Triethylamine → HCID 69080391, compound

HRID 2404996Notes

Reaction equation

HRID 2404996 reaction equation
I[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.C(N(CC)CC)C.[CH2:15]([C:17]1[N:18]([CH2:31][CH2:32][CH2:33][C:34]#[CH:35])[C:19]2[C:28]3[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=3[N:22]=[C:21]([NH2:29])[C:20]=2[N:30]=1)[CH3:16]>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>[CH2:15]([C:17]1[N:18]([CH2:31][CH2:32][CH2:33][C:34]#[C:35][C:3]2[CH:2]=[CH:7][CH:6]=[CH:5][N:4]=2)[C:19]2[C:28]3[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=3[N:22]=[C:21]([NH2:29])[C:20]=2[N:30]=1)[CH3:16]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 707143-IodopyridineHCID 86626645HCID 86626645, compound

Product 1

HCID 69080391HCID 69080391, compoundYield 18.8%

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 (0.095 g, 0.03 eq.), 3-iodopyridine (0.626 g, 1.1 eq.), triethylamine (0.923 g, 3 eq.), and copper (I) iodide (0.035 g, 0.06 eq.) were added sequentially to a solution of 2-ethyl-1-(4-pentynyl) 1H-imidazo[4,5-c]quinolin-4-amine (0.85 g, 3.0 mmol, 1.0 eq.) in DMF. The reaction mixture was stirred for 1 hour and then concentrated under reduced pressure. The residue was purified by column chromatography (silica gel eluting with 4/96 methanol/dichloromethane). The product was recrystallized from a mixture of ethanol and 1,2-dichloroethane. The resulting solid was dissolved in 1:1 mixture of ethanol and 1,2-dichloroethane, treated with activated charcoal, combined with a few drops of 10% sodium hydroxide, heated and then filtered while still hot. The filtrate was concentrated under reduced pressure to provide 0.2 g of 2-ethyl-1-[5-(pyridin-2-yl)-4-pentynyl]-1H-imidazo[4,5-c]quinolin-4-amine as light brown granules, mp 188.0-192.0° C. 1H NMR (300 MHz, CDCl3) δ 8.70 (d, J=0.9 Hz, 1H), 8.55 (dd, J=4.7, 1.3 Hz, 1H), 8.06 (dd, J=8.2, 0.9 Hz, 1H), 7.82 (dd, J=8.4, 0.7 Hz, 1H), 7.71 (ddd, J=7.9, 1.7, 1.7 Hz, 1H), 7.48 (ddd, J=8.3, 7.2, 1.2 Hz, 1H), 7.25 (m, 2H), 5.46 (br s, 2H), 4.66 (t, J=7.9 Hz, 2H), 3.00 (q, J=7.4 Hz, 2H), 2.64 (t, J=6.5 Hz, 2H), 2.26 (m, 2H), 1.49 (t, J=7.4 Hz, 3H); MS (APCI) m/z 356 (M+H)+; Anal. calcd for C22H21N5.0.65H2O: C, 71.97; H, 6.12; N, 19.07. Found: C, 72.03; H, 6.06; N, 19.16.

Workup

  1. concentrationconcentrated under reduced pressure
  2. customThe residue was purified by column chromatography (silica gel eluting with 4/96 methanol/dichloromethane)
  3. customThe product was recrystallized from a mixture of ethanol and 1,2-dichloroethane
  4. dissolutionThe resulting solid was dissolved in 1:1 mixture of ethanol and 1,2-dichloroethane
  5. additiontreated with activated charcoal
  6. temperatureheated
  7. filtrationfiltered while still hot
  8. concentrationThe filtrate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-78907b07aa5045bfa9a49c00793f14e9
Source dataset
uspto-grants-2014_08
Patent number
US08802853B2

Reaction notes

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