Sodium Iodide → HCID 178509804, compound

HRID 2081150Notes

Reaction equation

HRID 2081150 reaction equation
C[Si](Cl)(C)C.C[O:7][CH2:8][C@H:9]1[CH2:14][CH2:13][C@H:12]([C:15]2[CH:20]=[CH:19][C:18]([C:21]#[N:22])=[CH:17][CH:16]=2)[CH2:11][CH2:10]1.[I-].[Na+]>C(#N)C>[C:21]([C:18]1[CH:19]=[CH:20][C:15]([C@H:12]2[CH2:13][CH2:14][C@H:9]([CH2:8][OH:7])[CH2:10][CH2:11]2)=[CH:16][CH:17]=1)#[N:22]

Participants

5

Reactant 3

HCID 5238Sodium IodideHCID 6397ChlorotrimethylsilaneHCID 178495621HCID 178495621, compound

Product 1

HCID 178509804HCID 178509804, compoundYield 60.1%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
35 °C

Procedure

Trimethylsilyl chloride (305.6 g, 2.81 mol) was dropwise added to trans-4-methoxymethyl-1-(4-cyanophenyl)cyclohexane (322.5 g, 1.41 mol), sodium iodide (421.6 g, 2.81 mol) and acetonitrile (2.5 l), with stirring in nitrogen atmosphere at 35° C. over 30 minutes, followed by agitating the mixture for 20 minutes, cooling it down to 10° C., filtering the reaction mixture by suction, pouring the mother liquor in ice water (2 Kg), extracting with chloroform (1.5 l), twice washing the chloroform solution with a 10% by weight aqueous solution of sodium thiosulfate (0.5 l), further three times washing with water (1 l), distilling off chloroform, and three times recrystallizing the residue from toluene (300 ml) for purification to obtain trans-4-(4-cyanophenyl)cyclohexylcarbinol (182.5 g, 0.848 mol). M.P.: 108.5-110.8° C. A solution of this trans-4-(4-cyanophenyl)cyclohexylcarbinol (107.6 g, 0.500 mol) in dichloromethane (0.7 l) was instantaneously added to a solution of pyridinium chlorochromate (161.7 g, 0.750 mol) in dichloromethane (1 l), prepared in advance, with stirring, at room temperature, followed by agitating the mixture at room temperature for 1.5 hour, adding diethyl ether (1 l) to the resulting reaction solution, and subjecting the supernatant to column chromatography using Florisil® (made by Floridin Co., Ltd.) as a filler to obtain trans-4-(4-cyanophenyl)cyclohexylcarbaldehyde (101.2 g, 0.474 mol).

Workup

  1. stirringby agitating the mixture for 20 minutes
  2. temperaturecooling it down to 10° C.
  3. filtrationfiltering the reaction mixture by suction
  4. additionpouring the mother liquor in ice water (2 Kg)
  5. extractionextracting with chloroform (1.5 l)
  6. washtwice washing the chloroform solution with a 10% by weight aqueous solution of sodium thiosulfate (0.5 l), further three times
  7. washwashing with water (1 l)
  8. distillationdistilling off chloroform, and three times
  9. customrecrystallizing the residue from toluene (300 ml)
  10. customfor purification

Sources & evidence

ORD record
ord-ec2a20e8644b45898aa3db08f2d731d5
Source dataset
uspto-grants-1993_02
Patent number
US05183587

Reaction notes

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