Acetic Acid → [(1S)-2-(3,5-dichloro-1-oxido-pyridin-1-ium-4-yl)-1-(3,4-dimethoxyphenyl)ethyl]3-[(2-chloroanilino)methyl]benzoate

HRID 1497991Notes

Reaction equation

HRID 1497991 reaction equation
[Cl:1][C:2]1[CH:3]=[N+:4]([O-:32])[CH:5]=[C:6]([Cl:31])[C:7]=1[CH2:8][C@H:9]([O:20][C:21](=[O:30])[C:22]1[CH:27]=[CH:26][CH:25]=[C:24]([CH:28]=O)[CH:23]=1)[C:10]1[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[C:12]([O:18][CH3:19])[CH:11]=1.[Cl:33][C:34]1[CH:40]=[CH:39][CH:38]=[CH:37][C:35]=1[NH2:36].C(O)(=O)C.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>C(Cl)Cl.O>[Cl:1][C:2]1[CH:3]=[N+:4]([O-:32])[CH:5]=[C:6]([Cl:31])[C:7]=1[CH2:8][C@H:9]([O:20][C:21](=[O:30])[C:22]1[CH:27]=[CH:26][CH:25]=[C:24]([CH2:28][NH:36][C:35]2[CH:37]=[CH:38][CH:39]=[CH:40][C:34]=2[Cl:33])[CH:23]=1)[C:10]1[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[C:12]([O:18][CH3:19])[CH:11]=1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 72402-ChloroanilineHCID 5049666Sodium triacetoxyborohydrideHCID 86720715[(1S)-2-(3,5-Dichloro-1-oxido-pyridin-1-ium-4-yl)-1-(3,4-dimethoxyphenyl)ethyl]3-formylbenzoate

Product 1

HCID 86720716[(1S)-2-(3,5-dichloro-1-oxido-pyridin-1-ium-4-yl)-1-(3,4-dimethoxyphenyl)ethyl]3-[(2-chloroanilino)methyl]benzoateYield 67%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of [(1S)-2-(3,5-dichloro-1-oxido-pyridin-1-ium-4-yl)-1-(3,4-dimethoxyphenyl)ethyl]3-formylbenzoate (332 mg, 0.697 mmol) and 2-chloroaniline (0.077 mL, 0.732 mmol) in anhydrous DCM (3.5 mL) was added acetic acid (0.042 mL, 0.732 mmol). The mixture was stirred at room temperature for 24 hours. NaBH(OAc)3 (369 mg, 1.74 mmol) was added, and the mixture was stirred at room temperature for 24 hours. After addition of water (2.5 mL), the mixture was stirred at room temperature for 1 hour. The reaction mixture was filtered through a phase separator, and the solvent was removed in vacuo. The crude material was purified by silica gel column chromatography eluting with 1:1 DCM:EtOAc to afford the title compound as a white solid (274 mg, 67%).

Workup

  1. stirringthe mixture was stirred at room temperature for 24 hours
  2. stirringthe mixture was stirred at room temperature for 1 hour
  3. filtrationThe reaction mixture was filtered through a phase separator
  4. customthe solvent was removed in vacuo
  5. customThe crude material was purified by silica gel column chromatography
  6. washeluting with 1:1 DCM

Sources & evidence

ORD record
ord-f7561fab2d70403ebe1c58bab269d97b
Source dataset
uspto-grants-2015_12
Patent number
US09199980B2

Reaction notes

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