Dimethyl Disulfide → 4-Chloro-5-(methylsulfanyl)-7H-pyrrolo[2,3-D]pyrimidine

HRID 1937410Notes

Reaction equation

HRID 1937410 reaction equation
Br[C:2]1[C:10]2[C:9]([Cl:11])=[N:8][CH:7]=[N:6][C:5]=2[NH:4][CH:3]=1.C([Li])CCC.[CH3:17][S:18]SC>C1COCC1.[NH4+].[Cl-]>[Cl:11][C:9]1[C:10]2[C:2]([S:18][CH3:17])=[CH:3][NH:4][C:5]=2[N:6]=[CH:7][N:8]=1

Participants

6

Reactant 3

HCID 12232Dimethyl DisulfideHCID 53807105-Bromo-4-chloro-7H-pyrrolo[2,3-d]pyrimidineHCID 178418339Butyllithium

Product 1

HCID 107743844-Chloro-5-(methylsulfanyl)-7H-pyrrolo[2,3-D]pyrimidineYield 97.6%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 25517Ammonium ChlorideSolvent

Procedure

To 5-bromo-4-chloro-7H-pyrrolo[2,3-d]pyrimidine (0.18 g, 0.77 mmol) in dry THF (2 ml), cooled in a dry ice-acetone bath, was added dropwise n-butyllithium (0.77 ml, 1.9 mmol, 2.5 M in hexanes). The mixture was stirred for 1 hour, then dimethyldisulfide (0.077 mL, 0.77 mmol) suspended in dry THF (1 ml) was added. The solution was stirred for 2.5 hours at −78° C. and then diluted with aqueous NH4Cl. The phases were separated and the water extracted 2 times with ethyl acetate. The combined organic phases were dried over Na2SO4, and concentrated in vacuo to afford 4-chloro-5-methylsulfanyl-7H-pyrrolo[2,3-d]pyrimidine as an orange solid (150 mg).

Workup

  1. additionwas added
  2. stirringThe solution was stirred for 2.5 hours at −78° C.
  3. customThe phases were separated
  4. extractionthe water extracted 2 times with ethyl acetate
  5. dry with materialThe combined organic phases were dried over Na2SO4
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-4dcde31afcfa4b27a7c9cafc37f71e86
Source dataset
uspto-grants-2002_05
Patent number
US06395733B1

Reaction notes

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