Pyridine → HCID 69558786, compound

HRID 1934423Notes

Reaction equation

HRID 1934423 reaction equation
[CH3:1][O:2][C:3](=[O:26])[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][CH:21]=3)[C:8]=2[N:9]=[C:10]([S:12][CH3:13])[N:11]=1.[C:27](Cl)(=[O:31])[C:28](Cl)=[O:29].[N:33]1C=CC=CC=1.[OH-].[NH4+]>C(Cl)(Cl)Cl.C(OC)(C)(C)C.O>[CH3:1][O:2][C:3](=[O:26])[CH2:4][O:5][C:6]1[C:7]2[C:16]([C:27](=[O:31])[C:28]([NH2:33])=[O:29])=[C:15]([CH2:17][CH3:18])[N:14]([CH2:19][C:20]3[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=3)[C:8]=2[N:9]=[C:10]([S:12][CH3:13])[N:11]=1

Participants

8

Reactant 4

HCID 1049PyridineHCID 14923Ammonium HydroxideHCID 65578Oxalyl chlorideHCID 69558215HCID 69558215, compound

Product 1

HCID 69558786HCID 69558786, compoundYield 60%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6212ChloroformSolventHCID 15413tert-Butyl methyl etherSolvent

Procedure

To a solution of 5.17 g (13.9 mmol) of [[2-(methylthio)-6-ethyl-7-(phenylmethyl)-7H-pyrrolo[2,3-d]pyrimidin-4-yl]oxy]acetic acid methyl ester in 100 mL of chloroform was added 3.64 mL of oxalyl chloride followed by 1.66 mL of pyridine. The reaction was stirred for 3 days at ambient temperature then poured into a solution prepared from 11 mL of concentrated ammonium hydroxide and 40 mL of water. The reaction was partitioned by the addition of 45 mL of water and 150 mL of methylene chloride. The organic phase was washed with 40 mL of water, dried with sodium sulfate, and concentrated to 5.90 g of yellow solid. The solid was first purified by flash chromatography (500 g of silica, ethyl acetate) and the product obtained was then slurried in 100 mL of methyl tert-butyl ether to provide 3.70 g (60%) of [[2-(methylthio)-5-(aminooxoacetyl)-6-ethyl-7-(phenylmethyl)-7H-pyrrolo[2,3-d]pyrimidin-4-yl]oxy]acetic acid methyl ester as a yellow solid. nmr (500 MHz, CDCl3) δ1.12 (t, J=7.5 Hz, 3H), 2.52 (s, 3H), 2.91 (q, J=7.5 Hz, 2H), 3.78 (s, 3H), 5.02 (s, 2H), 5.46 (s, 2H), 5.66 (s, 1H), 6.56 (s, 1H), 7.16.(d, J=6.9 Hz, 2H), 7.28 (m, 3H)

Workup

  1. additionthen poured into a solution
  2. customThe reaction was partitioned by the addition of 45 mL of water and 150 mL of methylene chloride
  3. washThe organic phase was washed with 40 mL of water
  4. dry with materialdried with sodium sulfate
  5. concentrationconcentrated to 5.90 g of yellow solid
  6. customThe solid was first purified by flash chromatography (500 g of silica, ethyl acetate)
  7. customthe product obtained

Sources & evidence

ORD record
ord-6c1308a8105b4ada92dc69855fe8ac60
Source dataset
uspto-grants-2002_05
Patent number
US06384041B1

Reaction notes

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