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

HRID 1472773ノート

反応式

HRID 1472773 の反応式
[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

参加物

4

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 10421208Zinc bromide触媒

反応条件

温度
110 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-66d7deb3ad7645bd975067133c23edc0
出典データセット
uspto-grants-2015_04
特許番号
US09012655B2

反応ノート

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