CN115055207A - Method for preparing aryl phosphine by reducing aryl phosphine oxide - Google Patents

Abstract

The invention discloses a method for preparing aryl phosphine by reducing aryl phosphine oxide, which comprises the steps of generating aryl phosphorus by aryl phosphine oxide and a reducing agent under the action of an organophosphorus catalyst; the organophosphorus catalyst is a compound which has simple structure, simple synthetic route or is commercially available, is stable in air and easy to operate, and can efficiently reduce aryl phosphine oxide into 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 to be used in organic chemical transformations. For example, Appel reaction, Mitsunobu reaction, Staudinger reaction, Wittig reaction, etc. commonly used in industry and laboratory all require the use of an equivalent amount of triphenylphosphine as a reactant. 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. Triphenylphosphine oxide, which is produced in large quantities in industry, poses 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 my country is facing severe resource consumption pressure. In addition, arylphosphines are also the most important class of ligands in organometallic chemistry, which provides a new synthetic method for the preparation of high-value phosphorus-containing ligands by reducing arylphosphine oxides to the corresponding arylphosphines.

In the related art, the method for reducing aryl phosphine oxide requires the use of a strong negative hydrogen reducing reagent, including lithium aluminum tetrahydrogen, borane, calcium hydride, and the like. These reducing agents are expensive and the reaction is violently exothermic, limiting their widespread use. Silane is an inexpensive, low-toxicity reducing agent that can also be used to reduce arylphosphine oxides. In 1964, Fritsche et al. found that active trichlorosilane (Cl ₃ SiH) can reduce phosphine oxide. Since the 1990s, it has been discovered that phenylsilane (PhSiH ₃ ) can react with 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 the reduction of phosphine oxide to phosphine under the catalysis of trifluoromethanesulfonic acid. However, these methods have some drawbacks, including: generally higher catalyst loading and higher temperature (eg, reaction temperature of 60-120° C.) are used, and the strong acidity of the catalyst limits the range of reaction substrates. Therefore, the development of an inexpensive, sustainable and mild method for the reduction of arylphosphine oxides to arylphosphines is particularly important for scientific research and industrial production.

SUMMARY 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, an object of the present invention is to propose a catalyst composition for catalytic reduction of arylphosphine oxides to prepare arylphosphines.

Another object of the embodiments of the present invention is to propose the use of an organic phosphorus catalyst in catalytic reduction of aryl phosphorus oxide to prepare aryl phosphorus.

Another object of the embodiments of the present invention is to propose a method for preparing aryl phosphine by catalytic reduction of aryl phosphine oxide using an organic phosphorus catalyst, which can efficiently prepare aryl phosphine products under mild conditions.

The catalyst composition of the embodiment of the present invention includes the compound of formula (I) and the 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, the n is 0 or 1 or 2, and the n' is 0 or 1 or 2;

The R ¹ is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituent in the substituted phenyl is selected from halogen, C1-C6 alkyl, C1-C6 alkoxy or halogen One or more of the C1-C6 alkyl groups;

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

表示单键或双键；said

Indicates a single bond or a 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 compound with 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 react under mild reaction conditions. Aryl phosphine oxides prepare aryl phosphines.

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, and 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 (I) is such as formula (I-11), formula (I-12), formula (I-13), formula (I-21) or formula (I-31) shown:

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 the use of an organic phosphorus catalyst in catalytic reduction of aryl phosphorus oxide to prepare aryl phosphorus, where the organic phosphorus 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 the formula (III), the n is 0 or 1 or 2, and the n' is 0 or 1 or 2;

The R ¹ is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituent in the substituted phenyl is selected from halogen, C1-C6 alkyl, C1-C6 alkoxy or halogen One or more of the C1-C6 alkyl groups;

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

表示单键或双键；said

Indicates a single bond or a double bond;

Described X ^— is a kind of in halide ion, nitrate ion, perchlorate ion, carbanion;

The structural formula of the aryl phosphorus 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 C1-C6 alkyl, halogenated One of C1-C6 alkyl group, C3-C6 cycloalkyl group, C6-C12 aryl group, or substituted C6-C12 aryl group, the substituent group in the substituted C6-C12 aryl group is selected from halogen or halogenated One or more of C1-C6 alkyl groups.

In the embodiment of the present invention, an organophosphorus catalyst is used for catalytic reduction of arylphosphorus oxide to prepare arylphosphorus, and the organophosphorus catalyst can efficiently reduce arylphosphine oxide to prepare arylphosphine under mild reaction conditions.

In some embodiments, in the compound of formula (III), the R ¹ is one of methyl, ethyl, cyclopropyl or phenyl, and 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 halogen ion.

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

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

The structural formula of the aryl phosphorus 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 C1-C6 alkyl, halogenated One of C1-C6 alkyl group, C3-C6 cycloalkyl group, C6-C12 aryl group, or substituted C6-C12 aryl group, the substituent group in the substituted C6-C12 aryl group is selected from halogen or halogenated One or more of C1-C6 alkyl groups;

The organophosphorus catalyst is the above-mentioned catalyst composition 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 the formula (III), the n is 0 or 1 or 2, and the n' is 0 or 1 or 2;

The R ¹ is one of C1-C6 alkyl, C3-C6 cycloalkyl, phenyl or substituted phenyl, and the substituent in the substituted phenyl is selected from halogen, C1-C6 alkyl, C1 One or more of -C6 alkoxy or halogenated C1-C6 alkyl;

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

表示单键或双键；said

Indicates a single bond or a double bond;

Described X is a kind ^of 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, and 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, described X ^- is halogen ion.

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

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 carried out under nitrogen or argon conditions.

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

When the organophosphorus catalyst is a combination of the compound of formula (I) and the 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 the compound of formula (III), the molar ratio of the arylphosphine oxide, the reducing agent, and the 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 compound with a simple structure, a simple synthetic route or a commercially available compound, which is stable in air and easy to operate, and the catalyst composition of the embodiment of the present invention can efficiently perform under mild reaction conditions Arylphosphines are prepared by reduction of arylphosphine oxides.

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

(4) The method for preparing aryl phosphine by reducing aryl phosphine oxide in 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 readily understood from the following description of embodiments taken 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

The embodiments of the present invention are described in detail below, and the embodiments described below are exemplary and intended to be used to explain the present invention, but should not be construed as a limitation of the present invention.

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

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

For example, the compound of formula (I) in the embodiment of the present invention can be synthesized by referring to the methods 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 meaning commonly understood by one of ordinary skill in the art to which this invention belongs.

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

The term "C1-C6 alkyl" refers to a saturated straight or branched monovalent hydrocarbon group containing 1-6 carbon atoms; in one embodiment, containing 1-4 carbon atoms; in another embodiment , containing 1-3 carbon atoms; non-limiting examples of "C1-C6 alkyl" include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertiary Butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl base-1-butyl and so on.

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

The term "C1-C6 alkoxy" means "C1-C6 alkyl" attached to the remainder of the molecule through an oxygen atom, wherein "C1-C6 alkyl" has the 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" denotes a monovalent or polyvalent saturated monocyclic, bicyclic ring system containing 3 to 6 carbon atoms. Non-limiting examples of "C3-C6 cycloalkyl" include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

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

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

The term "substituted" means that one or more hydrogen atoms in a given structure have been replaced with a specified substituent. Unless otherwise indicated, a substituent group may be substituted at each substitutable position of a given structure. When more than one position in a given structure can be substituted with one or more substituents selected from a particular group, the substituents may be substituted at each position identically 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 includes the compound of formula (I) and the 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 ¹ is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituent in substituted phenyl is selected from halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 one or more of the alkyl groups;

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

表示单键或双键；said

Indicates a single bond or a 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 compound with 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 react under mild reaction conditions. Aryl phosphine oxides prepare aryl phosphines.

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

In some embodiments, R ¹ is one of methyl, ethyl, cyclopropyl, or phenyl, and 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 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 the use of an organic phosphorus catalyst in catalytic reduction of aryl phosphorus oxide to prepare aryl phosphorus, where the organic phosphorus 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 ¹ is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituent in substituted phenyl is selected from halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 one or more of the alkyl groups;

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

表示单键或双键；

Indicates a single bond or a double bond;

X ^— is a kind of in halide ion, nitrate ion, perchlorate ion, carbanion;

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

Wherein, X ₁ and X ₂ are each independently one of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C12 aryl; R is C1-C6 alkyl, halogenated C1-C6 alkane one of C3-C6 cycloalkyl, C6-C12 aryl, or substituted C6-C12 aryl, and the substituent 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, an organophosphorus catalyst is used for catalytic reduction of arylphosphorus oxide to prepare arylphosphorus, and the organophosphorus catalyst can efficiently reduce arylphosphine oxide to prepare arylphosphine under mild reaction conditions.

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

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

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

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

Wherein, X ₁ and X ₂ are each independently one of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C12 aryl; R is C1-C6 alkyl, halogenated C1-C6 alkane one of C3-C6 cycloalkyl, C6-C12 aryl, or substituted C6-C12 aryl, and the substituent 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 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), n is 0 or 1 or 2, and n' is 0 or 1 or 2;

R ¹ is one of C1-C6 alkyl, C3-C6 cycloalkyl, phenyl or substituted phenyl, and the substituted group in substituted phenyl is selected from halogen, C1-C6 alkyl, C1-C6 alkoxy one or more of a group or a halogenated C1-C6 alkyl group;

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

表示单键或双键；

Indicates a single bond or a double bond;

X ^— is a kind of 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), R ¹ is one of methyl, ethyl, cyclopropyl or phenyl, and R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently is H, methyl or ethyl; R ⁷ is H, methyl, ethyl or phenyl; R ⁸ is H, methyl, ethyl or phenyl; R ⁹ and R ¹⁰ are 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 halogen ion.

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

In some embodiments, the method includes: performing a reduction reaction with an arylphosphine oxide and a reducing agent under the action of an organic phosphorus catalyst to generate arylphosphorus; 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 , 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 the arylphosphine oxide to the reducing agent is: 1:(1˜1.5).

In some embodiments, the reduction reaction is carried out under nitrogen or argon conditions.

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

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

As shown in FIG. 1 , in the embodiment of the present invention, the compound of formula (I-11) and diethyl bromomalonate (DEBM) are used as catalysts, and phenylsilane is used as a reducing agent to catalyze triphenylphosphine oxide to generate triphenylphosphine To illustrate the reaction principle of the present invention, wherein:

Taking 1,2,2,3,4,4-hexamethylphosphine oxide (catalyst I-11) and diethyl bromomalonate (DEBM) as catalyst combination to reduce triphenylphosphine oxide as an example to illustrate The reaction mechanism of the present invention. In this reaction, the catalyst 1,2,2,3,4,4-hexamethylphosphine oxide is first reduced to 1,2,2,3,4,4-hexamethylphosphine (A Mode). Then, it reacts with diethyl bromomalonate to generate the corresponding phosphobromonium ion (Formula B). B then undergoes metathesis reaction with triphenylphosphine oxide to produce triphenylphosphine bromium (form C) and catalyst I-11. Catalyst I-11 is again rapidly reduced to A by the reducing agent phenylsilane. A and C undergo a bromonium transfer reaction to obtain the products triphenylphosphine and B. B continues to react with triphenylphosphine oxide to start the next catalytic reaction cycle, and goes through 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 argon protection, triphenylphosphine oxide (0.5mmol, 131mg, IV-1), diethyl bromomalonate (DEBM) (0.05mmol, 23.9mg) and 1,2,2 , 3,4,4-hexamethylphosphine oxide (0.075 mmol, 13.1 mg, 1-11) was dissolved in 2.0 mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). At room temperature, stirred 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). 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 (101MHz, CDCl3)δ: 137.20(d, J=10.9Hz), 133.74(d, J ＝19.5Hz), 128.70, 128.49(d, J＝7.0Hz). 31P{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 (0.075 mmol, 11.0 mg, 1-12) was dissolved in 2.0 mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). At room temperature, stirred 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). Yield was 99%.

Example 3

Prepare according to the following equation:

Preparation method: under argon protection, triphenylphosphine oxide (1.0mmol, 262mg, IV-1), diethyl bromomalonate (DEBM) (0.025mmol, 6.0mg) and 4-methyl- 1-Phenyl-2,3-dihydrophosphine-1-oxide (0.025 mmol, 4.8 mg, 1-13) was dissolved in 1.0 mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stirred 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). Yield was 99%.

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

Example 4

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 5-phenyl- 5H-Benzo[b]phosphinoindole (0.075 mmol, 19.5 mg, 1-21) was dissolved in 2.0 mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). At room temperature, stirred 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). Yield was 85%.

Example 5

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 1,3-diethyl tert-Butyl-2-methyl-1,3,2-diazaphosphine (0.075 mmol, 17.3 mg, 1-31) was dissolved in 2.0 mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). At room temperature, stirred 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). Yield 31%.

Example 6

Prepare according to the following equation:

Preparation method: under the protection of argon, triphenylphosphine oxide (0.5mmol, 131mg, IV-1) and bromide 1-bromo-1,2,2,3,4,4-hexamethylphosphorus-1 - Onium (0.075 mmol, 23.8 mg, III-11) was dissolved in 2.0 mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). At room temperature, stirred 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). Yield was 98%.

Example 7

Prepare according to the following equation:

Preparation method: under argon protection, triphenylphosphine oxide (0.5mmol, 131mg, IV-1) and bromide 1-bromo-4-methyl-1-phenyl-2,3-dihydro-1H - Phosphorus-1-onium (0.075 mmol, 25.2 mg, III-12) was dissolved in 2.0 mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). At room temperature, stirred 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). Yield was 98%.

Example 8

Prepare according to the following equation:

Preparation method: under argon protection, 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 (0.075 mmol, 13.1 mg, 1-11) was dissolved in 2.0 mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). At room temperature, stirred 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). Yield was 95%.

The NMR data of the product are as follows: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.25 (ddd, J=8.8, 7.0, 5.6 Hz, 6H), 7.04 (t, J=8.6 Hz, 6H). ¹⁹ F NMR (376 MHz) , CDCl ₃ )δ-111.90 (tq, J=9.7, 5.4Hz). ³¹ P{1H}NMR (162MHz, CDCl ₃ )δ-9.02.

Example 9:

Prepare according to the following equation:

Preparation method: under argon protection, methyldiphenylphosphine oxide (1.0mmol, 216mg, IV-3), diethyl bromomalonate (DEBM) (0.05mmol, 12.0mg) and 4-methyl Alkyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05 mmol, 9.6 mg, 1-13) was dissolved in 1.0 mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stirred for 12h. After stopping the reaction, separation and purification by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) gave pure product methyldiphenylphosphine (V-3). Yield was 91%.

The NMR data of the product are as follows: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.40 (m, 4H), 7.36-7.23 (m, 6H), 1.61 (d, J=3.6 Hz, 3H). ¹³ C NMR (101 MHz) , CDCl ₃ )δ140.35,140.23,132.32,132.13,128.52,128.48,128.46,12.73,12.59. 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, tris-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 (0.05 mmol, 9.6 mg, 1-13) was dissolved in 1.0 mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stirred 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). Yield 64%.

The NMR data of the product are as follows: ¹ H NMR (400MHz, CDCl ₃ ) δ 7.27(m, 6H), 7.20(d, J=6.6Hz, 6H), 2.40(s, 9H). ¹³ C NMR (101MHz, CDCl ) ₃ ) δ138.55, 134.28, 134.19, 133.80, 133.60, 129.34, 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, tri-p-chlorophenylphosphine oxide (1.0mmol, 382mg, IV-5), diethyl bromomalonate (DEBM) (0.05mmol, 12.0mg) and 4-methyl Alkyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05 mmol, 9.6 mg, 1-13) was dissolved in 1.0 mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stirred 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). Yield 84%.

The NMR data of the product are as follows: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.33 (dd, J=8.4, 1.3 Hz, 6H), 7.23-7.16 (m, 6H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 135 .59, 134.96, 134.94, 134.82, 134.76, 129.06, 128.99. ³¹ P{1H}NMR (162MHz, _CDCl3 )δ-8.51.

Example 12:

Prepare according to the following equation:

Preparation method: under argon protection, 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 (0.05 mmol, 9.6 mg, 1-13) were dissolved in 1.0 mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stirred 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). Yield 84%.

The NMR data of the product are as follows: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.26 (dd, J=8.8, 7.3 Hz, 6H), 6.91 (m, 6H), 3.83 (s, 9H). ¹³ C NMR (101 MHz) , CDCl ₃ )δ160.15,135.08,134.88,128.81,128.74,114.21,114.14,55.21. ³¹ P{1H}NMR (162MHz, CDCl ₃ )δ-10.17.

Example 13:

Prepare according to the following equation:

Preparation method: under argon protection, tri-m-tolyl phosphine oxide (0.5mmol, 160mg, IV-7), diethyl bromomalonate (DEBM) (0.05mmol, 23.9mg) and 1,2, 2,3,4,4-Hexamethylphosphine oxide (0.075 mmol, 13.1 mg, 1-11) was dissolved in 2.0 mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). At room temperature, stirred 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-m-tolylphosphine (V-7). Yield was 99%.

The NMR data of the product are as follows: ¹ H NMR (400MHz, CDCl ₃ )δ7.32-7.23(m, 6H), 7.21(d, J=7.5Hz, 3H), 7.15(t, J=7.3Hz, 3H), 2.37(s, 9H). ¹³ C NMR(101MHz, CDCl ₃ ) ^{δ138.04,137.96,137.25,137.15,134.65,134.43,130.86,130.70,129.54,128.42,128.35,21.50.CDCl} P{1H}NMR(162MHz ₃ ) δ-5.18.

Example 14:

Prepare according to the following equation:

Preparation method: under argon protection, cyclohexyldiphenylphosphine oxide (0.5mmol, 142mg, IV-8), diethyl bromomalonate (DEBM) (0.05mmol, 23.9mg) and 1,2 , 2,3,4,4-hexamethylphosphine oxide (0.075 mmol, 13.1 mg, 1-11) was dissolved in 2.0 mL of acetonitrile. To this was added phenylsilane (0.6 mmol, 64.9 mg). At room temperature, stirred 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 cyclohexyldiphenylphosphine (V-8). Yield was 75%.

The NMR data of the product are as follows: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.50 (ddt, J=7.3, 5.1, 2.4 Hz, 4H), 7.33 (dt, J=5.5, 1.5 Hz, 6H), 2.38-2.11 (m, 1H), 1.85–1.65 (m, 5H), 1.35–1.15 (m, 5H). ¹³ CNMR (101MHz, CDCl ₃ ) δ136.80, 136.68, 133.78, 133.59, 128.71, 128.36, 128.28, 35.43, 35.35, 29.63, 29.48, 26.87, 26.76, 26.36. ³¹ P{1H}NMR (162MHz, _CDCl3 )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, 12.0 mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05 mmol, 9.6 mg, 1-13) were dissolved in 1.0 mL of 1,2-dichloroethane middle. To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stirred for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain a pure product (3-methoxyphenyl)diphenylphosphine (V-9). The yield was 88%.

The NMR data of the product are as follows: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.32 (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 argon protection, (2-methoxyphenyl) diphenylphosphine oxide (1.0mmol, 308mg, IV-10), diethyl bromomalonate (DEBM) (0.05mmol, 12.0 mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05 mmol, 9.6 mg, 1-13) were dissolved in 1.0 mL of 1,2-dichloroethane middle. To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stirred for 12h. The reaction was stopped, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v) to obtain a pure product (2-methoxyphenyl)diphenylphosphine (V-10). 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 argon protection, (4-methoxyphenyl) diphenylphosphine oxide (1.0mmol, 308mg, IV-11), diethyl bromomalonate (DEBM) (0.05mmol, 12.0 mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05 mmol, 9.6 mg, 1-13) were dissolved in 1.0 mL of 1,2-dichloroethane middle. To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stirred for 12h. The reaction was stopped, and the purified product (4-methoxyphenyl)diphenylphosphine (V-11) was obtained by separation and purification by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v). Yield was 90%.

The NMR data of the product are as follows: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.41-7.27 (m, 12H), 6.93 (dd, J=8.8, 1.0 Hz, 2H), 3.84 (s, 3H). ¹³ C NMR (101MHz, _{CDCl 3 )} 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. 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 (0.05 mmol, 9.6 mg, 1-13) were dissolved in 1.0 mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stirred for 12h. The reaction was stopped, and the purified product (4-fluorophenyl)diphenylphosphine (V-12) was obtained by separation and purification by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v). Yield was 98%.

^{13C _} _{_} ^_ _{_} NMR(101MHz,CDCl ₃ )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 . ³¹ P{1H}NMR (162MHz, CDCl ₃ )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 (0.05 mmol, 9.6 mg, 1-13) were dissolved in 1.0 mL of 1,2-dichloroethane. To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stirred 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 (4-chlorophenyl)diphenylphosphine (V-13). Yield was 99%.

The NMR data of the product are as follows: ¹ H NMR (400MHz, CDCl ₃ )δ 7.44-7.32 (m, 12H), 7.29 (dd, J=8.6, 6.7 Hz, 2H). ¹³ C NMR (101 MHz, CDCl ₃ )δ 136 .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 argon protection, (4-trifluoromethylphenyl)diphenylphosphine oxide (1.0mmol, 346mg, IV-14), diethyl bromomalonate (DEBM) (0.05mmol , 12.0 mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05 mmol, 9.6 mg, 1-13) were dissolved in 1.0 mL of 1,2-dichloroethane in alkane. To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stirred for 12h. The reaction was stopped, and the purified product (4-trifluoromethylphenyl)diphenylphosphine (V-14) was obtained by separation and purification by silica gel column chromatography (petroleum ether/ethyl acetate=100/1, v/v). Yield 59%.

The NMR data of the product are as follows: ¹ H NMR (400MHz, CDCl ₃ )δ7.59 (d, J=7.9Hz, 2H), 7.38m, 12H). ³¹ P{1H}NMR (162MHz, CDCl ₃ )δ-5.30 . ¹⁹ F NMR (376MHz, _{CDCl 3} ) δ- ^62.71 , 125.08.

Example 21:

Prepare according to the following equation:

Preparation method: under argon protection, methyl (phenyl) (o-tolyl) phosphine oxide (1.0 mmol, 230 mg, IV-15), diethyl bromomalonate (DEBM) (0.05 mmol, 12.0 mg) and 4-methyl-1-phenyl-2,3-dihydrophosphine-1-oxide (0.05 mmol, 9.6 mg, 1-13) were dissolved in 1.0 mL of 1,2-dichloroethane . To this was added phenylsilane (1.2 mmol, 130 mg). At room temperature, stirred 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). Yield was 97%.

The NMR data of the product are as follows: ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.39 (ddt, J=7.3, 5.4, 2.4 Hz, 2H), 7.33 (tq, J=5.7, 3.7, 2.7 Hz, 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). ³¹ P NMR(162MHz, CDCl ₃ )δ-36.29. ¹³ C NMR(101MHz,CDCl ₃ )δ142.26,142.02,140.11,139.99,137.77,137.65,132.30,132.12,130.26,130.10,130.06,128.52,128.45,128.39,128.28,126.02,21.29,21.08 , 12.24, 12.11.

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

In this disclosure, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples" and the like mean a specific feature, structure, material, or description described in connection with the embodiment or example. Features are included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, those skilled in the art may combine and combine the different embodiments or examples described in this specification, as well as the features of the different embodiments or examples, without conflicting each other.

Although the embodiments of the present invention have been shown and described above, it should be understood that the above-mentioned embodiments are exemplary and should not be construed as limiting the present invention. Embodiments are subject to variations, modifications, substitutions and variations.

Claims (16)

1. A catalyst composition comprising a compound of formula (I) and a compound of formula (II);

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

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

the R is ¹ Is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituent 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 is ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ Each independently is H, C1-C6 alkyl, phenyl or one of substituted phenyl, and the substituent group in the substituted phenyl is selected from one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkylSeed growing;

the above-mentioned

Represents a single bond or a double bond;

the structural formula of the compound of the formula (II) is as follows:

wherein, R is ¹¹ 、R ¹² Each independently is one of methyl, ethyl, isopropyl and benzyl, and R is ¹³ Is H or methyl.

2. The catalyst composition of claim 1, wherein R is ¹ Is one of methyl, ethyl, cyclopropyl or phenyl, and R is ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ Each independently is H, methyl or ethyl; the R is ⁷ Is H, methyl, ethyl or phenyl; the R is ⁸ Is H, methyl, ethyl or phenyl; the R is ⁹ 、R ¹⁰ Each independently is H or C1-C4 alkyl.

3. The catalyst composition of claim 1, wherein the formula of the compound of formula (I) is represented by formula (I-11), formula (I-12), formula (I-13), formula (I-21), or formula (I-31):

4. the catalyst composition of claim 1, wherein the molar ratio of the compound of formula (I) to the compound of formula (II) is: 1 (0.4-2).

5. Use of an organophosphorus catalyst in the catalytic reduction of aryl phosphorus oxide to aryl phosphorus, wherein the organophosphorus catalyst is the catalyst composition according to any one of claims 1 to 4, or is a compound of formula (III);

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

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

the R is ¹ Is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituent 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 is ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ Each independently is H, C1-C6 alkyl, phenyl or substituted phenyl, and the substituent 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 above-mentioned

Represents a single bond or a double bond; said X ^— Is one of halogen ion, nitrate ion, perchlorate ion and carbanion;

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

wherein, X is ₁ 、X ₂ Each independently is one of halogen, C1-C6 alkyl, C1-C6 alkoxy and C6-C12 aryl; r is C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aryl, or substituted C6-C12 aryl, wherein the substituent group in the substituted C6-C12 aryl is selected from one or more of halogen or halogenated C1-C6 alkyl.

6. Use according to claim 5, characterized in that in the compound of formula (III), the R is ¹ Is one of methyl, ethyl, cyclopropyl or phenyl, and R is ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ Each independently is H, methyl or ethyl; the R is ⁷ Is H, methyl, ethyl or phenyl; the R is ⁸ Is H, methyl, ethyl or phenyl; the R is ⁹ 、R ¹⁰ Each independently H or C1-C4 alkyl.

7. Use according to claim 6, wherein the compound of formula (III) has the formula (III-11) or (III-12):

wherein, X is ^— Is a halogen ion.

8. A method for preparing aryl phosphine by reducing aryl phosphine oxide is characterized by comprising the following steps:

the aryl phosphine oxide generates the aryl phosphorus under the action of an organophosphorus catalyst;

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

wherein, X is ₁ 、X ₂ Each independently of the others being halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C12 arylOne kind of the material is selected; the R is one of C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aryl or substituted C6-C12 aryl, and a substituent group in the substituted C6-C12 aryl is selected from one or more of halogen or halogenated C1-C6 alkyl;

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 the formula (III) is shown as a formula (III-1), a formula (III-2) or a formula (III-3):

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

the R is ¹ Is one of C1-C6 alkyl, phenyl or substituted phenyl, and the substituent 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 is ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ Each independently is H, C1-C6 alkyl, phenyl or substituted phenyl, and the substituent 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 above-mentioned

Represents a single bond or a double bond; said X ^— Is one of halogen ion, nitrate ion, perchlorate ion and carbanion.

9. The method of claim 8, wherein R in the compound of formula (III) is selected from the group consisting of ¹ Is one of methyl, ethyl, cyclopropyl or phenyl, and R is ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ Each independently is H, methyl or ethyl; the R is ⁷ Is H, methyl, ethyl or phenyl; the R is ⁸ Is H, methyl, ethyl or phenyl; the R is ⁹ 、R ¹⁰ Each independently is H or C1-C4 alkyl.

10. The method of claim 9, wherein the compound of formula (III) has the formula (III-11) or (III-12):

wherein, X is ^— Is a halogen ion.

11. The method of claim 8 for preparing an aryl phosphine by reducing an aryl phosphine oxide, comprising: the aryl phosphine oxide and a reducing agent are subjected to reduction reaction under the action of the organophosphorus catalyst to generate the aryl phosphorus; the structural formula of the reducing agent is shown as a formula (VI):

wherein, R is ¹⁴ 、R ¹⁵ 、R ¹⁵ Each independently is one of H, C1-C6 alkyl, C1-C6 alkoxy and C6-C12 aryl.

12. The method of claim 11, wherein the reducing agent is phenylsilane.

13. The method of claim 11, wherein the molar ratio of aryl phosphine oxide to reducing agent is: 1 (1-1.5).

14. The method for preparing aryl phosphine oxide by reducing aryl phosphine oxide according to any one of claims 8 to 13, wherein the reduction reaction is carried out under nitrogen or argon conditions.

15. The method for preparing aryl phosphine oxide by reducing aryl phosphine 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 hours.

16. The method for preparing aryl phosphine by reducing aryl phosphine oxide according to any one of claims 8 to 13, wherein when the organophosphorus catalyst is a composition of a compound of formula (I) and a compound of formula (II), the molar ratio of the aryl phosphine oxide, the reducing agent, the compound of formula (I) and the compound of formula (II) is as follows: 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 aryl phosphine oxide, the reducing agent and the compound of formula (III) is 1 (1-1.5) to (0.1-0.2).

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