Preparation method of 3-(3-isopropyl phenyl) butyraldehyde

Abstract

The invention belongs to the field of catalyst technology application, and relates to a preparation method of 3-(3-isopropyl phenyl) butyraldehyde. The method comprises the following steps: by taking m-isopropenyl isopropyl benzene, organic alkali and H2 as raw materials, adding a prepared high-activity rhodium catalyst and a corresponding phosphine ligand, and optimizing a reaction process to obtain high-yield and high-purity 3-(3-isopropyl phenyl) butyraldehyde. The production method has the advantages of simple steps, mild reaction conditions, high yield of the obtained 3-(3-isopropyl phenyl) butyraldehyde, realization of solvent-free reaction, great cost saving, and suitableness for large-scale industrial production.

Description

Technical Field

[0001] The invention belongs to the technical field of compound preparation, and specifically relates to a method for preparing 3-(3-isopropylphenyl)butyraldehyde. Background Art

[0002] The hydroformylation reaction of functional olefins is a very useful synthetic tool in the chemical production process, which can be used to prepare a large number of fine chemicals. In particular, hydroformylation is widely used in international flavors and perfumes and plays a very important role. The traditional mainstream process is to use isopropenyl isopropylbenzene and rhodium catalyst to prepare 3-(3-isopropylphenyl)butyraldehyde, 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 to prepare it 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] The invention adopts the following new process to prepare 3-(3-isopropylphenyl)butyraldehyde. Meta-isopropenyl isopropylbenzene is used as a raw material without solvent. In the presence of a rhodium catalyst, a phosphorus ligand and a base, a H2-CO mixed gas with a volume ratio of 1:1 is introduced to carry out a hydroformylation reaction. 3-(3-isopropylphenyl)butyraldehyde can be prepared by a simple preparation technology. The method has a high reaction yield, greatly reduces the production cost and complies with the concept of green chemistry.

[0004]

[0005] Specifically, the present invention provides a method for preparing 3-(3-isopropylphenyl)butyraldehyde, comprising the following steps:

[0006] Step 1, adding a rhodium catalyst and a phosphine ligand into a high-pressure reactor;

[0007] Step 2, adding m-isopropenyl cumene and an organic base compound into the high-pressure reactor described in step 1 in sequence to obtain a mixed system;

[0008] Step 3: In an atmosphere of a mixture of hydrogen and carbon monoxide, the mixed system of step 2 is subjected to a hydroformylation reaction at a temperature of 90° C. to 140° C. and a pressure of 1 MPa to 5 MPa for 6 to 10 hours to obtain 3-(3-isopropylphenyl)butyraldehyde.

[0009] More specifically, the rhodium catalyst is selected from one or more of Rh(CO)2C5H7O2, RhHCO(PPh3)3, Rh(C5H7O2)(CO)(PPh3). The phosphine ligand is selected from one or more of 2-(di-tert-butylphosphine)biphenyl, triphenylphosphine tris-sulfonic acid sodium salt (TPPTS), bis(3,5-dimethylphenyl)phosphine oxide, preferably 2-(di-tert-butylphosphine)biphenyl. The base is selected from one or more of triethylamine, triethanolamine, N,N-diisopropylethylamine, preferably triethylamine.

[0010] More specifically, the ratio of the amount of rhodium catalyst to the raw material in the hydroformylation reaction is 0.05%-0.1%:1. The molar ratio of the phosphine ligand to the rhodium catalyst in the hydroformylation reaction is 20:1. The amount ratio of the base to the raw material in the hydroformylation reaction is 1.2%-3%:1. The reaction temperature of step 3 in the hydroformylation reaction is 120°C and the pressure is 3MPa.

[0011] Beneficial Effects of the Invention

[0012] (1) The method for preparing 3-(3-isopropylphenyl)butyraldehyde of the present invention uses m-isopropenyl isopropylbenzene as a raw material and performs a one-step hydroformylation reaction to prepare 3-(3-isopropylphenyl)butyraldehyde. 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.

[0013] (2) In the preparation method of 3-(3-isopropylphenyl)butyraldehyde of the present invention, a rhodium catalyst is used as a catalyst, and a phosphine ligand and an organic base compound are used as auxiliary agents. The catalyst can be repeatedly used during the reaction process to achieve recycling, which is in line with the concept of green chemistry. DETAILED DESCRIPTION

[0014] For a better understanding of the present invention, the present invention is illustrated by the following examples. It should be clear to those skilled in the art that the examples are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0015] In this implementation case, we first screened a suitable rhodium catalyst for the reaction, then screened the phosphine ligand, and finally screened a suitable organic base to ensure that the system reaction achieves the optimal reaction. In addition, a comparative example is added to verify that the catalyst can be reused and recycled.

[0016] Example 1

[0017] Provided is a method for preparing 3-(3-isopropylphenyl)butyraldehyde, comprising the following steps:

[0018] Step 1, adding 0.1% rhodium catalyst and 20eq phosphine ligand into the polytetrafluoroethylene lining of the autoclave; the rhodium catalyst is Rh(CO)2C5H7O2, and the phosphine ligand is 2-(di-tert-butylphosphine)biphenyl;

[0019] Step 2, adding 90g of m-isopropenyl cumene and 1.0800g of an organic base to the polytetrafluoroethylene liner of the high-pressure reactor in step 1 in sequence, replacing it three times, and then introducing a mixture of hydrogen and carbon monoxide to replace it 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;

[0020] Step 3, in an atmosphere of a mixture of hydrogen and carbon monoxide in a volume ratio of 1:1, the stirring speed is set to 800r / min, the temperature of the mixed system of step 2 is set to 110°C, and the pressure is 3MPa for hydroformylation reaction. After the reaction is continued for 6 hours, the temperature is lowered to stop the reaction, and the system after the reaction is sampled and analyzed by gas chromatography. The chromatographic results show that 3-(3-isopropylphenyl)butyraldehyde, the raw material conversion rate is 98.6%, and the yield is 83.8%.

[0021] Comparative Example 1

[0022] The preparation method of 3-(3-isopropylphenyl)butyraldehyde in this comparative example is the same as that in Example 1, except that the catalyst in Example 1 is filtered out and continuously added to the next kettle, and the amount of raw materials, ligands and organic base remains unchanged. In this comparative example, the raw material conversion rate is 94.1%, and the yield of 3-(3-isopropylphenyl)butyraldehyde is 81.9%.

[0023] Example 2

[0024] Provided is a method for preparing 3-(3-isopropylphenyl)butyraldehyde, comprising the following steps:

[0025] Step 1, adding 0.1% rhodium catalyst and 20eq phosphine ligand into the polytetrafluoroethylene lining of the autoclave; the rhodium catalyst is RhHCO(PPh3)3, and the phosphine ligand is 2-(di-tert-butylphosphine)biphenyl;

[0026] Step 2, adding 90g of m-isopropenyl isopropylbenzene and 1.0800g of an organic base compound to the polytetrafluoroethylene liner of the high-pressure reactor in step 1 in sequence, adding a rotor and covering the reactor cover, connecting nitrogen for leak detection, replacing it with nitrogen three times after no leakage, and then introducing a mixture of hydrogen and carbon monoxide for replacement 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;

[0027] Step 3, in an atmosphere of a mixture of hydrogen and carbon monoxide in a volume ratio of 1:1, the stirring speed is set to 800r / min, the temperature of the mixed system of step 2 is set to 110°C, and the pressure is 3MPa for hydroformylation reaction. After the reaction is continued for 6 hours, the temperature is lowered to stop the reaction, and the system after the reaction is sampled and analyzed by gas chromatography. The chromatographic results show that 3-(3-isopropylphenyl)butyraldehyde, the raw material conversion rate is 94.2%, and the yield is 81.8%.

[0028] Example 3

[0029] Provided is a method for preparing 3-(3-isopropylphenyl)butyraldehyde, comprising the following steps:

[0030] Step 1, adding 0.1% rhodium catalyst and 20eq phosphine ligand into the polytetrafluoroethylene lining of the autoclave; the rhodium catalyst is Rh(C5H7O2)(CO)(PPh3), and the phosphine ligand is 2-(di-tert-butylphosphine)biphenyl;

[0031] Step 2, adding 90g of m-isopropenyl isopropylbenzene and 1.0800g of an organic base compound to the polytetrafluoroethylene liner of the high-pressure reactor in step 1 in sequence, adding a rotor and covering the reactor cover, connecting nitrogen for leak detection, replacing it with nitrogen three times after no leakage, and then introducing a mixture of hydrogen and carbon monoxide for replacement 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;

[0032] Step 3, in an atmosphere of a mixture of hydrogen and carbon monoxide in a volume ratio of 1:1, the stirring speed is set to 800r / min, the temperature of the mixed system of step 2 is set to 110°C, and the pressure is 3MPa for hydroformylation reaction. After the reaction is continued for 6 hours, the temperature is lowered to stop the reaction, and the system after the reaction is sampled and analyzed by gas chromatography. The chromatographic results show that 3-(3-isopropylphenyl)butyraldehyde, the raw material conversion rate is 90.7%, and the yield is 80.3%.

[0033] Example 4

[0034] Provided is a method for preparing 3-(3-isopropylphenyl)butyraldehyde, comprising the following steps:

[0035] Step 1, adding 0.1% rhodium catalyst and 20eq phosphine ligand into the polytetrafluoroethylene lining of the autoclave; the rhodium catalyst is Rh(CO)2C5H7O2, and the phosphine ligand is triphenylphosphine tris-sulfonic acid sodium salt (TPPTS);

[0036] Step 2, adding 90g of m-isopropenyl isopropylbenzene and 1.0800g of an organic base compound to the polytetrafluoroethylene liner of the high-pressure reactor in step 1 in sequence, adding a rotor and covering the reactor cover, connecting nitrogen for leak detection, replacing it with nitrogen three times after no leakage, and then introducing a mixture of hydrogen and carbon monoxide for replacement 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;

[0037] Step 3, in an atmosphere of a mixture of hydrogen and carbon monoxide in a volume ratio of 1:1, the stirring speed is set to 800r / min, the temperature of the mixed system in step 2 is set to 110°C, and the pressure is 3MPa for hydroformylation reaction. After the reaction is continued for 6 hours, the temperature is lowered to stop the reaction, and the system after the reaction is sampled and analyzed by gas chromatography. The chromatographic results show that 3-(3-isopropylphenyl)butyraldehyde, the raw material conversion rate is 56.3%, and the yield is 39.2%

[0038] Example 5

[0039] Provided is a method for preparing 3-(3-isopropylphenyl)butyraldehyde, comprising the following steps:

[0040] Step 1, adding 0.1% rhodium catalyst and 20eq phosphine ligand into the polytetrafluoroethylene lining of the autoclave; the rhodium catalyst is Rh(CO)2C5H7O2, and the phosphine ligand is bis(3,5-dimethylphenyl)phosphine oxide;

[0041] Step 2, adding 90g of m-isopropenyl cumene and 1.0800g of an organic base to the polytetrafluoroethylene liner of the high-pressure reactor in step 1 in sequence, replacing it three times, and then introducing a mixture of hydrogen and carbon monoxide to replace it 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;

[0042] Step 3, in an atmosphere of a mixture of hydrogen and carbon monoxide in a volume ratio of 1:1, the stirring speed is set to 800r / min, the temperature of the mixed system of step 2 is set to 110°C, and the pressure is 3MPa for hydroformylation reaction. After the reaction is continued for 6 hours, the temperature is lowered to stop the reaction, and the system after the reaction is sampled and analyzed by gas chromatography. The chromatographic results show that 3-(3-isopropylphenyl)butyraldehyde, the raw material conversion rate is 79.2%, and the yield is 67.5%.

[0043] Example 6

[0044] Provided is a method for preparing 3-(3-isopropylphenyl)butyraldehyde, comprising the following steps:

[0045] Step 1, adding 0.1% rhodium catalyst and 20eq phosphine ligand into the polytetrafluoroethylene lining of the autoclave; the rhodium catalyst is Rh(CO)2C5H7O2, and the phosphine ligand is 2-(di-tert-butylphosphine)biphenyl;

[0046] Step 2, adding 90g of m-isopropenyl cumene and 1.0800g of an organic base to the polytetrafluoroethylene liner of the high-pressure reactor in step 1 in sequence, replacing it three times, and then introducing a mixture of hydrogen and carbon monoxide to replace it 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;

[0047] Step 3, in an atmosphere of a mixture of hydrogen and carbon monoxide in a volume ratio of 1:1, the stirring speed is set to 800r / min, the temperature of the mixed system of step 2 is set to 110°C, and the pressure is 3MPa for hydroformylation reaction. After the reaction is continued for 6 hours, the temperature is lowered to stop the reaction, and the system after the reaction is sampled and analyzed by gas chromatography. The chromatographic results show that 3-(3-isopropylphenyl)butyraldehyde, the raw material conversion rate is 85.7%, and the yield is 70.8%.

[0048] Example 7

[0049] Provided is a method for preparing 3-(3-isopropylphenyl)butyraldehyde, comprising the following steps:

[0050] Step 1, adding 0.1% rhodium catalyst and 20eq phosphine ligand into the polytetrafluoroethylene lining of the autoclave; the rhodium catalyst is Rh(CO)2C5H7O2, and the phosphine ligand is 2-(di-tert-butylphosphine)biphenyl;

[0051] Step 2, adding 90g of m-isopropyl cumene and 1.0800g of an organic base to the polytetrafluoroethylene liner of the high-pressure reactor in step 1 in sequence, replacing it three times, and then introducing a mixture of hydrogen and carbon monoxide to replace it three times; the organic base compound is N,N-diisopropylethylamine; the volume ratio of hydrogen to carbon monoxide in the mixture of hydrogen and carbon monoxide is 1:1;

[0052] Step 3, in an atmosphere of a mixture of hydrogen and carbon monoxide in a volume ratio of 1:1, the stirring speed is set to 800r / min, the temperature of the mixed system of step 2 is set to 110°C, and the pressure is 3MPa for hydroformylation reaction. After the reaction is continued for 6 hours, the temperature is lowered to stop the reaction, and the system after the reaction is sampled and analyzed by gas chromatography. The chromatographic results show that 3-(3-isopropylphenyl)butyraldehyde, the raw material conversion rate is 83.2%, and the yield is 75.2%.

[0053] From Examples 1-3, it can be seen that the Rh(CO)2C5H7O2 rhodium catalyst has excellent catalyst performance, and from the comparative example, it can be seen that the catalyst can be reused and can also maintain a high reaction yield; in Examples 4-5, we screened phosphine ligands, and compared with Example 1, we found that 2-(di-tert-butylphosphine)biphenyl is more suitable for the current reaction system; in Examples 6-7, it can be seen that the other two organic bases have a low conversion rate compared to triethylamine, so triethylamine is preferred. This application has achieved significant results in both the innovation and practicality of the process. The present invention greatly reduces the production cost of 3-(3-isopropylphenyl)butyraldehyde, and provides a green and efficient new synthesis process for the industrial manufacture of 3-(3-isopropylphenyl)butyraldehyde.

[0054] For any technician familiar with the art, without departing from the scope of the technical solution of the present invention, the technical content disclosed above can be used to make many possible changes and modifications to the technical solution of the present invention, or modified into equivalent embodiments with equivalent changes. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention should still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing 3-(3-isopropylphenyl)butyraldehyde, characterized in that: The method comprises the following reaction steps: taking m-isopropenyl cumene as a raw material, introducing a mixed gas of H2 and CO in a volume ratio of 1:1 in the presence of a rhodium catalyst, a phosphine ligand and a base without solvent, and carrying out a hydroformylation reaction.

2. The method for preparing 3-(3-isopropylphenyl)butyraldehyde according to claim 1, characterized in that: The preparation method comprises the following steps: Step 1, adding a rhodium catalyst and a phosphine ligand into a high-pressure reactor; Step 2, adding m-isopropenyl cumene and an organic base compound into the high-pressure reactor described in step 1 in sequence to obtain a mixed system; Step 3: In an atmosphere of a mixture of hydrogen and carbon monoxide, the mixed system of step 2 is subjected to a hydroformylation reaction at a temperature of 90° C. to 140° C. and a pressure of 1 MPa to 5 MPa for 6 to 10 hours to obtain 3-(3-isopropylphenyl)butyraldehyde.

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, 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-butylphosphino)biphenyl, triphenylphosphine tris-sulfonic acid sodium salt (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 usage ratio of the rhodium catalyst raw material in the hydroformylation reaction is 0.05%-0.1%:

1.

7. According to the preparation method of claim 1 or 2, the molar ratio of the phosphine ligand to the 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. According to the preparation method of claim 1 or 2, the phosphine ligand is preferably 2-(di-tert-butylphosphino)biphenyl, and the base is preferably triethylamine.

10. The preparation method according to claim 2, characterized in that: In step 3, the reaction temperature is 120° C. and the pressure is 3 MPa.

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