Boron trifluoride etherate → HCID 58764257, compound

HRID 2387166Notes

Reaction equation

HRID 2387166 reaction equation
B(F)(F)F.CC[O:7][CH2:8][CH3:9].[Cl:10][C:11]1[N:16]=[CH:15][C:14](N)=[C:13]([I:18])[CH:12]=1.N(OC(C)(C)C)=[O:20]>COCCOC.C(Cl)Cl>[Cl:10][C:11]1[N:16]=[CH:15][C:14]([O:7][C:8](=[O:20])[CH3:9])=[C:13]([I:18])[CH:12]=1

Participants

6

Reactant 3

HCID 8000Boron trifluoride etherateHCID 10906Tert-Butyl nitriteHCID 184070406-Chloro-4-iodopyridin-3-amine

Product 1

HCID 58764257HCID 58764257, compoundYield 49%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
-10 °C

Procedure

Boron trifluoride diethyl etherate (6.2 mL, 48.9 mmol) was slowly added to a cooled −15° C. solution of 6-chloro-4-iodo-pyridin-3-ylamine (5.82 g, 22.9 mmol) dissolved in DME (36 mL) and CH2Cl2 (12 mL). Tert-butyl nitrite (3.6 mL, 27.6 mmol) was slowly added maintaining the temperature below −5° C. The reaction was stirred at −10° C. for 25 minutes and then at 0° C. for 20 minutes. The mixture was diluted with pentanes (100 mL) and the tetrafluoroborate diazonium salt was collected by filtration. The salt was dissolved immediately by dissolving it in acetic anhydride (20 mL) and heated to 95° C. for 2 hours. The reaction was cooled to room temperature and partitioned between diethyl ether and saturated NaHCO3. The organic layer was dried over MgSO4 and concentrated. Purification by silica gel chromatography (0% to 60% EtOAc in hexanes) gave the product as a white solid (3.34 g, 49%). 1H NMR (300 MHz, CDCl3): δ 2.40 (s, 3 H), 7.82 (s, 1 H), 8.09 (s, 1 H).

Workup

  1. temperaturemaintaining the temperature below −5° C
  2. waitat 0° C. for 20 minutes
  3. filtrationthe tetrafluoroborate diazonium salt was collected by filtration
  4. dissolutionThe salt was dissolved immediately
  5. dissolutionby dissolving it in acetic anhydride (20 mL)
  6. temperatureheated to 95° C. for 2 hours
  7. temperatureThe reaction was cooled to room temperature
  8. custompartitioned between diethyl ether and saturated NaHCO3
  9. dry with materialThe organic layer was dried over MgSO4
  10. concentrationconcentrated
  11. customPurification by silica gel chromatography (0% to 60% EtOAc in hexanes)

Sources & evidence

ORD record
ord-a2787ad280494a9d84bec4f6effaa55f
Source dataset
uspto-grants-2012_09
Patent number
US08268835B2

Reaction notes

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