Ammonium Chloride → Ethyl (20Z)-20-formamido-9alpha-hydroxy-3-methoxypregna-3,5,17(20)-trien-21-oate

HRID 1613973ノート

反応式

HRID 1613973 の反応式
CC(C)([O-:4])C.[K+].[N+:7]([CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])#[C-:8].[OH:15][C@:16]12[CH2:33][CH2:32][C@@:30]3([CH3:31])[C@@H:26]([CH2:27][CH2:28][C:29]3=O)[C@@H:25]1[CH2:24][CH:23]=[C:22]1[C@:17]2([CH3:37])[CH2:18][CH2:19][C:20]([O:35][CH3:36])=[CH:21]1.[Cl-].[NH4+]>O1CCCC1>[CH:8]([NH:7]/[C:9](=[C:29]1/[CH2:28][CH2:27][C@@H:26]2[C@:30]/1([CH3:31])[CH2:32][CH2:33][C@@:16]1([OH:15])[C@H:25]2[CH2:24][CH:23]=[C:22]2[C@:17]1([CH3:37])[CH2:18][CH2:19][C:20]([O:35][CH3:36])=[CH:21]2)/[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[O:4]

参加物

6

反応物 4

HCID 25517Ammonium ChlorideHCID 533707Ethyl isocyanoacetateHCID 108600603-Methoxy-9alpha-hydroxyandrosta-3,5-dien-17-oneHCID 23665647Potassium tert-butoxide

生成物 1

HCID 86746637Ethyl (20Z)-20-formamido-9alpha-hydroxy-3-methoxypregna-3,5,17(20)-trien-21-oate収率 22.7%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
0 °C

実験手順

Potassium tert. butoxide (1.71 g) was added to dry tetrahydrofuran (60 ml) under nitrogen. The solution was cooled to 0° C. and a solution of ethyl isocyanoacetate (1.64 g) in tetrahydrofuran (10 ml) was added dropwise, while keeping the temperature below 0° C. Next, a solution of 9α-hydroxy-3-methoxyandrosta-3,5-dien-17-one (3.21 g) in tetrahydrofuran (60 ml) was added. After stirring for 5 hours at room temperature the mixture was poured into 400 ml of saturated aqueous ammonium chloride solution and extracted twice with ethyl acetate. The combined organic layers were washed three times with water, dried (MgSO4) and concentrated under reduced pressure. The crude product (3.20 g) was purified by chromatography (silica gel, toluene/acetone 4/1 containing 0.1% triethylamine) to provide 0.99 g of the title compound. NMR spectra showed the formation of the Z-isomer of the title compound as a mixture of the two rotamer forms of the 20-formamido group.

後処理

  1. customthe temperature below 0° C
  2. extractionextracted twice with ethyl acetate
  3. washThe combined organic layers were washed three times with water
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated under reduced pressure
  6. customThe crude product (3.20 g) was purified by chromatography (silica gel, toluene/acetone 4/1 containing 0.1% triethylamine)

出典と根拠

ORDレコード
ord-ec1702c06b8e4e89ac07e790e4ccbb2d
出典データセット
uspto-grants-1993_03
特許番号
US05194602

反応ノート

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