CN104262224A - Preparation method and industrialized production method of pyrrolidinium with tetrafluoroborate anions - Google Patents
Preparation method and industrialized production method of pyrrolidinium with tetrafluoroborate anions Download PDFInfo
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- CN104262224A CN104262224A CN201410514849.0A CN201410514849A CN104262224A CN 104262224 A CN104262224 A CN 104262224A CN 201410514849 A CN201410514849 A CN 201410514849A CN 104262224 A CN104262224 A CN 104262224A
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- pyrrolidinium
- acid salt
- tetrafluoroboric acid
- salt anionic
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- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 title claims abstract description 50
- -1 tetrafluoroborate anions Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004821 distillation Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000012429 reaction media Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 45
- 239000000047 product Substances 0.000 claims description 42
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 239000006227 byproduct Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000004879 turbidimetry Methods 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 11
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 230000006837 decompression Effects 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000001308 synthesis method Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 239000011591 potassium Chemical group 0.000 claims description 2
- 229910052700 potassium Chemical group 0.000 claims description 2
- 239000011734 sodium Chemical group 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 238000001914 filtration Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 9
- 229910001961 silver nitrate Inorganic materials 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 7
- 238000010025 steaming Methods 0.000 description 6
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000383 hazardous chemical Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical class OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- ONQBOTKLCMXPOF-UHFFFAOYSA-N 1-ethylpyrrolidine Chemical compound CCN1CCCC1 ONQBOTKLCMXPOF-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 241000270725 Caiman Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241001083492 Trapa Species 0.000 description 1
- 235000014364 Trapa natans Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005885 boration reaction Methods 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
Abstract
The invention provides a preparation method of pyrrolidinium with tetrafluoroborate anions, which comprises the following steps: (1) the one-step synthesis of a coarse product: by taking a non-proton organic solvent as a reaction medium, dropwise adding haloalkanes into a mixture consisting of N-alkyl pyrrolidine and tetrafluoroborate, reacting for obtaining a coarse product liquid, filtering the coarse product liquid by using a centrifuge, and carrying out reduced pressure distillation on filter liquor so as to obtain a coarse product solid; and (2) heating and stirring the coarse product solid so as to dissolve the coarse product solid into an alcohol organic solvent, and sequentially carrying out cooling crystallization, filtration, rinsing and vacuum drying on the obtained product, so that a refined finished product is obtained. The invention also discloses an industrialized production method of pyrrolidinium with tetrafluoroborate anions. The methods disclosed by the invention are implemented through one-step synthesis, cheap and easily-obtained in raw materials, short in synthetic route, mild in reaction conditions, short in reaction time, simple in operation, and relatively low in production cost; prepared products are high in product purity, good in crystal form and high in yield; and environmentally harmful substances are not produced in the production process, thereby facilitating industrialized continuous mass production.
Description
Technical field
The present invention relates to a kind of preparation method and industrialized preparing process of the pyrrolidinium with Tetrafluoroboric acid salt anionic.
Background technology
At present, the good conductivity that a lot of salt has because it is spontaneous and wider electrochemical window and be widely used in the conducting salt of ultracapacitor and the dielectric medium field of superbattery, the salt of part salt especially in liquid state under room temperature, due to it, there is non-volatility and be easy to advantages such as being separated from reaction system, being considered to a kind of green solvent and the green catalyst with wide application prospect.According to the designability of salt, in salt synthesis, introduce the zwitterion with different qualities functional group salt then can be made to have certain characteristic functions maybe can meet specificity requirement.Present liquid state under wherein combining salt room temperature by large volume, the organic cation of low symmetry and the inorganic anion of small volume, be included into ion liquid system.Under the tide of chemical greenization, this kind of pyrrolidinium is again subject to countries in the world and pays close attention to, its research exceeds chemical field, show up prominently in the field such as the energy, material, be widely used in the aspects such as catalysis, organic synthesis, compartment analysis, electrochemistry, clean energy, functional fluid, nanotechnology, functional materials, functional additive at present, and present fast-developing situation.Due to pyrrolidinium particularly character specific to a tetrafluoro borate, it is as class new function material and a medium, also good application prospect is demonstrated in fields such as the energy, information, life science, national defence, the combination of ionic liquid and existing supercutical fluid, electrochemistry, nanotechnology, microelectronics etc., makes the development space of these technology strengthen further and function is more perfect.
But, because China starts late with superbattery concerning ultracapacitor with the relative western developed country of dielectric research, the production of Tetrafluoroboric acid pyrrolidinium not yet enters the suitability for industrialized production stage, cause its manufacturing cost to remain high always, use popularization to bring huge obstruction to its market.What have document to record relates to tetrafluoro boron salt anionic pyrrolidinium production method such as: application people is East China Normal University, application number is Chinese patent-" a kind of alkali ionic liquid of CN200610116874.9, preparation method and application thereof ", although mention preparation method's (two-step synthesis method: first by quaternized acquisition ionic halogenide of alkali ionic liquid, then ion-exchange is passed through, obtain target alkali ionic liquid), but itself and not mentioned concrete substantial synthetic method and purification process, and the basic quaternary ammonium ionic liquid clearly stating this patent disclosure is in the description stablized water and air, be liquid under room temperature, and fusing point is not suitable for higher than the synthesis technique of 200 DEG C of solid kind quaternary ammonium salts very easily absorbed water in atmosphere and process for refining, application people is Haiyangwang Lighting Technology Co., Ltd., Shenzhen City Haiyangwang LIGHTING TECHNOLOGY CO.,LTD, Shenzhen City Haiyangwang Illumination Engineering Co., Ltd, application number is Chinese patent-" pyrrolidinium ions liquid and preparation method thereof and electrolytic solution and the electrical condenser " of CN201310042656.5, although relate to the preparation of pyrrolidinium ions liquid, but the substituting group be connected with tetramethyleneimine of this patent requirements is only confined to by methyl and CH3O (CH2) n, wherein n is 2, 3 or 4 two kind of substituting group scope, and be also two-step synthesis method, reaction process does not relate to the process for purification of selecting of organic medium and product, for very easily water-soluble inapplicable with a tetrafluoro borate anion salt the method, application people be Merck Patent GmbH, application number is CN200580041219.5 Chinese patent-" halide content minimizing, with the preparation method of a tetrafluoro borate anion salt ", its boration process is confined on the high raw material of the prices such as trialkyl oxygen a tetrafluoro borate, trialkyl sulphur a tetrafluoro borate, triphenyl positive carbon a tetrafluoro borate, and the process for purification of also not mentioned product, market is difficult to obtain alkyl oxygen class raw material, is therefore difficult to carry out suitability for industrialized production, Chinese patent-" preparation method of high-purity conductive salt for super capacitor " that application people is Wuhan caiman Science and Technology Ltd., Guangzhou Kaimen Fine Chemicals Co., Ltd., application number are CN200910041553.0 discloses three-step synthesis method, its raw material N-ethyl pyrrolidine is domestic there is not yet industrialization, so raw materials for production are subject to severely restricts, and synthesis step is loaded down with trivial details, temperature is higher, is unfavorable for saving energy and reduce the cost, other synthetic methods such as Mitsui chemistry, Mitsubishi Chemical, three are oxidized to, water chestnut gas etc. in the synthetic method of Japanese publication because adopting the corrosive raw materials such as Tetrafluoroboric acid, boron trifluoride, hydrogen fluoride, therefore higher to the requirement for anticorrosion of equipment starting material, and raw material easily forms the by product being difficult to remove in reaction process, is not easy to industrialization promotion.
For above problem, the invention provides the industrial one-step synthesis of the pyrrolidinium crystal with Tetrafluoroboric acid salt anionic of a kind of high purity, high yield, this synthetic method cheaper starting materials is easy to get, synthetic route is short, reaction conditions is gentle, and the reaction times is short, and technological operation is simple, production cost relative moderate, obtained product purity is high, and crystal formation is good, and yield is high, whole production process does not produce environmentally hazardous substance in addition, is convenient to industrialization and produces in enormous quantities continuously.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method and industrialized preparing process of the pyrrolidinium with Tetrafluoroboric acid salt anionic, one-step synthesis, and cheaper starting materials is easy to get, synthetic route is short, reaction conditions is gentle, and the reaction times is short, and technological operation is simple, production cost relative moderate, obtained product purity is high, and crystal formation is good, and yield is high, whole production process does not produce environmentally hazardous substance in addition, is convenient to industrialization and produces in enormous quantities continuously.
For solving the problems of the technologies described above, the preparation method of a kind of pyrrolidinium with Tetrafluoroboric acid salt anionic provided by the invention, comprises the following steps:
(1) one-step synthesis method is with the thick product of pyrrolidinium of Tetrafluoroboric acid salt anionic:
Take aprotic organic solvent as reaction medium, the haloalkane with general formula (III) is dripped in the mixture be made up of the N-alkyl pyrrolidine with general formula (II) and a tetrafluoro borate with general formula (IV), the obtained thick product solution with the pyrrolidinium with Tetrafluoroboric acid salt anionic of general formula (I) after reaction, filter through whizzer, obtain the thick product solid of pyrrolidinium with Tetrafluoroboric acid salt anionic after filtrate decompression distillation, reaction formula is as follows:
(2) with the thick product purification of pyrrolidinium of Tetrafluoroboric acid salt anionic:
The thick product of the pyrrolidinium with Tetrafluoroboric acid salt anionic that step (1) is obtained, heated and stirred is dissolved in alcohol organic solvent, crystallisation by cooling obtains mixed crystal, by mixed crystal centrifuging, the crystal recrystallisation solvent leached carries out rinsing, obtain rinsing liquid, detect the halogen ion content in rinsing liquid, after the detection of halogen ion content is qualified, mixed crystal after rinsing is filtered dry, vacuum-drying, obtains the pyrrolidinium finished product with Tetrafluoroboric acid salt anionic refined.
Preferably, the aprotic organic solvent in described step (1) is acetone, acetonitrile or ethanol, and the reaction times is 24 ~ 72 hours.
Preferably, in described step (1), the mol ratio of N-alkyl pyrrolidine, a tetrafluoro borate, haloalkane is 1:1 ~ 3:1 ~ 3.
Preferably, the temperature of reaction in described step (1) is 0 ~ 55 DEG C, and reaction environment pressure is normal pressure.
Preferably, in described step (1), R1 and R2 is independently selected from low alkyl group, the low alkyl group that maybe can be substituted; X is chlorine or bromine; Y is hydrogen, amine, sodium or potassium.
Preferably, the alcohol organic solvent in described step (2) is Virahol, and Heating temperature is 40 DEG C ~ 95 DEG C, and cooling temperature is 0 DEG C ~ room temperature.
Preferably, the detection method of the halogen ion content in described step (2) in rinsing liquid is acetone-silver halide turbidimetry or ion selective electrode method.Wherein, acetone-silver halide turbidimetry, be similar to " the mensuration acetone-silver chloride turbidimetry of GB/T1348.18-2005 cl content ", its principle uses halogen ion (to be mainly bromide anion, chlorion) react to generate with the Silver Nitrate of acidifying and precipitate, precipitation a small amount of under acetone effect can exist with colloidal state, in colloid silver halide level certain limit class and absorbancy linear, corresponding with typical curve by the filtrate sample absorbancy recorded, the content of chlorion can be drawn; Ion selective electrode method, directly detects halogen ion content by chlorion ion selective electrode, bromide anion ion selective electrode.If need more high purity can by product crystallization again, whether up to standardly then detect filtrate, two kinds of detection methods be all very quick.
Preferably, in described step (2), during the detection of the halogen ion content in rinsing liquid, halogen ion content be not more than 100ppm be considered as detecting qualified.
The industrialized preparing process of a kind of pyrrolidinium with Tetrafluoroboric acid salt anionic provided by the invention, comprises the following steps:
(1) respectively by aprotic organic solvent, there is the N-alkyl pyrrolidine of general formula (II), the a tetrafluoro borate with general formula (IV) drops in reactor, unlatching reactor stirs, the haloalkane reaction with general formula (III) is dripped in reactor, the obtained thick product solution with the pyrrolidinium with Tetrafluoroboric acid salt anionic of general formula (I) after reaction, filter through whizzer, remove the by product halogen being insoluble to aprotic organic solvent, filtrate pumps into vacuum distillation equipment, aprotic organic solvent is reclaimed in underpressure distillation, obtain the thick product solid of pyrrolidinium with Tetrafluoroboric acid salt anionic, reaction formula is as follows:
Recrystallisation solvent is injected to vacuum distillation equipment, heating up makes the thick product solid of pyrrolidinium with Tetrafluoroboric acid salt anionic dissolve completely, then lower the temperature, it is 5 ~ 15 DEG C/h that cooling rate controls, in time having crystal to separate out, cooling rate is adjusted to 2 ~ 10 DEG C/h, cooling is stopped to during complete crystallization, mixed crystal is carried out centrifuging, in the mixed crystal after centrifugal, add recrystallisation solvent carry out rinsing, obtain rinsing liquid, detect the halogen ion content of rinsing liquid, after halogen ion detection is qualified, mixed crystal after rinsing is added Vacuumdrier, drying under reduced pressure is to complete drying, obtain the pyrrolidinium finished product with Tetrafluoroboric acid salt anionic refined.
Compared with prior art, the present invention has following beneficial effect:
(1) cheaper starting materials that the present invention is used is easy to get, and building-up process is one-step synthesis, and route is short, and reaction conditions is gentle, production cost relative moderate, and obtained product purity is high, and crystal formation is good, total recovery higher (can reach more than 95%);
(2) produce with traditional two-step approach compared with decrease the usage quantity of reaction medium, because the intermediate generated participates in reaction directly, so substantially reduce the reaction times, simplify technical operation flow, the easy Distillation recovery of reacted solvent, thus greatly reduce production cost;
(3) generate without environmentally hazardous substance in production process, be convenient to industrialization and produce in enormous quantities continuously;
(4) reaction raw materials toxicity used is less, and lower to equipment corrosion, quality product easily controls;
(5) reaction system selects specific aprotic organic solvent, due to by product halogen (bromine salt, villaumite) solubleness (such as Sodium Bromide solubleness in acetone only has about 8ppm) within 100ppm in selected solvent, and target product solubleness in selected organic solvent is larger, so facilitate the carrying out of reaction on the one hand, reduce on the other hand halogen to be mixed into finished product and to cause halogen contaminants, ensure that high conversion and the high purity of product.
(6) thick product is through recrystallization, on the one hand the purity of product is improved, and products obtained therefrom is the product after crystallization on the other hand, uniform particles.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Embodiment 1
Get 1000mL there-necked flask in cooling bath, add N-crassitude 129.43g, Sodium tetrafluoroborate 183.60g, acetone 130mL also stirs, arranging stirring frequency is 35Hz, 182.19g monobromethane is added dropwise to complete in lower 5 hours in 30 DEG C of conditions, dropwise rear continuation stirring 19 hours, through whizzer removed by filtration solid by-product, filtrate decompression is distilled, obtain white solid (namely with the thick product of pyrrolidinium of Tetrafluoroboric acid salt anionic), add Virahol 150g, stirring is warming up to 65 DEG C, slowly decrease temperature crystalline after white solid dissolves completely, controlling cooling rate is 10 DEG C/h, separate out completely to mixed crystal, by mixed crystal centrifuging, the mixed crystal Virahol leached carries out rinsing, obtain rinsing liquid, rinsing liquid acetone-silver halide turbidimetry detects ionic bromide content, namely add Silver Nitrate without precipitation generation be considered as detect qualified, then mixed crystal is put into Rotary Evaporators and revolve steaming to constant weight, obtain white crystal thing 292.4g, N-crassitude transformation efficiency 95.7%.
Embodiment 2
Get 1000mL there-necked flask in cooling bath, add N-crassitude 129.43g, Sodium tetrafluoroborate 183.60g, acetone 130mL also stirs, arranging stirring frequency is 35Hz, 182.19g monobromethane is added dropwise to complete in lower 25 hours in 0 DEG C of condition, dropwise rear continuation stirring 47 hours, through whizzer removed by filtration solid by-product, filtrate decompression is distilled, obtain white solid (namely with the thick product of pyrrolidinium of Tetrafluoroboric acid salt anionic), add Virahol 150g, stirring is warming up to 40 DEG C, slowly decrease temperature crystalline after white solid dissolves completely, controlling cooling rate is 5 DEG C/h, separate out completely to mixed crystal, by mixed crystal centrifuging, the mixed crystal Virahol leached carries out rinsing, obtain rinsing liquid, rinsing liquid acetone-silver halide turbidimetry detects ionic bromide content, namely add Silver Nitrate without precipitation generation be considered as detect qualified, then mixed crystal is put into Rotary Evaporators and revolve steaming to constant weight, obtain white crystal thing 293.6g, N-crassitude transformation efficiency 96.1%.
Embodiment 3
N-crassitude 129.43kg is added in 1000L glassed steel reaction vessels, Sodium tetrafluoroborate 183.60kg, acetone 130L also stirs, arranging stirring frequency is 35Hz, 182.19kg monobromethane is added dropwise to complete in lower 5 hours in 55 DEG C of conditions, dropwise rear continuation stirring 25 hours, solid by-product is removed in centrifuging, filtrate injects the underpressure distillation of underpressure distillation still to flowing out without component by infusion pump, obtain white solid (namely with the thick product of pyrrolidinium of Tetrafluoroboric acid salt anionic), then in white solid, Virahol 150kg is added, stirring is warming up to 95 DEG C, slowly decrease temperature crystalline after white solid dissolves completely, controlling cooling rate is 15 DEG C/h, about about 55 DEG C observations have mixed crystal to separate out, cooling rate is adjusted to 10 DEG C/h, continue to be cooled to mixed crystal to separate out completely, centrifuging, the mixed crystal Virahol leached carries out rinsing, obtain rinsing liquid, rinsing liquid acetone-silver halide turbidimetry detects ionic bromide content, namely add Silver Nitrate without precipitation generation be considered as detect qualified, then mixed crystal is put into Vacuumdrier 85 DEG C of drying under reduced pressure to constant weight, obtain white crystalline powder 294.34kg, N-crassitude transformation efficiency 97.62%.
Embodiment 4
N-crassitude 129.43kg is added in 1000L glassed steel reaction vessels, fluoroboric acid amine 173.13kg, acetone 130L also stirs, arranging stirring frequency is 35Hz, 182.19kg monobromethane is added dropwise to complete in lower 15 hours in 45 DEG C of conditions, dropwise rear continuation stirring 29 hours, solid by-product is removed in centrifuging, filtrate injects the underpressure distillation of underpressure distillation still to flowing out without component by infusion pump, obtain white solid (namely with the thick product of pyrrolidinium of Tetrafluoroboric acid salt anionic), then in white solid, Virahol 150kg is added, stirring is warming up to 50 DEG C, slowly decrease temperature crystalline after white solid dissolves completely, controlling cooling rate is 5 DEG C/h, about about 55 DEG C observations have mixed crystal to separate out, cooling rate is adjusted to 2 DEG C/h, continue to be cooled to mixed crystal to separate out completely, centrifuging, the mixed crystal Virahol leached carries out rinsing, obtain rinsing liquid, rinsing liquid acetone-silver halide turbidimetry detects ionic bromide content, namely add Silver Nitrate without precipitation generation be considered as detect qualified, then mixed crystal is put into Vacuumdrier 85 DEG C of drying under reduced pressure to constant weight, obtain white crystalline powder 290.68kg, N-crassitude transformation efficiency 96.41%.
Detected by product obtained for embodiment 1 ~ 4, result is as following table 1:
Table 1
Embodiment 5
Get 250mL there-necked flask in cooling bath, add N-crassitude 86.2g, ammonium borofluoride 115.32g, acetonitrile 250mL also stirs, arranging stirring frequency is 35Hz, 150.7g bromination of n-butane is added dropwise to complete in lower 10 hours in 50 DEG C of conditions, dropwise rear continuation stirring 26 hours, through whizzer removed by filtration solid by-product, filtrate decompression is distilled, obtain white solid (namely with the thick product of pyrrolidinium of Tetrafluoroboric acid salt anionic), add Virahol 200g, stirring is warming up to 80 DEG C, slowly decrease temperature crystalline after white solid dissolves completely, controlling cooling rate is 9 DEG C/h, separate out completely to mixed crystal, by mixed crystal centrifuging, the mixed crystal Virahol leached carries out rinsing, obtain rinsing liquid, rinsing liquid acetone-silver halide turbidimetry detects ionic bromide content, namely add Silver Nitrate without precipitation generation be considered as detect qualified, then mixed crystal is put into Rotary Evaporators and revolve steaming to constant weight, obtain white crystal thing 222.72g, N-crassitude transformation efficiency 97.23%.
Embodiment 6
Get 250mL there-necked flask in cooling bath, add N-crassitude 86.2g, fluoroboric acid (30% ethanolic soln) 292.7g stirs, arranging stirring frequency is 35Hz, 150.7 monobromethanes are added dropwise to complete in lower 25 hours in 20 DEG C of conditions, dropwise rear continuation stirring 39 hours, through whizzer removed by filtration solid by-product, filtrate decompression is distilled, obtain white solid (namely with the thick product of pyrrolidinium of Tetrafluoroboric acid salt anionic), add Virahol 200g, stirring is warming up to 55 DEG C, slowly decrease temperature crystalline after white solid dissolves completely, controlling cooling rate is 8 DEG C/h, separate out completely to mixed crystal, by mixed crystal centrifuging, the mixed crystal Virahol leached carries out rinsing, obtain rinsing liquid, rinsing liquid acetone-silver halide turbidimetry detects ionic bromide content, namely add Silver Nitrate without precipitation generation be considered as detect qualified, then mixed crystal is put into Rotary Evaporators and revolve steaming to constant weight, obtain white crystal thing 220.6g, N-crassitude transformation efficiency 96.3%.
Embodiment 7
Get 250mL there-necked flask in cooling bath, add N-crassitude 86.2g, ammonium borofluoride 115.32g, acetonitrile 250mL also stirs, arranging stirring frequency is 35Hz, 150.7g n-propylcarbinyl chloride is added dropwise to complete in lower 10 hours in 40 DEG C of conditions, dropwise rear continuation stirring 19 hours, through whizzer removed by filtration solid by-product, filtrate decompression is distilled, obtain white solid (namely with the thick product of pyrrolidinium of Tetrafluoroboric acid salt anionic), add Virahol 200g, stirring is warming up to 75 DEG C, slowly decrease temperature crystalline after white solid dissolves completely, controlling cooling rate is 7 DEG C/h, separate out completely to mixed crystal, by mixed crystal centrifuging, the mixed crystal Virahol leached carries out rinsing, obtain rinsing liquid, rinsing liquid acetone-silver halide turbidimetry chlorine detection ion content, namely add Silver Nitrate without precipitation generation be considered as detect qualified, then mixed crystal is put into Rotary Evaporators and revolve steaming to constant weight, obtain white crystal thing 221.85g, N-crassitude transformation efficiency 96.85%.
Embodiment 8
Get 250mL there-necked flask in cooling bath, add N-crassitude 86.2g, ammonium borofluoride 115.32g, acetone 250mL also stirs, arranging stirring frequency is 35Hz, 150.7g n-propylcarbinyl chloride is added dropwise to complete in lower 5 hours in 35 DEG C of conditions, dropwise rear continuation stirring 32 hours, through whizzer removed by filtration solid by-product, filtrate decompression is distilled, obtain white solid (namely with the thick product of pyrrolidinium of Tetrafluoroboric acid salt anionic), add Virahol 200g, stirring is warming up to 70 DEG C, slowly decrease temperature crystalline after white solid dissolves completely, controlling cooling rate is 10 DEG C/h, separate out completely to mixed crystal, by mixed crystal centrifuging, the mixed crystal Virahol leached carries out rinsing, obtain rinsing liquid, rinsing liquid acetone-silver halide turbidimetry chlorine detection ion content, namely add Silver Nitrate without precipitation generation be considered as detect qualified, then mixed crystal is put into Rotary Evaporators and revolve steaming to constant weight, obtain white crystal thing 223.13g, N-crassitude transformation efficiency 97.41%.
Detected by product obtained for embodiment 5 ~ 8, result is as following table 2:
Table 2
From table 1 and table 2, the purity of the product that the present invention obtains is all higher, generates, be convenient to industrialization and produce in enormous quantities continuously without environmentally hazardous substance.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (9)
1. with a preparation method for the pyrrolidinium of Tetrafluoroboric acid salt anionic, it is characterized in that: comprise the following steps:
(1) one-step synthesis method is with the thick product of pyrrolidinium of Tetrafluoroboric acid salt anionic:
Take aprotic organic solvent as reaction medium, the haloalkane with general formula (III) is dripped in the mixture be made up of the N-alkyl pyrrolidine with general formula (II) and a tetrafluoro borate with general formula (IV), the obtained thick product solution with the pyrrolidinium with Tetrafluoroboric acid salt anionic of general formula (I) after reaction, filter through whizzer, obtain the thick product solid of pyrrolidinium with Tetrafluoroboric acid salt anionic after filtrate decompression distillation, reaction formula is as follows:
(2) with the thick product purification of pyrrolidinium of Tetrafluoroboric acid salt anionic:
The thick product of the pyrrolidinium with Tetrafluoroboric acid salt anionic that step (1) is obtained, heated and stirred is dissolved in alcohol organic solvent, crystallisation by cooling obtains mixed crystal, by mixed crystal centrifuging, the mixed crystal recrystallisation solvent leached carries out rinsing, obtain rinsing liquid, detect the halogen ion content in rinsing liquid, after the detection of halogen ion content is qualified, mixed crystal after rinsing is filtered dry, vacuum-drying, obtains the pyrrolidinium finished product with Tetrafluoroboric acid salt anionic refined.
2. the preparation method of a kind of pyrrolidinium with Tetrafluoroboric acid salt anionic according to claim 1, it is characterized in that: the aprotic organic solvent in described step (1) is acetone, acetonitrile or ethanol, the reaction times is 24 ~ 72 hours.
3. the preparation method of a kind of pyrrolidinium with Tetrafluoroboric acid salt anionic according to claim 1, is characterized in that: in described step (1), the mol ratio of N-alkyl pyrrolidine, a tetrafluoro borate, haloalkane is 1:1 ~ 3:1 ~ 3.
4. the preparation method of a kind of pyrrolidinium with Tetrafluoroboric acid salt anionic according to claim 1, it is characterized in that: the temperature of reaction in described step (1) is 0 ~ 55 DEG C, reaction environment pressure is normal pressure.
5. the preparation method of a kind of pyrrolidinium with Tetrafluoroboric acid salt anionic according to claim 1, is characterized in that: R in described step (1)
1and R
2independently selected from low alkyl group, the low alkyl group that maybe can be substituted; X is chlorine or bromine; Y is hydrogen, amine, sodium or potassium.
6. the preparation method of a kind of pyrrolidinium with Tetrafluoroboric acid salt anionic according to claim 1, it is characterized in that: the alcohol organic solvent in described step (2) is Virahol, Heating temperature is 40 DEG C ~ 95 DEG C, and cooling temperature is 0 DEG C ~ room temperature.
7. the preparation method of a kind of pyrrolidinium with Tetrafluoroboric acid salt anionic according to claim 1, is characterized in that: the detection method of the halogen ion content in described step (2) in rinsing liquid is acetone-silver halide turbidimetry or ion selective electrode method.
8. the preparation method of a kind of pyrrolidinium with Tetrafluoroboric acid salt anionic according to claim 1, it is characterized in that: in described step (2), during the detection of the halogen ion content in rinsing liquid, halogen ion content be not more than 100ppm be considered as detecting qualified.
9. with an industrialized preparing process for the pyrrolidinium of Tetrafluoroboric acid salt anionic, it is characterized in that: comprise the following steps:
(1) respectively by aprotic organic solvent, there is the N-alkyl pyrrolidine of general formula (II), the a tetrafluoro borate with general formula (IV) drops in reactor, unlatching reactor stirs, the haloalkane reaction with general formula (III) is dripped in reactor, the obtained thick product solution with the pyrrolidinium with Tetrafluoroboric acid salt anionic of general formula (I) after reaction, filter through whizzer, remove the by product halogen being insoluble to aprotic organic solvent, filtrate pumps into vacuum distillation equipment, aprotic organic solvent is reclaimed in underpressure distillation, obtain the thick product solid of pyrrolidinium with Tetrafluoroboric acid salt anionic, reaction formula is as follows:
(2) recrystallisation solvent is injected to vacuum distillation equipment, heating up makes the thick product solid of pyrrolidinium with Tetrafluoroboric acid salt anionic dissolve completely, then lower the temperature, it is 5 ~ 15 DEG C/h that cooling rate controls, in time having crystal to separate out, cooling rate is adjusted to 2 ~ 10 DEG C/h, cooling is stopped to during complete crystallization, mixed crystal is carried out centrifuging, in the mixed crystal after centrifugal, add recrystallisation solvent carry out rinsing, obtain rinsing liquid, detect the halogen ion content of rinsing liquid, after halogen ion detection is qualified, mixed crystal after rinsing is added Vacuumdrier, drying under reduced pressure is to complete drying, obtain the pyrrolidinium finished product with Tetrafluoroboric acid salt anionic refined.
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