Methyl iodide → HCID 18009397、化合物

HRID 987589ノート

反応式

HRID 987589 の反応式
[C:1]([C:4]1[CH:5]=[C:6](C(OC)=O)[C:7]([C:10]2[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][C:11]=2[O:18][CH3:19])=[CH:8][CH:9]=1)(=[O:3])C.[Li+].CC([N-][CH:29]([CH3:31])[CH3:30])C.[CH3:32]I.[C:34]([O-:37])(O)=[O:35].[Na+]>COCCOC>[CH3:19][O:18][C:11]1[CH:12]=[C:13]([O:16][CH3:17])[CH:14]=[CH:15][C:10]=1[C:7]1[C:8]([C:34]([O:37][CH3:32])=[O:35])=[CH:9][C:4]([C:1](=[O:3])[CH:29]([CH3:30])[CH3:31])=[CH:5][CH:6]=1

参加物

6

反応物 4

HCID 6328Methyl iodide2 回HCID 516892Sodium BicarbonateHCID 2724682Lithium diisopropylamide2 回HCID 11324480HCID 11324480、化合物

生成物 1

HCID 18009397HCID 18009397、化合物収率 24%

試薬・触媒・溶媒 1

HCID 80711,2-Dimethoxyethane溶媒

反応条件

温度
-20 °C

実験手順

The compound from step B (1.03 g, 3.2 mmol) was dissolved in DME (40 ml) under argon and cooled to −20° C. and LDA (1.6 ml, 3.2 mmol) was added. The mixture was then warmed to room temperature and stirred for 30 min. Methyl iodide (0.2 ml, 3.2 mmol) was slowly added over 15 min. to give a cloudy suspension. The mixture was again cooled to −20 C. and a second portion of LDA (1.6 ml, 3.2 mmol) was added. After the mixture was warmed to room temperature and stirred for 30 min a second portion of methyl iodide (0.2 ml, 3.2 mmol) was added and the mixture stirred for 60 h. The mixture was added to cold NaHCO3 (100 ml) and extracted with ethyl acetate (3×100 ml). The organic layer was washed with 5% HCl (3×25 ml) then dried and evaporated. The residue was chromatographed on silica gel with hexane/ethyl acetate (2:1) to give 0.208 g (24%) of the title compound. 1H-NMR (400 MHz, CDCl3) δH 1.24 (6H, t, CH(CH3)2), 3.60 (1H, m, CH(CH3)2, 3.71 (3H, s, OCH3), 3.89 (3H, s, OCH3), 3.93 (3H, s, OCH3), 6.86-8.32 (6H, ArH).

後処理

  1. temperatureThe mixture was then warmed to room temperature
  2. customto give a cloudy suspension
  3. temperatureThe mixture was again cooled to −20 C
  4. temperatureAfter the mixture was warmed to room temperature
  5. additionwas added
  6. stirringthe mixture stirred for 60 h
  7. extractionextracted with ethyl acetate (3×100 ml)
  8. washThe organic layer was washed with 5% HCl (3×25 ml)
  9. customthen dried
  10. customevaporated
  11. customThe residue was chromatographed on silica gel with hexane/ethyl acetate (2:1)

出典と根拠

ORDレコード
ord-500f62a164b24e348541cc849e12c082
出典データセット
uspto-grants-2003_10
特許番号
US06632835B2

反応ノート

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