CN110330570A - A kind of preparation method of 6- amino -6- deoxycellulose - Google Patents
A kind of preparation method of 6- amino -6- deoxycellulose Download PDFInfo
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Abstract
The present invention relates to a kind of methods for synthesizing 6- amino -6- deoxycellulose, steps are as follows: 1) by cellulose dissolution lithium bromide N, in N- dimethylacetamide solution, then the DMAc solution of triphenylphosphine and bromo-succinimide is successively instilled in above-mentioned cellulose solution, it is stirred to react, obtains the bromo- 6- deoxycellulose of 6-；2) the bromo- 6- deoxycellulose of 6- that step 1) obtains is dissolved in dimethyl sulfoxide solution, excessive sodium azide is added, 6- nitrine -6- deoxycellulose is obtained after reaction；3) the 6- nitrine -6- deoxycellulose that step 2) obtains is dissolved in dimethyl sulfoxide solution, excess sodium borohydrate is added, reaction obtains 6- amino -6- deoxycellulose.Azido can be reduced to completely amino with sodium borohydride by the present invention, the 6- amino -6- deoxycellulose of high-purity, high substituted degree can be obtained, the technological operation of use is simple, efficient, and required raw material is easy to get.
Description
Technical field
The present invention relates to natural polymer and its chemical modification methods, and in particular to the system of 6- amino -6- deoxycellulose
Preparation Method.
Technical background
Glycosaminoglycan is a kind of important saccharide compound, and the amino in structure makes it have many unique physiology, medicine
Manage function and chemical property.Chitosan is a kind of glycosaminoglycan being widely present in nature, and the presence of amino is assigned on the position C-2
The more physiological activity of chitosan and reactivity worth are given, such as in terms of chiral Recognition, after amino and hydroxyl are modified respectively
Obtained chitosan derivatives not only have good organic solvent tolerance, and possess good Chiral Separation
Energy.Cellulose is wider existing a kind of natural polysaccharide in nature, and amino deoxy cellulose and chitosan have similar knot
Structure has important application value.But it there is no the 6- amino -6- deoxidation of energy prepare with scale high substituted degree, high-purity at present
The method of cellulose.
[(1) .Teshirogi T, Yamamoto H, the Sakamoto M, Tonami such as Teshirogi
H.1979.Synthesis of 6-amino-6-deoxycellulose.Sen-I Gakkaishi 35:T525-T529] with
Cellulose 2,3- bis- (carbanilate) are raw material, and C-6 hydroxyls are converted to p-methyl benzenesulfonic acid ester, then use azido
Replace the p-methyl benzenesulfonic acid ester on C-6, is most restored afterwards, is deprotected to obtain the 6- amino -6- deoxidation that amino group substitution degree is 0.90
Cellulose.This synthetic method, which needs to react by eight steps, could be made 6- amino -6- deoxycellulose, cumbersome.As used
When p-methyl benzene sulfonic chloride is reacted with C6-OH, the reaction time is up to 95 hours；Using sodium azide replace C6 on to toluene sulphur
Acid esters the reaction time is 72 hours.In short, this method is time-consuming and yield only has 26%.
Liu and Baumann [(2) .Liu C, Baumann H.2002.Exclusive and complete
introduction of amino groups and their N-sulfonyl and N-carboxymethyl groups
into the 6-position of cellulose without the use of protecting
Groups.Carbohydrate Research, 337 (14): not protecting cellulose C-2 and C-3 hydroxyls 1297-1307],
C-6 hydroxyl is directly modified into p-methyl benzenesulfonic acid ester, and has extra p-methyl benzenesulfonic acid ester on other sites, then uses nitrine
Base replaces the p-methyl benzenesulfonic acid ester of C-6 to obtain C-6 nitrine in specific manner, the p-methyl benzenesulfonic acid ester that contains on last other sites and
Nitrine on C-6 is restored together with lithium aluminium hydride reduction, obtains 6- amino -6- deoxycellulose.Due to using lithium aluminium hydride reduction for reduction
Agent, the synthetic method is inconvenient, and the isolation and purification process of product is cumbersome, time-consuming after reduction, as product needs first to be washed with ethyl alcohol
It washs, then dialyses three days in aqueous solution, finally freeze-drying obtains 6- amino -6- deoxycellulose, and due to more in macromolecule
Hydroxyl and polyamino can be with aluminium ion complexings, and after dialysis, the aluminium ion in product is still had, it is difficult to which purifying is clean, yield
It is 44%, because product loss is more in isolating and purifying, which is not suitable for being prepared on a large scale 6- amino -6- deoxidation yet
Cellulose.
[(3) .Furuhata K I, Koganei K, Chang H S, et such as Furuhata
al.1992.Dissolution of cellulose in lithium bromide-organic solvent systems
and homogeneous bromination of cellulose with N-bromosuccinimide-
triphenylphosphine in lithium bromide-N,N-dimethylacetamide.Carbohydrate
Research, 230 (1): 165-177] bromine using NBS and triphenylphosphine regioselectivity is converted by cellulose C-6 hydroxyl,
Obtain the bromo- 6- deoxycellulose of 6- that bromine degree of substitution is 0.91.Matsui etc. [(4) .Matsui Y, Ishikawa J,
Kamitakahara H,et al.2005.Facile synthesis of 6-amino-6-
Deoxycellulose.Carbohydrate Research, 340 (7): 1403-1406] on the basis of Furuhata method
C-6 bromine is converted into C-6 nitrine, azido is then reduced to amino with sodium borohydride, obtains the 6- amino -6- of high substituted degree
Deoxycellulose.But when replacing the bromine in the bromo- 6- deoxycellulose of 6- with azido by condition described in document 4, solvent makes
Dosage is big, and the reaction time is long；When using sodium borohydride reduction azido, by method described in document 4, it is small that 48 are reacted at 60 DEG C
When, although the reaction time is long, azido can not be reduced to completely to amino, and solvent-oil ratio is big.
[(5) .Fox S C, Edgar the K J.2012.Staudinger reduction chemistry of such as Fox
cellulose:Synthesis of selectively O-acylated 6-amino-6-deoxy-
Cellulose.Biomacromolecules, 13 (4): 992-1001] on the basis of the method for Matsui etc., with NBS and triphen
Base phosphine by C-6 hydroxyl modified at C-6 bromine after, acylated C-2 and C-3, acid anhydrides hydroxyl is added directly in reaction solution, obtains C6-
Bromine cellulose esters, then with azido replace C-6 bromine, reacted by Staudinger, with triphenylphosphine by nitrine selectively
It is reduced to amino.Also contain a certain amount of triphenylphosphine and triphenyl in the 6- amino -6- deoxycellulose synthesized with this method
Phosphine oxide can not be completely removed at all with purification process such as washing, extractings, and products therefrom is insoluble in acidic aqueous solution, no
Further derivatization and application are carried out conducive to it.
In the method for above-mentioned synthesis 6- amino -6- deoxycellulose, when the solution formed using DMAc and LiBr is molten
When agent, can all there be the generation of by-product acetic acid ester.
Summary of the invention
For the status of above-mentioned synthesis 6- amino -6- deoxycellulose, in order to obtain, high substituted degree, dissolubility be good, high area
6- amino -6- the deoxycellulose of field selectivity, high yield, the present invention is not in the case where protecting C-2, C-3 hydroxyls, energy
Prepare the 6- amino -6- deoxycellulose of C-6 high regioselectivities, high substituted degree.Moreover, intermediate 6- nitrine -6- is de-
Azido in oxygen cellulose can be reduced into amino completely within a short period of time, meanwhile, a small amount of remaining acetic acid esters is also by boron
Sodium hydride is reduced into hydroxyl.
The purpose of the present invention is for the deficiencies of the prior art, propose a kind of preparation side of 6- amino -6- deoxycellulose
Method.
A kind of preparation method of 6- amino -6- deoxycellulose comprising have the following steps: 6- nitrine -6- deoxidation is fine
Dimension element be dissolved in solvent dimethyl sulfoxide (DMSO), the solvent DMSO dosage be every gram of 6- nitrine -6- deoxycellulose extremely
DMSO 50mL is needed less, and excessive NaBH is added4, react that (reaction temperature is higher 5-28 hours at being 110-120 DEG C in temperature
Then the required reaction time is shorter), the pH value of reaction mixture is first adjusted to acid range with acid solution, it is excessive to quench
NaBH4, the pH value of reaction mixture is then adjusted to alkaline range with alkaline solution again, reaction mixture is stirred overnight, mistake
The solid in mixture is filtered, is washed with water, it is dry, obtain 6- amino -6- deoxycellulose.
According to the above scheme, the synthesis of the 6- nitrine -6- deoxycellulose includes following steps:
1) synthesis of the bromo- 6- deoxycellulose of 6-: by cellulose in DMAC N,N' dimethyl acetamide (DMAc) at 130 DEG C
Stirring two hours is cooled to 100 DEG C, lithium bromide is added, stirring to cellulose is completely dissolved, at a certain temperature with a certain amount of
DMAc dilutes above-mentioned cellulose solution, then the cellulose solution after dilution is cooled to certain temperature, at this temperature by stirring
Triphenylphosphine is added into cellulose solution and N- bromo-succinimide (NBS) is dissolved in the solution of DMAc, reaction solution is heated
To 70 DEG C, it is stirred to react two hours, after reaction, reaction solution is poured into and generates precipitating in precipitating reagent, by being filtered, washed,
The bromo- 6- deoxycellulose of 6- is obtained after drying；
2) 6- nitrine -6- deoxycellulose synthesizes: the bromo- 6- deoxycellulose of 6- that step 1) obtains is dissolved in solvent
In DMSO, excessive sodium azide is added, heating reaction obtains 6- nitrine -6- deoxycellulose.
According to the above scheme, the acid solution is one of aqueous acidic solution or a variety of, is adjusted with acid solution
For reaction mixture pH value to 5-7, the alkaline solution is one of water-soluble alkali solution or a variety of, is adjusted with alkaline solution
Reaction mixture pH value is to 8-9.
According to the above scheme, the concentration of lithium bromide before being diluted with DMAc of cellulose solution described in step 1) is at least
0.23g/mL。
According to the above scheme, described in step 1) with DMAc dilute cellulose solution, to reduce the concentration of lithium bromide, with
After DMAc dilution, the temperature of cellulose solution is 70 DEG C or more.
According to the above scheme, the addition sequence of triphenylphosphine described in step 1) and NBS solution is that triphenylphosphine is first added,
After be added NBS, and when triphenylphosphine and NBS solution is added, the temperature of cellulose solution is 0-5 DEG C.
According to the above scheme, precipitating reagent described in step 1) is distilled water.
According to the above scheme, the dosage of solvent DMSO described in step 2) is that the bromo- 6- deoxycellulose of every gram of 6- at least needs
40mL DMSO。
According to the above scheme, it is single to be at least the bromo- 6- deoxycellulose repetition of 6- for the dosage of sodium azide described in step 2)
8 times of first mole.
Reaction equation according to the present invention is as follows:
The beneficial effects of the present invention are:
1) in the present invention the bromo- 6- deoxycellulose of 6- preparation method favorable reproducibility, by-product acetic acid ester is few, and yield is high,
Bromine degree of substitution is high.
The bromo- 6- deoxycellulose of 6- is prepared according to method described in document (4), in the LiBr/DMAc using 0.23g/mL
After solution dissolves cellulose, when temperature is reduced to 11 DEG C, under the conditions of this high concentration lithium bromide, reaction solution will form solid
State, after be warming up to 40 DEG C and dissolve solid, and a certain amount of DMAc dilution is added, but when temperature is down to 15 DEG C, reaction solution
Still it can solidify.Therefore, the present invention first uses the LiBr/DMAc solution of higher concentration to dissolve cellulose, obtains cellulose solution, so
Cellulose solution is diluted with DMAc under 70 DEG C or temperatures above afterwards, to reduce the concentration of lithium bromide, because dilute at 70 DEG C or less
When releasing cellulose solution, the cellulose solution after dilution can still solidify under cryogenic.If disposably using DMAc more,
Because the concentration of LiBr is inadequate, even if using the identical DMAc of total volume, cellulose can not dissolve well.And work as cellulose
It is dissolved in the higher LiBr/DMAc solution of concentration, and after being diluted under 70 DEG C or temperatures above with DMAc, LiBr in solution
Concentration decreases, so that reaction solution be enable to keep solution state at a lower temperature, realizes homogeneous reaction.In addition, this hair
If NBS is first added in bright also found, triphenylphosphine is added afterwards, reaction solution can also solidify at a lower temperature, and heating can not
It is completely dissolved decorating film, the yield and its bromine degree of substitution of the bromo- 6- deoxycellulose of the 6- reacted are all lower.If with first adding
After NBS plus the bromo- 6- deoxycellulose of 6- of the method for triphenylphosphine preparation is raw material, synthesizes 6- nitrine -6- deoxycellulose,
Nitrogen content is significantly relatively low in elemental analysis value, shows that the bromine degree of substitution in the bromo- 6- deoxycellulose of its precursor 6- is also relatively low, because
Bromine can be made to be replaced completely by azido with method of the invention.
According to document (3) it is found that in the bromo- 6- deoxycellulose of preparation 6-, the hydroxyl on cellulose can be handed over DMAc
It changes reaction and generates by-product acetic acid ester, is i.e. small part hydroxyl in the bromo- 6- deoxycellulose of 6- has been derivatized into acetic acid esters.?
It is found in research of the invention, when triphenylphosphine and NBS being added at 0-5 DEG C, generated by-product cellulose ethanoate is very
Few, when triphenylphosphine and NBS being added at relatively high temperatures, by-product cellulose ethanoate increased significantly (attached drawing 1).As synthesis 6-
Bromo- 6- deoxycellulose after reaction, is that product is precipitated out by precipitating reagent with distilled water, has greatly saved synthesis
Cost.
2) preparation method of 6- nitrine -6- deoxycellulose is practical in the present invention.
In the method that document (4) prepares 6- nitrine -6- deoxycellulose, the bromo- 6- of 0.2g 6- is dissolved with 20mL DMSO
Deoxycellulose, the i.e. ratio of the bromo- 6- deoxycellulose of used DMSO and 6- are 100mL/g.And in the present invention program,
The ratio of the bromo- 6- deoxycellulose of the DMSO and 6- used is 40mL/g, this is to being prepared on a large scale 6- nitrine -6- deoxycellulose
It is highly beneficial.
3) in the present invention 6- nitrine -6- deoxycellulose reduction conversion ratio and gained 6- amino -6- deoxycellulose
Amino group substitution degree is very high.
According to method described in document (4), by 6- nitrine -6- deoxycellulose with the sodium borohydride of 20 times of moles 60
It is restored 48 hours at DEG C, tests the infrared spectrogram (attached drawing 3) of products therefrom 6- amino -6- deoxycellulose, which shows
In about 2113cm-1Place illustrates that azido is not completely reduced there are also the absorption peak of azido.This 6- amino -6- deoxidation is fine
Dimension element carries out acetylation, tests its nuclear magnetic resonance spectroscopy (attached drawing 5), and the substitution for learning amino is calculated from the figure integral area ratio
Degree is 0.70.Thus further illustrating can not be by the azido in 6- nitrine -6- deoxycellulose according to the method for document (4)
Reduction completely.It in the present invention, the use of the sodium borohydride of 20 times of moles in temperature is 110-by many experiments exploration discovery
Reacted at 120 DEG C 5-28 hours (reaction temperature more it is high then needed for the reaction time it is shorter), can will be in 6- nitrine-6- deoxycellulose
Azido restore completely.And use ratio of the DMSO in document to 6- nitrine -6- deoxycellulose is down to by 200mL/g
50mL/g considerably reduces the dosage of solvent.With the infrared spectroscopy of 6- amino -6- deoxycellulose prepared by the method for the present invention
Absorption peak as shown in attached drawing 3B and 3C, in spectrogram without azido and ester group.Obtained 6- amino -6- deoxycellulose is carried out
Acetylamino and benzamido generate 6- acetylaminohydroxyphenylarsonic acid 6- deoxycellulose and 6- benzamido -6- deoxidation fiber
Element, nuclear magnetic resonance spectroscopy calculate amino group substitution degree according to integral area ratio and are at least as shown in attached drawing 4A and attached drawing 4B
97%.In addition, according to document (5), the 6- amino -6- deoxycellulose prepared with triphenylphosphine reduction method still contains in product
There are a certain amount of triphenylphosphine and triphenylphosphine oxide, can not be completely removed using the methods of conventional washing, extracting, it is made
Obtain the cellulose ethanoate that 6- amino -6- deoxycellulose cannot preferably be dissolved in dilute acid soln, and generate in reaction process
There is no removings.And the present invention is using the azido in sodium borohydride reduction 6- nitrine -6- deoxycellulose, it is first after reaction
Acid, alkaline solution treatment reaction mixture are used afterwards, then the 6- amino -6- deoxidation fiber that can obtain high-purity is simply washed with water
Element, this 6- amino -6- deoxycellulose dissolve in 1% hydrochloric acid solution, have established base for subsequent derivatization or application
Plinth.Furthermore according to method described in document (4), inventor is repeated with sodium borohydride reduction 6- nitrine -6- deoxycellulose
Reaction when being post-processed by literature method, is first generated with 1mol/L hydrochloric acid solution quenching reaction to bubble-free, and discovery reaction is mixed
The pH value of liquid is closed substantially without significant change, saturated sodium bicarbonate is then still added in still aobvious alkalinity into reaction mixture
Solution, filtering, then product is washed with distilled water to remove water-soluble inorganic matter, 6- amino -6- deoxycellulose is obtained, but send out
Existing yield only has 23%.And in the present invention, the pH value of reaction mixture is first adjusted to 5-7 with acid solution, to quench reduction
Reaction, then pH value is adjusted to 8-9 generation precipitatings with aqueous slkali, it is washed with distilled water product after filtering, obtains 6- amino-6- deoxidation
Cellulose, yield 72% improve yield compared with preparing 6- amino -6- deoxycellulose with literature method significantly.It is comprehensive
Upper explanation prepares 6- amino -6- deoxycellulose favorable reproducibility with the method for the present invention, time-consuming short, restores the conversion ratio of azido
Height, practical, obtained 6- amino -6- deoxycellulose has very high degree of substitution.
4) the 6- amino -6- deoxycellulose prepared by the present invention has a good application prospect.
Since the structure and chitosan of 6- amino -6- deoxycellulose are more similar, thus its property and application may
There is similitude, for example it has biocompatibility, has stronger suction-operated etc. to metal ion.Furthermore 6- amino -6- deoxidation is fine
Amino in dimension element is different with the reactivity of hydroxyl, can selectively be modified, prepare the macromolecule material of Various Functions
Material.
Detailed description of the invention
Fig. 1 be the embodiment of the present invention 1, the bromo- 6- deoxycellulose of 6- prepared by embodiment 2 and comparative experiments 3 it is infrared
Spectrogram；
Fig. 2 is the infrared spectrogram of 6- nitrine -6- deoxycellulose prepared by the embodiment of the present invention 3；
Fig. 3 is with 6- amino -6- prepared in document 4 (comparative experiments 1) (A) and embodiment 4 (B), embodiment 5 (C)
The infrared spectrogram of deoxycellulose；
Fig. 4 is that the 6- acetylaminohydroxyphenylarsonic acid 6- that the 6- amino -6- deoxycellulose prepared in the process of the present invention is Material synthesis is de-
The hydrogen nuclear magnetic resonance spectrogram of oxygen cellulose (A) and 6- benzamido -6- deoxycellulose (B)；
Fig. 5 is to prepare 6- amino -6- deoxycellulose as the 6- second of Material synthesis in method (comparative experiments 1) in document 4
The hydrogen nuclear magnetic resonance spectrogram of acylamino- -6- deoxycellulose.
Specific embodiment
In order to enable those skilled in the art to better understand the present invention, the present invention is done further in detail below with reference to embodiment
Explanation, but the contents of the present invention are not limited solely to the following examples.
DMAc and DMSO used in the present invention use preceding warpMolecular sieve is dried 3 times, and cellulose uses preceding use drying
Refluxing toluene azeotropic water removing.
Embodiment 1
The preparation of the bromo- 6- deoxycellulose of 6-: triphenylphosphine and NBS are added at 0 DEG C
The dry cellulose of 4g is weighed in 500mL three-necked flask, the dry DMAc of 220mL is added, is heated to 130 DEG C,
It stirs 2 hours at this temperature.Mixture is cooled to 100 DEG C, 56.5g lithium bromide is added, it is saturating that stirring to mixture becomes clarification
It is bright, obtain cellulose solution.The dry DMAc of 180mL is added, is stirred 30 minutes at 100 DEG C.It is cold by cellulose with ice-water bath
But to the solution that 16.2g triphenylphosphine is dissolved in 40mL DMAc after 0 DEG C, is added, stirring is added dropwise 11.0g NBS and is dissolved in solution
The solution of 30mL DMAc drips off in 30min.Reaction solution is warming up to 70 DEG C, is stirred to react 2 hours.Reaction terminates, and will react
Drop adds in 1200mL distilled water, is stirred overnight, filtering, with acetone washing to filtrate in 254 nanometers without UV absorption, then
Three times with ethanol washing, dry, obtain the bromo- 6- deoxycellulose of 5.47g 6-, yield: 98.7%.The bromo- 6- deoxycellulose of 6-
Infrared spectrogram is as shown in figure 1: IR (KBr, cm-1) υ: 3416 (- OH), 2896 (- C-H), 1726 (- O-C=O), 664 (-
C-Br).The 1726cm on attached drawing 1A-1Neighbouring ester group peak and 1640cm-1Cellulose skeleton peak compared to more faint.
Embodiment 2
The preparation of the bromo- 6- deoxycellulose of 6-: triphenylphosphine and NBS are added at 5 DEG C
The temperature of reaction solution is adjusted to 5 DEG C, and keeps that triphenylphosphine and NBS are added at this temperature, remaining method with
The bromo- 6- deoxycellulose of identical preparation 6- in embodiment 1.Yield is 97%, infrared spectrogram as shown in fig. 1b, IR
(KBr,cm-1) υ: 3464 (- OH), 2899 (- C-H), 1726 (- O-C=O), 664 (- C-Br).The 1726cm on attached drawing 1B-1It is attached
Close ester group peak and 1637cm-1Cellulose skeleton peak compared to more faint, and it is unobvious with the peak intensity difference in A spectrum.
Embodiment 3
The preparation of 6- nitrine -6- deoxycellulose: the bromo- 6- deoxycellulose ratio of reaction dissolvent DMSO and 6- is 40mL/g
The bromo- 6- deoxycellulose ratio of reaction dissolvent DMSO and 6- is adjusted to 40mL/g, remaining method and comparative experiments 1
In identical preparation 6- nitrine -6- deoxycellulose.Yield is 78%, and infrared spectrogram is as shown in Fig. 2: IR (KBr, cm-1)
υ:3433(-OH),2890(-C-H),2110(-N3), in 2110cm-1There is very strong azido absorption peak at place, illustrates to generate 6-
Nitrine -6- deoxycellulose.
Embodiment 4
The preparation of 6- amino -6- deoxycellulose: the reduction temperature of 6- nitrine -6- deoxycellulose is 115 DEG C, when reduction
Between be 7 hours
5.89g dry 6- nitrine -6- deoxycellulose and 300mL DMSO are mixed, stir to clarify it is transparent, then
24.30g NaBH is added4, 7h is reacted at 115 DEG C.It after reaction, is 5-7 with the pH value of 1mol/L hydrochloric acid tune reaction solution,
Adding saturated sodium bicarbonate aqueous solution to pH value is 8-9, is stirred overnight.Filtering is washed with distilled water for several times, dry, is obtained
3.65g 6- amino -6- deoxycellulose.Yield: 72%, infrared spectrogram as illustrated in figure 3b, IR (KBr, cm-1)υ:3437
(-OH,-NH2), 2893 (- C-H), in 2110cm-1Nearby there is no azido absorption peak, illustrates the azido under the conditions of present invention
It is completely reduced.
Embodiment 5
The preparation of 6- amino -6- deoxycellulose: the reduction temperature of 6- nitrine -6- deoxycellulose is 110 DEG C, when reduction
Between be 24 hours
Reaction temperature is adjusted to 110 DEG C, the reaction time is adjusted to for 24 hours, remaining method preparation 6- identical as embodiment 4
Amino -6- deoxycellulose.Yield is 55%, and infrared spectrogram is as shown in attached drawing 3C, IR (KBr, cm-1)υ:3416(-OH,-
NH2), 2898 (- C-H), in 2110cm-1Nearby almost without azido absorption peak, illustrate that azido is several under the conditions of the present invention
It is completely reduced.
Embodiment 6
Investigate the reproducibility for preparing 6- amino -6- deoxycellulose method:
It repeats embodiment 1 and prepares the bromo- 6- deoxycellulose of 6-, yield: 98.7%；IR(KBr,cm-1) υ: 3450 (- OH),
2990-2890 (- C-H), 1725 (- O-C=O), 676, (- C-Br).
It repeats embodiment 3 and prepares 6- nitrine -6- deoxycellulose, yield: 78%；IR(KBr,cm-1) υ: 3430 (- OH),
2890 (- C-H), 2110 (- N3)。
It repeats embodiment 4 and prepares 6- amino -6- deoxycellulose, yield: 84%；IR(KBr,cm-1)υ:3423(-OH,-
NH2), 2890 (- C-H).
Embodiment 7
The preparation of 6- acetylaminohydroxyphenylarsonic acid 6- deoxycellulose: 0.5g glacial acetic acid is dissolved in 21.9g water, 0.73g is added and exists
6- amino -6- the deoxycellulose prepared in embodiment 4 is warming up to 64 DEG C, stirs completely molten to 6- amino -6- deoxycellulose
Solution.7 DEG C are cooled to, 3.90g acetic anhydride is added and is dissolved in the solution in 120mL methanol, is stirred to react 7h.Reaction solution is poured into
It in the ethanol solution of 143mL0.5mol/L potassium hydroxide, is stirred overnight, filters, successively for several times with ethyl alcohol, distillation water washing, obtain
To 0.5g6- acetylaminohydroxyphenylarsonic acid 6- deoxycellulose, yield: 54%.IR(KBr,cm-1)υ:3336(-OH),2886(-C-H),
1660 (areas-CO-NH amide I), 1553 (areas-CO-NH amide II)；1H NMR schemes as shown in fig 4,1H NMR(25℃,
CF3COOD):1.72—2.80(m,-CH3), 3.16-5.65 (m, cellulose skeleton hydrogen) calculate ammonia according to integral area ratio
Base degree of substitution about 97% illustrates that the 6- amino -6- deoxycellulose of present case preparation has very high substituted degree.
Embodiment 8
The preparation of 6- benzamido -6- deoxycellulose: at 70 DEG C, the 6- amino-that will be prepared in 0.3g embodiment 6
6- deoxycellulose is dissolved in the benzoic acid aqueous solution that 9g mass fraction is 2%, and after being down to 25 DEG C, 20g methanol is added.To 6- ammonia
The methanol solution that 3.37g benzoyl oxide is dissolved in 16g is added in the solution of base -6- deoxycellulose, is stirred 7 hours at 25 DEG C.
Reaction terminates, and reaction solution is poured into the ethanol solution of 65mL 0.5mol/L potassium hydroxide, is stirred overnight, and second is successively used in filtering
Alcohol, distillation water washing for several times, obtain 6- benzamido -6- deoxycellulose.1H NMR(25℃,CF3COOD):7.00—
8.05 (m, the protons on phenyl ring), 3.16-5.65 (m, cellulose skeleton hydrogen) (attached drawing 4B) are calculated according to integral area ratio
Amino group substitution degree is 97%, illustrates that the 6- amino -6- deoxycellulose of present case preparation has very high substituted degree, and reproducibility
It is good.
Comparative experiments 1
6- amino -6- deoxycellulose is prepared according to the method in document 4
The preparation of the bromo- 6- deoxycellulose of 6-: the dry cellulose of 1.0g is weighed in 250mL three-necked flask, is added
60mL dry DMAc, is heated to 130 DEG C, stirs 2 hours at this temperature.Mixture is cooled to 100 DEG C, 14.08g is added
Lithium bromide stirs mixture to it at this temperature and becomes clear (about half an hour), obtains cellulose solution.Cooling fiber
Solution of the 4.05g triphenylphosphine dissolved in 30mL DMAc is added to 0 DEG C in plain solution, then 2.75g NBS dissolution is slowly added dropwise
Solution in 30mL DMAc, about 30min add.After being added dropwise, reaction solution is warming up to 70 DEG C, is stirred 2 hours.Reaction
Terminate, reaction solution is poured into acetone, is precipitated, filters, three times with acetone washing, residue is placed in acetone and stirs two
Hour, filtering is washed with water.Precipitating is mixed with 0.07mol/L sodium bicarbonate solution, is stirred overnight, filters at room temperature, use
Water washing is for several times, mixed with water again by precipitating, and stirs two hours, and filtering is washed with water for several times, dry, and it is bromo- to obtain 1.3g 6-
6- deoxycellulose, yield: 93%, IR (KBr, cm-1) υ: 3446 (- OH), 2887 (- C-H), 1726 (- O-C=O), 671 (-
C-Br)。
The preparation of 6- nitrine -6- deoxycellulose: the bromo- 6- deoxycellulose of 6-, the 2.89g NaN of 1g drying3With
0.165g n-Bu4NI is added in the dry DMSO of 100mL, stirs to clarify transparent, reacts 48h at 70 DEG C.Reaction terminates
Afterwards, reaction solution is poured into 300ml distilled water, filters, is washed with distilled water, precipitating is added to the water stirring two hours, is filtered,
Successively methanol is drunk with water to wash, it is dry, obtain 0.68g 6- nitrine -6- deoxycellulose, yield: 82%, IR (KBr, cm-1)υ:
3437 (- OH), 2891 (- C-H), 2111 (- N3)。
The preparation of 6- amino -6- deoxycellulose: 0.2g dry 6- nitrine -6- deoxycellulose and 40mL is dry
DMSO is mixed, and stirring is completely dissolved to decorating film, obtains 6- nitrine -6- deoxycellulose solution.It is added into above-mentioned solution
0.81g NaBH4, 48h is reacted at 60 DEG C.After reaction, 1mol/L hydrochloric acid bubble-free into reaction solution is added dropwise to generate, then
Saturated sodium bicarbonate aqueous solution is added, filtering is washed with distilled water for several times, obtains 40mg 6- amino -6- deoxycellulose, produces
Rate: 23%.Infrared spectrogram as shown in fig. 3 a, IR (KBr, cm-1)υ:3393(-OH,-NH2),2890(-C-H),2113(-
N3)。
Comparative experiments 2
With the method in embodiment 7,6- is prepared with the 6- amino -6- deoxycellulose of the method preparation in comparative experiments 1
Acetylaminohydroxyphenylarsonic acid 6- deoxycellulose, yield: 79%.1H NMR is as shown in Fig. 5, (25 DEG C, CF3COOD):1.70—2.80
(m,-CH3), 3.16-5.65 (m, the hydrogen of cellulose skeleton).
According to document 4 prepare 6- amino -6- deoxycellulose infrared spectrogram as shown in fig. 3 a, which shows folded
Nitrogen base is not completely reduced.The complete acetylate of its amino1H NMR spectra is as shown in Fig. 5, according to the product in the spectrogram
It is about 70% that point area ratio, which calculates amino group substitution degree,.And according to not having in 6- amino -6- deoxycellulose prepared by embodiment 4
There is remaining azido, and the degree of substitution of amino is at least 97%.It is real in the reproducibility for preparing 6- amino -6- deoxycellulose
In testing, benzoylation is carried out to amino, nuclear magnetic resonance spectroscopy shows amino group substitution degree about 97%, favorable reproducibility.In conclusion
6- amino -6- the deoxycellulose of high substituted degree, high-purity, and the weight of synthesis technology can be prepared with the method in the present invention
Existing property is good.
Comparative experiments 3
The preparation of the bromo- 6- deoxycellulose of 6-: triphenylphosphine and NBS are added at 50 DEG C
The temperature of reaction mixture when triphenylphosphine and NBS is added is adjusted to 50 DEG C, the phase of remaining method and embodiment 1
With the preparation bromo- 6- deoxycellulose of 6-.Yield is 61%, and infrared spectrogram is as shown in attached drawing 1C, IR (KBr, cm-1)υ:3434(-
OH), 2887 (- C-H), 1732 (- O-C=O), 685 (- C-Br).1732cm in attached drawing 1C-1Neighbouring ester group peak significantly more than
1634cm-1Cellulose skeleton peak intensity, illustrate that triphenylphosphine and NBS are added at relatively high temperatures to be easy to generate by-product acetic acid
Ester.
Claims (9)
1. a kind of preparation method of 6- amino -6- deoxycellulose comprising have the following steps: by 6- nitrine -6- deoxidation fiber
Element is dissolved in solvent dimethyl sulfoxide, and the solvent DMSO dosage is that every gram of 6- nitrine -6- deoxycellulose at least needs
Excessive NaBH is added in DMSO50mL4, it is reacted at being 110-120 DEG C in temperature 5-28 hours, it is first with acid solution that reaction is mixed
The pH value for closing object is adjusted to acid range, to quench excessive NaBH4, then again with alkaline solution by the pH value tune of reaction mixture
To alkaline range, reaction mixture is stirred overnight, the solid in mixture is filtered, is washed with water, it is dry, obtain 6- amino-
6- deoxycellulose.
2. the synthetic method of 6- amino -6- deoxycellulose according to claim 1, it is characterised in that the 6- is folded
The synthesis of nitrogen -6- deoxycellulose includes following steps:
1) synthesis of the bromo- 6- deoxycellulose of 6-: by cellulose, stirring two is small at 130 DEG C in DMAC N,N' dimethyl acetamide
When, 100 DEG C are cooled to, lithium bromide is added, stirring to cellulose is completely dissolved, and is diluted at a certain temperature with a certain amount of DMAc
Above-mentioned cellulose solution, stirring, is then cooled to certain temperature for the cellulose solution after dilution, at this temperature to cellulose
Triphenylphosphine is added in solution and N- bromo-succinimide is dissolved in the solution of DMAc, reaction solution is heated to 70 DEG C, stirring is anti-
It answers two hours, after reaction, reaction solution is poured into and generates precipitating in precipitating reagent, obtains 6- after being filtered, washed, drying
Bromo- 6- deoxycellulose；
2) 6- nitrine -6- deoxycellulose synthesizes: the bromo- 6- deoxycellulose of 6- that step 1) obtains is dissolved in solvent DMSO
In, excessive sodium azide is added, heating reaction obtains 6- nitrine -6- deoxycellulose.
3. the synthetic method of 6- amino -6- deoxycellulose according to claim 1, it is characterised in that the acidity is molten
Liquid is one of aqueous acidic solution or a variety of, adjusts reaction mixture pH value to 5-7 with acid solution, the alkalinity is molten
Liquid is one of water-soluble alkali solution or a variety of, adjusts reaction mixture pH value to 8-9 with alkaline solution.
4. the synthetic method of 6- amino -6- deoxycellulose according to claim 2, it is characterised in that described in step 1)
Cellulose solution before being diluted with DMAc the concentration of lithium bromide be at least 0.23g/mL.
5. the synthetic method of 6- amino -6- deoxycellulose according to claim 2, it is characterised in that described in step 1)
Dilute cellulose solution with DMAc, to reduce the concentration of lithium bromide, after being diluted with DMAc, the temperature of cellulose solution is 70
DEG C or more.
6. the synthetic method of 6- amino -6- deoxycellulose according to claim 2, it is characterised in that described in step 1)
Triphenylphosphine and the addition sequence of NBS solution be that triphenylphosphine is first added, be added NBS afterwards, and triphenylphosphine and NBS is being added
When solution, the temperature of cellulose solution is 0-5 DEG C.
7. the synthetic method of 6- amino -6- deoxycellulose according to claim 2, it is characterised in that described in step 1)
Precipitating reagent be distilled water.
8. the synthetic method of 6- amino -6- deoxycellulose according to claim 2, it is characterised in that described in step 2)
Solvent DMSO dosage be the bromo- 6- deoxycellulose of every gram of 6- at least need 40mL DMSO.
9. the synthetic method of 6- amino -6- deoxycellulose according to claim 2, it is characterised in that described in step 2)
The dosage of sodium azide be at least 8 times of the bromo- 6- deoxycellulose repetitive unit mole of 6-.
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| CN110357977B (en) * | 2019-07-19 | 2022-03-15 | 武汉工程大学 | Preparation method of 6-amino-6-deoxy amylose |
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