Method for preparing 3-(3-isopropylphenyl)butyraldehyde
The preparation of 3-(3-isopropylphenyl)butanal by hydroformylation under solvent-free conditions solves the problems of complex reaction routes and high costs in existing technologies, and realizes efficient and low-cost industrial production.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- HANGZHOU COLORIFIC CHEMICALS CO LTD
- Filing Date
- 2025-12-11
- Publication Date
- 2026-06-25
AI Technical Summary
In existing technologies, the reaction routes for preparing 3-(3-isopropylphenyl)butanal are complex and not conducive to large-scale industrial production. Post-processing is troublesome and costly.
Using m-isopropylpropylbenzene as raw material, 3-(3-isopropylphenyl)butanal was prepared by hydroformylation under solvent-free conditions in the presence of a rhodium catalyst, phosphorus ligand, and base, using a 1:1 volume ratio of H2-CO mixed gas. The hydroformylation reaction was carried out at a temperature of 90℃-140℃ and a pressure of 1MPa-5MPa.
It achieves high raw material conversion rate and product yield, reduces production costs, conforms to the concept of green chemistry, and the catalyst can be reused, making it suitable for industrial production.
Smart Images
Figure PCTCN2025141795-FTAPPB-I100001
Abstract
Description
A method for preparing 3-(3-isopropylphenyl)butyraldehyde Technical Field
[0001] This invention belongs to the field of compound preparation technology, specifically relating to a method for preparing 3-(3-isopropylphenyl)butanal. Background Technology
[0002] The hydroformylation reaction of functional olefins is a very useful synthetic tool in chemical production processes, which can facilitate the preparation of a large number of fine chemicals. In particular, hydroformylation-based reactions are widely used in fragrances and perfumes internationally and hold a very important position. The traditional mainstream process is to prepare 3-(3-isopropylphenyl)butanal by reacting isopropylbenzene with a rhodium catalyst, such as Abate A, Brenna E, Negri CD, et al. Biocatalysed synthesis of the enantiotners of the floral odorant Florhydral(R)[J].Tetrahedron Asymmetry,2002,13(8):899-904, or by acetic anhydride-sodium nitrite oxidation reaction, such as Zhuo Zhencheng, Yan Feng, Guan Jin, et al. Optimization of the synthesis process of anthocyanin[J]. Synthetic Chemistry,2020,28(1):5. However, this method has a complicated reaction route and troublesome post-processing, which is not conducive to large-scale industrial production. Summary of the Invention
[0003] This invention employs a novel process to prepare 3-(3-isopropylphenyl)butanal. Using m-isopropylbenzene as a raw material, without solvent, a hydroformylation reaction is carried out by introducing a 1:1 volume ratio of H2-CO mixed gas in the presence of a rhodium catalyst, phosphorus ligand, and a base. This simple preparation technique yields 3-(3-isopropylphenyl)butanal with a high reaction yield, significantly reducing production costs and conforming to the principles of green chemistry.
[0004] Specifically, this invention provides a method for preparing 3-(3-isopropylphenyl)butyraldehyde, comprising the following steps:
[0005] Step 1: Add the rhodium catalyst and phosphine ligand to the high-pressure reactor;
[0006] Step 2: Add m-isopropylbenzene and organic base compound sequentially to the high-pressure reactor described in Step 1 to obtain a mixed system;
[0007] Step 3: In an atmosphere of mixed hydrogen and carbon monoxide, the mixture from Step 2 is subjected to hydroformylation at a temperature of 90℃-140℃ and a pressure of 1MPa-5MPa for 6-10 hours to obtain 3-(3-isopropylphenyl)butanal.
[0008] More specifically, the rhodium catalyst is selected from one or more of Rh(CO)₂C₅H₇O₂, RhHCO(PPh₃)₃, and Rh(C₅H₇O₂)(CO)(PPh₃). The phosphine ligand is selected from one or more of 2-(di-tert-butylphosphine)biphenyl, sodium triphenylphosphine tri-m-sulfonate (TPPTS), and bis(3,5-dimethylphenyl)phosphine oxide, preferably 2-(di-tert-butylphosphine)biphenyl. The base is selected from one or more of triethylamine, triethanolamine, and N,N-diisopropylethylamine, preferably triethylamine.
[0009] More specifically, in the hydroformylation reaction, the ratio of rhodium catalyst to raw material is 0.05%-0.1%:1. The molar ratio of phosphine ligand to rhodium catalyst in the hydroformylation reaction is 20:1. The ratio of base to raw material in the hydroformylation reaction is 1.2%-3%:1. The reaction temperature in step three of the hydroformylation reaction is 120℃, and the pressure is 3MPa.
[0010] Beneficial effects of the present invention
[0011] (1) The method for preparing 3-(3-isopropylphenyl)butanal of the present invention uses m-isopropylpropylbenzene as raw material to prepare 3-(3-isopropylphenyl)butanal through a one-step hydroformylation reaction. The raw material conversion rate is higher than 98%, the product yield is higher than 83%, and no solvent is added during the reaction process, which greatly reduces the production cost and is beneficial to industrial production.
[0012] (2) In the preparation method of 3-(3-isopropylphenyl)butanal of the present invention, a rhodium catalyst is used as the catalyst, and phosphine ligands and organic base compounds are used as auxiliary agents. The catalyst can be reused repeatedly during the reaction process to achieve recycling, which is in line with the concept of green chemistry. Detailed Implementation
[0013] To better understand this invention, the following examples are provided. Those skilled in the art should understand that these examples are merely illustrative and should not be considered as specific limitations of the invention.
[0014] In this implementation case, a suitable rhodium catalyst was first screened for the reaction. Next, phosphine ligands were screened, and finally, a suitable organic base was selected to ensure the system achieved optimal reaction performance. Additionally, a comparative example was included to verify that the catalyst can be reused and recycled.
[0015] Example 1
[0016] A method for preparing 3-(3-isopropylphenyl)butanal is provided, comprising the following steps:
[0017] Step 1: Add 0.1% rhodium catalyst and 20 eq phosphine ligand to the polytetrafluoroethylene liner of the high-pressure reactor; the rhodium catalyst is Rh(CO)2C5H7O2, and the phosphine ligand is 2-(di-tert-butylphosphine)biphenyl;
[0018] Step 2: 90g of m-isopropylbenzene and 1.0800g of organic base are added sequentially to the polytetrafluoroethylene liner of the high-pressure reactor described in Step 1. After purging the liner three times, a mixture of hydrogen and carbon monoxide is introduced for further purging three times. The organic base compound is triethylamine. The volume ratio of hydrogen to carbon monoxide in the mixture of hydrogen and carbon monoxide is 1:1.
[0019] Step 3: In an atmosphere of hydrogen and carbon monoxide mixed in a volume ratio of 1:1, the stirring speed was set to 800 r / min, the temperature of the mixture from Step 2 was set to 110℃, and the pressure to 3 MPa for the hydroformylation reaction. After 6 hours, the temperature was lowered to stop the reaction. The system after the reaction was sampled and analyzed by gas chromatography. The chromatographic results showed that 3-(3-isopropylphenyl)butanal was obtained, with a raw material conversion rate of 98.6% and a yield of 83.8%.
[0020] Comparative Example 1
[0021] The preparation method of 3-(3-isopropylphenyl)butanal in this comparative example is the same as that in Example 1, except that the catalyst in Example 1 is filtered out and added to the next batch, while the amounts of raw materials, ligands, and organic base remain unchanged. In this comparative example, the conversion rate of the raw materials is 94.1%, and the yield of 3-(3-isopropylphenyl)butanal is 81.9%.
[0022] Example 2
[0023] A method for preparing 3-(3-isopropylphenyl)butanal is provided, comprising the following steps:
[0024] Step 1: Add 0.1% rhodium catalyst and 20 eq phosphine ligand to the polytetrafluoroethylene liner of the high-pressure reactor; the rhodium catalyst is RhHCO(PPh3)3, and the phosphine ligand is 2-(di-tert-butylphosphine)biphenyl;
[0025] Step 2: Add 90g of m-isopropylbenzene and 1.0800g of an organic base compound sequentially to the polytetrafluoroethylene liner of the high-pressure reactor described in Step 1. Add the rotor, cover the reactor, and introduce nitrogen gas for leak testing. After confirming no leaks, purge the reactor three times with nitrogen gas, followed by purging three times with a mixture of hydrogen and carbon monoxide. The organic base compound is triethylamine. The volume ratio of hydrogen to carbon monoxide in the hydrogen-carbon monoxide mixture is 1:1.
[0026] Step 3: In an atmosphere of hydrogen and carbon monoxide mixed at a volume ratio of 1:1, the stirring speed was set to 800 r / min, the temperature of the mixture from Step 2 was set to 110℃, and the pressure to 3 MPa for the hydroformylation reaction. After 6 hours, the temperature was lowered to stop the reaction. The system after the reaction was sampled and analyzed by gas chromatography. The chromatographic results showed that 3-(3-isopropylphenyl)butanal was obtained, with a raw material conversion rate of 94.2% and a yield of 81.8%.
[0027] Example 3
[0028] A method for preparing 3-(3-isopropylphenyl)butanal is provided, comprising the following steps:
[0029] Step 1: Add 0.1% rhodium catalyst and 20 eq phosphine ligand to the polytetrafluoroethylene liner of the high-pressure reactor; the rhodium catalyst is Rh(C5H7O2)(CO)(PPh3), and the phosphine ligand is 2-(di-tert-butylphosphine)biphenyl;
[0030] Step 2: Add 90g of m-isopropylbenzene and 1.0800g of an organic base compound sequentially to the polytetrafluoroethylene liner of the high-pressure reactor described in Step 1. Add the rotor, cover the reactor, and introduce nitrogen gas for leak testing. After confirming no leaks, purge the reactor three times with nitrogen gas, followed by purging three times with a mixture of hydrogen and carbon monoxide. The organic base compound is triethylamine. The volume ratio of hydrogen to carbon monoxide in the hydrogen-carbon monoxide mixture is 1:1.
[0031] Step 3: In an atmosphere of hydrogen and carbon monoxide mixed in a volume ratio of 1:1, the stirring speed was set to 800 r / min. The temperature of the mixture from Step 2 was set to 110℃ and the pressure to 3 MPa for the hydroformylation reaction. After 6 hours, the temperature was lowered to stop the reaction. The system after the reaction was sampled and analyzed by gas chromatography. The chromatographic results showed that 3-(3-isopropylphenyl)butanal was obtained, with a raw material conversion rate of 90.7% and a yield of 80.3%.
[0032] Example 4
[0033] A method for preparing 3-(3-isopropylphenyl)butanal is provided, comprising the following steps:
[0034] Step 1: Add 0.1% rhodium catalyst and 20 eq phosphine ligand to the polytetrafluoroethylene liner of the high-pressure reactor; the rhodium catalyst is Rh(CO)2C5H7O2, and the phosphine ligand is sodium triphenylphosphine tri-m-sulfonate (TPPTS).
[0035] Step 2: Add 90g of m-isopropylbenzene and 1.0800g of an organic base compound sequentially to the polytetrafluoroethylene liner of the high-pressure reactor described in Step 1. Add the rotor, cover the reactor, and introduce nitrogen gas for leak testing. After confirming no leaks, purge the reactor three times with nitrogen gas, followed by purging three times with a mixture of hydrogen and carbon monoxide. The organic base compound is triethylamine. The volume ratio of hydrogen to carbon monoxide in the hydrogen-carbon monoxide mixture is 1:1.
[0036] Step 3: In an atmosphere of hydrogen and carbon monoxide (volume ratio 1:1), with a stirring speed of 800 r / min, the hydroformylation reaction was carried out at a temperature of 110℃ and a pressure of 3 MPa. After 6 hours, the reaction was stopped by cooling. A sample was taken and analyzed by gas chromatography. The chromatographic results yielded 3-(3-isopropylphenyl)butanal, with a raw material conversion rate of 56.3% and a yield of 39.2%.
[0037] Example 5
[0038] A method for preparing 3-(3-isopropylphenyl)butanal is provided, comprising the following steps:
[0039] Step 1: Add 0.1% rhodium catalyst and 20 eq phosphine ligand to the polytetrafluoroethylene liner of the high-pressure reactor; the rhodium catalyst is Rh(CO)2C5H7O2, and the phosphine ligand is bis(3,5-dimethylphenyl)phosphine oxide;
[0040] Step 2: 90g of m-isopropylbenzene and 1.0800g of organic base are added sequentially to the polytetrafluoroethylene liner of the high-pressure reactor described in Step 1. After purging the liner three times, a mixture of hydrogen and carbon monoxide is introduced for further purging three times. The organic base compound is triethylamine. The volume ratio of hydrogen to carbon monoxide in the mixture of hydrogen and carbon monoxide is 1:1.
[0041] Step 3: In an atmosphere of hydrogen and carbon monoxide mixed in a volume ratio of 1:1, the stirring speed was set to 800 r / min, the temperature of the mixture from Step 2 was set to 110℃, and the pressure to 3 MPa for the hydroformylation reaction. After 6 hours of reaction, the temperature was lowered to stop the reaction. The system after the reaction was sampled and analyzed by gas chromatography. The chromatographic results showed that 3-(3-isopropylphenyl)butanal was obtained, with a raw material conversion rate of 79.2% and a yield of 67.5%.
[0042] Example 6
[0043] A method for preparing 3-(3-isopropylphenyl)butanal is provided, comprising the following steps:
[0044] Step 1: Add 0.1% rhodium catalyst and 20 eq phosphine ligand to the polytetrafluoroethylene liner of the high-pressure reactor; the rhodium catalyst is Rh(CO)2C5H7O2, and the phosphine ligand is 2-(di-tert-butylphosphine)biphenyl;
[0045] Step 2: 90g of m-isopropylbenzene and 1.0800g of organic base are added sequentially to the polytetrafluoroethylene liner of the high-pressure reactor described in Step 1. After purging the liner three times, a mixture of hydrogen and carbon monoxide is introduced for further purging three times. The organic base compound is triethanolamine. The volume ratio of hydrogen to carbon monoxide in the mixture of hydrogen and carbon monoxide is 1:1.
[0046] Step 3: In an atmosphere of hydrogen and carbon monoxide mixed in a volume ratio of 1:1, the stirring speed was set to 800 r / min, the temperature of the mixture from Step 2 was set to 110℃, and the pressure to 3 MPa for the hydroformylation reaction. After 6 hours, the temperature was lowered to stop the reaction. The system after the reaction was sampled and analyzed by gas chromatography. The chromatographic results showed that 3-(3-isopropylphenyl)butanal was obtained, with a raw material conversion rate of 85.7% and a yield of 70.8%.
[0047] Example 7
[0048] A method for preparing 3-(3-isopropylphenyl)butanal is provided, comprising the following steps:
[0049] Step 1: Add 0.1% rhodium catalyst and 20 eq phosphine ligand to the polytetrafluoroethylene liner of the high-pressure reactor; the rhodium catalyst is Rh(CO)2C5H7O2, and the phosphine ligand is 2-(di-tert-butylphosphine)biphenyl;
[0050] Step 2: 90g of m-isopropylbenzene and 1.0800g of organic base are sequentially added to the polytetrafluoroethylene liner of the high-pressure reactor described in Step 1. After purging the liner three times, a mixture of hydrogen and carbon monoxide is introduced for further purging three times. The organic base compound is N,N-diisopropylethylamine. The volume ratio of hydrogen to carbon monoxide in the mixture is 1:1.
[0051] Step 3: In an atmosphere of hydrogen and carbon monoxide mixed at a volume ratio of 1:1, the stirring speed was set to 800 r / min. The temperature of the mixture from Step 2 was set to 110℃ and the pressure to 3 MPa for the hydroformylation reaction. After 6 hours, the temperature was lowered to stop the reaction. The system after the reaction was sampled and analyzed by gas chromatography. The chromatographic results showed that 3-(3-isopropylphenyl)butanal was obtained, with a raw material conversion rate of 83.2% and a yield of 75.2%.
[0052] Examples 1-3 demonstrate that the Rh(CO)₂C₅H₇O₂ rhodium catalyst exhibits excellent catalytic performance. The comparative examples show that the catalyst can be reused while maintaining a high reaction yield. In Examples 4-5, we screened phosphine ligands, and compared with Example 1, found that 2-(di-tert-butylphosphine)biphenyl is more suitable for the current reaction system. Examples 6-7 show that the other two organic bases have lower conversion rates compared to triethylamine; therefore, triethylamine is preferred. This application achieves significant results in both process innovation and practicality. This invention greatly reduces the production cost of 3-(3-isopropylphenyl)butanal, providing a green and efficient new synthetic process for the industrial production of 3-(3-isopropylphenyl)butanal.
[0053] For anyone skilled in the art, many possible variations and modifications can be made to the technical solutions of this invention, or equivalent embodiments can be modified based on the disclosed technical content, without departing from the scope of the technical solutions of this invention. Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of this invention without departing from the content of the technical solutions of this invention should still fall within the protection scope of the technical solutions of this invention.
Claims
1. A method for preparing 3-(3-isopropylphenyl)butyraldehyde, characterized in that, The reaction includes the following steps: using m-isopropenyl cumene as a raw material, without solvent, in the presence of a rhodium catalyst, phosphine ligand and base, a mixture of H2 and CO gas with a volume ratio of 1:1 is introduced to carry out a hydroformylation reaction.
2. The method for preparing 3-(3-isopropylphenyl)butyraldehyde according to claim 1, characterized in that, The preparation method includes the following steps: Step 1: Add the rhodium catalyst and phosphine ligand to the high-pressure reactor; Step 2: Add m-isopropylbenzene and organic base compound sequentially to the high-pressure reactor described in Step 1 to obtain a mixed system; Step 3: In an atmosphere of mixed hydrogen and carbon monoxide, the mixture from Step 2 is subjected to hydroformylation at a temperature of 90℃-140℃ and a pressure of 1MPa-5MPa for 6-10 hours to obtain 3-(3-isopropylphenyl)butanal.
3. The preparation method according to claim 1 or 2, characterized in that, The rhodium catalyst is selected from one or more of Rh(CO)2C5H7O2, RhHCO(PPh3)3, and Rh(C5H7O2)(CO)(PPh3).
4. The preparation method according to claim 1 or 2, characterized in that, The phosphine ligand is selected from one or more of 2-(di-tert-butylphosphine)biphenyl, sodium triphenylphosphine tri-m-sulfonate (TPPTS), and bis(3,5-dimethylphenyl)phosphine oxide.
5. The preparation method according to claim 1 or 2, characterized in that, The base is selected from one or more of triethylamine, triethanolamine, and N,N-diisopropylethylamine.
6. According to the preparation method of claim 1 or 2, the ratio of rhodium catalyst raw material used in the hydroformylation reaction is 0.05%-0.1%:
1.
7. In the preparation method according to claim 1 or 2, the molar ratio of phosphine ligand to rhodium catalyst in the hydroformylation reaction is 20:
1.
8. According to the preparation method of claim 1 or 2, the content ratio of alkali to raw material in the hydroformylation reaction is 1.2%-3%:
1.
9. The preparation method according to claim 1 or 2, wherein the phosphine ligand is preferably 2-(di-tert-butylphosphine)biphenyl, and the base is preferably triethylamine.
10. The preparation method according to claim 2, characterized in that, The reaction temperature in step three is 120℃ and the pressure is 3MPa.