Benzyl chloroformate → Benzyl 7-nitro-1,2,3,4-tetrahydroisoquinoline-2-carboxylate

HRID 1524292Notes

Reaction equation

HRID 1524292 reaction equation
Cl.[N+:2]([C:5]1[CH:14]=[C:13]2[C:8]([CH2:9][CH2:10][NH:11][CH2:12]2)=[CH:7][CH:6]=1)([O-:4])=[O:3].C([O-])([O-])=O.[K+].[K+].Cl[C:22]([O:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)=[O:23]>CCOC(C)=O.O>[CH2:25]([O:24][C:22]([N:11]1[CH2:10][CH2:9][C:8]2[C:13](=[CH:14][C:5]([N+:2]([O-:4])=[O:3])=[CH:6][CH:7]=2)[CH2:12]1)=[O:23])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

6

Reactant 3

HCID 10387Benzyl chloroformateHCID 11430Potassium CarbonateHCID 135216707-Nitro-1,2,3,4-tetrahydroisoquinoline hydrochloride

Product 1

HCID 53419203Benzyl 7-nitro-1,2,3,4-tetrahydroisoquinoline-2-carboxylateYield 91.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 7-nitro-1,2,3,4-tetrahydroisoquinoline hydrochloride (11.0 g, 51.25 mmol) in EtOAc (150 mL) at 0° C. in an ice bath add a solution of K2CO3 (15.65 g, 113.25 mmol) in water (150 mL) followed by benzyl chloroformate (8.37 mL, 56.37 mmol) and vigorously stir the reaction at room temperature for 24 h. Separate the layers and extract the aqeuous with more EtOAc (150 mL). Wash the organics with sat. NaHCO3 (200 mL), sat. NH4Cl (200 mL) and water (200 mL), then dry (Na2SO4). Concentrate in vacuo to give 14.70 g of 7-nitro-3,4-dihydro-1H-isoquinoline-2-carboxylic acid benzyl ester as an oil which partially crystallizes.

Workup

  1. customthe reaction at room temperature for 24 h
  2. customSeparate the layers
  3. extractionextract the aqeuous with more EtOAc (150 mL)
  4. washWash the organics with sat. NaHCO3 (200 mL), sat. NH4Cl (200 mL) and water (200 mL)
  5. dry with materialdry (Na2SO4)
  6. concentrationConcentrate in vacuo

Sources & evidence

ORD record
ord-3ae326eec657426ebaa0390190a2c4ad
Source dataset
uspto-grants-2015_07
Patent number
US09079880B2

Reaction notes

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