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

HRID 2091995Notes

Reaction equation

HRID 2091995 reaction equation
[CH3:1][O:2][C:3](=[O:7])[CH2:4][CH:5]=[CH2:6].[Cl:8][C:9]([Cl:14])(Cl)[C:10](Cl)=[O:11]>C(OCC)C.[Cu].[Zn]>[CH3:1][O:2][C:3](=[O:7])[CH2:4][CH:5]1[CH2:6][C:10](=[O:11])[C:9]1([Cl:14])[Cl:8]

Participants

5

Reactant 2

HCID 6420Trichloroacetyl chlorideHCID 77314Methyl 3-butenoate

Product 1

HCID 57686758Methyl 2-(2,2-dichloro-3-oxocyclobutyl)acetateYield 138.8%

Reagents, catalysts & solvents 2

HCID 10290809Zinc copper coupleCatalystHCID 3283Diethyl EtherSolvent

Procedure

To a mixture of but-3-enoic acid methyl ester (1.00 g, 10 mmol) and zinc-copper couple (1.97 g) in 1,2-dimethoxyothane (4.89 ml) and diethyl ether (37 ml), trichloroacetyl chloride (2.98 ml, 26.7 mmol) is added at room temperature under nitrogen. The mixture is stirred at room temperature for 3 days. The mixture is filtrated and washed with diethyl ether. The filtrate is concentrated under reduced pressure, and the obtained residue is purified by silica gel column chromatography to give (2,2-dichloro-3-oxo-cyclobutyl)-acetic acid methyl ester (2.93 g, quant.); TLC (hexane/AcOEt, 3:1) Rf 0.35, 1H NMR (400 MHz, chloroform-d) δ ppm 2.68-2.74 (m, 1H), 2.94-3.00 (m, 1H), 3.06-3.13 (m, 1H), 3.33-3.41 (m, 1H), 3.51-3.57 (m, 1H), 3.75 (s, 3H).

Workup

  1. additionis added at room temperature under nitrogen
  2. filtrationThe mixture is filtrated
  3. washwashed with diethyl ether
  4. concentrationThe filtrate is concentrated under reduced pressure
  5. customthe obtained residue is purified by silica gel column chromatography

Sources & evidence

ORD record
ord-8125e362340d40a896195420cc4e403c
Source dataset
uspto-grants-2013_05
Patent number
US08440682B2

Reaction notes

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