Tetraethyltin → 3-Ethyl-6-fluoro-1,2,4-benzotriazine 1-Oxide

HRID 1160637Notes

Reaction equation

HRID 1160637 reaction equation
Cl[C:2]1[N:3]=[N+:4]([O-:13])[C:5]2[CH:11]=[CH:10][C:9]([F:12])=[CH:8][C:6]=2[N:7]=1.[CH2:14]([Sn](CC)(CC)CC)[CH3:15]>COCCOC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:14]([C:2]1[N:3]=[N+:4]([O-:13])[C:5]2[CH:11]=[CH:10][C:9]([F:12])=[CH:8][C:6]=2[N:7]=1)[CH3:15]

Participants

5

Reactant 2

HCID 11704TetraethyltinHCID 160793903-Chloro-6-fluoro-1,2,4-benzotriazine 1-oxide

Product 1

HCID 160793913-Ethyl-6-fluoro-1,2,4-benzotriazine 1-OxideYield 93%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

Pd(PPh3)4 (196 mg, 0.17 mmol) was added to a stirred solution of chloride 27 (329 mg, 1.7 mmol) and tetraethyltin (0.7 mL, 3.3 mmol) in DME (20 mL), the solution degassed, and stirred under N2 at reflux temperature for 16 h. The solvent was evaporated and the residue purified by chromatography, eluting with 20% EtOAc/pet. ether to give an oil which was further purified by chromatography, eluting with 5% EtOAc/DCM, to give 1-oxide 28 (295 mg, 93%) as a white solid, mp (EtOAc/pet. ether) 122-124° C.; 1H NMR δ 8.48 (dd, J=9.5, 5.5 Hz, 1 H, H-8), 7.60 (dd, J=8.7, 2.6 Hz, 1 H, H-5), 7.38 (m, 1 H, H-7), 3.04 (q, J=7.6 Hz, 2 H, CH2), 1.43 (t, J=7.6 Hz, 3 H, CH3); 13C NMR δ 168.6 (q, J=175 Hz), 165.1, 149.5(d, J=15 Hz), 130.5, 123.2 (d, J=11 Hz), 120.0 (d, J=26 Hz), 112.7 (d, J=22 Hz), 30.7, 12.2. Anal. Calcd for C9H8FN3O: C, 56.0; H, 4.2; N, 21.8. Found: C, 56.0; H, 4.2; N, 21.8%.

Workup

  1. customthe solution degassed
  2. temperatureat reflux temperature for 16 h
  3. customThe solvent was evaporated
  4. customthe residue purified by chromatography
  5. washeluting with 20% EtOAc/pet. ether
  6. customto give an oil which
  7. customwas further purified by chromatography
  8. washeluting with 5% EtOAc/DCM

Sources & evidence

ORD record
ord-a37ae4b2a9ea48d9b13fce06f19974d1
Source dataset
uspto-grants-2010_10
Patent number
US07816521B2

Reaction notes

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