Ammonia → (RS)-2-methyl-4-methylidene-3-(2,2,2-trifluoroethyl)cyclopent-2-en-1-yl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate

HRID 1379937Notes

Reaction equation

HRID 1379937 reaction equation
[CH3:1][C:2]([CH3:12])=[CH:3][C@@H:4]1[C@@H:6]([C:7](Cl)=[O:8])[C:5]1([CH3:11])[CH3:10].[CH3:13][C:14]1[CH:15]([OH:25])[CH2:16][C:17](=[CH2:24])[C:18]=1[CH2:19][C:20]([F:23])([F:22])[F:21].N1C=CC=CC=1.N>CN(C)C1C=CN=CC=1.O1CCCC1.C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C>[CH3:1][C:2]([CH3:12])=[CH:3][C@@H:4]1[C@@H:6]([C:7]([O:25][CH:15]2[CH2:16][C:17](=[CH2:24])[C:18]([CH2:19][C:20]([F:21])([F:22])[F:23])=[C:14]2[CH3:13])=[O:8])[C:5]1([CH3:11])[CH3:10]

Participants

8

Reactant 4

HCID 222AmmoniaHCID 1049PyridineHCID 10867076(1R,3R)-2,2-Dimethyl-3-(2-methyl-1-propen-1-yl)cyclopropanecarbonyl chlorideHCID 15389979(RS)-2-methyl-4-methylidene-3-(2,2,2-trifluoroethyl)cyclopent-2-en-1-ol

Product 1

HCID 15389978(RS)-2-methyl-4-methylidene-3-(2,2,2-trifluoroethyl)cyclopent-2-en-1-yl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylateYield 52.4%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 314042,6-Di-tert-butyl-4-methylphenolCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Under ice-water cooling, 350 mg of (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid chloride was added dropwise to the mixed solution of 300 mg of (RS)-2-methyl-4-methylidene-3-(2,2,2-trifluoroethyl)cyclopent-2-en-1-ol, 5 mg of 2,6-di-tert-butyl-4-methylphenol, 185 mg of pyridine and 5 mg of 4-dimethylaminopyridine in 10 ml of dry terahydrofuran and then the resultant reaction mixture was allowed to react further 6 hours at room temperature. Then 10 ml of 10% aqueous ammonia solution was added to the solution and vigorously stirred for 2 hours. The reaction mixture was extracted three times with diethyl ether and the ether layers were combined. The combined layer was washed with brine and dried over anhydrous magnesium sulfate. After removal of the drying agent, the solvent was evaporated. The obtained residue was subjected to silica gel column chromatography to afford 280 mg of the desired (RS)-2-methyl-4-methylidene-3-(2,2,2-trifluoroethyl)cyclopent-2-en-1-yl (1R)-trans-3-(2-methyl-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (Compound No.15). Yield 52% (Eluent: n-hexane/ethyl acetate=30/1, 2,6-di-tert-butyl-4-methylphenol 0.1% ) nD21 1.4805

Workup

  1. customthe resultant reaction mixture
  2. customto react further 6 hours at room temperature
  3. extractionThe reaction mixture was extracted three times with diethyl ether
  4. washThe combined layer was washed with brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. customAfter removal of the drying agent
  7. customthe solvent was evaporated

Sources & evidence

ORD record
ord-10f5fe48b1964152a2e3375c3c90d617
Source dataset
uspto-grants-1997_09
Patent number
US05672779

Reaction notes

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