Potassium Cyanide → N-[(Phenyloxy)carbonyl]-6-[3(Z)-hexene-1,5-diynyl]-6a,10a-epoxy-2-methoxy-10-oxo-5,6,6a,7,8,9,10,10a,-octahydrophenanthridine

HRID 260405노트

반응식

HRID 260405 반응식
[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[C:25]/[CH:26]=[CH:27]\[C:28]#[C:29][Si](C)(C)C)[C:22]34[O:34][C:17]3([C:18](=[O:35])[CH2:19][CH2:20][CH2:21]4)[C:16]3[CH:15]=[C:14]([O:36][CH3:37])[CH:13]=[CH:12][C:11]2=3)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C-]#N.[K+]>O.CCO.C1COCC1.[N+]([O-])([O-])=O.[Ag+]>[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[C:25]/[CH:26]=[CH:27]\[C:28]#[CH:29])[C:22]34[O:34][C:17]3([C:18](=[O:35])[CH2:19][CH2:20][CH2:21]4)[C:16]3[CH:15]=[C:14]([O:36][CH3:37])[CH:13]=[CH:12][C:11]2=3)=[O:9])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

참가 물질

5

반응물 2

HCID 9032Potassium CyanideHCID 86747542N-[(Phenyloxy)carbonyl)-6-[6-(trimethylsilyl)-3(Z)-hexene-1,5-diynyl]-6a,10a-epoxy-2-methoxy-10-oxo-5,6,6a,7,8,9,10,10a-octahydrophenanthridine

생성물 1

HCID 88413792N-[(Phenyloxy)carbonyl]-6-[3(Z)-hexene-1,5-diynyl]-6a,10a-epoxy-2-methoxy-10-oxo-5,6,6a,7,8,9,10,10a,-octahydrophenanthridine수율 88%

시약·촉매·용매 2

HCID 24470Silver Nitrate촉매HCID 18504229Ethanol tetrahydrofuran water용매

실험 절차

Silver nitrate (1.43 g, 8.44 mmol) was added to a solution of Compound 315 (1.08 g, 2.11 mmol) in 48 mL of H2O-EtOH-THF (1:1:1) at 25° C. followed by stirring for 15 minutes. Potassium cyanide (0.962 g, 14.8 mmol) was then added and the mixture was stirred for one hour, concentrated in vacuo to 20 mL, poured into saturated aqueous sodium bicarbonate (30 mL), and extracted with dichloromethane (3×40 mL). The combined organic layers were dried (MgSO4) and evaporated in vacuo, and the residue was purified by flash column chromatography (silica, 35 percent ethyl ether in petroleum ether) to give 0.807 g (88 percent) of Compound 316: white foam Rf =0.22 (silica, 40 percent ethyl ether in petroleum ether); IR (CHCl3) νmax 3299, 2947, 1716, 1609, 1590, 1501, 1493, 1380, 1299, 1253 cm-1 ; 1H NMR (500 MHz, CDCl3 ) 7.96 (d, J=2.9 Hz, 1 H, aromatic), 7.38-7.07 (m, 6 H, aromatic), 6.89 (dd, J=8.9, 2.9 Hz, 1 H, aromatic), 5.88 (s, 1 H, H6), 5.77 and 5.74 (ABq, J=11.2 Hz, 2 H, olefinic), 3.81 (s, 3 H, OCH3), 3.16 (d, J=1.5 Hz, 1 H, C≡CH), 2.74 (dt, J=15.3, 5.0 Hz, 1 H, H9), 2.67 (ddd, J=15.3, 10.1, 6.1 Hz, 1 H, H9), 2.36-2.26 (m, 2 H, H7), 1.99-1.89 (m, 2 H, H8); 13C NMR (125 MHz, CDCl3) δ 201.5, 157.2, 154.1, 151.0, 129.3, 128.7, 128.5, 125.7, 124.1, 121.4, 120.4, 120.3, 114.8, 114.7, 90.6, 85.1, 82.7, 80.3, 74.9, 57.4, 55.5, 48.3, 38.8, 23.8, 18.6; MS (FAB+) m/e (rel intensity) 439 (M+, 100), 364 (8), 176 (19), 120 (10); HRMS for C27H21NO5 (M+), calcd 439.1420, found 439.1434.

후처리

  1. stirringthe mixture was stirred for one hour
  2. concentrationconcentrated in vacuo to 20 mL
  3. additionpoured into saturated aqueous sodium bicarbonate (30 mL)
  4. extractionextracted with dichloromethane (3×40 mL)
  5. dry with materialThe combined organic layers were dried (MgSO4)
  6. customevaporated in vacuo
  7. customthe residue was purified by flash column chromatography (silica, 35 percent ethyl ether in petroleum ether)

출처 및 근거

ORD 기록
ord-066367dfec5a4db08065f0ccdb4d0a8f
출처 데이터셋
uspto-grants-1996_06
특허 번호
US05527805

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