Trichloroisocyanuric Acid → HCID 89157840, compound

HRID 716182Notes

Reaction equation

HRID 716182 reaction equation
N([CH2:4][C:5]1[N:6]=[N:7][C:8]([C:11]2[C:16]([F:17])=[CH:15][CH:14]=[CH:13][N:12]=2)=[CH:9][CH:10]=1)=[N+]=[N-].FC1C(C2N=NC(C)=CC=2)=NC=CC=1.[Cl:32]N1C(=O)N(Cl)C(=O)N(Cl)C1=O>ClCCCl>[Cl:32][CH2:4][C:5]1[N:6]=[N:7][C:8]([C:11]2[C:16]([F:17])=[CH:15][CH:14]=[CH:13][N:12]=2)=[CH:9][CH:10]=1

Participants

5

Reactant 3

HCID 6909Trichloroisocyanuric AcidHCID 70981701HCID 70981701, compoundHCID 89158414HCID 89158414, compound

Product 1

HCID 89157840HCID 89157840, compound

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Conditions

Temperature
90 °C

Procedure

3-(azidomethyl)-6-(3-fluoropyridin-2-yl)pyridazine. A solution of 3-(3-fluoropyridin-2-yl)-6-methylpyridazine (200 mg, 1.05 mmol) in 5 mL of DCE was treated with trichloroisocyanuric acid (98 mg, 0.42 mmol). The mixture was heated at 90° C. for 1 h. The mixture was cooled to RT and the precipitate was filtered off with a fritted funnel and rinsed with 2×20 mL of DCM. The brown solid was discarded. The filtrate was washed with 2×5 mL of 0.5 M NaOH (aq.) followed by brine (5 mL), dried over Na2SO4, and concentrated. The residue was purified by silica gel chromatography (55-75% EtOAc in hexanes) to give 3-(chloromethyl)-6-(3-fluoropyridin-2-yl)pyridazine as a brown crystalline solid. MS (ESI, pos. ion) m/z: 224.0 (M+1). A solution of the 3-(chloromethyl)-6-(3-fluoropyridin-2-yl)pyridazine in 1 mL of DMF at RT was treated with NaN3 (69 mg, 1.05 mmol) and stirred at RT for 5 h. The mixture was filtered through a fritted funnel and the collected solid was rinsed with 2×5 mL of EtOAc. The solid was discarded and the filtrate was concentrated and the crude material was purified by silica gel chromatography (35-75% EtOAc in hexanes) to give 3-(azidomethyl)-6-(3-fluoropyridin-2-yl)pyridazine (100 mg, 41% yield) as an off white amorphous solid. MS (ESI, pos. ion) m/z: 231.1 (M+1). 1H NMR (400 MHz, DMSO-d6) δ ppm 8.64 (1 H, m), 8.27 (1 H, d, J=8.8 Hz), 8.00 (1 H, m), 7.94 (1 H, m), 7.69 (1 H, dt, J=8.4, 4.2 Hz), 4.89 (2 H, s). 19F NMR (376 MHz, DMSO-d6) δ ppm-121.47.

Workup

  1. temperatureThe mixture was cooled to RT
  2. filtrationthe precipitate was filtered off with a fritted funnel
  3. washrinsed with 2×20 mL of DCM
  4. washThe filtrate was washed with 2×5 mL of 0.5 M NaOH (aq.)
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe residue was purified by silica gel chromatography (55-75% EtOAc in hexanes)

Sources & evidence

ORD record
ord-df0658a2c54e400096b8ca310b5fba1d
Source dataset
uspto-grants-2015_11
Patent number
US09187486B2

Reaction notes

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