Sodium Hydroxide → HCID 178444403, compound

HRID 370673Notes

Reaction equation

HRID 370673 reaction equation
Br[C:2](Br)=[CH:3][C:4]1[CH:9]=[CH:8][C: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)=[CH:6][CH:5]=1.C([Li])CCC.C1(O[C:36]#[N:37])C=CC=CC=1.[OH-].[Na+]>O1CCCC1.CCCCCC>[CH2:18]([C@H:15]1[CH2:16][CH2:17][C@H:12]([CH2:11][CH2:10][C:7]2[CH:8]=[CH:9][C:4]([C:3]#[C:2][C:36]#[N:37])=[CH:5][CH:6]=2)[CH2:13][CH2:14]1)[CH2:19][CH2:20][CH2:21][CH3:22]

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 70740Phenyl cyanateHCID 178418339ButyllithiumHCID 178444401HCID 178444401, compound

Product 1

HCID 178444403HCID 178444403, compoundYield 69%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of 1.55 g of β,β-dibromo-p-[2-(trans-4-pentylcyclohexyl)ethyl]styrene in 35 ml of absolute tetrahydrofuran was placed at about -45° C. in a sulphonation flask under argon gasification and treated within 5 minutes with 8.8 ml of a 1.2N solution of butyl lithium in hexane. After completion of the addition, the mixture was stirred at the same temperature for a further 90 minutes, then cooled to -78° C. and treated with 0.79 ml of phenyl cyanate. The mixture was subsequently stirred at -78° C. for a further 3 hours, then poured into 50 ml of 1N sodium hydroxide and extracted three times with 50 ml of diethyl ether/petroleum ether (1:1) each time. The organic phases were washed with 50 ml of 1N sodium hydroxide and 50 ml of saturated sodium chloride solution, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.5 bar) of the residue (1.17 g) on silica gel with hexane followed by 3% ethyl acetate/petroleum ether gave 740 mg (69%) of p-[2-(trans-4-pentylcyclohexyl)ethyl]phenylpropiolonitrile as colourless crystals (purity 97.3%) which were recrystallized further from methanol; m.p. (C-N) 36.7° C., cl.p. (N-I) 105.5° C.

Workup

  1. additionAfter completion of the addition
  2. stirringThe mixture was subsequently stirred at -78° C. for a further 3 hours
  3. extractionextracted three times with 50 ml of diethyl ether/petroleum ether (1:1) each time
  4. washThe organic phases were washed with 50 ml of 1N sodium hydroxide and 50 ml of saturated sodium chloride solution
  5. dry with materialdried over magnesium sulphate
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-18e23a9a8fa14cd2be6139e04fa1c6ed
Source dataset
uspto-grants-1985_07
Patent number
US04528114

Reaction notes

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