Hydrochloric Acid → HCID 11022977、化合物

HRID 1357477ノート

反応式

HRID 1357477 の反応式
CCC(C)[BH-](C(C)CC)C(C)CC.[Li+].[CH3:15][O:16][C:17]1[C:18]([OH:36])=[CH:19][C:20]2[CH2:21][CH:22]=[C:23]3[C@@H:32]([C:33]=2[CH:34]=1)[CH2:31][CH2:30][C@@:28]1([CH3:29])[C@H:24]3[CH2:25][CH2:26][C:27]1=[O:35].Cl>C1COCC1.CO.[OH-].[K+].OO.O>[CH3:15][O:16][C:17]1[C:18]([OH:36])=[CH:19][C:20]2[CH2:21][CH:22]=[C:23]3[C@@H:32]([C:33]=2[CH:34]=1)[CH2:31][CH2:30][C@@:28]1([CH3:29])[C@H:24]3[CH2:25][CH2:26][C@@H:27]1[OH:35]

参加物

9

反応物 3

HCID 313Hydrochloric AcidHCID 30827972-MethoxyequilinHCID 3611392Lithium tri-s-butylborohydride

生成物 1

HCID 11022977HCID 11022977、化合物収率 74%

試薬・触媒・溶媒 5

HCID 784Hydrogen Peroxide触媒HCID 887Methanol触媒HCID 14797Potassium Hydroxide触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

Under nitrogen, a solution of L-Selectride in THF (1 M, 0.081 mL, 0.081 mmol) was added dropwise to a solution of 2-methoxy-3-hydroxyestra-1,3,5(10),7-tetraen-17-one (19) (0.008 g, 0.027 mmol) in dry THF (1.0 mL) cooled to 0° C. in an ice bath. The reaction was allowed to warm to room temperature and stirred for 45 m. Methanol (3 drops) followed by methanolic KOH (3%, 3 drops) were added and the mixture was cooled to 0° C. in an ice bath. Hydrogen peroxide solution (30%, 5 drops) was added and the mixture was allowed to warm to room temperature. The reaction was diluted with water, acidified with HCl, and extracted with methylene chloride (3x). The organic fractions were washed with water (1x) and brine (1x), filtered through sodium sulfate, combined and concentrated in vacuo to give 0.006 g residue. This material was crystallized from ether/hexanes to give the purified product (20) (0.0037 g, 45.9%). NMR (300 MHz, CDCl3) δ 0.662 (s, 18-CH3), 3.376 (m, 17-H), 3.867 (s, 2-OMe), 5.402 (t, J=1.65 Hz, 7-H), 6.662 (s, 4-H), 6.692 (s, 1-H) ppm. Analysis Calc. for Cl9H24O3

後処理

  1. temperatureto warm to room temperature
  2. additionwere added
  3. temperaturethe mixture was cooled to 0° C. in an ice bath
  4. temperatureto warm to room temperature
  5. extractionextracted with methylene chloride (3x)
  6. washThe organic fractions were washed with water (1x) and brine (1x)
  7. filtrationfiltered through sodium sulfate
  8. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-72826e7346104ef5be65477519e121b8
出典データセット
uspto-grants-2003_07
特許番号
US06593321B2

反応ノート

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