CN114437141A - Preparation method of chiral diphenyl ethylene diamine ruthenium complex - Google Patents
Preparation method of chiral diphenyl ethylene diamine ruthenium complex Download PDFInfo
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- CN114437141A CN114437141A CN202210138821.6A CN202210138821A CN114437141A CN 114437141 A CN114437141 A CN 114437141A CN 202210138821 A CN202210138821 A CN 202210138821A CN 114437141 A CN114437141 A CN 114437141A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
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- 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
- C07B2200/07—Optical isomers
Abstract
The invention belongs to the technical field of preparation of ruthenium noble metal catalysts for the fields of medicine synthesis, pesticides, fine chemical engineering and the like, and discloses a preparation method of chiral diphenyl ethylenediamine ruthenium complex { [ (1R,2R) or (1S,2S) - (-) -2-amino-1, 2-diphenyl ethyl ] (p-toluenesulfonyl) amino } (mesitylene) ruthenium chloride. The invention obtains the target product by one-step synthesis reaction through the regulation of an alkali reagent under the anaerobic condition and a mixed solvent system, has simple and convenient integral operation steps, short synthesis period and improved production efficiency, and the yield of the target product reaches more than 90.0 percent and the purity is more than 98.5 percent.
Description
Technical Field
The invention relates to the technical field of preparation of ruthenium noble metal catalysts for the fields of medicine synthesis, pesticides, fine chemical engineering and the like, in particular to a preparation method of a chiral diphenyl ethylene diamine ruthenium complex.
Background
The chiral ligand and the chiral catalyst are the core of the field of chiral catalytic synthesis, and have wide application in the production of medicines, liquid crystal materials, agricultural chemistry and fine chemical industry. At present, the complex of { [ (1R,2R) or (1S,2S) - (-) -2-amino-1, 2-diphenylethyl ] (p-toluenesulfonyl) amino) } (mesitylene) ruthenium chloride makes a major breakthrough in the field of specific asymmetric catalysis, and is widely applied to asymmetric catalytic hydrogenation of ketone and imine, Michael reaction, Diels-Alder reaction, Henry reaction and the like. Compared with a small-molecule chiral diamine catalyst, the chiral diamine coordination metal ruthenium catalyst has more active sites, has the advantages of high reaction speed, high yield, high selectivity and the like, and has extremely high application value.
Currently, the synthesis process of { [ (1R,2R) or (1S,2S) - (-) -2-amino-1, 2-diphenylethyl ] (p-toluenesulfonyl) amino } (mesitylene) ruthenium chloride is mainly prepared by a two-step reaction. Firstly, performing ligand replacement reaction on 1,3, 5-trimethylbenzene and p-cymene ruthenium chloride dimer as raw materials, and after the reaction is finished, purifying to obtain mesitylene ruthenium chloride dimer; and secondly, performing coordination reaction on the prepared mesitylene ruthenium chloride dimer and ligand [ (1R,2R) or (1S,2S) -N- (2-amino-1, 2-diphenylethyl) ] p-toluenesulfonamide to obtain a target product, wherein the reaction preparation process is complicated, the post-treatment period is long, the purity of the obtained product is low, and the obtained product needs to be further recrystallized and purified, so that the product yield is reduced, and the metal consumption is increased. Therefore, the design of the synthesis process of { [ (1R,2R) or (1S,2S) - (-) -2-amino-1, 2-diphenylethyl ] (p-toluenesulfonyl) amino } (mesitylene) ruthenium chloride with simple preparation process, short post-treatment time and high product purity and yield is an urgent need in the art.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a chiral diphenyl ethylene diamine ruthenium complex, which solves the problems that the reaction preparation process is complicated, the post-treatment period is long, the purity of the obtained product is low, the obtained product needs to be further recrystallized and purified, the product yield is reduced, and the metal consumption is increased in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a chiral diphenyl ethylene diamine ruthenium complex, which comprises the following steps:
(a) mixing (1, 5-cyclooctadiene) ruthenium dichloride, an organic solvent and 1,3, 5-trimethylbenzene, and then reacting to obtain a solution system A;
(b) mixing [ (1R,2R) or (1S,2S) -N- (2-amino-1, 2-diphenylethyl) ] p-toluenesulfonamide with an organic solvent to obtain a solution system B;
(c) mixing the solution system A and the solution system B with an alkali reagent, reacting, and after the reaction is finished, sequentially cooling, filtering, washing, pumping, and vacuum drying to obtain a chiral diphenyl ethylene diamine ruthenium complex;
the chiral diphenyl ethylene diamine ruthenium complex is { [ (1R,2R) or (1S,2S) - (-) -2-amino-1, 2-diphenylethyl ] (p-toluenesulfonyl) amino } (mesitylene) ruthenium chloride.
Preferably, the reactions in steps (a), (b) and (c) are carried out independently in an oxygen-free atmosphere.
Preferably, in step (a), the organic solvent is absolute ethanol and/or isopropanol; the mass volume ratio of the (1, 5-cyclooctadiene) ruthenium dichloride to the organic solvent is 1 g: 4-10 mL; the mass ratio of the (1, 5-cyclooctadiene) ruthenium dichloride to the 1,3, 5-trimethylbenzene is 1: 3 to 6.
Preferably, in the step (b), the organic solvent is one or two of petroleum ether, cyclohexane and toluene; the mass volume ratio of the [ (1R,2R) or (1S,2S) -N- (2-amino-1, 2-diphenylethyl) ] p-toluenesulfonamide to the organic solvent is 1 g: 3-30 mL; the amount of the [ (1R,2R) or (1S,2S) -N- (2-amino-1, 2-diphenylethyl) ] p-toluenesulfonamide substance is 1.05-1.2 times of the amount of the (1, 5-cyclooctadiene) ruthenium dichloride substance in the step (a); the volume of the organic solvent in the step (b) is 1-3 times of the volume of the organic solvent in the step (a).
Preferably, in step (c), the alkali agent is anhydrous sodium acetate or anhydrous sodium carbonate; the amount of the substance of the alkali reagent is 4-8 times of the amount of the substance of (1, 5-cyclooctadiene) ruthenium dichloride in the step (a).
Preferably, in the step (a), the reaction temperature is 50-80 ℃, and the reaction time is 3-8 h.
Preferably, in the step (c), the reaction temperature is 50-80 ℃, and the reaction time is 2-8 h.
Preferably, in the step (c), the solution system a and the solution system B are mixed with the alkali reagent in a manner that: and mixing the solution system A with an alkali reagent to obtain a mixed solution, and dropwise adding the solution system B into the mixed solution.
Preferably, in the step (c), the solution system B is dripped into the mixed solution, and the dripping time of the solution system B is 10-30 min.
Preferably, in the step (c), the temperature of the vacuum drying is 50-80 ℃, the time of the vacuum drying is 3-10 h, and the vacuum drying is carried out until the vacuum degree is less than or equal to-0.05 MPa.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the invention adopts a one-step synthesis method, takes (1, 5-cyclooctadiene) ruthenium dichloride as a metal precursor, 1,3, 5-trimethylbenzene and ligand [ (1R,2R) or (1S,2S) -N- (2-amino-1, 2-diphenylethyl) ] p-toluenesulfonamide as reaction raw materials, and directly heats and reacts to synthesize a target product by matching with an alkali reagent in a mixed solvent system, so that the operation steps are simple and convenient, the metal utilization rate is improved, the production cost is greatly reduced, the product yield reaches more than 90.0 percent, and the purity is more than 98.5 percent; the whole reaction process does not involve dangerous chemicals, the operation environment is better and safer, and the method is suitable for industrial production.
Detailed Description
The invention provides a preparation method of a chiral diphenyl ethylene diamine ruthenium complex, which comprises the following steps:
(a) mixing (1, 5-cyclooctadiene) ruthenium dichloride, an organic solvent and 1,3, 5-trimethylbenzene, and then reacting to obtain a solution system A;
(b) mixing [ (1R,2R) or (1S,2S) -N- (2-amino-1, 2-diphenylethyl) ] p-toluenesulfonamide with an organic solvent to obtain a solution system B;
(c) mixing the solution system A and the solution system B with an alkali reagent, reacting, and after the reaction is finished, sequentially cooling, filtering, washing, pumping, and vacuum drying to obtain a chiral diphenyl ethylene diamine ruthenium complex;
the chiral diphenyl ethylene diamine ruthenium complex is { [ (1R,2R) or (1S,2S) - (-) -2-amino-1, 2-diphenylethyl ] (p-toluenesulfonyl) amino } (mesitylene) ruthenium chloride.
In the present invention, the reactions in steps (a), (b) and (c) are independently performed in an oxygen-free atmosphere.
In the present invention, the specific steps of step (a) are: under the anaerobic condition, (1, 5-cyclooctadiene) ruthenium dichloride is mixed with an organic solvent, and then a raw material 1,3, 5-trimethylbenzene is added to be stirred and reacted to obtain a solution system A;
in the present invention, the specific steps of step (b) are: mixing ligand [ (1R,2R) or (1S,2S) -N- (2-amino-1, 2-diphenylethyl) ] p-toluenesulfonamide and an organic solvent at room temperature under an anaerobic condition, and stirring until the mixture is clear to obtain a solution system B;
in the present invention, the specific steps of step (c) are: under the stirring and oxygen-free state, the solution system A and the solution system B are mixed with an alkali reagent for reaction, and after the reaction is finished, the reaction product is sequentially cooled, filtered, washed, drained and dried in vacuum, so that the target product { [ (1R,2R) or (1S,2S) - (-) -2-amino-1, 2-diphenylethyl ] (p-toluenesulfonyl) amino } (mesitylene) ruthenium chloride is obtained.
In the present invention, in step (a), the organic solvent is preferably absolute ethanol and/or isopropanol, and is more preferably absolute ethanol; the mass volume ratio of the (1, 5-cyclooctadiene) ruthenium dichloride to the organic solvent is preferably 1 g: 4-10 mL, more preferably 1 g: 5-8 mL; the mass ratio of the (1, 5-cyclooctadiene) ruthenium dichloride to the 1,3, 5-trimethylbenzene is preferably 1: 3-6, and more preferably 1: 4 to 5.
In the present invention, in step (b), the organic solvent is preferably one or two of petroleum ether, cyclohexane and toluene, and is further preferably petroleum ether and/or cyclohexane; the mass-to-volume ratio of the [ (1R,2R) or (1S,2S) -N- (2-amino-1, 2-diphenylethyl) ] p-toluenesulfonamide to the organic solvent is preferably 1 g: 3-30 mL, more preferably 1 g: 15-25 mL; the amount of the substance of [ (1R,2R) or (1S,2S) -N- (2-amino-1, 2-diphenylethyl) ] p-toluenesulfonamide is preferably 1.05 to 1.2 times of the amount of the substance of (1, 5-cyclooctadiene) ruthenium dichloride in the step (a), and is further preferably 1.1 to 1.15 times of the amount of the substance of (1, 5-cyclooctadiene) ruthenium dichloride in the step (a); the volume of the organic solvent in the step (b) is preferably 1 to 3 times of the volume of the organic solvent in the step (a), and more preferably 2 to 2.5 times of the volume of the organic solvent in the step (a).
In the present invention, in step (c), the alkali agent is preferably anhydrous sodium acetate or anhydrous sodium carbonate, and is more preferably anhydrous sodium acetate; the amount of the substance of the alkali reagent is preferably 4 to 8 times the amount of the substance of (1, 5-cyclooctadiene) ruthenium dichloride in step (a), and more preferably 5 to 6 times the amount of the substance of (1, 5-cyclooctadiene) ruthenium dichloride in step (a).
In the invention, in the step (a), the reaction temperature is preferably 50-80 ℃, and more preferably 65-70 ℃; the reaction time is preferably 3 to 8 hours, and more preferably 4 to 6 hours.
In the invention, in the step (c), the reaction temperature is preferably 50-80 ℃, and more preferably 60-75 ℃; the reaction time is preferably 2 to 8 hours, and more preferably 4 to 7 hours.
In the present invention, in the step (c), the solution system a and the solution system B are mixed with the alkali reagent in the following manner: adding an alkali reagent into the solution system A obtained in the step (a), stirring for 5-15 min to obtain a mixed solution, and dropwise adding the solution system B obtained in the step (B) into the mixed solution.
In the invention, in the step (c), the solution system B is dripped into the mixed solution, and the dripping time of the solution system B is preferably 10-30 min, and more preferably 15-25 min.
In the invention, in the step (c), the temperature of the vacuum drying is preferably 50-80 ℃, and more preferably 60-75 ℃; the time for vacuum drying is preferably 3-10 h, and more preferably 4-8 h; the vacuum drying is preferably performed until the vacuum degree is less than or equal to-0.05 MPa, and is more preferably performed until the vacuum degree is less than or equal to-0.07 MPa.
The chemical reaction process of the preparation method of the chiral diphenyl ethylene diamine ruthenium complex { [ (1R,2R) or (1S,2S) - (-) -2-amino-1, 2-diphenyl ethyl ] (p-toluenesulfonyl) amino } (mesitylene) ruthenium chloride is as follows:
the technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(a) Mixing 14.01g of (1, 5-cyclooctadiene) ruthenium dichloride and 60mL of absolute ethyl alcohol at 65 ℃ in an oxygen-free atmosphere, adding 24.04g of raw material 1,3, 5-trimethylbenzene, and stirring for reaction for 5 hours to obtain a solution system A;
(b) mixing 19.30g of ligand (1R,2R) -N- (2-amino-1, 2-diphenylethyl) p-toluenesulfonamide and 60mL of petroleum ether at room temperature under an anaerobic condition, and stirring until the mixture is clear to obtain a solution system B;
(c) adding 20.51g of anhydrous sodium acetate into the solution system A obtained in the step (a) under stirring and an oxygen-free state, stirring for 5min to obtain a mixed solution, then dropwise adding the solution system B obtained in the step (B) into the mixed solution for 10min, continuously stirring and reacting for 3h at 65 ℃, after the reaction is finished, cooling, filtering, washing, pumping, and vacuum drying at 60 ℃ for 5h to obtain 28.40g of a target product, wherein the yield is 91.3%, and the purity of the product is 98.9%.
Elemental analysis of the compound prepared in example 1 gave C57.94%, H4.95%, Ru 16.06%; the theoretical values are C57.91%, H4.86% and Ru 16.24%.
Example 2
(a) Mixing 14.01g of (1, 5-cyclooctadiene) ruthenium dichloride and 90mL of isopropanol at 75 ℃ in an oxygen-free atmosphere, adding 30.14g of 1,3, 5-trimethylbenzene as a raw material, and stirring for reacting for 4 hours to obtain a solution system A;
(b) mixing 20.14g of ligand (1S,2S) -N- (2-amino-1, 2-diphenylethyl) p-toluenesulfonamide and 150mL of cyclohexane at room temperature under an anaerobic condition, and stirring until the mixture is clear to obtain a solution system B;
(c) adding 26.51g of anhydrous sodium acetate into the solution system A obtained in the step (a) under stirring and an anaerobic state, stirring for 15min to obtain a mixed solution, dropwise adding the solution system B obtained in the step (B) into the mixed solution for 15min, continuously stirring and reacting for 2.5h at 75 ℃, after the reaction is finished, cooling, filtering, washing, pumping out, and vacuum drying at 70 ℃ for 4h to obtain 28.19g of a target product, wherein the yield is 90.6%, and the product purity is 98.7%.
Elemental analysis of the compound prepared in example 2 gave C57.86%, H4.98%, Ru 16.03%; the theoretical values are C57.91%, H4.86% and Ru 16.24%.
Example 3
(a) Mixing 14.01g of (1, 5-cyclooctadiene) ruthenium dichloride and 130mL of absolute ethyl alcohol at 80 ℃ in an oxygen-free atmosphere, adding 35.14g of raw material of 1,3, 5-trimethylbenzene, and stirring for reaction for 3.5 hours to obtain a solution system A;
(b) 21.64g of ligand (1R,2R) -N- (2-amino-1, 2-diphenylethyl) p-toluenesulfonamide and 300mL of toluene are mixed at room temperature under an anaerobic condition, and stirred until the mixture is clear, so that a solution system B is obtained;
(c) adding 40.50g of anhydrous sodium carbonate into the solution system A obtained in the step (a) under stirring and oxygen-free conditions, stirring for 10min to obtain a mixed solution, dropwise adding the solution system B obtained in the step (B) into the mixed solution for 25min, continuously stirring and reacting for 2h at 80 ℃, after the reaction is finished, cooling, filtering, washing, pumping, and vacuum drying at 75 ℃ for 3.5h to obtain 28.25g of a target product, wherein the yield is 90.8%, and the purity of the product is 98.6%.
Elemental analysis of the compound prepared in example 3 gave C57.87%, H4.99%, Ru 16.01%; the theoretical values are C57.91%, H4.86% and Ru 16.24%.
Example 4
(a) Mixing 14.01g of (1, 5-cyclooctadiene) ruthenium dichloride with a mixed system of 40mL of absolute ethyl alcohol and 40mL of isopropanol at 50 ℃ in an oxygen-free atmosphere, adding 26.14g of raw material 1,3, 5-trimethylbenzene, and stirring for reacting for 8 hours to obtain a solution system A;
(b) mixing 20.34g of ligand (1R,2R) -N- (2-amino-1, 2-diphenylethyl) p-toluenesulfonamide with a mixed system of 100mL of cyclohexane and 100mL of toluene at room temperature under an anaerobic condition, and stirring until the mixed system is clear to obtain a solution system B;
(c) adding 23.80g of anhydrous sodium acetate into the solution system A obtained in the step (a) under stirring and an anaerobic state, stirring for 10min to obtain a mixed solution, dropwise adding the solution system B obtained in the step (B) into the mixed solution for 15min, continuously stirring and reacting for 7h at 50 ℃, after the reaction is finished, cooling, filtering, washing, pumping, and vacuum drying at 80 ℃ for 3h to obtain 28.28g of a target product, wherein the yield is 90.9%, and the purity of the product is 98.6%.
Elemental analysis results for the compound prepared in example 4 were C57.87%, H5.01%, Ru 16.01%; the theoretical values are C57.91%, H4.86% and Ru 16.24%.
Example 5
(a) Mixing 14.01g of (1, 5-cyclooctadiene) ruthenium dichloride with a mixed system of 60mL of absolute ethyl alcohol and 50mL of isopropanol at 70 ℃ in an oxygen-free atmosphere, adding 31.54g of 1,3, 5-trimethylbenzene as a raw material, and stirring for reacting for 5 hours to obtain a solution system A;
(b) mixing 21.24g of ligand (1S,2S) -N- (2-amino-1, 2-diphenylethyl) p-toluenesulfonamide with a mixed system of 200mL of petroleum ether and 100mL of cyclohexane at room temperature under an anaerobic condition, and stirring until the mixed system is clear to obtain a solution system B;
(c) adding 30.80g of anhydrous sodium acetate into the solution system A obtained in the step (a) under stirring and an anaerobic state, stirring for 15min to obtain a mixed solution, dropwise adding the solution system B obtained in the step (B) into the mixed solution for 25min, continuously stirring and reacting for 4.5h at 70 ℃, after the reaction is finished, cooling, filtering, washing, pumping out, and vacuum drying at 70 ℃ for 3.5h to obtain 28.15g of a target product, wherein the yield is 90.5%, and the product purity is 98.7%.
Elemental analysis of the compound prepared in example 5 gave C57.89%, H4.97%, Ru 16.03%; the theoretical values are C57.91%, H4.86% and Ru 16.24%.
Example 6
(a) Mixing 14.01g of (1, 5-cyclooctadiene) ruthenium dichloride with a mixed system of 80mL of absolute ethanol and 60mL of isopropanol at 80 ℃ in an oxygen-free atmosphere, adding 36g of 1,3, 5-trimethylbenzene as a raw material, and stirring for reacting for 3 hours to obtain a solution system A;
(b) mixing 21.85g of ligand (1R,2R) -N- (2-amino-1, 2-diphenylethyl) p-toluenesulfonamide with a mixed system of 200mL of petroleum ether and 200mL of toluene at room temperature under an anaerobic condition, and stirring until the mixed system is clear to obtain a solution system B;
(c) adding 40.5g of anhydrous sodium carbonate into the solution system A obtained in the step (a) under stirring and oxygen-free conditions, stirring for 15min to obtain a mixed solution, then dropwise adding the solution system B obtained in the step (B) into the mixed solution for 30min, continuously stirring and reacting for 2.5h at the temperature of 80 ℃, after the reaction is finished, cooling, filtering, washing, pumping, and drying under vacuum at the temperature of 80 ℃ for 5.5h to obtain 28.22g of a target product, wherein the yield is 90.7%, and the product purity is 98.7%.
Elemental analysis results for the compound prepared in example 6 were C57.93%, H4.96%, Ru 16.03%; the theoretical values are C57.91%, H4.86% and Ru 16.24%.
Example 7
(a) 560.32g of (1, 5-cyclooctadiene) ruthenium dichloride and 2.5L of absolute ethyl alcohol are mixed at 65 ℃ in an oxygen-free atmosphere, 961.60g of 1,3, 5-trimethylbenzene is added into the mixture, and the mixture is stirred and reacted for 4.5 hours to obtain a solution system A;
(b) 772g of ligand (1R,2R) -N- (2-amino-1, 2-diphenylethyl) p-toluenesulfonamide and 2.5L of petroleum ether are mixed at room temperature under the anaerobic condition and stirred until the mixture is clear to obtain a solution system B;
(c) adding 820.4g of anhydrous sodium acetate into the solution system A obtained in the step (a) under stirring and in an oxygen-free state, stirring for 10min to obtain a mixed solution, dropwise adding the solution system B obtained in the step (B) into the mixed solution for 20min, continuously stirring and reacting for 2.5h at 65 ℃, after the reaction is finished, cooling, filtering, washing, pumping, and vacuum drying at 70 ℃ for 3.5h to obtain 1137.35g of a target product, wherein the yield is 91.4%, and the purity of the product is 98.8%.
Elemental analysis of the compound prepared in example 7 gave C57.87%, H4.96%, Ru 16.05%; the theoretical values are C57.91%, H4.86% and Ru 16.24%.
Comparative example 1
The difference from example 1 is that the reaction process is carried out in an aerobic atmosphere, anaerobic conditions are changed to the aeration of air, and the other steps are the same as example 1. 26.04g of target product is obtained, the yield is 83.7 percent, and the product purity is 95.4 percent.
The method shows that the ligand is deteriorated or byproducts are generated in the reaction process under the aerobic condition in the reaction process, and the yield and the purity of the target product are greatly influenced.
Comparative example 2
The difference from example 2 is that the organic solvent in step (b) is isopropanol, and otherwise, the obtained substance is purified by recrystallization before vacuum drying as in example 2. 16.55g of the target product was obtained with a yield of 53.2%.
The method is characterized in that when the same solvent is adopted in the reaction step (a) and the reaction step (b), the ligand (1R,2R) -N- (2-amino-1, 2-diphenylethyl) p-toluenesulfonamide and the reaction intermediate mesitylene ruthenium chloride dimer generate side reaction, and the chiral ruthenium complex without chlorine is synthesized, and further purification and separation of side products are required.
Comparative example 3
The difference from the example 1 is that the obtained substance needs to be recrystallized and purified before vacuum drying as in the other example 1 without adding an alkali reagent. 13.22g of the target product was obtained with a yield of 42.5%.
The reaction is difficult to carry out or extremely slow under the condition of no alkali reagent, and the reaction process is accompanied by the generation of byproducts.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of chiral diphenyl ethylene diamine ruthenium complex is characterized by comprising the following steps:
(a) mixing (1, 5-cyclooctadiene) ruthenium dichloride, an organic solvent and 1,3, 5-trimethylbenzene, and then reacting to obtain a solution system A;
(b) mixing [ (1R,2R) or (1S,2S) -N- (2-amino-1, 2-diphenylethyl) ] p-toluenesulfonamide with an organic solvent to obtain a solution system B;
(c) mixing the solution system A and the solution system B with an alkali reagent, reacting, and after the reaction is finished, sequentially cooling, filtering, washing, pumping, and vacuum drying to obtain a chiral diphenyl ethylene diamine ruthenium complex;
the chiral diphenyl ethylene diamine ruthenium complex is { [ (1R,2R) or (1S,2S) - (-) -2-amino-1, 2-diphenylethyl ] (p-toluenesulfonyl) amino } (mesitylene) ruthenium chloride.
2. The method for preparing chiral diphenyl ethylene diamine ruthenium complex according to claim 1, characterized in that the reactions in steps (a), (b) and (c) are independently carried out in an oxygen-free atmosphere.
3. The method for preparing chiral diphenyl ethylene diamine ruthenium complex according to claim 1, characterized in that in step (a), the organic solvent is absolute ethanol and/or isopropanol; the mass volume ratio of the (1, 5-cyclooctadiene) ruthenium dichloride to the organic solvent is 1 g: 4-10 mL; the mass ratio of the (1, 5-cyclooctadiene) ruthenium dichloride to the 1,3, 5-trimethylbenzene is 1: 3 to 6.
4. The method for preparing chiral diphenyl ethylene diamine ruthenium complex according to claim 2 or 3, characterized in that in step (b), the organic solvent is one or two of petroleum ether, cyclohexane and toluene; the mass volume ratio of the [ (1R,2R) or (1S,2S) -N- (2-amino-1, 2-diphenylethyl) ] p-toluenesulfonamide to the organic solvent is 1 g: 3-30 mL; the amount of the [ (1R,2R) or (1S,2S) -N- (2-amino-1, 2-diphenylethyl) ] p-toluenesulfonamide substance is 1.05-1.2 times of the amount of the (1, 5-cyclooctadiene) ruthenium dichloride substance in the step (a); the volume of the organic solvent in the step (b) is 1-3 times of the volume of the organic solvent in the step (a).
5. The method for preparing chiral diphenyl ethylene diamine ruthenium complex according to claim 1, characterized in that in step (c), the alkali agent is anhydrous sodium acetate or anhydrous sodium carbonate; the amount of the substance of the alkali reagent is 4-8 times of the amount of the substance of (1, 5-cyclooctadiene) ruthenium dichloride in the step (a).
6. The method for preparing chiral diphenyl ethylene diamine ruthenium complex as claimed in any one of claims 1 to 3, wherein the reaction temperature in step (a) is 50 to 80 ℃ and the reaction time is 3 to 8 hours.
7. The method for preparing chiral diphenyl ethylene diamine ruthenium complex as claimed in claim 1, wherein in the step (c), the reaction temperature is 50-80 ℃ and the reaction time is 2-8 h.
8. The method for preparing chiral diphenyl ethylene diamine ruthenium complex as claimed in claim 7, wherein in the step (c), the solution system A and the solution system B are mixed with the alkali reagent in a way that: and mixing the solution system A with an alkali reagent to obtain a mixed solution, and dropwise adding the solution system B into the mixed solution.
9. The method for preparing the chiral diphenyl ethylene diamine ruthenium complex as claimed in claim 8, wherein in the step (c), the solution system B is dripped into the mixed solution, and the dripping time of the solution system B is 10-30 min.
10. The method for preparing the chiral diphenyl ethylene diamine ruthenium complex as claimed in claim 1, wherein in the step (c), the temperature of vacuum drying is 50-80 ℃, the time of vacuum drying is 3-10 h, and the vacuum degree is less than or equal to-0.05 MPa.
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