Tetrabutylammonium Fluoride → 6-Chloro-9-[1-(diethoxyphosphorylmethoxy)-3-hydroxyprop-2-oxy]-2-formamidopurine

HRID 345064Notes

Reaction equation

HRID 345064 reaction equation
[Si]([O:8][CH2:9][CH:10]([O:22][N:23]1[CH:31]=[N:30][C:29]2[C:24]1=[N:25][C:26]([NH:33][CH:34]=[O:35])=[N:27][C:28]=2[Cl:32])[CH2:11][O:12][CH2:13][P:14]([O:19][CH2:20][CH3:21])([O:16][CH2:17][CH3:18])=[O:15])(C(C)(C)C)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>O1CCCC1>[Cl:32][C:28]1[N:27]=[C:26]([NH:33][CH:34]=[O:35])[N:25]=[C:24]2[C:29]=1[N:30]=[CH:31][N:23]2[O:22][CH:10]([CH2:9][OH:8])[CH2:11][O:12][CH2:13][P:14]([O:16][CH2:17][CH3:18])([O:19][CH2:20][CH3:21])=[O:15]

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 545026429-(1-t-Butyldimethylsilyloxy-3-diethoxyphosphorylmethoxyprop-2-oxy)-6-chloro-2-formamidopurine

Product 1

HCID 199934976-Chloro-9-[1-(diethoxyphosphorylmethoxy)-3-hydroxyprop-2-oxy]-2-formamidopurineYield 38.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 9-[1-(t-butyldimethylsilyloxy) -3-(diethoxyphosphorylmethoxy)prop-2-oxy]-6-chloro-2-formamidopurine (100mg, 0.18 mmol) in tetrahydrofuran (5 ml) was treated. with tetrabutylammonium fluoride (60mg, 0.18 mmol) and the solution stirred for 4 h at 20° C. The solvent was reduced in vacuo and the residue partitioned between saturated sodium hydrogen carbonate and dichloromethane. The dichloromethane was separated and dried (MgSO4) and the solvent evaporated in vacuo. The residue was chromatographed on silica, eluting with chloroform-methanol 20:1, affording 6-chloro-9-[1-(diethoxyphosphorylmethoxy) -3-hydroxyprop-2-oxy]2-formamidopurine (30mg, 37%) as a clear oil. νmax (film) 3400, 3250, 1700, 1610, 1570 and 1500 cm-1 ; δH (CDCl3) 1.37 (6H, t, J7.1 Hz, 2×CH2CH3), 3.84-3.96 (7H, m, CH2OH+CH2OCH2P), 4.21 (4H, m, 2×CH2CH3), 4.57 (1H, m, CHON), 8.37 (1H, s, H-8), 8.67 (1H, d, J10.1 Hz, D2O exchangeable, NH), 9.50 (1H, d, J10.1 Hz, CHO); m/z (FAB+ve Ion) 438 (MH+).

Workup

  1. customthe residue partitioned between saturated sodium hydrogen carbonate and dichloromethane
  2. customThe dichloromethane was separated
  3. dry with materialdried (MgSO4)
  4. customthe solvent evaporated in vacuo
  5. customThe residue was chromatographed on silica
  6. washeluting with chloroform-methanol 20:1

Sources & evidence

ORD record
ord-e6dad29fa1e144938afead5ac6d60a99
Source dataset
uspto-grants-1991_10
Patent number
US05055458

Reaction notes

Loading…