Trichloroacetonitrile → (3S,4aR,4bS,6S,8R,8aR,10aR)-3-Furan-3-yl-4a,8a-dimethyl-1,5-dioxo-6-(2,2,2-trichloro-acetimidoyloxy)-dodecahydro-2-oxa-phenanthrene-8-carboxylic acid methyl ester

HRID 12318

反応式

HRID 12318 の反応式
[CH3:1][O:2][C:3]([C@@H:5]1[CH2:18][C@H:17]([OH:19])[C:16](=[O:20])[C@H:15]2[C@@:6]1([CH3:28])[CH2:7][CH2:8][C@H:9]1[C@:14]2([CH3:21])[CH2:13][C@@H:12]([C:22]2[CH:26]=[CH:25][O:24][CH:23]=2)[O:11][C:10]1=[O:27])=[O:4].[Cl:29][C:30]([Cl:34])([Cl:33])[C:31]#[N:32]>ClC(Cl)C>[CH3:1][O:2][C:3]([C@@H:5]1[CH2:18][C@H:17]([O:19][C:31](=[NH:32])[C:30]([Cl:34])([Cl:33])[Cl:29])[C:16](=[O:20])[C@H:15]2[C@@:6]1([CH3:28])[CH2:7][CH2:8][C@@H:9]1[C@:14]2([CH3:21])[CH2:13][C@@H:12]([C:22]2[CH:26]=[CH:25][O:24][CH:23]=2)[O:11][C:10]1=[O:27])=[O:4]

参加物

4

反応物 2

HCID 11011TrichloroacetonitrileHCID 11395172(2S,4aS,6aR,7R,9S,10aS,10bR)-9-(hydroxy)-2-(3-furanyl)dodecahydro-6a,10b-dimethyl-4,10-dioxo-2H-naphtho[2,1-c]pyran-7-carboxylic acid methyl ester

生成物 1

HCID 11341622(3S,4aR,4bS,6S,8R,8aR,10aR)-3-Furan-3-yl-4a,8a-dimethyl-1,5-dioxo-6-(2,2,2-trichloro-acetimidoyloxy)-dodecahydro-2-oxa-phenanthrene-8-carboxylic acid methyl ester収率 37%

試薬・触媒・溶媒 1

HCID 63651,1-Dichloroethane溶媒

実験手順

A solution of 8a (0.05 g, 0.13 mmol), trichloroacetonitrile (0.1 mL, 1.0 mmol), 1,8-Diazobicylo[5.4.0]undec-7-ene (0.05 mL, 0.3 mmol) in dichloroethane (20 mL) was stirred at 0° C. for 24 h. The reaction mixture was then washed with saturated NaHCO3 (10 mL) and H2O (10 mL) and dried (Na2SO4). The solvent was removed under reduced pressure to give a crude oil. The oil was purified by column chromatography (eluent: ethyl acetate/n-hexanes) to afford 21 (0.02 g, 37%) as a white solid, mp 120-123° C.; 1H NMR (CDCl3): δ 1.18 (s, 3H); 1.50 (s, 3H); 1.52-1.76 (m, 4H); 1.85 (dd, Ja=2.6, Jb=10.1, 1H); 2.10 (dd, Ja=2.9, Jb=11.6, 1H); 2.20 (m, 1H); 2.24 (s, 1H); 2.35-2.58 (m, 3H); 2.80 (dd, Ja=4.1, Jb=12.5, 1H); 3.75 (s, 3H); 5.34 (dd, Ja=7.7, Jb=12.2, 1H); 6.40 (dd, Ja=0.9, Jb=1.5, 1H); 7.41 (dd, 1H, 1.5, 1.5, 1H); 7.43 (dd, Ja=0.9, Jb=1.5, 1H); 8.38 (s, 1H).

後処理

  1. washThe reaction mixture was then washed with saturated NaHCO3 (10 mL) and H2O (10 mL)
  2. dry with materialdried (Na2SO4)
  3. customThe solvent was removed under reduced pressure
  4. customto give a crude oil
  5. customThe oil was purified by column chromatography (eluent: ethyl acetate/n-hexanes)

出典と根拠

ORDレコード
ord-aa8df4840fe94da7921b80707f1ba252
出典データセット
uspto-grants-2010_06
特許番号
US07728001B2

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