Water → (4'-Pentyl-4-biphenylyl)propiolonitrile

HRID 370666Notes

Reaction equation

HRID 370666 reaction equation
Br[C:2](Br)=[CH:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:15]=[CH:14][C:13]([CH2:16][CH2:17][CH2:18][CH2:19][CH3:20])=[CH:12][CH:11]=2)=[CH:6][CH:5]=1.C([Li])CCC.C1(O[C:34]#[N:35])C=CC=CC=1.O>O1CCCC1.CCCCCC>[CH2:16]([C:13]1[CH:14]=[CH:15][C:10]([C:7]2[CH:8]=[CH:9][C:4]([C:3]#[C:2][C:34]#[N:35])=[CH:5][CH:6]=2)=[CH:11][CH:12]=1)[CH2:17][CH2:18][CH2:19][CH3:20]

Participants

7

Reactant 4

HCID 962WaterHCID 70740Phenyl cyanateHCID 202749594-(2,2-Dibromovinyl)-4'-pentylbiphenylHCID 178418339Butyllithium

Product 1

HCID 13587815(4'-Pentyl-4-biphenylyl)propiolonitrileYield 58%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-10 °C

Procedure

A solution of 2.60 g of 4-(2,2-dibromovinyl)-4'-pentylbiphenyl in 50 ml of absolute tetrahydrofuran was placed at -78° C. in a sulphonation flask under argon gasification and treated within 5 minutes with 14.5 ml of a 1.2N solution of butyl lithium in hexane. After completion of the addition, the mixture was warmed to -10° C. within 10 minutes and then, after renewed cooling to -78° C., treated with a solution of 1.5 ml of phenyl cyanate in 10 ml of absolute tetrahydrofuran. The mixture was subsequently stirred at -78° C. for a further 30 minutes, then poured into 100 ml of water and extracted three times with 100 ml of diethyl ether each time. The organic phases were washed twice with 50 ml of water each time, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.5 bar) of the residue (2.51 g) on silica gel with hexane followed by 2% ethyl acetate/petroleum ether and subsequent recrystallization from methanol gave 1.02 g (58%) of (4'-pentyl-4-biphenylyl)propiolonitrile as colourless crystals (purity 99.6%); m.p. (C-N) 51.0° C., cl.p. (N-I) 120.2° C.

Workup

  1. additionAfter completion of the addition
  2. temperatureafter renewed cooling to -78° C.
  3. extractionextracted three times with 100 ml of diethyl ether each time
  4. washThe organic phases were washed twice with 50 ml of water each time
  5. dry with materialdried over magnesium sulphate
  6. concentrationconcentrated
  7. customLow-pressure chromatography (0.5 bar) of the residue (2.51 g) on silica gel with hexane followed by 2% ethyl acetate/petroleum ether and subsequent recrystallization from methanol

Sources & evidence

ORD record
ord-289edbff2afd49e583d3077ad6666dfe
Source dataset
uspto-grants-1985_07
Patent number
US04528114

Reaction notes

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