1,3-Dibromobenzene → (+/-)-trans-6-(3-Bromophenyl)-1,2,3,4,4a,5,6,7,8,8a-decahydro-2-ethyl-4a-(3-methoxyphenyl)-6-isoquinolinol

HRID 1739781

Reaktionsgleichung

Reaktionsgleichung von HRID 1739781
C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([Br:13])[CH:8]=1.[CH2:14]([N:16]1[CH2:25][CH2:24][C@@:23]2([C:26]3[CH:31]=[CH:30][CH:29]=[C:28]([O:32][CH3:33])[CH:27]=3)[C@@H:18]([CH2:19][CH2:20][C:21](=[O:34])[CH2:22]2)[CH2:17]1)[CH3:15]>CCCCCC.C1COCC1>[NH4+:16].[OH-:32].[Br:13][C:9]1[CH:8]=[C:7]([C:21]2([OH:34])[CH2:20][CH2:19][C@@H:18]3[C@:23]([C:26]4[CH:31]=[CH:30][CH:29]=[C:28]([O:32][CH3:33])[CH:27]=4)([CH2:24][CH2:25][N:16]([CH2:14][CH3:15])[CH2:17]3)[CH2:22]2)[CH:12]=[CH:11][CH:10]=1

Komponenten

7

Edukt 3

HCID 79271,3-DibromobenzeneHCID 10517409(+/-)-trans-1,2,3,4,4a,5,6,7,8,8a-Decahydro-2-ethyl-4a-(3-methoxyphenyl)-6-isoquinolinoneHCID 178418339Butyllithium

Produkt 2

HCID 14923Ammonium HydroxideHCID 86754623(+/-)-trans-6-(3-Bromophenyl)-1,2,3,4,4a,5,6,7,8,8a-decahydro-2-ethyl-4a-(3-methoxyphenyl)-6-isoquinolinolAusbeute 47,5 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittel

Versuchsvorschrift

8.9 ml (12.5 mmol) of a 1.4 M solution of n-butyllithium in hexane were added dropwise, under a nitrogen atmosphere and at -55° C., to a solution of 2.95 g (12.5 mmol) of 1,3-dibromobenzene in 10 ml of dry THF. After 90 min this solution was added via cannula to a solution of 1.2 g (4.17 mmol) of (±)-trans-1,2,3,4,4a,5,6,7,8,8a-decahydro-2-ethyl-4a-(3-methoxyphenyl)-6-isoquinolinone in 10 ml of dry THF and at -20° C. The reaction mixture was allowed to warm up to room temperature overnight, then it was quenched with a saturated NH4Cl solution. The aqueous phase was extracted with AcOEt and the solvent was removed in vacuo. The residue was taken up in Et2O and washed with a 10% HCl solution; the phases were separated and the aqueous phase was brought to pH 14 with a 2N NaOH solution, then extracted with CH2Cl2. The organic phase was dried over Na2SO4, the solvent was removed in vacuo and the crude reaction mixture was purified by flash chromatography, eluting with a mixture CH2Cl2 /MeOH/conc. NH4OH 94.5:5:0.5 respectively, yielding 0.44 g of the title compound.

Aufarbeitung

  1. customit was quenched with a saturated NH4Cl solution
  2. extractionThe aqueous phase was extracted with AcOEt
  3. customthe solvent was removed in vacuo
  4. washwashed with a 10% HCl solution
  5. customthe phases were separated
  6. extractionextracted with CH2Cl2
  7. dry with materialThe organic phase was dried over Na2SO4
  8. customthe solvent was removed in vacuo
  9. customthe crude reaction mixture
  10. customwas purified by flash chromatography
  11. washeluting with a mixture CH2Cl2 /MeOH/conc

Quellen und Nachweise

ORD-Eintrag
ord-80b29c1eea714875a3ea9661f6672ec4
Quelldatensatz
uspto-grants-1999_10
Patentnummer
US05968949

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