Sodium Azide → HCID 178426092, compound

HRID 1472770Notes

Reaction equation

HRID 1472770 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[C:10]([C:21]#[N:22])[S:11][C:12]=2[C:13]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=2[CH3:20])=[C:4]([CH3:23])[CH:3]=1.[N-:24]=[N+:25]=[N-:26].[Na+]>[Br-].[Zn+2].[Br-]>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[C:10]([C:21]3[NH:24][N:25]=[N:26][N:22]=3)[S:11][C:12]=2[C:13]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=2[CH3:20])=[C:4]([CH3:23])[CH:3]=1

Participants

4

Reactant 2

HCID 33557Sodium AzideHCID 682936344,5-Bis(4-chloro-2-methylphenyl)thiophene-2-carbonitrile

Product 1

HCID 178426092HCID 178426092, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 10421208Zinc bromideCatalyst

Conditions

Temperature
110 °C

Procedure

A round-bottomed flask was charged with 4,5-bis(4-chloro-2-methylphenyl)thiophene-2-carbonitrile (600 mg, 1.67 mmol), zinc bromide (945 mg, 4.20 mmol) and sodium azide (273 mg, 4.20 mmol). After degassed, DMF (5 mL) was added. The reaction mixture was heated to 110° 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). 603 mg (90%) of product was obtained as a white solid, 1H NMR (DMSO, 500 MHz) δ 7.82 (s, 1H), 7.36 (d, J=2.04 Hz, 1H), 7.34 (d, J=1.94 Hz, 1H), 7.31 (d, J=8.25 Hz, 1H), 7.28 (dd, J1=8.26 Hz, J2=1.99 Hz, 1H), 7.17 (dd, J1=8.20 Hz, J2=2.05 Hz, 1H), 7.02 (d, J=8.28 Hz, 1H), 2.17 (s, 3H), 2.03 (s, 3H); 13C NMR (DMSO, 125 MHz) δ 140.58, 139.14, 139.12, 138.19, 133.59, 133.39, 132.94, 132.47, 131.71, 131.17, 130.57, 130.17, 130.11, 126.00, 125.80, 19.69, 19.57.

Workup

  1. customAfter degassed
  2. additionDMF (5 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-b70980c576cb4e259c4189f46ddbfd8d
Source dataset
uspto-grants-2015_04
Patent number
US09012655B2

Reaction notes

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