Hydrochloric Acid → 3-[3-(4,4-Dimethyl-2-oxo-1,4-dihydro-2H-benzo[d][1,3]oxazin-6-yl)Phenyl]propynenitrile

HRID 1725057ノート

反応式

HRID 1725057 の反応式
[I-].[Na+].[C:3]([C:5]1[CH:6]=[C:7]([C:11]2[CH:23]=[CH:22][C:14]3[NH:15][C:16](=[O:21])[O:17][C:18]([CH3:20])([CH3:19])[C:13]=3[CH:12]=2)[CH:8]=[CH:9][CH:10]=1)#[CH:4].Cl[Si](C)(C)C.Cl.[C:30](#[N:32])C>O.CS(C)=O>[CH3:19][C:18]1([CH3:20])[O:17][C:16](=[O:21])[NH:15][C:14]2[CH:22]=[CH:23][C:11]([C:7]3[CH:6]=[C:5]([C:3]#[C:4][C:30]#[N:32])[CH:10]=[CH:9][CH:8]=3)=[CH:12][C:13]1=2

参加物

8

反応物 5

HCID 313Hydrochloric AcidHCID 5238Sodium IodideHCID 6342AcetonitrileHCID 6397ChlorotrimethylsilaneHCID 98141916-(3-Ethynyl-phenyl)-4,4-dimethyl-1,4-dihydro-benzo[d][1,3]oxazin-2-one

生成物 1

HCID 98575553-[3-(4,4-Dimethyl-2-oxo-1,4-dihydro-2H-benzo[d][1,3]oxazin-6-yl)Phenyl]propynenitrile収率 4.6%

試薬・触媒・溶媒 2

HCID 679Dimethyl Sulfoxide溶媒HCID 962Water溶媒

反応条件

温度
50 °C

実験手順

To a stirred mixture of DMSO, acetonitrile and water (9 mL/3 mL/0.5 mL) was added at rt under nitrogen cuprous cyanide (0.193 g, 2.2 mmol), sodium iodide (11 mg, 0.072 mmol), and 6-(3-ethynyl-phenyl)-4,4-dimethyl-1,4-dihydro-benzo[d][1,3]oxazin-2-one (0.2 g, 0.72 mmol). Chlorotrimethylsilane was then added to the above mixture in a dropwise manner. After addition, the mixture was heated at 50° C. for 72 hours. The reaction mixture was then cooled to rt and treated with 0.5 N aqueous HCl cold solution (50 mL). The precipitate obtained was collected on a filter and washed with water. The solid was purified on a silica gel column (hexane:ethyl acetate/2:1) to give the title compound as an off-white solid (10 mg, 4.6%): mp 212-213° C.; 1H-NMR (CHCl3-d6) δ 7.96 (s, 1H), 7.77 (s, 1H), 7.65 (d, 1H, J=7.8 Hz), 7.60 (d, 1H, J=7.69 Hz), 7.51 (d, 1H, J=7.77 Hz), 7.45 (dd, 1H, J=8.67, 2.21 Hz), 7.31 (d, 1H, J=1.55 Hz), 6.91 (d, 1H, J=8.19 Hz), 1.8 (s, 6H); MS (EI) m/z 302 ([M+], 30%).

後処理

  1. additionwas added at rt under nitrogen cuprous cyanide (0.193 g, 2.2 mmol)
  2. additionAfter addition
  3. temperatureThe reaction mixture was then cooled to rt
  4. customThe precipitate obtained
  5. customwas collected on
  6. filtrationa filter
  7. washwashed with water
  8. customThe solid was purified on a silica gel column (hexane:ethyl acetate/2:1)

出典と根拠

ORDレコード
ord-6d306f74c2f741699e3376043271942e
出典データセット
uspto-grants-2009_02
特許番号
US07488822B2

反応ノート

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