Methanol → Androsta-4,16-dien-3-one

HRID 1418317

반응식

HRID 1418317 반응식
[CH3:1][C@@:2]12[C@@H:10](O)[CH2:9][CH2:8][C@H:7]1[C@@H:6]1[CH2:12][CH2:13][C:14]3[C@@:20]([CH3:21])([C@H:5]1[CH2:4][CH2:3]2)[CH2:19][CH2:18][C:16](=[O:17])[CH:15]=3.ClC(OC)=O.N1C=CC=CC=1.CO.C(=O)([O-])OC>C1(C)C=CC=CC=1>[CH3:1][C@:2]12[CH2:3][CH2:4][C@H:5]3[C@@H:6]([CH2:12][CH2:13][C:14]4[C@:20]3([CH3:21])[CH2:19][CH2:18][C:16](=[O:17])[CH:15]=4)[C@@H:7]1[CH2:8][CH:9]=[CH:10]2

참가 물질

6

반응물 4

HCID 887MethanolHCID 6013TestosteroneHCID 4585885MethylcarbonateHCID 86585582Methyl chloroformate pyridine

생성물 1

HCID 92979Androsta-4,16-dien-3-one수율 90%

시약·촉매·용매 1

HCID 1140Toluene용매

실험 절차

This synthesis is depicted in FIG. 1. Several methods are known for the conversion of testosterone into Androsta-4,16-dien-3-one (Brooksbank et al., Biochem. J. (1950) AZ:36). Alternatively, thermolysis (460°) of the methyl carbonate of testosterone gives Androsta-4,16-dien-3-one in 90% yield. 17B-MethoxyCarbonyioxy-androst-4-en-3-one (IV) was prepared from testosterone (III. Fluka) with methyl chloroformate/pyridine (a) in 76% yield (after recrystallization from MeOH). M.p. 140-°141°, [a]D =+95.4° (c=1.10) - IR. (CDCl3): 1740s, 1665s, 1450s, 1280s, - 1H-NMR. (360 MHz): 0.87 (s, 3 H); 1.20 (s, 3H); 3.77 (s, 3H); 4.53 (br. t, J 8, 1H); 5.75 (s, 1H). A solution of the methyl carbonate IV in toluene was pyrolyzed (b) as described for I. Recrystallization of the crude product from acetone at RT. gave pure ketone 4 in 90% yield. M.p. 127°-129.5°, (a)D +118.9° (C=1.32) ([3]: m.p. 131.5°-133.5° (hexane), [a]D16 =+123°±3.5° (C=1.03)). - IR. (CDCl3): 3050w, 1660s, 1615m. - 1H-NMR. (360 MHz): 0.82 (s, 3H); 1.22 (s, 3H); 5.70 (m, 1H); 5.73 (s, 1H); 5.84 (m, 1H).

후처리

  1. customM.p. 140-°141°, [a]D =+95.4° (c=1.10) - IR
  2. customRecrystallization of the crude product from acetone at RT

출처 및 근거

ORD 기록
ord-8358af0c603a4740b130347c4b9ca920
출처 데이터셋
uspto-grants-1999_03
특허 번호
US05883087

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