Novel carboxy ligands and use thereof in catalysts

Patent metadata

Field	Value
Publication number	US-2025381554-A1
Application number	US-202318878315-A
Country	US
Kind code	A1
Filing date	Jun 22, 2023
Priority date	Jun 24, 2022
Publication date	Dec 18, 2025
Grant date	—

Abstract

The invention relates to a carboxy ligand such as those defined via the general formula (I) specified in the following text. The invention additionally relates to a bismuth-containing catalyst such as those according to the general formula (II), wherein the bismuth-containing catalyst comprises carboxy ligands of the general formula (I). The invention additionally relates to a method for producing such a carboxy ligand and to a method for producing such a bismuth-containing catalyst. During the production of the carboxy ligand according to the invention, a precursor of a ligand according to the general formula (III) is likewise obtained according to the invention. The invention also relates to the use of such a bismuth-containing catalyst for producing compounds which contain a urethane group.

First claim

1 . A ligand of formula (I)

in which the variables are defined as follows:
A is N or (NH) + (X) − ,
B is CH 2 , CH, CR 5 or CR 5 H,
D is CH 2 , CH, CR 6 or CR 6 H,
E is H or an alkali metal,
R 1 is H or a C 1 -C 10 -alkyl,
R 2 is H or a C 1 -C 10 -alkyl,
R 3 is H or a C 1 -C 10 -alkyl,
R 4 is H or a C 1 -C 10 -alkyl,
R 5 is a C 1 -C 10 -alkyl,
R 6 is a C 1 -C 10 -alkyl, or R 5 and R 6 together form a bridge having four carbon atoms,
B, D, R 5 and R 6 together optionally form a benzene fragment that is optionally at least monosubstituted by one R 7 radical,
R 7 is a C 1 -C 10 -alkyl, and
X is BF 4 , OH or a halogen.

2 . The ligand according to claim 1 , wherein
i) B and D, and optionally R 5 and R 6 , each have the same definition, where B, D, R 5 and R 6 together optionally form a benzene fragment which is optionally unsubstituted, and/or ii) R 1 and R 2 each have the same definition, and/or iii) R 3 and R 4 each have the same definition, and/or iv) with the proviso that E is an alkali metal, the alkali metal is sodium or potassium, and/or v) with the proviso that X is a halogen, the halogen is chlorine or bromine.

3 . A ligand according to claim 1 , wherein the ligand is 4-carboxy-N-(1,3-diisopropyl-1,3-dihydro-2H-benzo[d]imidazol-2-ylidene)-2,6-dimethylbenzenaminium tetrafluoroborate or 4-carboxy-N-(1,3-di-tert-butylimidazolidin-2-ylidene)benzenaminium tetrafluoroborate.

4 . A bismuth catalyst of formula (II)

in which the variables are defined as follows:
A is N or (NH) + (X) − ,
B is CH 2 , CH, CR 5 or CR 5 H,
D is CH 2 , CH, CR 6 or CR 6 H,
R 1 is H or a C 1 -C 10 -alkyl,
R 2 is H or a C 1 -C 10 -alkyl,
R 3 is H or a C 1 -C 10 -alkyl,
R 4 is H or a C 1 -C 10 -alkyl,
R 5 is a C 1 -C 10 -alkyl,
R 6 is a C 1 -C 10 -alkyl, or R 5 and R 6 together form a bridge having four carbon atoms,
B, D, R 5 and R 6 together optionally form a benzene fragment that is optionally at least monosubstituted by one R 7 radical,
R 7 is a C 1 -C 10 -alkyl, and
X is BF 4 , OH or a halogen,
wherein
all the three ligands of the bismuth catalyst are the same or the respective variables in each of the three ligands are defined independently of the respective other ligands, and
a double bond rather than a single bond is optionally present between B and D.

5 . The bismuth catalyst according to claim 4 , wherein all the three ligands of the bismuth catalyst are the same.

6 . The bismuth catalyst according to claim 4 , wherein
i) B and D, and optionally R 5 and R 6 , each have the same definition, where B, D, R 5 and R 6 together optionally form a benzene fragment which is optionally unsubstituted, and/or ii) R 1 and R 2 each have the same definition, and/or iii) R 3 and R 4 each have the same definition, and/or iv) with the proviso that X is a halogen, the halogen is is chlorine or bromine.

7 . The bismuth catalyst according to claim 4 , wherein
A is (NH) + (X) − , R 1 is a C 2 -C 4 -alkyl, R 2 is a C 2 -C 4 -alkyl, R 3 is H or methyl, R 4 is H or methyl, R 5 and R 6 together form a bridge having four carbon atoms unless B and D are CH 2 or CH, in which case B, D, R 5 and R 6 together optionally form an unsubstituted benzene fragment, and X is BF 4 .

8 . The bismuth catalyst according to claim 4 , wherein the bismuth catalyst is bismuth (III) (4-((1,3-di-tert-butylimidazolidin-2-ylidene)ammonio)benzoate)tetrafluoroborate) 3 ([Bi(O 2 C(PNsItBu)H) 3 ][BF 4 ] 3 ).

9 . A precursor of a ligand of formula (III)

in which the variables are defined as follows:
A is N or (NH) + (X) − ,
B is CH 2 , CH, CR 5 or CR 5 H,
D is CH 2 , CH, CR 6 or CR 6 H,
R 1 is H or a C 1 -C 10 -alkyl,
R 3 is H or a C 1 -C 10 -alkyl,
R 4 is H or a C 1 -C 10 -alkyl,
R 5 is a C 1 -C 10 -alkyl,
R 6 is a C 1 -C 10 -alkyl, or R 5 and R 6 together form a bridge having four carbon atoms,
B, D, R 5 and R 6 together optionally form a benzene fragment that is optionally at least monosubstituted by one R 7 radical,
R 7 is a C 1 -C 10 -alkyl,
X is BF 4 , OH or a halogen, and
Y is a halogen.

10 . A process for preparing a ligand, the process comprising:
subjecting the precursor of a ligand of the formula (III) according to claim 9 to carboxylation in the presence of a catalyst.

11 . A process for preparing the bismuth catalyst of the formula (II) according to claim 4 the process comprising: reacting
i) at least one compound of formula (I) with
ii) at least one bismuth compound selected from the group consisting of Bi 2 O 3 , bismuth carbonate, bismuth hydrogencarbonate, a bismuth halide, a bismuth carboxylate, Bi(C 6 -C 14 -aryl) 3 , Bi(C 1 -C 12 -alkyl) 3 and metallic bismuth;

wherein E is H or an alkali metal, and all the other variables in the formula (I) have the same definitions as the corresponding variables in the formula (II).

12 . The process according to claim 11 , wherein the at least one bismuth-containing compound is selected from the group consisting of Bi 2 O 3 , BiCl 3 , Bi(C 6 H 5 ) 3 and metallic bismuth.

13 . The process according to claim 11 , wherein
i) the reaction is conducted under a protective atmosphere and/or in the presence of at least one solvent, and/or ii) the reaction is conducted for at least 10 hours and/or at a temperature of at least 100° C., and/or iii) after the reaction, volatile constituents are removed, the bismuth catalyst is dried under reduced pressure and/or a recrystallization is carried out.

14 . A process for preparing a compound comprising a urethane group, the process comprising:
preparing the compound in the presence of at least one bismuth catalyst according to claim 4 .

15 . The ligand according to claim 1 , wherein
A is (NH) + (X) − , E is H, R 1 is a C 2 -C 4 -alkyl, R 2 is a C 2 -C 4 -alkyl, R 3 is H or methyl, R 4 is H or methyl, R 5 and R 6 together form a bridge having four carbon atoms unless B and D are CH 2 or CH, in which case B, D, R 5 and R 6 together optionally form an unsubstituted benzene fragment, and X is BF 4 .

16 . The process according to claim 13 , wherein the reaction is conducted in the presence of at least one solvent selected from the group consisting of toluene, acetonitrile, and tetrahydrofuran.

Assignees

• Basf Se

Inventors

• Dielmann Fabian
• Levent Emre

Classifications

• C07D233/50

  with carbocyclic radicals directly attached to said nitrogen atoms · CPC title

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J31/04

  containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)} · CPC title

• C07F9/94

  Bismuth compounds · CPC title

• C07F5/022

  without C-boron linkages · CPC title