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

HRID 1708091Notes

Reaction equation

HRID 1708091 reaction equation
C([O:4][P:5](/[CH:11]=[CH:12]/[CH2:13][CH2:14][O:15][N:16]1[CH:24]=[N:23][C:22]2[C:17]1=[N:18][CH:19]=[N:20][C:21]=2[NH2:25])([O:7]C(C)C)=[O:6])(C)C.Br[Si](C)(C)C>ClCCl>[P:5](/[CH:11]=[CH:12]/[CH2:13][CH2:14][O:15][N:16]1[CH:24]=[N:23][C:22]2[C:17]1=[N:18][CH:19]=[N:20][C:21]=2[NH2:25])([OH:6])([OH:7])=[O:4]

Participants

4

Reactant 2

HCID 76113BromotrimethylsilaneHCID 10067662(E)-9-[4-(diisopropoxyphosphoryl)but-3-enyloxy]adenine

Product 1

HCID 6474323[(E)-4-(6-aminopurin-9-yl)oxybut-1-enyl]phosphonic acidYield 84%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of (E)-9-[4-(diisopropoxyphosphoryl)but-3-enyloxy]adenine (105 mg, 284 μmol) in dichloromethane was added bromotrimethylsilane (0.87 g, 5.68 mmol). The resulting white suspension was stirred at room temperature under dry nitrogen for 18 hr. The solution was evaporated to dryness and the residue azeotroped with methanol (×3). The residue was purified by column chromatography on reverse phase silica gel eluting with water to give (E)-9-(4-phosphonobut-3-enyloxy)adenine as a white solid (68 mg, 84%), m.p. 249°-251° C.; λmax (MeOH) 260 (11,985)nm; υmax (KBr) 3110, 2300, 1695, 1470, 1410, 1330 and 1030 cm-1 ; δH[(CD3)2SO] 2.62 (2H, m, CH2), 4.50 (2t, t, J 7 Hz, CH2O ), 5.94 (1H, dd, J 17 Hz and 22 Hz, PCH=CH), 6.50 (1H, ddt, J 6 Hz, 17 Hz and 22 Hz, PCH=CH), 7.39 (2H, br.s, NH2), 8.16 (1H, s, H-2/H-8), 8.35 (1H, s, H-2/H-8); FABMS (thioglycerol) 286 (MH+) (Found: C, 35.75; H, 4.00; N, 23.14; Br, 5.41%. C9H12N5O4P.0.2HBr requires C, 35.86; H, 4.08; N, 23.24; Br, 5.30%).

Workup

  1. customThe solution was evaporated to dryness
  2. customthe residue azeotroped with methanol (×3)
  3. customThe residue was purified by column chromatography on reverse phase silica gel eluting with water

Sources & evidence

ORD record
ord-f6d2aabe74ee4756b4a3b191f4c04e2c
Source dataset
uspto-grants-1994_10
Patent number
US05356886

Reaction notes

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