Triaryl phosphorus oxygen-containing ligand and preparation method thereof
Technical Field
The invention belongs to the technical field of organic compound synthesis, and particularly relates to a triaryl phosphorus-oxygen-containing ligand and a preparation method thereof.
Background
Transition metal-catalyzed carbon-hydrogen bond activation and functionalization are receiving increasing attention due to the advantages of wide substrate application range, atom economy and the like. Among these catalytic conversion reactions, influencing the activity and selectivity of metal catalysts by changing the structure of the ligand is one of the most powerful means. The ligand can change the electrical property of the metal to influence the catalytic activity, and can also change the steric effect around the metal to influence the stereoselectivity of the reaction. Among these, phosphorus ligands are receiving increasing attention due to their important role in transition metal catalyzed reactions (Scheme 1).
In recent years, phosphorus-oxygen directed carbon-hydrogen bond functionalization has become a hot spot of controversy. According to the transition state during the reaction, the following can be classified: a six-membered ring palladium transition state, a five-membered ring rhodium transition state, a five-membered ring iridium transition state, a five-membered ring ruthenium transition state, a five-membered ring palladium transition state, a five-membered ring cobalt transition state, etc. (Scheme 2).
Organophosphorus oxygen ligands play an important role in transition metal catalyzed reactions. Therefore, the search for a simple and efficient method for synthesizing various organophosphorus oxygen ligands has been the goal of many chemists. Although great progress has been made in this respect over the last few years, the number of types of phosphorus oxygen-based ligands synthesized at present is not so great that the development of more novel and highly efficient phosphorus oxygen ligands is still indispensable.
Disclosure of Invention
The invention aims to provide a triaryl phosphorus-oxygen-containing ligand which has multiple rings, a more complex structure and a wide application prospect.
The invention also provides a preparation method of the triaryl phosphorus-oxygen-containing ligand, which is simple, convenient, green and high in atom economy.
The technical scheme adopted by the invention is as follows:
a triaryl phosphorus oxygen-containing ligand, wherein the structural general formula of the triaryl phosphorus oxygen-containing ligand is as follows:
wherein R is1Is a linear alkyl, branched alkyl, saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon group;
R2is halogen, straight chain alkyl, branched chain alkyl, ester group, alkoxy and corresponding derivatives thereof; r2Can be in any position of the benzene ring.
Further, said R1Preferably a linear alkyl group, branched alkyl group, saturated hydrocarbon group, unsaturated hydrocarbon group or aromatic hydrocarbon group of four or less carbons; r2Preferably halogen, straight chain alkyl of four carbons or less, branched alkyl, ester group, alkoxy and corresponding derivatives thereof; r2Can be in any position of the benzene ring.
Further, said R1Preferably ethyl; r2Hydrogen is preferred.
The invention also provides a preparation method of the triaryl phosphorus-oxygen-containing ligand, which comprises the following steps:
(1) synthesizing a precursor compound having the structural formula
Wherein R is1Is a linear alkyl, branched alkyl, saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon group;
R2is halogen, straight chain alkyl, branched chain alkyl, ester group, alkoxy and corresponding derivatives thereof; r2Can be positioned at any position of a benzene ring;
(2) and reacting the precursor compound with diphenylphosphorus in anhydrous toluene, and separating and purifying after the reaction is finished to obtain the triaryl phosphorus oxygen-containing ligand.
In the step (1), the R1Preferably ethyl; r2Hydrogen is preferred.
In the step (1), the preparation method of the precursor compound comprises the following steps:
(1-1) reacting malonate and propargyl bromide in an anhydrous acetonitrile solvent for 5-8 hours in an ice-water bath by using sodium hydride as a catalyst, and separating and purifying to obtain a compound a;
the malonic ester has the general formula:
(1-2) reacting the compound a obtained in the step (1) with a substituent of phenyl bromoacetylene in an anhydrous acetonitrile solvent at 0-5 ℃ for 10-14 hours under the action of a catalyst and an organic base under anhydrous and oxygen-free conditions, and separating and purifying to obtain a precursor compound, namely a compound b;
the chemical structural formula of the substituent of the phenyl bromoacetylene is as follows:
in the step (1-1), the ratio of the amounts of the malonic ester, propargyl bromide and sodium hydride is 1: 2.2-3.2: 4-5, wherein the concentration of the malonate in the anhydrous acetonitrile is 0.8-1.5 mol/L.
In the step (1-2), the catalyst is Pd (PPh)3)2Cl2And CuI, the organic base is triethylamine. Pd (PPh)3)2Cl2And CuI is 3: 1.
in the step (1-2), the ratio of the amounts of the substance among the compound a, the substituent of phenyl bromoacetylene, the catalyst and the organic base is 1: 2.2-3.2: 0.03-0.05: 4-5, and the concentration of the compound a in anhydrous acetonitrile is 0.5-0.8 mol/L.
The separation and purification method adopted in the step (1-2) comprises the following steps: the crude product is separated by extraction with ethyl acetate and water, concentrated and then purified by distillation in a volume ratio of 1: 40-60% of ethyl acetate: and (4) performing column chromatography separation and purification by using petroleum ether as an eluent.
In the step (2), the reaction condition is that the reaction is carried out for 8 to 10 hours at the temperature of between 95 and 110 ℃.
In the step (2), the ratio of the amounts of the precursor compound and the diphenylphosphorus substance is 1: 1.0-1.2.
In the step (2), the concentration of the precursor compound in the anhydrous toluene is 0.3 to 1.0mol/L, preferably 0.5 mol/L.
In the step (2), the separation and purification method comprises the following steps: the crude product is separated by extraction with ethyl acetate and water, concentrated and then purified by distillation in a volume ratio of 1: 20-40 of ethyl acetate: and (4) performing column chromatography separation and purification by using petroleum ether as an eluent.
Compared with the prior art, the invention provides a series of novel triaryl phosphorus oxygen-containing ligands. Different multiple alkyne substrates are used for constructing the triaryl phosphorus oxygen-containing ligand through a series reaction, the reaction overcomes the defects of long route, strict requirements on the substrates and reaction conditions, limited expansion of substituted functional groups and the like in the prior reaction, the reaction has the advantages of simple substrate synthesis, cheap reagent, high atom economy, simplicity and high efficiency, and provides a brand new way for the application of the triaryl phosphorus oxygen-containing ligand in the field of carbon-hydrogen bond activation catalyzed by transition metal.
The synthesis mechanism of the triaryl phosphorus-oxygen ligand is shown as 8: firstly, obtaining a benzyne intermediate A from a precursor compound through HDDA reaction; then, the benzyne intermediate A and diphenyl phosphorus which is a compound with strong nucleophilicity undergo nucleophilic addition reaction to obtain an intermediate B; and finally, quickly oxidizing the intermediate B to obtain the triaryl phosphorus-oxygen ligand.
Compared with the common ligand containing triaryl phosphorus oxygen, the ligand containing triaryl phosphorus oxygen prepared by the invention has multiple rings, has more complex and diversified structures, and has wider application prospect in organic synthetic chemistry. Moreover, the preparation method provided by the invention is simple, convenient and efficient, and has short reaction time and high efficiency.
Drawings
FIG. 1 is a general structural formula of a triarylphosphine-oxygen-containing ligand;
FIG. 2 is a diagram of a synthetic scheme for triarylphosphine oxide-containing ligands;
FIG. 3 is a synthetic scheme of triarylphosporoxy-containing ligand c-1 prepared in example 1;
FIG. 4 is a NMR spectrum of triarylphosphine oxy-containing ligand c-1 prepared in example 1;
FIG. 5 is a carbon NMR spectrum of triarylphosphine oxide-containing ligand c-1 prepared in example 1;
FIG. 6 is a NMR spectra of phosphorus containing triaryl phosphorus-oxygen ligand c-1 prepared in example 1;
FIG. 7 is an XRD single crystal diffractogram of triarylphosphorus oxo-containing ligand c-1 prepared in example 1;
FIG. 8 is a diagram showing the mechanism of synthesis of triarylphosphine oxide-containing ligands in example 1.
Detailed Description
Example 1
A triaryl phosphorus oxygen-containing ligand, wherein the structural formula of the triaryl phosphorus oxygen-containing ligand is as follows:
a preparation method of a triaryl phosphorus-oxygen-containing ligand comprises the following steps:
(1) adding 200mmol of diethyl malonate and 440mmol of propargyl bromide into 210mL of anhydrous acetonitrile in an ice water bath by using 830mmol of sodium hydride as a catalyst, stirring for reacting for 8 hours, adding water into the product for washing, extracting by using ethyl acetate, and performing reduced pressure spin drying to obtain a white solid product, namely a compound a-1;
(2) 80mmol of the compound a-1 was mixed with 200mmol of phenylethynyl bromide in Pd (PPh)3)2Cl2In the anhydrous oxygen-free catalytic system of CuI (2.56mmol/0.85mmol), the molar ratio is Pd (PPh)3)2Cl2: CuI ═ 3: 1, using 336mmol triethylamine as a base, using 150mL anhydrous acetonitrile as a solvent, stirring and reacting at 0 ℃ for 12 hours, washing a product with water, extracting with ethyl acetate, performing reduced pressure spin drying, and performing reaction on the product by using a solvent with a volume ratio of 1: ethyl acetate of 40: and (4) performing column chromatography separation on petroleum ether to obtain a white solid product, namely the compound b-1.
(3) Reacting 1.0mmol of the compound b-1 prepared in the step (2) with 1.1mmol of diphenylphosphine in 2mL of anhydrous toluene solvent at 110 ℃ for 10 hours to obtain a compound c-1, namely a crude product containing triaryl phosphorus oxygen ligand; washing the prepared crude product containing the triaryl phosphorus-oxygen ligand by using water, extracting by using ethyl acetate, performing reduced pressure spin drying, and performing volume ratio on the obtained product by using ethyl acetate: petroleum ether is 1: and (3) performing column chromatography separation by 20 to obtain a white solid product, namely the product containing the triaryl phosphorus oxygen ligand c-1, wherein the column chromatography yield is about 85 percent.
The product structure is passed through1H NMR、13C NMR、31P NMR, as follows:
1H NMR(500MHz,CDCl3)δ7.34-7.27(m,8H),7.25-7.17(m,8H),7.11-7.07(m,4H),6.80(s,1H),4.24(q,J=8.5Hz,4H),3.81(s,2H),3.57(s,2H),1.28(t,J=7.0Hz,6H);
13C NMR(125MHz,CDCl3)δ171.5,148.6.(d,JC-P=25Hz),143.1,139.7,139.6,139.0,137.2,137.1,135.9,135.8,133.9,133.7,131.2,130.3,130.2,128.5,128.3,128.2,128.1,127.9,127.1,127.0,123.0,120.0,119.9,96.8,86.7,61.7,59.2,40.7,13.9;
31P NMR(202MHz,CDCl3)δ-12.88(s)。
the above detailed description of a triaryl phosphorus oxygen-containing ligand and the method for preparing the same, with reference to the examples, is illustrative and not restrictive, and several examples are set forth within the scope of the invention, so that variations and modifications thereof can be made without departing from the general inventive concept and are intended to be within the scope of the invention.