Succinic anhydrides from epoxides

1. A process for the double carbonylation of an epoxide to succinic anhydride in a reaction which comprises reacting an epoxide, where the epoxide is ethylene oxide, with carbon monoxide in a solvent in the presence of a catalytically effective amount of a catalyst, where the catalyst comprises a Lewis acid in combination with a transition metal carbonyl complex, where the Lewis acid is of the following formula:

where:

M is aluminum;

R d at each occurrence is independently selected from the group consisting of: —H; C 1 -C 12 alkyl; C 2 -C 12 alkenyl; C 2 -C 12 alkynyl; halogen; —OR 10 ; —OC(O)R 13 ; —OC(O)OR 13 ; —OC(O)NR 11 R 12 ; —CN; —CNO; —C(O)R 13 ; —C(R 13 ) z H (3-z) ; —C(O)OR 13 ; —C(O)NR 11 R 12 ; —NR 11 R 12 ; —NR 11 C(O)R 10 ; —NR 11 C(O)OR 13 ; —NR 11 SO 2 R 13 ; —NCO; —N 3 ; —NO 2 ; —S(O) x R 13 ; —SO 2 NR 11 R 12 ; —C(R 13 ) z H (3-z) ; —(CH 2 ) k R 14 ; —(CH 2 ) k -Z-R 16 —; and —(CH 2 ) k -Z-(CH 2 ) m -R 14 , and

R 10 at each occurrence is independently selected from the group consisting of: —C(R 13 ) z H (3-z) ; C 1 to C 12 alkyl; C 2 to C 12 alkenyl; C 2 to C 12 alkynyl; up to a C 12 carbocycle; —S(O) 2 R 13 ; —Si(R 15 ) 3 ; —H; and a hydroxyl protecting group,

R 11 and R 12 at each occurrence are independently selected from the group consisting of: —H; C 1 to C 12 alkyl; C 2 to C 12 alkenyl; C 2 to C 12 alkynyl; and —C(R 13 ) z H (3-z) ;

where R 11 and R 12 ; when both present, can optionally be taken together with the atom to which they are attached to form a 3- to 10-membered ring,

R 13 at each occurrence is independently selected from the group consisting of: —H; C 1 to C 12 alkyl; C 2 to C 12 alkenyl; C 2 to C 12 alkynyl; and up to a C 12 carbocycle,

R 14 at each occurrence is independently selected from the group consisting of: halogen; —OR 10 ; —OC(O)R 13 ; —OC(O)OR 13 ; —OC(O)NR 11 R 12 ; —CN; —CNO; —C(R 13 ) z H (3-z) ; —C(O)R 13 ; —C(O)OR 13 ; —C(O)NR 11 R 12 ; —NR 11 C(O)R 13 ; —NR 11 C(O)OR 10 ; —NR 11 SO 2 R 13 ; —NCO; —N 3 ; —NO 2 ; —S(O) x R 13 ; —SO 2 NR 11 R 12 ; and up to a C 12 carbocycle,

R 15 at each occurrence is independently selected from the group consisting of: C 1 to C 6 alkyl; C 2 to C 6 alkenyl; C 2 to C 6 alkynyl; and up to a C 12 carbocycle,

R 16 at each occurrence is independently selected from the group consisting of: C 1 to C 12 alkyl; C 2 to C 12 alkenyl; C 2 to C 12 alkynyl; up to a C 12 carbocycle; and —C(R 13 ) z H (3-z) ,

Z is a divalent linker selected from the group consisting of:

—(CH═CH) a —; —(CH≡CH) a —; —C(O)—; —C(═NOR 11 )—; —C(═NNR 11 R 12 )—; —O—; —N(R 11 )—; —N(C(O)R 13 )—; and —S(O) x —,

a is 1, 2, 3, or 4,

k is an integer from 1 to 8 inclusive,

m is an integer from 1 to 8 inclusive,

x is 0, 1, or 2,

z is 1, 2, or 3; and

where the solvent includes a Lewis base and the crude yield of succinic anhydride is at least 10 percent.

2. The process of claim 1 , where R d at each occurrence is independently selected from the group consisting of: —H and C 1 -C 12 alkyl.

3. The process of claim 1 , where the Lewis acid includes one or more neutral coordinating ligands.

4. The process of claim 1 , where the Lewis acid includes one or more tetrahydrofuran ligands.

5. The process of claim 1 , where the transition metal carbonyl complex is a monoanionic carbonyl complex of a metal from groups 5, 7 or 9.

6. The process of claim 5 , where the transition metal carbonyl complex contains cobalt, manganese or rhodium.

7. The process of claim 6 , where the transition metal carbonyl complex contains cobalt.

8. The process of claim 6 , where the catalyst includes a transition metal carbonyl complex of formula [Co(CO) 4 ] − .

9. The process of claim 1 , where the Lewis acid is cationic and the transition metal carbonyl complex is anionic.

10. The process of claim 1 , where the catalyst comprises a complex of formula 1a, 1b, 1c, 1d, 1e or 1f:

11. The process of claim 10 , where the catalyst comprises a complex of formula 1c.

12. The process of claim 1 , where the catalyst comprises a complex of formula 1g:

13. The process of claim 1 , where the catalyst comprises a complex of formula 1a:

14. The process of claim 1 , where the reaction is performed in a vessel and the catalyst was formed in situ by adding the Lewis acid and the transition metal carbonyl complex to the vessel.

15. The process of claim 1 , where the solvent includes a Lewis base with the same polarity as 1,4-dioxane.

16. The process of claim 1 , where the solvent includes a Lewis base with lower electron donicity than tetrahydrofuran.

17. The process of claim 1 , where the solvent includes a Lewis base with the same electron donicity as 1,4-dioxane.

18. The process of claim 1 , where the solvent includes 1,4-dioxane, tetrahydrofuran, tetrahydropyran, dimethoxyethane, glyme, diethyl ether, t-butyl methyl ether, 2,5-dimethyl tetrahydrofuran, ethyl acetate, propyl acetate, butyl acetate, acetone, 2-butanone, cyclohexanone, toluene, acetonitrile, difluorobenzene, or a combination thereof.

19. The process of claim 1 , where the solvent includes 1,4-dioxane, toluene, dimethoxyethane, or a combination thereof.

20. The process of claim 1 , where the solvent includes 1,4-dioxane.

21. The process of claim 1 , where the solvent includes a mixture of two or more solvents.

22. The process of claim 1 , where the solvent includes a mixture of 1,4-dioxane and toluene.

23. The process of claim 1 , where the solvent and epoxide are the same.

24. The process of claim 1 , where the reaction is conducted under a carbon monoxide pressure from about 40 psi to about 2500 psi.

25. The process of claim 1 , where the crude yield of succinic anhydride is at least 80%.

26. The process of claim 1 , where the crude yield of succinic anhydride is at least 90%.

27. The process of claim 1 , where the crude yield of succinic anhydride is at least 95%.