Benzaldehyde → 4-Benzylamino-phthalic acid dimethyl ester

HRID 1357376Notes

Reaction equation

HRID 1357376 reaction equation
[CH:1](=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([BH3-])#N.[Na+].[CH3:13][O:14][C:15](=[O:27])[C:16]1[C:17](=[CH:22][C:23]([NH2:26])=[CH:24][CH:25]=1)[C:18]([O:20][CH3:21])=[O:19].Cl>CO>[CH3:13][O:14][C:15](=[O:27])[C:16]1[C:17](=[CH:22][C:23]([NH:26][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[CH:24][CH:25]=1)[C:18]([O:20][CH3:21])=[O:19]

Participants

6

Reactant 4

HCID 240BenzaldehydeHCID 313Hydrochloric AcidHCID 95886Dimethyl 4-aminophthalateHCID 5003444Sodium cyanoborohydride

Product 1

HCID 670196894-Benzylamino-phthalic acid dimethyl esterYield 39%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

Benzaldehyde (1.64 ml, 16.2 mmol) and sodium cyanoborohydride (1.02 g, 16.2 mmol) were added to a solution of 4-aminophthalic acid dimethyl ester (1.7 g, 8.1 mmol) in dry methanol (50 ml) and pH was adjusted to 5.5-5 with 2 M hydrogen chloride in methanol (approx. 1 ml). The reaction mixture was stirred at room temperature for 20 hours and evaporated to dryness in vacuo. The residue was partitioned between methylene chloride (50 ml) and water (30 ml). pH was adjusted to 8 and the organic phase was isolated, dried over magnesium sulphate and evaporated to dryness in vacuo. The crude product was purified on silica gel (eluent: ether:heptane (1:1)) to give 4-benzylaminophthalic acid dimethyl ester as a golden oil (yield: 0.94 g, 39%). 1H—NMR (CDCl3) in ppm: γ 3.82 (3H,s); 3.88 (3H,s); 4.35 (2H,d); 4.66 (1H, broad d); 6.57 (1H,d.d.); 6.65 (1H,d); 7.23-7.35 (5H,m); 7.73 (1H,d).

Workup

  1. customevaporated to dryness in vacuo
  2. customThe residue was partitioned between methylene chloride (50 ml) and water (30 ml)
  3. customthe organic phase was isolated
  4. dry with materialdried over magnesium sulphate
  5. customevaporated to dryness in vacuo
  6. customThe crude product was purified on silica gel (eluent: ether:heptane (1:1))

Sources & evidence

ORD record
ord-0e11802358e64c2b8530bf401ae25739
Source dataset
uspto-grants-2003_07
Patent number
US06590118B1

Reaction notes

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