cl.[Pd].[Pd].[Cu]I>[IH:1].[NH2:31][C:23]1[C:22]2[N:32]=[C:19]([CH2:17][CH3:18])[N:20]([CH2:33][C:34]#[C:35][C:2]3[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=3)[C:21]=2[C:30]2[CH:29]=[CH:28][CH:27]=[CH:26][C:25]=2[N:24]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 764674-IodobenzonitrileHCID 86626642HCID 86626642, compound

Product 1

HCID 69076751HCID 69076751, compoundYield 6.3%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 11029508Palladium, tris[mu-[(1,2-eta:4,5-eta)-(1E,4E)-1,5-diphenyl-1,4-pentadien-3-one]]di-, compd. with trichloromethane (1:1)CatalystHCID 6228DimethylformamideSolvent

Procedure

Tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (62.1 mg, 0.03 eq.), 4-iodobenzonitrile (0.50 g, 0.11 eq.), triethylamine (0.61 g, 3 eq.), and copper (I) iodide (23 mg, 0.06 eq.) were added sequentially to a solution of 2-ethyl-1-(2-propynyl)-1H-imidazo[4,5-c]quinolin-4-amine (0.5 g, 2.0 mmol, 1.0 eq) in DMF. The reaction mixture was stirred at ambient temperature for 3.5 hours. The reaction mixture was concentrated under reduced pressure to provide crude product which was purified by column chromatography (silica gel eluting with 5/95 methanol/dichloromethane). The residue was purified by recrystallization from 1,2-dichloroethane to provide 60 mg of 4-[3-(4-amino-2-ethyl-1H-imidazo[4,5-c]quinolin-1-yl)-1-propynyl]benzonitrile hydroiodide as a brown powder, mp 180-241° C. (dec). 1H NMR (300 MHz, DMSO-d6) δ 13.23 (br s, 1H), 8.47 (d, J=8.1 Hz, 1H), 8.44 (br, 2H), 7.82 (m, 3H), 7.69 (t, J=7.2 Hz, 1H), 7.60 (t, J=7.1 Hz, 1H), 7.54 (d, J=8.7 Hz, 2H), 5.84 (s, 2H), 3.13 (q, J=7.4 Hz, 2H), 1.42 (t, J=7.4 Hz, 3H); MS m/z 352 (M+H)+; Anal. calcd for C22H17N5.HI.0.09 1,2-dichloroethane: C, 54.50; H, 3.79; N, 14.33. Found: C, 54.54; H, 3.59; N, 14.26.

Workup

  1. concentrationThe reaction mixture was concentrated under reduced pressure
  2. customto provide crude product which
  3. customwas purified by column chromatography (silica gel eluting with 5/95 methanol/dichloromethane)
  4. customThe residue was purified by recrystallization from 1,2-dichloroethane

Sources & evidence

ORD record
ord-64a23f6616e84f16857491ce4bc5e773
Source dataset
uspto-grants-2014_08
Patent number
US08802853B2

Reaction notes

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