m-Chloroperbenzoic acid → HCID 57500639, compound

HRID 2420942Notes

Reaction equation

HRID 2420942 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:10]([Br:11])=[CH:9][N:8]=[C:7](SC)[N:6]=1)=[O:4].ClC1C=CC=C(C(OO)=O)C=1.Cl.CN.C[CH2:29][N:30](C(C)C)C(C)C>C(Cl)Cl.C1COCC1>[Br:11][C:10]1[C:5]([C:3]([O:2][CH3:1])=[O:4])=[N:6][C:7]([NH:30][CH3:29])=[N:8][CH:9]=1

Participants

7

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 81531DiisopropylethylamineHCID 2794729Methyl 5-bromo-2-(methylsulfanyl)pyrimidine-4-carboxylateHCID 6364545Methylamine hydrochloride

Product 1

HCID 57500639HCID 57500639, compoundYield 75%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Methyl-5-bromo-2-(methylthio)pyrimidine-4-carboxylate (1.0 eq, 661 mg, 2.52 mmol) was dissolved in CH2Cl2 (10 ml). meta-chloro perbenzoic acid (m-cpba, 77% pure grade, 2.5 eq, 1.42 g, 6.34 mmol) was added and the mixture was stirred at room temperature for 1 hour. To the resulting suspension was added anhydrous THF (10 ml), methylamine hydrochloride (10 eq, 1.7 g, 25.18 mmol) and DIEA (10 eq, 4.3 ml, 24.69 mmol) and the mixture stirred at room temperature overnight. The solvents were removed in vacuo prior to adding CH2Cl2 and a saturated aqueous sodium bicarbonate solution. The two phases were decanted and two further CH2Cl2 extractions were carried out. The combined extracts were dried over Na2SO4 and the solvents evaporated. Purification by flash chromatography on silica gel (20-30% ethylacetate in hexanes) provided methyl 5-bromo-2-(methylamino)pyrimidine-4-carboxylate as an off-white solid (461 mg, 75% yield). LCMS (ES): >95% pure, m/z 246 [M]+, 248 [M+2]+.

Workup

  1. stirringthe mixture stirred at room temperature overnight
  2. customThe solvents were removed in vacuo
  3. additionto adding CH2Cl2
  4. customThe two phases were decanted
  5. extractiontwo further CH2Cl2 extractions
  6. dry with materialThe combined extracts were dried over Na2SO4
  7. customthe solvents evaporated
  8. customPurification by flash chromatography on silica gel (20-30% ethylacetate in hexanes)

Sources & evidence

ORD record
ord-07f37193ad864b108544ce9a4b04f3fa
Source dataset
uspto-grants-2011_06
Patent number
US07956064B2

Reaction notes

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