CN106397508B - 2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-α-L- rock algae pyranoside - Google Patents
2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-α-L- rock algae pyranoside Download PDFInfo
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Abstract
The present invention relates to the field of chemical synthesis, specifically disclose the synthesis of 2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside and hydrolysate.It is using four acetylation fucoses and 2- mercaptopyridine 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- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside, then 1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside is obtained through hydrolysis.The starting material for preparing 1- (2- pyridyl group) sulfydryl-alpha-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
Technical field
The present invention relates to chemosynthesis technical field more particularly to 2,3,4- triacetyl -1- (2- pyridyl group) sulfydryls -
The synthesis of alpha-L- rock algae pyranoside and hydrolysate.
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 synthesis of (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside and hydrolysate.
The specific technical solution of the present invention is as follows:
2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside has structure shown in Formulas I:
1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside (PT-AFU) has structure shown in Formula II:
1- (2- pyridyl group) sulfydryl-alpha-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- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside
Method, synthetic technology route are as follows:
Using four acetylation fucoses and 2- mercaptopyridine as starting material, to contain phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid
(PFIL) it is reaction medium, using lewis' acid as catalyst, under microwave irradiation, carries out glycosylation reaction and be prepared 2,3,4-
Triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside, then 1- (2- pyridyl group) sulfydryl-is obtained through hydrolysis
Alpha-L- rock algae pyranoside.
Wherein, the molar ratio of four acetylation fucose of raw material and 2- mercaptopyridine is 1:1~5, preferably 1:1~3, into one
Step is 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, R4 are hydrogen, methyl, ethyl, propyl, butyl, amyl, hexyl, alkoxy, phenyl.
As a preferred embodiment, ion liquid of quaternaries (PFIL-1) in the present invention, preferably R1, 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 R1, R2=ethyoxyl, phenyl in the present invention；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 R1, R2=ethyoxyl, phenyl in the present invention.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) in the present invention, preferably R1=methyl, ethyl, propyl, butyl, amyl, hexyl；
R2=hydrogen；R3, R4=ethyoxyl, phenyl.Preparation method is as follows: by glyoxaline compound and bromo alkyl dipheny oxide
Phosphine, 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
In reaction unit, microwave power be 280W~500W, reaction temperature be 80 DEG C~120 DEG C, the reaction time be 60min~
150min obtains crude product, removes unreacting material, obtains imidazoles bromide ionic liquid.The imidazoles bromide ionic liquid that will be obtained
The bis trifluoromethyl imine lithium or hexafluorophosphoric acid nak response of body and equimolar amounts obtain the imidazole salt ionic liquid (PFIL-
4), structure is as shown in Formula IV.
Double phosphoryl functionalized imidazole ionic liquids (PFIL-5), preferably R1, R2=ethyoxyl, phenyl in the present invention.
The preparation method is as follows: by imidazoles and bromo alkyl diphenyl phosphine oxide, bromo alkyl phenyl-phosphonic acid ethyl ester or bromo alkylphosphines
Diethyl phthalate is dissolved in organic solvent with the molar ratio of 1:2~4, adds water soluble carbonate, is then placed into microwave reaction
Carrying out microwave reaction in device, microwave power is 280~500W, and reaction temperature is 80~110 DEG C, the reaction time is 5~
40min obtains crude product after reaction, removes unreacted raw material, and anion exchanger is added in the crude product, carries out anion
Exchange obtains double phosphoryl functionalized imidazole ionic liquids (PFIL-5), and 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.
After catalysis reaction obtains 2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside, 2,
3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside water preferably in the methanol containing sodium methoxide
Solution obtains 1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside.1- (2- pyridyl group) sulfydryl-alpha- being prepared
L- rock algae pyranoside can be used as substrate and be 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- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside preparation method of the invention is relatively just
Preferably, synthesizing mean is simple, quick.2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyrans of the invention
Used functionalized ion liquid may be reused glucosides during the preparation process, further reduce costs.With 1- (2- pyridine
Base) sulfydryl-alpha-L- rock algae pyranoside cost for preparing fucosidase diagnostic reagent as substrate is low, is 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 implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
In following embodiment, for convenience's sake, by 2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L-
Rock algae pyranoside is denoted as glucosides 1, and 1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside is denoted as glucosides 2.
The preparation of embodiment 1:2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside
Weigh 0.486 gram of FeCl3 respectively, four 0.33 gram of acetylation fucoses, 0.167 gram of 2- mercaptopyridine, in parallel anti-
Ying Guanzhong.10mL methylene chloride, ionic liquid PFIL-1 [R1, R2, R3=ethyl, n=3, X=are separately added under nitrogen atmosphere
(CF3SO2) 2N] 0.5mL, confined reaction test tube is stirred to react, and for microwave irradiation using intermittent, power 350W irradiates 5 every time
Minute, stop irradiation 1 minute.Reaction 5 hours, temperature are controlled in 40 degrees centigrades.End of reaction adds water to terminate reaction.Through silicon
Glue chromatography post separation obtains 0.27 gram of glucosides 1, yield 70%.Ionic liquid is reusable, and yield is without significant change.
The preparation of embodiment 2:2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside
Four 0.33 gram of acetylation fucoses, 0.167 gram of 2- mercaptopyridine, in parallel reaction pipe.Add respectively under nitrogen atmosphere
Enter 10mL chloroform, ionic liquid PFIL-3 [R1, R2=phenyl, n=3, X=(CF3SO2) 2N] 1mL and 0.345mL without
Water SnCl4, confined reaction test tube, is stirred to react, and microwave irradiation uses intermittent, power 400W, every time irradiation 5 minutes, stops
Irradiation 1 minute.Reaction 3 hours, temperature are controlled in 60 degrees centigrades.End of reaction adds water to terminate reaction.Through silica gel chromatographic column
Separation, obtains 0.21 gram of glucosides 1, yield 55%.Ionic liquid is reusable, and yield is without significant change.
The preparation of embodiment 3:2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside
Weigh 0.591 gram of Nd (OTf) 3 respectively, four 0.33 gram of acetylation fucoses, 0.167 gram of 2- mercaptopyridine, Yu Pinghang
In reaction tube.It is separately added into 10mL1 under nitrogen atmosphere, 2- dichloroethanes, ionic liquid PFIL-2 [R1, 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 subradius
According to 5 minutes, stop irradiation 1 minute.Reaction 5 hours, temperature are controlled in 80 degrees centigrades.End of reaction adds water to terminate reaction.
Through silica gel chromatograph post separation, 0.26 gram of glucosides 1, yield 68% are obtained.Ionic liquid is reusable, and yield is without significant change.
The preparation of embodiment 4:2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside
Weigh 0.391 gram of Yb (NO3) 3 respectively, four 0.33 gram of acetylation fucoses, 0.167 gram of 2- mercaptopyridine, Yu Pinghang
In reaction tube.Ionic liquid PFIL-4 [R1=propyl, R2=hydrogen, R3, R4=ethyoxyl, n=5, X=are added under nitrogen atmosphere
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 0.30 gram of glucosides 1, yield 79%.Ionic liquid is reusable, and yield is without significant change.
The preparation of embodiment 5:2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside
Weigh 0.30 gram of ScCl3 respectively, four 0.33 gram of acetylation fucoses, 0.167 gram of 2- mercaptopyridine, in parallel reaction
Guan Zhong.Ionic liquid PFIL-5 [R1, R2=ethyoxyl, n=3, X=(CF3SO2) 2N] 3mL, confined reaction are added under nitrogen atmosphere
Test tube is stirred to react, and microwave irradiation uses intermittent, power 350W, every time irradiation 5 minutes, stops irradiation 1 minute.It is small to react 5
When, temperature is controlled in 40 degrees centigrades.End of reaction adds water to terminate reaction.Through silica gel chromatograph post separation, 0.20 gram of sugar is obtained
Glycosides 1, yield 53%.Ionic liquid is reusable, and yield is without significant change.
The preparation of embodiment 6:2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside
Weigh 0.30 gram of ScCl3 respectively, four 0.33 gram of acetylation fucoses, 0.167 gram of 2- mercapto-pyridine, in parallel anti-
Ying Guanzhong.Ionic liquid PFIL-5 [R1, R2=ethyoxyl, n=3, X=(CF3SO2) 2N] 2mL and common is added under nitrogen atmosphere
Ionic liquid 3- butyl -1- methylimidazole hexafluorophosphate 2mL, confined reaction test tube are stirred to react, and microwave irradiation is using interval
Formula, power 350W, irradiation 5 minutes, stop irradiation 1 minute every time.Reaction 5 hours, temperature are controlled in 40 degrees centigrades.Reaction
It finishes plus water terminates reaction.Through silica gel chromatograph post separation, 0.24 gram of glucosides 1, yield 64% are obtained.Ionic liquid is repeatable to be made
With yield is without significant change.
The preparation of embodiment 7:1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside
0.766 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, 0.41 gram of 2 compound of glucosides, yield 80% are obtained.Mass spectrum (positive ion mode):
m/z 258.07(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)
- The preparation method of 1.2,3,4- triacetyl -1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside, feature exist In using four acetylation fucoses and 2- mercaptopyridine as starting material, to be anti-containing phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid Medium is answered, using lewis' acid as catalyst, under microwave irradiation, glycosylation reaction is carried out and 2,3,4- triacetyls-is prepared 1- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranoside；The phosphinylidyne polymerization of olefin using catalyst functionalized ion liquid is ion liquid of quaternaries with structure shown in formula III, has formula The quaternary phosphonium salt ionic liquid of structure shown in IV, the pyridine salt ionic liquid with structure shown in Formula V have and tie shown in Formula IV One of the imidazole salt ionic liquid of structure and double phosphoryl functionalized imidazoles with structure shown in Formula VII are a variety of Mixture: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- (2- pyridyl group) sulfydryl-alpha-L- rock algae pyranosides have structure shown in Formulas I:
- 2. the method according to claim 1, wherein the reaction medium contains phosphinylidyne polymerization of olefin using catalyst functionalization ion Liquid and chloralkane.
- 3. the method according to claim 1, wherein the reaction medium contains phosphinylidyne polymerization of olefin using catalyst functionalization ion Liquid and dialkylimidazolium salt, the alkyl of the dialkylimidazolium salt are methyl, ethyl, propyl, butyl, amyl, hexyl, described The anion of dialkylimidazolium salt is bis trifluoromethyl imines ion or hexafluorophosphate ion.
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