Allylamine → 2-Allylamino-6-methoxy-isonicotinic acid

HRID 1664220Notes

Reaction equation

[CH2:1]([NH2:4])[CH:2]=[CH2:3].C([N:8]([C:23]([O:25][CH2:26]C1C=CC=CC=1)=O)[C:9]1[CH:10]=[C:11]([CH:15]=C(C2OC=CN=2)C=1)[C:12]([OH:14])=[O:13])C=C>O.C(O)(=O)CC(CC(O)=O)(C(O)=O)O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Cu+2]>[CH2:1]([NH:4][C:9]1[CH:10]=[C:11]([CH:15]=[C:23]([O:25][CH3:26])[N:8]=1)[C:12]([OH:14])=[O:13])[CH:2]=[CH2:3]

Participants

Conditions

Temperature: 160 °C

Procedure

A mixture of 3.97 ml (52 mmol, 10 eq) allylamine, 0.97 g (5.2 mmol, 1 eq) 2-chloro-6-methoxy-isonicotinic acid (see building block A3) and 1.29 g (5.2 mmol, 1 eq)-copper(II) sulfate pentahydrate in 10 ml water is heated in a closed vessel during 2.5 h at a bath temperature of 160° C. After cooling to rt the mixture is diluted with 400 ml aq 10% citric acid and extracted with EtOAc. The extracts are washed with water and brine, dried over sodium sulfate and the solvents are evaporated at reduced pressure. The residue is dissolved in about 20 ml hot DCM/MeOH (2/1). On addition of about 25 ml of hexane, partial evaporation of the solvents to a volume of about 20 ml and keeping at 4° C. for 4 h the product precipitates and is filtered off and dried in vacuum.

Workup

temperatureAfter cooling to rt the mixture
extractionextracted with EtOAc
washThe extracts are washed with water and brine
dry with materialdried over sodium sulfate
customthe solvents are evaporated at reduced pressure
dissolutionThe residue is dissolved in about 20 ml hot DCM/MeOH (2/1)
additionOn addition of about 25 ml of hexane, partial evaporation of the solvents to a volume of about 20 ml
customthe product precipitates
filtrationis filtered off
customdried in vacuum

Sources & evidence

ORD record: ord-0971f7496c86489d975fba27dff40d08
Source dataset: uspto-grants-2011_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08039455B2

Reaction notes

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