4-(Bromomethyl)benzonitrile → HCID 18989291, compound

HRID 2395809Notes

Reaction equation

HRID 2395809 reaction equation
[N+:1]([CH2:3][C:4]([N:6]1[CH2:11][CH2:10][CH2:9][CH2:8][CH2:7]1)=[O:5])#[C-:2].[CH:12]([N-]C(C)C)(C)C.[Li+].[C:20]([C:22]1[CH:29]=[CH:28][C:25](CBr)=[CH:24][CH:23]=1)#[N:21].C(Cl)Cl.CO>C1COCC1.O>[C:20]([C:22]1[CH:29]=[CH:28][C:25]([CH:8]2[CH2:9][CH2:10][CH2:11][N:6]([C:4](=[O:5])[CH:3]([N+:1]#[C-:2])[CH3:12])[CH2:7]2)=[CH:24][CH:23]=1)#[N:21]

Participants

7

Reactant 4

HCID 869964-(Bromomethyl)benzonitrileHCID 2724682Lithium diisopropylamideHCID 6455474Piperidine, 1-(isocyanoacetyl)-HCID 21226129Dichloromethane methanol

Product 1

HCID 18989291HCID 18989291, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

22.0 g (144.5 mmol) of N-isocyanoacetylpiperidine in 160 ml of THF were added dropwise to 159 mmol of lithium diisopropylamide in 430 ml of THF at -70° C. Subsequently 28.3 g (144.5 mmol) of p-cyanobenzyl bromide dissolved in 300 ml of THF were added dropwise to the mixture at -70° C. and, after stirring at this temperature for 3 h (reaction complete according to TLC, mobile phase CH2Cl2 /CH3OH 9/1), 70 ml of water were added dropwise. The solution was concentrated under reduced pressure, the residue was acidified with 1N HCl and extracted with methylene chloride, and the organic phase was dried over magnesium sulfate and evaporated. The solid product was mixed with ether, stirred overnight and filtered off with suction. 30.9 g (plus 3.3 g by working up the mother liquor) of 3-(p-cyanophenyl)-2-isocyanopropionylpiperidine were obtained as a white solid (86% of theory).

Workup

  1. additionwere added dropwise to the mixture at -70° C.
  2. additionwere added dropwise
  3. concentrationThe solution was concentrated under reduced pressure
  4. extractionextracted with methylene chloride
  5. dry with materialthe organic phase was dried over magnesium sulfate
  6. customevaporated
  7. additionThe solid product was mixed with ether
  8. stirringstirred overnight
  9. filtrationfiltered off with suction
  10. customwere obtained as a white solid (86% of theory)

Sources & evidence

ORD record
ord-8151bf27ff10466cac27aaa714931eda
Source dataset
uspto-grants-1996_02
Patent number
US05489583

Reaction notes

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