CN100455584C - Microwave assisted process of synthesizing tetraphenyl porphyrin inside ionic liquid - Google Patents
Microwave assisted process of synthesizing tetraphenyl porphyrin inside ionic liquid Download PDFInfo
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- CN100455584C CN100455584C CNB2006101347397A CN200610134739A CN100455584C CN 100455584 C CN100455584 C CN 100455584C CN B2006101347397 A CNB2006101347397 A CN B2006101347397A CN 200610134739 A CN200610134739 A CN 200610134739A CN 100455584 C CN100455584 C CN 100455584C
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Abstract
The present invention relates to synthesis of tetraphenyl porphyrin, and is especially microwave assisted process of synthesizing tetraphenyl porphyrin inside ionic liquid. By using ionic liquid as reaction medium and heteropoly acid as catalyst, benzaldehyde and pyrrole are reacted under continuous microwave radiation of 500-800 W power at 150-190 deg.c for 5-25 min, and through further adding anhydrous alcohol, stilling for 24-30 hr, suction filtering, washing filter cake with anhydrous alcohol, and vacuum drying at 45-55 deg.c for 24-30 hr, the purified target product is obtained. The present invention has ionic liquid easily separated and recovered for reuse, short reaction time, low production cost, simple technological process and less environmental pollution.
Description
Technical field:
The present invention relates to a kind of method of synthetic tetraphenylporphyrin.Be particularly related to and adopt ionic liquid, the synthetic fast tetraphenylporphyrin of microwave radiation means as solvent.
Background technology:
Tetraphenylporphyrin is one of compound very important in the porphyrin analog derivative.Traditional synthetic method is utilized high volatilities such as pyridine, methyl alcohol, dimethylbenzene and methylene dichloride, organic solvent that toxicity is big, and the catalyzer of use is difficult for recycling, causes environmental pollution.In addition, traditional method exists the reaction times longer, and the product difficulty is separated, productive rate is low.
Summary of the invention:
In order to address the above problem, the invention provides a kind of is reaction medium with the ionic liquid, and heteropolyacid is a catalyzer, utilizes the method for the synthetic tetraphenylporphyrin of microwave radiation.This method environmental pollution is little, the reaction times is short, product is easy to separations, productive rate height, the recyclable utilization again of catalyzer.The technical solution used in the present invention is: the method for synthetic tetraphenylporphyrin in a kind of microwave-assisted ionic liquid, with the ionic liquid is reaction medium, heteropolyacid is a catalyzer, add phenyl aldehyde and pyrroles, microwave power 500～800W, temperature of reaction under 150～190 ℃, continuous microwave radiation 5～25 minutes, add dehydrated alcohol then and left standstill 24～30 hours, suction filtration, the filter cake absolute ethanol washing, 45～55 ℃ of following vacuum-drying 24～30 hours, purify target product.Wherein: catalyzer and ion liquid mol ratio are 1: 75～260; Phenyl aldehyde and pyrroles and ion liquid mol ratio are 1: 0.5～1.5: 2～3
Described ionic liquid is by BF
4 -Negatively charged ion and glyoxaline cation are formed.Described heteropolyacid is a kind of of silicotungstic acid, phospho-wolframic acid or phospho-molybdic acid, preferred silicotungstic acid.
Ion liquid synthetic:
(1) chlorination 1-butyl-3-Methylimidazole (BMIC) is synthetic
(1.8mol, ρ=0.883g/mL) n-propylcarbinyl chloride is added in the 500mL round-bottomed flask, 115 ℃ of control oil bath temperatures, back flow reaction 48h to take by weighing 147.6g (1.8mol) Methylimidazole, 188.3mL.Reaction mixture is poured into and is cooled off generation precipitation in back in the beaker, filters, and solid acetonitrile recrystallization 2～3 times, vacuum-drying gets white crystal 238.6g, productive rate 76.0%.Utilize fusing point and nucleus magnetic resonance to characterize product.
(2) Tetrafluoroboric acid 1-butyl-3-Methylimidazole (BMIBF
4) ion liquid synthetic
Take by weighing 5.4910g (0.05mol) NaBF
4, 8.7250g (0.05mol) chlorination 1-butyl-3-Methylimidazole in the band drying tube 250mL ground Erlenmeyer flask in, add 50mL acetone again, stirring reaction 24h.Filter, filtrate steams acetone with Rotary Evaporators, and vacuum-drying to constant weight gets colourless transparent liquid, and output 9.9699g, productive rate are 88.3%.Utilize infrared spectra and nuclear magnetic resonance spectrum to characterize product.
Experimental example 1 chamber is by experiment tested and is verified the present invention.
Material: silicotungstic acid (H
4O
40SiW
12.26H
2O) Beijing Yili Fine Chemicals Co., Ltd.
BMIBF
4(Tetrafluoroboric acid-1-butyl-3-first imidazoles) Liaoning University provides
Phenyl aldehyde (C
6H
5CHO) Chinese Medicine group Shanghai chemical reagent company limited
Pyrroles (C
4H
5N) Alfa Aesar
Instrument: microwave generator, XH-100 type, the auspicious swan microwave technology in Beijing company limited
Infrared spectrometer, PE Spectrum one fourier-transform infrared spectrophotometer
With 0.3346g (1 * 10
-4Mol) silicotungstic acid, 5.8965g (0.026mol) ionic liquid BMIBF
4, 1.01mL (0.01mol) phenyl aldehyde and 0.69mL (0.01mol) pyrroles add and be connected with in two mouthfuls of round-bottomed flasks of 25mL of prolong, at microwave power 500W, selects different temperature of reaction, continuous gamma radiation 5min.Reaction mixture becomes the atropurpureus viscous fluid, adds the 100mL dehydrated alcohol immediately, leaves standstill 24h.Suction filtration, unreacted reactant is removed in filter cake absolute ethanol washing 3 times.50 ℃ of following vacuum-drying 24h, utilize column chromatography purify purple crystals.Product is verified through infrared spectrometer, the results are shown in Table 1.
Table 1 temperature of reaction is to the influence of productive rate
As can be seen from Table 1, temperature of reaction has certain influence to productive rate.Temperature of reaction is had to the trace product in the time of 130 ℃, along with the rising of temperature of reaction, reaction yield increases to some extent, and when temperature reached 160 ℃, productive rate reached 27.8%.Continue elevated temperature, productive rate does not increase, and almost remains unchanged.Optimal reaction temperature is 160 ℃ among the present invention.
Experimental example 2
Repeated experiments example 1, temperature of reaction are 160 ℃, select different microwave powers to react, and the results are shown in Table 2.
Table 2 microwave initial power is to the influence of productive rate
As can be seen from Table 2, in temperature-rise period and the temperature maintenance process, different initial setting power is influential to productive rate.When setting power was 400W, reaction yield was 16.6%, and when initial power was 600W, productive rate reached 34.4%.Continue to increase power, productive rate almost remains unchanged.Best microwave power is 600W among the present invention.
Experimental example 3
Repeated experiments example 1, temperature of reaction are 160 ℃, and microwave irradiation power is 600W, select the different reaction times to react, and the results are shown in Table 3.
Table 3 microwave irradiation time is to the influence of productive rate
As can be seen from Table 3, compare with the synthetic tetraphenylporphyrin (about 2h) of conventional heating means, micro-wave energy significantly shortens the reaction times, and side reaction is reduced, and productive rate improves.This is because from porphyrin compound synthetic reaction mechanism, and it is the rate determining step of entire reaction that the polymkeric substance of intermediate-chain four phenyl aldehydes and tetrapyrrole closes ring.Under microwave induced effect, increase of polar particle relative movement energy and movement velocity are very fast, and atomic collision frequency in polarity two ends is accelerated greatly, the also corresponding increase of effective collision number of times, thus speed of reaction is improved greatly.When radiated time reached 15min, productive rate reached 39.5%, and along with the increase of radiated time, productive rate is almost constant.Optimum reacting time is 15min among the present invention.
Experimental example 4
Take by weighing silicotungstic acid, same 5.8965g (0.026mol) ionic liquid BMIBF respectively by table 4
4, 1.01mL (0.01mol) phenyl aldehyde and 0.69mL (0.01mol) pyrroles add and be connected with in two mouthfuls of round-bottomed flasks of 25mL of prolong, at microwave power 600W, under 160 ℃ of the temperature of reaction, continuous gamma radiation 15min.Reaction mixture becomes the atropurpureus viscous fluid, adds the 100ml dehydrated alcohol immediately, leaves standstill 24h.Suction filtration, unreacted reactant is removed in filter cake absolute ethanol washing 3 times.50 ℃ of following vacuum-drying 24h, utilize column chromatography purify purple crystals.Product is verified through infrared spectrometer, the results are shown in Table 4.
Table 4 catalyzer and BMIBF
4Ion liquid mol ratio is to the influence of productive rate
Data in the table 4 show that catalyst acidity has considerable influence to productive rate.Catalyst acidity is excessive, and the pyrroles easily with the acid effect ring-opening polymerization takes place; Acidity is too little, and a little less than the catalytic capability, speed of response is slow.Silicotungstic acid and ion liquid mol ratio best among the present invention are 1: 87.
Experimental example 5
Repeated experiments example 4, getting silicotungstic acid and ion liquid mol ratio is 1: 87, selecting different ionic liquids is that medium reacts, and the results are shown in Table 5.
Table 5 different ionic liquid is to the influence of productive rate
As seen from Table 5, remove BMIBF
4Outside ionic liquid can react under microwave radiation, other four kinds of ionic liquids at room temperature reacted immediately and emit a large amount of heat, at BMINO
3Middle reaction back generates the black jelly, at BPBF
4And BPNO
3In all generate red-purple solid and part black jelly, at BMIPF
6The middle atropurpureus solid that generates.Wherein the black jelly of Sheng Chenging is pyrroles's a straight-chain polymer, may be because acidity of catalyst too strong due to.BMIBF among the present invention
4Ionic liquid is the optimum response medium.
Embodiment 6
Repeated experiments example 4, getting silicotungstic acid and ion liquid mol ratio is 1: 87, directly adds reactant in the ionic liquid-catalyst system that reclaims, and the results are shown in Table 6.
Table 6 ionic liquid is reused the influence to productive rate
The product tetraphenylporphyrin is insoluble to ethanol, and ionic liquid and catalyzer all dissolve in ethanol, therefore can realize recycling of ionic liquid and catalyst system by the ethanol in the evaporated filtrate.Data from table 6 find out that after ionic liquid and catalyst system were reused, the productive rate of tetraphenylporphyrin was still higher.
Beneficial effect of the present invention: compared with prior art, owing to do not use high volatility, organic solvent that toxicity is big in process of production, thereby alleviated pollution on the environment; Ionic liquid is as a kind of green solvent, it has the many character that is different from water and ordinary organic solvents, as have high workability, low melting point, liquid wide ranges, not volatile, hypotoxicity, nonflammable, high conductivity, the multiple material of solubilized and do not have characteristics such as measurable vapour pressure, thereby can not pollute environment yet, and easily separate with product, be easy to reclaim, can use repeatedly; Microwave heating is compared with traditional heating means has higher speed of reaction and good selectivity, can shorten the reaction times, increases output, but investigates the feasibility of reaction within a short period of time.Ionic liquid has stronger polarity, can the strong absorption microwave add fast response and carry out, the time microwave reaction perfect medium.The present invention has overcome the organic solvent high volatility, the shortcoming that toxicity is big, under microwave irradiation effect, at green solvent---prepare tetraphenylporphyrin in the ionic liquid fast and efficiently, ionic liquid can use repeatedly, and production cost is low, technology is simple, alleviated pollution on the environment.
Embodiment:
The starting material that embodiment adopted, instrument, the same experimental example of equipment.
Embodiment 1:
With 1.0038g (3 * 10
-4Mol) silicotungstic acid, 5.8965g (0.026mol) ionic liquid BMIBF
4, 1.0612g (0.01mol) phenyl aldehyde and 0.6709g (0.01mol) pyrroles add and be connected with in two mouthfuls of round-bottomed flasks of 25mL of prolong, at microwave power 600W, under 160 ℃ of the temperature of reaction, continuous gamma radiation 15min, reaction mixture becomes the atropurpureus viscous fluid, add the 100ml dehydrated alcohol immediately, leave standstill 24h.Suction filtration, unreacted reactant is removed in filter cake absolute ethanol washing 3 times.50 ℃ of following vacuum-drying 24h get the purple solid, utilize column chromatography purify purple crystals.Productive rate is 64.3%.
Embodiment 2
With 0.2576g (7.7 * 10
-5Mol) silicotungstic acid, 4.5358g (0.02mol) ionic liquid BMIBF
4, 1.0612g (0.01mol) phenyl aldehyde and 0.3355g (0.005mol) pyrroles add and be connected with in two mouthfuls of round-bottomed flasks of 25mL of prolong, fixing microwave power 500W, under 150 ℃ of temperature of reaction, continuous gamma radiation 5min.Reaction mixture becomes the atropurpureus viscous fluid, adds the 100ml dehydrated alcohol immediately, standing over night.Suction filtration, unreacted reactant is removed in filter cake absolute ethanol washing 3 times.45 ℃ of following vacuum-drying 24h get the purple solid, utilize column chromatography purify purple crystals.Productive rate is 20.3%.
Embodiment 3
With 1.3384g (4 * 10
-4Mol) silicotungstic acid, 6.8038g (0.03mol) ionic liquid BMIBF
4, 1.0612g (0.01mol) phenyl aldehyde and 1.0064g (0.015mol) pyrroles add and be connected with in two mouthfuls of round-bottomed flasks of 25mL of prolong, at microwave power 800W, under 190 ℃ of the temperature of reaction, continuous gamma radiation 25min.Reaction mixture becomes the atropurpureus viscous fluid, adds the 100ml dehydrated alcohol immediately, standing over night.Suction filtration, unreacted reactant is removed in filter cake absolute ethanol washing 3 times.55 ℃ of following vacuum-drying 30h get the purple solid, utilize column chromatography purify purple crystals.Productive rate is 37.2%.
Embodiment 4:
With 0.5584g (3 * 10
-4Mol) phospho-molybdic acid, 5.8965g (0.026mol) ionic liquid BMIBF
4, 1.0612g (0.01mol) phenyl aldehyde and 0.6709g (0.01mol) pyrroles add and be connected with in two mouthfuls of round-bottomed flasks of 25mL of prolong, at microwave power 600W, under 160 ℃ of the temperature of reaction, continuous gamma radiation 15min, reaction mixture becomes the atropurpureus viscous fluid, add the 100ml dehydrated alcohol immediately, leave standstill 24h.Suction filtration, unreacted reactant is removed in filter cake absolute ethanol washing 3 times.50 ℃ of following vacuum-drying 24h get the purple solid, utilize column chromatography purify purple crystals.Productive rate is 61.9%.
Embodiment 5:
With 0.8640g (3 * 10
-4Mol) phospho-wolframic acid, 5.8965g (0.026mol) ionic liquid BMIBF
4, 1.0612g (0.01mol) phenyl aldehyde and 0.6709g (0.01mol) pyrroles add and be connected with in two mouthfuls of round-bottomed flasks of 25mL of prolong, at microwave power 600W, under 160 ℃ of the temperature of reaction, continuous gamma radiation 15min, reaction mixture becomes the atropurpureus viscous fluid, add the 100ml dehydrated alcohol immediately, leave standstill 24h.Suction filtration, unreacted reactant is removed in filter cake absolute ethanol washing 3 times.50 ℃ of following vacuum-drying 24h get the purple solid, utilize column chromatography purify purple crystals.Productive rate is 61.3%.
Claims (2)
1, the method for synthetic tetraphenylporphyrin in a kind of microwave-assisted ionic liquid, it is characterized in that with the ionic liquid being reaction medium, heteropolyacid is a catalyzer, adds phenyl aldehyde and pyrroles, under 160 ℃ of microwave power 600W, temperature of reaction, continuous microwave radiation 15 minutes, add dehydrated alcohol then and leave standstill 24～30h, suction filtration, filter cake absolute ethanol washing, 45～55 ℃ of following vacuum-drying 24～30h, purify target product, wherein:
Catalyzer and ion liquid mol ratio are 1: 87;
Phenyl aldehyde and pyrroles and ion liquid mol ratio are 1: 0.5～1.5: 2～3;
Described heteropolyacid is a kind of of silicotungstic acid, phospho-wolframic acid or phospho-molybdic acid;
Described ionic liquid is by BF
4 -Negatively charged ion and imidazoles cation composition.
2, the method for synthetic tetraphenylporphyrin in the microwave-assisted ionic liquid according to claim 1 is characterized in that described heteropolyacid is a silicotungstic acid.
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| EP1194227B1 (en) * | 1999-05-26 | 2004-09-15 | Biotage AB | Preparation and use of ionic liquids in microwave-assisted chemical transformations |
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| EP1194227B1 (en) * | 1999-05-26 | 2004-09-15 | Biotage AB | Preparation and use of ionic liquids in microwave-assisted chemical transformations |
Non-Patent Citations (10)
| Title |
|---|
| Synthesis of Transition Metal Porphyrins from Free-Base5,10,15,20-Tetraarylporphyrins Under Microwave Irradiation inIonic Liquids. Nidhi Jain et. al.Synthetic Communications,Vol.35 . 2005 |
| Synthesis of Transition Metal Porphyrins from Free-Base5,10,15,20-Tetraarylporphyrins Under Microwave Irradiation inIonic Liquids. Nidhi Jain et. al.Synthetic Communications,Vol.35 . 2005 * |
| 卟啉类物质的基本合成方法. 杨彪.精细化工，第16卷第2期. 1999 |
| 卟啉类物质的基本合成方法. 杨彪.精细化工，第16卷第2期. 1999 * |
| 四苯基卟啉及其衍生物的合成. 潘继刚等.有机化学，第13卷. 1993 |
| 四苯基卟啉及其衍生物的合成. 潘继刚等.有机化学，第13卷. 1993 * |
| 离子液体中微波促进的有机反应. 毕晓静，肖军华.中国化学会全国微波化学学术研讨会论文摘要集. 2005 |
| 离子液体中微波促进的有机反应. 毕晓静，肖军华.中国化学会全国微波化学学术研讨会论文摘要集. 2005 * |
| 离子液体在微波有机合成中的应用. 陈小兵.中国化学会全国微波化学学术研讨会论文摘要集. 2005 |
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