Water → HCID 178455747, compound

HRID 370690Notes

Reaction equation

HRID 370690 reaction equation
Br[C:2](Br)=[CH:3][C@H:4]1[CH2:9][CH2:8][C@H:7]([CH2:10][CH2:11][C@H:12]2[CH2:17][CH2:16][C@H:15]([CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])[CH2:14][CH2:13]2)[CH2:6][CH2:5]1.C([Li])CCC.O>O1CCCC1.CCCCCC>[C:3]([C@H:4]1[CH2:9][CH2:8][C@H:7]([CH2:10][CH2:11][C@H:12]2[CH2:13][CH2:14][C@H:15]([CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])[CH2:16][CH2:17]2)[CH2:6][CH2:5]1)#[CH:2]

Participants

6

Reactant 3

HCID 962WaterHCID 178418339ButyllithiumHCID 178444459HCID 178444459, compound

Product 1

HCID 178455747HCID 178455747, compoundYield 88%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of 2.66 g of trans-1-(2,2-dibromovinyl)-4-[2-(trans-4-pentylcyclohexyl)ethyl]cyclohexane in 120 ml of absolute tetrahydrofuran was placed at -78° C. in a sulphonation flask under argon gasification and treated within 10 minutes with 15.2 ml of a 0.1N solution of butyl lithium in hexane. After completion of the addition, the mixture was stirred at -78° C. for a further 2 hours, then poured into 100 ml of water and extracted three times with 100 ml of petroleum ether each time. The organic phases were washed twice with 50 ml of water each time and once with 50 ml of saturated sodium chloride solution, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.5 bar) of the residue (1.90 g) on silica gel with hexane gave 1.48 g (88%) of trans-1-ethynyl-4-[2-(trans-4-pentylcyclohexyl)ethyl]cyclohexane as a trans/cis epimer mixture (about 9:1). Fractional crystallization from 50 ml of methanol yielded 883 mg of pure trans-1-ethynyl-4-[2-(trans-4-pentylcyclohexyl)ethyl]cyclohexane as colourless crystals; m.p. (C-N) 51.3° C., cl.p. (N-I) 68.0° C.

Workup

  1. additionAfter completion of the addition
  2. extractionextracted three times with 100 ml of petroleum ether each time
  3. washThe organic phases were washed twice with 50 ml of water each time
  4. dry with materialonce with 50 ml of saturated sodium chloride solution, dried over magnesium sulphate
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-44519c01ca634780a76330301c1a8b88
Source dataset
uspto-grants-1985_07
Patent number
US04528114

Reaction notes

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