Triethylamine → 4-Ethylthio-3-(3-methanesulfonyloxy-1-propyl)-5-(4-methyl-1,2-dioxocyclobut-3-en-3-yl)amino indole

HRID 441102ノート

反応式

HRID 441102 の反応式
[CH2:1]([S:3][C:4]1[C:12]([NH:13][C:14]2[C:15](=[O:20])[C:16](=[O:19])[C:17]=2[CH3:18])=[CH:11][CH:10]=[C:9]2[C:5]=1[C:6]([CH2:21][CH2:22][CH2:23][OH:24])=[CH:7][NH:8]2)[CH3:2].CCN(CC)CC.[CH3:32][S:33](Cl)(=[O:35])=[O:34]>C1COCC1.C(Cl)Cl.C(Cl)Cl>[CH2:1]([S:3][C:4]1[C:12]([NH:13][C:14]2[C:15](=[O:20])[C:16](=[O:19])[C:17]=2[CH3:18])=[CH:11][CH:10]=[C:9]2[C:5]=1[C:6]([CH2:21][CH2:22][CH2:23][O:24][S:33]([CH3:32])(=[O:35])=[O:34])=[CH:7][NH:8]2)[CH3:2]

参加物

6

反応物 3

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 224057163-(4-Ethylthio-5-(4-methyl-1,2-dioxocyclobut-3-en-3-yl)amino-3-indolyl)1-propanol

生成物 1

HCID 224056664-Ethylthio-3-(3-methanesulfonyloxy-1-propyl)-5-(4-methyl-1,2-dioxocyclobut-3-en-3-yl)amino indole

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 21919333Tetrahydrofurane dichloromethane溶媒

反応条件

温度
23 °C

実験手順

A cold (5° C.) mixture of 3-(4-ethylthio-5-(4-methyl-1,2-dioxocyclobut-3-en-3-yl) amino-3-indolyl)1-propanol (0.708 g, 2.1 mmol) and Et3N (0.697 ml, 5.0 mmol) in THF:CH2Cl2 (1:2, 45 ml) mixture kept under argon atm. was treated dropwise with MsCl (0.387 ml, 5.0 mmol) and stirred at 23° C. for 1.5 h. The reaction mixture was diluted with CH2Cl2 (40ml) and washed with H2O (10ml) and saturated NaHCO3 solution. The organic phase was dried (MgSO4) and concentrated in vacuo. The crude material was purified on silica gel dry column using a mixture of CH2Cl2 :EtOAc (7.3) as eluting solvent. Appropriate fractions were concentrated in vacuo giving a yellow oil, 0.70 g, 79%. 1H NMR (DMSO-d6) δ (ppm): 11.26, 11.20, 10.81 and 10.53 (4 br s, 2H, indolic NH and 5-NH), 7.42 (br s, 1H), 7.32 (s, 1H), 7.09 (d, J=8.2 Hz, 1H), 4.27 (t, J=6.4 Hz, 2H, CH2OSO2), 3.17 (s, 3H, CH3SO2), 3.11 (t, J=7 Hz, 2H, CH2CH2CH2O), 2.67 (br s, 2H, CH3CH2S), 2.28 (br, s, 1H, CH3 of dioxocyclobutene), 2.0-2.15 (m, 2H, CH2CH2CH2O), 1.59 (br s, 2H CH3 of dioxocyclobutene), 0.9-1.1 (m, 3H, CH3CH2S). IR (film) n:3710, 3180, 1783, 1728, 1590, 1340 and 1170 cm-1.

後処理

  1. washwashed with H2O (10ml) and saturated NaHCO3 solution
  2. dry with materialThe organic phase was dried (MgSO4)
  3. concentrationconcentrated in vacuo
  4. customThe crude material was purified on silica gel
  5. customdry column
  6. additiona mixture of CH2Cl2
  7. washEtOAc (7.3) as eluting solvent
  8. concentrationAppropriate fractions were concentrated in vacuo
  9. customgiving a yellow oil, 0.70 g, 79%

出典と根拠

ORDレコード
ord-d52bd4e513cb4a59a20f3a78ffee7fff
出典データセット
uspto-grants-1996_05
特許番号
US05521188

反応ノート

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