4-Nitrophenol → (6-chloro-3-cyano-pyridin-2-yl)-acetic Acid 4-nitro-phenyl Ester

HRID 1171062Notes

Reaction equation

HRID 1171062 reaction equation
C(N=C=NC(C)C)(C)C.[Cl:10][C:11]1[N:16]=[C:15]([CH2:17][C:18]([OH:20])=[O:19])[C:14]([C:21]#[N:22])=[CH:13][CH:12]=1.[CH:23]1[C:28]([N+:29]([O-:31])=[O:30])=[CH:27][CH:26]=[C:25](O)[CH:24]=1>CN(C1C=CN=CC=1)C.C(Cl)Cl>[N+:29]([C:28]1[CH:23]=[CH:24][C:25]([O:19][C:18](=[O:20])[CH2:17][C:15]2[C:14]([C:21]#[N:22])=[CH:13][CH:12]=[C:11]([Cl:10])[N:16]=2)=[CH:26][CH:27]=1)([O-:31])=[O:30]

Participants

6

Reactant 3

HCID 9804-NitrophenolHCID 12734DiisopropylcarbodiimideHCID 58972900HCID 58972900, compound

Product 1

HCID 58972958(6-chloro-3-cyano-pyridin-2-yl)-acetic Acid 4-nitro-phenyl Ester

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

Diisopropylcarbodiimide (3.00 mL, 19.2 mmol) was added dropwise over 2 min at 0° C. with stirring to a homogeneous dark amber solution of crude (6-chloro-3-cyano-pyridin-2-yl)-acetic acid (3.1 g, 16 mmol; mixture of regioisomers), as prepared in the previous step, p-nitrophenol (3.35 g, 24 mmol), DMAP (11 mg, 0.8 mmol) and DCM (20 mL). The ice bath was removed immediately following the completion of DIC addition, and the dark amber solution was stirred at rt overnight. The crude reaction was allowed to stand at rt for some time, and was then loaded directly onto a silica flash column (90 mm×6″). Elution with 97:3 toluene/acetone afforded the impure title compound, but as a single regioisomer (566 mg, 14% from 2,6-dichloro-nicotinonitrile).

Workup

  1. customThe ice bath was removed immediately
  2. additionthe completion of DIC addition
  3. customThe crude reaction
  4. customto stand at rt for some time
  5. washElution with 97:3 toluene/acetone

Sources & evidence

ORD record
ord-f6240ed9ee6f4dcdbabf741b024b06ee
Source dataset
uspto-grants-2010_11
Patent number
US07829584B2

Reaction notes

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