Nitrogen → HCID 66652116, compound

HRID 418919Notes

Reaction equation

HRID 418919 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:14](=[CH:15][CH:16]=1)[C:13](=[O:17])[CH2:12][CH:11]1[CH:6]2[CH2:7][C:8]([CH3:19])([CH3:18])[CH2:9][CH2:10]1.Br[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=1[O:27][CH3:28].N#N.CC(C)([O-])C.[Na+]>O1CCOCC1>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:14](=[CH:15][CH:16]=1)[C:13](=[O:17])[CH:12]([C:25]1[CH:24]=[CH:23][C:22]([O:27][CH3:28])=[CH:21][CH:26]=1)[CH:11]1[CH:6]2[CH2:7][C:8]([CH3:19])([CH3:18])[CH2:9][CH2:10]1

Participants

6

Reactant 4

HCID 947Nitrogen2×HCID 113582-BromoanisoleHCID 23676156Sodium t-butoxideHCID 66652077HCID 66652077, compound

Product 1

HCID 66652116HCID 66652116, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

Using a 2 neck v shaped flask, combine 6-Methoxy-3,3-dimethyl-2,3,4,4a,10,10a-hexahydro-1H-phenanthren-9-one (1.3 g, 4.9 mmol), and 4 bromoanisole (0.16 ml, 4.9 mmol) in dioxane (40 ml) exchange with N2 add sodium t-butoxide, Add Pd[P(C4H9)3]2 exchange with N2. Heat at 80° stirring over night. Keeping reaction under N2 quench with acetic acid (6 ml). Dilute with ethyl acetate (50 ml), wash with saturated aqueous sodium bicarbonate 3× (50 ml), with brine (40 ml), dry, and concentrate. Chromatograph residue on an biotage eluting with 0-10% ethyl acetate in hexanes to give the title compound (1.6 g, 90%): 1H NMR (CDCl3) δ 8.02-7.99 (d, 1H), 7.07-7.05 (d, 2H), 6.9-6.88 (d, 2H), 6.85-6.82 (dd, 1H), 6.69-6.68 (d, 1H), 3.88 (s, 3H), 3.81 (s, 3H), 3.17-3.12 (m, 1H), 2.68-2.62 (m, 1H), 1.68-1.60 (m, 1H), 1.52-1.44 (m, 3H), 1.41-1.37 (m, 1H), 1.30-1.24 (m, 1H), 1.18-1.13 (m, 1H), 1.1 (s, 3H), 0.99 (s, 3H).

Workup

  1. temperatureHeat at 80°
  2. customreaction under N2
  3. customquench with acetic acid (6 ml)
  4. additionDilute with ethyl acetate (50 ml)
  5. washwash with saturated aqueous sodium bicarbonate 3× (50 ml), with brine (40 ml)
  6. customdry
  7. concentrationconcentrate
  8. washChromatograph residue on an biotage eluting with 0-10% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-43ae744fbcc047879ba8a39407bbe8a4
Source dataset
uspto-grants-2012_01
Patent number
US08093302B2

Reaction notes

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