CN103145769B - Bis-cyclometallated compound of heteronuclear ruthenium palladium and its preparation method and application - Google Patents

Abstract

The invention discloses a heteronuclear ruthenium-palladium bicyclic metal compound, a preparation method and an application of the metal compound, and belongs to the technical field of organic synthesis. The metal compound has the advantages of easy preparation, modification, heat and air stability, high catalytic activity, and long life. It can simultaneously exert the catalytic properties of ruthenium and palladium in the synthesis and preparation of benzylic derivatives of the indene ring. Substituted acetophenone and aryl benzyl alcohol directly react to generate indene ring benzyl-substituted derivatives, which have high catalytic activity. The method for preparing the heteronuclear ruthenium palladium bicyclic metal compound is simple, has strong operability and high yield, and the prepared heteronuclear ruthenium palladium bicyclic metal compound can catalyze the direct reaction of o-halogenated acetophenone and aryl benzyl alcohol, and has the advantages of The reaction has the advantages of wide range of substrates, mild conditions, high yield, high efficiency and practicality, etc., and the amount of catalyst is small, and cheap weak base can be used for reaction.

Description

Heteronuclear ruthenium palladium bicyclic metal compound and its preparation method and application

technical field

The invention specifically relates to a heteronuclear ruthenium-palladium bicyclic metal compound, a preparation method and an application of the metal compound, and belongs to the technical field of organic synthesis.

Background technique

Indanone and its derivatives are a very important class of organic compounds. Many natural products and drug molecules contain indanone structural units. In addition, indanone derivatives are important intermediates in organic synthesis and are widely used in the synthesis of many drugs. Among the numerous indenone derivatives, many compounds with an aryl group at the benzyl position of the indenyl ring exhibit various interesting biological activities. In view of the important applications of indanones in organic chemistry and medicinal chemistry, their synthetic methods have also received extensive attention. Indanone compounds are often formed from phenylpropionic acid and its derivatives by ring closure under the catalysis of various strong acids. Catalysts such as chlorosulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, polyphosphoric acid, etc., are relatively harmful to the environment. Large, harsh reaction conditions, lack of stable and reliable synthetic methods with a wide range of substrates and mild conditions.

In recent years, great progress has been made in the synthesis of benzylic derivatives of indene rings from α, β-unsaturated carbonyl compounds catalyzed by transition metals. This method avoids the use of a large amount of strong acid, but requires various special α, β-unsaturated carbonyl compounds as substrates, which limits its application in production. Alcohols are widely available, relatively cheap, non-toxic, and have high atom economy. The by-product of the reaction is water, which is environmentally friendly. Transition metals can catalyze the automatic transfer process of alcohols through hydrogen, and directly react with carbonyl compounds to obtain α, β - unsaturated carbonyl compounds. Among many transition metal complexes, cyclometallic compounds have the advantages of easy preparation, modification, heat and air stability, high catalytic activity, and long life, which make them play a very important role in organic synthesis and catalytic chemistry. There are many reports on cyclometallic compounds, but there are few reports on heteronuclear cyclometallic compounds. Up to now, there is no synthesis of heteronuclear ruthenium-palladium bicyclic metal compound and its use as a bimetallic catalyst to catalyze the coupling reaction of o-halogenated acetophenone and aryl benzyl alcohol to synthesize and prepare benzyl-substituted derivatives of indene ring reports.

Contents of the invention

The purpose of the present invention is to provide a heteronuclear ruthenium palladium bicyclic metal compound.

At the same time, the invention also provides a preparation method of the heteronuclear ruthenium palladium bicyclic metal compound.

In order to achieve the above object, the technical solution adopted in the present invention is:

Heteronuclear ruthenium palladium bicyclic metal compound, its general structural formula is:

In the formula: X, X ₁ , Y, and Y ₁ are independently selected from C atoms or N atoms, X and Y are different and take the same atom, X ₁ and Y ₁ are different and take the same atom, Z and Z ₁ are independently selected from Cl ^- , Br ^- , I ^- , L, L ₁ are independently selected from tertiary phosphine ligands or imidazoline ring carbene ligands.

The general structural formula of the tertiary phosphine ligand is: In the formula: R ₁₁ , R ₁₂ , and R ₁₃ are each independently selected from an alkyl group with 1 to 6 C, benzene, substituted benzene, or biphenyl.

The tertiary phosphine ligand is or

The general structural formula of the imidazoline ring carbene ligand is: In the formula: R ₁₅ is selected from 1 to 3 C alkyl groups, benzene or substituted benzenes.

The imidazoline ring carbene ligand is or

The preparation method of heteronuclear ruthenium palladium bicyclic metal compound, the steps are as follows: according to the molar ratio, it is the mononuclear palladium compound containing the boron ester group: the mononuclear ruthenium compound containing the halogen atom: basic substance A=(1 ~1.5): 1: (1~5) Take each substance and add it to solvent A, heat and reflux at a temperature of 80~120°C under the protection of an inert gas for 10~24 hours, filter after the reaction, evaporate to dryness, and reassemble Crystallization, that is, heteronuclear ruthenium palladium bicyclic metal compound.

The general structural formula of the mononuclear ring ruthenium compound containing halogen atoms is:

In the formula: X and Y are independently selected from C atoms or N atoms, but X and Y are different and take the same atom, Z is selected from Cl ^- , Br ^- or I ^- ; Z ₂ is selected from Cl, Br or I; L is Tertiary phosphine ligand or imidazoline ring carbene ligand.

The general structural formula of the tertiary phosphine ligand is: In the formula: R ₁₁ , R ₁₂ , and R ₁₃ are each independently selected from an alkyl group with 1 to 6 C, benzene, substituted benzene, or biphenyl.

The tertiary phosphine ligand is or

The general structural formula of the imidazoline ring carbene ligand is: In the formula: R ₁₅ is selected from 1 to 3 C alkyl groups, benzene or substituted benzenes.

The imidazoline ring carbene ligand is or

The general structural formula of the mononuclear cyclopalladium compound containing boronate group is:

In the formula: X ₁ and Y ₁ are independently selected from C atom or N atom, but X ₁ and Y ₁ are different and take the same atom, Z ₁ is selected from Cl ^- , Br ^- or I ^- , L ₁ is a tertiary phosphine ligand or imidazoline ring carbene ligands.

The general structural formula of the tertiary phosphine ligand is: In the formula: R ₁₁ , R ₁₂ , and R ₁₃ are each independently selected from an alkyl group with 1 to 6 C, benzene, substituted benzene, or biphenyl.

The tertiary phosphine ligand is or

The general structural formula of the imidazoline ring carbene ligand is: In the formula: R ₁₅ is selected from 1 to 3 C alkyl groups, benzene or substituted benzenes.

The imidazoline ring carbene ligand is or

The alkaline substance A is sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate or potassium phosphate.

The solvent A is dioxane, benzene, toluene, isopropanol, tetrahydrofuran or N or N-dimethylformamide.

The inert gas is nitrogen or helium.

The solvent used for the recrystallization is a mixed solvent of dichloromethane/petroleum ether.

Furthermore, the present invention also provides the application of a heteronuclear ruthenium-palladium bicyclic metal compound as a bimetallic catalyst to catalyze the coupling reaction of o-halogenated acetophenone and aryl benzyl alcohol to prepare indene ring benzylic derivatives.

The general structural formula of the benzylic position substituted derivatives of the indene ring is: In the formula: R is at any position of 1, 2, 3, and 4, R ₁ is at any position of 1', 2', and 3', and R and R ₁ are independently selected from -H, -CH ₃ , -OCH ₃ , -NO ₃ , -C ₂ H ₃ , -C ₃ H ₇ , -C ₄ H ₉ , Cl ^- , Br ^- , I ^- or Aryl-; said Aryl- is or

The reaction process is as follows:

The general structural formula of the o-halogenated acetophenone is: In the formula: R is -H, -CH ₃ , -OCH ₃ , -NO ₃ , -C ₂ H ₃ , -C ₃ H ₇ , -C ₄ H ₉ , Cl ^- , Br ^- , I ^- or Aryl-, The Aryl - for or The R is at any position of 1, 2, 3, 4; X is selected from Cl, Br or I.

The structural general formula of described aryl benzyl alcohol is: In the formula: R ₁ is -H, -CH ₃ , -OCH ₃ , -NO ₃ , -C ₂ H ₃ , -C ₃ H ₇ , -C ₄ H ₉ , Cl ^- , Br ^- , I ^- or Aryl- , the said Aryl- is or Said R ₁ is at any position of 1', 2', 3'.

The described heteronuclear ruthenium-palladium bicyclic metal compound catalyzes the coupling reaction of o-halogenated acetophenone and aryl benzyl alcohol to synthesize and prepare the steps of indene ring benzyl-substituted derivatives as follows: according to the molar ratio, the heteronuclear ruthenium-palladium bicyclic metal compound: o-halogenated acetophenone: aryl benzyl alcohol: basic substance B=(0.05～0.1):1:(1～3):(1～6) Take each substance and add it to solvent B, at a temperature of 80 ~120°C, under the protection of inert gas, heat and reflux for 12-48 hours, after the reaction is completed, cool down to room temperature, add a extinguishing agent to extinguish the reaction, separate, concentrate, purify, and dry to obtain the indene ring benzyl-substituted derivative.

The alkaline substance B is sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, sodium hydroxide, potassium hydroxide or triethylamine.

The solvent B is ethanol, propanol, isopropanol, dioxane, benzene, toluene, tetrahydrofuran or N,N-dimethylformamide.

Described extinguishing agent is water.

The separation method is extraction and separation with dichloromethane.

Beneficial effects of the present invention:

The heteronuclear ruthenium-palladium bicyclic metal compound of the present invention has the advantages of easy preparation, modification, heat and air stability, high catalytic activity, long life, etc., and can simultaneously play the role of ruthenium and palladium in the synthesis and preparation reaction of the benzylic position substituted derivatives of the indene ring. Catalytic properties, direct reaction of o-halogenated acetophenone and aryl benzyl alcohol to generate indene ring benzyl-substituted derivatives, with high catalytic activity. The method for preparing the heteronuclear ruthenium-palladium bicyclic metal compound is simple, has strong operability and high yield, and the prepared heteronuclear ruthenium-palladium bicyclic metal compound can be used as a bimetallic catalyst to catalyze o-halogenated acetophenone and aryl benzyl alcohol Direct reaction has the advantages of wide range of reaction substrates, mild conditions, high yield, high efficiency and practicality, etc., and the amount of catalyst is small, and cheap weak base can be used for reaction. Using heteronuclear ruthenium-palladium bicyclic metal compounds to catalyze the synthesis and preparation of benzylic derivatives of indene ring can significantly improve the atom economy and synthesis efficiency of the reaction.

The present invention utilizes a metal Ru to catalyze the automatic hydrogen transfer process of o-halogenated acetophenone and aryl benzyl alcohol to generate α, β-unsaturated carbonyl compounds, and at the same time, another metal Pd is used to catalyze the ortho-position halogen atom and Alkenes in α, β-unsaturated carbonyl compounds undergo Heck reactions, and finally form indene ring benzylic substituted derivatives. This transitional metal-catalyzed cascade reaction avoids the separation of reaction intermediates and is an economical, efficient and practical synthesis method.

detailed description

The present invention will be described in further detail below in conjunction with specific examples, but does not constitute any limitation to the present invention.

The general structural formula of the heteronuclear ruthenium palladium bicyclic metal compound of embodiment 1～20 is as follows:

In the formula, the group structure in each embodiment is shown in Table 1 below.

The structure of each group in table 1 embodiment 1～20 heteronuclear ruthenium palladium bicyclic metal compound

x Y _x1 Y ₁ Z Z ₁ L L ₁ product Example 1 N C C N ^{Br- Cl-} P(C ₂ H ₅ ) ₃ P(C ₆ H ₅ ) ₃ 1 Example 1 N C C N ^{Cl- Cl-} P(C ₂ H ₅ ) ₃ P(C ₆ H ₁₁ ) ₃ 2 Example 3 N C C N ^{Br- Cl-} P(C ₆ H ₅ ) ₃ P(C ₆ H ₅ ) ₃ 3 Example 4 N C C N ^{Cl- Cl-} P(C ₂ H ₅ ) ₃ P(C ₆ H ₅ ) ₃ 4 Example 5 C N N C ^{Br- Cl-} P(C ₆ H ₅ ) ₃ P(CH ₃ ) ₃ 5 Example 6 C N N C I ^{- Cl-} P(C ₆ H ₅ ) ₃ P(CH ₃ ) ₃ 6 Example 7 C N N C I ^{- Cl-} P(CH ₃ ) ₃ P(C ₆ H ₁₁ ) ₃ 7 Example 8 C N N C ^Br- I ^- P(C ₂ H ₅ ) ₃ P(CH ₃ ) ₃ 8 Example 9 N C C N I ^- I ^- P(C ₆ H ₅ ) ₃ P(CH ₃ ) ₃ 9 Example 10 N C C N ^{Cl- Cl-} P(C ₆ H ₅ ) ₃ [(C ₃ N ₂ H ₂ )-(CH ₃ ) ₂ ] 10 Example 11 C N N C ^{Cl- Cl-} [(C ₃ N ₂ H ₂ )(C ₆ H ₄ -OCH ₃ ) ₂ ] P(C ₆ H ₁₁ ) ₃ 11 Example 12 N C C N ^{Cl- Cl-} [(C ₃ N ₂ H ₂ )(C ₆ H ₃ -2C ₃ H ₇ ) ₂ ] P(C ₆ H ₅ ) ₃ 12 Example 13 N C C N ^{Cl- Cl-} [(C ₃ N ₂ H ₂ )(C ₆ H ₂ -3CH ₃ ) ₂ ] P(CH ₃ ) ₃ 13 Example 14 C N N C ^{Cl- Cl-} [(C ₃ N ₂ H ₂ )-(CH ₃ ) ₂ ] P(C ₂ H ₅ ) ₃ 14 Example 15 C N N C ^{Br- Cl-} P(CH ₃ ) ₃ [(C ₃ N ₂ H ₂ )(C ₆ H ₄ -OCH ₃ ) ₂ ] 15 Example 16 N C C N ^{Cl- Cl-} [(C ₃ N ₂ H ₂ )(C ₆ H ₄ -OCH ₃ ) ₂ ] [(C ₃ N ₂ H ₂ )(C ₆ H ₄ -OCH ₃ ) ₂ ] 16 Example 17 N C C N ^{Cl- Cl-} [(C ₃ N ₂ H ₂ )-(CH ₃ ) ₂ ] [(C ₃ N ₂ H ₂ )-(CH ₃ ) ₂ ] 17 Example 18 N C C N I ^{- Cl-} P(C ₆ H ₅ ) ₃ [(C ₃ N ₂ H ₂ )(C ₆ H ₄ -OCH ₃ ) ₂ ] 18 Example 19 C N N C I ^{- Cl-} P(C ₆ H ₁₁ ) ₃ [(C ₃ N ₂ H ₂ )(C ₆ H ₃ -2C ₃ H ₇ ) ₂ ] 19 Example 20 C N N C I ^{- Cl-} P(CH ₃ ) ₃ [(C ₃ N ₂ H ₂ )(C ₆ H ₂ -3CH ₃ ) ₂ ] 20

Example 1

The preparation method of the heteronuclear ruthenium palladium bicyclic metal compound in this example is as follows: in a 50ml three-neck flask equipped with a stirring reflux device, add a triethylphosphine mononuclear ruthenium compound (1 mmol) containing a bromine atom, and boronic acid containing Triphenylphosphine mononuclear cyclopalladium compound (1.05mmol) of ester group, potassium carbonate (2.0mmol) and 20ml of anhydrous toluene, stirred and reacted for 12 hours at a temperature of 110°C under a nitrogen atmosphere, filtered, and evaporated the solvent Recrystallized with a mixed solvent of CH2Cl2 and petroleum ether to obtain a yellow product 1 heteronuclear triethylphosphinerutheniumtriphenylphosphinepalladium bicyclic metal compound with a yield of 85.8%. The resulting product was analyzed by nuclear magnetic resonance, and the data are as follows: ¹ HNMR: δ=8.60(d, 1H, Ph-H), 8.58(d, 1H, Ph-H), 8.02(d, 2H, Ph-H), 7.80 -7.71(m,14H,Ph-H),7.38-7.22(m,9H,Ph-H),6.97(m,2H,Ph-H),1.66(m,12H,CH ₂ ),1.01(m, 18H, _CH3 ).

Example 3

The preparation method of the heteronuclear ruthenium-palladium bicyclic metal compound in this example is: add bromine-containing triphenylphosphine mononuclear ruthenium compound (1 mmol), boronic acid-containing Triphenylphosphine mononuclear cyclopalladium compound (1.1mmol) of ester group, cesium carbonate (2.5mmol) and 20ml of anhydrous dioxane, stirred and reacted for 10 hours at a temperature of 110°C under a nitrogen atmosphere, filtered, evaporated After removing the solvent, recrystallize with a mixed solvent of dichloromethane (CH ₂ Cl ₂ ) and petroleum ether to obtain the yellow product 3 heteronuclear triphenylphosphine ruthenium palladium bicyclic metal compound with a yield of 85.2%. The resulting product was analyzed by nuclear magnetic resonance, and the data are as follows: ¹ HNMR: δ=8.63(d, 1H, Ph-H), 8.53(d, 1H, Ph-H), 7.98(d, 2H, Ph-H), 7.85 -7.78 (m, 18H, Ph-H), 7.38-7.21 (m, 35H, Ph-H), 6.93 (m, 2H, Ph-H).

Example 5

The preparation method of the heteronuclear ruthenium-palladium bicyclic metal compound in this example is: add bromine-containing triphenylphosphine mononuclear ruthenium compound (1 mmol), boronic acid-containing Trimethylphosphine mononuclear cyclopalladium compound (1.2mmol) of ester group, sodium carbonate (2.5mmol) and 20ml of anhydrous tetrahydrofuran, stirred and reacted for 18 hours at a temperature of 80°C under a nitrogen atmosphere, filtered, and evaporated the solvent Recrystallization with a mixed solvent of dichloromethane (CH ₂ Cl ₂ ) and petroleum ether gave the yellow product 5 heteronuclear triphenylphosphine ruthenium trimethylphosphine palladium bicyclic metal compound with a yield of 92.3%. The resulting product was analyzed by nuclear magnetic resonance, and the data are as follows: ¹ HNMR: δ=8.61(d, 1H, Ph-H), 8.56(d, 1H, Ph-H), 8.02(d, 2H, Ph-H), 7.81 -7.75 (m, 18H, Ph-H), 7.37-7.28 (m, 20H, Ph-H), 6.95 (m, 2H, Ph-H), 1.08 (s, 9H, _CH3 ).

Example 8

The preparation method of the heteronuclear ruthenium palladium bicyclic metal compound in this example is as follows: in a 50ml three-neck flask equipped with a stirring reflux device, add a triethylphosphine mononuclear ruthenium compound (1 mmol) containing a bromine atom, and boronic acid containing Trimethylphosphine mononuclear cyclopalladium compound (1.05mmol) of ester group, sodium phosphate (3.0mmol) and 20ml of anhydrous benzene, stirred and reacted for 20 hours at a temperature of 100°C under a nitrogen atmosphere, filtered, and evaporated the solvent Recrystallized with a mixed solvent of CH ₂ Cl ₂ and petroleum ether to obtain the yellow product 8 heteronuclear triethylphosphine ruthenium trimethylphosphine palladium bicyclic metal compound with a yield of 90.5%. The resulting product was analyzed by nuclear magnetic resonance, and the data are as follows: ¹ HNMR: δ=8.68(d, 1H, Ph-H), 8.53(d, 1H, Ph-H), 8.06(d, 2H, Ph-H), 7.79 -7.71(m,5H,Ph-H),7.38-7.27(m,3H,Ph-H),6.97(m,2H,Ph-H),1.63(m,6H,CH ₂ ),1.02(m, 9H, _CH3 ), 1.05 (s, 18H, _CH3 ).

Example 10

The preparation method of the heteronuclear ruthenium-palladium bicyclic metal compound in this example is as follows: in a 50ml three-neck flask equipped with a stirring reflux device, add a triphenylphosphine mononuclear ruthenium compound (1 mmol) containing a chlorine atom, and boronic acid containing N-methyl-N′-methylimidazolecarbene mononuclear cyclopalladium compound (1.1mmol) of ester group, potassium phosphate (4.5mmol) and 20ml of anhydrous isopropanol were stirred at a temperature of 100°C under a nitrogen atmosphere After reacting for 16 hours, filter, distill off the solvent and recrystallize with a mixed solvent of CH ₂ Cl ₂ and petroleum ether to obtain the yellow product 10 heteronuclear triphenylphosphine ruthenium N-methyl-N'-methylimidazolcarbene palladium bicyclic metal Compound, yield 87.2%. The resulting product was analyzed by nuclear magnetic resonance, and the data are as follows: ¹ HNMR: δ=8.63(d, 1H, Ph-H), 8.55(d, 1H, Ph-H), 8.08(d, 2H, Ph-H), 7.83 -7.76(m,18H,Ph-H),7.53(m,2H,NCHCHN),7.39-7.26(m,20H,Ph-H),6.98(m,2H,Ph-H),4.18(s,6H , CH ₃ ).

Example 12

The preparation method of the heteronuclear ruthenium-palladium bicyclic metal compound in this example is: add N-o-isopropylphenyl-N′-o-isopropylphenyl containing chlorine atoms in a 50ml three-necked flask equipped with a stirring reflux device Imidazolcarbene mononuclear ruthenium compound (1mmol), triphenylphosphine mononuclear palladium compound (1.05mmol) containing bona borate group, potassium carbonate (2.2mmol) and 20ml of anhydrous N,N-dimethyl Dimethyl formamide, stirred and reacted at 120°C under nitrogen atmosphere for 24 hours, then filtered, evaporated the solvent and recrystallized with a mixed solvent of CH ₂ Cl ₂ and petroleum ether to obtain the yellow product 12 heteronuclear N-o-isopropyl Phenyl-N'-o-isopropylphenylimidazocarbene ruthenium triphenylphosphine palladium bicyclic metal compound, yield 93.8%. The resulting product was analyzed by nuclear magnetic resonance, and the data are as follows: ¹ HNMR: δ=8.58(d, 1H, Ph-H), 8.53(d, 1H, Ph-H), 7.96(d, 2H, Ph-H), 7.81 -7.72(m,15H,Ph-H),7.51(m,4H,NCHCHN),7.43-7.49(m,13H,Ph-H),7.37-7.13(m,21H,Ph-H),6.95(m ,2H,Ph-H),2.91-2.95(m,8H,CH),1.65(s,12H,CH ₃ ),1.53(d,6H,CH ₃ ),1.41(d,6H,CH ₃ ),1.13 (d, 6H, CH ₃ ), 0.96 (d, 6H, CH ₃ ), 0.81 (d, 6H, CH ₃ ), 0.52 (d, 6H, CH ₃ ).

Example 15

The preparation method of the heteronuclear ruthenium-palladium bicyclic metal compound in this example is: add bromine-containing triphenylphosphine mononuclear ruthenium compound (1 mmol), boronic acid-containing N-p-methoxyphenyl-N′-p-methoxyphenyl imidazocarbene mononuclear cyclopalladium compound (1.05mmol), cesium carbonate (2.0mmol) and 20ml of anhydrous tetrahydrofuran at a temperature of 80 ℃, stirred and reacted under nitrogen atmosphere for 20 hours, then filtered, evaporated the solvent and recrystallized with a mixed solvent of CH ₂ Cl ₂ and petroleum ether to obtain the yellow product 15 heteronuclear N-p-methoxyphenyl-N′-p-methyl Oxyphenyl imidazole carbene ruthenium triphenylphosphine palladium bicyclic metal compound with a yield of 86.2%. The resulting product was analyzed by nuclear magnetic resonance, and the data are as follows: ¹ HNMR: δ=8.62(d, 1H, Ph-H), 8.53(d, 1H, Ph-H), 8.03(d, 2H, Ph-H), 7.80 -7.68(m,12H,Ph-H),7.56(m,4H,NCHCHN),7.43-7.51(m,16H,Ph-H),7.39-7.15(m,18H,Ph-H),6.92(m , 4H, Ph-H), 6.86 (d, 4H, Ph-H), 3.78 (s, 12H, CH ₃ ).

Example 17

The preparation method of the heteronuclear ruthenium-palladium bicyclic metal compound in the present embodiment is: in the 50ml there-necked bottle that is equipped with stirring reflux device, add the N-methyl-N '-methylimidazolcarbene mononuclear ruthenium compound containing chlorine atom ( 1mmol), N-methyl-N′-methylimidazolcarbene mononuclear cyclopalladium compound (1.15mmol), potassium hydroxide (4mmol) and 20ml of anhydrous toluene, at a temperature of 110 ℃, stirring and reacting under a nitrogen atmosphere for 16 hours, then filtered, distilled off the solvent, and recrystallized with a mixed solvent of CH ₂ Cl ₂ and petroleum ether to obtain the yellow product 17 heteronuclear N-methyl-N'-methylimidazole carbene ruthenium palladium Bicyclic metal compound, yield 83.9%. The resulting product was analyzed by nuclear magnetic resonance, and the data are as follows: ¹ HNMR: δ=8.68(d, 1H, Ph-H), 8.55(d, 1H, Ph-H), 8.01(d, 2H, Ph-H), 7.79 -7.61(m,12H,Ph-H),7.36(m,2H,NCHCHN),6.93(m,2H,Ph-H),4.20(s,12H,CH ₃ ),4.16(s,6H,CH ₃ ).

Example 20

The preparation method of the heteronuclear ruthenium-palladium bicyclic metal compound in this example is: add triphenylphosphine mononuclear ruthenium compound (1 mmol) containing iodine atom, boronic acid containing boric acid N-2,4,6-trimethylphenyl-N′-2,4,6-trimethylphenylimidazocarbene mononuclear palladium compound (1.05mmol), potassium carbonate (3mmol) and 20ml of anhydrous dioxane, stirred and reacted for 20 hours at a temperature of 110°C under a nitrogen atmosphere, then filtered, evaporated the solvent and recrystallized with a mixed solvent of CH ₂ Cl ₂ and petroleum ether to obtain the yellow product 20 heteronuclear triphenyl Ruthenium N-2,4,6-trimethylphenyl-N'-2,4,6-trimethylphenylimidazocarbene palladium bicyclic metal compound with a yield of 90.5%. The resulting product was analyzed by nuclear magnetic resonance, and the data are as follows: ¹ HNMR: δ=8.67(d, 1H, Ph-H), 8.56(d, 1H, Ph-H), 8.03(d, 2H, Ph-H), 7.79 -7.59(m,18H,Ph-H),7.38-7.29(m,24H,Ph-H),6.90(m,2H,Ph-H),4.21(s,12H,CH ₃ ),4.18(s, 6H, _CH3 ).

Example 21

In this example, the heteronuclear ruthenium-palladium bicyclic metal compound prepared in Example 1 is used to catalyze the synthesis of 3-phenyl-1-indanone. The preparation method is as follows: under the protection of high-purity nitrogen, add 0.05 mmol isocyanate to a 10 ml Schlek reaction tube Nuclear ruthenium palladium bicyclic metal compound 1, 1mmol o-iodoacetophenone, 2.5mmol benzyl alcohol, 2mmol potassium hydroxide and 3ml of dioxane, replace the reaction tube with nitrogen for 3 times, then heat to 110°C, the reaction was refluxed for 30 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract _three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter, and the filtrate is concentrated with a rotary evaporator, and the residue is washed with two Chloromethane/petroleum ether mixed solution is used as developing solvent, and the pure product 3-phenyl-1-indanone is obtained by silica gel thin-layer chromatography. The NMR analysis data of this compound are as follows: ¹ HNMR: δ=7.81(d, 1H, Ph-H), 7.56(t, 1H, Ph-H), 7.43(t, 1H, Ph-H), 7.24-7.35( m, 4H, Ph-H), 7.14 (m, 2H, Ph-H), 4.57 (dd, 1H, CH), 3.24 (dd, 1H, _CH2 ), 2.73 (dd, 1H, _CH2 ).

Example 22

In this example, the heteronuclear ruthenium-palladium bicyclic metal compound prepared in Example 3 is used to catalyze the synthesis of 3-(p-methoxyphenyl)-1-indanone. The preparation method is: under the protection of high-purity nitrogen, react with 10ml of Schlek Add 0.08mmol heteronuclear ruthenium palladium bicyclic metal compound 3, 1mmol o-bromoacetophenone, 2.0mmol p-methoxybenzyl alcohol, 2mmol sodium hydroxide and 3ml toluene to the tube, replace the reaction tube with nitrogen for 3 times, and then Heated to 110°C with an oil bath while stirring, and the reaction was refluxed for 36 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract _three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate was concentrated with a rotary evaporator, and the residue was washed with two Chloromethane/petroleum ether mixed solution is used as developing solvent, and the pure product 3-(p-methoxyphenyl)-1-indanone is obtained by silica gel thin-layer chromatography. The NMR analysis data of this compound are as follows: ¹ HNMR: δ=7.82(d, 1H, Ph-H), 7.57(t, 1H, Ph-H), 7.42(t, 1H, Ph-H), 7.27(d, 1H, Ph-H), 7.04 (m, 2H, Ph-H), 6.88 (m, 2H, Ph-H), 4.55 (dd, 1H, CH), 3.80 (s, 1H, CH ₃ ), 3.22 ( dd,1H, _CH2 ), 2.66 (dd,1H, _CH2 ).

Example 23

In this example, the heteronuclear ruthenium-palladium bicyclic metal compound prepared in Example 6 is used to catalyze the synthesis of 3-(p-chlorophenyl)-1-indanone. The preparation method is: under the protection of high-purity nitrogen, add 10ml of Schlek reaction tube Add 0.15mmol heteronuclear ruthenium palladium bicyclic metal compound 6, 1mmol o-bromoacetophenone, 1.5mmol p-chlorobenzyl alcohol, 3mmol sodium phosphate and 3ml tetrahydrofuran, replace the reaction tube with nitrogen for 3 times, and then use an oil bath under magnetic stirring Heat to 80°C and reflux the reaction for 36 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract _three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate was concentrated with a rotary evaporator, and the residue was washed with two Chloromethane/petroleum ether mixed solution is used as developing solvent, and the pure product 3-(p-chlorophenyl)-1-indanone is obtained by silica gel thin-layer chromatography. The NMR analysis data of this compound are as follows: ¹ HNMR: δ=7.80(d, 1H, Ph-H), 7.59(t, 1H, Ph-H), 7.43(t, 1H, Ph-H), 7.24-7.29( m, 3H, Ph-H), 7.05 (m, 2H, Ph-H), 4.56 (dd, 1H, CH), 3.23 (dd, 1H, _CH2 ), 2.62 (dd, 1H, _CH2 ).

Example 24

In this example, the heteronuclear ruthenium-palladium bicyclic metal compound prepared in Example 9 is used to catalyze the synthesis of 3-(2-furyl)-1-indanone. The preparation method is: under the protection of high-purity nitrogen, add 10ml of Schlek reaction tube Add 0.10 mmol heteronuclear ruthenium palladium bicyclic metal compound 9, 1 mmol o-chloroacetophenone, 2.5 mmol 2-furyl methanol, 3 mmol potassium phosphate and 3 ml of dioxane, replace the reaction tube with nitrogen for 3 times, and then Heated to 110°C with an oil bath, and the reaction was refluxed for 40 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract _three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate was concentrated with a rotary evaporator, and the residue was washed with two Chloromethane/petroleum ether mixed solution is used as developing solvent, and the pure product 3-(2-furyl)-1-indanone is obtained by silica gel thin-layer chromatography. The NMR analysis data of this compound are as follows: ¹ HNMR: δ=7.80(d,1H,Ph-H),7.62(t,1H,Ph-H),7.52(d,1H,Ph-H),7.44(t, 1H,Ph-H),7.35(m,1H,Ph-H),6.32(m,1H,Ph-H),6.11(d,1H,Ph-H),4.69(dd,1H,CH),3.12 (dd, 1H, CH ₂ ), 2.85 (dd, 1H, CH ₂ ).

Example 25

In this example, the heteronuclear ruthenium-palladium bicyclic metal compound prepared in Example 12 is used to catalyze the synthesis of 4-methyl-3-phenyl-1-indanone. The preparation method is: under the protection of high-purity nitrogen, add a 10ml Schlek reaction tube Add 0.05mmol of heteronuclear ruthenium palladium bicyclic metal compound 12, 1mmol of 3-methyl-o-iodoacetophenone, 3.0mmol of benzyl alcohol, 3mmol of potassium carbonate and 3ml of N,N-dimethylformamide, and replace the reaction tube with nitrogen 3 times, and then heated to 120° C. with an oil bath under magnetic stirring, and the reaction was refluxed for 35 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract _three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate was concentrated with a rotary evaporator, and the residue was washed with two Chloromethane/petroleum ether mixed solution was used as developing solvent, and the pure product 4-methyl-3-phenyl-1-indanone was obtained by silica gel thin-layer chromatography. The NMR analysis data of the compound are as follows: ¹ HNMR: δ=7.80(d,1H,Ph-H),7.65(m,1H,Ph-H),7.31-7.36(m,2H,Ph-H),7.15- 7.25(m,3H,Ph-H),7.00(m,2H,Ph-H),4.55(dd,1H,CH),3.20(dd,1H, _CH2 ),2.56(dd,1H, _CH2 ) , 1.98 (s, 3H, CH ₃ ).

Example 26

This example uses the heteronuclear ruthenium-palladium bicyclic metal compound prepared in Example 15 to catalyze the synthesis of 6-methoxy-3-phenyl-1-indanone. The preparation method is: under the protection of high-purity nitrogen, react with 10ml of Schlek Add 0.06mmol heteronuclear ruthenium palladium bicyclic metal compound 15, 1mmol 5-methoxy-o-chloroacetophenone, 1.8mmol benzyl alcohol, 2.5mmol sodium carbonate and 3ml toluene to the tube, replace the reaction tube with nitrogen for 3 times, and then in Heated to 110°C with an oil bath under magnetic stirring, and the reaction was refluxed for 30 hours. The oil bath was removed, and the water bath was lowered to room temperature; 3ml of water was added to the reaction solution, extracted three times with 5ml of dichloromethane, the organic phases _were combined and dried with anhydrous MgSO for 30 minutes, the filtrate was concentrated with a rotary evaporator, and the residue was dissolved in dichloromethane /petroleum ether mixed solution as a developing solvent, separated by silica gel thin layer chromatography to obtain the pure product 6-methoxyl-3-phenyl-1-indanone. The NMR analysis data of this compound are as follows: ¹ HNMR: δ=7.22-7.30(m, 4H, Ph-H), 7.17(m, 2H, Ph-H), 7.13(m, 2H, Ph-H), 4.53( dd, 1H, CH), 3.87 (s, 1H, CH ₃ ), 3.27 (dd, 1H, CH ₂ ), 2.71 (dd, 1H, CH ₂ ).

Example 27

In this example, the heteronuclear ruthenium palladium bicyclic metal compound prepared in Example 17 is used to catalyze the synthesis of 6-methyl-3-p-chlorophenyl-1-indanone. The preparation method is: under the protection of high-purity nitrogen, add 10 ml of Schlek Add 0.09mmol of heteronuclear ruthenium palladium bicyclic metal compound 17, 1mmol of 5-methyl-o-bromoacetophenone, 2.0mmol of p-chlorobenzyl alcohol, 2.5mmol of potassium hydroxide and 3ml of dioxane in the reaction tube, and replace the reaction with nitrogen tube 3 times, and then heated to 110°C with an oil bath under magnetic stirring, and the reaction was refluxed for 24 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract _three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate was concentrated with a rotary evaporator, and the residue was washed with two Chloromethane/petroleum ether mixture was used as developing solvent, and the pure product 6-methoxy-3-p-chlorophenyl-1-indanone was obtained by silica gel thin-layer chromatography. The NMR analysis data of this compound are as follows: ¹ HNMR: δ=7.24-7.31(m, 3H, Ph-H), 7.17(m, 2H, Ph-H), 7.13(m, 2H, Ph-H), 4.50( dd, 1H, CH), 3.25 (dd, 1H, CH ₂ ), 2.61 (dd, 1H, CH ₂ ), 1.89 (s, 1H, CH ₃ ).

Example 28

In this example, the heteronuclear ruthenium-palladium bicyclic metal compound prepared in Example 20 is used to catalyze the synthesis of 6-methoxy-3-m-p-dichlorophenyl-1-indanone. The preparation method is: under the protection of high-purity nitrogen, to Add 0.10mmol heteronuclear ruthenium palladium bicyclometalate 20, 1mmol 5-methoxy-o-chloroacetophenone, 2.0mmol o-p-dichlorobenzyl alcohol, 5mmol triethylamine and 3ml dioxane to a 10ml Schlek reaction tube , the reaction tube was replaced with nitrogen for 3 times, and then heated to 110° C. in an oil bath under magnetic stirring, and the reaction was refluxed for 48 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract _three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate was concentrated with a rotary evaporator, and the residue was washed with two Chloromethane/petroleum ether mixture was used as a developing solvent, and the pure product 6-methoxy-3-m-p-dichlorophenyl-1-indanone was obtained by silica gel thin-layer chromatography. The NMR analysis data of this compound are as follows: ¹ HNMR: δ=7.35(d, 1H, Ph-H), 7.12-7.22(m, 4H, Ph-H), 6.93(dd, 1H, Ph-H), 4.48( dd,1H,CH), 3.86(s,1H, _CH3 ), 3.85(s,3H, _CH3 ), 3.23(dd,1H, _CH2 ), 2.60(dd,1H, _CH2 ).

Claims (4)

1. the bis-cyclometallated compound of heteronuclear ruthenium palladium, is characterized in that: its general structure is:

In formula: X, X ₁, Y, Y ₁independently be selected from C atom or atom N, when X and Y is different, get same atoms, X ₁with Y ₁asynchronously get same atoms, Z, Z ₁independently be selected from Cl ^-, Br ^-, I ^-, L, L ₁independently be selected from tertiary phosphine-ligand or tetrahydroglyoxaline ring carbenes;

The general structure of described tertiary phosphine-ligand is: described tertiary phosphine-ligand is

The general structure of described tetrahydroglyoxaline ring carbenes is: described tetrahydroglyoxaline ring carbenes is

2. the preparation method of the bis-cyclometallated compound of heteronuclear ruthenium palladium as claimed in claim 1, it is characterized in that: step is as follows: be the monokaryon ring palladium compound containing Knit-the-brows any borate group according to mol ratio: the monokaryon ring ruthenium compound of halogen atom: alkaline matter A=(1 ~ 1.5): 1:(1 ~ 5) get each material and join in solvent orange 2 A, temperature be 80 ~ 120 DEG C, heating reflux reaction 10 ~ 24 hours under protection of inert gas, reaction terminates rear filtration, evaporate to dryness, recrystallization, obtains the bis-cyclometallated compound of heteronuclear ruthenium palladium;

The general structure of the monokaryon ring ruthenium compound of described halogen atom is:

In formula: X, Y are independently selected from C atom or atom N, but get same atoms when X and Y is different, and Z is selected from Cl ^-, Br ^-or I ^-, Z ₂be selected from Cl, Br or I, L is tertiary phosphine-ligand or tetrahydroglyoxaline ring carbenes;

The general structure of the described monokaryon ring palladium compound containing which borate group of Knit-the-brows is:

In formula: X ₁, Y ₁independently be selected from C atom or atom N, but X ₁with Y ₁asynchronously get same atoms, Z ₁be selected from Cl ^-, Br ^-or I ^-, L ₁for tertiary phosphine-ligand or tetrahydroglyoxaline ring carbenes;

Described alkaline matter A is sodium carbonate, salt of wormwood, cesium carbonate, sodium phosphate or potassiumphosphate, and described solvent orange 2 A is dioxane, benzene, toluene, Virahol, tetrahydrofuran (THF) or DMF.

3. the bis-cyclometallated compound of heteronuclear ruthenium palladium as claimed in claim 1 prepares an application for indenes ring benzyl position substitutive derivative at the adjacent halo acetophenone of catalysis and the synthesis of benzylalcohol linked reaction, and the general structure of described indenes ring benzyl position substitutive derivative is: in formula: R in 1,2,3,4 any position, R ₁in 1 ', 2 ', 3 ' any position;

The general structure of described adjacent halo acetophenone is: in formula: R is-H ,-CH ₃,-OCH ₃,-NO ₃,-C ₂h ₃,-C ₃h ₇,-C ₄h ₉, Cl, Br, I or Aryl-, described Aryl-is described R is in 1,2,3,4 any position; X is selected from Cl, Br or I;

The general structure of described benzylalcohol is: in formula: R ₁for-H ,-CH ₃,-OCH ₃,-NO ₃,-C ₂h ₃,-C ₃h ₇,-C ₄h ₉, Cl, Br, I or Aryl-, described Aryl-is described R ₁in 1 ', 2 ', 3 ' any position.

4. the application of the bis-cyclometallated compound of heteronuclear ruthenium palladium according to claim 3, it is characterized in that: the step that indenes ring benzyl position substitutive derivative is prepared in the adjacent halo acetophenone of described heteronuclear ruthenium palladium bis-cyclometallated compound catalysis and the synthesis of benzylalcohol linked reaction is as follows: be the bis-cyclometallated compound of heteronuclear ruthenium palladium according to mol ratio: adjacent halo acetophenone: benzylalcohol: alkaline matter B=(0.05 ~ 0.1): 1:(1 ~ 3): (1 ~ 6) is got each material and is joined in solvent B, it is 80 ~ 120 DEG C in temperature, heating reflux reaction 12 ~ 48 hours under protection of inert gas, react complete and be down to room temperature, add and urge agent of going out to urge reaction of going out, be separated, concentrated, purifying, namely indenes ring benzyl position substitutive derivative is obtained after drying,

Described alkaline matter B is sodium carbonate, salt of wormwood, sodium phosphate, potassiumphosphate, sodium hydroxide, potassium hydroxide or triethylamine, and described solvent B is ethanol, propyl alcohol, Virahol, dioxane, benzene, toluene, tetrahydrofuran (THF) or DMF.