Tetrahydrofuran → HCID 54530479, compound

HRID 1657550Notes

Reaction equation

HRID 1657550 reaction equation
C([Li])CCC.C1([C:12](=[S:18](=[O:20])=[O:19])[C:13]([CH3:17])=[CH:14][CH2:15][OH:16])C=CC=CC=1.O1CCCC1.Cl[CH2:27][CH:28]=[C:29]([CH3:41])[CH:30]=[CH:31][C:32]1[C:37]([CH3:39])([CH3:38])[CH2:36][CH2:35][CH2:34][C:33]=1[CH3:40].[CH3:42][CH2:43][CH2:44][CH2:45][CH2:46][CH3:47]>>[OH:16][CH2:15][CH:14]=[C:13]([CH3:17])[CH:12]([S:18]([C:44]1[CH:43]=[CH:42][CH:47]=[CH:46][CH:45]=1)(=[O:20])=[O:19])[CH2:27][CH:28]=[C:29]([CH3:41])[CH:30]=[CH:31][C:32]1[C:37]([CH3:39])([CH3:38])[CH2:36][CH2:35][CH2:34][C:33]=1[CH3:40]

Participants

6

Reactant 5

HCID 8028Tetrahydrofuran2×HCID 8058HexaneHCID 54063363HCID 54063363, compoundHCID 86733507HCID 86733507, compoundHCID 178418339Butyllithium

Product 1

HCID 54530479HCID 54530479, compoundYield 48%

Conditions

Temperature
-70 °C

Procedure

A solution of n-butyllithium in hexane (46.5 ml., 1.95 M) was added over 45 minutes to a solution of 10.4 g. of 1-phenyl sulfonyl-2-methyl-4-hydroxy-but-2-ene in 200 ml. of tetrahydrofuran at -65° to -70°C. The reaction mixture was stirred at -70°C. for 40 minutes and a solution of 1-chloro-3-methyl-5-(2,6,6-trimethylcyclohexen-1-yl)-penta-2,4-diene in 45 ml. of THF was added over 10 minutes at -65° to -70°C. The solution was stirred at this temperature for one hour and then raised to 0°C. over 15 minutes. The reaction mixture was then poured into 250 ml. of 4% by weight aqueous hydrochloric acid and extracted with ethyl acetate. The extract was washed with sodium bicarbonate solution and water and dried. Evaporation of the solvent gave 23.22 g. of crude product. Chromatography of a 19 g. portion on alumina afforded 7.71 g. of pure 1-hydroxy-3,7-dimethyl-4-(phenylsulfonyl)-9-(2,6,6-trimethylcyclohexen-1-yl)-nona-2,6,8-triene (48% yield) as a pale yellow oil having a UV in isopropanol at λ max= 272- 3 mμ (ε=16800).

Workup

  1. customat -65° to -70°C
  2. stirringThe solution was stirred at this temperature for one hour
  3. temperatureraised to 0°C. over 15 minutes
  4. additionThe reaction mixture was then poured into 250 ml
  5. extractionof 4% by weight aqueous hydrochloric acid and extracted with ethyl acetate
  6. washThe extract was washed with sodium bicarbonate solution and water
  7. customdried
  8. customEvaporation of the solvent
  9. customgave 23.22 g
  10. customportion on alumina afforded 7.71 g

Sources & evidence

ORD record
ord-dc4e13e12ba94f61a5f43be546a54c60
Source dataset
uspto-grants-1976_06
Patent number
US03960967

Reaction notes

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