Sodium Azide → HCID 178422382, compound

HRID 1472788Notes

Reaction equation

HRID 1472788 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]([CH3:25])=[C:10]([C:23]#[N:24])[S:11][C:12]=2[C:13]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=2[CH:20]([CH3:22])[CH3:21])=[C:4]([CH:26]([CH3:28])[CH3:27])[CH:3]=1.[N-:29]=[N+:30]=[N-:31].[Na+]>[Br-].[Zn+2].[Br-]>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]([CH3:25])=[C:10]([C:23]3[NH:31][N:30]=[N:29][N:24]=3)[S:11][C:12]=2[C:13]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=2[CH:20]([CH3:22])[CH3:21])=[C:4]([CH:26]([CH3:28])[CH3:27])[CH:3]=1

Participants

4

Reactant 2

HCID 33557Sodium AzideHCID 68293613HCID 68293613, compound

Product 1

HCID 178422382HCID 178422382, compoundYield 91%

Reagents, catalysts & solvents 1

HCID 10421208Zinc bromideCatalyst

Conditions

Temperature
130 °C

Procedure

A round-bottomed flask was charged with 4,5-bis(4-chloro-2-isopropylphenyl)-3-methylthiophene-2-carbonitrile (190.5 mg, 0.44 mmol), zinc bromide (338 mg, 1.50 mmol) and sodium azide (97.5 mg, 1.50 mmol). After degassed, DMF (3 mL) was added. The reaction mixture was heated to 130° C. and stirred at this temperature until complete. The reaction was cooled to rt and 30 mL of 0.1 N aqueous HCl was added. The reaction mixture was extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulphate and then concentrated. The residue was purified by flash chromatography (hexane:EtOAc:AcOH=30:10:1). 188.7 mg (90%) of product was obtained as a white solid, 1H NMR (CDCl3, 500 MHz) δ 7.25-7.22 (m, 2H), 7.18 (dd, J1=8.18 Hz, J2=2.13 Hz, 1H), 7.09-7.06 (m, 2H), 7.02 (d, J=8.20 Hz, 1H), 3.04 (sep, J=6.75 Hz, 1H), 2.74 (sep, J=6.80 Hz, 1H), 2.37 (s, 3H), 1.12 (d, J=6.80 Hz, 3H), 1.05 (d, J=6.80 Hz, 6H), 0.90 (d, J=6.80 Hz, 3H); 13C NMR (CDCl3, 125 MHz) δ 150.32, 149.87, 141.11, 140.81, 140.72, 135.33, 134.47, 132.72, 132.02, 131.51, 129.01, 126.30, 126.20, 125.84, 125.52, 30.35, 30.10, 24.76, 23.60, 23.13, 15.78.

Workup

  1. customAfter degassed
  2. additionDMF (3 mL) was added
  3. temperatureThe reaction was cooled to rt
  4. addition30 mL of 0.1 N aqueous HCl was added
  5. extractionThe reaction mixture was extracted with ethyl acetate
  6. dry with materialThe organic phase was dried over anhydrous sodium sulphate
  7. concentrationconcentrated
  8. customThe residue was purified by flash chromatography (hexane:EtOAc:AcOH=30:10:1)

Sources & evidence

ORD record
ord-e473018213de4f9e9a4e092fb0863e65
Source dataset
uspto-grants-2015_04
Patent number
US09012655B2

Reaction notes

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