Hydrochloric Acid → 3beta-(3,4-Dichlorophenyl)-2beta-chloromethyltropane

HRID 1597719노트

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HRID 1597719 반응식
[Mg].[Cl:2][C:3]1[CH:4]=[C:5](I)[CH:6]=[CH:7][C:8]=1[Cl:9].[CH3:11][N:12]1[C@H:16]2[C:17]([C:20](OC)=O)=[CH:18][CH2:19][C@@H:13]1[CH2:14][CH2:15]2.FC(F)(F)C(O)=O.[ClH:31]>CCOCC.C(N(CC)CC)C.CCOCC>[Cl:2][C:3]1[CH:4]=[C:5]([C@H:18]2[CH2:19][C@H:13]3[N:12]([CH3:11])[C@H:16]([CH2:15][CH2:14]3)[C@H:17]2[CH2:20][Cl:31])[CH:6]=[CH:7][C:8]=1[Cl:9]

참가 물질

8

반응물 5

HCID 313Hydrochloric AcidHCID 6422Trifluoroacetic acidHCID 88591Benzene, 1,2-dichloro-4-iodo-HCID 119478(-)-Anhydroecgonine methyl esterHCID 5462224Magnesium

생성물 1

HCID 696847063beta-(3,4-Dichlorophenyl)-2beta-chloromethyltropane수율 9%

시약·촉매·용매 2

HCID 3283Diethyl Ether용매HCID 22234951Ether triethylamine용매

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온도
-78 °C

실험 절차

To a three-neck, round-bottomed flask containing freshly distilled ether (125 mL) and magnesium turnings (268 mg, 11.0 mmol),was added 3,4-dichloroiodobenzene (2.26 g, 8.27 mmol). After 2 h, the reaction flask was equipped with a mechanical stirrer, and the Grignard reagent was cooled to -55° C. before adding anhydroecgonine methyl ester (500 mg, 2.75 mmol). The resulting solution was stirred for an additional 2.5 h before being cooled to -78° C. After 1 h, 2 mL of trifluoroacetic acid was added to the solution followed by 2 h of stirring. The quenched reaction mixture was then diluted with 1N HCl (100 mL) and extracted with ether (3×100 mL). The ethereal layers were discarded, and the aqueous layer was basified with conc. ammonium hydride and then extracted with chloroform (3×50 mL). The combined organic layers were dried (MgSO4) and concentrated under reduced pressure to yield the crude product as a colorless oil. Flash chromatography (ether triethylamine, 9:1) yielded 71 mg (9.0%) of pure product: 1H NMR (250 MHz, CDCl3) δ1.52-1.76 (m, 2), 1.81-1.95 (m, 2), 1.96-2.22 (m, 2), 2.38 (s, 3), 3.07-3.15 (br s, 2), 3.21-3.32 (br s, 1), 3.45-3.65 (m, 1), 3.50 (s, 3), 7.10-7.38 (m, 3).

후처리

  1. customthe reaction flask was equipped with a mechanical stirrer
  2. waitAfter 1 h
  3. waitfollowed by 2 h
  4. stirringof stirring
  5. customThe quenched reaction mixture
  6. extractionextracted with ether (3×100 mL)
  7. extractionextracted with chloroform (3×50 mL)
  8. dry with materialThe combined organic layers were dried (MgSO4)
  9. concentrationconcentrated under reduced pressure
  10. customto yield the crude product as a colorless oil

출처 및 근거

ORD 기록
ord-1739749da49543aa9839a37576ae0dff
출처 데이터셋
uspto-grants-1998_04
특허 번호
US05736123

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