2-Aminopyridine → HCID 59560286, compound

HRID 1177058Notes

Reaction equation

HRID 1177058 reaction equation
[Cl-].C[Al+]C.[NH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][N:7]=1.C[O:13][C:14]([C:16]1[CH:17]=[C:18]([O:26][C:27]2[CH:32]=[CH:31][C:30]([S:33]([CH3:36])(=[O:35])=[O:34])=[CH:29][CH:28]=2)[CH:19]=[C:20]2[O:24][CH:23]([CH3:25])[CH2:22][C:21]=12)=O>>[N:7]1[CH:8]=[CH:9][CH:10]=[CH:11][C:6]=1[NH:5][C:14]([C:16]1[CH:17]=[C:18]([O:26][C:27]2[CH:32]=[CH:31][C:30]([S:33]([CH3:36])(=[O:34])=[O:35])=[CH:29][CH:28]=2)[CH:19]=[C:20]2[O:24][CH:23]([CH3:25])[CH2:22][C:21]=12)=[O:13]

Participants

4

Reactant 3

HCID 104392-AminopyridineHCID 16686359Dimethylalumanylium chlorideHCID 595604376-(4-Methanesulfonyl-phenoxy)-2-methyl-2,3-dihydro-benzofuran-4-carboxylic acid methyl ester

Product 1

HCID 59560286HCID 59560286, compoundYield 53%

Procedure

Dimethylaluminum chloride (1.0 M solution in hexanes, 3 mL, 3.0 mmol) was added to a solution of 2-aminopyridine (282 mg, 3.0 mmol) in 1,2-dichloromethane at 0° C. The mixture was stirred at room temperature for 15 min and then 6-(4-methanesulfonyl-phenoxy)-2-methyl-2,3-dihydro-benzofuran-4-carboxylic acid methyl ester (1f) (108 mg, 0.30 mmol) in 1,2-dichloromethane (3 mL) was added. The mixture was stirred at room temperature overnight, and carefully quenched with 20% aqueous potassium sodium tartrate tetrahydrate (5 mL), diluted with H2O (30 mL), extracted with CH2Cl2 (2×50 mL) and concentrated in vacuo. The residue was purified by flash column chromatography eluting with 50% EtOAc in hexane to give a white solid (67 mg, 53% yield). 1H NMR (400 MHz, CDCl3) δ 8.39 (br. s., 1 H) 8.21-8.34 (m, 2 H) 7.87-7.96 (m, 2 H) 7.70-7.81 (m, 1 H) 7.04-7.17 (m, 3 H) 6.94 (d, J=2.02 Hz, 1 H) 6.67 (d, J=1.77 Hz, 1 H) 4.97-5.18 (m, 1 H) 3.71 (dd, J=16.67, 8.84 Hz, 1 H) 3.19 (dd, J=16.67, 7.58 Hz, 1 H) 3.07 (s, 3 H) 1.53 (d, J=6.32 Hz, 3 H); LCMS for C22H20N2O5S m/z 425.10 (M+H)+; Anal. Calcd. for C22H20N2O5S.0.2H2O: C, 61.73; H, 4.80; N, 6.54. Found: C, 61.71; H, 4.81; N, 6.41.

Workup

  1. stirringThe mixture was stirred at room temperature overnight
  2. customcarefully quenched with 20% aqueous potassium sodium tartrate tetrahydrate (5 mL)
  3. additiondiluted with H2O (30 mL)
  4. extractionextracted with CH2Cl2 (2×50 mL)
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by flash column chromatography
  7. washeluting with 50% EtOAc in hexane

Sources & evidence

ORD record
ord-eeabae26f77a442886a8c8895f947f14
Source dataset
uspto-grants-2010_11
Patent number
US07842713B2

Reaction notes

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