Dimethylformamide → 2,4,6-triiodo-5-isocyanato-N,N,N'-trimethylisophthalamide

HRID 27989

Reaction equation

HRID 27989 reaction equation
OC1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1N.C(=O)([O-])[O-].[K+].[K+].[C:19]([NH:22][C:23]1[C:24]([I:38])=[C:25]([C:30]([I:37])=[C:31](N=C=O)[C:32]=1[I:33])[C:26]([NH:28][CH3:29])=[O:27])(=[O:21])C.[CH3:39][N:40]([CH3:43])[CH:41]=[O:42]>>[I:37][C:30]1[C:25]([C:26]([NH:28][CH3:29])=[O:27])=[C:24]([I:38])[C:23]([N:22]=[C:19]=[O:21])=[C:32]([I:33])[C:31]=1[C:41]([N:40]([CH3:43])[CH3:39])=[O:42]

Participants

5

Reactant 4

HCID 6228Dimethylformamide2×HCID 11430Potassium CarbonateHCID 439213D-GlucosamineHCID 233410673-acetamido-2,4,6-triiodo-5-isocyanato-N-methylbenzamide

Product 1

HCID 233340132,4,6-triiodo-5-isocyanato-N,N,N'-trimethylisophthalamide

Procedure

To glucosamine (1.97 g., 0.011 mole) and potassium carbonate (4.14 g.; 0.03 mole) in dimethylformamide (49 ml.) was added dropwise (required about 5 minutes) 3-acetamido-2,4,6-triiodo-5-isocyanato-N-methylbenzamide (III; 6.11 g.; 0.01 mole) dissolved in dimethylformamide (20 ml.). After being stirred overnight, the reaction mixture was filtered and concentrated in vacuo. The residue was dissolved in water (64 ml.) and the aqueous solution was adjusted to pH 1 with concentrated hydrochloric acid. The solution was extracted with aqueous 90% phenol (4×25 ml.). The combined, phenolic layers were washed with water (4×25 ml.), diluted with ether (300 ml.) and extracted with water (4×25 ml.). The combined aqueous layers were washed with chloroform-isopropyl alcohol (3:1; 5×100 ml., contact time 15 min.), treated with "Darco G-60" (0.25 g.) overnight, and evaporated under reduced pressure at 40° C. (water bath), to give 3-acetamido-5-{3-[2-D-gluco-2-deoxy-3,4,5,6-tetrahydroxy-1-oxohexyl]ureido}-2,4,6-triiodo-N-methylbenzamide (IV) as faint-yellow foam, 5.08 g. (64.5%), m.p. 186°-251° C. (dec.). The infrared and nuclear magnetic resonance spectra were consistent with the assigned structure. The material was homogeneous by thin-layer chromatography (chloroform-methanol-triethylamine, 65:35:5) and the aqueous solubility was determined to be 18-20% (w/v).

Workup

  1. filtrationthe reaction mixture was filtered
  2. concentrationconcentrated in vacuo
  3. dissolutionThe residue was dissolved in water (64 ml.)
  4. extractionThe solution was extracted with aqueous 90% phenol (4×25 ml.)
  5. washphenolic layers were washed with water (4×25 ml.)
  6. additiondiluted with ether (300 ml.)
  7. extractionextracted with water (4×25 ml.)
  8. washThe combined aqueous layers were washed with chloroform-isopropyl alcohol (3:1; 5×100 ml., contact time 15 min.)
  9. additiontreated with "Darco
  10. custom" (0.25 g.) overnight, and evaporated under reduced pressure at 40° C. (water bath)

Sources & evidence

ORD record
ord-e7c00b34f9b6476e8e420426c25ddbf0
Source dataset
uspto-grants-1980_09
Patent number
US04224440

Linked notes

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