CN112940019A - Preparation method of tetraphenyl borate - Google Patents
Preparation method of tetraphenyl borate Download PDFInfo
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- CN112940019A CN112940019A CN201911174716.2A CN201911174716A CN112940019A CN 112940019 A CN112940019 A CN 112940019A CN 201911174716 A CN201911174716 A CN 201911174716A CN 112940019 A CN112940019 A CN 112940019A
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- tetraphenylborate
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title description 7
- -1 salt compound Chemical class 0.000 claims abstract description 147
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 230000002195 synergetic effect Effects 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 25
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 229910001415 sodium ion Inorganic materials 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical group 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 3
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- 239000011734 sodium Substances 0.000 abstract description 7
- 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 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 26
- 239000002244 precipitate Substances 0.000 description 16
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 15
- 238000001914 filtration Methods 0.000 description 14
- 150000003839 salts Chemical group 0.000 description 14
- 238000004255 ion exchange chromatography Methods 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 11
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 8
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- YXBSOQIDSJOJRD-UHFFFAOYSA-N C(C=C1)=CC=C1P(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.Br Chemical compound C(C=C1)=CC=C1P(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.Br YXBSOQIDSJOJRD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a method for preparing tetraphenyl borate, which comprises the step of reacting sodium tetraphenyl borate with a quaternary salt compound under the synergistic action of water and an organic solvent to prepare a tetraphenyl borate product, wherein the organic solvent is an organic solution which can dissolve the quaternary salt compound and does not participate in the reaction.
Description
Technical Field
The invention relates to a preparation method of tetraphenyl borate, in particular to a method for efficiently synthesizing tetraphenyl borate, belonging to the technical field of organic synthesis.
Background
Organic tetraphenylborate salts, such as quaternary ammonium tetraphenylborate salts, quaternary phosphonium tetraphenylborate salts, can be used as bases, catalysts or reaction components in a series of organic reactions. Since these quaternary salts are not readily available on the market and the starting materials for synthesizing these salts are relatively expensive, efficient synthesis of these salts is desirable.
In the existing process for synthesizing organic tetraphenylborate, the quaternary salt ((Q) is used as raw materialn+)m(Ym-)n) Often, the reaction is not sufficiently carried out and the metal salt produced as a by-product is not efficiently removed. For example: zhaoqiang et al, in the paper "synthesis and characterization of N, N, N, N-tetrabutyl-B, B, B, B-tetraphenyl-ammonium borate" (proceedings of the university of Rockyang, 2 nd, 2007: 62-64) introduced a method for preparing tetrabutylammonium tetraphenyl borate, which comprises preparing tetrabutylammonium bromide and sodium tetraphenyl borate as aqueous solutions, first adding a small amount of tetrabutylammonium bromide to the aqueous solution of sodium tetraphenyl borate to form precipitates and seed crystals, then continuously adding dropwise to complete the reaction, and finally washing to remove by-product sodium bromide to obtain tetrabutylammonium tetraphenyl borate. Although the method realizes the preparation of tetrabutylammonium tetraphenylborate, it has the great drawbacks and limitations that, on the one hand, it requires the formation of precipitates and seeds by early feeding, reaction control, which would be difficult to implement and control effectively in large-scale production; on the other hand, sodium bromide as a by-product is precipitated in the form of very fine crystals in tetrabutylammonium tetraphenylborate and is difficult to remove efficiently. The limitation exists in that a single water is used as a reaction medium, and when other quaternary salt compounds with low solubility or insolubility in water are used as reaction raw materials, the target product cannot be obtained by adopting the method obviously, and the popularization and the application of the organic tetraphenyl borate synthesis process are not facilitated.
In addition, Li Shiqiang et al, in the paper "the synthesis of borate compounds and their resistance to flow and corrosion of their treated materials" (China forestry science research institute, 5.2010) introduced a chemical synthesis of quaternary ammonium salts of tetraphenyl borate, which comprises preparing sodium tetraphenyl borate and dodecyltrimethyl ammonium chloride as aqueous solutions, adding dropwise a small amount of dodecyltrimethyl ammonium chloride solution into the sodium tetraphenyl borate solution to produce white turbidity, stopping the dropwise addition after the small amount of the solution is added, allowing the solution to react for 10min to form crystals, continuing the dropwise addition for 1 hour to produce dodecyltrimethyl ammonium tetraphenyl borate and sodium chloride, and removing the sodium chloride by washing and recrystallization of filter cakes. In the synthesis method, although the influence of by-products such as sodium bromide and the like on the purity of the product is solved, the synthesis method also takes water as a single reaction medium, and when the selected quaternary salt compound has low water solubility or cannot be dissolved, the acquisition of the target product is also influenced.
Disclosure of Invention
In order to overcome the problems and defects of the existing tetraphenylborate synthesis process, the invention provides a method for preparing tetraphenylborate, which realizes the process of almost quantitatively reacting sodium tetraphenylborate with quaternary salt compounds in a mixed reaction system consisting of water and organic solution to obtain organic tetraphenylborate quaternary salt products, has high product purity, and completely dissolves sodium salts of byproducts in water, so that the method is free of interference byproducts and suitable for efficient and high-purity large-scale preparation and production of organic tetraphenylborate.
The invention is realized by the following technical scheme: a process for preparing tetraphenylborate, which comprises reacting sodium tetraphenylborate with a quaternary compound under the synergistic action of water and an organic solvent to obtain a tetraphenylborate product,
wherein the organic solvent is organic solution capable of dissolving quaternary salt compound and not participating in reaction, and the quaternary salt compound has a structural formula of (Q)n+)m(Ym-)nThe structural formula of the tetraphenylborate is (Q)n+)[(C6H5)4B]n，
In the above structural formula, Q n+Is of the structural formula (XR)o +)nQuaternary cation of (A), Ym-Is a negatively charged ion or group, m and n are natural numbers, X is an atom of group Va or VIa, o is a natural number of 0-4, and R is C6An aryl group of C18, an aralkyl group of C7-C18, an alkyl group of C1-C18, or a cycloalkyl group of C1-C18.
Mixing sodium tetraphenylborate aqueous solution with quaternary salt compound dissolved in organic solvent, and fully contacting and reacting under the combined action of stirring and ultrasonic oscillation.
The molar ratio of the sodium tetraphenylborate to the quaternary salt compound is greater than or equal to m/n.
The volume ratio of the sodium tetraphenylborate aqueous solution to the organic solvent in which the quaternary salt compound is dissolved is controlled to be 0.5-5.
The reaction temperature is controlled to be 5-95 ℃.
Said Q n+Selected from tetramethylammonium ion, tetra-n-butylammonium ion, benzyltributylammonium ion, phenyltrimethylammonium ion, tetraphenylammonium ion, tetraphenylphosphonium ion, benzyltributylphosphonium ion, phenyltrimethylphosphonium ion, etc.
Said Y ism-One selected from the group consisting of halogen ions, sulfate ions, nitrate ions, carbonate ions, phosphate ions, tetrafluoroborate ions, carboxylate ions, hexafluorophosphate ions, and the like.
The organic solvent is at least one selected from benzene, toluene, chlorobenzene, acetonitrile, tetrahydrofuran, dimethylacetamide, ether, ketone, cyclohexane and 1, 4-dioxane.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method adopts the full contact and reaction of the aqueous solution of the sodium tetraphenylborate and the organic solution of the quaternary salt compound, can synthesize organic quaternary tetraphenylborate products, can separate and remove the generated sodium salt without additional post-treatment such as recrystallization and the like, can overcome the defects and limitations of the prior art that the by-product is sodium bromide and the reaction medium is single water, and lays a foundation for the large-scale production of the quaternary tetraphenylborate.
(2) In the method, the molar ratio of the sodium tetraphenylborate to the quaternary compound can be controlled to be more than or equal to m/n for fully and effectively reacting and utilizing the quaternary compound, so that the quaternary compound can be converted nearly stoichiometrically to generate the target quaternary tetraphenylborate, the content of sodium ions in the product can be effectively separated and controlled in an extremely low range, and generally, the content of the sodium ions in the quaternary tetraphenylborate can be controlled to be at least within 20ppm or further within 5ppm, thereby realizing the high-purity production of the quaternary tetraphenylborate product.
(3) In the method, the process conditions are easy to control, wherein the volume ratio of the aqueous solution of the sodium tetraphenylborate to the organic solution of the quaternary salt compound can be controlled within a wide range, and for example, the volume ratio of the aqueous phase to the organic phase can be controlled within 0.5-5 in order to meet the requirements of contact, actual operation and other factors. In addition, the reaction temperature can be selected within a wide range of 5-95 ℃, and the process is simple to control and easy to realize.
(4) The invention can realize the large-scale production of tetraphenyl borate quaternary salt products, the reaction process is simple and easy to control, sodium tetraphenyl borate aqueous solution and organic solution of quaternary salt compounds are respectively used as raw materials to be fully contacted and reacted, conventional equipment such as stirring equipment, an ultrasonic oscillator and the like is adopted, the reaction can be realized within a wider control range, for example, the stirring rotating speed can reach more than 100 r/min, and the power (W, watt) of the ultrasonic oscillator relative to the feeding amount (V, liter) can reach W/V more than 10.
(5) The organic tetraphenyl borate quaternary salt prepared by the method can be efficiently prepared, the yield can reach at least 99.5%, and the generated byproduct sodium salt is completely dissolved in water and can be removed by simple separation and filtration, so that the interference of the byproduct is avoided, the reaction speed and the yield can be effectively improved when the organic tetraphenyl borate quaternary salt is used as reaction components such as alkali, a catalyst and the like in other organic reactions, and particularly when the organic tetraphenyl borate quaternary salt is used as the catalyst, the reaction efficiency can be improved, and the process cost can be effectively reduced.
Detailed Description
The objects, technical solutions and advantageous effects of the present invention will be described in further detail below.
It is to be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention claimed, and unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention relates to a method for efficiently synthesizing organic tetraphenylborate products with high purity by quaternary salt exchange reaction between sodium tetraphenylborate and organic quaternary salt solution in sodium tetraphenylborate aqueous solution and separating sodium salts as byproducts, wherein the product content can reach more than 99.5%, the sodium salts as byproducts are completely dissolved in water, additional treatment such as recrystallization and the like is not needed, and the sodium ion content in the products can be controlled below 20ppm by simple separation such as filtration and the like.
The synthesis method related by the invention can be summarized as follows:
under the synergistic action of water and organic solvent, sodium tetraphenylborate Na (C)6H5)4B and Quaternary salt Compound (Q)n+)m(Ym-)nCarrying out a reaction, namely: mixing sodium tetraphenylborate aqueous solution with quaternary salt compound dissolved in organic solvent, and fully contacting and reacting under the combined action of stirring and ultrasonic oscillation.
In the implementation process, the used stirring equipment, ultrasonic oscillators and other equipment are conventional equipment, and the stirring rotating speed can be controlled in a wide range, for example, the rotating speed per minute can reach more than 100 revolutions; the power (W, watt) of the ultrasonic oscillator can be in a wider range and can be determined according to the reaction feeding amount (V, liter), and when the ultrasonic oscillator is actually used, the power of the ultrasonic oscillator can reach more than 10 relative to the reaction feeding amount (W/V). The volume ratio of the organic phase to the aqueous phase and the reaction temperature are also required to be controlled, the volume ratio of the organic phase to the aqueous phase can be selected within a wide range, but the volume ratio of the sodium tetraphenylborate aqueous solution to the organic solvent in which the quaternary salt compound is dissolved can be controlled within 0.5-5 due to factors such as contact, actual operation and the like; the reaction temperature can also be selected within a wide range of 5 to 95 ℃.
Preparation of organic Quaternary tetraphenylboronic acid salts ((Q) from this inventionn+)[(C6H5)4B]n) is derived fromIn view of the cost of raw materials used, it is preferable to carry out the reaction under the condition that the molar ratio of sodium tetraphenylborate to the quaternary salt compound is larger than m/n, which is advantageous for the use of the quaternary salt compound while sufficiently effective reaction is achieved, but excessive sodium tetraphenylborate easily causes residue or requires removal by means of repeated washing or the like, which is an unavoidable influence in the use case where the content of metal sodium ions needs to be strictly controlled. In the present invention, it has surprisingly been found that even when the molar ratio of sodium tetraphenylborate to quaternary compound is equal to m/n, the quaternary compound is converted almost stoichiometrically and forms the quaternary tetraphenylborate salt of interest; when the molar ratio of sodium tetraphenylborate to quaternary compound is greater than m/n, the sodium ion content of the product can be effectively separated and controlled to a very low level. By adopting the preparation method of the invention, the sodium ion content in the product tetraphenyl borate quaternary salt can be less than about 20ppm, and even further controlled within 10ppm or 5 ppm.
In the above quaternary salt compound and quaternary organic tetraphenylboronic acid salt, Q n+Is of the structural formula (XR)o +)nQuaternary cation of (A), Ym-Is a negative charge ion or group, m and n are natural numbers, X is an atom of Va or VIa group, o is a natural number of 0-4, R is an aryl group of C6-C18, an aralkyl group of C7-C18, an alkyl group of C1-C18 or a cycloalkyl group of C1-C18.
Quaternary cation Q n+May be one of cations such as tetramethylammonium ion, tetra-n-butylammonium ion, benzyltributylammonium ion, phenyltrimethylammonium ion, tetraphenylammonium ion, tetraphenylphosphonium ion, benzyltributylphosphonium ion, phenyltrimethylphosphonium ion, etc., particularly tetraalkylammonium ion such as tetra-n-butylammonium ion or tetraphenylphosphonium ion.
Anion Ym-May be one of anions such as a halogen ion, a sulfate ion, a nitrate ion, a carbonate ion, a phosphate ion, a tetrafluoroborate ion, a carboxylate ion, a hexafluorophosphate ion, etc., particularly a halogen ion such as a bromide anion.
By organic solvent is meant a single solvent or a mixture which is only partially miscible with water, but which readily dissolves the quaternary salt compound and is inert to the substance used, for example benzene, toluene, chlorobenzene, acetonitrile, tetrahydrofuran, dimethylacetamide, ethers, ketones, cyclohexane, mixtures of one or more of 1, 4-dioxane, especially benzenes such as chlorobenzene and/or alkanes.
The following examples are provided to illustrate specific embodiments of the present invention, and it is understood that the scope of the present invention is not limited to the following examples.
Example 1:
at the temperature of 25 ℃, oscillating by a 100 watt ultrasonic oscillator, and controlling the stirring speed to be 100rmp, 50ml of chlorobenzene solution dissolved with 21.2g of tetraphenylphosphonium bromide is dripped into a three-neck flask filled with 100ml of aqueous solution dissolved with 18.2g of sodium tetraphenylborate (5% excess), the dripping is completed within 10-15min, and then the reaction is continued for 1h, and the reaction is stopped. The precipitate generated by the reaction was collected by filtration to obtain 33g of a white product tetraphenylphosphonium tetraphenylborate with a yield of 99%, a sodium ion content of 8ppm by ion chromatography and a purity of 99.6% for the tetraphenylphosphonium tetraphenylborate.
Example 2:
at the temperature of 25 ℃, oscillating by a 100 watt ultrasonic oscillator, and controlling the stirring speed to be 100rmp, 50ml of chlorobenzene solution dissolved with 16g of tetra-n-butylammonium bromide is dropwise added into a three-neck flask filled with 100ml of sodium tetraphenylborate (5% excess) aqueous solution, the dropwise addition is completed within 10-15min, and then the reaction is continued for 1h, and the reaction is stopped. The precipitate formed by the reaction was collected by filtration to obtain 27.8g of a white product tetra-n-butylammonium tetraphenylborate, with a yield of 99.3%, a sodium ion content of 7.5ppm by ion chromatography, and a purity of the tetra-n-butylammonium tetraphenylborate of 99.8%.
Example 3:
under the conditions of 25 ℃, oscillation by a 100 watt ultrasonic oscillator and 100rmp controlled stirring rate, 50ml of toluene solution in which 7.8g of tetramethylammonium bromide is dissolved is dropwise added into a three-neck flask containing 100ml of aqueous solution in which 18.2g of sodium tetraphenylborate (5% excess) is dissolved, the dropwise addition is completed within 10-15min, and then the reaction is continued for 1h, and the reaction is stopped. The precipitate produced by the reaction was collected by filtration to give 19.8g of a white product, tetramethylammonium tetraphenylborate salt, in a yield of 99.1%, having a sodium ion content of 9ppm and a tetramethylammonium tetraphenylborate salt purity of 99.7% as measured by ion chromatography.
Example 4:
at the temperature of 25 ℃, oscillating by a 100 watt ultrasonic oscillator, and controlling the stirring speed to be 100rmp, 50ml of chlorobenzene solution dissolved with 21.2g of tetraphenyl phosphine bromide is dripped into a three-neck flask containing 100ml of aqueous solution dissolved with 17.3g of sodium tetraphenylborate (and the like in stoichiometric amount) and is dripped within 10-15min, and then the reaction is continued for 1h, and the reaction is stopped. The precipitate generated by the reaction was collected by filtration to obtain 33g of a white product tetraphenylphosphonium tetraphenylborate with a yield of 99%, a sodium ion content of 4ppm by ion chromatography and a purity of 99.8% for the tetraphenylphosphonium tetraphenylborate.
Example 5:
under the conditions of 5 ℃ temperature, oscillation of a 100-watt ultrasonic oscillator and 100rmp controlled stirring speed, 20ml of chlorobenzene solution dissolved with 21.2g of tetraphenylphosphonium bromide is dripped into a 100ml three-neck flask containing 17.3g of sodium tetraphenylborate (equal to stoichiometric) aqueous solution, the dripping is completed within 10-15min, and then the reaction is continued for 1h, and the reaction is stopped. The precipitate generated by the reaction was collected by filtration to obtain 33g of a white product tetraphenylphosphonium tetraphenylborate with a yield of 99%, a sodium ion content of 20ppm by ion chromatography and a purity of 99.5% for the tetraphenylphosphonium tetraphenylborate.
Example 6:
at the temperature of 95 ℃, oscillating by a 100 watt ultrasonic oscillator, and controlling the stirring speed to be 100rmp, dropwise adding 200ml of toluene solution containing 7.8g of tetramethylammonium bromide into 100ml of a three-neck flask containing 18.2g of sodium tetraphenylborate (5% excess) aqueous solution, wherein the dropwise adding is completed within 10-15min, then continuously reacting for 1h, and stopping the reaction. The precipitate formed by the reaction was collected by filtration to obtain 19.3g of a white product tetraphenylphosphonium tetraphenylborate with a yield of 99%, a sodium ion content of 10ppm by ion chromatography and a purity of 99.6% for the tetraphenylphosphonium tetraphenylborate.
Comparative example 1:
at the temperature of 25 ℃, under the condition of controlling the stirring speed to be 100rmp, 50ml of chlorobenzene solution dissolved with 21.2g of tetraphenylphosphonium bromide is dripped into a three-neck flask containing 100ml of sodium tetraphenylborate (5% excess) aqueous solution, the dripping is completed within 10-15min, and then the reaction is continued for 1h, and the reaction is stopped. The precipitate formed by the reaction was collected by filtration to obtain 28.3 g of a white product tetraphenylphosphonium tetraphenylborate with a yield of 85%, a sodium ion content of 110ppm by ion chromatography and a purity of 95.8% for the tetraphenylphosphonium tetraphenylborate.
Comparative example 2:
at the temperature of 25 ℃, under the condition of controlling the stirring speed to be 100rmp, 50ml of chlorobenzene solution dissolved with 21.2g of tetraphenylphosphonium bromide is dripped into a 100ml of three-neck flask containing 17.3g of sodium tetraphenylborate (equal to stoichiometric) aqueous solution, the dripping is completed within 10-15min, and then the reaction is controlled to be continued for 1h and stopped. The precipitate formed by the reaction was collected by filtration to obtain 27 g of a white product tetraphenylphosphonium tetraphenylborate with a yield of 81%, a sodium ion content of 50ppm by ion chromatography and a purity of 94% for the tetraphenylphosphonium tetraphenylborate.
Comparative example 3:
50ml of chlorobenzene solution dissolved with 16g of tetra-n-butylammonium bromide is dripped into a 150ml three-neck flask containing 18.2g of sodium tetraphenylborate (5% excess) aqueous solution under the conditions of 50 ℃ and 100rmp of stirring speed, the dripping is completed within 10-15min, and then the reaction is continued for 2h and stopped. The precipitate produced by the reaction was collected by filtration to obtain 24.4 g of a white product tetra-n-butylammonium tetraphenylborate with a yield of 87%, a sodium ion content of 65ppm by ion chromatography and a purity of 95% of the tetra-n-butylammonium tetraphenylborate.
Comparative example 4:
50ml of chlorobenzene solution dissolved with 16g of tetra-n-butylammonium bromide is dripped into a 150ml three-neck flask containing 17.3g of sodium tetraphenylborate (equal to stoichiometric) aqueous solution at the temperature of 50 ℃ under the condition of controlling the stirring speed to be 100rmp, the dripping is completed within 10-15min, and then the reaction is continued for 2h and stopped. The precipitate generated by the reaction was collected by filtration to obtain 22.4 g of a white product tetra-n-butylammonium tetraphenylborate with a yield of 80%, a sodium ion content of 40ppm by ion chromatography and a purity of 96% of the tetra-n-butylammonium tetraphenylborate.
Comparative example 5:
19.056 tetrabutylammonium bromide solid is dissolved in distilled water at room temperature, 20.23g of sodium tetraphenylborate solid solution is placed in a 500ml flask filled with 80 ℃ hot distilled water under magnetic stirring, a small amount of tetrabutylammonium bromide aqueous solution is dripped into the sodium tetraphenylborate aqueous solution, after a large amount of white precipitate appears, the dripping is stopped for about 10min to form seed crystals, the dripping is continued until the dripping is finished, and the reaction is carried out for 1 h. The resultant precipitate was collected by filtration and washed with distilled water until the washing solution was free of bromide (checked with silver nitrate solution) to obtain 30.2g of tetrabutylammonium tetraphenylborate salt in a yield of 91%, a sodium ion content of 125ppm by ion chromatography, a bromide ion content of 118ppm by ion chromatography and a tetrabutylammonium tetraphenylborate salt purity of 95%.
Comparative example 6:
0.98g of sodium tetraphenylborate is weighed into a 250ml single-neck flask, then 25ml of water is added, the mixture is heated to 85 ℃, and the mixture is stirred to completely dissolve the sodium tetraphenylborate. Weighing 0.79g of dodecyl trimethyl ammonium chloride, adding 10ml of water, dissolving at normal temperature, then dropwise adding into a sodium tetraphenylborate solution dissolved at 85 ℃, generating white precipitate, stopping dropwise adding after a small amount of solution is dropwise added, reacting for 10min to form seed crystals, and then continuously reacting for 1h after the dropwise adding is finished. The precipitate formed by the reaction was collected by filtration to give 1.44g of dodecyltrimethyltetraphenylammonium borate as a product in a yield of 92%, the sodium ion content was 123ppm by ion chromatography and the dodecyltrimethylammonium tetraphenylammonium borate purity was 94%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (9)
1. A method for preparing tetraphenyl borate is characterized in that: reacting sodium tetraphenylborate with a quaternary salt compound under the synergistic action of water and an organic solvent to obtain a tetraphenylborate product,
wherein the organic solvent is organic solution capable of dissolving quaternary salt compound and not participating in reaction, and the quaternary salt compound has a structural formula of (Q)n+)m(Ym-)nThe structural formula of the tetraphenylborate is (Q)n+)[(C6H5)4B]n，
In the above structural formula, Q n+Is of the structural formula (XR)o +)nQuaternary cation of (A), Ym-Is a negative charge ion or group, m and n are natural numbers, X is an atom of Va or VIa group, o is a natural number of 0-4, R is an aryl group of C6-C18, an aralkyl group of C7-C18, an alkyl group of C1-C18 or a cycloalkyl group of C1-C18.
2. The method for preparing tetraphenylborate according to claim 1, wherein the reaction is carried out in the presence of a solvent selected from the group consisting of: mixing sodium tetraphenylborate aqueous solution with quaternary salt compound dissolved in organic solvent, and fully contacting and reacting under the combined action of stirring and ultrasonic oscillation.
3. The method for preparing tetraphenylborate according to claim 1, wherein the reaction is carried out in the presence of a solvent selected from the group consisting of: the molar ratio of the sodium tetraphenylborate to the quaternary salt compound is greater than or equal to m/n.
4. The method for preparing tetraphenylborate according to claim 2, wherein: the volume ratio of the sodium tetraphenylborate aqueous solution to the organic solvent in which the quaternary salt compound is dissolved is controlled to be 0.5-5.
5. The method for preparing tetraphenylborate according to claim 1, wherein the reaction is carried out in the presence of a solvent selected from the group consisting of: the reaction temperature is controlled to be 5-95 ℃.
6. The method for preparing tetraphenylborate according to claim 1, wherein the reaction is carried out in the presence of a solvent selected from the group consisting of: said Q n+Selected from tetramethylammonium ion, tetra-n-butylammonium ion, benzylA tributylammonium ion, a phenyltrimethylammonium ion, a tetraphenylammonium ion, a tetraphenylphosphonium ion, a benzyltributylphosphonium ion, a phenyltrimethylphosphonium ion.
7. The method for preparing tetraphenylborate according to claim 1, wherein the reaction is carried out in the presence of a solvent selected from the group consisting of: said Y ism-One selected from the group consisting of a halogen ion, a sulfate ion, a nitrate ion, a carbonate ion, a phosphate ion, a tetrafluoroborate ion, a carboxylate ion, and a hexafluorophosphate ion.
8. The method for preparing tetraphenylborate according to claim 1, wherein the reaction is carried out in the presence of a solvent selected from the group consisting of: the organic solvent is at least one selected from benzene, toluene, chlorobenzene, acetonitrile, tetrahydrofuran, dimethylacetamide, ether, ketone, cyclohexane and 1, 4-dioxane.
9. The method for preparing tetraphenylborate according to claim 1, wherein the reaction is carried out in the presence of a solvent selected from the group consisting of: the tetraphenylborate product satisfies: the purity is more than or equal to 99.5 percent, and the content of sodium ions is less than or equal to 20 ppm.
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