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

HRID 2054182ノート

反応式

HRID 2054182 の反応式
[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

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6342Acetonitrile溶媒

反応条件

温度
80 °C

実験手順

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%.

後処理

  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

出典と根拠

ORDレコード
ord-06d11aa3aba7448b910aaf93f1253e2a
出典データセット
uspto-grants-2008_02
特許番号
US07329660B2

反応ノート

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