TWI790442B - Acyl phosphine oxide compound and its preparation method - Google Patents

Abstract

The application discloses an acyl phosphine oxide compound and a preparation method thereof, belonging to the field of initiators. The method comprises: reacting compound B and compound C under the condition of an organic base and an organic solvent to obtain an acyl phosphine oxide compound; wherein, the chemical structural formula of compound B is as follows:

The chemical structural formula of compound C is as follows:

The chemical structural formula of acyl phosphine oxide compound is as follows:

Wherein, R ^is hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino) phenyl , α-naphthyl, β-naphthyl or (9-ethyl-9H-oxazol)-3-yl; R ² and R ¹ are the same or different, independently represented as hydrogen, C ₁ -C ₆ alkyl, Methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, α-naphthyl, β-naphthyl or (9-ethyl Base- 9H -oxazol)-3-yl; n is the substitution number of ^R1 on the corresponding benzene ring, n is 1, 2 or 3, wherein, n is 2 or 3, and ^R1 is used as a substituent group, It can be the same or different at different substituent positions; m is the substitution number of R ² on the corresponding benzene ring, m is 1, 2 or 3, wherein, m is 2 or 3, R ² is used as a substituting group, in Different substituents may be the same or different.

The preparation method is safe, environment-friendly and high in yield.

Description

Acyl phosphine oxide compound and its preparation method

The invention relates to the field of initiators, in particular to an acyl phosphine oxide compound and a preparation method thereof.

Photoinitiator, also known as photosensitizer or photocuring agent, is a reagent that can absorb radiation energy and undergo chemical changes to produce active intermediates with the ability to initiate polymerization. Among them, the acyl phosphine oxide compound is a kind of photoinitiator with high photoinitiating activity, and it is widely used.

The related art provides a commercially used (2,4,6-trimethylbenzoyl)diphenylphosphine oxide ((2,4,6-trimethylbenzoyl)diphenylphosphine oxide, TPO), whose chemical structural formula is as follows :

Among them, the industrial preparation method of TPO mainly includes two kinds: first, make diphenyl phosphine chloride carry out esterification reaction with methanol in alkaline environment to prepare methyl diphenyl phosphinate intermediate, diphenyl phosphonite The methyl phosphonate intermediate is condensed with 2,4,6-trimethylbenzoyl chloride to obtain TPO. Second, diphenylphosphine chloride is hydrolyzed to obtain diphenylphosphine oxide, and diphenylphosphine oxide is condensed with 2,4,6-trimethylbenzaldehyde and oxidized to obtain TPO. And the preparation method of diphenylphosphine chloride is: after benzene and phosphorus trichloride are catalyzed by aluminum trichloride, first normal pressure distillation collects unreacted benzene and phosphorus trichloride, phenylphosphine chloride, and then Diphenylphosphine chloride was collected by distillation after decomplexing the still residue with sodium chloride.

In the process of preparing diphenylphosphine chloride, free phosphorus is easily produced, which has potential safety hazards, and the yield of diphenylphosphine chloride is low, and process wastes such as hydrogen chloride and aluminum trichloride are easily produced, polluting the environment. Because there are many problems in the production process of diphenylphosphine chloride, the production of TPO is limited, and in the second method for preparing TPO, there are also potential safety hazards in the oxidation process.

The embodiment of the present disclosure provides an acyl phosphine oxide compound and a preparation method thereof, which can solve the above technical problems. The specific technical scheme is as follows:

On the one hand, the embodiment of the present disclosure provides a method for preparing an acyl phosphine oxide compound, wherein the method comprises: reacting compound B and compound C under the conditions of an organic base and an organic solvent to obtain the acyl group Phosphine oxide compounds; wherein, the chemical structural formula of the compound B is as follows:

The chemical structural formula of the compound C is as follows:

The chemical structural formula of described acyl phosphine oxide compound is as follows:

Wherein, R ^is hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino) phenyl , α-naphthyl, β-naphthyl or (9-ethyl-9 H -oxazol)-3-yl; R ² and R ¹ are the same or different, independently represented as hydrogen, C ₁ -C ₆ alkyl , methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, α-naphthyl, β-naphthyl or (9- Ethyl- 9H -oxazol)-3-yl; n is the substitution number of ^R1 on the corresponding benzene ring, n is 1, 2 or 3, wherein, n is 2 or 3, and ^R1 is used as a substituting group , can be the same or different at different substituent positions; m is the number of substitutions of R ² on the corresponding benzene ring, m is 1, 2 or 3, wherein, m is 2 or 3, and R ² is used as a substituent group, They may be the same or different at different substituent positions.

In a possible design, the method further includes: adding Lewis acid to the reaction system formed by the compound B and the compound C.

In a possible design, the molar ratio of the compound B, the compound C, the organic base, and the Lewis acid is 1:1-2:1-5:0.01-2.

In a possible design, the Lewis acid is selected from trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, triethylchlorosilane, tripropylchlorosilane, tributylchlorosilane, tert-butyldimethylchlorosilane, tert-butyldiphenylchlorosilane, trimethylchlorosilane-sodium bromide, trimethylchlorosilane-sodium iodide, trimethylsilyl methanesulfonate, methanesulfonic acid At least one of tert-butyldimethylsilicon, trimethylsilicon trifluoromethanesulfonate, and tert-butyldimethylsilicon trifluoromethanesulfonate.

In a possible design, the organic base is selected from triethylamine, tripropylamine, N,N-diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6-lutidine , 2-picoline, 3-picoline, 4-picoline at least one.

In a possible design, the organic solvent is selected from toluene, xylene, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, dichloromethane, 1 , at least one of 2-dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyloxide, and cyclobutane .

In a possible design, the reaction temperature of the compound B and the compound C is -20°C-150°C, and the reaction time is 1-8 hours.

In a possible design, the reacting compound B and compound C under the conditions of an organic base and an organic solvent includes: obtaining a first mixed solution comprising the compound C and the organic solvent, and mixing it with the organic The base is mixed in the first reactor; the compound B is added to the first reactor, and the compound B and the compound C are reacted.

In a possible design, adding the compound B to the first reactor includes: obtaining a second mixed liquid containing the compound B and the organic solvent; Add the second mixed solution dropwise.

In a possible design, the obtaining the first mixed solution comprising the compound C and the organic solvent includes: reacting the Grignard reagent and diethyl phosphite in the organic solvent, and then passing the acid solution After the quenching reaction, the first mixed solution comprising the compound C and the first organic solvent is obtained; the chemical structural formula of the Grignard reagent is as follows:

Wherein, R ^is hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino) phenyl , α-naphthyl, β-naphthyl or (9-ethyl- 9H -oxazol)-3-yl; m is the number of substitutions of R on the ^{corresponding} benzene ring, and m is 1, 2 or 3, Wherein, m is 2 or 3, and R ² is used as a substituting group, which can be the same or different at different substituting positions; X is chlorine, bromine or iodine.

In a possible design, the molar ratio of the diethyl phosphite to the Grignard reagent is 1:3-5.

In a possible design, the acid solution is at least one selected from hydrochloric acid solution, hydrobromic acid solution, hydroiodic acid solution, sulfuric acid solution, acetic acid solution, oxalic acid solution, and citric acid solution.

In a possible design, the reaction temperature of the Grignard reagent and the diethyl phosphite is -20°C-150°C, and the reaction time is 1-4 hours.

In a possible design, the Grignard reagent and diethyl phosphite are reacted in an organic solvent, and then quenched by an acid solution for post-reaction treatment, including: adding the Grignard reagent and the organic solvent to a third The diethyl phosphite is added into the second reactor of the mixed liquid, the Grignard reagent is reacted with the diethyl phosphite, and then the reaction is quenched by the acid solution for post-treatment.

In a possible design, the third mixed solution of the Grignard reagent and the organic solvent is prepared by the following method:

其中，R²為氫、C₁-C₆烷基、甲氧基、甲硫基、二甲氨基、氯甲醯基、苯基、苯甲醯基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-哢唑)-3-基；m為R²在對應苯環上的取代個數，m為1、2或3，其中，m為2或3，R²作為取代基團，在不同的取代位上可以相同也可以不同；X為氯、溴或碘。 Under the conditions of the initiator and the organic solvent, the magnesium powder and the aromatic halide are reacted to obtain a third mixed solution comprising the Grignard reagent and the organic solvent; wherein, the chemical structural formula of the aromatic halide is as follows:

Wherein, R ^is hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino) phenyl , α-naphthyl, β-naphthyl or (9-ethyl- 9H -oxazol)-3-yl; m is the number of substitutions of R on the ^{corresponding} benzene ring, and m is 1, 2 or 3, Wherein, m is 2 or 3, and R ² is used as a substituting group, which can be the same or different at different substituting positions; X is chlorine, bromine or iodine.

In a possible design, the molar ratio of the aromatic halide to the magnesium powder is 1:1-2.

In a possible design, the initiator is at least one selected from iodine and dibromoethane.

In a possible design, the reaction time of the magnesium powder and the aromatic halide is 2-4 hours.

On the other hand, an embodiment of the present disclosure provides an acyl phosphine oxide compound, wherein the chemical structural formula of the compound is as follows:

Wherein, R ^is hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino) phenyl , α-naphthyl, β-naphthyl or (9-ethyl-9 H -oxazol)-3-yl; R ² and R ¹ are the same or different, independently represented as hydrogen, C ₁ -C ₆ alkyl , methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, α-naphthyl, β-naphthyl or (9- Ethyl- 9H -oxazol)-3-yl; n is the substitution number of ^R1 on the corresponding benzene ring, n is 1, 2 or 3, wherein, n is 2 or 3, and ^R1 is used as a substituting group , can be the same or different at different substituent positions; m is the number of substitutions of R ² on the corresponding benzene ring, m is 1, 2 or 3, wherein, m is 2 or 3, and R ² is used as a substituent group, They may be the same or different at different substituent positions.

The beneficial effects brought by the technical solutions provided by the embodiments of the present disclosure at least include: the preparation method of the acylphosphine oxide compound provided by the embodiments of the present disclosure, under the conditions of an organic base and an organic solvent, compound B and compound C are reacted to obtain Acyl phosphine oxide compounds. The preparation method does not use diphenylphosphine chloride as a production raw material, does not involve oxidation operation, has the characteristics of safety, environmental protection, easy operation, high yield and the like, and is beneficial to the production of acylphosphine oxide compounds. The acyl phosphine oxide compound prepared by the method has stable quality, high purity, high yield and low cost, and is beneficial to industrial production.

In order to make the purpose, technical solution and advantages of the present disclosure clearer, the implementation manners of the present disclosure will be further described in detail below in conjunction with the accompanying drawings.

On the one hand, an embodiment of the present disclosure provides a method for preparing an acyl phosphine oxide compound, the method comprising: reacting compound B and compound C under the conditions of an organic base and an organic solvent to obtain an acyl phosphine oxide compound; Wherein, the chemical structural formula of compound B is as follows:

The chemical structural formula of compound C is as follows:

The chemical structural formula of acyl phosphine oxide compound is as follows:

Wherein, R ^is hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino) phenyl , α-naphthyl, β-naphthyl or (9-ethyl-9 H -oxazol)-3-yl; R ² and R ¹ are the same or different, independently represented as hydrogen, C ₁ -C ₆ alkyl , methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, α-naphthyl, β-naphthyl or (9- Ethyl- 9H -oxazol)-3-yl; n is the substitution number of ^R1 on the corresponding benzene ring, n is 1, 2 or 3, wherein, n is 2 or 3, and ^R1 is used as a substituting group , can be the same or different at different substituent positions; m is the number of substitutions of R ² on the corresponding benzene ring, m is 1, 2 or 3, wherein, m is 2 or 3, and R ² is used as a substituent group, They may be the same or different at different substituent positions.

It should be noted that the substitution position of ^R1 on the corresponding benzene ring can be the ortho, meta or para position of the acyl group. The substitution position of R ² on the corresponding benzene ring can be the ortho, meta or para position of the phosphine group.

In the embodiment of the present invention, the acylphosphine oxide compound can be used as a photoinitiator, which has the advantages of high polymerization initiation activity, fast photocuring speed, excellent thermal stability, low post-polymerization effect, and no residue, etc., and can be applied to ultraviolet Photocurable coatings, printing inks, UV-curable adhesives, optical fiber coatings, photoresists, photopolymerizable printing plates, stereolithographic resins, dental fillings, etc.

In the embodiments of the present disclosure, there is no specific limitation on the usage amount of the organic solvent, as long as it is sufficient to dissolve each component and react.

The chemical reaction between compound B and compound C can refer to the following chemical equation:

The preparation method of the acyl phosphine oxide compound provided in the embodiment of the present disclosure is to react the compound B and the compound C under the condition of an organic base and an organic solvent to obtain the acyl phosphine oxide compound. The preparation method does not use diphenylphosphine chloride as a raw material for production, and does not involve oxidation operations, and it has the advantages of safety, environmental protection, The characteristics of easy operation and high yield are beneficial to the production of acyl phosphine oxide compounds. The acyl phosphine oxide compound prepared by the method has stable quality, high purity, high yield and low cost, and is beneficial to industrial production.

The preparation method of the acyl phosphine oxide compound provided in the embodiment of the present disclosure further includes: adding Lewis acid to the reaction system formed by the compound B and the compound C.

It can be understood that the reaction system formed by compound B and compound C includes: compound B, compound C, an organic base, and an organic solvent.

By adding Lewis acid to the reaction system formed by compound B and compound C, compound B and compound C can be promoted to form compound A without side reactions.

The molar ratio of compound B, compound C, organic base, and Lewis acid has an important influence on the efficient preparation of acylphosphine oxide compounds. Based on this, the molar ratio of compound B, compound C, organic base, and Lewis acid can be 1:1-2:1-5:0.01-2, and the molar ratio of compound B, compound C, organic base, and Lewis acid can also be It can be 1:1:1-3:1.

For example, the molar ratio of compound B, compound C, organic base, and Lewis acid can be 1:1:1:0.01, 1:1.1:1.1:0.3, 1:1.4:2:0.5, 1:1.7:2.4 :0.7, 1:1.8:3:0.9, 1:1:1:1, 1:1:2:1, 1:1:3:1, 1:1.9:4:1.5, 1:2:5:2 wait.

In this way, compound B and compound C can be fully reacted, and the reaction rate is fast, which is conducive to the preparation of acylphosphine oxide compounds with high efficiency and high yield.

The embodiment of the present disclosure gives an example of the type of Lewis acid: the Lewis acid is selected from trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, triethylchlorosilane, tripropylchlorosilane, Tributylchlorosilane, tert-butyldimethylchlorosilane, tert-butyldiphenylchlorosilane, trimethylchlorosilane-sodium bromide, trimethylchlorosilane-sodium iodide, trimethyl methanesulfonate At least one of silicon ester, tert-butyldimethylsilicon methanesulfonate, trimethylsilicon trifluoromethanesulfonate, and tert-butyldimethylsilicon trifluoromethanesulfonate.

Wherein, the Lewis acid can be selected from any one, two, three, four, five, six, seven, . . . When the Lewis acid is a mixture, the ratio of each component is not particularly limited.

The above-mentioned Lewis acids can effectively promote the reaction of compound B and compound C, have good miscibility with other components, and are cheap and easy to obtain.

After adding the Lewis acid, it can be stirred for 0.8-1.5 hours, such as 0.8 hours, 0.9 hours, 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, etc.

In this way, the catalytic effect of the Lewis acid can be effectively guaranteed to promote the reaction of compound B and compound C.

The organic base can absorb the hydrogen chloride produced by the reaction of compound B and compound C, and the organic base will not produce side reactions. The embodiment of the present disclosure gives an example of the type of organic base: the organic base is selected from triethylamine, tripropylamine, N,N-diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6 - at least one of lutidine, 2-picoline, 3-picoline and 4-picoline.

That is, the organic base is selected from any one, two, three, four, five, six, seven, eight, or nine of the above. When the organic base is a mixture, the ratio of each component is not particularly limited. For example, when the organic base is a mixture of triethylamine and N,N-diisopropylethylamine, the mass ratio of the two can be 1:1, 1:2, 1:3, 2:1, 2 : 3 etc. When the organic base is a mixture of triethylamine, N,N-diisopropylethylamine, and N,N-dimethylaniline, the mass ratio of the three can be 1:1:1, 1:2: 1. 1:3:1, 2:1:1, 2:3:1, 2:2:1, 2:3:1, 2:1:3, 2:3:3, etc.

The above-mentioned several organic bases can not only effectively promote the reaction of compound B and compound C to form compound A. And it's cheap and easy to get.

The organic solvent can fully and uniformly disperse the compound B and the compound C, which is conducive to the uniform reaction of the two. The embodiment of the present disclosure gives an example of the type of organic solvent: the organic solvent is selected from toluene, xylene, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, Dichloromethane, 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyloxide, cyclobutane at least one of them.

That is, the organic solvent can be selected from any one, two, three, four, ..., or all of the above. When the organic solvent is a mixture, the ratio of each component is not particularly limited. For example, when the organic solvent is a mixture of toluene and tetrahydrofuran, the mass ratio of toluene and tetrahydrofuran can be 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.7, 1:1.9, 1:2 wait.

The above-mentioned several organic solvents make compound B and compound C have good mutual solubility, and are cheap and easy to obtain.

The reaction temperature of compound B and compound C can be -20°C-150°C, for example, it can be -20°C, -10°C, -5°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, etc. The reaction time can be 1-8 hours, such as 1 hour, 1.8 hours, 1.9 hours, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours , 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, etc.

In this way, it can be ensured that compound B and compound C fully react under the conditions of organic base and organic solvent.

The embodiment of the present disclosure gives the following two examples about how to make compound B, compound C, organic base and organic solvent mixed reaction:

(1) As the first example, compound B, compound C, organic base, and organic solvent are all added to the first reactor, stirred and mixed for reaction.

(2) As a second example, under the conditions of an organic base and an organic solvent, compound B and compound C are reacted, including:

Step A, obtaining the first mixed solution including compound C and organic solvent, and mixing it with organic base in the first reactor.

Wherein, obtaining the first mixed solution comprising compound C and an organic solvent can be obtained by mixing compound C and an organic solvent, and can also be obtained by the following steps:

The Grignard reagent and diethyl phosphite are reacted in an organic solvent, and then quenched with an acid solution to obtain the first mixed solution comprising compound C and an organic solvent; the chemical structural formula of the Grignard reagent is as follows:

Wherein, R ^is hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino) phenyl , α-naphthyl, β-naphthyl or (9-ethyl- 9H -oxazol)-3-yl; m is the substitution number of R on the ^{corresponding} benzene ring, and m is 1, 2 or 3; X is chlorine, bromine or iodine.

In this way, the step of isolating compound C can be omitted to efficiently prepare acylphosphine oxide compounds.

Wherein, the molar ratio of diethyl phosphite and Grignard reagent has an important impact on whether the two can fully react, based on this, in the disclosed embodiment, the molar ratio of diethyl phosphite to Grignard reagent It can be 1:3-5, and the molar ratio of diethyl phosphite to Grignard reagent can also be 1:3-3.5. For example, the molar ratio of diethyl phosphite to Grignard reagent can be 1:3, 1:3.1, 1:3.3, 1:3.5, 1:3.7, 1:3.9, 1:4, 1:4.1, 1: 4.3, 1:4.5, 1:4.7, 1:4.9, 1:5, etc.

The reaction temperature of Grignard reagent and diethyl phosphite can be -20°C-150°C, for example, it can be -20°C, -10°C, -5°C, 0°C, 10°C, 20°C, 30°C, 40°C , 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, etc. The reaction time of Grignard reagent and diethyl phosphite can be 1-4 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 2.8 hours, 2.9 hours, 3 hours, 3.1 hours, 3.2 hours, 3.3 hours Hours, 3.4 hours, 3.5 hours, 4 hours, etc.

In this way, the diethyl phosphite and the Grignard reagent are fully reacted through the cooperation of the molar ratio of the diethyl phosphite and the Grignard reagent, the reaction temperature and the reaction time.

After diethyl phosphite and Grignard reagent are reacted in an organic solvent, the first mixed solution including compound C and the organic solvent can be obtained in high yield by quenching the reaction with an acid solution.

As an example, the acid solution is selected from at least one of hydrochloric acid solution, hydrobromic acid solution, hydroiodic acid solution, sulfuric acid solution, acetic acid solution, oxalic acid solution, and citric acid solution.

That is, the acid solution is selected from any one, two, three, four, five, six, or seven of the above. When the acid solution is a mixture, the ratio of each component is not particularly limited. For example, when the acid solution is a mixture of acetic acid solution and citric acid solution, the molar ratio of the acetic acid solution to the citric acid solution can be 1:1, 1:2, 1:3, 2:1, 2:3, etc.

The above-mentioned acid solutions are cheap, easy to obtain, and have good quenching effect and hydration effect.

Wherein, the mass concentration of the acid solution may be 30%-60%.

The chemical reaction between diethyl phosphite and Grignard reagent can refer to the following chemical equation:

Step B, adding compound B into the first reactor to make compound B and compound C react.

Adding compound B into the first reactor includes but not limited to the following methods: obtaining a second mixed liquid including compound B and an organic solvent; adding the second mixed liquid into the first reactor dropwise.

In this way, it is beneficial for compound B and compound C to react efficiently and fully.

The embodiment of the present disclosure provides the following example about how to add Grignard reagent and diethyl phosphite in step A:

making the Grignard reagent and diethyl phosphite react in an organic solvent, and then quenching the reaction with an acid solution for post-treatment, including: adding phosphorous acid to the second reactor with the third mixed solution of the Grignard reagent and the organic solvent Diethyl ester, react the Grignard reagent with diethyl phosphite, and then quench the reaction with acid solution.

Wherein, the third mixed solution of Grignard reagent and organic solvent can be directly obtained by mixing Grignard reagent with organic solvent, and can also be prepared by the following method:

Under the conditions of the initiator and the organic solvent, the magnesium powder and the aromatic halide are reacted to obtain the third mixed solution including the Grignard reagent and the organic solvent.

其中，R²為氫、C₁-C₆烷基、甲氧基、甲硫基、二甲氨基、氯甲醯基、苯基、苯甲醯基、(4-二甲胺基)苯基、α-萘基、β-萘基或(9-乙基-9H-哢唑)-3-基；m為R²在對應苯環上的取代個數，m為1、2或3；X為氯、溴或碘。 Wherein, the chemical structural formula of aryl halide is as follows:

Wherein, R ^is hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino) phenyl , α-naphthyl, β-naphthyl or (9-ethyl- 9H -oxazol)-3-yl; m is the substitution number of R on the ^{corresponding} benzene ring, and m is 1, 2 or 3; X is chlorine, bromine or iodine.

In this way, the step of isolating the Grignard reagent can be omitted to efficiently prepare the acylphosphine oxide compound.

The molar ratio of aromatic halogen and magnesium powder has an important influence on whether the two can fully react. Based on this, the molar ratio of aromatic halogen and magnesium powder can be 1:1-2, and the molar ratio of aromatic halogen and magnesium powder can also be 1:1-1.2. For example, the molar ratio of aromatic halide and magnesium powder can be 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.7, 1:1.9, 1:2, etc.

The initiator may be selected from at least one of iodine and dibromoethane. That is, the initiator is selected from iodine, dibromoethane, a mixture of iodine and dibromoethane.

The initiation effects of the above-mentioned several initiators are good, which can ensure that the aromatic halide and the magnesium powder fully react. Moreover, the above-mentioned several initiators are cheap and easy to obtain.

The reaction time of magnesium powder and aromatic halogen can be 2-4 hour, for example can be 2 hours, 2.2 hours, 2.5 hours, 2.7 hours, 2.8 hours, 2.9 hours, 3 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.7 hours, 4 hours, etc. In this way, it can be ensured that the aromatic halide and the magnesium powder fully react under the action of the initiator.

When mixing the magnesium powder and the aromatic halide, the mixed liquid of the initiator, the aromatic halide and the organic solvent can be added dropwise to the second reactor first, and then the mixed liquid of the aromatic halide and the organic solvent can be added dropwise into the second reactor. By dripping in two steps, the initiator can trigger the reaction between the magnesium powder and the aromatic halide, and the added aromatic halide continues to react, which is beneficial to reduce the amount of the initiator.

The chemical reaction between aromatic halide and magnesium powder can be referred to the following chemical equation:

Diethyl phosphite can be added dropwise to the second reactor to react the Grignard reagent with diethyl phosphite to obtain a reaction liquid, which is stirred for 1-4 hours and then cooled to room temperature. Then the reaction solution was added dropwise into the acid solution to quench the reaction, and compound C was finally obtained.

The room temperature involved in the embodiments of the present disclosure may be 20°C-30°C, for example, it may be 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C , 30°C, etc. The specific room temperature can be determined according to the actual operating environment.

In an embodiment of the present disclosure, the first reactor and the second reactor may be the same reactor. When preparing the mixed solution of compound C and organic solvent, the Grignard reagent and compound C are not separated separately, and the corresponding mixed solution is directly used for preparation, which avoids the discharge of intermediates and facilitates industrial production.

After the reaction of compound B and compound C is completed, the acyl phosphine oxide compound can be obtained through washing treatment and separation treatment.

Wherein, the washing treatment can wash away the impurities in the mixed liquid, and the washing treatment can be performed by organic solvent or water. Separation treatment may be treatment such as vacuum distillation and extraction.

The preparation method of the acyl phosphine oxide compound provided in the embodiment of the present disclosure is to react the compound B and the compound C under the conditions of an organic base, an organic solvent and a Lewis acid to obtain the acyl phosphine oxide compound. The preparation method does not use diphenylphosphine chloride as a production raw material, does not involve oxidation operation, has the characteristics of safety, environmental protection, easy operation, high yield and the like, and is beneficial to the production of acylphosphine oxide compounds. The acyl phosphine oxide compound prepared by the method has stable quality, high purity, high yield and low cost, and is beneficial to industrial production.

On the other hand, an embodiment of the present disclosure provides an acyl phosphine oxide compound, wherein the chemical structural formula of the compound is as follows:

Wherein, R ^is hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino) phenyl , α-naphthyl, β-naphthyl or (9-ethyl-9 H -oxazol)-3-yl; R ² and R ¹ are the same or different, and can be independently hydrogen, C ₁ -C ₆ alkyl, Methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, α-naphthyl, β-naphthyl or (9-ethyl Base- 9H -oxazol)-3-yl; n is the substitution number of ^R1 on the corresponding benzene ring, n is 1, 2 or 3, wherein, n is 2 or 3, and ^R1 is used as a substituent group, It can be the same or different at different substituent positions; m is the substitution number of R ² on the corresponding benzene ring, m is 1, 2 or 3, wherein, m is 2 or 3, R ² is used as a substituting group, in Different substituents may be the same or different.

Preferably, ^R can be independently hydrogen, methyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, α-naphthyl, β-naphthyl or (9-ethyl- 9H -oxazol)-3-yl.

Preferably, ^R can be independently hydrogen, methyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino)phenyl, α-naphthyl, β-naphthyl or (9-ethyl- 9H -oxazol)-3-yl.

The acylphosphine oxide compound provided in the examples of the present disclosure is obtained by reacting compound B and compound C under the conditions of an organic base and an organic solvent. The product quality of the acylphosphine oxide compound is stable and high in purity, and its photoinduced High activity, can be widely used in industrial production.

Exemplarily, this example provides a kind of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO), and its chemical structural formula is as follows:

The TPO is prepared by the following method:

Under the conditions of anhydrous and oxygen-free, slight reflux at 60°C and stirring, a mixed solution of 75 grams of magnesium powder and 500 milliliters of tetrahydrofuran was placed in the flask. Under stirring condition, dropwise add the mixed solution of 5 grams of dibromoethane, 20 grams of chlorobenzene and 200 milliliters of tetrahydrofuran in the flask, dropwise time is 1 hour, to trigger the reaction of magnesium powder and chlorobenzene. Then the mixed solution of 320 grams of chlorobenzene and 300 milliliters of tetrahydrofuran was added dropwise in the flask, and the dropping time was 3 hours. After the dropwise addition, the stirring reaction was continued for 3 hours under slight reflux to obtain a mixed solution including Grignard reagent and tetrahydrofuran.

Make the temperature of the mixture of Grignard reagent and tetrahydrofuran in the flask be 40°C-50°C, add 138 g of diethyl phosphite dropwise to the flask under stirring condition, and the dropwise addition time is 30 minutes. After continuing to stir the reaction under slight reflux for 3 hours, the temperature was lowered to room temperature. Then slowly add 500 milliliters of citric acid solutions with a mass concentration of 50% in the flask under stirring, continue to stir for 30 minutes, and let the layers stand for 30 minutes. The organic phase was separated and concentrated under reduced pressure at 40°C-50°C to obtain organic residues (including diphenyl phosphine oxide), and recover tetrahydrofuran. The aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes to separate the layers, then the toluene phase was separated and combined with the aforementioned separated organic residue to obtain a compound comprising diphenylphosphine oxide (compound C), A mixture of impurities such as toluene and hydrogen chloride. Wash the mixture with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and distill about 400 ml of toluene under reduced pressure at 50°C-60°C, and the rest is diphenyl oxide. A mixture of phosphine and toluene.

At room temperature and under stirring conditions, mix the mixture of diphenylphosphine oxide and toluene with 220 grams of triethylamine in a flask, and add 105 grams of trimethyl chloride dropwise to the flask under the condition of 40°C-50°C The mixed solution of silane and 100 ml of toluene was added dropwise for 1 hour, and the stirring was continued for 1 hour after the addition was completed. Then, a mixed solution of 185 grams of 2,4,6-trimethylbenzoyl chloride (compound B) and 200 milliliters of toluene was added dropwise to the flask for 2 hours. Then the reaction was stirred at 50° C. for 2 hours, and cooled to room temperature.

At room temperature, the reaction solution in the flask was washed with 500 ml of water for 2 times. After washing, the organic phase was separated and the volatiles were evaporated under reduced pressure at 40°C-50°C. Then add 600 ml of isopropyl ether to the organic phase, stir and beat for 2 hours under the condition of 55°C-65°C, then continue to stir and beat for 1 hour under the condition of 5°C-10°C, and filter with suction to obtain a filter cake. After the filter cake was washed with cold isopropyl ether, it was dried under reduced pressure at 40°C-50°C to obtain 324 grams of TPO provided in this example, with a purity of 99.6%. The yield of TPO was calculated as diethyl phosphite. The rate is 93%.

Exemplarily, this example provides a kind of (2,4,6-trimethylbenzoyl) bis (p-tolyl) phosphine oxide, its chemical structural formula is as follows:

The (2,4,6-trimethylbenzoyl) bis(p-tolyl)phosphine oxide is prepared by the following method:

Under the conditions of anhydrous and oxygen-free, slight reflux at 60°C and stirring, a mixed solution of 75 grams of magnesium powder and 500 milliliters of tetrahydrofuran was placed in the flask. Under the condition of stirring, add dropwise the mixed solution of 5 grams of dibromoethane, 30 grams of p-chlorotoluene and 200 milliliters of tetrahydrofuran in the flask, dropwise time is 1 hour, to initiate the reaction of magnesium powder and p-chlorotoluene. Then, in the flask, a mixed solution of 353 grams of p-chlorotoluene and 300 milliliters of tetrahydrofuran was added dropwise, and the addition time was 3 hours. After the dropwise addition, the stirring reaction was continued for 3 hours under slight reflux to obtain a mixed solution including Grignard reagent and tetrahydrofuran.

Make the temperature of the mixture of Grignard reagent and tetrahydrofuran in the flask be 40°C-50°C, add 138 g of diethyl phosphite dropwise to the flask under stirring condition, and the dropwise addition time is 30 minutes. After continuing to stir the reaction under slight reflux for 3 hours, the temperature was lowered to room temperature. Then slowly add 500 milliliters of citric acid solutions with a mass concentration of 50% in the flask under stirring, continue to stir for 30 minutes, and let the layers stand for 30 minutes. The organic phase was separated and concentrated under reduced pressure at 40°C-50°C to obtain organic residues (including bis(p-tolyl)phosphine oxide), and tetrahydrofuran was recovered. The aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, allowed to stand for layering for 30 minutes, then separated the toluene phase and combined with the aforementioned organic residues separated to obtain a mixture comprising two (p-tolyl) phosphine oxide ( Compound C), a mixture of impurities such as toluene and hydrogen chloride. Wash the mixture with 300 milliliters of 10% sodium bicarbonate aqueous solution and 300 milliliters of water successively, and distill about 400 milliliters of toluene under reduced pressure at 50°C-60°C, and the rest is di(p- A mixture of tolyl) phosphine oxide and toluene.

At room temperature and under stirring conditions, mix the mixture of bis(p-tolyl)phosphine oxide and toluene with 220 grams of triethylamine in a flask, and add 197 grams of The mixed solution of iodotrimethylsilane and 100 ml of toluene was added dropwise for 1 hour, and the stirring was continued for 1 hour after the addition was completed. Then, a mixed solution of 195 grams of 2,4,6-trimethylbenzoyl chloride (compound B) and 200 milliliters of toluene was added dropwise to the flask for 2 hours. Then the reaction was stirred at 50° C. for 2 hours, and cooled to room temperature.

At room temperature, the reaction solution in the flask was washed with 500 ml of water for 2 times. After washing, the organic phase was separated and the volatiles were evaporated under reduced pressure at 40°C-50°C. Then add 600 ml of isopropyl ether to the organic phase, stir and beat for 2 hours under the condition of 55°C-65°C, then continue to stir and beat for 1 hour under the condition of 5°C-10°C, and filter with suction to obtain a filter cake. After the filter cake was washed with cold isopropyl ether, it was dried under reduced pressure at 40°C-50°C to obtain 346 grams of (2,4,6-trimethylbenzoyl)bis(p- -tolyl)phosphine oxide with a purity of 99.7% and a yield of (2,4,6-trimethylbenzoyl)bis(p-tolyl)phosphine oxide based on diethyl phosphite of 92% .

Illustratively, this example provides a kind of (p-dimethylaminobenzoyl) diphenylphosphine oxide, its chemical structural formula is as follows:

This (p-dimethylaminobenzoyl) diphenylphosphine oxide is prepared by the following method:

Under the conditions of anhydrous and oxygen-free, slight reflux at 60°C and stirring, a mixed solution of 75 grams of magnesium powder and 500 milliliters of tetrahydrofuran was placed in the flask. Under stirring condition, dropwise add the mixed solution of 5 grams of dibromoethane, 20 grams of chlorobenzene and 200 milliliters of tetrahydrofuran in the flask, dropwise time is 1 hour, to trigger the reaction of magnesium powder and chlorobenzene. Then the mixed solution of 320 grams of chlorobenzene and 300 milliliters of tetrahydrofuran was added dropwise in the flask, and the dropping time was 3 hours. After the dropwise addition, the stirring reaction was continued for 3 hours under slight reflux to obtain a mixed solution including Grignard reagent and tetrahydrofuran.

Make the temperature of the mixture comprising Grignard reagent and tetrahydrofuran in the flask be 40°C-50°C, and add 138 g of diethyl phosphite dropwise to the flask under stirring condition for 30 minutes. After continuing to stir the reaction under slight reflux for 3 hours, the temperature was lowered to room temperature. Then slowly add 500 milliliters of citric acid solutions with a mass concentration of 50% in the flask under stirring, continue to stir for 30 minutes, and leave to stand for stratification for 30 minutes bell. The organic phase was separated and concentrated under reduced pressure at 40° C. to 50° C. to obtain organic residues (including diphenylphosphine oxide), and tetrahydrofuran was recovered. The aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes to separate the layers, then the toluene phase was separated and combined with the aforementioned separated organic residue to obtain a compound comprising diphenylphosphine oxide (compound C), A mixture of impurities such as toluene and hydrogen chloride. Wash the mixture with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and distill about 400 ml of toluene under reduced pressure at 50°C-60°C, and the rest is diphenyl oxide. A mixture of phosphine and toluene.

At room temperature and under stirring conditions, mix the mixture of diphenylphosphine oxide and toluene with 220 grams of triethylamine in a flask, and add 148 grams of trimethyl bromide dropwise to the flask under the condition of 40°C-50°C The mixed solution of silane and 100 ml of toluene was added dropwise for 1 hour, and the stirring was continued for 1 hour after the addition was completed. Then in the flask, a mixed solution of 176 grams of p-dimethylaminobenzyl chloride (compound B) and 200 milliliters of toluene was added dropwise for 2 hours. Then the reaction was stirred at 50° C. for 2 hours, and cooled to room temperature.

At room temperature, the reaction solution in the flask was washed with 500 ml of water for 2 times. After washing, the organic phase was separated and the volatiles were evaporated under reduced pressure at 40°C-50°C. Then add 600 ml of isopropyl ether to the organic phase, stir and beat for 2 hours under the condition of 55°C-65°C, then continue to stir and beat for 1 hour under the condition of 5°C-10°C, and filter with suction to obtain a filter cake. After the filter cake was washed with cold isopropyl ether, it was dried under reduced pressure at 40°C-50°C to obtain 318 grams of (p-dimethylaminobenzoyl)diphenylphosphine oxide provided in this example. Its purity is 99.6%, and the yield of (p-dimethylaminobenzoyl) diphenylphosphine oxide based on diethyl phosphite is 91%.

Exemplarily, this example provides a kind of (p-methoxybenzoyl) diphenylphosphine oxide, its chemical structural formula is as follows:

This (p-methoxybenzoyl) diphenylphosphine oxide is prepared by the following method:

Under the conditions of anhydrous and oxygen-free, slight reflux at 60°C and stirring, a mixed solution of 75 grams of magnesium powder and 500 milliliters of tetrahydrofuran was placed in the flask. Under stirring condition, dropwise add the mixed solution of 5 grams of dibromoethane, 20 grams of chlorobenzene and 200 milliliters of tetrahydrofuran in the flask, dropwise time is 1 hour, to trigger the reaction of magnesium powder and chlorobenzene. Then the mixed solution of 320 grams of chlorobenzene and 300 milliliters of tetrahydrofuran was added dropwise in the flask, and the dropping time was 3 hours. After the dropwise addition, the stirring reaction was continued for 3 hours under slight reflux to obtain a mixed solution including Grignard reagent and tetrahydrofuran.

Make the temperature of the mixture of Grignard reagent and tetrahydrofuran in the flask be 40°C-50°C, add 138 g of diethyl phosphite dropwise to the flask under stirring condition, and the dropwise addition time is 30 minutes. After continuing to stir the reaction under slight reflux for 3 hours, the temperature was lowered to room temperature. Then slowly add 500 milliliters of citric acid solutions with a mass concentration of 50% in the flask under stirring, continue to stir for 30 minutes, and let the layers stand for 30 minutes. The organic phase was separated and concentrated under reduced pressure at 40° C. to 50° C. to obtain organic residues (including diphenylphosphine oxide), and tetrahydrofuran was recovered. The aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes to separate the layers, then the toluene phase was separated and combined with the aforementioned separated organic residue to obtain a compound comprising diphenylphosphine oxide (compound C), A mixture of impurities such as toluene and hydrogen chloride. Wash the mixture with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and distill about 400 ml of toluene under reduced pressure at 50°C-60°C, and the rest is diphenyl oxide. A mixture of phosphine and toluene.

At room temperature and under stirring conditions, mix the mixture of diphenylphosphine oxide and toluene with 220 grams of triethylamine in a flask, and add 105 grams of trimethyl chloride dropwise to the flask under the condition of 40°C-50°C Silane and The mixed solution of 100 ml of toluene was added dropwise for 1 hour, and the stirring was continued for 1 hour after the addition was completed. Then in the flask, a mixed solution of 164 grams of p-methoxybenzoyl chloride (compound B) and 200 milliliters of toluene was added dropwise for 2 hours. Then the reaction was stirred at 50° C. for 2 hours, and cooled to room temperature.

At room temperature, the reaction solution in the flask was washed with 500 ml of water for 2 times. After washing, the organic phase was separated and the volatiles were evaporated under reduced pressure at 40°C-50°C. Then add 600 ml of isopropyl ether to the organic phase, stir and beat for 2 hours under the condition of 55°C-65°C, then continue to stir and beat for 1 hour under the condition of 5°C-10°C, and filter with suction to obtain a filter cake. After the filter cake was washed with cold isopropyl ether, it was dried under reduced pressure at 40°C-50°C to obtain 309 grams of (p-methoxybenzoyl)diphenylphosphine oxide provided in this example. The purity is 99.8%, and the yield of (p-methoxybenzoyl) diphenylphosphine oxide based on diethyl phosphite is 92%.

Exemplarily, this example provides a kind of (p-methylthiobenzoyl) diphenylphosphine oxide, its chemical structural formula is as follows:

This (p-methylthiobenzoyl) diphenylphosphine oxide is prepared by the following method:

Under the conditions of anhydrous and oxygen-free, slight reflux at 60°C and stirring, a mixed solution of 75 grams of magnesium powder and 500 milliliters of tetrahydrofuran was placed in the flask. Under stirring condition, dropwise add the mixed solution of 5 grams of dibromoethane, 20 grams of chlorobenzene and 200 milliliters of tetrahydrofuran in the flask, dropwise time is 1 hour, to trigger the reaction of magnesium powder and chlorobenzene. Then the mixed solution of 320 grams of chlorobenzene and 300 milliliters of tetrahydrofuran was added dropwise in the flask, and the dropping time was 3 hours. After the dropwise addition, the stirring reaction was continued for 3 hours under slight reflux to obtain a mixed solution including Grignard reagent and tetrahydrofuran.

Make the temperature of the mixture of Grignard reagent and tetrahydrofuran in the flask be 40°C-50°C, add 138 g of diethyl phosphite dropwise to the flask under stirring condition, and the dropwise addition time is 30 minutes. After continuing to stir the reaction under slight reflux for 3 hours, the temperature was lowered to room temperature. Then slowly add 500 milliliters of citric acid solutions with a mass concentration of 50% in the flask under stirring, continue to stir for 30 minutes, and let the layers stand for 30 minutes. The organic phase was separated and concentrated under reduced pressure at 40° C. to 50° C. to obtain organic residues (including diphenylphosphine oxide), and tetrahydrofuran was recovered. The aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes to separate the layers, then the toluene phase was separated and combined with the aforementioned separated organic residue to obtain a compound comprising diphenylphosphine oxide (compound C), A mixture of impurities such as toluene and hydrogen chloride. Wash the mixture with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and distill about 400 ml of toluene under reduced pressure at 50°C-60°C, and the rest is diphenyl oxide. A mixture of phosphine and toluene.

At room temperature and under stirring conditions, mix the mixture of diphenylphosphine oxide and toluene with 220 grams of triethylamine in a flask, and add 105 grams of trimethyl chloride dropwise to the flask under the condition of 40°C-50°C The mixed solution of silane and 100 ml of toluene was added dropwise for 1 hour, and the stirring was continued for 1 hour after the addition was completed. Then in the flask, a mixed solution of 181 grams of p-methylthiobenzoyl chloride (compound B) and 200 milliliters of toluene was added dropwise for 2 hours. Then the reaction was stirred at 50° C. for 2 hours, and cooled to room temperature.

At room temperature, the reaction solution in the flask was washed with 500 ml of water for 2 times. After washing, the organic phase was separated and the volatiles were evaporated under reduced pressure at 40°C-50°C. Then add 600 ml of isopropyl ether to the organic phase, stir and beat for 2 hours under the condition of 55°C-65°C, then continue to stir and beat for 1 hour under the condition of 5°C-10°C, and filter with suction to obtain a filter cake. After the filter cake was washed with cold isopropyl ether, it was dried under reduced pressure at 40°C-50°C to obtain 310 grams of (p-methylthiobenzoyl)diphenylphosphine oxide provided in this example. The purity is 99.6%, and the yield of (p-methylthiobenzoyl) diphenylphosphine oxide based on diethyl phosphite is 88%.

Exemplarily, this example provides a kind of (p-tolylbenzoyl) diphenylphosphine oxide, its chemical structural formula is as follows:

This (p-tolylbenzoyl) diphenylphosphine oxide is prepared by the following method:

Under the conditions of anhydrous and oxygen-free, slight reflux at 60°C and stirring, a mixed solution of 75 grams of magnesium powder and 500 milliliters of tetrahydrofuran was placed in the flask. Under stirring condition, dropwise add the mixed solution of 5 grams of dibromoethane, 20 grams of chlorobenzene and 200 milliliters of tetrahydrofuran in the flask, dropwise time is 1 hour, to trigger the reaction of magnesium powder and chlorobenzene. Then the mixed solution of 320 grams of chlorobenzene and 300 milliliters of tetrahydrofuran was added dropwise in the flask, and the dropping time was 3 hours. After the dropwise addition, the stirring reaction was continued for 3 hours under slight reflux to obtain a mixed solution including Grignard reagent and tetrahydrofuran.

Make the temperature of the mixture of Grignard reagent and tetrahydrofuran in the flask be 40°C-50°C, add 138 g of diethyl phosphite dropwise to the flask under stirring condition, and the dropwise addition time is 30 minutes. After continuing to stir the reaction under slight reflux for 3 hours, the temperature was lowered to room temperature. Then slowly add 500 milliliters of citric acid solutions with a mass concentration of 50% in the flask under stirring, continue to stir for 30 minutes, and let the layers stand for 30 minutes. The organic phase was separated and concentrated under reduced pressure at 40° C. to 50° C. to obtain organic residues (including diphenylphosphine oxide), and tetrahydrofuran was recovered. The aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes to separate the layers, then the toluene phase was separated and combined with the aforementioned separated organic residue to obtain a compound comprising diphenylphosphine oxide (compound C), A mixture of impurities such as toluene and hydrogen chloride. Wash the mixture with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and distill about 400 ml of toluene under reduced pressure at 50°C-60°C, and the rest is diphenyl oxide. A mixture of phosphine and toluene.

At room temperature and under stirring conditions, mix the mixture of diphenylphosphine oxide and toluene with 220 grams of triethylamine in a flask, and add 105 grams of trimethyl chloride dropwise to the flask under the condition of 40°C-50°C Silane and The mixed solution of 100 ml of toluene was added dropwise for 1 hour, and the stirring was continued for 1 hour after the addition was completed. Then in the flask, a mixed solution of 208 grams of p-phenylbenzoyl chloride (compound B) and 200 milliliters of toluene was added dropwise for 2 hours. Then the reaction was stirred at 50° C. for 2 hours, and cooled to room temperature.

At room temperature, the reaction solution in the flask was washed with 500 ml of water for 2 times. After washing, the organic phase was separated and the volatiles were evaporated under reduced pressure at 40°C-50°C. Then add 600 ml of isopropyl ether to the organic phase, stir and beat for 2 hours under the condition of 55°C-65°C, then continue to stir and beat for 1 hour under the condition of 5°C-10°C, and filter with suction to obtain a filter cake. After the filter cake was washed with cold isopropyl ether, it was dried under reduced pressure at 40°C-50°C to obtain 344 grams of (p-tolylbenzoyl)diphenylphosphine oxide provided by the present example. It is 99.6%, and the yield of (p-tolylbenzoyl) diphenylphosphine oxide is 90% based on diethyl phosphite.

Illustratively, this example provides a kind of (1,4-phthalyl) bis(diphenylphosphine oxide), whose chemical structural formula is as follows:

The (1,4-phthalyl) bis(diphenylphosphine oxide) is prepared by the following method:

Under the conditions of anhydrous and oxygen-free, slight reflux at 60°C and stirring, a mixed solution of 75 grams of magnesium powder and 500 milliliters of tetrahydrofuran was placed in the flask. Under stirring condition, dropwise add the mixed solution of 5 grams of dibromoethane, 20 grams of chlorobenzene and 200 milliliters of tetrahydrofuran in the flask, dropwise time is 1 hour, to trigger the reaction of magnesium powder and chlorobenzene. Then the mixed solution of 320 grams of chlorobenzene and 300 milliliters of tetrahydrofuran was added dropwise in the flask, and the dropping time was 3 hours. After the dropwise addition, the stirring reaction was continued for 3 hours under slight reflux to obtain a mixed solution including Grignard reagent and tetrahydrofuran.

Make the temperature of the mixture of Grignard reagent and tetrahydrofuran in the flask be 40°C-50°C, add 138 g of diethyl phosphite dropwise to the flask under stirring condition, and the dropwise addition time is 30 minutes. After continuing to stir the reaction under slight reflux for 3 hours, the temperature was lowered to room temperature. Then slowly add 500 milliliters of citric acid solutions with a mass concentration of 50% in the flask under stirring, continue to stir for 30 minutes, and let the layers stand for 30 minutes. The organic phase was separated and concentrated under reduced pressure at 40° C. to 50° C. to obtain organic residues (including diphenylphosphine oxide), and tetrahydrofuran was recovered. The aqueous phase was mixed with 1 liter of toluene, stirred at room temperature for 30 minutes, and allowed to stand for 30 minutes to separate the layers, then the toluene phase was separated and combined with the aforementioned separated organic residue to obtain a compound comprising diphenylphosphine oxide (compound C), A mixture of impurities such as toluene and hydrogen chloride. Wash the mixture with 300 ml of 10% sodium bicarbonate aqueous solution and 300 ml of water in sequence, and distill about 400 ml of toluene under reduced pressure at 50°C-60°C, and the rest is diphenyl oxide. A mixture of phosphine and toluene.

At room temperature and under stirring conditions, mix the mixture of diphenylphosphine oxide and toluene with 220 grams of triethylamine in a flask, and add 203 grams of trifluoromethanesulfonate dropwise to the flask under the condition of 40°C-50°C The mixed solution of acid trimethylsilyl ester and 100 ml of toluene was added dropwise for 1 hour, and the stirring was continued for 1 hour after the addition was completed. Then, a mixed solution of 97 grams of 1,4-phthaloyl chloride (compound B) and 200 milliliters of toluene was added dropwise to the flask for 2 hours. Then the reaction was stirred at 50° C. for 2 hours, and cooled to room temperature.

Under the condition of room temperature, wash the reaction liquid in the flask with 500 ml of water, and wash twice. After washing, the organic phase was separated and the volatiles were evaporated under reduced pressure at 40°C-50°C. Then add 600 ml of isopropyl ether to the organic phase, stir and beat for 2 hours under the condition of 55°C-65°C, then continue to stir and beat for 1 hour under the condition of 5°C-10°C, and filter with suction to obtain a filter cake. After the filter cake was washed with cold isopropyl ether, it was dried under reduced pressure at 40°C-50°C to obtain 243 grams of (1,4-phthalyl)bis(diphenylphosphine oxide) provided in this example ), its purity is 99.8%, and the yield of (1,4-phthalyl) bis(diphenylphosphine oxide) based on diethyl phosphite is 91%.

To sum up, by adopting the preparation method of the acylphosphine oxide compound provided in the embodiment of the present disclosure, a product with stable product quality, high purity and high yield can be obtained, which is beneficial to industrial production.

The above are only illustrative examples of the present disclosure, and are not intended to limit the present disclosure. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present disclosure shall be included in the protection of the present disclosure. within range.

Claims (18)

A preparation method of an acylphosphine oxide compound, which comprises: reacting a compound B and a compound C under an organic base and an organic solvent to obtain the acyl phosphine oxide compound; wherein, the chemical structural formula of the compound B is as follows:

The chemical structural formula of compound C is as follows:

The chemical structural formula of this acyl phosphine oxide compound is as follows:

Wherein, R ^is hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino) phenyl , α-naphthyl or β-naphthyl; R ² and R ¹ are the same or different, independently represented by hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl , phenyl, benzoyl, (4-dimethylamino) phenyl, α-naphthyl or β-naphthyl; n is the substitution number of R ¹ on the corresponding benzene ring, and n is 1, 2 or 3, wherein, n is 2 or 3, and ^R1 is used as a substituent group, which can be the same or different at different substituent positions; m is the number of substitutions of ^R2 on the corresponding benzene ring, and m is 1, 2 or 3 , wherein, m is 2 or 3, and R ² is used as a substituent group, which can be the same or different at different substituent positions. The method as described in Claim 1, further comprising: adding Lewis acid to the reaction system formed by compound B and compound C. The method as described in Claim 2, wherein the molar ratio of compound B, compound C, organic base, and Lewis acid is 1:1-2:1-5:0.01-2. The method as described in claim 2, wherein the Lewis acid is selected from trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, triethylchlorosilane, tripropylchlorosilane, tributylchlorosilane Silane, tert-butyldimethylchlorosilane, tert-butyldiphenylchlorosilane, trimethylchlorosilane-sodium bromide, trimethylchlorosilane-sodium iodide, trimethylsilyl methanesulfonate, methyl At least one of tert-butyldimethylsilicon sulfonate, trimethylsilicon trifluoromethanesulfonate, and tert-butyldimethylsilicon trifluoromethanesulfonate. The method as described in claim 1, wherein the organic base is selected from triethylamine, tripropylamine, N,N-diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6-dimethyl At least one of base pyridine, 2-picoline, 3-picoline, 4-picoline. The method as described in claim item 1, wherein the organic solvent is selected from toluene, xylene, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, dichloromethane , 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyloxide, cyclobutylene at least one. The method according to claim 1, wherein the reaction temperature of compound B and compound C is -20°C-150°C, and the reaction time is 1-8 hours. The method as described in claim 1, wherein, under the conditions of an organic base and an organic solvent, reacting compound B and compound C includes: obtaining a first mixed solution comprising compound C and an organic solvent, and mixing it with an organic base in the first Mixing in the reactor; adding compound B to the first reactor to react compound B and compound C. The method according to claim 8, wherein adding the compound B into the first reactor comprises: obtaining a second mixed liquid including the compound B and an organic solvent; adding the second mixed liquid into the first reactor dropwise. The method as described in claim 8 or 9, wherein obtaining the first mixed solution comprising compound C and an organic solvent comprises: reacting the Grignard reagent and diethyl phosphite in an organic solvent, and then quenching with an acid solution The post-reaction treatment obtains the first mixed solution comprising compound C and an organic solvent; the chemical structural formula of the Grignard reagent is as follows:

Wherein, R ^is hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino) phenyl , α-naphthyl or β-naphthyl; m is the number of substitutions of R ² on the corresponding benzene ring, m is 1, 2 or 3; X is chlorine, bromine or iodine. The method according to claim 10, wherein the molar ratio of diethyl phosphite to Grignard reagent is 1:3-5. The method according to claim 10, wherein the acid solution is selected from at least one of hydrochloric acid solution, hydrobromic acid solution, hydroiodic acid solution, sulfuric acid solution, acetic acid solution, oxalic acid solution, and citric acid solution. The method according to claim 10, wherein the reaction temperature of the Grignard reagent and diethyl phosphite is -20°C-150°C, and the reaction time is 1-4 hours. The method as described in claim item 10, wherein, making the Grignard reagent and diethyl phosphite react in an organic solvent, and then quenching the reaction with an acid solution for post-treatment, including: Diethyl phosphite is added into the second reactor of the mixed solution to make the Grignard reagent react with the diethyl phosphite, and then quench the reaction with an acid solution for post-treatment. The method as described in claim item 14, wherein, the third mixed solution of Grignard reagent and organic solvent is prepared by the following method: under the condition of initiator and organic solvent, magnesium powder and aromatic halide are reacted to obtain The third mixed liquid of reagent and organic solvent; Wherein, the chemical structural formula of aryl halide is as follows:

Wherein, R ^is hydrogen, C ₁ -C ₆ alkyl, methoxy, methylthio, dimethylamino, chloroformyl, phenyl, benzoyl, (4-dimethylamino) phenyl , α-naphthyl or β-naphthyl; m is the number of substitutions of R ² on the corresponding benzene ring, m is 1, 2 or 3; X is chlorine, bromine or iodine. The method according to claim 15, wherein the molar ratio of the aromatic halide to the magnesium powder is 1:1-2. The method according to claim 15, wherein the initiator is selected from at least one of iodine and dibromoethane. The method as claimed in item 15, wherein the reaction time of the magnesium powder and the aromatic halogen is 2-4 hours.