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Trimethylsilylacetylene → HCID 86745213, Verbindung

HRID 973797
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 973797
N([C@@H:4]1[C@@H](CO)O[C@@H](N2C=C(C)C(=S)NC2=O)[CH2:5]1)=[N+]=[N-].C([CH:23]([OH:41])[C@H:24]1[O:28][C@@H:27]([N:29]2[CH:36]=[C:35](I)[C:33](=[O:34])[NH:32][C:30]2=[O:31])[CH2:26][C@@H:25]1[N:38]=[N+:39]=[N-:40])(=O)C.C[Si](C#C)(C)C>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I>[N:38]([C@@H:25]1[C@@H:24]([CH2:23][OH:41])[O:28][C@@H:27]([N:29]2[CH:36]=[C:35]([C:4]#[CH:5])[C:33](=[O:34])[NH:32][C:30]2=[O:31])[CH2:26]1)=[N+:39]=[N-:40]
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

6

Edukt 3

HCID 66111TrimethylsilylacetyleneHCID 30002543'-Azido-3'-deoxy-4-thiothymidineHCID 86745214HCID 86745214, Verbindung

Produkt 1

HCID 86745213HCID 86745213, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)
Katalysator
HCID 6102075Dichlorobis(triphenylphosphine)palladiumKatalysator

Versuchsvorschrift

The title compound was prepared in a manner analogous to the procedure described in (1). 5'-Acetyl-3'-azido-2',3'-dideoxy-5-iodouridine (0.4 g, 0.94 mMol) was dissolved in anhydrous, deoxygenated triethylamine (50 mL) and treated with trimethylsilyl acetylene (0.37 g, 3.8 mMol), bis(triphenylphosphine)palladium(II)chloride (14 mg), and CuI (14 mg) at 55° C. under N2 for 4 hours. The reaction was evaporated to dryness and the residue dissolved in CHCl3. The CHCl3 was washed with 5% EDTA (2×25 mL) then H2O (1×25 mL) followed by drying over Na2SO4. The CHCl3 solution was filtered and evaporated to a solid which was dissolved in 0.5N NaOCH3 in MeOH (50 mL) at ambient temperature. After 1 hour the solution was neutralized DOW 50 H+, filtered and evaporated in vacuo. The residue was chromatographed on silica gel and eluted with 9:1 CHCl3/MeOH (v/v). Combination and evaporation of the appropriate fractions yields the title compound as a solid, 80 mg(0.29 mMol, 30%): mp=134°-136° C.; UV(nm): at pH 1 λmax=286,225(ε=11300,10700), λmin=251(ε=3100); at pH 13 λmax=282(ε=9700), λmin=255(ε=5000); H NMR(DMSO-d6) δ11.6(s,1H,--NH), 8.26(s,1H,H6), 6.01(t,1H,H1',J=6.01 Hz), 5.35-5.30(m,1H,5'OH), 4.4-4.3(m,1H,H3'), 4.08(s,1H,C CH), 3.85-3.80(m,1H,H4'), 3.7-3.6(m,2H,H5'), 2.5-2.3(m,2H,H2').

Aufarbeitung

  1. customThe title compound was prepared in a manner analogous to the procedure
  2. customdeoxygenated triethylamine (50 mL)
  3. customThe reaction was evaporated to dryness
  4. dissolutionthe residue dissolved in CHCl3
  5. washThe CHCl3 was washed with 5% EDTA (2×25 mL)
  6. dry with materialby drying over Na2SO4
  7. filtrationThe CHCl3 solution was filtered
  8. customevaporated to a solid which
  9. dissolutionwas dissolved in 0.5N NaOCH3 in MeOH (50 mL) at ambient temperature
  10. filtrationDOW 50 H+, filtered
  11. customevaporated in vacuo
  12. customThe residue was chromatographed on silica gel
  13. washeluted with 9:1 CHCl3/MeOH (v/v)
  14. customCombination and evaporation of the appropriate fractions

Quellen und Nachweise

ORD-Eintrag
ord-dbb962597230484c8a3547b3c5d70b6b
Quelldatensatz
uspto-grants-1991_11
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US05064946

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