Methylamine → Methyl 4-(methylamino)-3-nitrobenzoate

Temperature

80 °C

Methylamine (2M in THF) (23.19 mL, 46.4 mmol) was added to a solution of methyl 4-chloro-3-nitrobenzoate (5 g, 23.19 mmol) (available, for example, from Lancaster Synthesis Ltd.) in N,N-dimethylformamide (DMF) (8 mL) at rt under nitrogen. The reaction mixture was heated to 80° C. and stirred overnight. LCMS showed major peak product, but reaction had not gone to completion. Further methylamine (2M in THF, 10 ml) was added and the reaction heated to 90° C. for 6 h. Further methylamine (2M in THF, 6 ml) was added and the reaction stirred for 1 h at rt and 72 h at 70° C. Further methylamine (2M in THF, 10 ml) was added and the reaction heated to 80° C. for 3 h. The reaction was allowed to cool to rt and then the product was precipitated by the addition of water (50 mL). The resultant suspension was cooled to 0° C. and then filtered. The residue was washed with further water (3×25 mL) and allowed to dry on the filter pad for 15 mins. The solid was collected and dried in vacuo to afford the title compound as a yellow solid (4.54 g, 21.60 mmol, 93% yield).

1. custompeak product, but reaction
2. temperaturethe reaction heated to 90° C. for 6 h
3. stirringthe reaction stirred for 1 h at rt and 72 h at 70° C
4. temperaturethe reaction heated to 80° C. for 3 h
5. temperatureto cool to rt
6. customthe product was precipitated by the addition of water (50 mL)
7. temperatureThe resultant suspension was cooled to 0° C.
8. filtrationfiltered
9. washThe residue was washed with further water (3×25 mL)
10. customto dry on the filter pad for 15 mins
11. customThe solid was collected
12. customdried in vacuo

ORD record

ord-e87ff4915d1f4c5ba33f0c0e58e05fd7

Source dataset

uspto-grants-2015_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09127003B2