Dimethylformamide → HCID 18787036, compound

HRID 1107292Notes

Reaction equation

HRID 1107292 reaction equation
[H-].[Na+].[Br:3][C:4]1[CH:9]=[C:8]([C:10]2[NH:14][N:13]=[N:12][N:11]=2)[CH:7]=[CH:6][C:5]=1[O:15][CH3:16].[CH3:17]N(C)C=O>O>[Br:3][C:4]1[CH:9]=[C:8]([C:10]2[N:11]=[N:12][N:13]([CH3:17])[N:14]=2)[CH:7]=[CH:6][C:5]=1[O:15][CH3:16]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 24758Sodium hydrideHCID 178489164HCID 178489164, compound

Product 1

HCID 18787036HCID 18787036, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A mixture of 3-bromo-4-methoxybenzonitrile (9 g, 42 mmol), sodium azide (3.03 g, 46.7 mmol) and ammonium chloride (2.5 g, 46.7 mmol) in N,N-dimethylforlmamide (50 ml) was heated at 90° C. for 18 hours. The reaction was cooled, poured onto ice (200 ml) and acidified with 1N HCl to pH1. The resultant solid was filtered, dried and recrystallized from ethanol/water to give 2-bromo-4-(tetrazol-5-yl)anisole (9.2 g). 1H NMR 360 MHz, DMSO-d6) δ 3.95 (3H, s), 7.35 (1H, d, J=8.6 Hz), 8.05 (1H, d, =8.6 Hz), 8.23 (1H, s). To a suspension of sodium hydride (60% dispersed, 1.5 g, 37 mmol) in N,N-dimethylformamide was added the foregoing anisole (5 g, 32.5 mmol) and the reaction stirred at room temperature for 2 hours. The reaction was diluted with water (70 ml) and the resultant solid filtered, dried and chromatographed on silica eluting with 60% ethyl acetate/hexane to give 2-bromo-4-(2-methyltetrazol-5-yl)anisole (3.2 g), 1H NMR (360 MHz, CDCl3) δ 3.97 (3H, s), 4.39 (3H, s), 7.00 (1H, d, J=12.4 Hz), 8.07 (1H, dd, J=12.4 and 3.0 Hz), 8.34 (1H, d, J=3.0 Hz); and 2-bromo-4-(1-methyltetrazol-5-yl)anisole (0.8 g), 1H NMR (360 MHz, CDCl3) δ 3.94 (3H, s), 4.13 (3H, s), 7.01 (1H, d, J=8.6 Hz), 7.66 (1H, dd, J=8.6 and 2.2 Hz), 7.90 (1H, d, J=2.2 Hz).

Workup

  1. filtrationthe resultant solid filtered
  2. customdried
  3. customchromatographed on silica eluting with 60% ethyl acetate/hexane

Sources & evidence

ORD record
ord-092e1384fa6e41009eb61dd012f5cdfe
Source dataset
uspto-grants-2000_05
Patent number
US06060469

Reaction notes

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