Ethyl diazoacetate → Ethyl 3-(chloromethyl)-2-methyl-2-(3-nitrophenyl)cyclopropanecarboxylate

HRID 1826403Notes

Reaction equation

HRID 1826403 reaction equation
[Cl:1][CH2:2]/[CH:3]=[C:4](/[C:6]1[CH:11]=[CH:10][CH:9]=[C:8]([N+:12]([O-:14])=[O:13])[CH:7]=1)\[CH3:5].[N+](=[CH:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])=[N-]>ClCCl.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.[Rh].[Rh]>[Cl:1][CH2:2][CH:3]1[CH:17]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[C:4]1([CH3:5])[C:6]1[CH:11]=[CH:10][CH:9]=[C:8]([N+:12]([O-:14])=[O:13])[CH:7]=1

Participants

5

Reactant 2

HCID 12192Ethyl diazoacetate2×HCID 695554961-[(E)-3-Chloro-1-methyl-1-propenyl]-3-nitrobenzene

Product 1

HCID 22141336Ethyl 3-(chloromethyl)-2-methyl-2-(3-nitrophenyl)cyclopropanecarboxylate

Reagents, catalysts & solvents 2

HCID 423677Acetic acid, rhodium salt (4:2)CatalystHCID 6344DichloromethaneSolvent3×

Procedure

To a solution of 1-[(E)-3-chloro-1-methyl-1-propenyl]-3-nitrobenzene (Preparation 3, 36 g, 0.17 mol) in dichloromethane (50 ml) was added rhodium (II) acetate dimer (1 g, 2.3 mmol). To the mixture was added dropwise at room temperature over 8 h a solution of ethyl diazoacetate (50 ml, 54.25 g, 0.475 mol) in dichloromethane (50 ml), then the mixture was stirred at room temperature for 16 h. To the mixture was added dropwise at room temperature over 7 h a further solution of ethyl diazoacetate (50 ml, 54.25 g, 0.475 mol) in dichloromethane (50 ml), then the mixture was stirred at room temperature for a further 16 h. The mixture was concentrated in vacuo and the residue purified by silica column (1 kg) chromatography, eluting with 1:1 hexane/dichloromethane then dichloromethane. Product-containing fractions were combined and concentrated in vacuo, then concentrated under a stream of nitrogen for 16 h. The residue was purified further by silica column (2 kg) chromatography, eluting with 1:1 hexane/dichloromethane then dichloromethane. Product containing fractions were combined and concentrated in vacuo, to give the title compound as a very pale yellow oil (14.2 g, 29%).

Workup

  1. stirringthe mixture was stirred at room temperature for a further 16 h
  2. concentrationThe mixture was concentrated in vacuo
  3. customthe residue purified by silica column (1 kg) chromatography
  4. washeluting with 1:1 hexane/dichloromethane
  5. concentrationconcentrated in vacuo
  6. concentrationconcentrated under a stream of nitrogen for 16 h
  7. customThe residue was purified further by silica column (2 kg) chromatography
  8. washeluting with 1:1 hexane/dichloromethane
  9. additionProduct containing fractions
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-a90dee2d004e49c0b75a5ce4be0af6b4
Source dataset
uspto-grants-2006_05
Patent number
US07049444B2

Reaction notes

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