Toluene → Ethyl 2-[2,6-bis(methoxymethoxy)-3-methyl-phenyl]prop-2-enoate

HRID 2278303ノート

反応式

HRID 2278303 の反応式
C[Si]([N-][Si](C)(C)C)(C)C.[K+].[C:11]1(C)C=CC=CC=1.[CH3:18][O:19][CH2:20][O:21][C:22]1[C:27]([CH3:28])=[CH:26][CH:25]=[C:24]([O:29][CH2:30][O:31][CH3:32])[C:23]=1[C:33](=O)[C:34]([O:36][CH2:37][CH3:38])=[O:35]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1>[CH3:18][O:19][CH2:20][O:21][C:22]1[C:27]([CH3:28])=[CH:26][CH:25]=[C:24]([O:29][CH2:30][O:31][CH3:32])[C:23]=1[C:33](=[CH2:11])[C:34]([O:36][CH2:37][CH3:38])=[O:35]

参加物

6

反応物 3

HCID 1140TolueneHCID 3251421Potassium bis(trimethylsilyl)amideHCID 67958347Ethyl 2-[2,6-bis(methoxymethoxy)-3-methyl-phenyl]-2-oxo-acetate2 回

生成物 1

HCID 67958720Ethyl 2-[2,6-bis(methoxymethoxy)-3-methyl-phenyl]prop-2-enoate収率 83.1%

試薬・触媒・溶媒 2

HCID 74505Methyltriphenyliphosphonium bromide触媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

To a suspension of methyltriphenylphosphonium bromide (8.78 g, 24.6 mmol) in dry tetrahydrofuran (50 ml) at 0° C. KHMDS 0.5M solution in toluene (44.22 ml, 22.11 mmol) was slowly added and the reaction mixture was stirred for 15 minutes at 0° C. and for 45 minutes at room temperature. The reaction mixture was cooled to 0° C. and it was slowly added to a solution of ethyl 2-[2,6-bis(methoxymethoxy)-3-methyl-phenyl]-2-oxo-acetate (Intermediate 8, 4.6 g, 14.74 mmol) in dry tetrahydrofuran (25 mL) at 0° C. and the reaction mixture was stirred for 2 hours at 0° C. The reaction was quenched with water (50 ml), diluted with brine (50 ml) and extracted with ethyl acetate (2×100 ml). The organic layer was dried over sodium sulphate, filtered and evaporated. The residue was purified by flash chromatography (Biotage system) on silica gel using a 100 g SNAP column and cyclohexane to cyclohexane/ethyl acetate 8:2 as eluents affording the title compound (3.8 g) as a colourless oil.

後処理

  1. temperatureThe reaction mixture was cooled to 0° C.
  2. stirringthe reaction mixture was stirred for 2 hours at 0° C
  3. customThe reaction was quenched with water (50 ml)
  4. additiondiluted with brine (50 ml)
  5. extractionextracted with ethyl acetate (2×100 ml)
  6. dry with materialThe organic layer was dried over sodium sulphate
  7. filtrationfiltered
  8. customevaporated
  9. customThe residue was purified by flash chromatography (Biotage system) on silica gel using a 100 g SNAP column and cyclohexane to cyclohexane/ethyl acetate 8:2 as eluents

出典と根拠

ORDレコード
ord-fefe6a330b2a42348bac89da064ff925
出典データセット
uspto-grants-2015_09
特許番号
US09133175B2

反応ノート

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