# US 10,766,833 B2 · Hydroformylation method and catalyst using rhodium-ruthenium dual metal and tetradentate phosphine ligand

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- Number: US 10,766,833 B2
- Document ID: US10766833B2
- Status: Granted
- Kind: B2
- Application number: 16/509,530
- Filed: 2019-07-12
- Published: 2019-11-07
- Granted: 2020-09-08
- Earliest claimed: 2017-01-12
- Assignees: Wuhan Catalys Technology CO., LTD
- Applicants: Wuhan Catalys Technology Co., Ltd
- Inventors: Xumu Zhang
- Web page: https://patentgrep.com/patent/US10766833B2

## CPC

- C07B 41/06: of carbonyl groups
- B01J 31/181: {Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine}
- B01J 31/20: Carbonyls
- B01J 31/2409: {with more than one complexing phosphine-P atom}
- C07C 45/69: by addition to carbon-to-carbon double or triple bonds
- C07F 9/52: Halophosphines
- C07F 15/0073: {Rhodium compounds}
- C07F 15/008: {without a metal-carbon linkage}
- B01J 2231/321: Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
- B01J 2231/52: Isomerisation reactions
- B01J 2531/0258: 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
- B01J 2531/821: Ruthenium
- B01J 2531/822: Rhodium
- C07F 9/5027: {Polyphosphines}
- C07F 9/58: Pyridine rings
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

A homogeneous catalytic reaction method and a catalyst for isomerization and hydroformylation of long-chain internal olefins are disclosed. A rhodium-ruthenium metal complex is used as a catalyst; and the ligands are tetradentate phosphine ligands. By means of the catalytic system, homogeneous internal olefin isomerization aid hydroformylation can be performed under a certain temperature and pressure to obtain aldehyde products having high normal to iso ratios. The present invention is applicable to not only long-chain internal olefins (≥C8) but also internal olefins having a carbon number less than 8.

## Claims

### Claim 1

A catalyst comprising a rhodium complex and a ruthenium compound, wherein the rhodium complex is formed by complexing a rhodium compound with a biphenyl tetraphosphine ligand, and the ruthenium compound does not complex with the biphenyl tetraphosphine ligand, the rhodium compound and the rhodium complex.

### Claim 2 (depends on 1)

The catalyst according to claim 1, wherein the molar ratio of the rhodium complex to the ruthenium compound is ranged from 1:1 to 5:1, and the molar ratio of the biphenyl tetraphosphine ligand to the rhodium compound is ranged from 1:1 to 10:1.

### Claim 3 (depends on 1)

The catalyst according to claim 1, wherein the rhodium compound is selected from a group consisting of: RhCl3, (Rh(NBD)Cl)2, (Rh(COD)Cl)2, (RH(ethylene)2(CI))2, RhCl(PPh3)3, (Rh(CO)2Cl)2, Rh(acac)(CO)2, Rh(acac)(COD), Rh6(CO)12, Rh4(CO)12, Rh2(OAc)4, Rh(NO3)3, (Rh(NBD)2)X and (Rh(COD)2)X, wherein X is a conjugated anion, NBD is a bicycloheptadiene; and COD is cyclooctadiene.

### Claim 4 (depends on 1)

The catalyst according to claim 1, wherein the biphenyl tetraphosphine ligand has a structure illustrated as follows:
in formula 1, Ar is selected from a group consisting of: benzene, p-methylbenzene, m-trifluoromethylbenzene, p-trifluoromethylbenzene, 3,5-ditrifluoromethylbenzene, 3,5-difluorobenzene, 3,5-dimethylbenzene, 3,5-di-tert-butylbenzene, 3,5-di-tert-butyl-4-methoxybenzene, p-methoxybenzene, p-dimethylaminobenzene, 2-pyridine, p-fluorobenzene, and 2,3,4,5,6-pentafluorobenzene.

### Claim 5 (depends on 1)

The catalyst according to claim 1, wherein the ruthenium compound is selected from a group consisting of: Ru3(CO)12, RuCl3, RuCl2(PPh3)3, (RuCl2(CO)3)2, RuH(CO)2(PPh3)3, Ru(Ar)X2, Ru(ArH)Cl2, Ru(Ar)X2(PPh3)3, Ru(COD)(COT), Ru(COD)(COT)X, Ru(COD)n, RuCl2(COD), (Ru(COD)2)X, (RuCl2(COD))n, Ru(COD)(methallyl)2, RuX2(cymene), RuX2(PN), RuX2(PN), RuH(CI)(PNN(CO), and RuH(PNN)(CO), wherein Ar is a group having an aromatic ring; X is a conjugated anion, COD is cyclooctadiene; and COT is cyclooctadiene.

### Claim 6

A reaction method for isomerization and hydroformylation of internal olefins, comprising:
first, under inert gas protection, transferring certain amount of a complexed rhodium-ruthenium catalyst solution, certain amount of isopropanol as an additive, certain amount of solvent, and finally a substrate-internal olefin into a reaction flask equipped with a magnetic stirrer; wherein the complexed rhodium-ruthenium catalyst solution comprises a rhodium complex and a ruthenium compound, the rhodium complex is formed by complexing a rhodium compound with a biphenyl tetraphosphine ligand, and the ruthenium compound does not complex with the biphenyl tetraphosphine ligand, the rhodium compound and the rhodium complex;
second, charging certain amount of CO and H2 with a certain pressure into a autoclave containing the reaction flask, and wherein a pressure ratio of H2 to CO is ranged between 1.5:1 and 10:1, and the total pressure is ranged from 0.2 MPa to 4 MPa: and placing the autoclave at oil bath temperature between 80° C. and 140° C. and stirring for 1 to 12 hours.

### Claim 7 (depends on 6)

The reaction method according to claim 6, wherein the organic solvent is selected from a group consisting of: methylbenzene, dichloromethane, dichloroethane, hexane, ethyl acetate, methanol, ethanol, trifluoroethanol, isopropanol, dioxane, acetonitrile and tetrahydrofuran.

### Claim 8 (depends on 6)

The reaction method according to claim 6, wherein the internal olefin is selected from a group consisting of: 2-butene, cis-trans-2-pentene, cis-trans-2-hexene, cis-trans-3-hexene, cis-trans-2-heptene, cis-trans-3-heptene, cis-trans-2-octene, cis-trans-3-octene, cis-trans-4-octene, cis-trans-2-nonene, cis-trans-3-nonene, cis-trans-4-nonene, cis-trans-2-decene, cis-trans-3-decene, cis-trans-4-decene, and cis-trans-5-decene.