CN106397507B - 2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside - Google Patents

2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside Download PDF

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CN106397507B
CN106397507B CN201610791565.5A CN201610791565A CN106397507B CN 106397507 B CN106397507 B CN 106397507B CN 201610791565 A CN201610791565 A CN 201610791565A CN 106397507 B CN106397507 B CN 106397507B
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陈梦莹
梁洪泽
梁炜达
陈浩
朱文明
黄会燕
陆震宇
陈伟婷
李咏梅
赵玲玲
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Ningbo University
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Abstract

The present invention relates to the field of chemical synthesis, specifically disclose 2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside.It is using four acetylation fucoses and the bromo- 2- mercaptopyridine of 5- as starting material; to contain phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid as reaction medium; using lewis' acid as catalyst; under microwave irradiation; it carries out glycosylation reaction and is prepared 2; 3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside, then 1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside is obtained through hydrolysis.The starting material for preparing 1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside is relatively cheap, and synthesizing mean is simple, quick, and functionalized ion liquid used may be reused, and substantially reduce cost.

Description

2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyrans Glucosides
Technical field
The present invention relates to chemosynthesis technical field more particularly to 2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) mercaptos Base-α-L- rock algae pyranoside.
Background technique
Saccharide compound and protein, nucleic acid form important living matter.With the development of modern science and technology, related sugar The research of compound also achieves very big development.Correlative study be further differentiated into carbohydrate chemistry, sugared materia medica, glycobiology, Sugar engineering, Tang Zuxuedeng branch field.Sugar is not only energy substance, prior closely related with life process.Sugar can As biological information molecule, multiple processes such as Organism immunoregulation, cell differentiation, embryonic development are participated in.Containing pyridine groups and Sulfur-containing compound has bioactivity, has pyridine structure in a variety of drugs, pesticide and contains element sulphur.Design synthesis and This kind of compound is researched and developed to have great importance and application prospect.
Traditional glucosides synthetic method (such as Chinese patent 95118925.5,201010101523.7 etc.) has the following problems: The factors such as poor repeatability, stereoselectivity are poor, synthetic route is cumbersome, the prices of raw materials are more expensive or intermediate is unstable, it is difficult to Meet the requirement of purity and scale market, it is therefore desirable to research and develop new synthetic method.In glycosylation reaction, lewis Acid catalysis is commonly used method, and reaction medium is generally molecule-type organic solvent.Due to the space of lewis' acid metal salt Steric hindrance is small, during being catalyzed glycosylation, it is difficult to adequately be regulated and controled to glycosylation stereoselectivity.Therefore, in tradition Catalyst system in, in most cases, stereoselectivity is not satisfactory.It must be able to adjust catalyst center space environment Control, is possible to improve glycosylation stereoselectivity.On the other hand, green solvent ionic liquid developed in recent years, It is used to substitution conventional molecular type organic solvent, used in chemically reacting.Due to the polarity of reaction medium, from neutral or pole Property molecule-type become ionic so that glycosylation reaction mechanism is more rich and varied, provided more for optimization reaction condition Selection.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of compound, specially 2,3,4- triacetyl -1- The synthetic method of (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside and hydrolysate.
The specific technical solution of the present invention is as follows:
2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside has knot shown in Formulas I Structure:
1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside (5-BPT-AFU) has structure shown in Formula II:
1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside can be used as a kind of new fucoside zymolyte.
The present invention also provides the preparation sides of above compound 1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside Method, synthetic technology route are as follows:
Using four acetylation fucoses and the bromo- 2- mercaptopyridine of 5- as starting material, with containing phosphinylidyne polymerization of olefin using catalyst functionalization from Sub- liquid is reaction medium, using lewis' acid as catalyst, under microwave irradiation, carries out glycosylation reaction and is prepared 2,3,4- Triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside, then 1- (5- bromo-2-pyridyl base) is obtained through hydrolysis Sulfydryl-α-L- rock algae pyranoside.
Wherein, the molar ratio of four acetylation fucose of raw material and the bromo- 2- mercaptopyridine of 5- be 1:1~5, preferably 1:1~ 3, it is further 1:1.
Phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid (PFIL) of the present invention is the quaternary ammonium salt (PFIL-1) of having structure, season Microcosmic salt (PFIL-2), pyridiniujm (PFIL-3), imidazole salts (PFIL-4), one in double phosphoryl functionalized imidazoles (PFIL-5) Kind or a variety of mixtures:
Wherein, R1, R2, R3, R4=hydrogen, alkyl, alkoxy, aryl；N=1,2,3,4,5,6；X=(CF3SO2) N, PF6。
Preferably, R1, R2, R3, R4For hydrogen, methyl, ethyl, propyl, butyl, amyl, hexyl, alkoxy, phenyl.
As a preferred embodiment, ion liquid of quaternaries (PFIL-1), preferably R in the present invention1、R2=second Oxygroup, phenyl；R3=ethyl, propyl, butyl.Preparation method is as follows, by triethylamine, tripropyl amine (TPA), tri-n-butylamine or triamylamine with Bromo alkyl diphenyl phosphine oxide or bromo alkyl ethoxy phenyl phosphine oxide are 1: 1~1.2 mixing in molar ratio, are added organic Solvent is placed in microwave reaction device, is 350W~500W in microwave power, reaction temperature is 80 DEG C~110 DEG C, when reaction Between to be stirred to react under conditions of 60min~150min, obtain crude product, remove unreacting material, obtain quaternary ammonium bromide ion Liquid.By the bis trifluoromethyl imine lithium or hexafluorophosphoric acid nak response of obtained quaternary ammonium bromide ionic liquid and equimolar amounts, obtain To the ion liquid of quaternaries (PFIL-1), structure is as shown in formula III.
Quaternary phosphonium salt ionic liquid (PFIL-2), preferably R in the present invention1、R2=ethyoxyl, phenyl；R3=phenyl.It is made Preparation Method is as follows: by triphenylphosphine and bromo alkyl diphenyl phosphine oxide, bromo alkyl phenyl-phosphonic acid ethyl ester or bromo alkylphosphines Diethyl phthalate is 1: 1~1.2 mixing in molar ratio, and organic solvent is added, is placed in microwave reaction device, is in microwave power 350W~500W, reaction temperature are 80 DEG C~110 DEG C, and the reaction time to be stirred to react under conditions of 60min~150min, obtains Crude product removes unreacting material, obtains quaternary phosphonium bromide ionic liquid.The quaternary phosphonium bromide ionic liquid and equimolar amounts that will be obtained Bis trifluoromethyl imine lithium or hexafluorophosphoric acid nak response, obtain the quaternary phosphonium salt ionic liquid (PFIL-2), structure such as formula Shown in IV.
Pyridine salt ionic liquid (PFIL-3), preferably R in the present invention1、R2=ethyoxyl, phenyl.Preparation method is such as Under, by pyridine compounds and their and bromo alkyl diphenyl phosphine oxide, bromo alkyl phenyl-phosphonic acid ethyl ester or bromo alkyl phosphonic acid two Ethyl ester is 1: 1~1.2 mixing in molar ratio, and organic solvent is added, is placed in microwave reaction device and is stirred to react, microwave power For 350W~500W, reaction temperature is 80 DEG C~110 DEG C, and the reaction time is 60min~150min, obtains crude product, is removed not Reaction raw materials obtain pyridinium tribromide ionic liquid.By the bis trifluoromethyl of obtained pyridinium tribromide ionic liquid and equimolar amounts Imine lithium or hexafluorophosphoric acid nak response obtain the pyridine salt ionic liquid (PFIL-3), and structure is shown as a formula V.
Imidazolium ionic liquid (PFIL-4), preferably R in the present invention1=methyl, ethyl, propyl, butyl, amyl, hexyl； R2=hydrogen；R3、R4=ethyoxyl, phenyl.Preparation method is as follows: by glyoxaline compound and bromo alkyl diphenyl phosphine oxide, Bromo alkyl phenyl-phosphonic acid ethyl ester or bromo alkyl diethyl phosphonate are 1: 1~1.2 mixing in molar ratio, are placed in microwave reaction It is 280W~500W in microwave power in device, reaction temperature is 80 DEG C~120 DEG C, and the reaction time is 60min~150min, Crude product is obtained, unreacting material is removed, obtains imidazoles bromide ionic liquid.By obtained imidazoles bromide ionic liquid with etc. rub The bis trifluoromethyl imine lithium or hexafluorophosphoric acid nak response of your amount, obtain the imidazole salt ionic liquid (PFIL-4), structure As shown in Formula IV.
Double phosphoryl functionalized imidazole ionic liquids (PFIL-5), preferably R in the present invention1、R2=ethyoxyl, phenyl.'s The preparation method is as follows: by imidazoles and bromo alkyl diphenyl phosphine oxide, bromo alkyl phenyl-phosphonic acid ethyl ester or bromo alkyl phosphonic acid Diethylester is dissolved in organic solvent with the molar ratio of 1:2~4, adds water soluble carbonate, is then placed into microwave reaction dress Middle carry out microwave reaction is set, microwave power is 280~500W, and reaction temperature is 80~110 DEG C, and the reaction time is 5~40min, Crude product is obtained after reaction, removes unreacted raw material, anion exchanger is added in the crude product, carries out anion exchange, Double phosphoryl functionalized imidazole ionic liquids (PFIL-5) are obtained, structure is as shown in Formula VII.
The lewis' acid include nickel salt, mantoquita, molysite, pink salt or scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, Dysprosium, holmium, erbium, ytterbium, lutetium salt.
The salt includes villaumite, sulfate, nitrate, fluoroform sulphonate or hexafluorophosphate.
For example, lewis' acid is ferric trichloride, tin tetrachloride, ytterbium nitrate, trifluoromethanesulfonic acid neodymium etc. in the present invention.
The present invention is catalyzed reaction in microwave-assisted lower progress.The power that microwave can be adjusted according to the degree of reaction is timely Between.In the present invention, microwave power is preferably 200~700W, is further 300~600W, further for 350~ 500W.In a preferred embodiment of the present invention, it is irradiated using intermittent type microwave, i.e. 3~10min of irradiation, rests 0.5~2min Circulation irradiation.4~8min is preferably irradiated, rests 1~1.5min.Catalytic temperature be 35 DEG C~90 DEG C, preferably 40 DEG C~ 60 DEG C, be further 45 DEG C~55 DEG C.
It further include alkyl chloride in reaction medium, i.e., with phosphinylidyne polymerization of olefin using catalyst functionalization in above-mentioned catalysis reaction of the invention The mixed solvent of ionic liquid and chloralkane is as reaction medium.Wherein, chloralkane is methylene chloride, chloroform and 1, One of 2- dichloroethanes or a variety of mixtures.The present invention does not limit phosphoryl coordination functionalized ion liquid and alkyl chloride The usage ratio of hydrocarbon, using the arbitrary proportion containing phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid protection scope of the present invention it It is interior.It is preferred that the volume ratio of phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid and chloralkane be 0.2~0.8:10~20, further for 0.3~0.7:13~18 are further 0.5:15.
It further include general ionic liquid in reaction medium, i.e., with phosphinylidyne polymerization of olefin using catalyst in above-mentioned catalysis reaction of the invention The mixed solvent of general ionic liquid in functionalized ion liquid and this field is as reaction medium.Wherein general ionic liquid For commercial goods dialkylimidazolium salt, the alkyl of the dialkylimidazolium salt be methyl, ethyl, propyl, butyl, amyl, oneself Base, the anion of the dialkylimidazolium salt are bis trifluoromethyl imines ion or hexafluorophosphate ion.The present invention does not limit phosphorus Acyl group be coordinated functionalized ion liquid and general ionic liquid usage ratio, using contain phosphinylidyne polymerization of olefin using catalyst functionalization ionic liquid The arbitrary proportion of body is within the scope of the present invention.It is preferred that phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid and conventional ion liquid The volume ratio of body is 1:1~20, is further 1:4~10, is further 1:5.
The lower reaction of catalysis obtains 2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside Afterwards, 2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside is preferably in the first containing sodium methoxide Hydrolysis obtains 1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside in alcohol.1- (the 5- bromo-2-pyridyl being prepared Base) sulfydryl-α-L- rock algae pyranoside can be used as substrate and is used to prepare fucosidase diagnostic reagent.
Beneficial effects of the present invention are as follows:
(1) present invention is complexed with lewis' acid catalyst metals center using coordination functionalized ion liquid, is passed through change Functionalized ion liquid structure, to regulate and control the steric hindrance size of metal ion center, to change the solid of glycosylation reaction Selectivity；
(2) microwave heating reaction be material in electromagnetic field since dielectric loss generates fuel factor, have heating response it is fast, The features such as being heated simultaneously inside and outside substance.And ionic liquid has very high polarizability, is a kind of good microwave absorbing material.By same When use microwave heating technique and ion liquid medium, accelerate heating speed, make reaction more evenly, it is high-efficient.
(3) functionalized ion liquid used in is not only used as reaction medium, but also as metal-ion ligand, has both two kinds of functions.
The starting material of 1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside preparation method of the invention is opposite Cheaply, synthesizing mean is simple, quick.2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae of the invention Used functionalized ion liquid may be reused pyranoside during the preparation process, further reduce costs.With 1- (5- Bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside cost for preparing fucosidase diagnostic reagent as substrate is low, Be conducive to effective universal use of fucosidase diagnostic reagent.
Specific embodiment
Below in conjunction with the embodiment in the present invention, technical solution in the embodiment of the present invention is carried out clearly and completely Description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this hair Embodiment in bright, every other reality obtained by those of ordinary skill in the art without making creative efforts Example is applied, shall fall within the protection scope of the present invention.
In following embodiment, for convenience's sake, by 2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- Rock algae pyranoside is denoted as glucosides 1, and 1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside is denoted as glucosides 2.
The preparation of embodiment 1:2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside
0.486 gram of FeCl is weighed respectively3, four 0.33 gram of acetylation fucoses, 0.19 gram of the bromo- 2- mercaptopyridine of 5-, Yu Ping In row reaction tube.10mL methylene chloride, ionic liquid PFIL-1 [R are separately added under nitrogen atmosphere1,R2,R3=ethyl, n=3, X= (CF3SO2)2N] 0.5mL, confined reaction test tube is stirred to react, and microwave irradiation uses intermittent, power 350W, every time 5 points of irradiation Clock stops irradiation 1 minute.Reaction 5 hours, temperature are controlled in 40 degrees centigrades.End of reaction adds water to terminate reaction.Through silica gel Chromatography post separation obtains 0.25 gram of glucosides 1, yield 50%.Mass spectrum (positive ion mode): m/z 462.02 (M+H)+.Ionic liquid Body is reusable, and yield is without significant change.
The preparation of embodiment 2:2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside
Four 0.33 gram of acetylation fucoses, 0.19 gram of the bromo- 2- mercaptopyridine of 5-, in parallel reaction pipe.Lower point of nitrogen atmosphere Not Jia Ru 10mL chloroform, ionic liquid PFIL-3 [R1,R2=phenyl, n=3, X=(CF3SO2)2N] 1mL and 0.345mL Anhydrous SnCl4, confined reaction test tube is stirred to react, and microwave irradiation uses intermittent, power 400W, and irradiation 5 minutes, stop every time Only irradiate 1 minute.Reaction 3 hours, temperature are controlled in 60 degrees centigrades.End of reaction adds water to terminate reaction.Through silica gel chromatograph Post separation obtains 0.258 gram of glucosides 1, yield 56%.Ionic liquid is reusable, and yield is without significant change.
The preparation of embodiment 3:2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside
0.591 gram of Nd (OTf) is weighed respectively3, four 0.33 gram of acetylation fucoses, 0.19 gram of the bromo- 2- mercaptopyridine of 5-, in In parallel reaction pipe.10mL1,2- dichloroethanes, ionic liquid PFIL-2 [R are separately added under nitrogen atmosphere1,R2,R3=phenyl, n =4, X=(CF3SO2)2N] 0.5mL, confined reaction test tube is stirred to react, and microwave irradiation uses intermittent, power 500W, every time Irradiation 5 minutes stops irradiation 1 minute.Reaction 5 hours, temperature are controlled in 80 degrees centigrades.It is anti-that end of reaction adds water to terminate It answers.Through silica gel chromatograph post separation, 0.336 gram of glucosides 1, yield 73% are obtained.Ionic liquid is reusable, and yield becomes without obvious Change.
The preparation of embodiment 4:2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside
0.391 gram of Yb (NO is weighed respectively3)3, four 0.33 gram of acetylation fucoses, 0.19 gram of the bromo- 2- mercaptopyridine of 5-, in In parallel reaction pipe.Ionic liquid PFIL-4 [R is added under nitrogen atmosphere1=propyl, R2=hydrogen, R3、R4=ethyoxyl, n=5, X= PF6] 3mL, confined reaction test tube is stirred to react, and microwave irradiation uses intermittent, power 500W, every time irradiation 5 minutes, stops Irradiation 1 minute.Reaction 5 hours, temperature are controlled in 40 degrees centigrades.End of reaction adds water to terminate reaction.Through silica gel chromatographic column Separation, obtains 0.327 gram of glucosides 1, yield 71%.Ionic liquid is reusable, and yield is without significant change.
The preparation of embodiment 5:2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside
0.30 gram of ScCl is weighed respectively3, four 0.33 gram of acetylation fucoses, 0.19 gram of the bromo- 2- mercaptopyridine of 5-, Yu Pinghang In reaction tube.Ionic liquid PFIL-5 [R is added under nitrogen atmosphere1、R2=ethyoxyl, n=3, X=(CF3SO2)2N] 3mL is closed anti- Test tube is answered, is stirred to react, microwave irradiation uses intermittent, power 350W, every time irradiation 5 minutes, stops irradiation 1 minute.Reaction 5 Hour, temperature is controlled in 40 degrees centigrades.End of reaction adds water to terminate reaction.Through silica gel chromatograph post separation, 0.318 gram is obtained Glucosides 1, yield 69%.Ionic liquid is reusable, and yield is without significant change.
The preparation of embodiment 6:2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside
0.30 gram of ScCl is weighed respectively3, four 0.33 gram of acetylation fucoses, 0.19 gram of the bromo- pyridine of 5-, in parallel reaction pipe In.Ionic liquid PFIL-5 [R is added under nitrogen atmosphere1、R2=ethyoxyl, n=3, X=(CF3SO2)2N] 2mL and conventional ion liquid Body 3- butyl -1- methylimidazole hexafluorophosphate 2mL, confined reaction test tube are stirred to react, and microwave irradiation uses intermittent, function Rate 350W, irradiation 5 minutes, stop irradiation 1 minute every time.Reaction 5 hours, temperature are controlled in 40 degrees centigrades.End of reaction Water is added to terminate reaction.Through silica gel chromatograph post separation, 0.304 gram of glucosides 1, yield 66% are obtained.Ionic liquid is reusable, receives Rate is without significant change.
The preparation of embodiment 7:1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside
0.92 gram of glucosides 1 is taken, is added in the 20mL methanol containing 0.1 gram of sodium methoxide, after reaction being stirred at room temperature 1 hour, Stop reaction.After silica gel column chromatography separates, 0.56 gram of 2 compound of glucosides, yield 84% are obtained.Mass spectrum (positive ion mode): m/z 335.99(M+H)+。
Above embodiment, which is intended to illustrate the present invention, to be realized or use for professional and technical personnel in the field, to above-mentioned Embodiment, which is modified, will be readily apparent to those skilled in the art, therefore the present invention includes but is not limited to Above embodiment, it is any to meet the claims or specification description, meet with principles disclosed herein and novelty, The method of inventive features, technique, product, fall within the scope of protection of the present invention.

Claims (3)

  1. The preparation method of 1.2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside, feature It is, using four acetylation fucoses and the bromo- 2- mercaptopyridine of 5- as starting material, to contain phosphinylidyne polymerization of olefin using catalyst functionalization ionic liquid Body is reaction medium, using lewis' acid as catalyst, under microwave irradiation, carries out glycosylation reaction and 2,3,4- tri- second are prepared Acyl group -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside；The phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid is tool There is the ion liquid of quaternaries of structure shown in formula III, the quaternary phosphonium salt ionic liquid with structure shown in formula IV, there is Formula V The pyridine salt ionic liquid of shown structure, the imidazole salt ionic liquid with structure shown in Formula IV and have shown in Formula VII One of double phosphoryl functionalized imidazoles of structure or a variety of mixtures:
    Wherein, R1, R2, R3, R4 are hydrogen, methyl, ethyl, propyl, butyl, amyl, hexyl, alkoxy, phenyl；N=1,2,3, 4,5,6；X=(CF3SO2) N, PF6；
    The lewis' acid be nickel salt, mantoquita, molysite, pink salt or scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, Erbium, ytterbium, lutetium salt；
    The salt is villaumite, sulfate, nitrate, fluoroform sulphonate or hexafluorophosphate；
    Described 2,3,4- triacetyl -1- (5- bromo-2-pyridyl base) sulfydryl-α-L- rock algae pyranoside has knot shown in Formulas I Structure:
  2. 2. the method according to claim 1, wherein the reaction medium contains phosphinylidyne polymerization of olefin using catalyst functionalization ion Liquid and chloralkane.
  3. 3. the method according to claim 1, wherein the reaction medium contains phosphinylidyne polymerization of olefin using catalyst functionalization ion Liquid and with dialkylimidazolium salt, the alkyl of the dialkylimidazolium salt is methyl, ethyl, propyl, butyl, amyl, hexyl, institute The anion for stating dialkylimidazolium salt is bis trifluoromethyl imines ion or hexafluorophosphate ion.
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