Hydrochloric Acid → Ethyl (4-{[5-bromo-4-(methylthio)pyrimidin-2-yl]amino}phenyl)(methyl)oxido-lambda-sulfanylidenecarbamate

HRID 238150Notes

Reaction equation

HRID 238150 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([CH3:16])(=[N:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])=[O:9])=[CH:4][CH:3]=1.[Br:17][C:18]1[C:19]([S:25][CH3:26])=[N:20][C:21](Cl)=[N:22][CH:23]=1.Cl>O1CCOCC1.C(#N)C.O>[CH2:14]([O:13][C:11]([N:10]=[S:8]([C:5]1[CH:6]=[CH:7][C:2]([NH:1][C:21]2[N:20]=[C:19]([S:25][CH3:26])[C:18]([Br:17])=[CH:23][N:22]=2)=[CH:3][CH:4]=1)([CH3:16])=[O:9])=[O:12])[CH3:15]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 122647965-Bromo-2-chloro-4-(methylthio)pyrimidineHCID 44122615Ethyl [(4-aminophenyl)(methyl)oxido-sulfanylidene]carbamate

Product 1

HCID 50742701Ethyl (4-{[5-bromo-4-(methylthio)pyrimidin-2-yl]amino}phenyl)(methyl)oxido-lambda-sulfanylidenecarbamate

Reagents, catalysts & solvents 2

HCID 312751,4-DioxaneSolventHCID 18373917Acetonitrile--water (1/1)Solvent

Procedure

(RS)—S-(4-aminophenyl)-N-(ethoxycarbonyl)-S-methylsulfoximide (10 g, 42 mmol), 5-bromo-2-chloro-4-methylsulfanyl-pyrimidine (10 g, 42 mmol) and 5M HCl (8 mL) in dioxane is stirred at 60° C. in 90% acetonitrile-water (250 mL) for 36 h. TLC indicates almost complete consumption of starting sulfoximine. The reaction mixture is poured into 800 mL of aq. NaHCO3, the pasty precipitate filtered, washed with 70 mL of EtOAc, then crude material (7.5 g) is recrystallized from boiling EtOH (200 mL) to yield 6 g (35%).

Workup

  1. customconsumption of starting sulfoximine
  2. additionThe reaction mixture is poured into 800 mL of aq. NaHCO3
  3. filtrationthe pasty precipitate filtered
  4. washwashed with 70 mL of EtOAc
  5. customcrude material (7.5 g) is recrystallized
  6. customto yield 6 g (35%)

Sources & evidence

ORD record
ord-609eeef5aea540ccb335561e18c97e31
Source dataset
uspto-grants-2014_02
Patent number
US08642611B2

Reaction notes

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