Methanol → HCID 11439410、化合物

HRID 326981

反応式

HRID 326981 の反応式
[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.[CH3:35][O:36][C:37]([O:39][C@H:40]1[CH2:45][CH2:44][C@H:43]2[C@H:46]3[C@H:56]([CH2:57][CH2:58][C@:41]12[CH3:42])[C@:54]1([CH3:55])[C:49](=[CH:50][C:51](=[O:59])[CH2:52][CH2:53]1)[CH2:48][CH2:47]3)=[O:38]>C1(C)C=CC=CC=1>[CH3:35][O:36][C:37]([O:39][C@H:40]1[CH2:45][CH2:44][C@H:43]2[C@H:46]3[C@H:56]([CH2:57][CH2:58][C@:41]12[CH3:42])[C@:54]1([CH3:55])[C:49](=[CH:50][C:51](=[O:59])[CH2:52][CH2:53]1)[CH2:48][CH2:47]3)=[O:38].[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

参加物

7

反応物 4

HCID 887MethanolHCID 6013TestosteroneHCID 11439410HCID 11439410、化合物HCID 86585582Methyl chloroformate pyridine

生成物 2

HCID 92979Androsta-4,16-dien-3-oneHCID 11439410HCID 11439410、化合物収率 76%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

This synthesis is depicted in FIG. 2. Several methods are known for the conversion of testosterone into Androsta-4,16-dien-3-one (Brooksbank et al., Biochem. J. (1950) 47:36). Alternatively, thermolysis (460°) of the methyl carbonate of testosterone gives Androsta-4,16-dien-3-one in 90% yield. 17β-Methoxycarbonyloxy-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, 3 H); 3.77 (s, 3 H); 4.53 (br. t, J=8, 1 H); 5.75 (s, 1 H). A solution of the methyl carbonate IV in toluene was pyrolyzed (b) as described for 1. 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, 3 H); 1.22 (s, 3 H); 5.70 (m, 1 H); 5.73 (s, 1 H); 5.84 (m, 1 H).

後処理

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

出典と根拠

ORDレコード
ord-68b3e55668ff4bcba87b284403cb1040
出典データセット
uspto-grants-1993_12
特許番号
US05272134

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