CN1733781A - Methyl rhenium trioxide synthesis method - Google Patents
Methyl rhenium trioxide synthesis method Download PDFInfo
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- CN1733781A CN1733781A CN 200510047118 CN200510047118A CN1733781A CN 1733781 A CN1733781 A CN 1733781A CN 200510047118 CN200510047118 CN 200510047118 CN 200510047118 A CN200510047118 A CN 200510047118A CN 1733781 A CN1733781 A CN 1733781A
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- rhenium trioxide
- methyl rhenium
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Abstract
Disclosed is a method for synthesizing methyltrioxorhenium, which comprises charging trimethylchlorosilan and tetramethylstannane when the solubility of silver perrhenate in solvent reaches a maximum value, controlling the reaction temperature between 40-70 deg. C, subjecting the reaction product to de-solvent and sublimation treatment to obtain the refined methltrioxorhenium.
Description
Technical field: the present invention relates to a kind of manufacture method of organometallic compound, relate to the organic compound method for making of rare and scatter element rhenium specifically.
Background technology: methyl rhenium trioxide (CH
3ReO
3) be abbreviated as MTO, be a kind ofly to emerge in recent years, and the transition metal organic catalyst of being familiar with by people gradually, it has efficiently, highly selective catalysis is such as the unsaturated hydrocarbons oxidation, the oxidation of aromatic compound and the organic synthesis such as oxidation that contain heteroatomic organic compound originate in 1979 for the research of MTO, at I.R.Beattie, P.J.Jones,, lnorg, chem.1979.18.2318. report to some extent, just provided Re up to 1988
2O
7And Sn (CH
3)
4Synthetic method (W.A.Herrmann.J.G.Kuchler, J.K.Felixberger.E.Herdtweck, W.Wagner, Angerer.chem.Int.Ed.Engl.1988.27.394) has actual synthetic meaning, thereafter at Herrmann W.A.Kuhn, F.E., Fischer, R.W., Thiel, W.R..Romao, C, C, lnorg.chem.1992,31,4431-4432 has reported with Re
2O
7Be raw material and (CH
3)
3SiCl is again with Sn (CH
3)
4MTO is produced in reaction, though this method productive rate is very high, but the raw material rhenium heptoxide is very responsive to airborne moisture, as easy as rolling off a log deliquescence, the difficult control of reaction, thereafter at document Jacob, J,, Espenson, J.H, lnorg, chem.Acta.1998,270.55. have reported that existing perrhenate is as the synthetic MTO of starting raw material, this method reaction control easily, but this synthetic method is at room temperature to react 22 hours, and the aftertreatment time is also very long, directly influences MTO production efficiency and cost, it is short to have not yet to see the reaction times, the MTO synthetic method report that productive rate is high.
Summary of the invention: the present invention is directed to existing long defective of MTO manufacturing cycle, it is short to propose the manufacturing cycle, the MTO synthetic method that productive rate is high, concrete technical scheme of the present invention is: the synthetic of MTO is perrhenic acid silver, in solvent, react with trimethylchlorosilane, with the tin tetramethide reaction, reaction product is handled through sublimation purifying and is made MTO again, and its reaction process is:
Total reaction
With perrhenic acid silver is the existing MTO synthetic method of starting raw material, normally carries out under the room temperature in solvent, and entire reaction need be carried out 22 hours, carries out suction filtration then, and at room temperature 0.1mm-Hg extracts solvent down out, carries out sublimation purifying and handle under 50 ℃.
The present invention by to perrhenic acid silver solubility change rule in solvent acetonitrile, proposes to add (CH on original preparation method basis
3)
3SiCl and Sn (CH
3)
4Best Times, experimental data show, AgReO
4At room temperature at CH
3Solubleness time to time change among the CN, solubleness reaches as high as 19～25g/L solubleness decline subsequently in initial 4～15 minutes, and is substantially constant at 12～14g/L, at 40～50 ℃ of following AgReO
4At CH
3The solubleness of CN increases in time gradually and increases from initial 8g/L, can reach 16g/L in 80 minutes, and according to above-mentioned data, MTO synthetic method of the present invention is with AgReO
4At room temperature be dissolved in CH
3Among the CN, and when solubleness is maximum, add (CH
3)
3SiCl and Sn (CH
3)
4, this not only can reduce solvent load, and reaction is carried out fast.This reaction of conventional art is at room temperature to carry out, and the reaction times reaches 22 hours, and the inventor shows AgReO through experimental study
4Reaction improve with temperature, speed of response is accelerated, and side reaction do not occur, because CH
3The boiling point of CN is 81.6 ℃, and temperature is too high, and not only conversion unit need increase the good reflux of condensation effect, and the MTO that generates very easily distils to aftertreatment brings difficulty, thereby reaction should be at CH
3Carry out below the CN boiling point, with 40～70 ℃ suitable, 50～55 ℃ is optimal reaction temperature.The MTO generated time has shortening significantly than the prior art method.
MTO uses as catalyzer, higher to purity requirement, generally should reach 99%, general last handling process is that the reactant suction filtration is removed AgCl and other throw out, gained filtrate is carried out underpressure distillation except that desolvating, underpressure distillation in document in the past below 40 ℃, carry out underpressure distillation under the vacuum tightness 0.1mm-Hg, this method requires vacuum tightness than higher, and general vacuum apparatus is difficult to reach requirement in batch process, the inventor is through experiment, the desolventizing temperature is brought up to 40～50 ℃, and vacuum tightness 30～40mm-Hg can reach the purpose that removes solvent equally, and shortened time of desolventizing, for reclaiming CH
3CN, according to a conventional method, cooling system is to adopt cooled with liquid nitrogen, this not only brings difficulty to operation, and the cost height, according to CH
3The boiling point of CN and reduced vacuum degree situation select the subcooling recycle pump to carry out condensation CH under-40～-35 ℃
3CN, this method obtains the effect same of cooled with liquid nitrogen.The MTO of output is after removing solvent, according to the sublimable character of MTO, refining MTO adopts at normal temperatures or usually in that to carry out vacuum-sublimation below 50 ℃ refining and since at low temperatures distillation thereby refining time long, the present invention brings up to 65～70 ℃ with sublimation temperature, the sublimation purifying time is shortened, in above-mentioned last handling process,, in solvent, bring a certain amount of MTO into owing to improve treatment temp, for reducing the loss solvent C H
3CN recycles, according to above-mentioned experiment and research, methyl rhenium trioxide synthesis method of the present invention, it is characterized in that: in solvent, add a certain amount of perrhenic acid silver, under agitation make its dissolving, when solubleness is maximum, add trimethylchlorosilane, add tin tetramethide again, improve temperature of reaction to 40～70 ℃, stirring reaction to reaction solution becomes the faint yellow stirring reaction that stops by orange-yellow, cooling, carry out suction filtration, isolate throw out, filtrate is at 40～50 ℃ of decompression desolventizings, begin to carry out sublimation purifying when resistates has the solid that is oily liquids on a small quantity to invest on the distillation wall, the gained methyl rhenium trioxide promptly obtains refining methyl rhenium trioxide through overweight distillation again.
Solvent of the present invention is an acetonitrile, and usage quantity is 8～10 times of the silver amount of perrhenic acid.
Described reactant ratio (mol) be the ordinary method consumption promptly: perrhenic acid silver: trimethylchlorosilane: tin tetramethide=1: 2～3: 1～2.
Adding trimethylchlorosilane of the present invention and tin tetramethide are to add at perrhenic acid silver to add when solubleness is maximum in the solvent, promptly add in 4～15 minutes after perrhenic acid silver adds solvent, and described temperature of reaction is an optimal reaction temperature for 50～55 ℃.
Its vacuum tightness of decompression desolventizing of the present invention is 30～40mm-Hg, and the solvent condenses temperature is-40～-35 ℃.
Beneficial effect of the present invention: methyl rhenium trioxide synthesis method of the present invention, owing to be chosen in AgReO at the very start from reaction
4Add trimethylchlorosilane and tin tetramethide when solubleness is maximum, not only save solvent load, and initial reaction is speeded up, improve temperature of reaction and add fast response thereafter, by original 22 hours, shorten to 2-3 hour, aftertreatment, owing to improve solvent distillation and sublimation temperature, distillation time and sublimation purifying time are all shortened significantly, especially use the cooling of 30～40mm-Hg vacuum tightness and cold cycle pump instead, make operation easier, for the realization suitability for industrialized production is laid a good foundation, method of the present invention is to produce methyl rhenium trioxide cycle weak point, method capable of being industrialized easy and simple to handle.
Embodiment:
Instrument:
The DF-101S type heat collecting type thermostatically heating magnetic agitation Ying Yu of Gongyi City gives magnificent instrument plant
2 α-1 rotary-vane vaccum pump Shenyang City Vacuum Pump Factory
The DLSB-subcooling recycle pump Ying Yu of Gongyi City gives magnificent instrument plant
SCHLENK operating instrument and equipment Germany
Elemental analyser Flash 1114
The 3rd optical instrument factory, X4 fusing point measuring microscope Beijing
Medicine:
The self-control of perrhenic acid silver
Acetonitrile AR Shanghai Lu Zhong chemical reagent factory
Trimethylchlorosilane CP Shanghai chemical reagents corporation
Tin tetramethide AR Belgium
Embodiment 1: in reactor; under nitrogen protection; add perrhenic acid silver 3.6g (10mmol) in room temperature; acetonitrile 35mL; stirred 4-5 minute; adding the trimethylchlorosilane 3.13mL (25mmol) give first weighing adds tin tetramethide 1.7mL (25mmol) again and begins to heat up; keep 52 ℃ of temperature of reaction; observing response liquid colour-change; when reaction solution transfers faint yellow stopped reaction to by orange-yellow; cooling; with the reactant suction filtration, filter residue washes with minor amounts of acetonitrile, and filtrate moving to is full of in the distillation sublimer of Ar gas; connect vacuum pump and subcooling recycle pump; 30mm-Hg 40 ℃ down ℃ following condensations of distillation acetonitriles-35 reclaim acetonitriles, when distillation proceeds to the solid that oily liquids is arranged on the sublimer and occurs, stop distillation; pipe processings that distil under 0.1mm-Hg70 ℃ is installed in the sublimer, and the products obtained therefrom methyl rhenium trioxide obtains highly finished product methyl rhenium trioxide 1.86g through heavily distilling.The refining methyl rhenium trioxide of gained is through fusing point test, and melting range is 105～106 ℃, consistent with literature value (Kleine, M, Ph, D.Thesis, Technische univer-sitat Muchen.1994).
Ultimate analysis:
Elements C H O Re
Theoretical value 4.81% 1.21% 19.26% 30.706ppm
Observed value 4.70% 1.15% 19.44% 30.378ppm
Its result and theoretical value are approximate, thereby can determine that synthetic product is CH
3ReO
3
Embodiment 2: in reactor; under nitrogen protection; add perrhenic acid silver 3.6g (10mmol) in room temperature; acetonitrile 30mL; stirred 10 minutes; adding the trimethylchlorosilane 2.5mL (25mmol) give first weighing adds tin tetramethide 1.36mL (20mmol) again and begins to heat up; keep 40 ℃ of temperature of reaction; observing response liquid colour-change; when reaction solution transfers faint yellow stopped reaction to by orange-yellow; cooling; with the reactant suction filtration, filter residue washes with minor amounts of acetonitrile, and filtrate moving to is full of in the distillation sublimer of Ar gas; connect vacuum pump and subcooling recycle pump; 30mm-Hg 40 ℃ down ℃ following condensations of distillation acetonitriles-35 reclaim acetonitriles, when distillation proceeds to the solid that oily liquids is arranged on the sublimer and occurs, stop distillation; pipe processings that distil under 70 ℃ of 0.1mm-Hg is installed in the sublimer, and the products obtained therefrom methyl rhenium trioxide obtains highly finished product methyl rhenium trioxide 1.27g through heavily distilling.
Embodiment 3: in reactor; under nitrogen protection; add perrhenic acid silver 3.6g (10mmol) in room temperature; acetonitrile 36mL; stirred 15 minutes; the trimethylchlorosilane 3.75mL (30mmol) that adds weighing in advance adds tin tetramethide 2.04mL (30mmol) again to begin to heat up; keep 70 ℃ of temperature of reaction; observing response liquid colour-change; when reaction solution transfers faint yellow stopped reaction to by orange-yellow; cooling; with the reactant suction filtration, filter residue washes with minor amounts of acetonitrile, and filtrate moving to is full of in the distillation sublimer of Ar gas; connect vacuum pump and subcooling recycle pump; 40mm-Hg 50 ℃ down ℃ following condensations of distillation acetonitriles-40 reclaim acetonitriles, when distillation proceeds to the solid that oily liquids is arranged on the sublimer and occurs, stop distillation; pipe processings that distil under 0.1mm-Hg70 ℃ is installed in the sublimer, and the products obtained therefrom methyl rhenium trioxide obtains highly finished product methyl rhenium trioxide 1.23g through heavily distilling.
Comparative example: according to ordinary method synthesizing methyl rhenium trioxide, the 35mL acetonitrile solvent is joined in the 3.6g perrhenic acid silver, stirring and dissolving at room temperature adds the 3.13mL trimethylchlorosilane, add the 1.7mL tin tetramethide again, at room temperature reacted 22 hours, suction filtration then, filtrate is desolventizing under room temperature 0.1mm-Hg, distil and heavily distillation gained MTO1.48g then under the same conditions.
The comparative result of embodiment and comparative example is as shown in the table:
。
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Reaction times (hour) | 3 | ?2.5 | ?2 | ?22 |
| The desolventizing time (minute) | 58 | ?45 | ?62 | ?720 |
| The distillation time (hour) | 8 | ?7 | ?8 | 15 |
| Productive rate % | 70％ | 60％ | 58％ | 55.7％ |
Claims (4)
1, a kind of methyl rhenium trioxide synthesis method, it is characterized in that: in solvent, add a certain amount of perrhenic acid silver, under agitation make its dissolving, when solubleness is maximum, add trimethylchlorosilane, add tin tetramethide again, improve temperature of reaction to 40～70 ℃, stirring reaction to reaction solution becomes the faint yellow stirring reaction that stops by orange-yellow, cooling, carry out suction filtration, isolate throw out, filtrate is at 40～50 ℃ of decompression desolventizings, begin to carry out sublimation purifying when resistates has to be on a small quantity when the buttery solid invests on the distillation wall, the gained methyl rhenium trioxide promptly obtains refining methyl rhenium trioxide through overweight distillation again.
2, by the said methyl rhenium trioxide synthesis method of claim 1, it is characterized in that: described temperature of reaction is optimal reaction temperature for 50～55 ℃.
3, by the said methyl rhenium trioxide synthesis method of claim 1, it is characterized in that: describedly in solvent, add a certain amount of perrhenic acid silver, under agitation make its dissolving, when solubleness is maximum, add trimethylchlorosilane, add tin tetramethide again, promptly in 4～15 minutes, add.
4, by the said methyl rhenium trioxide synthesis method of claim 1, it is characterized in that: described decompression desolventizing, its vacuum tightness are 30～40mm-Hg.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217774A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Method for catalytic oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid |
| CN114315907A (en) * | 2021-12-06 | 2022-04-12 | 洛阳双罗铼材料科技有限公司 | Porous methyl rhenium trioxide and application method thereof |
-
2005
- 2005-09-01 CN CNB2005100471180A patent/CN100334097C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217774A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Method for catalytic oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid |
| CN111217774B (en) * | 2018-11-25 | 2022-08-02 | 中国科学院大连化学物理研究所 | Method for catalytic oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid |
| CN114315907A (en) * | 2021-12-06 | 2022-04-12 | 洛阳双罗铼材料科技有限公司 | Porous methyl rhenium trioxide and application method thereof |
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| CN100334097C (en) | 2007-08-29 |
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Granted publication date: 20070829 Termination date: 20100901 |