CN101735227A - Water-soluble N-confused porphyrin sulfonate and synthesizing method thereof - Google Patents
Water-soluble N-confused porphyrin sulfonate and synthesizing method thereof Download PDFInfo
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- CN101735227A CN101735227A CN200910117545A CN200910117545A CN101735227A CN 101735227 A CN101735227 A CN 101735227A CN 200910117545 A CN200910117545 A CN 200910117545A CN 200910117545 A CN200910117545 A CN 200910117545A CN 101735227 A CN101735227 A CN 101735227A
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Abstract
The invention provides water-soluble N-confused porphyrin sulfonate, which is prepared by the following steps: heating N-confused porphyrin used as a raw material and concentrated sulfuric acid used as a sulfonating agent to between 110 and 130 DEG C, reacting the mixture for 3 to 4 hours at the constant temperature, cooling a reaction product to the normal temperature, adjusting pH to between 8 and 9 with sodium hydroxide solution or sodium bicarbonate solution, concentrating the solution, filtering the solution to remove the generated sodium sulfate, concentrating the filtered solution, and then drying the concentrated solution at the temperature of between 80 and 100 DEG C to obtain a coarse product; and grinding the coarse product, extracting the coarse product for 48 to 72 hours with methanol, evaporating the methanol, extracting the solution with ethyl acetate, filtering the solution, washing a filtered product with ether, and drying the product to obtain a purified product of the water-soluble N-confused porphyrin sulfonate. The N-confused porphyrin sulfonate of the invention becomes a soluble substance due to the introduction of a sulfonic group so that the amphipathy and selectivity of the N-confused porphyrin sulfonate are remarkably improved, the N-confused porphyrin sulfonate can well enter the body, and the application of the N-confused porphyrin sulfonate in treating diseases such as cancer and the like is expanded.
Description
Technical field
The invention belongs to chemosynthesis technical field, relate to a kind of preparation of water-soluble porphyrin, relate in particular to a kind of water-soluble N-confused derivatives of porphyrin---N-confused porphyrin sulfonate and preparation thereof.
Background technology
Porphyrin compound with the big ∏ conjugated structure in plane has caused the very big interest of many scientists and other chemist because of its biological activity and structural singularity.Through broad research, derivatives of porphyrin has related to all respects such as medicine, electronics, substitute energy.And in cancer therapy, porphyrin compound also is often used as the photosensitive reagents into photodynamic therapy (PDT), and deep day by day along with photodynamic therapy research, and the photosensitizers with suitable lypohydrophilic character becomes the phototherapy medicament of tool prospect.Therefore, water-soluble porphyrin and metal porphyrins also cause people's growing interest.Up to the present, more existing water-soluble porphyrin compounds are used as the photosensitive reagents of photodynamic therapy (PDT).
Along with the porphyrin CHEMICAL DEVELOPMENT, the expansion porphyrin, derivatives of porphyrin such as porphyrin isomers are because its unique character also causes people's growing interest.The chaotic porphyrin of N-is 5,10,15, and a kind of isomers of 20-tetraphenylporphyrin is considered to a kind of up-and-coming photosensitizers owing to can produce creating singlet oxygen by using.But, because the chaotic porphyrin of N-is water insoluble, be difficult to be accepted by human body, its application in diseases such as treatment cancer is restricted.
Goal of the invention
The purpose of this invention is to provide a kind of water-soluble N-confused derivatives of porphyrin---N-confused porphyrin sulfonate.
Another object of the present invention provides a kind of preparation method of water-soluble N-confused porphyrin sulfonate.
(1) water-soluble N-confused porphyrin sulfonate
Water-soluble N-confused porphyrin sulfonate of the present invention, its structural formula is as follows:
Chaotic porphyrin itself is water-fast organic big conjugated molecule, when introducing sulfonate group, becomes soluble substance, can significantly improve its amphipathic and selectivity, can better enter in the body, and its application in diseases such as treatment cancer is expanded.
(2) preparation of water-soluble N-confused porphyrin sulfonate
The preparation method of water-soluble N-confused porphyrin sulfonate of the present invention, be that the chaotic porphyrin of N-is dissolved in the vitriol oil, be heated to 110～130 ℃, isothermal reaction 3～4 hours, be cooled to room temperature, regulate PH to 8～9 with saturated soda-lye or dilute solution of sodium bicarbonate, concentrate, remove by filter the sodium sulfate of generation; It is dry under 80～100 ℃ that filtrate concentrates the back, gets thick product; With methyl alcohol extracting 48～72h, boil off methyl alcohol then behind the thick product porphyrize, use ethyl acetate extraction, filter, wash, be drying to obtain the pure product of water-soluble N-confused porphyrin sulfonate again with ether.
Below by infrared spectra, nucleus magnetic resonance, ultraviolet-visible spectrum detect the product of the present invention's preparation.
1, infrared spectrum characterization
With the infrared spectra of KBr pressed disc method mensuration product, Fig. 1 is the infrared spectra of the product of the present invention's preparation.Among Fig. 1,3445.88cm
-1Being N-H stretching vibration absorption peak on the porphin ring, is the eigen vibration of porphyrin ring.1645.28,1556.55,1459.90cm
-1It is the absorption peak of phenyl ring; 1193.08,1124.89,1040.83cm
-1Be-the SO2 absorption peak to illustrate that the benzene ring hydrogen is replaced by sulfonate radical.
2, ultraviolet-visible spectrum characterizes:
Adopt Schimadzu160 type ultraviolet-visual spectrometer (UV-Vis), make solvent with methyl alcohol, measure the UV spectrum of product, ultraviolet spectrogram is seen Fig. 2, and the ultraviolet spectrum data of product sees Table 1.The monomeric ultraviolet-visible spectrum basically identical of this result and chaotic porphyrin.As seen, the N-confused porphyrin sulfonate generates the transition regime that does not change the porphyrin molecule.
Table 1 ultraviolet spectrum data
3, nucleus magnetic resonance
Adopt Varian type nuclear magnetic resonance analyser (400M) testing product,
1HNMR (CDCl
3) δ: 8.70 (s, 1H, " confused pyrrole "), 8.35 (s, 2H pyrrole), 8.27 (d, 2H pyrrole), 8.25 (d, 2H pyrrole), 8.20-7.60 (m, 16H, o, m-ph) ,-0.98 (s, 2H, NH) ,-2.7 (s, 1H, " confused pyrrole "), by the sign of nucleus magnetic hydrogen spectrum, proved that further target product forms.
In sum, by infrared spectra, nucleus magnetic resonance, ultraviolet-visible spectrum illustrate to obtain target product.
It is short that the present invention has technical process, three-waste pollution seldom, technology is simple, characteristics easy and simple to handle.
Description of drawings
Fig. 1 is the infrared spectra of N-confused porphyrin sulfonate
Fig. 2 is the UV spectrum of N-confused porphyrin sulfonate
Embodiment
Further specify the preparation and the solubility property of water-soluble N-confused porphyrin sulfonate of the present invention below by concrete experiment.
The preparation of water-soluble N-confused porphyrin sulfonate: in single neck round-bottomed flask of 50ml, the chaotic porphyrin of 200mgN-is dissolved in the 4ml vitriol oil, be heated to 120 ℃ under stirring, constant temperature successive reaction 4 hours is carefully poured in the 20ml frozen water after being cooled to room temperature.Regulating pH value with saturated soda-lye or dilute solution of sodium bicarbonate is 8-9, be concentrated into about 8ml after, the frozen water cooling removes by filter sodium sulfate.Consider cake to light green with the 20ml methanol wash.Add 40ml methyl alcohol in the filtrate, separate out sodium sulfate and remove by filter.Use the 80ml dissolve with methanol after being spin-dried for filtrate, remove by filter a small amount of sodium sulfate once more.Got thick product down in dry 4 hours at 100 ℃ behind the concentrated filtrate.Use 100ml methyl alcohol extracting 72h in Soxhlet extractor behind the porphyrize, boil off methyl alcohol to the 10ml, add the 100ml ethyl acetate, precipitation is separated out in stirring, filter green solid, wash twice with ether, repeat aforesaid operations three times, the gained solid was got pure product 75mg, yield 22.5% down in dry 4 hours at 100 ℃.
Its synthetic route is as follows:
Claims (2)
1. water-soluble N-confused porphyrin sulfonate, its structural formula is as follows:
2. the preparation method of water-soluble N-confused porphyrin sulfonate according to claim 1, it is characterized in that: be that the chaotic porphyrin of N-is dissolved in the vitriol oil, be heated to 110～130 ℃, isothermal reaction 3～4 hours, be cooled to normal temperature, regulate PH to 8～9, concentrate with saturated sodium hydroxide solution or sodium hydrogen carbonate solution, remove by filter the sodium sulfate of generation, filtrate concentrates back at 80～100 ℃ of following dry thick products that get; With methyl alcohol extracting 48～72h, boil off behind the methyl alcohol behind the thick product porphyrize with ethyl acetate extraction, filtration, again with the ether washing, the pure product of dry water-soluble N-confused porphyrin sulfonate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167704A (en) * | 2011-03-20 | 2011-08-31 | 扬州大学 | Water-soluble porphyrin gold (III) anticancer compounds and preparation method thereof |
| CN102417510A (en) * | 2011-09-22 | 2012-04-18 | 西北师范大学 | Conjugated Schiff base Zn (zinc) porphyrin as well as preparation and application thereof |
| CN109970746A (en) * | 2019-04-26 | 2019-07-05 | 三峡大学 | A kind of N- mixes-two pyrroles's alkenes optoacoustic developer of porphyrin and its synthetic method |
-
2009
- 2009-10-28 CN CN200910117545A patent/CN101735227A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167704A (en) * | 2011-03-20 | 2011-08-31 | 扬州大学 | Water-soluble porphyrin gold (III) anticancer compounds and preparation method thereof |
| CN102167704B (en) * | 2011-03-20 | 2014-05-14 | 扬州大学 | Water-soluble porphyrin gold (III) anticancer compounds and preparation method thereof |
| CN102417510A (en) * | 2011-09-22 | 2012-04-18 | 西北师范大学 | Conjugated Schiff base Zn (zinc) porphyrin as well as preparation and application thereof |
| CN109970746A (en) * | 2019-04-26 | 2019-07-05 | 三峡大学 | A kind of N- mixes-two pyrroles's alkenes optoacoustic developer of porphyrin and its synthetic method |
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Open date: 20100616 |