CN115490726B - Preparation method of diphenyl phosphine oxide hydrogen - Google Patents
Preparation method of diphenyl phosphine oxide hydrogen Download PDFInfo
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- CN115490726B CN115490726B CN202210919990.3A CN202210919990A CN115490726B CN 115490726 B CN115490726 B CN 115490726B CN 202210919990 A CN202210919990 A CN 202210919990A CN 115490726 B CN115490726 B CN 115490726B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids R2=P—OH; Thiophosphinous acids; Aminophosphines R2-P-NH2 including R2P(=O)H; derivatives thereof
Abstract
The invention discloses a preparation method of diphenyl phosphine oxide hydrogen, and belongs to the technical field of organic synthesis. It comprises the following steps:
step b1: under the atmosphere of inert gas or nitrogen, to Ph 2 Adding solid acid into PONa, ph at-30-150deg.C 2 The PONa is sufficiently quenched by solid acid to generate Ph 2 P (O) H, the solid acid is converted into sodium salt of the solid acid, and after the reaction is finished, the solid acid and sodium salt of the solid acid are used to be insoluble but Ph 2 P (O) H-soluble organic solvents, using Ph 2 P (O) H is dissolved in organic solvent, and solid acid sodium salt are insoluble in organic solvent, so that Ph generated by the reaction 2 P (O) H is separated from the reaction system to obtain anhydrous Ph 2 P (O) H; the solid acid is selected from one or more of silica gel powder, high molecular organic acid and inorganic solid acid. The preparation method of diphenyl phosphine oxide hydrogen provided by the invention can prepare anhydrous Ph 2 The preparation method of P (O) H has simple post-treatment and easy operation.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of diphenyl phosphine oxide hydrogen.
Background
Diphenyl phosphine oxide hydrogen Ph 2 P (O) H is a very useful organophosphorus source. It contains a chemically active P-H bond such that the diphenyl phosphine oxide is 2 P (O) H can be added, substituted or the like to produce various organic phosphorus compounds; phosphorus compounds have various uses in industrial production.
Triphenylphosphine oxide Ph 3 P (O) is an industrial waste which is a large amount of by-products of the Wittig reaction used in the vitamin production process.
Description of Ph in the prior literature 3 Conversion of P (O) to diphenylphosphine oxide Ph 2 The method of P (O) H is as follows: first Ph 3 P (O) reacts with sodium to produce Ph 2 PONa, hydrochloric acid or saturated ammonium chloride aqueous solution is added to convert into diphenyl phosphine oxide hydrogen Ph 2 P(O)H(Zhang，J.-Q.et al COMMUNICATIONS CHEMISTRY(2020)3：1|https：//doi.org/10.1038/s42004-019-0249-6|www.nature.com/commschem)。
However, it is difficult to prepare pure diphenylphosphine oxide hydrogen Ph by such a treatment method 2 P(O)H。
Ph described in the document 2 The preparation method of P (O) H has the following defects:
1. pure Ph 2 P (O) H is a solid at room temperature, ph 2 P (O) H is extremely easy to absorb water, and Ph prepared by the preparation method 2 P (O) H is typically an oily product after water absorption, rather than anhydrous Ph 2 P (O) H and Ph obtained 2 P (O) H is impure.
The P (O) compound easily forms a complex with an acid, and if the acid is to be removed from the product, a subsequent step such as washing with alkali water is required.
3.Ph 2 P (O) H is easily oxidized by air to Ph 2 PO 2 H, in the case of impure Ph 2 When P (O) H is purified, the exposure time of the P (O) H to air needs to be reduced as much as possible, which greatly increases Ph 2 Production cost of P (O) H.
In order to solve the technical problems, the invention aims to develop a preparation method for preparing purer diphenyl phosphine oxide hydrogen with less post-treatment steps.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method of diphenyl phosphine oxide hydrogen, which can prepare anhydrous Ph 2 The preparation method of P (O) H has simple post-treatment and easy operation.
2. Technical proposal
In order to solve the problems, the invention adopts the following technical scheme.
A process for the preparation of diphenyl phosphine oxide, said process comprising the steps of:
step b1: under the atmosphere of inert gas or nitrogen, to Ph 2 Adding solid acid into PONa, ph at-30-150deg.C 2 The PONa is sufficiently quenched by solid acid to generate Ph 2 P (O) H, the solid acid is converted into sodium salt of the solid acid, and after the reaction is finished, the solid acid and sodium salt of the solid acid are used to be insoluble but Ph 2 P (O) H-soluble organic solvents, using Ph 2 P (O) H is dissolved in organic solvent, and solid acid sodium salt are insoluble in organic solvent, so that Ph generated by the reaction 2 P (O) H is separated from the reaction system to obtain anhydrous Ph 2 P(O)H；
The solid acid is selected from one or more of silica gel powder, high molecular organic acid and inorganic solid acid.
Further, in the step b1, the solid acid may be added to Ph 2 The addition of solid acid and sodium salt of solid acid into PONa is insoluble but Ph 2 After the reaction, filtering to separate out sodium salt and solid acid, and vacuum rotary evaporating to eliminate organic solvent to obtain anhydrous Ph 2 P(O)H。
Further, in the step b1, after the reaction is completed, solid acid and solid acid sodium salt are both insoluble but Ph is added into the reaction system 2 P (O) H-soluble organic solvent, ph formed by reaction 2 Dissolving P (O) H in organic solvent, filtering to obtain solid acid sodium salt and solid acidSeparating, removing the organic solvent by rotary evaporation under reduced pressure to obtain anhydrous Ph 2 P(O)H。
Further, solid acid and Ph 3 The weight ratio of P (O) is 0.1-20:1.
Further, in the step b1, the inorganic acid is Al 2 O 3 One or more of powder, acid resin Amberlite, ZSM-5 zeolite and montmorillonite.
Further, in the step b1, the polymer organic acid is Nafion powder or heteropolyacid H 3 PW 12 O 40 。
Further, in the step b1, the solid acid is silica gel powder.
Further, in the step b1, the organic solvent is one or more of toluene, benzene, diethyl ether, tetrahydrofuran, diethyl acetate, methanol, ethanol, chloroform and dichloromethane.
Further, the solid acid has-OH groups thereon, -OH groups quench Ph 2 PONa to obtain Ph 2 P(O)H。
The invention is illustrated by taking solid acid as silica gel powder as an example;
step b1: under the atmosphere of inert gas or nitrogen, to Ph 2 Adding silica gel powder into PONa, ph at-30-150deg.C 2 The PONa is sufficiently quenched by solid acid to generate Ph 2 P (O) H, silica gel powder is converted into solid acid sodium salt, and after the reaction is finished, the silica gel powder and the solid acid sodium salt are insoluble but Ph is adopted 2 P (O) H-soluble organic solvents, using Ph 2 P (O) H is dissolved in organic solvent, silica gel powder and solid acid sodium salt are insoluble in organic solvent, ph generated by reaction is generated 2 P (O) H is separated from the reaction system to obtain anhydrous Ph 2 P(O)H；
Ph 2 When the PONa reacts with the silica gel powder, the PONa and the silica gel powder are insoluble, and the sodium salt of the silica gel powder is insoluble but Ph 2 In the presence of P (O) H-soluble organic solventsReaction, ph 2 After the reaction of the PONa and the solid acid is finished, firstly filtering and separating the reaction system to obtain silica gel powder, solid acid sodium salt and organic solution, and finally performing reduced pressure rotary evaporation on the organic solution to remove the organic solvent to obtain anhydrous Ph 2 P(O)H。
Ph 2 PONa reacts with silica gel powder, or can react under the condition of no organic solvent, ph 2 After the reaction of the PONa and the silica gel powder is finished, adding the silica gel powder and solid acid sodium salt which are insoluble but Ph into a reaction system 2 Organic solvent soluble in P (O) H to be Ph 2 Dissolving P (O) H in organic solvent, filtering to obtain silica gel powder, solid acid sodium salt and organic solution, and vacuum rotary evaporating to remove organic solvent to obtain anhydrous Ph 2 P(O)H。
The preparation method of anhydrous Ph 2 P (O) H method, utilizing OH quenching Ph on silica gel powder surface 2 PONa, producing Ph 2 P (O) H, after quenching, is insoluble but Ph with silica gel powder and solid acid sodium salt 2 P (O) H-soluble organic solvents, using Ph 2 P (O) H is dissolved in an organic solvent, and silica gel powder and solid acid sodium salt are both insoluble in the organic solvent, so that Ph generated by the reaction is generated 2 P (O) H is separated from the reaction system to obtain anhydrous Ph 2 P(O)H。
Further, before the step b1, the method further comprises a step a1, a step a2 and a step a3, wherein the step a1, the step a2 and the step a3 are sequentially carried out;
the step a1: under inert gas or nitrogen atmosphere, ph 3 Mixing PO with a proton compound to obtain a mixture;
the proton compound is selected from water, alcohol, organic acid or inorganic acid;
the Ph is 3 The mol ratio of PO to the proton compound is 0.2-3:1;
step a2: adding sodium metal, ph, to the mixture obtained in step a1 3 Fully reacting PO, proton compound and metal sodium to generate NaOH or proton compound sodium salt, ph 2 Organic substances of the PONa and Ph series;
step a3: after the reaction, separatingNaOH or proton compound sodium salt and Ph generated by reaction 2 PONa and Ph organic matters to obtain Ph 2 PONa。
Further, ph in the step a1 3 After mixing PO with the protic compound, ph in the mixture 3 The PO reacts with the proton compound to form a complex, and after the complex is formed, the step a2 is performed.
Further, ph in the step a1 3 After mixing PO with the protic compound, ph in the mixture 3 PO and the proton compound do not react to form a complex, and the process directly enters the step a2.
Further, in the step a2, at Ph 3 Before PO, proton compound and sodium metal react, ph can be added 3 And adding a first solvent into a mixture formed by PO and the proton compound, wherein the first solvent is one or a mixture of any more of alkane, aromatic hydrocarbon or organic ether.
Further, in the step a2, at Ph 3 PO, proton compound and sodium metal are not reacted to Ph 3 And adding a first solvent into a mixture formed by PO and the proton compound, wherein the first solvent is one or a mixture of any more of alkane, aromatic hydrocarbon or organic ether.
Further, when the first solvent is a non-ether organic solvent, in the step a3, after the reaction is completed, a second solvent is added to the reaction system to generate Ph 2 Dissolving PONa, filtering to remove NaOH or proton compound sodium salt, and removing the first solvent, the second solvent and R-series organic matter to obtain solid Ph 2 PONa; the second solvent is Ph 2 Organic ethers that are soluble in PONa but insoluble in the sodium salt of the protic compound.
That is, if Ph 3 PO, protic compound, and metallic sodium in the absence of first solvent or in Ph 2 Under the condition of a first solvent in which the PONa is insoluble and the sodium salt of the proton compound is insoluble, after the reaction is finished in the third step, adding a second solvent into the reaction system to generate Ph 2 Dissolving PONa, filtering to remove NaOH or proton compound sodium saltFinally, the first solvent, the second solvent and the R-series organic matters are removed by reduced pressure rotary evaporation to obtain solid R 2 PONa; the second solvent is R 2 Organic ethers that are soluble in PONa but insoluble in the sodium salt of the protic compound.
The second solvent may be an organic ether such as THF.
Further, the first solvent is Ph 2 When organic ether with soluble PONa but insoluble proton compound sodium salt is used, in the step a3, after the reaction is finished, naOH or proton compound sodium salt generated by the reaction is directly filtered and removed to obtain an organic phase, and finally the organic phase is subjected to reduced pressure rotary evaporation to remove a first solvent and Ph organic matters to obtain solid Ph 2 PONa。
Further, the first solvent is selected from n-hexane, n-heptane, polyethylene, polypropylene, benzene, toluene, xylene, trimethylbenzene, THF, dioxane, meOCH 2 CH 2 One or more of OMe.
Further, the first solvent is selected from one or a mixture of any of tetrahydrofuran, toluene and dioxane.
Further, metallic sodium and Ph 3 The molar ratio of PO is 0.1-5:1.
Further, metallic sodium and Ph 3 The molar ratio of PO is 1-2:1.
Further, the first solvent is mixed with Ph 3 The weight ratio of PO is 0.5-20:1.
Further, the first solvent is mixed with Ph 3 The weight ratio of PO is 2-5:1.
Further, the Ph 3 The reaction temperature of the PO, the proton compound and the sodium metal is 0-170 ℃.
Further, the Ph 3 The reaction temperature of the PO, the proton compound and the sodium metal is 60-150 ℃.
Further, the structural formula of the proton compound is X-OH or Y-H.
Further, when the proton compound is selected from the group consisting of X-OH structures, in the step a2, ph 3 PO, proton compound and sodium metal are fully reactedNaOH, proton compound sodium salt PhX and Ph should be produced 2 PONa; the reaction is
The preparation process comprises the following steps: ph (Ph) 3 PO reacts with sodium metal to form Ph 2 PONa and PhNa, wherein the PhNa does not react with the first solvent, and the PhNa reacts with the proton compound X-OH in the reaction system to generate PhX and NaOH;
when Ph is to be 3 When the mixture obtained by mixing PO and proton compound X-OH is free of first solvent or the first solvent is non-ether organic solvent, after the reaction is finished and before separation, adding second solvent into the reaction system to produce Ph 2 Dissolving PONa; the second solvent is organic ether; ph (Ph) 2 The PONa is easy to dissolve in the second solvent, the NaOH is not dissolved in the organic ether and the first solvent, then the white precipitate NaOH generated by the reaction is removed by filtration, finally the first solvent, the second solvent and the generated Ph organic matter PhX are removed by reduced pressure rotary evaporation to obtain solid Ph 2 PONa。
When Ph is to be 3 The mixture obtained by mixing PO and the proton compound X-OH is carried out under the condition of a first solvent, wherein the first solvent is organic ether, ph 2 Dissolving PONa in organic ether, dissolving NaOH in organic ether, filtering to remove white precipitate NaOH to obtain organic phase, vacuum rotary evaporating to remove first solvent and obtain Ph organic PhX to obtain solid Ph 2 PONa。
Further, if the proton compound is selected from Y-H structure, in the step a2, ph 3 PO, proton compound and sodium metal are fully reacted to generate proton compound sodium salt NaY, phH and Ph 2 PONa; the reaction is
The preparation process comprises the following steps: ph (Ph) 3 PO reacts with sodium metal to form Ph 2 PONa and PhNa,the PhNa does not react with the first solvent in the reaction system, and reacts with the proton compound Y-H in the reaction system to generate NaY and Ph organic benzene;
when Ph is to be 3 When the mixture obtained by mixing PO and proton compound Y-H is free of first solvent or the first solvent is non-ether organic solvent, after the reaction is finished and before separation, adding second solvent into the reaction system to produce Ph 2 Dissolving PONa; the second solvent is organic ether; the proton compound sodium salt NaY is insoluble in organic ether, then the organic phase is obtained by filtering and removing the proton compound sodium salt NaY generated by the reaction, and finally the first solvent, the second solvent and the generated Ph organic benzene are removed by reduced pressure rotary evaporation to obtain solid Ph 2 PONa。
When Ph is to be 3 The mixture obtained by mixing PO and proton compound Y-H is carried out under the condition of a first solvent, wherein the first solvent is organic ether, ph 2 Dissolving PONa in organic ether, dissolving proton compound sodium salt NaY in organic ether, filtering to remove proton compound sodium salt NaY generated by reaction to obtain organic phase, and removing first solvent, second solvent and Ph organic benzene to obtain solid Ph 2 PONa。
Further, the proton compound is water, H 2 O、MeOH、EtOH、MeCO 2 H. One or more of HCl and PhSH are mixed.
Further, the proton compound is water.
Further, the Ph 3 The molar ratio of PO to protonic compound is 0.5-1.5:1.
Further, ph 2 The chinese name of PONa is sodium diphenyl hypophosphite.
Ph 2 The structural formula of the PONa is as follows:
it can react under air or water, and it needs to be preserved under inert gas or nitrogen atmosphere.
Sodium at Ph 3 Mixture system of PO and proton compoundWherein the Ph with the purity of more than 99% can be prepared by carrying out the reaction under the condition of the presence or absence of the first solvent and separating and purifying 2 PONa, pure Ph prepared 2 The PONa can be used for preparing other phosphine oxide compounds, and can obtain a better yield.
The Ph prepared by the steps provided in the step a1, the step a2 and the step a3 2 The purity of the PONa is high, the proton compound is water, and the first solvent is THF solvent; ph under inert gas or nitrogen atmosphere 3 PO is firstly reacted with metallic sodium to generate Ph 2 PONa and PhNa; the activity of the generated PhNa is relatively active, the PhNa reacts with water to generate benzene and NaOH, the NaOH is insoluble in THF solvent, and the Ph 2 Dissolving PONa in THF solvent, filtering under inert gas or nitrogen atmosphere to remove white precipitate NaOH generated by reaction, and removing THF solvent and benzene by rotary evaporation under reduced pressure to obtain pure solid Ph 2 PONa；
Ph 3 PO+Na＝Ph 2 PONa+PhNa，PhNa+H 2 O＝PhH+NaOH。
The prior art document (Zhang, J.et al J.Org.chem.2020, 85, 14166-14173) describes: in polar ether solvent such as THF, ph 3 The reaction of P (O) and Na may produce Ph 2 PONa, the process produces more by-products, which are compared to product Ph 2 PONa is dissolved in the solvent, so Ph is not easy to be dissolved 2 PONa is separated from byproducts generated in the preparation process, and finally purer Ph cannot be obtained 2 PONa; as can be seen by comparison, the steps a1, a2 and a3 provide a step of preparing Ph 2 The purity of the PONa is far superior to that described in the background art.
Further, before step b1, step b0 is further included, where step b0:
under the atmosphere of inert gas or nitrogen, the phosphine oxide compound Ph 3 PO and metallic sodium are fully reacted under the condition of nonpolar hydrocarbon solvent at the temperature of 0 ℃ to 250 ℃ to generate Ph 2 PONa and Ph compounds, filtering after the reaction, and purifying the solid to obtain Ph 2 PONa。
Further, the nonpolar hydrocarbon solvent is one or a mixture of any of alkanes and aromatic hydrocarbons.
Further, the nonpolar hydrocarbon solvent is selected from one or more of n-hexane, n-heptane, polyethylene, polypropylene, benzene, toluene, ethylbenzene, xylene, and trimethylbenzene.
Further, the nonpolar hydrocarbon solvent is toluene.
Further, the reaction temperature in the step b0 is 60-150 ℃.
Further, a nonpolar hydrocarbon solvent and a phosphine oxide compound Ph 3 The weight ratio of PO is 0.5-20:1.
Further, a nonpolar hydrocarbon solvent and a phosphine oxide compound Ph 3 The weight ratio of PO is 2-5:1.
Further, the binding reaction speed of the nonpolar hydrocarbon solvent and the Ph free radical is greater than that of the Ph free radical and the sodium metal.
Step b0 is further described below:
ph under inert gas or nitrogen atmosphere 3 PO fully reacts with metallic sodium under the condition of nonpolar hydrocarbon solvent to generate Ph 2 Filtering after the reaction of PONa and Ph compound to obtain solid, dissolving the solid in ether organic solvent, filtering to remove insoluble substances, and removing volatile substances such as solvent under reduced pressure to obtain yellowish solid Ph 2 PONa；
Due to Ph 3 Ph formed by reaction of PO and metallic sodium 2 The PONa is insoluble in the nonpolar hydrocarbon solvent, the raw materials and the benzene series compound are soluble in the nonpolar hydrocarbon solvent, and after the reaction is finished, the Ph can be directly filtered 2 Separation of PONaThe separated solid Ph is then subjected to 2 Dissolving PONa in ether organic solvent, filtering, steaming under reduced pressure, and drying to obtain pure solid Ph 2 PONa。
Ph in the step b0 3 PO is reacted with sodium metal, 1mol Ph 3 PO only consumes 1mol of metal Na;
and the reference Ph described in the prior document (Zhang, J.et al J.org.chem.2020, 85, 14166-14173) 3 PO is reacted with sodium metal, 1mol Ph 3 PO consumes 2mol of metal Na, which not only increases the production cost, but also has sodium compounds which are byproducts generated by the decomposition of PhNa and the reaction of PhNa with a solvent, and are difficult to react with the product Ph 2 The PONa was effectively isolated.
PhNa reacts with the solvent to form RONa, etc. The RONa and Ph2PONa were difficult to separate and only the mixture was used.
Ph in the step b0 3 The reaction mechanism of the reaction of PO and metallic sodium is that
The reaction solvent is exemplified by toluene, ph 3 The reaction of PO and metallic sodium in nonpolar hydrocarbon solvent forms benzene free radical, which has the reaction mechanism in the step b0:
①Ph·+Ph·→Ph-Ph；
②Ph·+PhCh 3 →Ph-H+PhCh 2 ·；
③PhCh 2 ·+PhCh 2 ·→PhCh 2 -Ch 2 Ph。
Ph 3 PO reacts with metallic sodium in nonpolar hydrocarbon solvent to generate Ph 2 PONa and formation of benzene radical, benzene after formation of benzene radicalThe free radicals can combine with each other or the benzene free radicals react with the nonpolar hydrocarbon solvent to generate benzene series compounds, and the benzene series compounds do not combine with the metal sodium to generate PhNa.
Ph described in the prior art document (Zhang, J.et al J.org.chem.2020, 85, 14166-14173) 3 The reaction mechanism of the reaction of PO and metallic sodium is that
The reaction mechanism described in the prior art (Zhang, j.et al j.org.chem.2020, 85, 14166-14173) is:
Ph·+Na→PhNa。
after the benzene free radical is combined with the metal sodium, phNa is generated, the generated PhNa reacts with the solvent to generate sodium compounds as byproducts, and decomposition of PhNa also exists, some byproducts generated by the reaction are dissolved in the organic solvent, and some byproducts react with Ph 2 PONa properties are similar, these byproducts are similar to Ph 2 The PONa is mixed together, so that effective and rapid separation is difficult to perform; such as RONa and Ph 2 The PONa has similar properties and is dissolved in the same solvent, so that it is difficult to perform efficient and rapid separation.
The invention is further described below:
the invention prepares anhydrous Ph 2 There are four methods for P (O) H:
first kind:
step b1: under the atmosphere of inert gas or nitrogen, to Ph 2 Adding solid acid into PONa, ph at-30-150deg.C 2 The PONa is sufficiently quenched by solid acid to generate Ph 2 P (O) H, the solid acid is converted into sodium salt of the solid acid, and after the reaction is finished, the solid acid and sodium salt of the solid acid are used to be insoluble but Ph 2 P (O) H-soluble organic solvents, using Ph 2 P (O) H is soluble in organic solvent, and solid acid sodium salt are insoluble in organic solvent, and the reaction is carried outThe Ph generated 2 P (O) H is separated from the reaction system to obtain anhydrous Ph 2 P(O)H；
The solid acid is selected from one or more of silica gel powder, high molecular organic acid and inorganic solid acid.
Ph used in the first method 2 PONa is anhydrous Ph 2 PONa。
Second kind:
step a1: under inert gas or nitrogen atmosphere, ph a Mixing PO with a proton compound Y-H to obtain a mixture;
the proton compound is selected from water, alcohol, organic acid or inorganic acid;
the Ph is 3 The mol ratio of PO to the proton compound is 0.2-3:1;
step a2: adding sodium metal, ph, to the mixture obtained in step a1 3 PO, proton compound and sodium metal are fully reacted to generate proton compound sodium salt NaY, benzene and Ph 2 PONa；
Step a3: after the reaction is finished, separating proton compound sodium salt NaY, phH and Ph generated by the reaction 2 PONa to obtain Ph 2 PONa。
Step b1: under inert gas or nitrogen atmosphere, the Ph obtained in the step a3 is added 2 Adding solid acid into PONa, ph at-30-150deg.C 2 The PONa is sufficiently quenched by solid acid to generate Ph 2 P (O) H, the solid acid is converted into sodium salt of the solid acid, and after the reaction is finished, the solid acid and sodium salt of the solid acid are used to be insoluble but Ph 2 P (O) H-soluble organic solvents, using Ph 2 P (O) H is dissolved in organic solvent, and solid acid sodium salt are insoluble in organic solvent, so that Ph generated by the reaction 2 P (O) H is separated from the reaction system to obtain anhydrous Ph 2 P(O)H；
The solid acid is selected from one or more of silica gel powder, high molecular organic acid and inorganic solid acid.
Third kind:
step a1: under inert gas or nitrogen atmosphere, ph 3 Mixing PO with a proton compound X-OH to obtain a mixture;
the proton compound is selected from water, alcohol, organic acid or inorganic acid;
the Ph is 3 The mol ratio of PO to the proton compound is 0.2-3:1;
step a2: adding sodium metal, ph, to the mixture obtained in step a1 3 PO, proton compound X-OH and sodium metal are fully reacted to generate NaOH, phX and Ph 2 PONa；
Step a3: after the reaction is finished, separating NaOH, phX and Ph generated by the reaction 2 PONa to obtain Ph 2 PONa。
Step b1: under the atmosphere of inert gas or nitrogen, the Ph obtained in the step a3 is added 2 Adding solid acid into PONa, ph at-30-150deg.C 2 The PONa is sufficiently quenched by solid acid to generate Ph 2 P (O) H, the solid acid is converted into sodium salt of the solid acid, and after the reaction is finished, the solid acid and sodium salt of the solid acid are used to be insoluble but Ph 2 P (O) H-soluble organic solvents, using Ph 2 P (O) H is dissolved in organic solvent, and solid acid sodium salt are insoluble in organic solvent, so that Ph generated by the reaction 2 P (O) H is separated from the reaction system to obtain anhydrous Ph 2 P(O)H；
The solid acid is selected from one or more of silica gel powder, high molecular organic acid and inorganic solid acid.
Fourth kind:
step b0: under the atmosphere of inert gas or nitrogen, the phosphine oxide compound Ph 3 PO and metallic sodium are fully reacted under the condition of nonpolar hydrocarbon solvent at the temperature of 0 ℃ to 250 ℃ to generate Ph 2 PONa and Ph compounds, after the reaction is completed, the reaction mixture is fedFiltering and purifying the solid to obtain Ph 2 PONa。
Step b1: under inert gas or nitrogen atmosphere, to Ph obtained in the step b0 2 Adding solid acid into PONa, ph at-30-150deg.C 2 The PONa is sufficiently quenched by solid acid to generate Ph 2 P (O) H, the solid acid is converted into sodium salt of the solid acid, and after the reaction is finished, the solid acid and sodium salt of the solid acid are used to be insoluble but Ph 2 P (O) H-soluble organic solvents, using Ph 2 P (O) H is dissolved in organic solvent, and solid acid sodium salt are insoluble in organic solvent, so that Ph generated by the reaction 2 P (O) H is separated from the reaction system to obtain anhydrous Ph 2 P(O)H；
The solid acid is selected from one or more of silica gel powder, high molecular organic acid and inorganic solid acid.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) Ph provided by the invention 2 The preparation method of P (O) H can prepare anhydrous and pure Ph 2 P(O)H。
(2) The invention utilizes solid acid to quench Ph 2 PONa gives anhydrous Ph 2 P (O) H, then insoluble in some organic solvents, ph, using solid acids and sodium salts of solid acids 2 P (O) H is soluble in some solvents, and solid acid and sodium are filtered with pH 2 Separating the solution of P (O) H, and removing solvent by reduced pressure rotary evaporation to obtain anhydrous solid Ph 2 P (O) H, the method is simple and easy to operate, and greatly reduces the production Ph 2 Post-treatment step of P (O) H.
(3) Ph provided by the invention 2 The preparation method of P (O) H has no water participation, reduces Ph containing water 2 Conversion of P (O) H to Ph free of Water 2 The step of P (O) H greatly improves the preparation of anhydrous Ph 2 Efficiency of P (O) H.
(4) Ph provided by the invention 2 The preparation method of P (O) H avoids various defects of the previous quenching method using hydrochloric acid or saturated ammonium chloride aqueous solution, has simple process, low cost, safety and controllability, and is easy to workCan be used for industrialized production to produce Ph more efficiently 2 P(O)H。
(5) The invention uses Ph 3 The mixture formed by PO and proton compound reacts with metal sodium in the condition of no first solvent or first solvent to prepare purer Ph 2 PONa with purity of more than 99 percent, and finally leading the prepared Ph to 2 P (O) H is purer, and the whole preparation method has simpler post-treatment steps and easy operation.
(6) The invention uses Ph 3 Fully reacting PO with metallic sodium under the condition of nonpolar hydrocarbon solvent to obtain Ph 2 Preparation of anhydrous Ph by reaction of PONa with solid acid 2 P (O) H, the preparation process not only can reduce Ph 3 PO reacts with sodium metal, the usage amount of sodium metal is that Ph can be simply and rapidly separated 3 The reaction product of PO and metallic sodium obtains pure Ph 2 PONa, pure Ph 2 The PONa can react with solid acid to prepare pure anhydrous Ph 2 P(O)H。
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
the Ph is prepared from triphenylphosphine oxide raw material 2 Preparation of Ph by PONa for the steps provided in the steps a1, a2 and a3 2 PONa is further described, but the scope of the invention is not limited thereto:
example 1Ph 2 Production, separation and purification of PONa
10mmol of triphenylphosphine oxide, 10mmol of water and 20mL of THF are mixed and stirred for 30 minutes under nitrogen and nitrogen, and then 20mmol of sodium metal is cut into small pieces at room temperature and added into the mixed solution; stirring at room temperature overnight to obtain dark orange solution containing white precipitate; then filtering to remove white precipitate NaOH under nitrogen atmosphere, and removing volatile matters such as solvent under reduced pressure to obtain pale yellow solid Ph 2 PONa, yield 92%.
The following nuclear magnetism and elemental analysis characterization prove that the obtained compound is pure Ph 2 PONa. This is the worldPure Ph obtained successfully for the first time 2 PONa。
Sodium diphenylhypophosphite (Sodium diphenylphosphinite, ph) 2 ONa) pale yellow solid, melting point 355 ℃ (decomposition). 1 H NMR(400MHz，d 8 -THF)：δ7.47-7.44(m，4H)，7.18-7.14(m，4H)，7.07-7.03(m，2H)； 13 C{1H}NMR(100MHz，d 8 -THF)：δ155.1(d，J p-c ＝40.0Hz)，128.1(d，J p-c ＝20.0Hz)，127.6(d，J p-c ＝4.4Hz)，126.2. 31 P NMR(162MHz，d 8 -THF)：δ91.2.Elemental analysis，calculated for C12H10NaOP：C，64.29；H，4.50.Found：C，64.56；H，4.68.
Example 2
Example 1 under the same conditions, water was changed to MeOH to carry out the reaction, and a yield of 95% was obtained 31 P NMR yield) Ph 2 PONa。
Example 3
Example 1 under the same conditions, water is changed into ethanol EtOH to carry out reaction, and 97 percent yield is obtained 31 P NMR yield) Ph 2 PONa。
Example 4
Example 1 under the same conditions, the reaction was carried out by changing water into isopropyl alcohol i-PrOH, and 93% yield [. About. 31 P NMR yield) Ph 2 PONa。
Example 5
Example 1 under the same conditions, water is changed into t-BuOH to carry out reaction, and 91 percent yield is obtained 31 P NMR yield) Ph 2 PONa。
Example 6
EXAMPLE 1 under the same conditions, THF was replaced with MeOCH 2 CH 2 OMe performs reaction to obtain the product with 98 percent of yield 31 P NMR yield) Ph 2 PONa。
Example 7
Example 1 under the same conditions, THF was changed to dioxane to conduct the reaction to obtain 93% yield [ (] 31 P NMR yield) Ph 2 PONa。
Example 8
Example 1 under the same conditions, THF was changed to toluene to conduct the reaction, and a yield of 90% was obtained 31 P NMR yield) Ph 2 PONa。
As can be seen from examples 1 to 8, the yields were all greater than 50%, triphenylphosphine oxide Ph 3 PO can be reacted with different protonic compounds in the absence of a first solvent or with sodium metal to produce Ph 2 PONa, step a1, step a2 and step a3 provide steps for preparing Ph 2 PONa is easy to separate relatively pure Ph from the reaction system 2 PONa is used as the raw material in the step b1, and Ph 3 PO reacts with sodium metal, the amount of sodium metal used becomes smaller, and 1mol of Ph is used before 3 PO requires consumption of 2 moles of metallic sodium, now 1 mole of Ph 3 PO only needs to consume 1mol of metallic sodium to prepare Ph 2 PONa。
Preparation of Ph from triphenylphosphine oxide 2 The step b0 of the present invention is further described by way of example of PONa:
example 9 below is with triphenylphosphine oxide Ph 3 Preparation of Ph by taking PO as raw material 2 PONa and prepared product Ph 2 Examples of PONa isolation
Example 9
Putting 0.5mmol triphenylphosphine oxide, 0.5mmol metallic sodium and 2mL toluene into a glass tube, heating to 110 ℃ under the protection of nitrogen, preserving heat for 3h, and cooling to room temperature; filtering under nitrogen atmosphere, and recovering solid; the obtained solid was put into 5ml of HF solvent, stirred at room temperature for half an hour, filtered to remove insoluble matters, and then the volatile matters such as solvent were removed under reduced pressure to obtain pale yellow solid Ph 2 PONa, yield 65%.
As can be seen from example 9, the yield of example 9 is greater than 60%, the process provided in step b0 is simple in work-up and allows for easy separation of relatively pure Ph from the reaction system 2 PONa is used as the raw material in the step b 1.
Examples 10 to 18 below illustrate the preparation of Ph from triphenylphosphine oxide 2 PONa, after the reaction, to Ph 2 Preparation of diphenylphosphine by quenching of PONaOxyhydrogen to Ph 2 Examples of quantitative analysis of PONa.
Example 10
Putting 0.5mmol triphenylphosphine oxide, 0.5mmol metallic sodium and 2mL toluene into a glass tube, heating to 110 ℃ under the protection of nitrogen, preserving heat for 3h, cooling to room temperature, adding saturated NH 4 After the reaction was completed, 0.35mmol of diphenylphosphine oxide was obtained in a yield of 70%.
Example 11
Under the same conditions as in example 10, 80℃for 3 hours gave 0.36mmol of diphenylphosphine oxide in 72% yield.
Example 12
Under the same conditions as in example 10, ethyl benzene was used to obtain 0.40mmol of diphenyl phosphine oxide in 80% yield.
Example 13
Example 10 under the same conditions, using benzene, 80 degrees reaction for 3 hours, to obtain diphenyl phosphine oxide hydrogen 0.38mmol, yield 77%.
Example 14
Example 10 was carried out under the same conditions as in example 10, using ethylbenzene at 60℃for 3 hours to give 0.36mmol of diphenylphosphine oxide with a yield of 72%.
Example 15
Example 10 was carried out under the same conditions as described above using ethylbenzene at 60℃for 12 hours to give 0.38mmol of diphenylphosphine oxide with a yield of 77%.
Example 16
Example 10 was carried out under the same conditions as in example 10, using ethylbenzene at 130℃for 3 hours to give 0.35mmol of diphenylphosphine oxide with a yield of 70%.
Example 17
Example 10 under the same conditions, i-PrC was used 6 H 5 The reaction was carried out at 110℃for 3 hours to give 0.37mmol of diphenylphosphine oxide in 74% yield.
Example 18
Example 10 under the same conditions, t-BuC H was used 5 The reaction was carried out at 110℃for 3 hours to give 0.36mmol of diphenylphosphine oxide in 71% yield.
Can be sent out by examples 10 to 18At present, the yield is more than 50%, triphenylphosphine oxide is fully reacted with metallic sodium under the condition of different nonpolar hydrocarbon solvents at different temperatures in the atmosphere of inert gas to prepare Ph 2 PONa, simple post-treatment and easy Ph conversion 2 Separating out PONa and separating out Ph 2 The purity of the PONa is high.
Examples 19-25 below illustrate the preparation of anhydrous Ph for the preparation of diphenylphosphine oxide provided by the present invention 2 Examples of P (O) H:
example 19
30g of triphenylphosphine oxide, 5g of metallic sodium, and 150mL MeOCH at room temperature were placed in a glass flask under nitrogen 2 CH 2 Stirring in OMe for 18 hours until metallic sodium disappears, placing a glass bottle into ice water, adding 15g of silica gel powder (60 mesh) under nitrogen, removing ice bath, stirring at room temperature for 1 hour, and filtering to remove insoluble solid to obtain colorless liquid; removing volatile solvent under reduced pressure to obtain white solid Ph 2 P (O) H was obtained in 92% yield.
Example 20
EXAMPLE 19 under the same conditions, the silica gel powder was changed to Nafion powder to obtain white solid Ph 2 P (O) H was obtained in 93% yield.
Example 21
EXAMPLE 19 under the same conditions, the silica gel powder was changed to Al 2 O 3 Powder to obtain white solid Ph 2 P (O) H was obtained in a yield of 90%.
Example 22
EXAMPLE 19 under the same conditions, the silica gel powder was changed to an acidic resin Amberlite (15 Wet) to give a white solid Ph 2 P (O) H was obtained in 92% yield.
Example 23
EXAMPLE 19 under the same conditions, the silica gel powder was changed to ZSM-5 zeolite to give white solid Ph 2 P (O) H, yield 91%.
Example 24
EXAMPLE 19 under the same conditions, the silica gel powder was changed to heteropolyacid H 3 PW 12 O 40 Obtain white solid Ph 2 P (O) H was obtained in a yield of 96%.
Example 25
EXAMPLE 19 under the same conditions, the silica gel powder was changed to montmorillonite to give white solid Ph 2 P (O) H was obtained in a yield of 95%.
As can be seen from examples 19 to 25, the step b0 according to the invention provides the preparation of anhydrous Ph 2 The method of P (O) H is simple, easy to operate and simple in post-treatment, and can avoid the prior quenching of Ph by hydrochloric acid or saturated ammonium chloride aqueous solution 2 Preparation of Ph by PONa 2 Various defects of P (O) H.
In addition to the embodiments described above, other embodiments of the invention are possible. All technical schemes formed by equivalent substitution or equivalent transformation fall within the protection scope of the invention.
Claims (12)
1. A preparation method of diphenyl phosphine oxide hydrogen is characterized in that: the method comprises the following steps:
step a1: under inert gas atmosphere, ph 3 Mixing PO with a proton compound to obtain a mixture;
the proton compound is selected from water, methanol or ethanol with an X-OH structure;
the Ph is 3 The mol ratio of PO to the proton compound is 0.2-3:1, a step of;
step a2: adding sodium metal, ph, to the mixture obtained in step a1 3 PO, proton compound and sodium metal react fully to produce NaOX, ph 2 PONa and benzene; in the step a2, at Ph 3 Before PO, proton compound and sodium metal react, ph is added 3 Adding a first solvent into a mixture formed by PO and a proton compound, wherein the first solvent is one or a mixture of any more of alkane, aromatic hydrocarbon or organic ether;
step a3: after the reaction is finished, separating NaOX and Ph generated by the reaction 2 PONa and benzene to obtain Ph 2 PONa；
Step b1: at the position ofUnder inert gas atmosphere, to Ph 2 Adding solid acid into PONa, ph at-30-150deg.C 2 The PONa is sufficiently quenched by solid acid to generate Ph 2 P (O) H, the solid acid is converted into sodium salt of the solid acid, and after the reaction is finished, the solid acid and sodium salt of the solid acid are used to be insoluble but Ph 2 P (O) H-soluble organic solvents, using Ph 2 P (O) H is dissolved in organic solvent, and solid acid sodium salt are insoluble in organic solvent, so that Ph generated by the reaction 2 P (O) H is separated from the reaction system to obtain anhydrous Ph 2 P(O)H；
The solid acid is selected from one or a mixture of more than one of silica gel powder, high molecular organic acid and inorganic solid acid; in the step b1, the inorganic solid acid is Al 2 O 3 One or more of powder, acid resin Amberlite, ZSM-5 zeolite and montmorillonite; in the step b1, the polymer organic acid is Nafion powder or heteropolyacid H 3 PW 12 O 40 。
2. The method for preparing diphenyl phosphine oxide according to claim 1, wherein: in the step b1, after the reaction is finished, solid acid and solid acid sodium salt are all insoluble but Ph is added into the reaction system 2 P (O) H-soluble organic solvent, ph formed by reaction 2 Dissolving P (O) H in organic solvent, filtering to remove solid acid sodium salt and solid acid, and removing organic solvent by rotary evaporation under reduced pressure to obtain anhydrous Ph 2 P(O)H。
3. The method for preparing diphenyl phosphine oxide according to claim 1, wherein: solid acid and Ph 3 The weight ratio of P (O) is 0.1-20:1.
4. The method for preparing diphenyl phosphine oxide according to claim 1, wherein: in the step b1, the solid acid is silica gel powder.
5. A process for the preparation of diphenyl phosphine oxide according to any of claims 1-2, characterized in that: in the step b1, the organic solvent is one or more of toluene, benzene, diethyl ether, tetrahydrofuran, diethyl acetate, methanol, ethanol, chloroform and dichloromethane.
6. The method for preparing diphenyl phosphine oxide according to claim 1, wherein: the first solvent is selected from n-hexane, n-heptane, benzene, toluene, xylene, trimethylbenzene, THF, dioxane, meOCH 2 CH 2 One or more of OMe.
7. The method for preparing diphenyl phosphine oxide according to claim 6, wherein: the first solvent is selected from one or a mixture of any more of tetrahydrofuran, toluene and dioxane.
8. The method for preparing diphenyl phosphine oxide according to claim 1, wherein: metallic sodium and Ph 3 The mol ratio of PO is 0.1-5:1.
9. the method for preparing diphenyl phosphine oxide according to claim 1, wherein: the first solvent is mixed with Ph 3 The weight ratio of PO is 0.5-20:1.
10. the method for preparing diphenyl phosphine oxide according to claim 1, wherein: the Ph is 3 The reaction temperature of the PO, the proton compound and the sodium metal is 0-170 ℃.
11. The method for preparing diphenyl phosphine oxide according to claim 1, wherein: the proton compound is water.
12. The method for preparing diphenyl phosphine oxide according to claim 1, wherein: the Ph is 3 The mol ratio of PO to the proton compound is 0.5-1.5:1.
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