Sodium Carbonate → 1,4-bis(7-bromo-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazol-4-yl)benzene

HRID 1050681

反応式

HRID 1050681 の反応式
Br[C:2]1[C:10]2[C:6](=[N:7][N:8]([C:11]3[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=3)[N:9]=2)[C:5]([Br:17])=[CH:4][CH:3]=1.[C:18]1(B(O)O)[CH:23]=[CH:22][C:21](B(O)O)=[CH:20][CH:19]=1.C(=O)([O-])[O-].[Na+].[Na+].[OH-].[Na+]>O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1.C(O)CCC>[Br:17][C:5]1[C:6]2=[N:7][N:8]([C:11]3[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=3)[N:9]=[C:10]2[C:2]([C:18]2[CH:23]=[CH:22][C:21]([C:2]3[C:10]4[C:6](=[N:7][N:8]([C:11]5[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=5)[N:9]=4)[C:5]([Br:17])=[CH:4][CH:3]=3)=[CH:20][CH:19]=2)=[CH:3][CH:4]=1

参加物

9

反応物 4

HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 2304781,4-Benzenediboronic acidHCID 866799014,7-dibromo-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

生成物 1

HCID 866799041,4-bis(7-bromo-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazol-4-yl)benzene

試薬・触媒・溶媒 4

HCID 178418397HCID 178418397、化合物触媒HCID 2631-Butanol溶媒HCID 962Water溶媒2 回HCID 1140Toluene溶媒

反応条件

温度
110 °C

実験手順

A mixture of Intermediate A (90%, 2.40 g, 6.14 mmol), 1,4-benzenediboronic acid (248 mg, 1.5 mmol), sodium carbonate (530 g, 5 mmol) in water (4 mL), tetrakis(triphenylphosphine)palladium (0) (500 mg, 0.43 mmol), n-butanol (20 mL), and toluene (20 mL) was stirred and heated under argon at 110° C. for 68 hours. The reaction mixture was poured into water (300 mL), treated with 5N NaOH (50 mL), stirred for 1 hour, and extracted with dichloromethane (3×200 mL, low solubility in dichloromethane). The volatiles were removed under reduced pressure, and the residue was chromatographed (silica gel, chloroform/tetrahydrofuran 9:1). The obtained product was triturated with ethyl acetate (30 mL), filtered off and dried in a vacuum oven to give 1,4-bis(7-bromo-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazol-4-yl)benzene (Intermediate G), yellow crystals, 610 mg (purity 80%, yield 65%). 1H NMR (400 MHz, CDCl3): δ 8.86 (m, 4H, pyridine), 8.39 (m, 4H, pyridine), 8.26 (s, 4H, benzotriazole), 7.79 (d, J=7.7 Hz, 2H, benzene), 7.62 (d, J=7.7 Hz, 2H, benzene).

後処理

  1. stirringstirred for 1 hour
  2. extractionextracted with dichloromethane (3×200 mL, low solubility in dichloromethane)
  3. customThe volatiles were removed under reduced pressure
  4. customthe residue was chromatographed (silica gel, chloroform/tetrahydrofuran 9:1)
  5. customThe obtained product was triturated with ethyl acetate (30 mL)
  6. filtrationfiltered off
  7. customdried in a vacuum oven

出典と根拠

ORDレコード
ord-9255c0789fcb4f03a16a9e677ecb0aeb
出典データセット
uspto-grants-2016_07
特許番号
US09382424B2

関連ノート

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