CN109134705A - A kind of method of regional choice sex modification chitosan - Google Patents
A kind of method of regional choice sex modification chitosan Download PDFInfo
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- CN109134705A CN109134705A CN201811310206.9A CN201811310206A CN109134705A CN 109134705 A CN109134705 A CN 109134705A CN 201811310206 A CN201811310206 A CN 201811310206A CN 109134705 A CN109134705 A CN 109134705A
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
The present invention provides a kind of method of regional choice sex modification chitosan; it is characterized in that; first chitosan 2- bit amino is protected using 4- methyl nadic anhydride; chitosan 3 later; 6- amino carries out formic acid esterification reaction; chitosan 2- bit amino is deprotected later, finally chitosan 2- bit amino is acylated, obtains chitosan-two (carbanilate)-(phenylurea；The present invention provides a kind of protection by chitosan 2- bit amino and deprotection methods, and the method for two kinds of different substituents is controllably introduced on chitosan 2- and the position 3,6-；The group that the chitosan derivative that provides introduces with 2- different structure due to 3,6- is invented, can be used for the research of chitosan derivatives structure-activity relationship；The method of regional choice sex modification chitosan provided by the invention efficiently uses amino of chitosan, improves the designability of chitosan, to obtain the more diverse chitosan derivatives of structure, and then expands the application range of chitosan.
Description
Technical field
The present invention relates to a kind of method for modifying chitosan more particularly to a kind of sides of regional choice sex modification chitosan
Method.
Background technique
Chitosan be a kind of degradable circulation with the advantageous properties such as chirality, nontoxicity, biocompatibility, antibiotic property again
Green material has broad application prospects in the multiple fields such as biomedicine, agricultural, food fresh keeping.However, chitosan does not dissolve in
Any organic solvent is dissolved only in the property of the weakly acidic solution of water, greatly hinders the business development of chitosan.Study table
Bright, chitosan tool is there are three the different functional group of reactivity, respectively sugar unit 3, the amino of 6- hydroxyls and 2-, this
Allow chitosan to pass through regioselectivity method of modifying to improve dissolubility, prepares its structure and function then can be more more
The derivative of sample, to expand its application range.
1991, Nishimura etc. first used phthalic anhydride in n,N-Dimethylformamide dicyandiamide solution to shell
Glycan 2- are modified, then using pyridine as solvent under conditions of in 6- introducing trityl groups of chitosan as protecting group
Group, further, is reacted with 3- hydroxyls of chitosan using acid anhydrides, has synthesized and possessed side group not of the same race on 2,3,6- positions
Chitosan analog derivative.2015, it is derivative that Bai Zhengwu et al. reports chitosan-two (carbanilate)-(amide) class
The preparation method of object, this method obtains N- acylation chitosan using chitosan and excessive anhydride reaction, then the acylated shell of N- is gathered
Sugar is dissolved in the n,N-dimethylacetamide solution containing lithium chloride, is reacted with excessive phenyl isocyanate, is obtained target
Product.The analog derivative is successively introduced not at chitosan 2- with 3,6- using the difference of hydroxyl and amino reactivity
Similar group.2016, Zhang Lili et al. was prepared for 2- bit amino and is first protected by phthalimide, and 3,6- hydroxyls are by 4
The chitosan derivatives that kind phenyl isocyanate is modified respectively.2017, Chen Wei et al. first repaired amino with benzoyl oxide
Decorations obtain N- benzoyl chitosan, then it is anti-with 3,5- dimethylphenyl isocyanate and 4- methylphenyl isocyanate respectively
It answers, is prepared for two kinds of chitosan derivatives.The chitosan derivatives of above-mentioned preparation are that first modification amino reacts 3,6- again
Made from the hydroxyl of position, structure is more diversified.But the derivatization reagent of such chitosan derivatives can only be with the ammonia of chitosan
Base reaction, and do not chemically reacted with hydroxyl, therefore, such derivatization reagent selection type is less, so that also part limits
The structure of chitosan.
2017, Zhang Lili et al. patent report chitin-2-phenylurea-3- carbanilate-6- hydroxy kind
The preparation method of derivative, this method first use triphenylchloromethane to protect chitosan 6-, then not ipsilateral with having
The phenyl isocyanate of base is reacted, and finally deprotection obtains target derivative.Wherein, 6- hydroxyls can be modified further, be used for
The more diversified chitosan derivatives of preparation structure function.This patent will be using the side of protection and deprotection to 2- bit amino
Method reinforces the effective use to amino of chitosan, prepares the more diversified chitosan derivatives of structure function.
Summary of the invention
The purpose of the invention is to keep chitosan derivatives structure more diversified, the work of chitosan is studied for the later period
Property, the structure-activity relationship of the performance of position and its derivative and structure and a kind of method of regional choice sex modification chitosan is provided.
The object of the present invention is achieved like this:
A kind of method of regional choice sex modification chitosan, first using 4- methyl nadic anhydride to 2- ammonia of chitosan
Base is protected, later chitosan 3, and 6- amino carries out formic acid esterification reaction, is taken off later to chitosan 2- bit amino
Protection, is finally acylated chitosan 2- bit amino, obtains chitosan-two (carbanilate)-(phenylurea),
Structural formula are as follows:
Wherein, R1、R2For the substituent group on phenyl ring and not identical, the substituent group is 1-5, when the number of substituent group is big
When 1, each substituent group is identical or not identical, and the substituent group is halogen atom, alkyl, alkoxy, nitro, amino or alkane sulphur
Base.
The invention also includes features some in this way:
1. it is described first using 4- methyl nadic anhydride to chitosan 2- bit amino carry out protection specifically include: will be complete
Deacetylated chitosan is dissolved in the solvent of lithium chloride, and 4- methyl nadic anhydride is added, and is 100-140 in reaction temperature
Flow back 8-12h at DEG C, and wherein the ratio between molal quantity of chitosan and 4- methyl nadic anhydride is 1:1-3, obtains chitin-2-
N- (4- methyl phthalimide)；
2. the chitosan 3,6- amino carries out formic acid esterification reaction specifically: by chitin-2-N-, (4- methyl is adjacent
Phthalimide) it is dissolved in the solvent of lithium chloride, the phenyl isocyanate for having side group is added, is 50-150 in reaction temperature
12-36h is reacted at DEG C, wherein phenyl isocyanate and 3, the ratio between total mole number of 6- hydroxyls is 1.5-3:1, and it is poly- to obtain shell
Sugar -2-N- (4- methyl phthalimide) -3,6- two (carbanilate)；
3. described be deprotected chitosan 2- bit amino specifically: by chitin-2-N- (4- methyl phthalyl
Imines) -3,6- bis- (carbanilate) is dissolved in hydrazine hydrate, and 9-24h is reacted at being 80-120 DEG C in reaction temperature, is obtained
Chitin-2-amino-3,6- two (carbanilate)；
4. described be acylated chitosan 2- bit amino specifically: by chitin-2-two (phenylamino of amino-3,6-
Carbamate) it is dissolved in the solvent of lithium chloride, the phenyl isocyanate for having side group is added, in the case where reaction temperature is 50-150 DEG C
12-36h is reacted, wherein the ratio between molal quantity of phenyl isocyanate and 2- bit amino is 1.5-3:1, obtains chitin-2-phenyl
Urea -3,6- bis- (carbanilate), i.e. chitosan-two (carbanilate)-(phenylurea)；
5. the phenyl isocyanate with side group is structural formula are as follows:
6. the phenyl isocyanate with side group is structural formula are as follows:
7. the solvent is dimethyl sulfoxide, pyridine or N,N-dimethylformamide；
8. the concentration of the lithium chloride is 0.075-0.100g/mL；
9. the reaction carries out under the protection of nitrogen.
Compared with prior art, the beneficial effects of the present invention are:
1. the present invention provides a kind of protection by chitosan 2- bit amino and deprotection methods, at chitosan 2-
With the method for controllably introducing two kinds of different substituents on the position 3,6-；
2. the group that chitosan derivative provided by the invention introduces with 2- different structure due to 3,6-, can
Research for chitosan derivatives structure-activity relationship；
3. the method for regional choice sex modification chitosan provided by the invention can efficiently use amino of chitosan,
The designability of chitosan is improved, to obtain the more diverse chitosan derivatives of structure, and then expands the application model of chitosan
It encloses.
Detailed description of the invention
Fig. 1 is chitin-2-N- prepared by step of the embodiment of the present invention (1) (4- methyl phthalimide)1H-NMR spectrum；
Fig. 2 is chitin-2-N- prepared by step of the embodiment of the present invention (2) (4- methyl phthalimide)-3,
6-'s bis- (carbanilate)1H-NMR spectrum；
Fig. 3 is chitin-2 prepared by step of the embodiment of the present invention (3)-amino -3,6- two (carbanilate)
's1H-NMR spectrum；
Fig. 4 is two (benzene of chitin-2-prepared by step of the embodiment of the present invention (4) (3,5- 3,5-dimethylphenyl urea)-3,6-
Aminocarbamic acid ester)1H-NMR spectrum；
Fig. 5 is reaction equation according to the present invention；
Fig. 6 is substituent R of the invention1、R2Example.
Specific embodiment
Present invention is further described in detail with specific embodiment with reference to the accompanying drawing.
The present invention provides a kind of successively modification chitosan 3, the method for 6- hydroxyls and 2- bit amino, and with the method system
Obtained chitosan-two (carbanilate)-(phenylurea) analog derivative.The method is not only synthesis containing there are two types of not ipsilateral
The chitosan derivatives of base provide new way, while also making chitosan derivatives structure more diversified, study shell for the later period
Activity, the performance of position and its derivative and the structure-activity relationship of structure of glycan provide a kind of effective approach, such is spread out
It is even more with good application prospect that biology, which is prepared into chiral stationary phase,.
Chitosan-two (carbanilate)-(phenylurea) of the invention is just like flowering structure:
Wherein R1, R2 are one of halogen atom, alkyl, alkoxy, nitro, amino and alkylthio group or a variety of, are occupied
One or more of phenyl 2-6
Chitosan-two (carbanilate)-(phenylurea) of the invention the preparation method comprises the following steps:
Step (1): the protection of 2- bit amino: completely deacetylated chitosan is dissolved in the solvent of lithium chloride, is added
Excessive 4- methyl nadic anhydride, flow back 8-12h at 100-140 DEG C, wherein chitosan and 4- methylphthalic acid
The mole ratio of acid anhydride is 1:1-3, is made chitin-2-(4- methyl phthalimide).
Step (2): the urethane that chitosan is 3,6-: (4- methyl is adjacent for the chitin-2-that step (1) is obtained
Phthalimide) it is dissolved in the solvent of lithium chloride, the excessive phenyl isocyanate containing different substituents is added, in 50-
150 DEG C of reaction 12-36h, wherein phenyl isocyanate and 3, the ratio between total mole number of 6- hydroxyls are 1.5-3:1, and it is poly- that shell is made
Sugar -2- (4- methyl phthalimide) -3,6- two (carbanilate).
Step (3): the deprotection of 2- bit amino: (4- methyl phthalyl is sub- for the chitin-2-that step (2) is obtained
Amine) -3,6- two (carbanilate) is dissolved in hydrazine hydrate (NH2-NH2/H2O in), 9-24h is reacted at 80-120 DEG C, is made
Chitin-2-amino-3,6- two (carbanilate).
Step (4): the acylation of 2- bit amino: the chitin-2 that step (3) is obtained-two (phenyl amino of amino -3,6-
Formic acid esters) it is dissolved in the solvent of lithium chloride, the excessive phenyl isocyanide containing different substituents different from step (2) is added
Acid esters, in 50-150 DEG C of reaction 12-36h, wherein the ratio between molal quantity of phenyl isocyanate and 2- bit amino is 1.5-3:1, system
It obtains chitin-2-phenylurea-3,6- bis- (carbanilate), i.e. chitosan-two (carbanilate)-(phenyl
Urea).
In above-mentioned steps, chitosan is by completely deacetylated, and molecular weight is in 50000-300000；Reaction is protected in nitrogen
Shield is lower to be carried out；The concentration of lithium chloride is 0.075-0.100g/mL.
Solvent described in step (1) (2), (4) be N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and
One of pyridine is configured to the solution that mass concentration is 0.013-0.025/mL with chitosan or chitosan derivatives.
Phenyl isocyanate structural formula described in step (2), (4) containing different substituents is respectively as follows:
Wherein R1、R2For one of halogen atom, alkyl, alkoxy, nitro, amino and alkylthio group or a variety of, benzene is occupied
One or more of 2-6, base.
Deacetylating degree of chitosan used in the present invention is greater than 99%, and chitosan and its derivative, lithium chloride are before use
12h is dried in vacuo at 60 DEG C.
The preparation of chitin-2-(3,5- 3,5-dimethylphenyl urea)-3,6- two (carbanilate) derivative:
(1) protection of 2- bit amino: in nitrogen atmosphere, 0.4g chitosan is in the anhydrous N,N-dimethylformamide of 12mL
(DMF) in, for 24 hours in 80 DEG C of swellings；0.8g lithium chloride is added and stirs 4h at room temperature；1.20g 4- methylphthalic acid is added
Acid anhydride is in 120 DEG C of reflux 12h；Reaction terminates, and instills in 200mL distilled water solution using rubber head dropper, chitosan derivative is precipitated
Object precipitating；Precipitating is washed with methanol, finally in 60 DEG C of vacuum drying 48h, chitin-2-is made, and (4- methyl phthalyl is sub-
Amine) derivative.
1H-NMR spectrum is as shown in Fig. 1:1H-NMR(500MHZ,80℃,DMSO-d6, δ/ppm): 3.19-5.32 (m,
9H, glucose-H ,-OH), 7.26 (s, 3H, phenyl-H), 2.45 (s, 3H ,-CH3).From going out from ppm=7.26 in nuclear-magnetism figure
Show phenyl peak, the methyl peak occurred at ppm=2.45 can illustrate that chitosan 2- are modified simultaneously by 4- methyl nadic anhydride
Protection.
(2) chitosan 3,6- urethanes: in nitrogen atmosphere, chitosan derivative made from 0.6g step (1)
Object, in 20mL anhydrous pyridine, for 24 hours in 80 DEG C of swellings；1.2g lithium chloride is added and stirs 4h at room temperature；0.94mL phenyl is added
Isocyanates is in 80 DEG C of reaction 12h；Reaction terminates, and chitosan derivatives precipitating is precipitated with methanol, dry in 60 DEG C of vacuum after washing
Chitin-2-(4- methyl phthalimide)-3,6- bis- (carbanilate) derivative is made in dry 48h.
1H-NMR spectrum is as shown in Fig. 2:1H-NMR(500MHZ,80℃,DMSO-d6, δ/ppm): 9.06 (s, 1H,
Carbamate-H), 8.74 (s, 1H, carbamate-H), 6.30-7.67 (m, 13H, phenyl-H)；3.31-5.92(m,7H,
Glucose-H), 2.09-1.88 (m, 3H ,-CH3).
(3) deprotection of 2- bit amino: in nitrogen atmosphere, chitosan derivatives made from 0.45g step (2), in 9mL water
Close hydrazine (NH2-NH2/H2O, 1/2, v/v) in, in 100 DEG C of reaction 18h；Reaction terminates, and chitosan is precipitated with 200mL distilled water and spreads out
Chitin-2-amino-3,6- bis- (carbanilate) is made in 60 DEG C of vacuum drying 48h after methanol washing in biogenic sediment
Derivative.
1H-NMR spectrum is as shown in Fig. 3:1H-NMR(500MHZ,80℃,DMSO-d6, δ/ppm): 9.35 (s, 1H,
Carbamate-H), 9.00 (s, 1H, carbamate-H), 6.74-7.61 (m, 10H, phenyl-H), 3.35-5.66 (m, 9H,
glucose-H、-NH2)。
(4) urea groups of 2- bit amino: in nitrogen atmosphere, chitosan derivatives made from 0.4g step (3), in 16mL bis-
In methyl sulfoxide, for 24 hours in 80 DEG C of swellings；0.8g lithium chloride is added and stirs 4h at room temperature；0.37mL 3,5- dimethyl benzene is added
Aminocarbamic acid ester reacts 12h at 80 DEG C；Reaction terminates, and chitosan derivatives precipitating is precipitated with methanol, in 60 DEG C after washing
It is dried in vacuo 48h, chitin-2-(3,5- 3,5-dimethylphenyl urea)-3,6- bis- (carbanilate) derivative is made.
1H-NMR spectrum is as shown in Fig. 4:1H-NMR(500MHZ,80℃,DMSO-d6, δ/ppm): 9.07 (s, 1H,
Carbamate-H), 8.83 (s, 1H, carbamate-H), 7.99 (s, 1H, phenyl-NH)；6.25-7.73(m,13H,
Phenyl-H), 5.93 (s, 1H, glucose-NH), 3.22-5.14 (m, 7H, glucose-H)；2.13(s,6H,-CH3).
In summary: the present invention relates to one kind successively to introduce not isoplastic regional choice at chitosan 3,6- and 2-
Property substitution technique and the preparation of chitosan-two (carbanilate)-(phenylurea) derivative.Amino of chitosan is by 4- methyl
Phthalic anhydride protection, then reacted with the phenyl isocyanate on phenyl ring containing different substituents, after deprotection again with benzene
Phenyl isocyanate reaction on ring containing different substituents, two secondary responses use different isocyanates, obtain chitosan-two
(carbanilate)-(phenylurea) derivative.The method is conducive to making full use of for amino of chitosan, is beneficial to chitosan
The exploitation of class specific function material and the research of structure-activity relationship.
Claims (10)
1. a kind of method of regional choice sex modification chitosan, characterized in that first poly- to shell using 4- methyl nadic anhydride
Sugared 2- bit amino is protected, later chitosan 3, and 6- amino carries out formic acid esterification reaction, later to 2- ammonia of chitosan
Base is deprotected, and is finally acylated to chitosan 2- bit amino, and chitosan-two (carbanilate)-(benzene is obtained
Base urea), structural formula are as follows:
Wherein, R1、R2For the substituent group on phenyl ring and not identical, the substituent group is 1-5, when the number of substituent group is greater than 1
When, each substituent group is identical or not identical, and the substituent group is halogen atom, alkyl, alkoxy, nitro, amino or alkylthio group.
2. the method for regional choice sex modification chitosan according to claim 1, characterized in that described first to use 4- methyl
Phthalic anhydride carries out protection to chitosan 2- bit amino and specifically includes: completely deacetylated chitosan is dissolved in lithium chloride
Solvent in, 4- methyl nadic anhydride is added, flows back 8-12h at being 100-140 DEG C in reaction temperature, wherein chitosan with
The ratio between molal quantity of 4- methyl nadic anhydride is 1:1-3, obtains chitin-2-N- (4- methyl phthalimide).
3. the method for regional choice sex modification chitosan according to claim 1, characterized in that the chitosan 3,6-
Amino carry out formic acid esterification reaction specifically: chitin-2-N- (4- methyl phthalimide) is dissolved in lithium chloride
In solvent, the phenyl isocyanate for having side group is added, reacts 12-36h at being 50-150 DEG C in reaction temperature, wherein phenyl is different
Cyanate and 3, the ratio between total mole number of 6- hydroxyls are 1.5-3:1, and obtaining chitin-2-N-, (4- methyl phthalyl is sub-
Amine) -3,6- two (carbanilate).
4. the method for regional choice sex modification chitosan according to claim 1, characterized in that described to chitosan 2-
Amino is deprotected specifically: by two (phenylcarbamic acid of chitin-2-N- (4- methyl phthalimide)-3,6-
Ester) it is dissolved in hydrazine hydrate, 9-24h is reacted at being 80-120 DEG C in reaction temperature, obtains bis- (phenyl of chitin-2-amino-3,6-
Carbamate).
5. the method for regional choice sex modification chitosan according to claim 1, characterized in that described to chitosan 2-
Amino is acylated specifically: chitin-2-amino-3,6- two (carbanilate) is dissolved in the solvent of lithium chloride
In, the phenyl isocyanate for having side group is added, reacts 12-36h at being 50-150 DEG C in reaction temperature, wherein phenyl isocyanic acid
The ratio between molal quantity of ester and 2- bit amino is 1.5-3:1, obtains chitin-2-phenylurea-3,6- bis- (carbanilate),
That is chitosan-two (carbanilate)-(phenylurea).
6. the method for regional choice sex modification chitosan according to claim 2, characterized in that the benzene with side group
Based isocyanate is structural formula are as follows:
7. the method for regional choice sex modification chitosan according to claim 5, characterized in that the benzene with side group
Based isocyanate is structural formula are as follows:
8. according to the method for regional choice sex modification chitosan described in claim 2,3 or 5, characterized in that the solvent is
Dimethyl sulfoxide, pyridine or N,N-dimethylformamide.
9. according to the method for regional choice sex modification chitosan described in claim 2,3 or 5, characterized in that the lithium chloride
Concentration be 0.075-0.100g/mL.
10. according to the method for regional choice sex modification chitosan described in claim 2-5 any one, characterized in that described
Reaction carries out under the protection of nitrogen.
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| CN103951763A (en) * | 2014-04-22 | 2014-07-30 | 大连民族学院 | O-alkyl carbamic acid ester chitosan, transgenic compound particle and preparation method thereof |
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| CN104250312A (en) * | 2013-06-28 | 2014-12-31 | 株式会社大赛璐 | Chitosan carbanilate-carbamido derivative preparation method |
| CN103951763A (en) * | 2014-04-22 | 2014-07-30 | 大连民族学院 | O-alkyl carbamic acid ester chitosan, transgenic compound particle and preparation method thereof |
| CN105199011A (en) * | 2015-10-28 | 2015-12-30 | 武汉工程大学 | Chitosan-di(aromatic carbamate)-(alkoxy formamide) and chiral stationary phase, and preparation methods thereof |
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