Anthranilic Acid → 2-(3-chlorophenylamino)-6-octyl-4H-3,1-benzoxazin-4-one

HRID 502506ノート

反応式

HRID 502506 の反応式
[C:1]([OH:10])(=[O:9])[C:2]1[C:3](=[CH:5][CH:6]=[CH:7][CH:8]=1)[NH2:4].[Cl:11][C:12]1[CH:13]=[C:14]([N:18]=[C:19]=O)[CH:15]=[CH:16][CH:17]=1.O1[C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][C:25]=2[CH2:24][C:23](=O)N1.NC(N)=O>C1COCC1>[Cl:11][C:12]1[CH:13]=[C:14]([NH:18][C:19]2[O:9][C:1](=[O:10])[C:2]3[CH:8]=[C:7]([CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH3:30])[CH:6]=[CH:5][C:3]=3[N:4]=2)[CH:15]=[CH:16][CH:17]=1

参加物

6

反応物 4

HCID 227Anthranilic AcidHCID 1176UreaHCID 17968Benzene, 1-chloro-3-isocyanato-HCID 199374482H-1,2-Benzoxazin-3(4H)-one

生成物 1

HCID 187626302-(3-chlorophenylamino)-6-octyl-4H-3,1-benzoxazin-4-one

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

The anthranilic acid (200 mg, 0.8 mmol) was dissolved in anhydrous THF (1 ml), and to this was added 3-chlorophenylisocyanate (117 μl, 0.96 mmol). The mixture was stirred for 3 h before being concentrated. The residue was partitioned between water and ethyl acetate. The organic layer was washed with 5% aqueous citric acid, saturated aqueous sodium bicarbonate and brine then dried (MgSO4) and concentrated to give an orange solid. This was purified by flash chromatography on silica (15% EtOAc/hexane to 100% EtOAc, then 10% EtOH/EtOAc) which gave, in order of elution, the benzoxazinone (18 mg, 0.05 mmol); δH (400 MHz, CDCl3) 0.77-0.82 (3H, m, Me), 1.19-1.24 (10H, m, 5×CH2), 1.55-1.57 (2H, m, ArCH2CH2), 2.56-2.62 (2H, m, ArCH2), 7.00-7.32 (4H, m, 3×ArH, NH), 7.40-7.49 (2H, m, 2×ArH), 7.81-7.83 (2H, m, ArH); m/z (ES+) 385 (MH+) and the urea (160 mg, 0.4 mmol); m/z (ES−) 401 (M-H)−.

後処理

  1. concentrationbefore being concentrated
  2. customThe residue was partitioned between water and ethyl acetate
  3. washThe organic layer was washed with 5% aqueous citric acid, saturated aqueous sodium bicarbonate and brine
  4. dry with materialthen dried (MgSO4)
  5. concentrationconcentrated
  6. customto give an orange solid
  7. customThis was purified by flash chromatography on silica (15% EtOAc/hexane to 100% EtOAc
  8. custom10% EtOH/EtOAc) which gave, in order of elution

出典と根拠

ORDレコード
ord-b67fe8018c5342f29d2eb43d0efb18cb
出典データセット
uspto-grants-2010_08
特許番号
US07776853B2

反応ノート

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