Compound and synthesis method thereof

Abstract

The invention discloses a compound and a synthesis method thereof, the synthesis method of the compound takes heptafluorobutanol as a raw material, and the compound is synthesized through five-step reaction, and the synthesis method comprises the following synthesis steps: S1, taking heptafluorobutanol as the raw material, and carrying out esterification reaction with benzene sulfonyl chloride to obtain an intermediate 1; s2, carrying out substitution reaction on the intermediate 1 to obtain an intermediate 2; s3, carrying out substitution reaction on the intermediate 2 to obtain an intermediate 3; s4, adding inorganic acid into the intermediate 3, dropwise adding a NaClO solution, and reacting to obtain an intermediate 4; and S5, carrying out fluorination reaction on the intermediate 4 to obtain the compound heptafluorobutanol sulfonyl fluoride. According to the synthesis method of the compound, heptafluorobutanol is used as a starting raw material, heptafluorobutanol sulfonyl fluoride is obtained through five-step reaction, use of a dangerous material hydrogen fluoride is avoided, special equipment is not needed, production is safer, and industrial production is more facilitated.

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 the 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 heptafluorobutanol sulfonyl fluoride through a five-step reaction, thereby avoiding the use of dangerous hydrogen fluoride, not requiring special equipment, making production safer, and more conducive to industrial production.

[0005] To achieve the above object, 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 five steps, and the synthesis route is as follows:

[0008]

[0009] The synthetic route comprises the following steps:

[0010] Step S1: using heptafluorobutanol as a raw material, and reacting it 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 compound heptafluorobutanolsulfonyl fluoride.

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

[0016] According to one aspect of the present invention, 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 invention, the substitution reaction in step S3 further includes quenching with water, extraction, washing with water, and stratification.

[0018] According to one aspect of the present invention, in step S4, the mass ratio of the inorganic acid, the 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 invention, in step S4, the mass ratio of the inorganic acid, the NaClO solution and the intermediate 2 is 5.0:10.0:1.

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

[0021] According to one aspect of the present invention, 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, the reaction time is 3-4 hours, and the first solvent is dichloromethane.

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

[0023] According to one aspect of the present invention, in step S2, intermediate 1 is mixed with diethylene glycol and sodium bromide for substitution reaction, the molar ratio of 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 invention, the molar ratio of the intermediate 4 to potassium fluoride in step S5 is 1:1.0-2.0, preferably 1:1.5. The third solvent can be acetonitrile or acetone.

[0025] According to one aspect of the present invention, in step S5, the reaction is stirred at room temperature for 3-5 hours, filtered, 70-80% of the third solvent is concentrated, and vacuum distillation is performed to obtain a high-purity heptafluorobutanol sulfonyl fluoride product.

[0026] Advantages of the present invention: The present invention discloses a compound and a synthesis method thereof, wherein heptafluorobutanol is used as a starting material, and a compound heptafluorobutanol sulfonyl fluoride is obtained through a five-step reaction. The use of highly toxic and dangerous goods is avoided during the synthesis process, making the production operation safer, and no special equipment is required. Conventional equipment can be used for production, and the operation is simple and convenient, which is more conducive to 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 drawings required for use in the embodiments will be briefly introduced below. 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 creative work.

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

[0029] Figure 2 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 be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. 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 creative work are within the scope of protection of the present invention.

[0032] A compound having the structural formula: The name is heptafluorobutylsulfonyl fluoride. The heptafluorobutylsulfonyl fluoride is liquid at room temperature and is mainly used in the fields of 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 into a three-necked flask, stir and mix evenly, cool to 0-10 degrees, and drop 46.3 g of benzenesulfonyl chloride; react for 4 hours after the addition is complete, and detect the completion of the reaction by GC; wash with water 3 times, separate the layers, and concentrate the organic phase to obtain 87 g of intermediate 1;

[0035] S2: Add 87g of intermediate 1, 108g of diethylene glycol and 29g 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 out the liquid and wash with water; redistill to obtain 42.3g of intermediate 2 with a purity of more than 98%;

[0036] S3: 42.3 g of intermediate 2 was added to a reaction bottle, added to 42.3 g of DMF, added 29.3 g of potassium thioacetate, and heated to react for 8 hours; after GC detection, the reaction was completed, 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 by separation, and then used for standby;

[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 completed, the mixture was kept warm for 1 hour; the layers were separated, washed with NaHSO3 solution, washed with ice water; dried over anhydrous sodium sulfate, 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, stirred at room temperature for 4 hours to obtain a crude product, and the reaction was detected by GC. After the reaction was completed, the product was filtered and 70-80% of the acetonitrile was concentrated. The product was subjected to vacuum distillation to obtain 15 g of heptafluorobutylsulfonyl fluoride with a purity of 98.3% and a total yield of 22.5% in five steps.

[0039] Example 2

[0040] S1: Add 128g of heptafluorobutanol, 68.6g of triethylamine and 384g of dichloromethane into a three-necked flask, stir and mix evenly, cool to 0-10 degrees, and drop 118.5g of benzenesulfonyl chloride; react for 3 hours after the addition is complete, and detect the completion of the reaction by GC; wash with water 3 times, separate the layers, and concentrate the organic phase to obtain 221g 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 out the liquid and wash with water; redistill to obtain 105g of intermediate 2 with a purity of more than 98%;

[0042] S3: Add 105g of intermediate 2 to a reaction bottle, add 105g of DMF, add 72.8g of potassium thioacetate, and heat to react for 5 hours; after GC detection, add water to quench, extract with dichloromethane, and wash with water 3 times; separate the layers to obtain the organic phase of intermediate 3 for standby use

[0043] S4: The organic phase of intermediate 3 was cooled to 0-5°C, 525 g of 50% sulfuric acid was added, and 1050 g of NaClO solution was added dropwise; after the addition was completed, the mixture was kept warm for 1 hour; the layers were separated, washed with NaHSO3 solution, washed with ice water; dried over anhydrous sodium sulfate, concentrated; and distilled under reduced pressure to obtain 63.2 g of intermediate 4;

[0044] S5: 63.2 g of intermediate 4, 19.5 g of potassium fluoride and 316 g of acetonitrile were mixed, stirred at room temperature for 5 hours, and the reaction was completed by GC detection. The mixture was filtered, 70-80% of the acetonitrile was concentrated, and vacuum distillation was performed to obtain 41.5 g of heptafluorobutanesulfonyl fluoride product with a purity of 98.3% and a total yield of 24.4% in five steps.

[0045] Example 3

[0046] S1: Add 128g of heptafluorobutanol, 129.4g of triethylamine and 384g of dichloromethane into a three-necked flask, stir and mix evenly, cool to 0-10 degrees, and drop 209g of benzenesulfonyl chloride; react for 3 hours after the addition is complete, and detect the completion of the reaction by GC; wash with water 3 times, separate the layers, and concentrate the organic phase to obtain 235g of intermediate 1;

[0047] S2: Add 235g of intermediate 1, 353g of diethylene glycol and 142.1g 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 out the liquid and wash with water; redistill to obtain 108g of intermediate 2 with a purity of more than 98%;

[0048] S3: 108g of intermediate 2 was added to a reaction bottle, added to 108g of DMF, added 93.8g of potassium thioacetate, and heated to react for 5 hours; GC detection was completed, water was added to quench, dichloromethane was extracted, and water was washed 3 times; layering was performed to obtain the organic phase of intermediate 3 for standby use;

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

[0050] S5: 64.0 g of intermediate 4, 26.3 g of potassium fluoride and 320 g of acetonitrile were mixed, stirred at room temperature for 5 hours, and the reaction was completed by GC detection. The mixture was filtered, 70-80% of the acetonitrile was concentrated, and vacuum distillation was performed to obtain 42 g of heptafluorobutanesulfonyl fluoride product with a purity of 98% and a total yield of 24.7% in five steps.

[0051] Comparative Example 1

[0052] S1: Add 50 g of heptafluorobutanol, 26.8 g of triethylamine and 150 g of dichloromethane into a three-necked flask, stir and mix evenly, cool to 0-10 degrees, and drop 46.3 g of benzenesulfonyl chloride; react for 4 hours after the addition is complete, and detect the completion of the reaction by GC; wash with water 3 times, separate the layers, and concentrate the organic phase to obtain 87 g of intermediate 1;

[0053] S2: Add 87g of intermediate 1, 108g of diethylene glycol and 29g 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 out the liquid and wash with water; redistill to obtain 42.3g of intermediate 2 with a purity of more than 98%;

[0054] S3: Add 42.3g of intermediate 2 to a reaction bottle, add 108g of DMF, add 93.8g of potassium thioacetate, and react at room temperature for 8 hours; quench with water, extract with dichloromethane, and wash with water 3 times; separate the layers to obtain the organic phase of intermediate 3 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 completed, the mixture was kept warm for 1 hour; the layers were separated, washed with NaHSO3 solution, washed with ice water; dried over anhydrous sodium sulfate, 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, stirred at room temperature for 4 hours, and the reaction was completed by GC detection. The mixture was filtered, 70-80% of the acetonitrile was concentrated, and vacuum distillation was performed to obtain 12.1 g of heptafluorobutylsulfonyl fluoride product. 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 into a three-necked flask, stir and mix evenly, cool to 0-10 degrees, and drop 46.3 g of benzenesulfonyl chloride; react for 4 hours after the addition is complete, and detect the completion of the reaction by GC; wash with water 3 times, separate the layers, and concentrate the organic phase to obtain 87 g of intermediate 1;

[0059] S2: Add 87g of intermediate 1, 108g of diethylene glycol and 29g 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 out the liquid and wash with water; redistill to obtain 42.3g of intermediate 2 with a purity of more than 98%;

[0060] S3: 42.3 g of intermediate 2 was added to a reaction bottle, added to 42.3 g of DMF, added 29.3 g of potassium thioacetate, and heated to react for 8 hours; after GC detection, the reaction was completed, 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 by separation, and then used for standby;

[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 completed, the mixture was kept warm for 1 hour; the layers were separated, washed with NaHSO3 solution, washed with ice water; dried over anhydrous sodium sulfate, 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, stirred at room temperature for 4 hours, and the reaction was completed by GC detection. The mixture was filtered, 70-80% of the acetonitrile was concentrated, and 8.5 g of heptafluorobutylsulfonyl fluoride product was obtained by vacuum distillation. The total yield of the five steps was 12.8%.

[0063] Test Example 1

[0064] The crude product and heptafluorobutylsulfonyl 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 fuel 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 heptafluorobutylsulfonyl fluoride, 5.9min for the acetonitrile peak. The gas chromatograms of the crude product and heptafluorobutylsulfonyl fluoride product were obtained as follows: Figure 2 and Figure 3 shown.

[0065] By analyzing the synthesis methods of heptafluorobutanol sulfonyl fluoride in Examples 1-3 and Comparative Examples 1-2 of the present application, it can be seen that in Examples 1-3, the total yield of heptafluorobutanol sulfonyl fluoride reaches 22.5-24.7%, while in Comparative Examples 1-2, the total yield of heptafluorobutanol sulfonyl fluoride is 12.8-18.2%. It can be seen that the compound heptafluorobutanol sulfonyl fluoride is obtained by five steps of reaction using heptafluorobutanol as a raw material, which is simple to operate, and the reaction conditions of each step have a significant effect on the yield of the target product.

[0066] Advantages of the present invention: The present invention discloses a compound and a synthesis method thereof, wherein heptafluorobutanol is used as a starting material and a compound heptafluorobutanol sulfonyl fluoride is obtained through a five-step reaction. The use of highly toxic and dangerous goods is avoided during the synthesis process, making the production operation safer, and no special equipment is required. Conventional equipment can be used for production, and the operation is simple and convenient, which is more conducive to industrial production.

[0067] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with the art within the technical scope disclosed in the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention shall be based on the protection scope of the claims.

Claims

1. A compound, characterized in that Its structural formula is:

2. A method for synthesizing a compound, characterized in that: Heptafluorobutanol is used as the 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, and reacting it with benzenesulfonyl chloride to obtain intermediate 1; Step S2: intermediate 1 undergoes substitution reaction to obtain intermediate 2; Step S3: intermediate 2 undergoes substitution reaction to obtain intermediate 3; Step S4: adding inorganic acid to intermediate 3, and dropping NaClO solution to react to obtain intermediate 4; Step S5: Intermediate 4 is subjected to fluorination reaction to obtain compound heptafluorobutanolsulfonyl fluoride.

3. The method for synthesizing a compound according to claim 2, characterized in that: In the step S3, the intermediate 2 and potassium thioacetate undergo a substitution reaction in the second solvent, and the molar ratio of the intermediate 2 to potassium thioacetate is 1:1.0-2.

0.

4. The method for synthesizing a compound according to claim 3, characterized in that: In step S3, the reaction temperature is 45-50° C. and the reaction time is 5-8 hours.

5. The method for synthesizing a compound according to claim 4, characterized in that: After the substitution reaction in step S3, the steps further include quenching with water, extraction, washing with water, and stratification.

6. The method for synthesizing a compound according to claim 2, characterized in that: In the step S4, the mass ratio of the inorganic acid, the NaClO solution and the intermediate 2 is 3.0-8.0:8.0-15.0:1, and the reaction temperature is 0-5°C.

7. The method for synthesizing a compound according to claim 2, characterized in that: In the 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 an 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.

8. The method for synthesizing a compound according to claim 7, characterized in that: The first solvent is dichloromethane, and the organic base is one or more of triethylamine, pyridine and / or diisopropylamine.

9. The method for synthesizing a compound according to claim 2, characterized in that: In the step S2, the intermediate 1 is mixed with diethylene glycol and sodium bromide to carry out 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.

10. The method for synthesizing a compound according to claim 2, characterized in that: In the step S5, the molar ratio of the intermediate 4 to potassium fluoride is 1:1.0-2.0, and the third solvent is acetonitrile or acetone.

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