Sodium Azide → 5-(4-(4-Chloro-2-methylphenyl)-5-(4-methylnaphthalen-1-yl)thiophen-2-yl)-1H-tetrazole

HRID 1472773Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1472773
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[C:10]([C:24]#[N:25])[S:11][C:12]=2[C:13]2[C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[C:16]([CH3:23])=[CH:15][CH:14]=2)=[C:4]([CH3:26])[CH:3]=1.[N-:27]=[N+:28]=[N-:29].[Na+]>[Br-].[Zn+2].[Br-]>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[C:10]([C:24]3[NH:29][N:28]=[N:27][N:25]=3)[S:11][C:12]=2[C:13]2[C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[C:16]([CH3:23])=[CH:15][CH:14]=2)=[C:4]([CH3:26])[CH:3]=1

Komponenten

4

Edukt 2

HCID 33557Sodium AzideHCID 682936984-(4-Chloro-2-methylphenyl)-5-(4-methylnaphthalen-1-yl)thiophene-2-carbonitrile

Produkt 1

HCID 1784260915-(4-(4-Chloro-2-methylphenyl)-5-(4-methylnaphthalen-1-yl)thiophen-2-yl)-1H-tetrazoleAusbeute 84 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 10421208Zinc bromideKatalysator

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

A round-bottomed flask was charged with 4-(4-chloro-2-methylphenyl)-5-(4-methylnaphthalen-1-yl)thiophene-2-carbonitrile (209 mg, 0.56 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). 196 mg (84%) of product was obtained as a white solid, 1H NMR (DMSO, 500 MHz) δ 8.03 (d, J=8.40 Hz, 1H), 7.88 (s, 1H), 7.80 (d, J=8.05 Hz, 1H), 7.55 (t, J=7.68 Hz, 1H), 7.48 (t, J=7.65 Hz, 1H), 7.45 (d, J=7.19 Hz, 1H), 7.37 (d, J=7.30 Hz, 1H), 7.23 (d, J=1.95 Hz, 1H), 7.09 (d, J=8.25 Hz, 1H), 7.04 (dd, J=8.25 Hz, J2=2.06 Hz, 1H), 2.65 (s, 3H), 2.17 (s, 3H); 13C NMR (DMSO, 125 MHz) δ 172.05, 141.01, 139.65, 138.35, 135.93, 133.73, 132.18, 132.10, 131.64, 131.31, 131.26, 129.80, 129.23, 127.62, 126.45, 126.26, 126.02, 125.53, 125.51, 124.67, 21.08, 19.82.

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-66d7deb3ad7645bd975067133c23edc0
Quelldatensatz
uspto-grants-2015_04
Patentnummer
US09012655B2

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