Sodium Azide → Racemic 6-azido-5-oxo-5,6,7,8-tetrahydronaphthalene-2-carbonitrile

HRID 470586Notes

Reaction equation

HRID 470586 reaction equation
Br[CH:2]1[CH2:11][CH2:10][C:9]2[CH:8]=[C:7]([C:12]#[N:13])[CH:6]=[CH:5][C:4]=2[C:3]1=[O:14].[N-:15]=[N+:16]=[N-:17].[Na+]>CN(C=O)C.C(O)(=O)C.O>[N:15]([CH:2]1[CH2:11][CH2:10][C:9]2[CH:8]=[C:7]([C:12]#[N:13])[CH:6]=[CH:5][C:4]=2[C:3]1=[O:14])=[N+:16]=[N-:17]

Participants

6

Reactant 2

HCID 33557Sodium AzideHCID 675113086-Bromo-5-oxo-5,6,7,8-tetrahydronaphthalene-2-carbonitrile

Product 1

HCID 89799662Racemic 6-azido-5-oxo-5,6,7,8-tetrahydronaphthalene-2-carbonitrileYield 41.2%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a solution of racemic 6-bromo-5-oxo-5,6,7,8-tetrahydronaphthalene-2-carbonitrile (100 mg, 0.4 mmol) in DMF (2611 mL) and acetic acid (65.3 mL) was added a solution of sodium azide (52.0 mg, 0.8 mmol) in water (522 mL) dropwise at 0° C. After 1 hour, the reaction was complete. The mixture was directly loaded to a 24 g ISCO column and purified by ISCO Combiflash Companion (0% ethyl acetate-hexane for 3 min then ramped to 20% ethyl acetate-hexane over 7 min then 20% ethyl acetate-hexane for 5 more minutes. The product came out 8-10 min) to afford racemic 6-azido-5-oxo-5,6,7,8-tetrahydronaphthalene-2-carbonitrile (35 mg, 0.16 mmol, 41.2%) as a white solid: LCMS=213.22 [M+H]+.

Workup

  1. custompurified by ISCO Combiflash Companion (0% ethyl acetate-hexane for 3 min
  2. waitthen ramped to 20% ethyl acetate-hexane over 7 min
  3. waitThe product came out 8-10 min

Sources & evidence

ORD record
ord-247b44a0422343d797d664b20b28e6da
Source dataset
uspto-grants-2014_01
Patent number
US08629282B2

Reaction notes

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