Ethyl diazoacetate → HCID 22141267, compound

HRID 428909Notes

Reaction equation

HRID 428909 reaction equation
[Cl:1][CH2:2]/[CH:3]=[C:4](/[C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([N+:13]([O-:15])=[O:14])[CH:8]=1)\[CH2:5][CH3:6].[N+](=[CH:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])=[N-]>ClCCl.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.[Rh].[Rh]>[Cl:1][CH2:2][CH:3]1[CH:18]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[C:4]1([CH2:5][CH3:6])[C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([N+:13]([O-:15])=[O:14])[CH:8]=1

Participants

5

Reactant 2

HCID 12192Ethyl diazoacetate2×HCID 69554424HCID 69554424, compound

Product 1

HCID 22141267HCID 22141267, compoundYield 15.3%

Reagents, catalysts & solvents 2

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

Procedure

To a solution of 1-[(E)-3-chloro-1-ethyl-1-propenyl]-3-nitrobenzene (Preparation 15, 50 g, 0.22 mol) in dichloromethane (40 ml) was added rhodium (11) acetate dimer (2.0 g, 4.6 mmol). To the mixture was added dropwise at room temperature over 6 hours a solution of ethyl diazoacetate (50 ml, 54.25 g, 0.475 mol) in dichloromethane (50 ml), then the mixture stirred at room temperature for 16 hours. To the mixture was added dropwise at room temperature over 7 hours a solution of ethyl diazoacetate (20 ml, 21.70 g, 0.190 mol) in dichloromethane (20 ml), then the mixture was stirred at room temperature for 16 h. The mixture was concentrated in vacuo and the residue purified by silica column (1 kg) chromatography, eluting with 1:1 hexane/dichloromethane. Product-containing fractions were combined and concentrated in vacuo to give the title compound as a pale orange oil (10.5 g, 15%).

Workup

  1. stirringthe mixture was stirred at room temperature for 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

Sources & evidence

ORD record
ord-95f8a37af9aa4a21ae6bd7220266485a
Source dataset
uspto-grants-2001_11
Patent number
US06313312B1

Reaction notes

Loading…