Ammonium Chloride → HCID 178443899, compound

HRID 622275Notes

Reaction equation

HRID 622275 reaction equation
C[Li].[CH2:3]([Mg]Br)[CH2:4][CH2:5][CH:6]=[CH2:7].[C:10]([C:12]1[CH:17]=[CH:16][C:15]([C@H:18]2[CH2:23][CH2:22][C@H:21]([CH2:24]I)[CH2:20][CH2:19]2)=[CH:14][CH:13]=1)#[N:11].[Cl-].[NH4+]>CCCCCC.O1CCCC1.[Cu]I>[CH2:24]([C@H:21]1[CH2:22][CH2:23][C@H:18]([C:15]2[CH:16]=[CH:17][C:12]([C:10]#[N:11])=[CH:13][CH:14]=2)[CH2:19][CH2:20]1)[CH2:7][CH2:6][CH2:5][CH:4]=[CH2:3]

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 178418348HCID 178418348, compoundHCID 178445862HCID 178445862, compoundHCID 178509802HCID 178509802, compound

Product 1

HCID 178443899HCID 178443899, compoundYield 118.8%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of 705 mg of dry copper-(I) iodide and 7 ml of tetrahydrofuran was treated dropwise with 2.5 ml of a 1.5M solution of methyl lithium in hexane at -78° C. while stirring vigorously and then warmed slowly to 0° C. Subsequently, the mixture was again cooled to -78° C. and treated dropwise by means of a syringe with a 4-pentenyl-magnesium bromide solution (prepared from 90 mg of magnesium and 0.44 ml of 5-bromo-1-pentene in 2 ml of tetrahydrofuran). The reaction mixture was warmed gradually until a red-violet suspension had formed and was then held at 5° C. for 20 minutes. Thereafter, the reaction mixture was again cooled to -78° C., treated dropwise with a solution of 600 mg of trans-4-(p-cyanophenyl)-iodomethylcyclohexane in 5 ml of tetrahydrofuran and then warmed slowly to room temperature. The reaction mixture was stirred at room temperature for a further 30 minutes and then treated with saturated ammonium chloride solution and extracted with diethyl ether. The organic phases were dried over magnesium sulphate and concentrated. Chromatographic separation on silica gel with ethyl acetate/petroleum ether (vol. 5:95) and two-fold recrystallization from methanol gave 165 mg of p-[trans-4-(5-hexenyl)cyclohexyl]benzonitrile (purity 99.75%) as colourless crystals of m.p. (C-N) 45.5° C. and cl.p. (N-I) 52.5° C.

Workup

  1. temperatureSubsequently, the mixture was again cooled to -78° C.
  2. temperatureThe reaction mixture was warmed gradually until a red-violet suspension
  3. customhad formed
  4. temperatureThereafter, the reaction mixture was again cooled to -78° C.
  5. temperaturewarmed slowly to room temperature
  6. stirringThe reaction mixture was stirred at room temperature for a further 30 minutes
  7. extractionextracted with diethyl ether
  8. dry with materialThe organic phases were dried over magnesium sulphate
  9. concentrationconcentrated
  10. customChromatographic separation on silica gel
  11. customwith ethyl acetate/petroleum ether (vol. 5:95) and two-fold recrystallization from methanol

Sources & evidence

ORD record
ord-3ff8eb09d695430bb02b86f1c1599b49
Source dataset
uspto-grants-1988_09
Patent number
US04770503

Reaction notes

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