CN109824799A - A kind of chitosan derivatives and preparation method thereof of sulfur-bearing urea structure - Google Patents
A kind of chitosan derivatives and preparation method thereof of sulfur-bearing urea structure Download PDFInfo
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- CN109824799A CN109824799A CN201910071523.8A CN201910071523A CN109824799A CN 109824799 A CN109824799 A CN 109824799A CN 201910071523 A CN201910071523 A CN 201910071523A CN 109824799 A CN109824799 A CN 109824799A
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Abstract
The invention belongs to marine chemical industry engineering technology, and in particular to a kind of chitosan derivatives and preparation method thereof of sulfur-bearing urea structure.General structure is as shown in formula I, wherein n=4-100, R=-CH3OrIn the present invention, first by chitosan and 1, the reaction of 2- Bromofume generates bromoethyl chitosan derivatives, then with hydration hydrazine reaction, it obtains finally obtaining the chitosan derivatives containing thiocarbamide structure with isosulfocyanate substance reaction again containing hydrazine ethyl chitosan derivative.Gained derivative determines its structure through infrared spectrum analysis, and the group of chitosan and access is effectively combined the chitosan derivatives for generating sulfur-bearing urea structure, improves the bioactivity of chitosan.
Description
Technical field
The invention belongs to marine chemical industry engineering technology, and in particular to a kind of chitosan derivatives and its system of sulfur-bearing urea structure
Preparation Method.
Background technique
In agricultural production, crops cause crops dead or the underproduction often vulnerable to the infringement of phytopathogen, for solution
Certainly this problem, the use of agricultural drugs are essential, but as chemical pesticide more and more uses, and give nature ring
Border and ecology also bring more serious influence, and the residual problem of agriculture is also increasingly valued by people.Therefore, develop low toxicity,
Efficiently, the good environment friendly agricultural of Environmental compatibility is the task of top priority.
Chitosan is a kind of natural macromolecule amylose, by chitin it is deacetylated from.Chitosan is nontoxic, it is degradable,
Environmental compatibility is good.And it is numerous studies have shown that chitosan has good bacteriostatic activity, reason may be its unique cation
Characteristic allows to combine with the anion of phage surface, to destroy the functionality of cell membrane, inhibits thalli growth.But its
Bacteriostatic activity is compared with traditional pesticide, and there are still certain gaps.Structural modification is carried out to chitosan, enhances its bioactivity, is
The hot spot studied both at home and abroad.
Thiourea pesticide is one of composition type of modern, is applied to agricultural mainly as fungicide, agrochemical
Production, significant effect, typical such as thiophanate-methyl, C-9140.But as most of pesticides, the pesticide of Thiourea exists
The serious problem of environmental pollution, therefore its harmfulness is reduced while guaranteeing its effect, it is assistant officer's problem to be solved.
Summary of the invention
It is an object of that present invention to provide a kind of chitosan derivatives of the good sulfur-bearing urea structure of structure novel, bacteriostatic activity
Object and preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of chitosan derivatives of sulfur-bearing urea structure, structural formula as shown in formula I,
In formula, n=4-100, R=-CH3Or
A kind of preparation method of the chitosan derivatives of sulfur-bearing urea structure:
Hydrazine ethyl chitosan derivative is swollen in dehydrated alcohol, under the conditions of 60-70 DEG C, is reacted with isothiocyanates
9-18h obtains the chitosan derivatives of sulfur-bearing urea structure.Wherein, on the basis of chitosan monosaccharide, hydrazine ethyl chitosan and different sulphur
Cyanate molar ratio is 1:1-3；It filters after reaction, filter cake is washed with dehydrated alcohol, collect filter cake and done at 50-60 DEG C
It is dry.
The acquisition of the hydrazine ethyl chitosan derivative is to swell in bromoethyl chitosan derivatives in dehydrated alcohol,
Under the conditions of 60 DEG C, with 85% hydration hydrazine reaction 12-18h, hydrazine ethyl chitosan derivative is obtained；Wherein, it is with chitosan monosaccharide
Benchmark, bromoethyl chitosan and hydrazine hydrate molar ratio are 1:3-7；It filters after reaction, filter cake is washed with dehydrated alcohol, is collected
Filter cake is dry at 50-60 DEG C.
The acquisition of the bromoethyl chitosan derivatives is to swell in chitosan in n,N-Dimethylformamide, is tiing up acid
In the presence of agent triethylamine, 12h is reacted at 50-60 DEG C with 1,2- Bromofume, generates bromoethyl chitosan derivatives；Wherein,
On the basis of chitosan monosaccharide, chitosan and 1,2- Bromofume, triethylamine molar ratio are 1:1-3:1-3；It takes out after reaction
Filter washs filter cake with dehydrated alcohol, it is dry at 50-60 DEG C to collect filter cake.
A kind of application of the chitosan derivatives of sulfur-bearing urea structure, the chitosan derivative of sulfur-bearing urea structure shown in the formula I
Object is applied in the drug as controlling plant diseases.
Principle: in the presence of acid binding agent, 1,2- Bromofume can be with-OH and-NH on chitosan2Substitution reaction occurs,
Bromine atom is easy to leave away on bromoethyl, and substitution reaction can occur with hydrazine hydrate, contain unstable N=C=S in isothiocyanates
Cumulated double bond can occur addition reaction with the diazanyl being connect on chitosan, generate the chitosan derivatives of sulfur-bearing urea structure.
Advantages of the present invention: Thiourea pesticide is one of composition type of modern, thiourea group life with higher
Object activity.The present invention splices method using active substructure, using natural polysaccharide chitosan as carrier, introduces the Thiourea base that N replaces
Group plays the antibacterial effect of both thiocarbamide structure and chitosan, the good chitosan derivative of bacteriostatic activity is prepared, to open
Green-emitting environmental protection, the efficient novel biopesticide of low toxicity opened up a new way.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of chitosan 1 provided in an embodiment of the present invention, and infrared signature absorbs (cm-1): 3242,
1621,1515,1062,1021.
Fig. 2 is the infrared spectrogram of chitosan 2 provided in an embodiment of the present invention, and infrared signature absorbs (cm-1): 3237,
1606,1507,1060,1031.
Fig. 3 is the infrared spectrogram of bromoethyl chitosan 1 provided in an embodiment of the present invention, and infrared signature absorbs (cm-1):
3272,1538,1022.
Fig. 4 is the infrared spectrogram of bromoethyl chitosan 2 provided in an embodiment of the present invention, and infrared signature absorbs (cm-1):
3278,1632,1518,1025
Fig. 5 is the infrared spectrogram of hydrazine ethyl chitosan 1 provided in an embodiment of the present invention, and infrared signature absorbs (cm-1):
3282,1583,1026
Fig. 6 is the infrared spectrogram of hydrazine ethyl chitosan 2 provided in an embodiment of the present invention, and infrared signature absorbs (cm-1):
3314,1580,1027
Fig. 7 is the infrared spectrogram of derivative 1 provided in an embodiment of the present invention, and infrared signature absorbs (cm-1): 3278,
1556,1257,1026
Fig. 8 is the infrared spectrogram of derivative 2 provided in an embodiment of the present invention, and infrared signature absorbs (cm-1): 3271,
1591,1543,1498,1256,1026
Specific embodiment
The invention is further explained in the following combination with the attached drawings of the specification, and protection scope of the present invention is not only limited to
Following embodiment.
Embodiment 1
Taking 12.0g molecular weight is that 7700 chitosan 1 is swollen in 120mL n,N-Dimethylformamide, and 20.7mL is added
Triethylamine adds 12.8mL 1, and 2- Bromofume is warming up to 50 DEG C, is stirred to react 12h, filters, and filter cake is rushed with dehydrated alcohol
It washes, it is dry at 60 DEG C, obtain Tan solid, as bromoethyl chitosan 1.
It takes 8.0g bromoethyl chitosan derivatives 1 to swell in 80mL dehydrated alcohol, 85% hydrazine hydrate of 6.4mL is added, rise
Temperature is stirred to react 18h to 60 DEG C, filters, and filter cake is rinsed with dehydrated alcohol, dry at 50 DEG C, obtains white-yellowish solid, as hydrazine
Ethyl chitosan 1.
It takes 1.0g hydrazine ethyl chitosan 1 to swell in 15mL dehydrated alcohol, 0.67g methyl-isorhodanate is added, is warming up to
It 70 DEG C, back flow reaction 7h, filtering, filter cake is rinsed with dehydrated alcohol, and it is dry at 50 DEG C, obtain faint yellow solid, as derivative
1: methylthiourea amine ethyl chitosan, structure are shown in general formula I, R=-CH3
Infrared spectroscopy shows: infrared spectrum (Fig. 1) phase of the infrared spectrum (Fig. 3) of bromoethyl chitosan 1 and chitosan 1
Than chitosan 1515cm-1Place-NH2Absorption peak obviously weaken, explanation-NH2On reacted, 1062cm-1Locate C-O to absorb
Peak obviously weakens, and is reacted on explanation-OH, it was demonstrated that bromoethyl chitosan 1 is successfully prepared；Hydrazine ethyl chitosan 1 it is infrared
Spectrogram (Fig. 5) is compared with the infrared spectrum (Fig. 3) of bromoethyl chitosan 1, in 1583cm-1There is-NH on diazanyl in place2Absorption
Peak, it was demonstrated that hydrazine ethyl chitosan 1 is successfully prepared；The infrared spectrum of infrared spectrum (Fig. 7) and hydrazine ethyl chitosan 1 of derivative 1
(Fig. 5) is compared, 1583cm-1Locate ,-NH on diazanyl2Absorption peak disappear, in 1556cm-1There is the feature of N-C=S structure in place
Absorption peak, and in 1257cm-1There is the characteristic absorption peak of C=S structure in place, it was demonstrated that derivative 1 is successfully prepared.
Embodiment 2
Taking 10.0g molecular weight is that 4000 chitosan 2 is swollen in 100mL n,N-Dimethylformamide, and 17.3mL is added
Triethylamine adds 10.7mL 1, and 2- Bromofume is warming up to 50 DEG C, is stirred to react 12h, filters, and filter cake is rushed with dehydrated alcohol
It washes, it is dry at 60 DEG C, obtain khaki solid, as bromoethyl chitosan 2.
It takes 8.0g bromoethyl chitosan 2 to swell in 80mL dehydrated alcohol, 85% hydrazine hydrate of 6.4mL is added, is warming up to 60
DEG C, it is stirred to react 18h, is filtered, filter cake is rinsed with dehydrated alcohol, and it is dry at 50 DEG C, obtain light tan solid, as hydrazine ethyl shell
Glycan 2.
It takes 2.0 hydrazine ethyl chitosans 2 to swell in 30mL dehydrated alcohol, 2.185mL phenyl isothiocyanate is added, is warming up to
It 60 DEG C, back flow reaction 18h, filtering, filter cake is rinsed with dehydrated alcohol, and it is dry at 50 DEG C, obtain light yellow solid, as derivative
2: phenylthiourea amine ethyl chitosan, structure are shown in general formula I,
Infrared spectroscopy shows: infrared spectrum (Fig. 2) phase of the infrared spectrum (Fig. 4) of bromoethyl chitosan 2 and chitosan 2
Than chitosan 1507cm-1Place-NH2Absorption peak obviously weaken, explanation-NH2On reacted, 1060cm-1Locate C-O to absorb
Peak obviously weakens, and is reacted on explanation-OH, it was demonstrated that bromoethyl chitosan 2 is successfully prepared；Hydrazine ethyl chitosan 2 it is infrared
Spectrogram (Fig. 6) is compared with the infrared spectrum (Fig. 4) of bromoethyl chitosan 2, in 1580cm-1There is-NH on diazanyl in place2Absorption
Peak, it was demonstrated that hydrazine ethyl chitosan 2 is successfully prepared；The infrared spectrum of infrared spectrum (Fig. 8) and hydrazine ethyl chitosan 2 of derivative 2
(Fig. 6) is compared, 1580cm-1Locate-NH on diazanyl2Absorption peak obviously weaken and be transferred to 1591cm-1Place, in 1543cm-1Place occurs
The characteristic absorption peak of N-C=S structure, in 1498cm-1There is the characteristic absorption peak of C=C on phenyl ring in place, and in 1256cm-1
There is the characteristic absorption peak of C=S structure in place, it was demonstrated that derivative 2 is successfully prepared.
Application examples Antibacterial Activity
Using growth rate method measurement sample to the bacteriostatic activity of fusarium solani.It tests under 3 sample concentrations i.e.:
200 μ g/ml, 400 μ g/ml, 800 μ g/ml, to the inhibitory effect of fusarium solani.
Experiment, for positive control, is sky with distilled water with the good general oligosaccharides medicament (the commercially available aqua for being 2%) of same concentrations
White control.Culture medium is uniformly poured into the culture dish that 2 diameters are 9cm, after solidifying completely, is inoculated in each culture dish
The bacteria cake that 3 pieces of diameters are 5mm.After being cultivated 48 hours at 28 DEG C, colony diameter is measured, the bacteriostasis rate of sample is calculated.Place every time
Reason 2 culture dishes of setting, every ware are inoculated with 3 bacterium colonies, to each Detection of colony maximum gauge (Dmax) and minimum diameter (Dmin),
It is averaged as sample antibacterial circle diameter D sample, total Test is repeated once.Bacteriostasis rate is calculated according to the following formula.
Bacteriostasis rate (%)=(D blank-D sample)/(D blank -5) × 100%
Experimental result is shown in Table 1
Inhibitory activity of 1 general formula of table, I chitosan derivatives to fusarium solani
As described in table 1, the antibacterial activity of the chitosan derivatives of two kinds of sulfur-bearing urea structures described in general formula I is significantly better than
Chitosan raw material, and to compose oligosaccharides well 10-30 percentage points strong for the antibacterial agent than being commercialized at present, therefore, sulfur-bearing of the present invention
The chitosan derivatives of urea structure have preferable bacteriostatic activity.
Claims (6)
1. a kind of chitosan derivatives of sulfur-bearing urea structure, it is characterised in that: sulfur-bearing urea structure chitosan derivatives general structure
As shown in formula I,
In formula, n=4-100, R=-CH3Or
2. a kind of preparation method of the chitosan derivatives of sulfur-bearing urea structure, it is characterised in that:
1) in the presence of acid binding agent triethylamine, chitosan and 1,2- Bromofume reacts 12h at 50-60 DEG C, generates bromoethyl
Chitosan derivatives；
2) bromoethyl chitosan derivatives and 85% hydrazine hydrate react 12-18h, obtain hydrazine ethyl chitosan under the conditions of 60 DEG C
Derivative；
3) hydrazine ethyl chitosan derivative and isothiocyanates react 9-18h, obtain sulfur-bearing urea structure under the conditions of 60-70 DEG C
Chitosan derivatives.
3. the preparation method of the chitosan derivatives of sulfur-bearing urea structure according to claim 2, it is characterised in that step 1)
Middle solvent is N,N-dimethylformamide；On the basis of chitosan monosaccharide, chitosan and 1,2- Bromofume, triethylamine molar ratio
For 1:1-3:1-3；It filters after reaction, filter cake is washed with dehydrated alcohol, it is dry at 50-60 DEG C to collect filter cake.
4. the preparation method of the chitosan derivatives of sulfur-bearing urea structure according to claim 2, it is characterised in that step 2)
Middle solvent is dehydrated alcohol, and on the basis of chitosan monosaccharide, bromoethyl chitosan and hydrazine hydrate molar ratio are 1:3-7；Reaction knot
It is filtered after beam, filter cake is washed with dehydrated alcohol, it is dry at 50-60 DEG C to collect filter cake.
5. the preparation method of the chitosan derivatives of sulfur-bearing urea structure according to claim 2, it is characterised in that step 3)
Middle solvent is dehydrated alcohol, and on the basis of chitosan monosaccharide, hydrazine ethyl chitosan and isothiocyanates molar ratio are 1:1-3；Instead
It is filtered after answering, filter cake is washed with dehydrated alcohol, it is dry at 50-60 DEG C to collect filter cake.
6. the preparation method of the chitosan derivatives of sulfur-bearing urea structure according to claim 2, it is characterised in that: described logical
The chitosan derivatives of sulfur-bearing urea structure shown in Formulas I are applied in preparing fungicide.
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| JP2000264902A (en) * | 1999-03-15 | 2000-09-26 | Univ Miyazaki | Thiourea derivative of chitosan |
| CN101121759A (en) * | 2007-07-27 | 2008-02-13 | 中国科学院海洋研究所 | Chitosan thiosemicarbazone derivatives and preparation method thereof |
| CN102718886A (en) * | 2011-11-24 | 2012-10-10 | 中国科学院海洋研究所 | Novel 1,2,4-triazole derivative of chitosan and preparation method thereof |
| CN107312110A (en) * | 2017-07-06 | 2017-11-03 | 山东师范大学 | A kind of N thiosemicarbazides O quaternary ammonium salts chitosan oligosaccharide and preparation method and application |
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Non-Patent Citations (11)
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