Ethylenediamine → N-methyl-N-(3-styryl-1H-indazol-6-yl)-benzene-1,3-diamine

HRID 1861070ノート

反応式

HRID 1861070 の反応式
[CH3:1][N:2]([C:10]1[CH:18]=[C:17]2[C:13]([C:14]([CH:27]=[CH:28][C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)=[N:15][N:16]2COCC[Si](C)(C)C)=[CH:12][CH:11]=1)[C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([NH2:9])[CH:4]=1.CCCC[N+](CCCC)(CCCC)CCCC.[F-].C1COCC1.C(N)CN>>[CH3:1][N:2]([C:10]1[CH:18]=[C:17]2[C:13]([C:14]([CH:27]=[CH:28][C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)=[N:15][NH:16]2)=[CH:12][CH:11]=1)[C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([NH2:9])[CH:4]=1

参加物

5

反応物 4

HCID 3301EthylenediamineHCID 8028TetrahydrofuranHCID 2724141Tetrabutylammonium FluorideHCID 69369951HCID 69369951、化合物

生成物 1

HCID 69370903N-methyl-N-(3-styryl-1H-indazol-6-yl)-benzene-1,3-diamine収率 70.5%

反応条件

温度
70 °C

実験手順

To N-methyl-N-{3-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazol-6-yl}-benzene-1,3-diamine (237 mg, 0.5 mmol) was added 1M TBAF in THF (10.1 mL, 10.1 mmol), followed by ethylenediamine (0.34 mL, 5.04 mmol, 10 equiv). The resulting mixture was heated to 70° C. for 5 h. The reaction was then quenched with saturated NaHCO3 (10 mL) and extracted 3×35 mL EtOAc. The pooled EtOAc phase was washed 5×20 mL H2O, then brine (20 mL), dried with Na2SO4, decanted and concentrated under reduced pressure to a foam. The crude material was purified by silica gel chromatography (9:1 dichloromethane/ethyl acetate) to give N-methyl-N-(3-styryl-1H-indazol-6-yl)-benzene-1,3-diamine as a foam (120 mg, 70% yield). Rf sm 0.73, Rf p 0.27 (dichloromethane:ethylacetate 7:3); 13C NMR (75 MHz, CDCl3) δ 150.3, 148.8, 147.5, 147.5, 143.9, 143.4, 137.5, 131.1, 130.3, 129.3, 128.9, 128.2, 127.9, 126.7, 121.0, 120.5, 117.0, 116.0, 112.6, 109.8, 109.0, 98.3, 40.7; LCMS (ESI) [M+H]/z Calc'd 341, Found 341. Anal. Calc'd: C, 77.62; H, 5.92; N, 16.46. Found: C, 76.16; H, 5.88; N, 15.95.

後処理

  1. customThe reaction was then quenched with saturated NaHCO3 (10 mL)
  2. extractionextracted 3×35 mL EtOAc
  3. washThe pooled EtOAc phase was washed 5×20 mL H2O
  4. dry with materialbrine (20 mL), dried with Na2SO4
  5. customdecanted
  6. concentrationconcentrated under reduced pressure to a foam
  7. customThe crude material was purified by silica gel chromatography (9:1 dichloromethane/ethyl acetate)

出典と根拠

ORDレコード
ord-ac236768194d484b9fa98c44bbc10d95
出典データセット
uspto-grants-2003_03
特許番号
US06531491B1

反応ノート

読み込み中…