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Triethylamine → Acetic acid 2-acetoxy-1-{3-chlorocarbonyl-5-[(2,2-dimethyl-[1,3]-dioxolan-4-ylmethyl)-(2-hydroxy-ethyl)-carbamoyl]-2,4,6-triiodo-phenylcarbamoyl}-ethyl ester

HRID 219501
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Reaktionsgleichung von HRID 219501
[C:1]([O:4][CH2:5][CH:6]([O:25][C:26](=[O:28])[CH3:27])[C:7](=[O:24])[NH:8][C:9]1[C:14]([I:15])=[C:13]([C:16](Cl)=[O:17])[C:12]([I:19])=[C:11]([C:20]([Cl:22])=[O:21])[C:10]=1[I:23])(=[O:3])[CH3:2].[CH3:29][C:30]1([CH3:40])[O:34][CH:33]([CH2:35][NH:36][CH2:37][CH2:38][OH:39])[CH2:32][O:31]1.C(N(CC)CC)C>CC(N(C)C)=O>[C:1]([O:4][CH2:5][CH:6]([O:25][C:26](=[O:28])[CH3:27])[C:7](=[O:24])[NH:8][C:9]1[C:14]([I:15])=[C:13]([C:16](=[O:17])[N:36]([CH2:35][CH:33]2[CH2:32][O:31][C:30]([CH3:40])([CH3:29])[O:34]2)[CH2:37][CH2:38][OH:39])[C:12]([I:19])=[C:11]([C:20]([Cl:22])=[O:21])[C:10]=1[I:23])(=[O:3])[CH3:2]
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Komponenten

5

Edukt 3

HCID 8471TriethylamineHCID 205536662-[(2,2-Dimethyl-[1,3]dioxolan-4-yl-methyl)-amino]-ethanolHCID 59413986Acetic acid 2-acetoxy-1-(3,5-bis-chlorocarbonyl-2,4,6-triiodo-phenylcarbamoyl)-ethyl ester

Produkt 1

HCID 59470592Acetic acid 2-acetoxy-1-{3-chlorocarbonyl-5-[(2,2-dimethyl-[1,3]-dioxolan-4-ylmethyl)-(2-hydroxy-ethyl)-carbamoyl]-2,4,6-triiodo-phenylcarbamoyl}-ethyl esterAusbeute 38,5 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 31374DimethylacetamideLösungsmittel2×

Versuchsvorschrift

To a ice cooled solution of acetic acid 2-acetoxy-1-(3,5-bis-chlorocarbonyl-2,4,6-triiodo-phenylcarbamoyl)-ethyl ester (20 g, 0.026 mol) in anhydrous DMAC (20 ml) were added dropwise a solution of 2-[(2,2-Dimethyl-[1,3]dioxolan-4-yl-methyl)-amino]-ethanol (4.6 g, 0.026 mol) in DMAC (20 mL) followed by triethylamine (˜3 g). The mixture was stirred at room temperature for 24 h and then poured over icewater (0.75 litre). A white precipitate formed. This was collected and washed with cold water. The filter cake was then dissolved in ethyl acetate and washed with brine. The organics were collected, dried over MgSO4, filtered and evaporated to dryness. The product was purified by silica column chromatography eluting with Petroleum ether/ethyl acetate. Two peaks closely eluting at 80% ethyl acetate were analysed by NMR and mass spec, and show to both contain the desired material. These were combined post analysis to give the desired product (10 mmol, Yield=38%). The structure was confirmed by Mass Spec (ESI) m/z: Calculated for C23H26Cl I3N2O10 [M+H]+906.64. Found 906.93. 1H NMR (CDCl3; 300 MHz) δ=1.33 (2s, 3H) 1.45 (2s, 3H) 2.02 (s, 3H) 2.26 (s, 3H) 3-3.5 (m, 4H) 3.5-3.9 (m, 3H) 3.9-4.3 (m, 2H) 4.5 (m, 1H) 4.6-4.8 (m, 2H) 5.62 (NH singlet, 1H)

Aufarbeitung

  1. additionpoured over icewater (0.75 litre)
  2. customA white precipitate formed
  3. customThis was collected
  4. washwashed with cold water
  5. dissolutionThe filter cake was then dissolved in ethyl acetate
  6. washwashed with brine
  7. customThe organics were collected
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customevaporated to dryness
  11. customThe product was purified by silica column chromatography
  12. washeluting with Petroleum ether/ethyl acetate
  13. washTwo peaks closely eluting at 80% ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-180f03b2ce8348499f19f262f2bf64cd
Quelldatensatz
uspto-grants-2012_06
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08202511B2

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