Method for preparing cyclic sulfate from cyclic sulfite

Abstract

The invention relates to a method for preparing cyclic sulfate from cyclic sulfite, which comprises the following steps: carrying out reaction on the cyclic sulfite and an oxidant in the presence of a catalyst, and after the reaction is finished, carrying out post-treatment to obtain the cyclic sulfate, the catalyst is an organic iron catalyst; the molar ratio of the cyclic sulfite to the catalyst is 1: (0.0001-0.01). The preparation method disclosed by the invention is simple to operate, mild in reaction condition, small in catalyst dosage, high in product yield, environment-friendly, simple in product separation and purification and easy for industrial production.

Description

Technical Field

[0001] The present invention belongs to the field of fine chemicals, medicine and material technology. Specifically, the present invention relates to a method for preparing cyclic sulfate from cyclic sulfite. Background Art

[0002] Cyclic sulfates are a class of organic compounds containing cyclic sulfate groups in their molecules. They can be used as additives for lithium battery electrolytes to improve the kinetic properties of electrode / electrolyte interface reactions, inhibit the decrease in initial battery capacity, increase initial discharge capacity, and reduce battery expansion after high-temperature storage. In addition, they can also be used to improve battery charge and discharge performance and cycle times.

[0003] Among them, vinyl sulfate is a new type of excellent sulfate organic film-forming additive for lithium battery electrolyte. Since the central sulfur atom of vinyl sulfate has a strong electronegativity and its reducibility at the graphite negative electrode interface is stronger than that of carbonate additives, vinyl sulfate will preferentially form a more stable solid electrolyte interface film (SEI film) at the electrode interface. By adding vinyl sulfate to the lithium battery electrolyte, the decrease in the initial capacity of the lithium battery can be suppressed, the initial discharge capacity can be increased, the expansion of the battery after high temperature placement can be reduced, the battery charge and discharge performance can be improved, and the number of cycles can be increased. Since vinyl sulfate can significantly improve the performance of lithium battery electrolyte, it has huge market demand and development prospects. People are eager to achieve continuous, efficient and low-cost large-scale production of vinyl sulfate.

[0004] In the related art, the preparation method of cyclic sulfate mainly includes acylation method, substitution method, addition method, dioxane synthesis method and oxidation method, among which the oxidation method is more suitable for industrial production than other methods due to its low cost and simple preparation method. The oxidation method is usually prepared by first using alcohols and dichlorothionyl to react to generate an intermediate cyclic sulfite, and then oxidizing the product cyclic sulfate with an oxidant. At present, the main oxidation methods in the preparation of cyclic sulfate include: 1. using sodium hypochlorite or sodium periodate as an oxidant, oxidizing under the catalysis of ruthenium chloride aqueous solution; 2. direct oxidation with potassium permanganate and the like as an oxidant. However, in the actual preparation process, the precious metal ruthenium chloride used in the former is expensive and difficult to recover; the latter uses ozone and the like as an oxide, which has the disadvantages of low yield, difficulty in product purification, and large environmental pollution.

[0005] For example, Chinese patent 201711123931.0 discloses that ethylene glycol is dissolved in dichloromethane, thionyl chloride is added thereto under nitrogen protection for reaction, and vacuum distillation is performed to obtain a transparent liquid; the above-mentioned transparent liquid is then dissolved in dichloromethane, and a ruthenium catalyst is added thereto under ice-water bath conditions, and then an oxidant (aqueous solution of sodium hypochlorite or sodium periodate) is added thereto to obtain a reaction solution in which an aqueous phase and an organic phase coexist, and vinyl sulfate is obtained after separation, washing, drying, and filtering. This synthesis method has a large amount of heat release in the oxidation reaction, is difficult to control the reaction temperature, has a low yield, and requires the use of oxides or chlorides of heavy metals such as ruthenium and palladium as catalysts, which is costly, has more wastewater, and causes environmental pollution.

[0006] World patent WO9842675A1 uses the same route and catalyst as Chinese patent 201711123931.0 to produce propylene sulfate. This method also has the above-mentioned problems.

[0007] For example, Chinese patent CN108822073A discloses a method for preparing vinyl sulfate by oxidizing vinyl sulfite using ozone as an oxidant and manganese oxide, nickel oxide, and copper powder as catalysts. This method has high requirements for reaction equipment, large amounts of catalyst, and great environmental pollution.

[0008] Therefore, there is an urgent need to provide a new method for preparing cyclic sulfate, which has a high safety factor, low cost, high yield and purity, and is suitable for industrial production. Summary of the invention

[0009] The invention aims at solving many problems existing in the existing synthesis technology and provides a method for preparing cyclic sulfate from cyclic sulfite.

[0010] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0011] The present invention provides a method for preparing a cyclic sulfate from a cyclic sulfite, the preparation method comprising the following steps:

[0012] The cyclic sulfite is reacted with an oxidant in the presence of a catalyst, and after the reaction is completed, the cyclic sulfate is obtained by post-treatment;

[0013] The catalyst is an organic iron catalyst;

[0014] The molar ratio of the cyclic sulfite to the catalyst is 1:(0.0001-0.01).

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] The present invention provides a new method for preparing cyclic sulfate from cyclic sulfite. The preparation method has the advantages of simple operation, mild reaction conditions, small amount of catalyst, high product yield, total yield of more than 86%, which can be as high as 93.8%, environmental friendliness, simple product separation and purification, and easy industrial production. DETAILED DESCRIPTION

[0017] The following detailed description specifically discloses an embodiment of the method for preparing cyclic sulfate from a cyclic sulfite of the present application. However, there may be cases where unnecessary detailed descriptions are omitted. For example, there may be cases where detailed descriptions of well-known matters and repeated descriptions of actually identical structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the following description is provided for those skilled in the art to fully understand the present application and is not intended to limit the subject matter described in the claims.

[0018] The words "preferred", "more preferred" and the like in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0019] When a numerical range is disclosed herein, the above range is deemed to be continuous and includes the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all sub-ranges included therein. For example, a specified range from "1 to 10" should be deemed to include any and all sub-ranges between a minimum of 1 and a maximum of 10. Exemplary sub-ranges of ranges 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, etc.

[0020] [Method for preparing cyclic sulfate from cyclic sulfite]

[0021] The present invention provides a method for preparing a cyclic sulfate from a cyclic sulfite, the preparation method comprising the following steps:

[0022] The cyclic sulfite is reacted with an oxidant in the presence of a catalyst, and after the reaction is completed, the cyclic sulfate is obtained by post-treatment;

[0023] The catalyst is an organic iron catalyst;

[0024] The molar ratio of the cyclic sulfite to the catalyst is 1:(0.0001-0.01).

[0025] In the method for preparing cyclic sulfate from cyclic sulfite provided by the present invention, the cyclic sulfite is compound ⅠⅠ-1, compound ⅠⅠ-2 or compound ⅠⅠ-3, and the cyclic sulfate is compound ⅠⅠⅠ-1, compound ⅠⅠⅠ-2 or compound ⅠⅠⅠ-3;

[0026] The chemical reaction formula is selected from one of the following:

[0027]

[0028] Wherein, R1 and R2 are independently selected from hydrogen and C1-C5 alkyl; n is 1-3.

[0029] Optionally, R1, R2 are each independently selected from hydrogen, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like.

[0030] The cyclic sulfite is prepared by reacting thionyl chloride with a polyol. The polyol is compound I-1, compound I-2 or compound I-3.

[0031]

[0032] Wherein, R1 and R2 are independently selected from hydrogen and C1-C5 alkyl; n is 1-3.

[0033] Optionally, R1, R2 are each independently selected from hydrogen, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like.

[0034] When n=1, the chemical reaction formula is

[0035]

[0036] When n=2, the chemical reaction formula is

[0037]

[0038] When n=3, the chemical reaction formula is

[0039]

[0040] Wherein, R1 and R2 are as defined above.

[0041] In the method for preparing cyclic sulfate from cyclic sulfite provided by the present invention, thionyl chloride and polyol are reacted to obtain cyclic sulfite. Specifically:

[0042] In the preparation method of the cyclic sulfite of the present invention, the polyol is selected from one or more of ethylene glycol, 1,2-dimethyl ethylene glycol, 1-ethyl ethylene glycol, 2-tert-butyl-1,3-propylene glycol, 1,3-dimethyl-2-isopropyl-1,3-propylene glycol, 1,3-diethyl-1,3-propylene glycol, 1,4-butanediol, 1,4-dimethyl-1,4-butanediol, 2,3-diethyl-1,4-butanediol, 1,2,3,4-butanetetrol, 1,4-dimethyl-1,2,3,4-butanetetrol, pentaerythritol and the like.

[0043] In the method for preparing cyclic sulfite of the present invention, the molar ratio of thionyl chloride to polyol is 1:(1-2). Optionally, the molar ratio of thionyl chloride to polyol is 1:(1-1.5), 1:(1.5-2), etc.

[0044] In the method for preparing cyclic sulfite of the present invention, the reaction temperature is 10-20° C. and the reaction time is 0.5 to 3 hours.

[0045] In the method for preparing cyclic sulfate from cyclic sulfite provided by the present invention, the cyclic sulfite is reacted with an oxidant in the presence of a catalyst, and after the reaction, the cyclic sulfate is obtained by post-treatment. Specifically:

[0046] In the preparation method of the cyclic sulfate of the present invention, the oxidant is selected from one or more of sodium hypochlorite, calcium hypochlorite, potassium persulfate, potassium persulfate, sodium persulfate, ammonium persulfate, sodium percarbonate, sodium perborate, and hydrogen peroxide. Preferably, the oxidant is selected from one of sodium hypochlorite, calcium hypochlorite, potassium persulfate, sodium percarbonate, sodium perborate, and hydrogen peroxide. The concentration of hydrogen peroxide can be, for example, 30% to 40%. The concentration of the sodium hypochlorite aqueous solution can be, for example, 5% to 15%.

[0047] In the preparation method of the cyclic sulfate ester of the present invention, the organic iron catalyst is selected from one or more of porphyrin iron, phthalocyanine iron, tetrachlorophenylporphyrin iron, tetraphenylporphyrin iron, hematin, N,N'-bis(salicylidene)ethylenediamine iron and the like.

[0048] In the preparation method of the cyclic sulfate ester of the present invention, the molar ratio of the cyclic sulfite ester to the catalyst is 1:(0.0001-0.01). The molar ratio of the cyclic sulfite ester to the catalyst is 1:(0.0001-0.0005), 1:(0.0001-0.001), (0.0001-0.0015), (0.0001-0.002), (0.0001-0.003), (0.0001-0.004), (0.0001-0.005), 1:(0.0001-0.006), 1:(0.0001-0.007), 1:(0.0001-0.008), 1:(0.0001-0.009), 1:(0.0001-0.01) , 1:(0.0015-0.006), 1:(0.0015-0.007), 1:(0.0015-0.008), 1:(0.0015-0.009), 1:(0.001~0.0015), 1:(0.0015~0.01), 1:(0.001~0.005), 1:(0.005~0.01), 1:(0.001~0.006), 1:(0.006~0.01), 1:(0.001~0.009), 1:(0.009~0.01) or 1:(0.0001~0.009), etc.

[0049] In the preparation method of the cyclic sulfate ester of the present invention, the molar ratio of the cyclic sulfite to the oxidant is 1:(1-6). Optionally, the molar ratio of the cyclic sulfite to the oxidant is 1:(1-3), 1:(3-6), 1:(1-2), 1:(2-4) or 1:(4-6), etc.

[0050] In the preparation method of the cyclic sulfate of the present invention, the cyclic sulfite and the oxidant react in the presence of a catalyst at a reaction temperature of -10 to 20° C. Alternatively, the reaction temperature may be, for example, -10 to 0° C., 0 to 10° C. or 10 to 20° C.

[0051] In the preparation method of the cyclic sulfate ester of the present invention, the cyclic sulfite ester and the oxidant react in the presence of a catalyst, and the reaction time is 3 to 6 hours.

[0052] The method for preparing the cyclic sulfate of the present invention may optionally further include a solvent, wherein the solvent is selected from one or more of acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dichloromethane, dichloroethane, and water.

[0053] In the preparation method of the cyclic sulfate ester of the present invention, the post-treatment includes filtration, concentration, etc., and may also include crystallization, etc.

[0054]

Cyclic sulfate

[0055] The present invention also provides a cyclic sulfate ester prepared by the method of the first aspect of the present invention.

[0056]

application

[0057] The present invention also provides the application of the aforementioned cyclic sulfate in the fields of fine chemicals, medicine, and materials, for example, in electrolyte additives for new energy batteries.

[0058] The technical solution of the present application is described clearly and completely below in conjunction with the embodiments of the present invention. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by professionals and technicians in this field based on the above-mentioned contents of the present invention still belong to the scope of protection of the present invention.

[0059] The present invention is specifically described below by way of examples. In addition, unless otherwise specified, all raw materials used are commercially available.

[0060] Example

[0061] Example 1

[0062] Example 1 provides a method for preparing vinyl sulfate using ethylene glycol and thionyl chloride as raw materials, after obtaining vinyl sulfite, using porphyrin iron as a catalyst and hydrogen peroxide as an oxidant. The synthetic reaction formula is as follows:

[0063]

[0064] The steps for preparing vinyl sulfate include:

[0065] Accurately weigh 62g of ethylene glycol in a 1000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 119g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 105.9g of vinyl sulfite, with a yield of 98.1%. Weigh 65.1mg of porphyrin iron and add it to the reaction bottle, slowly add 291g of 35% hydrogen peroxide, and control the temperature at 10-20°C. After the addition is complete, keep warm for 4 hours. Add 400g of DCM (dichloromethane) to extract the organic phase, dry, filter, and desolventize to obtain 120g of vinyl sulfate, with a GC purity of 99.5% and a total yield of 93.8%.

[0066] Example 2

[0067] Example 2 provides a method for preparing 2,3-dimethyl vinyl sulfate by using 1,2-dimethylethylene glycol and thionyl chloride as raw materials, after obtaining 2,3-dimethyl vinyl sulfite, using tetraphenylporphyrin iron as a catalyst and potassium persulfate as an oxidant. The synthetic reaction formula is as follows:

[0068]

[0069] The preparation steps of 2,3-dimethyl vinyl sulfate include:

[0070] Accurately weigh 90g of 1,2-dimethylethylene glycol in a 1000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 119g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 132.7g of 2,3-dimethylvinyl sulfite, with a yield of 97.6%. Weigh 70.4mg of tetraphenylporphyrin iron, 400g of water, and 400g of diethyl carbonate into the reaction bottle, slowly add 270g of potassium persulfate, and control the temperature at 0-10°C. After the addition is complete, keep warm for 4 hours. Separate the liquid, take the organic phase, dry, filter, and desolventize to obtain 141.3g of 2,3-dimethylvinyl sulfate, with a GC purity of 99.3% and a total yield of 90.6%.

[0071] Example 3

[0072] Example 3 provides a method for preparing 2-ethyl vinyl sulfate using 1-ethyl glycol and thionyl chloride as raw materials, after obtaining 2-ethyl vinyl sulfite, using N,N'-bis(salicylidene)ethylenediamine iron as a catalyst and sodium hypochlorite as an oxidant. The synthetic reaction formula is as follows:

[0073]

[0074] The preparation steps of 2-ethyl vinyl sulfate include:

[0075] Accurately weigh 90g of 1-ethyl glycol in a 2000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 119g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 132.5g of 2-ethyl vinyl sulfite, with a yield of 97.4%. Weigh 3.24g of N, N'-bis (salicylidene) ethylenediamine iron and add it to the reaction bottle, slowly add 1490g of 10% sodium hypochlorite aqueous solution, and control the temperature at 0-10°C. After the addition is complete, keep warm for 4 hours. Add 500g of DCM to extract the organic phase, dry, filter, and desolventize to obtain 137.8g of 2-ethyl vinyl sulfate, GC purity 99.0%, and total yield 88.3%.

[0076] Example 4

[0077] Example 4 provides a method for preparing 3-tert-butyl propylene sulfate by using 2-tert-butyl-1,3-propylene glycol and thionyl chloride as raw materials, after obtaining 3-tert-butyl propylene sulfite, using iron phthalocyanine as a catalyst and sodium percarbonate as an oxidant. The synthetic reaction formula is as follows:

[0078]

[0079] The preparation steps of 3-tert-butyl vinyl sulfate include:

[0080] Accurately weigh 132g of 2-tert-butyl-1,3-propanediol in a 1000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 119g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 173.7g of 3-tert-butyl propylene sulfite, with a yield of 97.6%. Weigh 568mg of iron phthalocyanine, 400g of water and 400g of acetonitrile into the reaction bottle, slowly add 180g of sodium percarbonate, and control the temperature at -10-0°C. After the addition is complete, keep warm for 4 hours. Separate the liquid, take the organic phase, dry, filter, and desolventize to obtain 184.2g of 3-tert-butyl propylene sulfate, with a GC purity of 99.1% and a total yield of 93.0%.

[0081] Example 5

[0082] Example 5 provides a method for preparing 2,4-dimethyl-3-isopropyl propylene sulfate by using 1,3-dimethyl-2-isopropyl-1,3-propanediol and thionyl chloride as raw materials, after obtaining 2,4-dimethyl-3-isopropyl propylene sulfate, using tetrakis-p-chlorophenylporphyrin iron as a catalyst and calcium hypochlorite as an oxidant. The synthetic reaction formula is as follows:

[0083]

[0084] The preparation steps of 2,4-dimethyl-3-isopropyl vinyl sulfate include:

[0085] Accurately weigh 146g of 1,3-dimethyl-2-isopropyl-1,3-propanediol in a 1000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 119g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 186.4g of 2,4-dimethyl-3-isopropyl propylene sulfite, with a yield of 97.1%. Weigh 841mg of tetrachlorophenylporphyrin iron, 400g of water and 400g of dichloromethane into the reaction bottle, slowly add 286g of calcium hypochlorite, and control the temperature at -10-0°C. After the addition is complete, keep warm for 4 hours. Separate the liquid, take the organic phase, dry, filter, and desolventize to obtain 192.5g of 2,4-dimethyl-3-isopropyl propylene sulfate, with a GC purity of 99.2% and a total yield of 90.8%.

[0086] Example 6

[0087] Example 6 provides a method for preparing 2,4-diethyl propylene sulfate by using 1,3-diethyl-1,3-propylene glycol and thionyl chloride as raw materials, after obtaining 2,4-diethyl propylene sulfate, using hematoxylin as a catalyst and sodium perborate as an oxidant. The synthetic reaction formula is as follows:

[0088]

[0089] The preparation steps of 2,4-diethyl vinyl sulfate include:

[0090] Accurately weigh 132g of 1,3-diethyl-1,3-propanediol in a 1000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 119g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 174.0g of 2,4-diethyl propylene sulfite, with a yield of 97.8%. Weigh 631mg of hydroxyhematin, 400g of water and 400g of dichloroethane into the reaction bottle, slowly add 168g of sodium perborate, and control the temperature at -10-0°C. After the addition is complete, keep warm for 4 hours. Separate the liquid, take the organic phase, dry, filter, and desolventize to obtain 175.6g of 2,4-diethyl propylene sulfate, with a GC purity of 99.0% and a total yield of 88.7%.

[0091] Example 7

[0092] Example 7 provides a method for preparing butylene sulfate using 1,4-butanediol and thionyl chloride as raw materials, after obtaining butylene sulfite, using porphyrin iron as a catalyst and hydrogen peroxide as an oxidant. The synthetic reaction formula is as follows:

[0093]

[0094] The steps of preparing butylene sulfate include:

[0095] Accurately weigh 90g of 1,4-butanediol in a 1000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 119g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 131.1g of butylene sulfite, with a yield of 96.4%. Weigh 65.1mg of porphyrin iron and add it to the reaction bottle, slowly add 291g of 35% hydrogen peroxide, and control the temperature at 10-20°C. After the addition is complete, keep warm for 4 hours. Add 400g of DCM to extract the organic phase, dry, filter, and desolventize to obtain 140.1g of butylene sulfate, with a GC purity of 98.5% and a total yield of 89.8%.

[0096] Example 8

[0097] Example 8 provides a method for preparing 2,5-dimethyl butyl sulfate by using 1,4-dimethyl-1,4-butanediol and thionyl chloride as raw materials, after obtaining 2-5-dimethyl butyl sulfate, using porphyrin iron as a catalyst and hydrogen peroxide as an oxidant. The synthetic reaction formula is as follows:

[0098]

[0099] The preparation steps of 2,5-dimethyl butylene sulfate include:

[0100] Accurately weigh 118g of 1,4-dimethyl-1,4-butanediol in a 1000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 119g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 155.9g of 2-5-dimethyl butyl sulfate, with a yield of 95.1%. Weigh 65.1mg of porphyrin iron and add it to the reaction bottle, slowly add 291g of 35% hydrogen peroxide, and control the temperature at 10-20°C. After the addition is complete, keep warm for 4 hours. Add 400g of DCM to extract the organic phase, dry, filter, and desolventize to obtain 162.8g of 2,5-dimethyl butyl sulfate, with a GC purity of 98.7% and a total yield of 88.5%.

[0101] Example 9

[0102] Example 9 provides a method for preparing 3,4-diethyl butylene sulfate by using 2,3-diethyl-1,4-butanediol and thionyl chloride as raw materials, after obtaining 3,4-diethyl butylene sulfate, using porphyrin iron as a catalyst and hydrogen peroxide as an oxidant. The synthetic reaction formula is as follows:

[0103]

[0104] The preparation steps of 3,4-diethyl butylene sulfate include:

[0105] Accurately weigh 146g of 2,3-diethyl-1,4-butanediol in a 1000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 119g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 182.6g of 3,4-diethyl butyl sulfate, with a yield of 95.1%. Weigh 65.1mg of porphyrin iron and add it to the reaction bottle, slowly add 291g of 35% hydrogen peroxide, and control the temperature at 10-20°C. After the addition is complete, keep warm for 4 hours. Add 400g of DCM to extract the organic phase, dry, filter, and desolventize to obtain 185.9g of 3,4-diethyl butyl sulfate, with a GC purity of 98.0% and a total yield of 87.7%.

[0106] Example 10

[0107] Example 10 provides a method for preparing vinyl bisulfate using 1,2,3,4-butanetetrol and thionyl chloride as raw materials, after obtaining vinyl bisulfite, using porphyrin iron as a catalyst and hydrogen peroxide as an oxidant. The synthetic reaction formula is as follows:

[0108]

[0109] The steps of preparing vinyl sulfate include:

[0110] Accurately weigh 122g of 1,2,3,4-butanetetrol in a 1000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 238g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 207.6g of vinyl bisulfite, with a yield of 97.0%. Weigh 130.2mg of porphyrin iron and add it to the reaction bottle, slowly add 582g of 35% hydrogen peroxide, and control the temperature at 10-20°C. After the addition is complete, keep warm for 4 hours. Add 400g of DCM to extract the organic phase, dry, filter, and desolventize to obtain 232.2g of vinyl bisulfate, with a GC purity of 98.3% and a total yield of 91.4%.

[0111] Embodiment 11

[0112] Example 11 provides a method for preparing 2,5-dimethylvinyl bisulfate using 1,4-dimethyl-1,2,3,4-butanetetrol and thionyl chloride as raw materials, after obtaining 2,5-dimethylvinyl bisulfite, using porphyrin iron as a catalyst and hydrogen peroxide as an oxidant. The synthetic reaction formula is as follows:

[0113]

[0114] The preparation steps of 2,5-dimethylvinyl sulfate include:

[0115] Accurately weigh 150g of 1,4-dimethyl 1,2,3,4-butanetetrol in a 1000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 238g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 234.9g of 2,5-dimethyl vinyl disulfite, with a yield of 97.1%. Weigh 130.2mg of porphyrin iron and add it to the reaction bottle, slowly add 582g of 35% hydrogen peroxide, and control the temperature at 10-20°C. After the addition is complete, keep warm for 4 hours. Add 400g of DCM to extract the organic phase, dry, filter, and desolventize to obtain 259.4g of 2,5-dimethyl vinyl disulfite, with a GC purity of 98.5% and a total yield of 92.0%.

[0116] Example 12

[0117] Example 12 provides a method for preparing spiropropene sulfate using pentaerythritol and thionyl chloride as raw materials, after obtaining spiropropene sulfate, using porphyrin iron as a catalyst and hydrogen peroxide as an oxidant. The synthetic reaction formula is as follows:

[0118]

[0119] The preparation steps of spiropropene sulfate include:

[0120] Accurately weigh 136g of pentaerythritol in a 1000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 238g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 216.8g of spirosulfite propylene ester with a yield of 95.1%. Weigh 130.2mg of porphyrin iron and add it to the reaction bottle, slowly add 582g of 35% hydrogen peroxide, and control the temperature at 10-20°C. After the addition is complete, keep warm for 4 hours. Add 400gDCM to extract the organic phase, dry, filter, and desolventize to obtain 224.6g of spirosulfate propylene ester, GC purity 98.5%, and total yield 86.4%.

[0121] The applicant declares that the present invention illustrates the method for preparing cyclic sulfate from cyclic sulfite through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0122] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0123] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. A method for preparing a cyclic sulfate from a cyclic sulfite, characterized in that: The steps include: The cyclic sulfite is reacted with an oxidant in the presence of a catalyst, and after the reaction is completed, the cyclic sulfate is obtained by post-treatment; The catalyst is an organic iron catalyst; The molar ratio of the cyclic sulfite to the catalyst is 1:(0.0001-0.01).

2. The method for preparing cyclic sulfate from cyclic sulfite according to claim 1, characterized in that: The cyclic sulfite is compound ⅠⅠ-1, compound ⅠⅠ-2 or compound ⅠⅠ-3, and the cyclic sulfate is compound ⅠⅠⅠ-1, compound ⅠⅠⅠ-2 or compound ⅠⅠⅠ-3; The chemical reaction formula is selected from one of the following: Wherein, R1 and R2 are independently selected from hydrogen and C1-C5 alkyl; n is 1-3.

3. The method for preparing cyclic sulfate from cyclic sulfite according to claim 1, characterized in that: The cyclic sulfite is prepared by reacting thionyl chloride with a polyol; the polyol is compound I-1, compound I-2 or compound I-3, Wherein, R1 and R2 are independently selected from hydrogen and C1-C5 alkyl; n is 1-3.

4. The method for preparing cyclic sulfate from cyclic sulfite according to claim 2 or 3, characterized in that: R1 and R2 are each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

5. The method for preparing cyclic sulfate from cyclic sulfite according to claim 3, characterized in that: Also includes any one or more of the following features: A1) the polyol is selected from one or more of ethylene glycol, 1,2-dimethyl ethylene glycol, 1-ethyl ethylene glycol, 2-tert-butyl-1,3-propylene glycol, 1,3-dimethyl-2-isopropyl-1,3-propylene glycol, 1,3-diethyl-1,3-propylene glycol, 1,4-butanediol, 1,4-dimethyl-1,4-butanediol, 2,3-diethyl-1,4-butanediol, 1,2,3,4-butanetetrol, 1,4-dimethyl-1,2,3,4-butanetetrol, and pentaerythritol; A2) the molar ratio of thionyl chloride to polyol is 1:(1-2); A3) The reaction temperature is 10-20°C.

6. The method for preparing cyclic sulfate from cyclic sulfite according to claim 1, characterized in that: The oxidant is selected from one or more of sodium hypochlorite, calcium hypochlorite, potassium persulfate, potassium persulfate, sodium persulfate, ammonium persulfate, sodium percarbonate, sodium perborate, and hydrogen peroxide.

7. The method for preparing cyclic sulfate from cyclic sulfite according to claim 6, characterized in that: The oxidant is selected from one of sodium hypochlorite, calcium hypochlorite, potassium persulfate, sodium percarbonate, sodium perborate and hydrogen peroxide.

8. The method for preparing cyclic sulfate from cyclic sulfite according to claim 1, characterized in that: The organic iron catalyst is selected from one or more of porphyrin iron, phthalocyanine iron, tetrachlorophenylporphyrin iron, tetraphenylporphyrin iron, hematin, and N,N'-bis(salicylidene)ethylenediamine iron.

9. The method for preparing cyclic sulfate from cyclic sulfite according to claim 1, characterized in that: The molar ratio of the cyclic sulfite to the oxidant is 1:(1-6).

10. The method for preparing cyclic sulfate from cyclic sulfite according to claim 1, characterized in that: Also includes any one or more of the following features: B1) The reaction temperature is -10 to 20°C. B2) further comprising a solvent, wherein the solvent is selected from one or more of acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dichloromethane, ethylene dichloride, and water; B3) The post-treatment includes filtration and concentration.

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