CN109970767A - The four of a kind of sulfur-bearing-sulfide linkage gather big ring trinuclear iron complex and its in-situ synthetic method - Google Patents

The four of a kind of sulfur-bearing-sulfide linkage gather big ring trinuclear iron complex and its in-situ synthetic method Download PDF

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CN109970767A
CN109970767A CN201910324850.XA CN201910324850A CN109970767A CN 109970767 A CN109970767 A CN 109970767A CN 201910324850 A CN201910324850 A CN 201910324850A CN 109970767 A CN109970767 A CN 109970767A
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iron complex
sulfur
sulfide linkage
bearing
big ring
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蒋毅民
王慧
许小陵
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Guangxi Normal University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/02—Local antiseptics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00—Antineoplastic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

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  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
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  • Communicable Diseases (AREA)
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Abstract

What the present invention disclosed a kind of sulfur-bearing-sulfide linkage four gathers big ring trinuclear iron complex and its in-situ synthetic method, the chemical formula of the iron complex are as follows: [Fe3(L1)·5H2O], wherein H8L1The macrocyclic ligand formed for four 3,3 '-two (5- sulfydryl -1,2,4- triazole) by sulphur-sulfide linkage.The in-situ synthetic method of the iron complex includes the following steps: that (1) weighs 0.04-0.05g 3,3 '-two (5- sulfydryl -1,2,4- triazole) and 0.08-0.09g Fe(NO3)39H2O Fe (NO3)3·9H2O is mixed in 8-9 mL dimethylformamide, and reaction 6-7h is stirred at room temperature in mixed liquor；(2) above-mentioned mixed liquor is filtered, filtrate is placed in a beaker, volatilized naturally at room temperature, obtain monocrystalline grade black flaky crystal.Iron complex of the present invention antibacterial, it is antitumor and as drug targeting release in terms of have potential application, this method has wide application prospects in terms of the fabricated in situ of sulfur-bearing-sulfide linkage Macrocyclic metal complex.

Description

The four of a kind of sulfur-bearing-sulfide linkage gather big ring trinuclear iron complex and its in-situ synthetic method
Technical field
The present invention relates to iron complex, the four of specifically a kind of sulfur-bearing-sulfide linkage gather big ring trinuclear iron complex and its original position Synthetic method.
Background technique
Reaction in-situ is one of the hot spot of Coordinative Chemistry research.Though there are much document reports about reaction in-situ at present, But it there are no 3,3 '-two (5- sulfydryl -1,2,4- triazoles) and be oxidized the poly- macrocyclic ligand of generation sulfur-bearing-sulfide linkage four and then shape At the report of trinuclear iron complex.
Sulfur-bearing triazole is widely used in the fields such as medicine, pesticide as intermediate, the cooperation formed with metal ion Object also has preferable antibacterial and anticancer activity.It, can be because in cell when due to reaching tumour cell containing sulphur-sulfide linkage compound A large amount of existing glutathione and the reaction of sulphur-sulfide linkage scission of link occurs, therefore, by 3,3 '-two (5- sulfydryl -1,2,4- triazoles) It is oxidized the carrier that can be used as potential drug targeting release containing sulphur-sulfide linkage macrocyclic complex of generation.
Summary of the invention
In order to obtain new sulfur-bearing-sulfide linkage macrocyclic complex, one aspect of the present invention is to provide a kind of sulfur-bearing-sulfide linkage Four gather big ring trinuclear iron complex, on the other hand also provide with 3,3 '-two (5- sulfydryl -1,2,4- triazole) (H4It L) is raw material The complex in-situ synthetic method.
The four of a kind of sulfur-bearing-sulfide linkage of the present invention gather big ring trinuclear iron complex, chemical formula are as follows: [Fe3(L1)·5H2O], Wherein H8L1The macrocyclic ligand formed for four 3,3 '-two (5- sulfydryl -1,2,4- triazole) by sulphur-sulfide linkage, H8L1Structural formula It is as follows:
。
The four of sulfur-bearing-sulfide linkage of the present invention gather big ring trinuclear iron complex, and crystal belongs to rhombic system,Fdd2 space groups, Z =8, cell parameter are as follows:a=23.464 (2),b=28.246 (3),c=20.3233 (19),α=90.00 °,β= 90.00 °,γ=90.00 °,V = 13470(2) Å3。
The four of sulfur-bearing-sulfide linkage of the present invention gather the in-situ synthetic method of big ring trinuclear iron complex, include the following steps:
(1) 0.04-0.05g 3,3 '-two (5- sulfydryl -1,2,4- triazole) (H is weighed4L) and 0.08-0.09g nine is hydrated nitre Sour iron Fe (NO3)3·9H2Reaction 6-7h is stirred at room temperature in O, the mixing in 8-9 mL dimethylformamide (DMF), mixed liquor；
(2) above-mentioned mixed liquor is filtered, filtrate is placed in a beaker, volatilized naturally at room temperature, obtain monocrystalline grade black flaky Crystal.
During the reaction in-situ that the four of sulfur-bearing-sulfide linkage of the present invention gathers big ring trinuclear iron complex, first wife's body 3,3 '-two (5- sulfydryl -1,2,4- triazole) (H4L) during the reaction by the oxygen and part Fe in air3+It is aoxidized, two sulfydryls It joins end to end, generates four pairs of sulphur-sulfide linkages, by four 3,3 '-two (5- sulfydryl -1,2,4- triazole) (H4L) ligand connects into greatly Ring H8L1, and then and Fe3+And Fe2+Ion coordination generates macrocyclic complex.
The four of sulfur-bearing-sulfide linkage of the present invention gather big ring trinuclear iron complex in antibacterial, antitumor and release as drug targeting Carrier put etc. has potential application, fabricated in situ of this method in sulfur-bearing-sulfide linkage Macrocyclic metal complex Aspect has wide application prospects.
Detailed description of the invention
Fig. 1 is the schematic arrangement that embodiment sulfur-bearing-sulfide linkage four gathers big ring trinuclear iron complex.
Specific embodiment
The content of present invention is further described below with reference to embodiment, but is not limitation of the invention.
Embodiment
The four of a kind of sulfur-bearing-sulfide linkage gather the in-situ synthetic method of big ring trinuclear iron complex, include the following steps:
(1) 0.0400g 3,3 '-two (5- sulfydryl -1,2,4- triazole) (H is weighed4) and 0.0808g Fe(NO3)39H2O Fe L (NO3)3·9H2Reaction 6h is stirred at room temperature in O, the mixing in 8 mL dimethylformamides (DMF), mixed liquor；
(2) above-mentioned mixed liquor is filtered, filtrate is placed in 50 mL beakers, volatilized naturally at room temperature, obtain monocrystalline grade black Flat crystal.
Referring to Fig. 1, embodiment sulfur-bearing-sulfide linkage four gathers the schematic arrangement of big ring trinuclear iron complex, Cong Tuke , it is evident that the complex is a three core iron constructions, by three iron ions [2 Fe(III) and 1 Fe (II)], one big Ring ligand and five water compositions.Wherein Fe1 is coordinated with four N atoms (N1, N4, N7, N12) of macrocyclic ligand constitutes octahedral respectively The equatorial plane of body, the O atom (O1, O2) in water occupy the upper and lower of equatorial plane respectively, form a deformation FeN4O2It is octahedra；And Fe2 respectively with O atom in other four N atom (N9, N11, N9A, N11A) and a water from ligand (O3) it is coordinated, forms the FeN of a deformation4The cubic wimble structure of O, oxygen atom are in the top of tetragonal pyramid.At this point, macrocyclic ligand H8L1In proton all slough, in the form of anion with iron be coordinated；Fe2 in an intermediate position is ferrous ion Fe2+, This may be due to part Fe3+Caused by being restored during the reaction by sulfydryl.
Embodiment sulfur-bearing-sulfide linkage four gathers the crystal structure determination of big ring trinuclear iron complex:
The all proper complex monocrystal of size and shape is selected, is placed on SuperNova single crystal diffractometer, using graphite list Color Mo-KαRadiation (λ= 0.71073 Å).Respectively certain under the conditions of 298 (2) KθIn range withφ-ωScanning side Formula collects point diffraction and is used for structure elucidation and amendment.Non-hydrogen atom is solved with direct method, and to their coordinate and its respectively to different Property thermal parameter corrected with complete matrix least square method.Mixed hydrogenation, hydrogen atom use isotropism thermal parameter；Non-hydrogen atom Using anisotropy thermal parameter.The parsing of crystal structure and structural modifications respectively by SHELX-97 (Sheldrick, 1990) and SHELXL-97 (Sheldrick, 1997) program bag is completed.1 is shown in Table in relation to crystallography and structural modifications data.
The crystallography and structural modifications data of the big ring trinuclear iron complex of table 1

Claims (3)

1. the four of a kind of sulfur-bearing-sulfide linkage gather big ring trinuclear iron complex, it is characterized in that: four change for gathering big ring trinuclear iron complex Formula are as follows: [Fe3(L1)·5H2O], wherein H8L1Pass through sulphur-sulfide linkage shape for four 3,3 '-two (5- sulfydryl -1,2,4- triazole) At macrocyclic ligand.
2. the four of sulfur-bearing-sulfide linkage according to claim 1 gather big ring trinuclear iron complex, it is characterized in that:
Described four gather big ring trinuclear iron complex, and crystal belongs to rhombic system,Fdd2 space groups, Z=8, cell parameter are as follows:a =23.464 (2),b=28.246 (3),c=20.3233 (19),α =90.00 °,β =90.00 °,γ= 90.00 °,V = 13470(2) Å3。
3. the four of sulfur-bearing-sulfide linkage according to claim 1 gather the in-situ synthetic method of big ring trinuclear iron complex, feature It is to include the following steps:
(1) 0.04-0.05g 3,3 '-two (5- sulfydryl -1,2,4- triazole) and 0.08-0.09g Fe(NO3)39H2O Fe is weighed (NO3)3·9H2O is mixed in 8-9 mL dimethylformamide, and reaction 6-7h is stirred at room temperature in mixed liquor；
(2) above-mentioned mixed liquor is filtered, filtrate is placed in a beaker, volatilized naturally at room temperature, obtain monocrystalline grade black flaky Crystal.
CN201910324850.XA 2019-04-22 2019-04-22 The four of a kind of sulfur-bearing-sulfide linkage gather big ring trinuclear iron complex and its in-situ synthetic method Pending CN109970767A (en)

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Application publication date: 20190705