1,8-Diazabicyclo(5.4.0)undec-7-ene → HCID 18001111, compound

HRID 478166Notes

Reaction equation

HRID 478166 reaction equation
[CH:1]([C:3]1[CH:13]=[CH:12][C:6]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:5][C:4]=1[N+:14]([O-])=O)=O.N12CCCN=C1CCCCC2.C1C=CC([P+](C2C=CC=CC=2)(C2C=CC=CC=2)[CH2:35][C:36]2[CH:41]=[C:40]([C:42]#[N:43])[CH:39]=[CH:38][CH:37]=2)=CC=1.[Br-]>C1(C)C=CC=CC=1>[NH2:14][C:4]1[CH:5]=[C:6]([CH:12]=[CH:13][C:3]=1[CH2:1][CH2:35][C:36]1[CH:37]=[CH:38][CH:39]=[C:40]([C:42]#[N:43])[CH:41]=1)[C:7]([O:9][CH2:10][CH3:11])=[O:8]

Participants

5

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 2778355(3-Cyanobenzyl)triphenylphosphonium bromideHCID 18001104Ethyl 4-formyl-3-nitrobenzoate

Product 1

HCID 18001111HCID 18001111, compoundYield 136%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

Ethyl 4-formyl-3-nitrobenzoate (5.81 g) was dissolved in 70 ml of toluene, then 2.1 ml of 1,8-diazabicyclo[5.4.0]-undec-7-ene and the mixture was stirred at 80° C. for one hour. To the reaction solution, 2.69 g of 3-[(1,1,1-triphenylphosphonio)methyl]benzonitrile bromide was added, and the mixture was stirred at 80° C. for 24 hours. Insoluble matters were filtered out and the filtrate was concentrated in vacuo. The resulting residue was purified by silica gel column chromatography using hexane-ethyl acetate (10:1) as an eluting solvent. The resulting intermediate (3.1 g) was dissolved in a mixed solvent of 50 ml of ethanol and 10 ml of tetrahydrofuran, then 1 g of a palladium oxide-barium sulfate complex was added and the mixture was stirred in a hydrogen atmosphere at room temperature for 3 days. The reaction solution was filtered through Celite and the filtrate was concentrated in vacuo. The resulting residue was purified by silica gel column chromatography using hexane-ethyl acetate (2:1) as an eluting solvent to give 2.35 g of ethyl 3-amino-4-[2-(3-cyanophenyl)ethyl]benzoate.

Workup

  1. filtrationInsoluble matters were filtered out
  2. concentrationthe filtrate was concentrated in vacuo
  3. customThe resulting residue was purified by silica gel column chromatography
  4. dissolutionThe resulting intermediate (3.1 g) was dissolved in a mixed solvent of 50 ml of ethanol and 10 ml of tetrahydrofuran
  5. addition1 g of a palladium oxide-barium sulfate complex was added
  6. stirringthe mixture was stirred in a hydrogen atmosphere at room temperature for 3 days
  7. filtrationThe reaction solution was filtered through Celite
  8. concentrationthe filtrate was concentrated in vacuo
  9. customThe resulting residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-6f69add9b0ba4deb95995cdd0913e586
Source dataset
uspto-grants-2003_11
Patent number
US06642224B1

Reaction notes

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