Triphenylphosphine → (E)-6-chloro-9-[4-(diisopropoxyphosphoryl)but-3-enyl]purine

HRID 1708092

反応式

HRID 1708092 の反応式
[Cl:1][C:2]1[N:10]=[CH:9][N:8]=[C:7]2[C:3]=1[NH:4][CH:5]=[N:6]2.O[CH2:12][CH2:13]/[CH:14]=[CH:15]/[P:16](=[O:25])([O:21][CH:22]([CH3:24])[CH3:23])[O:17][CH:18]([CH3:20])[CH3:19].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[Cl:1][C:2]1[N:10]=[CH:9][N:8]=[C:7]2[C:3]=1[N:4]=[CH:5][N:6]2[CH2:12][CH2:13]/[CH:14]=[CH:15]/[P:16]([O:21][CH:22]([CH3:23])[CH3:24])([O:17][CH:18]([CH3:19])[CH3:20])=[O:25]

参加物

6

反応物 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 53592776-ChloropurineHCID 10399205diisopropyl (E)-4-hydroxybut-1-enylphosphonate

生成物 1

HCID 10067914(E)-6-chloro-9-[4-(diisopropoxyphosphoryl)but-3-enyl]purine収率 37.2%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

To a mixture of 6-chloropurine (414 mg, 2.67 mmol), diisopropyl (E)-4-hydroxybut-1-enylphosphonate (630 mg, 2.67 mmol) and triphenyl phosphine (1.05 g, 4.00 mmol) in dry tetrahydrofuran (30 ml) stirred at 0° C. was added diethyl azodicarboxylate (0.70 g, 4.02 mmol). The mixture was allowed to warm to room temperature and stirred for 27.5 hr. The solvent was removed and the residue Was purified by column chromatography on silica gel eluting with dichloro-methane-methanol (24:1, 13:1) to give (E)-6-chloro-9-[4-(diisopropoxyphosphoryl)but-3-enyl]purine as a white solid (0.37 g, 37%), m.p. 105° C.; λmax (EtOH) 266 (9,260)nm; υmax (KBr) 3435, 2980, 1590, 1560, 1330, 1230 and 1210 cm-1 ; δH (CDCl3) 1.25 (12H, dd, J 6 Hz and 21 Hz, CH(CH3)2), 2.88 (2H, m, CH2), 4.45 (2H, t, J 7 Hz, CH2N), 4.55 (2H, m, CH(CH3)2), 5.68 (1H, dd, J 17 Hz and 20 Hz PCH=CH), 6.70 (1H, ddt, J 7 Hz, 17 Hz and 22 Hz, PCH=CH), 8.10 (1H, s, H-2/H-8), 8.77 (1H, s, H-2/H-8); FABMS (thioglycerol) 373 (MH+) (Found: C, 48.40; H, 6.03; N, 14.81%. C15H22ClN4O3P requires C, 48.33; H, 5.95; N, 15.03%).

後処理

  1. temperatureto warm to room temperature
  2. stirringstirred for 27.5 hr
  3. customThe solvent was removed
  4. customthe residue Was purified by column chromatography on silica gel eluting with dichloro-methane-methanol (24:1, 13:1)

出典と根拠

ORDレコード
ord-2ce9467bafca43759eadb142f202b8f4
出典データセット
uspto-grants-1994_10
特許番号
US05356886

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