CN1159317C - Meso-tetra (2,5-difluorophenyl) porphyrin containing fluoroporphyrin developer, its synthesis and application - Google Patents
Meso-tetra (2,5-difluorophenyl) porphyrin containing fluoroporphyrin developer, its synthesis and application Download PDFInfo
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- CN1159317C CN1159317C CNB021123578A CN02112357A CN1159317C CN 1159317 C CN1159317 C CN 1159317C CN B021123578 A CNB021123578 A CN B021123578A CN 02112357 A CN02112357 A CN 02112357A CN 1159317 C CN1159317 C CN 1159317C
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Abstract
The present invention relates to a fluorinated porphyrin color-developing agent, namely meson-tetra (2, 5-difluorophenyl) porphyrin, and the synthesis and the application thereof, which belongs to the field of organic reagent synthesis. The synthesis technology comprises: dripping the mixture of pyrrole and a small amount of propionic acid into a mixture system of 2, 5-difluorobenzaldehyde and propionic acid under the condition of high-speed stir, stirring the mixture for reflux at 135 to 140 DEG C for 20 to 30 minutes, distilling and concentrating the mixture to a certain quantity by pressure reduction to obtain crude products by still positioning and separation, and obtaining pure products by recrystallization with three groups of mixed solvents and column chromatography. In the photometric analysis of the reagent to plumbum (II), a microemulsion system whose sensitivity is improved by 60% than that of conventional surfactant, namely Tween-80 micellar systems, is introduced. The trace amount of the plumbum (II) can be directly measured without separation. The synthesis method has the advantages of reasonable and simple design and easy purification. When used for measuring the plumbum (II), the color-developing agent and the improved analysis method are high in sensitivity and selectivity, and have certain application value in analysis fields, such as food, environment, chemistry, etc.
Description
Technical field
The present invention relates to a kind of new fluorine-containing porphin series meso-four (2, the 5-difluorophenyl) porphyrin and synthetic and application thereof, belong to the synthetic and applied technical field of organic reagent.
Background technology
Synthetic and the application of fluorine-containing porphin series causes concern just day by day.Successful at present such reagent of synthetic is few, existing bibliographical information has synthesized meso-four (4-fluorophenyl) porphyrin [Lei Yuwu, Guo Cancheng, Ceng Dezhang, chemical reagent, 1994,16 (2): 105～106], the pyrroles of amount of substance such as utilization and 4-fluorobenzaldehyde are at neutral DMF solvent and anhydrous AlCl
3Catalysis refluxed 2 hours down and makes, and introduced a fluoro substituents on the porphyrin phenyl ring.Because building-up reactions produces water, has seriously reduced the anhydrous AlCl of catalyzer
3Activity, the catalyzer add-on is big, the anhydrous condition of initial action is harsh, and with the carrying out of reaction, the catalyzer hydrolysis produces Al (OH)
3Mix and be difficult for removing in product, post-processing difficulty is big.Neutral DMF with higher makes solvent, and reflux temperature is higher, and the reaction times reach 2 hours, easily cause self condensation side reaction of reactant pyrroles, easily cause the porphyrin caking, adhere to the reaction vessel inwall, influence stirring efficiency.As for the Application in Photometric Analysis of meso-four (4-fluorophenyl) porphyrin, do not see bibliographical information so far as yet at plumbous (II).Harmful element lead (II) is important environmental monitoring object.Often, be difficult to popularize because of instrument is expensive with aas determination; Though dithizone method is classical luminosity development process, it is big to have toxicity, complex operation and muting sensitivity (ε=8 * 10
4L/ (molcm)) shortcoming; Porphin series is applied in photometric analysis with its higher sensitivity, but selectivity waits to improve.
Summary of the invention
The present invention proposes a kind of new fluorine-containing porphin series, it is characterized in that, this developer be title and molecular structural formula be respectively meso-four (2, the 5-difluorophenyl) porphyrin and
Fluorine-containing porphin series.
The technical problem that the present invention will solve is to release a kind of method of synthetic new fluorine-containing porphin series meso-four (2, the 5-difluorophenyl) porphyrin.This method has following advantage: temperature of reaction is low, has reduced the byproduct of reactant pyrroles self condensation and in the phenomenon of the inwall of reaction vessel caking; Reaction times is short; Avoid harsh anhydrous condition; Do not adopt the anhydrous solid catalyzer; The meso-four that fluoro substituents quantity in the molecular structure of the new fluorine-containing porphin series of synthetic has been reported more (4-fluorophenyl) porphyrin doubles, increased colour developing conjugated system and developing sensitivity, and the space steric effect of the phenyl ring ortho position fluoro substituents that increases is influencing the selectivity that has improved reagent photometric analysis lead (II) on the little basis to sensitivity.
The present invention makes above-mentioned technical problem be resolved by the following technical programs.A kind of synthetic method of synthetic new fluorine-containing porphin series meso-four (2, the 5-difluorophenyl) porphyrin is characterized in that,
Synthetic: as in there-necked flask, to add 14.2g 2, the 5-difluorobenzaldehyde is dissolved in the 250ml propionic acid, and oil bath is heated to 140 ℃, quick stirring and refluxing, drip the new pyrroles who steams of 7.2ml and the mixture of 30ml propionic acid, drip off in 4～5 minutes, reflux in 135～140 ℃ again and stirred 20～30 minutes, cooling was placed 4～12 hours, the reaction solution underpressure distillation goes out 1/2～2/3 propionic acid solvent, and the concentrated solution suction filtration gets crude product, the solid of purple;
Purify: respectively with propionic acid solvent and Yi Rong impurity in the ethanol flush away crude product of 50ml hot water and 20ml 50%, respectively crude product is carried out recrystallization with three groups of each 20ml of mixed solvent again, the quality proportioning of mixed solvent ethanol-ethyl acetate-trichloromethane is 1: 1: 0,1: 1: 1,0: 1: 1, crystallisate is that developping agent carries out the silica-gel plate thin-layer chromatography with the ethyl acetate after vacuum-drying, three spots appear, the main violet spot of intermediary is a product chromatography thing, Rf=0.89, product chromatography thing is carried out column chromatography for separation, the silica gel granularity of column chromatography and activity are respectively 100-200 order and III level, make eluent with ethyl acetate, three colour bands occur, collect second lilac band, evaporate to dryness, through 60～70 ℃ of vacuum-dryings 10 hours, get purple pressed powder product 1.61g again.
The building-up reactions equation is
Principle of work:
Because the existence of pyrroles's condensation side reaction, pyrroles's add-on should be big by 5% than theoretical amount.Solvent propionic acid large usage quantity, the pyrroles should with splash into after an amount of propionic acid mixes, can prevent from directly to be exposed in the air and variable color and splash into self condensation side reaction under the acidic conditions that the back produces because of high local concentrations, at the uniform velocity the time of splashing into is about 4～5 minutes, the too fast or inhomogeneous condensation that also causes the pyrroles.The simple propionic acid of boiling point that drips off the back mixed system descends to some extent, and oil bath temperature also suitably descends, and keeps slight boiling condition, prevents pyrroles's condensation and porphyrin caking under the high temperature.Because propionic acid double as catalyzer, the reaction times can shorten to 20～30 minutes.After reacting by heating finished, suitable room temperature was placed 4～12 hours, impelled to react completely, and placed for a long time, also easily produced pyrroles's condensation.Because the synthetic general productive rate not high (about 10%) of porphyrin, and quantity of solvent is big, often needs to concentrate the back suction filtration and gets product.Productive rate is relevant with concentrating degree.During this is synthetic, concentrates and to be controlled at about 1/2 ~ 2/3.The content of product is seldom in the mother liquor behind this moment concentrated solution suction filtration.Underconcentration causes product loss, excessively concentrates and is mixed with more byproduct, is difficult for purifying.Concentration process must be finished under underpressure distillation condition preferably fast, and vacuum tightness causes distillation temperature to raise inadequately, and the time is long, easily makes pyrroles's condensation.
Compare with background technology, the synthetic method that the present invention relates to has following outstanding effect:
1. the quantity of the fluoro substituents that contains on the molecular structure of the new fluorine-containing porphin series of product is the twice of the fluorine-containing porphin series of background technology, both increase the developing sensitivity of product, improved the selectivity of product photometric analysis harmful element lead (II) again.
2. propionic acid had both been made solvent, made catalyzer again, did not adopt anhydrous solid catalyst A lCl
3, the anhydrous condition of harshness when having avoided synthetic initial.
3. the reaction times weak point is 20 ~ 30 minutes.
4. temperature of reaction is low, is 135 ~ 140 ℃.
Another technical problem that the present invention will solve is the application of new fluorine-containing porphin series meso-four (2, the 5-difluorophenyl) porphyrin: photometric analysis lead (II).
The present invention is resolved by making above-mentioned second technical problem by the following technical solutions.The application of fluorine-containing porphin series meso-four (2, the 5-difluorophenyl) porphyrin is characterized in that, this developer carries out photometric analysis to plumbous (II) in microemulsion, operate as follows:
The lead (II), 6.0 * 10 that in the 25ml volumetric flask, adds 1～12 μ g
-4The meso-four (2 of mol/L, the 5-difluorophenyl) the DMF solution 1ml of porphyrin, the phenanthroline solution 1ml of secondary additive 0.5% and the Fluorinse 1ml of sequestering agent 0.1%, under the borax-sodium hydroxide buffer condition of pH8.2～11, add microemulsion 15ml, the microemulsion proportioning is Tween-80: propyl carbinol: normal heptane: water=0.5 ~ 5%WT: 0.2 ~ 5%WT: 0.1 ~ 0.2%WT:＞90%WT, in 80 ~ 90 ℃ of water-baths, heated 15 ~ 20 minutes, reagent blank with correspondence is made reference, measures the absorbancy at 465nm place.
Principle of work:
The meso-four of bibliographical information (4-fluorophenyl) porphyrin is not seen the photometric analysis that is applied to lead (II) as yet.Porphyrin class reagent mensuration plumbous (II) is mainly carried out in the micellar system of tensio-active agent at present, the more single surfactant micelle system of being made up of tensio-active agent-cosurfactant-oil-water of microemulsion has higher developing sensitivity, the existing application in non-porphyrin class color development system.The present invention is applied to meso-four (2 with microemulsion system, the 5-difluorophenyl) porphyrin photometric analysis lead (II), done the conventional micellar system and the comparison test of microemulsion system simultaneously, found that microemulsion color development system absorbancy can improve a lot on the basis of micellar system.
In containing the conventional micellar system of Tween-80, record ε=1.7 * 10
5L/ (molcm), and in microemulsion system ε=2.7 * 10
5L/ (molcm), enhanced sensitivity are 60%.The microemulsion of different proportionings has considerable influence to sensitivity and stability, and the water that water content is big-oil type microemulsion has stable effect of enhanced sensitivity.The scope of the allowance of tensio-active agent Tween-80 and cosurfactant propyl carbinol is bigger.The amount of oil phase normal heptane is big to sensitivity especially circulation ratio influence, measures when bigger than normal, and sensitivity sometimes surpasses the test-results value, but circulation ratio is not good; Measure when on the low side, sensitivity is near micellar system.The microemulsion proportioning that test is taken is Tween-80-propyl carbinol-normal heptane-water (mass percent)=(0.5 ~ 5%): (0.2 ~ 5%): (0.1 ~ 0.2%): (＞90%), total amount are 100%.Because the thermostability of microemulsion is limit,, in 80 ~ 90 ℃ water-bath, heat and be advisable in 15 ~ 20 minutes so color reaction should not be carried out in the boiling water bath that porphyrin class reagent is used always.Do the interference that sequestering agent can further lower Cd (II), Cr (III), Mg (II), Zn (II), Hg (II) etc. with Sodium Fluoride, this color development system successfully is applied to the mensuration of trace lead in beer, lime-preserved egg, the tealeaves (II).
Embodiment
The synthetic method that the present invention relates to is particularly suitable for being used for synthesizing fluorine-containing porphin series meso-four (2, the 5-difluorophenyl) porphyrin, and this product is particularly suitable for being used for harmful element lead (II) is carried out photometric analysis.
Claims (2)
1. the synthetic method of synthetic new fluorine-containing porphin series meso-four (2, a 5-difluorophenyl) porphyrin is characterized in that,
Synthetic: as in there-necked flask, to add 14.2g 2, the 5-difluorobenzaldehyde is dissolved in the 250ml propionic acid, and oil bath is heated to 140 ℃, quick stirring and refluxing, drip the new pyrroles who steams of 7.2ml and the mixture of 30ml propionic acid, drip off in 4 ~ 5 minutes, reflux in 135 ~ 140 ℃ again and stirred 20 ~ 30 minutes, cooling was placed 4 ~ 12 hours, the reaction solution underpressure distillation goes out 1/2 ~ 2/3 propionic acid solvent, and the concentrated solution suction filtration gets crude product, the solid of purple;
Purify: respectively with propionic acid solvent and Yi Rong impurity in the ethanol flush away crude product of 50ml hot water and 20ml 50%, respectively crude product is carried out recrystallization with three groups of each 20ml of mixed solvent again, the quality proportioning of mixed solvent ethanol-ethyl acetate-trichloromethane is 1: 1: 0,1: 1: 1,0: 1: 1, crystallisate is that developping agent carries out the silica-gel plate thin-layer chromatography with the ethyl acetate after vacuum-drying, three spots appear, the intermediary violet spot is a product chromatography thing, R
f=0.89, product chromatography thing is carried out column chromatography for separation, the silica gel granularity of column chromatography and activity are respectively 100-200 order and III level, make eluent with ethyl acetate, three colour bands occur, collect second lilac band, evaporate to dryness, through 60 ~ 70 ℃ of vacuum-dryings 10 hours, get purple pressed powder product 1.61g again.
2. the application of the fluorine-containing porphin series meso-four of the described method synthetic of claim 1 product (2, the 5-difluorophenyl) porphyrin is characterized in that, this developer carries out photometric analysis to plumbous (II) in microemulsion, operate as follows:
The lead (II), 6.0 * 10 that in the 25ml volumetric flask, adds 1～12 μ g
-4The meso-four (2 of mol/L, the 5-difluorophenyl) the DMF solution 1ml of porphyrin, the phenanthroline solution 1ml of secondary additive 0.5% and the Fluorinse 1ml of sequestering agent 0.1%, under the borax-sodium hydroxide buffer condition of pH8.2～11, add microemulsion 15ml, the microemulsion proportioning is Tween-80: propyl carbinol: normal heptane: water=0.5 ~ 5%WT: 0.2 ~ 5%WT: 0.1 ~ 0.2%WT:＞90%WT, total amount is 100%WT, in 80 ~ 90 ℃ of water-baths, heated 15 ~ 20 minutes, reagent blank with correspondence is made reference, measures the absorbancy at 465nm place.
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| CNB021123578A CN1159317C (en) | 2002-07-02 | 2002-07-02 | Meso-tetra (2,5-difluorophenyl) porphyrin containing fluoroporphyrin developer, its synthesis and application |
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| CN100361994C (en) * | 2004-12-10 | 2008-01-16 | 吉林大学 | Tetraphenyl porphyrin derivative and its application in organic electroluminescent device |
| JP4964887B2 (en) * | 2006-08-28 | 2012-07-04 | 興和株式会社 | Reagent for measuring lead concentration and method for measuring lead concentration |
| JP5032577B2 (en) * | 2007-07-20 | 2012-09-26 | 興和株式会社 | Reagent for measuring lead concentration and method for measuring lead concentration |
| CN103940955A (en) * | 2013-08-06 | 2014-07-23 | 江苏天瑞仪器股份有限公司 | Reagent pack for detection of lead ions in water |
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