Diethyl Ether → Vitamin K

HRID 2058938ノート

反応式

HRID 2058938 の反応式
[CH3:1][C:2]([CH2:8][CH2:9][CH2:10][CH:11]([CH3:23])[CH2:12][CH2:13][CH2:14][CH:15]([CH3:22])[CH2:16][CH2:17][CH2:18][CH:19]([CH3:21])[CH3:20])=[CH:3][CH2:4][C:5]#[C:6][CH3:7].[CH2:24](Br)/[CH:25]=[C:26](/[CH2:28][CH2:29][CH2:30][C@@H](CCC[C@@H](CCCC(C)C)C)C)\C.CC[O:47][CH2:48][CH3:49].[O-:50]S([O-])(=O)=O.[Mg+2]>C(OCCCC)CCC.C(=[Cr](=C=O)(=C=O)(=C=O)(=C=O)=C(OC)C1C=CC=CC=1)=O.[Ag-]=O>[CH3:7][C:6]1[C:48](=[O:47])[C:49]2[C:25](=[CH:26][CH:28]=[CH:29][CH:30]=2)[C:24](=[O:50])[C:5]=1[CH2:4]/[CH:3]=[C:2](/[CH2:8][CH2:9][CH2:10][CH:11]([CH2:12][CH2:13][CH2:14][CH:15]([CH2:16][CH2:17][CH2:18][CH:19]([CH3:21])[CH3:20])[CH3:22])[CH3:23])\[CH3:1]

参加物

8

反応物 4

HCID 3283Diethyl EtherHCID 24083Sulfuric acid magnesium salt (1:1)HCID 12905048(7R,11R,E)-1-bromo-3,7,11,15-tetramethylhexadec-2-eneHCID 539063656,10,14,18-Tetramethylnonadec-5-EN-2-yne

生成物 1

HCID 5280483Vitamin K収率 56%

試薬・触媒・溶媒 3

HCID 178418778HCID 178418778、化合物触媒HCID 178494494HCID 178494494、化合物触媒HCID 8909Butyl ether溶媒

実験手順

A solution of 1 mmol of pentacarbonyl[methoxy(phenyl)carbene]chromium and 1.1 mmol of 6,10,14,18-tetramethyl-5-nonadecen-2-yne from phytyl bromide (isomer ratio E/Z=90/10) in 5 ml of dibutyl ether is heated to 55° C. under nitrogen for 1 hour. After the removal of the solvent, the 1-naphthol-tricarbonyl-chromium complex can be isolated (yield 95%) by chromatography on silica gel at -30° C. with methylene chloride/pentane (2/1), or directly oxidised to the quinone after addition of 10 ml of ether by one-hours stirring with 1.5 mmol of silver (I) oxide in the presence of MgSO4. The obtained mixture is filtered, the solvent removed and the residue purified by chromatography at 10° C. on silica gel with pentane/ether (100/1). There is obtained vitamin K1(20) as a light yellow oil in a total yield of 56%.

後処理

  1. customAfter the removal of the solvent
  2. customthe 1-naphthol-tricarbonyl-chromium complex can be isolated (yield 95%) by chromatography on silica gel at -30° C. with methylene chloride/pentane (2/1)
  3. filtrationThe obtained mixture is filtered
  4. customthe solvent removed
  5. customthe residue purified by chromatography at 10° C. on silica gel with pentane/ether (100/1)

出典と根拠

ORDレコード
ord-5646f7ab81a94240aaf50eb84e5c844b
出典データセット
uspto-grants-1982_03
特許番号
US04320065

反応ノート

読み込み中…