Methyl chloroformate → 3-Methoxy-9-(4-methoxy-phenyl)-4b,5,6,7,8,8a,9,10-octahydro-phenanthrene-2-carboxylic acid methyl ester

HRID 418942Notes

Reaction equation

HRID 418942 reaction equation
Br[C:2]1[CH:15]=[C:14]2[C:5]([CH:6]3[CH:11]([CH:12]([C:16]4[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=4)[CH2:13]2)[CH2:10][CH2:9][CH2:8][CH2:7]3)=[CH:4][C:3]=1[O:24][CH3:25].C[Li].[Li]C(C)(C)C.Cl[C:34]([O:36][CH3:37])=[O:35]>O1CCCC1>[CH3:37][O:36][C:34]([C:2]1[C:3]([O:24][CH3:25])=[CH:4][C:5]2[CH:6]3[CH:11]([CH2:10][CH2:9][CH2:8][CH2:7]3)[CH:12]([C:16]3[CH:17]=[CH:18][C:19]([O:22][CH3:23])=[CH:20][CH:21]=3)[CH2:13][C:14]=2[CH:15]=1)=[O:35]

Participants

6

Reactant 4

HCID 6586Methyl chloroformateHCID 666520557-Bromo-6-methoxy-10-(4-methoxy-phenyl)-1,2,3,4,4a,9,10,10a-octahydro-phenanthreneHCID 178418306HCID 178418306, compoundHCID 178418348HCID 178418348, compound

Product 1

HCID 666521243-Methoxy-9-(4-methoxy-phenyl)-4b,5,6,7,8,8a,9,10-octahydro-phenanthrene-2-carboxylic acid methyl esterYield 110.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

At −78° C., combine 7-Bromo-6-methoxy-10-(4-methoxy-phenyl)-1,2,3,4,4a,9,10,10a-octahydro-phenanthrene (0.2 g, 0.5 mmol), tetrahydrofuran (4 ml), CH3Li (0.623 ml, 1.6M), then add t-BuLi (0.59 ml, 1.7M). After 30 minutes add methyl chloroformate (0.19 g, 2.0 mmol) and remove cooling. After 2 hours at r.t., add ammonium chloride solution solution and ethyl acetate. Wash organic layer with water, dry over anhydrous sodium sulfate, remove solvent in vacuo to yield the titled compound (0.21 g, 100%). MS m/z 381 (M−1).

Workup

  1. customAt −78° C.
  2. customremove
  3. temperaturecooling
  4. additionadd ammonium chloride solution solution and ethyl acetate
  5. dry with materialWash organic layer with water, dry over anhydrous sodium sulfate
  6. customremove solvent in vacuo

Sources & evidence

ORD record
ord-be87a583eeb841f4bf45f85d8d2a4013
Source dataset
uspto-grants-2012_01
Patent number
US08093302B2

Reaction notes

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