Pyridine → HCID 69557664, compound

HRID 1934450Notes

Reaction equation

HRID 1934450 reaction equation
[CH3:1][O:2][C:3](=[O:25])[CH2:4][O:5][C:6]1[C:7]2[CH:14]=[C:13]([CH2:15][CH3:16])[N:12]([CH2:17][C:18]3[CH:23]=[CH:22][CH:21]=[C:20]([Cl:24])[CH:19]=3)[C:8]=2[N:9]=[CH:10][N:11]=1.[C:26](Cl)(=[O:30])[C:27](Cl)=[O:28].[N:32]1C=CC=CC=1>C(Cl)(Cl)Cl>[CH3:1][O:2][C:3](=[O:25])[CH2:4][O:5][C:6]1[C:7]2[C:14]([C:26](=[O:30])[C:27]([NH2:32])=[O:28])=[C:13]([CH2:15][CH3:16])[N:12]([CH2:17][C:18]3[CH:23]=[CH:22][CH:21]=[C:20]([Cl:24])[CH:19]=3)[C:8]=2[N:9]=[CH:10][N:11]=1

Participants

5

Reactant 3

HCID 1049Pyridine2×HCID 65578Oxalyl chloride2×HCID 69558443HCID 69558443, compound

Product 1

HCID 69557664HCID 69557664, compoundYield 53%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a suspension of 110 mg (0.30 mmol) of [[6-ethyl-7-[(3-chlorophenyl)methyl]-7H-pyrrolo[2,3-d]pyrimidin-4-yl)oxy]acetic acid methyl ester in 3 mL of chloroform was added 0.106 mL of oxalyl chloride followed by 0.10 mL of pyridine. The reaction was stirred for 48 hours at ambient temperature then an additional 0.100 mL of oxalyl chloride and 0.100 mL of pyridine was added. This mixture was stirred and additional 4 days then quenched into solution prepared from 4 mL of water and 2 mL of concentrated ammonium hydroxide. The mixture was partitioned by the addition of 20 mL of ethyl acetate and 10 mL of water. The organic phase was dried with sodium sulfate and concentrated to 91 mg of crude solid. The residue was purified by flash chromatography (7 g of silica, ethyl acetate) to provide 69 mg (53%) of [[5-(aminooxoacetyl)-6-ethyl-7-[(3-chlorophenyl)methyl]-7H-pyrrolo[2,3-d]pyrimidin-4-yl]oxy]acetic acid methyl ester as a white solid. nmr (500 MHz, CDCl3) δ1.15 (t, J=7.4 Hz, 3H), 2.95 (q, J=7.4 Hz, 2H), 3.78 (s, 3H), 5.05 (s, 2H), 5.50 (s, 2H), 5.68 (br s, 1H), 6.60 (br s, 1H), 6.98 (d, J=7.4 Hz, 1H), 7.2 (s, 1H), 7.26 (m, 2H), 8.46 (s, 1H)

Workup

  1. stirringThis mixture was stirred and additional 4 days
  2. customthen quenched into solution
  3. customprepared from 4 mL of water and 2 mL of concentrated ammonium hydroxide
  4. customThe mixture was partitioned by the addition of 20 mL of ethyl acetate and 10 mL of water
  5. dry with materialThe organic phase was dried with sodium sulfate
  6. concentrationconcentrated to 91 mg of crude solid
  7. customThe residue was purified by flash chromatography (7 g of silica, ethyl acetate)

Sources & evidence

ORD record
ord-44251dfa91524a86afc03b6f41d0b804
Source dataset
uspto-grants-2002_05
Patent number
US06384041B1

Reaction notes

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