Formaldehyde → HCID 13578833、化合物

HRID 1285310ノート

反応式

HRID 1285310 の反応式
C[O-].[Na+].[CH3:4][C@:5]12[CH2:22][CH:21]=[C:20]3[C@@H:10]([CH2:11][CH2:12][C:13]4[C@:18]3([CH3:19])[CH:17]=[CH:16][C:15](=[O:23])[CH:14]=4)[C@@H:9]1[CH2:8][CH2:7][C:6]2=[O:24].[CH3:25]OC(=O)C(OC)=O.C=O>CO.C1COCC1.C(Cl)Cl.O.C(N(CC)CC)C.C(O)(=O)C>[CH2:25]=[C:7]1[CH2:8][C@H:9]2[C@H:10]3[C:20](=[CH:21][CH2:22][C@:5]2([CH3:4])[C:6]1=[O:24])[C@:18]1([CH3:19])[C:13](=[CH:14][C:15](=[O:23])[CH:16]=[CH:17]1)[CH2:12][CH2:11]3

参加物

11

反応物 4

HCID 712FormaldehydeHCID 11120Dimethyl oxalateHCID 10265807Androsta-1,4,9(11)-triene-3,17-dioneHCID 10942334Sodium Methoxide

生成物 1

HCID 13578833HCID 13578833、化合物

試薬・触媒・溶媒 6

HCID 176Acetic Acid溶媒HCID 887Methanol溶媒2 回HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒HCID 8471Triethylamine溶媒

実験手順

Sodium methoxide in methanol (25%, 6.85 ml) is added dropwise to a mixture of androst-1,4,9(11)-triene-3,17-dione (IB, 7.05 g) in THF (80 ml) and methylene chloride (8 ml) containing dimethyloxalate (4.38 g) previously cooled to 4°. After one hour at 4°, the preparation of the 16-oxalate salt is complete and the following reagents were added sequentially: acetic acid (0.5 ml), triethylamine (2.6 ml), methanol (10 ml), and aqueous formaline (37%, 2.8 ml). The reaction mixture was warmed to 20°-25° and after one hour the reaction was complete. The reaction mixture was poured into water and extracted twice with ethyl acetate. The ethyl acetate extracts were combined, washed with water, dried over sodium sulfate, and concentrated under reduced pressure to a solid. The solid was dissolved in methylene chloride (2.5 ml), following which the methylene chloride was evaporated. The solid was again dissolved in dry THF (25 ml), following which the THF was evaporated. The solid was then dissolved in dry THF (50 ml) for use in the following reaction.

後処理

  1. temperaturepreviously cooled to 4°
  2. additionthe following reagents were added sequentially
  3. temperatureThe reaction mixture was warmed to 20°-25° and after one hour the reaction
  4. extractionextracted twice with ethyl acetate
  5. washwashed with water
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated under reduced pressure to a solid
  8. dissolutionThe solid was dissolved in methylene chloride (2.5 ml)
  9. customwas evaporated
  10. dissolutionThe solid was again dissolved in dry THF (25 ml)
  11. customwas evaporated
  12. dissolutionThe solid was then dissolved in dry THF (50 ml) for use in the following reaction

出典と根拠

ORDレコード
ord-45c51960a26d4961abdf2d8e6e0fa701
出典データセット
uspto-grants-1986_01
特許番号
US04567001

反応ノート

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