CN106083866B - A kind of phthalocyanine derivates of arginine substitution and its synthetic method and application - Google Patents
A kind of phthalocyanine derivates of arginine substitution and its synthetic method and application Download PDFInfo
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- CN106083866B CN106083866B CN201610534617.0A CN201610534617A CN106083866B CN 106083866 B CN106083866 B CN 106083866B CN 201610534617 A CN201610534617 A CN 201610534617A CN 106083866 B CN106083866 B CN 106083866B
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- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
- A61K41/0076—PDT with expanded (metallo)porphyrins, i.e. having more than 20 ring atoms, e.g. texaphyrins, sapphyrins, hexaphyrins, pentaphyrins, porphocyanines
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Abstract
Phthalocyanine derivates and its synthetic method and its application in photodynamic therapy the invention discloses a kind of substitution of arginine.The phthalocyanine derivates of the arginine substitution have structure shown in following formula.Not only synthetic method is simple for the phthalocyanine derivates of the arginine substitution, without the methylating reagent of toxicity, and positively charged in physiological conditions, active oxygen generation ability is strong, and photosensitive antitumor activity is good, and dark toxicity is low, has good photodynamic therapy application prospect.
Description
Technical field
The invention belongs to the photosensitizer technical field with photodynamic activity, it is related to a kind of phthalocyanine derivates, particularly relates to
And phthalocyanine derivates and its synthetic method and the application in photodynamic therapy of a kind of arginine substitution.
Background technology
Photodynamic therapy (photodynamic therapy, abbreviation PDT) is also known as photosensitization therapy, photochemotherapy, is near
A kind of a little novel methods using photochemical reaction treatment tumour to grow up in year.Its therapeutic process is as follows：Photosensitizer passes through
Injection enters patient's body, and by blood-transmitted, and after metabolism after a while, the retention of photosensitizer selectivity is in disease
Become in tissue.Then, lesion tissue is irradiated with the light to match with photosensitizer wavelength, photosensitizer issues the third contact of a total solar or lunar eclipse in the participation of oxygen and moves
Power is reacted, so that playing curative effect finally kills tumour cell.PDT can be used for the treatment of a variety of diseases.With traditional operation, change
The methods for the treatment of, radiotherapy, is compared, and PDT is small with toxic side effect, and high selectivity, postoperative complications are few, repetitive treatment, low drug resistance etc.
Feature.Therefore, PDT is considered as a kind of method of preferably treatment tumour and has been to be concerned by more and more people.
PDT includes three fundamentals：Light source, oxygen and photosensitizer.Wherein with to treatment light source progress of research and
The problem of development of oxygenerating technology, light source and oxygen during optical dynamic therapy, is resolved to a certain extent.Phase
Although there has also been very big progress and development than the key element photosensitizer in light and oxygen, PDT, but still face many problems and
Challenge, therefore, the research of photosensitizer become the hot spot of current PDT researchs.
Preferable Phthalocyanines available for PDT should possess preferable water solubility, excellent security (dark toxicity), light
Quick active and certain tumor-targeting.With reference to reported in literature it can be found that：The phthalocyanine of positively charged has water solubility in aqueous solution
Well, easily by tumour cell intake and good photosensitive antitumor activity the advantages that.However, the phthalocyanine of general positively charged is quaternary ammonium salt shape
Formula, its preparation process needs to use the methylating reagent (such as iodomethane) of severe toxicity, and the quaternary ammonium salt phthalocyanine prepared is thin to tumour
Born of the same parents do not have targeting yet.The amino phthalocyanine of protonation also positively charged in water, preparation process is relatively easy, the methyl without toxicity
Change reagent, but its charging property is very easy to be influenced by pH, and deprotonation is easy under physiological environment, and to tumor group
Knit also without specific target tropism.
Guanidine, also referred to as carbotriamine, are made of three amino and a carbon atom, are that one kind is widely present in the organic of nature
Strong alkali compound.The aqueous solution PKa values of guanidine are up to 13.5, this causes it to keep electropositive in the range of very wide pH.Remove
Go outside These characteristics, guanidine compound also has the advantages that itself small toxicity, stability height and good physiological activity, therefore extensive
Applied to fields such as pharmacy, molecular recognition and sterilizations.In numerous applications, application of the guanidine compound in antitumor drug is outstanding
Its is noticeable.The introducing of guanidine radicals is mainly used for increasing the activity of antitumor drug, cell to the uptake ratio and tumor target of medicine
Tropism.
The content of the invention
Phthalocyanine derivates the object of the present invention is to provide a kind of substitution of arginine and preparation method thereof.The phthalocyanine spreads out
Biological positively charged in physiological conditions, photosensitive antitumor activity is good, and its preparation method is simple, the examination that methylates without toxicity
Agent, has good photodynamic therapy application prospect.
The phthalocyanine derivates that another object of the present invention also resides in the substitution of the arginine described in providing are being made as photosensitizer
Application in standby photo-dynamical medicine.
For achieving the above object, the present invention uses following technical scheme：
A kind of phthalocyanine derivates of arginine substitution, its structural formula are as follows：
In formula,M=Zn, Fe, Co or Cu.
The phthalocyanine derivates of the arginine substitution are prepared using following methods, are included the following steps：
(1) under basic catalyst catalytic condition, 4- nitrophthalonitriles are reacted with 4-HBA, obtain adjacent benzene two
Nitrile intermediate 1；
(2) under metal salt existence condition, phthalic nitrile intermediate 1 carries out cyclization using DBU catalysis, obtains carboxylic acid and takes
The phthalocyanine 2 in generation；
(3) with 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) and 1- hydroxy benzos
Triazole (HOBT) is condensing agent, and phthalocyanine and the arginine ethyl ester hydrochloride of the carboxylic acid-substituted that step (2) obtains carry out acid amide condensation
Reaction, obtains the phthalocyanine derivates of the arginine substitution.
By taking the ZnPc (ArgZnPc) of arginine substitution as an example, the reaction process of the method is shown below：
In aforementioned preparation process, the DBU is 1,8- diazabicylos, 11 carbon -7- alkene；
The basic catalyst is organic alkali catalyst or inorganic base catalyst, and wherein organic alkali catalyst is preferably three
Ethamine, inorganic base catalyst are preferably K2CO3Or LiOH etc.；
The metal salt preferably is selected from Zn (Ac)2、ZnCl2、CoCl2、Cu(Ac)2Or FeCl2Deng.
More specifically, in the above method,
The reaction condition of step (1) is：4- nitrophthalonitriles and 4-HBA and mole of basic catalyst
Than for 1:1~4:1~5, solvent is preferably n,N-Dimethylformamide (DMF), and protective atmosphere is preferably nitrogen；Reaction temperature is
20-100℃。
The reaction condition of step (2) is：Metal salt is 1 with the molar ratio of phthalic nitrile intermediate 1 and DBU:1~4:1~
5, solvent is preferably n-amyl alcohol, and protective atmosphere is preferably nitrogen；Temperature is 100~160 DEG C.
The reaction condition of step (3) is：The phthalocyanine of carboxylic acid-substituted and the molar ratio of arginine ethyl ester hydrochloride are 1:1~
15, the phthalocyanine of carboxylic acid-substituted is 1 with the molar ratio of EDCHCl and HOBT:1~14:1~15, solvent is preferably DMF, reaction temperature
Spend for 0~30 DEG C.
The phthalocyanine derivates of arginine substitution according to the present invention, include arginine structure in its structure, in physiological condition
Lower positively charged, and photosensitive antitumor activity is good, it is strong that active oxygen produces ability.Arginine is a kind of basic amino acid containing guanidine radicals,
Its PKa value is about 12.48, positively charged in neutral and alkaline conditions.In addition to there is guanidine compound, essence
Propylhomoserin also has many oneself unique properties and function., can be with as arginine has critically important immune related antitumor properties
The chemical conversion for preventing carcinogenic compound (7,12- dimethylanthracenes, N-methyl-N-nitrosourea etc.) from inducing；Oxygen can also be passed through
Change approach generates the NO of bioactivity, so as to play cytotoxicity, inducing apoptosis of tumour cell, suppress tumour cell stick and
Propagation.
By taking ArgZnPc as an example, zeta current potentials are as shown in Figure 1 in different PH.Medicine dark toxicity, reactive oxygen species produce
Ability and anti tumor activity in vitro difference are as shown in Figure 2,3, 4.Show the phthalocyanine derivates active oxygen of the arginine substitution
Generation ability is strong, and photosensitive antitumor activity is good, and dark toxicity is low.
Thus, the phthalocyanine derivates substituted the invention further relates to foregoing arginine are preparing light power medicine as photosensitizer
Applied in thing.
Beneficial effect：The present invention designs and synthesizes a kind of phthalocyanine derivates of arginine substitution, will as the core in PDT
Plain photosensitizer, not only synthetic method is simple for the phthalocyanine derivates, without the methylating reagent of toxicity, and in physiological conditions
Positively charged, active oxygen generation ability is strong, and photosensitive antitumor activity is good and dark toxicity is low, before having good photodynamic therapy application
Scape.Specifically, the phthalocyanine derivates of arginine of the invention substitution have following advantages：
(1) the phthalocyanine derivates active oxygen generation ability of the arginine substitution obtained by is strong, in physiological conditions positively charged.
(2) methylating reagent of the phthalocyanine derivates of the arginine substitution obtained by without toxicity.
(3) In vitro cell experiment shows, the phthalocyanine derivates of obtained arginine substitution have good extracorporeal anti-tumor
Activity, and dark toxicity is low.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, described in detail below with presently preferred embodiments of the present invention as after.But in embodiment
Described content does not form limiting the scope of the invention, and protection scope of the present invention is limited by claim
It is fixed.
Brief description of the drawings
Fig. 1 is the zeta current potentials of ArgZnPc prepared by embodiment 1 under different pH.
Fig. 2 is the dark toxicity of ArgZnPc and unsubstituted ZnPc under different pharmaceutical concentration.As seen from the figure, ArgZnPc is showed
Go out very low dark toxicity.
Fig. 3 is the active oxygen comparison diagrams of ArgZnPc in the cell.A figures are the cell controls picture of not dosing, and c figures are not
The Fluorescencecontro picture of dosing, b figures be add medicine after photodynamic therapy effect under cellular damage picture, d figures be addition medicine
Cell produces active oxygen fluorescence picture after thing, and as seen from the figure, ArgZnPc shows the reactive oxygen species yield of higher, in advance
Show that it has very high antitumor activity.
Fig. 4 is the anti tumor activity in vitro of ArgZnPc and unsubstituted ZnPc under different pharmaceutical concentration.As seen from the figure,
ArgZnPc shows very high antitumor activity.
Embodiment
In following embodiments, DBU 1,11 carbon -7- alkene of 8- diazabicylos.Basic catalyst uses inorganic base such as
K2CO3, LiCO3, Na2CO3Deng and organic base such as triethylamine etc., metal salt can use Zn (Ac)2、ZnCl2、CoCl2、Cu(Ac)2With
FeCl2Deng.The preparation of empty core phthalocyanine is not added with metal salt, and other conditions are identical.
Embodiment 1
(1) under nitrogen protection, 4- nitrophthalonitriles, 4-HBA and basic catalyst in molar ratio 1:1:2
Stirring reaction, using DMF as solvent, reacts 6h at 40 DEG C, obtains phthalic nitrile intermediate 1；
(2) under nitrogen protection, using n-amyl alcohol as solvent, Zn (OAc)2, phthalonitrile intermediate 1 and DBU molar ratio
For 1:2:3；120 DEG C~140 DEG C, reaction time 24h of reaction temperature, vacuum distillation removing is molten after reaction solution is cooled to room temperature
Agent.Solid KOH aqueous dissolutions, 6h postcoolings are handled under heated reflux condition to room temperature.Filter cake is collected by filtration.Filter cake is used again
Alkali soluble solution, is filtered to remove undissolved part.Filtrate tune pH separates out product for acidity.So collect solid afterwards in triplicate.
Obtained solid is washed successively with redistilled water and acetone, be dried in vacuo blue solid be carboxylic acid-substituted phthalocyanine
(CbZnPc)。
(3) CbZnPc, EDCHCl and HOBT are with molar ratio 1：9：10 dissolved with DMF after stirring at normal temperature reaction 1h.Frozen water
Under bath, above-mentioned solution constant pressure is instilled and (ties up acid with the L-arginine ethyl ester hydrochloride and n,N-diisopropylethylamine of DMF dissolvings
Agent) in, the molar ratio of CbZnPc, L-arginine ethyl ester hydrochloride and n,N-diisopropylethylamine are 1：10：2,0 after completion of dropwise addition
The reaction was continued at DEG C 1h.Above-mentioned reaction solution is poured into CH2Cl2In, obtained solid is dissolved with acid water, and insoluble part discards；Dissolving
Part NaOH solution tune pH to 12 or so, separates out product.Repeat to adjust soda acid three times by above-mentioned steps, last obtained solid is used
Alkaline water and acetone wash successively, are dried in vacuo to obtain dark green solid 2,9 (10), 16 (17), 23 (24)-four-(4- ((arginine
Ethoxycarbonyl) formamido) phenoxy group) Phthalocyanine Zinc (ArgZnPc).
Infrared and nucleus magnetic hydrogen spectrum data IR (KBr, the cm of products therefrom ArgZnPc-1):3399,1730 (ROC=O), 1650
(C=O), 1486,1228,1090.1H NMR(400MHz,DMSO-d6):δ (ppm) 9.22 (d, 4H, J=22.0Hz, CONH),
8.78-8.91(m,8H,H of guanidino),8.09-8.17(m,8H,ArH),7.79-7.92(m,8H,ArH),6.92-
7.54(m,12H,PcH),4.47(s,4H,CH),4.13-4.19(m,8H,CH2),3.17(s,8H,CH2), 1.89 (t, 8H, J=
7.4Hz,CH2), 1.65 (d, 8H, J=6.0Hz, CH2),1.20-1.26(m,12H,CH3).
Zeta current potentials of the ArgZnPc of preparation under different pH is as shown in Figure 1.The result shows that ArgZnPc due to carboxyl
Into ester, containing only guanidine radicals in molecule, therefore the equal positively charged in the range of pH=5-9, it is also positive electricity under physiological environment to show it
Property.Embodiment 2
(1) under nitrogen protection, 4- nitrophthalonitriles, 4-HBA and basic catalyst in molar ratio 1:3:4
Stirring reaction, using DMF as solvent, reacts 6h at 40 DEG C, obtains phthalic nitrile intermediate 1；
(2) under nitrogen protection, using n-amyl alcohol as solvent, Cu (Ac)2, phthalonitrile intermediate 1 and DBU molar ratio be
1:2:4；120 DEG C~140 DEG C, reaction time 24h of reaction temperature, vacuum distillation removing solvent after reaction solution is cooled to room temperature.
Solid KOH aqueous dissolutions, 6h postcoolings are handled under heated reflux condition to room temperature.Filter cake is collected by filtration.Filter cake uses alkali again
Dissolving, is filtered to remove undissolved part.Filtrate tune pH is to be acid so that product separates out.So collect solid afterwards in triplicate.
Obtained solid is washed successively with redistilled water and acetone, be dried in vacuo blue solid carboxylic acid-substituted phthalocyanine Cb Cu
Pc。
(3) Cb Cu Pc, EDCHCl and HOBT are with molar ratio 1：5：10 dissolved with DMF after stirring at normal temperature reaction 1h.Ice
Under water-bath, above-mentioned solution constant pressure is instilled in L-arginine ethyl ester hydrochloride and n,N-diisopropylethylamine with DMF dissolvings and (is tied up
Sour agent), the molar ratio of Cb Cu Pc, L-arginine ethyl ester hydrochloride and n,N-diisopropylethylamine are 1：9：2, after completion of dropwise addition
The reaction was continued at 0 DEG C 1h.Above-mentioned reaction solution is poured into CH2Cl2In, obtained solid is dissolved with acid water, and insoluble part discards；It is molten
Solution part NaOH solution tune pH to 12 or so, separates out product.Repeat to adjust soda acid three times by above-mentioned steps, last obtained solid
Washed successively with alkaline water and acetone, be dried in vacuo solid arginine substitution phthalocyanine derivates.
Technical scheme is described in detail in above-described embodiment, it should be understood that more than
Described is only presently preferred embodiments of the present invention, is not intended to limit the invention, any person skilled in the art, is not taking off
In the range of technical solution of the present invention, when the technology contents using the disclosure above make few modifications or are modified to equivalent variations
Equivalent embodiment, still, all any modification or improvement for being made etc. in the spirit of the present invention, should be included in this hair
Within the scope of bright.
Claims (8)
1. a kind of phthalocyanine derivates of arginine substitution, it is characterised in that the general structure of the phthalocyanine derivates is as follows：
Wherein,M=Zn, Co, Fe or Cu.
A kind of 2. preparation method of the phthalocyanine derivates of the arginine substitution described in claim 1, it is characterised in that the system
Preparation Method includes the following steps：
(1) under basic catalyst catalytic condition, 4- nitrophthalonitriles are reacted with 4-HBA, are obtained in phthalic nitrile
Mesosome 1；
(2) metal salt Zn (Ac)2、ZnCl2、CoCl2、Cu(Ac)2Or FeCl2Under existence condition, phthalic nitrile intermediate 1 uses
DBU catalysis carries out cyclization, obtains the phthalocyanine 2 of carboxylic acid-substituted；
(3) using 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate and I-hydroxybenzotriazole as condensing agent, step
Suddenly the phthalocyanine 2 for the carboxylic acid-substituted that (2) obtain carries out acid amide condensation reaction with arginine ethyl ester hydrochloride, obtains the arginine
Substituted phthalocyanine derivates.
3. the preparation method of the phthalocyanine derivates of arginine substitution according to claim 2, it is characterised in that the alkali
Property catalyst is inorganic base catalyst or organic alkali catalyst.
4. the preparation method of the phthalocyanine derivates of arginine substitution according to claim 3, it is characterised in that the alkali
Property catalyst for triethylamine, K2CO3Or LiOH.
5. the preparation method of the phthalocyanine derivates of arginine substitution according to claim 2, it is characterised in that step (1)
In, 4- nitrophthalonitriles are 1: 1~4: 1~5 with the molar ratio of 4-HBA and basic catalyst, solvent N, N-
Dimethylformamide, protective atmosphere are nitrogen；Reaction temperature is 20-100 DEG C.
6. the preparation method of the phthalocyanine derivates of arginine substitution according to claim 2, it is characterised in that step (2)
In, metal salt is 1: 1~4: 1~5 with the molar ratio of phthalic nitrile intermediate 1 and DBU, and solvent is n-amyl alcohol, and protective atmosphere is
Nitrogen；Temperature is 100~160 DEG C.
7. the preparation method of the phthalocyanine derivates of arginine substitution according to claim 2, it is characterised in that step (3)
In, the phthalocyanine 2 of carboxylic acid-substituted is 1: 1~15 with the molar ratio of arginine ethyl ester hydrochloride, phthalocyanine 2 and the 1- second of carboxylic acid-substituted
The molar ratio of base-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate and I-hydroxybenzotriazole is 1: 1~14: 1~15,
Solvent is DMF, and reaction temperature is 0~30 DEG C.
8. the phthalocyanine derivates of the arginine substitution described in claim 1 are applied as photosensitizer in photo-dynamical medicine is prepared.
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| CN108658995B (en) * | 2018-05-29 | 2020-05-05 | 南京师范大学 | Zinc phthalocyanine modified by dipyridyl disulfide and preparation method and application thereof |
| CN112480377B (en) * | 2020-12-01 | 2021-09-28 | 山西大学 | Preparation method and application of conjugated polymer with arginine as side chain |
| CN113880849B (en) * | 2021-08-31 | 2022-12-16 | 南京师范大学 | Chiral lysine modified zinc phthalocyanine and preparation method and application thereof |
| CN113717183B (en) * | 2021-09-27 | 2023-03-31 | 福州大学 | Phthalocyanine modified by pericyclic asymmetric arginine, preparation thereof and application thereof in pharmaceutical field |
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