Water → 10-[(tert-Butyldimethylsilyl)oxy]-3-[(2-nitrobenzyl)oxy]-7,8,9,10-tetrahydrophenanthridine

HRID 1198794ノート

反応式

HRID 1198794 の反応式
[Si:1]([O:8][CH:9]1[C:22]2[C:13](=[CH:14][N:15]=[C:16]3[C:21]=2[CH:20]=[CH:19][C:18]([OH:23])=[CH:17]3)[CH2:12][CH2:11][CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[H-].[Na+].[N+:26]([C:29]1[CH:36]=[CH:35][CH:34]=[CH:33][C:30]=1[CH2:31]Br)([O-:28])=[O:27].O>C1COCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[Si:1]([O:8][CH:9]1[C:22]2[C:13](=[CH:14][N:15]=[C:16]3[C:21]=2[CH:20]=[CH:19][C:18]([O:23][CH2:31][C:30]2[CH:33]=[CH:34][CH:35]=[CH:36][C:29]=2[N+:26]([O-:28])=[O:27])=[CH:17]3)[CH2:12][CH2:11][CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

参加物

7

反応物 4

HCID 962WaterHCID 24758Sodium hydrideHCID 77569alpha-Bromo-2-nitrotolueneHCID 13576196710-[(tert-Butyldimethylsilyl)oxy]-3-hydroxy-7,8,9,10-tetrahydrophenanthridine

生成物 1

HCID 1503834510-[(tert-Butyldimethylsilyl)oxy]-3-[(2-nitrobenzyl)oxy]-7,8,9,10-tetrahydrophenanthridine収率 90.2%

試薬・触媒・溶媒 2

HCID 67553Tetrabutylammonium Iodide触媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a suspension of Compound 141a (1.00 g, 3.03 mmol) in dry THF (20 mL) cooled in an ice-water bath was added NaH (60 percent, 128 mg, 3.19 mmol) followed by stirring for 10 minutes. To the resultant solution was added 2-nitrobenzyl bromide (0.689 g, 3.19 mmol) and tetra-n-butylammonium iodide (0.11 g, 0.3 mmol), and the mixture was then stirred at 25° C. for one hour. Water was added to the reaction mixture followed by extraction with ethyl acetate (50 mL), washing with brine, dry over anhydrous Na2SO4, and concentration in vacuo to give a crude product. Flash column chromatography of the crude product (silica gel, 20 percent ethyl ether in benzene) afforded Compound 143a (1.27 g, 90 percent): pale-yellow solid; mp 150°-152° C.; Rf =0.33 (silica, 20 percent ethyl ether in benzene); IR (CHCl3) νmax 2953, 2933, 1623, 1528, 1343, 1090, 1027, 838 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 8.60 (s, 1 H, H6), 8.21 (dd, J=8.0, 0.9 Hz, 1 H, aromatic), 8.01 (d, J=9.2 Hz, 1 H, H1), 7.92 (d, J=7.8 Hz, 1 H, aromatic), 7.68 (dt, J=7.8, 0.9 Hz, 1 H, aromatic), 7.50 (t, J=8.0 Hz, 1 H, aromatic), 7.44 (d, J=2.6 Hz, 1 H, H4), 7.32 (dd, J=9.2, 2.6 Hz, 1 H, H2), 5.66 (s, 2 H, benzylic), 5.42 (t, J=3.1 Hz, 1 H, H10), 2.97 (br dd, J=14.0, 4.0 Hz, 1 H, H7), 2.86-2.72 (m, 1 H, H7), 2.25-2.15 (m, 2 H, H8 or H9), 1.90-1.80 (m, 2 H, H8 or H9), 0.85 (s, 9 H, SiC(CH3)3), 0.22 (s, 6 H, Si(CH3)2); MS (FAB+) m/e (rel intensity) 465 (M+Cs, 100), 407 (19), 330 (26), 198 (17), 136 (18); HRMS for C26H32N2O4SiCs (M+Cs), calcd 465.2210, found 465.2210. Anal. Calcd for C26H32N2O4Si: C, 67.21; H, 6.94; N, 6.03. Found: C, 67.31; H, 6.91; N, 5.96.

後処理

  1. temperaturecooled in an ice-water bath
  2. stirringthe mixture was then stirred at 25° C. for one hour
  3. extractionfollowed by extraction with ethyl acetate (50 mL)
  4. washwashing with brine
  5. dry with materialdry over anhydrous Na2SO4, and concentration in vacuo
  6. customto give a crude product

出典と根拠

ORDレコード
ord-0035a2ab25d14075b54730c31230151f
出典データセット
uspto-grants-1994_01
特許番号
US05281710

反応ノート

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