# US 2025/0083137 A1 · Supported hydroformylation catalyst and preparation method thereof, and method for synthesizing 4-acetyloxy-2-methyl-2-butenal

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- Number: US 2025/0083137 A1
- Document ID: US20250083137A1
- Status: Published application
- Kind: A1
- Application number: 18/503,250
- Filed: 2023-11-07
- Published: 2025-03-13
- Earliest claimed: 2023-09-12
- Assignees: Shaoxing University
- Applicants: Shaoxing University
- Inventors: Xuemei Wei; Guoqi Yu; Hualiang Shen; Tao Cai; Yanjuan Luo; Tianbo Shang; Runpu Shen; Huiting Xu; Chunlei Wu; Kai Wang
- Web page: https://patentgrep.com/patent/US20250083137A1

## CPC

- B01J 31/28: of the platinum group metals, iron group metals or copper
- B01J 21/18: Carbon
- B01J 23/464: {Rhodium}
- B01J 31/189: {containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand}
- B01J 31/2442: {comprising condensed ring systems}
- B01J 35/45: Nanoparticles
- B01J 37/0201: {Impregnation}
- B01J 37/0236: {Drying, e.g. preparing a suspension, adding a soluble salt and drying}
- B01J 37/086: {Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid}
- B01J 37/18: with gases containing free hydrogen
- B01J 37/343: {of ultrasonic wave energy}
- C07C 67/293: by isomerisation; by change of size of the carbon skeleton
- C07C 67/38: by addition to an unsaturated carbon-to-carbon bond
- B01J 2231/321: Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
- B01J 2531/004: Ligands
- B01J 2531/822: Rhodium
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

A supported hydroformylation catalyst and an application method thereof, and a method for synthesizing a 4-acetyloxy-2-methyl-2-butenal are provided. A structure expression of the supported hydroformylation catalyst is Rh@P—N/AC, Rh of which represents an active center of the catalyst and P—N/AC of which represents carriers of the catalyst including an AC carrier and a P—N carrier. The AC carrier in the P—N/AC is an activated carbon and the P—N carrier in the P—N/AC is a phosphine-nitrogen (P—N) organic ligand with one structural formula selected from the group consisting of structural formulas I-IV. The catalyst is capable of achieving catalytic cycling of precious metal and phosphine ligand and has high activity and C2 selectivity.

## Claims

### Claim 1

A supported hydroformylation catalyst, wherein a structure expression of the supported hydroformylation catalyst is Rh@P—N/AC, Rh represents rhodium (Rh) atoms that are configured to be an active center of the supported hydroformylation catalyst, and P—N/AC represents carriers of the supported hydroformylation catalyst comprising an AC carrier and a P—N carrier; and
wherein the AC carrier in the P—N/AC is an activated carbon; and the P—N carrier in the P—N/AC is a phosphine-nitrogen (P—N) organic ligand with one structural formula selected from the group consisting of the following structural formulas I-IV:

### Claim 2 (depends on 1)

The supported hydroformylation catalyst as claimed in claim 1, wherein a particle size of each of the Rh atoms is in a range of 1-3 nanometers (nm); a supported capacity of the Rh atoms is in a range of 2% to 5%; and the activated carbon is powdered with a specific surface in a range of 800 square meters per gram (m2/g) to 1,000 m2/g.

### Claim 3 (depends on 1)

The supported hydroformylation catalyst as claimed in claim 1, wherein a preparation method of the P—N organic ligand comprises the following steps:
performing a coupled reaction on a 2-bromocarbazole and a bipyridine bromide to obtain an N-bipyridine carbazole intermediate, and then performing a couple reaction on the N-bipyridine carbazole intermediate and a chlorodiphenyl phosphine to obtain the P—N organic ligand.

### Claim 4 (depends on 1)

A preparation method of the supported hydroformylation catalyst as claimed in claim 1, comprising the following steps:
step 1, performing pre-coordination on the P—N organic ligand and a Rh precursor to obtain a mixed solution;
step 2, adding the activated carbon to the mixed solution obtained in the step 1, performing ultra-sonication on the mixed solution added with the activated carbon to disperse the carriers and obtaining a solid catalyst sample by impregnation, and rotary evaporating and drying the solid catalyst sample to obtain a solid sample; and
step 3, performing hydrogenation reduction and roasting carbonization on the solid sample obtained in the step 2 at a temperature of 500 degrees Celsius (° C.) to 700° C. with a heating rate of 5-10° C. per minute (° C./min), thereby obtaining the supported hydroformylation catalyst.

### Claim 5 (depends on 4)

The preparation method as claimed in claim 4, wherein in the step 1, a molar ratio of Rh element in the Rh precursor to the P—N organic ligand is (0.5-10): 1.

### Claim 6 (depends on 4)

The preparation method as claimed in claim 4, wherein the Rh precursor is a rhodium chloride trihydrate or a dicarbonylacetylacetonato rhodium.

### Claim 7 (depends on 5)

The preparation method as claimed in claim 5, wherein reaction conditions of the pre-coordination in the step 1 comprise: a room temperature, an atmospheric pressure, and a reaction time in a range of 2-5 hours (h).

### Claim 8 (depends on 5)

The preparation method as claimed in claim 5, wherein a time for the roasting carbonization is 2 h.

### Claim 9 (depends on 1)

A method for synthesizing a 4-acetyloxy-2-methyl-2-butenal, comprising:
performing hydroformylation of a but-3-ene-1,2-diyl diacetate by using the Rh@P—N/AC supported hydroformylation catalyst as claimed in claim 1 to obtain the 4-acetyloxy-2-methyl-2-butenal.