CN110590835B - Method for preparing 2-iodo-1-phosphoryl substituted alkane compound by high-efficiency double functionalization of olefin - Google Patents

Method for preparing 2-iodo-1-phosphoryl substituted alkane compound by high-efficiency double functionalization of olefin Download PDF

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CN110590835B
CN110590835B CN201910897273.3A CN201910897273A CN110590835B CN 110590835 B CN110590835 B CN 110590835B CN 201910897273 A CN201910897273 A CN 201910897273A CN 110590835 B CN110590835 B CN 110590835B
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熊碧权
王刚
祝雨
刘宇
许卫凤
唐课文
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Hunan Institute of Science and Technology
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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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/094—Esters of phosphoric acids with arylalkanols
    • 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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • 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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3229—Esters of aromatic acids (P-C aromatic linkage)
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    • C07—ORGANIC CHEMISTRY
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3288—Esters with arylalkanols

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Abstract

Hair brushThe invention provides a method for efficiently and selectively synthesizing 2-iodo-1-phosphoryl substituted alkane compounds containing different functional groups, which adoptsNIodosuccinimide (NIS) is used as an accelerator, a compound containing P (O) -OH and olefin are used as reaction substrates, and an organic solvent is added into a reaction system. The method has the advantages that: the accelerant is cheap and easy to obtain; the substrate applicability is high; the reaction condition is mild, safe and reliable; the selectivity of the obtained target product is close to 100 percent, and the yield is up to more than 90 percent. The method develops a new way for synthesizing the substituted 2-iodo-1-phosphoryl substituted alkane compound containing different functional groups, solves the defects of poor reaction selectivity, complicated reaction steps, low yield, the need of using reagents harmful to the environment and the like in the traditional synthesis of the 2-iodo-1-phosphoryl substituted alkane compound, and has good industrial application prospect. The invention also provides corresponding 2-iodine-1-phosphoryl substituted alkane derivatives containing different functional groups.

Description

Method for preparing 2-iodo-1-phosphoryl substituted alkane compound by high-efficiency double functionalization of olefin
Technical Field
The invention relates to the field of application catalytic synthesis of organic phosphate compounds, in particular to a method for preparing 2-iodo-1-phosphoryl substituted alkane compounds by using a P (O) -OH compound and olefin to perform high-efficiency bifunctional reaction.
Background
The organic phosphate ester compound is an important organic compound in organic synthesis, and the compound has good catalytic activity, optical activity and biological activity, so that the compound has wide application in the aspects of biological, medical and optical active materials, asymmetric catalytic synthesis and the like. Phosphorus and organic phosphorus compounds are known to be important substrates in life, such as ADP, ATP, RNA, organic phospholipid bilayers and the like in human bodies. However, it is difficult to find out a natural organic phosphate compound in nature, and most of phosphorus exists in nature in the form of inorganic salt, and most of organic phosphate compounds known at present are synthesized by a chemical method.
In recent years, with the continuous expansion of the application field of organic phosphate (especially as organic ligand), the market demand is also increasing, and the development of new synthesis technology of the compounds is also receiving more and more attention. The synthesis method of the 2-iodo-1-phosphoryl substituted alkane compound reported in the literature at present mainly comprises the following steps: (1) Atherton-Todd reaction: catalyzing a compound containing a corresponding P (O) -H bond to perform cross coupling reaction with alpha-iodophenethyl alcohol in the presence of reagents such as carbon tetrachloride, triethylamine and the like; (2) nucleophilic substitution reaction: the compound containing P (O) -H or P (O) -OH reacts with a halogenating agent to prepare a corresponding compound containing P (O) -Cl, and then the compound and alpha-iodophenethyl alcohol are subjected to cross coupling reaction; (3) ester exchange reaction: the catalyst is prepared by the ester exchange reaction of alpha-iodophenethyl alcohol and diaryl methyl phosphonate. However, the above methods generally employ air-sensitive reagents (p (o) -H compounds, carbon tetrachloride, sulfonyl chloride, etc.), and have the disadvantages of complicated experimental steps, expensive catalyst, difficult recycling, harsh reaction conditions, cross-reactivity of substrates, low yield, and great environmental pollution.
So far, the high-efficiency synthesis of 2-iodine-1-phosphoryl substituted alkane compounds still has the problems of raw material quality, production safety (the compounds such as phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like have strong corrosiveness) and stability, purity and the like of products, the synthesis technology has great difficulty, only a plurality of companies in countries such as the United states and the Japan are used for production at present, and the current situation of high-end organic phosphate products in China mainly depends on import.
Aiming at the defects of the existing synthesis process of 2-iodo-1-phosphoryl substituted alkane compounds, the industry is developing a method for efficiently and selectively synthesizing corresponding organic phosphate compounds by using stable, cheap and easily obtained P (O) -OH-containing compounds as raw materials.
Disclosure of Invention
The object of the present invention is to provide a method for producing a polymer with low cost and easy availabilityNThe method for synthesizing the corresponding 2-iodo-1-phosphoryl substituted alkane compound containing different substituted functional groups by promoting the double functionalization reaction of the P (O) -OH compound and the alkene compound with high efficiency and high selectivity by using the iodo-succinimide so as to overcome the defects in the prior art.
The invention provides a novel compound which is cheap and easily availableNThe method for synthesizing the corresponding 2-iodo-1-phosphoryl substituted alkane compound containing different functional group substitutions by promoting the P (O) -OH compound and the alkene compound to perform the bifunctional reaction with high efficiency and high selectivity by using the iodosuccinimide comprises the following steps: taking reaction amount of P (O) -OH compound, olefin, iodinating agent and organic solvent in N2Placing the mixture in a reaction container under protection for mixing, and stirring the mixture at 25 to 80 DEGoAnd reacting for 3-12 hours under the condition of C to obtain the corresponding 2-iodo-1-phosphoryl substituted alkane compound containing different functional groups. The specific reaction formula is as follows:
Figure 115872DEST_PATH_IMAGE001
wherein the content of the first and second substances,
R1is selected from phenyl, 4-methylphenyl, 4-bromophenyl, 3-bromophenyl, 2-bromophenyl, 4-fluorophenyl, benzyl, acetoxy, undecanoyl, 4-methoxyphenyl;
R2is hydrogen, methyl;
R3is phenyl, 4-methylphenyl, 3, 5-dimethylphenyl, 4-methoxyphenyl, 1-naphthyl, 2-naphthyl, 3-fluorophenyl, ethoxy, butoxy, benzyloxy, phenoxy;
R4is phenyl, methyl, 4-methylphenyl, 3, 5-dimethylphenyl, 4-methoxyphenyl, 1-naphthyl, 2-naphthyl, 3-fluorophenyl, ethoxy, butoxy, benzyloxy, phenoxy.
In the above method for efficiently bifunctional synthesis of a 2-iodo-1-phosphoryl-substituted alkane compound from a p (o) -OH compound and an olefin, the p (o) -OH compound in the reaction step is selected from diphenyl phosphate, bis (4-methyl-phenyl) phosphate, bis (3, 5-dimethyl-phenyl) phosphate, bis (4-methoxy-phenyl) phosphate, bis (1-naphthyl) phosphate, bis (2-naphthyl) phosphate, bis (3-fluoro-phenyl) phosphate, phenylmethyl phosphate, diethoxy phosphate, dibutoxy phosphate, dibenzyloxy phosphate, and diphenoxy phosphate.
In the method for efficiently bifunctional synthesis of 2-iodo-1-phosphoryl substituted alkane compound from P (O) -OH compound and olefin, the olefin compound in the reaction step is selected from styrene, 4-methylstyrene, 4-bromostyrene, 3-bromostyrene, 2-bromostyrene, 4-fluorostyrene, allyl benzene, vinyl acetate, vinyl undecanoate, 4-methoxystyrene, and 1-propenylbenzene.
In the method for synthesizing the 2-iodo-1-phosphoryl substituted alkane compound by efficiently bifunctional synthesis of the P (O) -OH compound and the olefin, the organic solvent refers to dichloromethane, dichloroethane, tetrahydrofuran, acetonitrile, toluene, or mixtures thereof,N, N-dimethylformamide, dimethyl sulfoxide, methanol, ethanol, 1, 4-dioxane, ethyl acetate.
In the method for synthesizing the 2-iodo-1-phosphoryl substituted alkane compound by efficiently bifunctional synthesis of the P (O) -OH compound and the olefin, the iodinating reagent refers toN-iodosuccinimide.
In the method for synthesizing the 2-iodo-1-phosphoryl substituted alkane compound by efficiently bifunctional synthesis of the P (O) -OH compound and the olefin, the molar ratio of the P (O) -OH compound to the olefin is 1: [ 1.0-2.0 ], wherein the molar ratio of the P (O) -OH compound to the iodinating agent is 1: [1.0 to 1.5 ].
The invention provides a method for synthesizing 2-iodo-1-phosphoryl substituted alkane compounds by promoting a bifunctional reaction of a P (O) -OH compound and an alkene compound to efficiently and selectively react by using an iodinating reagent, and the reaction process is mild and easy to control. The method is simple and easy to implement while obtaining higher yield and 100 percent selectivity, and the used accelerant is cheap and easy to obtain, the preparation is simple, and the method has good industrial application prospect.
[ detailed description ] embodiments
The invention is further illustrated below with reference to examples of the invention:
first, testing and analyzing
The structural analysis of the reaction products in the following examples of the present invention employed GC/MS (6890N/5973N) gas-mass spectrometer equipped with HP-5MS capillary chromatography column (30 m.times.0.45 mm.times.0.8 μm) manufactured by Agilent and Bruker Avance-III 500 NMR analyzer manufactured by Bruker. The selectivity and yield of the target product were analyzed by Agilent GC 7820A, a gas chromatograph equipped with a hydrogen flame detector, AB-FFAP capillary chromatography column (30 m. times.0.25 mm. times.0.25 μm), manufactured by Agilent.
Second, example
Example 1
0.5 mmol of diphenylphosphoric acid, 1.0 mmol of styrene and 0.6 mmol ofNIodosuccinimide (NIS) was added to a Schlenk tube under nitrogen and 1.0 mL of an organic solvent (dichloromethane, dichloroethane, tetrahydrofuran, acetonitrile, toluene, etc.),N, N-dimethylformamide, dimethyl sulfoxide, methanol, ethanol, 1, 4-dioxane, ethyl acetate) and stirred at room temperature for reaction for 12 hours. The yield of the bifunctional reaction was 66% when tetrahydrofuran was used as the reaction solvent, as analyzed by GC detection.
Example 2
0.5 mmol of diphenylphosphoric acid, 1.0 mmol of styrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere, at the indicated temperature (25)oC, 40 oC, 60 oC, 80 oC) The reaction was stirred for 12 hours. Analysis by GC detection at 40oAt C, the yield of the bifunctional reaction was 96%.
Example 3
0.5 mmol of diphenylphosphoric acid, styrene (0.5 mmol, 0.6 mmol, 0.75 mmol, 1.0 mmol) and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. The yield of the bifunctional reaction was 96% at a styrene content of 0.5 mmol, as determined by GC.
Example 4
0.5 mmol of diphenylphosphoric acid, 0.5 mmol of styrene andNiodo-succinimide (0.5 mmol, 0.6 mmol, 0.7 mmol)5 mmol, 1.0 mmol) under nitrogen were added to a Schlenk tube, and 1.0 mL of tetrahydrofuran under nitrogen were added at 40 deg.CoThe reaction was stirred for 12 hours at C. Analysis by GC detection inNThe yield of the bifunctional reaction was 96% when the amount of iodosuccinimide was 0.6 mmol.
Example 5
Preparation of 2-iodo-1- (4-methylphenyl) -ethyl diphenylphosphonate: 0.5 mmol of diphenyl phosphoric acid, 0.5 mmol of 4-methylstyrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with 88% yield can be obtained by column chromatography separation and purification.
Example 6
Preparation of 2-iodo-1- (4-bromophenyl) -ethyl diphenylphosphonate: 0.5 mmol of diphenyl phosphoric acid, 0.5 mmol of 4-bromostyrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with the yield of 85% can be obtained by column chromatography separation and purification.
Example 7
Preparation of 2-iodo-1- (3-bromophenyl) -ethyl diphenylphosphonate: 0.5 mmol of diphenyl phosphoric acid, 0.5 mmol of 3-bromostyrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with the yield of 92% can be obtained by column chromatography separation and purification.
Example 8
Preparation of 2-iodo-1- (2-bromophenyl) -ethyl diphenylphosphonate: 0.5 mmol of diphenyl phosphoric acid, 0.5 mmol of 2-bromostyrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with the yield of 90% can be obtained by column chromatography separation and purification.
Example 9
Preparation of 2-iodo-1- (4-fluorophenyl) -ethyl diphenylphosphonate: 0.5 mmol of diphenyl phosphoric acid, 0.5 mmol of 4-fluorostyrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with 86% yield can be obtained by column chromatography separation and purification.
Example 10
Preparation of 1-iodo-3-phenylpropyl-2-diphenylphosphonate: 0.5 mmol of diphenylphosphoric acid, 0.5 mmol of allylbenzene and 0.6 mmol of allylbenzene were mixedNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with the yield of 58% can be obtained by column chromatography separation and purification.
Example 11
Preparation of 2-iodo-1-phenylethyl-bis (4-methylphenyl) phosphonate: 0.5 mmol of bis (4-methyl-phenyl) phosphoric acid, 0.5 mmol of styrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with 89% yield can be obtained by column chromatography separation and purification.
Example 12
Preparation of 2-iodo-1-phenylethyl-bis (3-methylphenyl) phosphonate: 0.5 mmol of bis (3-methyl-phenyl) phosphoric acid, 0.5 mmol of styrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with the yield of 92% can be obtained by column chromatography separation and purification.
Example 13
Preparation of 2-iodo-1-phenylethyl-bis (3, 5-dimethylphenyl) phosphonate: 0.5 mmol of bis (3, 5-dimethyl-phenyl) phosphoric acid, 0.5 mmol of styrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with 89% yield can be obtained by column chromatography separation and purification.
Example 14
Preparation of 2-iodo-1-phenylethyl-bis (4-methoxyphenyl) phosphonate: 0.5 mmol of bis (4-methoxy-phenyl) phosphoric acid, 0.5 mmol of styrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with 83% yield can be obtained by column chromatography separation and purification.
Example 15
Preparation of 2-iodo-1-phenylethyl-di (1-naphthyl) phosphonate: 0.5 mmol of bis (1-naphthyl) phosphoric acid, 0.5 mmol of styrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with the yield of 80% can be obtained by column chromatography separation and purification.
Example 16
Preparation of 2-iodo-1-phenylethyl-di (2-naphthyl) phosphonate: 0.5 mmol of bis (2-naphthyl) phosphoric acid, 0.5 mmol of styrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with 78% yield can be obtained by column chromatography separation and purification.
Example 17
2-iodo-1-phenylethyl-bis (3-fluorophenyl)) Preparation of phosphonate ester: 0.5 mmol of bis (3-fluorophenyl) phosphoric acid, 0.5 mmol of styrene and 0.6 mmol ofNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with 68% yield can be obtained by column chromatography separation and purification.
Example 18
Preparation of 2-iodo-1-phenylethyl-phenylmethylphosphonate: 0.5 mmol of phenylmethylphosphoric acid, 0.5 mmol of styrene and 0.6 mmol of styreneNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with the yield of 85% can be obtained by column chromatography separation and purification.
Example 19
Preparation of diethyl (2-iodo-1-phenylethyl) phosphate: 0.5 mmol of diethoxyphosphoric acid, 0.5 mmol of styrene and 0.6 mmol of styreneNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with 89% yield can be obtained by column chromatography separation and purification.
Example 20
Preparation of dibutyl (2-iodo-1-phenylethyl) phosphate: 0.5 mmol of dibutoxyphosphoric acid, 0.5 mmol of styrene and 0.6 mmol of styrene were reactedNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with 77 percent of yield can be obtained by column chromatography separation and purification.
Example 21
Preparation of dibenzyl (2-iodo-1-phenylethyl) phosphate: 0.5 mmol of dibenzyloxyphosphoric acid, 0.5 mmol of styrene and 0.6 mmol of styrene are mixedNIodosuccinimide was added to a Schlenk tube under nitrogen atmosphere, protected with a nitrogen gas ring1.0 mL of tetrahydrofuran was added at ambient temperature at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with the yield of 75% can be obtained by column chromatography separation and purification.
Example 22
Preparation of diphenyl (2-iodo-1-phenylethyl) phosphate: 0.5 mmol of diphenoxyphosphoric acid, 0.5 mmol of styrene and 0.6 mmol of styreneNIodosuccinimide under nitrogen atmosphere into a Schlenk tube, 1.0 mL tetrahydrofuran under nitrogen atmosphere at 40oThe reaction was stirred for 12 hours at C. After the reaction is finished, the target product with the yield of 69% can be obtained by column chromatography separation and purification.
As can be seen from the above examples, the invention usesNThe method for preparing the corresponding 2-iodo-1-phosphoryl substituted alkane compound containing different functional group substitutions by promoting the efficient bifunctional reaction of the P (O) -OH compound and the alkene compound by the-iodosuccinimide has the advantages of mild reaction conditions, cheap and easily obtained accelerant, simple preparation and the like. In addition, the method also has the advantages of wide substrate applicability, high yield, high selectivity (100%) and the like, and provides a method for efficiently synthesizing the 2-iodo-1-phosphoryl substituted alkane compound containing different functional groups.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (4)

1. With R3(R4) The P (O) -OH compound and olefin are prepared by double functionalization（I）The preparation method of the 2-iodo-1-phosphoryl substituted alkane compound comprises the following steps:
Figure DEST_PATH_IMAGE001
（I）
the method is characterized by comprising the following steps:
get R3(R4) P (O) -OH compound, olefin, iodinating agent and organic solvent in N2Placing the mixture in a reaction container under protection for mixing, and stirring the mixture at 25 to 80 DEGoReacting for 3-12 hours under C to obtain corresponding 2-iodo-1-phosphoryl substituted alkane compounds containing different functional groups;
wherein the content of the first and second substances,
the iodinating agent isN-iodosuccinimide; r3(R4) The molar ratio of the P (O) -OH compound to the olefin is 1: [1.0 to 2.0 [ ]]；R3(R4) The molar ratio of the P (O) -OH compound to the iodinating agent is 1: [1.0 to 1.5]]；
R1Is selected from phenyl, 4-methylphenyl, 4-bromophenyl, 3-bromophenyl, 2-bromophenyl, 4-fluorophenyl, benzyl, acetoxy, undecanoyl, 4-methoxyphenyl;
R2is hydrogen, methyl;
R3is phenyl, 4-methylphenyl, 3, 5-dimethylphenyl, 4-methoxyphenyl, 1-naphthyl, 2-naphthyl, 3-fluorophenyl, ethoxy, butoxy, benzyloxy, phenoxy;
R4is phenyl, methyl, 4-methylphenyl, 3, 5-dimethylphenyl, 4-methoxyphenyl, 1-naphthyl, 2-naphthyl, 3-fluorophenyl, ethoxy, butoxy, benzyloxy, phenoxy.
2. The method according to claim 1, wherein the R-containing compound is3(R4) The P (O) -OH compound is selected from diphenyl phosphate, bis (4-methylphenyl) phosphate, bis (3, 5-dimethyl-phenyl) phosphate, bis (4-methoxyphenyl) phosphate, bis (1-naphthyl) phosphate, bis (2-naphthyl) phosphate, bis (3-fluoro-phenyl) phosphate, phenylmethyl phosphate, diethoxy phosphate, dibutoxy phosphate, dibenzyloxy phosphate,Diphenoxyphosphoric acid.
3. The method of claim 1, wherein the olefin is selected from the group consisting of styrene, 4-methylstyrene, 4-bromostyrene, 3-bromostyrene, 2-bromostyrene, 4-fluorostyrene, allylbenzene, vinyl acetate, vinyl undecanoate, 4-methoxystyrene, and 1-propenylbenzene.
4. The method according to claim 1, wherein the organic solvent is dichloromethane, dichloroethane, tetrahydrofuran, acetonitrile, toluene, or a mixture thereof,N, N-dimethylformamide, dimethyl sulfoxide, methanol, ethanol, 1, 4-dioxane, ethyl acetate.
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