Ethyl diazoacetate → Ethyl 2-(bromomethyl)-3-(3-nitrophenyl)cyclopropane Carboxylate

HRID 428913Notes

Reaction equation

HRID 428913 reaction equation
[Br:1][CH2:2]/[CH:3]=[CH:4]/[C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([N+:11]([O-:13])=[O:12])[CH:6]=1.[N+](=[CH:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])=[N-]>ClCCl.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.[Rh].[Rh]>[Br:1][CH2:2][CH:3]1[CH:4]([C:5]2[CH:10]=[CH:9][CH:8]=[C:7]([N+:11]([O-:13])=[O:12])[CH:6]=2)[CH:16]1[C:17]([O:19][CH2:20][CH3:21])=[O:18]

Participants

5

Reactant 2

HCID 12192Ethyl diazoacetateHCID 58409941-[(E)-3-bromo-1-propenyl]-3-nitrobenzene

Product 1

HCID 22141287Ethyl 2-(bromomethyl)-3-(3-nitrophenyl)cyclopropane CarboxylateYield 7%

Reagents, catalysts & solvents 2

HCID 423677Acetic acid, rhodium salt (4:2)CatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 1-[(E)-3-bromo-1-propenyl]-3-nitrobenzene (Preparation 22, 820 mg, 3.23 mmol) in dichloromethane (3 ml) was added rhodium (II) acetate dimer (20 mg, 0.046 vmnol). To the mixture was added dropwise at room temperature over 3 h a solution of ethyl diazoacetate (0.47 ml, 510 mg, 4.47 mmol) in dichloromethane (3 ml), then the mixture was stirred at room temperature for 66 h. The mixture was purified by silica (100 g) column chromatography eluting with hexane:dichloromethane 100:0 to 50:50. Product containing fractions were combined and concentrated in vacuo to afford the title compound as a colourless oil (65 mg, 7%).

Workup

  1. customThe mixture was purified by silica (100 g) column chromatography
  2. washeluting with hexane:dichloromethane 100:0 to 50:50
  3. additionProduct containing fractions
  4. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-53b1264eeebf4f6fb441c709d4be614e
Source dataset
uspto-grants-2001_11
Patent number
US06313312B1

Reaction notes

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