tert-Butyl hydroperoxide → 1-(3-Methylanilino)-4-([1,3,5]trioxan-2-yl)phthalazine

HRID 2054182

Reaktionsgleichung

Reaktionsgleichung von HRID 2054182
[CH3:1][C:2]1[CH:3]=[C:4]([CH:16]=[CH:17][CH:18]=1)[NH:5][C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[N:8][N:7]=1.[O:19]1[CH2:24][O:23][CH2:22][O:21][CH2:20]1.FC(F)(F)C(O)=O.C(OO)(C)(C)C>C(#N)C.O>[CH3:1][C:2]1[CH:3]=[C:4]([CH:16]=[CH:17][CH:18]=1)[NH:5][C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[C:9]([CH:20]2[O:21][CH2:22][O:23][CH2:24][O:19]2)=[N:8][N:7]=1

Komponenten

7

Edukt 4

HCID 6410tert-Butyl hydroperoxideHCID 6422Trifluoroacetic acidHCID 80811,3,5-TrioxaneHCID 223864691-(3-Methylanilino)phthalazine

Produkt 1

HCID 223864601-(3-Methylanilino)-4-([1,3,5]trioxan-2-yl)phthalazine

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6342AcetonitrileLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

To a suspension of 9.6 g (40.8 mmol) 1-(3-methylanilino)phthalazine and 173 g 1,3,5-trioxane in 570 ml acetonitrile, 3.12 ml (40.8 mmol) trifluoroacetic acid, 11.0 ml (80% in tBuOOtBu; 87.4 mmol) tBuOOH and 190 mg (0.68 mmol) FeSO4.7 H2O are added, and the mixture stirred for 17 h at 80° C. The cooled reaction mixture is partly evaporated in the RE, diluted with EtOAc and water and adjusted to an alkaline pH with 1 N NaOH. The aqueous phase is separated off and twice extracted with EtOAc. The organic phases are washed twice with water and brine, dried (Na2SO4) and evaporated. Column chromatography (SiO2; EtOAc/toluene 1:3; applied as solution in dichloromethane/acetone 9:1) yields the title compound after crystallization with the addition of DIPE; m.p. 161° C.; DC (EtOAc/toluene 1:3) Rf=0.27; 1H-NMR (DMSO-d6) 9.27 (s, HN), 8.74 (m, 1H), 8.61 (m, 1H), 8.00 (m, 2H), 7.72 (s, 1H), 7.68 (d, 1H), 7.25 (t, 1H), 6.89 (d, 1H), 6.39 (s, 1H), 5.47 (d, 2H), 5.41 (d, 2H), 2.33 (s, 3H); FAB-MS (M+H)+=324; anal. calc.(C18H17N3O3) C, 66.86%; H, 5.30%; N, 13.00%; meas. C, 66.83%; H, 5.36%; N, 12.81%.

Aufarbeitung

  1. customThe cooled reaction mixture
  2. customis partly evaporated in the RE
  3. additiondiluted with EtOAc and water
  4. customThe aqueous phase is separated off
  5. extractiontwice extracted with EtOAc
  6. washThe organic phases are washed twice with water and brine
  7. dry with materialdried (Na2SO4)
  8. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-06d11aa3aba7448b910aaf93f1253e2a
Quelldatensatz
uspto-grants-2008_02
Patentnummer
US07329660B2

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