CN106496268B - A kind of phosphono substitution carbinol derivatives and the preparation method and application thereof - Google Patents
A kind of phosphono substitution carbinol derivatives and the preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- 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
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
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- 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
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5333—Arylalkane phosphine oxides or thioxides
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/60—Quinoline or hydrogenated quinoline ring systems
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
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- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
Abstract
The invention discloses a kind of phosphonos to replace carbinol derivatives and the preparation method and application thereof.The present invention uses（It is miscellaneous）Aryl carbinol derivatives are starting material, and raw material is easy to get, and there are many type；The product types obtained using the method for the present invention are various, widely used, are coordinated as ligand and rhodium for catalyzing and synthesizing all kinds of aldehyde；Phosphono replaces（It is miscellaneous）Aryl methanol can easily be converted into phosphono base class compound, such compound is as photoinitiator, in the production that can be widely used for high molecular material, coating, adhesive and adhesive tape etc..In addition, method disclosed by the invention, reaction carries out in air, reaction condition is mild, target product high income, the small, operation of pollution and last handling process are simple, is suitable for industrialized production.
Description
Technical field
The invention belongs to the preparing technical fields of organic compound, and in particular to a kind of phosphono substitution carbinol derivatives and
Preparation method and application.
Background technology
In in the past few decades, people replace the relevant report of carbinol derivatives few phosphono；Phosphono replaces
Methanol（1）And its derivative can be used as ligand, in the hydroformylation reaction of rhodium catalysis.Hydroformylation reaction is industrial
The essential industry method of aldehyde is synthesized from common raw material of industry alkene, carbon monoxide and hydrogen.Aldehyde can further add
Work is alcohol, acid and its derivative, and the latter is made extensively as plasticizer, fabric additive, surfactant, solvent and fragrance etc.
For in industrial production and daily life（Referring to:Clark H J, Wang R, Alper H.The Journal of Organic Chemistry, 2002, 67, 6224）.
Meanwhile phosphono replaces（It is miscellaneous）Aryl carbinol derivatives can easily be converted into phosphono aryl ketone derivative
Object can be used as a photoinitiator, be widely used in the production of coating, adhesive, adhesive tape and high molecular material etc..1997
Year, the prior art reports diphenyl phosphine oxide base trimethylphenyl ketone as photoinitiator, can be used for causing free radical polymerization,
One of most widely used photoinitiator in polymerisation is become.So far, a variety of diphenyl phosphine oxide base aryl ketones are as light
Initiator is used in the synthesis of various high molecular materials.
The synthesis of existing phosphono substitution carbinol derivatives is obtained by the reaction by aldehyde and phosphorus reagent, needs to use aldehyde,
Aldehyde has the taste stimulated very much, and larger injury can be caused to operating personnel and environment；Aldehyde is oxidized easily simultaneously, increases storage
Difficulty and cost.Therefore find that a kind of raw material sources are simple, meet Green Chemistry and require, reaction condition is mild, it is easy to operate,
The good preparation method of universality is necessary effectively to synthesize phosphono substitution carbinol derivatives.
Invention content
The object of the present invention is to provide a kind of methods for preparing phosphono and replacing carbinol derivatives, with raw material sources letter
Singly, the advantages that reaction condition is mild, reaction process is environmentally protective, post-processing is simple, yield is high.
To achieve the above object of the invention, the technical solution adopted by the present invention is：It is a kind of to prepare phosphono substitution methanol derivative
The method of object, includes the following steps：Carbinol derivatives, phosphorus reagent, potassium peroxydisulfate are dissolved in solvent, it is anti-at room temperature ~ 100 DEG C
It answers, obtains phosphono and replace carbinol derivatives；
The carbinol derivatives are as shown in following chemical structure of general formula：
The one kind of wherein Ar in following general formula：：
Wherein R is selected from：One kind in alkyl, aryl, alkoxy, halogen, nitro, ester group, pyridyl group；X is selected from：O、S、N
In one kind；
The phosphorus reagent is as shown in following chemical structure of general formula：
Wherein R1One kind in following group：
The phosphono replaces carbinol derivatives as shown in following chemical structure of general formula：
The solvent is selected from：Methanol, ethyl alcohol, acetonitrile, acetone, ethyl acetate, water, 1,2- dichloroethanes, toluene, N, N- bis-
One kind in methylformamide.
In above-mentioned technical proposal, the carbinol derivatives are selected from:Benzylalcohol, 2- chlorobenzyl alcohols, 3- chlorobenzyl alcohols, 4- chlorobenzyl alcohols, 4-
Bromobenzyl alcohol, 4- fluoro benzyl alcohols, 2- xylyl alcohols, 3- xylyl alcohols, 4- xylyl alcohols, 2- methoxyl groups benzylalcohol, 4- methoxyl groups benzylalcohol, 4-
Methyl hydroxy-benzoate, 4- nitrobenzyl alcohols, 2- pyridinemethanols, 4- pyridinemethanols, 1- naphthalenes methanol, 2- hydroxymethylfurans, 2- hydroxyls
One kind in methylthiophene, 2- hydroxymethylpyrrols, 2- hydroxymethylpyrimidines, 2- hydroxymethyl quinolines；The phosphorus reagent is selected from:Diformazan
Base phosphite ester, diethyl phosphite, diphenyl phosphine oxide, two（4- methoxyphenyls）Phosphine oxide, two（4- cyano-phenyls）In phosphine oxide
One kind.
In above-mentioned technical proposal, thin-layer chromatography is utilized（TLC）Tracking reaction is until be fully completed.
In above-mentioned technical proposal, in molar ratio,（It is miscellaneous）Aryl carbinol derivatives: phosphorus reagent: potassium peroxydisulfate is（1~3）∶（1~
3）∶（1~3）.
In above-mentioned technical proposal, column chromatography for separation purification processes are carried out to product after reaction.
The present invention further discloses the phosphonos for being replaced the preparation method of carbinol derivatives to prepare according to above-mentioned phosphono
Replace carbinol derivatives, aldehyde derivatives can be prepared by hydrolysis, therefore the present invention further discloses the substitutions of above-mentioned phosphono
Application of the carbinol derivatives in preparing phosphono aldehyde derivatives；The phosphono substitution carbinol derivatives of the present invention can turn simultaneously
Phosphono ketone derivatives are turned to, therefore the present invention further discloses above-mentioned phosphono substitution carbinol derivatives to prepare phosphono
Application in base aldehyde derivatives.
The invention also discloses above-mentioned phosphono substitution carbinol derivatives to prepare plasticizer, photoinitiator, surface-active
Application in agent.The product structure of the present invention is various, can directly use, it is particularly possible to be further obtained by the reaction as intermediate
Downstream compound has expanded the application of organic compound significantly.
The reaction process of above-mentioned technical proposal is represented by：
Due to the application of the above technical scheme, the present invention has following advantages compared with prior art:
1, the present invention is starting material using 01 derivatives, and product is prepared in the presence of phosphorus reagent, potassium peroxydisulfate for the first time
Phosphono replaces carbinol derivatives；Have the advantages that raw material is easy to get, toxicity is low, of low cost, product structure type is more.
2, using 01 derivatives as starting material, alcohol derives the method disclosed by the invention for preparing phosphono substitution carbinol derivatives
Object is small on operating personnel and environment influence, and convenient for storage；Solve that prior art material toxicity is big, be not easy to store lacks
It falls into.
3, in the method disclosed by the invention for preparing phosphono substitution carbinol derivatives, reaction carries out in air, reacts
Mild condition, the reaction time is short, the high income of target product, and operation and last handling process are simple, and product structure is various, can
Directly to use, it is particularly possible to downstream compound further be obtained by the reaction as intermediate, expanded organic compound significantly
Using being suitable for industrialized production.
Specific implementation mode
With reference to embodiment, the invention will be further described：
Embodiment one：The synthesis of diphenyl phosphine oxide base benzyl alcohol
Using benzylalcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
Benzylalcohol is added in reaction bulb（0.054 g, 0.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5 mmol）、
Potassium peroxydisulfate（0.270 g, 1.0 mmol）And methanol（2 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 76%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ 7.97 - 7.72 (m,
4H), 7.64 – 7.37 (m, 6H), 7.34 – 7.09 (m, 5H), 6.55 (d, J = 17.1 Hz, 1H),
5.64 (s, 1H).The product can be used for the formylation reaction of alkene in the industrial production as ligand.
Embodiment two：The synthesis of diphenyl phosphine oxide base (2- chlorphenyls) methanol
Using 2- chlorobenzyl alcohols, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- chlorobenzyl alcohols are added in reaction bulb（0.143 g, 1.0 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And ethyl alcohol（2 mL）, 30 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 73%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.81 (dd, J = 11.2,
7.7 Hz, 2H), 7.74 (dd, J = 11.5, 7.7 Hz, 2H), 7.64 – 7.44 (m, 6H), 7.35 –
7.14 (m, 4H), 6.70 (dd, J = 18.3, 5.8 Hz, 1H), 5.96 (t, J = 6.1 Hz, 1H).
Embodiment three：The synthesis of diphenyl phosphine oxide base (3- chlorphenyls) methanol
Using 3- chlorobenzyl alcohols, diphenyl phosphine oxide as raw material, reaction step is as follows：
3- chlorobenzyl alcohols are added in reaction bulb（0.214 g, 1.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And water（2 mL）, 40 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 75%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ7.91 – 7.75 (m,
4H), 7.64 – 7.44 (m, 6H), 7.36 – 7.12 (m, 4H), 6.65 (dt, J = 24.7, 12.3 Hz,
1H), 5.70 (t, J = 6.7 Hz, 1H).
Example IV：The synthesis of diphenyl phosphine oxide base (4- chlorphenyls) methanol
Using 4- chlorobenzyl alcohols, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- chlorobenzyl alcohols are added in reaction bulb（0.071 g, 0.5 mmol）, diphenyl phosphine oxide（0.202 g, 1.0
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And ethyl acetate（2 mL）, 50 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 80%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ7.86 – 7.77 (m,
4H), 7.58 – 7.44 (m, 6H), 7.33 – 7.19 (m, 4H), 6.61 (dd, J = 17.4, 5.8 Hz,
1H), 5.68 (t, J = 6.5 Hz, 1H).
Embodiment five：The synthesis of diphenyl phosphine oxide base (2- aminomethyl phenyls) methanol
Using 2- xylyl alcohols, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- xylyl alcohols are added in reaction bulb（0.061 g, 0.5 mmol）, diphenyl phosphine oxide（0.303 g, 1.5
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And acetone（2 mL）, 50 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 83%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.91 – 7.75 (m,
4H), 7.62 – 7.53 (m, 2H), 7.52 – 7.46 (m, 4H), 7.14 – 7.03 (m, 3H), 7.01 –
6.89 (m, 1H), 6.43 (dd, J = 20.2, 5.2 Hz, 1H), 5.78 (dd, J = 7.9, 5.3 Hz,
1H), 2.29 (s, 3H).
Embodiment six：The synthesis of diphenyl phosphine oxide base (4- aminomethyl phenyls) methanol
Using 4- xylyl alcohols, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- xylyl alcohols are added in reaction bulb（0.061 g, 0.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.135 g, 0.5 mmol）And acetonitrile（2 mL）, 60 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 71%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.89 – 7.70 (m,
4H), 7.61 – 7.38 (m, 6H), 7.14 (d, J = 7.0 Hz, 2H), 7.00 (d, J = 7.6 Hz, 2H),
6.44 (dd, J = 17.7, 5.7 Hz, 1H), 5.58 (t, J = 6.0 Hz, 1H), 2.22 (s, 3H).
Embodiment seven：The synthesis of diphenyl phosphine oxide base (3- aminomethyl phenyls) methanol
Using 3- xylyl alcohols, diphenyl phosphine oxide as raw material, reaction step is as follows：
3- xylyl alcohols are added in reaction bulb（0.061 g, 0.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.405 g, 1.5 mmol）With 1,2- dichloroethanes（2 mL）, 70 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 82%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.90 -7.70 (m, 4H),
7.60 – 7.39 (m, 6H), 7.13 – 6.90 (m, 4H), 6.44 (dd, J = 17.8, 5.6 Hz, 1H),
5.56 (t, J = 6.2 Hz, 1H), 2.17 (s, 3H).
Embodiment eight：The synthesis of diphenyl phosphine oxide base (4- methoxyphenyls) methanol
Using 4- methoxyl groups benzylalcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- methoxyl group benzylalcohols are added in reaction bulb（0.069 g, 0.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And toluene（2 mL）, 80 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 83%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.82 (dd, J =
18.1, 9.8 Hz, 4H), 7.59 – 7.41 (m, 6H), 7.18 (d, J = 7.7 Hz, 2H), 6.77 (d, J
= 8.2 Hz, 2H), 6.42 (dd, J = 17.7, 5.6 Hz, 1H), 5.58 (t, J = 5.5 Hz, 1H),
3.70 (s, 3H).
Embodiment nine：The synthesis of diphenyl phosphine oxide base (2- methoxyphenyls) methanol
Using 2- methoxyl groups benzylalcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- methoxyl group benzylalcohols are added in reaction bulb（0.069 g, 0.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And N,N-dimethylformamide（2 mL）, 90 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 79%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.86 – 7.70 (m,
2H), 7.67 – 7.46 (m, 6H), 7.44 – 7.36 (m, 2H), 7.28 (d, J = 7.6 Hz, 1H), 7.18
(t, J = 7.8 Hz, 1H), 6.84 (t, J = 7.4 Hz, 1H), 6.79 (d, J = 8.3 Hz, 1H), 6.28
(dd, J = 16.1, 6.3 Hz, 1H), 5.96 (dd, J = 6.1, 4.2 Hz, 1H), 3.47 (s, 3H).
Embodiment ten：The synthesis of diphenyl phosphine oxide base (4- nitrobenzophenones) methanol
Using 4- nitrobenzyl alcohols, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- nitrobenzyl alcohols are added in reaction bulb（0.076 g, 0.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And N,N-dimethylformamide（2 mL）, 100 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 71%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ8.08 (d, J = 8.6
Hz, 2H), 7.85 (dd, J = 10.8, 7.1 Hz, 2H), 7.78 (dd, J = 10.5, 7.2 Hz, 2H),
7.61 – 7.44 (m, 8H), 6.85 (dd, J = 17.0, 5.8 Hz, 1H), 5.88 (dd, J = 9.4, 5.9
Hz, 1H).
Embodiment 11：The synthesis of diphenyl phosphine oxide base (4- bromophenyls) methanol
Using 4- bromobenzyls alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- bromobenzyl alcohol is added in reaction bulb（0.093 g, 0.5 mmol）, diphenyl phosphine oxide（0.152 g, 0.75
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And ethyl alcohol（2 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 86%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ7.81 (dd, J =
17.5, 7.1 Hz, 4H), 7.60 – 7.44 (m, 6H), 7.40 (d, J = 8.2 Hz, 2H), 7.19 (d, J
= 7.0 Hz, 2H), 6.61 (dd, J = 17.4, 5.8 Hz, 1H), 5.66 (t, J = 6.6 Hz, 1H).
Embodiment 12：The synthesis of diphenyl phosphine oxide base (4- fluorophenyls) methanol
Using 4- fluoro benzyl alcohols, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- fluoro benzyl alcohols are added in reaction bulb（0.063 g, 0.5 mmol）, diphenyl phosphine oxide（0.152 g, 0.75
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And ethyl alcohol（2 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 77%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ7.83 (dd, J = 9.5,
8.3 Hz, 2H), 7.77 (dd, J = 9.6, 8.3 Hz, 2H), 7.64 – 7.43 (m, 6H), 7.25 (t, J
= 6.7 Hz, 2H), 7.05 (dd, J = 16.6, 8.7 Hz, 2H), 6.58 (dd, J = 17.7, 5.9 Hz,
1H), 5.83 (t, J = 6.0 Hz, 1H).
Embodiment 13：The synthesis of diphenyl phosphine oxide base (4- methoxycarbonyl-phenyls) methanol
Using 4- methyl hydroxy-benzoates, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- methyl hydroxy-benzoates are added in reaction bulb（0.083 g, 0.5 mmol）, diphenyl phosphine oxide（0.152
G, 0.75 mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And N,N-dimethylformamide（2 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the petroleum ether obtained after reaction:Ethyl acetate=4:1) target, is obtained
Product（Yield 74%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.87 – 7.73 (m,
6H), 7.60 – 7.33 (m, 8H), 6.68 (dd, J = 17.3, 5.7 Hz, 1H), 5.75 (dd, J = 7.7,
6.3 Hz, 1H), 3.81 (s, 3H).
Embodiment 14：The synthesis of diphenyl phosphine oxide base (pyridine -2- bases) methanol
Using 2- pyridinemethanols, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- pyridinemethanols are added in reaction bulb（0.544 g, 0.5 mmol）, diphenyl phosphine oxide（0.152 g, 0.75
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And N,N-dimethylformamide（2 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 71%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ8.35 (d, J = 4.3
Hz, 1H), 7.84 – 7.74 (m, 4H), 7.70 (td, J = 7.7, 1.4 Hz, 1H), 7.59 – 7.43 (m,
6H), 7.36 (d, J = 7.8 Hz, 1H), 7.25 – 7.18 (m, 1H), 6.45 (dd, J = 13.8, 6.1
Hz, 1H), 5.72 (t, J = 5.8 Hz, 1H).
Embodiment 15：The synthesis of diphenyl phosphine oxide base (pyridin-4-yl) methanol
Using 4- pyridinemethanols, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- pyridinemethanols are added in reaction bulb（0.544 g, 0.5 mmol）, diphenyl phosphine oxide（0.152 g, 0.75
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And N,N-dimethylformamide（2 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 71%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ8.46 – 8.30 (m,
2H), 7.89 – 7.73 (m, 4H), 7.62 – 7.43 (m, 6H), 7.28 – 7.16 (m, 2H), 6.77 (dd,J = 16.6, 5.7 Hz, 1H), 5.75 (dd, J = 9.1, 5.9 Hz, 1H).
Embodiment 16：The synthesis of diphenyl phosphine oxide base (naphthalene -2- bases) methanol
Using β-naphthalene methanol, diphenyl phosphine oxide as raw material, reaction step is as follows：
β-naphthalene methanol is added in reaction bulb（0.079 g, 0.5 mmol）, diphenyl phosphine oxide（0.152 g, 0.75
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And N,N-dimethylformamide（2 mL）, 30 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 85%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ8.32 (d, J = 8.0
Hz, 1H), 7.93 – 7.82 (m, 4H), 7.78 (d, J = 8.0 Hz, 1H), 7.59 (t, J = 7.0 Hz,
1H), 7.54 – 7.37 (m, 8H), 7.32 (t, J = 7.7 Hz, 1H), 6.61 (dd, J = 19.0, 5.4
Hz, 1H), 6.49 – 6.40 (m, 1H).
Embodiment 17：The synthesis of diphenyl phosphine oxide base (furans -2- bases) methanol
Using 2- hydroxymethylfurans, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- hydroxymethylfurans are added in reaction bulb（0.078 g, 0.8 mmol）, diphenyl phosphine oxide（0.242 g, 1.2
mmol）, potassium peroxydisulfate（0.432 g, 1.6 mmol）And acetonitrile（2 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 79%）.The analysis data of product are as follows： 1H NMR (400 MHz, CDCl3): δ 7.80 ( dd, J = 7.8
Hz, 4 H ), 7.55 (t, J = 7.6 Hz, 6 H), 7.23 (dd, J = 3.2 Hz, 1 H), 6.28 (dd, J
= 3.6 Hz, 1H), 6.21 (dd, J = 3.6 Hz, 1 H), 5.50 (d, J = 5.6 Hz, 1 H), 4.98
(s, 1 H).
Embodiment 18：The synthesis of diphenyl phosphine oxide base (thiophene -2- bases) methanol
Using 2- hydroxymethyl thiophenes, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- hydroxymethyl thiophenes are added in reaction bulb（0.090 g, 0.8 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.432 g, 1.6 mmol）And acetonitrile（2 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 75%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ 7.94 – 7.75 (m,
4H), 7.62 – 7.42 (m, 6H), 7.36 (d, J = 4.3 Hz, 1H), 6.98 – 6.87 (m, 2H), 6.84
(dd, J = 16.3, 6.0 Hz, 1H), 5.90 (t, J = 6.1 Hz, 1H).
Embodiment 19：The synthesis of diphenyl phosphine oxide base (pyrroles -2- bases) methanol
Using 2- hydroxymethylpyrrols, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- hydroxymethylpyrrols are added in reaction bulb（0.078 g, 0.8 mmol）, diphenyl phosphine oxide（0.242 g, 1.2
mmol）, potassium peroxydisulfate（0.432 g, 1.6 mmol）And acetonitrile（2 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 71%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ11.85 (s, 1H), 7.87
– 7.69 (m, 4H), 7.62 – 7.42 (m, 6H), 6.64 (d, J = 4.3 Hz, 1H), 6.11 (t, J =
6.1 Hz, 1H), 5.88 (d, J = 4.3 Hz, 1H), 5.84 (dd, J = 16.3, 6.0 Hz, 1H), 5.12
(t, J = 6.1 Hz, 1H).
Embodiment 20：The synthesis of diphenyl phosphine oxide base (pyrimidine -2-base) methanol
Using 2- hydroxymethylpyrimidines, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- hydroxymethylpyrimidines are added in reaction bulb（0.088 g, 0.8 mmol）, diphenyl phosphine oxide（0.242 g, 1.2
mmol）, potassium peroxydisulfate（0.432 g, 1.6 mmol）And acetone（2 mL）, 40 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 81%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ8.70 (d, J = 4.3
Hz, 2H), 7.84 – 7.74 (m, 4H), 7.59 – 7.43 (m, 6H), 7.39 (t, J = 6.1 Hz, 1H),
6.45 (dd, J = 13.8, 6.1 Hz, 1H), 5.72 (t, J = 5.8 Hz, 1H).
Embodiment 21：The synthesis of diphenyl phosphine oxide base (quinoline -2- bases) methanol
Using 2- hydroxymethyl quinolines, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- hydroxymethyl quinolines are added in reaction bulb（0.127 g, 0.8 mmol）, diphenyl phosphine oxide（0.242 g, 1.2
mmol）, potassium peroxydisulfate（0.432 g, 1.6 mmol）And acetone（2 mL）, 40 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 76%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ8.16 (d, J = 8.0
Hz, 1H), 8.04 (d, J = 8.0 Hz, 1H), 7.86 – 7.63 (m, 6H), 7.58 – 7.43 (m, 7H),
7.30 (d, J = 8.0 Hz, 1H), 6.61 (dd, J = 19.0, 5.4 Hz, 1H), 6.49 (t, J = 5.8
Hz, 1H).
Embodiment 22：The synthesis of dimethoxyphosphinvl benzyl alcohol
Using benzylalcohol, dimethyl phosphinate as raw material, reaction step is as follows：
Benzylalcohol is added in reaction bulb（0.086 g, 0.8 mmol）, dimethyl phosphinate（0.132g, 1.2
mmol）, potassium peroxydisulfate（0.648 g, 2.4 mmol）And acetone（2 mL）, 40 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 75%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ7.27-7.47 (m, 5H),
5.12 (s, 1H), 5.05 (d, J = 12 Hz, 1H), 3.64-3.72 (m, 6H).
Embodiment 23：The synthesis of diethoxy phosphinyl benzyl alcohol
Using benzylalcohol, diethyl phosphinate as raw material, reaction step is as follows：
Benzylalcohol is added in reaction bulb（0.086 g, 0.8 mmol）, diethyl phosphinate（0.168,1.2
mmol）, potassium peroxydisulfate（0.648 g, 2.4 mmol）And acetone（2 mL）, 40 DEG C of reactions；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 81%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ7.38-7.41 (m, 2H),
7.22-7.25 (m, 3H), 5.12 (s, 1H), 4.92 (d, J = 10 Hz, 1H), 3.90-3.98 (m, 4H),
1.08-1.19 (m, 6H).
Embodiment 24：Two（4- methoxyphenyls）Phosphinyl（4- chlorphenyls）The synthesis of methanol
With 4- chlorobenzyl alcohols, two（4- methoxyphenyls）For phosphine oxide as raw material, reaction step is as follows：
4- chlorobenzyl alcohols are added in reaction bulb（0.114 g, 0.8 mmol）, two（4- methoxyphenyls）Phosphine oxide（0.314
G, 1.2 mmol）, potassium peroxydisulfate（0.648 g, 2.4 mmol）And acetone（2 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 87%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.77 (dd, J = 9.5,
8.3 Hz, 4H), 7.38 (d, J = 8.3 Hz, 2H), 7.22 (d, J = 8.3 Hz, 2H), 7.16 (dd, J
= 9.6, 8.3 Hz, 4H), 6.58 (dd, J = 17.7, 5.9 Hz, 1H), 5.83 (t, J = 6.0 Hz,
1H).
Embodiment 25：Two（4- cyano-phenyls）Phosphinyl（4- chlorphenyls）The synthesis of methanol
With 4- chlorobenzyl alcohols, two（4- cyano-phenyls）For phosphine oxide as raw material, reaction step is as follows：
4- chlorobenzyl alcohols are added in reaction bulb（0.114 g, 0.8 mmol）, two（4- cyano-phenyls）Phosphine oxide（0.302
G, 1.2 mmol）, potassium peroxydisulfate（0.648 g, 2.4 mmol）And acetone（2 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object（Yield 84%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ7.83 (dd, J = 9.5,
8.3 Hz, 4H), 7.77 (dd, J = 9.6, 8.3 Hz, 4H), 7.38 (d, J = 6.7 Hz, 2H), 7.22
(d, J = 6.7 Hz, 2H), 6.58 (dd, J = 17.7, 5.9 Hz, 1H), 5.83 (t, J = 6.0 Hz,
1H).
Embodiment 26：The synthesis of 4- dimethylamino benzoyl diphenyl phosphine oxides
Using 4- dimethylaminobenzyl alcohols, diphenyl phosphine oxide as raw material, reaction step is as follows：
The synthesis step of compound 26-2：
4- dimethylaminobenzyl alcohols are added in reaction bulb（0.151 g, 1.0 mmol）, diphenyl phosphine oxide（0.304 g,
1.5 mmol）, potassium peroxydisulfate（0.540 g, 2.0 mmol）And acetone（5 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object 26-2（Yield 82%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ7.30−7.82 (m,
10H), 7.03 (dd, J = 1.5, 2.0 Hz, 2H), 6.52 (d, J = 8.5 Hz, 1H), 5.36 (d, J =
4 Hz, 1H), 4.13 (s, 1H), 2.90 (s, 1H), 2.51 (s, 6H).
The synthesis step of compound 26-3：
Compound 26-2 is added in reaction bulb（0.176 g, 0.5 mmol）, manganese dioxide (0.870 g, 10
Mmol) and dichloromethane (10 mL), mixture is stirred to react at room temperature；
TLC tracking reactions are until be fully completed；
The crude product obtained after reaction with re crystallization from toluene through obtaining target product 26-3（Yield 94%）.Product
Analysis data it is as follows：1H NMR (400 MHz, CDCl3): δ8.51 (d, J = 9.0 Hz, 2H), 7.89−7.85
(m, 4H), 7.50−7.42 (m, 6H), 6.63 (d, J=9.0 Hz, 2H), 2.53 (s, 6H) compounds 26-
3 can be used for the photoinitiator of synthesis of polymer material.
Embodiment 27：The synthesis of 4- di-n-hexyl amino benzoyl diphenyl phosphine oxides
Using 4- di-n-hexyls aminobenzyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
The synthesis step of compound 27-2：
4- di-n-hexyl aminobenzyl alcohols are added in reaction bulb（0.291 g, 1.0 mmol）, diphenyl phosphine oxide（0.304
G, 1.5 mmol）, potassium peroxydisulfate（0.540 g, 2.0 mmol）And acetone（5 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object 27-2（Yield 84%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ7.80−7.35 (m,
10H), 6.99 (d, J = 7.5 Hz, 2H), 6.45 (d, J = 9.0 Hz, 2H), 5.34 (s, 1H), 3.22
(t, J = 15.5 Hz, 4H), 1.54−1.50 (m, 8H), 1.33−1.27 (m, 8H), 0.88 (t, J = 13.5
Hz, 6H).
The synthesis step of compound 27-3：
Compound 27-2 is added in reaction bulb（0.246 g, 0.5 mmol）, manganese dioxide (0.870 g, 10
Mmol) and dichloromethane (10 mL), mixture is stirred to react at room temperature；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the n-hexane obtained after reaction:Ethyl acetate=5:1) target, is obtained
Product 27-3（Yield 96%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ8.47 (d, J =
9.0 Hz, 2H), 7.93−7.85 (m, 4H), 7.54−7.43(m, 6H), 6.59 (d, J = 9.0 Hz, 2H),
3.31 (t, J = 15.5 Hz, 4H), 1.61−1.56 (m, 8H), 1.31−1.24 (m, 8H), 0.88 (t, J =
13.5 Hz, 6H) compounds 27-3 can be used for the photoinitiator of synthesis of polymer material.
Embodiment 28：The synthesis of 4- methyl benzoyl diphenyl phosphine oxides
Using 4- xylyl alcohols, diphenyl phosphine oxide as raw material, reaction step is as follows：
Embodiment six is shown in the synthesis of compound 28-1.
The synthesis step of compound 28-2：
Compound 28-1 is added in reaction bulb（0.161 g, 0.5 mmol）, manganese dioxide (0.870 g, 10
Mmol) and dichloromethane (10 mL), mixture is stirred to react at room temperature；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the n-hexane obtained after reaction:Ethyl acetate=5:1) target, is obtained
Product 28-2（Yield 97%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.90 – 7.70
(m, 4H), 7.63 – 7.30 (m, 6H), 7.12 (d, J = 7.0 Hz, 2H), 7.01 (d, J = 7.6 Hz,
2H), 2.26 (s, 3H) compounds 28-2 can be used for the photoinitiator of synthesis of polymer material.
Embodiment 29：The synthesis of 4- methoxybenzoyl base diphenyl phosphine oxides
Using 4- methoxyl groups benzylalcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
Embodiment eight is shown in the synthesis of compound 29-1.
The synthesis step of compound 29-2：
Compound 29-1 is added in reaction bulb（0.169 g, 0.5 mmol）, manganese dioxide (0.870 g, 10
Mmol) and dichloromethane (10 mL), mixture is stirred to react at room temperature；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the n-hexane obtained after reaction:Ethyl acetate=5:1) target, is obtained
Product 29-2（Yield 95%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.85 (dd, J =
18.1, 9.8 Hz, 4H), 7.61 – 7.41 (m, 6H), 7.21 (d, J = 7.7 Hz, 2H), 6.79 (d, J
=8.2 Hz, 2H), 3.74 (s, 3H) compounds 29-2 can be used for the photoinitiator of synthesis of polymer material.
Embodiment 30：The synthesis of 2,4,6- trimethyl benzoyl diphenyl phosphine oxides
With 2,4,6- trimethyl benzylalcohols, diphenyl phosphine oxide as raw material, reaction step is as follows：
The synthesis step of compound 30-2：
2,4,6- trimethyl benzylalcohols are added in reaction bulb（0.150 g, 1.0 mmol）, diphenyl phosphine oxide（0.304
G, 1.5 mmol）, potassium peroxydisulfate（0.540 g, 2.0 mmol）And acetone（5 mL）, room temperature reaction；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the dichloromethane obtained after reaction:Methanol=40:1) target production, is obtained
Object 30-2（Yield 79%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ7.40−7.90 (m,
10H), 6.90−7.10 (m, 2H), 5.49 (d, J = 4.0 Hz, 1H), 4.41 (s, 1H), 2.31 (s,
6H), 2.17 (s, 3H)
The synthesis step of compound 30-3：
Compound 30-2 is added in reaction bulb（0.175 g, 0.5 mmol）, manganese dioxide (0.870 g, 10
Mmol) and dichloromethane (10 mL), mixture is stirred to react at room temperature；
TLC tracking reactions are until be fully completed；
Crude by column chromatography separation (the n-hexane obtained after reaction:Ethyl acetate=5:1) target, is obtained
Product 29-2（Yield 98%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ7.40−7.90 (m,
10H), 7.11 7.30 (m, 2H), 2.52 (s, 6H), 2.29 (s, 3H) compounds 30-3 can be used for macromolecule material
Expect the photoinitiator of synthesis.
Claims (5)
1. a kind of method preparing phosphono substitution carbinol derivatives, which is characterized in that include the following steps：Methanol is derived
Object, phosphorus reagent, potassium peroxydisulfate are dissolved in solvent, are reacted at room temperature ~ 100 DEG C, and phosphono substitution carbinol derivatives are obtained；
The carbinol derivatives are as shown in following chemical structure of general formula：
The one kind of wherein Ar in following structural formula：
Wherein R is selected from：One kind in alkyl, aryl, alkoxy, halogen, nitro, ester group, pyridyl group；X is selected from：O, in S, N
It is a kind of；
The phosphorus reagent is as shown in following chemical structure of general formula：
Wherein R1One kind in following group：
The phosphono replaces carbinol derivatives as shown in following chemical structure of general formula：
The solvent is selected from：Methanol, ethyl alcohol, acetonitrile, acetone, ethyl acetate, water, 1,2- dichloroethanes, toluene, N, N- dimethyl
One kind in formamide.
2. the preparation method of phosphono substitution carbinol derivatives according to claim 1, it is characterised in that：In molar ratio, first
01 derivatives: phosphorus reagent: potassium peroxydisulfate is（1~3）∶（1~3）∶（1~3）.
3. the preparation method of phosphono substitution carbinol derivatives according to claim 1, it is characterised in that：It is right after reaction
Product carries out column chromatography for separation purification processes.
4. the preparation method of phosphono substitution carbinol derivatives according to claim 1, it is characterised in that：The methanol derives
Object is selected from:Benzylalcohol, 2- chlorobenzyl alcohols, 3- chlorobenzyl alcohols, 4- chlorobenzyl alcohols, 4- bromobenzyls alcohol, 4- fluoro benzyl alcohols, 2- xylyl alcohols, 3- methyl benzyls
Alcohol, 4- xylyl alcohols, 2- methoxyl groups benzylalcohol, 4- methoxyl groups benzylalcohol, 4- methyl hydroxy-benzoates, 4- nitrobenzyl alcohols, 2- pyridines
Methanol, 4- pyridinemethanols, 1- naphthalenes methanol, 2- hydroxymethylfurans, 2- hydroxymethyl thiophenes, 2- hydroxymethylpyrrols, 2- hydroxymethylpyrimidines,
One kind in 2- hydroxymethyl quinolines；The phosphorus reagent is selected from:Dimethyl phosphite, diethyl phosphite, diphenyl phosphine oxide,
Two（4- methoxyphenyls）Phosphine oxide, two（4- cyano-phenyls）One kind in phosphine oxide.
5. the preparation method of phosphono substitution carbinol derivatives according to claim 1, it is characterised in that：Utilize thin-layer chromatography
Tracking reaction is until be fully completed.
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