KR20230012771A - A method for producing cyclic sulfate by oxidation - Google Patents
A method for producing cyclic sulfate by oxidation Download PDFInfo
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- KR20230012771A KR20230012771A KR1020210093453A KR20210093453A KR20230012771A KR 20230012771 A KR20230012771 A KR 20230012771A KR 1020210093453 A KR1020210093453 A KR 1020210093453A KR 20210093453 A KR20210093453 A KR 20210093453A KR 20230012771 A KR20230012771 A KR 20230012771A
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- potassium
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- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title description 16
- 230000003647 oxidation Effects 0.000 title description 3
- -1 cyclic sulfate compound Chemical class 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007800 oxidant agent Substances 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 18
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 10
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229910019093 NaOCl Inorganic materials 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 241000872931 Myoporum sandwicense Species 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 claims description 4
- 239000012425 OXONE® Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005526 alkyl sulfate group Chemical group 0.000 claims description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 3
- 125000005360 alkyl sulfoxide group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 3
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 3
- 229940011051 isopropyl acetate Drugs 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- YHTPVDJKWQQLPM-UHFFFAOYSA-N 2,4,8,10-tetraoxa-3$l^{6},9$l^{6}-dithiaspiro[5.5]undecane 3,3,9,9-tetraoxide Chemical compound C1OS(=O)(=O)OCC21COS(=O)(=O)OC2 YHTPVDJKWQQLPM-UHFFFAOYSA-N 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 30
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 16
- 230000008569 process Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
본 발명은 리튬이온 2차전지에 대한 비수계 전해액의 첨가제 등으로서 사용되는 고리형 설페이트 화합물의 제조 방법에 관한 것으로, 산화제를 이용하여 고리형 설파이트 화합물을 산화시키는 방법에 관한 것이다.The present invention relates to a method for producing a cyclic sulfate compound used as an additive for a non-aqueous electrolyte solution for a lithium ion secondary battery and the like, and relates to a method for oxidizing a cyclic sulfite compound using an oxidizing agent.
고리형 설페이트는, 예를 들면, 리튬이온 2차전지에 있어서, 각각의 전지특성을 향상시킬 수 있는 비수계 전해액의 첨가제로서 유용한 화합물인 것이 알려져 있다. 구체적으로는, 예를 들면, 고리형 설페이트를 비수계 전해액에 첨가하는 것으로 부극상에서 전해액의 환원분해반응을 억제하는 효과를 기대할 수 있을 뿐만 아니라, 고온보존 시험이나 사이클 시험시의 전지의 용량저하를 억제할 수 있고, 또, 전해액의 분해에 수반하는 가스발생을 억제할 수 있는 것이 알려져 있다. It is known that cyclic sulfate is a useful compound as an additive for a non-aqueous electrolyte solution capable of improving the characteristics of each battery in, for example, a lithium ion secondary battery. Specifically, for example, by adding cyclic sulfate to the non-aqueous electrolyte solution, not only can the effect of suppressing the reduction and decomposition reaction of the electrolyte solution on the negative electrode be expected, but also the decrease in battery capacity during high-temperature storage tests and cycle tests can be expected. It is known that it can be suppressed and that gas generation accompanying decomposition of the electrolyte solution can be suppressed.
이러한, 고리형 설페이트 제조 방법으로서 예를 들면 J.Am.Chem.Soc.,1988년,7538-7539페이지에 있어서 Ru촉매에 의한 산화 방법, J.Org.Chem.,1990년,1211-1217페이지에 있어서 과망간산칼륨을 산화제로서 이용하는 산화 방법 등이 보고되어 있다. As such a method for producing cyclic sulfate, for example, J. Am. Chem. Soc., 1988, pp. 7538-7539, Ru-catalyzed oxidation method, J. Org. Chem., 1990, pp. 1211-1217 An oxidation method using potassium permanganate as an oxidizing agent has been reported.
또한, 고리형 설페이트는 산화 반응에 의해 설파이트 화합물로부터 제조하게 되었는데, 이 때 사용되는 산화제로는 차아염소산나트륨(NaOCl), 차아염소산칼슘(Ca(OCl)2), 과요오드산칼륨(KIO4), 과요오드산나트륨(NaIO4), 과망간산칼륨(KMnO4), 과산화모노황산칼륨(Oxone), 과산화수소(H2O2) 등이 있다.In addition, cyclic sulfate was prepared from sulfite compounds by an oxidation reaction. The oxidizing agents used at this time are sodium hypochlorite (NaOCl), calcium hypochlorite (Ca(OCl) 2 ), potassium periodate (KIO 4 ), sodium periodate (NaIO 4 ), potassium permanganate (KMnO 4 ), potassium peroxymonosulfate (Oxone), and hydrogen peroxide (H 2 O 2 ).
상기의 산화제들은 각기 다른 특성을 가지고 있어, 산화 반응에 사용되는 물질의 구조, 상태, 용매 및 용해도 등에 따라 반응성이 크게 달라진다. 이와 같은 산화제 이용에 있어 공업적 이용을 위한 부피 효율, 단가 및 공정 안정성 등을 고려하여 생산 효율을 극대화 하기 위해 보다 정밀하고 세심한 반응 조건의 개발이 요망되고 있다.The above oxidizing agents have different characteristics, and their reactivity varies greatly depending on the structure, state, solvent and solubility of the material used in the oxidation reaction. In the use of such an oxidizing agent, it is desired to develop more precise and meticulous reaction conditions in order to maximize production efficiency in consideration of volumetric efficiency, unit cost, and process stability for industrial use.
본 발명은 산화제를 이용하여 고리형 설페이트를 제조하는데, 공업적으로 활용 가능한 부피 효율, 단가 및 공정 안정성 등을 고려하여 생산 효율을 극대화 할 수 있는 방법을 제공하고자 한다.An object of the present invention is to provide a method capable of maximizing production efficiency by considering industrially usable volumetric efficiency, unit cost, and process stability in producing cyclic sulfate using an oxidizing agent.
본 발명에 따른 방법은, 하기 [화학식 1]로 표시되는 고리형 설파이트를 유기 용매 및 물이 혼합되어 있는 혼합 용매계 상태에서, pH를 조절하며 촉매 및 산화제를 부가하여 산화시킴으로써 하기 [화학식 2]의 고리형 설페이트를 제조하는 방법이다.In the method according to the present invention, the cyclic sulfite represented by the following [Formula 1] is oxidized by adding a catalyst and an oxidizing agent while adjusting the pH in a mixed solvent system in which an organic solvent and water are mixed, thereby oxidizing the cyclic sulfite represented by the following [Formula 2] ] is a method for producing cyclic sulfate.
[화학식 1] [화학식 2][Formula 1] [Formula 2]
상기 [화학식 1]과 [화학식 2]에서, In [Formula 1] and [Formula 2],
1) R1 및 R2는 서로 독립적으로 수소; 탄소수 1 내지 3의 선형 또는 고리형의 알킬기; 알킬설파이트기; 알킬설폭사이드기; 알킬설포닐기; 알킬설페이트기; 또는 에테르기이고,1) R 1 and R 2 are each independently hydrogen; A linear or cyclic alkyl group having 1 to 3 carbon atoms; Alkyl sulfite group; Alkyl sulfoxide group; Alkyl sulfonyl group; Alkyl sulfate group; Or an ether group,
2) 상기 n은 0 내지 2의 정수이다.2) The n is an integer from 0 to 2.
상기 pH 조절을 위해 중탄산나트륨(NaHCO3), 탄산나트륨(Na2CO3), 제일인산나트륨(NaH2PO4), 제이인산나트륨(Na2HPO4), 제삼인산나트륨(Na3PO4), 중탄산칼륨(KHCO3), 탄산칼륨(K2CO3), 인산이수소칼륨(KH2PO4), 인산일수소칼륨(K2HPO4), 인산칼륨(K3PO4) 또는 이들의 조합을 사용하는 것이 바람직하다.Sodium bicarbonate (NaHCO 3 ), sodium carbonate (Na 2 CO 3 ), sodium phosphate monobasic (NaH 2 PO 4 ), sodium phosphate dibasic (Na 2 HPO 4 ), sodium phosphate tribasic (Na 3 PO 4 ), Potassium bicarbonate (KHCO 3 ), potassium carbonate (K 2 CO 3 ), potassium dihydrogen phosphate (KH 2 PO 4 ), potassium monohydrogen phosphate (K 2 HPO 4 ), potassium phosphate (K 3 PO 4 ), or combinations thereof. It is preferable to use
상기 pH는 산화제 투입전 3 < pH < 10 범위인 것이 바람직하다. The pH is preferably in the range of 3 < pH < 10 before the introduction of the oxidizing agent.
상기 산화제가 차아염소산나트륨(NaOCl), 차아염소산칼슘(Ca(OCl)2), 과요오드산칼륨(KIO4), 과요오드산나트륨(NaIO4), 과망간산칼륨(KMnO4), 과산화모노황산칼륨(KHSO5), 과산화수소(H2O2) 또는 이들의 조합인 것이 바람직하다.The oxidizing agent is sodium hypochlorite (NaOCl), calcium hypochlorite (Ca(OCl) 2 ), potassium periodate (KIO 4 ), sodium periodate (NaIO 4 ), potassium permanganate (KMnO 4 ), potassium peroxymonosulfate (KHSO 5 ), hydrogen peroxide (H 2 O 2 ), or a combination thereof is preferred.
상기 유기 용매는 아세토니트릴, 아세톤, 다이옥산, 테트라히드로퓨란, 메탄올, 에탄올, 이소프로판올, 디클로로메탄, 클로로포름, 디클로로에탄, 톨루엔, 자일렌, 탄산디메틸, 탄산에틸렌, 탄산디에틸, 에틸아세테이트, 이소프로필아세테이트, 메틸이소부틸키톤 중 어느 하나 이상을 포함하는 것이 바람직하다.The organic solvent is acetonitrile, acetone, dioxane, tetrahydrofuran, methanol, ethanol, isopropanol, dichloromethane, chloroform, dichloroethane, toluene, xylene, dimethyl carbonate, ethylene carbonate, diethyl carbonate, ethyl acetate, isopropyl acetate , It is preferable to include any one or more of methyl isobutyl ketone.
상기 물과 유기 용매의 중량 비율은 1:1 내지 1:20의 범위인 것이 바람직하다.The weight ratio of the water to the organic solvent is preferably in the range of 1:1 to 1:20.
상기 유기용매는 고리형 설파이트 화합물에 대하여 중량비로 1~100배의 범위인 것이 바람직하다.The organic solvent is preferably in the range of 1 to 100 times the weight ratio of the cyclic sulfite compound.
상기 화학식 2로 표시되는 화합물은 2,4,8,10-테트라옥사-3,9-디티아스피로[5.5]운데칸 3,3,9,9-테트라옥시드인 것이 바람직하다.The compound represented by Formula 2 is preferably 2,4,8,10-tetraoxa-3,9-dithiaspiro[5.5]undecane 3,3,9,9-tetraoxide.
본 발명에 따른 방법은 특정한 pH 범위에서 안정적이고 효율적으로 산화 반응을 진행시켜, 공업적 규모로서 활용 가능한 부피 효율, 단가 및 공정 안정성 등을 확보하며 생산 효율을 극대화 할 수 있다.The method according to the present invention proceeds the oxidation reaction stably and efficiently in a specific pH range, thereby securing volumetric efficiency, unit cost and process stability usable on an industrial scale, and maximizing production efficiency.
이하, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시형태를 들어 상세히 설명한다. 본 발명의 실시형태는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 더욱 완전하게 설명하기 위해서 제공되는 것이다. 따라서, 본 발명의 실시형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시형태로 한정되는 것은 아니다.Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art. Accordingly, the embodiments of the present invention can be modified in many different forms, and the scope of the present invention is not limited to the embodiments described below.
본 발명의 명세서 전체에서, 어떤 부분이 어떤 구성요소를 “포함”한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함하는 것을 의미한다.Throughout the specification of the present invention, when a part "includes" a certain component, it means that it further includes other components, not excluding other components unless otherwise stated.
본 발명의 명세서 전체에서, 어떤 단계가 다른 단계와 “상에” 또는 “전에” 위치하고 있다고 할 때, 이는 어떤 단계가 다른 단계와 직접적 시계열적인 관계에 있는 경우뿐만 아니라, 각 단계 후의 혼합하는 단계와 같이 두 단계의 순서에 시계열적 순서가 바뀔 수 있는 간접적 시계열적 관계에 있는 경우와 동일한 권리를 포함할 수 있다.Throughout the specification of the present invention, when a step is said to be located “on” or “before” another step, this is not only the case where a step is in a direct time-series relationship with another step, but also the mixing step after each step As such, the order of the two steps may include the same rights as in the case of an indirect time-series relationship in which the time-series order may change.
본 발명의 명세서 전체에서 사용되는 정도의 용어 “약”, “실질적으로” 등은 언급된 의미에 고유한 제조 및 물질 허용 오차가 제시될 때 그 수치에서 또는 그 수치에 근접한 의미로 사용되고, 본 발명의 이해를 돕기 위해 정확하거나 절대적인 수치가 언급된 개시 내용을 비양심적인 침해자가 부당하게 이용하는 것을 방지하기 위해 사용된다. 본원 명세서 전체에서 사용되는 용어 “~(하는) 단계” 또는 “~의 단계”는 “~를 위한 단계”를 의미하지 않는다.The terms "about," "substantially," and the like used throughout the specification of the present invention are used at or close to that value when manufacturing and material tolerances inherent in the stated meaning are given, and the present invention Accurate or absolute figures are used to prevent unfair use by unscrupulous infringers of the disclosed disclosures mentioned for the sake of understanding. The term “step of (doing)” or “step of” used throughout the present specification does not mean “step for”.
본 발명은 고리형 설파이트 화합물을 설페이트 화합물로 산화시키는 방법으로 하기 [화학식 1]로부터 [화학식 2]를 제조하는 것에 관한 것이다.The present invention relates to preparing [Formula 2] from [Formula 1] by a method of oxidizing a cyclic sulfite compound to a sulfate compound.
반응물로서 사용되는 고리형 설파이트는 하기와 같은 [화학식 1]의 구조를 가지고,Cyclic sulfite used as a reactant has a structure of [Chemical Formula 1] as follows,
[화학식 1][Formula 1]
생성물로서 수득되는 고리형 설페이트 화합물은 하기 [화학식 2]와 같은 구조를 가진다.The cyclic sulfate compound obtained as a product has a structure shown in [Formula 2] below.
[화학식 2][Formula 2]
상기 [화학식 1]과 [화학식 2]에서 R1 및 R2는 서로 독립적으로 수소; 탄소수 1 내지 3의 선형 또는 고리형의 알킬기; 알킬설파이트기; 알킬설폭사이드기; 알킬설포닐기; 알킬설페이트기; 또는 에테르기를 나타낸다.In [Formula 1] and [Formula 2], R 1 and R 2 are each independently hydrogen; A linear or cyclic alkyl group having 1 to 3 carbon atoms; Alkyl sulfite group; Alkyl sulfoxide group; Alkyl sulfonyl group; Alkyl sulfate group; or an ether group.
상기 n은 0 내지 2의 정수이다.Said n is an integer of 0-2.
본 발명은 유기 용매 및 물의 존재 하에 촉매 및 산화제를 사용하여 일정한 pH 범위 내에서 고리형 설파이트 화합물을 산화시키는 단계를 포함한다.The present invention includes the step of oxidizing a cyclic sulfite compound within a certain pH range using a catalyst and an oxidizing agent in the presence of an organic solvent and water.
상기 반응에서 반응 용매는 유기용매와 물이 혼합된 조건에서 사용하는 것이 반응성이 가장 좋다. 반응에서 물의 사용은 필수적으로 예를 들면, 차아염소산나트륨(NaOCl) 수용액(8~15%)이나 과산화수소(HOOH) 용액(28~30%)과 같은 산화제는 물을 포함하고 있으므로, 물을 사용하지 않는 공정은 불가능하다. 또한, 물을 사용할 수 있는 공정이 물을 사용하지 않는 공정에 비하여 산화제의 선택 범위가 더 넓다. 따라서 물을 사용하지 않는 공정은 공정상 제약이 많아 효율적이지 못하고 대부분의 산화 반응에서 반응성이 떨어지는 것이 일반적이다.In the above reaction, the reaction solvent has the best reactivity when used in a mixture of an organic solvent and water. The use of water in the reaction is essential, for example, sodium hypochlorite (NaOCl) aqueous solution (8-15%) or hydrogen peroxide (HOOH) solution (28-30%) contains water, so water is not used. process is impossible. In addition, the process that can use water has a wider selection range of oxidizing agents than the process that does not use water. Therefore, a process that does not use water is not efficient due to many process limitations, and generally has poor reactivity in most oxidation reactions.
물을 사용하지 않을 수 있는 산화제, 예를 들어, 차아염소산칼슘(Ca(OCl)2)과 같은 고체 산화제를 물 없이 탄산디메틸 등의 유기 용매에서만 반응을 진행할 경우, 5% 이하로 반응이 진행되어 반응성이 현저히 떨어진다. 반대로 물만 사용하여 반응을 진행할 경우 반응이 전혀 진행되지 않는다.When an oxidizing agent that may not use water, for example, a solid oxidizing agent such as calcium hypochlorite (Ca(OCl) 2 ) is reacted only in an organic solvent such as dimethyl carbonate without water, the reaction proceeds at less than 5% Reactivity is significantly reduced. Conversely, when the reaction proceeds using only water, the reaction does not proceed at all.
물의 사용량은 유기 용매와 물이 혼합되는 정도와 반응 속도, 성상 등을 고려하여 정하는 것이 좋다. 구체적으로 물과 유기 용매의 사용 비율은 중량비로 1:1 내지 1:20의 범위에서 수행되는 것이 바람직하며, 더욱 바람직하게는 1:1 내지 1:10의 범위에서 수행하는 것이 좋다. 상기 범위를 벗어나는 경우, 공정상 비효율적이므로 바람직하지 않다. The amount of water used is preferably determined in consideration of the degree of mixing of the organic solvent and water, the reaction rate, and the properties. Specifically, the ratio of water and organic solvent used is preferably in the range of 1:1 to 1:20, more preferably in the range of 1:1 to 1:10 by weight. If it is out of the above range, it is not preferable because it is inefficient in terms of the process.
산화 반응에서 유기 용매로서 구체적으로 아세토니트릴, 아세톤, 다이옥산, 테트라히드로퓨란, 메탄올, 에탄올, 이소프로판올, 디클로로메탄, 클로로포름, 디클로로에탄, 톨루엔, 자일렌, 탄산디메틸, 탄산에틸렌, 탄산디에틸, 에틸아세테이트, 이소프로필아세테이트, 메틸이소부틸케톤 중 하나 이상이 사용될 수 있으며, 당업자에게 자명한 범위내에서 이에 한정되지 않는다. As an organic solvent in the oxidation reaction, specifically acetonitrile, acetone, dioxane, tetrahydrofuran, methanol, ethanol, isopropanol, dichloromethane, chloroform, dichloroethane, toluene, xylene, dimethyl carbonate, ethylene carbonate, diethyl carbonate, ethyl acetate , isopropyl acetate, one or more of methyl isobutyl ketone may be used, and is not limited thereto within the scope apparent to those skilled in the art.
유기용매는 고리형 설파이트 화합물에 대하여 중량비로 1~100배의 범위에서 용해도를 고려하여 사용하는 것이 좋으며, 바람직하게는 5~40배를 사용하여 반응 효율을 높이는 것이 바람직하다. 상기 유기 용매를 단일 용매 또는 두 가지 이상의 용매를 혼합하여 사용하는 것도 좋다. 상기 범위를 벗어나는 경우, 공정상 비효율적이므로 바람직하지 않다.The organic solvent is preferably used in the range of 1 to 100 times the weight ratio of the cyclic sulfite compound in consideration of solubility, preferably 5 to 40 times to increase reaction efficiency. It is also good to use the organic solvent as a single solvent or a mixture of two or more solvents. If it is out of the above range, it is not preferable because it is inefficient in terms of the process.
본 발명의 제조 방법은 적절한 pH 범위 내에서 반응이 진행될 수 있도록 pH를 조절하고 유지하는 것이다. 적절한 pH 범위 조건에서 유기 용매, 물 및 촉매 존재 하에서 산화제를 사용하여 산화 반응이 수행된다.The production method of the present invention is to adjust and maintain the pH so that the reaction can proceed within an appropriate pH range. The oxidation reaction is carried out using an oxidizing agent in the presence of an organic solvent, water and a catalyst at appropriate pH range conditions.
본 발명에서 수행되는 고리형 설파이트 화합물의 산화 반응에서 pH는 일반적으로 측정되는 방법으로 유기 용매와 물의 혼합 상태에서 물의 pH를 pH 측정기 또는 pH paper를 사용하여 측정하는 것이다. In the oxidation reaction of the cyclic sulfite compound performed in the present invention, the pH is generally measured by measuring the pH of water in a mixed state of an organic solvent and water using a pH meter or pH paper.
본 발명에서 수행되는 산화 반응은 pH가 반응 진행 속도 및 반응성에 영향을 줄 수 있으므로, 본 발명에서는 산화제 투입전 3 < pH < 11(아래 실시예를 고려하여 “산화제 투입전”이라는 표현을 부가함)의 범위에서 수행되어야 하고, 바람직하게는 pH 5 내지 10 범위에서 수행되는 것이 좋다. Since the pH of the oxidation reaction performed in the present invention can affect the reaction progress rate and reactivity, in the present invention, 3 < pH < 11 before adding the oxidizing agent (in consideration of the following examples, the expression “before adding the oxidizing agent” is added) ), and preferably in the range of pH 5 to 10.
pH 3 이하의 반응 조건에서는 산화 반응이 완결되지 않으며, 물질의 분해가 일어나 생성물의 손실을 가져올 수 있다. 과량의 산화제를 추가로 사용하여 반응을 완결시킬 수 있다 하더라도 부피 효율이 굉장히 낮아지고 반응에 대한 재현성이 확보되지 못하여 공업적 이용에 큰 장애가 된다. 또한 비용적인 측면도 고려해야 하는 문제가 생겨난다. Under the reaction conditions of pH 3 or less, the oxidation reaction is not completed, and the decomposition of the material may result in product loss. Even if the reaction can be completed by additionally using an excessive amount of oxidizing agent, the volumetric efficiency is extremely low and the reproducibility of the reaction is not secured, which is a great obstacle to industrial use. In addition, there is a problem that needs to be considered in terms of cost.
또한, pH가 11 이상이면 오히려 산화제의 반응성이 낮아질 수 있어 바람직하지 않다.In addition, when the pH is 11 or more, the reactivity of the oxidizing agent may be lowered, which is not preferable.
본 발명은 이러한 산화 반응의 저해 요인을 해결하기 위하여 많은 반응 조건을 검토하고 실험하여, 결국 반응이 원활히 진행될 수 있는 효과적 조건으로서 pH 범위를 확인하였으며, 일정한 pH 범위 내에서 산화 반응을 효과적으로 진행할 수 있었다.In the present invention, many reaction conditions were reviewed and tested to solve the factors inhibiting the oxidation reaction, and eventually the pH range was identified as an effective condition for the reaction to proceed smoothly, and the oxidation reaction could effectively proceed within a certain pH range. .
상기 화학식 1로 표시되는 고리형 설파이트 화합물은 통상적으로 디올 화합물과 염화티오닐과 같은 할로겐화 티오닐과의 반응을 통하여 합성할 수 있다. 이렇게 합성된 고리형 설파이트 화합물은 pH가 낮은 경우가 많고, pH가 높다 하더라도 장기간 보관할 경우 지속적으로 pH가 낮아져 산화 반응을 일정하게 진행하는데 영향을 줄 수 있다. The cyclic sulfite compound represented by Chemical Formula 1 can usually be synthesized through a reaction between a diol compound and a thionyl halide such as thionyl chloride. The cyclic sulfite compound thus synthesized often has a low pH, and even if the pH is high, when stored for a long period of time, the pH is continuously lowered, which may affect the uniform progress of the oxidation reaction.
이러한 영향을 제거하고 안정적으로 반응을 진행시키기 위하여, pH를 조절하고 유지시킬 수 있는 방법으로서, 중탄산나트륨(NaHCO3), 탄산나트륨(Na2CO3), 제일인산나트륨(NaH2PO4), 제이인산나트륨(Na2HPO4), 제삼인산나트륨(Na3PO4), 중탄산칼륨(KHCO3), 탄산칼륨(K2CO3), 인산이수소칼륨(KH2PO4), 인산일수소칼륨(K2HPO4), 인산칼륨(K3PO4) 등과 이들의 조합의 무기 염기류를 사용하는 것이 바람직하며, 당업자게 자명한 범위내에서 이에 제한되지 않는다.In order to remove these effects and proceed with the reaction stably, as a method for adjusting and maintaining the pH, sodium bicarbonate (NaHCO 3 ), sodium carbonate (Na 2 CO 3 ), sodium phosphate monobasic (NaH 2 PO 4 ), Sodium Phosphate (Na 2 HPO 4 ), Trisodium Phosphate (Na 3 PO 4 ), Potassium Bicarbonate (KHCO 3 ), Potassium Carbonate (K 2 CO 3 ), Potassium Dihydrogen Phosphate (KH 2 PO 4 ), Potassium Monohydrogen Phosphate (K 2 HPO 4 ), potassium phosphate (K 3 PO 4 ), etc. It is preferable to use inorganic bases in combination thereof, and is not limited thereto within the scope apparent to those skilled in the art.
본 발명에서 사용되는 산화제는 일반적으로 사용되는 차아염소산나트륨(NaOCl), 차아염소산칼슘(Ca(OCl)2), 과요오드산칼륨(KIO4), 과요오드산나트륨(NaIO4), 과망간산칼륨(KMnO4), 과산화모노황산칼륨(KHSO5), 과산화수소(H2O2)와 같은 산화제 및 이들의 조합을 사용하여 수행될 수 있으며, 당업자에게 자명한 범위내에서 이에 제한되지 않는다. The oxidizing agent used in the present invention is commonly used sodium hypochlorite (NaOCl), calcium hypochlorite (Ca(OCl) 2 ), potassium periodate (KIO 4 ), sodium periodate (NaIO 4 ), potassium permanganate ( KMnO 4 ), potassium peroxymonosulfate (KHSO 5 ), hydrogen peroxide (H 2 O 2 ) It can be carried out using an oxidizing agent such as and combinations thereof, but is not limited thereto within the scope apparent to those skilled in the art.
본 발명에서는 차아염소산나트륨(NaOCl), 차아염소산칼슘(Ca(OCl)2), 과요오드산나트륨(NaIO4)을 사용하여 수행하는 것을 실시예를 통하여 주로 설명하고 있으나, 본 발명의 범위가 실시예에 의해 제한되지는 않는다.In the present invention, the use of sodium hypochlorite (NaOCl), calcium hypochlorite (Ca(OCl) 2 ), and sodium periodate (NaIO 4 ) is mainly described through examples, but the scope of the present invention is not limited by examples.
본 발명에서 촉매는 무수 염화루테늄(RuCl3) 또는 텅스텐산나트륨(Na2WO2ㆍ2H2O)이 사용된다. 일반적으로 염화루테늄은 0.1 당량 내지 0.00001 당량의 범위에서 수행되고, 바람직하게는 0.01 당량 내지 0.00001 당량을 사용하여 수행된다. In the present invention, anhydrous ruthenium chloride (RuCl 3 ) or sodium tungstate (Na 2 WO 2 ㆍ2H 2 O) is used as a catalyst. In general, ruthenium chloride is carried out in the range of 0.1 equivalent to 0.00001 equivalent, preferably carried out using 0.01 equivalent to 0.00001 equivalent.
또한, 텅스텐산나트륨은 0.001 당량 내지 0.01 당량을 사용하는 것이 좋다. 촉매는 고가의 물질이므로 경제적인 측면을 고려할 때 반응에 필요량 이상의 과량을 사용하는 것은 바람직하지 않다. 또는 최소량 이하로 적게 사용하는 경우에는 반응이 되지 않으므로 바람직하지 않다. In addition, it is preferable to use 0.001 equivalent to 0.01 equivalent of sodium tungstate. Since the catalyst is an expensive material, it is undesirable to use an excess of the amount required for the reaction in consideration of economic aspects. Or, if less than the minimum amount is used, it is not preferable because the reaction does not occur.
본 발명의 상기 반응 조건은 고리형 설파이트로부터 설페이트를 합성하기 위한 산화 반응의 조건에서 공업적 스케일에서도 안정적으로 반응이 진행될 수 있는 방법을 제시하여, 목적으로 하는 화합물을 보다 효율적으로 얻을 수 있는 우수한 제조 방법이다.The reaction conditions of the present invention suggest a method for stably proceeding the reaction on an industrial scale under oxidation reaction conditions for synthesizing sulfate from cyclic sulfite, thereby providing an excellent method for obtaining a target compound more efficiently. manufacturing method.
상기에서 서술된 본 발명의 제조 방법의 구체적인 예는 하기의 비교예 및 실시예에 의해 예시적으로 설명될 수 있다.Specific examples of the manufacturing method of the present invention described above can be exemplarily described by the following Comparative Examples and Examples.
(비교예 1) (Comparative Example 1)
2,4,8,10-테트라옥사-3,9-디티아스피로-[5,5]운데칸,3,9-디옥시드 200g을 탄산디메틸 8000ml에 용해시킨 반응기에 물 1000ml 및 염화루테늄을 첨가하였다. 수층의 pH가 2.1인 것을 확인한 후, 차아염소산칼슘 358g을 가하여 pH 7.0(본 발명의 범위내입니다?)에서 반응을 진행하였다. 반응이 완결되지 않고 미반응물이 4.8% 잔존하였고, 반응 종료 후 pH는 3.5였다. 반응물의 수층을 분리하여 제거하고, 분리된 유기층을 농축하여 미반응물이 포함된 2,4,8,10-테트라옥사-3,9-디티아스피로-[5,5]운데칸,3,3,9,9-테트라옥시드 123.1g(수율 54%)을 수득하였다.1000 ml of water and ruthenium chloride were added to a reactor in which 200 g of 2,4,8,10-tetraoxa-3,9-dithiaspiro-[5,5]undecane,3,9-dioxide was dissolved in 8000 ml of dimethyl carbonate. did After confirming that the pH of the aqueous layer was 2.1, 358 g of calcium hypochlorite was added and the reaction proceeded at pH 7.0 (within the scope of the present invention?). The reaction was not completed, 4.8% of unreacted material remained, and the pH was 3.5 after completion of the reaction. The aqueous layer of the reactants was separated and removed, and the separated organic layer was concentrated to obtain 2,4,8,10-tetraoxa-3,9-dithiaspiro-[5,5]undecane,3,3 containing unreacted materials. 123.1 g (54% yield) of ,9,9-tetraoxide was obtained.
(실시예 1) (Example 1)
2,4,8,10-테트라옥사-3,9-디티아스피로-[5,5]운데칸,3,9-디옥시드 200g을 탄산디메틸 8000ml에 용해시킨 반응기에 물 1000ml 및 염화루테늄을 첨가하였다. 수층의 pH가 4.0인 것을 확인한 후, 차아염소산칼슘 268g을 가하여 pH 8.5에서 반응을 진행하였다. 반응 종료 후 pH는 4.2로 확인되었다. 수층을 분리하여 제거하고 분리된 유기층을 농축하여 흰색 결정의 형태로 2,4,8,10-테트라옥사-3,9-디티아스피로-[5,5]운데칸,3,3,9,9-테트라옥시드 155.1g(수율 68%)을 수득하였다.1000 ml of water and ruthenium chloride were added to a reactor in which 200 g of 2,4,8,10-tetraoxa-3,9-dithiaspiro-[5,5]undecane,3,9-dioxide was dissolved in 8000 ml of dimethyl carbonate. did After confirming that the pH of the aqueous layer was 4.0, 268 g of calcium hypochlorite was added to proceed with the reaction at pH 8.5. After completion of the reaction, the pH was confirmed to be 4.2. The aqueous layer was separated and removed, and the separated organic layer was concentrated to obtain 2,4,8,10-tetraoxa-3,9-dithiaspiro-[5,5]undecane,3,3,9, 155.1 g (yield 68%) of 9-tetraoxide was obtained.
(실시예 2) (Example 2)
2,4,8,10-테트라옥사-3,9-디티아스피로-[5,5]운데칸,3,9-디옥시드 200g을 탄산디메틸 8000ml에 용해시킨 반응기에 물 1000ml 및 염화루테늄을 첨가하였다. 수층의 pH가 2.1인 것을 확인 후 중탄산나트륨 6g을 첨가하여 pH 7.5로 조절하고 차아염소산칼슘 268g을 가하여 pH 12.1에서 반응을 진행하였다. 반응 종료 후 pH는 5.5로 확인되었다. 수층을 분리하여 제거하고, 분리된 유기층을 농축하여 흰색 결정의 형태로 2,4,8,10-테트라옥사-3,9-디티아스피로-[5,5]운데칸,3,3,9,9-테트라옥시드 200.7g(수율 88%)을 수득하였다.1000 ml of water and ruthenium chloride were added to a reactor in which 200 g of 2,4,8,10-tetraoxa-3,9-dithiaspiro-[5,5]undecane,3,9-dioxide was dissolved in 8000 ml of dimethyl carbonate. did After confirming that the pH of the aqueous layer was 2.1, 6 g of sodium bicarbonate was added to adjust the pH to 7.5, and 268 g of calcium hypochlorite was added to proceed with the reaction at pH 12.1. After completion of the reaction, the pH was confirmed to be 5.5. The aqueous layer was separated and removed, and the separated organic layer was concentrated to obtain 2,4,8,10-tetraoxa-3,9-dithiaspiro-[5,5]undecane,3,3,9 in the form of white crystals. 200.7 g (yield 88%) of ,9-tetraoxide was obtained.
(실시예 3) (Example 3)
2,4,8,10-테트라옥사-3,9-디티아스피로-[5,5]운데칸,3,9-디옥시드 200g을 아세토니트릴 2000ml에 용해시킨 반응기에 염화루테늄을 첨가하였다. pH가 2.1인 것을 확인 후 중탄산나트륨 6g을 첨가하여 pH 7.5로 조절하였다. 차아염소산나트륨 수용액(함량 10%) 1793g을 가하여 pH 13.4인 것을 확인 후 반응을 진행하였다. 반응 종료 후 pH는 8.1이었다. 수층을 분리하여 제거하고 분리된 유기층을 농축하여 2,4,8,10-테트라옥사-3,9-디티아스피로-[5,5]운데칸,3,3,9,9-테트라옥시드 161.9g(수율 71%)을 수득하였다.Ruthenium chloride was added to a reactor in which 200 g of 2,4,8,10-tetraoxa-3,9-dithiaspiro-[5,5]undecane,3,9-dioxide was dissolved in 2000 ml of acetonitrile. After confirming that the pH was 2.1, 6 g of sodium bicarbonate was added to adjust the pH to 7.5. 1793 g of sodium hypochlorite aqueous solution (content 10%) was added and the reaction proceeded after confirming that the pH was 13.4. After completion of the reaction, the pH was 8.1. The aqueous layer was separated and removed, and the separated organic layer was concentrated to obtain 2,4,8,10-tetraoxa-3,9-dithiaspiro-[5,5]undecane,3,3,9,9-tetraoxide 161.9 g (yield 71%) was obtained.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and variations are possible without departing from the technical spirit of the present invention described in the claims. It will be obvious to those skilled in the art.
Claims (8)
[화학식 1] [화학식 2]
상기 [화학식 1]과 [화학식 2]에서,
1) R1 및 R2는 서로 독립적으로 수소; 탄소수 1 내지 3의 선형 또는 고리형의 알킬기; 알킬설파이트기; 알킬설폭사이드기; 알킬설포닐기; 알킬설페이트기; 또는 에테르기이고,
2) 상기 n은 0 내지 2의 정수이다.Cyclic sulfate of [Formula 2] is prepared by oxidizing the cyclic sulfite represented by the following [Formula 1] by adding a catalyst and an oxidizing agent while adjusting the pH in a mixed solvent system in which an organic solvent and water are mixed. How to:
[Formula 1] [Formula 2]
In [Formula 1] and [Formula 2],
1) R 1 and R 2 are each independently hydrogen; A linear or cyclic alkyl group having 1 to 3 carbon atoms; Alkyl sulfite group; Alkyl sulfoxide group; Alkyl sulfonyl group; Alkyl sulfate group; Or an ether group,
2) The n is an integer from 0 to 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 |
| KR20160016897A (en) | 2013-05-29 | 2016-02-15 | 바스프 에스이 | Process for the oxidation of sulfoxides |
| KR20170094966A (en) * | 2016-02-12 | 2017-08-22 | 삼성에스디아이 주식회사 | Additive for electrolyte of lithium battery, organic electrolytic solution comprising the same and Lithium battery using the solution |
| KR102080198B1 (en) | 2018-08-22 | 2020-04-07 | 주식회사 알이피 | Method of oxidizing using calcium hypochloride and manufacturing for sulfone or sulfide |
| CN111909129A (en) * | 2020-09-03 | 2020-11-10 | 常熟市常吉化工有限公司 | Method for preparing cyclic sulfate by direct oxidation of hydrogen peroxide |
| CN112592353A (en) * | 2020-12-21 | 2021-04-02 | 上海彩迩文生化科技有限公司 | Industrial preparation method of cyclic sulfate |
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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 |
| KR20160016897A (en) | 2013-05-29 | 2016-02-15 | 바스프 에스이 | Process for the oxidation of sulfoxides |
| KR20170094966A (en) * | 2016-02-12 | 2017-08-22 | 삼성에스디아이 주식회사 | Additive for electrolyte of lithium battery, organic electrolytic solution comprising the same and Lithium battery using the solution |
| KR102080198B1 (en) | 2018-08-22 | 2020-04-07 | 주식회사 알이피 | Method of oxidizing using calcium hypochloride and manufacturing for sulfone or sulfide |
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| CN112592353A (en) * | 2020-12-21 | 2021-04-02 | 上海彩迩文生化科技有限公司 | Industrial preparation method of cyclic sulfate |
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