CN115055207B - A kind of method of reducing aryl phosphine oxide to prepare aryl phosphine - Google Patents

Abstract

The invention discloses a method for preparing aryl phosphine by reducing aryl phosphine oxide. The method comprises the steps of generating aryl phosphine by aryl phosphine oxide and a reducing agent under the action of the organophosphorus catalyst of the invention; the organophosphorus catalyst of the invention is a compound with simple structure and simple synthesis route or is commercially available, stable in air and easy to operate, and can efficiently reduce aryl phosphine oxide to aryl phosphine under mild reaction conditions.

Description

A kind of method of reducing aryl phosphine oxide to prepare aryl phosphine

technical field

The invention belongs to the field of catalytic organic synthesis, in particular, the invention relates to a method for preparing aryl phosphine by reducing aryl phosphine oxide.

Background technique

Arylphosphines are important reagents used in organic chemical transformations. For example, the Appel reaction, Mitsunobu reaction, Staudinger reaction, Wittig reaction, etc. commonly used in industry and laboratories all require the use of equivalent triphenylphosphine as a reaction reagent. In these reactions triphenylphosphine oxide is produced as a by-product of the reaction. Triphenylphosphine oxide is a common industrial discharge and an important phosphorus-containing organic pollutant in water. The large amount of triphenylphosphine oxide produced in industry has brought great challenges to the environment. On the other hand, phosphate rock is a non-renewable resource. China is the world's largest consumer of phosphate rock, and our country is facing severe pressure of resource consumption. In addition, arylphosphine is also the most important class of ligands in organometallic chemistry. The reduction of arylphosphine oxides to the corresponding arylphosphine provides a new synthetic method for the preparation of high-value phosphorus-containing ligands.

In the related art, the method for reducing aryl phosphine oxide requires the use of strong negative hydrogen reducing reagents, including lithium aluminum hydride, borane, calcium hydride and the like. These reducing agents are expensive and the reaction is violently exothermic, which limits their wide application. Silanes are inexpensive, low-toxicity reducing agents that can also be used to reduce arylphosphine oxides. In 1964, Fritsche et al. found that active trichlorosilane (Cl ₃ SiH) could reduce phosphine oxide. Since the 1990s, it has been found that phenylsilane (PhSiH ₃ ) can reduce phosphine oxide to phosphine under the catalysis of strong Lewis acids, such as Ti(Oi-Pr) ₄ , InBr ₃ , Cu(OTf) ₂ , B(C ₆ F ₅ ) ₃ , or strong protonic acids, such as trifluoromethanesulfonic acid. However, these methods have some disadvantages, including: generally higher catalyst loading and higher temperature (for example, the reaction temperature is 60-120°C) are used, and the strong acidity of the catalyst limits the scope of the reaction substrate. Therefore, it is particularly important for scientific research and industrial production to develop an inexpensive, sustainable, and mild method for the reduction of arylphosphine oxides to arylphosphine.

Contents of the invention

The present invention aims to solve one of the technical problems in the related art at least to a certain extent. To this end, it is an object of the present invention to propose a catalyst composition for the catalytic reduction of arylphosphine oxides to prepare arylphosphines.

Another purpose of the embodiments of the present invention is to propose the use of an organophosphorus catalyst in the catalytic reduction of aryl phosphorus oxides to prepare aryl phosphorus.

Another purpose of the embodiments of the present invention is to propose a method for preparing arylphosphine by catalytic reduction of arylphosphine oxide with an organophosphorus catalyst, which can efficiently prepare arylphosphine products under mild conditions.

The catalyst composition of the embodiment of the present invention comprises a compound of formula (I) and a compound of formula (II);

The structural formula of the compound of formula (I) is shown in formula (I-1), formula (I-2) or formula (I-3):

Wherein, said n is 0 or 1 or 2, and said n' is 0 or 1 or 2;

The R ^is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituting group in the substituted phenyl is selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl;

The R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently one of H, C1-C6 alkyl, phenyl or substituted phenyl, and the substituents in the substituted phenyl are selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl;

said Indicates a single or double bond;

The structural formula of the compound of formula (II) is:

Wherein, the R ¹¹ and R ¹² are each independently one of methyl, ethyl, isopropyl or benzyl, and R ¹³ is H or methyl.

The composition of the catalyst composition of the embodiment of the present invention is a simple structure, simple synthetic route or a commercially available compound, which is stable in the air and easy to operate. The catalyst composition of the embodiment of the present invention can efficiently prepare aryl phosphine from aryl phosphine oxide under mild reaction conditions.

In some embodiments, the halogen is fluorine, chlorine, bromine or iodine.

In some embodiments, the R ¹ is one of methyl, ethyl, cyclopropyl or phenyl, the R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently H, methyl or ethyl; the R ⁷ is H, methyl, ethyl or phenyl; the R ⁸ is H, methyl, ethyl or phenyl; and the R ⁹ and R ¹⁰ are each independently H or C1-C4 alkyl.

In some embodiments, the structural formula of the compound of formula (I) is shown in formula (I-11), formula (I-12), formula (I-13), formula (I-21) or formula (I-31):

In some embodiments, the compound of formula (II) is diethyl bromomalonate.

In some embodiments, the molar ratio of the compound of formula (I) to the compound of formula (II) is: 1:(0.4-2), preferably, the molar ratio is 1:(0.5-1).

The embodiment of the present invention also provides a use of an organophosphorus catalyst in the catalytic reduction of aryl phosphorus oxide to prepare aryl phosphorus, the organophosphorus catalyst being the above catalyst composition, or a compound of formula (III);

The structural formula of the compound of formula (III) is shown in formula (III-1), formula (III-2) or formula (III-3):

In the compound of formula (III), the n is 0 or 1 or 2, and the n' is 0 or 1 or 2;

The R ^is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituting group in the substituted phenyl is selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl;

The R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently one of H, C1-C6 alkyl, phenyl or substituted phenyl, and the substituents in the substituted phenyl are selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl;

said Indicates a single or double bond;

Said X ^— is one of halide ion, nitrate ion, perchlorate ion, carbanion;

The structural formula of the aryl phosphine oxide is shown in formula (IV), and the corresponding structural formula of the aryl phosphine is shown in formula (V):

Wherein, the X ₁ and X ₂ are each independently one of halogen, C1-C6 alkyl, C1-C6 alkoxy, and C6-C12 aryl; the R is one of C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aryl, or a substituted C6-C12 aryl, and the substituting group in the substituted C6-C12 aryl is selected from halogen or halogenated C1-C6 alkyl one or more of.

In the embodiment of the present invention, the organophosphorus catalyst is used to catalyze the reduction of aryl phosphorus oxide to prepare aryl phosphorus, and the organophosphorus catalyst can efficiently reduce aryl phosphine oxide to prepare aryl phosphine under mild reaction conditions.

In some embodiments, in the compound of formula (III), the R ¹ is one of methyl, ethyl, cyclopropyl or phenyl, the R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently H, methyl or ethyl; the R ⁷ is H, methyl, ethyl or phenyl; the R ⁸ is H, methyl, ethyl or phenyl; the R ⁹ and R ¹⁰ are each independently H or C1-C4 alkyl.

In some embodiments, the structural formula of the compound of formula (III) is shown in formula (III-11) or formula (III-12):

Wherein, X ^— is a halide ion.

In some embodiments, the X ^— is Cl ^— or Br ^— .

The embodiment of the present invention also provides a method for preparing arylphosphine by reducing arylphosphine oxide, comprising the following steps: the arylphosphine oxide generates the arylphosphine under the action of an organic phosphorus catalyst;

The structural formula of the aryl phosphine oxide is shown in formula (IV), and the corresponding structural formula of the aryl phosphine is shown in formula (V):

Wherein, the X ₁ and X ₂ are each independently one of halogen, C1-C6 alkyl, C1-C6 alkoxy, and C6-C12 aryl; the R is one of C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aryl, or a substituted C6-C12 aryl, and the substituting group in the substituted C6-C12 aryl is selected from halogen or halogenated C1-C6 alkyl one or more of

The organophosphorus catalyst is the above-mentioned catalyst composition or a compound of formula (III);

The structural formula of the compound of formula (III) is shown in formula (III-1), formula (III-2) or formula (III-3):

In the compound of formula (III), the n is 0 or 1 or 2, and the n' is 0 or 1 or 2;

The R ^is one of C1-C6 alkyl, C3-C6 cycloalkyl, phenyl or substituted phenyl, and the substituting group in the substituted phenyl is selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl;

The R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently one of H, C1-C6 alkyl, C3-C6 cycloalkyl, phenyl or substituted phenyl, and the substituents in the substituted phenyl are selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl;

said Indicates a single or double bond;

Described X ^is one in halide ion, nitrate ion, perchlorate ion, carbanion.

In some embodiments, the halogen is fluorine, chlorine, bromine or iodine.

In some embodiments, in the compound of formula (III), the R ¹ is one of methyl, ethyl, cyclopropyl or phenyl, the R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently H, methyl or ethyl; the R ⁷ is H, methyl, ethyl or phenyl; the R ⁸ is H, methyl, ethyl or phenyl; the R ⁹ and R ¹⁰ are each independently H or C1-C4 alkyl.

In some embodiments, the structural formula of the compound of formula (III) is shown in formula (III-11) or formula (III-12):

Wherein, the ^X- is a halide ion.

In some embodiments, the method includes: performing a reduction reaction between the aryl phosphine oxide and a reducing agent under the action of the organophosphorus catalyst to generate the aryl phosphorus; the structural formula of the reducing agent is shown in formula (VI):

Wherein, the R ¹⁴ , R ¹⁵ , and R ¹⁵ are each independently one of H, C1-C6 alkyl, C1-C6 alkoxy, and C6-C12 aryl.

In some embodiments, the reducing agent is phenylsilane.

In some embodiments, the molar ratio of the arylphosphine oxide to the reducing agent is: 1:(1˜1.5).

In some embodiments, the reduction reaction is performed under nitrogen or argon.

In some embodiments, the reduction reaction temperature is normal temperature, and the reaction time is 6-15 hours.

When the organophosphorus catalyst is a combination of a compound of formula (I) and a compound of formula (II), the molar ratio of the arylphosphine oxide, reducing agent, compound of formula (I) and compound of formula (II) is: 1:(1～1.5):(0.01～0.15):(0.01～0.1);

When the organophosphorus catalyst is a compound of formula (III), the molar ratio of the arylphosphine oxide, reducing agent, and compound of formula (III) is 1:(1-1.5):(0.1-0.15).

The advantages and beneficial effects of the embodiments of the present invention are:

(1) The composition of the catalyst composition of the present invention is a simple structure, a simple synthetic route or a commercially available compound, which is stable in the air and easy to operate. The catalyst composition of the embodiment of the present invention can efficiently reduce aryl phosphine oxide to prepare aryl phosphine under mild reaction conditions.

(2) The method for preparing arylphosphine by reducing arylphosphine oxide in the embodiment of the present invention has mild conditions and fast reaction speed, and the product can be efficiently prepared at room temperature.

(3) The method for preparing arylphosphine by reducing arylphosphine oxide in the embodiment of the present invention has a low catalyst content, and the product can be obtained in a high yield under a relatively low catalyst loading condition.

(4) The method of reducing aryl phosphine oxide to prepare aryl phosphine according to the embodiment of the present invention has mild reaction conditions and wide functional group tolerance.

Description of drawings

The above and/or additional aspects and advantages of the present invention will become apparent and comprehensible from the following description of the embodiments in conjunction with the accompanying drawings.

Fig. 1 is a schematic diagram of the reaction principle of the embodiment of the present invention.

Detailed ways

Embodiments of the present invention are described in detail below, and the embodiments described below are exemplary and intended to explain the present invention, but should not be construed as limiting the present invention.

The experimental methods used in the following examples are conventional methods unless otherwise specified.

Materials, reagents, devices, etc. used in the following examples, unless otherwise specified, can be obtained from commercial sources or prepared according to methods in published literature.

For example, the compound of formula (I) in the embodiment of the present invention can be synthesized by referring to the method of Org.Synth.2015, 92, 267; J.Am.Chem.Soc.2022, 144, 8242;

The compound of formula (III) in the embodiment of the present invention can be synthesized by referring to the method of J.Am.Chem.Soc.2019, 141, 12507.

The following is a description of terms or words, and unless otherwise defined, all technical and scientific terms used herein have the meanings commonly understood by those skilled in the art to which this invention belongs.

As used herein, the words "comprising" and "comprising" and their variations mean that other elements or integers that are allowed but not specifically described may be included.

The term "C1-C6 alkyl" means a saturated linear or branched monovalent hydrocarbon group containing 1-6 carbon atoms; in one embodiment, 1-4 carbon atoms; in another embodiment, 1-3 carbon atoms; non-limiting examples of "C1-C6 alkyl" include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methyl -2-butyl, 3-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl and the like.

The term "halogenated C1-C6 alkyl" refers to a C1-C6 alkyl group as defined above, substituted with one or more halogen atoms. Non-limiting examples of "halogenated C1-C6 alkyl" include: fluoromethyl, fluoroethyl, difluoromethyl, difluoroethyl, trifluoromethyl, trifluoroethyl, bromomethyl, bromoethyl, dibromomethyl, dibromoethyl, tribromomethyl, tribromoethyl, and the like.

The term "C1-C6 alkoxy" means that a "C1-C6 alkyl" is attached to the rest of the molecule through an oxygen atom, wherein "C1-C6 alkyl" has a meaning as described herein. Non-limiting examples of "C1-C6 alkoxy" include: methoxy, ethoxy, 1-propoxy, 2-propoxy, and the like.

The term "C3-C6 cycloalkyl" means a monovalent or multivalent saturated monocyclic or bicyclic ring system containing 3-6 carbon atoms. Non-limiting examples of "C3-C6 cycloalkyl" include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

The term "C6-C12 aryl" means a monocyclic, bicyclic and tricyclic carbocyclic ring system containing 6-12 ring atoms, wherein at least one ring system is aromatic, non-limiting examples of "C6-C12 aryl" include: phenyl, indenyl, naphthyl and the like.

The term "halogen" means fluorine, chlorine, bromine or iodine.

The term "substituted" means that one or more hydrogen atoms in a given structure are replaced by a specified substituent. Unless otherwise indicated, a substituent group may substitute at each substitutable position of a given structure. When more than one position in a given structure can be substituted by one or more substituents selected from a particular group, then the substituents may be substituted at each position the same or differently.

The terms "normal temperature" and "room temperature" generally refer to 25±5°C.

The catalyst composition of the embodiment of the present invention comprises a compound of formula (I) and a compound of formula (II);

The structural formula of the compound of formula (I) is shown in formula (I-1), formula (I-2) or formula (I-3):

Wherein, n is 0 or 1 or 2, and n' is 0 or 1 or 2;

R ^is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituent group in substituted phenyl is selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl;

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each independently one of H, C1-C6 alkyl, phenyl or substituted phenyl, and the substituents in substituted phenyl are selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl;

said Indicates a single or double bond;

The structural formula of the compound of formula (II) is:

Wherein, R ¹¹ and R ¹² are each independently one of methyl, ethyl, isopropyl and benzyl, and R ¹³ is H or methyl.

The composition of the catalyst composition of the embodiment of the present invention is a simple structure, simple synthetic route or a commercially available compound, which is stable in the air and easy to operate. The catalyst composition of the embodiment of the present invention can efficiently prepare aryl phosphine from aryl phosphine oxide under mild reaction conditions.

In some embodiments, the halogen is fluorine, chlorine, bromine or iodine.

In some embodiments, R ¹ is one of methyl, ethyl, cyclopropyl or phenyl, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently H, methyl or ethyl; R ⁷ is H, methyl, ethyl or phenyl; R ⁸ is H, methyl, ethyl or phenyl; R ⁹ , R ¹⁰ are each independently H or C1-C4 alkyl.

In some embodiments, the structural formula of the compound of formula (I) is shown in formula (I-11), formula (I-12), formula (I-13), formula (I-21) or formula (I-31):

In some embodiments, the compound of formula (II) is diethyl bromomalonate.

In some embodiments, the molar ratio of the compound of formula (I) to the compound of formula (II) is: 1:(0.4-2), preferably, the molar ratio is 1:(0.5-1).

The embodiment of the present invention also provides a use of an organophosphorus catalyst in the catalytic reduction of aryl phosphorus oxides to prepare aryl phosphorus, where the organophosphorus catalyst is the above catalyst composition, or a compound of formula (III);

The structural formula of the compound of formula (III) is shown in formula (III-1), formula (III-2) or formula (III-3):

In the compound of formula (III), n is 0 or 1 or 2, and n' is 0 or 1 or 2;

^R is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituting group in substituted phenyl is selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl;

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each independently one of H, C1-C6 alkyl, phenyl or substituted phenyl, and the substituents in substituted phenyl are selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl;

Indicates a single or double bond;

X ^— is one of halogen ion, nitrate ion, perchlorate ion, carbanion;

The structural formula of aryl phosphorus oxide is as shown in formula (IV), and the structural formula of corresponding aryl phosphine is as shown in formula (V):

Wherein, X ₁ and X ₂ are each independently one of halogen, C1-C6 alkyl, C1-C6 alkoxy, and C6-C12 aryl; R is one of C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aryl, or one of substituted C6-C12 aryl, and the substituent group in substituted C6-C12 aryl is selected from one of halogen or halogenated C1-C6 alkyl or more.

In the embodiment of the present invention, the organophosphorus catalyst is used to catalyze the reduction of aryl phosphorus oxide to prepare aryl phosphorus, and the organophosphorus catalyst can efficiently reduce aryl phosphine oxide to prepare aryl phosphine under mild reaction conditions.

In some embodiments, in the compound of formula (III), R ¹ is one of methyl, ethyl, cyclopropyl or phenyl, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently H, methyl or ethyl; R ⁷ is H, methyl, ethyl or phenyl; R ⁸ is H, methyl, ethyl or phenyl; R ⁹ , R ¹⁰ are each independently H or C1-C4 alkyl.

In some embodiments, the structural formula of the compound of formula (III) is as shown in formula (III-11) or formula (III-12):

Wherein, X ^— is a halide ion.

In some embodiments, X ^— is Cl ^— or Br ^— .

The embodiment of the present invention also provides a method for preparing arylphosphine by reducing arylphosphine oxide, which includes the following steps: arylphosphine oxide generates arylphosphine under the action of an organic phosphorus catalyst;

The structural formula of aryl phosphorus oxide is as shown in formula (IV), and the structural formula of corresponding aryl phosphine is as shown in formula (V):

Wherein, X ₁ and X ₂ are each independently one of halogen, C1-C6 alkyl, C1-C6 alkoxy, and C6-C12 aryl; R is one of C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aryl, or one of substituted C6-C12 aryl, and the substituent group in substituted C6-C12 aryl is selected from one of halogen or halogenated C1-C6 alkyl or more;

The organophosphorus catalyst is the above-mentioned catalyst composition or a compound of formula (III);

The structural formula of the compound of formula (III) is shown in formula (III-1), formula (III-2) or formula (III-3):

In the compound of formula (III), n is 0 or 1 or 2, and n' is 0 or 1 or 2;

R ^is one of C1-C6 alkyl, C3-C6 cycloalkyl, phenyl or substituted phenyl, and the substituent group in substituted phenyl is selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl;

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently one of H, C1-C6 alkyl, C3-C6 cycloalkyl, phenyl or substituted phenyl, and the substituents in the substituted phenyl are selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl;

Indicates a single or double bond;

X ^— is one of halogen ion, nitrate ion, perchlorate ion, carbanion.

In some embodiments, the halogen is fluorine, chlorine, bromine or iodine.

In some embodiments, in the compound of formula (III), R ¹ is one of methyl, ethyl, cyclopropyl or phenyl, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently H, methyl or ethyl; R ⁷ is H, methyl, ethyl or phenyl; R ⁸ is H, methyl, ethyl or phenyl; R ⁹ , R ¹⁰ are each independently H or C1-C4 alkyl.

In some embodiments, the structural formula of the compound of formula (III) is as shown in formula (III-11) or formula (III-12):

Wherein, X ^— is a halide ion.

In some embodiments, X ^— is Cl ^— or Br ^— .

In some embodiments, the method includes: performing a reduction reaction between an aryl phosphine oxide and a reducing agent under the action of an organic phosphorus catalyst to generate aryl phosphorus; the structural formula of the reducing agent is shown in formula (VI):

Wherein, R ¹⁴ , R ¹⁵ , and R ¹⁵ are each independently one of H, C1-C6 alkyl, C1-C6 alkoxy, and C6-C12 aryl.

In some embodiments, at least one of R ¹⁴ , R ¹⁵ , and R ¹⁶ is a C6-C12 aryl group.

In some embodiments, at least one of R ¹⁴ , R ¹⁵ , and R ¹⁶ is phenyl.

In some embodiments, the reducing agent is phenylsilane.

In some embodiments, the molar ratio of arylphosphine oxide to reducing agent is: 1:(1˜1.5).

In some embodiments, the reduction reaction is performed under nitrogen or argon.

In some embodiments, the reduction reaction temperature is normal temperature, and the reaction time is 6-15 hours.

When the organophosphorus catalyst is a combination of a compound of formula (I) and a compound of formula (II), the molar ratio of arylphosphine oxide, reducing agent, compound of formula (I) and compound of formula (II) is: 1:(1～1.5):(0.01～0.15):(0.01～0.1);

When the organophosphorus catalyst is a compound of formula (III), the molar ratio of aryl phosphine oxide, reducing agent, and compound of formula (III) is 1:(1-1.5):(0.1-0.15).

As shown in Figure 1, the embodiment of the present invention uses the compound of formula (I-11) and diethyl bromomalonate (DEBM) as a catalyst, and phenylsilane as a reducing agent to catalyze triphenylphosphine oxide to generate triphenylphosphine to illustrate the reaction principle of the present invention, wherein:

The reaction mechanism of the present invention is illustrated by taking 1,2,2,3,4,4-hexamethylphosphine oxide (catalyst I-11) and diethyl bromomalonate (DEBM) as an example to reduce triphenylphosphine oxide. In this reaction, the catalyst 1,2,2,3,4,4-hexamethylphosphine oxide is firstly reduced to 1,2,2,3,4,4-hexamethylphosphine (Formula A) by the reducing agent phenylsilane. This is then reacted with diethyl bromomalonate to generate the corresponding phosphobromium ion (Formula B). B then undergoes a metathesis reaction with triphenylphosphine oxide to produce triphenylphosphine bromide (formula C) and catalyst I-11. Catalyst I-11 was again rapidly reduced to A by the reducing agent phenylsilane. The bromium transfer reaction of A and C gives the products triphenylphosphine and B. B continues to react with triphenylphosphine oxide to start the next catalytic reaction cycle, and undergoes the above steps to finally reduce triphenylphosphine oxide to triphenylphosphine.

The arylphosphine compounds synthesized in Examples 1-21 of the present invention were identified as pure compounds by ¹ H NMR, ³¹ P NMR, ^{and 13} C NMR.

Example 1:

Prepare according to the following equation:

Preparation method: Under the protection of argon, triphenylphosphine oxide (0.5mmol, 131mg, IV-1), diethyl bromomalonate (DEBM) (0.05mmol, 23.9mg) and 1,2,2,3,4,4-hexamethylphosphine oxide (0.075mmol, 13.1mg, I-11) were dissolved in 2.0mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product triphenylphosphine (V-1). The yield was 99%.

The NMR data of the product are as follows: ¹ H NMR (400MHz, CDCl3) δ: 7.27-7.20 (m, 15H). ¹³ C NMR (101 MHz, CDCl3) δ: 137.20 (d, J = 10.9 Hz), 133.74 (d, J = 19.5 Hz), 128.70, 128.49 (d, J = 7.0 Hz).31 P{1H}NMR(162MHz, CDCl3)δ:-5.36.

Example 2

Prepare according to the following equation:

Preparation method: Under argon protection, triphenylphosphine oxide (0.5mmol, 131mg, IV-1), diethyl bromomalonate (DEBM) (0.05mmol, 23.9mg) and 1,2,2,4-tetramethylphosphine oxide (0.075mmol, 11.0mg, I-12) were dissolved in 2.0mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product triphenylphosphine (V-1). The yield was 99%.

Example 3

Prepare according to the following equation:

Preparation method: Under the protection of argon, triphenylphosphine oxide (1.0mmol, 262mg, IV-1), diethyl bromomalonate (DEBM) (0.025mmol, 6.0mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.025mmol, 4.8mg, I-13) were dissolved in 1.0mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product triphenylphosphine (V-1). The yield was 99%.

When the addition amounts of diethyl bromomalonate (DEBM) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide were both 0.01 mmol, the yield was 78%.

Example 4

Prepare according to the following equation:

Preparation method: Under the protection of argon, triphenylphosphine oxide (0.5mmol, 131mg, IV-1), diethyl bromomalonate (DEBM) (0.05mmol, 23.9mg) and 5-phenyl-5H-benzo[b]phosphindole (0.075mmol, 19.5mg, I-21) were dissolved in 2.0mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product triphenylphosphine (V-1). The yield was 85%.

Example 5

Prepare according to the following equation:

Preparation method: Under the protection of argon, triphenylphosphine oxide (0.5mmol, 131mg, IV-1), diethyl bromomalonate (DEBM) (0.05mmol, 23.9mg) and 1,3-di-tert-butyl-2-methyl-1,3,2-diazaphosphine (0.075mmol, 17.3mg, I-31) were dissolved in 2.0mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product triphenylphosphine (V-1). The yield was 31%.

Example 6

Prepare according to the following equation:

Preparation Methods: Under argon protection, triphenylphosphine oxide (0.5mmol, 131mg, IV-1) and 1-bromo-1,2,2,3,4,4-hexamethylphosphonium-1-ium bromide (0.075mmol, 23.8mg, III-11) were dissolved in 2.0mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product triphenylphosphine (V-1). The yield was 98%.

Example 7

Prepare according to the following equation:

Preparation method: Under the protection of argon, triphenylphosphine oxide (0.5mmol, 131mg, IV-1) and 1-bromo-4-methyl-1-phenyl-2,3-dihydro-1H-phosphonium-1-ium bromide (0.075mmol, 25.2mg, III-12) were dissolved in 2.0mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product triphenylphosphine (V-1). The yield was 98%.

Example 8

Prepare according to the following equation:

Preparation method: Under argon protection, dissolve tris(4-fluorophenyl)phosphine oxide (0.5mmol, 161mg, IV-2), diethyl bromomalonate (DEBM) (0.05mmol, 23.9mg) and 1,2,2,3,4,4-hexamethylphosphine oxide (0.075mmol, 13.1mg, I-11) in 2.0mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product tris(4-fluorophenyl)phosphine (V-2). The yield was 95%.

The NMR data of the product are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ7.25 (ddd, J=8.8,7.0,5.6Hz, 6H), 7.04 (t, J=8.6Hz, 6H). ¹⁹ F NMR (376MHz, CDCl ₃ ) δ-111.90 (tq, J=9.7,5.4Hz). ³¹ P{1H}N MR(162MHz, CDCl ₃ )δ-9.02.

Embodiment 9:

Prepare according to the following equation:

Preparation method: Under argon protection, dissolve methyldiphenylphosphine oxide (1.0mmol, 216mg, IV-3), diethyl bromomalonate (DEBM) (0.05mmol, 12.0mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05mmol, 9.6mg, I-13) in 1.0mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product methyldiphenylphosphine (V-3). The yield was 91%.

The NMR data of the product are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ7.40 (m, 4H), 7.36–7.23 (m, 6H), 1.61 (d, J=3.6Hz, 3H). ¹³ C NMR (101MHz, CDCl ₃ ) δ 140.35, 140.23, 132.32, 132.13, 128. 52, 128.48, 128.46, 12.73, 12.59. ³¹ P{1H}NMR (162MHz, CDCl ₃ )δ-26.81.

Example 10:

Prepare according to the following equation:

Preparation method: Under the protection of argon, tri-p-tolylphosphine oxide (1.0mmol, 320mg, IV-4), diethyl bromomalonate (DEBM) (0.05mmol, 12.0mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05mmol, 9.6mg, I-13) were dissolved in 1.0mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product tri-p-tolylphosphine (V-4). The yield was 64%.

The NMR data of the product are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ7.27 (m, 6H), 7.20 (d, J=6.6Hz, 6H), 2.40 (s, 9H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 138.55, 134.28, 134.19, 133.80, 133.60, 12 9.34, 129.27, 21.36. ³¹ P{1H} NMR (162MHz, CDCl ₃ ) δ-7.87.

Example 11:

Prepare according to the following equation:

Preparation method: Under argon protection, dissolve tri-p-chlorophenylphosphine oxide (1.0mmol, 382mg, IV-5), diethyl bromomalonate (DEBM) (0.05mmol, 12.0mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05mmol, 9.6mg, I-13) in 1.0mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product tri-p-chlorophenylphosphine (V-5). The yield was 84%.

The NMR data of the product are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ7.33 (dd, J=8.4, 1.3Hz, 6H), 7.23–7.16 (m, 6H). ¹³ C NMR (101MHz, CDCl ₃ ) δ135.59, 134.96, 134.94, 134.82, 134.76, 129. 06,128.99. ³¹ P{1H}NMR (162MHz, CDCl ₃ )δ-8.51.

Example 12:

Prepare according to the following equation:

Preparation method: Under argon protection, dissolve tris(4-methoxyphenyl)phosphine oxide (1.0mmol, 368mg, IV-6), diethyl bromomalonate (DEBM) (0.05mmol, 12.0mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05mmol, 9.6mg, I-13) in 1.0mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product tris(4-methoxyphenyl)phosphine (V-6). The yield was 84%.

The NMR data of the product are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ7.26 (dd, J=8.8, 7.3Hz, 6H), 6.91 (m, 6H), 3.83 (s, 9H). ¹³ C NMR (101MHz, CDCl ₃ ) δ 160.15, 135.08, 134.88, 128.81, 128.7 4,114.21,114.14,55.21. ³¹ P{1H}NMR (162MHz, CDCl ₃ )δ-10.17.

Example 13:

Prepare according to the following equation:

Preparation method: Under the protection of argon, tri-m-tolylphosphine oxide (0.5mmol, 160mg, IV-7), diethyl bromomalonate (DEBM) (0.05mmol, 23.9mg) and 1,2,2,3,4,4-hexamethylphosphine oxide (0.075mmol, 13.1mg, I-11) were dissolved in 2.0mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). Stir at room temperature for 12h. Stop the reaction, and separate and purify by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product tri-m-cresylphosphine (V-7). The yield was 99%.

The NMR data of the product are as follows:¹H NMR (400MHz, CDCl₃)δ7.32–7.23(m,6H),7.21(d,J=7.5Hz,3H),7.15(t,J=7.3Hz,3H),2.37(s,9H).¹³C NMR (101MHz, CDCl₃)δ138.04, 137.96, 137.25, 137.15, 134.65, 134.43, 130.86, 130.70, 129.54, 128.42, 128.35, 21.50.³¹P{1H}NMR (162MHz, CDCl₃)δ-5.18.

Example 14:

Prepare according to the following equation:

Preparation method: Under argon protection, dissolve cyclohexyldiphenylphosphine oxide (0.5mmol, 142mg, IV-8), diethyl bromomalonate (DEBM) (0.05mmol, 23.9mg) and 1,2,2,3,4,4-hexamethylphosphine oxide (0.075mmol, 13.1mg, I-11) in 2.0mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). Stir at room temperature for 12h. Stop the reaction, and separate and purify by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product cyclohexyldiphenylphosphine (V-8). The yield was 75%.

The NMR data of the product are as ^follows : ¹ H NMR (400MHz, CDCl ₃ ) ^δ7.50 (ddt, J=7.3,5.1,2.4Hz _{,4H),7.33(dt,J=5.5,1.5Hz,6H),2.38–2.11(m,1H),1.85–1.65(m,5H),1.35–1.15(m,5H ( 162MHz, CDCl 3 )} δ-3.58.

Example 15:

Prepare according to the following equation:

Preparation method: Under argon protection, (3-methoxyphenyl)diphenylphosphine oxide (1.0mmol, 308mg, IV-9), diethyl bromomalonate (DEBM) (0.05mmol, 12.0mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05mmol, 9.6mg, I-13) were dissolved in 1.0mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product (3-methoxyphenyl)diphenylphosphine (V-9). The yield was 88%.

The NMR data of the product are as follows: ¹ H NMR(400MHz,CDCl ₃ )δ7.32(m,10H),7.27–7.23(m,1H),6.91–6.82(m,3H),3.72(s,3H). ³¹ P{1H}NMR(162MHz,CDCl ₃ )δ-4.56.

Example 16:

Prepare according to the following equation:

Preparation method: Under the protection of radon, (2-methoxyzhenyl) dihexyl oxidation (1.0 mmol, 308mg, IV-10), bromate propadate (Debm) (0.05 mmol, 12.0mg) and 4-methyl-1-phenyl-2,3-dihydrogen-1-oxide (0.05 mmol, 9. 9. 6mg, i-13) Solk in 1,2-dichloropathane in 1.0ml. To this was added phenylsilane (1.2 mmol, 130 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product (2-methoxyphenyl)diphenylphosphine (V-10). The yield was 91%.

The NMR data of the product are as follows: ¹ H NMR(400MHz,CDCl ₃ )δ7.43–7.30(m,11H),6.97–6.87(m,2H),6.77–6.68(m,1H),3.79(s,3H). ³¹ P{1H}NMR(162MHz,CDCl ₃ )δ-16.65.

Example 17:

Prepare according to the following equation:

Preparation method: Under the protection of radon, (4-methoxyzhenyl) dilate oxidation (1.0 mmol, 308mg, IV-11), bromate proprobyl athyl (DEBM) (0.05 mmol, 12.0mg) and 4-methyl-1-phenyl-2,3-dihydr-oxide (0.05 mmol, 9. 9. 6mg, i-13) Solk in 1,2-dichloropathane in 1.0ml. To this was added phenylsilane (1.2 mmol, 130 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product (4-methoxyphenyl)diphenylphosphine (V-11). The yield was 90%.

The NMR data of the product are as follows:¹H NMR (400MHz, CDCl₃)δ7.41–7.27(m,12H),6.93(dd,J＝8.8,1.0Hz,2H),3.84(s,3H).¹³C NMR (101MHz, CDCl₃)δ160.45, 137.89, 137.79, 135.76, 135.54, 133.55, 133.36, 128.53, 128.49, 128.42, 127.60, 127.53, 114.33, 114.25, 55.22.³¹P{1H}NMR (162MHz, CDCl₃)δ-7.00.

Example 18:

Prepare according to the following equation:

Preparation method: Under argon protection, (4-fluorophenyl)diphenylphosphine oxide (1.0mmol, 296mg, IV-12), diethyl bromomalonate (DEBM) (0.05mmol, 12.0mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05mmol, 9.6mg, I-13) were dissolved in 1.0mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stir for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product (4-fluorophenyl)diphenylphosphine (V-12). The yield was 98%.

The NMR data of the product are as follows:¹H NMR (400MHz, CDCl₃)δ7.43–7.27(m,12H),7.11–6.99(m,2H).¹⁹F NMR (376MHz, CDCl₃)δ-112.34.¹³C NMR (101MHz, CDCl₃)δ164.66, 162.19, 137.24, 137.13, 135.98, 135.90, 135.77, 135.69, 133.69, 133.50, 132.76, 132.72, 132.65, 132.61, 128.84, 128.74, 128.65, 128.58, 115.90, 115.82, 115.69, 115.61.³¹P{1H}NMR (162MHz, CDCl₃)δ-6.67.

Example 19:

Prepare according to the following equation:

Preparation method: Under argon protection, (4-chlorophenyl)diphenylphosphine oxide (1.0mmol, 312mg, IV-13), diethyl bromomalonate (DEBM) (0.05mmol, 12.0mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05mmol, 9.6mg, I-13) were dissolved in 1.0mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). Stir at room temperature for 12h. Stop the reaction, and separate and purify by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product triphenylphosphine (4-chlorophenyl)diphenylphosphine (V-13). The yield was 99%.

The NMR data of the product are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ7.44–7.32 (m, 12H), 7.29 (dd, J=8.6, 6.7Hz, 2H). ¹³ C NMR (101MHz, CDCl ₃ ) δ136.83, 136.72, 136.08, 135.96, 135.14, 135 .08,134.94,133.83,133.64,128.99,128.82,128.75,128.71,128.64. ³¹ P{1H}NMR(162MHz,CDCl ₃ )δ-6.34.

Example 20:

Prepare according to the following equation:

Preparation method: Under the protection of argon, (4-trifluoromethylphenyl)diphenylphosphine oxide (1.0mmol, 346mg, IV-14), diethyl bromomalonate (DEBM) (0.05mmol, 12.0mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05mmol, 9.6mg, I-13) were dissolved in 1.0mL of 1,2-dichloroethane . To this was added phenylsilane (1.2 mmol, 130 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product (4-trifluoromethylphenyl)diphenylphosphine (V-14). The yield was 59%.

The NMR data of the product are as follows:¹H NMR (400MHz, CDCl₃)δ7.59(d,J＝7.9Hz,2H),7.38m,12H).³¹P{1H}NMR (162MHz, CDCl₃)δ-5.30.¹⁹F NMR (376MHz, CDCl₃)δ-62.71.¹³C NMR (101MHz, CDCl₃)δ143.00, 142.85, 136.13, 136.03, 134.05, 133.85, 133.69, 133.50, 129.25, 128.81, 128.74, 125.18, 125.14, 125.11, 125.08.

Example 21:

Prepare according to the following equation:

Preparation method: Under the protection of radon, methyl (benzene) (neighboring tither) oxidation (1.0 mmol, 230mg, IV-15), bromodyate melite (Debm) (0.05 mmol, 12.0mg) and 4-methyl-2,3-dihydrogen -1-oxide (0.05mmo (0.05mmo L, 9.6mg, I-13) Soluble in 1,2-dichloroethane soluble in 1.0ml. To this was added phenylsilane (1.2 mmol, 130 mg). Stir at room temperature for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain the pure product methyl(phenyl)(o-tolyl)phosphine (V-15). The yield was 97%.

The NMR data of the product are as follows:¹H NMR (400MHz, CDCl₃)δ7.39(ddt, J=7.3,5.4,2.4Hz,2H),7.33(tq,J=5.7,3.7,2.7Hz,4H),7.30–7.24(m,2H),7.21(ddd,J=6.8,4.4,1.7Hz,1H),2.42(s,3H),1.61(d,J=4. 1Hz,3H).³¹P NMR (162MHz, CDCl₃)δ-36.29.¹³C NMR (101MHz, CDCl₃)δ 142.26, 142.02, 140.11, 139.99, 137.77, 137.65, 132.30, 132.12, 130.26, 130.10, 130.06, 128.52, 128.45, 128.39, 128.28, 126.02, 21.29, 2 1.08, 12.24, 12.11.

In the description of the present invention, "plurality" means at least two, such as two, three, etc., unless otherwise specifically defined.

In the present invention, the terms "one embodiment", "some embodiments", "example", "specific examples", or "some examples" mean that specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the described specific features, structures, materials or characteristics may be combined in any suitable manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine different embodiments or examples and features of different embodiments or examples described in this specification without conflicting with each other.

Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and those skilled in the art can change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims (16)

1. A catalyst composition, characterized in that it comprises a compound of formula (I) and a compound of formula (II); The structural formula of the compound of formula (I) is shown in formula (I-1), formula (I-2) or formula (I-3): Wherein, said n is 0 or 1 or 2, and said n' is 0 or 1 or 2; The R ^is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituting group in the substituted phenyl is selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl; The R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently one of H, C1-C6 alkyl, phenyl or substituted phenyl, and the substituents in the substituted phenyl are selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl; said Indicates a single or double bond; The structural formula of the compound of formula (II) is: II Wherein, the R ¹¹ and R ¹² are each independently one of methyl, ethyl, isopropyl and benzyl, and the R ¹³ is H or methyl. 2. A catalyst composition according to claim 1, characterized in that, said R ¹ is one of methyl, ethyl or phenyl, said R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently H, methyl or ethyl; said R ⁷ is H, methyl, ethyl or phenyl; said R ⁸ is H, methyl, ethyl or phenyl; said R ⁹ , R ¹⁰ are each independently H or C1-C4 alkyl. 3. A catalyst composition according to claim 1, characterized in that, the structural formula of the compound of formula (I) is as shown in formula (I-11), formula (I-12), formula (I-13), formula (I-21) or formula (I-31): . 4. A kind of catalyst composition according to claim 1, is characterized in that, the molar ratio of described formula (I) compound and formula (II) compound is: 1: (0.4～2). 5. The use of an organophosphorus catalyst in the preparation of arylphosphine by catalytic reduction of arylphosphine oxide, characterized in that, the organophosphorus catalyst is the catalyst composition according to any one of claims 1 to 4, or the compound of formula (III); The structural formula of the compound of formula (III) is shown in formula (III-1), formula (III-2) or formula (III-3): In the compound of formula (III), the n is 0 or 1 or 2, and the n' is 0 or 1 or 2; The R ^is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituting group in the substituted phenyl is selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl; The R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently one of H, C1-C6 alkyl, phenyl or substituted phenyl, and the substituents in the substituted phenyl are selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl; said Represent single bond or double bond; Said X ^— is a kind of in halide ion, nitrate ion, perchlorate ion; The structural formula of the aryl phosphine oxide is shown in formula (IV), and the corresponding structural formula of the aryl phosphine is shown in formula (V): Wherein, the X ₁ and X ₂ are each independently one of halogen, C1-C6 alkyl, C1-C6 alkoxy, and C6-C12 aryl; the R is one of C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aryl, or a substituted C6-C12 aryl, and the substituting group in the substituted C6-C12 aryl is selected from halogen or halogenated C1-C6 alkyl one or more of. 6. The use according to claim 5, characterized in that, in the compound of formula (III), the R ¹ is one of methyl, ethyl or phenyl, the R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently H, methyl or ethyl; the R ⁷ is H, methyl, ethyl or phenyl; the R ⁸ is H, methyl, ethyl or phenyl; the R ⁹ and R ¹⁰ are each independently H or C1-C4 alkyl. 7. The use according to claim 6, characterized in that, the structural formula of the compound of formula (III) is as shown in formula (III-11) or formula (III-12): III-11III-12 Wherein, the ^X- is a halide ion. 8. A method for reducing aryl phosphine oxide to prepare aryl phosphine, characterized in that, comprising the steps of: The arylphosphine oxide generates the arylphosphine under the action of an organophosphorus catalyst; The structural formula of the aryl phosphine oxide is shown in formula (IV), and the corresponding structural formula of the aryl phosphine is shown in formula (V): Wherein, the X ₁ and X ₂ are each independently one of halogen, C1-C6 alkyl, C1-C6 alkoxy, and C6-C12 aryl; the R is one of C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aryl, or a substituted C6-C12 aryl, and the substituting group in the substituted C6-C12 aryl is selected from halogen or halogenated C1-C6 alkyl one or more of The organophosphorus catalyst is the catalyst composition or the compound of formula (III) according to any one of claims 1 to 4; The structural formula of the compound of formula (III) is shown in formula (III-1), formula (III-2) or formula (III-3): In the compound of formula (III), the n is 0 or 1 or 2, and the n' is 0 or 1 or 2; The R ^is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituting group in the substituted phenyl is selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl; The R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently one of H, C1-C6 alkyl, phenyl or substituted phenyl, and the substituents in the substituted phenyl are selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkyl; said Represent a single bond or a double bond; the X ^— is one of a halide ion, a nitrate ion, a perchlorate ion. 9. A method for preparing arylphosphine by reducing arylphosphine oxide according to claim 8, characterized in that, in the compound of formula (III), said R ¹ is one of methyl, ethyl or phenyl, said R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently H, methyl or ethyl; said R ⁷ is H, methyl, ethyl or phenyl; said R ⁸ is H, methyl, ethyl or phenyl; said R ⁹ , R ¹⁰ Each is independently H or C1-C4 alkyl. 10. A method for preparing arylphosphine by reducing arylphosphine oxide according to claim 9, characterized in that, the structural formula of the compound of formula (III) is as shown in formula (III-11) or formula (III-12): III-11III-12 Wherein, the ^X- is a halide ion. 11. A method for preparing aryl phosphine by reducing aryl phosphine oxide according to claim 8, characterized in that the method comprises: performing a reduction reaction between the aryl phosphine oxide and a reducing agent under the action of the organophosphorus catalyst to generate the aryl phosphine; the structural formula of the reducing agent is shown in formula (VI): VI Wherein, the R ¹⁴ , R ¹⁵ , and R ¹⁵ are each independently one of H, C1-C6 alkyl, C1-C6 alkoxy, and C6-C12 aryl. 12. A method for preparing arylphosphine by reducing arylphosphine oxide according to claim 11, characterized in that the reducing agent is phenylsilane. 13. a kind of reduction aryl phosphine oxide according to claim 11 prepares the method for aryl phosphine, it is characterized in that, the mol ratio of described aryl phosphine oxide and described reducing agent is: 1: (1～1.5). 14. A method for preparing arylphosphine by reducing arylphosphine oxide according to any one of claims 8 to 13, characterized in that the reduction reaction is carried out under nitrogen or argon. 15. A method for preparing arylphosphine by reducing arylphosphine oxide according to any one of claims 8 to 13, wherein the reduction reaction temperature is normal temperature, and the reaction time is 6 to 15 h. 16. The method for preparing arylphosphine by reducing arylphosphine oxide according to any one of claims 8 to 13, characterized in that, when the organophosphorus catalyst is a composition of formula (I) compound and formula (II) compound, the mol ratio of the arylphosphine oxide, reducing agent, formula (I) compound, and formula (II) compound is: 1: (1 ~ 1.5): (0.01 ~ 0.15): (0.01 ~ 0.1); When the organophosphorus catalyst is a compound of formula (III), the molar ratio of the arylphosphine oxide, reducing agent, and compound of formula (III) is 1: (1~1.5): (0.1~0.2).