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

HRID 1160637Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1160637
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]

Komponenten

5

Edukt 2

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 80711,2-DimethoxyethaneLösungsmittel

Versuchsvorschrift

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%.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-a37ae4b2a9ea48d9b13fce06f19974d1
Quelldatensatz
uspto-grants-2010_10
Patentnummer
US07816521B2

Notizen zur Reaktion

Wird geladen…