Tetrahydrofuran → 20-(5,5-Dimethyl-1,3-dioxan-2-yl)-1alpha, 2alpha-epoxy-7alpha-hydroxypregna-5-en-3beta-yl acetate

HRID 1708748ノート

反応式

HRID 1708748 の反応式
C(P(C[CH2:11][CH2:12][CH3:13])CCCC)CCC.[CH:14]([O-])=[O:15].[NH4+].[C:18]([O:21][C@H:22]1[CH2:40][CH2:39][C@@:38]2([CH3:41])[C:24]3[C@:25]4(O[C:23]1=3)[O:43][C@H:26]4[C@@H:27]1[C@@H:37]2[CH2:36][CH2:35][C@@]2(C)[C@H]1CC[C@@H]2CC)(=[O:20])[CH3:19].C(OCC)(=[O:47])C.[CH3:51][CH2:52][CH2:53][CH2:54][CH2:55][CH3:56].[O:57]1[CH2:61][CH2:60][CH2:59][CH2:58]1>C(Cl)Cl>[C:18]([O:21][C@H:22]1[C@@H:40]2[O:47][C@@H:39]2[C@@:38]2([CH3:41])[C:24](=[CH:25][C@@H:26]([OH:43])[C@@H:27]3[C@@H:37]2[CH2:36][CH2:35][C@@:52]2([CH3:51])[C@H:53]3[CH2:54][CH2:55][C@@H:56]2[CH:60]([CH:61]2[O:57][CH2:58][C:12]([CH3:11])([CH3:13])[CH2:14][O:15]2)[CH3:59])[CH2:23]1)(=[O:20])[CH3:19]

参加物

7

反応物 5

HCID 8028Tetrahydrofuran2 回HCID 13831TributylphosphineHCID 2723923Ammonium formateHCID 21226206Ethyl acetate hexaneHCID 867458006alpha,7alpha-Diepoxypregn-4-en-3beta-yl acetate

生成物 1

HCID 8674580220-(5,5-Dimethyl-1,3-dioxan-2-yl)-1alpha, 2alpha-epoxy-7alpha-hydroxypregna-5-en-3beta-yl acetate収率 40%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

A mixture of 11.6 mg (0.0112 mmole) of tris(dibenzylideneacetone)dipalladium(chloroform), 22.4 μl (0.0898 mmole) of tributylphosphine and 2 ml of dry tetrahydrofuran was stirred in an atmosphere of argon gas at room temperature for 10 minutes. To this mixture was added 14.2 mg (0.224 mmole) of ammonium formate, followed by stirring for 30 minutes. To the resulting mixture was further added a solution of 27.3 mg (0.0561 mmole) of 20-(5,5-dimethyl-1,3-dioxan-2-yl)-1α,2α;6α,7α-diepoxypregn-4-en-3β-yl acetate in 2 ml of dry tetrahydrofuran and the mixture was refluxed for 10 minutes. The reaction mixture was cooled to room temperature, diluted with methylene chloride and washed with cold 1N-hydrochioric acid. The aqueous layer (washings) was extracted with methylene chloride and the extract was combined with the organic layer. The resulting mixture was washed successively with cold saturated aqueous sodium hydrogen carbonate solution and aqueous sodium chloride solution and dried over magnesium sulfate. The solvent was then distilled off under reduced pressure. Purification of the residue by silica gel chromatography (eluent: ethyl acetate-hexane=1:5, v/v) gave 11.0 mg of 20-(5,5-dimethyl-1,3-dioxan-2-yl)-1α,2α-epoxy-7α-hydroxypregn-5-en-3β-yl acetate (yield: 40%). In addition, 11.8 mg of 20-(5,5-dimethyl-1,3-dioxan-2-yl )-1α,2α-epoxy-7α-hydroxypregn-4-en-3β-yl acetate was recovered as a byproduct (yield: 43%).

後処理

  1. stirringby stirring for 30 minutes
  2. additionTo the resulting mixture was further added a solution of 27.3 mg (0.0561 mmole) of 20-(5,5-dimethyl-1,3-dioxan-2-yl)-1α,2α
  3. temperatureThe reaction mixture was cooled to room temperature
  4. washwashed with cold 1N-hydrochioric acid
  5. extractionThe aqueous layer (washings) was extracted with methylene chloride
  6. washThe resulting mixture was washed successively with cold saturated aqueous sodium hydrogen carbonate solution and aqueous sodium chloride solution
  7. dry with materialdried over magnesium sulfate
  8. distillationThe solvent was then distilled off under reduced pressure
  9. customPurification of the residue by silica gel chromatography (eluent

出典と根拠

ORDレコード
ord-a73d1b555b1341fdbdb69a9dc35247e5
出典データセット
uspto-grants-1994_10
特許番号
US05359055

反応ノート

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