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

HRID 1296513ノート

反応式

HRID 1296513 の反応式
[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]

参加物

4

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-6a21242eec41448d8521ee29519e413d
出典データセット
uspto-grants-2007_07
特許番号
US07247625B2

反応ノート

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