CN109134551A - Water-soluble iron carbonyl complex and its preparation method and application - Google Patents
Water-soluble iron carbonyl complex and its preparation method and application Download PDFInfo
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- CN109134551A CN109134551A CN201810621364.XA CN201810621364A CN109134551A CN 109134551 A CN109134551 A CN 109134551A CN 201810621364 A CN201810621364 A CN 201810621364A CN 109134551 A CN109134551 A CN 109134551A
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- water
- soluble iron
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- carbonyl complex
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
Abstract
The invention discloses a kind of water-soluble iron carbonyl complex, structural formula is as follows:The compounds of this invention has good water-soluble and appropriateness stability, speculates that the product that it is degraded has good bio-compatibility from compound structure, or toxicity harmless to body is smaller, and the opportunity for discharging carbon monoxide is controllable.Meanwhile the synthetic method of compound involved by the invention, there is universality, the compound containing single sulfydryl (HS-R) under alkaline condition, can react to obtain similar [CpFe (CO) with iodo Dan Maotie2(SR)] the dicarbapentaborane list cyclopentadienyl iron compound of structure.
Description
Technical field
The present invention relates to iron carbonyl complex fields.It is more particularly related to a kind of water-soluble iron carbonyl class
Compound and its preparation method and application.
Background technique
Carbon monoxide (CO) is a kind of well-known poisonous gas, is often known as " noiseless killer ".CO can lead to
It crosses breathing to enter in human body by lung, in conjunction with the hemoglobin in blood, forms carbonyl haemoglobin.Since it is to blood red
The binding force of albumen is much higher than oxygen to (about 230 times, it is suppressed that O_2 transport is into red blood cell, tissue of binding force of hemoglobin
The oxygen of generation is insufficient, eventually results in body death.It can be seen that being directly sucked in CO gas is danger close: at the same it is a small amount of
Carbon monoxide be very important for the human body.Research shows that CO is a kind of important messenger molecule in body, in pathology
A large amount of defense mechanism is taken part under physiological condition.There is vasodilator and bronchial smooth muscle in vivo, inhibit blood small
Plate aggregation inhibits a variety of physiological roles such as inflammatory reaction, anti-oxidant, anti-apoptotic, antiproliferative；It is raw in nerve, breathing, circulation etc.
During cut and inhibit acute lung injury, internal organs ischemical reperfusion injury, also hair in the pathologic processes such as organ transplant rejection
Wave important regulative.
Use the metal complex containing CO that CO is sent to relevant organism position, scene release carbon monoxide point as CO carrier
Son, i.e., so-called carbon monoxide emitter (carbon monoxide-releasing molecules, CORM).It is most of
CORM is transition metal carbonyl compound.Transition metal carbonyl compound is a big metalloid-organic compound, appropriate
Under the conditions of can lead to leaving away for carbonyl (CO), such as illumination, substitution reaction, redox induction.It is mentioned with CORM through local application
It had both been not necessarily to for CO by organism metabolism process, without through respiratory system；Dosage size, medication time and rate of release are easy control
System, at the same it is also safer relative to CO is directly sucked in.But CO releasing agent water solubility, stability at present on the market is all bad,
Therefore it needs to develop a kind of water-soluble and all preferable CO releasing agent of stability.
Summary of the invention
The present invention provides a kind of water-soluble iron carbonyl complex, can releasable carbon monoxide.The compound has good
The stability of water solubility and appropriateness well, reacting related metal ion and organic ligand also all has good bio-compatible
Property, the residual substance after discharging CO is harmless to body or toxicity is smaller.
In order to achieve the goal above, the present invention provides a kind of water-soluble iron carbonyl complex, structural formula is as follows:
A kind of preparation method of the water-soluble iron carbonyl complex, comprising the following steps:
With CpFe (CO)2I (Cp=η5-C5H5), mercaptoethylmaine or Tiopronin be raw material, carry out substitution reaction, obtain mesh
Mark product.
Preferably, the preparation method of the water-soluble iron carbonyl complex, by CpFe (CO)2I (Cp=η5-
C5H5) and mercaptoethylmaine be dissolved in organic solvent and deionized water respectively, mercaptoethylmaine aqueous solution is added dropwise to dissolved with CpFe
(CO)2I (Cp=η5-C5H5) organic solution in, react, detected with infrared spectroscopy to CpFe (CO) under room temperature2I (Cp=
η5-C5H5) disappearing stops reaction, it isolates and purifies and the compound Fe is made1。
Preferably, the preparation method of the water-soluble iron carbonyl complex, by CpFe (CO)2I (Cp=η5-
C5H5) and Tiopronin be dissolved in organic solvent and deionized water respectively, Tiopronin aqueous solution is added dropwise to CpFe
(CO)2I (Cp=η5-C5H5) organic solution in and thereto be added triethylamine (NEt3), it reacts under room temperature, uses infrared light
Spectrum is detected to CpFe (CO)2I (Cp=η5-C5H5) disappearing stops reaction, it isolates and purifies and the compound Fe is made2。
Preferably, the preparation method of the water-soluble iron carbonyl complex, CpFe (CO)2I and mercaptoethylmaine
Molar ratio is 1:2~1:3.
Preferably, the preparation method of the water-soluble iron carbonyl complex, CpFe (CO)2I and mercaptoethylmaine and
The molar ratio of triethylamine is 1:2:2~1:3:3.
Preferably, the preparation method of the water-soluble iron carbonyl complex, reaction time are 3~5 hours；It is organic
Solvent is methanol.
Application of the water-soluble iron carbonyl complex in photoinduction release CO a kind of described in.
Preferably, application of the water-soluble iron carbonyl complex in photoinduction release CO, concrete operations step
It is rapid:
By the compound Fe1Or Fe2It is dissolved in 3mL physiological saline, is induced with the blue light that wavelength is 470-475nm
Release.
Preferably, application of the water-soluble iron carbonyl complex in photoinduction release CO, physiological saline are matched
During system, distilled water is replaced to prepare with deuterium-oxide；And the compound Fe1Or Fe2The concentration being dissolved in physiological saline is
0.013mol/L。
The present invention is include at least the following beneficial effects:
(1) compound has preferable water-soluble and appropriateness stability；
(2) metal ion and organic ligand involved in the compound have good bio-compatibility；
(3) opportunity of compound release carbon monoxide is easily-controllable.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Detailed description of the invention
Fig. 1 is compound Fe1Reacting flow chart；
Fig. 2 is compound Fe2Reacting flow chart；
Fig. 3 is compound Fe1And Fe2Infrared spectrogram；
Fig. 4 is compound Fe1Hydrogen nuclear magnetic resonance spectrogram；
Fig. 5 is compound Fe2Hydrogen nuclear magnetic resonance spectrogram；
Fig. 6 compound Fe1It degrades and schemes under blue light illumination in physiological saline；
Fig. 7 compound Fe1The relational graph of ln A and time t in degradation process；
Fig. 8 compound Fe2It degrades and schemes under blue light illumination in physiological saline；
Fig. 9 compound Fe2The relational graph of ln A and time t in degradation process.
Specific embodiment
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art referring to specification text
Word can be implemented accordingly.
One, the preparation of compound
As described in Figure 1, in 30mL methanol (CH3OH 303mg CpFe (CO) is added in)2I is added in 2mL deionized water
154.30mg mercaptoethylmaine, aqueous solution is added dropwise in methanol solution, reacts at room temperature 5h, obtains red solution, and rotation is steamed
Hair removes solvent (methanol and deionized water) therein, is then separated with silicagel column, eluant, eluent is ethyl acetate: methanol=
1:1.Pure Red oil substance is finally made, is temporarily named as compound Fe1
As described in Figure 2, in 30mL methanol (CH3OH 303mg CpFe (CO) is added in)2I is added in 2mL deionized water
326.38mg Tiopronin and 250 μ L triethylamine (NEt3), aqueous solution is added dropwise in methanol solution, 4h is reacted at room temperature,
Red solution is obtained, rotary evaporation removes solvent (methanol and deionized water) therein, then separated with silicagel column, elutes
Agent is ethyl acetate: methanol=1:1.Pure Red oil substance is finally made, is temporarily named as compound Fe2
The two compounds Fe1And Fe2Liquid it is infrared as shown in figure 3, wherein the stretching vibration of carbonyl (C ≡ O) be such
The characteristic absorption peak of compound, therefore in 2033cm-1And 1985cm-1Peak be compound Fe1In two carbonyls (C ≡ O) it is flexible
Vibration peak, in 2038cm-1And 1991cm-1Peak be compound Fe2In two carbonyls (C ≡ O) stretching vibration peak.Simultaneously because
The difference of the electron supplying capacity of group SR leads to the movement of the stretching vibration peak of carbonyl (C ≡ O).
Compound Fe1Nuclear-magnetism H spectrum as shown in figure 4, chemical shift δ=5.17ppm the unimodal luxuriant ring (Cp) of belonging to
Hydrogen (5H), the triplet of 2.99ppm belong to NCH2Hydrogen, the triplet of 2.32ppm belongs to SCH2Hydrogen.
Compound Fe2Nuclear-magnetism H spectrum as shown in figure 5, chemical shift δ=5.16ppm the unimodal luxuriant ring (Cp) of belonging to
Hydrogen (5H), the singlet of 3.79ppm belong to NCH2Hydrogen, the multiplet of 3.29-3.30ppm belongs to the hydrogen of SCH, 2.82-
The double peak of 2.84ppm belongs to the hydrogen of NH, and the double peak of 1.29-1.41ppm belongs to CH3Hydrogen.
Two, it applies
Compound Fe1And Fe2, it is with good stability under the conditions of dark and natural light, thus select blue light to its into
Row photoinduction CO release.
By the compound Fe of preparation1(10.1mg, 0.04mmol) is added in 3mL physiological saline, and reaction tube is added after dissolution
In, with the blue light illumination normal saline solution at 37 DEG C, primary infrared (Varian Scimitar is surveyed at regular intervals
600)。
If Fig. 6 is compound Fe1Degradation process, from figure it can be found that the compound two carbonyl peaks in 2040cm-1And 1991cm-1Place, as the irradiation time increases, carbonyl peak is constantly in attenuation process, and the position of carbonyl peak does not have
It migrates.It can speculate that compound CO release process is fairly simple, be not in other iron molybdenum cofactor intermediates.Than
It is easier to study its releasing mechanism, to instruct it in application pharmaceutically.
By to 2040cm-1Locate the infared spectrum data analysis of carbonyl peak, we obtain the releasing mechanism category of the compound
In first order kinetics process, its reaction rate constant is obtained as shown in Figure 7 and half-life period is respectively k=0.0415min-1, partly decline
Phase t1/2=16.7min.
By the compound Fe of preparation2(13.5mg, 0.04mmol) is added in 3mL physiological saline, and reaction tube is added after dissolution
In, with the blue light illumination normal saline solution at 37 DEG C, primary infrared (Varian Scimitar is surveyed at regular intervals
600)。
If Fig. 8 is compound Fe2Degradation process, from figure it can be found that the compound two carbonyl peaks in 2038cm-1And 1990cm-1Place, with compound Fe1Similar, as the irradiation time increases, carbonyl peak is constantly in attenuation process, and carbonyl
There is no migrations for the position of base peak.To 2038cm-1Locate the infared spectrum data analysis of carbonyl peak, we obtain the compound
Releasing mechanism also belongs to first order kinetics process, as shown in figure 9, obtaining its reaction rate constant and half-life period is respectively k=
0.0462min-1, half-life period t1/2=15.0min.
To compound Fe1And Fe2Induced by Blue Light release data it can be concluded that, ln A and time t have preferable linear close
System, the release of such compound belongs to first-order kinetics, and the carbonyl release of both compounds under blue light is dynamic
Mechanics rate is close to identical.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (10)
1. a kind of water-soluble iron carbonyl complex, which is characterized in that structural formula is as follows:
Fe1R=CH2CH2NH2
Fe2R=CH (CH3)CONHCH2COOH。
2. a kind of preparation method of water-soluble iron carbonyl complex as described in claim 1, which is characterized in that including following
Step:
With CpFe (CO)2I (Cp=η5-C5H5), mercaptoethylmaine or Tiopronin be raw material, carry out substitution reaction, obtain target production
Object.
3. the preparation method of water-soluble iron carbonyl complex as claimed in claim 2, which is characterized in that by CpFe (CO)2I
(Cp=η5-C5H5) and mercaptoethylmaine be dissolved in organic solvent and deionized water respectively, mercaptoethylmaine aqueous solution is added dropwise to
Dissolved with CpFe (CO)2I (Cp=η5-C5H5) organic solution in, react, detected with infrared spectroscopy to CpFe under room temperature
(CO)2I (Cp=η5-C5H5) disappearing stops reaction, it isolates and purifies to obtain the compound Fe1。
4. the preparation method of water-soluble iron carbonyl complex as claimed in claim 2, which is characterized in that by CpFe (CO)2I
(Cp=η5-C5H5) and Tiopronin be dissolved in organic solvent and deionized water respectively, Tiopronin aqueous solution is added dropwise to
CpFe(CO)2I (Cp=η5-C5H5) organic solution in and thereto be added triethylamine (NEt3), it reacts under room temperature, use is red
External spectrum is detected to CpFe (CO)2I (Cp=η5-C5H5) disappearing stops reaction, it isolates and purifies to obtain the compound Fe2。
5. the preparation method of water-soluble iron carbonyl complex as claimed in claim 2, which is characterized in that CpFe (CO)2I and
The molar ratio of mercaptoethylmaine is 1:2~1:3.
6. the preparation method of water-soluble iron carbonyl complex as claimed in claim 3, which is characterized in that CpFe (CO)2I and
The molar ratio of mercaptoethylmaine and triethylamine is 1:2:2~1:3:3.
7. the preparation method of water-soluble iron carbonyl complex as described in claim 3 or 4, which is characterized in that the reaction time
It is 3~5 hours；Organic solvent is methanol.
8. a kind of application of water-soluble iron carbonyl complex as described in claim 1 in photoinduction release CO.
9. application of the water-soluble iron carbonyl complex as claimed in claim 8 in photoinduction release CO, which is characterized in that
Concrete operation step:
By the compound Fe1Or Fe2It is dissolved in physiological saline, carries out induction release with the blue light that wavelength is 470-475nm.
10. application of the water-soluble iron carbonyl complex as claimed in claim 9 in photoinduction release CO, feature exist
In, during normal saline, with deuterium-oxide replace distilled water prepare；
And the compound Fe1Or Fe2The concentration being dissolved in physiological saline is 0.013mol/L.
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Cited By (2)
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| CN112920225A (en) * | 2021-01-26 | 2021-06-08 | 嘉兴学院 | Water-soluble iron carbonyl compound containing sulfonate, and preparation method and application thereof |
| CN115010939A (en) * | 2022-04-22 | 2022-09-06 | 深圳先进技术研究院 | Carbonyl iron carrier responding to release of carbon monoxide and preparation method and application thereof |
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| CN102850403A (en) * | 2012-05-29 | 2013-01-02 | 嘉兴学院 | Water-soluble iron carbonyl compound, and preparation method and application thereof |
| CN104814952A (en) * | 2015-04-16 | 2015-08-05 | 嘉兴学院 | Method for promoting carbon monoxide release of carbon monoxide-releasing molecules and preventing sedimentation |
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| ROBERT KRETSCHMER ET AL.: "Dicarbonyl-bis(cysteamine)iron(II): A light induced carbon monoxide releasing molecule based on iron(CORM-S1)", 《JOURNAL OF INORGANIC BIOCHEMISTRY》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920225A (en) * | 2021-01-26 | 2021-06-08 | 嘉兴学院 | Water-soluble iron carbonyl compound containing sulfonate, and preparation method and application thereof |
| CN112920225B (en) * | 2021-01-26 | 2024-04-12 | 嘉兴学院 | Sulfonate-containing water-soluble iron carbonyl compound and preparation method and application thereof |
| CN115010939A (en) * | 2022-04-22 | 2022-09-06 | 深圳先进技术研究院 | Carbonyl iron carrier responding to release of carbon monoxide and preparation method and application thereof |
| CN115010939B (en) * | 2022-04-22 | 2023-04-28 | 深圳先进技术研究院 | Carbonyl siderophore capable of responding to release of carbon monoxide and preparation method and application thereof |
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