Diethyl Ether → N,N'-Bis(2,3-dihydroxypropionyl)-N-(2-hydroxyethyl)-3,5-diamino-2,4,6-triiodobenzylalcohol

HRID 1604154Notes

Reaction equation

HRID 1604154 reaction equation
CC1(C)[O:6][CH:5]([C:7]([NH:9][C:10]2[C:11]([I:33])=[C:12]([C:18]([I:32])=[C:19]([NH:22][C:23]([CH:25]3[CH2:29][O:28]C(C)(C)[O:26]3)=[O:24])[C:20]=2[I:21])[CH2:13]CC([O-])=O)=[O:8])[CH2:4][O:3]1.C([O-])([O-])=[O:36].[Cs+].[Cs+].[C:41](OCCBr)(=[O:43])[CH3:42].CCOCC>CC(N(C)C)=O.CS(C)=O>[OH:26][CH:25]([CH2:29][OH:28])[C:23]([N:22]([CH2:42][CH2:41][OH:43])[C:19]1[C:18]([I:32])=[C:12]([C:11]([I:33])=[C:10]([NH:9][C:7](=[O:8])[CH:5]([OH:6])[CH2:4][OH:3])[C:20]=1[I:21])[CH2:13][OH:36])=[O:24]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 10796Cesium carbonateHCID 135641-Acetoxy-2-bromoethaneHCID 18429246N,N'-Bis(2,2-dimethyl-1,3-dioxolane-4-carbonyl)-3,5-diamino-2,4,6-triiodobenzylacetate

Product 1

HCID 18429366N,N'-Bis(2,3-dihydroxypropionyl)-N-(2-hydroxyethyl)-3,5-diamino-2,4,6-triiodobenzylalcoholYield 30%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 31374DimethylacetamideSolvent

Procedure

N,N'-Bis(2,2-dimethyl-1,3-dioxolane-4-carbonyl)-3,5-diamino-2,4,6-triiodobenzylacetate (204 mg, 0.25 mmol) was dissolved in a mixture of dimethylacetamide (4 ml) and DMSO (2.5 ml) containing Cs2CO3 (650 mg, 2.0 mmol) and 2-bromoethyl acetate (0.035 ml, 0.31 mmol). After stirring for 1 week, ether (150 ml) and a NaH2PO4 buffer (100 ml) were added, the organic phase was separated and the aqueous phase was extracted with ether (150 ml). The combined organic phases were then washed with water (6×100 ml), dried (Na2SO4) and evaporated. The residue was dissolved in a mixture of methanol (20 ml) and water (20 ml) and pH was adjusted to 12 with aqueous NaOH. After stirring for 1 h, the pH was adjusted to 1.5 with concentrated HCl and stirred for another 16 h. The solution was neutralized with aqueous NaH2PO4 and the solvents were evaporated. Preparative HPLC gave 55 mg (30%) of the pure product.

Workup

  1. customthe organic phase was separated
  2. extractionthe aqueous phase was extracted with ether (150 ml)
  3. washThe combined organic phases were then washed with water (6×100 ml)
  4. dry with materialdried (Na2SO4)
  5. customevaporated
  6. dissolutionThe residue was dissolved in a mixture of methanol (20 ml) and water (20 ml) and pH
  7. stirringAfter stirring for 1 h
  8. stirringstirred for another 16 h
  9. customthe solvents were evaporated

Sources & evidence

ORD record
ord-c730553ebed4444bac857e825d3dd89b
Source dataset
uspto-grants-1999_11
Patent number
US05993780

Reaction notes

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