Pyridine → HCID 69558002, compound

HRID 1934457Notes

Reaction equation

HRID 1934457 reaction equation
[CH3:1][O:2][C:3](=[O:30])[CH2:4][O:5][C:6]1[C:7]2[CH:16]=[C:15]([CH2:17][CH3:18])[N:14]([CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=3[C:26]([F:29])([F:28])[F:27])[C:8]=2[N:9]=[C:10]([S:12][CH3:13])[N:11]=1.[C:31](Cl)(=[O:35])[C:32](Cl)=[O:33].[N:37]1C=CC=CC=1>C(Cl)(Cl)Cl>[CH3:1][O:2][C:3](=[O:30])[CH2:4][O:5][C:6]1[C:7]2[C:16]([C:31](=[O:35])[C:32]([NH2:37])=[O:33])=[C:15]([CH2:17][CH3:18])[N:14]([CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=3[C:26]([F:28])([F:29])[F:27])[C:8]=2[N:9]=[C:10]([S:12][CH3:13])[N:11]=1

Participants

5

Reactant 3

HCID 1049PyridineHCID 65578Oxalyl chloride2×HCID 69557749HCID 69557749, compound

Product 1

HCID 69558002HCID 69558002, compoundYield 22%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a solution of 256 mg (0.582 mmol) of [[2-(methylthio)-6-ethyl-7-[[2-(trifluoromethyl)phenyl]methyl]-7H-pyrrolo[2,3-d]pyrimidin-4-yl]oxy]acetic acid methyl ester in 9 mL of chloroform was added 0.15 mL of oxalyl chloride followed by 0.07 mL of pyridine. The reaction was stirred at ambient temperature and was monitored by nmr for conversion to product. Additional oxalyl chloride (0.200 mL) was added in portions over 3 days. The reaction was quenched into 4.0 mL of dilute ammonium hydroxide and the product was extracted into 4.0 mL of methylene chloride. The organic phase was washed with water, dried with sodium sulfate and concentrated to 420 mg of yellow solid. The residue was purified by flash chromatography (42 g of silica, ethyl acetate) to provide 66 mg (22%) of [[2-(methylthio)-5-(aminooxoacetyl)-6-ethyl-7-[[2-(trifluoromethyl)phenyl]methyl]-7H-pyrrolo[2,3-d]pyrimidin-4-yl]oxy]acetic acid methyl ester as a solid. nmr (300 MHz, dmso-d6) δ1.00 (t,3H), 2.34 (s,3H), 2.81 (q,2H), 3.65 (s,3H), 4.97 (s,2H), 5.62 (s,2H), 6.47 (d, 1H), 7.53 (m,2H), 7.65(s, 1H), 7.83 (d, 1H), 806 (s, 1H)

Workup

  1. customThe reaction was quenched into 4.0 mL of dilute ammonium hydroxide
  2. extractionthe product was extracted into 4.0 mL of methylene chloride
  3. washThe organic phase was washed with water
  4. dry with materialdried with sodium sulfate
  5. concentrationconcentrated to 420 mg of yellow solid
  6. customThe residue was purified by flash chromatography (42 g of silica, ethyl acetate)

Sources & evidence

ORD record
ord-9aeb861d612c49a09e19370b3a92ff69
Source dataset
uspto-grants-2002_05
Patent number
US06384041B1

Reaction notes

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