Dimethylformamide → 4,4'-(Bicyclo[2.2.1]heptane-2,5-diyl)bis(2-methylphenol)

HRID 1776006Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[C:4]([CH3:9])[CH:3]=1.[C:10]12[CH2:16][C:13]([CH2:14][CH2:15]1)=[CH:12][CH:11]=2.CN([CH:20]=[O:21])C.C(N([CH2:27][CH3:28])CC)C>C(OCC)(=O)C.C(O)=O>[CH:10]12[CH2:16][CH:13]([CH:14]([C:2]3[CH:7]=[CH:6][C:5]([OH:8])=[C:4]([CH3:9])[CH:3]=3)[CH2:15]1)[CH2:12][CH:11]2[C:2]1[CH:3]=[CH:4][C:20]([OH:21])=[C:27]([CH3:28])[CH:7]=1

Participants

Conditions

Temperature: 75 °C

Procedure

4-Bromo-2-methylphenol (2.03 grams, 10.8 mmol), (tris-o-tolylphosphine)2PdCl2 (0.0422 gram, 0.0537 mmol), and norbornadiene (0.257 gram, 2.79 mmol) were charged to an appropriately sized and equipped reaction vessel under nitrogen. DMF (36 mL), triethylamine and formic acid were added to what was observed to be a yellow suspension. The mixture was then heated to 75° C. in an oil bath. Upon such heating, the reaction mixture became a yellow solution, black particles appeared and a very slow evolution of gas was observed. The reaction mixture was stirred overnight at this temperature. After cooling, the reaction mixture was diluted with ethyl acetate and washed with water. The organic layer was separated and dried over anhydrous MgSO4. PP308-2,5, (4,4′-(Bicyclo[2.2.1]heptane-2,5-diyl)bis(2-methylphenol)) was confirmed by GC-MS of the crude product (43% yield).

Workup

customequipped
customreaction vessel under nitrogen
temperatureAfter cooling
washwashed with water
customThe organic layer was separated
dry with materialdried over anhydrous MgSO4

Sources & evidence

ORD record: ord-f4797f90c77e43cba9b7cb224eb6f9a7
Source dataset: uspto-grants-2016_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09261781B2

Reaction notes

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