LU505007B1 - Synthesis method and application of 4',4''(5'')-di-tert-butyl dicyclohexylo-18-crown ether-6 - Google Patents
Synthesis method and application of 4',4''(5'')-di-tert-butyl dicyclohexylo-18-crown ether-6 Download PDFInfo
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- LU505007B1 LU505007B1 LU505007A LU505007A LU505007B1 LU 505007 B1 LU505007 B1 LU 505007B1 LU 505007 A LU505007 A LU 505007A LU 505007 A LU505007 A LU 505007A LU 505007 B1 LU505007 B1 LU 505007B1
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- tert
- catalyst
- synthesis method
- diethylene glycol
- crown ether
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 18
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 title abstract description 8
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 35
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 35
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 19
- BWERZOKUEPUTTM-UHFFFAOYSA-N 4-tert-butyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C(C)(C)C)CCC2OC21 BWERZOKUEPUTTM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- MLWGAEVSWJXOQJ-UHFFFAOYSA-N mdl 74156 Chemical compound C1=CC=C2C(C(=O)OC3CC4N5CC(C(CC5C3)C4)O)=CNC2=C1 MLWGAEVSWJXOQJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims description 39
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 239000012071 phase Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 239000003085 diluting agent Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000003983 crown ethers Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002927 high level radioactive waste Substances 0.000 description 3
- 239000010808 liquid waste Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- -1 alkaline earth metal cations Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 2
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 238000001959 radiotherapy Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/302—Ethers or epoxides
- C22B3/304—Crown ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method and application of 4',4''(5'')- di-tert-butyldicyclohexylo-18-crown ether-6, and belongs to the technical field of strontium extractant synthesis. The synthesis method comprises the following steps: dissolving diethylene glycol in an inert atmosphere, adding a catalyst, preheating and stirring until the catalyst is uniformly dispersed, heating up, adding 3-tert-butyl-7-oxabicyclo [4.1.0] heptane and diethylene glycol bis (p-toluenesulfonate), and obtaining 4',4''(5')-di-tert-butyl dicyclohexyl after the reaction is completed. By changing the synthesis reaction path and optimizing the synthesis reaction parameters, the invention overcomes the problems of hydrogenation danger and difficult purification in the synthesis reaction of DtBuCH18C6.
Description
DESCRIPTION LU505007
SYNTHESIS METHOD AND APPLICATION OF
4',4"(S"")-DI-TERT-BUTYL DICYCLOHEXYLO-18-CROWN ETHER-6
The invention relates to the technical field of synthesis of strontium extractant, in particular to a synthesis method and application of 4',4'(5")-di-tert-butyl dicyclohexylo -18-crown ether-6.
With the continuous improvement of nuclear science and technology at home and abroad, the number of nuclear power plants and reactors is increasing, and these nuclear power plants and reactors will produce a large amount of radioactive waste during operation. ’Sr is one of the fission products of >*U and ?‘’Pu in the reactor, and it is a highly toxic nuclide with a half-life of 28.9 years, with high heat release and strong heat release. Separation of “Sr can change High
Level Liquid Waste (HLLW) into medium-low level liquid waste, which is convenient for shallow formation disposal after cement solidification, and it is of positive significance for establishing advanced nuclear fuel cycle. In addition, *°Sr is a radioactive tracer widely used in medical radiotherapy and agriculture. If it can be separated from high-level radioactive waste liquid by effective means, it will have great economic and social effects.
The main methods for separating strontium at home and abroad are chemical precipitation, ion exchange and solvent extraction. Chemical precipitation method is to select a chemical reagent to react with Sr”’ in solution to generate insoluble or insoluble compounds, and then separate them. However, this method has some disadvantages, such as easy to block the pipeline and cause secondary pollution, complicated steps are not conducive to continuous treatment, and solid-liquid separation is difficult under strong radioactive conditions, so it has been rarely used at present. Ion exchange method is a reversible chemical reaction between ion exchanger and ions in liquid phase. Among them, organic ion exchange resin is easy to be damaged under high temperature or high radiation conditions, which reduces the adsorption capacity of metal ions and is not suitable for industrial extraction. Although inorganic ion exchangers such as zeolité/505007 and insoluble multivalent phosphate have the advantages of high temperature resistance and radiation resistance, their development is limited by their low exchange capacity and poor hydraulic properties. The law of solvent extraction is to use the different solubility of substances in two phases to transfer the extracted substance from one liquid phase to another with the help of extractant. This method is convenient for industrialization, because it has the characteristics of simple operation, low requirements for equipment and instruments, and is suitable for the treatment of a large number of high-level liquid waste, and is now widely used in post-treatment processes.
Crown ether is a kind of substance with cyclic structure, which has good selective complexing ability for alkali metal and alkaline earth metal cations. It can be widely used as an extractant in solvent extraction to quickly analyze and separate ’Sr in high-level radioactive waste liquid. 18 crown ether 6 (18-Crown-6, 18C6) and its derivatives have pore sizes that match the ionic radius of Sr”*, and can form stable complexes when interacting with each other, and they have good radiation resistance and hydrolysis stability, so they are the most important extractant in the research of removing ’Sr from high-level radioactive waste liquid. The extraction selectivity of 18C6 for Sr”” is good, but it is very soluble in water, so it is not suitable for use as an extractant. Dicyclohexyl -18- crown-6 (DCH18C6) with good hydrophobicity can be synthesized by grafting alkyl groups on the ring, but when it is dissolved in the organic phase, some of it still enters the water phase, which affects the extraction efficiency. In order to improve its lipophilicity, two tert-butyl groups were grafted to obtain 4',4"(S")-di-tert-butyl dicyclohexo-18-crown ether-6(4', 4" (5")-di-tert-butyl xantho-18-crown-6, DTBuch. The improved crown ether has high hydrophobicity and good lipophilicity, and can achieve high strontium extraction efficiency. It can be used as strontium extractant in SREX process and
CEEX-SREX process.
At present, the main route for the synthesis of DtBuCH18C6 is to synthesize di-tert-butyl dibenzo-18-crown ether-6 first, and then get the final product by hydrogenation. The specific method is to add dibenzo-18-crown-6(DB18C6) dissolved in dichloromethane into excess polyphosphoric acid (PPA) medium, then add excess tert-butanol, react at 60-70°C for a long)505007 time to separate, and then hydrogenate under high pressure to obtain the final product. However, the raw materials and products of this method are mostly flammable and combustible substances, and the hydrogenation conditions at high temperature and high pressure are very dangerous, which is not conducive to large-scale production.
The invention aims to provide a synthesis method and application of 4, 4 (S")-di-tert-butyldicyclohexylo-18-crown ether-6. The synthesis method is a non-hydrogenation synthesis method, and diethylene glycol, diethylene glycol bis (p-toluenesulfonate) and 3-tert-butyl-7-oxabicyclo [4.1.0] heptane are used as raw materials. By changing the synthesis reaction path and optimizing the synthesis reaction parameters, the problems of hydrogenation danger and difficulty in purification in DtBuCH18C6 synthesis reaction are overcome, and the synthesis of high-purity products is realized, thus providing a brand-new synthesis method of strontium extractant.
In order to achieve the above purpose, the present invention provides the following technical scheme:
One of the technical scheme of the invention is to provide a synthetic method of 4',4"(5")-di-tert-butyldicyclohexylo-18-crown ether-6, comprising: (1) dissolving diethylene glycol in an inert atmosphere; (2) adding catalyst, preheating and stirring until the catalyst is uniformly dispersed, heating, adding 3-tert-butyl-7-oxabicyclo [4.1.0] heptane and stirring; (3) adding catalyst, stirring until the catalyst is uniformly dispersed, adding diethylene glycol bis (p-toluenesulfonate), stirring at room temperature, and obtaining 4' 4'(5")-di-tert-butyldicyclohexylo-18-crown ether-6 after the reaction is completed.
Optionally, the synthetic method of 4'4"(5")-di-tert-butyldicyclohexylo-18-crown ether-6, comprising: (1) dissolving diethylene glycol in an inert atmosphere;
(2) adding catalyst, preheating and stirring until the catalyst is uniformly dispersed, heatink{505007 adding 3- tert-butyl -7- oxabicyclo [4.1.0] heptane and stirring; (3) adding a catalyst, stirring until the catalyst is uniformly dispersed, adding diethylene glycol bis (p-toluenesulfonate), stirring at room temperature, and obtaining 4' 4'(5")-di-tert-butyldicyclohexylo-18-crown ether-6 after the reaction is completed; (4) repeating step (3) for one or more times.
Optionally, the whole reaction is carried out in dimethyl sulfoxide system.
Optionally, the catalyst is sodium hydride.
Optionally, the molar ratio of diethylene glycol and diethylene glycol bis (p-toluenesulfonate) to the total amount of catalyst and 3-tert-butyl-7-oxabicyclo [4.1.0] heptane is 0.9-1.1:0.9-1.1:4 2-4 5:18 -2.2.
Optionally, the molar ratio of diethylene glycol and diethylene glycol bis (p-toluenesulfonate) to the total amount of catalyst and 3-tert-butyl-7-oxabicyclo [4.1.0] heptane 1s1.0:1.0:4.4:2.0.
Optionally, the preheating temperature is 70-90°C; the temperature is raise to 175-195C; the reaction time is 42-45 h.
Optionally, the preheating temperature is 70-90°C; the temperature is raise to 175-195C; the reaction time is 43 h.
Optionally, the inert atmosphere is nitrogen atmosphere.
Optionally, further comprising purification after completing the reaction, including: washing with deionized water, extraction, drying, vacuum evaporation, recrystallization with ether to obtain a crude product, and recrystallization and purification of the crude product with methanol to obtain purified 4',4"(5")-di-tert-butyldicyclohexylo-18-crown ether-6.
The second technical scheme of that invention is to provide a method for extracting strontum from a solution = containing strontium, = comprising: dissolving 4' 4'(5")-di-tert-butyldicyclohexylo-18-crown-6 synthesized by the synthesis method according to any one of claims 1 to 8 with n-octanol, adding into the solution containing strontium, oscillating and extracting, separating the organic phase, and removing the n-octanol.
The beneficial technical effects of the invention are as follows.
According to the invention, diethylene glycol, diethylene glycol bis (p-toluenesulfonate}505007 and 3-tert-butyl-7-oxabicyclo [4.1.0] heptane are used as raw materials, and by changing the synthesis reaction path and optimizing the synthesis reaction parameters, the problems of hydrogenation danger and difficult purification in the synthesis reaction of DtBuCH18C6 are overcome, the synthesis of high-purity products is realized, and a brand-new synthesis method of strontium extractant is provided.
When the synthesized DtBuCH18C6 is used as an extractant to extract strontium, n-octanol as a diluent has the best extraction efficiency. In addition, in this extraction system, the extraction efficiency of strontium is related to the concentration of extractant and nitric acid in water phase, and the time required for equilibrium reaction is short.
Fig. 1 1s a synthesis roadmap of Embodiment 1 of the present invention.
Fig. 2 is a one-dimensional NMR spectrum of DtBuCH18C6 prepared in Embodiment 1.
Fig. 3 1s the Fourier infrared spectrum of DtBuCH18C6 prepared in Embodiment 1.
Fig. 4 is the Raman spectrum of DtBuCH18C6 prepared in Embodiment 1.
Fig. 5 is a high-resolution mass spectrum of DtBuCH18C6 prepared in Embodiment 1.
Fig. 6 is a gas chromatogram of DtBuCH18C6 prepared in Embodiment 1.
Fig. 7 shows the extraction efficiency of different concentrations of DtBuCHI8C6 in
Embodiment 2.
Fig. 8 shows the extraction efficiency of different nitric acid concentrations in Embodiment 2.
Fig. 9 is a graph showing the extraction efficiency of different phases in Embodiment 2.
Fig. 10 is an extraction efficiency diagram of different extraction times in Embodiment 2.
A number of exemplary embodiments of the present invention will now be described in detail, and this detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects,
characteristics and embodiments of the present invention. It should be understood that th&/505007 terminology described in the present invention is only for describing specific embodiments and is not used to limit the present invention.
In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. Intermediate values within any stated value or stated range, as well as each smaller range between any other stated value or intermediate values within the stated range are also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.
Unless otherwise specified, 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 relates. Although the present invention only describes the preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention.
The terms "comprising", "including", "having" and "containing" used in this article are all open terms, which means including but not limited to.
DtBuCH18C6 standard used in the embodiment of the invention is purchased from
Sigma-Aldrich;
The reagents used in the embodiment of the invention are all commercially available analytical pure, and the experimental water is self-made ultrapure water.
The concentration of Sr”* in the Sr”* standard solution used in the embodiment of the invention is 1000 ug/mL, and the medium is 1.0 mol/L nitric acid.
Embodiment 1
Synthesis of DtBuCH18C6; (1) Under the protection of nitrogen, 5.06 g of sodium hydride is added to 10.70 g of diethylene glycol, and the reaction mixture is heated at 80°C until a solution is obtained. The temperature is raised to 184°C, and 30.85 g of 3-tert-butyl-7- oxabicyclo [4.1.0] heptane is added dropwise. The mixture is stirred at 184°C for 3 h and cooled to room temperature. After addingla)505007 proper amount of CH.Cl,, the solution was washed with brine, dried with MgSO4 and evaporated in vacuum to obtain an intermediate crude product; (2) Under the protection of nitrogen, add 20.72 g of crude intermediate product in step (1) into 18.20 g of 60% nah DMSO suspension, stir for 0.5 h, then add 41.45 g of diethylene glycol bis (p-toluenesulfonate), stir the mixture at room temperature for 40 h, wash it with deionized water, and extract it with ether for three times. The combined extracts are washed with brine, dried with MgSO4 and evaporated in vacuum. The crude product is obtained by recrystallization with ether, and then purified by recrystallization with methanol to obtain white viscous crystals.
The product is 7.57 g with a yield of 31.25%.
The synthesis roadmap of Embodiment 1 is shown in Fig. 1.
DtBuCH18C6 prepared in Embodiment 1 is characterized as follows.
One-dimensional NMR hydrogen spectrum of DtBuCH18C6 is shown in Fig. 2. From Fig. 2, it can be seen that four H's with chemical shifts of 3.94-3.77 belong to four H's on No.4, No.5,
No.16 and No.17 carbons (actually, No.4 C and No.5 carbons here are not completely symmetrical, but the influence of oxygen atoms on them is far greater than that of tert-butyl, and the oxygen atoms near them have the same influence on them. Sixteen H's with chemical shifts of 3.75-3.20 belong to 16 hydrogens on carbon 8, 11, 13, 14, 10, 25, 23 and 24. Four H's with chemical shifts of 2.02-1.72 belong to four hydrogens on carbon 6, 21, 3 and 18 (There are actually eight hydrogens here, but because these carbons are far away from oxygen atoms, the chemical environment changes slightly due to the influence of tert-butyl, and the other four hydrogens will move to high fields). The 10 H's with chemical shifts of 1.50-1.03 belong to the
H's on carbon 21, 6, 3, 1, 20, 18, 19 and 2. The 18 H's with chemical shifts of 0.84-0.82 belong to the 18 H's on carbon 32, 33, 34, 28, 29 and 30. 'HNMR (600MHz, CDCl3):63.94-3.77 (m, 4H), 83.75-3.20 (m, 16H), 82.02-1.72 (m, 4H), §1.50-1.03 (m, 10H), 50.84-0.82 (d, J = 12.0Hz 18H).
The Fourier infrared spectrum of DtBuCH18C6 is shown in Fig. 3. From Fig. 3, it can b&J505007 seen that the peaks of 2925 and 2856 cm” belong to the antisymmetric stretching vibration and symmetric stretching vibration peaks of C-H bond in methyl and methylene respectively. The peaks at 1460 and 1370 cm“ are the bending vibration peaks of C-H bond in methyl and methylene. The peaks of 1243, 1178 and 1082 em” are C-O bond stretching vibration peaks; The peak of 720 cm”! is the out-of-plane rocking vibration of C-H bond in long-chain hydrocarbon group. The peak of 1651 cm”! is H-O-H deformation vibration peak, which may be caused by crown ether absorbing a small amount of water. Because the sample prepared by the invention 1s an oily solid, it is dissolved with n-octanol before infrared detection, so the broad peak with wave number of 3374 cm” is the stretching vibration peak of hydroxyl -OH in n-octanol.
The Raman spectrum of DtBuCH18C6 is shown in Fig. 4. From Fig. 4, it can be seen that the weaker peak with the wave number of 973 cm”! is the C-O bond stretching vibration peak; the peak of 2413 cm”! is the CO; absorption peak in the background. The peak of 2929 cm”! is the stretching vibration peak of C-H bond in methyl or methylene; the peak of 3076 cm”! is the bending vibration peak of C-H bond; the peak of 3593 cm” is the stretching vibration peak of hydroxyl -OH.
The high-resolution mass spectrum of DtBuCH18C6 is shown in Fig. 5. As can be seen from Fig. 5, the chemical formula of DtBuCH18C6 is C28H5206, and its theoretical molecular weight after adding sodium is 507.3662, while its actual molecular weight after adding sodium is 507.3657, with a deviation of 0.0005. The analysis shows that the substance is DtBuCH18C6.
See Fig. 6 for the gas chromatogram of DtBuCH18C6. In Fig. 6, DtBuCH18C6(1) is the gas chromatogram of the standard and DtBuCH18C6(2) is the gas chromatogram of the sample.
From Fig. 6, it can be seen that the broad peak with retention time of 2.5-3.3 min is the solvent peak, the peak with retention time of 4.6-4.9 min is the characteristic peak of the sample, and the retention time of the sample is the same as that of the standard, which indicates that the synthesized substance is DtBuCH18C6.
Embodiment 2
The method of extracting strontium from strontium-containing solution by DtBuCH181&J505007 prepared in Embodiment 1 is investigated as follows.
Use a calibrated glass tube with a stopper to grind at room temperature, and seal the nozzle with a sealing film when oscillating. Adding DtBuCH18C6, diluent and Sr** solution, shaking for 5 min, standing for 30 min, and keeping the water phase. The concentration of strontium in water phase was measured by ICP-OES, and the concentration of strontium in organic phase is obtained by difference subtraction, and the distribution ratio D(Sr) and extraction efficiency E(Sr) are calculated. During the extraction process, the initial concentration of solution Sr** is 10 mg/L, which is obtained by diluting the standard solution of Sr>* by 100 times. (1) DtBuCH18C6 is used as extractant to extract strontium-containing solution, and the effects of n-octanol, sec-octanol, 1,2-dichloroethane, carbon tetrachloride and n-hexane as diluents on strontium extraction were investigated respectively. See Table 1 for the extraction of strontium by each diluent.
Table 1 Effect of DTBUCH 18C6 on Strontium Extraction with Different Organic Solvents as Diluents
DtBuCH18C6
Diluent c(DiBu ; ) D(Sr) | E(SD% (mol:L”)
N-octyl alcohol 18.05 | 9475
Carbon ; 0.1 2.91 74.42 tetrachloride 1,2- i 0.1 3.59 78.20
Dichloroethane
As can be seen from Table 1, under the conditions that the water phase is 10 mg/L strontium solution, the ratio 1s 1:1, the extraction time is 5 min, the concentration of nitric acid is 7 mol/L, and DtBuCH18C6- n-octanol is 0.1 mol/L, among these organic solvents selected in the experiment, n-octanol as diluent and DtBuCH18C6 are mixed into the organic phase, and both the distribution ratio and the extraction rate are the best.
(2) During the experiment, when the fixed water phase is 10 mg/L strontium solution, th&J505007 diluent in the organic phase is n-octanol, the concentration of nitric acid is 7 mol/L, the ratio is 1:1, and the extraction time is 5 min, the effects of the concentration of extractant DtBuCH18C6- n-octanol on strontium extraction are investigated. As can be seen from Fig. 7, E(Sr) increases with the increase of the concentration of DtBuCH18C6, and then decreases. When the concentration is higher than 0.1 mol/L, the extraction rate of strontium changes little, and basically remains above 90%. Therefore, considering the extraction rate, distribution ratio and economic cost, the concentration of DtBuCH18C6 is 0.1 mol/L, which is a more suitable extraction condition. (3) Under the condition that the stationary water phase is 10 mg/L strontium solution and the organic phase is 0.1 mol/L DtBuCH18C6- n-octanol, the ratio is 1:1, and the extraction time is 5 min, the effects of nitric acid concentrations of 1.0, 3.0, 5.0, 7.0 and 9.0 mol/L on strontium extraction are investigated respectively. See Figure 8 for the extraction efficiency of different nitric acid concentrations. As can be seen from Fig. 8, with the increase of acidity, the extraction efficiency of crown ether extraction system first increased and then decreased, and when the concentration of nitric acid in water phase was 7.0 mol/L, the value of E(Sr) reached the maximum. (4) DtBuCH18C6-n-octanol with 10 mg/L strontium solution as the stationary water phase, 7.0 mol/L nitric acid concentration in the water phase and 0.1 mol/L organic phase is extracted for 5 min, and the volume ratio (O/A) of the organic phase to the water phase is 1/3, 1/2, 1/1, 2/1 and 3 respectively. See Fig. 9 for the extraction efficiency of different phases. It can be seen from
Fig. 9 that when the O/A is less than 1, the extraction rate of strontium by crown ether is above 80%. With the increase of water phase, the extraction rate of strontium by crown ether shows a trend of first increasing and then decreasing, and the extraction rate is the highest when the O/A is 1:1, which is 94.75%. (5) DtBuCH18C6- n-octanol with 10 mg/L strontium solution as the stationary water phase, 7.0 mol/L nitric acid concentration in the water phase and 0.1 mol/L organic phase, compared with 1/1, the effects of extraction time for 1, 2, 3, 4, 5, 10 and 30 min on strontium extraction até/505007 shown in Fig. 10. As can be seen from Fig. 10, with the increase of oscillation time, the extraction efficiency E(Sr) of strontium increases slowly at first, and remains basically unchanged after 5 min, which indicates that the extraction of strontium with DtBuCH18C6 as extractant has reached equilibrium in 5 min.
The above-mentioned embodiments only describe the preferred mode of the invention, and do not limit the scope of the invention. Under the premise of not departing from the design spirit of the invention, various modifications and improvements made by ordinary technicians in the field to the technical scheme of the invention shall fall within the protection scope determined by the claims of the invention.
Claims (9)
1. A synthetic method of 4',4"(S")-di-tert-butyldicyclohexylo-18-crown ether-6, comprising: (1) dissolving diethylene glycol in an inert atmosphere; (2) adding catalyst, preheating and stirring until the catalyst is uniformly dispersed, heating, adding 3-tert-butyl-7-oxabicyclo [4.1.0] heptane and stirring; (3) adding catalyst, stirring until the catalyst is uniformly dispersed, adding diethylene glycol bis (p-toluenesulfonate), stirring at room temperature, and obtaining 4' 4'(5")-di-tert-butyldicyclohexylo-18-crown ether-6 after completing the reaction.
2. A synthetic method of 4',4"(5")-di-tert-butyldicyclohexylo-18-crown ether-6, comprising: (1) dissolving diethylene glycol in an inert atmosphere; (2) adding catalyst, preheating and stirring until the catalyst is uniformly dispersed, heating, adding 3-tert-butyl-7-oxabicyclo [4.1.0] heptane and stirring; (3) adding catalyst, stirring until the catalyst is uniformly dispersed, adding diethylene glycol bis (p-toluenesulfonate), stirring at room temperature, and obtaining 4' 4'(5")-di-tert-butyldicyclohexylo-18-crown ether-6 after completing the reaction; (4) repeating step (3) for one or more times.
3. The synthesis method according to claim 1, wherein the whole reaction is carried out in dimethyl sulfoxide system.
4. The synthesis method according to claim 1, wherein the catalyst is sodium hydride.
5. The synthesis method according to claim 4, wherein the molar ratio of diethylene glycol and diethylene glycol bis (p-toluenesulfonate) to the total amount of catalyst and 3-tert-butyl-7-oxabicyclo [4.1.0] heptane is 0.9-1.1:0.9-1.1:4.2-4.5:1.8 -2.2.
6. The synthesis method according to claim 1 or 2, wherein the preheating temperature is 70-90°C; the temperature is raise to 175-195°C; the reaction time is 42-45 h.
7. The synthesis method according to claim 1 or 2, wherein the inert atmosphere is nitrogé#/505007 atmosphere.
8. The synthesis method according to claim 1 or 2, further comprising purification after completing the reaction, including: washing with deionized water, extraction, drying, vacuum evaporation, recrystallization with ether to obtain a crude product, and recrystallization and purification of the crude product with methanol to obtain purified 4',4"(5")-di-tert-butyldicyclohexylo-18-crown ether-6.
9. A method for extracting strontium from a solution containing strontium, comprising: dissolving 4',4'(5")-di-tert-butyldicyclohexylo-18-crown-6 synthesized by the synthesis method according to any one of claims 1 to 8 with n-octanol, adding into the solution containing strontium, oscillating and extracting, separating the organic phase, and removing the n-octanol.
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