Chloranil → HCID 178472256, compound

HRID 2253313Notes

Reaction equation

HRID 2253313 reaction equation
[NH2:1][C:2]1[C:3]([C:20]([O:22][CH3:23])=[O:21])=[C:4]([CH:9]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:10]([O:12][CH2:13][CH3:14])=[O:11])[CH:5]=[CH:6][C:7]=1[NH2:8].[CH3:24][O:25][C:26]1[CH:33]=[CH:32][CH:31]=[CH:30][C:27]=1[CH:28]=O.C1(Cl)C(=O)C(Cl)=C(Cl)C(=O)C=1Cl>CC#N>[CH3:23][O:22][C:20]([C:3]1[C:2]2[NH:1][C:28]([C:27]3[CH:30]=[CH:31][CH:32]=[CH:33][C:26]=3[O:25][CH3:24])=[N:8][C:7]=2[CH:6]=[CH:5][C:4]=1[CH:9]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:15]([O:17][CH2:18][CH3:19])=[O:16])=[O:21]

Participants

5

Reactant 3

HCID 8371ChloranilHCID 86582-MethoxybenzaldehydeHCID 59645484HCID 59645484, compound

Product 1

HCID 178472256HCID 178472256, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A solution of diethyl [3,4-diamino-2-(methoxycarbonyl)phenyl]malonate (4.39 g, 13.5 mmol), 2-methoxybenzaldehyde (1.97 g, 14.5 mmol) and p-chloranil (6.10 g, 14.5 mmol) in MeCN (135 mL) was stirred at room temperature for 22 h. The resulting suspension was filtered and the solid recovered was washed with MeCN (filtrate 1 kept). The solid was dissolved in EtOAc (800 mL) and the resulting solution was successively washed with aqueous 1N NaOH solution (3×150 mL), water (150 mL) and brine (100 mL), dried (MgSO4), filtered and concentrated under reduced pressure. The resulting solid was triturated with hexane:EtOAc (1:1; 135 mL) to give the title compound (4.22 g) as a white solid (filtrate 2 kept). The filtrates 1 and 2 were combined and concentrated under reduced pressure. The residue was treated as the initial solid but the residue after washings was concentrated and purified by flash chromatography (10-40μ silica gel; hexane:EtOAc 1:1) before being triturated with hexane:EtOAc (3:2; 35 mL) to give an additional 0.72 g amount (total of 4.96 g, 83% yield) of the title compound.

Workup

  1. filtrationThe resulting suspension was filtered
  2. customthe solid recovered
  3. washwas washed with MeCN (filtrate 1 kept)
  4. dissolutionThe solid was dissolved in EtOAc (800 mL)
  5. washthe resulting solution was successively washed with aqueous 1N NaOH solution (3×150 mL), water (150 mL) and brine (100 mL)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe resulting solid was triturated with hexane:EtOAc (1:1; 135 mL)

Sources & evidence

ORD record
ord-8bc6520a868846ea9501334b697e2239
Source dataset
uspto-grants-2008_01
Patent number
US07323567B2

Reaction notes

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