Water → HCID 178455734, compound

HRID 370696Notes

Reaction equation

HRID 370696 reaction equation
Br[C:2](Br)=[CH:3][C@H:4]1[CH2:9][CH2:8][C@H:7]([CH2:10][CH2:11][C:12]2[CH:17]=[CH:16][C:15]([C:18]3[CH:23]=[CH:22][C:21]([CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])=[CH:20][CH:19]=3)=[CH:14][CH:13]=2)[CH2:6][CH2:5]1.C([Li])CCC.O>O1CCCC1.CCCCCC>[C:3]([C@H:4]1[CH2:5][CH2:6][C@H:7]([CH2:10][CH2:11][C:12]2[CH:13]=[CH:14][C:15]([C:18]3[CH:19]=[CH:20][C:21]([CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])=[CH:22][CH:23]=3)=[CH:16][CH:17]=2)[CH2:8][CH2:9]1)#[CH:2]

Participants

6

Reactant 3

HCID 962WaterHCID 178418339ButyllithiumHCID 178442084HCID 178442084, compound

Product 1

HCID 178455734HCID 178455734, compoundYield 98%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 2.87 g of 4-[2-[trans-4-(2,2-dibromovinyl)cyclohexyl]ethyl]-4'-pentylbiphenyl in 100 ml of absolute tetrahydrofuran was placed at -20° C. in a sulphonation flask under argon gasification and treated within 15 minutes with 20.6 ml of a 0.8N solution of butyl lithium in hexane (slight exothermic reaction). The mixture was subsequently stirred for a further 1.5 hours with gradual warming to 0° C., then poured into 100 ml of water and extracted three times with 100 ml of diethyl ether each time. The organic phases were washed a further twice with 100 ml of water each time, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.5 bar) of the residue (1.98 g) on silica gel with 1% ethyl acetate/petroleum ether as the eluant gave 1.94 g (98%) of 4-[2-(trans-4-ethynylcyclohexyl)ethyl]-4'-pentylbiphenyl. Two-fold recrystallization from ethanol and repeated low-pressure chromatography (0.5 bar) of the crystallizate on silica gel with hexane as the eluant finally yielded 732 mg of mixed fractions and 684 mg of pure 4-(2-(trans-4-ethynylcyclohexyl)ethyl]-4'-pentylbiphenyl with m.p. (C-S) 66.0° C., t.p. (S-S) 107° C., t.p. (S-N) 115.5° C. and cl.p. (N-I) 126.4° C.

Workup

  1. extractionextracted three times with 100 ml of diethyl ether each time
  2. washThe organic phases were washed a further twice with 100 ml of water each time
  3. dry with materialdried over magnesium sulphate
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-c8179ccf2ae349668a29763f69d635ec
Source dataset
uspto-grants-1985_07
Patent number
US04528114

Reaction notes

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