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-2020398261-A1
Application number	US-201916961053-A
Country	US
Kind code	A1
Filing date	Jan 10, 2019
Priority date	Jan 10, 2018
Publication date	Dec 24, 2020
Grant date	—

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 R 1 are identical or different and are each an organic radical having from 1 to 40 carbon atoms, and R 2 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

1 . A method of catalyzing a hydrogenation reaction or a dehydrogenative coupling reaction with a transition metal catalyst TMC1, the catalyst 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,
the method comprising:
forming a compound comprising at least one carboxylic acid ester functional group —O—C(═O)— by dehydrogenative coupling at least one primary alcohol with the transition metal catalyst TMC1, or
hydrogenating a compound comprising at least one carboxylic acid ester functional group —O—C(═O)— using the transition metal catalyst TMC1.

2 . The method of claim 1 , wherein the transition metal catalyst TMC1 is a transition metal complex of formula II

wherein M is ruthenium,
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 4 in each case is bound via a carbon atom to the oxygen atom, or
wherein R 3 together with R 1 , or R 3 together with R 2 , together with the atoms connecting them, form a divalent organic group having from 1 to 40 carbon atoms.

3 . The method of claim 1 , wherein R 1 and R 2 are identical.

4 . The method of claim 1 , wherein no base selected from the group consisting of a alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal alcoholate, and an alkaline earth metal alcoholate is combined with the transition metal catalyst TMC1.

5 . The method of claim 1 , wherein a compound comprising at least one carboxylic acid ester functional group —O—C(═O)— is hydrogenated, the hydrogenating comprising:
contacting the compound with molecular hydrogen H 2 in the presence of a catalytic amount of the transition metal catalyst TMC1,
wherein the compound comprises at least one carboxylic acid ester functional group —O—C(═O)— that is hydrogenated to at least one alcoholic hydroxy group.

6 . The method of claim 5 , wherein no base selected from the group consisting of an alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal hydroxide, an alkaline earth metal hydroxide, a alkali metal alcoholate, and an alkaline earth metal alcoholate is added to the compound or the transition metal catalyst TMC1 during the contacting.

7 . The method of claim 1 , wherein a compound comprising at least one carboxylic acid ester functional group —O—C(═O)— is formed by dehydrogenative coupling at least one primary alcohol, the forming comprising:
contacting a primary alcohol of formula IV and optionally an alcohol of formula V with a catalytic amount of the transition metal catalyst TMC1 to produce the compound of formula III comprising at least one carboxylic acid ester functional group —O—C(═O)—

wherein dehydrogenative coupling occurs between at least one primary alcohol of formula IV

comprising at least one hydroxy methylene group with a second primary alcohol of formula IV, or
wherein dehydrogenative coupling occurs intramolecularly between at least one primary alcohol of formula IV comprising at least one hydroxy methylene group with a second alcoholic OH group of the primary alcohol of formula IV if present, or
wherein if the alcohol of formula V is present, dehydrogenative coupling occurs between at least one primary alcohol of formula IV comprising at least one hydroxy methylene group with the alcohol of formula V comprising at least one alcoholic hydroxyl group,

wherein R 5 is an organic radical having from 1 to 40 carbon atoms, wherein R 5 is bound via a carbon atom to the hydroxy group,
wherein R 6 is hydrogen or an organic radical having from 1 to 40 carbon atoms, wherein R 6 is bound via a carbon atom to the carbonyl group, or
wherein R 5 and R 6 together with the atoms connecting them form a divalent organic group having from 1 to 40 carbon atoms, and
wherein R 7 is hydrogen or an organic radical having from 1 to 40 carbon atoms, wherein R 7 is bound via a carbon atom to the hydroxy methylene group.

8 . The method of claim 7 , wherein no base selected from the group consisting of an alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal hydroxide, an alkaline earth metal hydroxide, a alkali metal alcoholate, and an alkaline earth metal alcoholate is added to the primary alcohol of formula IV, the alcohol of formula V, or the transition metal catalyst TMC1 during the contacting.

9 . (canceled)

10 . A method of making 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,
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 4 in each case is bound via a carbon atom to the oxygen atom, or
wherein R 3 together with R 1 , or R 3 together with R 2 , together with the atoms connecting them, form a divalent organic group having from 1 to 40 carbon atoms,
the method comprising:
contacting a transition metal compound of formula VI

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

• B01J31/189 Primary

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title

• B01J2231/643

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

• C07C29/177

  with simultaneous reduction of a carboxy group · CPC title

• C07C67/40 Primary

  by oxidation of primary alcohols · CPC title