Hydrochloric Acid → 4-(1-Octenyl)-5-(6-methoxycarbonylhexylidene)-3-(t-butyldimethylsilyloxy) cyclopentanone

HRID 35485Notes

Reaction equation

HRID 35485 reaction equation
[CH:1]([CH:9]1[CH:13]([CH:14](O)[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][C:20]([O:22][CH3:23])=[O:21])[C:12](=[O:25])[CH2:11][CH:10]1[O:26][Si:27]([C:30]([CH3:33])([CH3:32])[CH3:31])([CH3:29])[CH3:28])=[CH:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].CN(C1C=CC=CN=1)C.CS(Cl)(=O)=O.Cl>ClCCl>[CH:1]([CH:9]1[C:13](=[CH:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][C:20]([O:22][CH3:23])=[O:21])[C:12](=[O:25])[CH2:11][CH:10]1[O:26][Si:27]([C:30]([CH3:31])([CH3:33])[CH3:32])([CH3:29])[CH3:28])=[CH:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 218852-Dimethylaminopyridine2×HCID 31297Methanesulfonyl chlorideHCID 54223813HCID 54223813, compound

Product 1

HCID 538681294-(1-Octenyl)-5-(6-methoxycarbonylhexylidene)-3-(t-butyldimethylsilyloxy) cyclopentanoneYield 61.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

3.1 g (6.4 millinmols) of 4-(1-octenyl)-5-(1-hydroxy-6-methoxycarbonylhexyl)-3-(t-butyldimethylsilyloxy)cyclopentanone was dissolved in 40 ml of dichloromethane, and 3.92 g (32.1 mmoles) of dimethylaminopyridine was added. With ice cooling and stirring, 1.0 ml (12.9 mmoles) of methanesulfonyl chloride was added. The mixture was stirred at 0° C. for 5 minutes, and then at room temperature for hours. Furthermore, 0.78 g (6.4 millimoles) of dimethylaminopyridine was added, and the mixture was stirred for 100 minutes. The mixture was poured into 200 ml of 0.5N hydrochloric acid and washed. The aqueous layer was extracted with dichloromethane. The organic layers were combined, washed first with a saturated aqueous solution of sodium bicarbonate and then with a saturated aqueous solution of sodium chloride, and dried over anhydrous sodium sulfate. The dried product was filtered, concentratd and subjected to silica gel column chromatography (silica gel 150 g; eluent, hexane:ethyl acetate=20:1 →7:1) to give 1.83 g (yield 61%) of 4-(1-octenyl)-5-(6-methoxycarbonylhexylidene)-3-(t-butyldimethylsilyloxy) cyclopentanone. The spectral data of this compound were as follows.

Workup

  1. stirringThe mixture was stirred at 0° C. for 5 minutes
  2. waitat room temperature for hours
  3. stirringthe mixture was stirred for 100 minutes
  4. washwashed
  5. extractionThe aqueous layer was extracted with dichloromethane
  6. washwashed first with a saturated aqueous solution of sodium bicarbonate
  7. dry with materialwith a saturated aqueous solution of sodium chloride, and dried over anhydrous sodium sulfate
  8. filtrationThe dried product was filtered

Sources & evidence

ORD record
ord-c72352d1d645491197d2f85e5df1b11c
Source dataset
uspto-grants-1988_08
Patent number
US04766147

Reaction notes

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