Citric Acid → (RS)-2-methyl-4-methylidene-3-ethyl-2-cyclopenten-1-yl (1R)-trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate

HRID 1079007Notes

Reaction equation

HRID 1079007 reaction equation
[CH3:1][C:2]1([CH3:12])[C@H:4]([CH:5]=[C:6]([CH3:8])[CH3:7])[C@H:3]1[C:9](Cl)=[O:10].[CH3:13][C:14]1[CH:15]([OH:22])[CH2:16][C:17](=[CH2:21])[C:18]=1[CH2:19][CH3:20].N1C=CC=CC=1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C1(C)C=CC=CC=1.C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C>[CH3:1][C:2]1([CH3:12])[C@H:4]([CH:5]=[C:6]([CH3:8])[CH3:7])[C@H:3]1[C:9]([O:22][CH:15]1[CH2:16][C:17](=[CH2:21])[C:18]([CH2:19][CH3:20])=[C:14]1[CH3:13])=[O:10]

Participants

7

Reactant 4

HCID 311Citric AcidHCID 1049PyridineHCID 10867076(1R,3R)-2,2-Dimethyl-3-(2-methyl-1-propen-1-yl)cyclopropanecarbonyl chlorideHCID 15389976(RS)-2-methyl-4-methylidene-3-ethylcyclopent-2-en-1-ol

Product 1

HCID 15389977(RS)-2-methyl-4-methylidene-3-ethyl-2-cyclopenten-1-yl (1R)-trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylateYield 90%

Reagents, catalysts & solvents 2

HCID 314042,6-Di-tert-butyl-4-methylphenolCatalystHCID 1140TolueneSolvent

Procedure

540 mg of (1R)-trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid chloride was added under ice-water cooling to a mixed solution of 400 mg of (RS)-2-methyl-4-methylidene-3-ethylcyclopent-2-en-1-ol, 5 mg of 2,6-di-t-butyl-4-methylphenol and 274 mg of pyridine in 6 ml of toluene. The reaction was allowed to react at an ambient temperature for eight hours. The reaction solution was added to a 5% citric acid solution under ice-water cooling and extracted three times with diethyl ether. The combined ether layer was washed successively with a saturated sodium hydrogencarbonate solution and a saturated sodium chloride solution and dried over anhydrous magnesium sulfate. After removal of the solvent under reduced pressure, the obtained residue was subjected to silica gel column chromatography to yield 751 mg of (RS)-2-methyl-4-methylidene-3-ethyl-2-cyclopenten-1-yl (1R)-trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate (Compound No.1). Yield 72% (Eluent: n-hexane/ethyl acetate=30/1, 2,6-di-t-butyl-4-methylphenol 0.1%)

Workup

  1. customto react at an ambient temperature for eight hours
  2. extractionextracted three times with diethyl ether
  3. washThe combined ether layer was washed successively with a saturated sodium hydrogencarbonate solution
  4. dry with materiala saturated sodium chloride solution and dried over anhydrous magnesium sulfate
  5. customAfter removal of the solvent under reduced pressure

Sources & evidence

ORD record
ord-a05c7cbeed2447fa90c0041a64b74415
Source dataset
uspto-grants-1996_08
Patent number
US05550258

Reaction notes

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