CN1974572A - Porphyrin derivative and its prepn process and use - Google Patents
Porphyrin derivative and its prepn process and use Download PDFInfo
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- CN1974572A CN1974572A CN 200610147341 CN200610147341A CN1974572A CN 1974572 A CN1974572 A CN 1974572A CN 200610147341 CN200610147341 CN 200610147341 CN 200610147341 A CN200610147341 A CN 200610147341A CN 1974572 A CN1974572 A CN 1974572A
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Abstract
The present invention relates to porphyrin derivative in the structure as shown and its preparation process and use. The preparation of the porphyrin derivative includes the following main steps: refluxing reaction of 3-trifluoro methyl benzaldehyde and pyrrole in propionic acid medium for 30-60 min, stilling for 6-12 hr, evaporating to eliminate propionic acid until the reacted material inside the reactor is reduced to 20 %-40 % of original volume, cooling to separate out precipitate, filtering and re-crystallizing the precipitate, column chromatographic separation and drying to obtain the target product. The porphyrin derivative is used in the spectrophotometric detection of metal cadmium (II), and has coordination capacity with trace amount cadmium (II) higher than available porphyrin compounds.
Description
Technical field
The present invention relates to a kind of derivatives of porphyrin and its production and use.
Background technology
Cadmium metal is a kind of harmful metal, and the property accumulated cadmium metal (II) is important environmental monitoring object.
So far, the porphyrins that is used for metal ion detection (spectrophotometry) has: four (2,3,4,5, the 6-pentafluorophenyl group) porphyrin (chemical reagent, 308～309), meso-four (2, the 5-difluorophenyl) porphyrin (Yu Shanhui etc. 2001,23 (5):, chemical reagent, 223～224) and (Wu Jikui such as meso-four [3,5-two (trifluoromethyl) phenyl] porphyrin 2002,24 (4):, Yu Shanhui etc., assay office, 2005,24 (4): 64～66), wherein meso-four [3,5-two (trifluoromethyl) phenyl] porphyrin is more suitable in the detection of cadmium metal (II).
Yet in the actual detected process, find that the coordination ability of meso-four [3,5-two (trifluoromethyl) phenyl] porphyrin and trace cadmium (II) is relatively poor (in other words, the sensitivity that promptly detects is lower).Cause this problem to have many-sided reason, but used porphyrins structure may play leading role, so this area press for the new porphyrins of development.
Summary of the invention
One of the object of the invention is, a kind of new derivatives of porphyrin is provided;
Two of the object of the invention is, a kind of method for preparing above-mentioned derivatives of porphyrin is provided;
Three of the object of the invention is, disclose a kind of above-mentioned derivatives of porphyrin purposes.
Through extensive and further investigation, the present inventor finds, in fluorine element and porphyrin phenyl ring directly link to each other [as: four (2,3,4,5, the 6-pentafluorophenyl group) porphyrin or meso-four (2, the 5-difluorophenyl) porphyrin] time, because of the cause of the pi-conjugated effect of p-, influence the porphyrin ring conjugated system, thereby hindered the coordination in metal ion and porphyrin hole; (as: meso-four [3 and when linking to each other with phenyl ring in the porphyrin with two (or more than two) trifluoromethyl replacement fluorine elements, 5-two (trifluoromethyl) phenyl] porphyrin) time, though can eliminate the influence of the pi-conjugated effect of p-, cross the coordination ability that has weakened by force with trace cadmium (II) owing to its inductive effect and steric effect.In view of the above, the contriver has designed and synthesized following derivatives of porphyrin (as shown in Equation 1):
The method for preparing the said derivatives of porphyrin of the present invention, its key step is: in the propionic acid medium, the 3-trifluoromethylated benzaldehyde (it prepares referring to chemical reagent, and 2000,22 (5): 305; 310) under reflux state, reacted 30～60 minutes with the pyrroles, left standstill again 6～12 hours, the volume that steam to remove propionic acid material to the reactor stops distillation for 20%～40% o'clock of original (steaming before removing propionic acid) volume, cooling, there is throw out to separate out, filter, the gained throw out is carried out promptly getting target compound behind recrystallization and the column chromatography.
The preparation feedback equation is as follows:
The using method of the said derivatives of porphyrin of the present invention is such:
Under 40 ℃～60 ℃ conditions, be that the tween-80 aqueous solution, the 0.4mL～1mL concentration of 5wt% is 3 * 10 successively with 0.1～4 μ g cadmium (II), 0.8mL～3mL concentration
-4Mol/L contains the aqueous solution of compound shown in the formula 1, oxammonium hydrochloride and the 2.5mL pH value that 0.1mL～1.5mL concentration is 2wt% is that 9～11 damping fluids place 25 milliliters of volumetric flasks, color reaction in boiling water bath again can be measured the content (can reach test purpose in 441nm place absorbancy by measuring it) of cadmium (II) behind the cooling constant volume.
The said derivatives of porphyrin of the present invention (compound shown in the formula 1) is when being used for the Spectrophotometric Assays of cadmium metal (II), and the apparent molar absorption coefficient of its system (ε) is 3.1 * 10
5L/molcm, and the apparent molar absorption coefficient (ε) of existing compound (meso-four [3,5-two (trifluoromethyl) phenyl] porphyrin) is 2.1 * 10
5L/molcm, this just illustrates the highly sensitive in existing compound of derivatives of porphyrin that the present invention designs and synthesizes.In other words, the coordination ability of said derivatives of porphyrin of the present invention and trace cadmium (II) is better than existing compound.
In addition, evidence is reinforced down in the room temperature (15 ℃～25 ℃) of routine, and the color development system dissolving is incomplete, even heat with boiling water bath after adding, circulation ratio is relatively poor again; And the part color reaction may take place in too high charge temperature (charge temperature is higher than 60 ℃) in reinforced process.Therefore the present invention selects to feed in raw material in 40 ℃～60 ℃, can guarantee circulation ratio and the selectivity analyzed.
Embodiment
Prepare the method for the said derivatives of porphyrin of the present invention (compound shown in the formula 1), comprise the steps:
(1) in the propionic acid medium, 3-trifluoromethylated benzaldehyde and pyrroles reacted under reflux state 30～60 minutes, left standstill again 6～12 hours, the volume that steam to remove propionic acid material to the reactor stops distillation for 20%～40% o'clock of original (steaming before removing propionic acid) volume, cooling, have throw out to separate out, filter, the gained throw out is thick product;
For reducing the generation of by product (pyrroles self condenses), reflux time should not be above one hour; In addition, (during underconcentration, product can't be separated out (to steam the amount of removing propionic acid) because concentrating degree and can have influence on the purity of product; Concentrate when excessive, then have a large amount of impurity to separate out, cause the product impure), find that after deliberation the propionic acid that steams 60%～80% (volume percent) is more suitable.
(2) will be first with the 50v/v% washing with alcohol by the thick product that step (1) makes, and then successively with equal-volume blended mixed solvent, they are respectively ethanol-ethyl acetate, ethanol-ethyl acetate-chloroform, ethyl acetate-methylene dichloride and ethanol-methylene dichloride-DMF, carry out recrystallization four times, thick product through four recrystallizations is carried out column chromatography (silica gel G 100～200 orders again, active II level, eluent is for being the mixture of forming at 5: 1 by volume by ethyl acetate and DMF), collect liquid and desolventize, after vacuum-drying, obtain product (purple gloss solid) again through steaming.
The invention will be further described with embodiment below,
Embodiment 1
Synthesizing of meso-four [3-trifluoromethyl] porphyrin (compound shown in the formula 1):
(1) in 1 liter there-necked flask, add 250mL propionic acid and 12.2g (0.07mol) 3-trifluoromethylated benzaldehyde, stirring and refluxing in 140 ℃ of oil baths, drip 4.7g (0.07mol) and newly steam pyrroles and 30mL propionic acid mixed solution, dripped off in 10 minutes, and continued reaction 40 minutes, pour out, refrigerator and cooled is hidden to place and is spent the night, and no crystal is separated out.Reaction solution goes out the propionic acid of 60v/v%～80v/v% through underpressure distillation, and the concentrated solution suction filtration gets the crude product that contains a large amount of impurity 6 grams of purple.
(2) crude product is earlier with 20mL 50v/v% washing with alcohol, four groups of mixed solvents that progressively increase progressively with solvability respectively carry out recrystallization again, and four groups of mixed solvents are followed successively by 40mL ethanol-ethyl acetate (volume ratio is 1: 1), 30mL ethanol-ethyl acetate-chloroform (volume ratio is 1: 1: 1), 20mL ethyl acetate-methylene dichloride (volume ratio is 1: 1), 15mL ethanol-methylene dichloride-DMF (volume ratio is 1: 1: 1).
To be that the mixture of forming at 5: 1 is that developping agent carries out thin-layer chromatography by volume by ethyl acetate and DMF, present three spots through the product of four recrystallizations, collect the second spot (R
f=0.78) gets gleanings, (the column chromatography post adopts silica gel G 100～200 orders again this gleanings to be carried out column chromatography, active II level, eluent is for being the mixture of forming at 5: 1 by volume by ethyl acetate and DMF), collect second colour band, gleanings is got 2.34g purple gloss product, total recovery 15.1% through 40 ℃ of vacuum-dryings again after 8 hours after removing eluent under reduced pressure.
IR (KBr compressing tablet, cm
-1): 3327 (υ
N-H); 1129,1327 (υ
C-F); 3101 (υ
C-H).
Embodiment 2
Meso-four [3-trifluoromethyl] porphyrin is used in the spectrophotometric analysis of cadmium (II):
Under 40 ℃～60 ℃ conditions, be 3 * 10 with 2 μ g cadmiums (II), 2mL 5% tween-80 solution, 0.8mL concentration successively
-4The oxammonium hydrochloride of the meso-four of mol/L [3-trifluoromethyl] porphyrin (compound shown in the formula 1) aqueous solution, 1mL 2wt% and 2.5mLpH value are that boric acid-sodium hydrate buffer solution of 10.4 places 25 milliliters of volumetric flasks, color reaction in boiling water bath again, measure this system in 441nm place absorbancy behind the cooling constant volume, just can reach the mensuration to cadmium (II), the apparent molar absorption coefficient of system (ε) is 3.1 * 10
5L/molcm.
Comparative Examples
Divided by meso-four [3,5-two (trifluoromethyl) phenyl] outside meso-four [3-trifluoromethyl] porphyrin in the porphyrin alternate embodiment 2, other condition is identical with described in the embodiment 2 all, and the gained system is measured, and recording its apparent molar absorption coefficient (ε) is 2.1 * 10
5L/molcm.The coordination ability of this explanation meso-four [3,5-two (trifluoromethyl) phenyl] porphyrin and trace cadmium (II) is weaker than meso-four [3-trifluoromethyl] porphyrin.
Claims (6)
1, a kind of derivatives of porphyrin, it has structure shown in the formula 1:
2, a kind of preparation is as the method for the said derivatives of porphyrin of claim 1, it is characterized in that, said preparation method's key step is: in the propionic acid medium, 3-trifluoromethylated benzaldehyde and pyrroles reacted under reflux state 30～60 minutes, left standstill 6～12 hours again, steam to remove propionic acid volume of material to the reactor and be to stop distillation at original 20%～40% o'clock, cooling, there is throw out to separate out, filters, the gained throw out is carried out promptly getting target compound after recrystallization, column chromatography and the drying.
3, as the said preparation method of claim 2, it is characterized in that, wherein said recrystallization is: successively with equal-volume blended mixed solvent, they are respectively ethanol-ethyl acetate, ethanol-ethyl acetate-chloroform, ethyl acetate-methylene dichloride and ethanol-methylene dichloride-DMF, carry out recrystallization four times.
As the said preparation method of claim 2, it is characterized in that 4, it is that the mixture of forming at 5: 1 is an eluent by volume that wherein said column chromatography adopts by ethyl acetate and DMF.
5, as the application of the said derivatives of porphyrin of claim 1 in the Spectrophotometric Assays of cadmium metal (II).
6, as the said application of claim 5, it is characterized in that, under 40 ℃～60 ℃ conditions, is that 5wt% tween-80 solution, 0.4mL～1mL concentration are 3 * 10 with 0.1～4 μ g cadmium (II), 0.8mL～3mL concentration successively
-4Mol/L contains the aqueous solution of compound shown in the formula 1, oxammonium hydrochloride and the 2.5mL pH value that 0.1mL～1.5mL concentration is 2wt% is that 9～11 damping fluids place 25 milliliters of volumetric flasks, color reaction in boiling water bath again can be measured the content of cadmium (II) behind the cooling constant volume.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010130065A1 (en) * | 2009-05-15 | 2010-11-18 | Guo Cancheng | A method for synthesizing tetraaryl porphyrin and its device |
| CN101550140B (en) * | 2009-05-15 | 2011-06-15 | 湖南大学 | Method and apparatus for synthesis of tetaraary porphyrin |
-
2006
- 2006-12-15 CN CNB2006101473417A patent/CN100497341C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010130065A1 (en) * | 2009-05-15 | 2010-11-18 | Guo Cancheng | A method for synthesizing tetraaryl porphyrin and its device |
| CN101550140B (en) * | 2009-05-15 | 2011-06-15 | 湖南大学 | Method and apparatus for synthesis of tetaraary porphyrin |
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