Ethyl Bromide → HCID 59243191, compound

HRID 1644616Notes

Reaction equation

HRID 1644616 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([OH:12])[CH:11]=1)[C:5](OC)=O.[CH2:13](Br)[CH3:14].[C:16](=O)([O-])[O-].[K+].[K+].[OH-].[Na+].[NH2:24][C:25]1[C:30]([NH2:31])=[CH:29][CH:28]=[CH:27][N:26]=1.N1[C:36]2[CH:37]=[CH:38][CH:39]=[N:40][C:35]=2N=C1>CO.CN(C(ON1N=NC2C=CC=CC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.CN(C=O)C.C(O)(=O)C.C(O)CCC.CCOCC>[CH2:13]([O:12][C:10]1[CH:9]=[C:4]([C:5]2[NH:31][C:30]3[C:25]([N:24]=2)=[N:26][CH:27]=[CH:28][CH:29]=3)[CH:3]=[C:2]([O:1][CH2:16][C:36]2[CH:35]=[N:40][CH:39]=[CH:38][CH:37]=2)[CH:11]=1)[CH3:14]

Participants

13

Reactant 6

HCID 6332Ethyl BromideHCID 99562,3-DiaminopyridineHCID 11430Potassium CarbonateHCID 14798Sodium HydroxideHCID 67504Imidazo(4,5-b)pyridineHCID 75076Methyl 3,5-Dihydroxybenzoate

Product 1

HCID 59243191HCID 59243191, compound

Reagents, catalysts & solvents 6

HCID 176Acetic AcidSolventHCID 2631-ButanolSolventHCID 887MethanolSolventHCID 3283Diethyl EtherSolvent3×HCID 6228DimethylformamideSolvent2×HCID 2733084Methanaminium, N-((1H-benzotriazol-1-yloxy)(dimethylamino)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)Solvent

Procedure

Reaction of Methyl 3,5-dihydroxybenzoate with ethyl bromide in the presence of potassium carbonate and dimethylformamide for 18 h at room temperature gave a 1:1 mixture of the mono and bis ether adducts. These compounds were separated by chromatography column. The mono adduct was reacted with 3-pyridylmethylbromide in the presence of potassium carbonate and dimethylformamide to give the desired bis ether. The ether was hydrolyzed with sodium hydroxide in methanol, acidified and the subsequent acid was reacted with 2,3-diaminopyridine in HBTU, TEA and DMF. The amide was cyclized to the imidazopyridine by reaction in the microwave at 180° C. for 30 min in 1:1 n-butanol:glacial acetic acid. 1H NMR (400 MHz, CDCl3) δ ppm 8.54 (s, 1H), 8.41 (m, 2H), 7.50 (m, 1H), 7.28 (m, 1H), 7.25 (m, 1H), 6.99 (m, 1H), 6.81 (m, 1H), 6.69 (m, 1H), 6.68 (m, 1H), 5.16 (s, 2H), 4.30 (br s, 1H), 4.09 (q, 2H, J=7 Hz), 1.43 (t, 3H, J=7 Hz); Calc'd for C20H18N4O2; m/z (M+H+)=347; found 347.

Workup

  1. customgave
  2. customThese compounds were separated by chromatography column
  3. customThe mono adduct was reacted with 3-pyridylmethylbromide in the presence of potassium carbonate and dimethylformamide

Sources & evidence

ORD record
ord-d31f86158af34e8189e781ba3f447d48
Source dataset
uspto-grants-2012_02
Patent number
US08124617B2

Reaction notes

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