Allyl bromide → 4-[10,11-dihydro-5-(2-propenyl)-5H-dibenzo[a,d]cyclohepten-5-yl]-1-methyl-1,2,5,6-tetrahydropyridine

HRID 128636

반응식

HRID 128636 반응식
[CH:1]1[C:11]2[CH2:10][CH2:9][C:8]3[CH:12]=[CH:13][CH:14]=[CH:15][C:7]=3[C:6](=[C:16]3[CH2:21][CH2:20][N:19]([CH3:22])[CH2:18][CH2:17]3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.[CH2:23]([Li])[CH2:24][CH2:25]C.C(Br)C=C>C1COCC1>[CH2:25]([C:6]1([C:16]2[CH2:17][CH2:18][N:19]([CH3:22])[CH2:20][CH:21]=2)[C:7]2[CH:15]=[CH:14][CH:13]=[CH:12][C:8]=2[CH2:9][CH2:10][C:11]2[CH:1]=[CH:2][CH:3]=[CH:4][C:5]1=2)[CH:24]=[CH2:23]

참가 물질

5

반응물 3

HCID 7841Allyl bromideHCID 1688974-(10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene)-1-methylpiperidineHCID 178418339Butyllithium

생성물 1

HCID 97975634-[10,11-dihydro-5-(2-propenyl)-5H-dibenzo[a,d]cyclohepten-5-yl]-1-methyl-1,2,5,6-tetrahydropyridine수율 70.2%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

반응 조건

온도
-78 °C

실험 절차

Dissolved 4-(10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene)-1-methylpiperidine (10 g, 34.6 mmol) in 200 mL of dry THF, and cooled to -78° C. under a nitrogen atmosphere. Added n-butyl lithium (15.2 mL of 2.5M in hexane, 38.0 mmol) dropwise via syringe. Warmed to 0° C, and stirred for 60 mins. Recooled to -78° C, and added allyl bromide (4.6 g, 3.3 mL, 38.0 mmol) dropwise via syringe. Warmed to room temperature slowly, and stirred for 5 hours. Added saturated NH4Cl, and extracted with ether. Dried the combined organic extracts with MgSO4, filtered, and evaporated. Purified the crude product by flash chromatography on silica gel eluting with 5:95:0.1MeOH:EtOAc:NH4OH. Combined appropriate fractions, and evaporated to give 8.0 g (70% yield) of 4-[10,11-dihydro-5-(2-propenyl)-5H-dibenzo[a,d]cyclohepten-5-yl]-1-methyl-1,2,5,6-tetrahydropyridine as an oil. Dissolved free base in ether, and added 19 weight % HCl-EtOH until acidic. Added additional ether, and let stand to precipitate hydrochloride salt. Recrystallized salt from acetonitrile-ether.

후처리

  1. temperatureWarmed to 0° C
  2. customRecooled to -78° C
  3. temperatureWarmed to room temperature slowly
  4. stirringstirred for 5 hours
  5. extractionAdded saturated NH4Cl, and extracted with ether
  6. dry with materialDried the combined organic extracts with MgSO4
  7. filtrationfiltered
  8. customevaporated
  9. customPurified the crude product by flash chromatography on silica gel eluting with 5:95:0.1MeOH
  10. customevaporated

출처 및 근거

ORD 기록
ord-b8b318ee6be64d839f225e10ae65e2a6
출처 데이터셋
uspto-grants-1995_11
특허 번호
US05464840

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