Dimethylamine → Methyl 3-cyano-2-methylbenzoate

HRID 906078Notes

Reaction equation

Br[C:2]1[C:3]([CH3:12])=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].C(=O)([O-])[O-].[Na+].[Na+].[CH3:19][NH:20]C>C(OCC)(=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[K+].[K+].[K+].[K+].[Fe+2]>[C:19]([C:2]1[C:3]([CH3:12])=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6])#[N:20]

Participants

Conditions

Temperature: 120 °C

Procedure

To a solution of methyl 3-bromo-2-methylbenzoate (0.646 g, 2.8 mmol) in 4 ml of dimethylamine was added Pd(OAc)2 (0.5 mol %), sodium carbonate (0.3 g, 2.8 mmol), K4[Fe(CN)6].3H2O (0.262 g, 0.62 mmol). The mixture was heated to 120° C. and stirred at this temperature for 4 hours then at RT for 18 hours. The reaction mixture was diluted with 30 ml of ethyl acetate and the resulting slurry was filtered through Celite. The filtrate was washed with water (2×15 ml) then 5% aqueous ammonium hydroxide (1×15 ml). The organic layer was dried over anhydrous sodium sulfate then filtered and concentrated to provide methyl 3-cyano-2-methylbenzoate (0.248 g, 50% yield) (S. Weissman, D. Zewge, C. Chen, J. Org. Chem. 2005, 70, 1508-1510). 1H-NMR (400 MHz, DMSO-d6): 8.09 (d, 1H), 8.04 (d, 1H), 7.53 (t, 1H), 3.87 (s, 3H), 2.66 (s, 3H).

Workup

waitat RT for 18 hours
filtrationthe resulting slurry was filtered through Celite
washThe filtrate was washed with water (2×15 ml)
dry with materialThe organic layer was dried over anhydrous sodium sulfate
filtrationthen filtered
concentrationconcentrated

Sources & evidence

ORD record: ord-f9f3157b97644e039c2ce203bf142725
Source dataset: uspto-grants-2011_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08012956B2

Reaction notes

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