Diethyl Ether → 10-[(tert-Butyldimethylsilyl)oxy]-3-(trimethylacetoxy)-7,8,9,10-tetrahydrophenanthridine

HRID 1197708ノート

反応式

HRID 1197708 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+].[CH3:26][C:27]([CH3:37])([CH3:36])[C:28](N1CCSC1=S)=[O:29].C(OCC)C>C1COCC1.C1C=CC=CC=1>[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][C:28](=[O:29])[C:27]([CH3:37])([CH3:36])[CH3:26])=[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 3283Diethyl EtherHCID 24758Sodium hydrideHCID 117695952,2-Dimethyl-1-(2-thioxothiazolidin-3-yl)propan-1-oneHCID 13576196710-[(tert-Butyldimethylsilyl)oxy]-3-hydroxy-7,8,9,10-tetrahydrophenanthridine

生成物 1

HCID 1181173110-[(tert-Butyldimethylsilyl)oxy]-3-(trimethylacetoxy)-7,8,9,10-tetrahydrophenanthridine収率 99.1%

試薬・触媒・溶媒 2

HCID 241Benzene溶媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a suspension of Compound 141a (1.28 g, 3.88 mmol) in dry THF (50 mL) cooled in an ice-water bath was added NaH (60 percent, 163 mg, 4.08 mmol) followed by stirring for 10 minutes. A yellow-colored solution of Compound 226 (0.789 g, 3.88 mmol) in dry THF (10 mL) was added, and the mixture was then stirred at 25° C. for five minutes. The reaction mixture was quenched with water, extracted with ethyl acetate (50 mL), washed with brine, dried over anhydrous Na2SO4, and evaporated in vacuo to give a residue. Flash column chromatography of the residue (silica gel, 20 percent ethyl ether in benzene) provided Compound 142a (1.59 g, 99 percent): white powder; mp 125°-126.5° C.; Rf =0.49 (silica, 20 percent ethyl ether in benzene); IR (CHCl3) νmax 2957, 2934, 1750, 1261, 1131, 1116, 1027 cm-1 ; 1H NMR (300 MHz, CDCl3) δ8.58 (s, 1 H, H6), 7.98 (d, J=9.1 Hz, 1 H, H1), 7.67 (d, J=2.1 Hz, 1 H, H4), 7.21 (dd, J=9.1 2.1 Hz, 1 H, H2), 5.33 (t, J=2.9 Hz, 1 H, H10), 2.90 (br dd, J=17.2, 3.3 Hz, 1 H, H7), 2.72 (ddd, J=17.2, 11.2, 5.7 Hz, 1 H, H7), 2.17-1.96 (m, 2 H, H8 or H9), 1.83-1.67 (m, 2 H, H8 or H9), 1.31 (s, 9 H, COC(CH3)3), 0.74 (s, 9 H, SiC(CH3)3), 0.12 (s, 6 H, Si(CH3)2); MS (FAB+) m/e (rel intensity) 414 (M+H, 100), 357 (9), 330 (12), 283 (5), 198 (10); HRMS for C24H36NO3Si (M+H), calcd 414.2464, found 414.2484. Anal. Calcd for C24H35NO3Si: C, 69.69; H, 8.53; N, 3.39. Found: C, 69.68; H, 8.44; N, 3.23.

後処理

  1. temperaturecooled in an ice-water bath
  2. stirringthe mixture was then stirred at 25° C. for five minutes
  3. customThe reaction mixture was quenched with water
  4. extractionextracted with ethyl acetate (50 mL)
  5. washwashed with brine
  6. dry with materialdried over anhydrous Na2SO4
  7. customevaporated in vacuo
  8. customto give a residue

出典と根拠

ORDレコード
ord-bccce03df94b481d99b09ad01f080aa4
出典データセット
uspto-grants-1994_01
特許番号
US05276159

反応ノート

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