Ammonium Chloride → 3-Amino-4-(2-cyano-ethylamino)-benzoic acid methyl ester

HRID 555283Notes

Reaction equation

HRID 555283 reaction equation
[Cl-].[NH4+].[CH3:3][O:4][C:5](=[O:20])[C:6]1[CH:11]=[CH:10][C:9]([NH:12][CH2:13][CH2:14][C:15]#[N:16])=[C:8]([N+:17]([O-])=O)[CH:7]=1>O.[Zn]>[CH3:3][O:4][C:5](=[O:20])[C:6]1[CH:11]=[CH:10][C:9]([NH:12][CH2:13][CH2:14][C:15]#[N:16])=[C:8]([NH2:17])[CH:7]=1

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 669876614-(2-Cyanoethylamino)-3-nitro-benzoic acid methyl ester

Product 1

HCID 669874673-Amino-4-(2-cyano-ethylamino)-benzoic acid methyl esterYield 76.3%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of ammonium chloride (21.7 g, 406.3 mmol) in water (200 mL) was added 4-(2-cyanoethylamino)-3-nitro-benzoic acid methyl ester (6.1 g, 24.5 mmol) followed by zinc powder (42.8 g, 655.9 mmol). The mixture was heated to 60° C. for 3 h. It was filtered hot and washed with EtOAc. The filtrate was further extracted with EtOAc and the combined organic phase washed with brine solution. The organic layer was evaporated to give 4.1 g (75%) of 3-amino-4-(2-cyano-ethylamino)-benzoic acid methyl ester. MS-ESI m/z 220 (M+1); 1H NMR (300 MHz, CDCl3) δ 2.7 (t, 2H), 3.6 (m, 2H), 3.8 (s, 3H), 4.3 (bs, 1H), 6.6 (d, 1H), 7.45 (d, 1H), 7.6 (d, 1H)

Workup

  1. filtrationIt was filtered hot
  2. washwashed with EtOAc
  3. extractionThe filtrate was further extracted with EtOAc
  4. washthe combined organic phase washed with brine solution
  5. customThe organic layer was evaporated

Sources & evidence

ORD record
ord-b6cbccf8716644b09ec8797bcede230e
Source dataset
uspto-grants-2011_11
Patent number
US08053431B2

Reaction notes

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