Potassium Carbonate → Ethyl 4-((3-((tert-butoxycarbonyl)amino)phenyl)amino)-2-(methylthio)pyrimidine-5-carboxylate

HRID 527392Notes

Reaction equation

[C:1]([NH:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([NH2:15])[CH:10]=1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].Cl[C:17]1[C:22]([C:23]([O:25][CH2:26][CH3:27])=[O:24])=[CH:21][N:20]=[C:19]([S:28][CH3:29])[N:18]=1.C([O-])([O-])=O.[K+].[K+]>CN(C=O)C>[C:4]([O:3][C:1]([NH:8][C:9]1[CH:10]=[C:11]([NH:15][C:21]2[C:22]([C:23]([O:25][CH2:26][CH3:27])=[O:24])=[CH:17][N:18]=[C:19]([S:28][CH3:29])[N:20]=2)[CH:12]=[CH:13][CH:14]=1)=[O:2])([CH3:7])([CH3:6])[CH3:5]

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of N-Boc-m-phenylenediamine (50a, prepared according to the procedures reported in: Duceppe, J.-S. et al. Org. Process. Res. Dev. 2009, 13, 1156-1160) (280 g, 1.35 mol) and ethyl 4-chloro-2-(methylthio)pyrimidine-5-carboxylate (Sigma-Aldrich; 303.7 g, 1.32 mol) in DMF (200 mL) at RT was treated with K2CO3 (361 g, 2.6 mol). The mixture was stirred at 80° C. in an oil bath overnight. It was cooled to RT and treated with ice water. The resulting white suspension was filtered and washed with water. The white solid was collected and dried to afford crude ethyl 4-((3-((tert-butoxycarbonyl)amino)phenyl)amino)-2-(methylthio)pyrimidine-5-carboxylate (50c) (450 g, 84% yield). 1H NMR (400 MHz, DMSO-d6) δ 10.22 (s, 1H), 9.44 (s, 1H), 8.72 (s, 1H), 7.90 (s, 1H), 7.35-7.33 (m, 1H), 7.28-7.24 (m, 1H), 7.14-7.12 (m, 1H), 4.38-4.33 (q, 2H), 2.51 (s, 3H), 1.48 (s, 9H), 1.35 (t, 3H). m/z (ESI, +ve ion) 405.0 (M+1)−.

Workup

customprepared
temperatureIt was cooled to RT
filtrationThe resulting white suspension was filtered
washwashed with water
customThe white solid was collected
customdried

Sources & evidence

ORD record: ord-bafff317481e4688820fca8e663ebf66
Source dataset: uspto-grants-2016_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09346801B2

Reaction notes

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