Sulfuric Acid → 5'-Deoxy-5'-[(2-hydrazinocarbonylethyl)methylamino]-8-methyladenosine sulfate

HRID 473578ノート

反応式

HRID 473578 の反応式
[C:1]([CH2:6][CH2:7][N:8]([CH3:28])[CH2:9][C@H:10]1[O:14][C@@H:13]([N:15]2[C:24]3[N:23]=[CH:22][N:21]=[C:19]([NH2:20])[C:18]=3[N:17]=[C:16]2[CH3:25])[C@H:12]([OH:26])[C@@H:11]1[OH:27])(OCC)=[O:2].O.[NH2:30][NH2:31].[OH:32][S:33]([OH:36])(=[O:35])=[O:34]>C(O)C>[S:33]([OH:36])([OH:35])(=[O:34])=[O:32].[NH:30]([C:1]([CH2:6][CH2:7][N:8]([CH3:28])[CH2:9][C@H:10]1[O:14][C@@H:13]([N:15]2[C:24]3[N:23]=[CH:22][N:21]=[C:19]([NH2:20])[C:18]=3[N:17]=[C:16]2[CH3:25])[C@H:12]([OH:26])[C@@H:11]1[OH:27])=[O:2])[NH2:31]

参加物

5

反応物 3

HCID 1118Sulfuric AcidHCID 24654Hydrazine hydrate (1:1)2 回HCID 252332505'-[(carboethoxyethyl)methyamino]-5'-Deoxy-8-methyladenosine

生成物 1

HCID 668562505'-Deoxy-5'-[(2-hydrazinocarbonylethyl)methylamino]-8-methyladenosine sulfate

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒2 回

実験手順

Compound 13a (115 mg, 0.29 mmol) was dissolved in 10 mL of anhydrous ethanol and hydrazine monohydrate (73 mg, 0.07 mL, 1.46 mmol) was added to the solution. The reaction mixture was heated to reflux overnight. Hydrazine monohydrate (0.07 mL) was added again and heating was continued overnight. The resulting solution was evaporated to dryness. The crude product was purified by column chromatography (4:1:0.5 chloroform:methanol:NH4OH). The desired fractions were collected, concentrated, and dried in vacuo to yield a sticky solid. The product was dissolved in 8 mL of EtOH and 2N H2SO4 was added drop wise. The salt that was precipitated out was filtered and washed with EtOH. This salt, which was hygroscopic in nature, was dissolved in water (2 mL) and lyophilized to give a white solid: yield 71 mg (65%), MS: m/z 381 (M+H)+; 1HNMR (D2O) δ 8.44 (s, 1H, H-2), 6.09 (d, 1H, H-1′, J1′,2′=5.6 Hz), 5.10 (dd, 1H, H-2′, J2′,3′=4.5 Hz), 4.53-4.62 (bm, 2H, H-3′, H-4′), 3.86-3.94 (m, 1H, 5′-CH2), 3.52-3.66 (m, 3H, 5′-CH2, N(CH3)—CH2), 2.95 (s, 3H, N—CH3), 2.86 (t, 2H, NHCO—CH2), 2.70 (s, 3H, 8-CH3); UV λmax, nm, pH 1, 258.4 (∈ 15,000), pH 7, 259.3 (∈ 15,200), pH 13, 260.4 (∈ 15,700). Anal. (C15H24N8O4.2.0H2SO4.2.7H2O) C, H, N, S.

後処理

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux overnight
  3. temperatureheating
  4. customThe resulting solution was evaporated to dryness
  5. customThe crude product was purified by column chromatography (4:1:0.5 chloroform:methanol:NH4OH)
  6. customThe desired fractions were collected
  7. concentrationconcentrated
  8. customdried in vacuo
  9. customto yield a sticky solid
  10. customThe salt that was precipitated out
  11. filtrationwas filtered
  12. washwashed with EtOH
  13. dissolutionwas dissolved in water (2 mL)
  14. customto give a white solid

出典と根拠

ORDレコード
ord-16cfa5c3d86f42e19ddca120347f404c
出典データセット
uspto-grants-2014_01
特許番号
US08637485B2

反応ノート

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