CATALYTIC CARBONYLATION CATALYSTS AND METHODS

• US 20170073463A1
• Filed: 04/15/2016
• Published: 03/16/2017
• Est. Priority Date: 05/13/2011
• Status: Active Grant

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: COATES, Geoff, LEE, Han, ALLEN, Scott D., FARMER, Jay J.
• Granted Patent: US 10,221,278 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• 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 for the carbonylation of heterocycles comprising the combination of:

i) one or more cationic functional moieties, where each cationic functional moiety comprises a linker and 1 to 4 cationic functional groups;

ii) one or more ligands to which at least one cationic functional moiety is covalently tethered wherein the one or more ligand(s) are coordinated to one or two metal atoms; and

iii) at least one anionic metal carbonyl species associated with a cation present on the metal complex.

2. The catalyst of claim 1, wherein the one or more ligands to which at least one cationic functional moiety is covalently tethered is selected from the group consisting of porphryin ligands and salen ligands.

3. The catalyst of claim 2, wherein catalyst comprises a salen or porphyrin complex of a metal 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), Mn(III).

4. The catalyst of claim 2, wherein the catalyst comprises a salen or porphyrin complex of aluminum.

5. The catalyst of claim 2, wherein the catalyst comprises a salen or porphyrin complex of chromium.

6. The catalyst of claim 1, wherein the one or more cationic functional groups comprise onium salts.

7. The catalyst of claim 1, wherein the onium salts comprise at least one of nitrogen and phosphorous.

8. The catalyst of claim 1, wherein the one or more cationic functional groups are selected from the group consisting of:

9. The catalyst of claim 8, wherein the one or more cationic functional groups are selected from the group consisting of:

10. The catalyst of claim 9, wherein the one or more cationic functional groups are selected from the group consisting of:

11. The catalyst of claim 9, wherein the one or more cationic functional groups are selected from the group consisting of:

12. The catalyst of claim 9, wherein the one or more cationic functional groups are selected from the group consisting of:

13. The catalyst of claim 1, wherein the cationic functional moiety comprises a linker selected from the group consisting of:

a bond, and moieties comprising 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.

14. The catalyst of claim 13, wherein the cationic functional moiety includes a linker comprising 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 nitrogen, oxygen, or sulfur, or an optionally substituted 8-10 membered bivalent saturated, partially unsaturated, or aryl bicyclic ring having 0-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and

each R^y is independently —

H, or an optionally substituted radical selected from the group consisting of C₁-₆ 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 nitrogen, oxygen, or sulfur, a 5-6 membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, and 8- to 10-membered aryl.

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

[Q_dM′

_e(CO)_w]^y−

, where Q is any 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 the stable anionic metal carbonyl complex, and x is the charge of the anionic metal carbonyl compound.

16. The catalyst of claim 15, wherein the 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.

17. The catalyst of claim 15, wherein the wherein the anionic metal 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]⁻

.

18. The catalyst of claim 1, wherein the anionic carbonyl species comprise [Co(CO)₄]⁻

.

19. The catalyst of claim 1, wherein the ligand to which at least one cationic functional moiety is covalently tethered and which is coordinated to one or two metal atoms the catalyst has a structure selected from the group consisting of:

20. The catalyst of claim 1, wherein ligand to which at least one cationic functional moiety is covalently tethered and which is coordinated to one or two metal atoms the catalyst has a structure selected from the group consisting of:

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

24. The method of claim 23, wherein the product consists substantially of beta propiolactone.

25. The method claim 23, wherein the product consists substantially of polypropiolactone.

26. The catalyst of claim 8, wherein the cationic functional moiety comprises a linker selected from the group consisting of:

21. A catalyst for the carbonylation of heterocycles comprising a compound selected from Catalyst Table 1, wherein M, is selected from the group consisting of:

22. A catalyst for the carbonylation of heterocycles comprising a compound selected from Catalyst Table 2, wherein M, is selected from the group consisting of: