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Trimethylsilylacetylene → HCID 86745213, 화합물

HRID 973797
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HRID 973797 반응식
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]
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참가 물질

6

반응물 3

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

생성물 1

HCID 86745213HCID 86745213, 화합물

시약·촉매·용매 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매
HCID 6102075
Dichlorobis(triphenylphosphine)palladium
촉매

실험 절차

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').

후처리

  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

출처 및 근거

ORD 기록
ord-dbb962597230484c8a3547b3c5d70b6b
출처 데이터셋
uspto-grants-1991_11
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05064946

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