WO2020175634A1 - Method for producing organophosphorus compound - Google Patents

Abstract

The present invention provides a method for producing an organophosphorus compound. A method for producing R¹R²PONa, which comprises a step for reacting R¹R²R³P(O) and sodium metal with each other, and which excludes the cases where a liquid ammonia is used as a solvent in the reaction, provided that each of R¹, R² and R³ independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Consequently, the present invention provides a novel method for producing an organophosphorus compound. A production method according to the present invention is a safe and inexpensive method since a liquid ammonia is not used as a solvent and a low temperature is not required therefor. According to the present invention, by-products are suppressed in comparison to conventional methods, and a desired reaction proceeds highly selectively. In addition, a desired product is able to be synthesized in a single pot without requiring isolation.

Description

Specification

Title of invention: Method for producing organic phosphorus compound

Technical field

The present invention relates to a method for producing an organic phosphorus compound.

Background technology

[0002] Phosphorus compounds are used in various applications due to their properties.

Many of the current methods for producing phosphorus compounds have a large impact on the environment, and in recent years, prices have risen significantly due to the tightening of environmental regulations in the country of origin, which is a factor that restricts industrial production using phosphorus compounds. Is becoming.

[0003] Triphenylphosphine oxide P h ₃ P (○) is an industrial waste that is produced as a large amount as a by-product from the W ittig (Wittig) reaction which is often used industrially. There is a strong demand for the development of effective utilization methods.

[0004] The reaction between P h ₃ P (○) and sodium has hitherto been carried out in liquid ammonia at low temperatures (Non-Patent Documents 1 and 2). Liquid ammonia is highly toxic and vaporizes rapidly when the temperature rises, making the reaction procedure complicated. Many by-products are also generated due to overreduction. Recently, it was also reported that P h ₃ P (○) was reduced by Na HL i I to generate P h ₂ P 〇 Na. However, the process was complicated because expensive Na and H had to be used at the same time (Non-Patent Document 3).

Prior art documents

Non-patent literature

Non-Patent Document 1: E s t e b a n R .N .B o r n a n c i n i et al., J .O r g .C h e m. 1 990, 55, 2332-2326

Non-patent document 2: Marek kT a n k e v ic et al., T e t r a h e d r o n 67 (201 1) 867 1 -8678

Non-Patent Document 3: C iputra T ejo et al., C he m. Comm u n., 2 01 8, 54, 1 782- 1 785. 〇 2020/175634 2 ((171?2020/008080)

Means for solving the problem

[0006] The present inventors are waste

As a result of earnest studies on the effective use of (○), a new method for producing an organophosphorus compound was found.

[0007] The present invention also provides the following items.

(Item 1)

formula

Including reacting a compound represented by (◯) with metallic sodium, Formula ¹

A method for producing the compound represented by 3,

² and ³ are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and the reaction is excluded unless liquid ammonia is used as a solvent.

(Item 2)

[¾ ^2, and ³ are each independently a substituted or unsubstituted aryl group, The method of claim 1.

(Item 3)

The method according to Item 1, wherein and are substituted phenyl groups.

(Item 4)

and

The method according to Item 1, wherein is an alkyl-substituted phenyl group or an alkoxy-substituted phenyl group.

(Item 5)

Is a substituted or unsubstituted aryl group, is a substituted or unsubstituted alkyl group,

The method according to Item 1, wherein is a substituted or unsubstituted aryl group.

(Item 6)

The method according to Item 1, wherein and are each independently a substituted or unsubstituted alkyl group, and is a substituted or unsubstituted aryl group.

(Item 7) 〇 2020/175634 3

The method according to Item 1, wherein and are each independently an unsubstituted alkyl group.

(Item 8)

(〇) is, |? 1 ₃ is (〇), The method of claim 1.

(Item 9)

9. The method according to any one of Items 1 to 8, wherein the reaction is performed in an organic solvent.

(Item 10)

Item 10. The method according to any one of Items 1 to 9, wherein the reaction is performed in an aprotic organic solvent.

(Item 11)

Item 10. The method according to any one of Items 1 to 10, wherein the reaction is carried out in an ether solvent.

(Item 12)

The reaction is tetrahydrofuran, diethyl ether, dioxane, 1, 2

— A method according to any one of items 1-11, which is carried out in dimethoxyethane, dioxolane, cyclopentyl methyl ether, or any mixture thereof.

(Item 13)

The reaction is carried out at a temperature between one 7 8 ^° 〇 ~ 2 0 0 ^° 〇 The method of claim 1-1 2 Neu Zureka 1 Section.

(Item 14)

Item 13. The method according to any one of Items 1 to 13, wherein the reaction is performed at room temperature.

(Item 15)

Item 15. The method according to any one of Items 1 to 14, wherein the sodium metal is in the form of lumps.

(Item 16)

The metallic sodium is fine particles, the items 1 to 14 20/175634 4 卩 (: 171? 2020 /008080

The method according to any one of items.

(Item 17)

Item 17. The method according to Item 16, wherein the average particle size of the metallic sodium is 1 to 10 10.

(Item 18)

a)

A step of reacting the compound represented by (◯) with metallic sodium, the step excluding the case where the reaction uses liquid ammonia as a solvent;

b) Product and formula of step 3)

Including,

And are each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,

88 is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group,

Is a leaving group,

Method.

(Item 19)

Item 18. The method according to Item 18, wherein the leaving group is 0 ^to 1 or halogen.

(Item 20)

(◯) is ₃ (◯), and the above-mentioned [¾ _ 1-is water, The method according to item 18 or 19.

(Item 21)

(O) is ₃ (O), and the above is n-octyl, The method according to Item 18 or 19.

(Item 2 2)

(〇) is, |? Is 1 ₃ (〇), said is, 2, 4, 6 20/175634 5 卩 (: 171? 2020 /008080

— A method according to item 18 or 19 which is trimethylbenzoyl.

(Item 23)

Item 18. The method according to Item 18 or 19, wherein [¾ 3 (○) is (- 1 0 | So |) ₃ (○), and [¾ 8 _ 1-is water.

(Item 24)

(〇) is, | \ / |? 6 ₂ is a (〇), the [¾ eight _ 1 - is selected from the group consisting of water other the method described in 1 9. (○) is ( _|3 — methoxyphenyl) ₃ (○),

The method according to item 18 or 19.

(Item 2 6)

Formula (〇)

a)

A step of reacting the compound represented by (◯) with metallic sodium, the step excluding the case where the reaction uses liquid ammonia as a solvent;

b) Product and formula of step 3)

Reacting with a compound represented by (0),

〇) A step of reacting the product of step S) with water

Including,

And are each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,

And are each independently hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,

Method.

(Item 27)

The method according to Item 26, wherein (○) is benzaldehyde.

(Item 28) 〇 2020/175634 6

(○) is

The method according to item 26, which is benzophenone.

(Item 29)

Manufactured by the method according to any one of Items 1 to 17, [¾ ¹ ,

Eq. ¹ as specified in eye ¹

○ The compound represented by 3.

(Item 30)

Manufactured by the method according to any one of items 18 to 25,

[8 is as defined in item 18, compounds represented by formula (○) _ [8.

(Item 31)

Manufactured by the method according to any one of items 26 to 28,

Is as specified in item 26, the formula? (〇) Compounds represented by 10 [¾ ⁸ [¾ 〇 〇 1 ^to 1].

[0008] In the present invention, it is contemplated that one or more of the above features may be provided in addition to the explicit combinations. Still further embodiments and advantages of the present invention will be appreciated by those of ordinary skill in the art upon reading and understanding the following detailed description, as necessary.

Effect of the invention

[0009] A new method for producing an organophosphorus compound is provided. The production method of the present invention is a safe and inexpensive method because it does not use liquid ammonia as a solvent and does not require low temperature. Compared with the conventional method, there are few by-products and the target reaction proceeds with high selectivity. The desired product can be synthesized in one pot without the need for isolation.

Brief description of the drawings

[0010] [FIG. 1] FIG. 1 is a ^{3 1} IV! spectrum of the product of Example 1.

[Fig. 2] Fig. 2 shows an example

IV! spectrum.

[FIG. 3] FIG. 3 is a ³¹ IV! spectrum of the product of Example 3.

[Fig. 4] Fig. 4 shows an example

IV! spectrum. 〇 2020/175634 7 卩(: 171-1?2020/008080

[Fig. 5] Fig. 5 is a ○○ 1\/1 3 spectrum of the product of Example 4.

FIG. 6 is a ^{3 1} IV! spectrum of the product of Example 5.

[FIG. 7] FIG. 7 is a spectrum of the product of Example 5.

FIG. 8 is a ^{3 1} IV! spectrum of the product of Example 6.

[FIG. 9] FIG. 9 is a spectrum of the product of Example 7.

[FIG. 10] FIG. 10 is a ◦ 〇 1\/1 3 spectrum of the product of Example 8.

[Fig. 11] Fig. 11 shows the (-○ I So I) ₂ 3 ^{3 3 1} ? 1\/| [¾ spectrum of Example 9.

[FIG. 12] FIG. 12 is a ^{3 11} 1/|[¾ spectrum of the product of Example 9.

[FIG. 13] FIG. 13 is a ◦ ○ IV! 3 spectrum of the product of Example 9.

[Fig. 14] Fig. 14 shows an example

It is a spectrum.

[FIG. 15] FIG. 15 is a ^{3 1} IV! spectrum of the product of Example 10. [Fig. 16] Fig. 16 is a ◦ 〇 IV! 3 spectrum of the product of Example 10.

MODE FOR CARRYING OUT THE INVENTION

[001 1] The present invention will be described below with reference to the best mode. It is to be understood that throughout this specification, the use of the singular includes the concept of the plural unless specifically stated otherwise. Therefore, it is understood that singular articles (eg, "8", "311", "1:116" in English, etc.) also include their plural concept unless otherwise stated. Should be. Further, it should be understood that the terms used in the present specification have meanings commonly used in the art, unless otherwise specified. Therefore, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

[0012] (Definition of terms)

The terms used in this specification are explained below.

[0013] In the present specification, "substitution" refers to other than a specific hydrogen atom of an organic compound. 〇 2020/175 634 8

It means replacing with atoms or atomic groups.

[0014] In the present specification, the "substituent" means an atom or a functional group in which another is substituted in the chemical structure.

[0015] In the present specification, unless otherwise specified, the substitution is a substitution of one or more hydrogen atoms in an organic compound or a substituent with another atom or atomic group, or a double bond. Alternatively, it means a triple bond. It is possible to remove one hydrogen atom and replace it with a monovalent substituent, or combine it with a single bond to form a double bond, and remove two hydrogen atoms to create a divalent substituent. Can also be substituted with, or combined with a single bond to form a triple bond.

[0016] Examples of the substituent in the present invention include hydrogen, a halogen group, an alkyl group, an alkoxy group, 10 1 ^to 1 group, 1 1\10 ₂ group,

Examples include, but are not limited to, 10 (= 0) 1 ^to 1 groups, alkylcarbonyl groups, and alkoxycarbonyl groups. The preferred group of substituents in the present invention, halogen, alkyl, ^_ 〇 alkyl,

—N 0 _2% ^_ 1^1 1 ^to 1 ₂ , ^— 0 (= 〇) 1 ^to 1, — 0 (= 0 )alkyl, and 1 0 (= 〇) 〇 alkyl. Further preferred group of substituents of the present invention, halogen, 10 1 Rei_4 alkyl (eg if one Rei_1 ^~ 1 _3), one hundred 1-Rei_4 alkyl (e.g., single Rei_rei_1 ^~ 1 ₃ ), 10 ^~ 1

For example, ten (= 0) Rei_1 ^~ 1 _3), and include ten (= 0) hundred 1 Rei_4 alkyl. All the substituents may have a substituent other than hydrogen.

In the present specification, 0 1, 0 2,..., C _n represent the number of carbon atoms (where n represents any positive integer). Therefore, 0 is used to represent a substituent having 1 carbon atom.

[0018] In the present specification, the "alkyl (group)" refers to a monovalent group formed by the loss of one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane and propane, and is generally

Represented by 1 ^~ 1 ₂ „ _{+ 1} — (where is a positive integer)

.. Alkyl can be straight or branched. In the present specification, the “substituted alkyl (group)” means that 1 ^to 1 of alkyl is substituted by the substituent defined above. 〇 2020/175 634 9 卩 (：171? 2020 /008080

Refers to alkyl. Specific examples of these are 01 to 0 2 alkyl, 01 to 0 3 alkyl, 0 1 to 0 4 alkyl, 0 1 to 0 5 alkyl, 0 1 to 0 6 alkyl, 0 1 to 0 7 alkyl, 0 1 to 〇8 alkyl, 〇1 to 〇9 alkyl, 〇1 to 〇10 alkyl, 〇1 to 〇11 alkyl or 〇1 to 〇20 alkyl, 〇1 to 〇2 substituted alkyl, 01 to 〇3 substituted alkyl, 01 ~ 04 substituted alkyl, 0 1 ~ 0 5 substituted alkyl, 01 ~ 0 6 substituted alkyl, 01 ~ 0 7 substituted alkyl,

O 1 to 08 substituted alkyl, 01 to 09 substituted alkyl, 01 to 01 0 substituted alkyl, 0 1 to 0 11 substituted alkyl or 0 1 to 0 20 substituted alkyl. Here, for example, The 〇 1 ~ 〇 1 0 alkyl means a straight or branched alkyl of 1-1 0 have a carbon atom, methyl ^(<31-1 ₃ -), ethyl (〇 21 ^~ 1 ₅ _) n _ propyl (Rei_1 ^~ 1 ₃ Rei_1 ^~ 1 ₂ Rei_1 ^to 1 ₂ _), isopropyl ((Rei_1 ^~ 1 ₃₎ 2_Rei_1 ^- 1_), n _ butyl (〇 1 ^to 1 ₃ 〇 1 ^to 1 ₂ 〇 1 ^to 1 ₂ 〇 _{^{1 ~ 1 2 _), n}} _ pentyl (Rei_1 ^to 1 ₃ Rei_1 ^to 1 ₂ Rei_1 ^to 1 ₂ Rei_1 ^to 1 ₂ Rei_1 ^to 1 ₂ -), n-hexyl (〇 1 ^to 1 ₃ 〇 1 ^to 1 ₂ 〇 1 ^to 1 ₂ 〇 1 ^to 1 ₂ 〇 1 ^to 1 ₂ 〇 1 ^to 1 ₂ -), clo-heptyl (〇 1 ^to 1 ₃ 〇 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ -), 1-octyl (○ 1 ^~ 1 ₃ ○ 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ 〇 1 ^~ 1 ₂ 〇 1 ^- 1 ₂ 〇 1 ^- 1 ₂ 〇 1 ^- 1 ₂ 〇 1 ^- 1 ₂ -), n - nonyl (Rei_1 ^~ 1 ₃ Rei_1 ^~ 1 ₂ Rei_1 ^- 1 ₂ Rei_1 ^- 1 ₂ Rei_1 ^- 1 ₂ Rei_1 ^- 1 ₂ Rei_1 ^- 1 ₂ Rei_1 ^- 1 ₂ Rei_1 ^- 1 ₂ -),门Deshiru (Rei_1 ^~ 1 ₃ 〇 1 ^to 1 ₂ 〇 1 ^- 1 ₂ 〇 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ ○ 1 ^~ 1 ₂ -),-○ (○ 1 ^~ 1 ₃ ) ₂ ○ H ₂ CH ₂ CH (Rei_1 _{^{~ 1 3) 2, _CH 2}} CH ( Rei_1 ^~ 1 _{3) 2} and the like. In addition, for example, ∘ to ∘10 substituted alkyl refers to ∘ to ∘10 alkyl, in which one or more hydrogen atoms are substituted with a substituent.

[0019] In the present specification, the "alkoxy (group)" refers to a monovalent group generated by the loss of the hydrogen atom of the hydroxy group of alcohols, and is generally

(Where is an integer greater than or equal to 1). The “substituted alkoxy (group)” means an alkoxy in which 1 ^to 1 of the alkoxy is substituted by the substituent defined above. As specific examples, 〇1-2 alkoxy, 〇1- 〇3 alkoxy, 〇1〜〇4 alkoxy, 〇1〜〇5 alkoxy, 〇1〜〇6 alkoxy, 〇1〜〇7 alkoxy, 〇1〜 〇8 alkoxy, 〇1 to 〇9 alkoxy, 〇1 to 〇 〇 2020/175 634 10 卩 (: 171? 2020 /008080

10 alkoxy, 〇 1 to 〇 11 alkoxy, 〇 1 to 〇 20 alkoxy, 〇 1 to 〇 2 substituted alkoxy, 01 to 03 substituted alkoxy, 01 to 〇 4 substituted alkoxy, 〇 1 to 〇 5 substituted alkoxy, 〇 1 to 0 6 substituted alkoxy, 0 1 to 0 7 substituted alkoxy, 0 1 to 0 8 substituted alkoxy, 0 1 to 0 9 substituted alkoxy,

It can be a 〇 1 to 〇 10 substituted alkoxy, a 〇 1 to 〇 11 substituted alkoxy or a 〇 1 to 〇 20 substituted alkoxy. Here, for example, a 〇 1 ~ 〇 1 0 an alkoxy means a straight or branched alkoxy containing 1-1 0 carbon atoms, main butoxy (Rei_1 ^~ 1 ₃ 〇 I), ethoxy (〇 ₂ 1 ^~ 1 ₅ 〇_) 1-1- like propoxy (Rei_1 ^~ 1 3_Rei_1 ^~ 1 ₂ Rei_1 ^- 1 ₂ 〇_) are exemplified.

[0020] In the present specification, "alkoxycarbonyl (group)" means (alkoxy)

〇 (= 〇) It means one group, and alkoxy is as described in “Alkoxy (group)” above.

[0021] In the present specification, the "aryl (group)" refers to a group formed by the elimination of one hydrogen atom bonded to the ring of an aromatic hydrocarbon. The benzene phenyl group (〇 ₆ 1 ^~ 1 ₅ -), tolyl (Rei_1 ^~ 1 ₃ 〇 ₆ 1 ^~ 1 ₄ -) from toluene, xylene Lil groups from xylene ((Rei_1 ^~ 1 _{3) 2} 〇 ₆ 1 ^~ 1 ₃ -), and naphthyl group (〇 ₁₀ 1 ^~ ₁₈ -) is derived from naphthalene. The number of carbon atoms may be 6 to 12.

[0022] In the present specification, "halogen (group)" refers to chlorine (○I), bromine (Mi), which belongs to Group 17 (referred to as Group 17 in the latest definition) of the periodic table. A monovalent group of an element such as iodine (I).

[0023] In the present specification, "alkylcarbonyl (group)" refers to carboxylic acid

A monovalent group formed by excluding 1 ^to 1. As a typical example of the alkylcarbonyl group, acetyl (○ 1 ^to 1 ₃ 001),

*1 etc. The number of carbon atoms in the alkyl moiety is, for example, 1 to 6. "Substituted alkylcarbonyl (group)" refers to an acyl having hydrogen substituted with a substituent as defined above.

[0024] In the present specification, the "arylcarbonyl (group)" refers to carboxylic acid

A monovalent group formed by excluding 1 ^to 1. Typical examples of the arylcarbonyl group include phenylcarbonyl (001) and the like. "Substituted Aryl 〇 2020/175634 1 1 卩(: 171-1?2020/008080

"Rubonyl (group)" refers to an aryl having a hydrogen atom substituted with a substituent group as defined above.

[0025] The term "liquid ammonia" as used herein refers to ammonia as a liquid.

[0026] In the present specification, the "aprotic organic solvent" refers to an organic solvent having a significantly low ability to donate a proton. Hydrocarbons, carbon tetrachloride, dioxane, ether and the like can be mentioned.

[0027] In the present specification, the "ether solvent" refers to a solvent for a neutral compound having the general formula [¾[¾']. here,

And [V is a hydrocarbon group such as alkyl or aryl. Included are linear ethers and cyclic ethers. Tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, dioxolane, cyclopentyl methyl ether and the like can be mentioned. [0028] The compound of the present invention is not limited to a specific isomer, and all possible isomers (keto-enol isomer, imine-enamine isomer, diastereoisomer, optical isomer, rotational isomer, etc.) And racemates.

[0029] One or more hydrogen, carbon or other atoms of a compound of the invention may be replaced with isotopes of hydrogen, carbon or other atoms. The compounds of the present invention include all radiolabels of the compounds of the present invention. Examples of isotopes that can be incorporated into the compound of the present invention include ² 1 ^to 1, ³ 1 ^to 1, ^{1 1} 0, ^{1 3} 0, ^{1 4} 0, and

^{1 8} 〇, ^{1 7} 〇, 3 1, 3 2 | 3, 3 5 _{3% 1,} 1 23 | and 3 6_Rei | way of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine, and iodine Includes chlorine isotopes

[0030] (Description of preferred embodiments)

Preferred embodiments of the present invention will be described below. It is understood that the embodiments provided below are provided for better understanding of the present invention, and the scope of the present invention should not be limited to the following description. Therefore, it is clear that a person skilled in the art can make appropriate modifications within the scope of the present invention in consideration of the description in the present specification. The following embodiments of the present invention may also be used alone. 〇 2020/175 634 12 卩 (：171? 2020 /008080

Alternatively, it is understood that they can be used in combination.

[0031] In one aspect, the present invention provides

Including reacting a compound represented by (○) with metallic sodium,

○ Provide a method for producing the compound represented by 3. here,

[¾ ² , and

Are each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. One of the characteristics of this reaction is that liquid ammonia is used as a solvent.

[0032] In one embodiment,

[¾ ² , and

Are each independently a substituted or unsubstituted aryl group. In another embodiment,

And 2 are unsubstituted phenyl groups. In another embodiment,

And are substituted phenyl groups. In another embodiment,

and

Is an alkyl-substituted phenyl group or an alkoxy-substituted phenyl group. In another embodiment,

And are methyl-substituted phenyl groups. In another embodiment,

And are -methoxyphenyl groups. Oite to another embodiment, but a substituted or unsubstituted aryl group, but if substituted Ku is an unsubstituted alkyl group, 8 ³ is a substituted or unsubstituted aryl group. In another embodiment,

There is a phenyl group, 8 ² is methyl group,

Is a phenyl group. In another embodiment,

and

Are each independently a substituted or unsubstituted alkyl group,

Is a substituted or unsubstituted aryl group. In another embodiment,

And are each independently an unsubstituted alkyl group. In another embodiment, (◯) is ₃ (◯).

[0033] In one embodiment, the reaction is performed in an organic solvent. In another embodiment, the reaction is carried out in an aprotic organic solvent. In another embodiment, the reaction is performed in an ethereal solvent. In another embodiment, the reaction is tetrahydrofuran, diethyl ether, dioxane, 1, 2

— Dimethoxyethane, dioxolane, cyclopentyl methyl ether, or any mixture thereof. 〇 2020/175 634 13

[0034] In one embodiment, the reaction is carried out at a temperature between 178° and 200°. In another embodiment, at a temperature of between 1 5 ^° 〇 ~ 1 1 0 ^° 〇. In another embodiment, the reaction is performed at room temperature. In another embodiment, the reaction is carried out at any temperature from room temperature to the boiling point of the solvent. The lower limit of reaction temperature is _78° 〇, _70° 〇, _60° 〇, _50° 〇, _40° 〇, -3.0, -20. .. ,-1 0. 0, 0. 0, 5.0, 1 0. 0, 1 5.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, 50 0, 55.0, 60.0, 65.0, 70.0, 75.0, 80.0, 85.0, 90.0, 95.0, 100. .. , 1 05. .. , 110 ^° 〇, etc. The upper limit of the reaction temperature is 200 ^° 〇, 190 ^° 〇, 180. .. , 1 70. .. , 1 60. .. , 1 50. .. , 1 40. .. , 1 30. .. , 1 20 ° 0, 1 1 0. .. , 100. .. , 90.0, 80.0, 70.0, 60.0, 50.0, 40° 0, 30 ^° 〇, 20 ^° 〇, 10 ^° 〇, 0 ^° 〇, etc. The reaction temperature range may be any combination of these values.

[0035] In one embodiment, the metallic sodium is in a lump form. In another embodiment, the metallic sodium is fine particles. In another embodiment, the average particle size of the metallic sodium is 1 to 10. The finely divided metallic sodium may have a distribution in particle size.

[0036] In one aspect, the present invention provides

(0) _ [a method for producing a compound represented by

A step of reacting the compound represented by (○) with sodium metal, the step excepting the case where liquid ammonia is used as a solvent, and the product of the step 3) and the formula

And a step of reacting with a compound represented by here,

, And are each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,

Is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group, and 1- is a leaving group. In another embodiment, the leaving group is 0 ^to 1 or halogen (eg, chlorine, bromine, iodine). In another embodiment,

(○) is 11 ₃ 〇 2020/175 634 14 卩 (: 171? 2020 /008080

(0) and the above [¾_!_#, water. In another embodiment, the above (O) is, and the above is methyl, ethyl, n

,, _ petit, isoptyl, ㊀ "1: _ petit,

,,, hexyl,

Chill or-octyl. In another embodiment,

(○) is ₃ (○),

It is 2, 4, 6-trimethylbenzoyl. In another embodiment, said? (〇) is (－ 〇 丨 V 丨) ₃ (〇), and

-Is water. In another embodiment,

(○) is 1\/16 ₂ ?(○), and the above-mentioned [¾81 1-is water. In another embodiment, the (O) is (-methoxyphenyl) ₃ (O), and the [¾_1-is water.

[0037] In one aspect, the formula (O)

The manufacturing method of 3)

A step of reacting the compound represented by (○) with sodium metal, the step excepting the case where liquid ammonia is used as a solvent, and the product of the step 3) and the formula

There is provided a method comprising a step of reacting a compound represented by (◯) and a step of reacting the product of ◯) step () with water. here,

[¾ ² , and

Are each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,

and

Are each independently hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. In another embodiment,

(〇) is, 11 is _3? (〇), the [is ¾ ⁶ 〇 (〇), benzaldehyde. In another embodiment,

(○) is benzophenone.

[0038] In one aspect, produced by the above method,

Is as defined above,

○ A compound represented by 3 is provided. In another aspect, manufactured by the above method,

A compound represented by the formula (O) 1 [8] is provided, wherein is as defined above. Another aspect 〇 2020/175 634 15

In, manufactured by the above method,

, Is as defined above, the formula (0)

A compound represented by is provided. The method of the present invention produces less by-products, and the organophosphorus compound produced by the method of the present invention can be obtained with high purity.

[0039] (Method for producing compound of the present invention)

The present invention relates to a method for producing phosphine oxysodium ([¾ ₂ 0 ₃ :2 8) by reacting phosphine oxide (? (O): 18) with metallic sodium (N 3), and phosphine oxysodium. To more organic phosphorus compounds (8 ₂ (0) 1 ^to 1, R ₂ P (0)

Provide a method for producing R ₂ P (0) carbonyl [¾丫: 38, 48, 58, etc.].

[Chemical 1]

(In the formula,

[The following are hydrocarbon groups such as alkyl and aryl. ) [0040] The method of the present invention is characterized in that the reaction of phosphine oxide ([¾ ₃ (0): 18) and sodium metal (N 3) is excluded unless liquid ammonia is used as a solvent. One [¾ ₂ 〇 3 is obtained with high selectivity. [¾ ₂ 〇 3 is a leaving group! -Containing reactant

(E.g., 1 ^to 1 ₂ 〇, [VX and [¾丫〇 (0) 0 1) reacts with, to produce the _{[¾ 2 (0) _ [} ¾.

[0041] As a preferred embodiment of the starting phosphine oxide ([¾ ₃ (○) ), the compound represented by the formula: A compound represented by (○)

[ ³ and ² are each independently a compound which is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. As a preferred embodiment of the phosphine oxy de of starting material, [¾ ^2, and but are each independently a substituted or unsubstituted aryl group. Starting material phosphine oxide 〇 2020/175634 16 卩(: 171-1?2020/008080

A preferred embodiment of

Is a substituted phenyl group. As a preferred embodiment of the phosphine oxide as a starting material,

And are an alkyl-substituted phenyl group or an alkoxy-substituted phenyl group. As a preferred embodiment of the phosphine oxide as a starting material,

But if substituted Ku is an unsubstituted aryl group, 8 ² is a substituted or unsubstituted alkyl group, but a substituted or unsubstituted aryl group. Preferred embodiments of the starting phosphine oxide include:

And are each independently a substituted or unsubstituted alkyl group, 8 ³ is a substituted or unsubstituted aryl group. Preferred embodiments of the starting phosphine oxide include:

And are each independently an unsubstituted alkyl group. As a preferred embodiment,

(○) is 11 ₃ ?(○).

[0042] Preferred embodiments of the organophosphorus compound of the products of the above formulas 3, 4, and 5 include:

and

, Each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, 8 is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or It is a substituted or non-substituted arylcarbonyl group.

[0043] The above formula

As a preferred embodiment of the compound represented by

, And are each independently a substituted or unsubstituted aryl group,

It is hydrogen. The above formula

(0) _ [The preferred embodiment of the compound represented by

¹ is a substituted or unsubstituted aryl group, 8 ² is a substituted or unsubstituted alkyl group, 8 is hydrogen. Up

¹ and are each independently a substituted or unsubstituted alkyl group, and [¾ is hydrogen.

[0044] The above formula

(0)-[A preferred embodiment of the compound represented by is and are each independently a substituted or unsubstituted aryl group,

Is a substituted or unsubstituted alkyl group. The above formula (〇 〇 2020/175 634 17 卩 (：171? 2020 /008080

) As a preferred embodiment of the compound represented by

Is a substituted or unsubstituted aryl group, is a substituted or unsubstituted alkyl group, and is a substituted or unsubstituted alkyl group. The above formula

(O) _ [The preferred embodiment of the compound represented by

and

Each independently a substituted or unsubstituted alkyl group,

Is a substituted or unsubstituted alkyl group.

[0045] The above formula

As a preferred embodiment of the compound represented by

, And are each independently a substituted or unsubstituted aryl group,

Is a substituted or unsubstituted alkylcarbonyl group. Formula 1 [¾ ² (0)

As a preferred embodiment of the compound represented by:

There is a substituted or unsubstituted aryl group, 8 ² is a substituted or unsubstituted aralkyl kill group,

Is a substituted or unsubstituted alkylcarbonyl group.

As a preferred embodiment of the compound represented by:

Independently, it is a substituted or unsubstituted alkyl group, and 8 is a substituted or unsubstituted alkylcarbonyl group.

[0046] The above formula

As a preferred embodiment of the compound represented by

, And are each independently a substituted or unsubstituted aryl group, and 8 is a substituted or unsubstituted arylcarbonyl group. Equation 8 1 [¾ ² (0)

As a preferred embodiment of the compound represented by:

There is a substituted or unsubstituted aryl group, 8 ² is a substituted or unsubstituted aralkyl kill group,

Is a substituted or unsubstituted arylcarbonyl group.

As a preferred embodiment of the compound represented by:

Independently, it is a substituted or unsubstituted alkyl group, and 8 is a substituted or unsubstituted arylcarbonyl group.

[0047] As a preferred embodiment of the organophosphorus compound of the above product, 11 ₂ ?(○)

It is 1 ^to 1. A preferred embodiment of the organophosphorus compound of the above product is II ₂ (0) _ octyl. Preferred embodiments of the organophosphorus compound of the above product include: 〇 2020/175 634 18 卩 (: 171? 2020 /008080

[Chemical 2]

Is. Preferred embodiments of the organophosphorus compound of the above product include (_

I ○ IVI) ₂ ? (0) 1 ^to 1. A preferred embodiment of the organophosphorus compound of the above product is (-methoxyphenyl) ₂ (◯) 1 ^to 1.

[0048] For example, when triphenylphosphine oxide is used, the following compound can be produced.

[Chemical 3]

[0049] The present invention also reacts phosphine oxide ([¾ ₃ (0): 18) with sodium metal (N 3) to produce phosphine oxysodium ([¾ ₂ 0 3 :2 8). And reacting with an aldehyde or ketone to produce a further organophosphorus compound.

[Chemical 4]

It is the street. )

[0050] A preferred embodiment of the phosphine oxide ([¾ ₃ (○) ), which is the starting material of the reaction for forming the compound of the above formula 6, is It can be the same as the starting phosphine oxide.

[0051] Preferred embodiments of the organophosphorus compound of the product of the above formula 6 include: 〇 2020/175 634 19 卩 (：171? 2020 /008080

R ² P (〇)

And are each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,

And are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group.

[0052] The above formula

As a state,

and

Are each independently a substituted or unsubstituted aryl group,

And are hydrogen. The above formula

(O) As a preferred embodiment of the compound represented by 10 R ^B Rc O H,

But if substituted Ku is an unsubstituted aryl group, 8 ² is a substituted or unsubstituted alkyl group,

And are hydrogen. The above formula

(O) _CR ^B R ^C O H is a preferred embodiment of the compound represented by:

and

Are each independently a substituted or unsubstituted alkyl group,

And are hydrogen.

[0053] The above formula

As a state,

and

Are each independently a substituted or unsubstituted aryl group,

And are each independently hydrogen or a substituted or unsubstituted alkyl group. The above formula

(0) — as a preferred embodiment of the compound represented by CR ^B R ^C O H,

¹ is a substituted or unsubstituted a is a substituted or unsubstituted alkyl group,

And

Independently, it is hydrogen or a substituted or unsubstituted alkyl group. The above formula

As an embodiment,

And and are each independently a substituted or unsubstituted alkyl group,

and

Are each independently hydrogen or a substituted or unsubstituted alkyl group.

[0054] The above formula

As a state,

And and are each independently a substituted or unsubstituted aryl group,

And are each independently hydrogen, substituted or 〇 2020/175 634 20 卩 (：171? 2020 /008080

It is an unsubstituted alkyl group or a substituted or unsubstituted alkylcarbonyl group. The above formula

As a form, is a substituted or unsubstituted aryl group, is a substituted or unsubstituted alkyl group,

and

Are each independently hydrogen, a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkylcarbonyl group. The above formula

Preferred embodiments of the compound include

And are each independently a substituted or unsubstituted alkyl group,

And are each independently hydrogen, a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkylcarbonyl group.

[0055] The above formula

As a state,

and

Are each independently a substituted or unsubstituted aryl group,

And are each independently hydrogen or a substituted or unsubstituted alkylcarbonyl group. The above formula

As a preferred embodiment of the compound represented by ○ ○ 1 ^~ 1,

A substituted or unsubstituted aryl group, 8 ² is a substituted or unsubstituted alkyl groups, and are each independently hydrogen or substituted or unsubstituted A Le kill carbonyl group. The above formula

(0) — As a preferred embodiment of the compound represented by CR ^B R ^C OH,

and

Are each independently a substituted or unsubstituted alkyl group,

And are each independently hydrogen or a substituted or unsubstituted alkylcarbonyl group.

[0056] The above formula

As a state,

and

Are each independently a substituted or unsubstituted aryl group,

And are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkylcarbonyl group. Up

A preferred embodiment of the compound represented by is: is a substituted or unsubstituted aryl group, is a substituted or unsubstituted alkyl group, and is each independently a substituted 〇 2020/175 634 21

Alternatively, it is an unsubstituted alkyl group or a substituted or unsubstituted alkylcarbonyl group. The above formula

As a preferred embodiment,

And are each independently a substituted or unsubstituted alkyl group,

And are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkylcarbonyl group.

[0057] The above formula

As a state,

and

Are each independently a substituted or unsubstituted aryl group,

And are each independently hydrogen, a substituted or unsubstituted alkyl group or a substituted or unsubstituted arylcarbonyl group. The above formula

As a form, is a substituted or unsubstituted aryl group, is a substituted or unsubstituted alkyl group,

and

Are each independently hydrogen, a substituted or unsubstituted alkyl group or a substituted or unsubstituted arylcarbonyl group. The above formula

Preferred embodiments of the compound include

And are each independently a substituted or unsubstituted alkyl group,

And are each independently hydrogen, a substituted or unsubstituted alkyl group or a substituted or unsubstituted arylcarbonyl group.

[0058] The above formula

As a state,

and

Are each independently a substituted or unsubstituted aryl group,

And are each independently hydrogen or a substituted or unsubstituted arylcarbonyl group. The above formula

(0) as the preferred embodiment of the compounds represented by -〇_8 Snake [¾ ^Rei_rei_1-1,

A substituted or unsubstituted aryl group, 8 ² is a substituted or unsubstituted alkyl groups, and are each independently hydrogen or substituted or unsubstituted A reel carbonyl group. Preferred embodiments of the compound represented by the above formula (0) — CR ^B R ^C O H include:

But each independently 〇 2020/175 634 22 卩 (：171? 2020 /008080

A substituted or unsubstituted alkyl group,

And are each independently hydrogen or a substituted or unsubstituted arylcarbonyl group.

[0059] The above formula

As a state,

and

Are each independently a substituted or unsubstituted aryl group,

And are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted arylcarbonyl group. Up

Is a substituted or unsubstituted aryl group, is a substituted or unsubstituted alkyl group,

And are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted arylcarbonyl group. The above formula

As a preferred embodiment,

And are each independently a substituted or unsubstituted alkyl group,

And are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted arylcarbonyl group.

[0060] Preferred embodiments of the organophosphorus compound as the product of formula 6 include:

[Chemical 5]

[Chemical 6]

Is mentioned.

[0061] In the present specification, the reaction of triphenylphosphine oxide with sodium \\0 2020/175 63 4 23 (: 17 2020 /008080

The resulting product by, is shown as ₂ 〇 3, considered the equilibrium state shown below are present.

[0062] [Chemical 7]

[0063] It is considered that the above equilibrium state is the same in a compound produced by the reaction of another organic phosphorus compound and sodium.

[Chemical 8]

?¾ (0 3 〇

(In the formula,

Represents a hydrocarbon group such as alkyl and aryl. )

[0064] (Use)

The organophosphorus compound of the present invention is useful as a raw material for producing another organophosphorus compound. The organophosphorus compound of the present invention is also useful as a raw material for forming a metal complex. The organophosphorus compound of the present invention is also an anti-fog agent, a flame retardant, an electric/electronic-related component, a 08 related component, an automobile component, a train component, an aircraft component or fiber, a sheet, a film, or an acrylic glass. It can be used as a polymer additive, a surface modifier, and the like. Furthermore, it can be used as a material for lithium-ion secondary batteries, metal extractants, wastewater treatment agents, etc.

[0065] References such as scientific literatures, patents, and patent applications cited in the present specification are incorporated by reference in the present specification in their entirety to the same extent as each of them is specifically described.

The present invention has been described above with reference to the preferred embodiments for easy understanding. Hereinafter, the present invention will be described based on Examples. \¥0 2020/175 63 24 24 (: 17 2020 /008080

The examples below are provided for illustrative purposes only and are not intended to limit the invention. Accordingly, the scope of the invention is not limited to the embodiments or examples specifically described herein, but only by the claims.

Example

[0067] The present invention will be described more specifically according to the following examples and comparative examples, but the present invention is not construed as being limited thereto, and may be obtained by appropriately combining the technical means disclosed in each example. Examples which are also included in the scope of the present invention

Further, the abbreviations used in the present specification have the following meanings.

Gas chromatograph mass spectrometer

IV!㊀: Methyl group

IV!㊀ 3: Mesityl group

10 000 So 1: Door-octyl

Nuclear magnetic resonance

11: Phenyl group

° °

7 9 0:

[Chemical 9]

[0069] The compounds of the invention and their syntheses are further described by the following examples. The following examples are provided to further define the invention, but the invention is not limited to the features of these examples. In the specific examples, common names are used and it is understood that these common names will be recognized by those skilled in the art. 〇 2020/175 634 25 卩 (：171? 2020 /008080

[0070] Measuring device

All of the ○ and IV! used in the following experiments were measured using the following equipment.

〇 〇 1\/13: 〇 〇 1\/13-〇? 201 0

Columns used ··· 9 \ 1 6 doors 6 ○ 1”1 |·! 0 1 09) 65 companies 06—

1

_ [¾: "" 跳〇!_ _ _-巳〇乂丁

Measurement condition: ³¹ 1\/^ (1 62

No solvent)

(Example 1)

Synthesis of 2 3

Dissolve 9 h ₃ P (○) (○ 0.50 1 0 1 0 1) in GH F (3 1_), and add 3 0 3 (sodium particles) at room temperature.

〇 I 1 _%

It was confirmed (Fig. 1, 5 9 1.3).

(Example 2)

Synthesis of 2 3

9 h ₃ P (○) (○ 0.5 0 1 0 1 0 1) was dissolved in GH F (3 1_), and 3 0 N 3 (1.5 0 丨) was added at room temperature. The mixture was heated at 60° for 1 hour with stirring. 1\/|[¾ completely disappeared ₃ (○) of the raw material,

It was confirmed that 8 was obtained (Fig. 2, 5 91.4).

(Example 3)

Synthesis of 2 3

Dissolve 9 h ₃ P (○) (○ 0.5 0 1 0 1 0 1) in GH F (3 1_), and agglomerate metallic sodium at room temperature.

(1.5 〇丨) was added. Heated for 1 hour with stirring at 60°. ³¹ of raw materials

(0) is completely disappeared, ₂ 〇 3 it was confirmed that have been obtained in about 80% yield (Fig. 3, \¥02020/175634 26 ?01/1?2020/008080

5 9 1. 3).

[0074] (Example 4)

|1 ₂ (〇) Synthesis of 1 ^to 1

Dissolve 9 h ₃ P (○) (○ 0.50 1 0 1 0 1) in GH F (3 1_) and let it stand at room temperature for 3

○ ₃ (1.5 ○ 丨) was added. The mixture was stirred at room temperature for 2 hours. Saturated ammonium chloride aqueous solution (201_) was added. The organic layer was extracted with ethyl acetate. ³¹ ?

(○) has completely disappeared. 11 ₂ (〇

) It was confirmed that 1 ^to 1 were generated (Fig. 4, 5 22.1). ◦ 1 1/13 The molecular weight of the target compound was confirmed by measurement (Fig. 5, [IV!] = 202). Remove the solvent in a vacuum,

(〇) 1 ^to 1 was obtained quantitatively.

[0075] (Example 5)

11 ₂ ?(〇) 1 ¹ 〇 〇 1 Synthesis

Dissolve 9 h ₃ P (○) (○ 0.50 1 0 1 0 1) in GH F (3 1_) and let it stand at room temperature for 3

○ N 3 (1.5 丨) was added. After stirring at room temperature for 2 hours, octyl bromide (2. 00 丨) was added and the mixture was stirred at room temperature for 1 hour. After adding a saturated aqueous solution of ammonium chloride (2!_), the organic layer was extracted with ethyl acetate. ³¹

(0) disappeared completely,

(0) — It was confirmed that the I-So was generated (Fig. 6, 5 28.

4) (97%, ³ ₁ 1\/|[¾ yield). The molecular weight of the target compound was confirmed by measuring ___1\/13 (Fig. 7, [|\/|] = 3 14). Remove the solvent in vacuo, 11 ₂

(0)-"00 IVI was obtained in high yield.

[0076] (Example 6)

Reaction with acid chloride, Synthetic method

Dissolve 9 h ₃ P (○) (○ 0.50 1 0 1 0 1) in GH F (3 1_) and let it stand at room temperature for 3

〇 ₃ (1.

Was added. After stirring at room temperature for 2 hours, the solution was cooled to -30°C, 1//163 〇 (〇) 〇 1 (2.0 〇 101 〇 1) was added and stirred for 1 hour. After returning to room temperature, saturated aqueous ammonium chloride solution (201_) was added, and the organic layer was extracted with ethyl acetate. ³¹

〇 2020/175 634 27 卩 (：171? 2020 /008080

It was confirmed that (○) had completely disappeared and that the desired product had been produced (Fig. 8, 5 1 2.2) (52%, yield). The solvent was removed in vacuo to give a pad.

IV! 3 measurement was performed and it was confirmed that the target compound was produced.

(Example 7)

Reaction with benzaldehyde

Dissolve 9 h ₃ P (○) (○ 0.5 0 1 0 1 0 1) in GH F (3 1_), and at room temperature 30 N 3 (1.

Was added. After stirring at room temperature for 2 hours, benzaldehyde (2.001010 I) was added and the mixture was stirred at room temperature for 1 hour. After adding a saturated ammonium chloride aqueous solution (201_), the organic layer was extracted using ethyl acetate.

The molecular weight of the target compound was confirmed by the measurement (Fig. 9, [1\/1] = 308).

[0078] (Example 8)

Reaction with benzophenone

Dissolve 9 h ₃ P (○) (○ 0.5 0 1 0 1 0 1) in GH F (3 1_), and at room temperature, 30 3 (1.

Was added. After stirring at room temperature for 2 hours, benzophenone (2.0 〇! 〇! 〇 丨) was added and stirred at room temperature for 1 hour. After adding a saturated aqueous ammonium chloride solution (201_), the organic layer was extracted with ethyl acetate.

The molecular weight of the target compound was confirmed by measurement (Fig. 10, [IV!] = 384) ₀

[0079] (Example 9)

(1 1: 〇 1 71 ) ₂ ? (〇) 1 ^~ 1 synthesis

(-○ IVI) ₃ (○) (○. 501010I) was dissolved in GH F (3 mL), 30 3 (1.50 10 10 丨) was added at room temperature, and the mixture was stirred at room temperature for 1 hour.

〇 ³¹ 9 1 \ / | [that is (one 1 〇 1 Seo 1) ₂ 〇 3 are obtained by ¾ was confirmed (FIG. 1 1, 5 9 1.7). Saturated ammonium chloride solution (2 11_

) Was added and the organic layer was extracted with ethyl acetate. ³¹ 1\/|[¾ confirmed that (- I 〇 IVI) ₂ ? (〇) 1 ^to 1 were generated (Fig. 12, 5 〇 2020/175 634 28 卩 (：171? 2020 /008080

20.5) (79%, ³ ₁ 1\/|[¾ yield). The molecular weight of the target compound was confirmed by 1/13/13 measurement (Fig. 13, [IV!] = 230).

[0080] (Example 10)

Synthesis of IV! 6 (〇) 1 ^to 1

1\/16 ₂ ?(〇) (1.0 〇! 〇! 〇 I) dissolved in GH F (6 〇11_) at room temperature

86.8). A saturated ammonium chloride aqueous solution (410_) was added, and the organic layer was extracted with ethyl acetate. ³¹

(○) It was confirmed that 1 ^to 1 were generated (Fig. 15, 5 21.4) (45% ³¹ 1\/^ yield). ◦ (3 _1\/13 measurement confirmed the molecular weight of the target compound (Fig. 16, interval = 140) ₀

As described above, the present invention has been illustrated by using the preferred embodiments of the present invention, but it is understood that the scope of the present invention should be construed only by the claims. .. The patents, patent applications, and other references cited herein should be incorporated by reference in their content as if they were specifically described in their own right. Be understood. The present application claims priority to Japanese Patent Application No. 201 9-35997 (filed on February 28, 2009), the contents of which are incorporated by reference in their entireties. .. The patents, patent applications and other references cited herein, as well as their content being specifically set forth herein, should be incorporated by reference in their content. It is understood that there is.

Industrial availability

[0082] A method for producing an organic phosphorus compound is provided.

Claims

\¥02020/175 634 29 卩 (: 17 2020 /008080

The scope of the claims

[Claim 1] Expression

Including reacting the compound represented by (○) with metallic sodium,

And

[¾ ² , and

Are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, except when the reaction uses liquid ammonia as a solvent.

[Claim 2]

[The method according to claim 1, wherein [ ^2] and [ ^3] are each independently a substituted or unsubstituted aryl group.

[Claim 3]

The method according to claim 1, wherein and are substituted phenyl groups.

[Claim 4]

The method according to claim 1, wherein is an alkyl-substituted phenyl group or an alkoxy-substituted phenyl group.

[Claim 5] is a substituted or unsubstituted aryl group, but substituted or is unsubstituted alkyl group, 8 ³ is a substituted or unsubstituted A reel group to claim 1 The described method.

[Claim 6]

And are each independently a substituted or unsubstituted alkyl group,

The method according to claim 1, wherein is a substituted or unsubstituted aryl group.

[Claim 7]

The method according to claim 1, wherein and are each independently an unsubstituted alkyl group.

[Claim 8]

The method according to claim 1, wherein (◯) is ₃ (◯).

[Claim 9] The method according to any one of claims 1 to 8, wherein the reaction is carried out in an organic solvent.

[Claim 10] The method according to any one of claims 1 to 9, wherein the reaction is carried out in an aprotic organic solvent.

11. The method according to any one of claims 1 to 10, wherein the reaction is carried out in an ether solvent. 〇 2020/175 634 30 卩 (：171? 2020 /008080

Or the method described in paragraph 1.

[Claim 12] The reaction is tetrahydrofuran, diethyl ether, dioxane,

1,2-dimethyethane, dioxolane, cyclopentylmethyl ethane

-The method according to any one of claims 1-11, which is carried out in tellurium or any mixture thereof.

[Claim 13] wherein the reaction is carried out at a temperature between one 7 8 ^° 〇 ~ 2 0 0 ^° 〇 claim 1

1 The method described in any one of 1.

[Claim 14] The method according to any one of claims 1 to 13, wherein the reaction is performed at room temperature.

[Claim 15] The metallic sodium is in the form of lumps,

14. The method according to any one of 1 to 4.

[Claim 16] The method according to any one of claims 1 to 14, characterized in that the metallic sodium is fine particles.

[Claim 17] The method according to claim 16, wherein the average particle size of the metallic sodium is 1 to 10 10.

[Claim 18] formula

A method for producing a compound represented by (0):

a)

A step of reacting the compound represented by (◯) with metallic sodium, the step excluding the case where the reaction uses liquid ammonia as a solvent;

b) Product and formula of step 3)

A step of reacting with a compound represented by

Including,

And are each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,

Is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted aryl carbonyl group,

Is a leaving group, 〇 2020/175 634 31 卩 (：171? 2020 /008080

Method.

[Claim 19] The method according to claim 18, wherein the leaving group is 0 ^to 1 or halogen.

[Claim 20]

The method according to claim 18 or 19, wherein (◯) is ₃ (◯), and [¾8_1-is water.

[Claim 21]

The method according to claim 18 or 19, wherein (o) is ₃ (o), and said is n-octyl.

[Claim 22]

(〇) is, |? Is 1 ₃ (〇), said is, 2

The method according to claim 18 or 19, which is 4,4,6-trimethylbenzoyl.

[Claim 23] The above [¾ 3 (○) is (-1 1 | |) ₃ (○),

The method according to claim 18 or 19, which is water.

[Claim 24]

(○) is 1\/16 ₂ ?(○), and the above [¾8_

The method according to claim 18 or 19, wherein !_ is water.

[Claim 25]

(〇) is - a (1 ₃ main Tokishifueniru) ₃ (〇), wherein [¾ -! _ #, Is water, The method of claim 1 8 or 1 9.

[Claim 26] Formula (0)

There

a)

A step of reacting the compound represented by (◯) with metallic sodium, the step excluding the case where the reaction uses liquid ammonia as a solvent;

b) Product and formula of step 3)

Reacting with a compound represented by (0),

〇) including the step of reacting the product of step step) with water,

And are each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, 〇 2020/175 634 32 卩 (：171? 2020 /008080

And are each independently hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

[Claim 27]

(○) is ₃ (○),

The method according to claim 26, wherein (◯) is benzaldehyde.

[Claim 28]

(○) is ₃ (○),

The method according to claim 26, wherein (o) is benzophenone.

[Claim 29] manufactured by the method according to any one of claims 1 to 17,

A compound represented by the formula [^ [¾ ² ??3, wherein ¹ and 8 ² are as defined in claim 1.

[Claim 30] manufactured by the method according to any one of claims 18 to 25,

\ [¾ ² , [¾ 8 are as defined in claim 18;

The compound represented by.

[Claim 31] manufactured by the method according to any one of claims 26 to 28,