Benzaldehyde → 3-Amino-2-phenylpyridine

HRID 429518ノート

反応式

HRID 429518 の反応式
ClC1C(N)=CC=CN=1.C(=O)C1C=CC=CC=1.[CH:17](=[N:24][C:25]1C(Cl)=[N:27][CH:28]=[CH:29][CH:30]=1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.C1(B(O)O)C=CC=CC=1.C(=O)([O-])[O-].[Na+].[Na+].[OH-].[Na+]>C1(C)C=CC=CC=1.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>[C:18]1([C:17]2[C:28]([NH2:27])=[CH:29][CH:30]=[CH:25][N:24]=2)[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1

参加物

10

反応物 6

HCID 240BenzaldehydeHCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 66827Phenylboronic AcidHCID 805282-Chloro-3-pyridylamineHCID 11390312Benzylidene-(2-chloro-pyridin-3-yl)-amine

生成物 1

HCID 27627843-Amino-2-phenylpyridine

試薬・触媒・溶媒 3

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

実験手順

To 2-chloro-3-aminopyridine (1.06 g, 8.24 mmol) in toluene (25 mL) was added benzaldehyde (0.878 g, 8.27 mmol). The reaction mixture was stirred at reflux in a Dean-Stark apparatus until GC/MS analysis of the reaction mixture no longer showed starting material. The reaction mixture was cooled to room temperature and the toluene solution containing benzylidene-(2-chloro-pyridin-3-yl)-amine was added to a mixture of phenylboronic acid (1.30 g, 10.7 mmol), sodium carbonate (2.66 g, 25.1 mmol), and tetrakis(triphenylphosphine)palladium(0) (47 mg, 0.38mol %) in water (10 mL). The reaction mixture was heated to 100° C. for 30 minutes, cooled to room temperature and poured into 1N aqueous sodium hydroxide (10 mL). The aqueous layer was removed and the toluene layer was extracted with 1N aqueous hydrochloric acid (twice with 15 mL). The aqueous layer was neutralized to pH 12 with 6N aqueous sodium hydroxide and extracted with MTBE (twice with 20 mL). The MTBE extracts were dried over magnesium sulfate, filtered and concentrated to afford 2-phenyl-3-aminopyridine as a solid which crystallized from diisopropyl ether (1.26 g, 90% yield). M. p.=87-68° C. 1H NMR (300 MHz, CDCl3) δ3.88 (bs, 2), 7.02-7.11 (m, 2), 7.28-7.53 (m, 3), 7.6714 7.71 (m, 2), 8.13-8.16 (m, 1). 13C NMR (100 MHz, CDCl3) δ122.57, 122.96, 128.14, 128.38, 128.72, 138.54, 139.86, 139.93, 144.93.

後処理

  1. temperatureat reflux in a Dean-Stark apparatus until GC/MS analysis of the reaction mixture
  2. temperatureThe reaction mixture was heated to 100° C. for 30 minutes
  3. temperaturecooled to room temperature
  4. customThe aqueous layer was removed
  5. extractionthe toluene layer was extracted with 1N aqueous hydrochloric acid (twice with 15 mL)
  6. extractionextracted with MTBE (twice with 20 mL)
  7. dry with materialThe MTBE extracts were dried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated

出典と根拠

ORDレコード
ord-e31ee0a058e9476c8a92978c45732d6a
出典データセット
uspto-grants-2001_11
特許番号
US06316632B1

反応ノート

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