Diisopropylethylamine → (1S)-(+)-N-[2-[[(2,3-Dihydro-1,4-benzodioxin-2-yl)methyl]amino]ethyl]-7,7-dimethyl-2-oxobicyclo[2,2,1]heptane-1-methanesulfonamide

HRID 893731Notes

Reaction equation

HRID 893731 reaction equation
[NH2:1][CH2:2][CH2:3][NH:4][CH2:5][CH:6]1[O:11][C:10]2[CH:12]=[CH:13][CH:14]=[CH:15][C:9]=2[O:8][CH2:7]1.C(N(C(C)C)CC)(C)C.[CH3:25][C:26]1([CH3:39])[C:30]2([CH2:34][S:35](Cl)(=[O:37])=[O:36])[C:31]([CH2:33][CH:27]1[CH2:28][CH2:29]2)=[O:32]>ClCCl>[O:11]1[C:10]2[CH:12]=[CH:13][CH:14]=[CH:15][C:9]=2[O:8][CH2:7][CH:6]1[CH2:5][NH:4][CH2:3][CH2:2][NH:1][S:35]([CH2:34][C@:30]12[C:26]([CH3:25])([CH3:39])[CH:27]([CH2:28][CH2:29]1)[CH2:33][C:31]2=[O:32])(=[O:37])=[O:36]

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 26579910-Camphorsulfonyl chlorideHCID 146529492-[N-(2-aminoethyl)]aminomethyl-2,3-dihydrobenzodioxin

Product 1

HCID 22844792(1S)-(+)-N-[2-[[(2,3-Dihydro-1,4-benzodioxin-2-yl)methyl]amino]ethyl]-7,7-dimethyl-2-oxobicyclo[2,2,1]heptane-1-methanesulfonamideYield 28.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 2.1 g (10 mmole) of 2-{N-(2-aminoethyl)]aminomethyl-2,3-dihydrobenzodioxin and 1.3 g (10 mmole) of diisopropylethylamine in 100 ml of dichloromethane stored in an ice bath was added 2.5 g (10 mmole) (+)-10-camphorsulfonyl chloride. The mixture was allowed to stir overnight at room temperature. The reaction was next washed with saturated aqueous sodium bicarbonate, with saturated sodium chloride, dried over sodium sulfate, filtered and evaporated in vacuum. Column chromatography on 75 g of silica gel with chloroform as eluant, followed by crystallization from 100 ml of isopropanol with the addition of 5 ml of 4 N HCl/isopropyl alcohol and 300 ml of diethyl ether gave 1.2 g of the title compound as a monohydrochloride, m.p. 143°-146° C.

Workup

  1. washThe reaction was next washed with saturated aqueous sodium bicarbonate, with saturated sodium chloride
  2. dry with materialdried over sodium sulfate
  3. filtrationfiltered
  4. customevaporated in vacuum
  5. customColumn chromatography on 75 g of silica gel with chloroform as eluant, followed by crystallization from 100 ml of isopropanol with the addition of 5 ml of 4 N HCl/isopropyl alcohol and 300 ml of diethyl ether

Sources & evidence

ORD record
ord-67e0ceb3f16944d695f22c701742219b
Source dataset
uspto-grants-1992_06
Patent number
US05126367

Reaction notes

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