4-phenylacetylene phthalic anhydride synthesis

Abstract

The application discloses a synthesis method of 4-phenylacetylene phthalic anhydride, which has the following steps: ①a halogenated benzene, 4-halogenated phthalic anhydride and acetylene are used as starting materials, and a 4-phenylacetylene phthalic anhydride crude product is obtained through catalytic coupling reaction in the presence of a palladium catalyst, a catalyst ligand, a cocatalyst and an organic amine base; ②hydrolysis is carried out to obtain 4-phenylacetylene phthalic acid; and ③dehydration is carried out to obtain 4-phenylacetylene phthalic anhydride finished product. According to the synthesis method, the halogenated benzene and the 4-halogenated phthalic anhydride are mixed into a reaction system with acetylene gas, two different substituents are connected to both ends of the acetylene group at one time in the same reaction system, the reaction efficiency is high, and after the reaction, the by-products and impurities generated in the reaction process can be completely removed through the method of hydrolyzing into an acid first and then dehydrating into an anhydride, so that high-quality products with a purity of greater than or equal to 99.5% are obtained.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of 4-phenylacetylene phthalic anhydride. BACKGROUND

[0002] 4-phenylacetylene phthalic anhydride, full name 4-phenylacetylene phthalic anhydride, abbreviated as 4-PEPA, is a white to light yellow powder, molecular formula: C 16 H8O3, relative molecular weight: 248.23, CAS number: 119389-05-8, and structural formula as follows:

[0003] .

[0004] The polyimide prepared by using 4-phenylacetylene phthalic anhydride as a capping agent has high heat resistance, solvent resistance, creep resistance, wear resistance and excellent easy forming performance (see document US5681967A), and has high application prospect in the field of aerospace, and higher requirements are put forward for the product quality and manufacturing cost of 4-phenylacetylene phthalic anhydride.

[0005] However, the synthesis methods of 4-phenylacetylene phthalic anhydride disclosed in the prior art are basically as follows: phenylacetylene is used as a starting material, and 4-halophthalic anhydride (see documents 1-3) or 4-halophthalic acid (see documents 4-6) is subjected to catalytic coupling in the presence of a palladium catalyst, a catalyst ligand triphenylphosphine, a cocatalyst cuprous iodide and an organic base to obtain 4-phenylacetylene phthalic anhydride or 4-phenylacetylene phthalic acid, and the latter is dehydrated to obtain 4-phenylacetylene phthalic anhydride.

[0006] The disadvantages of such methods are:

[0007] (1) The price of phenylacetylene is relatively high and the stability is poor, resulting in high raw material cost.

[0008] (2) The raw material 4-halophthalic acid is relatively high in price and difficult to obtain, further resulting in high raw material cost.

[0009] (3) The reaction yield is low, mostly below 80%.

[0010] (4) The product purity is low, and the product quality is poor.

[0011] Document 1: US patent document US5681967A, published on October 28, 1997.

[0012] Document 2: Chinese patent document CN1544424A, published on November 10, 2004.

[0013] Document 3: Chinese patent document CN1603317A, published on April 6, 2005.

[0014] Document 4: Chinese patent document CN101550121A, publication date October 7, 2009.

[0015] Document 5: Chinese patent document CN101550122A, publication date October 7, 2009.

[0016] Document 6: Chinese patent document CN103641806A, publication date March 19, 2014. SUMMARY

[0017] The object of the present application is to solve the above-mentioned problems, and to provide a synthesis method of 4-phenylacetylene phthalic anhydride, which is cheap and easy to obtain, has low cost, high reaction yield and high product purity, and is suitable for industrial mass production.

[0018] The technical solution to achieve the object of the present application is: a synthesis method of 4-phenylacetylene phthalic anhydride, having the following steps:

[0019] ① Using halogenated benzene, 4-halogenated phthalic anhydride and acetylene as starting materials, in the presence of a palladium catalyst, a catalyst ligand, a cocatalyst and an organic amine acid binding agent, a catalytic coupling reaction is carried out to obtain 4-phenylacetylene phthalic anhydride crude product;

[0020] ② Hydrolyzing the 4-phenylacetylene phthalic anhydride crude product obtained in step ① to obtain 4-phenylacetylene phthalic anhydride;

[0021] ③ Dehydrating the 4-phenylacetylene phthalic anhydride obtained in step ② to obtain 4-phenylacetylene phthalic anhydride finished product.

[0022] The synthesis route is as follows:

[0023] .

[0024] Wherein: X = Cl, Br or I.

[0025] The halogenated benzene is chlorobenzene, bromobenzene or iodobenzene, preferably chlorobenzene.

[0026] The 4-halogenated phthalic anhydride is 4-chlorophthalic anhydride, 4-bromophthalic anhydride or 4-iodophthalic anhydride, preferably 4-chlorophthalic anhydride.

[0027] The molar ratio of the 4-halogenated phthalic anhydride to the halogenated benzene is 1:0.5-1:2, preferably 1:1.

[0028] The palladium catalyst is bis(triphenylphosphine)palladium dichloride PdCl2(PPh3)2; the amount of the bis(triphenylphosphine)palladium dichloride used is 0.1-3wt% of the weight of the halogenated benzene, preferably 0.5-1.5wt%.

[0029] The catalyst ligand is triphenylphosphine; the amount of the triphenylphosphine is 0.5-5wt% of the halobenzene, preferably 1-3wt%.

[0030] The co-catalyst is cuprous iodide; the amount of the cuprous iodide is 0.1-3wt% of the halobenzene, preferably 0.5-1.5wt%.

[0031] The organic amine base is one or two of triethylamine, pyridine, 4-dimethylaminopyridine, N,N-diisopropylethylamine, diazabicyclo; the molar ratio of the organic amine base to the halobenzene is 2:1-8:1, preferably 3.5:1-5.5:1.

[0032] The catalytic coupling is carried out in an organic solvent; the organic solvent is one or two of toluene, xylene, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), tetrahydrofuran (THF).

[0033] The catalytic coupling reaction temperature is 50-110℃, preferably 70-90℃.

[0034] The catalytic coupling reaction pressure is 0.1-1.0MPa, preferably 0.2-1.0MPa, more preferably 0.2-0.5MPa.

[0035] In the catalytic coupling reaction, the halobenzene and the 4-halophthalic anhydride are simultaneously added into the reaction system.

[0036] The hydrolysis reaction is carried out in the presence of a phase transfer catalyst; the phase transfer catalyst is one or two of benzyltriethylammonium bromide, hexyltriethylammonium bromide, octyltriethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium iodide, tetramethylammonium bromide, tetrapropylammonium chloride, benzyltriethylammonium chloride, methyltrioctylammonium chloride.

[0037] The amount of the phase transfer catalyst is 0.1-3wt% of the halobenzene, preferably 0.5-1.5wt%.

[0038] The hydrolysis reaction is carried out under alkaline conditions.

[0039] The dehydration to form anhydride is a conventional method in the art, such as acetic anhydride method or thermal sublimation method.

[0040] The present application has the following positive effects:

[0041] (1) The synthetic method of the present application uses halogenated benzene, 4-halogenated phthalic anhydride and acetylene as starting materials, drops the mixed solution of halogenated benzene and 4-halogenated phthalic anhydride into the reaction system with acetylene gas, and once connects two different substituents at both ends of the acetylenyl group in the same reaction system. The reaction efficiency is higher, and after the reaction, the by-products and impurities generated in the reaction process can be completely removed by the method of first hydrolysis into acid and then dehydration into anhydride, so that high-quality products with purity ≥ 99.5% are obtained, and the reaction yield can also reach more than 90%.

[0042] (2) The synthetic method of the present application uses raw material halogenated benzene, the price of which is less than 1 / 30 of that of phenylacetylene, so that the raw material cost can be greatly reduced, and it is suitable for industrial mass production. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 ESI-MS spectrum of the intermediate 4-phenylacetylene phthalic acid prepared in step ② of Example 1.

[0044] Figure 2 ESI-MS spectrum of the derivative obtained by esterification of the target product prepared in step ③ of Example 1. DETAILED DESCRIPTION

[0045] (Example 1)

[0046] The synthetic method of 4-phenylacetylene phthalic anhydride of the present embodiment has the following steps:

[0047] ① Add 500 mL of toluene, 253.0 g of triethylamine (2.5 mol), 0.3 g of bis(triphenylphosphine)palladium dichloride, 0.7 g of triphenylphosphine and 0.4 g of cuprous iodide into a 2L autoclave.

[0048] Close the autoclave, replace the air in the system with nitrogen three times, then empty the nitrogen, and introduce acetylene gas into the system, maintain the pressure at 0.2-0.4 MPa, and heat to 75-90°C. Then add a toluene solution (200 mL) containing 56.3 g (0.5 mol) of chlorobenzene and 91.3 g (0.5 mol) of 4-chlorophthalic anhydride into the system dropwise, about 8 h dropwise, then continue to stir for 1 h, and monitor the reaction to completion.

[0049] ② After the reaction is completed, stop introducing acetylene gas into the system, replace the acetylene gas with nitrogen three times, then add 500 mL of water to the system, then filter the material into a 3L reaction bottle, add 0.5 g of triethylbenzylammonium bromide and 100 g of 30 wt% sodium hydroxide solution to the filtrate, heat to 75-85°C and stir for 3 h.

[0050] After the reaction, the temperature was decreased to 40-50°C, and the mixture was allowed to stand and separate into layers. Concentrated hydrochloric acid was added to the water layer to adjust the pH to 1-2, and the temperature was decreased to 5-10°C. The mixture was filtered, washed with water, and dried to obtain 4-phenylacetylene phthalic acid 125.4 g, with a yield of 94.2% and an HPLC purity of 99.2%.

[0051] The ESI-MS spectrum of the 4-phenylacetylene phthalic acid obtained in this example is shown in Figure 1. Figure 1 As can be seen, the molecular weight thereof is 265.9 (M+H). Figure 1

[0052] The 4-phenylacetylene phthalic acid obtained in step 1 was added to a reaction bottle together with 110 g of acetic anhydride and 310 mL of dimethylbenzene, and the mixture was heated to reflux for 4 h. The temperature was then decreased to 5-10°C, and the mixture was crystallized, filtered, and dried to obtain white crystalline powder 4-phenylacetylene phthalic anhydride 71.5 g, with a yield of 95.8%, an HPLC purity of 99.6%, and a melting point of 155.4-156.7°C.

[0053] The ESI-MS spectrum of the derivative obtained by esterification of the 4-phenylacetylene phthalic anhydride obtained in this example is shown in Figure 2. Figure 2 As can be seen, the molecular weight thereof is 280.0 (M+H). Figure 2

[0054] (Example 2)

[0055] The 4-phenylacetylene phthalic anhydride of this example was synthesized by the following steps:

[0056] Step 1: 500 mL of dimethylbenzene, 263.1 g of triethylamine (2.6 mol), 0.5 g of bis(triphenylphosphine)palladium dichloride, 1.0 g of triphenylphosphine, and 0.5 g of cuprous iodide were added to a 2 L autoclave.

[0057] The autoclave was closed, and the air in the system was replaced with nitrogen three times. The nitrogen was then evacuated, and acetylene gas was introduced into the system. The pressure was maintained at 0.2-0.4 MPa, and the temperature was increased to 70-80°C. A solution containing 56.3 g (0.5 mol) of chlorobenzene and 91.3 g (0.5 mol) of 4-chlorophthalic anhydride in 200 mL of dimethylbenzene was then added dropwise to the system over about 10 h. The reaction was continued for 1 h with stirring, and the reaction was monitored until it was complete.

[0058] Step 2: After the reaction, the introduction of acetylene gas into the system was stopped, and the acetylene gas was replaced with nitrogen three times. 500 mL of water was then added to the system. The material was filtered into a 3 L reaction bottle, and 0.5 g of tetrabutylammonium bromide and 90 g of a 30 wt% sodium hydroxide solution were added to the filtrate. The temperature was increased to 75-85°C, and the mixture was stirred for 3.5 h.

[0059] ​​After the reaction was complete, the temperature was lowered to 40–50°C, and the mixture was allowed to stand and separate into layers. Concentrated hydrochloric acid was added to the aqueous layer to adjust the pH to 1–2. The temperature was then lowered to 5–10°C, filtered, washed with water, and dried to obtain 125.8 g of 4-phenylethynyl phthalic acid, with a yield of 94.5% and an HPLC purity of 99.3%. The ESI-MS spectrum was consistent with... Figure 1 Basically the same.

[0060] ③ Add 80.0g of 4-phenylethynyl phthalic acid obtained in step ①, 110g of acetic anhydride, and 310mL of xylene to a reaction flask, heat to reflux for 4h, then cool to 10-20℃, crystallize, filter, and dry to obtain 70.8g of white crystalline powder 4-phenylethynyl phthalic anhydride, with a yield of 94.9%, HPLC purity of 99.7%, and melting point of 155.6-156.7℃.

[0061] (Example 3)

[0062] The method for synthesizing 4-phenylacetylene phthalic anhydride in this embodiment includes the following steps:

[0063] ① Add 500 mL of toluene, 202.4 g of triethylamine (2.0 mol), 0.3 g of bis(triphenylphosphine)palladium dichloride, 0.6 g of triphenylphosphine and 0.3 g of cuprous iodide to a 2 L autoclave.

[0064] The autoclave was sealed, and the air in the system was replaced three times with nitrogen. Then the nitrogen was purged, and acetylene gas was introduced into the system. The pressure was maintained at 0.2-0.4 MPa, and the temperature was raised to 75-85℃. Then, a toluene solution (200 mL) containing 56.3 g (0.5 mol) of chlorobenzene and 113.5 g (0.5 mol) of 4-bromophthalic anhydride was added dropwise to the system over about 8 hours. The reaction was then stirred for another hour and monitored until it was complete.

[0065] ② After the reaction is complete, stop the acetylene gas from being introduced into the system, replace the acetylene gas with nitrogen three times, then add 500 mL of water to the system, then filter the material into a 3 L reaction flask, add 0.5 g of tetrabutylammonium bromide and 80 g of 30 wt% sodium hydroxide solution to the filtrate, and heat to 75-85 °C and stir for 3 h.

[0066] After the reaction was complete, the temperature was lowered to 40–50°C, and the mixture was allowed to stand to separate into layers. Concentrated hydrochloric acid was added to the aqueous layer to adjust the pH to 1–2. The temperature was then lowered to 5–10°C, filtered, washed with water, and dried to obtain 124.0 g of 4-phenylethynyl phthalic acid, with a yield of 93.1% and an HPLC purity of 99.1%. The ESI-MS spectrum was consistent with... Figure 1 Basically the same.

[0067] ③Into a reaction flask were introduced 80.0 g of 4-phenylacetylene phthalic acid obtained in step ①, 122 g of acetic anhydride, and 300 mL of xylene, and the reaction was carried out at elevated temperature under reflux for 4 h, and then the temperature was lowered to 5-10°C, and crystallization was performed, followed by filtration and drying to obtain 4-phenylacetylene phthalic anhydride in the form of white crystalline powder in an amount of 71.0 g and at a yield of 95.2%, and the HPLC purity was 99.5%, and the melting point was 155.3-156.6°C.

[0068] (Example 4)

[0069] The synthesis method of 4-phenylacetylene phthalic anhydride of the present example has the following steps:

[0070] ①Into a 2 L autoclave were introduced 500 mL of toluene, 205.7 g of pyridine (2.6 mol), 0.6 g of bis(triphenylphosphine)palladium dichloride, 1.2 g of triphenylphosphine, and 0.5 g of cuprous iodide.

[0071] The autoclave was closed, and the air in the system was replaced with nitrogen three times, and then the nitrogen was exhausted, and acetylene gas was introduced into the system, and the pressure was maintained at 0.2-0.4 MPa, and the temperature was raised to 75-85°C, and then a solution containing 56.3 g (0.5 mol) of chlorobenzene and 4-chlorophthalic anhydride 91.3 g (0.5 mol) in 200 mL of toluene was added dropwise into the system, and the dropping was completed in about 8 h, and then the reaction was continued for 1 h under stirring, and the reaction was monitored until completion.

[0072] ②After the completion of the reaction, the introduction of acetylene gas into the system was stopped, and the acetylene gas was replaced with nitrogen three times, and then 500 mL of water was added into the system, and then the materials were filtered into a 3 L reaction flask, and 0.5 g of tetrabutylammonium bromide and 90 g of 30 wt% sodium hydroxide solution were added into the filtrate, and the temperature was raised to 75-85°C, and the reaction was carried out under stirring for 3.5 h.

[0073] After the completion of the reaction, the temperature was lowered to 40-50°C, and the layers were separated after standing, and concentrated hydrochloric acid was added into the water layer to adjust the pH to 1-2, and then the temperature was lowered to 5-10°C, and the product was filtered, and washed with water, and dried to obtain 4-phenylacetylene phthalic acid in an amount of 124.6 g at a yield of 93.6%, and the HPLC purity was 99.2%, and the ESI-MS spectrum was substantially identical to that of the standard. Figure 1

[0074] ③Into a reaction flask were introduced 80.0 g of 4-phenylacetylene phthalic acid obtained in step ①, 122 g of acetic anhydride, and 300 mL of xylene, and the reaction was carried out at elevated temperature under reflux for 4 h, and then the temperature was lowered to 5-10°C, and crystallization was performed, followed by filtration and drying to obtain 4-phenylacetylene phthalic anhydride in the form of white crystalline powder in an amount of 71.0 g and at a yield of 95.2%, and the HPLC purity was 99.5%, and the melting point was 155.3-156.6°C.

[0075] (Example 5)​

[0076] The synthesis method of 4-phenylacetylene phthalic anhydride of the present embodiment has the following steps:

[0077] ① 400 mL of toluene, 100 mL of DMAc, 263.1 g of triethylamine (2.6 mol), 0.5 g of bis(triphenylphosphine)palladium dichloride, 1.0 g of triphenylphosphine, and 0.5 g of cuprous iodide are added into a 2 L autoclave.

[0078] The autoclave is closed, the air in the system is replaced with nitrogen three times, and then the nitrogen is exhausted. Acetylene gas is introduced into the system, the pressure is maintained at 0.2-0.4 MPa, and the temperature is raised to 70-80°C. Then a toluene solution (200 mL) containing 56.3 g (0.5 mol) of chlorobenzene and 91.3 g (0.5 mol) of 4-chlorophthalic anhydride is added dropwise into the system, and the dropping is completed in about 10 h. Then the reaction is continuously stirred for 1 h, and the reaction is monitored until it is completed.

[0079] ② After the reaction is completed, the introduction of acetylene gas into the system is stopped, and the acetylene gas is replaced with nitrogen three times. Then 500 mL of water is added into the system, and then the material is filtered into a 3 L reaction bottle. 0.5 g of tetrabutylammonium bromide and 90 g of 30 wt% sodium hydroxide solution are added into the filtrate, the temperature is raised to 75-85°C, and the reaction is stirred for 3.5 h.

[0080] After the reaction is completed, the temperature is lowered to 40-50°C, and the layers are separated after standing. Concentrated hydrochloric acid is added into the water layer to adjust the pH to 1-2, and then the temperature is lowered to 5-10°C. The mixture is filtered, washed with water, and dried to obtain 121.8 g of 4-phenylacetylene phthalic anhydride with a yield of 91.5% and a HPLC purity of 99.3%. The ESI-MS spectrum is basically consistent with that of the standard substance. Figure 1

[0081] ③ 80.0 g of 4-phenylacetylene phthalic anhydride obtained in step ①, 110 g of acetic anhydride, and 310 mL of toluene are added into a reaction bottle, and the reaction is refluxed at a high temperature for 4 h. Then the temperature is lowered to 10-20°C, and the mixture is crystallized, filtered, and then refined once with a mixed solution of acetic anhydride and toluene, and dried to obtain 69.4 g of white crystalline powder of 4-phenylacetylene phthalic anhydride with a yield of 93.0% and a HPLC purity of 99.9%. The melting point is 155.7-156.7°C.

[0082] (Example 6)

[0083] The synthesis method of 4-phenylacetylene phthalic anhydride of the present embodiment has the following steps:

[0084] ① 500 mL of toluene, 202.4 g of triethylamine (2.0 mol), 0.4 g of bis(triphenylphosphine)palladium dichloride, 0.8 g of triphenylphosphine, and 0.4 g of cuprous iodide are added into a 2 L reaction bottle. ​

[0085] Close the autoclave, replace the air in the system with nitrogen three times, then evacuate the nitrogen, continuously introduce acetylene gas into the system under normal pressure sealing conditions, heat to 75-85°C, then add a toluene solution (200 mL) containing chlorobenzene 56.3 g (0.5 mol) and 4-chlorophthalic anhydride 91.3 g (0.5 mol) dropwise into the system, drop for about 10 h, then continue to stir for 1 h, monitor the reaction to completion.

[0086] After the reaction is completed, stop introducing acetylene gas into the system, purge the remaining acetylene gas in the system with nitrogen, then add 500 mL of water to the system, then filter the material into a 3 L reaction bottle, add 0.5 g of tetrabutylammonium bromide and 90 g of 30 wt% sodium hydroxide solution to the filtrate, heat to 75-85°C and stir for 3.5 h.

[0087] After the reaction is completed, cool to 40-50°C, stand and separate the layers, add concentrated hydrochloric acid to the water layer to adjust the pH to 1-2, then cool to 5-10°C, filter, wash with water, and dry to obtain 4-phenylacetylenyl phthalic acid 115.2 g, with a yield of 86.5%, an HPLC purity of 98.5%, and an ESI-MS spectrum substantially consistent with Figure 1 .

[0088] ③Add 80.0 g of 4-phenylacetylenyl phthalic acid obtained in step ①, 110 g of acetic anhydride, and 310 mL of dimethylbenzene to the reaction bottle, heat to reflux for 4 h, then cool to 10-20°C, crystallize, filter, and dry to obtain white crystalline powder 4-phenylacetylenyl phthalic anhydride 69.7 g, with a yield of 93.4%, an HPLC purity of 99.1%, and a melting point of 155.3-156.5°C.

[0089] (Example 7)

[0090] The synthesis method of 4-phenylacetylenyl phthalic anhydride in this example has the following steps:

[0091] ①Add 1500 mL of toluene, 758.9 g of triethylamine (7.5 mol), 1.5 g of bis(triphenylphosphine)palladium dichloride, 3.0 g of triphenylphosphine, and 1.5 g of cuprous iodide to a 5 L autoclave.

[0092] Close the autoclave, replace the air in the system with nitrogen three times, then evacuate the nitrogen, introduce acetylene gas into the system, maintain the pressure at 0.3-0.5 MPa, heat to 70-80°C, then add a toluene solution (600 mL) containing chlorobenzene 168.8 g (1.5 mol) and 4-chlorophthalic anhydride 273.8 g (1.5 mol) dropwise into the system, drop for about 16 h, then continue to stir for 1 h, monitor the reaction to completion.

[0093] After the reaction, stop feeding acetylene gas to the system, replace the acetylene gas with nitrogen for three times, then add 500 mL water to the system, and then filter the material into a 5 L reaction bottle. Add 1.5 g of tetrabutylammonium bromide and 270 g of 30 wt% sodium hydroxide solution to the filtrate, and heat to 75-85 °C and stir for 3.5 h.

[0094] After the reaction, cool to 40-50 °C, stand and separate the layers, add concentrated hydrochloric acid to the water layer to adjust the pH to 1-2, and then cool to 5-10 °C, filter, wash with water, and dry to obtain 4-phenylacetylenyl phthalic acid 379.8 g, with a yield of 95.1% and an HPLC purity of 99.1%. The ESI-MS spectrum is basically consistent with that of the target product. Figure 1

[0095] ③Add 50.0 g of 4-phenylacetylenyl phthalic acid obtained in step ① to a sublimation apparatus, and perform normal pressure sublimation under nitrogen protection at a temperature of 160-180 °C to obtain white crystalline powder 4-phenylacetylenyl phthalic anhydride 44.7 g, with a yield of 95.9% and an HPLC purity of 99.8%. The melting point is 155.6-156.6 °C.​

Claims

1. A method for synthesizing 4-phenylacetylene phthalic anhydride, comprising the following steps: ①obtaining 4-phenylacetylene phthalic anhydride crude product by catalytic coupling reaction of halogenated benzene, 4-halogenated phthalic anhydride and acetylene in the presence of palladium catalyst, catalyst ligand, co-catalyst and organic amine acid binding agent, wherein the palladium catalyst is bis (triphenylphosphine) palladium dichloride, the catalyst ligand is triphenylphosphine, and the co-catalyst is cuprous iodide; ②obtaining 4-phenylacetylene phthalic acid by hydrolysis of 4-phenylacetylene phthalic anhydride crude product obtained in step ①; and ③obtaining 4-phenylacetylene phthalic anhydride product by dehydration of 4-phenylacetylene phthalic acid obtained in step ② into anhydride. The halogenated benzene is chlorobenzene, bromobenzene or iodobenzene; the 4-halogenated phthalic anhydride is 4-chlorophthalic anhydride, 4-bromophthalic anhydride or 4-iodophthalic anhydride; and the molar ratio of the 4-halogenated phthalic anhydride to the halogenated benzene is 1:0.5-1:

2. The halogenated benzene is chlorobenzene; the 4-halogenated phthalic anhydride is 4-chlorophthalic anhydride; and the molar ratio of the 4-halogenated phthalic anhydride to the halogenated benzene is 1:

1. The amount of the bis (triphenylphosphine) palladium dichloride is 0.5-1.5 wt% of the halogenated benzene; the amount of the triphenylphosphine is 1-3 wt% of the halogenated benzene; and the amount of the cuprous iodide is 0.5-1.5 wt% of the halogenated benzene.

2. The process for synthesis of 4-phenylacetylene phthalic anhydride as claimed in claim 1, wherein: The organic amine acid binding agent is one or two of triethylamine, pyridine, 4-dimethylaminopyridine, N, N-diisopropylethylamine and diazabicyclo; and the molar ratio of the organic amine acid binding agent to the halogenated benzene is 3.5:1-5.5:

1.

3. The process for synthesis of 4-phenylacetylene phthalic anhydride as claimed in claim 2, wherein: The catalytic coupling is carried out in an organic solvent; and the organic solvent is one or two of toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran.

4. The process for synthesis of 4-phenylacetylene phthalic anhydride as claimed in claim 1, wherein: The catalytic coupling reaction temperature is 50-110℃; and the catalytic coupling reaction pressure is 0.1-1.0 MPa.

5. The process for synthesis of 4-phenylacetylene phthalic anhydride as claimed in claim 1, wherein: The catalytic coupling reaction temperature is 70-90℃; and the catalytic coupling reaction pressure is 0.2-0.5 MPa.

6. The process for synthesis of 4-phenylacetylene phthalic anhydride as claimed in claim 1, wherein: The hydrolysis is carried out in the presence of alkaline condition and phase transfer catalyst; and the phase transfer catalyst is one or two of benzyltriethylammonium bromide, hexyltriethylammonium bromide, octyltriethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium iodide, tetramethylammonium bromide, tetrapropylammonium chloride, benzyltriethylammonium chloride and methyltrioctylammonium chloride.

7. The process for synthesis of 4-phenylacetylene phthalic anhydride as claimed in claim 1, wherein: ​ 8. The process for synthesis of 4-phenylacetylene phthalic anhydride as claimed in claim 7, wherein: ​ 9. The process for synthesis of 4-phenylacetylene phthalic anhydride as claimed in claim 7, wherein: ​

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