Preparation method of bis (4-tert-butylphenyl) iodonium bis (perfluorobutane sulfonyl) imine

Abstract

The invention provides a preparation method of bis (4-tert-butylphenyl) iodonium bis (perfluorobutane sulfonyl) imine, which comprises the following steps: in the environment of shielding gas, mixing and stirring bis (perfluorobutane sulfonyl) imine, alkali, an organic solvent and ultrapure water, then adding bis (4-tert-butylphenyl) iodine chloride for reaction, and after the reaction is finished, filtering to obtain the bis (4-tert-butylphenyl) iodonium bis (perfluorobutane sulfonyl) imine. And carrying out post-treatment to obtain the bis (4-tert-butylphenyl) iodonium bis (perfluorobutane sulfonyl) imine. The preparation method has the beneficial effects that the preparation method is simple, the reaction system is mild, the selectivity is good, the total preparation cost is low, and the yield is high.

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemical synthesis, and in particular relates to a preparation method of bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide. Background Art

[0002] UV curing technology, known as "green technology", has shown great vitality and potential due to its excellent performances such as energy saving, environmental protection and economy. However, the problem of oxygen inhibition has always plagued UV curing technology. In recent years, cationic photocuring technology has been greatly developed, basically solving the problem of oxygen inhibition, and has been successfully applied to photocurable coatings, inks, adhesives, electronic packaging materials, photoresists and other fields. Diaryl iodonium salts are an important class of high-efficiency cationic photoinitiators. They can be dissolved in most cationic polymerization monomers, have strong photoactivity and very high initiation efficiency. In addition, because diaryl iodonium salts have good high temperature resistance and thermal stability, they have very broad application prospects. Therefore, through molecular design, the efficient, simple and low-cost synthesis of bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide has high theoretical significance and practical application value.

[0003] The structural formula of bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide is as follows:

[0004] Summary of the invention

[0005] In view of this, the present invention aims to provide a method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide to solve at least one technical problem in the background technology. The synthetic route is simple, the reaction conditions are mild, the product yield is high, and it is suitable for industrial production.

[0006] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0007] A method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide comprises the following steps:

[0008] Under protective gas, bis(perfluorobutanesulfonyl)imide and a base are added to an organic solvent and ultrapure water, stirred and dissolved, and then bis(4-tert-butylphenyl)iodine chloride is added. After the reaction at room temperature is completed, the liquid is separated, the ultrapure water is washed, the organic phase is concentrated, the isopropyl ether is crystallized, filtered, and vacuum dried to obtain bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide;

[0009]

[0010] The synthetic route is as follows:

[0011]

[0012] Further, under protective gas, bis(perfluorobutanesulfonyl)imide and alkali are added to an organic solvent and ultrapure water, stirred to dissolve, and then bis(4-tert-butylphenyl)iodine chloride is added, and the reaction is stirred at room temperature. After HPLC detection reaction is completed, liquid separation, ultrapure water washing, organic phase concentration, isopropyl ether crystallization, filtration, vacuum drying to obtain bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide. By controlling the reaction time and the amount of bis(perfluorobutanesulfonyl)imide and alkali, the incomplete reaction of the raw material bis(4-tert-butylphenyl)iodine chloride is avoided to the greatest extent.

[0013] Furthermore, the molar ratio of bis(4-tert-butylphenyl)iodine chloride, bis(perfluorobutanesulfonyl)imide and base is 1.0:(1.1-2.0):(1.1-2.0). Within this range, the reaction of bis(4-tert-butylphenyl)iodine chloride is most complete and the yield is the highest.

[0014] Furthermore, the organic solvent is one or more of diethyl ether, 2-methyltetrahydrofuran, dichloromethane, dichloroethane, chloroform, and ethyl acetate.

[0015] Furthermore, the base is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide.

[0016] Furthermore, under protective gas, bis(perfluorobutanesulfonyl)imide and a base are added into an organic solvent and ultrapure water system, stirred to dissolve, and reacted at room temperature.

[0017] Further, the system was stirred at room temperature for 5-7 h.

[0018] Furthermore, the protective gas is an inert gas.

[0019] Furthermore, the protective gas is nitrogen.

[0020] Compared with the prior art, the method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide of the present invention has the following advantages:

[0021] The invention uses bis(4-tert-butylphenyl)iodonium chloride and bis(perfluorobutanesulfonyl)imide as main raw materials, ultrapure water and an organic solvent as reaction solvents, and performs coordination substitution reaction under base catalysis to obtain bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide. The reaction steps are simple and safe, the preparation method is easy to implement, the reaction conditions are mild, the side reactions are few, and the reaction yield is high. Therefore, the preparation method of the invention is novel, has good selectivity, is environmentally friendly, has low overall preparation cost, high yield, and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0023] Figure 1 This is a schematic diagram of the HPLC spectrum of bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide prepared in Example 5 of the present invention;

[0024] Figure 2 This is a schematic diagram of the H NMR spectrum of bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide prepared in Example 5 of the present invention using deuterated chloroform as solvent;

[0025] Figure 3 The NMR fluorine spectrum, hydrogen spectrum and fluorine spectrum of bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide prepared in Example 5 of the present invention using deuterated chloroform as solvent show the product. DETAILED DESCRIPTION

[0026] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments may be combined with each other.

[0027] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0028] like Figure 1 As shown in the figure, the synthetic route of bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide is as follows:

[0029]

[0030] Embodiment 1:

[0031] A method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide comprises the following steps:

[0032] The molar ratio of bis(4-tert-butylphenyl)iodine chloride and bis(perfluorobutanesulfonyl)imide is 1.0:1.1. Under nitrogen protection, 800 mL of ether and 400 mL of ultrapure water are added to a 2L four-necked bottle, and bis(perfluorobutanesulfonyl)imide (149.1 g, 1.1 eq) and lithium hydroxide (6.1 g, 1.1 eq) are added under stirring, and dissolved by stirring. Bis(4-tert-butylphenyl)iodine chloride (100.0 g, 1.0 eq) is added, and stirred at room temperature for 6 hours. After the reaction is completed by HPLC detection, the liquid is separated, washed with ultrapure water, the organic phase is concentrated, crystallized with isopropyl ether, filtered, and vacuum dried to obtain 217.1 g of the compound bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide, with a yield of 95.6%. The water content is 0.02%. Its hydrogen nuclear magnetic resonance spectrum and fluorine nuclear magnetic resonance spectrum data are as follows:

[0033] 1 H NMR (600MHz, CDCl3, δppm): 1.29 (s, 18H), 7.49 (d, 4H), 7.92 (d, 4H).

[0034] 19 F NMR (600MHz, CDCl3, δppm): -80.85 (s, 6F), -112.66 (t, 4F), -121.05 (d, 4F), -125.96 (d, 4F).

[0035] In the above reaction, in order to make the substrate 4-bis(4-tert-butylphenyl)iodine chloride react completely, bis(perfluorobutanesulfonyl)imide and base are excessive to make the raw materials react completely to the greatest extent.

[0036] Embodiment 2:

[0037] A method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide comprises the following steps:

[0038] The molar ratio of bis(4-tert-butylphenyl)iodine chloride and bis(perfluorobutanesulfonyl)imide is 1.0:1.3. Under nitrogen protection, 800 mL of 2-methyltetrahydrofuran and 400 mL of ultrapure water are added to a 2L four-necked bottle, and bis(perfluorobutanesulfonyl)imide (176.2 g, 1.3 eq) and sodium hydroxide (12.1 g, 1.3 eq) are added under stirring, and dissolved by stirring. Bis(4-tert-butylphenyl)iodine chloride (100.0 g, 1.0 eq) is added, and stirred at room temperature for 6 hours. After the reaction is completed by HPLC detection, the mixture is allowed to stand for separation, washed with ultrapure water, the organic phase is concentrated, crystallized with isopropyl ether, filtered, and vacuum dried to obtain 219.8 g of the compound bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide, with a yield of 96.8%. The water content is 0.01%.

[0039] Embodiment 3:

[0040] A method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide comprises the following steps:

[0041] The molar ratio of bis(4-tert-butylphenyl)iodine chloride and bis(perfluorobutanesulfonyl)imide is 1.0:1.5. Under nitrogen protection, 800 mL of dichloromethane and 400 mL of ultrapure water are added to a 2L four-necked bottle, and bis(perfluorobutanesulfonyl)imide (203.3 g, 1.5 eq) and potassium hydroxide (19.6 g, 1.5 eq) are added under stirring, and dissolved by stirring. Bis(4-tert-butylphenyl)iodine chloride (100.0 g, 1.0 eq) is added, and stirred at room temperature for 6 hours. After the reaction is completed by HPLC detection, the mixture is allowed to stand for separation, washed with ultrapure water, concentrated, crystallized with isopropyl ether, filtered, and dried in vacuo to obtain 223.4 g of the compound bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide, with a yield of 98.4%. The water content is 0.01%.

[0042] Embodiment 4:

[0043] A method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide comprises the following steps:

[0044] The molar ratio of 4-bis(4-tert-butylphenyl)iodine chloride and bis(perfluorobutanesulfonyl)imide is 1.0:1.8. Under nitrogen protection, 800 mL of chloroform and 300 mL of ultrapure water are added to a 2L four-necked bottle, and bis(perfluorobutanesulfonyl)imide (244.0 g, 1.8 eq) and tetramethylammonium hydroxide (25% aqueous solution, 153.1 g, 1.8 eq) are added under stirring, and dissolved by stirring. Bis(4-tert-butylphenyl)iodine chloride (100.0 g, 1.0 eq) is added, and stirred at room temperature for 6 hours. After the reaction is completed by HPLC detection, the liquid is separated, washed with ultrapure water, the organic phase is concentrated, crystallized with isopropyl ether, filtered, and vacuum dried to obtain 222.0 g of the compound bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide, with a yield of 97.8%. The water content is 0.03%. Example 5:

[0045] A method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide comprises the following steps:

[0046] The molar ratio of bis(4-tert-butylphenyl)iodine chloride and bis(perfluorobutanesulfonyl)imide is 1.0:2.0. Under nitrogen protection, 800 mL of ether and 200 mL of ultrapure water are added to a 2L four-necked bottle, and bis(perfluorobutanesulfonyl)imide (271.1 g, 2.0 eq) and tetrapropylammonium hydroxide (25% aqueous solution, 379.4 g, 2.0 eq) are added under stirring, and dissolved by stirring. Bis(4-tert-butylphenyl)iodine chloride (100.0 g, 1.0 eq) is added, and stirred at room temperature for 6 hours. After the reaction is completed by HPLC detection, the liquid is separated, washed with ultrapure water, the organic phase is concentrated, crystallized with isopropyl ether, filtered, and vacuum dried to obtain 222.5 g of the compound bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide, with a yield of 98.0%. The water content is 0.02%.

[0047] Bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide was prepared according to the method described in Example 3. Bis(perfluorobutanesulfonyl)imide and a base were added to a mixed system of dichloromethane and ultrapure water, and a coordination substitution reaction occurred under the catalysis of potassium hydroxide to obtain bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide. The HPLC spectrum of bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide synthesized in this example is shown in FIG. Figure 1 As shown, Figure 2 This is its H NMR spectrum using deuterated chloroform as solvent. Figure 3 Its NMR fluorine spectrum, hydrogen spectrum and fluorine spectrum using deuterated chloroform as solvent showed that the product had a correct structure.

[0048] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide, characterized in that: The steps include: In a protective gas environment, bis(perfluorobutanesulfonyl)imide, a base, an organic solvent and ultrapure water are mixed and stirred, and then bis(4-tert-butylphenyl)iodine chloride is added to react. After the reaction is completed, bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide (I) is obtained through post-treatment; 2. The method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide according to claim 1, characterized in that: The molar ratio of bis(4-tert-butylphenyl)iodochloride, bis(perfluorobutanesulfonyl)imide and the base is 1.0:(1.1-2.0):(1.1-2.0).

3. The method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide according to claim 1, characterized in that: Under the condition of protective gas, an organic solvent and ultrapure water are mixed to obtain a mixed solution, bis(perfluorobutanesulfonyl)imide and a base are added to the mixed solution, stirred and dissolved, and then bis(4-tert-butylphenyl)iodine chloride is added.

4. The method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide according to claim 1, characterized in that: The reaction temperature is room temperature.

5. The method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide according to claim 1, characterized in that: The reaction time is 5-7h.

6. The method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide according to claim 1, characterized in that: The organic solvent includes one or more of diethyl ether, 2-methyltetrahydrofuran, dichloromethane, dichloroethane, chloroform and ethyl acetate.

7. The method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide according to claim 1, characterized in that: The base includes one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide.

8. The method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide according to claim 1, characterized in that: The shielding gas is inert gas.

9. The method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide according to claim 1, characterized in that: The protective gas is nitrogen.

10. The method for preparing bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide according to claim 1, characterized in that: The post-treatment to obtain bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide includes separation, ultrapure water washing, organic phase concentration, isopropyl ether crystallization, filtration, and vacuum drying to obtain bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl)imide.

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