Iodine → HCID 68409296, compound

HRID 453879Notes

Reaction equation

HRID 453879 reaction equation
II.[Mg].Br[C:5]1[CH:10]=[CH:9]C=[CH:7][CH:6]=1.[CH2:11]([N:18]1[CH2:23][CH2:22][C:21]([N:26]([CH3:28])[CH3:27])([C:24]#N)[CH2:20][CH2:19]1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[NH4+].[Cl-]>C(OCC)C.CO.C(Cl)(Cl)Cl>[CH2:11]([N:18]1[CH2:19][CH2:20][C:21]([C:24]2[CH:9]=[CH:10][CH:5]=[CH:6][CH:7]=2)([N:26]([CH3:27])[CH3:28])[CH2:22][CH2:23]1)[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

8

Reactant 5

HCID 807IodineHCID 7961Bromobenzene2×HCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 164539151-Benzyl-4-(dimethylamino)piperidine-4-carbonitrile

Product 1

HCID 68409296HCID 68409296, compoundYield 160%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent3×HCID 21584188Chloroform methanolSolvent

Conditions

Temperature
80 °C

Procedure

A little iodine was added to a mixture of 34.5 g (3.5 eq.) magnesium and 100 ml dry diethyl ether, followed over a period of 10 min by 10 g (0.15 eq.) bromobenzene, and the mixture was stirred for a further 10 min. Once the reaction had started, 183 g (2.85 eq.) bromobenzene dissolved in 500 ml diethyl ether were added dropwise over a period of 2 h and the mixture was stirred for a further 15 min. 100 g (1 eq.) 1-benzyl-4-(dimethylamino)piperidine-4-carbonitrile dissolved in 900 ml diethyl ether were added over a period of 2 h to the Grignard reagent prepared in the preceding step and the mixture was then heated for 12 h at 80° C. The reaction course was monitored by thin-layer chromatography (10% MeOH/CHCl3). Once the conversion was complete, the reaction solution was cooled to 0° C., mixed with saturated NH4Cl solution, extracted with ethyl acetate (3×300 ml) and the combined organic phases were dried with Na2SO4. Following removal of the solvent under reduced pressure, the residue was purified by column chromatography (silica gel; 1% MeOH/CHCl3). 30 g (35%) of product were obtained in the form of a yellow solid.

Workup

  1. additionwere added dropwise over a period of 2 h
  2. stirringthe mixture was stirred for a further 15 min
  3. customprepared in the preceding step
  4. temperaturethe reaction solution was cooled to 0° C.
  5. extractionextracted with ethyl acetate (3×300 ml)
  6. dry with materialthe combined organic phases were dried with Na2SO4
  7. customremoval of the solvent under reduced pressure
  8. customthe residue was purified by column chromatography (silica gel; 1% MeOH/CHCl3)

Sources & evidence

ORD record
ord-d5b64f658ef94769bb957bba246a13e0
Source dataset
uspto-grants-2013_07
Patent number
US08492559B2

Reaction notes

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