Preparation method of bicyclic sultone

Abstract

The invention relates to a preparation method of bicyclic sultone. The preparation method comprises the following steps: (1) reacting a halogenated alkane diol compound with sulfite, and acidifying to obtain a dihydroxy alkyl disulfonic acid compound; and (2) carrying out cyclization reaction on the dihydroxy alkyl disulfonic acid compound obtained in the step (1) to obtain the bicyclic sultone. The preparation method of the bicyclic sultone is simple and convenient to operate, high in yield, high in purity and suitable for large-scale production.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and particularly relates to a preparation method of a bicyclic sulfonic acid lactone. Background Art

[0002] The application of cyclic sulfonic acid lactones in electrolytes has received extensive attention in recent years, especially in the research of lithium-ion batteries and other types of batteries. Due to its unique chemical structure and good electrochemical properties, it has become one of the ideal electrolyte components. The specific structure of cyclic sulfonic acid lactones not only endows it with high polarity but also enables it to effectively dissolve the active substances and electrolytes in the battery. At the same time, its excellent thermal stability and chemical stability enable it to remain stable under high-temperature and high-voltage conditions, well meeting the strict requirements for the use of electrolytes in batteries.

[0003] Most traditional lithium-ion battery electrolytes are mainly based on carbonate solvents, which are prone to decomposition under high-temperature and high-voltage environments, resulting in a decline in battery performance. While cyclic sulfonic acid lactones exhibit better thermal stability and chemical stability under these conditions, can effectively inhibit the occurrence of side reactions, and prolong the service life of the battery. In addition, the high dielectric constant property of cyclic sulfonic acid lactones also helps to improve the ionic conductivity of the electrolyte.

[0004] Therefore, it is of great significance to design and provide a preparation method of a bicyclic sulfonic acid lactone with a simple production process, excellent yield and purity. Summary of the Invention

[0005] To solve the above technical problems, the present invention provides a preparation method of a bicyclic sulfonic acid lactone. The preparation method of the bicyclic sulfonic acid lactone is simple to operate, has a high yield and high purity, and is suitable for large-scale production.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a preparation method of a bicyclic sulfonic acid lactone, and the preparation method includes the following steps:

[0008] (1) React a haloalkylene glycol compound with a sulfite, and after acidification, obtain a dihydroxyalkyl disulfonic acid compound;

[0009] (2) Cyclize the dihydroxyalkyl disulfonic acid compound obtained in step (1) to obtain the bicyclic sulfonic acid lactone.

[0010] In the present invention, a haloalkanediol compound and a sulfite are first used as starting materials for a substitution reaction. After acidification, a bicyclic sultone compound with a stable structure having two cyclic sulfonic acid lactones is prepared through a cyclization reaction. The preparation method has simple operation, and the synthesis reaction has the advantages of high yield and high purity, and is suitable for large-scale production.

[0011] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved.

[0012] As a preferred technical solution of the present invention, the haloalkanediol compound in step (1) includes 1,4-dibromo-2,3-butanediol and / or 1,4-dichloro-2,3-butanediol.

[0013] The haloalkanediol compound of the present invention is preferably 1,4-dibromo-2,3-butanediol, which has a wide source and is economically available; at the same time, the bicyclic sultone structure prepared therefrom is stable and has excellent yield and purity.

[0014] As a preferred technical solution of the present invention, the sulfite in step (1) includes sodium sulfite and / or potassium sulfite, and is further preferably sodium sulfite, which is easily obtained and has low cost.

[0015] As a preferred technical solution of the present invention, the molar ratio of the haloalkanediol compound to the sulfite is 1:(2.0 - 2.5), where (2.0 - 2.5) can be, for example, 2.0, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45 or 2.5, and the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. It is further preferably 1:(2.1 - 2.3).

[0016] Preferably, the reaction in step (1) is carried out in a solvent.

[0017] Preferably, the solvent includes water.

[0018] As a preferred technical solution of the present invention, the temperature of the reaction in step (1) is 75 - 100 °C, which can be, for example, 75 °C, 78 °C, 80 °C, 82 °C, 85 °C, 88 °C, 90 °C, 92 °C, 95 °C, 98 °C or 100 °C, and the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. It is further preferably 85 - 90 °C.

[0019] Preferably, the reaction time in step (1) is 6 - 12 h, for example, it can be 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h, 10 h, 10.5 h, 11 h, 11.5 h or 12 h, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is 8 - 10 h.

[0020] As a preferred technical solution of the present invention, the acidification method in step (1) includes treating with hydrochloric acid.

[0021] Preferably, the mass fraction of HCl in the hydrochloric acid is 20 - 38%, for example, it can be 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36% or 38%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0022] Preferably, the molar ratio of the haloalkylene glycol compound to hydrochloric acid is 1:(2.0 - 2.5), where (2.0 - 2.5) can be, for example, 2.0, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45 or 2.5, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is 1:(2.1 - 2.2).

[0023] Preferably, before the acidification in step (1), there is also a cooling step.

[0024] Preferably, the cooling method includes cooling to 40 - 70 °C, for example, it can be 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C or 70 °C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is 60 - 65 °C.

[0025] Preferably, after the acidification in step (1), there is also a post-treatment step.

[0026] Preferably, the post-treatment method includes extraction and separation.

[0027] Preferably, the extractant used for extraction includes any one or a combination of at least two of n-butanol, isoamyl alcohol, ethyl acetate or cyclohexanone. Further preferably, it is n-butanol.

[0028] In the present invention, the extractant is preferably n-butanol, which has better extraction effect, requires fewer extraction times in actual experimental operations, is beneficial to reducing the usage amount of the extractant, not only reduces environmental pollution, but also can improve production efficiency and reduce production costs.

[0029] It should be noted that in the present invention, the number of extraction times is not specifically limited, and any conventional number of extraction times in the art can be used. For example, it can be 3 - 7 times, specifically 3 times, 4 times, 5 times, 6 times or 7 times.

[0030] Preferably, the separation method includes filtration and vacuum concentration.

[0031] Preferably, the cyclization reaction in step (2) is carried out in an aprotic organic solvent.

[0032] Preferably, the aprotic organic solvent includes any one or a combination of at least two of dichloroethane, toluene, xylene, carbon tetrachloride or dimethyl sulfoxide, and is further preferably dichloroethane.

[0033] Preferably, the mass ratio of the aprotic organic solvent to the halogenated alkanediol compound in step (1) is (3 - 10):1, where (3 - 10) can be, for example, 3, 4, 5, 6, 7, 8, 9 or 10, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range, and is further preferably (5 - 8):1.

[0034] As a preferred technical solution of the present invention, the cyclization reaction in step (2) is carried out under a catalyst.

[0035] Preferably, the catalyst includes concentrated sulfuric acid and / or p-toluenesulfonic acid, and is further preferably p-toluenesulfonic acid.

[0036] The catalyst of the present invention is preferably p-toluenesulfonic acid, and its catalytic reaction rate is significantly higher than that of concentrated sulfuric acid, which not only improves safety, but also improves production efficiency and has stronger practicability.

[0037] Preferably, the molar ratio of the catalyst to the halogenated alkanediol compound in step (1) is (0.05 - 0.2):1, where (0.05 - 0.2) can be, for example, 0.05, 0.06, 0.08, 0.09, 0.1, 0.12, 0.14, 0.16, 0.18 or 0.2, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range, and is further preferably (0.08 - 0.12):1.

[0038] By optimizing the molar ratio of the catalyst to the haloalkanediol compound described in step (1) within a suitable range, the present invention is conducive to improving the purity and preparation rate of the obtained product. When the content of the catalyst is too low, the reaction rate is slow; when the content of the catalyst is too high, the reaction rate no longer increases, which not only increases the economic cost but also easily generates side reactions, thereby reducing the purity of the obtained product.

[0039] As a preferred technical solution of the present invention, the temperature of the cyclization reaction described in step (2) is 70 - 100 °C, for example, it can be 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C or 100 °C, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range, and it is preferably 75 - 85 °C.

[0040] Preferably, the time of the cyclization reaction described in step (2) is 4 - 8 h, for example, it can be 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h or 8 h, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range, and it is further preferably 5 - 6 h.

[0041] Preferably, after the cyclization reaction described in step (2), there is also a post-treatment step.

[0042] Preferably, the post-treatment method includes cooling, filtration, water washing and drying.

[0043] Preferably, the cooling is to cool down to 20 - 30 °C, for example, it can be 20 °C, 21 °C, 22 °C, 23 °C, 24 °C, 25 °C, 26 °C, 27 °C, 28 °C, 29 °C or 30 °C, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0044] Preferably, the drying method includes vacuum drying.

[0045] It should be noted that in the present invention, vacuum drying is carried out until the weight of the target product no longer changes, and the specific drying temperature is not limited. Conventional temperature settings in the art can be used, for example, it can be 50 - 70 °C, specifically it can be 50 °C, 52 °C, 54 °C, 56 °C, 58 °C, 60 °C, 62 °C, 64 °C, 66 °C, 68 °C or 70 °C, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0046] Preferably, the preparation method specifically includes the following steps:

[0047] Mix a halogenated alkanediol compound, a sulfite, and water, heat the mixture to 75 - 100 °C, keep the temperature for 6 - 12 h, then stop heating, cool down to 40 - 70 °C, add hydrochloric acid for acidification, and then separate to obtain a dihydroxyalkyl disulfonic acid compound after extraction with an extractant; dissolve the dihydroxyalkyl disulfonic acid compound in an aprotic organic solvent, add a catalyst concentrated sulfuric acid and / or p-toluenesulfonic acid, heat the mixture to 70 - 100 °C, keep the temperature for 4 - 8 h, then cool down to 20 - 30 °C, and obtain the bicyclic sultone after filtration, washing with water, and drying.

[0048] In the present invention, a halogenated alkanediol compound and a sulfite are used as starting materials. Through the selection and ratio of specific raw materials, and the setting of parameters such as reaction temperature and time, the involved reactions are precisely regulated to prepare a bicyclic sultone compound with high purity, high yield, and stable and definite structure.

[0049] The chemical reaction principle involved in the preparation process of the bicyclic sultone of the present invention is as follows:

[0050]

[0051] X is selected from halogens.

[0052] Exemplarily, using 1,4-dibromo-2,3-butanediol and sodium sulfite as starting materials, the synthesis route of the obtained bicyclic sultone is as follows:

[0053]

[0054] The bicyclic sultone prepared by the preparation method provided by the present invention has two cyclic sultone structures, endowing it with unique chemical properties and excellent electrochemical properties, and can be well applied to electrolytes, thereby providing a battery with excellent performance. The preparation method of the bicyclic sultone provided by the present invention can provide new possibilities for future energy storage solutions.

[0055] Compared with the prior art, the present invention has at least the following beneficial effects:

[0056] In the present invention, a substitution reaction is first carried out using a halogenated alkanediol compound and a sulfite as starting materials, and after acidification, a bicyclic sultone compound with two cyclic sultone structures and stable structure is prepared through a cyclization reaction. The preparation method is simple in operation, and the synthesis reaction has the advantages of high yield (66.94 - 90.91%) and high purity (99.32 - 99.62%), and is suitable for large-scale production. Description of the Drawings

[0057] Figure 1 is the nuclear magnetic resonance hydrogen spectrum of the bicyclic sultone obtained in Example 1;

[0058] Figure 2 It is the nuclear magnetic resonance carbon spectrum of the bicyclic sultone obtained in Example 1. Detailed implementation manners

[0059] The technical solution of the present invention will be further described below in conjunction with the accompanying drawings and through specific implementation manners. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the claimed protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0060] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products.

[0061] Example 1

[0062] This example provides a preparation method of a bicyclic sultone, which specifically includes the following steps:

[0063] In a 500 mL reaction device, under stirring, water (123.9 g), sodium sulfite (27.73 g, 0.22 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) were added in sequence. After mixing evenly, the temperature was raised to 85 °C and the reaction was kept at this temperature for 8 h. When the reaction reached the required reaction time, heating was stopped, and the temperature was slowly lowered to 60 °C. 20% hydrochloric acid (38.25 g, 0.21 mol) was slowly added dropwise, and n-butanol (500 mL) was added for liquid-liquid extraction twice. The organic phase was filtered, and the filtrate was concentrated under reduced pressure until no solvent remained. Dichloroethane (148.74 g) and p-toluenesulfonic acid (1.722 g, 0.01 mol) were added, and the mixture was stirred and heated to 80 °C. After reacting at this temperature for 5 h, the temperature was lowered to 25 °C. After filtration, washing with water, and vacuum drying, a bicyclic sultone compound (19.32 g, 0.09 mol) was obtained.

[0064] As Figure 1 and Figure 2 shown, the nuclear magnetic characterization data of the bicyclic sultone compound are as follows:

[0065] 1 H NMR(500MHz,CDCl3):δ5.89(ddd,J=7.0,4.9,2.1Hz,2H),3.68(ddd,J=14.1,4.9,2.0Hz,2H),3.43(ddd,J=14.1,4.9,2.0Hz,2H);

[0066] 13 C NMR(125MHz,CDCl3):δ75.71,50.36。

[0067] Example 2

[0068] This embodiment provides a method for preparing a bicyclic sultone, which specifically includes the following steps:

[0069] In a 500 mL reaction device, under stirring, water (123.9 g), sodium sulfite (27.73 g, 0.22 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) are added in sequence. After mixing evenly, the temperature is raised to 85 °C and the reaction is kept at this temperature for 8 h. When the holding reaction reaches the required reaction time, heating is stopped, and the temperature is slowly lowered to 60 °C. 20% hydrochloric acid (38.25 g, 0.21 mol) is slowly added dropwise, and n-butanol (500 mL) is added for liquid-liquid extraction twice. The organic phase is filtered, and the filtrate is concentrated under reduced pressure until the solvent-free state is reached. Xylene (148.74 g) and p-toluenesulfonic acid (1.722 g, 0.01 mol) are added, and the mixture is stirred and heated to 80 °C. After the reaction is kept at this temperature for 5 h, the temperature is lowered to 25 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sultone compound (18.93 g, 0.088 mol) is obtained.

[0070] Example 3

[0071] This embodiment provides a method for preparing a bicyclic sultone, which specifically includes the following steps:

[0072] In a 500 mL reaction device, under stirring, water (123.9 g), sodium sulfite (26.47 g, 0.21 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) are added in sequence. After mixing evenly, the temperature is raised to 85 °C and the reaction is kept at this temperature for 8 h. When the holding reaction reaches the required reaction time, heating is stopped, and the temperature is slowly lowered to 60 °C. 20% hydrochloric acid (38.25 g, 0.21 mol) is slowly added dropwise, and n-butanol (500 mL) is added for liquid-liquid extraction twice. The organic phase is filtered, and the filtrate is concentrated under reduced pressure until the solvent-free state is reached. Dichloroethane (123.95 g) and p-toluenesulfonic acid (1.3776 g, 0.008 mol) are added, and the mixture is stirred and heated to 80 °C. After the reaction is kept at this temperature for 5 h, the temperature is lowered to 25 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sultone compound (18.827 g, 0.088 mol) is obtained.

[0073] Example 4

[0074] This embodiment provides a method for preparing a bicyclic sultone, which specifically includes the following steps:

[0075] In a 500 mL reaction device, under stirring conditions, water (123.9 g), sodium sulfite (28.99 g, 0.23 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) were added successively. After mixing evenly, the temperature was raised to 85 °C and the reaction was maintained for 8 h. When the required reaction time for the heat preservation reaction was reached, heating was stopped, and the temperature was slowly lowered to 60 °C. 20% hydrochloric acid (40.1 g, 0.22 mol) was slowly added dropwise, and n-butanol (500 mL) was added for liquid-liquid extraction twice. The organic phase was filtered, and the filtrate was concentrated under reduced pressure to a solvent-free state. Dichloroethane (198.32 g) and p-toluenesulfonic acid (2.06 g, 0.012 mol) were added. The mixture was stirred and heated to 80 °C, and the reaction was maintained for 5 h and then cooled to 25 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sulfonic acid lactone compound (19.33 g, 0.09 mol) was obtained.

[0076] Example 5

[0077] This example provides a method for preparing bicyclic sulfonic acid lactone, which specifically includes the following steps:

[0078] In a 500 mL reaction device, under stirring conditions, water (123.9 g), sodium sulfite (27.73 g, 0.22 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) were added successively. After mixing evenly, the temperature was raised to 85 °C and the reaction was maintained for 8 h. When the required reaction time for the heat preservation reaction was reached, heating was stopped, and the temperature was slowly lowered to 60 °C. 20% hydrochloric acid (38.25 g, 0.21 mol) was slowly added dropwise, and n-butanol (500 mL) was added for liquid-liquid extraction twice. The organic phase was filtered, and the filtrate was concentrated under reduced pressure to a solvent-free state. Dichloroethane (148.74 g) and p-toluenesulfonic acid (1.722 g, 0.01 mol) were added. The mixture was stirred and heated to 75 °C, and the reaction was maintained for 5 h and then cooled to 25 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sulfonic acid lactone compound (18.52 g, 0.086 mol) was obtained.

[0079] Example 6

[0080] This example provides a method for preparing bicyclic sulfonic acid lactone, which specifically includes the following steps:

[0081] In a 500 mL reaction device, under stirring conditions, water (123.9 g), sodium sulfite (27.73 g, 0.22 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) were sequentially added. After mixing evenly, the temperature was raised to 90 °C and the reaction was maintained for 10 h. When the holding reaction reached the required reaction time, heating was stopped, and the temperature was slowly lowered to 65 °C. 20% hydrochloric acid (38.25 g, 0.21 mol) was slowly added dropwise, and n-butanol (500 mL) was added for liquid-liquid extraction twice. The organic phase was filtered, and the filtrate was concentrated under reduced pressure until the solvent-free state was reached. Dichloroethane (148.74 g) and p-toluenesulfonic acid (1.722 g, 0.01 mol) were added. The mixture was stirred and heated to 85 °C, and after maintaining the reaction for 6 h, the temperature was lowered to 25 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sulfonic acid lactone compound (19.47 g, 0.091 mol) was obtained.

[0082] Example 7

[0083] This example provides a method for preparing bicyclic sulfonic acid lactone, which specifically includes the following steps:

[0084] In a 500 mL reaction device, under stirring conditions, water (123.9 g), sodium sulfite (25.208 g, 0.2 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) were sequentially added. After mixing evenly, the temperature was raised to 85 °C and the reaction was maintained for 8 h. When the holding reaction reached the required reaction time, heating was stopped, and the temperature was slowly lowered to 60 °C. 20% hydrochloric acid (36.46 g, 0.2 mol) was slowly added dropwise, and n-butanol (500 mL) was added for liquid-liquid extraction twice. The organic phase was filtered, and the filtrate was concentrated under reduced pressure until the solvent-free state was reached. Dichloroethane (74.37 g) and p-toluenesulfonic acid (0.861 g, 0.005 mol) were added. The mixture was stirred and heated to 80 °C, and after maintaining the reaction for 5 h, the temperature was lowered to 25 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sulfonic acid lactone compound (15.98 g, 0.075 mol) was obtained.

[0085] Example 8

[0086] This example provides a method for preparing bicyclic sulfonic acid lactone, which specifically includes the following steps:

[0087] In a 500 mL reaction device, under stirring, water (123.9 g), sodium sulfite (31.51 g, 0.25 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) were added in sequence. After mixing evenly, the temperature was raised to 85 °C and the reaction was kept at this temperature for 8 h. When the holding reaction reached the required reaction time, heating was stopped, and the temperature was slowly lowered to 60 °C. 20% hydrochloric acid (45.575 g, 0.25 mol) was slowly added dropwise, and n-butanol (500 mL) was added for liquid-liquid extraction twice. The organic phase was filtered, and the filtrate was concentrated under reduced pressure until the solvent-free state was reached. Dichloroethane (247.9 g) and p-toluenesulfonic acid (3.44 g, 0.02 mol) were added. The mixture was stirred and heated to 80 °C, and after holding the reaction at this temperature for 5 h, the temperature was lowered to 25 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sulfonic acid lactone compound (17.317 g, 0.081 mol) was obtained.

[0088] Example 9

[0089] This example provides a method for preparing a bicyclic sulfonic acid lactone, which specifically includes the following steps:

[0090] In a 500 mL reaction device, under stirring, water (123.9 g), sodium sulfite (27.73 g, 0.22 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) were added in sequence. After mixing evenly, the temperature was raised to 75 °C and the reaction was kept at this temperature for 6 h. When the holding reaction reached the required reaction time, heating was stopped, and the temperature was slowly lowered to 40 °C. 20% hydrochloric acid (38.25 g, 0.21 mol) was slowly added dropwise, and n-butanol (500 mL) was added for liquid-liquid extraction twice. The organic phase was filtered, and the filtrate was concentrated under reduced pressure until the solvent-free state was reached. Dichloroethane (148.74 g) and p-toluenesulfonic acid (1.722 g, 0.01 mol) were added. The mixture was stirred and heated to 70 °C, and after holding the reaction at this temperature for 4 h, the temperature was lowered to 20 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sulfonic acid lactone compound (14.33 g, 0.067 mol) was obtained.

[0091] Example 10

[0092] This example provides a method for preparing a bicyclic sulfonic acid lactone, which specifically includes the following steps:

[0093] In a 500 mL reaction device, under stirring conditions, water (123.9 g), sodium sulfite (27.73 g, 0.22 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) were added in sequence. After mixing evenly, the temperature was raised to 95 °C and the reaction was kept at this temperature for 12 h. When the holding reaction reached the required reaction time, heating was stopped, and the temperature was slowly lowered to 70 °C. Then, 20% hydrochloric acid (38.25 g, 0.21 mol) was slowly added dropwise. N-butanol (500 mL) was added for liquid-liquid extraction twice. The organic phase was filtered, and the filtrate was concentrated under reduced pressure until no solvent remained. Dichloroethane (148.74 g) and p-toluenesulfonic acid (1.722 g, 0.01 mol) were added. The mixture was stirred and heated to 100 °C, and the reaction was kept at this temperature for 8 h and then cooled to 30 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sulfonic acid lactone compound (19.18 g, 0.09 mol) was obtained.

[0094] Example 11

[0095] This example provides a method for preparing a bicyclic sulfonic acid lactone, which specifically includes the following steps:

[0096] In a 500 mL reaction device, under stirring conditions, water (123.9 g), sodium sulfite (28.99 g, 0.23 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) were added in sequence. After mixing evenly, the temperature was raised to 85 °C and the reaction was kept at this temperature for 8 h. When the holding reaction reached the required reaction time, heating was stopped, and the temperature was slowly lowered to 60 °C. Then, 20% hydrochloric acid (40.106 g, 0.22 mol) was slowly added dropwise. N-butanol (500 mL) was added for liquid-liquid extraction twice. The organic phase was filtered, and the filtrate was concentrated under reduced pressure until no solvent remained. Dichloroethane (148.74 g) and p-toluenesulfonic acid (2.066 g, 0.012 mol) were added. The mixture was stirred and heated to 75 °C, and the reaction was kept at this temperature for 5 h and then cooled to 25 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sulfonic acid lactone compound (18.757 g, 0.088 mol) was obtained.

[0097] Example 12

[0098] This example provides a method for preparing a bicyclic sulfonic acid lactone, which specifically includes the following steps:

[0099] In a 500 mL reaction device, under stirring, water (123.9 g), sodium sulfite (26.47 g, 0.21 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) were added in sequence. After mixing evenly, the temperature was raised to 90 °C and the reaction was kept at this temperature for 10 h. When the holding reaction reached the required reaction time, heating was stopped, and the temperature was slowly lowered to 65 °C. 20% hydrochloric acid (38.28 g, 0.21 mol) was slowly added dropwise, and n-butanol (500 mL) was added for liquid-liquid extraction twice. The organic phase was filtered, and the filtrate was concentrated under reduced pressure to a solvent-free state. Dichloroethane (148.74 g) and p-toluenesulfonic acid (1.378 g, 0.008 mol) were added. The mixture was stirred and heated to 85 °C, and after holding the reaction for 6 h, the temperature was lowered to 25 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sulfonic acid lactone compound (19.121 g, 0.089 mol) was obtained.

[0100] Example 13

[0101] This example provides a method for preparing bicyclic sulfonic acid lactone, which specifically includes the following steps:

[0102] In a 500 mL reaction device, under stirring, water (123.9 g), sodium sulfite (26.47 g, 0.21 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) were added in sequence. After mixing evenly, the temperature was raised to 85 °C and the reaction was kept at this temperature for 8 h. When the holding reaction reached the required reaction time, heating was stopped, and the temperature was slowly lowered to 60 °C. 20% hydrochloric acid (38.28 g, 0.21 mol) was slowly added dropwise, and n-butanol (500 mL) was added for liquid-liquid extraction twice. The organic phase was filtered, and the filtrate was concentrated under reduced pressure to a solvent-free state. Dichloroethane (148.74 g) and p-toluenesulfonic acid (1.378 g, 0.008 mol) were added. The mixture was stirred and heated to 85 °C, and after holding the reaction for 5 h, the temperature was lowered to 25 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sulfonic acid lactone compound (18.559 g, 0.087 mol) was obtained.

[0103] Example 14

[0104] This example provides a method for preparing bicyclic sulfonic acid lactone, which specifically includes the following steps:

[0105] In a 500 mL reaction device, under stirring conditions, water (123.9 g), sodium sulfite (28.99 g, 0.23 mol), and 1,4-dibromo-2,3-butanediol (24.79 g, 0.1 mol) were added successively. After mixing evenly, the temperature was raised to 90 °C and the reaction was carried out under insulation for 10 h. When the required reaction time for the insulation reaction was reached, heating was stopped, and the temperature was slowly lowered to 65 °C. 20% hydrochloric acid (40.106 g, 0.22 mol) was slowly added dropwise, and n-butanol (500 mL) was added for liquid-liquid extraction twice. The organic phase was filtered, and the filtrate was concentrated under reduced pressure until the solvent-free state was reached. Dichloroethane (148.74 g) and p-toluenesulfonic acid (2.0664 g, 0.012 mol) were added. The mixture was stirred and heated to 85 °C, and after reacting under insulation for 6 h, the temperature was lowered to 25 °C. After filtration, washing with water, and vacuum drying, the finished product of the bicyclic sulfonic acid lactone compound (19.324 g, 0.09 mol) was obtained.

[0106] The yields and purities of the above Examples 1-14 are shown in Table 1.

[0107] Table 1

[0108] Yield (%) Purity (%) Example 1 90.20 99.58 Example 2 88.35 99.32 Example 3 87.89 99.62 Example 4 90.24 99.54 Example 5 86.48 99.48 Example 6 90.91 99.53 Example 7 74.62 99.33 Example 8 80.84 99.40 Example 9 66.94 99.46 Example 10 89.58 99.54 Example 11 87.60 99.47 Example 12 89.30 99.58 Example 13 86.68 99.52 Example 14 90.24 99.49

[0109] It can be seen from the test results that:

[0110] (1) It can be seen from Examples 1 to 14 that in the present invention, after a series of reactions using a halogenated alkanediol compound and a sulfite as starting materials, a bicyclic sulfonic acid lactone with a stable structure can be obtained, with a yield of 66.94 - 90.91% and a purity of 99.32 - 99.62%.

[0111] (2) By comparing Examples 1, 3-4 with Examples 7-8, it can be seen that the ratios of the respective raw materials in Examples 7 and 8 are lower and higher than their corresponding preferred ranges respectively, and the yields of the obtained bicyclic sulfonic acid lactone compounds are both significantly reduced, indicating that by further optimizing the ratios of the respective raw materials in the present invention, the yield of the obtained bicyclic sulfonic acid lactone can be not less than 87%.

[0112] (3) By comparing Examples 1, 5-6 with Examples 9-10, it can be seen that the reaction temperatures and times of each reaction in Examples 9 and 10 both exceed their corresponding preferred ranges, and the yields of the obtained bicyclic sulfonic acid lactone compounds are both significantly reduced, indicating that by further optimizing the settings of the reaction temperature and time in each reaction in the present invention, the yield of the obtained bicyclic sulfonic acid lactone can be higher than 86%.

[0113] In summary, the present invention uses a halogenated alkylene glycol compound and a sulfite as starting materials, and precisely controls the reactions involved through the selection and ratio of specific raw materials, and the setting of parameters such as reaction temperature and time, to prepare a bicyclic sultone compound with high purity, high yield and stable structure.

[0114] The applicant declares that the above description is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A preparation method of a bicyclic sultone, characterized in that, The preparation method includes the following steps: (1) React a halohydrin diol compound with a sulfite, and after acidification, obtain a dihydroxyalkyl disulfonic acid compound; (2) Carry out a cyclization reaction on the dihydroxyalkyl disulfonic acid compound obtained in step (1) to obtain the bicyclic sultone.

2. The preparation method according to claim 1, characterized in that, The halohydrin diol compound in step (1) includes 1,4-dibromo-2,3-butanediol and / or 1,4-dichloro-2,3-butanediol; Preferably, the sulfite in step (1) includes sodium sulfite and / or potassium sulfite; Preferably, the molar ratio of the halohydrin diol compound to the sulfite is 1:(2.0 - 2.5), and more preferably 1:(2.1 - 2.3).

3. The preparation method according to claim 1 or 2, characterized in that, The reaction in step (1) is carried out in a solvent; Preferably, the solvent includes water; Preferably, the temperature of the reaction in step (1) is 75 - 100 °C, and more preferably 85 - 90 °C; Preferably, the reaction time in step (1) is 6 - 12 h, and more preferably 8 - 10 h.

4. The preparation method according to any one of claims 1 to 3, characterized in that, The acidification method in step (1) includes treatment with hydrochloric acid; Preferably, the molar ratio of the halohydrin diol compound to hydrochloric acid is 1:(2.0 - 2.5), and more preferably 1:(2.1 - 2.2).

5. The preparation method according to any one of claims 1-4, characterized in that, Before the acidification in step (1), there is also a cooling step; Preferably, the cooling method includes cooling to 40 - 70 °C, and more preferably 60 - 65 °C.

6. The preparation method according to any one of claims 1-5, characterized in that, After the acidification in step (1), there is also a post-treatment step; Preferably, the post-treatment method includes extraction and separation; Preferably, the extractant used for extraction includes any one or a combination of at least two of n-butanol, isoamyl alcohol, ethyl acetate or cyclohexanone; Preferably, the separation method includes filtration and vacuum concentration.

7. The preparation method according to any one of claims 1-6, characterized in that, The cyclization reaction in step (2) is carried out in an aprotic organic solvent; Preferably, the aprotic organic solvent includes any one or a combination of at least two of dichloroethane, toluene, xylene, carbon tetrachloride or dimethyl sulfoxide, and more preferably dichloroethane; Preferably, the mass ratio of the aprotic organic solvent to the halohydrin diol compound in step (1) is (3 - 10):1, and more preferably (5 - 8):1; Preferably, the cyclization reaction in step (2) is carried out under a catalyst; Preferably, the catalyst includes concentrated sulfuric acid and / or p-toluenesulfonic acid, and more preferably p-toluenesulfonic acid; Preferably, the molar ratio of the catalyst to the halohydrin diol compound in step (1) is (0.05 - 0.2):1, and more preferably (0.08 - 0.12):

1.

8. The preparation method according to any one of claims 1-7, characterized in that, The temperature of the cyclization reaction in step (2) is 70 - 100 °C, preferably 75 - 85 °C; Preferably, the reaction time of the cyclization reaction in step (2) is 4 - 8 h, and more preferably 5 - 6 h.

9. The preparation method according to any one of claims 1-8, characterized in that, After the cyclization reaction in step (2), there is also a post-treatment step; Preferably, the post-treatment method includes cooling, filtration, washing with water and drying; Preferably, the cooling is to cool to 20 - 30 °C; Preferably, the drying method includes vacuum drying.

10. The preparation method according to any one of claims 1-9, characterized in that, The preparation method specifically includes the following steps: Mix a halogenated alkanediol compound, a sulfite, and a solvent, heat the mixture to 75 - 100 °C, keep the temperature for 6 - 12 h for the reaction, then stop heating, cool down to 40 - 70 °C, add hydrochloric acid for acidification, and then separate to obtain a dihydroxyalkyl disulfonic acid compound after extraction with an extractant; dissolve the dihydroxyalkyl disulfonic acid compound in an aprotic organic solvent, add a catalyst concentrated sulfuric acid and / or p-toluenesulfonic acid, heat the mixture to 70 - 100 °C, keep the temperature for 4 - 8 h for the reaction, then cool down to 20 - 30 °C, and obtain the bicyclic sultone after filtration, washing with water, and drying.

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