A method of esterification of aryl fluorosulfonate with aryl formate

Abstract

The application discloses an esterification method of aryl fluorosulfonate and aryl formate, and belongs to the technical field of organic compound synthesis. In the method, aryl fluorosulfonate and aryl formate are reacted in a solvent under the action of a catalyst, a ligand and a base in a one-pot method, and corresponding esters with good functional group tolerance can be obtained in a medium to good yield. The preparation method uses aryl fluorosulfonate as a coupling substrate, which is cheap and easy to obtain, and uses aryl formate instead of toxic, flammable and difficult-to-handle CO gas, so that the danger of reagent toxicity and potential explosion in the operation process is avoided. The preparation method has the characteristics of simple reaction condition, convenient post-treatment, green step, low pollution and high economic benefit.

Description

Technical Field

[0001] This invention belongs to the field of organic compound synthesis technology, specifically relating to an esterification method of aryl fluorosulfonate and aryl carbamate. Background Technology

[0002] Esters are not only widely found in natural products, biological and pharmaceutical active molecules, and functional materials, but also play a multifunctional and crucial role in organic synthesis. Many methods have been well-developed for ester synthesis; for example, transition metal-catalyzed carbonylation has proven to be an efficient method for ester construction. In various recognized carbonylation reactions, the use of formate esters instead of toxic, flammable, and difficult-to-handle CO gas has proven to be an effective method for ester preparation. In recent decades, the development of electrophilic agents to replace organohalides in carbonylation processes has also attracted widespread attention in the synthetic community. Aryl fluorosulfonates, as readily available and stable reagents, have proven to be effective electrophilic agents for various organic transformations. Summary of the Invention

[0003] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0004] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0005] One objective of this invention is to provide an esterification method for aryl fluorosulfonates and aryl carbamates, which features simple reaction conditions, convenient post-processing, green procedures, low pollution, and high economic benefits.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution: an esterification method for aryl fluorosulfonate and aryl carboxylate, wherein the aryl fluorosulfonate of Formula I and the aryl carboxylate of Formula II are reacted in a solvent under the action of a catalyst, a ligand and a base to obtain the compound of Formula III;

[0007] Ar-OSO2F (Formula I);

[0008]

[0009] In Formula I and Formula III, Ar is selected from one of the following: phenyl, p-nitro-substituted phenyl, p-cyano-substituted phenyl, p-methanesulfonyl-substituted phenyl, p-trifluoromethoxy-substituted phenyl, p-fluorine-substituted phenyl, p-chloro-substituted phenyl, p-tert-butyl-substituted phenyl, p-phenyl-substituted phenyl, 3,5-dimethyl-substituted phenyl, p-methoxy-substituted phenyl, m-methoxy-substituted phenyl, benzo[d][1,3]dioxanepentane-5-phenyl, 3-(dimethylamino)-substituted phenyl, naphthyl, and pyridyl.

[0010] In Formulas II and III, Ar' is selected from one of the following: phenyl, p-formyloxy-substituted phenyl, p-trifluoromethoxy-substituted phenyl, p-trifluoromethyl-substituted phenyl, p-fluorine-substituted phenyl, p-chloro-substituted phenyl, p-bromo-substituted phenyl, p-methyl-substituted phenyl, m-methyl-substituted phenyl, o-methyl-substituted phenyl, p-tert-butyl-substituted phenyl, p-phenyl-substituted phenyl, naphthyl-substituted, and pyrene-substituted.

[0011] As a preferred embodiment of the esterification method of aryl fluorosulfonate and aryl carboxylate of the present invention, wherein the molar ratio of aryl fluorosulfonate to aryl carboxylate is 1:2.

[0012] As a preferred embodiment of the esterification method of aryl fluorosulfonate and aryl carboxylate of the present invention, wherein: the catalyst is selected from palladium acetylacetonate, palladium chloride, bis(triphenylphosphine)dichloride palladium, tetra(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, palladium acetate, and the molar ratio of the catalyst to the aryl fluorosulfonate is 0.05 to 0.1:1.

[0013] In a preferred embodiment of the esterification method of aryl fluorosulfonate and aryl carboxylate of the present invention, the molar ratio of the catalyst to the aryl fluorosulfonate is 0.05:1.

[0014] As a preferred embodiment of the esterification method of aryl fluorosulfonate and aryl carboxylate of the present invention, wherein: the ligand is selected from one of 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,6-bis(diphenylphosphino)hexane, 1,2-bis(diphenylphosphino)benzene, bis(2-diphenylphosphine)ether, and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene, and the molar ratio of the ligand to the aryl fluorosulfonate is 0.05 to 0.1:1.

[0015] As a preferred embodiment of the esterification method of aryl fluorosulfonate and aryl carboxylate of the present invention, the molar ratio of the ligand to the aryl fluorosulfonate is 0.05:1.

[0016] As a preferred embodiment of the esterification method of aryl fluorosulfonate and aryl carboxylate of the present invention, wherein: the base is selected from one of triethylamine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, sodium tert-butoxide, potassium carbonate, and sodium bicarbonate, and the molar ratio of the base to the aryl fluorosulfonate is 1 to 2:1.

[0017] In a preferred embodiment of the esterification method of aryl fluorosulfonate and aryl carboxylate of the present invention, the molar ratio of the base to the aryl fluorosulfonate is 2:1.

[0018] As a preferred embodiment of the esterification method of aryl fluorosulfonate and aryl carboxylate of the present invention, the solvent is selected from one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylpropenylurea, dimethyl sulfoxide, acetonitrile, 1,4-dioxane, tetrahydrofuran, and toluene.

[0019] As a preferred embodiment of the esterification method of aryl fluorosulfonate and aryl carbamate of the present invention, the reaction is carried out at a temperature of 50-80°C.

[0020] In summary, the chemical equation for the optimal reaction conditions of this invention is as follows:

[0021]

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] This invention provides a palladium-catalyzed carbonylation reaction of aryl fluorosulfonates and aryl carbamates to efficiently synthesize esters. The reaction is carried out in a one-pot manner, using transition metal palladium as a catalyst, and under triethylamine as a base, in N,N-dimethylformamide solvent at 80°C for 12 hours, yielding the corresponding esters with good functional group tolerance in moderate to good yields. The preparation method of this invention features simple reaction conditions, convenient post-processing, green procedures, low pollution, and high economic efficiency. Attached Figure Description

[0024] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0025] Figure 1 The hydrogen spectrum of methyl benzoate, the target product of Example 1 of this invention;

[0026] Figure 2The carbon spectrum of methyl benzoate, the target product of Example 1 of the present invention;

[0027] Figure 3 The hydrogen spectrum of phenyl 4-cyanobenzoate, the target product of Example 2 of this invention;

[0028] Figure 4 The carbon spectrum of phenyl 4-cyanobenzoate, the target product of Example 2 of the present invention;

[0029] Figure 5 The 1H NMR spectrum of 4-(benzoyloxy)benzoate, the target product of Example 3 of this invention;

[0030] Figure 6 The carbon spectrum of 4-(benzoyloxy)benzoate, the target product of Example 3 of the present invention. Detailed Implementation

[0031] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0032] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0033] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0034] Unless otherwise specified, all raw materials used in the examples are commercially available.

[0035] The aryl fluorosulfonate (compound of formula I) was synthesized with reference to the following literature:

[0036] [1] J.-H.Na, X.Liu, J.-W.Jing, J.Wang,

[0037] The aryl carbamate (compound of formula II) was synthesized with reference to the following literature:

[0038] [2]

[0039] Example 1

[0040] (1) Place the sealed tube equipped with a magnetic stirrer in an oven to dry for one hour, take it out and while it is still hot, plug it with a rubber stopper and insert a nitrogen balloon;

[0041] (2) After the sealed tube cooled to room temperature, palladium acetate (5.7 mg, 0.025 mmol, 5 mol%) and 4,5-bis(diphenylphosphine-9,9-dimethyloxanthracene) (14.5 mg, 5 mmol, 5 mol%) were added. Then, the sealed tube was purged with nitrogen three times. Subsequently, 2 mL of ultra-dry N,N-dimethylformamide was added. Then, phenyl fluorosulfonate (88.1 mg, 0.5 mmol, 1 equiv.), phenyl formate (122.1 mg, 1 mmol, 2 equiv.), and triethylamine (101.2 mg, 1 mmol, 2 equiv.) were added to the sealed tube. The mixture was stirred at 80 °C for 12 hours.

[0042] (3) Subsequently, extraction was performed using ethyl acetate; the extract was washed with saturated brine, dried over anhydrous sodium sulfate, and then removed by rotary evaporation. The crude product was purified by silica gel column chromatography under the following conditions: stationary phase: 200-300 mesh silica gel powder; mobile phase: petroleum ether / ethyl acetate 200: 2-4. Finally, 83.3 mg of the target product, phenyl benzoate, was obtained. The structural formula of this compound is:

[0043]

[0044] The above-mentioned phenyl benzoate was characterized, such as Figure 1 and 2 As shown, the result is: a white solid; 1 H NMR (400MHz, CDCl3): δ8.29–8.23(m,2H),7.70–7.64(m,1H),7.55(dd,J=8.4,7.0Hz,2H),7.51–7.44(m,2H),7.35–7.24(m,3H)ppm. 13C NMR(100MHz, CDCl3): δ165.1,150.8,133.5,130.1,129.4(2C),128.5,125.8,121.6ppm.HRMS(m / z):calcd for C 13 H 11 O2 + [M+H] + 199.0754,found:199.0750.IR(KBr,neat):ν=3326,1730,1486,1262,1198,1062,751,704cm -1 .

[0045] Characterization data showed that the obtained reaction product was phenyl benzoate (purity > 98%); the product yield was calculated to be 84%.

[0046] Example 2

[0047] (1) Place the sealed tube equipped with a magnetic stirrer in an oven to dry for one hour, take it out and while it is still hot, plug it with a rubber stopper and insert a nitrogen balloon;

[0048] (2) After the sealed tube cooled to room temperature, palladium acetate (5.7 mg, 0.025 mmol, 5 mol%) and 4,5-bis(diphenylphosphine-9,9-dimethyloxanthracene) (14.5 mg, 0.025 mmol, 5 mol%) were added. Then, the sealed tube was purged with nitrogen three times. Subsequently, 2 mL of ultra-dry N,N-dimethylformamide was added. Then, 4-cyanophenyl fluorosulfonate (100.6 mg, 0.5 mmol, 1 equiv.), phenyl formate (122.1 mg, 1 mmol, 2 equiv.), and triethylamine (101.2 mg, 1 mmol, 2 equiv.) were added to the sealed tube. The mixture was stirred at 80 °C for 12 hours.

[0049] (3) Subsequently, extraction was performed using ethyl acetate; the extract was washed with saturated brine, dried over anhydrous sodium sulfate, and then the extract was removed by rotary evaporation. The crude product was purified by silica gel column chromatography. The column chromatography separation conditions were: 200-300 mesh silica gel powder as the stationary phase and petroleum ether / ethyl acetate 200:4-8 as the mobile phase. Finally, 98.2 mg of the target product, phenyl 4-cyanobenzoate, was obtained. The structural formula of this compound is:

[0050]

[0051] The above-mentioned 4-cyanobenzoic acid phenyl esteramine was characterized, such as Figure 3 and 4 As shown, the result is: a white solid; 1H NMR (400MHz, CDCl3): δ8.12–8.06(m,2H),7.62–7.56(m,2H),7.28–7.20(m,2H),7.12–7.06(m,1H),7.03–6.98(m,2H)ppm. 13 C NMR(100MHz, CDCl3): δ163.5,150.4,133.2,132.3,130.5,129.6,126.2,121.3,117.8,116.8ppm.HRMS(m / z):calcd for C 14 H 10 NO2 + [M+H] + 224.0706,found:224.0702.IR(KBr,neat):ν=3320,2233,1740,1483,1268,864,763,688cm -1 .

[0052] Characterization data showed that the obtained reaction product was phenyl 4-cyanobenzoate (purity > 98%); the product yield was calculated to be 88%.

[0053] Example 3

[0054] (1) Place the sealed tube equipped with a magnetic stirrer in an oven to dry for one hour, take it out and while it is still hot, plug it with a rubber stopper and insert a nitrogen balloon;

[0055] (2) After the sealed tube cooled to room temperature, palladium acetate (5.7 mg, 0.25 mmol, 5 mol%) and 4,5-bis(diphenylphosphine-9,9-dimethyloxanthracene) (14.5 mg, 0.025 mmol, 5 mol%) were added. The sealed tube was then evacuated with nitrogen three times. 2 mL of ultra-dry N,N-dimethylformamide was then added. Phenyl fluorosulfonate (88.1 mg, 0.5 mmol, 1 equiv.), phenyl 4-(formyloxy)formate (180.2 mg, 1 mmol, 2 equiv.), and triethylamine (101.2 mg, 1 mmol, 2 equiv.) were then added to the sealed tube. The mixture was stirred at 80 °C for 12 hours.

[0056] (3) Subsequently, extraction was performed using ethyl acetate; the extract was washed with saturated brine, dried over anhydrous sodium sulfate, and then the extract was removed by rotary evaporation. The crude product was purified by silica gel column chromatography under the following conditions: stationary phase was 200-300 mesh silica gel powder, and mobile phase was petroleum ether / ethyl acetate 200:4-8. The final product, 4-(benzoyloxy)benzoate, was obtained in the form of:

[0057]

[0058] The above 4-(benzoyloxy)benzoate esters were characterized, such as Figure 5 and 6 As shown, the result is: a white solid; 1 HNMR (400MHz, CDCl3): δ8.22–8.18(m,2H),8.14–8.10(m,2H),7.67–7.61(m,1H),7.54–7.48(m,2H),7.33–7.28(m,2H),3.92(s,3H)ppm. 13 C NMR(100MHz, CDCl3): δ166.3,164.5,154.5,133.8,131.1,130.2,129.0,128.6,127.7,121.7,52.1ppm.HRMS(m / z):calcd for C 15 H 13 O4 + [M+H] + 257.0808,found:257.0805.IR(KBr,neat):ν=3320,2956,1723,1602,1440,1266,761,698cm -1 .

[0059] Characterization data showed that the obtained reaction product was 4-(benzoyloxy)benzoate (purity > 98%); the product yield was calculated to be 82%.

[0060] Example 4

[0061] Example 4 is basically the same as Example 1, except that the catalyst in step (2) is different, as shown in Table 1 below:

[0062] Table 1

[0063] catalyst Yield (%) none 0 Iron acetylacetonate 0 Cobalt acetylacetonate 0 Manganese acetylacetone 0 Chromium acetylacetonate 0 Nickel acetylacetonate 0 Palladium acetylacetonate 73 Palladium chloride 39 bis(triphenylphosphine)palladium dichloride 28 Tetraphenylphosphine palladium 67 Tris(dibenzylacetone)dipalladium 75 Palladium acetate 75

[0064] As can be seen from Table 1, the reaction cannot proceed without the addition of a catalyst. Under the same reaction conditions, the reaction is almost impossible with different catalysts, such as iron acetylacetone, cobalt acetylacetone, manganese acetylacetone, chromium acetylacetone, and nickel acetylacetone. However, the reaction can be successfully synthesized with palladium acetylacetone, palladium chloride, palladium dichloride of bis(triphenylphosphine), palladium tetra(triphenylphosphine), palladium tri(dibenzylacetone), and palladium acetate as catalysts. Palladium acetate has the best effect and the highest yield of 75%.

[0065] Example 5

[0066] Example 5 is basically the same as Example 1, except that the ligand in step (2) is different, as shown in Table 2 below:

[0067] Table 2

[0068]

[0069]

[0070] As shown in Table 2, under the same reaction conditions, different para-ligands, such as tricyclohexylphosphine, triphenylphosphine, tris(4-fluorophenyl)phosphine, tris(2,4-di-tert-butyl)phosphite, 2-(di-tert-butylphosphine)biphenyl, 1,3-bis(diphenylphosphine)ethane, 1,1'-bis(diphenylphosphine)ferrocene, bis(dicyclohexylphosphine) ether, 4,5-bis(dicyclohexylphosphine)-dibenzopyran derivatives, 2-dicyclohexylphosphine-2',6'-dimethoxy-biphenyl, 2-dicyclohexylphosphine-2',6'-diisopropoxy-1,1'-biphenyl, and 2-dicyclohexylphosphine-2',6'-diisopropoxy-1,1'-biphenyl, etc., show that different para-ligands exhibit varying effects. The reactions for hexylphosphine-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphine-2'-(N,N-dimethylamine)-biphenyl, and 2-bipyridine were almost impossible. However, the reactions for 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,6-bis(diphenylphosphine)hexane, 1,2-bis(diphenylphosphine)benzene, bis(2-diphenylphosphine)ether, and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene were all successfully synthesized, with 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene showing the best results and achieving a maximum yield of 82%. Further experiments revealed that adjusting the amount of ligand added to above 0.05 mmol or below 0.025 mmol was detrimental to the synthesis of the product.

[0071] Example 6

[0072] Example 6 is basically the same as Example 1, except that the alkali used in step (2) is different, as shown in Table 3 below:

[0073] Table 3

[0074] Metal reducing agent Yield (%) none 0 Triethylamine 82 N,N-Diisopropylethylamine 79 4-Dimethylaminopyridine 77 1,8-Diazaheterocyclic[5,4,0]undecene-7 0 Pyridine 0 Sodium tert-butoxide 15 cesium carbonate <5 Potassium carbonate 28 Sodium bicarbonate 54 Sodium hydroxide <5

[0075] As can be seen from Table 2, the reaction cannot proceed without the addition of a metal reducing agent. Under the same reaction conditions, the reaction is almost impossible with different metal reducing agents, such as 1,8-diazacyclo[5,4,0]undecene-7, pyridine, cesium carbonate, and sodium hydroxide. However, the reaction can be successfully synthesized with triethylamine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, sodium tert-butoxide, potassium carbonate, and sodium bicarbonate. Triethylamine showed the best results, with the highest yield of 82%.

[0076] Example 7

[0077] Example 7 is basically the same as Example 1, except that the solvent in step (2) is different, as shown in Table 4 below:

[0078] Table 4

[0079] solvent Yield (%) N,N-Dimethylformamide 82 N,N-Dimethylacetamide 15 N-Methylpyrrolidone 18 N,N-Dimethylpropenylurea 13 Dimethyl sulfoxide 49 Acetonitrile 10 methanol 0 1,4-Dioxane 30 Tetrahydrofuran 80 Toluene 27

[0080] As can be seen from Table 4, under the same reaction conditions, the reaction is almost impossible to proceed with different solvents, such as methanol; however, the reaction can be successfully synthesized with N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylpropenylurea, dimethyl sulfoxide, acetonitrile, 1,4-dioxane, tetrahydrofuran, and toluene. The reaction is most effective when N,N-dimethylformamide is used as the solvent, with the highest yield of 82%.

[0081] Example 8

[0082] Example 8 is basically the same as Example 1, except that in step (2), the aryl fluorosulfonate and aryl carbamate are different, as shown in Table 5 below:

[0083] Table 5

[0084]

[0085]

[0086]

[0087] This invention provides a palladium-catalyzed carbonylation reaction of aryl fluorosulfonates and aryl carbamates to efficiently synthesize esters. The reaction is carried out in a one-pot manner, using transition metal palladium as a catalyst, and under triethylamine as a base, in N,N-dimethylformamide solvent at 80°C for 12 hours, yielding the corresponding esters with good functional group tolerance in moderate to good yields. The preparation method of this invention features simple reaction conditions, convenient post-processing, green procedures, low pollution, and high economic efficiency.

[0088] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A method of esterification of aryl fluorosulfonate with aryl formate, characterized by: The application relates to a preparation method of a compound of formula III. The compound of formula III is prepared by reacting aryl fluorosulfonate of formula I and aryl formate of formula II in a solvent under the action of a catalyst, a ligand and a base. (Formula I); (Formula II); (Formula III); Ar in formula I and formula III is selected from one of phenyl, p-nitro-substituted phenyl, p-cyano-substituted phenyl, p-methylsulfonyl-substituted phenyl, p-trifluoromethoxy-substituted phenyl, p-fluoro-substituted phenyl, p-chloro-substituted phenyl, p-tert-butyl-substituted phenyl, p-phenyl-substituted phenyl, 3,5-dimethyl-substituted phenyl, p-methoxy-substituted phenyl, m-methoxy-substituted phenyl, benzo[d][1,3]dioxol-5-phenyl, 3-(dimethylamino)-substituted phenyl, naphthyl and pyridyl. Ar' in formula II and formula III is selected from one of phenyl, p-formyloxy-substituted phenyl, p-trifluoromethoxy-substituted phenyl, p-trifluoromethyl-substituted phenyl, p-fluoro-substituted phenyl, p-chloro-substituted phenyl, p-bromo-substituted phenyl, p-methyl-substituted phenyl, m-methyl-substituted phenyl, o-methyl-substituted phenyl, p-tert-butyl-substituted phenyl, p-phenyl-substituted phenyl, naphthalene substituent and pyrene substituent. The catalyst is selected from one of acetylacetone palladium, palladium chloride, bis-triphenylphosphine palladium dichloride, tetraphenylphosphine palladium, tris(dibenzylideneacetone) dipalladium and palladium acetate. the ligand is selected from one of 1,3-bis(diphenylphosphino)propane, 1,4- bis(diphenylphosphino)butane, 1,6-bis(diphenylphosphino)hexane, 1,2- bis(diphenylphosphino)benzene, bis(2-diphenylphosphinophenyl)ether, 4,5- bisdiphenylphosphin-9,9-dimethylxanthene; the base is selected from one of triethylamine, N,N - diisopropylethylamine, 4-dimethylaminopyridine, sodium tert-butoxide, potassium carbonate, sodium bicarbonate. The solvent is selected from N,N - dimethylformamide, N,N - dimethylacetamide, N - methylpyrrolidone, N,N - one of dimethylpropylene urea, dimethylsulfoxide, acetonitrile, 1,4-dioxane, tetrahydrofuran, toluene.

2. The esterification process of aryl fluorosulfonate with aryl formate according to claim 1, characterized by: The molar ratio of the aryl fluorosulfonate to the aryl formate is 1:

2.

3. The esterification process of aryl fluorosulfonate with aryl formate according to claim 1 or 2, characterized in that: The molar ratio of the catalyst to the aryl fluorosulfonate is 0.05-0.1:

1.

4. The esterification process of aryl fluorosulfonate with aryl formate according to claim 3, characterized by: The molar ratio of the catalyst to the aryl fluorosulfonate is 0.05:

1.

5. The esterification process of aryl fluorosulfonate with aryl formate according to any one of claims 1, 2, 4, characterized in that: The molar ratio of the ligand to the aryl fluorosulfonate is 0.05-0.1:

1.

6. The esterification process of aryl fluorosulfonate with aryl formate according to claim 5, characterized by: The molar ratio of the ligand to the aryl fluorosulfonate is 0.05:

1.

7. The esterification process of aryl fluorosulfonate with aryl formate according to any one of claims 1, 2, 4, 6, characterized in that: The molar ratio of the base to the aryl fluorosulfonate is 1-2:

1.

8. The esterification process of aryl fluorosulfonate with aryl formate according to claim 7, characterized by: The molar ratio of the base to the aryl fluorosulfonate is 2:

1.

9. The esterification process of aryl fluorosulfonate with aryl formate according to any one of claims 1, 2, 4, 6, 8, characterized in that: The reaction temperature is 50-80 o C.

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