1-(5-Bromo-2-methoxyphenyl)adamantane → 1,1'-(4,4'-Bis(methoxy)biphenyl-3,3'-diyl)bis(tricyclo(3.3.1.13,7)decane)

HRID 541108Notes

Reaction equation

HRID 541108 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([O:18][CH3:19])=[C:6]([C:8]23[CH2:17][CH:12]4[CH2:13][CH:14]([CH2:16][CH:10]([CH2:11]4)[CH2:9]2)[CH2:15]3)[CH:7]=1>CC([O-])=O.CC([O-])=O.[Pd+2].O1CCCC1>[C:8]12([C:6]3[CH:7]=[C:2]([C:2]4[CH:3]=[CH:4][C:5]([O:18][CH3:19])=[C:6]([C:8]56[CH2:9][CH:10]7[CH2:16][CH:14]([CH2:13][CH:12]([CH2:11]7)[CH2:17]5)[CH2:15]6)[CH:7]=4)[CH:3]=[CH:4][C:5]=3[O:18][CH3:19])[CH2:17][CH:12]3[CH2:13][CH:14]([CH2:16][CH:10]([CH2:11]3)[CH2:9]1)[CH2:15]2

Participants

4

Reactant 1

HCID 32850241-(5-Bromo-2-methoxyphenyl)adamantane

Product 1

HCID 248802441,1'-(4,4'-Bis(methoxy)biphenyl-3,3'-diyl)bis(tricyclo(3.3.1.13,7)decane)Yield 79.9%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Next, 0.03 g of Pd(OAc)2 and 3.5 g of 1-(5-bromo-2-methoxyphenyl) adamantane were added to the mixture, followed by 25 mL of tetrahydrofuran in order to improve agitation, and the mixture was heated at reflux for approximately 24 hours. The resulting mixture was then evaporated to dryness and poured into 103 mL of 0.015 N HCl. Next, 150 mL of dichloromethane and 100 mL of water were added to yield a mixture consisting of a solid, an aqueous layer and an organic layer. The mixture was then filtered to separate the solid, the aqueous layer was discarded, and the organic layer was washed with 200 mL of water and decanted again. This process was repeated twice on the filtered solid. The three collected organic layers were evaporated to dryness, washed in methanol, and dried to yield 2.1 g of 3,3′-diadamantyl-4,4′-dimethoxybiphenyl (yield: 39.9%). Analytical data: Melting point: 288.1-289.1° C.; Elemental analysis: C 83.63%, H 8.73%; 1H-NMR (300 MHz, CDCl3): δ 1.78 (broad s, 12H), 2.08 (broad s, 6H), 2.15 (broad s, 12H), 3.86 (s, 6H), 6.92 (dm, 2H, J=8.1 Hz), 7.34 (dd, 2H, J=2.4, 8.1 Hz), 7.39 (d, 2H, J=2.4 Hz); 13C-NMR (75.4 MHz, CDCl3): δ 29.2, 37.1, 37.2, 40.6, 55.1, 111.9, 125.0, 125.5, 134.0, 138.5, 157.8; MS (EI, 70 eV): m/z=484 (6), 483 (36), 412 (M+, 100), 410 (5), 347 (8), 135 (22), 107 (7), 93 (14), 79 (17), 67 (9), 55 (6); IR (Selected absorption bands): 2992, 2964, 2898, 2850, 1603 cm−1.

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for approximately 24 hours
  3. customThe resulting mixture was then evaporated to dryness
  4. additionpoured into 103 mL of 0.015 N HCl
  5. additionNext, 150 mL of dichloromethane and 100 mL of water were added
  6. customto yield a mixture
  7. filtrationThe mixture was then filtered
  8. customto separate the solid
  9. washthe organic layer was washed with 200 mL of water
  10. customdecanted again
  11. customThe three collected organic layers were evaporated to dryness
  12. washwashed in methanol
  13. customdried

Sources & evidence

ORD record
ord-8671562b8f344df6bc2ca9a39ba113f3
Source dataset
uspto-grants-2014_10
Patent number
US08871972B2

Reaction notes

Loading…