Acetic Acid → HCID 67508190, compound

HRID 1468161

Reaction equation

HRID 1468161 reaction equation
[N:1]1([C:7]2[CH:8]=[C:9]([CH:12]=[CH:13][CH:14]=2)[C:10]#[N:11])[CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.[CH3:15][O:16][C:17](=[O:26])[C:18]1[CH:23]=[CH:22][CH:21]=[C:20]([CH:24]=O)[CH:19]=1.CC(O)=O.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].Cl>ClC(Cl)C>[CH3:15][O:16][C:17](=[O:26])[C:18]1[CH:23]=[CH:22][CH:21]=[C:20]([CH2:24][N:4]2[CH2:5][CH2:6][N:1]([C:7]3[CH:14]=[CH:13][CH:12]=[C:9]([C:10]#[N:11])[CH:8]=3)[CH2:2][CH2:3]2)[CH:19]=1

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 639145Methyl 3-formylbenzoateHCID 5049666Sodium triacetoxyborohydride2×HCID 114809021-(3-Cyanophenyl)piperazine

Product 1

HCID 67508190HCID 67508190, compoundYield 80.5%

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent

Procedure

Dissolve 3-piperazin-1-yl-benzonitrile (0.19 g, 1.00 mmol), 3-formyl-benzoic acid methyl ester (0.33 g, 2.00 mmol) and AcOH (0.64 mL, 10.0 mmol) in 5 mL dichloroethane. Add NaBH(OAc)3 (0.42 g, 2.00 mmol) and stir the mixture overnight. Add another portion of NaBH(OAc)3 (0.42 g, 2.00 mmol) and stir the mixture an additional 24 h. Concentrate the crude reaction mixture under a stream of N2. Dissolve the residue into 5% HCl and apply to a Dowex column. Wash the column with 1×50 mL 5% HCl, 2×50 mL H2O, 2×50 mL of MeOH and 2×50 mL of dichloromethane. Liberate the basic residues by washing the resin with 3×30 mL of 10% NH3/MeOH and 2×20 mL of dichloromethane. Concentrate the basic washings to give 0.27 g of 3-[4-(3-cyano-phenyl)-piperazin-1-ylmethyl]-benzoic acid methyl ester as a clear oil. 1H NMR indicates some contamination with starting amine. The mixture is carried on without further purification.

Workup

  1. concentrationConcentrate the crude
  2. customreaction mixture under a stream of N2
  3. washWash the column with 1×50 mL 5% HCl, 2×50 mL H2O, 2×50 mL of MeOH and 2×50 mL of dichloromethane
  4. washby washing the resin with 3×30 mL of 10% NH3/MeOH and 2×20 mL of dichloromethane
  5. concentrationConcentrate the basic washings

Sources & evidence

ORD record
ord-8d4599e273644e549f60421d34e908be
Source dataset
uspto-grants-2015_04
Patent number
US09000154B2

Linked notes

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