Reaction #1106660

Reaction equation

NaOH

MeOH

Maleic Anhydride

Phenyl Ethyl Norbornene

AIBN

→

MA PENB

Solvents

THF

EtOAc

Conditions

Workup

1. 1
   workup.ADDITIONcharged to a reaction vessel
2. 2
   OtherThe solution was sparged with nitrogen for 10 min
3. 3
   Otherto remove oxygen
4. 4
   ConcentrationThe reaction mixture was concentrated in vacuo
5. 5
   workup.DISSOLUTIONredissolved in THF (20 wt %)
6. 6
   workup.ADDITIONwere mixed at 70° C. for 1 hr
7. 7
   workup.STIRRINGto stir for 3 hr at 70° C.
8. 8
   Temperaturewas cooled to room temperature
9. 9
   workup.ADDITIONThe reaction mixture was treated with conc. HClaq for protonation
10. 10
    Washwashed three times
11. 11
    Otherto remove residual salts and acid
12. 12
    OtherThe organic phase was separated
13. 13
    Concentrationconcentrated in vacuo
14. 14
    workup.DISSOLUTIONredissolved in THF
15. 15
    Otherto form an approximately 20 wt % copolymer solution
16. 16
    Otherthe copolymer was precipitated
17. 17
    workup.ADDITIONby adding the THF solution to hexane (20 fold excess)
18. 18
    OtherThe copolymer was separated by filtration
19. 19
    Otherdried in a vacuum oven at 80° C. for 16 hr

Procedure

Maleic Anhydride (MA, 14.7 g, 150 mmol), Phenyl Ethyl Norbornene (PENB, 29.7 g, 150 mmol) and AIBN (2.5 g, 15.0 mmol) was dissolved in EtOAc (27.1 g) and charged to a reaction vessel. The solution was sparged with nitrogen for 10 min to remove oxygen and then heated to 60° C. The mixture was allowed to stir at 60° C. for 24 hr. The reaction mixture was concentrated in vacuo and redissolved in THF (20 wt %). The resulting solution was added to the suspension of NaOH (6.6 g, 165 mmol), MeOH (24.0 g, 750 mmol) and THF (24.0 g) which were mixed at 70° C. for 1 hr. The mixture was allowed to stir for 3 hr at 70° C. and then was cooled to room temperature. The reaction mixture was treated with conc. HClaq for protonation, and then washed three times to remove residual salts and acid. The organic phase was separated and then concentrated in vacuo, redissolved in THF to form an approximately 20 wt % copolymer solution and then the copolymer was precipitated by adding the THF solution to hexane (20 fold excess). The copolymer was separated by filtration and dried in a vacuum oven at 80° C. for 16 hr. Approximately, 30.4 g (61%) of the Ring-opening polymer of MA/PENB with MeOH was isolated (GPC Mw=9,700 Mn=5,300).

Source