CN105884834A - Preparation method of novel Ru(II) complex containing benzoxazole imidazo[1,10]phenanthroline and light cracking activity thereof - Google Patents
Preparation method of novel Ru(II) complex containing benzoxazole imidazo[1,10]phenanthroline and light cracking activity thereof Download PDFInfo
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- CN105884834A CN105884834A CN201410835378.3A CN201410835378A CN105884834A CN 105884834 A CN105884834 A CN 105884834A CN 201410835378 A CN201410835378 A CN 201410835378A CN 105884834 A CN105884834 A CN 105884834A
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Abstract
The invention discloses a preparation method of a novel Ru(II) complex containing benzoxazole imidazo[1,10]phenanthroline. The ruthenium complex is the Ru(II) complex, and 2--benzothiazole-imidazo[5,6-f]o-phenanthroline, 2--benzoxazole-imidazo[5,6-f]o-phenanthroline and 2--benzimidazole-imidazo[5,6-f] o-phenanthroline are adopted as main ligands, and dipyridyl (bpy) is adopted as an auxiliary ligand. The main ligands react with Ru(bpy)2Cl2.H2O respectively, and a product obtained by purifying solids through column chromatography is the Ru(II) complex. The preparation method of the complex is simple, the reaction conditions are mild, and the complex has the good solubility in water. Intermediate reaction products and target products are stable in structure. The synthesized ruthenium complex has the good light cracking activity.
Description
Technical field
The present invention relates to the preparation method of novel Ru (II) coordination compound of a series of imidazo [1,10] phenanthroline containing benzazoles, and the photodestruciton activity of described Ru (II) coordination compound.
Background technology
Chemistry Nuclease be a kind of can the reagent of specific site DNA breakage list double-strand, compared with traditional restricted enzyme, it not only has the specificity of height, and people can be pre-designed out different DNA break sites.Wherein, the operation of photodestruciton reagent is relatively easy, and the fracture of DNA just can occur under the irradiation of ultraviolet or visible ray, has the highest practical value.
Owing to Polypyridine Ru coordination compound and DNA molecular have stronger combination, it is directly inserted in the double-spiral structure of DNA molecular, and such coordination compound is the most stable for oxidant, the most sensitive to light, singlet oxygen can be generated under ultraviolet light or radiation of visible light, so that DNA cracks, thus can be as photodestruciton reagent.
The present invention is main part with 2--benzothiazole-imidazo [5,6-f] o-phenanthroline, 2--benzothiazole-imidazo [5,6-f] o-phenanthroline and 2--benzimidazole-imidazo [5,6-f] o-phenanthroline respectively, the ruthenium compound 1,2,3 that synthesis is corresponding.By changing part, it is possible to affinity, electron transfer direction, substitution reaction speed and the reduction potential between regulation and targeted molecular, it is achieved the activation of photoelectricity.
Summary of the invention
It is an object of the invention to provide a kind of preparation method simple, reaction condition is gentle, easily implements, the intermediate reaction product obtained in preparation process and the target product constitutionally stable Ru as photodestruciton reagent (II) coordination compound.
The one that the present invention provides novel Ru (II) coordination compound containing benzazoles-imidazo [1,10] phenanthroline, its molecular structural formula is:
Technical scheme:
A kind of preparation method containing benzazoles and novel Ru (II) coordination compound of imidazo [1,10] phenanthroline is as follows:
The preparation of ruthenium (II) coordination compound: 2-benzazoles-imidazo 1,10-phenanthroline and cis-two (2,2 '-bipyridyl) dichloro two are hydrated ruthenium (cis-Ru (bpy)2Cl2·2H2O) reaction prepares end product.By the cis-Ru (bpy) of certain mol proportion2Cl2·2H2O and 2-benzazoles-imidazo [5,6-f] o-phenanthroline, adds ethanol in proper amount, water, is heated to reflux under nitrogen protection.Cooling, sucking filtration, it is spin-dried for filtrate, obtains solid, then through column chromatography crystallization and purification, obtaining red solid productivity is 70%.
Whole parts is synthesized by following methods:
(1) 1,10-phenanthroline-5,6-diamidogen and hydroxyacetic acid synthesize 2-hydroxy methylimidazole also [5,6-f] phenanthroline: is dissolved in hydrochloric acid solution by hydroxyacetic acid, is subsequently adding 1,10-phenanthroline-5, and 6-diamidogen is heated to reflux 2h, adds Na2CO3Adjust PH with NaOH, after standing, obtain white solid.Reactant molar ratio is 1.5: 1.
(2) 2-hydroxy methylimidazole also [5,6-f] phenanthroline obtains 2-carboxylic acid imidazo [5,6-f] phenanthroline through potassium permanganate oxidation: 2-hydroxy methylimidazole also [5,6-f] phenanthroline and Na2CO3After dissolving with boiling water, heating, it is slowly added to KMnO4Solution, reaction terminate rear sucking filtration, washing, filtrate with spirit of vinegar neutralize, solid ethyl alcohol recrystallization.
(3) 2-carboxylic acid imidazo [5; 6-f] phenanthroline and 2-amino-3-phenyl substituent/synthesis 2-benzazoles-imidazo [5; 6-f] phenanthroline: under airtight condition; reactant is joined in polyphosphoric acids (PPA); it is heated to 200 DEG C under nitrogen protection, reacts 24h.Thermal response liquid is poured in trash ice, separates out solid, sucking filtration, adjust pH value to 8 with strong aqua ammonia filtrate.By gained solid sucking filtration, successively with water, washing with alcohol, it is vacuum dried to obtain greenish yellow solid.Reactant molar ratio is 1: 1.1.
The present invention's is helpful: Ru (II) coordination compound contains plane aromatic heterocycle, has the highest photodestruciton activity.
Accompanying drawing explanation
Fig. 1: coordination compound and the ultra-violet absorption spectrum of DNA effect
Detailed description of the invention
Embodiment one
(1) synthesis of 2-hydroxy methylimidazole also [5,6-f] phenanthroline
0.456g hydroxyacetic acid (6mmol) is added in 20mL4mol/LHCl, inserts and 100mL there-necked flask is subsequently adding 0.84g 1,10-phenanthroline-5,6-diamidogen (4mmol), it is heated to 100 DEG C of backflow 2h.Filter, add Na2CO3Adjust pH value of solution=5, add 20%NaOH and adjust pH value of solution=7, after standing, separate out white flaky solid 2-hydroxy methylimidazole also [5,6-f] phenanthroline 0.82g.
(2) synthesis of 2-carboxylic acid imidazo [5,6-f] phenanthroline
0.5g 2-hydroxy methylimidazole also [5,6-f] phenanthroline (2mmol) and and 0.30gNa2CO3It is mixed to join in 50ml there-necked flask after dissolving with a small amount of boiling water respectively, after heating in water bath, is slowly added to add the saturated KMnO of 2g4Solution, reacts 3h at 80 DEG C.Use Na2S2O3The KMnO that reaction is superfluous4, it is cooled to room temperature, sucking filtration, removes MnO2Obtaining weak yellow liquid, filtrate neutralizes with spirit of vinegar.Sucking filtration again, is dried, solid ethyl alcohol recrystallization.
(3) synthesis of 2-benzazoles-imidazo [5,6-f] phenanthroline
As a example by synthesizing with 2-[4-morpholinodithio-imidazo [5,6-f] phenanthroline:
By 20ml polyphosphoric acids (PPA); 2-carboxylic acid imidazo [5; 6-f] phenanthroline 1mmol and 2-amino-3-phenylmercaptan. 0.138g (1.1mmol) is added sequentially in 100ml there-necked flask, is heated to 200 DEG C under airtight condition under nitrogen protection, reacts 24h.Reactant liquor is poured into rapidly in 100g trash ice, is sufficiently stirred for Glass rod.A large amount of solid is had to separate out, sucking filtration, filtrate is poured in 150mL water, and adjusts pH value to alkalescence with strong aqua ammonia.Separating out a large amount of solid, sucking filtration, gained solid is successively with water, ethanol, solvent washing, vacuum drying.
(4) synthesis of Ru (II) coordination compound of 2-benzazoles-imidazo [1,10] phenanthroline
As a example by the synthesis of Ru (II) coordination compound 2 of 2-[4-morpholinodithio-imidazo [5,6-f] phenanthroline:
The there-necked flask of 100mL is sequentially added into 0.1g (0.19mmol) cis-Ru (bpy)2Cl2·2H2O, 0.13g 2-[4-morpholinodithio-imidazo [5,6-f] phenanthroline, 25mL ethanol, 4mL water, N2Under protection, heat up and be heated to 80 DEG C, react 24h.Reaction terminates rear filtered while hot, adds the NH that few drops is saturated in filtrate4PF6Aqueous solution, is dried gained red solid sucking filtration after standing a period of time.Drying solid uses column chromatography (neutral alumina column 200～300 mesh, eluent: acetonitrile/toluene=1.5/1).After to be separated, slough solvent and obtain orange-yellow to red solid powder.Powder joins in the small beaker of 25mL, dissolves with a small amount of acetonitrile and obtains solution.This beaker is placed on equipped with in the tool plug wide mouthed bottle of absolute ether.Treat that ether is slowly diffused in acetonitrile precipitation powder solid or acicular crystal.Filtering, discard filtrate, solid absolute ether washs.Solid is vacuum dried, obtains target product.
Embodiment two: coordination compound and the electronic of DNA effect
Coordination compound often results in coordination compound uv-vis spectra generation hypochromic effect with the interaction of DNA, and along with the red shift of absorption spectrum, determines ruthenium complex 1, and 2,3 at acetate buffer (pH=4.5), λirrThe uv-vis spectra of=355nm.Ultraviolet-visible spectrum electrochemistry experiment is to use OTTLE cell to measure at 25.0 ± 0.1 DEG C in acetonitrile.As seen from the figure, compound 3 to 1,2 have more preferable photodestruciton activity.
Claims (3)
- The most a series of Ru (II) coordination compounds with photodestruciton activity, it is characterised in that molecular structural formula is:
- 2. as claimed in claim 1 containing benzazoles and the preparation method of imidazo [1,10] phenanthroline Ru (II) coordination compound, it is special Levy is to comprise the following steps:(1) 1,10-phenanthroline-5,6-diamidogen synthesizes 2-hydroxy methylimidazole also [5,6-f] phenanthroline with hydroxyacetic acid: hydroxyacetic acid is dissolved in salt In acid solution, it is subsequently adding 1,10-phenanthroline-5,6-diamidogen, it is heated to reflux 2h, adds Na2CO3Adjust PH with NaOH, stand After white solid.(2) 2-hydroxy methylimidazole also [5,6-f] phenanthroline obtains 2-carboxylic acid imidazo [5,6-f] phenanthroline through potassium permanganate oxidation: 2-methylol miaow Azoles also [5,6-f] phenanthroline and Na2CO3After dissolving with boiling water, heating, it is slowly added to KMnO4Solution, reaction terminates rear sucking filtration, washes Wash, filtrate neutralizes with spirit of vinegar, solid ethyl alcohol recrystallization.(3) 2-carboxylic acid imidazo [5,6-f] phenanthroline and 2-amino-3-phenyl substituent/synthesis 2-benzazoles-imidazo [5,6-f] phenanthrene are coughed up Quinoline: under airtight condition, joins in polyphosphoric acids (PPA), reacting by heating 24h under nitrogen protection by reactant.Heat is anti- Answer liquid to pour in trash ice, separate out solid, sucking filtration, filtrate is adjusted pH value with strong aqua ammonia.By gained solid sucking filtration, successively with water, Washing with alcohol, is vacuum dried to obtain greenish yellow solid.Reactant molar ratio is 1: 1.1.(4) 2-benzazoles-imidazo [5,6-f] phenanthroline and cis-two (2,2 '-bipyridyl) dichloro two are hydrated Ru (II) and synthesize its ruthenium Coordination compound: with ethanol, water, DMF mixed solution as solvent, is heated to reflux stirring 24h, reactant molar ratio under nitrogen protection It is 2: 1, post layer analysis is recrystallized to give product.
- 3. Ru (II) coordination compound as claimed in claim 1 is as the application of photodestruciton reagent.
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| CN109293703A (en) * | 2018-05-15 | 2019-02-01 | 淮北师范大学 | Compound as DNA decomposition agent |
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| CN109293703A (en) * | 2018-05-15 | 2019-02-01 | 淮北师范大学 | Compound as DNA decomposition agent |
| CN109456364A (en) * | 2018-05-15 | 2019-03-12 | 淮北师范大学 | Compound as DNA decomposition agent |
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