Estrone → 3-Hydroxyestra-1,3,5(10)-triene-16,17-dione 16-oxime

HRID 1178260ノート

反応式

HRID 1178260 の反応式
CC(C)([O-])C.[K+].[K].[CH3:8][C@@:9]12[C:25](=[O:26])[CH2:24][CH2:23][C@H:22]1[C@H:21]1[C@@H:12]([C:13]3[CH:14]=[CH:15][C:16]([OH:27])=[CH:17][C:18]=3[CH2:19][CH2:20]1)[CH2:11][CH2:10]2.[N:28](OCCC(C)C)=[O:29]>C(O)(C)(C)C.O>[CH3:8][C@@:9]12[C:25](=[O:26])/[C:24](=[N:28]/[OH:29])/[CH2:23][C@H:22]1[C@@H:21]1[CH2:20][CH2:19][C:18]3[CH:17]=[C:16]([OH:27])[CH:15]=[CH:14][C:13]=3[C@H:12]1[CH2:11][CH2:10]2

参加物

7

反応物 4

HCID 5870EstroneHCID 8053Isoamyl NitriteHCID 5462222PotassiumHCID 23665647Potassium tert-butoxide

生成物 1

HCID 95617673-Hydroxyestra-1,3,5(10)-triene-16,17-dione 16-oxime

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6386tert-Butanol溶媒

実験手順

To a stirred solution of potassium tert-butoxide under an atmosphere of N2, freshly prepared by dissolving potassium metal (80 mg, 2.05 mmol) in 2 mL tert-butanol, oestrone (200 mg, 740 mmol) was added. The reaction mixture was then stirred for 1 hour at room temperature under N2 and isoamyl nitrite (180 μmol, 1.34 mmol) was added dropwise. The deep red mixture obtained was stirred overnight and then poured into water (20 mL). The resulting solution was extracted with ether (2×20 mL) and the aqueous layer was acidified with glacial acetic acid (10 mL) to give a light yellow precipitate. This was left separating for two hours after which the solid was filtered (140 mg, 63%): mp 223-225° C. (lit. 226-227° C.);43 TLC (chloroform/acetone, 9:1) Rf 0.27 cf. Rf 0.69 (E1); IR (KBr) 3385 (NOH), 2920-2860 (aliph CH), 1735 (C═O), 1605-1500 (arom C═C) cm−1; δH (DMSO-d6, 400 MHz) 0.89 (3H, s, C-18-H3), 1.30-2.85 (11H, m), 2.70-2.81 (2H, m, C-6-H2), 6.46 (1H, d, JC-2-H,C-4-H=2.3 Hz, C-4-H), 6.52 (1H, dd, JC-1-H,C-2-H=8.4 Hz and JC-4-H,C-2-H=2.3 Hz, C-2-H), 7.05 (1H, d, JC-2-H,C-1-H=8.2 Hz, C-1-H), 9.05 (1H, s, exchanged with D2O, OH) and 12.39 (1H, s, exchanged with D2O, NOH); δC (DMSO-d6, 100.4 MHz) 14.09 (q, C-18), 25.09 (t); 25.46 (t), 26.18 (t), 29.02 (t), 30.92 (t), 37.20 (d), 43.20 (d), 44.59 (d), 48.50 (s, C-13), 112.70 (d), 114.83 (d), 125.82 (d), 129.59 (s), 136.88 (s), 154.84 (s, C-3 or C-16), 155.23 (s, C-3 or C-16) and 204.64 (s, C═O); MS m/z (FAB+) 453.2 [30, (M+H+NBA)+], 300.1 [100, (M+H)+]; MS m/z (FAB−) 451.3 [38, (M−H+NBA)−], 298.2 [100, (M−H)−]; Ace MS m/z (FAB+) 300.15963, C18H22NO3 requires 30015997. CHN,

後処理

  1. additionwas added
  2. customThe deep red mixture obtained
  3. stirringwas stirred overnight
  4. extractionThe resulting solution was extracted with ether (2×20 mL)
  5. customto give a light yellow precipitate
  6. waitThis was left
  7. customseparating for two hours after which the solid
  8. filtrationwas filtered (140 mg, 63%)
  9. custommp 223-225° C. (lit. 226-227° C.);43 TLC (chloroform/acetone, 9:1) Rf 0.27

出典と根拠

ORDレコード
ord-e3627a4335424734b26272cd3320803f
出典データセット
uspto-grants-2007_10
特許番号
US07276513B2

反応ノート

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