Butylamine → N-[(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

HRID 260404ノート

反応式

HRID 260404 の反応式
[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[CH:25])[C:22]34[O:26][C:17]3([C:18](=[O:27])[CH2:19][CH2:20][CH2:21]4)[C:16]3[CH:15]=[C:14]([O:28][CH3:29])[CH:13]=[CH:12][C:11]2=3)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Cl[CH:31]=[CH:32][C:33]#[C:34][Si:35]([CH3:38])([CH3:37])[CH3:36].C(N)CCC>[Cu]I.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[C:25]/[CH:31]=[CH:32]\[C:33]#[C:34][Si:35]([CH3:38])([CH3:37])[CH3:36])[C:22]34[O:26][C:17]3([C:18](=[O:27])[CH2:19][CH2:20][CH2:21]4)[C:16]3[CH:15]=[C:14]([O:28][CH3:29])[CH:13]=[CH:12][C:11]2=3)=[O:9])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

参加物

6

反応物 3

HCID 8007ButylamineHCID 22401265N-[(Phenyloxy)carbonyl)-6a,10a-epoxy-6-ethynyl-2-methoxy-10-oxo-5,6,6a,7,8,9,10,10a-octahydrophenanthridineHCID 53822143(4-Chlorobut-3-en-1-yn-1-yl)(trimethyl)silane

生成物 1

HCID 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収率 73%

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 11979704Tetrakis(triphenylphosphine)palladium触媒

反応条件

温度
25 °C

実験手順

A solution of Compound 314 (5.69 g, 14.6 mmol) in dry degassed benzene (120 mL) was added to copper (I) iodide (0.666 g, 3.51 mmol), and to the resulting mixture was added 1-chloro-4-(trimethylsilyl)-but-1-en-3-yne (3.69 g, 23.4 mmol) followed by n-butylamine (2.89 mL, 29.2 mmol) and tetrakis (triphenylphosphine) palladium (0) (1.01 g, 0.877 mmol) in dry degassed benzene (60 mL). The reaction mixture was stirred at 25° C. for 2 hours, diluted with ethyl ether (200 mL), poured into saturated aqueous ammonium chloride (200 mL), and extracted with ethyl ether (2×70 mL). The combined organic layers were dried (MgSO4) and evaporated in vacuo. The residue was purified by flash column chromatography (silica, 25 percent ethyl ether in petroleum ether) to give 5.43 g (73 percent) of Compound 315: white foam; Rf =0.29 (silica, 30 percent ethyl ether in petroleum ether); IR (CHCl3) νmax 2958, 2836, 1717, 1609, 1590, 1493, 1380, 1299, 1251 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J=3.0 Hz, 1 H, aromatic), 7.38-7.06 (m, 6 H, aromatic), 6.89 (dd, J=8.9, 3.0 Hz, 1 H, aromatic), 5.92 (d, J=1.6 Hz, 1 H, H6), 5.86 (d, J=11.0 Hz, 1 H, olefinic), 5.65 (br d, J=11.0 Hz, 1 H, olefinic), 3.81 (s, 3 H, OCH3), 2.78-2.62 (m, 2 H, H9), 2.37-2.25 (m, 2 H, H7), 2.05-1.85 (m, 2 H, H8), 0.20 (s, 9 H, Si(CH3)3); 13C NMR (125 MHz, CDCl3) δ 201.2, 157.2, 154.1, 151.0, 129.3, 128.6, 128.5, 125.7, 124.0, 121.4, 120.7, 118.9, 114.8, 114.8, 103.5, 101.5, 90.5, 83.0, 74.6, 57.4, 55.4, 48.4, 38.8, 23.8, 18.2, -0.17; MS (FAB+) m/e (rel intensity) 511 (M+, 100), 390 (8), 362 (9), 176 (11), 120 (10); HRMS for C30H29NO5Si (M+), calcd 511.1815, found 511.1815.

後処理

  1. customdegassed benzene (120 mL)
  2. customin dry
  3. customdegassed benzene (60 mL)
  4. additiondiluted with ethyl ether (200 mL)
  5. additionpoured into saturated aqueous ammonium chloride (200 mL)
  6. extractionextracted with ethyl ether (2×70 mL)
  7. dry with materialThe combined organic layers were dried (MgSO4)
  8. customevaporated in vacuo
  9. customThe residue was purified by flash column chromatography (silica, 25 percent ethyl ether in petroleum ether)

出典と根拠

ORDレコード
ord-e6e5749d92d4413689b3c97c61bcd01c
出典データセット
uspto-grants-1996_06
特許番号
US05527805

反応ノート

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