Sodium Hydroxide → 1-methyl-5-(3-nitrophenyl)-1H-Tetrazole

HRID 1454243Notes

Reaction equation

HRID 1454243 reaction equation
[CH3:1][NH:2][C:3](=O)[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([N+:10]([O-:12])=[O:11])[CH:5]=1.[N-:14]=[N+:15]=[N-:16].[Na+].FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.[OH-].[Na+]>C(#N)C>[CH3:1][N:2]1[C:3]([C:4]2[CH:9]=[CH:8][CH:7]=[C:6]([N+:10]([O-:12])=[O:11])[CH:5]=2)=[N:16][N:15]=[N:14]1

Participants

6

Reactant 4

HCID 14798Sodium HydroxideHCID 33557Sodium AzideHCID 67749Trifluoromethanesulfonic anhydrideHCID 221964N-methyl-3-nitrobenzamide

Product 1

HCID 140450781-methyl-5-(3-nitrophenyl)-1H-TetrazoleYield 54%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
0 °C

Procedure

N-Methyl-3-nitro-benzamide (30.0 g, 167 mmol) was dissolved in acetonitrile (835 mL). Upon dissolution, sodium azide (10.9 g, 167 mmol) was added. The mixture was cooled in an ice bath, and trifluoromethanesulfonic anhydride (29 mL, 172 mmol) was added dropwise at a rate to maintain the reaction temperature below 3° C. The reaction mixture was stirred for 3.5 hours at 0° C. and then poured into 1N aqueous sodium hydroxide (100 mL). The organic layer was separated, dried over sodium sulfate and concentrated under vacuum to 50 mL. The solution was diluted with dichloromethane and water was added. The resuling precipitate was isolated by filtration to give a yellow solid (18.46 g, 54%). The filtrate was concentrated in vacuo and added to boiling ethyl acetate to give a second crop of crystals. Upon cooling to 0° C., additional material (6.07 g, 18%) was isolated by filtration. 1H NMR (300 MHz, CDCl3), δ8.67 (m, 1H), 8.49 (dd, J=8, 2 Hz, 1H), 8.31 (d, J=8 Hz, 1H), 7.94 (dd, J=8, 8 Hz, 1H), 4.22 (s, 3H).

Workup

  1. additionwas added
  2. temperatureThe mixture was cooled in an ice bath
  3. temperatureto maintain the reaction temperature below 3° C
  4. customThe organic layer was separated
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated under vacuum to 50 mL
  7. additionThe solution was diluted with dichloromethane and water
  8. additionwas added
  9. customThe resuling precipitate was isolated by filtration

Sources & evidence

ORD record
ord-e7d543e1f6f941d6b3a0b7ed3a09bc5c
Source dataset
uspto-grants-2009_01
Patent number
US07479496B2

Reaction notes

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