Ammonia → HCID 54000395, compound

HRID 1031074Notes

Reaction equation

HRID 1031074 reaction equation
[Si]([O:18][CH2:19][C@@H:20]([S:49][CH2:50][P:51]([O:56][CH2:57][CH3:58])([O:53][CH2:54][CH3:55])=[O:52])[CH2:21][O:22][N:23]1[CH:31]=[N:30][C:29]2[C:24]1=[N:25][C:26]([N:34](C(OC(C)(C)C)=O)C(OC(C)(C)C)=O)=[N:27][C:28]=2[O:32][CH3:33])(C(C)(C)C)(C1C=CC=CC=1)C1C=CC=CC=1.FC(F)(F)C(O)=O.N>O>[NH2:34][C:26]1[N:25]=[C:24]2[C:29]([N:30]=[CH:31][N:23]2[O:22][CH2:21][C@@H:20]([S:49][CH2:50][P:51]([O:56][CH2:57][CH3:58])([O:53][CH2:54][CH3:55])=[O:52])[CH2:19][OH:18])=[C:28]([O:32][CH3:33])[N:27]=1

Participants

5

Reactant 3

HCID 222AmmoniaHCID 6422Trifluoroacetic acidHCID 131717316HCID 131717316, compound

Product 1

HCID 54000395HCID 54000395, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

(R)- or (S)-9-[3-t-butyldiphenylsilyloxy-2-(diethoxyphosphorylmethylthio)propoxy]di-t-butoxycarbonylamino-6-methoxypurine (0.45%, 0.52 mmol) was added to a mixture of water (1.5 ml) and trifluoroacetic acid (4.5 ml), and the mixture was stirred at room temperature for 3 hr. The solution was then treated with saturated ethanolic ammonia solution to bring the pH to 11. The solution was extracted with chloroform (3×50 ml) and the organic layers were combined and dried (MgSO4). After filtration and evaporation in vacuo the residue was purified by column chromatography on silica, eluting with chloroform : methanol (95:5) to give (R) or (S)-2-Amino-9-[2-(diethoxyphosphorylmethylthio)-3-hydroxypropoxy]-6-methoxypurine as a colourless gum (0.16 g, 72%). υmax (film) 3340, 3220, 3120, 2980, 1620, 1585, 1500, 1480, 1450, 1390, 1330 and 1260 cm-1 ; 1H NMR δH [(CD)3SO] 1.22 (δH t, J 6Hz, CH3 × 2) 3.06 (2H,d, J=12.5Hz, PCH2S), 3.35 (1H, m, CH of CH2), 3.66 (1H, m, CH of CH2), 3.8 (1H, m, CH),3.96 (3H, s, OCH3), 4.02 (4H, m, CH2 ×2), 4.46 (2H, m, CH2), 5.06 (1H, t, J ™5.5Hz, D2O exchangeable OH), 6.6 (2H, brs, D2O exchangeable NH2), 8.1 (1H, s, 8-H): (Found: C, 39.03; H,5.70; N15.89 %. C14H24N5O6PS (0.5 H2O ) requires: C,39.06; H,5.80, N,16.24%; MS.(70eV): m/z=422 (MH+); [α] 25 CHCl3) (S)-enantiomer ™+1.8°; (R)-enantiomer=-1.3°.

Workup

  1. extractionThe solution was extracted with chloroform (3×50 ml)
  2. dry with materialdried (MgSO4)
  3. filtrationAfter filtration and evaporation in vacuo the residue
  4. customwas purified by column chromatography on silica
  5. washeluting with chloroform : methanol (95:5)

Sources & evidence

ORD record
ord-33c294bd33b340028767b100229046ef
Source dataset
uspto-grants-1992_04
Patent number
US05108994

Reaction notes

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