CN114349795B - Preparation method of tetra (dimethyl sulfoxide) ruthenium chloride - Google Patents
Preparation method of tetra (dimethyl sulfoxide) ruthenium chloride Download PDFInfo
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Abstract
The application discloses a preparation method of tetra (dimethyl sulfoxide) ruthenium chloride, which comprises the following steps: (1) Deoxidizing dimethyl sulfoxide, and then dissolving ruthenium trichloride trihydrate in dimethyl sulfoxide; (2) Under the protection of inert gas, heating the reaction system in the step (1) to 150-180 ℃, preserving heat, stirring, reacting for 5-10min, cooling and cooling to room temperature, adding a poor solvent of the tetra (dimethyl sulfoxide) ruthenium chloride into the reaction system, filtering after precipitation, washing a filter cake with acetone, rinsing with diethyl ether, and then performing filter pressing under the protection of inert gas to obtain the tetra (dimethyl sulfoxide) ruthenium chloride. The preparation method of the tetra (dimethyl sulfoxide) ruthenium chloride shortens the reaction time by changing the reaction environment and the reaction temperature, is convenient to operate, and the prepared product has high purity and high yield, and meets the requirement of industrial production.
Description
Technical Field
The application belongs to the technical field of ruthenium compound synthesis, and particularly relates to a preparation method of tetra (dimethyl sulfoxide) ruthenium chloride.
Background
Ruthenium tetra (dimethyl sulfoxide) chloride is a common metal ruthenium complex and has wide application in metal organic chemistry and organic synthesis chemistry. For this purpose, the radiation sensitizer may be attached to a metal that binds to the DNA, i.e., the metal may be used as a carrier for the radiation sensitizer, thereby increasing the concentration of the drug on the target to enhance the radiation sensitization. Early research on antitumor ruthenium complex-cis ruthenium dichloride (dimethyl sulfoxide) 4 The mechanism of binding to DNA is similar to that of the clinically successfully applied platinum complex, cis-diamino (dichloro) platinum (II).
Chinese patent CN 112079878A discloses a method for preparing a ruthenium metal organic compound of tetra (dimethyl sulfoxide) dichloride, which adopts dimethyl sulfoxide to react with ruthenium reagent, but the reaction time is too long, and requires 12-48 hours.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a preparation method of tetra (dimethyl sulfoxide) ruthenium chloride, which shortens the reaction time and can complete the reaction within 5-10min by changing the reaction conditions.
A preparation method of tetra (dimethyl sulfoxide) ruthenium chloride comprises the following steps:
(1) Deoxidizing dimethyl sulfoxide, and then dissolving ruthenium trichloride trihydrate in dimethyl sulfoxide;
(2) Under the protection of inert gas, heating the reaction system in the step (1) to 150-180 ℃, preserving heat, stirring, reacting for 5-10min, cooling and cooling to room temperature, adding a poor solvent of the tetra (dimethyl sulfoxide) ruthenium chloride into the reaction system, filtering after precipitation, washing a filter cake with acetone, rinsing with diethyl ether, and then performing filter pressing under the protection of inert gas to obtain the tetra (dimethyl sulfoxide) ruthenium chloride.
Preferably, the ratio of the amounts of the substances of ruthenium trichloride trihydrate to dimethyl sulfoxide is 1: (16-20).
Preferably, the poor solvent is acetone.
Preferably, the poor solvent is added in excess.
Preferably, the deoxidation treatment of dimethyl sulfoxide is specifically: an inert gas is bubbled into dimethyl sulfoxide for half an hour.
Preferably, the filter pressing adopts a sand plate filter pipe for filter pressing.
Preferably, the inert gas is nitrogen or argon.
In the application, dimethyl sulfoxide is used as a reaction solvent and a reaction raw material.
The application has the advantages that:
the preparation method of the tetra (dimethyl sulfoxide) ruthenium chloride shortens the reaction time by changing the reaction environment and the reaction temperature, is convenient to operate, and the prepared product has high purity and high yield, and meets the requirement of industrial production.
Drawings
FIG. 1 is an infrared spectrum of ruthenium tetra (dimethyl sulfoxide) chloride.
Detailed Description
Example 1
A preparation method of tetra (dimethyl sulfoxide) ruthenium chloride comprises the following steps:
(1) Nitrogen was bubbled through dimethyl sulfoxide for half an hour to carry out deoxidation treatment, and then 5g (0.0191 mol) of ruthenium trichloride trihydrate was dissolved in 25mL (0.3526 mol) of dimethyl sulfoxide;
(2) The air is replaced by nitrogen, the reaction system in the step (1) is heated to 150 ℃ under the protection of nitrogen, the temperature is maintained, stirring and reaction are carried out for 5min, the reaction liquid is changed into yellow turbid liquid from brown, the turbid liquid is cooled and cooled to room temperature, 100mL of poor solvent acetone is added into the turbid liquid to generate yellow precipitate, the yellow precipitate is filtered, the filter residue is washed by acetone and then rinsed by diethyl ether, and then 8.77g of tetra (dimethyl sulfoxide) ruthenium chloride is obtained by filter pressing by using a sand plate filter tube under the protection of nitrogen;
the yield is 95%, and the content of metal ruthenium in the product tetra (dimethyl sulfoxide) ruthenium chloride is 20.63% and the content of theoretical metal ruthenium is 20.9% through detection;
the infrared detection of the product obtained in this example shows FIG. 1, and the infrared absorption characteristic peak IR (KBr, v/cm) is shown in FIG. 1 -1 ) The method comprises the following steps: 3012, 2919, 1634, 1411, 1303, 1108, 1025, 930, 716, 678 cm -1 The absorption peak is consistent with a DMSO standard infrared spectrogram, and can be attributed to an absorption band of ligand DMSO, which indicates that the DMSO coordinates with ruthenium chloride to generate a complex of ruthenium chloride and DMSO, namely tetra (dimethyl sulfoxide) ruthenium chloride.
Example 2
A preparation method of tetra (dimethyl sulfoxide) ruthenium chloride comprises the following steps:
(1) Nitrogen was bubbled through dimethyl sulfoxide for half an hour to carry out deoxidation treatment, and then 10g (0.0382 mol) of ruthenium trichloride trihydrate was dissolved in 50mL (0.7051 mol) of dimethyl sulfoxide;
(2) The air is replaced by nitrogen, the reaction system in the step (1) is heated to 150 ℃ under the protection of nitrogen, the temperature is maintained, stirring and reaction are carried out for 5min, the reaction liquid is changed into yellow turbid liquid from brown, the turbid liquid is cooled and cooled to room temperature, 200mL of poor solvent acetone is added into the turbid liquid to generate yellow precipitate, the yellow precipitate is filtered, the filter residue is washed by acetone and then rinsed by diethyl ether, and then 17.36g of tetra (dimethyl sulfoxide) ruthenium chloride is obtained by filter pressing by using a sand plate filter tube under the protection of nitrogen;
the yield is 94%, and the content of metal ruthenium in the product tetra (dimethyl sulfoxide) ruthenium chloride is 20.72% and the content of theoretical metal ruthenium is 20.9% through detection; the infrared spectrum is similar to that of fig. 1.
Example 3
A preparation method of tetra (dimethyl sulfoxide) ruthenium chloride comprises the following steps:
(1) Nitrogen was bubbled through dimethyl sulfoxide for half an hour to carry out deoxidation treatment, and then 15g (0.0574 mol) of ruthenium trichloride trihydrate was dissolved in 75mL (1.0577 mol) of dimethyl sulfoxide;
(2) The air is replaced by nitrogen, the reaction system in the step (1) is heated to 150 ℃ under the protection of nitrogen, the temperature is maintained, stirring and reaction are carried out for 5min, the reaction liquid is changed into yellow turbid liquid from brown, the turbid liquid is cooled and cooled to room temperature, 300mL of poor solvent acetone is added into the turbid liquid to generate yellow precipitate, the yellow precipitate is filtered, the filter residue is washed by acetone and then rinsed by diethyl ether, and then 26.6g of tetra (dimethyl sulfoxide) ruthenium chloride is obtained by filter pressing by using a sand plate filter tube under the protection of nitrogen;
the yield is 96%, and the content of metal ruthenium in the product tetra (dimethyl sulfoxide) ruthenium chloride is 20.71% and the content of theoretical metal ruthenium is 20.9% through detection; the infrared spectrum is similar to that of fig. 1.
Example 4
A preparation method of tetra (dimethyl sulfoxide) ruthenium chloride comprises the following steps:
(1) Nitrogen was bubbled through dimethyl sulfoxide for half an hour to carry out deoxidation treatment, and then 25.64g (0.0980 mol) of ruthenium trichloride trihydrate was dissolved in 115.0mL (1.6218 mol) of dimethyl sulfoxide;
(2) And (3) replacing air with nitrogen, heating the reaction system in the step (1) to 150 ℃ under the protection of nitrogen, preserving heat, stirring and reacting for 10min, changing the reaction liquid from brown to yellow turbid liquid, cooling and cooling to room temperature, and performing the following post-treatment under the protection of nitrogen: 250mL of poor solvent acetone is added into the mixture to generate yellow precipitate, the yellow precipitate is filtered, filter residues are washed by acetone and then rinsed by diethyl ether, and then the filter residues are subjected to filter pressing by a sand plate filter tube under the protection of nitrogen to obtain 44.65g of tetra (dimethyl sulfoxide) ruthenium chloride;
the yield is 94%, and the content of metal ruthenium in the product tetra (dimethyl sulfoxide) ruthenium chloride is 20.70% and the content of theoretical metal ruthenium is 20.9% through detection; the infrared spectrum is similar to that of fig. 1.
Example 5
A preparation method of tetra (dimethyl sulfoxide) ruthenium chloride comprises the following steps:
(1) Nitrogen was bubbled through dimethyl sulfoxide for half an hour to carry out deoxidation treatment, and then 25.64g (0.0980 mol) of ruthenium trichloride trihydrate was dissolved in 138.0mL (0.6008 mol) of dimethyl sulfoxide;
(2) And (3) replacing air with argon, heating the reaction system in the step (1) to 180 ℃ under the protection of argon, preserving heat, stirring and reacting for 5min, changing the reaction liquid from brown to yellow turbid liquid, cooling and cooling to room temperature, and performing the following post-treatment under the protection of nitrogen: 250mL of poor solvent acetone is added to the mixture to generate yellow precipitate, the yellow precipitate is filtered, filter residues are washed by acetone and then rinsed by diethyl ether, and 45.60g of tetra (dimethyl sulfoxide) ruthenium chloride is obtained after the post-treatment;
the yield is 96%, and the content of metal ruthenium in the product tetra (dimethyl sulfoxide) ruthenium chloride is 20.71% and the content of theoretical metal ruthenium is 20.9% through detection; the infrared spectrum is similar to that of fig. 1.
Comparative example 1
Example 1 in chinese patent CN 112079878A.
Comparative example 2
A preparation method of tetra (dimethyl sulfoxide) ruthenium chloride comprises the following steps:
(1) 10. 10 mL (141.0 mol) dimethyl sulfoxide was added to 1.242g (4.75 mmol) ruthenium trichloride trihydrate;
(2) After the reaction is kept at 110 ℃ for 12 hours, yellow precipitation appears, the reaction is continued for 12 hours, yellow precipitation appears, and the yellow solid is obtained after filtration; washing the mixture with acetone (10 ml ×3) and diethyl ether (20 ml ×2), and air drying to obtain 1.886g of ruthenium tetra (dimethyl sulfoxide) chloride;
the yield is 82%, and the content of metal ruthenium in the product tetra (dimethyl sulfoxide) ruthenium chloride is 20.6% and the content of theoretical metal ruthenium is 20.9% through detection.
Comparative example 3
A preparation method of tetra (dimethyl sulfoxide) ruthenium chloride comprises the following steps:
(1) 10. 10 mL (141.0 mol) dimethyl sulfoxide was added to 1.242g (4.75 mmol) ruthenium trichloride trihydrate;
(2) Under the protection of nitrogen, after the reaction is kept at 110 ℃ for 12 hours, yellow precipitation appears, the reaction is continued for 12 hours, yellow precipitation appears, and the yellow solid is obtained through filtration; washing with acetone (10 ml ×3) and diethyl ether (20 ml ×2), and air drying to obtain 1.863g of ruthenium tetra (dimethyl sulfoxide) chloride;
the yield is 81%, and the content of metal ruthenium in the product tetra (dimethyl sulfoxide) ruthenium chloride is 20.6% and the content of theoretical metal ruthenium is 20.9% through detection.
Comparative example 4
(1) 10. 10 mL (140.8 mmol) of dimethyl sulfoxide was added to 1.242g (4.75 mmol) of ruthenium trichloride trihydrate;
(2) The reaction is kept at 110 ℃ for 5min, and no sediment is generated.
Claims (6)
1. A preparation method of tetra (dimethyl sulfoxide) ruthenium chloride is characterized in that: the method comprises the following steps:
(1) Deoxidizing dimethyl sulfoxide, and then dissolving ruthenium trichloride trihydrate in dimethyl sulfoxide;
(2) Under the protection of inert gas, heating the reaction system of the step (1) to 150-180 ℃, preserving heat, stirring, reacting for 5-10min, cooling and cooling to room temperature, adding a poor solvent of the tetra (dimethyl sulfoxide) ruthenium chloride into the reaction system, precipitating, filtering, washing a filter cake with acetone, rinsing with diethyl ether, and then performing filter pressing under the protection of inert gas to obtain the tetra (dimethyl sulfoxide) ruthenium chloride;
the poor solvent is acetone.
2. The method for preparing the tetra (dimethyl sulfoxide) ruthenium chloride according to claim 1, wherein the method comprises the following steps: the ratio of the amount of the substances of the ruthenium trichloride trihydrate to the dimethyl sulfoxide is 1:16-20.
3. The method for preparing the tetra (dimethyl sulfoxide) ruthenium chloride according to claim 2, wherein the method comprises the following steps: the poor solvent is added in excess.
4. The method for preparing the tetra (dimethyl sulfoxide) ruthenium chloride according to claim 1, wherein the method comprises the following steps: the deoxidation treatment of dimethyl sulfoxide is specifically as follows: an inert gas is bubbled into dimethyl sulfoxide for half an hour.
5. The method for preparing the tetra (dimethyl sulfoxide) ruthenium chloride according to claim 1, wherein the method comprises the following steps: the filter pressing adopts a sand plate filter pipe for filter pressing.
6. The method for producing ruthenium tetra (dimethyl sulfoxide) chloride according to claim 1 or 4, wherein: the inert gas is nitrogen or argon.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008155531A1 (en) * | 2007-06-19 | 2008-12-24 | Oxford Biosensors Ltd | Redox mediators |
| JP2012033444A (en) * | 2010-08-03 | 2012-02-16 | Fujifilm Corp | Photoelectric conversion element, photoelectrochemical battery using the same, and photoelectric conversion element composition |
| CN112079878A (en) * | 2020-09-23 | 2020-12-15 | 荆楚理工学院 | Preparation method of dichlorotetra (dimethyl sulfoxide) ruthenium metal organic compound |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008155531A1 (en) * | 2007-06-19 | 2008-12-24 | Oxford Biosensors Ltd | Redox mediators |
| JP2012033444A (en) * | 2010-08-03 | 2012-02-16 | Fujifilm Corp | Photoelectric conversion element, photoelectrochemical battery using the same, and photoelectric conversion element composition |
| CN112079878A (en) * | 2020-09-23 | 2020-12-15 | 荆楚理工学院 | Preparation method of dichlorotetra (dimethyl sulfoxide) ruthenium metal organic compound |
Non-Patent Citations (1)
| Title |
|---|
| 胡会利等.《电化学测量》.国防工业出版社,2007,(第第068781号版),69-70，参见第69页2.7部分. * |
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