Ethyl diazoacetate → HCID 22141229, compound

HRID 1826428Notes

Reaction equation

HRID 1826428 reaction equation
[Cl:1][CH2:2]/[CH:3]=[C:4](/[C:6]1[CH:7]=[C:8]([CH:11]=[CH:12][CH:13]=1)[C:9]#[N:10])\[CH3:5].[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]>[Cl:1][CH2:2][CH:3]1[CH:16]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:4]1([C:6]1[CH:13]=[CH:12][CH:11]=[C:8]([C:9]#[N:10])[CH:7]=1)[CH3:5]

Participants

5

Reactant 2

HCID 12192Ethyl diazoacetate2×HCID 69554694HCID 69554694, compound

Product 1

HCID 22141229HCID 22141229, compound

Reagents, catalysts & solvents 2

HCID 423677Acetic acid, rhodium salt (4:2)Catalyst2×HCID 6344DichloromethaneSolvent3×

Procedure

To a solution of 3-[(E)-3-chloro-1-methyl-1-propenyl]benzonitrile (Preparation 34, 13.1 g, 69.6 mmol) in dichloromethane (20 ml) was added rhodium (II) acetate dimer (0.46 g, 1.0 mmol). To the mixture was added dropwise at room temperature over 8 h (via a syringe pump) a solution of ethyl diazoacetate (14.6 ml, 0.14 mol) in dichloromethane (20 ml). The solvent was removed in vacuo and the crude residue was then partially purified by silica column chromatography eluting with dichloromethane:hexane (80:20). This material was then dissolved in dichloromethane (20 ml) containing rhodium (II) acetate dimer (0.46 g, 1.0 mmol). To this mixture was added dropwise a solution of ethyl diazoacetate (14.6 ml, 0.14 mol) in dichloromethane (20 ml) at room temperature over 8 h. The mixture was concentrated in vacuo and the residue purified by silica column chromatography eluting with hexane:dichloromethane (80:20) and then hexane:diethyl ether (80:20) to give the title compound as a colourless oil which solidified on standing (5.82 g, 30%).

Workup

  1. customThe solvent was removed in vacuo
  2. customthe crude residue was then partially purified by silica column chromatography
  3. washeluting with dichloromethane:hexane (80:20)
  4. dissolutionThis material was then dissolved in dichloromethane (20 ml)
  5. concentrationThe mixture was concentrated in vacuo
  6. customthe residue purified by silica column chromatography
  7. washeluting with hexane:dichloromethane (80:20)

Sources & evidence

ORD record
ord-8f5b56220e0d4a7797c31e847b4a29ea
Source dataset
uspto-grants-2006_05
Patent number
US07049444B2

Reaction notes

Loading…