JP2012229211A - Method for producing dialkyl aryl phosphate from aryl sulphonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a dialkyl aryl phosphate from an aryl sulphonate.SOLUTION: In the method for producing a dialkyl aryl phosphate from an aryl sulphonate, the dialkyl aryl phosphate can be obtained by reacting the aryl sulphonate with a trialkyl phosphite represented by a general formula P(OR)and an additive in the presence of the catalyst of a nickel salt or a palladium salt. The reaction temperature is 100 to 240°C. The above additive is a halogenated metal salt selected from lithium chloride, sodium chloride, potassium chloride, cesium chloride, lithium bromide, sodium bromide, potassium bromide or others; the above nickel salt is selected from nickel chloride, nickel bromide or others; and the above palladium salt is selected from palladium chloride, palladium bromide or others.

Description

  The present invention relates to a method for producing an aryl phosphoric acid dialkyl ester, specifically, a method for producing an aryl phosphoric acid dialkyl ester from a sulfonic acid aryl ester, and more specifically, nickel promoted by a metal halide salt. In this method, aryl phosphoric acid dialkyl ester is produced by reaction of sulfonic acid aryl ester and phosphorous acid trialkyl ester in the presence of a salt or palladium salt catalyst.

  Organophosphine compounds are widely applied in phase transfer catalysts, materials, pharmaceuticals and organometallics. Some organic phosphine compounds can be flame retardant materials. Some phosphine-containing compounds are potential drugs. In organometallic chemistry, phosphine ligands have an irreplaceable effect, and different phosphine ligands can have quite different catalytic effects. In these phosphine ligands, the phosphorus atom of most ligands is bonded to an aryl group, such as the famous Buchwald phosphine ligand, Xantphos ligand, chiral BINAP ligand, A chiral Segphos ligand.

  For the construction of the carbon-phosphorus bond in the aryl phosphine compound, a palladium or copper catalyst method or a nickel catalyst method may be used. Here, the nickel or palladium-catalyzed Arbuzov reaction is a method for constructing a carbon-phosphorus bond in an aryl phosphine compound that is easy to operate and inexpensive, and the resulting aryl phosphate ester has various phosphorus atoms. It is preferred by many chemists because it can be easily modified. However, non-patent literatures 1 and 2 were found by a search for the prior art, but the substrates used in the Albuzov reaction of nickel or palladium catalysts already reported are haloaromatic hydrocarbon compounds. It can be seen that when a sulfonic acid group-substituted aromatic hydrocarbon compound is used as a substrate, a desired product cannot be obtained. The raw material of the sulfonic acid aryl ester, ie phenol, is an easily obtainable raw material, and various types, ie, hydroxy-protected phenols, can introduce other substituents as protective groups or orientation groups. It is a useful method and it can be seen that realizing the Arbuzov reaction of the sulfonic acid aryl ester is very significant and has good applicability.

Tavs, “Reaction of Aryl Halides With Trialkylyl Phosphites and Dialkyl Benzene Phosphonites to Aromatic Phosphonates and Phosphonates By Nickel Acids Production of aryl phosphates and phosphites) ", Chemische Berichte (Chemical Report), 1970, No. 103, pp 2428-2436. Yuan et al., “Studies on Organic Phosphorus Compounds XL. An One-Pot Procedure for the Phenolic Phosphoric Acid: A Facile Synthesized Phosphoric Acid. Synthesis of -position alkylated phosphonic acid: simple and convenient method of synthesizing alkyl hydrogen P-position substituted phenylphosphonic acid ester) ", Synthesis (synthesis), 1990, No. 2, pp. 140-141

  The present invention provides a method for producing an aryl phosphate dialkyl ester from a sulfonic acid aryl ester, specifically, an aryl phosphate dialkyl ester from a sulfonic acid aryl ester, for the above-mentioned blank existing in the prior art. A method is provided, and more specifically, a nickel salt or palladium salt catalyzed sulfonic acid aryl ester promoted by a metal halide salt is reacted with a phosphite trialkyl ester to produce an aryl phosphate dialkyl ester Provide a method. The present invention overcomes the problem that current aryl sulfonic acid esters cannot perform nickel or palladium-catalyzed Arbuzov reactions.

前記添加剤は、塩化リチウム、塩化ナトリウム、塩化カリウム、塩化セシウム、臭化リチウム、臭化ナトリウム、臭化カリウム、臭化セシウム、塩化亜鉛、臭化亜鉛、塩化マグネシウム、臭化マグネシウム、ヨウ化ナトリウムおよびヨウ化カリウムから選ばれる少なくとも１種のハロゲン化金属塩であり、
前記ニッケル塩は、塩化ニッケル、臭化ニッケル、ヨウ化ニッケル、酢酸ニッケル、トリフルオロメタンスルホン酸ニッケル、アセチルアセトンニッケル、ビス（トリフェニルホスフィン）塩化ニッケル、ビス（トリシクロヘキシルホスフィン）塩化ニッケル、１，２−ビス（ジフェニルホスフィノ）エタン塩化ニッケル、１，３−ビス（ジフェニルホスフィノ）プロパン塩化ニッケル、１，４−ビス（ジフェニルホスフィノ）ブタン塩化ニッケルおよび１，１'−ビス（ジフェニルホスフィノ）フェロセン塩化ニッケルから選ばれる少なくとも１種の物質であり、
前記パラジウム塩は、塩化パラジウム、臭化パラジウム、ヨウ化パラジウム、酢酸パラジウム、トリフルオロ酢酸パラジウムおよびアセチルアセトンパラジウムから選ばれる少なくとも１種の物質であり、
一般式（Ｉ）において、Ａｒはアリール基、置換アリール基または複素環アリール基であり、
一般式（ＩＩ）において、２つのスルホン酸基の相対位置は、オルト位、メタ位またはパラ位であり、
一般式（Ｉ）、（ＩＩ）および（ＩＩＩ）において、Ｒ'はアルキル基、置換アルキル基、アリール基または置換アリール基であり、
一般式（ＩＶ）、（Ｖ）、（ＶＩ）および（ＶＩＩ）において、Ｒはアルキル基を示す、
ことを特徴とする。 The present invention is realized by the following technical scheme.
The present invention relates to a process for producing an aryl phosphate dialkyl ester from a sulfonic acid aryl ester, wherein the sulfonic acid aryl ester is represented by the general formula (VII) in the presence of a nickel salt or palladium salt catalyst. Reaction with an ester and an additive provides an aryl phosphate dialkyl ester, where:
When the sulfonic acid aryl ester is a compound represented by the general formula (I), an aryl phosphoric acid dialkyl ester represented by the general formula (IV) is obtained,
When the sulfonic acid aryl ester is a compound represented by the general formula (II), an aryl phosphoric acid dialkyl ester represented by the general formula (V) is obtained,
When the sulfonic acid aryl ester is a compound represented by the general formula (III), an aryl phosphoric acid dialkyl ester represented by the general formula (VI) is obtained,
Here, the reaction temperature is 100 to 240 ° C.

The additive is lithium chloride, sodium chloride, potassium chloride, cesium chloride, lithium bromide, sodium bromide, potassium bromide, cesium bromide, zinc chloride, zinc bromide, magnesium chloride, magnesium bromide, sodium iodide. And at least one metal halide salt selected from potassium iodide,
The nickel salt is nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel trifluoromethanesulfonate, nickel acetylacetone, bis (triphenylphosphine) nickel chloride, bis (tricyclohexylphosphine) nickel chloride, 1,2- Bis (diphenylphosphino) ethane nickel chloride, 1,3-bis (diphenylphosphino) propane nickel chloride, 1,4-bis (diphenylphosphino) butane nickel chloride and 1,1′-bis (diphenylphosphino) ferrocene At least one substance selected from nickel chloride,
The palladium salt is at least one substance selected from palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate and palladium acetylacetone.
In the general formula (I), Ar is an aryl group, a substituted aryl group or a heterocyclic aryl group,
In the general formula (II), the relative positions of the two sulfonic acid groups are ortho-position, meta-position or para-position,
In the general formulas (I), (II) and (III), R ′ is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group,
In the general formulas (IV), (V), (VI) and (VII), R represents an alkyl group,
It is characterized by that.

  In the method of the present invention, in the general formula (I), Ar is preferably a substituted aryl group whose substituent is an alkyl group, an alkoxy group, an acyloxy group, an amide group, a hydroxy group, an acyl group or a phenyl group. Specifically, in the general formula (I), the aryl group, substituted aryl group or heterocyclic aryl group as Ar is a phenyl group, a 4-tert-butylphenyl group, a 4-methoxyphenyl group, or a 4-phenylphenyl group. 4-formyloxyphenyl group, 4-acetylphenyl group, 4-acetoxyphenyl group, 4-acetamidophenyl group, 4-hydroxyphenyl group, 4-methylphenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 2-methylphenyl group, 2-methoxyphenyl group, 2-formyloxyphenyl group, 2-phenylphenyl group, 3,4-dimethylphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethylphenyl group, benzo [D] [1,3] dioxol-5-yl group, 1-naphthyl group, 2-naphthyl group or 3-pi It may be a lysyl group.

  In the method of the present invention, in the general formulas (I), (II) and (III), R ′ is a trifluoromethyl group, a methyl group, a phenyl group, a p-tolyl group, a p-nitrophenyl group or a p-chlorophenyl group. It is preferable that

  In the method of the present invention, in the general formulas (IV), (V), (VI) and (VII), R may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group. preferable.

  In the method of the present invention, the reaction temperature is preferably 130 to 200 ° C, and the reaction temperature is more preferably 160 to 185 ° C.

  In the method of the present invention, when calculating by molar ratio, sulfonic acid aryl ester / phosphorous acid trialkyl ester / metal halide salt / nickel salt or palladium salt = 1.0 / 1.0 to 100 / 1.0 to It is preferable that it is 20.0 / 0.01-1.0. Sulfonic acid aryl ester / phosphorous acid trialkyl ester / metal halide salt / nickel salt or palladium salt = 1.0 / 4.0 to 20.0 / 3.0 to 10.0 / 0.05 to 0.5 It is more preferable that

  In the method of the present invention, the reaction time is preferably 1 to 100 hours.

  According to the present invention, aryl phosphoric acid dialkyl esters can be produced from easily obtained raw materials, and the resulting aryl phosphoric acid dialkyl esters can be applied to the synthesis of pharmaceutical intermediates and various useful phosphine ligands. The synthesis of isomers and phosphine ligands is easy, low cost, makes it easier to convert steric and electronic effects, and has good applicability.

  In the general formula (I), the aryl group as Ar includes a mononuclear or polynuclear aromatic ring. Examples of the mononuclear aromatic ring include a phenyl group. A naphthyl group is mentioned as a binuclear aromatic ring. Examples of the trinuclear aromatic ring include an anthracenyl group and a phenanthrenyl group. Examples of the substituted aryl group as Ar include those in which at least one hydrogen atom in the aryl group described above is substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an acyloxy group, an amide group, a hydroxy group, an acyl group, and a phenyl group. When a plurality of hydrogen atoms in the aryl group are substituted by these substituents, the plurality of substituents in the aryl group may be the same or different.

  Among the substituents described above, the alkyl group includes a branched or straight chain group having preferably 1 to 6, more preferably 1 to 3 carbon atoms. Examples of those having 1 to 3 carbon atoms include methyl, ethyl, n-propyl and isopropyl groups. Examples of those having 4 to 6 carbon atoms include t-butyl, n-butyl, isobutyl, sec-butyl, pentyl and hexyl groups. As the alkoxy group, a branched or straight chain having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms is preferable. Examples of those having 1 to 4 carbon atoms include methoxyl group, ethoxyl group, n-propoxyl group, isopropoxyl group, n-butoxyl group, isobutoxyl group, sec-butoxyl group and t-butoxyl group. Examples of those having 5 or 6 carbon atoms include n-pentoxyl and n-hexoxyl groups. The acyloxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of those having 1 to 5 carbon atoms include an acetoxy group, an n-propionyloxy group, an n-butyryloxy group, an isobutyryloxy group, and a pivaloyloxy group. Examples of those having 6 carbon atoms include 2-ethylbutanoyloxy group. The amide group preferably has 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include an acetamido group. The acyl group preferably has 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms. Examples of those having 1 to 3 carbon atoms include formyl group, acetyl group and propionyl group. Examples of those having 4 to 7 carbon atoms include an n-butyryl group, an isobutyryl group, and a pivaloyl group.

  The heterocyclic aryl group as Ar includes a 5-membered or 6-membered ring containing at least one nitrogen atom, sulfur atom or oxygen atom as a hetero atom. Examples of the hetero atom containing a nitrogen atom include a pyridyl group, a quinolinyl group, and an isoquinolinyl group. A thing containing a sulfur atom as a hetero atom includes a thiophenyl group. A furanyl group is mentioned as what contains an oxygen atom as a hetero atom.

In general formulas (I), (II) and (III), the alkyl group as R ′ is preferably a branched or straight chain having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. It is done.
Examples of the substituted alkyl group as R ′ include those in which at least one hydrogen atom is substituted with a substituent in the alkyl group as R ′. Examples of the substituent include a halogen atom, an alkoxy group, and an aromatic group. Examples of the halogen atom include a fluorine atom. As the alkoxy group, a branched or straight chain having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms is preferable. Examples of the aromatic group include mononuclear or polynuclear aromatic rings.
Examples of the aryl group as R ′ include a mononuclear or polynuclear aromatic ring.
Examples of the substituted aryl group as R ′ include those in which at least one hydrogen atom is substituted with a substituent in the aryl group as R ′. Examples of the substituent include an alkyl group, a nitro group, a halogen atom, an alkoxy group, and an aromatic group. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 branched or straight chain carbon atoms, and examples thereof include a methyl group, an n-propyl group, and an isopropyl group. Examples of the halogen atom include a chlorine atom. As the alkoxy group, a branched or straight chain having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms is preferable. Examples of the aromatic group include mononuclear or polynuclear aromatic rings. When R ′ in the general formulas (I), (II) and (III) is a substituted phenyl group substituted by one or more substituents among these substituents, the one or more substituents Is preferably bonded to a carbon atom in the para position with respect to the sulfonic acid group in the phenyl group.

  The alkyl group represented by the general formula (II) and (III) as one compound R is preferably a branched or straight chain having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. It is done. Examples of those having 1 to 3 carbon atoms include methyl, ethyl, n-propyl and isopropyl groups. Examples of those having 4 to 6 carbon atoms include n-butyl group, t-butyl group, isobutyl group, sec-butyl group, pentyl group and hexyl group.

In addition, two R ′ in the general formula (II) may be the same or different. Three R ′ in the general formula (III) may be the same or different.
The three ORs bonded to the phosphorus atom in general formula (VII) may be the same or different. In the general formulas (IV), (V) and (VI), two ORs bonded to the same phosphorus atom may be the same or different.

  As described above, in the present invention, when the sulfonic acid aryl ester is a compound represented by the general formula (II), an aryl phosphoric acid dialkyl ester represented by the general formula (V) is obtained. And in general formula (II), the relative position of two sulfonic acid groups is an ortho position, a meta position, or a para position. Of course, in the general formula (V), the relative positions of the two phosphate groups are also in the ortho, meta or para position. In addition, when the relative position of the two sulfonic acid groups in the general formula (II) is the ortho position, the relative position of the two phosphoric acid groups in the obtained aryl phosphate dialkyl ester represented by the general formula (V) is also the ortho position. And when the relative position of the two sulfonic acid groups in the general formula (II) is the meta position, the relative position of the two phosphoric acid groups in the diaryl ester of an aryl phosphate represented by the general formula (V) obtained In the meta position and the relative position of the two sulfonic acid groups in the general formula (II) is in the para position, the two phosphate groups in the aryl phosphate dialkyl ester represented by the general formula (V) thus obtained The relative position is also para.

Specifically, the method for producing an aryl phosphate dialkyl ester from the sulfonic acid aryl ester of the present invention is preferably carried out as follows.
To the reaction flask, an additive, nickel salt or palladium salt, sulfonic acid aryl ester and phosphorous acid trialkyl ester are added, heated to a predetermined temperature (reaction temperature), and then maintained for a predetermined time (reaction time). ), While stirring under reflux, the sulfonic acid aryl ester is reacted with the phosphorous acid trialkyl ester. This reaction is preferably performed in an inert gas atmosphere such as nitrogen gas.

In the present invention, considering reaction efficiency, the reaction temperature is 100 to 240 ° C, the reaction temperature is preferably 130 to 220 ° C, and the reaction temperature is more preferably 130 to 200 ° C, The reaction temperature is more preferably 150 to 200 ° C, further preferably 160 to 185 ° C.
Furthermore, in the present invention, considering reaction efficiency, the reaction time is 1 to 100 hours, the reaction time is preferably 4 to 80 hours, more preferably 6 to 50 hours, and further more preferably 20 to 36 hours. preferable.
In the present invention, the range of the reaction temperature and the range of the reaction time can be arbitrarily combined as necessary.

  Hereinafter, embodiments of the present invention will be described in detail, and the embodiments will be carried out on the premise of the technical solution of the present invention, and a detailed implementation method and a specific operation process will be presented. The present invention is not limited to the following examples.

(Example 1) Production of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 468 mg (8.0 mmol) of sodium chloride, 452 mg of trifluoromethanesulfonic acid phenyl ester (2.0 mmol) and 1.66 g (10 mmol) of phosphorous acid triethyl ester are added. Heat to 200 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 352 mg of phenylphosphoric acid diethyl ester, and the yield was 82%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.82 (m, 2H), 7.55 (tq, J = 7.5, 1.4 Hz, 1H), 7.47 (m, 2H), 4 .12 (m, 4H), 1.32 (td, J = 7.0, 0.5 Hz, 6H)

(Example 2) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 44 mg (0.2 mmol) of nickel bromide, 468 mg (8.0 mmol) of sodium chloride, phenyl ester of trifluoromethanesulfonic acid 452 mg (2.0 mmol) and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 420 mg of phenylphosphoric acid diethyl ester, and the yield was 98%.

(Example 3) Production of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 63 mg (0.2 mmol) of nickel iodide, 468 mg (8.0 mmol) of sodium chloride, phenyl ester of trifluoromethanesulfonic acid 452 mg (2.0 mmol) and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 180 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 422 mg of phenylphosphoric acid diethyl ester, and the yield was 99%.

(Example 4) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 71 mg (0.2 mmol) of nickel trifluoromethanesulfonate, 468 mg (8.0 mmol) of sodium chloride, trifluoromethanesulfonic acid Add 452 mg (2.0 mmol) of phenyl ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 410 mg of phenylphosphoric acid diethyl ester, and the yield was 92%.

(Example 5) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester 52 mg (0.2 mmol) of acetylacetone nickel, 1.17 g (20 mmol) of sodium chloride, 452 mg of trifluoromethanesulfonic acid phenyl ester in a dry reaction flask (2.0 mmol) and 3.32 g (20 mmol) of phosphorous acid triethyl ester are added. Heat to 240 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 310 mg of phenylphosphoric acid diethyl ester, and the yield was 72%.

(Example 6) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 131 mg (0.2 mmol) of bis (triphenylphosphine) nickel chloride, 468 mg (8.0 mmol) of sodium chloride, trifluoro Add 452 mg (2.0 mmol) of lomethanesulfonic acid phenyl ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 165 ° C. under nitrogen protection and allow to react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 360 mg of phenylphosphoric acid diethyl ester, and the yield was 84%.

(Example 7) Preparation of phenylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester 53 mg (0.1 mmol) of 1,2-bis (diphenylphosphino) ethane nickel chloride, 468 mg of sodium chloride (8 0.0 mmol), 452 mg (2.0 mmol) of trifluoromethanesulfonic acid phenyl ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 360 mg of phenylphosphoric acid diethyl ester, and the yield was 84%.

(Example 8) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 1,3-bis (diphenylphosphino) propane nickel chloride 108 mg (0.2 mmol), sodium chloride 468 mg (8 0.0 mmol), 452 mg (2.0 mmol) of trifluoromethanesulfonic acid phenyl ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 350 mg of phenylphosphoric acid diethyl ester, and the yield was 82%.

(Example 9) Preparation of phenylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 1,4-bis (diphenylphosphino) butane nickel chloride 111 mg (0.2 mmol), sodium chloride 935 mg (16 mmol) ), 452 mg (2.0 mmol) of trifluoromethanesulfonic acid phenyl ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 365 mg of phenylphosphoric acid diethyl ester, and the yield was 85%.

(Example 10) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 1,1'-bis (diphenylphosphino) ferrocene nickel chloride 136 mg (0.2 mmol), sodium chloride 468 mg ( 8.0 mmol), 452 mg (2.0 mmol) of trifluoromethanesulfonic acid phenyl ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 365 mg of phenylphosphoric acid diethyl ester, and the yield was 85%.

(Example 11) Preparation of phenylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 1.7 g (40.0 mmol) of lithium chloride, phenyl trifluoromethanesulfonate 452 mg (2.0 mmol) of ester and 6.64 g (40 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 100 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 56 mg of phenylphosphoric acid diethyl ester, and the yield was 13%.

(Example 12) Production of phenylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, nickel chloride 26 mg (0.2 mmol), potassium chloride 596 mg (8.0 mmol), trifluoromethanesulfonic acid phenyl ester 452 mg (2.0 mmol) and 6.64 g (40 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 335 mg of phenylphosphoric acid diethyl ester, and the yield was 69%.

(Example 13) Preparation of phenylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 1.35 g (8.0 mmol) of cesium chloride, phenyl trifluoromethanesulfonate 452 mg (2.0 mmol) of ester and 6.64 g (40 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 363 mg of phenylphosphoric acid diethyl ester, and the yield was 86%.

(Example 14) Preparation of phenylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 1.09 g (8.0 mmol) of zinc chloride, phenyl trifluoromethanesulfonate 452 mg (2.0 mmol) of ester and 6.64 g (40 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 40 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 183 mg of phenylphosphoric acid diethyl ester, and the yield was 43%.

(Example 15) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 1.9 g (20.0 mmol) of magnesium chloride, phenyl trifluoromethanesulfonic acid 452 mg (2.0 mmol) of ester and 6.64 g (40 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 100 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 110 mg of phenylphosphoric acid diethyl ester, and the yield was 23%.

(Example 16) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 695 mg (8.0 mmol) of lithium bromide, phenyl ester of trifluoromethanesulfonic acid 452 mg (2.0 mmol) and 6.64 g (40 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 40 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 63 mg of phenylphosphoric acid diethyl ester, and the yield was 15%.

(Example 17) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 823 mg (8.0 mmol) of sodium bromide, phenyl ester of trifluoromethanesulfonic acid 452 mg (2.0 mmol) and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 423 mg of phenylphosphoric acid diethyl ester, and the yield was 99%.

(Example 18) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 952 mg (8.0 mmol) of potassium bromide, phenyl ester of trifluoromethanesulfonic acid 452 mg (2.0 mmol) and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 425 mg of phenylphosphoric acid diethyl ester, and the yield was 99%.

(Example 19) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 1.70 g (8.0 mmol) of cesium bromide, trifluoromethanesulfonic acid Add 452 mg (2.0 mmol) of phenyl ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 422 mg of phenylphosphoric acid diethyl ester, and the yield was 98%.

(Example 20) Preparation of phenylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 130 mg (1.0 mmol) of nickel chloride, 1.47 g (8.0 mmol) of magnesium bromide, trifluoromethanesulfonic acid 452 mg (2.0 mmol) of phenyl ester and 33.2 g (200.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 419 mg of phenylphosphoric acid diethyl ester, and the yield was 98%.

(Example 21) Production of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 450 mg (2.0 mmol) of zinc bromide, phenyl ester of trifluoromethanesulfonic acid 452 mg (2.0 mmol) and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 415 mg of phenylphosphoric acid diethyl ester, and the yield was 97%.

(Example 22) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 899 mg (6.0 mmol) of sodium iodide, phenyl ester of trifluoromethanesulfonic acid 452 mg (2.0 mmol) and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 420 mg of phenylphosphoric acid diethyl ester, and the yield was 98%.

(Example 23) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 1.33 g (8.0 mmol) of potassium iodide, trifluoromethanesulfonic acid Add 452 mg (2.0 mmol) of phenyl ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 1 hour. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 73 mg of phenylphosphoric acid diethyl ester, and the yield was 17%.

(Example 24) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 35 mg (0.2 mmol) of nickel acetate, 952 mg (8.0 mmol) of potassium bromide, phenyl ester of trifluoromethanesulfonic acid 452 mg (2.0 mmol) and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 425 mg of phenylphosphoric acid diethyl ester, and the yield was 99%.

(Example 25) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester 138 mg (0.2 mmol) of bis (tricyclohexylphosphine) nickel chloride, 952 mg (8.0 mmol) of potassium bromide in a dry reaction flask, Add 452 mg (2.0 mmol) of trifluoromethanesulfonic acid phenyl ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 220 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 425 mg of phenylphosphoric acid diethyl ester, and the yield was 99%.

(Example 26) Preparation of phenylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 35 mg (0.2 mmol) of palladium chloride, 952 mg (8.0 mmol) of potassium bromide, phenyl ester of trifluoromethanesulfonic acid 452 mg (2.0 mmol) and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 425 mg of phenylphosphoric acid diethyl ester, and the yield was 99%.

(Example 27) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester 53 mg (0.2 mmol) of palladium bromide, 952 mg (8.0 mmol) of potassium bromide, phenyl trifluoromethanesulfonic acid in a dry reaction flask 452 mg (2.0 mmol) of ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 6 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 278 mg of phenylphosphoric acid diethyl ester, and the yield was 65%.

(Example 28) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 72 mg (0.2 mmol) of palladium iodide, 952 mg (8.0 mmol) of potassium bromide, phenyl trifluoromethanesulfonic acid 452 mg (2.0 mmol) of ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 125 ° C. under nitrogen protection and react with stirring for 40 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 159 mg of phenylphosphoric acid diethyl ester, and the yield was 37%.

(Example 29) Preparation of phenylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester 45 mg (0.2 mmol) of palladium acetate, 952 mg (8.0 mmol) of potassium bromide, phenyl ester of trifluoromethanesulfonic acid in a dry reaction flask 452 mg (2.0 mmol) and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 4 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 206 mg of phenylphosphoric acid diethyl ester, and the yield was 48%.

Example 30 Preparation of phenylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 66 mg (0.2 mmol) of palladium trifluoroacetate, 952 mg (8.0 mmol) of potassium bromide, trifluoromethanesulfonic acid Add 452 mg (2.0 mmol) of phenyl ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 425 mg of phenylphosphoric acid diethyl ester, and the yield was 99%.

(Example 31) Preparation of phenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 61 mg (0.2 mmol) of acetylacetone palladium, 952 mg (8.0 mmol) of potassium bromide, phenyl ester of trifluoromethanesulfonic acid 452 mg (2.0 mmol) and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 279 mg of phenylphosphoric acid diethyl ester, and the yield was 65%.

(Example 32) Production of phenyl phosphoric acid diethyl ester compound from methanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 952 mg (8.0 mmol) of potassium bromide, 344 mg of methanesulfonic acid phenyl ester ( 2.0 mmol) and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 325 mg of phenylphosphoric acid diethyl ester, and the yield was 76%.

(Example 33) Preparation of phenylphosphoric acid diethyl ester compound from benzenesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 952 mg (8.0 mmol) of potassium bromide, 469 mg of benzenesulfonic acid phenyl ester ( 2.0 mmol) and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 320 mg of phenylphosphoric acid diethyl ester, and the yield was 75%.

(Example 34) Preparation of phenyl phosphoric acid diethyl ester compound from p-toluenesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 952 mg (8.0 mmol) of potassium bromide, p-toluenesulfonic acid 497 mg (2.0 mmol) of phenyl ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 30 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 365 mg of phenyl phosphoric acid diethyl ester, and the yield was 86%.

(Example 35) Preparation of phenylphosphoric acid diethyl ester compound from p-chlorobenzenesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 952 mg (8.0 mmol) of potassium bromide, p-chlorobenzenesulfonic acid 537 mg (2.0 mmol) of phenyl ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 240 mg of phenylphosphoric acid diethyl ester, and the yield was 56%.

(Example 36) Preparation of 4-methylphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (4-methylphenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg (8.0 mmol) of potassium bromide ), 452 mg (2.0 mmol) of trifluoromethanesulfonic acid (4-methylphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 450 mg of 4-methylphenylphosphoric acid diethyl ester, and the yield was 99%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.68-7.73 (m, 2H), 7.26-7.29 (m, 2H), 4.04-4.18 (m, 4H) ), 2.41 (s, 3H), 1.31 (t, J = 6.9 Hz, 6H)

Example 37 Production of 4-tert-butylphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (4-tert-butylphenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg of potassium bromide (8.0 mmol), 559 mg (2.0 mmol) of trifluoromethanesulfonic acid (4-tert-butylphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 535 mg of 4-tert-butylphenyl phosphate diethyl ester, and the yield was 99%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.80-7.86 (m, 2H), 7.62-7.66 (m, 2H), 4.04-4.18 (m, 4H) ), 2.41 (s, 3H), 1.31 (t, J = 6.9 Hz, 6H)

Example 38 Production of 4-methoxyphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (4-methoxyphenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg (8.0 mmol) of potassium bromide ), 512 mg (2.0 mmol) of trifluoromethanesulfonic acid (4-methoxyphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 366 mg of 4-methoxyphenyl phosphoric acid diethyl ester, and the yield was 75%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.72-7.77 (m, 2H), 6.96-6.98 (m, 2H), 4.04-4.13 (m, 4H) ), 3.85 (s, 3H), 1.31 (t, J = 7.4 Hz, 6H)

(Example 39) Preparation of 4-phenylphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (4-phenylphenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg (8.0 mmol) of potassium bromide ), 605 mg (2.0 mmol) of trifluoromethanesulfonic acid (4-phenylphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 551 mg of 4-phenylphenylphosphoric acid diethyl ester, and the yield was 95%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.86-7.91 (m, 2H), 7.67-7.70 (m, 2H), 7.59-7.62 (m, 2H) ), 7.44-7.48 (m, 2H), 7.37-7.41 (m, 1H), 4.09-4.22 (m, 4H), 1.35 (t, J = 7) .3Hz, 6H)

Example 40 Production of 4-formyloxyphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (4-formyloxyphenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg of potassium bromide (8 0.0 mmol), 568 mg (2.0 mmol) of trifluoromethanesulfonic acid (4-formyloxyphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 540 mg of 4-formyloxyphenyl phosphoric acid diethyl ester, and the yield was 99%.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 8.12 (dd, J = 3.8, = 8.2 Hz, 2H), 7.89 (dd, J = 8.2, 12.9 Hz, 2H), 4.14 (m, 4H), 3.95 (s, 3H), 1.33 (t, J = 7.1 Hz, 6H)

(Example 41) Preparation of 4-acetylphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (4-acetylphenyl) ester 26 mg (0.2 mmol) of nickel chloride and 952 mg (8.0 mmol) of potassium bromide in a dry reaction flask. ), 536 mg (2.0 mmol) of trifluoromethanesulfonic acid (4-acetylphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 440 mg of 4-acetylphenyl phosphate diethyl ester, and the yield was 86%.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 8.01-8.04 (m, 2H), 7.90-7.95 (m, 2H), 4.12-4.17 (m, 4H) ), 2.65 (s, 3H), 1.34 (t, J = 6.8 Hz, 6H)

Example 42 Production of 4-acetoxyphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (4-acetoxyphenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg (8.0 mmol) of potassium bromide ), 568 mg (2.0 mmol) of trifluoromethanesulfonic acid (4-acetoxyphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 430 mg of 4-acetoxyphenyl phosphoric acid diethyl ester, and the yield was 79%.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 7.66-7.73 (m, 2H), 6.96-7.00 (m, 2H), 4.02-4.15 (m, 4H) ), 2.28 (s, 3H), 1.31 (t, J = 7.2 Hz, 6H)

(Example 43) Preparation of 4-hydroxyphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (4-hydroxyphenyl) ester 26 mg (0.2 mmol) of nickel chloride and 952 mg (8.0 mmol) of potassium bromide in a dry reaction flask ), 484 mg (2.0 mmol) of trifluoromethanesulfonic acid (4-hydroxyphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 317 mg of 4-hydroxyphenylphosphoric acid diethyl ester, and the yield was 69%.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 7.59-7.68 (m, 2H), 6.96-7.01 (m, 2H), 4.00-4.17 (m, 4H) ), 1.31 (t, J = 7.0 Hz, 6H)

(Example 44) Preparation of 4-acetamidophenyl phosphate diethyl ester compound from trifluoromethanesulfonic acid (4-acetamidophenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg (8.0 mmol) of potassium bromide ), 566 mg (2.0 mmol) of trifluoromethanesulfonic acid (4-acetamidophenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 441 mg of 4-acetamidophenyl phosphate diethyl ester, and the yield was 78%.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 7.68 (m, 4H), 4.06 (m, 4H), 2.17 (s, 3H), 1.29 (t, J = 7. 2Hz, 6H)

Example 45 Production of 3-methylphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (3-methylphenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg (8.0 mmol) of potassium bromide ), 452 mg (2.0 mmol) of trifluoromethanesulfonic acid (3-methylphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 383 mg of 3-methylphenylphosphoric acid diethyl ester, and the yield was 84%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.05-8.02 (m, 2H), 7.98-7.91 (m, 2H), 4.19-4.10 (m, 4H) ), 2.66 (s, 3H), 1.35 (t, J = 6.8 Hz, 6H)

Example 46 Production of 3-methoxyphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (3-methoxyphenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg (8.0 mmol) of potassium bromide ), 512 mg (2.0 mmol) of trifluoromethanesulfonic acid (3-methoxyphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 357 mg of 3-methoxyphenyl phosphoric acid diethyl ester, and the yield was 73%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.32-7.40 (m, 3H), 7.07-7.10 (m, 1H), 4.05-4.18 (m, 4H) ), 3.87 (s, 3H), 1.33 (t, J = 6.9 Hz, 6H)

(Example 47) Preparation of 2-methylphenylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (2-methylphenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg (8.0 mmol) of potassium bromide ), 452 mg (2.0 mmol) of trifluoromethanesulfonic acid (2-methylphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 40 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 183 mg of 2-methylphenylphosphoric acid diethyl ester, and the yield was 40%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.92 (dd, 1H, J = 7.6, 14.2 Hz), 7.43 (t, J = 7.3 Hz, 1H), 7.26 (M, 1H), 4.12 (m, 4H), 2.57 (s, 3H), 1.33 (t, J = 6.9 Hz, 6H)

Example 48 Production of 2-methoxyphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (2-methoxyphenyl) ester 26 mg (0.2 mmol) of nickel chloride and 952 mg (8.0 mmol) of potassium bromide in a dry reaction flask. ), 512 mg (2.0 mmol) of trifluoromethanesulfonic acid (2-methoxyphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 36 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 215 mg of 2-methoxyphenylphosphoric acid diethyl ester, and the yield was 44%.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 7.82 (dd, 1H, J = 7.5, 14.9 Hz), 7.51 (t, 1H, J = 7.9 Hz), 7.02 (M, 1H), 6.95 (t, 1H, J = 7.6 Hz), 4.16 (m, 4H), 3.90 (s, 1H), 1.33 (t, J = 7.1 Hz) , 6H)

Example 49 Production of 2-formyloxyphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (2-formyloxyphenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg of potassium bromide (8 0.0 mmol), 568 mg (2.0 mmol) of trifluoromethanesulfonic acid (2-formyloxyphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 30 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 540 mg of 2-formyloxyphenyl phosphate diethyl ester, and the yield was 99%.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 7.97 (m, 1H), 7.72 (m, 1H), 7.57 (m, 1H), 4.16 (m, 4H), 3 .93 (s, 3H), 1.35 (t, J = 7.1 Hz, 6H)

(Example 50) Preparation of 2-phenylphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (2-phenylphenyl) ester 260 mg (2.0 mmol) of nickel chloride and 952 mg (8.0 mmol) of potassium bromide in a dry reaction flask ), 605 mg (2.0 mmol) of trifluoromethanesulfonic acid (2-phenylphenyl) ester and 3.32 g (20 mmol) of phosphorous acid triethyl ester. Heat to 185 ° C. under nitrogen protection and react with stirring for 30 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 482 mg of 2-phenylphenyl phosphoric acid diethyl ester, and the yield was 83%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.02 (ddd, J = 14.3, 7.7, 1.4 Hz, 1H), 7.52 (tt, J = 7.6, 1.. 5 Hz, 1H), 7.45-7.26 (m, 7H), 3.96-3.74 (m, 4H), 1.09 (t, J = 7.1 Hz, 6H)

Example 51 Production of 3,4-dimethylphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (3,4-dimethylphenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg of potassium bromide (8.0 mmol), 508 mg (2.0 mmol) of trifluoromethanesulfonic acid (3,4-dimethylphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 422 mg of 3,4-dimethylphenylphosphoric acid diethyl ester, and the yield was 87%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.30-6.95 (m, 3H), 4.10 (m, 4H), 2.28 (s, 3H), 2.26 (s, 3H), 1.33 (t, J = 7.2 Hz, 6H)

(Example 52) Production of 3,4-dimethoxyphenyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (3,4-dimethoxyphenyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 952 mg of potassium bromide (8.0 mmol), 572 mg (2.0 mmol) of trifluoromethanesulfonic acid (3,4-dimethylphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 36 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 389 mg of 3,4-dimethylphenylphosphoric acid diethyl ester, and the yield was 71%.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 7.41 (dd, 1H, J = 13.41, 4.5 Hz), 7.27 (d, J = 14.0 Hz, 1H), 6.94 (Dd, J = 4.51, 8.19 Hz, 1H), 4.13 (m, J = 7.1, 7.42 Hz, 4H), 3.93 (s, 6H), 1.35 (t, J = 7.1Hz, 6H)

Example 53 Production of 3,5-dimethylphenylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (3,5-dimethylphenyl) ester 26 mg (0.2 mmol) of nickel chloride and 952 mg of potassium bromide in a dry reaction flask (8.0 mmol), 508 mg (2.0 mmol) of trifluoromethanesulfonic acid (3,5-dimethylphenyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 373 mg of 3,5-dimethylphenylphosphoric acid diethyl ester, and the yield was 77%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.42 (s, 1H), 7.38 (s, 1H), 7.15 (s, 1H), 4.15-4.02 (m, 4H), 2.33 (s, 6H), 1.31 (t, J = 6.8 Hz, 6H)

Example 54 Preparation of benzo [d] [1,3] dioxole-5-phosphate diethyl ester compound from benzo [d] [1,3] dioxole 5-trifluoromethanesulfonate 26 mg nickel chloride in a dry reaction flask (0.2 mmol), 952 mg (8.0 mmol) of potassium bromide, 540 mg (2.0 mmol) of benzo [d] [1,3] dioxole 5-trifluoromethanesulfonate and 1.33 g (8. 0 mmol) is added. Heat to 185 ° C. under nitrogen protection and react with stirring for 36 hours. The stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 444 mg of benzo [d] [1,3] dioxole-5-phosphate diethyl ester, and the yield was 86%.
¹ H NMR (CDCl ₃ , 400 MHz): δ = 7.38 (dd, J = 8.3, 13.6 Hz, 1H), 7.21 (d, J = 12.9 Hz, 1H), 6.89 (Dd, J = 3.4, 7.9 Hz, 1H), 6.02 (s, 2H), 4.10 (m, 4H), 1.32 (t, J = 7.1 Hz, 6H)

Example 55 Production of 2-naphthyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (2-naphthyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 952 mg (8.0 mmol) of potassium bromide, trifluoro Add 552 mg (2.0 mmol) of lomethanesulfonic acid (2-naphthyl) ester and 1.33 g (8.0 mmol) of triethyl phosphite. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 386 mg of 2-naphthyl phosphoric acid diethyl ester, and the yield was 73%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.44 (d, J = 15.6 Hz, 1H), 7.87-7.95 (m, 3H), 7.74-7.78 (m , 1H), 7.55-7.62 (m, 2H), 4.19-4.25 (m, 4H), 1.34 (t, J = 7.3 Hz, 6H)

Example 56 Production of 1-naphthyl phosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (1-naphthyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 952 mg (8.0 mmol) of potassium bromide, trifluoro Add 552 mg (2.0 mmol) of lomethanesulfonic acid (1-naphthyl) ester and 1.33 g (8.0 mmol) of triethyl phosphite. Heat to 185 ° C. under nitrogen protection and react with stirring for 36 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 217 mg of 1-naphthyl phosphoric acid diethyl ester, and the yield was 41%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.52 (d, J = 8.7 Hz, 1H), 8.22-8.28 (m, 1H), 8.04 (d, J = 8 .3 Hz, 1H), 7.89 (d, J = 7.8 Hz, 1H), 7.51-7.63 (m, 3H), 4.17-4.26 (m, 2H), 4.04 -4.13 (m, 2H), 1.31 (t, J = 7.3 Hz, 6H)

Example 57 Production of 3-pyridylphosphoric acid diethyl ester compound from trifluoromethanesulfonic acid (3-pyridyl) ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 952 mg (8.0 mmol) of potassium bromide, trifluoro 454 mg (2.0 mmol) of lomethanesulfonic acid (3-pyridyl) ester and 1.33 g (8.0 mmol) of phosphorous acid triethyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 425 mg of 3-pyridyl phosphoric acid diethyl ester, and the yield was 99%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.94 (dd, 1H), 8.74 (m, 1H), 8.06 (ddt, 1H), 7.37 (m, 1H), 4 .13 (m, 4H), 1.31 (t, J = 7.0 Hz, 6H)

(Example 58) Preparation of phenylphosphoric acid dimethyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 952 mg (8.0 mmol) of potassium bromide, phenyl ester of trifluoromethanesulfonic acid 452 mg (2.0 mmol) and 1.98 g (16.0 mmol) phosphorous acid trimethyl ester are added. Heat to 100 ° C. under nitrogen protection and react with stirring for 50 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 233 mg of phenylphosphoric acid dimethyl ester, and the yield was 49%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.80 (dd, 2H), 7.64 (m, 1H), 7.54 (m, 2H), 3.76 (d, J = 11.1. 0Hz, 6H)

(Example 59) Preparation of phenyl phosphoric acid di-n-propyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 952 mg (8.0 mmol) of potassium bromide, trifluoromethanesulfone 452 mg (2.0 mmol) of acid phenyl ester and 3.31 g (16.0 mmol) of phosphorous acid tri-n-propyl ester are added. Heat to 180 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 378 mg of phenylphosphoric acid di-n-propyl ester, and the yield was 78%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.91 (m, 2H), 7.62 (m, 3H), 3.89 (m, 4H), 1.61 (m, 4H), 0 .89 (t, J = 6.6 Hz, 6H)

(Example 60) Preparation of phenylphosphoric acid diisopropyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 952 mg (8.0 mmol) of potassium bromide, phenyl ester of trifluoromethanesulfonic acid 452 mg (2.0 mmol) and 3.31 g (16.0 mmol) of phosphorous acid triisopropyl ester are added. Heat to 180 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 320 mg of phenylphosphoric acid diisopropyl ester with a yield of 66%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.79 (ddd, J = 13.5, 7.3, 1.6 Hz, 2H), 7.50 (tq, J = 7.6, 1.. 6 Hz, 1H) 7.42 (m, 2H), 4.66 (m, 2H), 1.35 and 1.20 (2 × d, J = 6.20 Hz, 12H)

(Example 61) Preparation of phenyl phosphoric acid di-n-butyl ester compound from trifluoromethanesulfonic acid phenyl ester In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride, 952 mg (8.0 mmol) of potassium bromide, trifluoromethanesulfone 452 mg (2.0 mmol) of acid phenyl ester and 2.0 g (8.0 mmol) of phosphorous acid tri-n-butyl ester are added. Heat to 185 ° C. under nitrogen protection and react with stirring for 20 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 540 mg of phenylphosphoric acid di-n-butyl ester, and the yield was 99%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.78 (2H, dd), 7.63 (m, 1H), 7.50 (m, 2H), 4.07 (m, 4H), 1 .71 (m, 4H), 1.45 (m, 4H), 0.94 (d, J = 8.0 Hz, 6H)

Example 62 Production of 1,4-dimethoxyphosphorylphenyl compound from phenyl 1,4-bistrifluoromethanesulfonate In a dry reaction flask, 26 mg (0.2 mmol) of nickel chloride and 1.90 mg (16.0 mmol) of potassium bromide ), 0.748 g (2.0 mmol) of phenyl 1,4-bistrifluoromethanesulfonate and 3.0 g (24.0 mmol) of trimethyl phosphite. Heat to 130 ° C. under nitrogen protection and react with stirring for 36 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 346 mg of 1,4-dimethoxyphosphorylphenyl, and the yield was 59%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.65 to 7.75 (m, 4H), 3.78 (d, J = 11.0 Hz, 12H)

(Example 63) Production of 1,3-dimethoxyphosphorylphenyl compound from phenyl 1,3-bistrifluoromethanesulfonate 26 mg (0.2 mmol) of nickel chloride and 1.90 mg (16.0 mmol) of potassium bromide were placed in a dry reaction flask. ), 0.748 g (2.0 mmol) of phenyl 1,3-bistrifluoromethanesulfonate and 3.0 g (24.0 mmol) of trimethyl phosphite. Heat to 160 ° C. under nitrogen protection and react with stirring for 36 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 547 mg of 1,3-dimethoxyphosphorylphenyl, and the yield was 93%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.90-8.11 (m, 3H), 7.75 (m, 1H), 3.80 (d, J = 11.2 Hz, 12H)

(Example 64) Production of 1,2-dimethoxyphosphorylphenyl compound from phenyl 1,2-bistrifluoromethanesulfonate 26 mg (0.2 mmol) of nickel chloride and 1.90 mg (16.0 mmol) of potassium bromide were placed in a dry reaction flask. ), 0.748 g (2.0 mmol) of phenyl 1,2-bistrifluoromethanesulfonate and 3.0 g (24.0 mmol) of trimethyl phosphite. Heat to 180 ° C. under nitrogen protection and react with stirring for 36 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 118 mg of 1,2-dimethoxyphosphorylphenyl, and the yield was 20%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.75-7.90 (m, 3H), 7.55-7.65 (m, 2H), 3.77 (d, J = 11.5 Hz) , 12H)

Example 65 Preparation of 1,3,5-trisdiethoxyphosphorylphenyl compound from phenyl 1,3,5-tristrifluoromethanesulfonate 26 mg (0.2 mmol) of nickel chloride and potassium bromide 1 in a dry reaction flask .90 mg (16.0 mmol), 1.04 g (2.0 mmol) of phenyl 1,3,5-tristrifluoromethanesulfonate and 6.65 g (40.0 mmol) of phosphorous acid triethyl ester are added. Heat to 180 ° C. under nitrogen protection and react with stirring for 40 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 233 mg of 1,3,5-trisdiethoxyphosphorylphenyl, and the yield was 24%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.42 to 8.28 (m, 3H), 4.24 to 4.00 (m, 12H), 1.31 (t, J = 7.0 Hz) , 18H)

Example 66 Production of 1,3,5-trisdiisopropoxyphosphorylphenyl compound from phenyl 1,3,5-tristrifluoromethanesulfonate Nickel chloride 26 mg (0.2 mmol), potassium bromide in a dry reaction flask 1.90 mg (16.0 mmol), 1.03 g (2.0 mmol) of phenyl 1,3,5-tristrifluoromethanesulfonate and 8.33 g (40.0 mmol) of phosphorous acid triisopropyl ester are added. Heat to 150 ° C. under nitrogen protection and react with stirring for 40 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 160 mg of 1,3,5-trisdiethylisopropoxyphosphorylphenyl, and the yield was 14%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.44 to 8.33 (m, 3H), 4.82 to 4.67 (m, 6H), 1.39 (d, J = 6.2 Hz) , 18H), 1.25 (d, J = 6.2 Hz, 18H)

(Example 67) Production of 1,3,5-trisdiethoxyphosphorylphenyl compound from phenyl 1,3,5-trimethanesulfonate 26 mg (0.2 mmol) of nickel chloride, potassium bromide 1. 90 mg (16.0 mmol), 721 mg (2.0 mmol) of phenyl 1,3,5-trimethanesulfonate and 6.65 g (40.0 mmol) of phosphorous acid triethyl ester are added. Heat to 180 ° C. under nitrogen protection and react with stirring for 80 hours. Stirring was stopped, the temperature was lowered to room temperature, and distillation was performed to obtain 33 mg of 1,3,5-trisdiethoxyphosphorylphenyl, and the yield was 3%.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.42 to 8.28 (m, 3H), 4.24 to 4.00 (m, 12H), 1.31 (t, J = 7.0 Hz) , 18H)

  The above examples are easy to operate and have a high yield. The realized Arbuzov reaction of sulfonic acid aryl ester can produce aryl phosphate ester, and can be applied to synthesis of pharmaceutical intermediates and useful compounds such as phosphine ligands, and has good applicability.

Claims (10)

A process for producing an aryl phosphate dialkyl ester from a sulfonic acid aryl ester comprising:
Reaction of a sulfonic acid aryl ester with a trialkyl phosphite represented by the general formula (VII) and an additive under a catalyst of a nickel salt or a palladium salt, gives an aryl phosphoric acid dialkyl ester,
When the sulfonic acid aryl ester is a compound represented by the general formula (I), an aryl phosphoric acid dialkyl ester represented by the general formula (IV) is obtained,
When the sulfonic acid aryl ester is a compound represented by the general formula (II), an aryl phosphoric acid dialkyl ester represented by the general formula (V) is obtained,
When the sulfonic acid aryl ester is a compound represented by the general formula (III), an aryl phosphoric acid dialkyl ester represented by the general formula (VI) is obtained,
Here, the reaction temperature is 100 to 240 ° C.

The additive is lithium chloride, sodium chloride, potassium chloride, cesium chloride, lithium bromide, sodium bromide, potassium bromide, cesium bromide, zinc chloride, zinc bromide, magnesium chloride, magnesium bromide, sodium iodide. And a metal halide salt selected from potassium iodide,
The nickel salt is nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel trifluoromethanesulfonate, nickel acetylacetone, bis (triphenylphosphine) nickel chloride, bis (tricyclohexylphosphine) nickel chloride, 1,2- Bis (diphenylphosphino) ethane nickel chloride, 1,3-bis (diphenylphosphino) propane nickel chloride, 1,4-bis (diphenylphosphino) butane nickel chloride and 1,1′-bis (diphenylphosphino) ferrocene A substance selected from nickel chloride,
The palladium salt is one substance selected from palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate and palladium acetylacetone,
In the general formula (I), Ar is an aryl group, a substituted aryl group or a heterocyclic aryl group,
In the general formula (II), the relative positions of the two sulfonic acid groups are ortho-position, meta-position or para-position,
In the general formulas (I), (II) and (III), R ′ is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group,
In the general formulas (IV), (V), (VI) and (VII), R represents an alkyl group,
A method for producing an aryl phosphoric acid dialkyl ester from a sulfonic acid aryl ester.   2. The general formula (I), wherein Ar is a substituted aryl group whose substituent is an alkyl group, an alkoxy group, an acyloxy group, an amide group, a hydroxy group, an acyl group, or a phenyl group. A process for producing an aryl phosphate dialkyl ester from a sulfonic acid aryl ester of   In the general formula (I), Ar is a phenyl group, 4-tert-butylphenyl group, 4-methoxyphenyl group, 4-phenylphenyl group, 4-formyloxyphenyl group, 4-acetylphenyl group, 4-acetoxyphenyl. Group, 4-acetamidophenyl group, 4-hydroxyphenyl group, 4-methylphenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 2-methylphenyl group, 2-methoxyphenyl group, 2-formyloxyphenyl group 2-phenylphenyl group, 3,4-dimethylphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethylphenyl group, benzo [d] [1,3] dioxol-5-yl group, 1-naphthyl The sulfonic acid aryl ester according to claim 1, which is a group, 2-naphthyl group or 3-pyridyl group. A method for producing an aryl phosphate dialkyl ester from tellurium.   In the general formulas (I), (II) and (III), R ′ is a trifluoromethyl group, a methyl group, a phenyl group, a p-tolyl group, a p-nitrophenyl group or a p-chlorophenyl group, A method for producing an aryl phosphoric acid dialkyl ester from the sulfonic acid aryl ester according to any one of claims 1 to 3.   2. In the general formulas (IV), (V), (VI) and (VII), R represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group. A method for producing an aryl phosphoric acid dialkyl ester from the sulfonic acid aryl ester according to any one of 1 to 4.   The method for producing an arylphosphoric dialkyl ester from the sulfonic acid aryl ester according to any one of claims 1 to 5, wherein the reaction temperature is 130 to 200 ° C.   The method for producing an arylphosphoric dialkyl ester from a sulfonic acid aryl ester according to any one of claims 1 to 6, wherein the reaction temperature is 160 to 185 ° C.   When calculating by molar ratio, sulfonic acid aryl ester / phosphorous acid trialkyl ester / metal halide salt / nickel salt or palladium salt = 1.0 / 1.0 to 100 / 1.0 to 20.0 / 0. The method for producing an aryl phosphoric acid dialkyl ester from the sulfonic acid aryl ester according to any one of claims 1 to 7, which is 01 to 1.0.   When calculating by molar ratio, sulfonic acid aryl ester / phosphorous acid trialkyl ester / metal halide salt / nickel salt or palladium salt = 1.0 / 4.0 to 20.0 / 3.0 to 10.0 / The method for producing an aryl phosphoric acid dialkyl ester from the sulfonic acid aryl ester according to any one of claims 1 to 8, which is 0.05 to 0.5.   The method for producing an aryl phosphoric acid dialkyl ester from the sulfonic acid aryl ester according to any one of claims 1 to 9, wherein the reaction time is 1 to 100 hours.