(3,4-Dichlorophenyl)methanesulfonyl chloride → 17-cyclopropylmethyl-3-tert-butyldimethylsilyloxy-14beta-hydroxy-4,5alpha-epoxy-6alpha-(N-methyl-3,4-dichlorophenylmethanesulfonamido)morphinan

HRID 430707

反応式

HRID 430707 の反応式
[Si:1]([O:8][C:9]1[CH:10]=[CH:11][C:12]2[CH2:13][C@H:14]3[N:26]([CH2:27][CH:28]4[CH2:30][CH2:29]4)[CH2:25][CH2:24][C@:20]45[C:21]=2[C:22]=1[O:23][C@H:19]4[C@@H:18]([NH:31][CH3:32])[CH2:17][CH2:16][C@@:15]35[OH:33])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[Cl:34][C:35]1[CH:36]=[C:37]([CH2:42][S:43](Cl)(=[O:45])=[O:44])[CH:38]=[CH:39][C:40]=1[Cl:41]>N1C=CC=CC=1>[Si:1]([O:8][C:9]1[CH:10]=[CH:11][C:12]2[CH2:13][C@H:14]3[N:26]([CH2:27][CH:28]4[CH2:29][CH2:30]4)[CH2:25][CH2:24][C@:20]45[C:21]=2[C:22]=1[O:23][C@H:19]4[C@@H:18]([N:31]([CH3:32])[S:43]([CH2:42][C:37]1[CH:38]=[CH:39][C:40]([Cl:41])=[C:35]([Cl:34])[CH:36]=1)(=[O:45])=[O:44])[CH2:17][CH2:16][C@@:15]35[OH:33])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

参加物

4

反応物 2

HCID 2794622(3,4-Dichlorophenyl)methanesulfonyl chlorideHCID 5380405917-Cyclopropylmethyl-3-tert-butyldimethylsilyloxy-14beta-hydroxy-4,5alpha-epoxy-6alpha-methylaminomorphinan

生成物 1

HCID 9122191517-cyclopropylmethyl-3-tert-butyldimethylsilyloxy-14beta-hydroxy-4,5alpha-epoxy-6alpha-(N-methyl-3,4-dichlorophenylmethanesulfonamido)morphinan収率 78.3%

試薬・触媒・溶媒 1

HCID 1049Pyridine溶媒

実験手順

203.9 mg of 3-tert-butyldimethylsilyloxy-17-cyclopropylmethyl-4,5α-epoxy-14β-hydroxy-6α-methylaminomorphinan 7 obtained in reference example 5 was dissolved in 3 ml of pyridine followed by the addition of 124 mg of 3,4-dichorophenylmethanesufonylchloride and stirring for 30 minutes at room temperature. After concentrating the reaction system, 3 ml of saturated aqueous sodium bicarbonate and 3 ml of chloroform were added to separate layers, after which the aqueous layer was extracted twice with 3 ml of chloroform. After drying with anhydrous sodium sulfate, the organic layer was concentrated to obtain the oily crude product. This was then purified with silica gel column chromatography (30 g benzene/ethyl acetate=5/1) to obtain 235.4 mg of the target compound (yield: 78%).

後処理

  1. concentrationAfter concentrating the reaction system, 3 ml of saturated aqueous sodium bicarbonate and 3 ml of chloroform
  2. additionwere added
  3. customto separate layers
  4. extractionafter which the aqueous layer was extracted twice with 3 ml of chloroform
  5. dry with materialAfter drying with anhydrous sodium sulfate
  6. concentrationthe organic layer was concentrated
  7. customto obtain the oily crude product
  8. customThis was then purified with silica gel column chromatography (30 g benzene/ethyl acetate=5/1)

出典と根拠

ORDレコード
ord-a8541dd64db44d0f81eac14c0eeb15a1
出典データセット
uspto-grants-2001_11
特許番号
US06323212B1

関連ノート

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