CN114380844B - Preparation method of spiro sulfite and preparation method of spiro sulfate - Google Patents
Preparation method of spiro sulfite and preparation method of spiro sulfate Download PDFInfo
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- CN114380844B CN114380844B CN202011132293.0A CN202011132293A CN114380844B CN 114380844 B CN114380844 B CN 114380844B CN 202011132293 A CN202011132293 A CN 202011132293A CN 114380844 B CN114380844 B CN 114380844B
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- 125000003003 spiro group Chemical group 0.000 title claims abstract description 148
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 title claims abstract description 99
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003960 organic solvent Substances 0.000 claims abstract description 41
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 18
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002798 polar solvent Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000012535 impurity Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000005708 Sodium hypochlorite Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000004651 carbonic acid esters Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- -1 spiro sulfites Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D497/10—Spiro-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
In order to solve the problems of more product impurities and low yield in the existing synthesis of spiro sulfite, the invention provides a preparation method of spiro sulfite, which comprises the following operation steps: mixing pentaerythritol with a first organic solvent, adding thionyl chloride, reacting to obtain a reaction solution containing spiro sulfite, and purifying to obtain spiro sulfite; the first organic solvent includes one or more of a carbonate or a carboxylate. Meanwhile, the invention also discloses a preparation method of the spiro sulfate comprising the preparation method. According to the preparation method of the spiro sulfite, provided by the invention, the generation of colored impurities in the reaction can be inhibited through the selection of the first organic solvent, and the yield and the purity of the finished product are effectively improved.
Description
Technical Field
The invention belongs to the technical field of spiro sulfate preparation, and particularly relates to a preparation method of spiro sulfite and a preparation method of spiro sulfate.
Background
The cyclic sulfate is used as an additive of the lithium ion battery electrolyte, and has the effects of inhibiting the reduction of initial capacity of the battery, increasing initial discharge capacity, reducing the expansion of the battery after high-temperature placement and improving the charge and discharge performance and cycle times of the battery.
In the existing reported synthetic route, the color of the spiro sulfite product obtained in the synthesis process of the spiro sulfite is yellow, and the spiro sulfite product can be purified by recrystallization, so that the yield of the product is reduced.
On the other hand, in the synthesis route reported in the prior art, partial raw material spiro sulfite remains in the process of oxidizing spiro sulfite to obtain spiro sulfate, so that the quality of spiro sulfate is affected, and repeated recrystallization and purification are needed.
Disclosure of Invention
Aiming at the problems of more product impurities and low yield in the existing synthesis of spiro sulfite, the invention provides a preparation method of spiro sulfite and a preparation method of spiro sulfate.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the invention provides a method for preparing spiro sulfite, comprising the following steps:
mixing pentaerythritol with a first organic solvent, adding thionyl chloride, reacting to obtain a reaction solution containing spiro sulfite, and purifying to obtain spiro sulfite;
the first organic solvent includes one or more of a carbonate or a carboxylate.
Optionally, the carbonic ester comprises one or more of dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate;
the carboxylic acid ester comprises one or more of methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate and butyl propionate.
Optionally, after pentaerythritol is mixed with the first organic solvent, the temperature is raised to 40-70 ℃, thionyl chloride is added dropwise, the temperature is controlled to 70-80 ℃ after the dropwise addition is finished, and the reaction is carried out for 8-10 hours, thus obtaining the reaction solution containing spiro sulfite.
Optionally, after the reaction is finished, evaporating the organic solvent to obtain white solid, washing with water, and suction filtering to obtain spiro sulfite.
Optionally, the molar ratio of the pentaerythritol to the thionyl chloride is 1:1.9 to 2.2.
In another aspect, the invention provides a method for preparing spiro sulfate, comprising the following steps:
preparing spiro sulfite by adopting the preparation method;
mixing spiro sulfite, a second organic solvent and a catalyst, adding an oxidant aqueous solution, reacting to obtain a reaction solution containing spiro sulfate, and purifying to obtain spiro sulfate;
the second organic solvent includes an organic polar solvent.
Optionally, the organic polar solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Optionally, mixing spiro sulfite, a second organic solvent and a catalyst, heating and dissolving, cooling to 30-50 ℃ to form supersaturated solution, dropwise adding an oxidant aqueous solution, continuously heating to 50-80 ℃ after dropwise adding, reacting for 2-4 h to obtain a reaction solution containing spiro sulfate, carrying out suction filtration on the reaction solution containing spiro sulfate to obtain first filter residues, washing and collecting the first filter residues, evaporating the solvent from the filtrate, carrying out suction filtration again to obtain second filter residues, washing and collecting the second filter residues, and recrystallizing the filter residues obtained in the two times by using a third organic solvent to obtain white crystal spiro sulfate.
Optionally, the third organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Optionally, the catalyst is selected from ruthenium trichloride, and the addition amount of the catalyst is 0.01% -0.05% of the mass of the spiro sulfite;
the oxidant in the oxidant aqueous solution is selected from hypochlorite, and the mol ratio of the spiro sulfite to the available chlorine in the hypochlorite is 1:2.0 to 2.2.
According to the preparation method of the spiro sulfite provided by the invention, the inventor finds that the color of the spiro sulfite substance is white through a large number of experiments, but a colorless and transparent reaction system in the preparation process of the traditional preparation process is gradually changed into light yellow, the prepared spiro sulfite presents light yellow, which shows that certain impurities are contained in the spiro sulfite, meanwhile, the inventor finds that one or more of carbonic acid esters or carboxylic acid esters are adopted as a first organic solvent in a reaction system of pentaerythritol and thionyl chloride through changing the solvent type, so that the discoloration problem of the spiro sulfite in the reaction process can be effectively inhibited, the system can keep a colorless and transparent state in the reaction process, the product is characterized through LC-MS (liquid chromatography-mass spectrometer) and NMR (nuclear magnetic resonance spectrometer), the product yield is effectively improved, and the purified spiro sulfite is white solid, which shows that the generation of the colored impurities existing in the reaction can be inhibited through the selection of the first organic solvent, and the yield and the finished product are not required to be effectively improved through recrystallization purification.
According to the preparation method of the spiro sulfate, the spiro sulfite can be effectively dissolved by adopting the organic polar solvent, meanwhile, the mixing of the oxidant aqueous solution and the spiro sulfite reaction system is facilitated, the occurrence of solid precipitation of raw materials in the reaction system is avoided, the reaction efficiency is effectively improved, meanwhile, the reaction is promoted to be carried out towards the direction of generating the spiro sulfate by adopting the organic polar solvent solution, the dosage of a catalyst is reduced, the residue of the spiro sulfite in the reaction solution is avoided, the product purification process is simple, and the product purity is higher and can reach more than 99.5%.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a preparation method of spiro sulfite, which comprises the following operation steps:
mixing pentaerythritol with a first organic solvent, adding thionyl chloride, reacting to obtain a reaction solution containing spiro sulfite, and purifying to obtain spiro sulfite;
the first organic solvent includes one or more of a carbonate or a carboxylate.
The inventor finds out through a large number of experiments that the color of a spiro sulfite substance is white, but a colorless and transparent reaction system in the traditional preparation process gradually turns yellow, the prepared spiro sulfite is light yellow, which shows that the spiro sulfite contains certain impurities, meanwhile, the inventor finds out that one or more of carbonic acid esters or carboxylic acid esters are adopted as a first organic solvent in a reaction system of pentaerythritol and thionyl chloride through changing the solvent type, so that the color change problem of the spiro sulfite in the reaction process can be effectively inhibited, the system can keep a colorless and transparent state in the reaction process, the product is characterized by LC-MS (liquid chromatography-mass spectrometer) and NMR (nuclear magnetic resonance) to prove that the yield of the product is effectively improved, and the purified spiro sulfite is white solid, which shows that the generation of colored impurities existing in the reaction can be inhibited through the selection of the first organic solvent, and the yield and the finished product are effectively improved without recrystallization purification.
In some embodiments, the carbonate comprises one or more of dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate;
the carboxylic acid ester comprises one or more of methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate and butyl propionate.
The above carbonates and carboxylic acid esters are preferred compounds for the claimed part of the present invention, but are not limited thereto and should not be construed as limiting the invention.
In some embodiments, after pentaerythritol is mixed with the first organic solvent, the temperature is raised to 40-70 ℃, thionyl chloride is added dropwise, the temperature is controlled to 70-80 ℃ after the dropwise addition is finished, and the reaction is carried out for 8-10 hours, so as to obtain the reaction solution containing spiro sulfite.
In the reaction process, hydrogen chloride gas and redundant thionyl chloride can be generated, and the tail gas absorbing device is arranged to absorb the hydrogen chloride gas and the redundant thionyl chloride, so that the pollution to the operation environment is avoided.
In some embodiments, the organic solvent is distilled off after the reaction is completed to give a white solid, which is washed with water and suction filtered to give the spiro sulfite.
The structural formula of the spiro sulfite is as follows:
in some embodiments, the molar ratio of pentaerythritol to thionyl chloride is 1:1.9 to 2.2.
If the addition amount of the thionyl chloride is too low, more reaction residues of pentaerythritol are easy to cause, and the yield of spiro sulfite is influenced; if the addition amount of thionyl chloride is too high, more unreacted thionyl chloride is generated, which is also unfavorable for improving the yield and increases the cost of raw materials.
Another embodiment of the present invention provides a method for preparing spiro sulfate, comprising the following steps:
preparing spiro sulfite by adopting the preparation method;
mixing spiro sulfite, a second organic solvent and a catalyst, adding an oxidant aqueous solution, reacting to obtain a reaction solution containing spiro sulfate, and purifying to obtain spiro sulfate;
the second organic solvent includes an organic polar solvent.
The spiro sulfite can be effectively dissolved by adopting the organic polar solvent, meanwhile, the mixing of the oxidant aqueous solution and the spiro sulfite reaction system is facilitated, the occurrence of solid precipitation of raw materials in the reaction system is avoided, the reaction efficiency is effectively improved, meanwhile, the reaction is promoted to be carried out towards the direction of generating the spiro sulfite by adopting the organic polar solvent solution, the dosage of the catalyst is reduced, the residue of the spiro sulfite in the reaction solution is avoided, the product purification process is simple, and the product purity is higher and can reach more than 99.5%.
In some embodiments, the organic polar solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone.
The above organic polar solvent is a preferred compound for the claimed part of the present invention, but is not limited thereto and should not be construed as limiting the invention.
In some embodiments, after mixing the spiro sulfite, the second organic solvent and the catalyst, heating and dissolving, cooling to 30-50 ℃ to form supersaturated solution, dropwise adding aqueous solution of oxidant, after the dropwise adding is finished, continuously heating to 50-80 ℃, reacting for 2-4 h to obtain reaction liquid containing spiro sulfate, carrying out suction filtration on the reaction liquid containing spiro sulfate to obtain first filter residues, washing and collecting the first filter residues, evaporating the solvent from the filtrate, carrying out suction filtration again to obtain second filter residues, washing and collecting the second filter residues, and recrystallizing the filter residues obtained in the two steps by using a third organic solvent to obtain white crystal spiro sulfate.
The reaction raw materials are heated to promote the dissolution of the spiro sulfite in the second organic solvent, so that the dissolution efficiency is improved, and meanwhile, the temperature is reduced to form supersaturated solution, and as the solubility of the spiro sulfite in the organic polar solvent is lower than that of the spiro sulfite, the spiro sulfate is separated out in the reaction process, the oxidation reaction is facilitated, the spiro sulfate is collected, and meanwhile, the solvent required to be distilled off in the follow-up process is reduced by adopting the supersaturated solution of the spiro sulfite for the reaction, so that the energy consumption and the raw material cost are effectively reduced.
In some embodiments, the third organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone.
In some embodiments, the catalyst is selected from ruthenium trichloride, and the catalyst is added in an amount of 0.01% to 0.05% of the mass of the spiro sulfite;
the oxidant in the oxidant aqueous solution is selected from hypochlorite, and the mol ratio of the spiro sulfite to the available chlorine in the hypochlorite is 1:2.0 to 2.2.
In the molar ratio of the spiro sulfite to the available chlorine in the hypochlorite, if the addition amount of the spiro sulfite is too high, the residue of the spiro sulfite in the reaction solution is easy to cause, and the purity of a target product is influenced; if the addition amount of the spiro sulfite is too low, hypochlorite cannot sufficiently participate in the oxidation reaction, resulting in waste of raw materials.
The invention is further illustrated by the following examples.
Example 1
The embodiment is used for illustrating a preparation method of spiro sulfite disclosed by the invention, and comprises the following operation steps:
136g of pentaerythritol solid and 650g of dimethyl carbonate are added into a reaction kettle at one time, mixed and stirred, the temperature of the system is increased to 50 ℃, 261.8g of thionyl chloride is added dropwise, and a tail gas absorption device is utilized to absorb hydrogen chloride gas and redundant thionyl chloride. After the dripping is finished, the reaction temperature is controlled at 80 ℃, the reaction is carried out for 8 hours, after the reaction is finished, the organic solvent is completely distilled off, the white solid is obtained, the solid is washed by water, and the finished product spiro sulfite is obtained by suction filtration.
Example 2
The embodiment is used for illustrating a preparation method of spiro sulfite disclosed by the invention, and comprises the following operation steps:
136g of pentaerythritol solid and 650g of ethyl acetate are added into a reaction kettle at one time, mixed and stirred, the temperature of the system is increased to 40 ℃, 250g of thionyl chloride is added dropwise, and a tail gas absorption device is utilized to absorb hydrogen chloride gas and redundant thionyl chloride. After the dripping is finished, the reaction temperature is controlled at 75 ℃, the reaction is carried out for 9 hours, after the reaction is finished, the organic solvent is completely distilled off, so that white solid is obtained, the solid is washed by water, and the finished product spiro sulfite is obtained by suction filtration.
Example 3
The embodiment is used for illustrating a preparation method of spiro sulfite disclosed by the invention, and comprises the following operation steps:
136g of pentaerythritol solid and 650g of ethyl propionate are added into a reaction kettle at one time, the mixture is mixed and stirred, the temperature of the system is increased to 60 ℃, 250g of thionyl chloride is added dropwise, and a tail gas absorption device is utilized to absorb hydrogen chloride gas and redundant thionyl chloride. After the dripping is finished, the reaction temperature is controlled at 70 ℃, the reaction is carried out for 10 hours, after the reaction is finished, the organic solvent is completely distilled off, the white solid is obtained, the solid is washed by water, and the finished product spiro sulfite is obtained by suction filtration.
Example 4
The embodiment is used for illustrating a preparation method of spiro sulfate disclosed by the invention, and comprises the following operation steps:
50g of the spiro sulfite prepared in example 1, 300g of N, N-dimethylformamide and 0.01g of ruthenium trichloride solid were added into a reaction kettle, and the temperature of the reaction system was raised to 70℃and cooled to 50℃to form a supersaturated solution. 240g of 15% sodium hypochlorite solution by mass fraction is added dropwise in sections. Performing constant temperature reaction for 4 hours, filtering the reaction liquid after the reaction is finished, washing filter residues with pure water, drying and collecting the filter residues to obtain first filter residues; and (3) removing the solvent by rotary evaporation of the filtrate, filtering to obtain a solid, washing with pure water to obtain a second filter residue, combining the first filter residue and the second filter residue, and recrystallizing with N, N-dimethylformamide to obtain the white crystal spiro sulfate.
Example 5
The embodiment is used for illustrating a preparation method of spiro sulfate disclosed by the invention, and comprises the following operation steps:
50g of the spiro sulfite prepared in example 1, 300g of N, N-dimethylacetamide and 0.02g of ruthenium trichloride solid were added into a reaction kettle, and the temperature of the reaction system was raised to 90℃and cooled to 40℃to form a supersaturated solution. 240g of 15% sodium hypochlorite solution by mass fraction is added dropwise in sections. And (3) reacting at constant temperature for 3 hours, after the reaction is finished, carrying out suction filtration on the reaction solution, washing filter residues with pure water, drying and collecting, removing a solvent by rotary evaporation of filtrate, carrying out suction filtration to obtain solid, washing the solid with pure water, combining two batches of solid, and recrystallizing with N, N-dimethylacetamide to obtain white crystal spiro sulfate.
Example 6
The embodiment is used for illustrating a preparation method of spiro sulfate disclosed by the invention, and comprises the following operation steps:
50g of the spiro sulfite prepared in example 1, 300. 300g N-methylpyrrolidone and 0.025g of ruthenium trichloride solid were added into a reaction kettle, the temperature of the reaction system was raised to 120 ℃, and after cooling, a supersaturated solution was formed. 240g of 15% sodium hypochlorite solution by mass fraction is added dropwise in sections. Performing constant temperature reaction for 2 hours, after the reaction is finished, performing suction filtration on the reaction solution, washing filter residues with pure water, drying and collecting the filter residues, and performing rotary evaporation on the filtrate to remove the solvent to obtain first filter residues; and washing the solid obtained by suction filtration with pure water to obtain second filter residue, combining the first filter residue and the second filter residue, and recrystallizing with N-methylpyrrolidone to obtain white crystal spiro sulfate.
Comparative example 1
This comparative example is used to comparatively illustrate the preparation of spiro sulfite disclosed herein, comprising the following steps:
136g of pentaerythritol solid and 650g of dichloroethane are added into a reaction kettle at one time, mixed and stirred, the temperature of the system is increased to 40 ℃, 250g of thionyl chloride is added dropwise, and a tail gas absorption device is used for absorbing hydrogen chloride gas and redundant thionyl chloride. After the dripping is finished, the reaction temperature is controlled at 80 ℃, the reaction is carried out for 9 hours, after the reaction is finished, the system is bright yellow, the organic solvent is completely distilled off to obtain a light yellow solid, the solid is washed by water, the filter residue is obtained by suction filtration, the filter residue is added into dichloroethane, the mixture is heated to a reflux state for dissolution, and the finished product spiro sulfite is obtained by suction filtration.
Comparative example 2
This comparative example is used to comparatively illustrate the preparation of spiro sulfite disclosed herein, comprising the following steps:
136g of pentaerythritol solid and 650g of toluene are added into a reaction kettle at one time, mixed and stirred, the temperature of the system is increased to 40 ℃, 250g of thionyl chloride is added dropwise, and a tail gas absorption device is utilized to absorb hydrogen chloride gas and redundant thionyl chloride. After the dripping is finished, the reaction temperature is controlled at 80 ℃, the reaction is carried out for 9 hours, after the reaction is finished, the system is bright yellow, the organic solvent is completely distilled off to obtain a light yellow solid, the solid is washed by water and filtered to obtain filter residues, the filter residues are added into toluene, heated to a reflux state and dissolved, and the filter residues are filtered to obtain the finished product spiro sulfite.
Comparative example 3
This comparative example is used to comparatively illustrate the preparation of spiro sulfite disclosed herein, comprising the following steps:
136g of pentaerythritol solid and 650g of N, N-dimethylformamide are added into a reaction kettle at one time, mixed and stirred, the temperature of the system is increased to 60 ℃, 250g of thionyl chloride is added dropwise, and a tail gas absorption device is utilized to absorb hydrogen chloride gas and redundant thionyl chloride. After the dripping is finished, the reaction temperature is controlled at 70 ℃ and the reaction is carried out for 10 hours, after the reaction is finished, the system is dark brown, the organic solvent is completely distilled off to obtain brown viscous solid, the solid is washed by water and filtered to obtain filter residues, the filter residues are added into N, N-dimethylformamide, the temperature is increased to 80 ℃ for dissolution, and the finished spiro sulfite is obtained through the filtering.
Comparative example 4
This comparative example is used to comparatively illustrate the preparation method of spiro sulfate disclosed in the present invention, and comprises the following steps:
50g of the spiro sulfite prepared in example 1, 600g of dichloroethane and 0.01g of ruthenium trichloride solid were added into a reaction kettle, the temperature of the reaction system was raised to 70 ℃, and after cooling, a supersaturated solution was formed. 240g of 15% sodium hypochlorite solution by mass fraction is added dropwise in sections. Performing constant temperature reaction for 8 hours, filtering the reaction liquid after the reaction is finished, washing filter residues with pure water, drying and collecting the filter residues to obtain first filter residues; removing the solvent from the filtrate by rotary evaporation, and performing suction filtration to obtain a solid, and washing the solid with pure water to obtain first filter residues; and combining the first filter residue and the second filter residue, and recrystallizing with dichloroethane and acetonitrile to obtain white crystal spiro sulfate.
Comparative example 5
This comparative example is used to comparatively illustrate the preparation method of spiro sulfate disclosed in the present invention, and comprises the following steps:
50g of the spiro sulfite prepared in example 1, 600g of toluene and 0.01g of ruthenium trichloride solid were added into a reaction kettle, the temperature of the reaction system was raised to 70 ℃, and after cooling, a supersaturated solution was formed. 240g of 15% sodium hypochlorite solution by mass fraction is added dropwise in sections. Performing constant temperature reaction for 9 hours, after the reaction is finished, performing suction filtration on the reaction solution, washing filter residues with pure water, drying and collecting the filter residues, and performing rotary evaporation on the filtrate to remove the solvent to obtain first filter residues; filtering to obtain solid, washing with pure water to obtain second filter residue; and combining the first filter residue and the second filter residue, and recrystallizing with toluene and acetonitrile to obtain white crystal spiro sulfate.
Performance testing
The following performance tests were carried out on the finished spiro sulfites prepared in examples 1 to 3 and comparative examples 1 to 3:
the ratio of the theoretical value of the spiro sulfite which can be prepared is calculated by the mass of the finished spiro sulfite obtained in a weighing way and the raw material theory, so that the yield is obtained.
The reaction systems and the finished spiro sulfite esters of the preparation processes of examples 1 to 3 and comparative examples 1 to 3 were visually observed, and visual color results were recorded.
And (3) adopting LC-MS (liquid chromatography-mass spectrometer) and NMR (nuclear magnetic resonance) to characterize the product, and obtaining the purity of the spiro sulfite in the finished spiro sulfite.
The test results obtained are filled in Table 1.
TABLE 1
As can be seen from the test results in Table 1, compared with other existing solvents, the spiro sulfite prepared by the preparation method provided by the invention has obviously higher yield and higher purity, and the fact that the carbonate or the carboxylate is adopted as the first organic solvent can inhibit the generation of colored impurities existing in the reaction, so that the yield is improved.
The spirocyclic sulfate esters prepared in examples 4 to 6 and comparative examples 4 to 5 were subjected to the following performance tests:
the ratio of the theoretical value of the spiro sulfite which can be prepared is calculated by the mass of the finished spiro sulfate obtained by a weighing mode and the raw material theory, so that the yield is obtained.
And (3) characterizing the product by adopting LC-MS (liquid chromatography-mass spectrometer) and NMR (nuclear magnetic resonance), so as to obtain the purity of the spiro sulfate in the finished spiro sulfate, and detecting whether the spiro sulfite remains.
The test results obtained are filled in table 2.
TABLE 2
As can be seen from the test results in Table 2, compared with other existing solvents, the spiro sulfate prepared by the preparation method provided by the invention has obviously higher yield and higher purity, and meanwhile, can promote the oxidation reaction of the spiro sulfite more fully, and avoid the residue of the spiro sulfite in the final product.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (8)
1. A method for preparing spiro sulfite, which is characterized by comprising the following operation steps:
mixing pentaerythritol with a first organic solvent, raising the temperature to 40-70 ℃, dropwise adding thionyl chloride, controlling the temperature to 70-80 ℃ after the dropwise adding is finished, reacting for 8-10 h to obtain a reaction solution containing spiro sulfite, and purifying to obtain spiro sulfite;
the first organic solvent comprises one or more of a carbonate or a carboxylate; the carbonic ester comprises one or more of dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate;
the carboxylic acid ester comprises one or more of methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate and butyl propionate.
2. The process for producing spiro sulfite as claimed in claim 1, wherein the spiro sulfite is obtained by evaporating the organic solvent after the reaction to obtain a white solid, washing with water, and suction-filtering.
3. The process for preparing spiro sulfite as claimed in claim 1, wherein the molar ratio of pentaerythritol to thionyl chloride is 1:1.9 to 2.2.
4. The preparation method of the spiro sulfate is characterized by comprising the following operation steps:
a spiro sulfite prepared by the preparation method according to any one of claims 1 to 3;
mixing spiro sulfite, a second organic solvent and a catalyst, adding an oxidant aqueous solution, reacting to obtain a reaction solution containing spiro sulfate, and purifying to obtain spiro sulfate;
the second organic solvent includes an organic polar solvent.
5. The process for preparing spiro sulfate according to claim 4, wherein the organic polar solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
6. The process for preparing spiro sulfate according to claim 4, wherein the spiro sulfate, the second organic solvent and the catalyst are mixed, heated and dissolved, cooled to 30-50 ℃ to form a supersaturated solution, an aqueous solution of an oxidant is added dropwise, the temperature is continuously raised to 50-80 ℃ after the dropwise addition is completed, the reaction is carried out for 2-4 hours to obtain a reaction solution containing spiro sulfate, the reaction solution containing spiro sulfate is filtered to obtain a first filter residue, the first filter residue is collected by washing with water, the solvent is distilled off from the filtrate, the second filter residue is obtained by filtering again, the second filter residue is collected by washing with water, and the filter residue obtained in the two times is recrystallized by using a third organic solvent to obtain white spiro sulfate crystals.
7. The process for preparing spiro sulfate according to claim 6, wherein the third organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
8. The method for preparing spiro sulfate according to claim 4, wherein the catalyst is selected from ruthenium trichloride, and the addition amount of the catalyst is 0.01% -0.05% of the mass of the spiro sulfite;
the oxidant in the oxidant aqueous solution is selected from hypochlorite, and the mol ratio of the spiro sulfite to the available chlorine in the hypochlorite is 1:2.0 to 2.2.
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| US6180799B1 (en) * | 2000-05-01 | 2001-01-30 | The United States Of America As Represented By The Secretary Of The Air Force | Sulfalation of tetraol |
| CN111285884A (en) * | 2018-12-10 | 2020-06-16 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of pentaerythritol sulfate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6180799B1 (en) * | 2000-05-01 | 2001-01-30 | The United States Of America As Represented By The Secretary Of The Air Force | Sulfalation of tetraol |
| CN111285884A (en) * | 2018-12-10 | 2020-06-16 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of pentaerythritol sulfate |
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