Trifluoroacetic acid → 2,4-Diamino-5-methylpyrimidine

HRID 41518Notes

Reaction equation

HRID 41518 reaction equation
Cl[C:2]1[N:7]=[C:6]([NH:8]C2C=CC3OC(=O)NC=3C=2)[C:5]([CH3:19])=[CH:4][N:3]=1.Cl.CS(C1C=C([NH2:31])C=CC=1)(=O)=O.C(O)(C(F)(F)F)=O>CC(O)C>[CH3:19][C:5]1[C:6]([NH2:8])=[N:7][C:2]([NH2:31])=[N:3][CH:4]=1

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 27351793-(Methylsulfonyl)aniline hydrochlorideHCID 580713875-(2-Chloro-5-methylpyrimidin-4-ylamino)benzo[d]oxazol-2(3H)-one

Product 1

HCID 652662,4-Diamino-5-methylpyrimidineYield 49%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Conditions

Temperature
87.5 °C

Procedure

To a vial with 5-(2-chloro-5-methylpyrimidin-4-ylamino)benzo[d]oxazol-2(3H)-one (138.3 mg, 0.5 mmol) and 3-(methylsulfonyl)benzenamine hydrochloride (207.7 mg, 1.0 mmol), i-PrOH (10 mL) was added, followed by TFA (116 μL, 1.5 mmol). The vial was tightly closed, and the reaction mixture was stirred at 85-90° C. for 40 h. The solvent was removed in vacuo, and the crude product was purified by RP-HPLC. N4-(benzo[d]oxazol-2(3H)-on-5-yl)-N2-(3-methylsulfonyl)phenyl)-5-methylpyrimidine-2,4-diamine was obtained as a mono-trifluoroacetate salt: an off-white solid, 129 mg (49% yield); 1H NMR (300 MHz, DMSO) δ 11.60 (s, 1H), 9.43 (s, 1H), 8.43 (s, 1H), 8.20 (s, 1H), 8.11 (br d, J=7.5, 1H), 7.96 (d, J=0.8, 1H), 7.49-7.33 (m, 4H), 7.27 (d, J=8.5, 1H), 3.13 (s, 3H), 2.16 (s, 3H); LCMS (M+) m/z 412.47.

Workup

  1. customThe vial was tightly closed
  2. customThe solvent was removed in vacuo
  3. customthe crude product was purified by RP-HPLC

Sources & evidence

ORD record
ord-b77679149cc8428da594bc27a962ea87
Source dataset
uspto-grants-2013_09
Patent number
US08530656B2

Reaction notes

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