Dimethylformamide → Benzyl 6-amino-3-cyano-2-methylbenzoate

HRID 1725888Notes

Reaction equation

HRID 1725888 reaction equation
Br[C:2]1[C:3]([CH3:26])=[C:4]([C:15]([NH:18]C(OC(C)(C)C)=O)=[CH:16][CH:17]=1)[C:5]([O:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[O:6].[CH3:27][N:28](C=O)C>[C-]#N.[Zn+2].[C-]#N.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:18][C:15]1[C:4]([C:5]([O:7][CH2:8][C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=2)=[O:6])=[C:3]([CH3:26])[C:2]([C:27]#[N:28])=[CH:17][CH:16]=1

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 68864148Benzyl 3-bromo-6-[(tert-butoxycarbonyl)amino]-2-methylbenzoate

Product 1

HCID 68863942Benzyl 6-amino-3-cyano-2-methylbenzoate

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Procedure

A mixture of Example 108A (2 g, 4.8 mmol), zinc cyanide (335 mg, 2.9 mmol), and DMF (48 mL) was degassed with argon for 30 minutes, treated with Pd(PPh3)4 (330 mg, 0.28 mmol), heated to reflux for 1.5 hours, cooled, and filtered. The filtrate was concentrated and purified using a Biotage 40 gram silica gel cartridge to provide the desired product. MS (ESI(−)) m/e 265 (M−H)−; (DCI) m/e 267 (M+H)+, 284 (M+NH4)+; 1H NMR (300 MHz, DMSO-d6) δ 7.45 (m, 6H), 6.66 (d, 1H), 6.57 (s, 2H), 5.34 (s, 2H), 3.27 (s, 3H).

Workup

  1. temperatureheated
  2. temperatureto reflux for 1.5 hours
  3. temperaturecooled
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated
  6. custompurified

Sources & evidence

ORD record
ord-11187595fc254604b93bd60a0e6d7913
Source dataset
uspto-grants-2009_02
Patent number
US07491718B2

Reaction notes

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