Ammonium Chloride → (7-alpha,17 beta)-17-(Acetyloxy)-7-propylestr-4-en-3-one

HRID 1421555노트

반응식

HRID 1421555 반응식
[CH2:1]([Li])[CH2:2][CH3:3].[C:5]([O:8][C@H:9]1[CH2:14][CH2:13][C@H:12]2[C@H:15]3[C@H:24]([CH2:25][CH2:26][C@:10]12[CH3:11])[C@@H:23]1[C:18](=[CH:19][C:20](=[O:27])[CH2:21][CH2:22]1)[CH:17]=[CH:16]3)(=[O:7])[CH3:6].[NH4+].[Cl-]>C1COCC1.[Cu]I>[C:5]([O:8][C@H:9]1[CH2:14][CH2:13][C@H:12]2[C@H:15]3[C@H:24]([CH2:25][CH2:26][C@:10]12[CH3:11])[C@@H:23]1[C:18](=[CH:19][C:20](=[O:27])[CH2:21][CH2:22]1)[CH2:17][C@H:16]3[CH2:1][CH2:2][CH3:3])(=[O:7])[CH3:6]

참가 물질

6

반응물 3

HCID 25517Ammonium ChlorideHCID 11088332(17beta)-3-Oxoestra-4,6-dien-17-yl acetateHCID 178506857HCID 178506857, 화합물

생성물 1

HCID 15380111(7-alpha,17 beta)-17-(Acetyloxy)-7-propylestr-4-en-3-one수율 35.4%

시약·촉매·용매 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 8028Tetrahydrofuran용매2회

실험 절차

A solution of propyl lithium (prepared from 1.4 g of Li and 9 ml of propyl bromide in 60 ml of ether at -20 C) was added at -40 C to 7.6 g of CuI in 60 ml of dry THF. After stirring for an additional 0.5 hr, a solution of 5.2 g of (17 beta)-17-(acetyloxy)estra-4,6-dien-3-one (1) in 20 ml of THF was added dropwise at -40 C. Upon stirring for an additional 15 minutes the reaction was complete, and the mixture was poured onto 300 ml of saturated NH4Cl solution, followed by extraction with ethyl acetate. The organic material, isolated after washing, drying and evaporation of the solvent, was taken up in 30 ml of THF and stirred in the presence of 3 ml of 6N H2SO4 to isomerize some Δ5,6 isomer to Δ4,5 isomer. After 1 hr the mixture was neutralized with saturated NaHCO3 solution and extracted with ethyl acetate. Chromatography of the crude product over silica gel (heptane/ethyl acetate 8/2) provided 2.1 g of 2, m.p. 97-100° C.

후처리

  1. stirringUpon stirring for an additional 15 minutes the reaction
  2. extractionfollowed by extraction with ethyl acetate
  3. customThe organic material, isolated
  4. washafter washing
  5. customdrying
  6. customevaporation of the solvent
  7. stirringstirred in the presence of 3 ml of 6N H2SO4
  8. waitAfter 1 hr the mixture was neutralized with saturated NaHCO3 solution
  9. extractionextracted with ethyl acetate

출처 및 근거

ORD 기록
ord-3de1a93ec59a47a289f6e54838d67d21
출처 데이터셋
uspto-grants-2000_06
특허 번호
US06077873

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