Lawesson's reagent → 6-(3,4-difluorophenylamino)-4,4-diethyl-1-methyl-1H-benzo[d][1,3]oxazine-2(4H)-thione

HRID 899227Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 899227
[F:1][C:2]1[CH:3]=[C:4]([NH:9][C:10]2[CH:11]=[CH:12][C:13]3[N:18]([CH3:19])[C:17](=O)[O:16][C:15]([CH2:23][CH3:24])([CH2:21][CH3:22])[C:14]=3[CH:25]=2)[CH:5]=[CH:6][C:7]=1[F:8].COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=[S:35])=CC=1>C1(C)C=CC=CC=1>[F:1][C:2]1[CH:3]=[C:4]([NH:9][C:10]2[CH:11]=[CH:12][C:13]3[N:18]([CH3:19])[C:17](=[S:35])[O:16][C:15]([CH2:23][CH3:24])([CH2:21][CH3:22])[C:14]=3[CH:25]=2)[CH:5]=[CH:6][C:7]=1[F:8]

Komponenten

4

Edukt 2

HCID 87949Lawesson's reagentHCID 247586596-(3,4-difluorophenylamino)-4,4-diethyl-1-methyl-1H-benzo[d][1,3]oxazin-2(4H)-one

Produkt 1

HCID 114171456-(3,4-difluorophenylamino)-4,4-diethyl-1-methyl-1H-benzo[d][1,3]oxazine-2(4H)-thioneAusbeute 36 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Versuchsvorschrift

To a stirred solution of 6-[(3,4-difluorophenyl)amino]-4,4-diethyl-1-methyl-1,4-dihydro-2H-3,1-benzoxazin-2-one (0.10 g, 0.29 mmol) in toluene (5 mL) was added Lawesson's reagent (0.09 g, 0.23 mmol). The reaction mixture was heated to reflux overnight and partitioned between ammonium chloride solution (sat.) and ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated. Flash silica gel column separation using 20% ethyl acetate/hexane followed by trituration with ether gave 6-[(3,4-difluorophenyl)amino]-4,4-diethyl-1-methyl-1,4-dihydro-2H-3,1-benzoxazine-2-thione as a white solid (0.03 g, 31%). 1H NMR (DMSO-d6): δ 8.44 (s, 1H), 7.32(q, J=9.1 Hz, 1H), 7.19(d, J=8.8 Hz, 1H), 7.12 (dd, J=8.8, 2.4 Hz, 1H), 6.97 (m, 1H), 6.88 (d, J=2.4 Hz, 1H), 6.81 (m, 1H), 3.75 (s, 3H), 1.99 (m, 4H), 0.85 (t, J=7.3 Hz, 6H); MS (ESI) m/z 363 ([M+H]+); MS (ESI) m/z 361 ([M−H]−); Anal. calcd for C19H20F2N2OS: C, 62.96; H, 5.56; N, 7.73. Found: C, 62.15; H, 5.65; N, 7.39.

Aufarbeitung

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux overnight
  3. custompartitioned between ammonium chloride solution (sat.) and ethyl acetate
  4. dry with materialThe organic layer was dried over magnesium sulfate
  5. concentrationconcentrated
  6. customFlash silica gel column separation

Quellen und Nachweise

ORD-Eintrag
ord-e679f7d4649d4e38a28f51acb7ce5389
Quelldatensatz
uspto-grants-2008_04
Patentnummer
US07354915B2

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