Hydrochloric Acid → 17-Methylene-estra-1,3,5(10)-trien-3-ol

HRID 275681

반응식

HRID 275681 반응식
[CH3:1]C(C)([O-])C.[K+].[CH3:7][C@@:8]12[C:24](=O)[CH2:23][CH2:22][C@H:21]1[C@H:20]1[C@@H:11]([C:12]3[CH:13]=[CH:14][C:15]([OH:26])=[CH:16][C:17]=3[CH2:18][CH2:19]1)[CH2:10][CH2:9]2.Cl>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CS(C)=O.C[C@H]1O[C@H]2[C@H](O)[C@@H](O)[C@H](OC3C4C(=CC5OCOC=5C=4)[C@@H](C4C=C(OC)C(O)=C(OC)C=4)[C@@H]4[C@@H]3COC4=O)O[C@@H]2CO1.C1COP(NCCCl)(=O)N(CCCl)C1.[NH2-].[NH2-].Cl[Pt+2]Cl>[CH2:1]=[C:24]1[CH2:23][CH2:22][C@H:9]2[C@H:10]3[C@H:11]([CH2:20][CH2:21][C@:8]12[CH3:7])[C:12]1[CH:13]=[CH:14][C:15]([OH:26])=[CH:16][C:17]=1[CH2:18][CH2:19]3

참가 물질

7

반응물 3

HCID 313Hydrochloric AcidHCID 5870EstroneHCID 23665647Potassium tert-butoxide

생성물 1

HCID 1445855217-Methylene-estra-1,3,5(10)-trien-3-ol수율 76.3%

시약·촉매·용매 3

HCID 74505Methyltriphenyliphosphonium bromide촉매HCID 56841950ICE protocol 1촉매HCID 679Dimethyl Sulfoxide용매2회

반응 조건

온도
74.5 °C

실험 절차

A suspension of methyltriphenylphosphonium bromide (100.03 g, 0.28001 mol) and potassium t-butoxide (31.42 g, 0.2800 mol) in anh. dimethylsulfoxide (DMSO, 320 mL) under argon was stirred in an oil bath (68-81° C.) 1 h, after which estrone (15.14 g, 55.99 mmol) in anh. DMSO (320 mL) was added via syringe. See FIG. 17. Stirring was continued 1 h and the reaction allowed to cool. The mixture was poured into 800 mL of ice-1 N hydrochloric acid and then extracted three times with 400 mL aliquots of ether. The combined organic extracts were washed with 350 mL of saturated sodium bicarbonate+400 mL of brine, dried over sodium sulfate, and flash filtered through a 58 mm high×84 mm dia. column of silica gel (200-40 mesh). Product continued eluting with additional ether. Concentration of appropriate fractions under reduced pressure and three-fold recrystallization from aqueous ethanol gave very fine white needles (11.47 g, 42.73 mmol, 76%), m.p. 134-136° C., homogeneous to TLC (20% ethyl acetate/hexanes on silica gel, Rf 0.45).

후처리

  1. stirringStirring
  2. waitwas continued 1 h
  3. temperatureto cool
  4. extractionextracted three times with 400 mL aliquots of ether
  5. washThe combined organic extracts were washed with 350 mL of saturated sodium bicarbonate+400 mL of brine
  6. dry with materialdried over sodium sulfate, and flash
  7. filtrationfiltered through a 58 mm high×84 mm dia
  8. washProduct continued eluting with additional ether
  9. customConcentration of appropriate fractions under reduced pressure and three-fold recrystallization from aqueous ethanol

출처 및 근거

ORD 기록
ord-a97a6f3223d346cfb1c6946c109fd299
출처 데이터셋
uspto-grants-2002_03
특허 번호
US06352980B1

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