CN103833791A - Microwave-assisted preparation method for polypyridyl ruthenium (II) complex - Google Patents
Microwave-assisted preparation method for polypyridyl ruthenium (II) complex Download PDFInfo
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Abstract
The invention relates to a microwave-assisted preparation method for a polypyridyl ruthenium (II) complex. The polypyridyl ruthenium (II) complex has a composition formula as [Ru(L)2HAIP].(PF6)2, wherein HAIP is 1, 8-dihydroxyl-9, 10-anthraquinone imidazole[4, 5-f][1, 10]phenanthroline, and L is bpy or phen. The preparation method comprises the steps of: a): synthesizing HAIP by reacting o-phenanthroline 5, 6-dione with 1, 8-dihydroxyl-9, 10-anthraquinone-3-aldehyde; b) synthesizing Cis-[Ru(L)2(Cl)2].2H2O; and c) subjecting Cis-[Ru(L)2(Cl)2].2H2O and HAIP to microwave assisted reaction for 10-60min at 80-200DEG C, thus generating [Ru(L)2HAIP].(PF6)2. The preparation method can significantly shorten the reaction time and increase the reaction conversion rate.
Description
Technical field
The present invention relates to compound technical, specifically, relate to the preparation method of many pyridines of microwave-assisted ruthenium (II) title complex.
background technology
In the metal complexes with anti-tumor activity, ruthenium complexe has been subject to widely paying close attention to, and generally believes in the world, and ruthenium and ruthenium complexe belong to hypotoxicity, easily absorbs and excretion very soon in vivo, will become one of the most promising cancer therapy drug.Preparing application aspect antitumor drug after deliberation for a long time for ruthenium complexe and cis-platinum ruthenium complexe, aspect some fields, also reach its maturity perfect, even existing some drugs molecule enters clinical stage, such as NAMI-A and KP1019 have entered clinical trial, and show good antitumous effect.In addition, ruthenium complexe also becomes one of the study hotspot in the fields such as pharmaceutical chemistry research in recent years, chemicobiology, bio-inorganic chemistry as the research of antitumor drug.For example, the people such as Clarke have summarized the antitumour activity of ruthenium complexe, particularly antimetastatic activity; Sava has summarized the antimetastatic activity of ruthenium complexe in " Metal Compounds in Cancer Therapy (metallic compound in cancer therapy) ".Along with going deep into ruthenium complexe inhibition tumor cell increment study on mechanism, more and more various types of ruthenium complexees are in the news, to coordinating machine-processed research, and various easy cross-films, high target, hypotoxic structural modification are also become to a very important research contents.The superior ruthenium complexe of research and development antitumous effect is of great significance for the treatment tool of tumour.
Chinese patent literature CN2007100289558, open day 2008.02.06, discloses a kind of ruthenium-anthraquinone conjugates and preparation method thereof and application as photosensitizer for photodynamic therapy.The ruthenium-anthraquinone conjugates of this invention, its composition formula is [Ru (L)
2hAIP] (PF
6)
2, HAIP is 1,8-dihydroxyl-9,10-anthraquinone imidazoles [4,5-f] [1,10] phenanthroline, and L is bpy or phen.The preparation method of ruthenium-anthraquinone conjugates comprises the steps: that (1) synthesize HAIP:1,8-dihydroxyl-9, and 10-anthraquinone-3-aldehyde and phenanthroline 5,6-bis-reactive ketones obtain HAIP; (2) Ru (L)
2cl
2with HAIP, NH
4pF
6reaction obtains [Ru (L)
2hAIP] (PF
6)
2.This invention is used rhabarberone as raw material, and the synthetic ruthenium complexe obtaining has single chemical constitution; Synthetic route is simple, and productive rate is higher; In experiment in vitro, compound all shows the light of growth of tumour cell is suppressed.But in this invention, the synthetic of intermediate HAIP need to be refluxed 2 hours, end product [Ru (L)
2hAIP] (PF
6)
2synthetic be within 8 hours, to complete by refluxing under argon shield, the productive rate of end product is respectively 67% and 72%, the defect of aforesaid method is long reaction time; reaction conditions is comparatively harsh; and productive rate is relatively low, simultaneously due to long reaction time, also may generate a large amount of by products.
Microwave be frequency greatly about 300 GHz-300 MHz, the hertzian wave of wavelength within the scope of 100 cm to 1 mm, is widely used in radar, communication.Compared with traditional oil bath or heating in water bath mode, microwave radiation can make temperature of reaction system raise rapidly at short notice, thus Reaction time shorten, and reduce the generation of side reaction, improve the transformation efficiency of reaction.From 1986 Canadian Richard Gedye seminar reported first since the application of microwave radiation in organic reaction, microwave-assisted organic synthesis has been widely used in the preparation of organic compound, mineral compound and various medicine intermediates, and demonstrated good result, produce huge economic benefit.
But have not been reported about using microwave-assisted synthetic technology to prepare anthraquinone-modified [Ru(bpy)2(dppzi) (being above-mentioned ruthenium-anthraquinone conjugates) at present.
summary of the invention
The object of the invention is for deficiency of the prior art, the preparation method of a kind of many pyridines ruthenium (II) title complex is provided.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of preparation method of many pyridines ruthenium (II) title complex, described many pyridines ruthenium (II) title complex composition formula is [Ru (L)
2hAIP] (PF
6)
2, HAIP is 1,8-dihydroxyl-9,10-anthraquinone imidazoles [4,5-
f] [1,10] phenanthroline, L is bpy or phen, structural formula is as follows:
Described preparation method comprises the following steps:
A) synthetic HAIP: phenanthroline 5,6-diketone and 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde reaction obtains HAIP;
B) synthetic
cis-[Ru (L)
2(Cl)
2] 2H
2o;
C)
cis-[Ru (L)
2cl
2] 2H
280-200 ℃ of reaction 10-60 min of O and HAIP microwave-assisted generates [Ru (L)
2hAIP] (PF
6)
2.
Preferably, described
cis-[Ru (L)
2cl
2] 2H
290-120 ℃ of reaction 15-30 min of O and HAIP microwave-assisted generates [Ru (L)
2hAIP] (PF
6)
2.
More preferably, described
cis-[Ru (L)
2cl
2] 2H
2110 ℃ of reaction 20 min of O and HAIP microwave-assisted generate [Ru (L)
2hAIP] (PF
6)
2.
Preferably, described step a) specifically: phenanthroline 5,6-diketone and 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde obtains HAIP with 80-200 ℃ of microwave radiation 10-60 min reaction.
More preferably, described step a) specifically: phenanthroline 5,6-diketone and 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde obtains HAIP with the 20 min reactions of 100 ℃ of microwave radiations.
The invention has the advantages that:
Synthetic route is simple, and microwave-assisted is synthetic fast, efficient, and productive rate is high, and especially microwave temperature is controlled at 60-200 ℃, and time 10-60min both can guarantee the shorter reaction times, can guarantee that again productive rate is higher than 80%, and reaction conversion ratio improves 20% more than.
embodiment
Below embodiment provided by the invention is elaborated.
the preparation (one) of embodiment pyridine more than 1 ruthenium (II) title complex
1,(1,8-dihydroxyl-9,10-anthraquinone) imidazoles [4,5-
f] preparation of [1,10] phenanthroline (HAIP)
In 30 mL microwave Pyrex reaction tubess, add: phenanthroline 5,6-diketone (0.315 g, 1.50 mmol), 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde (603.0 mg, 2.25 mmol), ammonium acetate 4.5 g and Glacial acetic acid 20 mL.With 100 ℃ of microwave radiation 20 min, after reaction finishes, reaction solution is poured in 27 mL distilled water, with strong aqua adjust pH to 7, produce precipitation in a large number.Filter, be dried to obtain yellow thick product, 60 – 80 order silicagel columns are crossed column purification, take dehydrated alcohol as eluent, and productive rate 89.5%.ESI-MS:?459.4?(M+H)。
, cis-[Ru (bpy)
2(Cl)
2] 2H
2o is synthetic
In the there-necked flask of 50 mL, add: dipyridyl (1.87 g; 12 mmol), lithium chloride (2.43 g, 57.6 mmol), ruthenium trichloride (1.57 g, 6 mmol); add again DMF and water, under argon shield, heat 140 ℃ of back flow reaction 8 h.After stopped reaction, cool to room temperature, adds acetone, and suction filtration obtains black crystals, after frozen water, washing with acetone filter cake several, is put in vacuum drier and is dried, and obtains atropurpureus crystal, productive rate 95.5%.
, cis-[Ru (phen)
2(Cl)
2] 2H
2o is synthetic
In the there-necked flask of 50 mL, add: phenanthroline (2.16 g; 12 mmol), lithium chloride (1.68 g, 28 mmol), ruthenium trichloride (1.56 g, 6 mmol); add again DMF and water, under argon shield, reflux 8 hours.Question response thing is cooled to room temperature, adds acetone to reactant.Reactant is placed 24 hours at 0 ℃, obtains purple crystals.With cold water and acetone drip washing crystal, vacuum-drying, productive rate 72%.
,[Ru (bpy)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (bpy)
2cl
2] 2H
2o (0.106 g, 0.20 mmol) and HAIP (0.095g, 0.20 mmol), add 15 mL ethylene glycol.110 ℃ of reaction 20 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 87%.Structural formula is as shown in (I).ESI-MS:?436.1?[M-2PF
6]
2+。
,[Ru (phen)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (phen)
2cl
2] 2H
2o (0.114 g, 0.20 mmol) and HAIP (0.095 g, 0.20 mmol), add 15 mL ethylene glycol.110 ℃ of reaction 20 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 89%.Structural formula is as shown in (II).ESI-MS:?460.3[M-2PF
6]
2+。
the preparation (two) of embodiment pyridine more than 2 ruthenium (II) title complex
1,the preparation of HAIP
In 30 mL microwave Pyrex reaction tubess, add: phenanthroline 5,6-diketone (0.315 g, 1.50 mmol), 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde (603.0 mg, 2.25 mmol), ammonium acetate 4.5 g and Glacial acetic acid 20 mL.With 80 ℃ of microwave radiation 60 min, after reaction finishes, reaction solution is poured in 27 mL distilled water, with strong aqua adjust pH to 7, produce precipitation in a large number.Filter, be dried to obtain yellow thick product, 60 – 80 order silicagel columns are crossed column purification, take dehydrated alcohol as eluent, and productive rate 84%.ESI-MS:?459.4?(M+H)。
, cis-[Ru (bpy)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
, cis-[Ru (phen)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
,[Ru (bpy)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (bpy)
2cl
2] 2H
2o (0.106 g, 0.20 mmol) and HAIP (0.095g, 0.20 mmol), add 15 mL ethylene glycol.80 ℃ of reaction 60 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 83%.Structural formula is as shown in (I).ESI-MS:?436.1?[M-2PF
6]
2+。
,[Ru (phen)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (phen)
2cl
2] 2H
2o (0.114 g, 0.20 mmol) and HAIP (0.095 g, 0.20 mmol), add 15 mL ethylene glycol.80 ℃ of reaction 60 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 83%.Structural formula is as shown in (II).ESI-MS:?460.3[M-2PF
6]
2+。
the preparation (three) of embodiment pyridine more than 3 ruthenium (II) title complex
1,the preparation of HAIP
In 30 mL microwave Pyrex reaction tubess, add: phenanthroline 5,6-diketone (0.315 g, 1.50 mmol), 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde (603.0 mg, 2.25 mmol), ammonium acetate 4.5 g and Glacial acetic acid 20 mL.With 200 ℃ of microwave radiation 10 min, after reaction finishes, reaction solution is poured in 27 mL distilled water, with strong aqua adjust pH to 7, produce precipitation in a large number.Filter, be dried to obtain yellow thick product, 60 – 80 order silicagel columns are crossed column purification, take dehydrated alcohol as eluent, and productive rate 83%.ESI-MS:?459.4?(M+H)。
, cis-[Ru (bpy)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
, cis-[Ru (phen)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
,[Ru (bpy)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (bpy)
2cl
2] 2H
2o (0.106 g, 0.20 mmol) and HAIP (0.095g, 0.20 mmol), add 15 mL ethylene glycol.200 ℃ of reaction 10 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 82%.Structural formula is as shown in (I).ESI-MS:?436.1?[M-2PF
6]
2+。
,[Ru (phen)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (phen)
2cl
2] 2H
2o (0.114 g, 0.20 mmol) and HAIP (0.095 g, 0.20 mmol), add 15 mL ethylene glycol.200 ℃ of reaction 10 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 83%.Structural formula is as shown in (II).ESI-MS:?460.3[M-2PF
6]
2+。
the preparation (four) of embodiment pyridine more than 4 ruthenium (II) title complex
1,the preparation of HAIP
In 30 mL microwave Pyrex reaction tubess, add: phenanthroline 5,6-diketone (0.315 g, 1.50 mmol), 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde (603.0 mg, 2.25 mmol), ammonium acetate 4.5 g and Glacial acetic acid 20 mL.With 90 ℃ of microwave radiation 30 min, after reaction finishes, reaction solution is poured in 27 mL distilled water, with strong aqua adjust pH to 7, produce precipitation in a large number.Filter, be dried to obtain yellow thick product, 60 – 80 order silicagel columns are crossed column purification, take dehydrated alcohol as eluent, and productive rate 87%.ESI-MS:?459.4?(M+H)。
, cis-[Ru (bpy)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
, cis-[Ru (phen)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
,[Ru (bpy)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (bpy)
2cl
2] 2H
2o (0.106 g, 0.20 mmol) and HAIP (0.095g, 0.20 mmol), add 15 mL ethylene glycol.90 ℃ of reaction 30 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 85%.Structural formula is as shown in (I).ESI-MS:?436.1?[M-2PF
6]
2+。
,[Ru (phen)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (phen)
2cl
2] 2H
2o (0.114 g, 0.20 mmol) and HAIP (0.095 g, 0.20 mmol), add 15 mL ethylene glycol.90 ℃ of reaction 30 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 87%.Structural formula is as shown in (II).ESI-MS:?460.3[M-2PF
6]
2+。
the preparation (five) of embodiment pyridine more than 5 ruthenium (II) title complex
1,the preparation of HAIP
In 30 mL microwave Pyrex reaction tubess, add: phenanthroline 5,6-diketone (0.315 g, 1.50 mmol), 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde (603.0 mg, 2.25 mmol), ammonium acetate 4.5 g and Glacial acetic acid 20 mL.With 120 ℃ of microwave radiation 15 min, after reaction finishes, reaction solution is poured in 27 mL distilled water, with strong aqua adjust pH to 7, produce precipitation in a large number.Filter, be dried to obtain yellow thick product, 60 – 80 order silicagel columns are crossed column purification, take dehydrated alcohol as eluent, and productive rate 88%.ESI-MS:?459.4?(M+H)。
, cis-[Ru (bpy)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
, cis-[Ru (phen)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
,[Ru (bpy)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (bpy)
2cl
2] 2H
2o (0.106 g, 0.20 mmol) and HAIP (0.095g, 0.20 mmol), add 15 mL ethylene glycol.120 ℃ of reaction 15 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 85%.Structural formula is as shown in (I).ESI-MS:?436.1?[M-2PF
6]
2+。
,[Ru (phen)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (phen)
2cl
2] 2H
2o (0.114 g, 0.20 mmol) and HAIP (0.095 g, 0.20 mmol), add 15 mL ethylene glycol.120 ℃ of reaction 15 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 86%.Structural formula is as shown in (II).ESI-MS:?460.3[M-2PF
6]
2+。
the preparation (six) of embodiment pyridine more than 6 ruthenium (II) title complex
1,the preparation of HAIP
In 30 mL microwave Pyrex reaction tubess, add: phenanthroline 5,6-diketone (0.315 g, 1.50 mmol), 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde (603.0 mg, 2.25 mmol), ammonium acetate 4.5 g and Glacial acetic acid 20 mL.With 180 ℃ of microwave radiation 12 min, after reaction finishes, reaction solution is poured in 27 mL distilled water, with strong aqua adjust pH to 7, produce precipitation in a large number.Filter, be dried to obtain yellow thick product, 60 – 80 order silicagel columns are crossed column purification, take dehydrated alcohol as eluent, and productive rate 83%.ESI-MS:?459.4?(M+H)。
, cis-[Ru (bpy)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
, cis-[Ru (phen)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
,[Ru (bpy)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (bpy)
2cl
2] 2H
2o (0.106 g, 0.20 mmol) and HAIP (0.095g, 0.20 mmol), add 15 mL ethylene glycol.180 ℃ of reaction 12 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 84%.Structural formula is as shown in (I).ESI-MS:?436.1?[M-2PF
6]
2+。
,[Ru (phen)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (phen)
2cl
2] 2H
2o (0.114 g, 0.20 mmol) and HAIP (0.095 g, 0.20 mmol), add 15 mL ethylene glycol.180 ℃ of reaction 12 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 84%.Structural formula is as shown in (II).ESI-MS:?460.3[M-2PF
6]
2+。
comparative example 1
1,the preparation of HAIP
In 30 mL microwave Pyrex reaction tubess, add: phenanthroline 5,6-diketone (0.315 g, 1.50 mmol), 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde (603.0 mg, 2.25 mmol), ammonium acetate 4.5 g and Glacial acetic acid 20 mL.With 205 ℃ of microwave radiation 9 min, after reaction finishes, reaction solution is poured in 27 mL distilled water, with strong aqua adjust pH to 7, produce precipitation in a large number.Filter, be dried to obtain yellow thick product, 60 – 80 order silicagel columns are crossed column purification, take dehydrated alcohol as eluent, and productive rate 84%.ESI-MS:?459.4?(M+H)。
, cis-[Ru (bpy)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
, cis-[Ru (phen)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
,[Ru (bpy)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (bpy)
2cl
2] 2H
2o (0.106 g, 0.20 mmol) and HAIP (0.095g, 0.20 mmol), add 15 mL ethylene glycol.205 ℃ of reaction 9 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 70%.Structural formula is as shown in (I).ESI-MS:?436.1?[M-2PF
6]
2+。
,[Ru (phen)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (phen)
2cl
2] 2H
2o (0.114 g, 0.20 mmol) and HAIP (0.095 g, 0.20 mmol), add 15 mL ethylene glycol.205 ℃ of reaction 9 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 71%.Structural formula is as shown in (II).ESI-MS:?460.3[M-2PF
6]
2+。
comparative example 2
1,the preparation of HAIP
In 30 mL microwave Pyrex reaction tubess, add: phenanthroline 5,6-diketone (0.315 g, 1.50 mmol), 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde (603.0 mg, 2.25 mmol), ammonium acetate 4.5 g and Glacial acetic acid 20 mL.With 78 ℃ of microwave radiation 70 min, after reaction finishes, reaction solution is poured in 27 mL distilled water, with strong aqua adjust pH to 7, produce precipitation in a large number.Filter, be dried to obtain yellow thick product, 60 – 80 order silicagel columns are crossed column purification, take dehydrated alcohol as eluent, and productive rate 82%.ESI-MS:?459.4?(M+H)。
, cis-[Ru (bpy)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
, cis-[Ru (phen)
2(Cl)
2] 2H
2o is synthetic
With embodiment 1.
,[Ru (bpy)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (bpy)
2cl
2] 2H
2o (0.106 g, 0.20 mmol) and HAIP (0.095g, 0.20 mmol), add 15 mL ethylene glycol.78 ℃ of reaction 70 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 71%.Structural formula is as shown in (I).ESI-MS:?436.1?[M-2PF
6]
2+。
,[Ru (phen)
2hAIP] (PF
6)
2preparation
In 30 mL microwave Pyrex reaction tubess, add: [Ru (phen)
2cl
2] 2H
2o (0.114 g, 0.20 mmol) and HAIP (0.095 g, 0.20 mmol), add 15 mL ethylene glycol.78 ℃ of reaction 70 min of microwave-assisted.Be cooled to after completion of the reaction room temperature, add water, solids removed by filtration impurity.Add NH
4pF
6remove dissolved impurity in solution.The crystal of separating out is dry, use a small amount of dissolve with methanol, take methyl alcohol-acetonitrile (10:1, v/v) as eluent alumina column chromatography purifying, productive rate: 71%.Structural formula is as shown in (II).ESI-MS:?460.3[M-2PF
6]
2+。
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the inventive method; can also make some improvement and supplement, these improvement and the supplementary protection scope of the present invention that also should be considered as.
Claims (5)
1. a preparation method for the ruthenium of pyridine more than (II) title complex, described many pyridines ruthenium (II) title complex composition formula is [Ru (L)
2hAIP] (PF
6)
2, HAIP is 1,8-dihydroxyl-9,10-anthraquinone imidazoles [4,5-
f] [1,10] phenanthroline, L is bpy or phen, it is characterized in that, described preparation method comprises the following steps:
A) synthetic HAIP: phenanthroline 5,6-diketone and 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde reaction obtains HAIP;
B) synthetic
cis-[Ru (L)
2(Cl)
2] 2H
2o;
C)
cis-[Ru (L)
2cl
2] 2H
280-200 ℃ of reaction 10-60 min of O and HAIP microwave-assisted generates [Ru (L)
2hAIP] (PF
6)
2.
2. the preparation method of many pyridines ruthenium according to claim 1 (II) title complex, is characterized in that, described
cis-[Ru (L)
2cl
2] 2H
290-120 ℃ of reaction 15-30 min of O and HAIP microwave-assisted generates [Ru (L)
2hAIP] (PF
6)
2.
3. the preparation method of many pyridines ruthenium according to claim 2 (II) title complex, is characterized in that, described
cis-[Ru (L)
2cl
2] 2H
2110 ℃ of reaction 20 min of O and HAIP microwave-assisted generate [Ru (L)
2hAIP] (PF
6)
2.
4. the preparation method of many pyridines ruthenium according to claim 1 (II) title complex, it is characterized in that, described step a) specifically: phenanthroline 5,6-diketone and 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde obtains HAIP with 80-200 ℃ of microwave radiation 10-60 min reaction.
5. the preparation method of many pyridines ruthenium according to claim 4 (II) title complex, it is characterized in that, described step a) specifically: phenanthroline 5,6-diketone and 1,8-dihydroxyl-9,10-anthraquinone-3-aldehyde obtains HAIP with the 20 min reactions of 100 ℃ of microwave radiations.
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Family
ID=
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238814A (en) * | 2015-09-02 | 2016-01-13 | 广东药学院 | Application of ruthenium complex serving as nucleic acid vector of target cell nucleus |
| CN111961088A (en) * | 2020-09-02 | 2020-11-20 | 昆明贵研新材料科技有限公司 | Method for preparing cis-bis (2, 2' -bipyridine) ruthenium dichloride dihydrate |
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| TW200502176A (en) * | 2003-05-09 | 2005-01-16 | Kojima Chemicals Co Ltd | Method for synthesizing metal complex |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238814A (en) * | 2015-09-02 | 2016-01-13 | 广东药学院 | Application of ruthenium complex serving as nucleic acid vector of target cell nucleus |
| CN105238814B (en) * | 2015-09-02 | 2018-11-09 | 广东药科大学 | Application of the ruthenium complex as targeting cell nucleus acid vectors |
| CN111961088A (en) * | 2020-09-02 | 2020-11-20 | 昆明贵研新材料科技有限公司 | Method for preparing cis-bis (2, 2' -bipyridine) ruthenium dichloride dihydrate |
| CN111961088B (en) * | 2020-09-02 | 2024-01-30 | 昆明贵研新材料科技有限公司 | Method for preparing cis-bis (2, 2' -bipyridine) ruthenium dichloride dihydrate |
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