A compound and a method for synthesizing the same

Abstract

The application discloses a compound and a synthesis method thereof. The synthesis method is synthesized from heptafluorobutanol as a raw material through five steps, and synthesis steps comprise the following steps. Step S1: heptafluorobutanol is used as a raw material, and esterification reaction is carried out with benzene sulfonyl chloride to obtain an intermediate 1; step S2: substitution reaction is carried out on the intermediate 1 to obtain an intermediate 2; step S3: substitution reaction is carried out on the intermediate 2 to obtain an intermediate 3; step S4: an inorganic acid is added to the intermediate 3, and NaClO solution is added dropwise to obtain an intermediate 4; and step S5: fluorination reaction is carried out on the intermediate 4 to obtain the compound heptafluorobutanol sulfonyl fluoride. The application provides a synthesis method of a compound, heptafluorobutanol is used as a starting raw material, and heptafluorobutanol sulfonyl fluoride is obtained through five steps, dangerous hydrogen fluoride is avoided, special equipment is not needed, production is safer, and the method is more beneficial to industrial production.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and in particular to a compound and a synthesis method thereof. Background Art

[0002] Perfluoro or polyfluoroalkylsulfonyl fluoride is a perfluorinated compound that is liquid at room temperature. Due to its unique physical and chemical properties, it is widely used in various fields, mainly in the synthesis of fluorocarbon surfactants, fluorine-containing pesticides, dyes, ion exchange resins, etc.

[0003] However, the current mainstream preparation process not only relies on dedicated electrolysis equipment, but also uses a large amount of high-risk hydrogen fluoride, which limits its widespread application in conventional production environments and equipment. Summary of the Invention

[0004] In view of the shortcomings of current preparation methods of perfluorinated compounds, the present invention provides a method for synthesizing a compound, which uses heptafluorobutanol as a starting material and obtains the compound heptafluorobutanolsulfonyl fluoride through a five-step reaction. This method avoids the use of dangerous hydrogen fluoride, does not require special equipment, is safer to produce, and is more conducive to industrial production.

[0005] To achieve the above objectives, the embodiments of the present invention adopt the following technical solutions:

[0006] A compound having the structural formula:

[0007] A method for synthesizing a compound, using heptafluorobutanol as a raw material, is synthesized through a five-step reaction. The synthetic route is as follows:

[0008]

[0009] The synthetic route comprises the following steps:

[0010] Step S1: using heptafluorobutanol as a raw material, reacting with benzenesulfonyl chloride to obtain intermediate 1;

[0011] Step S2: Intermediate 1 undergoes substitution reaction to obtain intermediate 2;

[0012] Step S3: Intermediate 2 undergoes substitution reaction to obtain intermediate 3;

[0013] Step S4: adding inorganic acid to intermediate 3, and dropping NaClO solution to react to obtain intermediate 4;

[0014] Step S5: Intermediate 4 is subjected to fluorination reaction to obtain the compound heptafluorobutanolsulfonyl fluoride.

[0015] According to one aspect of the present application, in step S3, the intermediate 2 and potassium thioacetate are subjected to a substitution reaction in a second solvent, and the molar ratio of the intermediate 2 to potassium thioacetate is 1:1.0-2.0. The second solvent can be selected from DMF, DMSO, DMAC or NMP.

[0016] According to one aspect of the present application, in step S3, the reaction temperature is 45-50°C, and the reaction time is 5-8 hours.

[0017] According to one aspect of the present application, in step S3, after the substitution reaction, water quenching, extraction, water washing and layer separation are further included.

[0018] According to one aspect of the present application, in step S4, the mass ratio of the inorganic acid, NaClO solution and the intermediate 2 is 3.0-8.0:8.0-15.0:1, and the reaction temperature is 0-5°C.

[0019] According to one aspect of the present application, in step S4, the mass ratio of the inorganic acid, NaClO solution and the intermediate 2 is 5.0:10.0:1.

[0020] According to one aspect of the present application, the inorganic acid is one of hydrochloric acid or sulfuric acid.

[0021] According to one aspect of the present application, in step S1, heptafluorobutanol is used as a raw material, mixed with an organic base and a first solvent, and phenylsulfonyl chloride is added dropwise for esterification to obtain the intermediate 1, the molar ratio of heptafluorobutanol, phenylsulfonyl chloride and the organic base is 1:1.0-2.0:1.0-2.0, the reaction time is 3-4 hours, and the first solvent is dichloromethane.

[0022] According to one aspect of the present application, in step S1, the organic base is one or more of triethylamine, pyridine and / or diisopropylamine.

[0023] According to one aspect of the present application, in step S2, the intermediate 1 is subjected to a substitution reaction by mixing with diethylene glycol and sodium bromide, the molar ratio of the intermediate 1 to sodium bromide is 1:1.0-2.0, and the reaction temperature is 180-185°C.

[0024] According to one aspect of the present application, in step S5, the molar ratio of the intermediate 4 to potassium fluoride is 1:1.0-2.0, and preferably 1:1.5. The third solvent can be selected from acetonitrile or acetone.

[0025] According to one aspect of the present application, in step S5, the reaction is stirred at room temperature for 3-5 hours, filtered, 70-80% of the third solvent is concentrated and removed, and high-purity heptafluorobutanol sulfonyl fluoride product is obtained by reduced pressure distillation.

[0026] Advantages of the present invention: The present invention discloses a compound and a synthesis method thereof, using heptafluorobutanol as a starting material and undergoing a five-step reaction to obtain the compound heptafluorobutanolsulfonyl fluoride. The synthesis process avoids the use of highly toxic and hazardous materials, making production operations safer. No special equipment is required, and conventional equipment can be used for production, resulting in simple operation and greater suitability for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0028] Figure 1 A synthetic route diagram of a method for synthesizing heptafluorobutanolsulfonyl fluoride according to the present invention;

[0029] Figure 2 This is the gas chromatogram of the crude product in Example 1 of the present application;

[0030] Figure 3 This is the gas chromatogram of the heptafluorobutanol sulfonyl fluoride product in Example 1 of the present application. DETAILED DESCRIPTION

[0031] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0032] A compound having the structural formula: Heptafluorobutanesulfonyl fluoride is a liquid at room temperature and is mainly used in surfactants, pesticides, dyes, ion exchange resins and electronic cleaning.

[0033] Example 1

[0034] S1: Add 50 g of heptafluorobutanol, 26.8 g of triethylamine and 150 g of dichloromethane to a three-necked flask, stir and mix evenly, cool to 0-10 degrees, and add 46.3 g of benzenesulfonyl chloride dropwise; react for 4 hours after the addition is complete, and detect the completion of the reaction by GC; wash with water three times, separate the layers, and concentrate the organic phase to obtain 87 g of intermediate 1;

[0035] S2: 87g of intermediate 1, 108g of diethylene glycol, and 29g of sodium bromide were added to a three-necked flask, mixed and stirred, and heated to 180-185 degrees. The mixture was distilled while reacting until no more liquid was produced; the liquid was distilled and washed with water; and redistilled to obtain 42.3g of intermediate 2 with a purity of more than 98%;

[0036] S3: 42.3g of intermediate 2 was added to a reaction flask, 42.3g of DMF was added, 29.3g of potassium thioacetate was added, and the reaction was heated for 8 hours; after GC detection, the reaction was quenched with water, extracted with dichloromethane, and washed with water 3 times; the organic phase of intermediate 3 was obtained by separation;

[0037] S4: The organic phase of intermediate 3 was cooled to 0-5°C, 210 g of 50% sulfuric acid was added, and 423 g of NaClO solution was added dropwise; after the addition was complete, the mixture was kept warm for 1 hour; the layers were separated, washed with NaHSO3 solution and ice water; dried over anhydrous sodium sulfate, and concentrated; and distilled under reduced pressure to obtain 25.5 g of intermediate 4;

[0038] S5: 25.5 g of intermediate 4, 7.9 g of potassium fluoride and 125 g of acetonitrile were mixed and stirred at room temperature for 4 hours to obtain a crude product. The reaction was detected by GC. The crude product was filtered and 70-80% of the acetonitrile was concentrated. The product was distilled under reduced pressure to obtain 15 g of heptafluorobutanesulfonyl fluoride with a purity of 98.3% and a total yield of 22.5% for the five steps.

[0039] Example 2

[0040] S1: Add 128 g of heptafluorobutanol, 68.6 g of triethylamine and 384 g of dichloromethane to a three-necked flask, stir and mix evenly, cool to 0-10 degrees, and add 118.5 g of benzenesulfonyl chloride dropwise; react for 3 hours after the addition is complete, and detect the completion of the reaction by GC; wash with water three times, separate the layers, and concentrate the organic phase to obtain 221 g of intermediate 1;

[0041] S2: Add 221g of intermediate 1, 276g of diethylene glycol, and 73.7g of sodium bromide into a three-necked flask, mix and stir, heat to 180-185 degrees, and distill while reacting until no more liquid is produced; distill the liquid and wash it with water; redistill to obtain 105g of intermediate 2 with a purity of more than 98%;

[0042] S3: 105g of intermediate 2 was added to a reaction flask, 105g of DMF was added, 72.8g of potassium thioacetate was added, and the reaction was heated for 5 hours; GC was performed to detect the reaction, water was added to quench, dichloromethane was extracted, and the mixture was washed with water 3 times; the organic phase of intermediate 3 was obtained and used for separation.

[0043] S4: The intermediate 3 organic phase was cooled to 0-5°C, 50% sulfuric acid 525g was added, and NaClO solution 1050g was added dropwise; after the dropwise addition was complete, the reaction was incubated for 1 hour; the layers were separated, washed with NaHSO3 solution, and washed with ice water; dried over anhydrous sodium sulfate, concentrated; distilled under reduced pressure to obtain 64.0g of intermediate 4;

[0044] S5: 64.0g of intermediate 4, 26.3g of potassium fluoride, and 320g of acetonitrile were mixed, and the reaction was stirred at room temperature for 5 hours; after the reaction was complete, it was detected by GC, filtered, 70-80% of the acetonitrile was concentrated off, and the product, 42g of heptafluorobutylsulfonyl fluoride, was obtained by distillation under reduced pressure, with a purity of 98%, and a total yield of 24.7% over five steps.

[0045] Example 3

[0046] S1: In a three-necked flask, heptafluorobutanol 128g, triethylamine 129.4g, and dichloromethane 384g were added, stirred and mixed uniformly, cooled to 0-10 degrees, and benzene sulfonyl chloride 209g was added dropwise; after the dropwise addition was complete, the reaction was allowed to proceed for 3 hours, and after the reaction was complete, it was detected by GC; water was added and washed 3 times, and the organic phase was concentrated to obtain 235g of intermediate 1;

[0047] S2: In a three-necked flask, 235g of intermediate 1 and diethylene glycol 353g, sodium bromide 142.1g were added, mixed and stirred, heated to 180-185 degrees, and distilled until no more liquid distilled off; the distilled liquid was washed with water; and distilled again to obtain 108g of intermediate 2 with a purity of more than 98%;

[0048] S3: In a reaction flask, 108g of intermediate 2 was added, followed by the addition of DMF 108g, and 93.8g of potassium thioacetate; the reaction was heated for 5 hours; after the reaction was complete, it was detected by GC, quenched with water, extracted with dichloromethane, and washed with water 3 times; the layers were separated, and the organic phase of intermediate 3 was obtained for use;

[0049] S4: The intermediate 3 organic phase was cooled to 0-5°C, 50% sulfuric acid 525g was added, and NaClO solution 1050g was added dropwise; after the dropwise addition was complete, the reaction was incubated for 1 hour; the layers were separated, washed with NaHSO3 solution, and washed with ice water; dried over anhydrous sodium sulfate, concentrated; distilled under reduced pressure to obtain 64.0g of intermediate 4;

[0050] S5: 64.0g of intermediate 4, 26.3g of potassium fluoride, and 320g of acetonitrile were mixed, and the reaction was stirred at room temperature for 5 hours; after the reaction was complete, it was detected by GC, filtered, 70-80% of the acetonitrile was concentrated off, and the product, 42g of heptafluorobutylsulfonyl fluoride, was obtained by distillation under reduced pressure, with a purity of 98%, and a total yield of 24.7% over five steps.

[0051] Comparative Example 1

[0052] S1: Add 50 g of heptafluorobutanol, 26.8 g of triethylamine and 150 g of dichloromethane to a three-necked flask, stir and mix evenly, cool to 0-10 degrees, and add 46.3 g of benzenesulfonyl chloride dropwise; react for 4 hours after the addition is complete, and detect the completion of the reaction by GC; wash with water three times, separate the layers, and concentrate the organic phase to obtain 87 g of intermediate 1;

[0053] S2: 87g of intermediate 1, 108g of diethylene glycol, and 29g of sodium bromide were added to a three-necked flask, mixed and stirred, and heated to 180-185 degrees. The mixture was distilled while reacting until no more liquid was produced; the liquid was distilled and washed with water; and redistilled to obtain 42.3g of intermediate 2 with a purity of more than 98%;

[0054] S3: 42.3g of intermediate 2 was added to a reaction flask, 108g of DMF was added, 93.8g of potassium thioacetate was added, and the reaction was carried out at room temperature for 8 hours; water was added to quench, dichloromethane was extracted, and the mixture was washed with water 3 times; the organic phase of intermediate 3 was obtained for standby use;

[0055] S4: The organic phase of intermediate 3 was cooled to 0-5°C, 210 g of 50% sulfuric acid was added, and 423 g of NaClO solution was added dropwise; after the addition was complete, the mixture was kept warm for 1 hour; the layers were separated, washed with NaHSO3 solution and ice water; dried over anhydrous sodium sulfate, and concentrated; and distilled under reduced pressure to obtain 21.5 g of intermediate 4;

[0056] S5: 21.5 g of intermediate 4, 6.7 g of potassium fluoride and 105 g of acetonitrile were mixed and stirred at room temperature for 4 hours. The reaction was detected by GC. The mixture was filtered and 70-80% of the acetonitrile was concentrated. The mixture was distilled under reduced pressure to obtain 12.1 g of heptafluorobutanesulfonyl fluoride. The total yield of the five steps was 18.2%.

[0057] Comparative Example 2

[0058] S1: Add 50 g of heptafluorobutanol, 26.8 g of triethylamine and 150 g of dichloromethane to a three-necked flask, stir and mix evenly, cool to 0-10 degrees, and add 46.3 g of benzenesulfonyl chloride dropwise; react for 4 hours after the addition is complete, and detect the completion of the reaction by GC; wash with water three times, separate the layers, and concentrate the organic phase to obtain 87 g of intermediate 1;

[0059] S2: 87g of intermediate 1, 108g of diethylene glycol, and 29g of sodium bromide were added to a three-necked flask, mixed and stirred, and heated to 180-185 degrees. The mixture was distilled while reacting until no more liquid was produced; the liquid was distilled and washed with water; and redistilled to obtain 42.3g of intermediate 2 with a purity of more than 98%;

[0060] S3: 42.3g of intermediate 2 was added to a reaction flask, 42.3g of DMF was added, 29.3g of potassium thioacetate was added, and the reaction was heated for 8 hours; after GC detection, the reaction was quenched with water, extracted with dichloromethane, and washed with water 3 times; the organic phase of intermediate 3 was obtained by separation;

[0061] S4: The organic phase of intermediate 3 was cooled to 10-15°C, 210 g of 50% sulfuric acid was added, and 423 g of NaClO solution was added dropwise; after the addition was complete, the mixture was kept warm for 1 hour; the layers were separated, washed with NaHSO3 solution and ice water; dried over anhydrous sodium sulfate, and concentrated; and distilled under reduced pressure to obtain 15.2 g of intermediate 4;

[0062] S5: 15.2 g of intermediate 4, 4.7 g of potassium fluoride and 75 g of acetonitrile were mixed and stirred at room temperature for 4 hours. The reaction was detected by GC. The mixture was filtered and 70-80% of the acetonitrile was concentrated. The mixture was subjected to vacuum distillation to obtain 8.5 g of heptafluorobutanesulfonyl fluoride. The total yield of the five steps was 12.8%.

[0063] Test Example 1

[0064] The crude product and heptafluorobutanesulfonyl fluoride product obtained in S5 of Example 1 were subjected to GC detection. The detection conditions of GC detection were as follows: instrument: Shimadzu GC 2030+HS-10; capillary column: HP-5 (30m X 0.32mm X 0.25μm); injection port temperature: 280°C; injection port split ratio: 50:1; carrier gas flow rate: nitrogen 0.5mL / min constant flow rate; detector temperature: 310°C; FID injection volume: 1μl direct injection; air flow rate: 400mL / min; hydrogen gas flow rate: 64mL / min; tail gas flow rate (N2): 24mL / min; program temperature rise: 35°C for 4 minutes, 10°C / min heating, heating to 310°C for 5 minutes; retention time 7.51min for the product heptafluorobutanesulfonyl fluoride, 5.9min for the acetonitrile peak. The gas chromatograms of the crude product and heptafluorobutanesulfonyl fluoride product were obtained as shown below. Figure 2 and Figure 3 shown.

[0065] An analysis of the synthesis methods of heptafluorobutanolsulfonyl fluoride in Examples 1-3 and Comparative Examples 1-2 of the present application reveals that in Examples 1-3, the total yield of heptafluorobutanolsulfonyl fluoride reached 22.5-24.7%, while in Comparative Examples 1-2, the total yield of heptafluorobutanolsulfonyl fluoride was 12.8-18.2%. This indicates that the five-step reaction method, using heptafluorobutanol as the starting material, yields heptafluorobutanolsulfonyl fluoride. The operation is simple, and the reaction conditions in each step significantly influence the yield of the target product.

[0066] Advantages of the present invention: The present invention discloses a compound and a synthesis method thereof, using heptafluorobutanol as a starting material and undergoing a five-step reaction to obtain the compound heptafluorobutanolsulfonyl fluoride. The synthesis process avoids the use of highly toxic and hazardous materials, making production operations safer. No special equipment is required, and conventional equipment can be used for production, resulting in simple operation and greater suitability for industrial production.

[0067] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A method for synthesizing a compound, characterized in that: Heptafluorobutanol is used as raw material and synthesized through five steps. The synthesis route is as follows: The synthetic route comprises the following steps: Step S1: using heptafluorobutanol as a raw material, reacting with benzenesulfonyl chloride to obtain intermediate 1; Step S2: Intermediate 1 undergoes substitution reaction to obtain intermediate 2; Step S3: Substitution reaction of the intermediate 2 with potassium thioacetate in a second solvent, wherein the molar ratio of the intermediate 2 to potassium thioacetate is 1:1.0-2.0, to obtain the intermediate 3; Step S4: adding inorganic acid to intermediate 3, and adding NaClO solution dropwise to react to obtain intermediate 4, wherein the mass ratio of inorganic acid, NaClO solution and intermediate 2 is 3.0-8.0:8.0-15.0:1, and the reaction temperature is 0-5°C; Step S5: Intermediate 4 is subjected to fluorination reaction to obtain the compound heptafluorobutanolsulfonyl fluoride.

2. The method for synthesizing a compound according to claim 1, wherein: In step S3, the reaction temperature is 45-50° C., and the reaction time is 5-8 hours.

3. The method for synthesizing a compound according to claim 2, characterized in that: After the substitution reaction in step S3, the steps further include quenching with water, extraction, washing with water, and layering.

4. The method for synthesizing a compound according to claim 1, wherein: In step S1, heptafluorobutanol is used as a raw material, mixed with an organic base and a first solvent, and benzenesulfonyl chloride is added dropwise for esterification reaction to obtain intermediate 1. The molar ratio of heptafluorobutanol, benzenesulfonyl chloride and organic base is 1:1.0-2.0:1.0-2.0, and the reaction time is 3-4 hours.

5. The method for synthesizing a compound according to claim 4, characterized in that: The first solvent is dichloromethane, and the organic base is one or more of triethylamine, pyridine or diisopropylamine.

6. The method for synthesizing a compound according to claim 1, wherein: In step S2, the intermediate 1 is mixed with diethylene glycol and sodium bromide to perform a substitution reaction, the molar ratio of the intermediate 1 to the sodium bromide is 1:1.0-2.0, and the reaction temperature is 180-185°C.

7. The method for synthesizing a compound according to claim 1, characterized in that: In step S5, the molar ratio of intermediate 4 to potassium fluoride is 1:1.0-2.0, and the solvent used is acetonitrile or acetone.

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