Tert-Butyl nitrite → 2,4-Dichloro-7H-pyrrolo[2,3-d]pyrimidine

HRID 1516829Notes

Reaction equation

HRID 1516829 reaction equation
[Cl:1][C:2]1[C:3]2[CH:11]=[CH:10][NH:9][C:4]=2[N:5]=[C:6](N)[N:7]=1.[Sb](Cl)(Cl)[Cl:13].C(ON=O)(C)(C)C>ClCCCl.C(Cl)(Cl)Cl>[Cl:13][C:6]1[N:7]=[C:2]([Cl:1])[C:3]2[CH:11]=[CH:10][NH:9][C:4]=2[N:5]=1

Participants

6

Reactant 3

HCID 10906Tert-Butyl nitriteHCID 24814Antimony trichlorideHCID 53244134-chloro-7H-pyrrolo(2,3-d)pyrimidin-2-amine

Product 1

HCID 141168712,4-Dichloro-7H-pyrrolo[2,3-d]pyrimidineYield 43%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 6212ChloroformSolvent

Procedure

To a suspension of 4-chloro-7H-pyrrolo[2,3-d]pyrimidin-2-ylamine (500 mg, 2.97 mmol) in 1,2-dichloroethane (40 mL) at −10° C. under argon was added antimony chloride (750 mg, 3.29 mmol). After stirring for 5 min, tert-butylnitrite (2.50 mL, 20.8 mmol) was added to the solution. The reaction was stirred at −10° C. for 3 h. The reaction was diluted with CHCl3 (100 mL) and poured into ice water (50 mL). The CHCl3 layer was separated, washed with brine (20 mL), dried with Na2SO4, and concentrated to dryness. Silica gel chromatography (Hexanes:EtOAc=50:50) yielded 239 mg (43%) of 2,4-dichloro-7H-pyrrolo[2,3-d]pyrimidine as a tan solid.

Workup

  1. stirringThe reaction was stirred at −10° C. for 3 h
  2. customThe CHCl3 layer was separated
  3. washwashed with brine (20 mL)
  4. dry with materialdried with Na2SO4
  5. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-8ff3acda7a2741d49889cf0eaf64a07e
Source dataset
uspto-grants-2012_07
Patent number
US08227601B2

Reaction notes

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