Sodium Azide → HCID 178423696, compound

HRID 1472782Notes

Reaction equation

HRID 1472782 reaction equation
[Cl:1][C:2]1[CH:26]=[CH:25][C:5]([CH2:6][C:7]2[S:11][C:10]([C:12]#[N:13])=[CH:9][C:8]=2[C:14]2[C:23]3[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=3)[C:17]([CH3:24])=[CH:16][CH:15]=2)=[CH:4][CH:3]=1.[N-:27]=[N+:28]=[N-:29].[Na+]>[Br-].[Zn+2].[Br-]>[Cl:1][C:2]1[CH:26]=[CH:25][C:5]([CH2:6][C:7]2[S:11][C:10]([C:12]3[NH:29][N:28]=[N:27][N:13]=3)=[CH:9][C:8]=2[C:14]2[C:23]3[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=3)[C:17]([CH3:24])=[CH:16][CH:15]=2)=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 33557Sodium AzideHCID 68293606HCID 68293606, compound

Product 1

HCID 178423696HCID 178423696, compoundYield 85.8%

Reagents, catalysts & solvents 1

HCID 10421208Zinc bromideCatalyst

Conditions

Temperature
110 °C

Procedure

A round-bottomed flask was charged with 5-(4-chlorobenzyl)-4-(4-methylnaphthalen-1-yl)thiophene-2-carbonitrile (170 mg, 0.45 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 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). 161 mg (85%) of product was obtained as a white solid, 1H NMR (CDCl3, 500 MHz) δ 8.05 (d, J=8.46 Hz, 1H), 7.73 (s, 1H), 7.63 (d, J=8.36 Hz, 1H), 7.53 (t, J=7.58 Hz, 1H), 7.42 (t, J=7.53 Hz, 1H), 7.33 (d, J=7.11 Hz, 1H), 7.23 (d, J=7.08 Hz, 1H), 7.14 (d, J=8.25 Hz, 2H), 6.92 (d, J=8.14 Hz, 2H), 3.86 (ABq, 2H, ΔδAB=0.06, JAB=15.90 Hz), 2.70 (s, 3H); 13C NMR (CDCl3, 125 MHz) δ 152.61, 145.54, 139.59, 137.96, 135.22, 132.97, 132.76, 132.69, 132.27, 131.09, 130.05, 128.81, 127.55, 126.33, 126.25, 126.20, 126.16, 124.75, 122.29, 34.24, 19.77.

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-824afcca68dc4f309f4df1275616a98a
Source dataset
uspto-grants-2015_04
Patent number
US09012655B2

Reaction notes

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