Catalytic carbonylation catalysts and methods

• US 10,221,278 B2
• Filed: 04/15/2016
• Issued: 03/05/2019
• Est. Priority Date: 05/13/2011
• Status: Active Grant

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: Lee, Han, Allen, Scott D., Farmer, Jay J., Coates, Geoff
• Primary Examiner(s): Aulakh, Charanjit
• Application Number:
  US15/130,810
• Publication Number:
  US 20170073463A1
• Time in Patent Office: 1,054 Days
• Field of Search: 502161, 502164, 544 64
• CPC Class Codes: B01J 2231/321 Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
• CPC Class Codes: B01J 2231/34 Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
• CPC Class Codes: B01J 2531/0216 Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
• CPC Class Codes: B01J 2531/025 Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
• CPC Class Codes: B01J 2531/0252 Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
• CPC Class Codes: B01J 2531/16 Copper
• CPC Class Codes: B01J 2531/22 Magnesium
• CPC Class Codes: B01J 2531/26 Zinc
• CPC Class Codes: B01J 2531/31 Aluminium
• CPC Class Codes: B01J 2531/32 Gallium
• CPC Class Codes: B01J 2531/33 Indium
• CPC Class Codes: B01J 2531/46 Titanium
• CPC Class Codes: B01J 2531/62 Chromium
• CPC Class Codes: B01J 2531/72 Manganese
• CPC Class Codes: B01J 2531/821 Ruthenium
• CPC Class Codes: B01J 2531/822 Rhodium
• CPC Class Codes: B01J 2531/824 Palladium
• CPC Class Codes: B01J 2531/842 Iron
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 2531/847 Nickel
• CPC Class Codes: B01J 2540/42 : Quaternary ammonium groups
• CPC Class Codes: B01J 2540/54 : Quaternary phosphonium groups
• CPC Class Codes: B01J 31/1815 : with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• CPC Class Codes: B01J 31/183 : with more than one complexing nitrogen atom, e.g. phenanthroline
• CPC Class Codes: B01J 31/20 : Carbonyls
• CPC Class Codes: B01J 31/2217 : At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
• CPC Class Codes: B01J 31/2243 : At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
• CPC Class Codes: C07C 51/54 : Preparation of carboxylic acid anhydrides by oxidation C07C51/16
• CPC Class Codes: C07C 55/10 : Succinic acid
• CPC Class Codes: C07D 305/08 : with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring atoms
• CPC Class Codes: C07D 307/20 : Oxygen atoms
• CPC Class Codes: C07D 487/22 : in which the condensed system contains four or more hetero rings
• CPC Class Codes: C07F 15/065 : without a metal-carbon linkage
• CPC Class Codes: C07F 5/069 : without C-aluminium linkages
• CPC Class Codes: C08G 63/823 : for the preparation of polylactones or polylactides

Abstract

In one aspect, the present invention provides catalysts for the carbonylation of heterocycles. The inventive catalysts feature metal-ligand complexes having cationic functional groups tethered to the ligand, wherein the tethered cationic groups are associated with anionic metal carbonyl species. The invention also provides methods of using the inventive catalysts to affect the ring opening carbonylation of epoxides.

Claims

1. A catalyst comprising:

i) a metal complex of formula;

2. The catalyst of claim 1, wherein M is selected from the group consisting of Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Co(II), Rh(II), Ni(II), Pd(II), Mg(II), Al(III), Cr(III), Cr(IV), Ti(IV), Fe(III), Co(III), Ti(III), In(III), Ga(III), and Mn(III).

3. The catalyst of claim 1, wherein M is aluminum.

4. The catalyst of claim 1, wherein M is chromium.

5. The catalyst of claim 1, wherein at least one anionic metal carbonyl species is X−

, and X−

is associated with at least on Z⁺, wherein Z⁺X⁻

is selected from the group consisting of;

6. The catalyst of claim 5, wherein Z⁺X⁻

is selected from the group consisting of;

7. The catalyst of claim 6, wherein Z⁺X⁻

is selected from the group consisting of;

8. The catalyst of claim 6, wherein Z⁺X⁻

is selected from the group consisting of;

9. The catalyst of claim 6, wherein Z⁺X⁻

is selected from the group consisting of;

10. The catalyst of claim 1, wherein the linker comprises 1-30 atoms including at least one carbon atom and optionally one or more atoms selected from the group consisting of N, O, S, Si, B, and P.

11. The catalyst of claim 10, wherein the linker is an optionally substituted C_2-30 aliphatic group wherein one or more methylene units are optionally and independently replaced by:

—

Cy-, —

NR^y—

, —

N(R^y)C(O)—

, —

C(O)N(R^y)—

, —

O—

, —

C(O)—

, —

OC(O)—

, —

C(O)O—

, —

S—

, —

SO—

, —

SO₂—

, —

C(═

S)—

, —

C(═

NR^y)—

, or —

N═

N—

,

wherein each —

Cy- is independently an optionally substituted 5-8 membered bivalent, saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;

or an optionally substituted 8-10 membered bivalent saturated, partially unsaturated, or aryl bicyclic ring having 0-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and

each R^y is independently —

H, or an optionally substituted group selected from the group consisting of;

C_1-6 aliphatic,

phenyl,

a 3-7 membered saturated or partially unsaturated carbocyclic ring,

a 3-7 membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur,

a 5-6 membered heteroaryl ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, and an

8- to 10- membered aryl.

12. The catalyst of claim 1, wherein the at least one anionic metal carbonyl species is a compound of formula:

[Q_dM′

_e(CO)_w]^y−

, wherein;

Q is a ligand and need not be present,

M′

is a metal atom,

d is an integer between 0 and 8 inclusive,

e is an integer between 1 and 6 inclusive,

w is a number such as to provide a stable anionic metal carbonyl complex, and

y is the charge of the anionic metal carbonyl species.

13. The catalyst of claim 12, wherein the at least one anionic metal carbonyl species is selected from the group consisting of:

monoanionic carbonyl complexes of metals from groups 5, 7 or 9 of the periodic table, and dianionic carbonyl complexes of metals from groups 4 or 8 of the periodic table.

14. The catalyst of claim 12, wherein the at least one anionic metal carbonyl species is selected from the group consisting of:

[Co(CO)₄]⁻

, [Ti(CO)_6]²⁻

, [V(CO)₆]⁻

, [Rh(CO)₄]⁻

, [Fe(CO)₄]²⁻

, [Ru(CO)₄]²⁻

, [Os(CO)₄]²⁻

, [Cr₂(CO)₁₀]²⁻

, [Fe₂(CO)₈]²⁻

, [Tc(CO)₅]⁻

, [Re(CO)₅]⁻

, and [Mn(CO)₅]⁻

.

15. The catalyst of claim 1, wherein the at least one anionic metal carbonyl species is [Co(CO)₄]⁻

.

16. The catalyst of claim 1, wherein the metal complex has a structure selected from the group consisting of:

18. A method comprising contacting ethylene oxide with carbon monoxide in the presence of a catalyst of claim 1, to provide a product comprising beta propiolactone, succinic anhydride, or polypropiolactone, or a mixture of any two or more of these.

19. The method of claim 18, wherein the product comprises beta propiolactone.

20. The method claim 18, wherein the product comprises polypropiolactone.

21. The catalyst of claim 1, wherein the linker is selected from the group consisting of:

22. The catalyst of claim 1, wherein the metal complex has a structure selected from the group consisting of:

23. The catalyst of claim 1, wherein the metal complex has a structure selected from the group consisting of:

24. The catalyst of claim 1, wherein the metal complex has a structure selected from the group consisting of:

25. The catalyst of claim 1, wherein q is 3.

26. The catalyst of claim 1, wherein Z⁺comprises an atom selected from the group consisting of nitrogen and phosphorous.

27. The catalyst of claim 23, wherein the coordinated solvent molecule is an ether, an epoxide, DMSO, an amine, or other Lewis basic moiety.

17. A catalyst comprising a compound selected from the group consisting of:

28. A method comprising contacting ethylene oxide with carbon monoxide in the presence of a catalyst of claim 17, to provide a product comprising beta propiolactone, succinic anhydride, or polypropiolactone, or a mixture of any two or more of these.

29. The method of claim 28, wherein the product comprises beta propiolactone.

30. The method claim 28, wherein the product comprises polypropiolactone.