CN118930438A - Preparation method of tetrapropyl ammonium homoruthenate (VII) - Google Patents
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- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 68
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 34
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000004891 communication Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- FGEKTVAHFDQHBU-UHFFFAOYSA-N dioxoruthenium;hydrate Chemical compound O.O=[Ru]=O FGEKTVAHFDQHBU-UHFFFAOYSA-N 0.000 claims description 6
- GJFJJZHAMZHQMO-UHFFFAOYSA-N dioxoruthenium dihydrate Chemical compound O.O.O=[Ru]=O GJFJJZHAMZHQMO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 abstract description 30
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 101100189356 Mus musculus Papolb gene Proteins 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 101100346893 Arabidopsis thaliana MTPA2 gene Proteins 0.000 description 1
- 101150006417 MTP3 gene Proteins 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- -1 as shown in fig. 2) Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
The invention relates to the technical field of noble metal ruthenium catalyst synthesis, and provides a preparation method of tetrapropyl ammonium homoruthenate (VII). Dropwise adding hydrogen peroxide into a hydrochloric acid solution of ruthenium dioxide to perform oxidation reaction, and continuously introducing generated ruthenium tetroxide gas into a tetrapropylammonium hydroxide aqueous solution to perform coordination reaction to obtain tetrapropylammonium homoruthenate (VII); the introduction time of the ruthenium tetroxide gas is 1-2 h; the oxidation reaction is carried out in a first reaction vessel, and the coordination reaction is carried out in a second reaction vessel; the gas outlet of the first reaction vessel is in communication with the gas inlet of the second reaction vessel. The invention adopts ruthenium oxide as a raw material, prepares tetrapropyl ammonium homoruthenate (VII) through continuous flow reaction, can greatly reduce cost, has high conversion rate, is easy to operate, is environment-friendly, has high product yield, is easy to realize batch industrialized preparation, and has important significance for promoting the application of tetrapropyl ammonium homoruthenate (VII).
Description
Technical Field
The invention relates to the technical field of noble metal ruthenium catalyst synthesis, in particular to a preparation method of tetrapropyl ammonium homoruthenate (VII).
Background
Tetrapropyl ammonium homoruthenate (VII) (also known as TPAP, having a molecular formula of C 12H28NO4 Ru) is a mild oxidant and is also a common chemical synthesis raw material in the chemical industry. At present, the preparation technology of tetrapropyl ammonium homoruthenate (VII) has higher difficulty and high requirement on reaction equipment, and the preparation technology disclosed in the prior art mainly comprises the following steps:
Griffith et al (Griffith W P,Ley S V,Whitcombe G P,White A D.Preparation and use of tetra-n-butylammonium per-ruthenate(TBAP reagent)and tetra-n-propylammonium per-ruthenate(TPAP reagent)t as new catalytic oxidants for alcohols[J].J.Chem.Soc.,Chem.Commun.,1987,21:1625-1627.) report a process for the synthesis of ammonium tetrapropyl homoruthenate (VII) in which ruthenium trichloride hydrate and sodium periodate are dissolved in water and stirred overnight, and the ruthenium tetroxide produced is transferred to tetrapropylammonium hydroxide and aqueous sodium hydroxide solution under oxygen conditions for reaction to give the TPAP product in 87% yield. The synthesis method has low yield, and the oxygen used belongs to inflammable gas and has high equipment requirement.
Bailley et al (Bailey A J,Griffith W P,Mostafa S I,Sherwood P A.Studies on transition-metal oxo and nitrido complexes.13.Perruthenate and ruthenate anions as catalytic organic oxidants[J].Inorg.Chem.,1993,32,268-271.) report a synthesis method of tetrapropyl ammonium homoruthenate (VII), wherein sodium carbonate and sodium bromate are dissolved in water, then aqueous solution of hydrated ruthenium trichloride is dripped, after a few hours of reaction, tetrapropyl sodium hydroxide solution is added, dichloromethane extraction is used after the reaction is finished, anhydrous sodium carbonate is dried, carbon tetrachloride solvent is added to precipitate solid, and finally the target compound is obtained. The method is a small batch synthesis method within gram level, is only suitable for preparation in a laboratory, has high operation requirement, and is difficult to realize large-batch synthesis after amplification.
Moore et al (Moore PrW,Read C D G,Bernhardt P V,Williams C M.ATP3and MTP3:easily prepared stable perruthenate salts for oxidation applications in synthesis[J].Chem.Eur.J.,2018,24,1-7.) synthesized TPAP by five methods based on Bailley and Griffith et al, the first synthesized according to Bailley et al, the second and third method only changed the carbon tetrachloride solvent used in the last step to pentanes or cyclohexanes, the fourth method did not use solvent precipitation during post-treatment, and the products were obtained by direct filtration, the yields of the four methods were 44%, 63%, 67%, 45% in order. The fifth method synthesizes TPAP according to Griffith's method, with a 33% yield. The synthesis yield is low, the steps are tedious, the operation requirement is high, and the batch industrialization is inconvenient to realize.
The Chinese patent with publication number CN112321437A discloses a preparation method of tetrapropyl ammonium homoruthenate (VII), which comprises the following steps: (1) Mixing anhydrous sodium carbonate, sodium bromate and water, stirring uniformly, and stirring for 1-2 h at 20-40 ℃; (2) Adding ruthenium chloride hydrate into the reaction system of the step (1), and reacting for 5-10 h at 20-40 ℃; (3) Dropwise adding 25wt% of tetrapropylammonium hydroxide into the reaction system in the step (2), and reacting for 5-10 h at 20-30 ℃ after the dropwise adding is finished; (4) Extracting with the extractive solution, concentrating at normal pressure until no liquid is discharged, adjusting temperature to 20-30deg.C, adding beating solvent, pulping, filtering, and vacuum drying. The method is complex in operation, long in time and not suitable for batch industrial production. In addition, the preparation methods all use ruthenium chloride as a raw material, and have high cost.
In summary, the existing preparation method of tetrapropyl ammonium homoruthenate (VII) has the defects of high cost, low yield, complicated steps and the like, and is difficult to realize batch industrial production.
Disclosure of Invention
In view of this, the present invention provides a process for the preparation of tetrapropyl ammonium homoruthenate (VII). The invention synthesizes tetrapropyl ammonium homoruthenate (VII) by adopting continuous flow reaction, can simultaneously carry out oxidation reaction and coordination reaction, has simple operation, low cost, environmental protection and easy realization of batch industrialized preparation, and has important significance for promoting the application of the tetrapropyl ammonium homoruthenate (VII).
In order to achieve the above object, the present invention provides the following technical solutions:
A method for preparing tetrapropyl ammonium homoruthenate (VII), comprising the following steps:
dropwise adding hydrogen peroxide into a hydrochloric acid solution of ruthenium dioxide for oxidation reaction, and continuously introducing the generated ruthenium tetroxide gas into a tetrapropylammonium hydroxide aqueous solution for coordination reaction to obtain tetrapropylammonium homoruthenate (VII); the introduction time of the ruthenium tetroxide gas is 1-2 h;
The oxidation reaction is carried out in a first reaction vessel, and the coordination reaction is carried out in a second reaction vessel; the gas outlet of the first reaction vessel is in communication with the gas inlet of the second reaction vessel.
Preferably, the ruthenium dioxide is hydrated ruthenium dioxide.
Preferably, the ruthenium dioxide hydrate comprises ruthenium dioxide monohydrate and/or ruthenium dioxide dihydrate.
Preferably, the preparation method of the hydrochloric acid solution of ruthenium dioxide comprises the following steps: and dissolving ruthenium dioxide in concentrated hydrochloric acid to obtain a hydrochloric acid solution of the ruthenium dioxide.
Preferably, the concentration of the hydrogen peroxide is 30-35%; the dropping rate of the hydrogen peroxide is 1-5 mL/min.
Preferably, the molar ratio of the ruthenium dioxide to the hydrogen peroxide in the hydrogen peroxide is 1:3-5.
Preferably, the molar ratio of ruthenium dioxide to tetrapropylammonium hydroxide is 1:3-5.
Preferably, the temperature of the oxidation reaction is 20 to 30 ℃.
Preferably, the ruthenium tetroxide gas is introduced into the tetrapropylammonium hydroxide aqueous solution under the low-temperature condition, and the temperature of the low-temperature condition is-5 ℃.
Preferably, after the coordination reaction is completed, the method further comprises the steps of sequentially filtering, washing and drying the obtained reaction liquid to obtain the tetrapropyl ammonium homoruthenate (VII). Dropwise adding hydrogen peroxide into a hydrochloric acid solution of ruthenium dioxide for oxidation reaction, and continuously introducing the generated ruthenium tetroxide gas into a tetrapropylammonium hydroxide aqueous solution for coordination reaction to obtain tetrapropylammonium homoruthenate (VII); the introduction time of the ruthenium tetroxide gas is 1-2 h; the oxidation reaction is carried out in a first reaction vessel, and the coordination reaction is carried out in a second reaction vessel; the gas outlet of the first reaction vessel is in communication with the gas inlet of the second reaction vessel. The application adopts ruthenium oxide as raw material, prepares tetrapropyl ammonium ruthenate (VII) through continuous flow reaction, can greatly reduce cost, and has high conversion rate and easy operation; in addition, the ruthenium tetroxide gas generated by the oxidation reaction is continuously introduced into the tetrapropylammonium hydroxide aqueous solution, the utilization rate of the ruthenium tetroxide gas is high, the oxidation reaction and the coordination reaction can be simultaneously carried out, the total time of the reaction is greatly shortened, and the production efficiency is improved; in addition, the application adopts hydrogen peroxide as an oxidant, has moderate oxidation performance, and can avoid excessively severe oxidation reaction, thereby continuously and stably introducing ruthenium tetroxide gas into tetrapropylammonium hydroxide aqueous solution, ensuring the sufficient progress of coordination reaction and further improving the product yield. Furthermore, the application takes ruthenium dioxide and hydrogen peroxide as raw materials, the oxidation reaction condition is mild, the method can be carried out at room temperature, and the energy consumption is low. The results of the examples show that the preparation of tetrapropyl ammonium homoruthenate (VII) by the process according to the application gives yields of up to 99.8% based on ruthenium. In conclusion, the preparation method provided by the application is simple to operate, low in cost, environment-friendly, high in product yield, easy to realize batch industrialized preparation, and has important significance in promoting the application of tetrapropyl ammonium homoruthenate (VII).
Drawings
FIG. 1 is a hydrogen spectrum of tetrapropyl ammonium homoruthenate (VII) prepared in example 1 of the present invention;
FIG. 2 is a carbon spectrum of tetrapropyl ammonium homoruthenate (VII) prepared in example 1 of the present invention;
FIG. 3 is a mass spectrum of tetrapropyl ammonium homoruthenate (VII) prepared in example 1 of the present invention;
FIG. 4 is an infrared spectrum of tetrapropyl ammonium homoruthenate (VII) prepared in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of tetrapropyl ammonium homoruthenate (VII), which comprises the following steps:
dropwise adding hydrogen peroxide into a hydrochloric acid solution of ruthenium dioxide for oxidation reaction, and continuously introducing the generated ruthenium tetroxide gas into a tetrapropylammonium hydroxide aqueous solution for coordination reaction to obtain tetrapropylammonium homoruthenate (VII); the introduction time of the ruthenium tetroxide gas is 1-2 h;
The oxidation reaction is carried out in a first reaction vessel, and the coordination reaction is carried out in a second reaction vessel; the gas outlet of the first reaction vessel is in communication with the gas inlet of the second reaction vessel.
In the present invention, the ruthenium dioxide is preferably hydrated ruthenium dioxide; the hydrated ruthenium dioxide preferably comprises ruthenium dioxide monohydrate and/or ruthenium dioxide dihydrate; the preparation method of the hydrochloric acid solution of ruthenium dioxide preferably comprises the following steps: dissolving ruthenium dioxide in concentrated hydrochloric acid to obtain a hydrochloric acid solution of the ruthenium dioxide; the invention has no special requirement on the concentrated hydrochloric acid, and the concentration is 36-38wt% by adopting commercial concentrated hydrochloric acid which is well known by the skilled in the art; the dosage mass ratio of the ruthenium dioxide to the concentrated hydrochloric acid is preferably 6-13; the invention adopts the concentrated hydrochloric acid to dissolve the ruthenium dioxide, can be quickly dissolved, is favorable for realizing liquid-liquid reaction and ensures that the reaction is more thorough.
In the invention, the concentration of the hydrogen peroxide is preferably 30-35%; the dropping rate of the hydrogen peroxide is preferably 1-5 mL/min, more preferably 2-4 mL/min; the molar ratio of the ruthenium dioxide to the hydrogen peroxide in the hydrogen peroxide is preferably 1:3-5, more preferably 1:3.5-4.5; the temperature of the oxidation reaction is 20-30 ℃.
In the present invention, the aqueous tetrapropylammonium hydroxide solution is preferably obtained by dissolving tetrapropylammonium hydroxide in distilled water; the concentration of the tetrapropylammonium hydroxide aqueous solution is preferably 1.6-2.2 mol/L; the molar ratio of ruthenium dioxide to tetrapropylammonium hydroxide is preferably 1:3-5, more preferably 1:3.5-4.5.
In the present invention, the ruthenium tetroxide gas is preferably introduced into the aqueous tetrapropylammonium hydroxide solution under a low temperature condition, and the temperature of the low temperature condition is preferably-5 to 5 ℃, more preferably-4 to 4 ℃.
In the specific embodiment of the present invention, preferably, the first reaction container and the second reaction container are both raw material pipes, the hydrochloric acid solution of ruthenium dioxide is placed in the first reaction container, the tetrapropylammonium hydroxide aqueous solution is placed in the second reaction container, the gas outlet of the first reaction container is communicated with the gas inlet of the second reaction container, the second reaction container is placed at a low temperature of-5 ℃, then hydrogen peroxide is dropwise added into the first reaction container, and the generated ruthenium tetroxide gas continuously enters the second reaction container to carry out coordination reaction with tetrapropylammonium hydroxide circulation in the second reaction container.
In the present invention, after the completion of the coordination reaction, the method preferably further comprises sequentially filtering, washing and drying the obtained reaction solution to obtain the tetrapropyl ammonium homoruthenate (VII); the washing is preferably carried out with distilled water.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The concentration of hydrogen peroxide used in the following examples was 35wt%.
Example 1
50G of ruthenium dioxide monohydrate (the ruthenium content is 66.9%) is dissolved in concentrated hydrochloric acid, and is injected into a first raw material pipe, 45g of hydrogen peroxide is slowly added dropwise, and the dropping rate is 3mL/min; simultaneously, 269g of tetrapropylammonium hydroxide is dissolved in a proper amount of distilled water and is injected into a second raw material pipe, and the second raw material pipe is always at the temperature of-4 ℃; continuously introducing the gas generated by the first raw material pipe into the second raw material pipe, maintaining the introducing time to 1.5h, ensuring that the cyclic reaction is carried out on the second raw material pipe, obtaining a tetrapropyl ammonium homoruthenate (VII) crude product after the reaction is completed, washing with a proper amount of cold distilled water, and drying to obtain 116.02g of green solid, wherein the yield is 99.8 percent based on ruthenium, and the purity is 98.6 percent.
The ammonium tetrapropyl homoruthenate (vii) prepared in example 1 was characterized as follows:
(1) Elemental analysis, theoretical (%): C41.01,H 8.03,N 3.99; measured value (%): C41.01,H 8.01,N 3.96. The measured value and the theoretical value are identical.
(2) Hydrogen spectrum (1 HNMR,500MHz,Chloroform-d, shown in fig. 1), chemical shift (ppm): 3.14 (m, 8H, -CH 2),1.89(s,8H,-CH2),1.12(s,12H,-CH3).
(3) Carbon spectrum (13C NMR,500MHz,CDCl3, as shown in fig. 2), chemical shift (ppm): 13.58,19.01,69.70.
(4) Mass spectrometry (ESI-MS, as shown in fig. 3): a186 molecular ion peak appears, which is the same as the molecular weight of C 12H28N+, indicating that this ion peak is the ligand absorption peak of tetrapropyl ammonium homoruthenate (VII).
(5) Infrared spectrum IR (cm -1, KBr, as shown in fig. 4): 754. 833, 967, 983, 1039, 1328, 1388, 1461, 1477, 2880, 2940, 2971.
The detection results of the element analysis, the hydrogen spectrum, the carbon spectrum, the mass spectrum and the infrared spectrum show that the product obtained by the method is identical with the target compound of tetrapropyl ammonium homoruthenate (VII), which shows that the successful preparation of the tetrapropyl ammonium homoruthenate (VII) is realized.
Example 2
50G of hydrated ruthenium dioxide (the ruthenium content is 66.9%) is dissolved in concentrated hydrochloric acid, and is injected into a first raw material pipe, 56g of hydrogen peroxide is slowly added dropwise, and the dropping rate is 3.5mL/min; simultaneously, 303g of tetrapropylammonium hydroxide is dissolved in a proper amount of distilled water and is injected into a second raw material pipe, and the second raw material pipe is always at the temperature of-5 ℃; and continuously introducing the gas generated by the first raw material pipe into the second raw material pipe, maintaining the introducing time to 1.7h, ensuring that the cyclic reaction is carried out on the second raw material pipe, obtaining a tetrapropyl ammonium homoruthenate (VII) crude product after the reaction is completed, washing with a proper amount of cold distilled water, and drying to obtain 116.01g of green solid, wherein the yield is 99.7 percent and the purity is 98.6 percent calculated by ruthenium.
Example 3
50G of ruthenium dioxide dihydrate (the ruthenium content is 59.9%) is dissolved in concentrated hydrochloric acid, and is injected into a first raw material pipe, 40g of hydrogen peroxide is slowly added dropwise, and the dropping rate is 4mL/min; simultaneously, 241g of tetrapropylammonium hydroxide is dissolved in a proper amount of distilled water and is injected into a second raw material pipe, and the second raw material pipe is always at the temperature of 0 ℃; and continuously introducing the gas generated by the first raw material pipe into the second raw material pipe, maintaining the introducing time to 1.5h, ensuring that the cyclic reaction is carried out on the second raw material pipe, obtaining a tetrapropyl ammonium homoruthenate (VII) crude product after the reaction is completed, washing with a proper amount of cold distilled water, and drying to obtain 103.95g of green solid, wherein the yield is 99.9 percent and the purity is 98.6 percent calculated by ruthenium.
Example 4
50G of ruthenium dioxide dihydrate (the ruthenium content is 59.9%) is dissolved in concentrated hydrochloric acid, and is injected into a first raw material pipe, and then 50g of hydrogen peroxide is slowly added dropwise, wherein the dropping rate is 3.5mL/min; simultaneously, 271g of tetrapropylammonium hydroxide is dissolved in a proper amount of distilled water and is injected into a second raw material pipe, and the second raw material pipe is always at the temperature of 0 ℃; and continuously introducing the gas generated by the first raw material pipe into the second raw material pipe, maintaining the introducing time to 1.7h, ensuring that the cyclic reaction is carried out on the second raw material pipe, obtaining a tetrapropyl ammonium homoruthenate (VII) crude product after the reaction is completed, washing with a proper amount of cold distilled water, and drying to obtain 103.87g of green solid, wherein the yield is 99.8 percent and the purity is 98.6 percent calculated by ruthenium.
Comparative example 1
Other conditions were the same as in example 1 except that only hydrogen peroxide was replaced with potassium permanganate, and the result showed that the purity of the obtained tetrapropyl ammonium homoruthenate (VII) was 92%, the mass was 98.81g, and the yield was 85% based on ruthenium.
Comparative example 2
Other conditions were the same as in example 1 except that only concentrated hydrochloric acid was replaced with concentrated sulfuric acid, and the result showed that the purity of the obtained tetrapropyl ammonium homoruthenate (VII) was 91%, the mass was 97.65g, and the yield was 84% based on ruthenium.
Comparative example 3
50G of ruthenium dioxide monohydrate (ruthenium content 66.9%) was dissolved in concentrated hydrochloric acid and added to a reaction flask; simultaneously, 269g of tetrapropylammonium hydroxide is dissolved in a proper amount of distilled water, and is continuously added into a reaction bottle, 45g of hydrogen peroxide is slowly added dropwise, and the dropping rate is 3mL/min; the reaction conditions are maintained at 20 ℃ for 4 hours to obtain a tetrapropyl ammonium homoruthenate (VII) crude product, and then the crude product is washed by a proper amount of cold distilled water and dried to obtain 20.24g of green solid, wherein the yield is 17.4 percent based on ruthenium, and the purity is 91.5 percent.
In summary, the invention provides a synthesis method of tetrapropyl ammonium homoruthenate (VII) which is simple in operation, high in conversion rate, low in cost and high in efficiency, and is suitable for batch industrial production.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing tetrapropyl ammonium homoruthenate (vii), comprising the steps of:
dropwise adding hydrogen peroxide into a hydrochloric acid solution of ruthenium dioxide for oxidation reaction, and continuously introducing the generated ruthenium tetroxide gas into a tetrapropylammonium hydroxide aqueous solution for coordination reaction to obtain tetrapropylammonium homoruthenate (VII); the introduction time of the ruthenium tetroxide gas is 1-2 h;
The oxidation reaction is carried out in a first reaction vessel, and the coordination reaction is carried out in a second reaction vessel; the gas outlet of the first reaction vessel is in communication with the gas inlet of the second reaction vessel.
2. The method of claim 1, wherein the ruthenium dioxide is hydrated ruthenium dioxide.
3. The method of claim 2, wherein the hydrated ruthenium dioxide comprises ruthenium dioxide monohydrate and/or ruthenium dioxide dihydrate.
4. The method according to claim 1, wherein the method for preparing a hydrochloric acid solution of ruthenium dioxide comprises: and dissolving ruthenium dioxide in concentrated hydrochloric acid to obtain a hydrochloric acid solution of the ruthenium dioxide.
5. The method according to claim 1, wherein the concentration of hydrogen peroxide is 30 to 35%; the dropping rate of the hydrogen peroxide is 1-5 mL/min.
6. The method according to claim 1, wherein the molar ratio of the ruthenium dioxide to the hydrogen peroxide in the hydrogen peroxide is 1:3-5.
7. The method according to claim 1, wherein the molar ratio of ruthenium dioxide to tetrapropylammonium hydroxide is 1:3-5.
8. The method according to claim 1, wherein the temperature of the oxidation reaction is 20 to 30 ℃.
9. The method according to claim 1, wherein the ruthenium tetroxide gas is introduced into the aqueous tetrapropylammonium hydroxide solution under a low temperature condition, and the temperature of the low temperature condition is-5 to 5 ℃.
10. The method according to claim 1, wherein after the completion of the coordination reaction, the obtained reaction solution is further subjected to filtration, washing and drying in this order to obtain the tetrapropyl ammonium homoruthenate (vii).
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| Publication Number | Publication Date |
|---|---|
| CN118930438A true CN118930438A (en) | 2024-11-12 |
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