Sodium Bicarbonate → HCID 178455744, compound

HRID 1982123Notes

Reaction equation

HRID 1982123 reaction equation
Br[C:2](Br)=[CH:3][C@H:4]1[CH2:9][CH2:8][C@H:7]([CH2:10][CH2:11][CH2:12][CH2:13][CH3:14])[CH2:6][CH2:5]1.C([Li])CCC.C(=O)([O-])O.[Na+]>O1CCCC1.CCCCCC>[C:3]([C@H:4]1[CH2:9][CH2:8][C@H:7]([CH2:10][CH2:11][CH2:12][CH2:13][CH3:14])[CH2:6][CH2:5]1)#[CH:2]

Participants

6

Reactant 3

HCID 516892Sodium BicarbonateHCID 178418339ButyllithiumHCID 178444390HCID 178444390, compound

Product 1

HCID 178455744HCID 178455744, compoundYield 91.1%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-70 °C

Procedure

A solution of 84.5 g of trans-1-(2,2-dibromovinyl)-4-pentylcyclohexane in 800 ml of absolute tetrahydrofuran was cooled to -75° C. under nitrogen gasification and treated dropwise within 30 minutes with 400 ml of an about 1.6M solution of butyl lithium in hexane. The mixture was subsequently stirred at -70° C. for a further 2 hour, then poured into 5.5 l of 2% (wt./vol.) sodium hydrogen carbonate solution and extracted with 1 l of hexane. The aqueous phase was back-extracted with 700 ml of hexane. The combined organic phases were dried over sodium sulphate and freed from solvent on a rotary evaporator. Distillation of the resulting light yellow oil in a high vacuum gave in the main run 40.6 g (91.1%) of trans-1-ethynyl-4-pentylcyclohexane as a colourless liquid which still contained cis-isomer; b.p. 52°-54° C./0.02 Torr. By recrystallization from ethanol at -25° C. and drying up to constant weight at 30° C. in a vacuum drying oven there could be obtained 20.4 g of product free from cis-isomer. From the mother liquor there could be isolated according to the same method a further 6.5 g of product which was almost free from cis-isomer.

Workup

  1. extractionextracted with 1 l of hexane
  2. extractionThe aqueous phase was back-extracted with 700 ml of hexane
  3. dry with materialThe combined organic phases were dried over sodium sulphate
  4. customfreed from solvent on a rotary evaporator
  5. distillationDistillation of the resulting light yellow oil in a high vacuum

Sources & evidence

ORD record
ord-c933153e13c24a9aaff0f139afc47718
Source dataset
uspto-grants-1986_06
Patent number
US04595521

Reaction notes

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