CN115160362B - Preparation method of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide - Google Patents

Preparation method of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide Download PDF

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CN115160362B
CN115160362B CN202211075485.1A CN202211075485A CN115160362B CN 115160362 B CN115160362 B CN 115160362B CN 202211075485 A CN202211075485 A CN 202211075485A CN 115160362 B CN115160362 B CN 115160362B
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diphenyl
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sodium
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CN115160362A (en
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王晓蒙
张建锋
武瑞
武锦鹏
毛桂红
张齐
赵国锋
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Tianjin Jiuri New Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5036—Phosphines containing the structure -C(=X)-P or NC-P
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/505—Preparation; Separation; Purification; Stabilisation
    • C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
    • C07F9/5068—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure >P-Hal

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Abstract

The invention relates to a preparation method of 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide, wherein potassium tert-butoxide and/or potassium carbonate are/is used as a catalyst in the reaction process of sodium sand and diphenyl phosphorus chloride, and a dissociation agent is added, so that the generation efficiency of an intermediate product, namely diphenyl phosphine sodium is improved; then reacting with mesitylene benzoyl chloride, adding hydrochloric acid for washing, separating liquid to obtain an organic phase, adding an oxidant, and reacting to obtain 2,4, 6-trimethylbenzene formyl diphenyl phosphine oxide; in the process, hydrochloric acid is added for washing before the oxidation reaction, which is beneficial to improving the effect of the oxidation reaction, thereby improving the yield and the purity of the product, and the sodium chloride solution obtained by acid washing and liquid separation has low content of organic impurities, thereby being convenient for purification and byproduct treatment; the method has the characteristics of less generation of three wastes, simple operation and small safety risk.

Description

Preparation method of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide
Technical Field
The invention belongs to the field of preparation of photoinitiators, and relates to a preparation method of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide.
Background
2,4, 6-trimethylbenzoyl diphenyl phosphine oxide is a free radical I type photoinitiator, is widely applied in the fields of ultraviolet curing coatings, printing ink, ultraviolet curing adhesives, optical fiber coatings and the like, and the traditional preparation process mainly comprises a rearrangement process and an addition oxidation process.
US4298738A discloses a rearrangement process for the preparation of 2,4,6-trimethylbenzoyl diphenylphosphine oxide by reacting diphenyl phosphine chloride with methanol as the starting material and then with mesitylene chloride; the above process generates ethyl chloride, and the distillation process is prone to fire and has safety risks.
U.S. Pat. No. 5,5504236A discloses an addition oxidation process, which comprises using diphenyl phosphine chloride as the initial raw material, hydrolyzing, reacting with 2,4,6-trimethylbenzaldehyde to prepare diphenyl phosphine oxide intermediate containing hydroxyl, and then carrying out oxidation reaction in the presence of catalyst and oxidant to obtain 2,4,6-trimethylbenzoyl diphenyl phosphine oxide; the process has the advantages of large amount of hazardous waste generated in the process and great difficulty in reducing the hazardous waste.
Therefore, the development of a preparation method of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide with less three wastes, simple operation and less safety risk is still of great significance.
Disclosure of Invention
The invention aims to provide a preparation method of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, wherein potassium tert-butoxide and/or potassium carbonate are/is used as a catalyst in the reaction process of sodium sand and diphenyl phosphorus monochloride, and a dissociation agent is added, so that the generation efficiency of an intermediate product, namely diphenyl phosphine sodium is improved; then reacting with mesitylene benzoyl chloride, adding hydrochloric acid for washing, separating liquid to obtain an organic phase, adding an oxidant, and reacting to obtain 2,4, 6-trimethylbenzene formyl diphenyl phosphine oxide; in the process, hydrochloric acid is added for washing before the oxidation reaction, which is beneficial to improving the effect of the oxidation reaction, thereby improving the yield and the purity of the product, and the sodium chloride solution obtained by acid washing and liquid separation has low content of organic impurities, thereby being convenient for purification and byproduct treatment; compared with the traditional processes (such as a rearrangement process and an oxidation process) of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, the method provided by the invention has the characteristics of less three wastes, simplicity in operation and small safety risk.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, which comprises the following steps:
(1) Mixing a sodium sand solution with a catalyst, adding diphenyl phosphorus monochloride, and reacting to obtain a first reaction solution; the catalyst is selected from potassium tert-butoxide and/or potassium carbonate;
(2) Adding a dissociating agent into the first reaction liquid obtained in the step (1) for reaction to obtain a second reaction liquid;
(3) Adding mesitylene benzoyl chloride into the second reaction liquid obtained in the step (2) for reaction;
(4) Adding hydrochloric acid into the reactant obtained in the step (3), mixing, and separating to obtain an organic phase;
(5) And (5) adding an oxidant into the organic phase obtained in the step (4) to carry out reaction to obtain 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide.
According to the invention, through research, potassium tert-butoxide and/or potassium carbonate are/is used as a catalyst in a reaction system of sodium sand solution and diphenyl phosphorus chloride, the reaction rate can be accelerated, the generation of diphenyl phosphine sodium dimer in the reaction system can be reduced, and a dissociation agent is added in the reaction process, so that the dimer generated by the reaction can be further promoted to be dissociated into diphenyl phosphine sodium, and the subsequent reaction is facilitated; adding mesitylene formyl chloride for reaction, adding hydrochloric acid for washing after the reaction is finished, separating liquid to obtain an organic phase and a sodium chloride solution water phase, adding an oxidant into the organic phase, mixing, and carrying out oxidation reaction to obtain 2,4, 6-trimethylbenzene formyl diphenyl phosphine oxide; the organic phase of the system is pickled before the oxidation reaction, so that the subsequent oxidation reaction effect is favorably improved, the organic impurities in the aqueous phase of the obtained sodium chloride solution are low in content, the purified aqueous phase can be treated as a byproduct, and the generation of three wastes is low.
In the preparation method, the yield of the target product can reach more than 82%, and the purity can reach more than 98%.
Preferably, the liquid separation in the step (4) is carried out to obtain a sodium chloride solution phase and an organic phase; the content of organic impurities in the obtained sodium chloride solution phase is low, and the quality of the byproduct sodium chloride is good after purification, and the byproduct sodium chloride can be treated as a byproduct.
Preferably, the sodium sand solution in step (1) is prepared by a method comprising: adding sodium into a solvent, heating to reflux under the protection of inert atmosphere, and starting stirring to obtain a sodium sand solution; preferably the solvent is selected from toluene or xylene.
Preferably, the inert atmosphere is selected from at least one of nitrogen, helium or argon.
Preferably, the dissociation agent in step (2) is selected from any one or a combination of at least two of tetrahydrofuran, dioxane or diethylene glycol dimethyl ether, and is preferably tetrahydrofuran.
The method adopts the dissociating agent, belongs to an aprotic solvent, and can promote the P-P bond of the sodium diphenylphosphinate dimer to be broken, so that the next reaction is facilitated, and the dissociating agent is convenient to separate and recycle subsequently.
Preferably, the solvent of the sodium sand solution is selected from toluene or xylene.
Preferably, the molar ratio of sodium to diphenyl phosphine chloride in the sodium sand solution in step (1) is 2 to 2.2, for example, a ratio of 2.02.
Preferably, the molar ratio of the catalyst to the diphenyl phosphine monochloride in step (1) is 0.005 to 0.05, such as 0.008.
Preferably, in step (1), the molar ratio of sodium, catalyst and diphenyl phosphonium monochloride in the sodium sand solution is 2 to 2.2.
Preferably, the manner of adding the diphenyl phosphorus monochloride in the step (1) is dropwise.
Preferably, the temperature of the reaction in step (1) is 80 ℃ to 110 ℃, such as 85 ℃, 90 ℃, 95 ℃,100 ℃ or 105 ℃, and the like.
Preferably, the reaction time in the step (1) is 1h to 3h.
Preferably, the ratio of the molar amount of the dissociation agent added in the step (2) to the molar amount of the diphenyl monochlorophosphorus chloride added in the step (1) is from 0.5 to 0.7.
Preferably, the temperature of the reaction in step (2) is 80 ℃ to 110 ℃, such as 85 ℃, 90 ℃, 95 ℃,100 ℃ or 105 ℃, and the like.
In the present invention, the temperature of the dissociation process is controlled within the above range, which is favorable for the sufficient dissociation of the diphenylphosphine sodium dimer.
Preferably, the ratio of the molar amount of mesitylbenzoyl chloride added in step (3) to the molar amount of diphenyl phosphorus monochloride added in step (1) is from 0.85 to 1, such as from 0.86.
Preferably, the manner of adding the mesitylene benzoyl chloride in the step (3) is dropwise.
Preferably, the temperature of the adding of the mesitylene benzoyl chloride in the step (3) is controlled to be 60-80 ℃, such as 65 ℃, 70 ℃ or 75 ℃ and the like.
Preferably, the temperature of the reaction in step (3) is 60 ℃ to 80 ℃, such as 65 ℃, 70 ℃ or 75 ℃, and the like, preferably 70 ℃ to 80 ℃.
Preferably, before adding the mesitylene chloride in the step (3), adding trityl alcohol into the second reaction solution, and washing the product with water after the reaction in the step (3) is finished.
In the method, the reaction solution obtained in the step (2) still contains part of unconsumed sodium, and in the subsequent process of adding the trimethyl benzoyl chloride, the sodium reacts with the acyl chloride to consume the acyl chloride and promote part of side reactions, thereby influencing the yield and the purity of the final product; based on solving the problems, the triphenylmethanol is added into the second reaction solution before the mesitylene benzoyl chloride is added, so that sodium in a reaction system can be consumed, and the produced triphenylsodium methoxide cannot further consume the mesitylene benzoyl chloride, so that the consumption of the mesitylene benzoyl chloride is reduced, and the cost of raw materials is reduced;
in the method of the invention, before the step (4), the reaction solution obtained in the step (3) is washed with water, and the sodium trityl methoxide generated in the reaction is dissolved in the water phase, so that the sodium trityl methoxide is convenient to separate and recycle.
In the process, when the tert-butyl alcohol is used for consuming excessive sodium, the tert-butyl alcohol reacts with the sodium to generate sodium tert-butoxide, and the sodium tert-butoxide has relatively small space steric resistance in the structure and can further react with the mesitylene chloride to cause the consumption of raw materials and the generation of byproducts.
Preferably, the ratio of the molar amount of trityl alcohol added to the molar amount of diphenyl phosphonium monochloride added in step (1) is 0.1 to 0.5, for example, 0.15.
According to the invention, the molar quantity of the added trityl alcohol is controlled within the range, and sodium in the second reaction liquid can be effectively consumed, so that the consumption of the trimethyl benzoyl chloride and the generation of byproducts are reduced, and the cost of raw materials is reduced.
Preferably, the concentration of hydrochloric acid in step (4) is 2wt% to 10wt%, such as 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, or 9wt%, etc.
Preferably, the ratio of the molar amount of hydrochloric acid added in step (4) to the molar amount of diphenyl phosphorus monochloride added in step (1) is from 0.05 to 0.5.
In the present invention, before the oxidation reaction is carried out by adding an oxidizing agent, hydrochloric acid is added to the reaction solution to adjust the oxidation pH.
Preferably, the oxidizing agent of step (5) is selected from an aqueous hydrogen peroxide solution.
Preferably, H in hydrogen peroxide solution is added in the step (5) 2 O 2 The ratio of the molar amount of (a) to the molar amount of the diphenyl phosphonium monochloride added in step (1) is 1 to 1.8, for example, 1.1.
Preferably, the oxidizing agent is added in step (5) in a dropwise manner.
Preferably, the temperature of the process of adding the oxidant in step (5) is controlled to be 10 ℃ to 30 ℃, for example, 15 ℃, 20 ℃ or 25 ℃.
Preferably, the temperature of the reaction in step (5) is 10 ℃ to 30 ℃, such as 15 ℃, 20 ℃ or 25 ℃, and the like, preferably 15 ℃ to 20 ℃.
Preferably, the step (5) further comprises liquid separation after the reaction is finished to obtain an organic phase, and then the organic phase is washed, desolventized and recrystallized to obtain the 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide.
Preferably, the washing includes alkaline washing and water washing.
Preferably, the alkaline wash is a sodium carbonate solution, preferably a sodium carbonate solution having a concentration of 2wt% to 10wt% (exemplary including 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, or 9wt%, etc.).
Preferably, the end point of the water wash is to neutral pH.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method, potassium tert-butoxide and/or potassium carbonate are/is used as a catalyst in a reaction system of sodium sand solution and diphenyl-phosphorus chloride, so that the reaction rate can be accelerated, and a dissociation agent is added in the reaction process, so that a dimer generated by the reaction can be further promoted to be dissociated into sodium diphenylphosphine, the subsequent reaction can be fully carried out, and the yield of 2,4, 6-trimethylbenzoyl diphenylphosphine oxide is further improved;
(2) The preparation method disclosed by the invention has the advantages of less generation of three wastes, simplicity in operation and low safety risk.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
This example provides a method for preparing 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, including the following steps:
(a) Adding 50g of toluene and 11g of sodium into a four-mouth bottle, heating to reflux under the protection of nitrogen, starting stirring, and beating the sodium into sodium sand;
(b) Adding 0.5g of catalyst potassium tert-butoxide into the sodium sand solution obtained in the step (a), slowly dropwise adding 50g of diphenyl phosphorus chloride, and after dropwise adding, keeping the temperature at 100 ℃ for reaction for 3 hours;
(c) Adding 10g of tetrahydrofuran into the reaction solution in the step (b) for dissociation, and carrying out heat preservation reaction at 80 ℃ for 2h;
(d) After the heat preservation reaction in the step (c) is finished, slowly cooling to 70 ℃, slowly adding 39.5g of mesitylene benzoyl chloride dropwise, and detecting the reaction in a liquid phase to be complete;
(e) Controlling the temperature of the reaction liquid in the step (d) to 35 ℃, adding 50g of hydrochloric acid with the concentration of 5%, stirring for 30min, standing for 30min, and separating liquid to obtain an upper organic phase and a lower water phase; purifying the lower water phase to obtain byproduct sodium chloride;
(f) Transferring the organic phase obtained in the step (e) into a four-mouth bottle, controlling the temperature to 20 ℃, slowly dripping 50g of hydrogen peroxide solution, keeping the temperature for reacting for 2 hours after finishing dripping, and standing and separating liquid to obtain an organic phase;
(g) Washing the organic phase obtained in the step (f) with 5% sodium carbonate solution once, washing with water to be neutral, desolventizing and recovering a solvent toluene, adding ethyl acetate to dissolve, cooling, crystallizing, filtering, and drying to obtain 67g of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide product with the yield of 85% (calculated by taking the addition amount of diphenyl phosphorus chloride as a standard); the purity was 98.5%.
In this embodiment, the lower aqueous phase obtained in step (e) is subjected to solvent extraction to remove organic substances, concentration crystallization, and drying, and the content of organic substances is tested by a burning method, and the content of organic substances is less than 0.5%.
Example 2
This example differs from example 1 only in that 20g of trityl alcohol was added to the reaction solution obtained in step (c) before the dropwise addition of mesitylene chloride in step (d) and mixed, the amount of mesitylene chloride added was changed to 36.5g, and after the completion of the reaction in step (d), water was added to the reaction solution and water washing was carried out, and the aqueous phase was separated and removed to obtain an organic phase, followed by the operation in step (e), and other parameters and conditions were exactly the same as in example 1. The yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this example was 85%; the purity was 99%.
In the embodiment, the addition amount of 2,4, 6-mesitylene chloride is reduced, a small amount of trityl alcohol is added before the 2,4, 6-mesitylene chloride is dropwise added, and reacts with unconsumed metal sodium in a reaction solution and is converted into organic salt, so that the generation of byproducts and the waste of raw material mesitylene chloride caused by the reduction of the mesitylene chloride by the metal sodium are avoided, and the yield is not reduced while the use amount of the mesitylene chloride is reduced; and the organic salt does not react with mesitylene formyl chloride, and the salt obtained by the conversion can be removed by washing; the water phase is NaCl solution phase, can be used as byproduct treatment by purification, and the organic salt in the water phase can be used for recycling the trityl alcohol by acidification for reuse.
Example 3
This example differs from example 1 only in that the amount of sodium added in step (a) was replaced by 10.5g and the amount of potassium tert-butoxide added as catalyst in step (b) was replaced by 0.26g, with the other parameters and conditions being exactly the same as in example 1;
the yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this example was 80%; the purity was 98.4%. In the example, the generation of sodium diphenylphosphine is influenced by reducing the use amount of the catalyst and sodium, but the impurity of alkali phosphate washing can be removed, so that the influence on the yield is large, and the influence on the purity is small.
Example 4
This example differs from example 1 only in that the amount of sodium added in step (a) was replaced with 11.35g, the amount of potassium tert-butoxide added in step (b) was replaced with 0.88g, and other parameters and conditions were exactly the same as in example 1;
the yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this example was 82%; the purity was 97%. In this example, the amount of sodium used was increased, and acyl chloride was subsequently consumed, which affected the yield and purity of the product.
Example 5
This example differs from example 1 only in that the amount of sodium added in step (a) was replaced by 10.7g and the amount of potassium tert-butoxide added as catalyst in step (b) was replaced by 0.63g, with the other parameters and conditions being exactly the same as in example 1;
the yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this example was 84%; the purity was 98.6%.
Example 6
This example differs from example 1 only in that the amount of tetrahydrofuran added in step (c) was replaced with 11.1g, and the other parameters and conditions were exactly the same as in example 1.
The yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this example was 85%; the purity was 98.6%. In this example, the amount of tetrahydrofuran is increased compared to example 1, which has little effect on the yield and purity of the product, but the amount of tetrahydrofuran should not be too large.
Example 7
This example differs from example 1 only in that the amount of tetrahydrofuran added in step (c) was replaced by 9g, and the other parameters and conditions were exactly the same as in example 1.
The yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this example was 83%; the purity was 98.5%. In this example, the yield of the product is reduced with a smaller amount of tetrahydrofuran, but the yield is still high.
Example 8
This example differs from example 1 only in that an equimolar amount of tetrahydrofuran was replaced with dioxane in step (c), and the other parameters and conditions were exactly the same as in example 1.
The yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this example was 72%; the purity was 98%. In this example, when tetrahydrofuran was replaced with dioxane, the yield of the product was decreased, which may be caused by the fact that dioxane coordinated with the reaction intermediate, which affects the production of the product.
Example 9
This example differs from example 1 only in that the equimolar amount of tetrahydrofuran in step (c) was replaced with diethylene glycol dimethyl ether and the other parameters and conditions were exactly the same as in example 1.
The yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this example was 73%; the purity was 97%. In this example, the product yield was decreased by replacing tetrahydrofuran with diethylene glycol dimethyl ether, which may be caused by the formation of coordination between diethylene glycol dimethyl ether and the reaction intermediate, thereby affecting the product formation.
Example 10
This example differs from example 2 only in that the amount of trityl alcohol added was replaced with 25g and the other parameters and conditions were exactly the same as in example 2.
The yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this example was 84%; the purity was 98.8%.
Example 11
This example differs from example 2 only in that the amount of trityl alcohol added was replaced with 12g and the other parameters and conditions were exactly the same as in example 2.
The yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this example was 82%; the purity is 98.5%.
Example 12
This example is different from example 2 only in that t-butanol was substituted for trityl alcohol in an equimolar amount, and other parameters and conditions were exactly the same as those of example 2.
The yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this example was 78%; the purity was 98.3%.
In the embodiment, the tert-butyl alcohol is adopted to remove the sodium which is not consumed in the reaction liquid, and the sodium tert-butyl alcohol is generated through reaction and can react with subsequently added mesitylene benzoyl chloride to generate a byproduct, so that the yield of the product is reduced.
Example 13
This example differs from example 1 only in that potassium tert-butoxide in step (b) is replaced by an equimolar amount of potassium carbonate, and the other parameters and conditions are exactly the same as in example 1.
The yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this example was 84%; the purity was 98.6%.
Comparative example 1
This comparative example is different from example 1 only in that the operation in step (c) was not performed, the reaction time at the holding temperature in step (b) was extended to 5 hours, and other parameters and conditions were exactly the same as those in example 1.
The yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this comparative example was 42%; the purity was 95%.
Comparative example 2
This comparative example differs from example 1 only in that no catalyst was added in step (b) and the other parameters and conditions were exactly the same as in example 1.
The yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this comparative example was 68%; the purity was 96%.
Comparative example 3
This comparative example differs from example 1 only in that no catalyst is added in step (b) and no cleavage agent is added in step (c); directly and slowly dripping diphenyl phosphorus monochloride into the sodium sand solution in the step (a), reacting for 5 hours, and then sequentially carrying out the operations of the steps (d), (e) (f) and (g), wherein other parameters and conditions are completely the same as those in the example 1;
the yield of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide in this comparative example was 36%.
The yield of the target product in the comparative example is obviously reduced, which may be caused by that no catalyst or dissociating agent is added in the reaction process, so that the products of sodium and diphenyl phosphorus monochloride mainly exist in the form of sodium diphenylphosphine dimer, thereby limiting the subsequent reaction and reducing the yield of the target product.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (9)

1. A method for preparing 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, comprising the steps of:
(1) Mixing a sodium sand solution with a catalyst, and then adding diphenyl phosphorus monochloride for reaction to obtain a first reaction solution; the catalyst is selected from potassium tert-butoxide and/or potassium carbonate;
(2) Adding a dissociating agent into the first reaction liquid obtained in the step (1) for reaction to obtain a second reaction liquid;
(3) Adding mesitylene benzoyl chloride into the second reaction liquid obtained in the step (2) for reaction;
(4) Adding hydrochloric acid into the reactant obtained in the step (3), mixing, and separating to obtain an organic phase;
(5) Adding an oxidant into the organic phase obtained in the step (4) for reaction to obtain 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide;
the dissociating agent in the step (2) is selected from tetrahydrofuran.
2. The method of claim 1, wherein the solvent of the sodium sand solution is selected from toluene or xylene; in the step (1), the molar weight ratio of sodium in the sodium sand solution to diphenyl phosphine chloride is 2-2.2;
the molar weight ratio of the catalyst to the diphenyl-phosphonium chloride in the step (1) is 0.005-0.05;
the mode of adding diphenyl phosphorus chloride in the step (1) is dropwise adding;
the reaction temperature in the step (1) is 80-110 ℃;
the reaction time in the step (1) is 1-3 h.
3. The process according to claim 1, wherein the ratio of the molar amount of the dissociating agent added in the step (2) to the molar amount of the diphenyl-phosphorus monochloride added in the step (1) is 0.5 to 0.7;
the reaction temperature in the step (2) is 80-110 ℃.
4. The method according to claim 1, wherein the ratio of the molar amount of mesitylbenzoyl chloride added in step (3) to the molar amount of diphenyl phosphorochloridate added in step (1) is 0.85 to 1;
dropwise adding the mesitylene benzoyl chloride in the step (3);
controlling the temperature to be 60-80 ℃ in the process of adding the mesitylene benzoyl chloride in the step (3);
the reaction temperature in the step (3) is 60-80 ℃.
5. The method according to claim 1, wherein the step (3) of adding mesitylene chloride further comprises adding trityl alcohol to the second reaction solution before adding mesitylene chloride, and washing the product with water after the reaction in the step (3) is completed;
the ratio of the molar weight of the added trityl alcohol to the molar weight of the diphenyl phosphorus monochloride added in the step (1) is 0.1-0.5.
6. The method according to claim 1, wherein the concentration of hydrochloric acid in the step (4) is 2 to 10wt%.
7. The process according to claim 1, wherein the ratio of the molar amount of hydrochloric acid added in step (4) to the molar amount of diphenyl-phosphorus monochloride added in step (1) is from 0.05 to 0.5.
8. The method according to claim 1, wherein the oxidizing agent of step (5) is selected from the group consisting of an aqueous hydrogen peroxide solution;
adding H in hydrogen peroxide solution in the step (5) 2 O 2 The ratio of the molar weight of the diphenyl monochlorophosphorus to the molar weight of the diphenyl monochlorophosphorus added in the step (1) is 1 to 1.8;
the oxidant is added in the step (5) in a dropwise manner;
controlling the temperature of the process of adding the oxidant in the step (5) to be 10-30 ℃;
the reaction temperature in the step (5) is 10-30 ℃.
9. The preparation method according to claim 1, wherein the step (5) further comprises separating the reaction solution after the reaction is finished to obtain an organic phase, and then washing, desolventizing and recrystallizing the organic phase to obtain 2,4, 6-trimethylbenzoyldiphenylphosphine oxide;
the washing comprises alkali washing and water washing;
the alkali washing adopts a sodium carbonate solution with the concentration of 2-10 wt%;
the end point of the water wash was to neutral pH.
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