Water → 1-Cyano-2-(2-ethoxycarbonylethyl)-5-methoxy-3,4-dihydronaphthalene

HRID 6401

反応式

HRID 6401 の反応式
[CH2:1]([O:3][C:4]([CH2:6][CH2:7][CH:8]1[CH2:17][CH2:16][C:15]2[C:10](=[CH:11][CH:12]=[CH:13][C:14]=2[O:18][CH3:19])[C:9]1=O)=[O:5])[CH3:2].[C:21](P(=O)(OCC)OCC)#[N:22].[C-]#N.[Li+].O>C1COCC1.CN(C=O)C>[C:21]([C:9]1[C:10]2[C:15](=[C:14]([O:18][CH3:19])[CH:13]=[CH:12][CH:11]=2)[CH2:16][CH2:17][C:8]=1[CH2:7][CH2:6][C:4]([O:3][CH2:1][CH3:2])=[O:5])#[N:22]

参加物

7

反応物 4

HCID 962WaterHCID 75478Lithium cyanideHCID 76257Diethyl cyanophosphonateHCID 197933962-(2-Ethoxycarbonylethyl)-3,4-dihydro-5-methoxy-1(2H)-naphthalenone

生成物 1

HCID 197931941-Cyano-2-(2-ethoxycarbonylethyl)-5-methoxy-3,4-dihydronaphthalene収率 70.1%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

2-(2-Ethoxycarbonylethyl)-3,4-dihydro-5-methoxy-1(2H)-naphthalenone (1.1 g, 4 mmol), from Step 1, was dissolved in 15 mL of dry THF and cooled to 0° C. Diethyl cyanophosphonate (1.18 mL, 8 mmol), commercially available from Aldrich Chemical Company, was added, followed by 8 mL of a 0.5M solution of lithium cyanide (4 mmol) in DMF. The reaction mixture was stirred at ambient temperature overnight and then poured into water. The aqueous mixture was extracted with three portions of diethyl ether/ethyl acetate. The organic extracts were washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was dissolved in 100 mL of toluene and 1.1 g of p-toluenesulfonic acid was added. The reaction mixture was heated at reflux for 2 h and allowed to cool to ambient temperature. The toluene solution was poured into 5% aqueous sodium bicarbonate and the aqueous mixture was extracted with ethyl acetate. The combined organic layers were dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The residue was purified by chromatography on silica gel eluted with 10% ethyl acetate in hexane to give 0.8 g (70% yield) of the title compound; MS DCl--NH3 M/Z: 286 (M+H)+, 303 (M+NH4)+.

後処理

  1. extractionThe aqueous mixture was extracted with three portions of diethyl ether/ethyl acetate
  2. washThe organic extracts were washed with brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. dissolutionThe residue was dissolved in 100 mL of toluene
  7. addition1.1 g of p-toluenesulfonic acid was added
  8. temperatureThe reaction mixture was heated
  9. temperatureat reflux for 2 h
  10. temperatureto cool to ambient temperature
  11. additionThe toluene solution was poured into 5% aqueous sodium bicarbonate
  12. extractionthe aqueous mixture was extracted with ethyl acetate
  13. dry with materialThe combined organic layers were dried over anhydrous magnesium sulfate
  14. filtrationfiltered
  15. concentrationconcentrated in vacuo
  16. customThe residue was purified by chromatography on silica gel
  17. washeluted with 10% ethyl acetate in hexane

出典と根拠

ORDレコード
ord-6e03421e3f554cada4678867b24aa606
出典データセット
uspto-grants-1993_09
特許番号
US05248677

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