CN106496291A - 2,3,4 triacetyl, 1 (6 methyl, 5 nitro, 2 pyridine radicals) sulfydryl alpha L rock algae pyranosides and the synthesis of hydrolyzate - Google Patents
2,3,4 triacetyl, 1 (6 methyl, 5 nitro, 2 pyridine radicals) sulfydryl alpha L rock algae pyranosides and the synthesis of hydrolyzate Download PDFInfo
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Abstract
The present invention relates to the field of chemical synthesis, specifically discloses the synthetic method of 2,3,4 triacetyl, 1 (6 methyl, 5 nitro, 2 pyridine radicals) sulfydryl alpha L rock algae pyranosides and hydrolyzate.Which is with four acetylation fucosees and 6 methyl, 5 nitro, 2 mercaptopyridine as initiation material; to contain phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid as reaction medium; with lewis' acid as catalyst; under microwave exposure; carry out glycosylation reaction and prepare 2; 3,4 triacetyl 1 (6 methyl, 5 nitro, 2 pyridine radicals) sulfydryl alpha L rock algae pyranosides, then 1 (6 methyl, 5 nitro, 2 pyridine radicals) sulfydryl alpha L rock algae pyranosides are obtained through hydrolysis.The initiation material for preparing 1 (6 methyl, 5 nitro, 2 pyridine radicals) sulfydryl alpha L rock algae pyranosides is relatively cheap, and synthesizing mean is simple, quick, and functionalized ion liquid used can be reused, and substantially reduce cost.
Description
Technical field
The present invention relates to chemosynthesis technical field, more particularly to 2,3,4- triacetyl -1- (6- methyl-5-nitro -2-
Pyridine radicals) sulfydryl-alpha-L- rock algae pyranosides, its hydrolyzate and preparation method.
Background technology
Saccharide compound constitutes important living matter with protein, nucleic acid.With the development of modern science and technology, relevant sugar
The research of compound also achieves very big development.Correlational study be further differentiated into carbohydrate chemistry, sugared materia medica, glycobiology,
Sugar engineering, Tang Zuxuedeng branches 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, fetal development are participated in.Containing pyridine groups and
Sulfur-containing compound, with biological activity, has pyridine structure in multi-medicament, pesticide and contains element sulphur.Design synthesis and
Research and develop this kind of compound to have great importance and application prospect.
There is problems with traditional glucosides synthetic method (such as Chinese patent 95118925.5,201010101523.7 etc.)：
The factor such as poor repeatability, stereo selectivity 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 in purity and scale market, it is therefore desirable to research and develop new synthetic method.In glycosylation reaction, lewis
Acid catalysiss are the methods being most frequently with, and reaction medium is generally molecule-type organic solvent.Space due to lewis' acid slaine
Steric hindrance is little, during catalysis is glycosylation, it is difficult to which glycosylation stereo selectivity is sufficiently regulated and controled.Therefore, in tradition
Catalyst system and catalyzing in, in most cases, stereo selectivity is not satisfactory.Must be able to adjust catalyst center spatial environmentss
Control, is possible to improve glycosylation stereo selectivity.On the other hand, green solvent ionic liquid developed in recent years,
Through be used to substitute conventional molecular type organic solvent, for chemical reaction in.Due to the polarity of reaction medium, from neutral or pole
Property molecule-type become ion-type so that glycosylation reaction mechanism is more rich and varied, for optimize reaction condition provide more
Selection.
Content of the invention
For problems of the prior art, the present invention provides a kind of compound, specially 2,3,4- triacetyl -1-
(6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyranosides and the synthetic method of hydrolyzate.
Specific technical scheme of the invention is as follows：
2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyranosides, tool
There is structure shown in Formulas I：
1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rocks algae pyranoside (6-M-5-NPT-AFU), tool
There is structure shown in Formula II：
1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algaes pyranosides can be used as a kind of new rock algae
Glucosides zymolyte.
The present invention also provides above-claimed cpd 1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyrans
The preparation method of glucosides, its synthetic technology route are as follows：
With four acetylation fucosees and 6- methyl-5-nitro -2- mercaptopyridines as initiation material, to contain phosphinylidyne polymerization of olefin using catalyst
Functionalized ion liquid is reaction medium, with lewis' acid as catalyst, under microwave exposure, carries out glycosylation reaction and is prepared into
To 2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyranosides, then through hydrolysis
Obtain 1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyranosides.
Wherein, the mol ratio of four acetylation fucose of raw material and 6- methyl-5-nitro -2- mercaptopyridines is 1：1～5, excellent
Elect 1 as:1～3, it is further 1:1.
Phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid (PFIL) of the present invention quaternary ammonium salt (PFIL-1), season for having structure
In microcosmic salt (PFIL-2), pyridiniujm (PFIL-3), imidazole salts (PFIL-4), double phosphoryl functionalized imidazoles (PFIL-5) one
Plant or multiple mixture：
Wherein, R1, R2, R3, R4=hydrogen, alkyl, alkoxyl, aryl；N=1,2,3,4,5,6；X=(CF3SO2) N, PF6.
Preferably, R1, R2, R3, R4For hydrogen, methyl, ethyl, propyl group, butyl, amyl group, hexyl, alkoxyl, phenyl.
As one kind preferred embodiment, ion liquid of quaternaries (PFIL-1) in the present invention, preferably R1、R2=second
Epoxide, phenyl；R3=ethyl, propyl group, butyl.Its 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, add organic
Solvent, is positioned in microwave reaction device, is 350W～500W in microwave power, and reaction temperature is 80 DEG C～110 DEG C, during reaction
Between for stirring reaction under conditions of 60min～150min, obtain crude product, remove unreacting material, obtain quaternary ammonium bromide ion
Liquid.By the quaternary ammonium bromide ionic liquid for obtaining and the bis trifluoromethyl imine lithium or hexafluorophosphoric acid nak response of equimolar amountss, obtain
The ion liquid of quaternaries (PFIL-1) is arrived, 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.Which 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, adds organic solvent, is positioned in microwave reaction device, in microwave power is
350W～500W, reaction temperature are 80 DEG C～110 DEG C, and the response time is stirring reaction under conditions of 60min～150min, obtains
Crude product, removes unreacting material, obtains quaternary phosphonium bromide ionic liquid.By the quaternary phosphonium bromide ionic liquid for obtaining and equimolar amountss
Bis trifluoromethyl imine lithium or hexafluorophosphoric acid nak response, obtain 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.Its 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, adds organic solvent, is positioned over stirring reaction in microwave reaction device, microwave power
For 350W～500W, reaction temperature is 80 DEG C～110 DEG C, and the response time is 60min～150min, obtains crude product, removes not
Reaction raw materials, obtain pyridinium tribromide ionic liquid.By the pyridinium tribromide ionic liquid for obtaining and the bis trifluoromethyl of equimolar amountss
Imine lithium or hexafluorophosphoric acid nak response, obtain 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 group, butyl, amyl group, hexyl；
R2=hydrogen；R3、R4=ethyoxyl, phenyl.Its 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 positioned over microwave reaction
In device, it is 280W～500W in microwave power, reaction temperature is 80 DEG C～120 DEG C, and the response time is 60min～150min,
Crude product is obtained, unreacting material is removed, is obtained imidazoles bromide ionic liquid.By the imidazoles bromide ionic liquid for obtaining with etc. rub
The bis trifluoromethyl imine lithium or hexafluorophosphoric acid nak response of your amount, obtains imidazole salt ionic liquid (PFIL-4), structure
As shown in Formula IV.
Double phosphoryls functionalized imidazole ionic liquid (PFIL-5), preferably R in the present invention1、R2=ethyoxyl, phenyl.'s
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 with 1:2～4 mol ratio is dissolved in organic solvent, adds water soluble carbonate, is then placed into microwave reaction dress
Microwave reaction is carried out in putting, and microwave power is 280～500W, and reaction temperature is 80～110 DEG C, and the response time is 5～40min,
Crude product is obtained after reaction, unreacted raw material is removed, and is added anion exchanger in the crude product, is carried out anion exchange,
Described double phosphoryl functionalized imidazole ionic liquid (PFIL-5) is obtained, structure is as shown in Formula VII.
The lewis' acid includes nickel salt, mantoquita, iron salt, pink salt, or scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium,
Dysprosium, holmium, erbium, ytterbium, the salt of lutecium.
The salt includes villaumite, sulfate, nitrate, fluoroform sulphonate or hexafluorophosphate.
For example, in the present invention, lewis' acid is ferric chloride, butter of tin, Ytterbium(III) nitrate., trifluoromethanesulfonic acid neodymium etc..
The catalytic reaction of the present invention is carried out under microwave-assisted.Can be timely according to the power of the degree of reaction adjustment microwave
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, using intermittent type microwave irradiation, i.e. 3～10min of irradiation rests 0.5～2min
Circulation irradiation.Preferably 4～8min of irradiation, 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.
In the above-mentioned catalytic reaction of the present invention, also include alkyl chloride in reaction medium, i.e., with phosphinylidyne polymerization of olefin using catalyst functionalization
The mixed solvent of ionic liquid and chloralkane is used as reaction medium.Wherein, chloralkane is dichloromethane, chloroform and 1,
The mixture of one or more in 2- dichloroethanes.The present invention does not limit phosphinylidyne polymerization of olefin using catalyst 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
Interior.It is preferred that phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid is 0.2～0.8 with the volume ratio of chloralkane：10～20, further for
0.3～0.7：13～18, it is further 0.5：15.
In the above-mentioned catalytic reaction of the present invention, also include general ionic liquid in reaction medium, i.e., with phosphinylidyne polymerization of olefin using catalyst
The mixed solvent of the general ionic liquid in functionalized ion liquid and this area is used as reaction medium.Wherein general ionic liquid
For commercial goods dialkylimidazolium salt, the alkyl of the dialkylimidazolium salt be methyl, ethyl, propyl group, butyl, amyl group, oneself
Base, the anion of the dialkylimidazolium salt is bis trifluoromethyl imines ion, or hexafluorophosphate ion.The present invention does not limit phosphorus
Acyl group coordination functionalized ion liquid and the usage ratio of general ionic liquid, adopt and contain phosphinylidyne polymerization of olefin using catalyst functionalization ionic liquid
The arbitrary proportion of body is within protection 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, it is further 1：4～10, it is further 1：5.
The lower reaction of catalysis obtains 2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L-
After rock algae pyranoside, 2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyrans
Glucosides is hydrolyzed preferably in the methanol containing Feldalat NM and obtains 1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rocks
Algae pyranoside.1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyranosides for preparing can be made
It is used for preparing fucosidase diagnostic reagent for substrate.
Beneficial effects of the present invention are as follows：
(1), using coordination functionalized ion liquid, and lewis' acid catalyst metals center complexation, by changing for the present invention
Functionalized ion liquid structure, regulates and controls the sterically hindered size of metal ion center, so as to change the solid of glycosylation reaction
Selectivity；
(2) microwave heating reaction be material in electromagnetic field as dielectric loss produces heat effect, with heating response fast,
Material is inside and outside while the features such as heating.And ionic liquid has very high polarizability, it is a kind of good microwave absorbing material.By same
When using microwave heating technique and ion liquid medium, accelerate firing rate, make reaction evenly, efficiency high.
(3) functionalized ion liquid used by is both as reaction medium, and as metal-ion ligand, has two kinds of functions concurrently.
1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyranoside preparation methoies of the present invention
Initiation material is relatively cheap, and synthesizing mean is simple, quick.2,3,4- triacetyl -1- (6- methyl-5-nitro-the 2- of the present invention
Pyridine radicals) sulfydryl-alpha-L- rock algae pyranosides functionalized ion liquid used in preparation process can reuse,
Reduce further cost.Using 1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyranosides the bottom of as
The cost that thing prepares fucosidase diagnostic reagent is low, is conducive to effective popularization of fucosidase diagnostic reagent to use.
Specific embodiment
Embodiment in below in conjunction with the present invention, to the embodiment of the present invention in technical scheme carry out clearly and completely
Description, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiment.It is based on this
Embodiment in bright, the every other enforcement obtained under the premise of creative work is not made by those of ordinary skill in the art
Example, belongs to the scope of protection of the invention.
In following examples, for convenience's sake, by 2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals)
Sulfydryl-alpha-L- rock algae pyranosides are designated as glucosides 1,1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rocks
Algae pyranoside is designated as glucosides 2.
Embodiment 1：2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyrroles
Mutter the preparation of glucosides
0.486 gram FeCl is weighed respectively3, four 0.33 gram of acetylation fucosees, 6- methyl-5-nitro -2- mercaptopyridines
0.17 gram, in parallel reaction pipe.10mL dichloromethane, ionic liquid PFIL-1 [R is separately added under blanket of nitrogen1,R2,R3=second
Base, n=3, X=(CF3SO2)2N] 0.5mL, confined reaction test tube, stirring reaction, microwave exposure adopt batch (-type), power 350W,
Irradiation 5 minutes, stops irradiation 1 minute every time.Reaction 5 hours, temperature control is in 40 degrees centigrades.Reaction finishes the termination that adds water
Reaction.Through silica gel chromatography post separation, 0.23 gram of glucosides 1, yield 52% is obtained.Ionic liquid is reusable, and yield is without obvious
Change.
Embodiment 2：2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyrroles
Mutter the preparation of glucosides
Four 0.33 gram of acetylation fucosees, 0.17 gram of 6- methyl-5-nitro -2- mercaptopyridines, in parallel reaction pipe.Nitrogen
10mL chloroform, ionic liquid PFIL-3 [R is separately added under atmosphere1,R2=phenyl, n=3, X=(CF3SO2)2N] 1mL with
And the anhydrous SnCl of 0.345mL4, confined reaction test tube, stirring reaction, microwave exposure adopt batch (-type), power 400W, each irradiation
5 minutes, stop irradiation 1 minute.Reaction 3 hours, temperature control is in 60 degrees centigrades.Reaction finishes the terminating reaction that adds water.Through
Silica gel chromatography post separation, obtains 0.256 gram of glucosides 1, yield 58%.Ionic liquid is reusable, and yield is without significant change.
Embodiment 3：2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyrroles
Mutter the preparation of glucosides
0.591 gram Nd (OTf) is weighed respectively3, four 0.33 gram of acetylation fucosees, 6- methyl-5-nitro -2- mercaptopyridines
0.17 gram, in parallel reaction pipe.10mL1,2- dichloroethanes, ionic liquid PFIL-2 [R is separately added under blanket of nitrogen1,R2,R3
=phenyl, n=4, X=(CF3SO2)2N] 0.5mL, confined reaction test tube, stirring reaction, microwave exposure adopt batch (-type), power
500W, each irradiation 5 minutes stop irradiation 1 minute.Reaction 5 hours, temperature control is in 80 degrees centigrades.Reaction finish plus
Water terminating reaction.Through silica gel chromatography post separation, 0.314 gram of glucosides 1, yield 71% is obtained.Ionic liquid is reusable, yield
Without significant change.
Embodiment 4：2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyrroles
Mutter the preparation of glucosides
0.391 gram Yb (NO is weighed respectively3)3, four 0.33 gram of acetylation fucosees, 6- methyl-5-nitro -2- mercaptopyridines
0.17 gram, in parallel reaction pipe.Ionic liquid PFIL-4 [R are added under blanket of nitrogen1=propyl group, R2=hydrogen, R3、R4=ethoxy
Base, n=5, X=PF6] 3mL, confined reaction test tube, stirring reaction, microwave exposure adopt batch (-type), power 500W, each irradiation
5 minutes, stop irradiation 1 minute.Reaction 5 hours, temperature control is in 40 degrees centigrades.Reaction finishes the terminating reaction that adds water.Through
Silica gel chromatography post separation, obtains 0.33 gram of glucosides 1, yield 75%.Ionic liquid is reusable, and yield is without significant change.
Embodiment 5：2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyrroles
Mutter the preparation of glucosides
0.30 gram ScCl is weighed respectively3, four 0.33 gram of acetylation fucosees, 6- methyl-5-nitro -2- mercaptopyridines 0.17
Gram, in parallel reaction pipe.Ionic liquid PFIL-5 [R are added under blanket of nitrogen1、R2=ethyoxyl, n=3, X=(CF3SO2)2N]
3mL, confined reaction test tube, stirring reaction, microwave exposure adopt batch (-type), power 350W, each irradiation 5 minutes to stop irradiation 1
Minute.Reaction 5 hours, temperature control is in 40 degrees centigrades.Reaction finishes the terminating reaction that adds water.Through silica gel chromatography post separation,
Obtain 0.30 gram of glucosides 1, yield 69%.Ionic liquid is reusable, and yield is without significant change.
Embodiment 6：2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyrroles
Mutter the preparation of glucosides
0.30 gram ScCl is weighed respectively3, four 0.33 gram of acetylation fucosees, 6- methyl-5-nitro -2- mercaptopyridines 0.17
Gram, in parallel reaction pipe.Ionic liquid PFIL-5 [R are added under blanket of nitrogen1、R2=ethyoxyl, n=3, X=(CF3SO2)2N]
2mL and general ionic liquid 3- butyl -1- Methylimidazole. hexafluorophosphate 2mL, confined reaction test tube, stirring reaction, microwave spoke
Stop irradiation 1 minute according to batch (-type), power 350W, each irradiation 5 minutes is adopted.Reaction 5 hours, temperature control is Celsius 40
Degree left and right.Reaction finishes the terminating reaction that adds water.Through silica gel chromatography post separation, 0.256 gram of glucosides 1, yield 58% is obtained.Ionic liquid
Body is reusable, and yield is without significant change.
Embodiment 7：The preparation of 1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyranosides
0.884 gram of glucosides 1 is taken, is added in the 20mL methanol containing 0.1 gram of Feldalat NM, after reaction being stirred at room temperature 1 hour,
Stopped reaction.After separating through silica gel column chromatography, 0.518 gram of 2 compound of glucosides, yield 82% is obtained.Mass spectrum (positive ion mode)：
m/z 317.08(M+H)+.
It can be that professional and technical personnel in the field realize or use that above-mentioned embodiment is intended to illustrate the present invention, to above-mentioned
Embodiment is modified, therefore the present invention is included but is not limited to
Above-mentioned embodiment, any meet the claims or description description, meet with principles disclosed herein and novelty,
The method of inventive features, technique, product, each fall within protection scope of the present invention.
Claims (10)
1.2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyranosides, have
Structure shown in Formulas I：
2.1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algae pyranosides, with structure shown in Formula II：
3. 2,3,4- triacetyls -1- described in claim 1 (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algaes
The preparation method of pyranoside, it is characterised in that with four acetylation fucosees and 6- methyl-5-nitro -2- mercaptopyridines as rising
Beginning raw material, to contain phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid as reaction medium, with lewis' acid as catalyst, in microwave exposure
Under, carry out glycosylation reaction and prepare 2,3,4- triacetyl -1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-
L- rock algae pyranosides.
4. method according to claim 3, it is characterised in that the phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid is with formula
The ion liquid of quaternaries of structure shown in III, have structure shown in formula IV quaternary phosphonium salt ionic liquid, have Formula V shown in
The pyridine salt ionic liquid of structure, have structure shown in Formula IV imidazole salt ionic liquid and have structure shown in Formula VII
Double phosphoryl functionalized imidazoles in one or more of mixture：
Wherein, R1, R2, R3, R4=hydrogen, alkyl, alkoxyl, aryl；N=1,2,3,4,5,6；X=(CF3SO2) N, PF6.
5. method according to claim 4, it is characterised in that the R of the phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid1, R2,
R3, R4For hydrogen, methyl, ethyl, propyl group, butyl, amyl group, hexyl, alkoxyl, phenyl.
6. method according to claim 3, it is characterised in that the lewis' acid includes nickel salt, mantoquita, iron salt, pink salt,
Or the salt of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, ytterbium, lutecium.
7. method according to claim 6, it is characterised in that the salt includes villaumite, sulfate, nitrate, fluoroform
Sulfonate or hexafluorophosphate.
8. method according to claim 3, it is characterised in that also include chloralkane in the reaction medium.
9. method according to claim 3, it is characterised in that also include dialkylimidazolium salt, institute in the reaction medium
State dialkylimidazolium salt alkyl be methyl, ethyl, propyl group, butyl, amyl group, hexyl, the anion of the dialkylimidazolium salt
For bis trifluoromethyl imines ion, or hexafluorophosphate ion.
10. 1- (6- methyl-5-nitro -2- pyridine radicals) sulfydryl-alpha-L- rock algaes pyranoside as claimed in claim 2 is in system
Application in standby fucosidase diagnostic reagent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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