CN101255179B - Novel amylaceum imine compound as well as preparation method and uses thereof - Google Patents
Novel amylaceum imine compound as well as preparation method and uses thereof Download PDFInfo
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- CN101255179B CN101255179B CN200810060280XA CN200810060280A CN101255179B CN 101255179 B CN101255179 B CN 101255179B CN 200810060280X A CN200810060280X A CN 200810060280XA CN 200810060280 A CN200810060280 A CN 200810060280A CN 101255179 B CN101255179 B CN 101255179B
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Abstract
The invention disclose new glucose imine compounds shown as the formula (V) N-(2, 3-O-di- methylsulphonyl-4, 6-O-benzylidene glucose) P-chlorobenzyl imine compounds, a method for making the same and the applications. The preparation method of the invention comprises: methyl sulfonylation reacting N-(4, 6-O-benzylidene glucose ) P-chlorobenzyl imine and methanesulfonyl chloride or p-toluene sulfonyl chloride in pyridine at-30-30 degree C, reacting completely, postprocessing the reaction liquor to obtain the compounds shown as the formula V. The preparing process of the intermediate is shown asthe reaction formula. N-(2, 3-O-di- methylsulphonyl-4, 6-O-benzylidene glucose) P-chlorobenzyl imine compounds have potential bio-pharmacological activity, and can be used to preparing medicine of antineoplastic cell.
Description
Technical field
The present invention relates to a kind of new glucose group with imine moiety N-(2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines and its production and application.
Background technology
The medicinal research of carbohydrate starts from nineteen forty-three, and over year, people extract, separated a large amount of glucides from animal, plant, microorganism surplus in the of 60, as treatment or adjuvant therapy medicaments.Owing to its have immunomodulatory, antitumor, suppress microorganism and promote that multiple functions such as cell growth, anti-inflammatory, analgesia, radioprotective are more and more paid close attention to and studied.
D-glucosamine and hydrochloride thereof can break up to scavenger cell cell sample by inducing leukemia cell K562, and can cause that the K562 cell-cycle arrest is in G
1Phase, can suppress its growth effectively.Recently, D-glucosamine is gone on the market and obtained approval to the FDA application by the Boston Lifescience company of the U.S..
Reports such as Chebrolu P.Rao, N-(2-phenol methylene)-4,6-O-butylidene-β-D-glucose imines, N-(2-hydroxy 3-methoxybenzene methylene radical)-4,6-O-ethylidene-β-D-glucose imines, N-(5-bromo-2-phenol methylene)-4,6-O-ethylidene-β-D-glucose imines, N-(5-nitro-2-phenol methylene)-4,6-O-ethylidene-β-D-glucose imines etc. has the compound of similar structure, being the important intermediate of synthetic N-nucleosides of a class and osamine heterocyclic active material, also is the preparation that potential suppresses Glycosylase and treatment diabetes.
Summary of the invention
The purpose of this invention is to provide a kind of new potential source biomolecule pharmacologically active feature glucose group with imine moiety N-(2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines and its production and application that has.
The invention provides a kind of compound shown in formula V, chemical name is N-(2,3-O-two methylsulfonyls-4, a 6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines,
The present invention also provides a kind of method for preparing compound shown in the above-mentioned described chemical combination formula V; described preparation method is as follows: suc as formula the N-(4 shown in (IV); 6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines and methylsulfonyl chloride or Tosyl chloride carry out the first sulfonation reaction in-30～30 ℃ in pyridine; react completely; reaction solution obtains N-(2 shown in formula V through aftertreatment; 3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) the p-chlorobenzyl imines.
Among the present invention, the amount of substance ratio that feeds intake of described N-(4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines and methylsulfonyl chloride or Tosyl chloride is recommended as 1: 2～and 5.
The consumption of described pyridine is counted 2～6mL/g with N-(4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines quality.
The reaction times of described first sulfonation reaction recommended 12～48 hours, preferred-5～0 ℃ of temperature of reaction.
Above-mentioned aftertreatment can be carried out according to following steps: reaction solution is poured in the mixture of ice and water, filtered and obtain crude product, crude product obtains product N-(2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines via the column chromatography wash-out.
Among the present invention, the intermediate N shown in the formula (IV) (4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines can be prepared as follows:
(1) be starting raw material with the glucose shown in the formula (I), under Catalyzed by p-Toluenesulfonic Acid, with benzaldehyde dimethyl acetal in DMF, feed nitrogen and under 60 ℃, 200～250torr condition, react to the solution clarification, use Et after the cooling
3The reaction of going out of N collection, reaction solution obtains 4 shown in the formula (II), 6-O-Ben Yajiaji glucose through aftertreatment;
(2) 4 shown in the formula (II), 6-O-Ben Yajiaji glucose, the methanol solution with ammonia under the 1Mpa pressure condition obtained 4 shown in the formula (III), 6-O-Ben Yajiaji glucosamine in 3 hours in 60～65 ℃ of reactions;
(3) under the room temperature, under Glacial acetic acid catalysis, 4 shown in the formula (III), 6-O-Ben Yajiaji glucosamine in organic solvent with the 4-chloro-benzaldehyde condensation reaction, fully reaction afterreaction liquid obtains the N-shown in the formula (IV) (4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines through aftertreatment.
In the above-mentioned steps (3), described 4,6-O-Ben Yajiaji glucosamine is recommended as 1: 1 with the amount of substance ratio that feeds intake of 4-chloro-benzaldehyde～and 3.
The described organic solvent of step (3) is methyl alcohol, ethanol, Virahol or DMF.
The described reaction times of step (3) is recommended as 6～9 hours.
To sum up, the preparation route of N-of the present invention (2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines, available following reaction formula is represented:
The N-that the present invention prepares (2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines can be used for preparing the antitumor cell medicine.
The preparation-obtained N-(2 of the present invention; 3-O-two methylsulfonyls-4; 6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines reveals the obvious suppression effect to the growth table of some tumour cell (as colorectal carcinoma LOVO cell), has purposes preferably aspect the preparation antitumor cell medicine.
Description of drawings
Fig. 1 is embodiment 4 prepared N-(2,3-O-two methylsulfonyls-4, a 6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines
1H-NMR result;
Fig. 2 is that the LOVO cell is handled the photo after 4 days in the nutrient solution that contains the compound of different concns (V).Fig. 2-a:100 μ mol/L wherein; Fig. 2-b:50 μ mol/L; Fig. 2-c:0.1 μ mol/L; Fig. 2-d: the blank that does not contain medicine.
Fig. 3 is the t check analysis figure of the compound (V) of different concns to LOVO cytosis MTT experimental result after three days.
Embodiment
With specific embodiment technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1:4, the preparation of 6-O-Ben Yajiaji-D-Glucopyranose
With 40gD-(+)-glucose 20mLN, dinethylformamide (DMF) dissolving obtains solution, adds 48mg tosic acid, 80mlN, dinethylformamide (DMF), 36.8ml benzaldehyde dimethyl acetal in gained solution, 60 ℃, under the 250Torr condition, feed nitrogen and remove methyl alcohol, continue 30 minutes, glucose dissolves fully, solution becomes is clear, shows to react completely, and uses Et after the cooling
3The reaction of going out of N collection.
0.1Kpa following underpressure distillation removes and desolvates, and obtains brown thickness syrup.The thickness syrup is dissolved in 1, and in the 4-dioxane, sample is crossed post on the adding silica gel dry method, and eluent is ethyl acetate (0.1%Et
3N), the maintenance flow velocity is 5cm/min, revolves to steam to remove to desolvate, and obtains white powder solid 36.71g, is 4,6-O-Ben Yajiaji-D-Glucopyranose productive rate 65.0%.
Embodiment 2:4, the preparation of 6-O-Ben Yajiaji-D-pyran glucosamine
With NH
3Methanol solution join fast and fill 4, airtight in the steel autoclave of 6-O-Ben Yajiaji-D-Glucopyranose (20g), temperature rose to 60 ℃ and sustained reaction 3 hours gradually.Reaction finishes the back takes out with water pump, removes unnecessary ammonia, has solid to separate out, and filters.Use recrystallizing methanol, it is 4 that vacuum-drying obtains white powder solid 8.39g, 6-O-Ben Yajiaji-D-pyran glucosamine.
Embodiment 3-1:N-(4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines
Under the room temperature, 0.11g 4-chlorobenzaldehyde is joined 0.27g 4, in the methanol solution of 6-O-Ben Yajiaji-D-pyran glucosamine, add a Glacial acetic acid and make catalyzer, continue to stir 6 hours, cooling, have solid precipitation to separate out, filter, recrystallizing methanol obtains white solid 0.23g, be N-(4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines.Productive rate: 76.3%.mp：167.2-169.9℃.IR(KBr，cm
-1)υ：1639.08。
1H-NMR(DMSO)：δ8.94(1H)，7.83-8.34(9)，6.19(1H)，5.01(1H)，4.74(1H)，3.82-4.28(6H).?
13C-NMR(DMSO)：δ159.7，138.1，136.8，135.4，130.4，129.1，129.0，128.2，126.8，101.1，97.0，81.1，75.0，74.2，68.7.
Embodiment 3-2:N-(4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines
Other conditions change reaction solvent into ethanol with embodiment 3-1, and aftertreatment is the same, obtain white solid N-(4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines 0.15g.Fusing point is 167.5-168.2.
Embodiment 4-1:N-(2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines
Under-5～0 ℃ of condition, the 0.76ml methylsulfonyl chloride is added drop-wise to 1.05g N-(4,6-O-Ben Yajiaji glucosyl group) in the 7ml pyridine solution of p-chlorobenzyl imines, spend the night, reaction finishes back (TLC monitoring) pours reaction solution in the mixture of ice and water into, has a large amount of precipitations to separate out, and filters and obtains little yellow solid, vacuum-drying, 1.3g weighs.Get wherein that 80mg crosses post, eluent is with ethyl acetate and sherwood oil (volume ratio is 1: 3) (1%Et
3N), be spin-dried for elutriant and obtain the 12mg white solid.This solid fusing point is 171.6-172.9 ℃.Further, by
1(DMSO TMS) is accredited as N-(2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines to H-NMR.
1H-NMR result as shown in Figure 1.
Embodiment 4-2:N-(2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines
Other conditions are with embodiment 4-1, and the reaction times changes 48 hours into, and aftertreatment is the same, obtain the 15mg white solid, by
1(DMSO TMS) is accredited as N-(2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines to H-NMR, and fusing point is 170.2-172.8 ℃.
Embodiment 4-3:N-(2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines
Other conditions are with embodiment 4-1, and the amount of substance ratio that feeds intake of N-(4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines and methylsulfonyl chloride is 1: 5, and aftertreatment is the same, obtains the 20mg white solid, by
1(DMSO TMS) is accredited as N-(2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines to H-NMR, and fusing point is 170.5-171.2 ℃.Embodiment 4-4:N-(2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines
Other conditions change temperature of reaction into 20-25 ℃ with embodiment 4-1, and last handling process is constant, obtain the 8mg white solid, by
1(DMSO TMS) is accredited as N-(2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines to H-NMR, and fusing point is 170.1-172.4 ℃.
Embodiment 5: biological activity
1.2.1 cell cultures
The LoVo cell routine is incubated in the RPMI-1640 nutrient solution that contains 10% calf serum, 5%CO
2, 37 ℃ of adherent culture are changed liquid once under the low light level behind the 48h, and the vegetative period cell of taking the logarithm experimentizes the trypsin solution had digestive transfer culture collecting cell with 0.25%.Adjusting cell concn is 1 * 10
4/ ml adds in 96 well culture plates, every hole 200 μ l.
1.2.2 medicine preparation
With dimethyl sulfoxide (DMSO) (DMSO) dissolved compound (V), become final concentration to be respectively the pastille nutrient solution of 0.1 μ mol/L, 1 μ mol/L, 5 μ mol/L, 10 μ mol/L, 50 μ mol/L, 100 μ mol/L with inoculum preparation then, adjust the volume percent of dimethyl sulfoxide (DMSO), make it be always 1 ‰ (V/V).
1.2.3 morphocytology is measured
Under this drug effect, obvious variation has taken place in the form and the quantity of colon cancer cell.Fig. 2 shows that this drug level is 100 μ mol/L, 50 μ mol/L, 0.1 μ mol/L and the result of blank after cultivating 4 days who does not contain medicine.As can be seen from the figure, under 100 μ mol/L and 50 μ mol/L mass actions, cell quantity has obviously tailed off, and cellular form diminishes round, is pleomorphic type; And under 0.1 μ mol/L, cell quantity increases than blank again.This explanation medicine when high density has restraining effect to the LoVo cell, and the medicine pair cell has short proliferation function when lower concentration.
1.2.4 cell proliferating determining
48h behind cell inoculation removes nutrient solution.Add the nutrient solution 200 μ l that contain different these drug levels, dividing 8 groups experimentizes, the 1st group for not containing the blank of this medicine and DMSO, the 2nd group is the blank that contains 1 ‰ DMSO, 3～8 groups are respectively that to contain this drug level be 100 μ mol/L, 50 μ mol/L, 10 μ mol/L, 5 μ mol/L, 1 μ mol/L, 0.1 the nutrient solution of μ mol/L, cultivating 2 days respectively with four 96 orifice plates, 3 days, 4 days, after 6 days, method with quick upset culture plate is removed nutrient solution, (MTT is dissolved in the PBS liquid to add MTT liquid, concentration is 5mg/ml) 30 μ l/ holes, cultivate and add DMSO 150 μ l/ holes after 4 hours, on the microwell plate oscillator, shake 10min under the room temperature, treat the microplate reader survey A of quality product dissolving Later Zhou Dynasty, one of the Five Dynasties value.(λ=570nm, the 630nm dual wavelength is measured.)
This drug effect cell is after three days, and A～H is respectively the medicine of 8 groups of different concns, and 1～12 is respectively 12 parts result of each group concentration, and MTT microplate reader scan-data is as shown in table 1:
Table 1 drug effect cell is MTT microplate reader measured value after three days
| ? | A? | B? | C? | D? | E? | F? | G? | H? |
| 1? | 0.415? | 0.393? | 0.383? | 0.361? | 0.373? | 0.395? | 0.363? | 0.404? |
| 2? | 0.386? | 0.418? | 0.343? | 0.327? | 0.370? | 0.362? | 0.437? | 0.309? |
| 3? | 0.376? | 0.354? | 0.382? | 0.331? | 0.395? | 0.362? | 0.356? | 0.371? |
| 4? | 0.345? | 0.375? | 0.314? | 0.323? | 0.338? | 0.402? | 0.396? | 0.384? |
| 5? | 0.348? | 0.371? | 0.319? | 0.345? | 0.308? | 0.375? | 0.398? | 0.361? |
| 6? | 0.371? | 0.368? | 0.345? | 0.327? | 0.295? | 0.370? | 0.336? | 0.415? |
| 7? | 0.350? | 0.329? | 0.330? | 0.298? | 0.344? | 0.373? | 0.376? | 0.373? |
| 8? | 0.365? | 0.352? | 0.340? | 0.311? | 0.303? | 0.372? | 0.311? | 0.388? |
| 9? | 0.328? | 0.348? | 0.321? | 0.312? | 0.345? | 0.330? | 0.366? | 0.374? |
| 10? | 0.344? | 0.326? | 0.324? | 0.332? | 0.342? | 0.362? | 0.358? | 0.367? |
| 11? | 0.306? | 0.309? | 0.392? | 0.267? | 0.330? | 0.341? | 0.327? | 0.365? |
| 12? | 0.371? | 0.309? | 0.299? | 0.292? | 0.301? | 0.330? | 0.395? | 0.360? |
The statistics of said determination value is as shown in table 2:
The statistics of table 2 drug effect cell microplate reader measured value after three days
| ? | MEAN? | MIN? | MAX? | DELTA? | S.D.? | DELTA％? | CV％? |
| A? | 0.395? | 0.306? | 0.415? | 0.109? | 0.028? | 30.44? | 7.928? |
| B? | 0.355? | 0.309? | 0.418? | 0.108? | 0.033? | 30.60? | 9.307? |
| C? | 0.333? | 0.292? | 0.383? | 0.091? | 0.028? | 27.42? | 8.511? |
| D? | 0.319? | 0.267? | 0.361? | 0.094? | 0.025? | 29.64? | 7.887? |
| E? | 0.336? | 0.295? | 0.395? | 0.100? | 0.031? | 29.81? | 9.376? |
| F? | 0.365? | 0.330? | 0.402? | 0.072? | 0.022? | 19.75? | 6.157? |
| G? | 0.365? | 0.311? | 0.437? | 0.126? | 0.034? | 34.37? | 9.323? |
| H? | 0.379? | 0.339? | 0.415? | 0.095? | 0.027? | 21.51? | 8.416? |
With each group concentration mean number (t check) as the experimental result of each group, the calculating inhibiting rate is an X-coordinate with concentration, is that 100 inhibiting rates that are converted are ordinate zou with the absorption value of blank, is Fig. 3.
1.2.5 interpretation of result
Under compound (V) effect, obvious variation has taken place in the form and the quantity of colon cancer cell.As can be seen, under 100 μ mol/L and 50 μ mol/L mass actions, cell quantity has obviously tailed off from Fig. 2 a-2d, and cellular form diminishes round, is pleomorphic type; And under 0.1 μ mol/L, cell quantity increases than blank again.This explanation compound when high density has restraining effect to the LoVo cell, and pair cell has short proliferation function when lower concentration.When compound (V) concentration is 100 μ mol/L, has significant inhibition effect.The experimental result of MTT shows that equally also the growth of cell compound (V) pair cell under the concentration of 100 μ mol/L has had strong inhibitory effects (P＜0.01), and along with the minimizing restraining effect of concentration reduces gradually, is certain concentration dependent relation.And below 5 μ mol/L concentration, compound (V) then has promoter action to the growth of LoVo, with 0.1 μ mol/L the most obviously (P＜0.01).
Claims (10)
1. compound shown in formula V, chemical name is N-(2,3-O-two methylsulfonyls-4, a 6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines,
2. method for preparing compound as claimed in claim 1, it is characterized in that described preparation method is as follows: suc as formula the N-(4 shown in (IV), 6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines and methylsulfonyl chloride carry out the first sulfonation reaction in-30～30 ℃ in pyridine, react completely, reaction solution obtains N-(2 shown in formula V through aftertreatment, 3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) the p-chlorobenzyl imines;
3. preparation method as claimed in claim 2, it is characterized in that described N-(4,6-O-Ben Yajiaji glucosyl group) the amount of substance ratio that feeds intake of p-chlorobenzyl imines and methylsulfonyl chloride is 1: 2～5, the consumption of described pyridine is counted 2～6mL/g with N-(4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines quality.
4. preparation method as claimed in claim 2, the reaction times that it is characterized in that described first sulfonation reaction is 12～48 hours.
5. preparation method as claimed in claim 2 is characterized in that described N-(4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines is prepared as follows:
(1) be starting raw material with the glucose shown in the formula (I), under Catalyzed by p-Toluenesulfonic Acid, with benzaldehyde dimethyl acetal in DMF, feed nitrogen and under 60 ℃, 200～250torr condition, react to the solution clarification, use Et after the cooling
3The reaction of going out of N collection, reaction solution obtains 4 shown in the formula (II), 6-O-Ben Yajiaji glucose through aftertreatment;
(2) 4 shown in the formula (II), 6-O-Ben Yajiaji glucose, the methanol solution with ammonia under the 1Mpa pressure condition obtained 4 shown in the formula (III), 6-O-Ben Yajiaji glucosamine in 3 hours in 60～65 ℃ of reactions;
(3) under the room temperature, under Glacial acetic acid catalysis, 4 shown in the formula (III), 6-O-Ben Yajiaji glucosamine in organic solvent with the 4-chloro-benzaldehyde condensation reaction, fully reaction afterreaction liquid obtains the N-shown in the formula (IV) (4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines through aftertreatment;
6. preparation method as claimed in claim 5 is characterized in that step (3) is described 4, and 6-O-Ben Yajiaji glucosamine is 1: 1～3 with the amount of substance ratio that feeds intake of 4-chloro-benzaldehyde.
7. preparation method as claimed in claim 5 is characterized in that the described organic solvent of step (3) is methyl alcohol, ethanol, Virahol or DMF.
8. preparation method as claimed in claim 5 is characterized in that the described reaction times of step (3) is 6～9 hours.
9. one kind is used to prepare the intermediate of compound according to claim 1, it is characterized in that described intermediate is that chemical name is N-(4, a 6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines suc as formula the compound shown in (IV),
10. the application of the N-shown in formula V (2,3-O-two methylsulfonyls-4,6-O-Ben Yajiaji glucosyl group) p-chlorobenzyl imines in preparation antitumor cell medicine.
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| Ajay K. Sah,et al.synthesis,characterisation and crystal structures of schiff bases from the reaction of 4,6-O-ethylidene-β-D-glucopyranosylamine with substituted salicylaldehydes.《Carbohydrate Research》.2001,第335卷(第1期),33-34. * |
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