CN110950745B

CN110950745B - Preparation method of phenylacetaldehyde

Info

Publication number: CN110950745B
Application number: CN201911104623.2A
Authority: CN
Inventors: 牟通; 王漭; 赵晶; 李俊平; 黎源
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2019-11-13
Filing date: 2019-11-13
Publication date: 2022-09-20
Anticipated expiration: 2039-11-13
Also published as: CN110950745A

Abstract

The invention discloses a preparation method of phenylacetaldehyde. 1, 4-diphenyl-2-butyne is taken as a raw material, an intermediate 1, 4-diphenyl-2-butene is obtained through Lindlar catalytic hydrogenation reaction, and phenylacetaldehyde is obtained through ozonization and catalytic reduction reaction of the intermediate. The method adopts simple raw materials, and is converted by hydrogenation and ozonization, the reaction process is green and environment-friendly, the product yield is high, the byproducts are few, and the atom economy is extremely high.

Description

Preparation method of phenylacetaldehyde

Technical Field

The invention belongs to the field of chemical synthesis, and relates to a green and efficient preparation method of phenylacetaldehyde.

Background

Phenylacetaldehyde is a perfume with fragrant of hosta plantaginea flower, is one of important perfumes for blending various fragrance essences, has important application in perfume and cosmetic industries, and is also an important raw material for synthesizing fine chemicals such as medicines, food additives, agricultural chemicals and the like. The Schiff base purified wastewater can be prepared in the aspect of environment; is a highly effective pest inhibitor in the aspect of pesticide.

Phenylacetaldehyde is active in property and easy to oxidize and polymerize, so that the prior industrial method cannot obtain the phenylacetaldehyde with high yield and high purity, but the application range of the phenylacetaldehyde is still continuously expanded, and the yield can not meet the market demand far.

Industrial production methods of phenylacetaldehyde are classified into an oxidation method, an isomerization method and a reduction method.

The oxidation method generally uses 2-phenylethyl alcohol as a raw material, and primary alcohol is oxidized into aldehyde group by air. The oxidation catalyst is usually copper or electrolytic silver, or an oxidizing inorganic salt is used as the catalyst, and a quaternary ammonium salt is used as the phase transfer catalyst. In addition, transition metal complex is used as a catalyst, so that the one-step conversion reaction condition is mild. The disadvantage of this type of catalyst is that both the phenylacetaldehyde yield and the catalyst efficiency are low.

In addition, the fermentation preparation method using 2-phenethyl alcohol as raw material is characterized by good selectivity, high product purity and limited selection of strains.

The isomerization process usually uses styrene oxide as a raw material, and realizes the conversion to phenylacetaldehyde in one step under mild conditions. Catalysts used in the isomerization process include molecular sieve catalysts, transition metal salt catalysts and solid acid catalysts, and there is a problem in that the activity or life of the catalyst is limited.

The reduction method generally uses phenylacetic acid or phenylacetic ester as a raw material, and directly converts carboxyl or ester group into aldehyde group under the action of an aluminum-containing reducing agent or a boron-containing reducing agent. The reduction method has the characteristics of simple and quick operation and high phenylacetaldehyde product yield; the disadvantages are high cost of the reducing agent and limited industrialized production.

In conclusion, in the preparation method of phenylacetaldehyde, products produced by an oxidation method are easily over-oxidized, so that the product yield is low, the activity or the service life of a catalyst in an isomerization method is limited, the cost of a reducing agent in a reduction method is high, and the scale-up production of various methods is limited. Therefore, there is a need to develop a more green and efficient process, avoid the above problems, and achieve a breakthrough in the technology for manufacturing perfume-grade phenylacetaldehyde.

Disclosure of Invention

The invention aims to provide a preparation method of phenylacetaldehyde. 1, 4-diphenyl-2-butyne is taken as a raw material, and a perfume-grade phenylacetaldehyde product with the purity of more than 98 percent is obtained through two steps of chemical conversion, namely hydrogenation reaction and ozonization. The catalyst system of the process is cheap and easy to obtain, has high atom economy and has the prospect of industrial production.

The technical scheme of the invention is as follows:

a preparation method of phenylacetaldehyde comprises the following steps:

1) 1, 4-diphenyl-2-butyne is taken as a raw material, and hydrogenation reaction is carried out under the action of a Lindlar catalyst to obtain an intermediate 1, 4-diphenyl-2-butene;

2) the method comprises the following steps of carrying out ozonization reaction on 1, 4-diphenyl-2-butene at a low temperature, carrying out catalytic reduction reaction under the action of a catalyst, and separating to obtain phenylacetaldehyde.

The Lindlar catalyst adopted in the step 1) is selected from Pd-CaCO ₃ Or Pd-BaSO ₄ Preference is given to Pd-CaCO ₃ 。

In the step 1) of the invention, the mass ratio of the catalyst to the 1, 4-diphenyl-2-butyne is 1: 10-1000, preferably 1: 20-200, more preferably 1: 100-200.

The adopted raw material 1, 4-diphenyl-2-butyne is an existing compound and can be obtained by self-making or direct purchase, and a double phenyl C4 skeleton of the compound already has 2 complete phenylacetaldehyde carbon atom skeleton units, so that the economy of high atoms in subsequent conversion is guaranteed.

In step 1), the hydrogenation reaction is carried out under the conditions from normal temperature to heating, and the reaction temperature is 25-100 ℃, preferably 25-80 ℃, and more preferably 50-80 ℃.

The hydrogenation reaction pressure is 0.5 to 5.0MPaG, preferably 1.0 to 3.0MpaG, more preferably 1.5 to 2.5 MpaG. The hydrogen dosage is controlled by pressure, and is not limited, the yield of reduction hydrogenation of acetylene bonds is improved by increasing the reaction pressure, but the excessive pressure can cause the increase of over-reduced products (saturated alkanes) and is not favorable for the subsequent ozonization reaction.

The hydrogenation reaction time is 0.5-8h, preferably 0.5-2 h.

In step 1) of the present invention, the hydrogenation reaction is preferably carried out in the presence of a solvent selected from one or more of alcohols or ethers, preferably one or more of linear or branched alcohols of C1 to C6, more preferably one or more of linear alcohols of C1 to C3, and further preferably methanol and/or ethanol, in order to facilitate the separation of phenylacetaldehyde. Preferably, the solvent is used in an amount of 1g/(3-10) mL, preferably 1g/(4-6) mL, in terms of the concentration of 1, 4-diphenyl-2-butyne dissolved therein.

In the step 1), the method also comprises the treatment processes of filtering, desolventizing and the like after the hydrogenation reaction is finished. Wherein, the catalyst must be separated by filtration, and the solvent can be removed or not removed, for example, the solvent is removed for ethers, and the obtained intermediate 1, 4-diphenyl-2-butene is directly transferred to ozonization reaction.

In step 2) of the present invention, in order to ensure high conversion rate of the raw material, the ozonization reaction needs to have a molar amount of ozone greater than that of 1, 4-diphenyl-2-butene, and the molar ratio of the ozone to the 1, 4-diphenyl-2-butene is in the range of 1.05-2: 1, preferably 1.05 to 1.1: 1.

preferably, the ozone used in the ozonization reaction is introduced by ozone-containing oxygen, the volume content of the ozone is not particularly limited, and the ozone is preferably generated at a concentration of about 20% according to the operating conditions of the ozone generator.

Ozone is a very oxidizing oxidant and therefore the reaction is usually carried out at very low temperatures. But in connection with the ozonisation reaction according to the invention said low temperature ranges from-70 to 50 c, preferably from-50 to 0 c, more preferably from-20 to 0 c.

The time of the olefin ozonization reaction is closely related to the temperature, the temperature is increased, the reaction rate is greatly increased, and the ozonization reaction time is in the range of 0.1 to 5 hours, preferably 0.5 to 3 hours, and more preferably 0.5 to 1.5 hours in the invention.

In the step 2), peroxide obtained by ozonization reaction of 1, 4-diphenyl-2-butene can be converted into phenylacetaldehyde product through catalytic reduction reaction. The reduction system generally adopted by the peroxide reduction reaction can be selected from an inorganic salt (sodium sulfite and the like) aqueous solution system, a reducing organic matter (dimethyl sulfide or triphenylphosphine) and the like, but all the methods generate a large amount of inorganic or organic waste, so that the aftertreatment is difficult, and therefore, the catalytic reduction reaction adopts a Lindlar catalyst and hydrogen as a reducing agent.

In the catalytic reduction reaction, the Lindlar catalyst is preferably Pd-CaCO ₃ Or Pd-BaSO ₄ The mass ratio of Lindlar catalyst to 1, 4-diphenyl-2-butene is 1: 100-10000, preferably 1: 200-2000, more preferably 1: 1000-2000.

The catalytic reduction reaction is carried out at the reaction temperature of 0-50 ℃, preferably 15-30 ℃; the reaction time is 0.5-8h, preferably 1-2 h.

In the hydrogenation reduction reaction, the consumption of the reducing agent hydrogen is not limited, and the excessive hydrogen is ensured in the reaction time, so that the raw material is completely converted.

In the invention, the Lindlar catalyst used in the hydrogenation reaction in the step 1) and the catalytic reduction reaction in the step 2) can be the same or different, and from the viewpoint of simplifying the process flow and saving the cost,preferably, both are the same and adopt Pd-CaCO ₃ 。

In step 2) of the present invention, the catalytic reduction reaction system further comprises a solvent selected from one or more alcohols, preferably one or more of C1-C6 linear or branched chain alcohols, preferably one or more of C1-C3 linear alcohols, and more preferably methanol and/or ethanol. Preferably, the solvent is used in an amount of 1g/(3-10) mL, preferably 1g/(4-6) mL, based on the concentration of 1, 4-diphenyl-2-butyne therein. The hydrogenation reaction in the step 1) and the catalytic reduction reaction in the step 2) adopt the same or different solvents; if the solvent is not removed after the hydrogenation reaction in the step 1) is finished, the solvent is directly used in the reaction system in the step 2), namely, the ozonization reaction and the catalytic reduction reaction in the step 2) are carried out in the solvent, and the type and the using amount of the adopted solvent are the same as those in the step 1); if the solvent is removed in step 1), the solvent can be added again in step 2) during the catalytic reduction reaction.

In the step 2), after the catalytic reduction reaction is finished, a phenylacetaldehyde product is obtained by distillation. The distillation is preferably carried out at a pressure of-98 kPaG and a temperature of 90-105 ℃.

Because phenylacetaldehyde is active and easily self-polymerized under storage conditions, so that the quality of products is reduced, a stabilizer is usually added into the phenylacetaldehyde for prolonging the storage time, and the stabilizer adopted by the invention is an organic acid, preferably tartaric acid and/or citric acid. The stabilizer is added in an amount of 0.1 to 1 wt%, preferably 0.2 to 0.5 wt%, and more preferably about 0.2 wt% for ensuring the effect and controlling the cost.

The phenylacetaldehyde prepared by the method has the purity of over 98 percent, is a spice-grade phenylacetaldehyde product, has the conversion rate of 1, 4-diphenyl-2-butyne of more than 99 percent as a raw material, has the total yield of over 95 percent, and can be stably stored for over 10 days.

Compared with the prior art, the preparation method of the phenylacetaldehyde has the following advantages:

1) the raw material 1, 4-diphenyl-2-butyne is subjected to hydrogenation reaction and catalytic reduction after ozonation reaction by using Lindlar catalyst, and the catalyst has high reaction activity, long service cycle and low average cost;

2) the adopted conversion schemes of hydrogenation reaction and ozonization reaction are green conversion processes with extremely high atom economy, and the generation amount of three wastes is low, thereby conforming to the development direction of green chemical industry;

3) the product phenylacetaldehyde has high purity, high yield, good stability, longer storage period and is beneficial to storage and transportation.

Drawings

FIG. 1 shows the NMR spectrum of 1, 4-diphenyl-2-butene prepared in example 1 (solvent CDCl) ₃ )。

Detailed Description

The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention as claimed.

The embodiment of the invention has the following main raw material sources:

1, 4-diphenyl-2-butyne, self-made, the preparation method comprises: research on the synthesis process of 2-butyne-1, 4-diphenyl (synthesis of 1.32-butyne-1, 4-diphenyl), Lvheng et al, chemical and biological engineering, 2014, Vol.31, No.05, P37-39; the method comprises the following specific steps: taking 0.1moL of benzene and 0.26moL of AlCl ₃ Adding into a 100mL three-neck flask, introducing nitrogen for protection, magnetically stirring at a constant temperature of 40 ℃ for 5min, then starting to dropwise add 0.1moL of 2-butyne-1, 4-di (p-toluenesulfonate) benzene solution, reacting at the same temperature for 2h, dropwise adding dilute hydrochloric acid to terminate the reaction, standing for 2h, and performing layered filtration; washing the filtrate with ice water to neutrality, adding anhydrous sodium sulfate, standing for 6h, and filtering; the filtrate was extracted with benzene, the supernatant was rotary evaporated to give a red oily substance, which was purified by column chromatography [ eluent: v (petroleum ether): v (dichloromethane) ═ 5: 2]Red solid powder was obtained.

Lindlar catalyst, Pd-CaCO ₃ 5% (poisoned with lead) Shanghai Aladdin Biotechnology GmbH;

methanol, ethanol (98%), west longu science, ltd;

tetrahydrofuran, west longa science, ltd;

tartaric acid, citric acid (98%), carbofuran technologies ltd;

starch potassium iodide test paper, merck life science;

dimethyl sulfide (99%), carbofuran technology;

skeletal nickel catalyst, graves catalyst ltd.

The embodiment of the invention adopts the following main instruments:

an ozone generator: CF-G-3-010, Qingdao national forest industries, Inc.;

GC instrument model: shimadzu GC-2010-plus;

model of nuclear magnetic instrument: bruker 400M, instrument frequency 400MHz, sampling times 16.

Examples 1 to 6

1) Hydrogenation reaction:

dissolving raw material 1, 4-diphenyl-2-butyne in a solvent, transferring the solution into a 500mL high-pressure reaction kettle, and adding Lindlar catalyst and N in one step ₂ After the replacement is carried out for three times, the reaction kettle is started to stir and heat, the temperature is raised to the reaction temperature, hydrogen is introduced to the reaction kettle to reach certain pressure, the stirring speed is kept at 500rpm, after the reaction is carried out for certain time, sampling is carried out from a sampling side pipe, and the conversion rate of the raw materials reaches more than 99 percent through GC analysis.

After the reaction kettle is cooled, the pressure is released to discharge the residual H ₂ By N, of ₂ And (3) replacing for three times, extracting reaction mother liquor from a reaction kettle filter to obtain a solution of the intermediate 1, 4-diphenyl-2-butene, and analyzing the purity of the intermediate after the solvent is removed by GC. The catalyst is left in the kettle for the next operation.

Examples 1-6 step 1) hydrogenation reaction conditions are shown in table 1, and the results are analyzed in table 2:

TABLE 1 examples 1-6 specific reaction conditions for hydrogenation reactions

TABLE 2 analysis of the results of hydrogenation reactions of examples 1-6

Examples	Product (g)	1, 4-diphenyl-2-	Yield of
				1	39.95	97.99% by weight	96.0％
2	70.41	86.36％	84.6％
				3	37.22	91.30％	89.5％
4	53.91	88.16％	86.4％
				5	26.47	86.56％	84.8％
6	100.29	98.40％	96.4％

The solution of the intermediate 1, 4-diphenyl-2-butene, example 3, 4, 6, in tetrahydrofuran, was subjected to distillation under reduced pressure to remove the solvent before the solution was used in the ozonization reaction in step 2), and then ethanol solvent was added in an amount equivalent to the volume of the solution in the hydrogenation reaction in the catalytic reduction reaction in step 2). Examples 1, 2, 5 were used directly in the reaction of step 2) without removing the solvent.

2) Ozonization and catalytic reduction:

transferring the intermediate 1, 4-diphenyl-2-butene obtained from the hydrogenation reaction in the step 1) into a glass bubbling tower reactor, keeping the reaction temperature, and introducing O into bubbles ₃ Oxygen at a concentration of 20% by volume, the progress of the reaction was checked by GC until complete conversion of the starting material.

Transferring ozonization reaction mother liquor to a reactor filled with Pd-CaCO ₃ In a reduction reaction kettle of the catalyst, the catalyst is reduced by N ₂ After the replacement, H is introduced ₂ And (3) carrying out reduction, and detecting by using a starch-potassium iodide test paper regularly until the starch-potassium iodide test paper does not change blue, which indicates that the reduction reaction is completely carried out.

After the solvent is removed, the obtained concentrate is distilled and purified to obtain a light yellow phenylacetaldehyde product, the purity of the product is analyzed by GC, and the total yield of the two steps of the step 1) and the step 2) is calculated.

Examples 1-6, step 2) reaction conditions are shown in table 3, and the results are analyzed in table 4:

TABLE 3 operating conditions for step 2) ozonation and reduction reactions in examples 1-6

TABLE 4 analytical results of phenylacetaldehyde products obtained in examples 1 to 6

Examples	Product (g)	Purity of phenylacetaldehyde	Overall yield of
				1	45.3	99.20％	93.6％
2	80.3	98.50％	82.4％
				3	43.4	97.80％	88.4％
4	55.3	98.0％	75.3％
				5	30.5	98.60％	83.5％
6	115.2	98.30％	94.4％

Comparative example 1

The difference from the embodiment 1 is that: in step 2), the catalytic reduction reaction temperature was 0 ℃ and a reducing agent dimethyl sulfide (12.5g, 0.21mol) was used.

The treated reaction solution was concentrated and distilled to obtain 43.4g of product with purity of 96.3% and overall yield of two steps of 87.1%. It can be seen that the purity and yield of the product obtained in comparative example 1 are lower than those of the product obtained in example 1, and in addition, dimethyl sulfide adopted in comparative example 1 has the defects of high price, large environmental hazard (odor) and the like.

Comparative example 2

The difference from example 1 is that: the hydrogenation uses a skeletal nickel catalyst.

The specific operation process is as follows: dissolving 41.2g (0.2mol) of raw material 1, 4-diphenyl-2-butyne in 200mL of methanol, transferring to a high-pressure reaction kettle, and adding a skeletal nickel catalyst (0.206g) and N at one time ₂ After the replacement is carried out for three times, the reaction kettle is started to stir and heat, the temperature is raised to 70 ℃, hydrogen is introduced until the pressure in the kettle reaches 2.0MPaG, the stirring speed is kept at 500rpm, and after the reaction is carried out for 1 hour, the GC analysis shows that the conversion rate of the raw materials reaches more than 99 percent.

After the reaction kettle is cooled, GC analysis shows that the content of 1, 4-diphenyl-2-butene is 62.3%, the main impurity is 1, 4-diphenyl butane, and the catalytic hydrogenation activity of the skeleton nickel is too high, so that the olefin intermediate is excessively hydrogenated into a saturated product.

Examples 7 to 8

Comparison of the stabilizers: the phenylacetaldehyde product obtained in example 1 and having a purity of more than 98% was used, and different stabilizers (tartaric acid and citric acid) were used to study the stabilizing effect.

The investigation conditions are as follows: the stabilizer dosage is 0.2 percent (wt%), the storage temperature is 10 ℃, the storage time is 10d, and the light is avoided.

Comparative examples 3 to 5

The differences from examples 7 to 8 are that: different stabilizers (blank, hydrochloric acid, acetic acid) were used.

The stabilizing effects of examples 7-8 and comparative examples 3-5 are shown in Table 5:

TABLE 5 Effect data of different stabilizers

	Stabilizer	Initial	2d	5d	10d
						Example 7	Blank space	99.2％	98.1％	96.4％	93.6％
Example 8	Tartaric acid	99.2％	99.0％	98.4％	97.5％
						Comparative example 3	Citric acid	99.2％	99.2％	98.8％	98.4％
Comparative example 4	Hydrochloric acid	99.2％	94.1％	88.7％	75.1％
						Comparative example 5	Acetic acid	99.2％	96.4％	92.1％	85.1％

The above results show that the addition of a suitable stabilizer greatly improves the storage stability of phenylacetaldehyde.

Claims

1. A preparation method of phenylacetaldehyde is characterized by comprising the following steps:

2) the method comprises the steps of firstly carrying out ozonization reaction on 1, 4-diphenyl-2-butene at low temperature ranging from-70 ℃ to 50 ℃, then carrying out catalytic reduction reaction by using Lindlar catalyst and hydrogen as a reducing agent under the action of the catalyst, and separating to obtain phenylacetaldehyde.

2. The method as claimed in claim 1, wherein the Lindlar catalyst used in step 1) is selected from Pd-CaCO ₃ Or Pd-BaSO ₄ ；

The mass ratio of the catalyst to 1, 4-diphenyl-2-butyne is 1: 10-1000.

3. The method of claim 2, wherein the Lindlar catalyst is Pd-CaCO ₃ 。

4. The method of claim 2, wherein the mass ratio of the catalyst to 1, 4-diphenyl-2-butyne is 1: 20-200.

5. The preparation method according to claim 4, wherein the mass ratio of the catalyst to 1, 4-diphenyl-2-butyne is 1: 100-200.

6. The preparation method of claim 1, wherein in the step 1), the hydrogenation reaction is carried out at a temperature of 25-100 ℃, a reaction pressure of 0.5-5.0MPaG and a reaction time of 0.5-8 h.

7. The method according to claim 6, wherein the reaction temperature is 25 to 80 ℃.

8. The method according to claim 7, wherein the reaction temperature is 50 to 80 ℃.

9. The process according to claim 6, wherein the pressure of the reaction is 1.0 to 3.0 MpaG.

10. The process according to claim 9, wherein the pressure of the reaction is 1.5 to 2.5 MpaG.

11. The process according to claim 6, wherein the reaction time is 0.5 to 2 hours.

12. The production method according to claim 1,

in the step 1), the hydrogenation reaction is carried out in the presence of a solvent, wherein the solvent is selected from one or more of alcohol or ether;

the dosage of the solvent is 1g/(3-10) mL based on the dissolution concentration of the 1, 4-diphenyl-2-butyne in the solvent; and/or

In the step 1), the hydrogenation reaction also comprises the processes of filtration and solvent removal after the hydrogenation reaction is finished; wherein the catalyst must be separated by filtration and the solvent can be removed or not removed.

13. The method of claim 12, wherein the solvent is selected from one or more of C1-C6 linear or branched alcohols.

14. The method of claim 13, wherein the solvent is selected from one or more of the group consisting of C1-C3 linear alcohols.

15. The method of claim 14, wherein the solvent is selected from methanol and/or ethanol.

16. The method according to claim 12, wherein the solvent is used in an amount of 1g/(4-6) mL in terms of a dissolved concentration of 1, 4-diphenyl-2-butyne therein.

17. The production method according to claim 1,

in the step 2), the ozonization reaction is carried out, wherein the molar ratio of ozone to 1, 4-diphenyl-2-butene is 1.05-2: 1.

18. the method of claim 17, wherein the molar ratio of ozone to 1, 4-diphenyl-2-butene is in the range of 1.05-1.1: 1.

19. the method of claim 17, wherein the ozone is introduced by ozone-containing oxygen.

20. The method according to claim 1, wherein the low temperature is in the range of-50 to 0 ℃ in step 2);

the ozonization reaction time is 0.1-5 h.

21. The method of claim 20, wherein the cryogenic temperature is in the range of-20 to 0 ℃.

22. The method of claim 20, wherein the ozonation reaction time is 0.5 to 3 hours.

23. The method of claim 22, wherein the ozonation reaction time is 0.5 to 1.5 hours.

24. The method as claimed in claim 1, wherein in step 2), the Lindlar catalyst is Pd-CaCO ₃ Or Pd-BaSO ₄ ；

The mass ratio of the Lindlar catalyst to 1, 4-diphenyl-2-butene is 1: 100-;

the Lindlar catalyst used in the hydrogenation reaction in step 1) and the catalytic reduction reaction in step 2) can be the same or different.

25. The method of claim 24, wherein the Lindlar catalyst to 1, 4-diphenyl-2-butene mass ratio is 1: 200-2000.

26. The method of claim 25, wherein the mass ratio of the Lindlar catalyst to 1, 4-diphenyl-2-butene is 1: 1000-2000.

27. The preparation method according to claim 1, wherein in the step 2), the catalytic reduction reaction is carried out at a temperature of 0-50 ℃ for 0.5-8 h.

28. The method of claim 27, wherein the reaction temperature is 15-30 ℃ and the reaction time is 1-2 hours.

29. The preparation method according to claim 1, wherein in the step 2), the catalytic reduction reaction system comprises a solvent selected from one or more of alcohols;

the dosage of the solvent is 1g/(3-10) mL based on the concentration of 1, 4-diphenyl-2-butyne in the solvent;

the hydrogenation reaction in step 1) and the catalytic reduction reaction in step 2) may be carried out using the same or different solvents.

30. The method as claimed in claim 29, wherein the solvent is one or more selected from the group consisting of linear or branched C1-C6 alcohols.

31. The method of claim 30, wherein the solvent is selected from one or more of the group consisting of C1-C3 linear alcohols.

32. The method of claim 31, wherein the solvent is selected from methanol and/or ethanol.

33. The method of claim 29, wherein the solvent is used in an amount of 1g/(4-6) mL, based on the concentration of 1, 4-diphenyl-2-butyne therein.

34. The method according to any one of claims 1 to 33, wherein a stabilizer is added to phenylacetaldehyde, and the stabilizer is an organic acid; the addition amount of the stabilizer is 0.1-1 wt%.

35. The method of claim 34, wherein the stabilizer is tartaric acid and/or citric acid.

36. The method of claim 34, wherein the stabilizer is added in an amount of 0.2 to 0.5 wt%.