Bromotrimethylsilane → [(Z)-4-(6-aminopurin-9-yl)oxybut-1-enyl]phosphonic acid

HRID 1708100Notes

Reaction equation

HRID 1708100 reaction equation
C([O:3][P:4](/[CH:9]=[CH:10]\[CH2:11][CH2:12][O:13][N:14]1[CH:22]=[N:21][C:20]2[C:15]1=[N:16][CH:17]=[N:18][C:19]=2[NH2:23])([O:6]CC)=[O:5])C.Br[Si](C)(C)C>ClCCl>[P:4](/[CH:9]=[CH:10]\[CH2:11][CH2:12][O:13][N:14]1[CH:22]=[N:21][C:20]2[C:15]1=[N:16][CH:17]=[N:18][C:19]=2[NH2:23])([OH:5])([OH:6])=[O:3]

Participants

4

Reactant 2

HCID 76113BromotrimethylsilaneHCID 10088675HCID 10088675, compound

Product 1

HCID 6474312[(Z)-4-(6-aminopurin-9-yl)oxybut-1-enyl]phosphonic acidYield 81%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of (Z)-9-[4-(diethoxyphosphoryl)-but-3-enyloxy]adenine (145 mg, 425 μmol) in dichlormethane (10 ml) was added bromotrimethylsilane (1.29 g, 8.48 mmol) and the resulting solution was stirred at room temperature under dry nitrogen for 18 hr. The solvent was removed and the residue was azeotroped with methanol (×5). The residue was purified by column chromatography on reverse phase silica gel eluting with water to give (Z)-9-(4-phosphonobut-3-enyloxy]adenine as a white solid (98 mg, 81%), m.p. 238° C.; λmax (MeOH) 260 (13,515)nm; υmax (KBr) 3420, 3200, 3085, 2970, 1700, 1610, 1485, 1415 and 1335 cm-1 ; δH [(CD3)2SO] 2.94 (2H, m, CH2), 4.43 (2H, t, J 7 Hz, CH2O ), 5.77 (1H, dd, J 14 Hz and 17 Hz, PCH=CH), 6.40 (1H, ddt, J 7 Hz, 14 Hz and 47 Hz, PCH=CH), 7.40 (2H, br.s, NH2). 8.15 (1H, s, H-2/H-8), 8.42 (1H, s, H-2/H-8); FABMS (thioglycerol) 286 (NH+) (Found: C, 36.71; H, 4.16; N, 23.96%. C9H12N5O4P.0.4H20 requires C, 36.96; H, 4.41; N, 23.95%).

Workup

  1. customThe solvent was removed
  2. customthe residue was azeotroped with methanol (×5)
  3. customThe residue was purified by column chromatography on reverse phase silica gel eluting with water

Sources & evidence

ORD record
ord-eeda8d0c4855473ab7781af81b6d8776
Source dataset
uspto-grants-1994_10
Patent number
US05356886

Reaction notes

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