Process for the production of acetals from carbon dioxide

Patent metadata

Field	Value
Publication number	US-12172953-B2
Application number	US-202017425805-A
Country	US
Kind code	B2
Filing date	Feb 5, 2020
Priority date	Feb 6, 2019
Publication date	Dec 24, 2024
Grant date	Dec 24, 2024

Abstract

The invention relates to a process for the preparation of acetals from carbon dioxide. The invention also relates to a mixture of phosphorus containing ligands comprising least one polydentate ligand and at least one monodentate ligand. Further, the invention also relates to the use of mixtures comprising at least one polydentate ligand and at least one monodentate ligand in transition metal complexes for the preparation of acetals.

First claim

What is claimed is:

1. A process for the production of a compound of the formula (I)

wherein
each R 1 is independently from each other selected from C 1 -C 40 alkyl, which is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents selected from OH, halogen, C 1 -C 6 alkoxy or C 6 -C 20 aryl;
or both R 1 form together a divalent bridging group R 2 selected from linear C 2 -C 9 -alkanediyl, wherein the alkanediyl is unsubstituted or substituted by 1, 2, 3 or 4 substituents selected from OH, halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy;
the process comprising at least one reaction step, in which carbon dioxide and hydrogen are reacted with at least one compound of the general formulae (II.a) or (II.b)
R 1 —OH  (II.a),

HO—R 2 —OH  (II.b),

wherein
R 1 is as defined above;
R 2 is a divalent group selected from linear C 2 -C 9 alkanediyl, wherein the alkanediyl is unsubstituted or substituted by 1, 2, 3 or 4 substituents selected from OH, halogen, C 1 -C 6 alkyl or C 1 -C 6 alkoxy;
in the presence of
at least one transition metal catalyst complex, comprising at least one polydentate ligand containing at least three phosphorus atoms which are capable of coordinating to the transition metal, wherein the transition metal is selected from metals of groups 7, 8, 9 and 10 of the periodic table of the elements according to IUPAC; and
at least one monodentate ligand containing one phosphorus atom; and
at least one Lewis acid.

2. The process according to claim 1 , wherein the molar ratio of the transition metal catalyst complex to the at least one monodentate ligand is in the range of 1:5.0 to 1:1.1.

3. The process according to claim 1 , wherein the metal of the transition metal catalyst complex is selected from ruthenium, iron, osmium, cobalt, rhodium, rhenium, iridium, nickel, platinum and palladium.

4. The process according to claim 3 , wherein the metal of the transition metal catalyst complex is ruthenium or cobalt.

5. The process according to claim 1 , wherein the polydentate ligand is selected from organo-phosphines, organo-phosphites, organo-phosphonites, organo-phosphinites and organo-phosphoramidites.

6. The process according to claim 5 , wherein the transition metal catalyst complex comprises at least one polydentate ligand of formula (III)

wherein
R A , R B , R C , R D , R E and R F are independently from each other alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the alkyl radicals may carry 1, 2, 3, 4 or 5 substituents selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, mercapto, polyalkylene oxide, polyalkyleneimine, carboxyl, P(aryl) 2, SO 3 H, sulfonate, NE 1 E 2, NE 1 E 2 E 3+ X − , halogen, nitro, formyl, acyl and cyano, wherein E1, E2 and E3 are the same or different and are selected from hydrogen, alkyl, cycloalkyl, and aryl and X is an anion equivalent, and
wherein the radicals cycloalkyl, heterocycloalkyl, aryl and hetaryl R A , R B , R C , R D , R E and R F may carry 1, 2, 3, 4 or 5 substituents selected from alkyl and the substituents mentioned for the alkyl radicals R A , R B , R C , R D , R E and R F before, or
R A and R B and/or R C and R D and/or R E and R F together with the P atom and, if present, the groups X 1, X 2, X 5, X 6, X 8 and X 9 to which they are bound, are a 5-to 8-membered heterocycle which is optionally fused with one, two or three groups selected from cycloalkyl, heterocycloalkyl, aryl and heteroaryl, wherein the heterocycle and, if present, the fused-on groups independently from each other may each carry 1, 2, 3 or 4 substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, mercapto, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, carboxyl, SO 3 H, sulfonate, NE 4 E 5, NE 4 E 5 E 6 X − , nitro, alkoxycarbonyl, formyl, acyl and cyano, wherein E 4, E 5 and E 6 are the same or different and are selected from hydrogen, alkyl, cycloalkyl and aryl and X is an anion equivalent,
X 1, X 2, X 5, X 6, X 8 and X 9 are independently from each other O, S, SiR x R y or NR z , wherein R x , R y and R z are independently from each other hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
X 3, X 4 and X 7 are independently from each other C 1 -C 10 alkanediyl, O, S, SiR x R y or NR z , wherein R x , R y and R z are independently from each other hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
Y is a bridging group, comprising C 1 -C 10 alkanetriyl, N or P,
a, b, c, d, e, f, g, h and i are independently from each other 0 or 1.

7. The process according to claim 6 , wherein the transition metal catalyst complex comprises at least one ligand of formula (III), wherein
R A , R B , R C , R D , R E and R F are independently from each other alkyl, aryl or heteroaryl, wherein the alkyl, aryl or heteroaryl radicals may carry 1, 2, 3, 4 or 5 substituents selected from alkoxy, NE 1 E 2 , NE 1 E 2 E 3+ X − , wherein E 1 , E 2 and E 3 are the same or different and are selected from hydrogen or alkyl and X − is an anion equivalent,
X 1 , X 2 , X 5 , X 6 , X 8 and X 9 are as defined in claim 6 ,
X 3 , X 4 and X 7 are methylene, ethylene, trimethylene, tetramethylene, pentamethylene and hexamethylene,
Y is a bridging group, selected from C 1 -C 6 -alkanetriyl or N, and
a, b, e, f, h and i are independently from each other 0 or 1.

8. The process according to claim 7 , wherein a, b, e, f, h, and i are 0, and c, d, and g are 1.

9. The process according to claim 1 , wherein the transition metal catalyst complex comprises at least one further ligand selected from the group consisting hydrido, halides, amides, carboxylates, acetylacetonate, aryl- or alkylsufonates, CO, olefins, dienes, cycloolefines, nitriles, aromatics and heteroaromatics.

10. The process according to claim 1 , where the transition metal catalyst complex is selected from the group consisting of [Ru(tris(diphenylphosphinomethyl)ethane)(2-methylallyl)], [Ru(tris(diphenylphosphinomethyl)ethane)(H) 2 ], [Ru(tris(diphenylphosphinomethyl)amine)(2-methylallyl)], [Ru(tris(diphenylphosphinomethyl)amine)(H) 2 ], [Ru(tris(diphenylphosphinoethyl)amine)(2-methylallyl)] and [Ru(tris(diphenylphosphinoethyl)amine)(H) 2 ].

11. The process according to claim 1 , wherein an amount of the transition metal catalyst complex is 50 mol % or less calculated as transition metal and based on the amount of compound (II.a) or (II.b) used.

12. The process according to claim 11 , wherein an amount of the transition metal catalyst complex at the most of 20 mol %, calculated as transition metal and based on the amount of compound (II.a) or (II.b), is used.

13. The process according to claim 12 , wherein an amount of the transition metal catalyst complex of from 0.001 mol % to 20 mol %, calculated as transition metal and based on the amount of compound (II.a) or (II.b), is used.

14. The process according to claim 1 , wherein the least one monodentate ligand is selected from the group consisting of organo phosphines, organo phosphites, organo phosphonites, organo phosphinites and organo phosphoramidites.

15. The process according to claim 14 , wherein the at least one monodentate ligand comprises at least one ligan

Assignees

• Basf Se
• Univ Heidelberg Ruprecht Karls
• Ruprecht Karis Univ Heidelberg

Inventors

• Schaub Thomas
• Jevtovikj Ivana
• Hashmi A Stephen K
• Sekine Kohei

Classifications

• B01J2531/821

  Ruthenium · CPC title

• B01J31/2409

  with more than one complexing phosphine-P atom · CPC title

• B01J31/2404

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring · CPC title

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title

• B01J31/2252

  Sulfonate ligands · CPC title