Use of a transition metal catalyst comprising a tetradentate ligand for hydrogenation of esters and/or formation of esters, a process for hydrogenation of esters, a process for formation of esters and a transition metal complex comprising said tetradentate ligand

Patent metadata

Field	Value
Publication number	US-11413610-B2
Application number	US-201916961053-A
Country	US
Kind code	B2
Filing date	Jan 10, 2019
Priority date	Jan 10, 2018
Publication date	Aug 16, 2022
Grant date	Aug 16, 2022

Abstract

The present invention relates to the use of a transition metal catalyst TMC1, which comprises a transition metal M selected from metals of groups 7, 8, 9 and 10 of the periodic table of elements according to IUPAC and a tetradentate ligand of formula I wherein R1 are identical or different and are each an organic radical having from 1 to 40 carbon atoms, and R2 are identical or different and are each an organic radical having from 1 to 40 carbon atoms, as catalyst in processes for formation of compounds comprising at least one carboxylic acid ester functional group —O—C(═O)— starting from at least one primary alcohol and/or hydrogenation of compounds comprising at least one carboxylic acid ester functional group —O—C(═O)—. The present invention further relates to a process for hydrogenation of a compound comprising at least one carboxylic acid ester functional group —O—C(═O)—, to a process for the formation of a compound comprising at least one carboxylic acid ester functional group —O—C(═O)— by dehydrogenase coupling of at least one primary alcohol with a second alcoholic OH-group, to a transition metal complex comprising the tetradentate ligand of formula I and to a process for preparing said transition metal complex.

First claim

The invention claimed is:

1. A transition metal catalyst TMC1 comprising:
ruthenium,
a tetradentate ligand of formula I,

wherein R 1 are each independently selected from the group consisting of a C 1 to C 40 alkyl radical, a C 3 to C 40 cycloalkyl radical, a C 2 to C 40 heterocycloalkyl radical, a C 6 to C 40 aryl radical, and a C 2 to C 40 heteroaromatic radical, and
wherein R 2 are each independently selected from the group consisting of a C 1 to C 40 alkyl radical, a C 3 to C 40 cycloalkyl radical, a C 2 to C 40 heterocycloalkyl radical, a C 6 to C 40 aryl radical, and a C 2 to C 40 heteroaromatic radical, and
a carbon monoxide ligand and comprising one or more additional ligands selected from the group consisting of hydrides, alkoxides, aryloxides, carboxylates and acyls.

2. The transition metal catalyst of claim 1 , wherein R 1 and R 2 are identical.

3. The transition metal catalyst of claim 1 , further comprising one or more additional ligands, comprising a neutral ligand selected from the group consisting of triaryl phosphines, amines, N-heterocyclic carbenes and isonitriles.

4. The transition metal catalyst of claim 1 , wherein R 1 are each identical and wherein R 2 are each identical.

5. The transition metal catalyst of claim 1 , wherein R 1 and R 2 are each independently an alkyl radical selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 1-hexyl, 1-octyl-iso-butyl, adamantyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, cyclohexyl, cyclopentyl, tert.-butyl, p-tert.-butyl-phenyl, o-tolyl, m-tolyl, p-tolyl, p-methoxy-phenyl, p-trifluoromethyl-phenyl, 4-biphenyl, naphthyl and phenyl.

6. A transition metal complex of formula II:

 wherein M is ruthenium,
wherein R 1 are each independently selected from the group consisting of a C 1 to C 40 alkyl radical, a C 3 to C 40 cycloalkyl radical, a C 2 to C 40 heterocycloalkyl radical, a C 6 to C 40 aryl radical, and a C 2 to C 40 heteroaromatic radical, and
wherein R 2 are each independently selected from the group consisting of a C 1 to C 40 alkyl radical, a C 3 to C 40 cycloalkyl radical, a C 2 to C 40 heterocycloalkyl radical, a C 6 to C 40 aryl radical, and a C 2 to C 40 heteroaromatic radical, and
wherein R 3 is selected from the group consisting of a C 1 to C 40 alkyl radical, a C 3 to C 40 cycloalkyl radical, a C 2 to C 40 heterocycloalkyl radical, a C 6 to C 40 aryl radical, a C 7 to C 40 arylalkyl radical, and a C 2 to C 40 heteroaromatic radical, or
wherein R 3 is C(═O)R 4 , wherein R 4 is selected from the group consisting of a hydrogen, a C 1 to C 40 alkyl radical, a C 3 to C 40 cycloalkyl radical, a C 2 to C 40 heterocycloalkyl radical, a C 6 to C 40 aryl radical, a C 7 to C 40 arylalkyl radical, and a C 2 to C 40 heteroaromatic radical, wherein R 3 in each case is bound via a carbon atom to the oxygen atom.

7. The transition metal complex of claim 6 , wherein R 1 are each identical and wherein R 2 are each identical.

8. The transition metal complex of claim 6 , wherein R 1 and R 2 are identical.

9. The transition metal complex of claim 6 , wherein R 1 and R 2 are each independently an alkyl radical selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 1-hexyl, 1-octyl-iso-butyl, adamantyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, cyclohexyl, cyclopentyl, tert.-butyl, p-tert.-butyl-phenyl, o-tolyl, m-tolyl, p-tolyl, p-methoxy-phenyl, p-trifluoromethyl-phenyl, 4-biphenyl, naphthyl and phenyl.

10. The transition metal complex of claim 6 , wherein R 3 is a C 1 to C 6 alkyl radical comprising methyl, ethyl, isopropyl, cyclohexyl, cyclopentyl or tert.-butyl, or a substituted or unsubstituted C 6 to C 18 aryl radical comprising p-tert.-butyl-phenyl, o-tolyl, m-tolyl, p-toly, naphthyl or phenyl, or a substituted or unsubstituted C 7 to C 18 arylalkyl radical comprising benzyl.

11. The transition metal complex of claim 6 , wherein R 3 is a C 1 to C 15 alkanoyl radical comprising formyl, acetyl or propionyl, or a substituted or unsubstituted benzoyl.

12. A transition metal catalyst comprising:
a transition metal complex of formula II:

 wherein M is ruthenium,
wherein R 1 are each independently selected from the group consisting of a C 1 to C 40 alkyl radical, a C 3 to C 40 cycloalkyl radical, a C 2 to C 40 heterocycloalkyl radical, a C 6 to C 40 aryl radical, and a C 2 to C 40 heteroaromatic radical, and
wherein R 2 are each independently selected from the group consisting of a C 1 to C 40 alkyl radical, a C 3 to C 40 cycloalkyl radical, a C 2 to C 40 heterocycloalkyl radical, a C 6 to C 40 aryl radical, and a C 2 to C 40 heteroaromatic radical, and
wherein R 3 is selected from the group consisting of a C 1 to C 40 alkyl radical, a C 3 to C 40 cycloalkyl radical, a C 2 to C 40 heterocy-cloalkyl radical, a C 6 to C 40 aryl radical, a C 7 to C 40 arylalkyl radical, and a C 2 to C 40 heteroaromatic radical, or
wherein R 3 is C(═O)R 4 , wherein R 4 is selected from the group consisting of a hydrogen, a C 1 to C 40 alkyl radical, a C 3 to C 40 cycloalkyl radical, a C 2 to C 40 heterocycloalkyl radical, a C 6 to C 40 aryl radical, a C 7 to C 40 arylalkyl radical, and a C 2 to C 40 heteroaromatic radical, wherein R 3 in each case is bound via a carbon atom to the oxygen atom; and
one or more ligand comprising an anion selected from the group consisting of hydrides, alkoxides, aryloxides, carboxylates and acyls, or a neutral ligand selected from the group consisting of carbon monoxide, triaryl phosphines, amines, N-heterocyclic carbenes and isonitriles.

13. A composition comprising:
the transition metal catalyst of claim 1 ; and
a liquid reaction mixture,
wherein the transition metal catalyst is in an amount of about 0.1 ppm to about 2000 ppm (parts per weight) based on the total weight of the liquid reaction mixture.

14. A composition comprising:
the transition metal complex of claim 6 ; and
a liquid reaction mixture,
wherein the transition metal complex is present in an amount of about 0.1 ppm to about 2000 ppm (parts per weight) based on the total weight of the liquid reaction mixture.

15. A method of using the transition metal catalyst of claim 1 for base-free hydrogenation of dimethyl terephthalate, comprising:
contacting the dimethyl terephthalate with the transition metal catalyst in the presence of hydrogen without adding a base,
wherein the transition metal catalyst provides about a 90% yield of 1,4-phenylenedimethanol.

Assignees

• Basf Se

Inventors

• Schaub Thomas
• Anaby Aviel
• Schelwies Mathias
• Paciello Rocco
• Schwaben Jonas
• Hashmi A Stephen K

Classifications

• B01J2531/0258

  Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane · CPC title

• C07C29/177

  with simultaneous reduction of a carboxy group · CPC title

• B01J2531/821

  Ruthenium · CPC title

• C07C67/40 Primary

  by oxidation of primary alcohols · CPC title

• B01J2231/643

  of R2C=O or R2C=NR (R= C, H) · CPC title