Potassium Carbonate → N,N-di(2-pyridyl)-N',N'-di(4-pyridyl)-1,4-phenylenediamine

HRID 242766

反応式

HRID 242766 の反応式
[CH:1]1[CH:6]=[C:5]([NH:7][C:8]2[N:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[N:4]=[CH:3][CH:2]=1.Br[C:15]1[CH:20]=[CH:19][C:18]([N:21]([C:28]2[CH:33]=[CH:32][N:31]=[CH:30][CH:29]=2)[C:22]2[CH:27]=[CH:26][N:25]=[CH:24][CH:23]=2)=[CH:17][CH:16]=1.C(=O)([O-])[O-].[K+].[K+].C1OCCOCCOCCOCCOCCOC1>CN(C=O)C>[N:13]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[N:7]([C:5]1[CH:6]=[CH:1][CH:2]=[CH:3][N:4]=1)[C:15]1[CH:16]=[CH:17][C:18]([N:21]([C:28]2[CH:33]=[CH:32][N:31]=[CH:30][CH:29]=2)[C:22]2[CH:23]=[CH:24][N:25]=[CH:26][CH:27]=2)=[CH:19][CH:20]=1

参加物

6

反応物 4

HCID 11430Potassium CarbonateHCID 145472,2'-DipyridylamineHCID 2855718-Crown-6HCID 68181005(4-Bromophenyl)-di(4-pyridyl)amine

生成物 1

HCID 68180746N,N-di(2-pyridyl)-N',N'-di(4-pyridyl)-1,4-phenylenediamine収率 41.2%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
145 °C

実験手順

A mixture of 2,2′-dipyridylamine (5.27 g, 30.76 mmol), (4-bromophenyl)-di(4-pyridyl)amine (2.50 g, 7.69 mmol), anhydrous potassium carbonate (2.66 g, 19.23 mmol), bronze powder (4.93 g, 77.64 mmol), 18-crown-6 (200 mg, 0.76 mmol), and DMF (125 mL) was heated at 145 degrees C. under nitrogen for 30 hours. The reaction was cooled and worked up by a procedure similar to that for L1. A yellowish solid was collected from a silica gel column, and was further purified by recrystallization from dichloromethane and petroleum ether, to afford a white solid of N,N-di(2-pyridyl)-N′,N′-di(4-pyridyl)-1,4-phenylenediamine (L2, 1.32 g, yield: 41%). 1H NMR (CDCl3, Bruker 400 MHz): 8.43 (d, J=4.4 Hz, 4H, pyridyl-H), 8.37 (d, J=3.6 Hz, 2H, pyridyl-H), 7.60-7.65 (m, 2H, pyridyl-H), 7.21 (d, J=8.8 Hz, 2H, phenylene-H), 7.14 (d, J=8.8 Hz, 2H, phenylene-H), 6.98-7.09 (m, 8H, pyridyl-H). Anal. Calcd (%) for C26H20N6: C, 74.98; H, 4.84; N, 20.18. Found: C, 74.53; H, 4.72; N, 19.89. IR (KBr pellet, cm−1): 1575(vs), 1505(s), 1490(s), 1467(s), 1431(vs), 1324(s), 1305.13 (s), 1276(s), 1218(m), 1163(w), 1103(w), 991(m), 811(m), 777(m), 737(w), 654(w), 622(m), 530(m).

後処理

  1. temperatureThe reaction was cooled
  2. customA yellowish solid was collected from a silica gel column
  3. customwas further purified by recrystallization from dichloromethane and petroleum ether

出典と根拠

ORDレコード
ord-78ebc610cdc3456cbd75251026448c5a
出典データセット
uspto-grants-2014_02
特許番号
US08653230B2

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