Oxalyl chloride → (+)-N-[2-[[(2,3-Dihydro-1,4-benzodioxin-2-yl)methyl]amino]ethyl]-7,7-dimethyl-2-oxobicyclo[2,2,1]heptane-1-carboxamide

HRID 893729ノート

反応式

HRID 893729 の反応式
[C:1](Cl)(=[O:5])[C:2](Cl)=O.[NH2:7][CH2:8][CH2:9][NH:10][CH2:11][CH:12]1[O:17][C:16]2[CH:18]=[CH:19][CH:20]=[CH:21][C:15]=2[O:14][CH2:13]1.C(N([CH:28]([CH3:30])[CH3:29])CC)(C)C>ClCCl.CN(C=O)C>[O:17]1[C:16]2[CH:18]=[CH:19][CH:20]=[CH:21][C:15]=2[O:14][CH2:13][CH:12]1[CH2:11][NH:10][CH2:9][CH2:8][NH:7][C:15]([C:16]12[C:28]([CH3:29])([CH3:30])[CH:20]([CH2:19][CH2:18]1)[CH2:2][C:1]2=[O:5])=[O:14]

参加物

6

反応物 3

HCID 65578Oxalyl chlorideHCID 81531DiisopropylethylamineHCID 146529492-[N-(2-aminoethyl)]aminomethyl-2,3-dihydrobenzodioxin

生成物 1

HCID 19891064(+)-N-[2-[[(2,3-Dihydro-1,4-benzodioxin-2-yl)methyl]amino]ethyl]-7,7-dimethyl-2-oxobicyclo[2,2,1]heptane-1-carboxamide収率 67.1%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide触媒HCID 6344Dichloromethane溶媒2 回

実験手順

To 2.0 g (10 mmole) (-)-ketopinic acid in 100 ml of dichloromethane was added 2.0 ml (23 mmole) oxalyl choride and 2 drops of DMF. The mixture was stirred for two hours at room temperature and then concentrated to dryness in vacuum. It was redissolved in 50 ml of methylenechloride and added to a cold solution of 2.1 g (10 mmole) 2-[N-(2-aminoethyl)]aminomethyl-2,3-dihydrobenzodioxin and 1.3 g (10 mmole) diisopropylethylamine in 100 ml of dichloromethane. The mixture was stirred at room temperature overnight. It was then washed with saturated aqueous sodium bicarbonate, with saturated sodium chloride, dried over sodium sulfate, filtered and evaporated in vacuum. The residue was column chromatographed on 100 g of silica gel with chloroform as eluant, and the product crystallized from 75 ml of isopropanol with the addition of 4 ml 4 N HCl/isopropyl alcohol and 225 ml of diethyl ether to produce 1.25 g of the title compound as the hydrochloride, quarter hydrate, m.p. 164°-166° C., [α]D25 =-31.3 (MeOH).

後処理

  1. concentrationconcentrated to dryness in vacuum
  2. dissolutionIt was redissolved in 50 ml of methylenechloride
  3. stirringThe mixture was stirred at room temperature overnight
  4. washIt was then washed with saturated aqueous sodium bicarbonate, with saturated sodium chloride
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. customevaporated in vacuum
  8. customchromatographed on 100 g of silica gel with chloroform as eluant
  9. customthe product crystallized from 75 ml of isopropanol with the addition of 4 ml 4 N HCl/isopropyl alcohol and 225 ml of diethyl ether

出典と根拠

ORDレコード
ord-9dd75add16f2455fb553cc42765150e8
出典データセット
uspto-grants-1992_06
特許番号
US05126367

反応ノート

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