N-methyl-2-pyrrolidone → Methyl 2-Amino-5-Cyano-3-Methylbenzoate

HRID 1754003Notes

Reaction equation

HRID 1754003 reaction equation
[NH2:1][C:2]1[C:11]([CH3:12])=[CH:10][C:9](Br)=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[Cu][C:15]#[N:16].CN1CCCC1=O>O>[NH2:1][C:2]1[C:11]([CH3:12])=[CH:10][C:9]([C:15]#[N:16])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

5

Reactant 3

HCID 13387N-methyl-2-pyrrolidoneHCID 2763413Methyl 2-amino-5-bromo-3-methylbenzoateHCID 178418546HCID 178418546, compound

Product 1

HCID 25156988Methyl 2-Amino-5-Cyano-3-Methylbenzoate

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
120 °C

Procedure

Methyl 2-amino-5-bromo-3-methylbenzoate (100 g, 0.393 mol, 96% of quantitative NMR), copper(I) cyanide (36.3 g, 0.401 mol) and N-methyl-2-pyrrolidinone (NMP) (206 g, 200 mL, 2.084 mol) are heated to 170° C. for 4 hours under agitation. The reaction batch is cooled down to 120° C., 350 mL of H2O (90° C.) are added dropwise in the course of 30 minutes and the suspension obtained is filtered. The solid obtained is washed twice with ammonia (200 g, 12% in H2O) and 2 times with 100 ml of water. Following drying in a vacuum drying cabinet at 50° C., methyl 2-amino-5-cyano-3-methylbenzoate is obtained as a grey solid. Yield: 69.0 g, 88.2% of theory, purity: 95.6% quantitative NMR, 1500 ppm Cu).

Workup

  1. customthe suspension obtained
  2. filtrationis filtered
  3. customThe solid obtained
  4. washis washed twice with ammonia (200 g, 12% in H2O) and 2 times with 100 ml of water
  5. customFollowing drying in a vacuum
  6. customdrying cabinet at 50° C.

Sources & evidence

ORD record
ord-ff0a61baa247464cb3a2c5ca7df0b27f
Source dataset
uspto-grants-2015_10
Patent number
US09169198B2

Reaction notes

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