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

HRID 1197708노트

반응식

HRID 1197708 반응식
[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]

참가 물질

7

반응물 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

생성물 1

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

시약·촉매·용매 2

HCID 241Benzene용매HCID 8028Tetrahydrofuran용매2회

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-bccce03df94b481d99b09ad01f080aa4
출처 데이터셋
uspto-grants-1994_01
특허 번호
US05276159

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