Carbon Dioxide → 7-Nitro-1,2,3,4-tetrahydroisoquinoline-1-acetonitrile

HRID 369943Notes

Reaction equation

HRID 369943 reaction equation
[N+:1]([C:4]1[CH:13]=[C:12]2[C:7]([CH2:8][CH2:9][N:10]=[CH:11]2)=[CH:6][CH:5]=1)([O-:3])=[O:2].[C:14]([CH2:16]C(O)=O)#[N:15].C(=O)=O>C(O)(=O)C>[N+:1]([C:4]1[CH:13]=[C:12]2[C:7]([CH2:8][CH2:9][NH:10][CH:11]2[CH2:16][C:14]#[N:15])=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

5

Reactant 3

HCID 280Carbon DioxideHCID 9740Cyanoacetic acidHCID 37512877-Nitro-3,4-dihydroisoquinoline

Product 1

HCID 215843867-Nitro-1,2,3,4-tetrahydroisoquinoline-1-acetonitrileYield 76.2%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A suspension of 7-nitro-3,4-dihydroisoquinoline (13.4 g, 76.1 mmol) and cyanoacetic acid (12.5 g, 150 mmol) in acetic acid (55 ml) was heated at reflux for 0.5 h. After evolution of carbon dioxide had ceased and the reaction mixture had cooled, the solvent was removed on the rotoevaporator. The residue was triturated with isopropanol (100 ml) and the solid was collected. The crude product was partitioned between ethyl acetate and dilute potassium carbonate solution. The dried (MgSO4) organic phase was concentrated to give the title compound as an orange solid (12.6 g, 76%), MS 218 (M+H)+. 1H NMR (CDCl3) 8.03 (dd, 1H), 7.99 (d, 1H), 7.31 (d, 1H), 4.45 (t, 1H), 3.1-3.4 (m, 3H), 2.9-3.0 (m, 3H), 2.07 (broad s, 1H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 0.5 h
  3. temperaturethe reaction mixture had cooled
  4. customthe solvent was removed on the rotoevaporator
  5. customThe residue was triturated with isopropanol (100 ml)
  6. customthe solid was collected
  7. customThe crude product was partitioned between ethyl acetate and dilute potassium carbonate solution
  8. dry with materialThe dried (MgSO4) organic phase
  9. concentrationwas concentrated

Sources & evidence

ORD record
ord-4aeb9f40b4cc4881b98d97d56516f228
Source dataset
uspto-grants-2000_10
Patent number
US06140322

Reaction notes

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