Hexane → (R)-9-[2-(diethoxyphosphorylmethoxy)-3-hydroxypropoxy)adenine

HRID 6267ノート

反応式

HRID 6267 の反応式
[Si]([O:18][CH2:19][C@@H:20]([O:33][CH2:34][P:35]([O:40][CH2:41][CH3:42])([O:37][CH2:38][CH3:39])=[O:36])[CH2:21][O:22][N:23]1[CH:31]=[N:30][C:29]2[C:24]1=[N:25][CH:26]=[N:27][C:28]=2[NH2:32])(C(C)(C)C)(C1C=CC=CC=1)C1C=CC=CC=1.CCCCCC>FC(F)(F)C(O)=O.O>[CH2:41]([O:40][P:35]([CH2:34][O:33][C@H:20]([CH2:19][OH:18])[CH2:21][O:22][N:23]1[CH:31]=[N:30][C:29]2[C:24]1=[N:25][CH:26]=[N:27][C:28]=2[NH2:32])([O:37][CH2:38][CH3:39])=[O:36])[CH3:42]

参加物

4

反応物 2

HCID 8058HexaneHCID 53833998(S)-9-[3-(t-Butyldiphenylsilyloxy)-2-(diethoxyphosphorylmethoxy)propoxy]adenine

生成物 1

HCID 54312423(R)-9-[2-(diethoxyphosphorylmethoxy)-3-hydroxypropoxy)adenine収率 80%

試薬・触媒・溶媒 1

HCID 22392675Trifluoroacetic acid water溶媒

実験手順

(S)-9-[3-(t-Butyldiphenylsilyloxy)-2-(diethoxyphosphorylmethoxy)propoxy]adenine (0.61 g, 1 mmol) was dissolved in trifluoroacetic acid/water, 2:1 (6 ml) and the solution stirred at ambient temperature for 3 hours. Hexane (10 ml) was added and the mixture shaken. The aqueous phase was separated, washed once more with hexane (10 ml) and evaporated to dryness. The residue was treated with ethanolic ammonia solution (5 ml), at ambient temperature, for 5 minutes after which the solution was evaporated to dryness. The residue was chromatographed on silica gel using dichloromethane/methanol 90:10 as eluant to give (R)-9-[2-(diethoxyphosphorylmethoxy)-3-hydroxypropoxy]adenine as a colourless oil (0.3 g, 80%) which on prolonged standing, crystallised as white needles m.p. 98°-102°. IR: νmax (film) 3340, 3210, 2995, 2930, 2910, 1660, 1645, 1600, 1470, 1445, 1415, 1395, 1370, 1330, 1300, 1240, 1210, 1165, 1125, 1045. 1020, 980, 825, 95, 735 cm-1. 1H NMR: δH [(CD3)2SO] 1.23 (6H, t, J=7 Hz (OCH2CH3)2), 3.5-3.7 (2H, m, CH2OH), 3.75-3.85 (1H, m, CH), 3.95-4.15 (6H, m, (OCH2CH3)2, OCH2P), 4.38 (1H, dd, J=11.3 Hz, J=6.6 Hz, NOCHB), 4.55 (1H, dd, J= 11.3 Hz, J=3.0 Hz, NOCHA), 4.88 (1H, t, J=5.5 Hz, D2O exchangeable OH), 7.38 (2H, br.s., D2O exchangeable NH2), 8.15 (1H, s, H-2 or H-8), 8.43 (1H, s, H-2 or H-8). Found: C, 39.26; H, 6.05; N, 17.33%. C13H22N5O6P 1.25 H2O requires: C, 39.25; H, 6.20; N, 17 61%. m/z: (FAB, thioglycerol matrix) 376 (MH+).

後処理

  1. stirringthe mixture shaken
  2. customThe aqueous phase was separated
  3. washwashed once more with hexane (10 ml)
  4. customevaporated to dryness
  5. additionThe residue was treated with ethanolic ammonia solution (5 ml), at ambient temperature, for 5 minutes after which the solution
  6. customwas evaporated to dryness
  7. customThe residue was chromatographed on silica gel

出典と根拠

ORDレコード
ord-582e76d720ad40bb92003abde5f4f836
出典データセット
uspto-grants-1993_09
特許番号
US05247085

反応ノート

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