Methyl iodide → 1-Cyano-3-methylthio-4-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[c]thiophene

HRID 1385293ノート

反応式

HRID 1385293 の反応式
[C:1]1(=[O:9])[CH2:7][CH2:6][CH2:5][CH2:4][C:3](=O)[CH2:2]1.[H-].[Na+].[C:12](=[S:14])=[S:13].[CH3:15]I.Br[CH2:18][C:19]#[N:20]>CN(C=O)C.O>[C:19]([C:18]1[S:13][C:12]([S:14][CH3:15])=[C:2]2[C:1](=[O:9])[CH2:7][CH2:6][CH2:5][CH2:4][C:3]=12)#[N:20]

参加物

8

反応物 5

HCID 6328Methyl iodideHCID 6348Carbon DisulfideHCID 11534BromoacetonitrileHCID 24758Sodium hydrideHCID 4072367Cycloheptane-1,3-dione

生成物 1

HCID 211845001-Cyano-3-methylthio-4-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[c]thiophene収率 32%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
0 °C

実験手順

Cycloheptan-1,3-dione (0.5 g, 4 mmol) was dissolved in DMF (10 mL) and cooled to 0° C. Sodium hydride (0.48 g of 60% dispersion in oil, 12 mmol) was added and the suspension stirred at 0-5° C. for 30 min. Carbon disulphide (0.45 g, 6 mmol) was added in one portion and the solution was stirred at 0-5° C. for 30 min. Methyl iodide (0.66 g, 4.4 mmol) was added in one portion and the mixture stirred at room temperature for 30 min. After cooling to 0-5° C., bromoacetonitrile (0.27 mL, 4.4 mmol) was added in one portion and the mixture was stirred at room temperature for 30 min. The mixture was then poured into water, extracted with ethyl acetate and the extracts dried (Na2SO4). After evaporating to dryness, the residue was purified by chromatographed on silica gel, eluting with ethyl acetate:hexane (1:4) to yield the title compound as a pale yellow solid (280 mg, 32%). 1HNMR (360 MHz, CDCl3) δ 1.88-1.96 (4H, m), 2.60 (3H, s), 2.75-2.78 (2H, m), 3.21-3.24 (2H, m). MS (ES+) 296 (M+1).

後処理

  1. stirringthe solution was stirred at 0-5° C. for 30 min
  2. stirringthe mixture stirred at room temperature for 30 min
  3. temperatureAfter cooling to 0-5° C.
  4. stirringthe mixture was stirred at room temperature for 30 min
  5. extractionextracted with ethyl acetate
  6. dry with materialthe extracts dried (Na2SO4)
  7. customAfter evaporating to dryness
  8. customthe residue was purified
  9. customby chromatographed on silica gel
  10. washeluting with ethyl acetate:hexane (1:4)

出典と根拠

ORDレコード
ord-ff07417bf9da4454a823c9f7c14b48d3
出典データセット
uspto-grants-2001_07
特許番号
US06262103B1

反応ノート

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