Method for catalytically synthesizing trifluoromethylsulfonyl chloride by using heteropolyacid solid catalyst

Abstract

The invention provides a method for catalytically synthesizing trifluoromethylsulfonyl chloride by using a heteropolyacid solid catalyst, which relates to the technical field of chemical synthesis and comprises the following steps: carrying out nucleophilic reaction on bis (trifluoromethyl) disulfide and chlorine under the action of a supported heteropolyacid solid catalyst to generate trifluoromethylthionyl chloride; trifluoromethyl sulfur chloride and a mixture of hydrogen peroxide and acetic acid are subjected to an oxidation reaction under the action of a supported heteropolyacid solid catalyst to generate trifluoromethylsulfonyl chloride, heteropolyacid is Dawson type heteropolyacid, the chemical formula of the heteropolyacid is X2W12O62, the central atom is silicon, and the coordination atom is tungsten or molybdenum. Under the action of the supported heteropolyacid solid catalyst, bis (trifluoromethyl) disulfide is taken as a raw material and is subjected to nucleophilic reaction with chlorine, the problem of non-condensable gas of chlorine in an acidic solvent environment is avoided, trifluoromethyl sulfur chloride is obtained, and trifluoromethyl sulfur chloride is obtained through catalysis of the same batch of supported heteropolyacid solid catalyst. And carrying out oxidation reaction with a mixture of hydrogen peroxide and acetic acid to generate trifluoromethylsulfonyl chloride, and the yield is higher than 90%.

Description

Technical Field

[0001] The present application relates to the technical field of chemical synthesis, and more specifically, to a method for synthesizing trifluoromethylsulfonyl chloride using a heteropolyacid solid catalyst. Background Art

[0002] Trifluoromethanesulfonyl chloride (TfCl), referred to as TfCl, is an important organic compound with the chemical formula CF3SO2Cl. It is often used to introduce trifluoromethanesulfonyl (triflates) functional groups in organic synthesis. Trifluoromethanesulfonyl chloride has a wide range of uses and can be used as a pharmaceutical intermediate for the preparation of a variety of antibacterial drugs, weight loss drugs, anticancer drugs and adjuvants. For example, it can be used to prepare resveratrol trimethyl ether, which is a key raw material for many antibacterial and anticancer drugs. In addition, it can also be used to prepare a variety of biologically active substances such as H-PGDS inhibitors and Rho-kinase inhibitors with anticancer effects. It also has important applications in electrolyte synthesis, such as for the preparation of bistrifluoromethylsulfonyl imide lithium salt. In the prior art, the synthesis schemes of trifluoromethylsulfonyl chloride are: (1) A Chinese invention patent with publication number CN111004155A, a method for preparing trifluoromethylsulfinyl halide, discloses the use of trichloromethylsulfinyl chloride to react with an oxidant to obtain trichloromethylsulfinyl chloride. Trifluoromethylsulfinyl chloride has high electrophilic trifluoromethylsulfonylation activity, but at the same time leads to poor stability and high toxicity, which affects production safety as a raw material.

[0003] (2) Chinese invention patent with publication number CN113149873A, a method for preparing trifluoromethylsulfenyl chloride, discloses a one-pot method for preparing trifluoromethylsulfenyl chloride using bis(trifluoromethyl) disulfide as a raw material in a solvent with a chlorination agent and an oxidant, the weight ratio of the solvent to bis(trifluoromethyl) disulfide is 1:1 to 500:1, the chlorination reaction temperature is -30°C to 80°C, and the oxidation reaction temperature is -30°C to 30°C. However, this scheme has a long reaction time, and uses a strong acidic solvent, which is highly corrosive to the reaction container, and there is also the problem of dissolution of chlorine gas as a chlorination agent.

[0004] (3) The U.S. invention patent with publication number US4970337A, Process for the preparation of trifluoromethanesulphonyl chloride, discloses that chlorine gas is introduced into a strong acid solution to react bis-(trifluoromethyl)-disulfide with chlorine and water in a liquid phase. This solution also has the problem of non-condensable chlorine gas as described in solution (2).

[0005] Therefore, a method for synthesizing trifluoromethylsulfonyl chloride is needed which has rapid reaction and safety that meets production requirements. Summary of the invention

[0006] In order to solve the above problems, the technical solution adopted in the present application is a method for synthesizing trifluoromethylsulfonyl chloride by catalysis of a heteropolyacid solid catalyst, wherein bis(trifluoromethyl) disulfide undergoes a nucleophilic reaction with chlorine under the action of a supported heteropolyacid solid catalyst to generate trifluoromethylsulfonyl chloride, and trifluoromethylsulfonyl chloride undergoes an oxidation reaction with a mixture of hydrogen peroxide and acetic acid under the action of a supported heteropolyacid solid catalyst to generate trifluoromethylsulfonyl chloride; the heteropolyacid of the supported heteropolyacid solid catalyst is a Dawson type heteropolyacid, and its chemical formula is X2W 12 O 62 , where X represents the central atom, which is silicon, W represents the coordinating atom, which is tungsten or molybdenum, and O represents oxygen.

[0007] Optionally, the supported molecular sieve of the supported heteropolyacid solid catalyst is a ZSM-5 zeolite molecular sieve, and the silicon-aluminum ratio of the ZSM-5 zeolite molecular sieve is 50-100.

[0008] Optionally, the reaction temperature of the nucleophilic reaction process is 0-90°C, and the reaction temperature of the oxidation reaction process is 0-100°C.

[0009] Optionally, the reaction temperature of the oxidation reaction process is 20-80°C.

[0010] Optionally, the reaction time of the nucleophilic reaction process is 0.25-1 h, and the reaction time of the oxidation reaction process is 0.2-0.3 h.

[0011] Optionally, the molar ratio of bis(trifluoromethyl)disulfide to chlorine is 1:1-3.

[0012] Optionally, in the mixture of hydrogen peroxide and acetic acid, the molar ratio of hydrogen peroxide to acetic acid is 1:0.8-2.

[0013] Optionally, the molar ratio of bis(trifluoromethyl)disulfide to the mixture of hydrogen peroxide and acetic acid is 1:2-3.

[0014] Optionally, the molar ratio of the supported heteropoly acid solid catalyst to bis(trifluoromethyl) disulfide is 0.1-1:1.

[0015] Optionally, after the nucleophilic reaction process is completed, the chlorine in the tail gas is removed by two-stage alkaline absorption treatment, and after the oxidation reaction process is completed, the trifluoromethylsulfonyl chloride product is obtained by distillation separation.

[0016] The beneficial effects of the present invention are: The method uses bis(trifluoromethyl) disulfide as a raw material to react with chlorine gas in a nucleophilic reaction under the action of a supported heteropoly acid solid catalyst, thereby avoiding the problem of non-condensable gas of chlorine gas in an acidic solvent environment, and obtaining trifluoromethyl sulfonyl chloride in a closed state. The trifluoromethyl sulfonyl chloride is used as a raw material to react with a mixture of hydrogen peroxide and acetic acid in an oxidation reaction under the catalytic action of the same batch of supported heteropoly acid solid catalysts to generate trifluoromethyl sulfonyl chloride. The method has the advantages of high safety, short reaction time, low requirements on corrosion resistance and high temperature resistance of equipment, reduced energy consumption, higher yield than 90%, and higher purity than 96.5%. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the embodiments or descriptions of the prior art.

[0018] Figure 1 This is a schematic diagram of the nucleophilic reaction between bis(trifluoromethyl) disulfide and chlorine provided in the examples of the present application; Figure 2 This is a schematic diagram of the oxidation reaction of trifluoromethyl sulfonyl chloride with a mixture of hydrogen peroxide and acetic acid provided in an embodiment of the present application; Figure 3 This is the standard spectrum of trifluoromethylsulfonyl chloride provided in the examples of this application; Figure 4 This is the product spectrum of trifluoromethanesulfonic acid chloride provided in the examples of this application. DETAILED DESCRIPTION

[0019] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0020] Example 1 Add bis(trifluoromethyl) disulfide and a supported heteropoly acid solid catalyst into a high pressure reactor. The supported heteropoly acid solid catalyst is a Dawson type heteropoly acid with a chemical formula of X2W 12 O 62 , where X represents the central atom, which is silicon, W represents the coordinating atom, which is tungsten, and O represents oxygen. The supported molecular sieve of the supported heteropoly acid solid catalyst is ZSM-5 zeolite molecular sieve, the silicon-aluminum ratio of ZSM-5 zeolite molecular sieve is 50, and the molar ratio of the supported heteropoly acid solid catalyst to bis(trifluoromethyl) disulfide is 0.1:1. Then chlorine is introduced, and the reaction temperature is controlled to be 0°C. After 0.25h after the chlorine ventilation is completed, the tail gas is discharged, and the chlorine in the tail gas is subjected to two-stage alkali absorption treatment, and the molar ratio of bis(trifluoromethyl) disulfide to chlorine is 1:1.

[0021] Reaction principle Figure 1 As shown, the lone pair of electrons on the perfluorosulfur acts as a nucleophile to attack the electrophile chlorine gas, and the chloride ion leaves to obtain an intermediate state with a sulfonium ion structure. Then, the chloride ion acts as a nucleophile to attack the intermediate with the sulfonium ion to obtain trifluoromethylsulfonium chloride.

[0022] The trifluoromethylsulfonyl chloride generated in the first step of the reaction is left in the autoclave, and then a mixture of hydrogen peroxide and acetic acid is added dropwise into the autoclave, the molar ratio of hydrogen peroxide to acetic acid is 1:0.8, and the molar ratio of bis(trifluoromethyl) disulfide to the mixture of hydrogen peroxide and acetic acid is 1:2. The reaction temperature is 0°C, and after the hydrogen peroxide is added dropwise, the reaction is continued for 0.2h. After the oxidation reaction process is completed, the trifluoromethylsulfonyl chloride product is obtained by distillation separation.

[0023] Reaction principle Figure 2 As shown, hydrogen peroxide is added with acetic acid to generate peracetic acid. The lone pair of electrons of sulfur in trifluoromethyl sulfenyl chloride acts as a nucleophile to attack the electrophile peracetic acid. The acetate leaves to form an intermediate containing a sulfonium ion. The acetate then acts as a base to extract hydrogen to obtain trifluoromethylsulfenyl chloride. Trifluoromethylsulfenyl chloride undergoes the same oxidation process to obtain trifluoromethylsulfonyl chloride.

[0024] Example 2 The difference from Example 1 is that the heteropolyacid coordinating atom of the supported heteropolyacid solid catalyst is molybdenum, the silicon-aluminum ratio of the ZSM-5 zeolite molecular sieve is 75, and the molar ratio of the supported heteropolyacid solid catalyst to bis(trifluoromethyl) disulfide is 0.3: 1. The reaction temperature of the nucleophilic reaction process is controlled to be 30° C. 0.5 h after the chlorine aeration is completed, the chlorine in the tail gas is subjected to a two-stage alkaline absorption treatment, and the molar ratio of bis(trifluoromethyl) disulfide to chlorine is 1:2.

[0025] The molar ratio of hydrogen peroxide to acetic acid was 1:1.1, and the molar ratio of bis(trifluoromethyl) disulfide to the mixture of hydrogen peroxide and acetic acid was 1:2.5. The reaction temperature of the oxidation reaction was 20°C, and the reaction was continued for 0.3h after the addition of hydrogen peroxide was completed.

[0026] Example 3 The difference from Example 1 is that the silicon-aluminum ratio of the ZSM-5 zeolite molecular sieve is 100, and the molar ratio of the supported heteropoly acid solid catalyst to bis(trifluoromethyl) disulfide is 0.6: 1. The reaction temperature of the nucleophilic reaction process is controlled to be 60° C., and 0.75 h after the chlorine aeration is completed, the chlorine in the tail gas is subjected to a two-stage alkaline absorption treatment, and the molar ratio of bis(trifluoromethyl) disulfide to chlorine is 1:3.

[0027] The molar ratio of hydrogen peroxide to acetic acid is 1:1.4, and the molar ratio of bis(trifluoromethyl) disulfide to the mixture of hydrogen peroxide and acetic acid is 1:3. The reaction temperature of the oxidation reaction process is 40°C.

[0028] Example 4 The difference from Example 1 is that the molar ratio of the supported heteropolyacid solid catalyst to bis(trifluoromethyl) disulfide is 1:1, the reaction temperature for controlling the nucleophilic reaction process is 90°C, and 1 hour after the chlorine ventilation is completed, the chlorine in the tail gas is subjected to a two-stage alkaline absorption treatment.

[0029] The molar ratio of hydrogen peroxide to acetic acid is 1:1.7. The reaction temperature of the oxidation reaction process is 60°C.

[0030] Example 5 The difference from Example 1 is that the molar ratio of hydrogen peroxide to acetic acid is 1:2. The reaction temperature of the oxidation reaction process is 80°C.

[0031] Example 6 The difference from Example 1 is that the reaction temperature of the oxidation reaction process is 100°C.

[0032] Test: The products obtained by distillation and separation in each embodiment were tested using a HF-901 gas chromatograph produced by Huifen Instruments. The test results of the standard sample of trifluoromethylsulfonyl chloride and the product of Example 4 are shown in FIG. Figure 3 and Figure 4 shown.

[0033] Table 1 Experimental parameters and statistical results of the examples

[0034] Table 1 (Continued) Example Experimental Parameters and Results Statistics

[0035] As shown in Table 1 and Table 1 (Continued), according to the method for synthesizing trifluoromethylsulfonyl chloride catalyzed by a heteropolyacid solid catalyst provided in the present application, the purity of the synthesized trifluoromethylsulfonyl chloride is higher than 97%, and the yield is higher than 90%.

[0036] The embodiments described above are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, a person skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present application, and should all be included in the protection scope of the present application.

Claims

1. A method for synthesizing trifluoromethylsulfonyl chloride using a heteropolyacid solid catalyst, characterized in that: Bis(trifluoromethyl) disulfide undergoes a nucleophilic reaction with chlorine gas under the action of a supported heteropoly acid solid catalyst to generate trifluoromethyl sulfonyl chloride, and the trifluoromethyl sulfonyl chloride undergoes an oxidation reaction with a mixture of hydrogen peroxide and acetic acid under the action of the supported heteropoly acid solid catalyst to generate trifluoromethyl sulfonyl chloride; the heteropoly acid of the supported heteropoly acid solid catalyst is a Dawson type heteropoly acid, and its chemical formula is X2W 12 O 62 , wherein X represents the central atom, which is silicon, W represents the coordinating atom, which is tungsten or molybdenum, and O represents oxygen.

2. The method for synthesizing trifluoromethylsulfonyl chloride using a heteropolyacid solid catalyst as claimed in claim 1, characterized in that: The supported molecular sieve of the supported heteropolyacid solid catalyst is a ZSM-5 zeolite molecular sieve, and the silicon-aluminum ratio of the ZSM-5 zeolite molecular sieve is 50-100.

3. The method for synthesizing trifluoromethylsulfonyl chloride using a heteropolyacid solid catalyst as claimed in claim 2, characterized in that: The reaction temperature of the nucleophilic reaction process is 0-90°C, and the reaction temperature of the oxidation reaction process is 0-100°C.

4. The method for synthesizing trifluoromethylsulfonyl chloride using a heteropolyacid solid catalyst as claimed in claim 3, characterized in that: The reaction temperature of the oxidation reaction process is 20-80°C.

5. The method for synthesizing trifluoromethylsulfonyl chloride using a heteropolyacid solid catalyst as claimed in claim 3, characterized in that: The reaction time of the nucleophilic reaction process is 0.25-1h, and the reaction time of the oxidation reaction process is 0.2-0.3h.

6. The method for synthesizing trifluoromethylsulfonyl chloride using a heteropolyacid solid catalyst as claimed in claim 5, characterized in that: The molar ratio of the bis(trifluoromethyl) disulfide to the chlorine gas is 1:1-3.

7. The method for synthesizing trifluoromethylsulfonyl chloride using a heteropolyacid solid catalyst as claimed in claim 5, characterized in that: In the mixture of hydrogen peroxide and acetic acid, the molar ratio of hydrogen peroxide to acetic acid is 1:0.8-2.

8. The method for synthesizing trifluoromethylsulfonyl chloride using a heteropolyacid solid catalyst as claimed in claim 5, characterized in that: The molar ratio of the bis(trifluoromethyl) disulfide to the mixture of hydrogen peroxide and acetic acid is 1:2-3.

9. The method for synthesizing trifluoromethylsulfonyl chloride using a heteropolyacid solid catalyst as claimed in claim 8, characterized in that: The molar ratio of the supported heteropoly acid solid catalyst to the bis(trifluoromethyl) disulfide is 0.1-1:

1.

10. The method for synthesizing trifluoromethylsulfonyl chloride using a heteropolyacid solid catalyst as claimed in claim 8, characterized in that: After the nucleophilic reaction process is completed, the chlorine in the tail gas is removed by two-stage alkali absorption treatment. After the oxidation reaction process is completed, the trifluoromethylsulfonyl chloride product is obtained by distillation separation.

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