CN112694484B - Preparation method of bicyclic sulfite and bicyclic sulfate - Google Patents
Preparation method of bicyclic sulfite and bicyclic sulfate Download PDFInfo
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- CN112694484B CN112694484B CN202011587546.3A CN202011587546A CN112694484B CN 112694484 B CN112694484 B CN 112694484B CN 202011587546 A CN202011587546 A CN 202011587546A CN 112694484 B CN112694484 B CN 112694484B
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- C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
- C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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Abstract
The invention provides a preparation method of bicyclic sulfite, wherein the bicyclic sulfite is prepared by mixing a compound A and thionyl chloride for reaction; the compound A has a structure shown in a formula (1); said bicyclic sulfite having the formula(2) The structure shown; wherein R is1～R8Each occurrence is independently selected from H, a halogen atom, a cyano group, a silane trifluoride or a C1-3 hydrocarbyl group substituted by at least one X; each X is independently selected from H, F, a silane group, a cyano group, or an isocyanate group. The preparation method has the advantages of mild reaction, no participation of solvent, short reaction time, easy process control and capability of preparing the bicyclic sulfite with high yield and high purity.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of bicyclic sulfite and bicyclic sulfate.
Background
In recent years, lithium secondary batteries have a very broad application prospect in electronics, batteries and energy sources due to their advantages of high energy density, long cycle life, no pollution and the like. However, the lithium ion battery is easy to generate gas under high temperature conditions, so that the battery is swelled or the internal pressure is too high, the battery has great potential safety hazard, and the service life of the battery is greatly reduced. In order to solve the problem of high-temperature gas generation of the lithium battery, some bicyclic sulfate additives are usually added into the electrolyte, and the additives can form SEI films on the surfaces of the positive electrode and the negative electrode of the lithium battery so as to inhibit the high-temperature gas generation of the battery, further inhibit the initial capacity reduction of the battery, improve the cycle life of the battery, and improve the high-temperature and low-temperature charge and discharge performance of the battery.
The traditional method for preparing the bicyclic sulfate of the tetrol alcohol comprises the following steps: pentaerythritol and dimethyl sulfate react at 120 deg.c and under the condition of benzene as solvent and titanate as catalyst for 10 hr. The method adopts a one-step method, has the problems of low reaction yield although the process is simple, and the raw material dimethyl sulfate is highly toxic, the benzene solvent is carcinogenic, and in addition, the reaction temperature is higher, the pressure in the production process is higher, and the requirements on safety and production are high.
Researches show that the yield can be improved by adopting a step method to prepare the bicyclic sulfate, and the bicyclic sulfite is firstly prepared and then the bicyclic sulfate is prepared. The conventional process for preparing bicyclic sulfites of the tetraol type comprises: reacting pentaerythritol with thionyl chloride under the condition of taking dichloroethane as a solvent, introducing nitrogen into a reactor, keeping the temperature at 60 ℃ after dropwise addition for 16 hours for reaction, then filtering while hot, washing with water, and removing part of solvent crystals. The method uses a large amount of organic solvent, and has the advantages of large amount of waste liquid, no environmental friendliness, long reaction time and relatively high requirements on environment-friendly and safe production.
Disclosure of Invention
Based on the above, the invention provides a preparation method of bicyclic sulfite, which has the advantages of mild reaction, no solvent participation, short reaction time, easily controlled process and capability of preparing the bicyclic sulfite with high yield and high purity.
The invention is realized by the following technical scheme.
A preparation method of bicyclic sulfite, wherein the bicyclic sulfite is prepared by mixing a compound A and thionyl chloride for reaction;
the compound A has a structure shown in a formula (1):
the bicyclic sulfite has a structure shown in formula (2):
wherein R is1～R8Each occurrence is independently selected from H, a halogen atom, a cyano group, a silane trifluoride or a C1-3 hydrocarbyl group substituted by at least one X;
each X is independently selected from H, F, a silane group, a cyano group, or an isocyanate group.
In one embodiment, R is1～R8Each occurrence is independently selected from H, F, cyano, silane trifluoride or C1-3 alkyl substituted with at least one X.
In one embodiment, the molar ratio of the thionyl chloride to the compound A is (1-14): 1.
In one embodiment, the molar ratio of the thionyl chloride to the compound A is (2-8): 1.
In one embodiment, the temperature for the reaction of the compound A and the thionyl chloride is-10 ℃ to 80 ℃.
In one embodiment, the temperature for the reaction of the compound A and the thionyl chloride is 30-50 ℃.
The invention also provides a preparation method of the bicyclic sulfate, which comprises the following steps:
the bicyclic sulfite prepared by the preparation method of the bicyclic sulfite is subjected to catalytic oxidation reaction with a solvent, a catalyst and an oxidant to prepare bicyclic sulfate, wherein the bicyclic sulfate has a structure shown in formula (3):
wherein R is1～R8The definitions of (a) are the same as above.
In one embodiment, the molar ratio of the oxidant to the bicyclic sulfite to the catalyst is (1-6): 1 (0.02% -5%).
In one embodiment, the molar ratio of the oxidant to the bicyclic sulfite to the catalyst is (1-4): 1 (0.02% -3%).
In one embodiment, the solvent is selected from at least one of acetonitrile, dichloromethane, dichloroethane, chloroform, and carbon tetrachloride.
In one embodiment, the oxidizing agent is selected from at least one of peroxysulfuric acid, peroxydisulfate, sodium hypochlorite, sodium periodate, potassium permanganate, and hydrogen peroxide.
In one embodiment, the catalyst is selected from at least one of titanate, ruthenium trichloride, rhodium trichloride, iridium trichloride, manganese sulfate, and manganese chloride.
In one embodiment, the temperature of the catalytic oxidation reaction is-20 ℃ to 40 ℃.
Compared with the prior art, the preparation method of the bicyclic sulfite has the following beneficial effects:
the preparation method of the bicyclic sulfate tries to prepare the intermediate product bicyclic sulfite under the condition of no solvent for the first time, not only avoids the harm caused by using an organic solvent, but also improves the utilization rate of reaction raw materials to a great extent, and the preparation method has the advantages of easily available raw materials, simple process and wide popularization and application.
Furthermore, the preparation method can avoid side reactions, and the product is easy to purify, so that the yield of the bicyclic sulfite prepared under the solvent-free condition is improved, the conditions in the whole reaction process are mild, and the reaction time is short.
Drawings
FIG. 1 is a NMR chart of the bicyclic sulfite product of example 3 of the present invention;
FIG. 2 is the NMR chart of the bicyclic sulfate product of example 3 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Term(s) for
Unless otherwise stated or contradicted, terms or phrases used herein have the following meanings:
in the present invention, "substituted" means that a hydrogen atom is substituted with a substituent.
The elemental carbon, hydrogen, oxygen, nitrogen or halogen referred to in the groups and compounds of the invention include isotopes thereof, and the elemental carbon, hydrogen, oxygen or nitrogen referred to in the groups and compounds of the invention are optionally further replaced by one or more of their corresponding isotopes, wherein isotopes of carbon include12C、13C and14c, isotopes of hydrogen including protium (H), deuterium (D, also called deuterium), tritium (T, also called deuterium), isotopes of oxygen including16O、17O and18isotopes of O, nitrogen including14N and15isotopes of N, chlorine including35Cl and37cl, isotopes of bromine including79Br and81Br。
the term "alkyl" refers to a saturated hydrocarbon containing a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof. The phrase including the term, for example, "alkyl group having 1 to 3 carbon atoms" may be, independently of each other, alkyl group having 1 carbon atom, alkyl group having 2 carbon atoms, and alkyl group having 3 carbon atoms at each occurrence.
The invention provides a preparation method of bicyclic sulfite, wherein the bicyclic sulfite is prepared by mixing a compound A and thionyl chloride for reaction;
compound a has the structure shown in formula (1):
the bicyclic sulfite has a structure shown in formula (2):
wherein R is1～R8Each occurrence is independently selected from H, halogen atom, cyano, triFluorinated silane or hydrocarbyl substituted by at least one X and having 1-3 carbon atoms;
each X is independently selected from H, F, a silane group, a cyano group, or an isocyanate group.
In one specific example, R1～R8Each occurrence is independently selected from H, F, cyano, silane trifluoride or C1-3 alkyl substituted with at least one X.
In a specific example, compound a is pentaerythritol, 3, 3-bis- (1-hydroxy-ethyl) -pentane-2, 4-diol, 1, 3-difluoro-2, 2-bishydroxymethylpropane-1, 3-propanediol, 1, 3-difluoro-2, 2-bis- (fluorohydroxymethyl) propane-1, 3-propanediol, 2-bis- (difluoro-hydroxymethyl) -1,1,3, 3-tetrafluoropropane-1, 3-propanediol, 2-bis- (hydroxytrifluorosilyl-methyl) -1, 3-bistrifluorosilyl-propane-1, 3-propanediol, 3, 3-bis- (cyano-hydroxy-methyl) -2, 4-dihydroxy-pentadienenitrile or 3, 3-bis- (1-hydroxy-2-isocyanato-ethyl) -1, 5-diisocyanatopentane-2, 4-diol.
In a specific example, the molar ratio of thionyl chloride to compound A is (1-14): 1; preferably, the molar ratio of the thionyl chloride to the compound A is (2-8) to 1; more preferably, the molar ratio of the thionyl chloride to the compound A is (3-8) to 1; more preferably, the molar ratio of the thionyl chloride to the compound A is (4.5-8): 1. It is understood that, in the present application, the molar ratio of thionyl chloride to compound a includes, but is not limited to, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8: 1.
In a specific example, the temperature for reacting the compound A with thionyl chloride is-10 ℃ to 80 ℃; preferably, the temperature for the reaction of the compound A and thionyl chloride is 15-80 ℃; more preferably, the temperature for the reaction of the compound A and the thionyl chloride is 20-60 ℃; it is understood that, in the present application, the temperature at which compound a reacts with thionyl chloride includes, but is not limited to: 20 ℃, 25 ℃, 30 ℃, 33 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 47 ℃, 50 ℃, 53 ℃, 55 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃.
In a specific example, the reaction time of the compound A and thionyl chloride is 5-7 hours; further, the reaction time of compound a with thionyl chloride was 6 hours.
In one particular example, compound a is reacted with thionyl chloride in a nitrogen-blanketed environment.
In a specific example, a product obtained after the compound A and thionyl chloride are reacted is taken, subjected to solid-liquid separation, washed with water and recrystallized.
The invention also provides a preparation method of the bicyclic sulfate, which comprises the following steps:
the bicyclic sulfite prepared by the preparation method of the bicyclic sulfite is taken to perform catalytic oxidation reaction with a solvent, a catalyst and an oxidant to prepare bicyclic sulfate, wherein the bicyclic sulfate has a structure shown in a formula (3):
wherein R is1～R8The definitions of (a) are the same as above.
In a specific example, the mole ratio of the oxidant, the bicyclic sulfite and the catalyst is (1-6) to 1 (0.02-5%); preferably, the molar ratio of the oxidant to the bicyclic sulfite to the catalyst is (1-4): 1 (0.02% -3%); more preferably, the molar ratio of the oxidant, the bicyclic sulfite and the catalyst is (1-3): 1 (0.1% -0.3%).
In a specific example, the solvent is selected from at least one of acetonitrile, dichloromethane, dichloroethane, chloroform, and carbon tetrachloride.
In a specific example, the oxidizing agent is selected from at least one of peroxysulfuric acid, peroxydisulfate, sodium hypochlorite, sodium periodate, potassium permanganate, and hydrogen peroxide; preferably, the oxidizing agent is selected from at least one of sodium hypochlorite, sodium periodate and potassium permanganate.
In a specific example, the catalyst is selected from at least one of a water-soluble metal salt and a hydrate of the water-soluble metal salt; further, the water-soluble metal salt is a water-soluble transition metal salt.
Further, the catalyst is selected from at least one of titanate, ruthenium trichloride, rhodium trichloride, iridium trichloride, manganese sulfate and manganese chloride; preferably, the catalyst is selected from at least one of titanate, ruthenium trichloride, rhodium trichloride and iridium trichloride.
In one specific example, the temperature of the catalytic oxidation reaction is-20 ℃ to 40 ℃; preferably, the temperature of the catalytic oxidation reaction is-5 ℃ to 30 ℃; it is to be understood that in the present application, the temperature of the catalytic oxidation reaction includes, but is not limited to: -5 ℃, -4 ℃, -3 ℃, -2 ℃, -1 ℃, 0 ℃,1 ℃,2 ℃,3 ℃,4 ℃,5 ℃,10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃.
In a specific example, the process for preparing the bicyclic sulfate further comprises the steps of: and (3) collecting the product after the catalytic oxidation reaction, collecting an organic layer, distilling and recrystallizing.
The crude bicyclic sulfate is obtained by distilling the solvent, and the refined bicyclic sulfate with the purity of 99.9 percent is obtained after recrystallization, the yield is improved to 85 percent, the whole reaction is mild, and the side reaction is less.
The preparation of bicyclic sulfites and bicyclic sulfates according to the present invention is described in further detail below with reference to specific examples. The starting materials used in the following examples are all commercially available products unless otherwise specified.
Example 1
The embodiment provides a preparation method of bicyclic sulfite and bicyclic sulfate, which comprises the following steps:
adding thionyl chloride (0.8mol) and pentaerythritol (0.2mol) into a reaction bottle with nitrogen circulation protection at normal temperature, stirring, raising the reaction temperature to 60 ℃, stirring for reaction for 6 hours, cooling to room temperature after the reaction is finished, carrying out solid-liquid separation, recycling liquid thionyl chloride, wherein the solid is bicyclic sulfite (3, 9-dioxide-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), the yield is 85.5%, and the purity is 99.23%;
and subsequently, sequentially adding acetonitrile, bicyclic sulfite (0.171mol) and ruthenium trichloride hydrate (0.3%) into a reaction bottle, cooling to-5 ℃ for stabilization, dropwise adding a sodium hypochlorite (0.38mol) solution, maintaining the temperature at room temperature after dropwise adding, collecting an organic phase after reaction for 1h, distilling the acetonitrile under reduced pressure, washing, recrystallizing and drying to obtain 41.96g of bicyclic sulfate (3,3,9, 9-tetraoxide-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the total yield is 80.70%, the purity GC (gas chromatography) is 99.9%, the water content is less than or equal to 30ppm, and the chloride ion content is less than or equal to 20 ppm.
Example 2
The embodiment provides a preparation method of bicyclic sulfite and bicyclic sulfate, which comprises the following steps:
at normal temperature, thionyl chloride (1.0mol) and pentaerythritol (0.2mol) are added into a reaction bottle with nitrogen circulation protection and stirred, the reaction temperature is raised to 40 ℃, the mixture is stirred and reacted for 6 hours, the mixture is cooled to room temperature, solid-liquid separation is carried out, liquid thionyl chloride is recycled, solid is bicyclic sulfite crude product (3, 9-dioxide-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), the yield is 86.7%, and the purity is 99.41%.
And then sequentially adding dichloromethane, bicyclic sulfite (0.173mol) and ruthenium trichloride hydrate (0.25%) into a reaction bottle, cooling to-5 ℃ for stabilization, dropwise adding a sodium hypochlorite (0.47mol) solution, keeping the temperature at room temperature after dropwise adding for reaction for 1h, collecting an organic phase, carrying out reduced pressure distillation to obtain dichloromethane, washing with water, recrystallizing and drying to obtain 43.41g of bicyclic sulfate (3,3,9, 9-tetraoxide-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the total yield is 83.50%, the purity GC (gas chromatography) is 99.9%, the water content is less than or equal to 30ppm, and the chloride ion content is less than or equal to 20 ppm.
Example 3
The embodiment provides a preparation method of bicyclic sulfite and bicyclic sulfate, which comprises the following steps:
at normal temperature, adding thionyl chloride (1.2mol) and pentaerythritol (0.2mol) into a reaction bottle with nitrogen circulation protection, stirring, raising the reaction temperature to 40 ℃, stirring for reaction for 6 hours, cooling to room temperature, carrying out solid-liquid separation to obtain solid bicyclic sulfite, recycling the liquid thionyl chloride, wherein the solid is a crude bicyclic sulfite (3, 9-dioxide-2, 4,8, 10-tetraoxa-3, 9-dithiaspiro [5.5] undecane), the yield is 92.31%, the purity is 99.89%, and the nuclear magnetic resonance hydrogen spectrum of the bicyclic sulfite is shown in figure 1;
and subsequently, adding acetonitrile, bicyclic sulfite (0.184mol) and ruthenium trichloride hydrate (0.15%) into a reaction bottle in sequence, cooling to-5 ℃ for stabilization, dropwise adding a sodium hypochlorite (0.55mol) solution, keeping the temperature at room temperature after dropwise adding for reaction for 1h, collecting an organic phase, carrying out reduced pressure distillation to remove acetonitrile, washing with water, recrystallizing and drying to obtain 44.45g of bicyclic sulfate (3,3,9, 9-tetraoxide-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the nuclear magnetic resonance hydrogen spectrogram of the bicyclic sulfate is shown in figure 2. The total yield is 85.50%, the purity GC detection is 99.9%, the water content is less than or equal to 30ppm, and the chloride ion content is less than or equal to 20 ppm.
Example 4
The embodiment provides a preparation method of bicyclic sulfite and bicyclic sulfate, which comprises the following steps: adding thionyl chloride (0.6mol) and 3, 3-bis- (1-hydroxy-ethyl) -pentane-2, 4-diol (0.1mol) into a reaction bottle with nitrogen circulation protection at normal temperature, stirring, raising the reaction temperature to 40 ℃, stirring for reacting for 6 hours, cooling to room temperature, and carrying out solid-liquid separation to obtain bicyclic sulfite (3, 9-dioxide-1, 5,7, 11-tetramethyl-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the yield is 90% and the purity is 99.57%;
and then acetonitrile, bicyclic sulfite (0.09mol) and ruthenium trichloride hydrate (0.15%) are sequentially added into a reaction bottle, the temperature is reduced to below-5 ℃ and stabilized, sodium hypochlorite (0.3mol) solution is dropwise added, the temperature is maintained at room temperature after dropwise addition is finished and the reaction is carried out for 1h, an organic phase is collected, acetonitrile is distilled under reduced pressure, and the bicyclic sulfate (3,3,9, 9-tetraoxide-1, 5,7, 11-tetramethyl-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane) is obtained by washing, recrystallization and drying, wherein the total yield is 83.2%, the purity is 99.8%, the water content is less than or equal to 30ppm, and the chloride ion content is less than or equal to 20 ppm.
Example 5
The embodiment provides a preparation method of bicyclic sulfite and bicyclic sulfate, which comprises the following steps:
adding thionyl chloride (0.6mol) and 1, 3-difluoro-2, 2-bis (hydroxymethyl) propane-1, 3-propanediol (0.1mol) into a reaction bottle with nitrogen circulation protection at normal temperature, stirring, raising the reaction temperature to 40 ℃, stirring for reacting for 6 hours, cooling to room temperature, and carrying out solid-liquid separation to obtain bicyclic sulfite (3, 9-dioxide-1, 7-difluoro-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the yield is 93% and the purity is 99.45%;
and then acetonitrile, bicyclic sulfite (0.093mol) and ruthenium trichloride hydrate (0.15%) are sequentially added into a reaction bottle, the temperature is reduced to-5 ℃ and stabilized, sodium hypochlorite (0.3mol) solution is dropwise added, the temperature is maintained at room temperature after dropwise addition is finished and the reaction is carried out for 1h, an organic phase is collected, acetonitrile is distilled under reduced pressure, and 25.15g of bicyclic sulfate (3,3,9, 9-tetraoxide-1, 7-difluoro-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane) is obtained by washing, recrystallization and drying, wherein the yield is 84.98%, the purity is 99.8%, the water content is less than or equal to 30ppm, and the chloride ion content is less than or equal to 20 ppm.
Example 6
The embodiment provides a preparation method of bicyclic sulfite and bicyclic sulfate, which comprises the following steps:
adding thionyl chloride (0.6mol) and 1, 3-difluoro-2, 2-bis- (fluoromethyl) propane-1, 3-propanediol (0.1mol) into a reaction bottle with nitrogen circulation protection at normal temperature, stirring, raising the reaction temperature to 40 ℃, stirring for reacting for 6 hours, cooling to room temperature, and carrying out solid-liquid separation to obtain bicyclic sulfite (3, 9-dioxide-1, 5,7, 11-tetrafluoro-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the yield is 92.7% and the purity is 99.37%;
and then adding acetonitrile, bicyclic sulfite (0.093mol) and ruthenium trichloride hydrate (0.15%) into a reaction bottle in sequence, cooling to below-5 ℃ for stabilization, dropwise adding a sodium hypochlorite (0.3mol) solution, keeping the temperature at room temperature after dropwise adding for reaction for 1h, collecting an organic phase, carrying out reduced pressure distillation to remove acetonitrile, washing with water, recrystallizing and drying to obtain 28.84g of bicyclic sulfate (3,3,9, 9-tetraoxide-1, 5,7, 11-tetrafluoro-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the total yield is 86.9%, the purity is 99.8%, the water content is less than or equal to 30ppm, and the chloride ion content is less than or equal to 20 ppm.
Example 7
The embodiment provides a preparation method of bicyclic sulfite and bicyclic sulfate, which comprises the following specific steps:
adding thionyl chloride (0.6mol) and 2, 2-bis- (difluoro-hydroxymethyl) -1,1,3, 3-tetrafluoropropane-1, 3-propanediol (0.1mol) into a reaction bottle with nitrogen circulation protection at normal temperature, stirring, raising the reaction temperature to 40 ℃, stirring for reacting for 6 hours, cooling to room temperature, and carrying out solid-liquid separation to obtain bicyclic sulfite (3, 9-dioxide-1, 1,5,5,7,7,11, 11-octafluoro-2, 4,8, 10-tetraoxa-3, 9-dithiaspiro [5.5] undecane), wherein the yield is 91.1% and the purity is 99.78%;
and then adding acetonitrile, bicyclic sulfite (0.091mol) and ruthenium trichloride hydrate (0.15%) into a reaction bottle in sequence, cooling to below-5 ℃ for stabilization, dropwise adding a sodium hypochlorite (0.3mol) solution, keeping the temperature at room temperature after dropwise adding for reaction for 1h, collecting an organic phase, carrying out reduced pressure distillation to remove acetonitrile, washing with water, recrystallizing and drying to obtain 32.37g of bicyclic sulfate (3,3,9, 9-tetraoxide-1, 1,5,5,7,7,11, 11-octafluoro-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the total yield is 80.16%, the purity is 99.8%, the water content is less than or equal to 30ppm, and the chloride ion content is less than or equal to 20 ppm.
Example 8
The embodiment provides a preparation method of bicyclic sulfite and bicyclic sulfate, which comprises the following steps:
adding thionyl chloride (0.5mol) and 2, 2-bis- (hydroxyl trifluoro silyl-methyl) -1, 3-bis-trifluoro silyl-propane-1, 3-propanediol (0.1mol) into a reaction bottle with nitrogen circulation protection at normal temperature, stirring, raising the reaction temperature to 40 ℃, stirring for reaction for 6 hours, cooling to room temperature, and carrying out solid-liquid separation to obtain bicyclic sulfite (3, 9-dioxide-1, 5,7, 11-tetra-trifluoro silyl-2, 4,8, 10-tetraoxa-3, 9-dithiaspiro [5.5] undecane), wherein the yield is 89.9% and the purity is 99.53%;
and then adding acetonitrile, bicyclic sulfite (0.09mol) and ruthenium trichloride hydrate (0.15%) into a reaction bottle in sequence, cooling to below-5 ℃ for stabilization, dropwise adding a sodium hypochlorite (0.3mol) solution, keeping the temperature at room temperature after dropwise adding for reaction for 1h, collecting an organic phase, carrying out reduced pressure distillation to remove acetonitrile, washing with water, recrystallizing and drying to obtain 49.33g of bicyclic sulfate (3,3,9, 9-tetraoxide-1, 5,7, 11-tetra-trifluoromethyl-silyl-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the total yield is 82.79%, the purity is 99.8%, the water content is less than or equal to 30ppm, and the chloride ion content is less than or equal to 20 ppm.
Example 9
The embodiment provides a preparation method of bicyclic sulfite and bicyclic sulfate, which comprises the following steps:
adding thionyl chloride (0.5mol) and 3, 3-bis- (cyano-hydroxy-methyl) -2, 4-dihydroxy-pentadiene nitrile (0.1mol) into a reaction bottle with nitrogen circulation protection at normal temperature, stirring, raising the reaction temperature to 40 ℃, stirring for reacting for 6h, cooling to room temperature, and carrying out solid-liquid separation to obtain bicyclic sulfite (3, 9-dioxide-1, 5,7, 11-tetramethylnitrile-2, 4,8, 10-tetraoxa-3, 9-dithiaspiro [5.5] undecane), wherein the yield is 86.18% and the purity is 99.37%;
and then adding acetonitrile, bicyclic sulfite (0.086mol) and ruthenium trichloride hydrate (0.15%) into a reaction bottle in sequence, cooling to below-5 ℃ for stabilization, dropwise adding a sodium hypochlorite (0.3mol) solution, keeping the temperature at room temperature after dropwise adding for reaction for 1h, collecting an organic phase, carrying out reduced pressure distillation to remove acetonitrile, washing with water, recrystallizing and drying to obtain 18.62g of bicyclic sulfate (3,3,9, 9-tetraoxide-1, 5,7, 11-tetramethacrylonitrile-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the total yield is 80.36%, the purity is 99.8%, the water content is less than or equal to 30ppm, and the chloride ion content is less than or equal to 20 ppm.
Example 10
The embodiment provides a preparation method of bicyclic sulfite and bicyclic sulfate, which comprises the following steps:
adding thionyl chloride (0.5mol) and 3, 3-bis- (1-hydroxy-2-isocyanato-ethyl) -1, 5-diisocyanatopentane-2, 4-diol (0.1mol) into a reaction bottle with nitrogen circulation protection at normal temperature, stirring, raising the reaction temperature to 40 ℃, stirring for reacting for 6 hours, cooling to room temperature, and carrying out solid-liquid separation to obtain bicyclic sulfite (3, 9-dioxide-1, 5,7, 11-tetraisocyanatomethyl ester-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the yield is 88.14% and the purity is 99.07%;
and then acetonitrile, bicyclic sulfite (0.88mol) and ruthenium trichloride hydrate (0.15%) are sequentially added into a reaction bottle, the temperature is reduced to-5 ℃ and stabilized, sodium hypochlorite (0.3mol) solution is dropwise added, the temperature is maintained at room temperature after dropwise addition is finished and the reaction is carried out for 1h, an organic phase is collected, acetonitrile is distilled under reduced pressure, and the bicyclic sulfate (3,3,9, 9-dioxide-1, 5,7, 11-methyl tetraisocyanate-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane) is obtained by washing, recrystallization and drying, wherein the yield is 81.72%, the purity is 99.8%, the water content is less than or equal to 30ppm, and the chloride ion content is less than or equal to 20 ppm.
Example 11
The embodiment provides a preparation method of bicyclic sulfite and bicyclic sulfate, which comprises the following steps:
adding thionyl chloride (1.0mol) and pentaerythritol (0.5mol) into a reaction bottle with nitrogen circulation protection at normal temperature, stirring, raising the reaction temperature to 40 ℃, stirring for reaction for 6 hours, cooling to room temperature, carrying out solid-liquid separation, recycling liquid thionyl chloride, wherein the solid is bicyclic sulfite (3, 9-dioxide-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), the yield is 47.93%, and the purity is 99.31%;
and then sequentially adding dichloromethane, bicyclic sulfite (0.29mol) and ruthenium trichloride hydrate (0.25%) into a reaction bottle, cooling to-5 ℃ for stabilization, dropwise adding a sodium hypochlorite (0.47mol) solution, keeping the temperature at room temperature after dropwise adding for reaction for 1h, collecting an organic phase, carrying out reduced pressure distillation to obtain dichloromethane, washing with water, recrystallizing and drying to obtain 59.01g of bicyclic sulfate (3,3,9, 9-tetraoxide-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the yield is 35.17%, the purity is 99.15%, the water content is less than or equal to 30ppm, and the chloride ion content is less than or equal to 20 ppm.
Example 12
The embodiment provides a preparation method of bicyclic sulfite and bicyclic sulfate, which comprises the following steps:
at normal temperature, adding thionyl chloride (1.0mol) and pentaerythritol (0.2mol) into a reaction bottle with nitrogen circulation protection, stirring, raising the reaction temperature to 90 ℃, stirring for reaction for 6 hours, cooling to room temperature, carrying out solid-liquid separation to obtain solid bicyclic sulfite (3, 9-dioxide-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the yield is 60.2%, the purity is 99.12%, the temperature exceeds the boiling point of thionyl chloride, the loss is large, and the reflux of hydrogen chloride tail gas in condensation reflux influences the reaction process;
and then sequentially adding dichloromethane, bicyclic sulfite (0.12mol) and ruthenium trichloride hydrate (0.25%) into a reaction bottle, cooling to-5 ℃ for stabilization, dropwise adding a sodium hypochlorite (0.47mol) solution, keeping the temperature at room temperature after dropwise adding for reaction for 1h, collecting an organic phase, carrying out reduced pressure distillation to obtain dichloromethane, washing with water, recrystallizing and drying to obtain 23.57g of bicyclic sulfate (3,3,9, 9-dioxide-2, 4,8, 10-tetraoxa-3, 9-dithiospiro [5.5] undecane), wherein the yield is 45.35%, the purity is 99.8%, the water content is less than or equal to 30ppm, and the chloride ion content is less than or equal to 20 ppm.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. The preparation method of the bicyclic sulfite is characterized in that the bicyclic sulfite is prepared by mixing and reacting a compound A and thionyl chloride under the solvent-free condition;
the compound A has a structure shown in a formula (1):
the bicyclic sulfite has a structure shown in formula (2):
wherein R is1～R8Each occurrence is independently selected from H, a halogen atom, a cyano group, a silane trifluoride or a C1-3 hydrocarbyl group substituted by at least one X;
each X is independently selected from H, F, a silane group, a cyano group, or an isocyanate group;
the reaction temperature of the compound A and the thionyl chloride is 40-60 ℃;
the molar ratio of the thionyl chloride to the compound A is (3-8): 1.
2. The method of claim 1, wherein R is selected from the group consisting of1～R8Each occurrence is independently selected from H, F, cyano, silane trifluoride or C1-3 alkyl substituted with at least one X.
3. A process for the preparation of a bicyclic sulfite according to claim 1 wherein compound a is pentaerythritol, 3-bis- (1-hydroxy-ethyl) -pentane-2, 4-diol or 3, 3-bis- (1-hydroxy-2-isocyanato-ethyl) -1, 5-diisocyanatopentane-2, 4-diol.
4. The method for preparing bicyclic sulfite according to claim 1, wherein the molar ratio of thionyl chloride to compound A is (4.5-8): 1.
5. A process according to any one of claims 1 to 4, characterized in that said compound A is reacted with said thionyl chloride in an environment protected by nitrogen recycle.
6. The method for preparing bicyclic sulfite according to any one of claims 1 to 4, wherein a product obtained by reacting the compound A with thionyl chloride is subjected to solid-liquid separation, water washing and recrystallization.
7. The method according to any one of claims 1 to 4, wherein the reaction time of compound A with thionyl chloride is 5 to 7 hours.
8. A process for the preparation of a bicyclic sulfite according to claim 7 wherein the reaction time of Compound A with thionyl chloride is 6 hours.
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