p-Toluenesulfonic acid → Etoposide

HRID 64605

反応式

HRID 64605 の反応式
[CH3:1][O:2][C:3]1[C:8]([OH:9])=[C:7]([O:10][CH3:11])[CH:6]=[C:5]([C@@H:12]2[C:25]3[C:20](=[CH:21][C:22]4[O:28][CH2:27][O:26][C:23]=4[CH:24]=3)[C@@H:19]([O:29][C@@H:30]3[O:35][C@H:34]([CH2:36][OH:37])[C@@H:33]([OH:38])[C@H:32]([OH:39])[C@H:31]3[OH:40])[C@H:14]3[CH2:15][O:16][C:17](=[O:18])[C@H:13]23)[CH:4]=1.[N+](C)([O-])=O.CO[CH:47](OC)[CH3:48].C1(C)C=CC(S(O)(=O)=O)=CC=1>O.C(Cl)(Cl)Cl.CO>[CH3:47][C@H:48]1[O:38][C@H:33]2[C@H:32]([OH:39])[C@@H:31]([OH:40])[C@H:30]([O:29][C@H:19]3[C@H:14]4[CH2:15][O:16][C:17](=[O:18])[C@@H:13]4[C@H:12]([C:5]4[CH:6]=[C:7]([O:10][CH3:11])[C:8]([OH:9])=[C:3]([O:2][CH3:1])[CH:4]=4)[C:25]4[CH:24]=[C:23]5[O:26][CH2:27][O:28][C:22]5=[CH:21][C:20]3=4)[O:35][C@@H:34]2[CH2:36][O:37]1

参加物

8

反応物 4

HCID 6101p-Toluenesulfonic acidHCID 6375NitromethaneHCID 107951,1-DimethoxyethaneHCID 1599494-Demethylepipodophyllotoxin 7'-O-beta-D-glucopyranoside

生成物 1

HCID 36462Etoposide

試薬・触媒・溶媒 3

HCID 887Methanol溶媒HCID 962Water溶媒HCID 6212Chloroform溶媒2 回

実験手順

1.5 g. of dry 4'-demethylepipodophyllotoxin-beta-D-glucoside was suspended in 30 ml. of nitromethane, and 6 ml. of acetaldehyde-dimethylacetal and 150 mg. of p-toluene-sulphonic acid was added. The mixture was stirred at room temperature in an atmosphere of nitrogen and in the absence of moisture for one hour. After this time, the initial suspension had turned into a clear solution, and no starting material could be detected in the thin layer chromatogram (silica gel plates, eluant: chloroform+6% of methanol). Working up was effected by diluting with 400 ml. of chloroform and shaking out three times with 25 ml. each of water. The crude material obtained after concentrating the dried organic phase by evaporation was subsequently chromatographed on 100 g. of silica gel "Merck" (grain size 0.05 to 0.2 mm.), whereby chloroform containing 6% of methanol was continuously used as eluant. 4'-demethylepipodophyllotoxin-beta-D-ethylidene-glucoside, which is uniform according to thin layer chromatography, was obtained. After recrystallization from methanol colorless crystals having a M.P. of 236°-251° C., [α ]D22 =-110.5° (c.=0.588 in chloroform), were obtained.

後処理

  1. additionby diluting with 400 ml
  2. customThe crude material obtained
  3. concentrationafter concentrating the dried organic phase
  4. customby evaporation
  5. customwas subsequently chromatographed on 100 g
  6. customwas obtained
  7. customAfter recrystallization from methanol colorless crystals
  8. custom[α ]D22 =-110.5° (c.=0.588 in chloroform), were obtained

出典と根拠

ORDレコード
ord-eb2ee955085243c680971b0331a05f57
出典データセット
uspto-grants-1986_09
特許番号
US04609644

関連ノート

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