Lithium diisopropylamide → HCID 53743827, compound

HRID 1657554Notes

Reaction equation

HRID 1657554 reaction equation
C([N-]C(C)C)(C)C.[Li+].[C:9]1([CH3:24])[CH:14]=[CH:13][C:12]([S:15]([CH2:18][C:19]([CH3:23])=[CH:20][CH2:21][OH:22])(=[O:17])=[O:16])=[CH:11][CH:10]=1.Br[CH2:26][CH:27]=[C:28]([CH3:40])[CH:29]=[CH:30][C:31]1[C:36]([CH3:38])([CH3:37])[CH2:35][CH2:34][CH2:33][C:32]=1[CH3:39]>O1CCCC1>[OH:22][CH2:21][CH:20]=[C:19]([CH3:23])[CH:18]([S:15]([C:12]1[CH:11]=[CH:10][C:9]([CH3:24])=[CH:14][CH:13]=1)(=[O:16])=[O:17])[CH2:26][CH:27]=[C:28]([CH3:40])[CH:29]=[CH:30][C:31]1[C:36]([CH3:38])([CH3:37])[CH2:35][CH2:34][CH2:33][C:32]=1[CH3:39]

Participants

5

Reactant 3

HCID 2724682Lithium diisopropylamideHCID 53788662HCID 53788662, compoundHCID 542708483-Methyl-4-(4-methylbenzene-1-sulfonyl)but-2-en-1-ol

Product 1

HCID 53743827HCID 53743827, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

The lithium diisopropylamide solution was then added over a 75 minute period to a -70°C. solution of 5.0 g. of 1-p-toluenesulfonyl-2-methyl-4-hydroxy-but-2-ene and 7.0 g. of 1-bromo-3-methyl-5-(2,6,6-trimethylcyclohexen-1-yl)-penta-2,4-diene in 50 ml. of tetrahydrofuran. After the addition, the reaction mixture was stirred for an additional 45 minutes at -70°C. and was then warmed to 0°C. and was poured onto 400 ml. of ice water. The mixture was extracted with three 300 ml. portions of diethyl ether, and the combined extracts were washed with two 400 ml. portions of brine and dried over anhydrous magnesium sulfate. Evaporation of the solvent at reduced pressure gave a yellow oil which was immediately chromatographed on 300 g. of silica gel eluting with 5 to 30% diethyl ether in benzene followed by ethyl acetate. From the chromotography there was obtained 6.43 g. of pure 1-hydroxy-3,7-dimethyl-4-p-toluenesulfonyl-9 -(2,6,6-trimethylcyclohexen-1-yl)-nona-2,6,8-triene (70% yield) and 1.21 g. of recovered hydroxysulfone starting material. The product had UV in isopropanol at λmax = 228-9 mμ ( ε= 25,740); 260-2 mμ ( ε = 17,070) and 274-5 mμ ( ε = 15,010).

Workup

  1. additionAfter the addition
  2. temperaturewas then warmed to 0°C.
  3. additionwas poured onto 400 ml
  4. extractionThe mixture was extracted with three 300 ml
  5. washportions of diethyl ether, and the combined extracts were washed with two 400 ml
  6. dry with materialportions of brine and dried over anhydrous magnesium sulfate
  7. customEvaporation of the solvent at reduced pressure
  8. customgave a yellow oil which
  9. customwas immediately chromatographed on 300 g
  10. customFrom the chromotography there was obtained 6.43 g

Sources & evidence

ORD record
ord-76d2c6d4904143c9a5af7ee04783df7f
Source dataset
uspto-grants-1976_06
Patent number
US03960967

Reaction notes

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