Edetate Trisodium → Racemic ethyl cis-3-acetoxymethyl-2,2-dimethylcyclopropanecarboxylate

HRID 2078487

Reaction equation

HRID 2078487 reaction equation
[C:1]([O:4][CH2:5][CH:6]=[C:7]([CH3:9])[CH3:8])(=[O:3])[CH3:2].[N+](=C[C:13]([O:15][CH2:16][CH3:17])=[O:14])=[N-].[CH2:18](N(CC([O-])=O)CC(O)=O)CN(CC([O-])=O)CC([O-])=O.[Na+].[Na+].[Na+].CC[C@@H]1N2C(N(C3C=CC(F)=CC=3)C(=O)[C@H]2CC2C3C(NC1=2)=CC=CC=3)=O>C(OCC)(=O)C.C1(C(C2C=CC=CC=2)(C2C=CC=CC=2)C([O-])=O)C=CC=CC=1.[Rh+3].C1(C(C2C=CC=CC=2)(C2C=CC=CC=2)C([O-])=O)C=CC=CC=1.C1(C(C2C=CC=CC=2)(C2C=CC=CC=2)C([O-])=O)C=CC=CC=1>[C:1]([O:4][CH2:5][C@@H:6]1[C@H:8]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[C:7]1([CH3:18])[CH3:9])(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 9008Edetate TrisodiumHCID 12192Ethyl diazoacetateHCID 14489Prenyl acetateHCID 24978618trans-Body

Product 1

HCID 67120924Racemic ethyl cis-3-acetoxymethyl-2,2-dimethylcyclopropanecarboxylate

Reagents, catalysts & solvents 2

HCID 71464060Rhodium triphenyl acetateCatalystHCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
50 °C

Procedure

Rhodium triphenylacetate, 6.78 mg (0.01 mmol), was dissolved in 9.0 g of ethyl acetate, and 2.56 g (20.0 mmol) of 1-acetoxy-3-methyl-2-butene was added, then, the temperature thereof was raised to 50° C. Into this solution, a solution composed of 1.14 g (10.0 mmol) of ethyl diazoacetate and 3.6 g of ethyl acetate was dropped over a period of 2 hours, and the mixture was, thermally kept at the same temperature for 0.5 hours. To this solution was added an aqueous solution containing 0.5 mol of trisodium ethylenediaminetetraacetate per liter and the solution was mixed and separated, and a solution containing 1.82 g of ethyl 3-acetoxymethyl-2,2-dimethylcyclopropanecarboxylate was obtained (yield based on ethyl diazoacetate: 84.8%). The cis body/trans body ratio was 72/28.

Workup

  1. additionwas dropped over a period of 2 hours
  2. additionTo this solution was added an aqueous solution
  3. additionthe solution was mixed
  4. customseparated
  5. additiona solution containing 1.82 g of ethyl 3-acetoxymethyl-2,2-dimethylcyclopropanecarboxylate
  6. customwas obtained
  7. custom(yield based on ethyl diazoacetate: 84.8%)

Sources & evidence

ORD record
ord-d0790c9840c94fa5bdb44412e7d5bb07
Source dataset
uspto-grants-2011_04
Patent number
US07928253B2

Linked notes

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