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

HRID 1296513노트

반응식

HRID 1296513 반응식
[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]

참가 물질

4

반응물 2

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

생성물 1

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

시약·촉매·용매 1

HCID 1140Toluene용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-6a21242eec41448d8521ee29519e413d
출처 데이터셋
uspto-grants-2007_07
특허 번호
US07247625B2

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