p-Toluenesulfonic acid → HCID 178468548, compound

HRID 877659Notes

Reaction equation

[NH2:1][N:2]1[CH:6]=[C:5]([C:7]([O:9][CH2:10][CH3:11])=[O:8])[CH:4]=[C:3]1[C:12]([O:14]CC)=O.C(O[C:20](OCC)([CH3:23])[C:21]#[N:22])C.CC1C=CC(S(O)(=O)=O)=CC=1.C1CCN2C(=NCCC2)CC1>C(Cl)Cl>[C:21]([C:20]1[CH:23]=[N:1][N:2]2[CH:6]=[C:5]([C:7]([O:9][CH2:10][CH3:11])=[O:8])[CH:4]=[C:3]2[C:12]=1[OH:14])#[N:22]

Participants

Conditions

Temperature: 125 °C

Procedure

To a round bottom flask was added diethyl 1-amino-1H-pyrrole-2,4-dicarboxylate (40 g, 177 mmol), diethoxypropionitrile (53 mL) and p-TSA (10 g, 0.052 mmol). The reaction was heated at 125° C. for 3 hours and the EtOH was removed. The reaction was cooled to room temperature before DBU (30 g, 340 mmol) was added. The reaction was then heated at 80° C. for 2 hours. The reaction was cooled to room temperature and diluted with CH2Cl2. The mixture was washed with 5% citric acid solution (2×), water and brine solution. The organic layer was concentrated and the residue was purified by flash silica gel column chromatography (10% MeOH in CHCl3) to yield 20 g (50%) of the title compound as a brown oil. LCMS (condition A): m/z=230.2 −ve. H1 NMR (400 MHz, CDCl3) δ ppm: 9.53 (1H, br s), 8.32 (1H, s), 7.75 (1H, s), 6.75 (1H, s), 4.25 (2H, q), 1.28 (3H, t).

Workup

customthe EtOH was removed
additionwas added
temperatureThe reaction was then heated at 80° C. for 2 hours
temperatureThe reaction was cooled to room temperature
washThe mixture was washed with 5% citric acid solution (2×), water and brine solution
concentrationThe organic layer was concentrated
customthe residue was purified by flash silica gel column chromatography (10% MeOH in CHCl3)

Sources & evidence

ORD record: ord-c8689aada9c4446a8f2c54ec64a88046
Source dataset: uspto-grants-2015_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08987268B2

Reaction notes

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