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

HRID 1708091ノート

反応式

HRID 1708091 の反応式
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]

参加物

4

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

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%).

後処理

  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

出典と根拠

ORDレコード
ord-f6d2aabe74ee4756b4a3b191f4c04e2c
出典データセット
uspto-grants-1994_10
特許番号
US05356886

反応ノート

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