Trichloroacetyl chloride → Methyl 2-(2,2-dichloro-3-oxocyclobutyl)acetate

HRID 520383

反応式

HRID 520383 の反応式
[C:1]([O:6][CH3:7])(=[O:5])[CH2:2][CH:3]=[CH2:4].[Cl:8][C:9]([Cl:14])(Cl)[C:10](Cl)=[O:11]>COCCOC.CCOCC.[Cu].[Zn]>[Cl:8][C:9]1([Cl:14])[C:10](=[O:11])[CH2:4][CH:3]1[CH2:2][C:1]([O:6][CH3:7])=[O:5]

参加物

6

反応物 2

HCID 6420Trichloroacetyl chlorideHCID 77314Methyl 3-butenoate

生成物 1

HCID 57686758Methyl 2-(2,2-dichloro-3-oxocyclobutyl)acetate収率 47.4%

試薬・触媒・溶媒 3

HCID 10290809Zinc copper couple触媒HCID 3283Diethyl Ether溶媒HCID 80711,2-Dimethoxyethane溶媒

実験手順

To a reaction mixture of methyl but-3-enoate (1.0 g, 10 mmol) and zinc-copper couple (2.0 g, 15.5 mmol) in DME (5 mL) and ether (30 mL) was added trichloroacetyl chloride (2.98 mL, 26.7 mmol) under N2 at rt. The reaction mixture was stirred at rt for 2.5 days. The reaction mixture was filtrated through diatomaceous earth (Celite®) and washed with DCM. The filtrate was concentrated and purified by 80 g silica gel cartridge which was eluted with a 20 min gradient of 0-60% EtOAc in hexane to yield methyl 2-(2,2-dichloro-3-oxocyclobutyl)acetate (1.0 g). 1H NMR (400 MHz, CDCl3) ppm 3.66-3.70 (3H, m), 3.42-3.55 (1H, m), 3.23-3.39 (1H, m), 3.05 (1H, dd, J=17.82, 8.78 Hz), 2.90 (1H, dd, J=16.94, 6.65 Hz), 2.67 (1H, dd, J=16.94, 8.16 Hz).

後処理

  1. filtrationThe reaction mixture was filtrated through diatomaceous earth (Celite®)
  2. washwashed with DCM
  3. concentrationThe filtrate was concentrated
  4. custompurified by 80 g silica gel cartridge which
  5. washwas eluted with a 20 min gradient of 0-60% EtOAc in hexane

出典と根拠

ORDレコード
ord-728029bb49324341b6175dd63544f003
出典データセット
uspto-grants-2016_05
特許番号
US09326973B2

関連ノート

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