Ethyl diazoacetate → HCID 22141229, compound

HRID 428921Notes

Reaction equation

HRID 428921 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)CatalystHCID 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 md) 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 (I) 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 irn 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. additioncontaining rhodium (I) acetate dimer (0.46 g, 1.0 mmol)
  6. concentrationThe mixture was concentrated irn vacuo
  7. customthe residue purified by silica column chromatography
  8. washeluting with hexane:dichloromethane (80:20)

Sources & evidence

ORD record
ord-305574dd1b2641fe99bafc5b3903108b
Source dataset
uspto-grants-2001_11
Patent number
US06313312B1

Reaction notes

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