Acetaldehyde → Methyl 4-cyano-2-(ethylamino)benzoate

HRID 1442579Notes

Reaction equation

HRID 1442579 reaction equation
[CH:1](=O)[CH3:2].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].[NH2:18][C:19]1[CH:28]=[C:27]([C:29]#[N:30])[CH:26]=[CH:25][C:20]=1[C:21]([O:23][CH3:24])=[O:22].C(=O)([O-])O.[Na+]>C(O)(=O)C>[C:29]([C:27]1[CH:26]=[CH:25][C:20]([C:21]([O:23][CH3:24])=[O:22])=[C:19]([NH:18][CH2:1][CH3:2])[CH:28]=1)#[N:30]

Participants

6

Reactant 4

HCID 177AcetaldehydeHCID 516892Sodium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 10103677Benzoic acid, 2-amino-4-cyano-, methyl ester

Product 1

HCID 23076867Methyl 4-cyano-2-(ethylamino)benzoateYield 23%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Acetaldehyde (90%)(10 mL) and sodium triacetoxyborohydride (7.71 g, 36.4 mmol) were added to an acetic acid solution (10 mL) of methyl 2-amino-4-cyanobenzoate (3.04 g, 17.3 mmol) under ice cooling. The mixture was stirred at the same temperature for an hour and at room temperature for 2 hours. Ice water was added to the reaction mixture, the mixture was neutralized with sodium hydrogencarbonate, followed by extraction with ethyl acetate. The combined organic layers were washed with water and then saturated brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crystals obtained were washed with diisopropyl ether-hexane to give the title compound (800 mg, 23%). The residue was applied to silica gel column chromatography (hexane/ethyl acetate=50:1 and then 30:1). The crystals obtained were washed with hexane to give the title compound (920 mg, 26%).

Workup

  1. extractionfollowed by extraction with ethyl acetate
  2. washThe combined organic layers were washed with water
  3. dry with materialsaturated brine, dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe crystals obtained
  7. washwere washed with diisopropyl ether-hexane

Sources & evidence

ORD record
ord-74a073dbcb8f45c58f6674ad07984e17
Source dataset
uspto-grants-2010_02
Patent number
US07659267B2

Reaction notes

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