Tri-o-tolylphosphine → HCID 16212642, compound

Temperature

80 °C

A 2000 mL three-necked, round bottomed flask with bottom drain port, outfitted with a mechanical stirrer, pressure equalizing addition funnel and condenser with attached nitrogen inlet was charged with potassium acetate (125.6 g, 1.28 mol) and deionized (DI) water (60 mL). The solution was stirred for 10 min. and then trimethylolpropane propoxylate triacrylate having an average of 2 propoxylate groups (107.1 g, 165.9 mmol), 100 mL dimethylformamide (DMF), palladium acetate (0.27 g, 1.18 mmol) and tri(o-tolyl)phosphine (1.14 g, 3.75 mmol) were added to the vessel and the mixture was sparged with nitrogen with stirring for 30 min. The pressure equalizing addition funnel was charged with a solution of 3-bromobenzocyclobutane (91.46 g, 499.6 mmol) in DMF (50 mL). This solution was then de-gassed via nitrogen sparge for 20 min. The reaction solution was slowly heated to 80° C. followed by slow addition of the 3-bromobenzocyclobutane. Reaction completeness was monitored by the disappearance of 3-bromobenzocyclobutane via gas chromatography, which took 27 hr. Toluene (200 mL) was added to the solution which was then cooled to room temperature. The aqueous layer, which was laden with suspended solids, was removed via the reactor bottom drain. The organic layer was filtered over a pad of celite via vacuum filtration. The filtrate was washed with deionized water, resulting in an emulsion which would not separate. The emulsion was filtered again through celite to separate the organic and aqueous layers. The organic layer was isolated, dried over anhydrous magnesium sulfate, filtered and condensed to afford the product as a clear yellow colored viscous oil. Yield: 140.4 g (88.9%).

1. customA 2000 mL three-necked, round bottomed flask with bottom drain port, outfitted with a mechanical stirrer
2. additionaddition funnel and condenser with attached nitrogen inlet
3. customthe mixture was sparged with nitrogen
4. stirringwith stirring for 30 min
5. additionaddition funnel
6. customThis solution was then de-gassed via nitrogen
7. customsparge for 20 min
8. additionfollowed by slow addition of the 3-bromobenzocyclobutane
9. customReaction completeness
10. waittook 27 hr
11. temperaturewas then cooled to room temperature
12. customwas removed via the reactor bottom drain
13. filtrationThe organic layer was filtered over a pad of celite via vacuum filtration
14. washThe filtrate was washed with deionized water
15. customresulting in an emulsion which would not
16. customseparate
17. filtrationThe emulsion was filtered again through celite
18. customto separate the organic and aqueous layers
19. customThe organic layer was isolated
20. dry with materialdried over anhydrous magnesium sulfate
21. filtrationfiltered
22. customcondensed

ORD record

ord-f1262a14857e4629b9a9730a6eba265e

Source dataset

uspto-grants-2016_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09441055B1