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

HRID 1708092

반응식

HRID 1708092 반응식
[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]

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

반응 조건

온도
0 °C

실험 절차

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%).

후처리

  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)

출처 및 근거

ORD 기록
ord-2ce9467bafca43759eadb142f202b8f4
출처 데이터셋
uspto-grants-1994_10
특허 번호
US05356886

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