CN109021033A - A kind of chitosan oligosaccharide derivative and preparation method thereof containing thiocarbamide and diethoxy phosphinylidyne amine structure - Google Patents
A kind of chitosan oligosaccharide derivative and preparation method thereof containing thiocarbamide and diethoxy phosphinylidyne amine structure Download PDFInfo
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- CN109021033A CN109021033A CN201810810737.8A CN201810810737A CN109021033A CN 109021033 A CN109021033 A CN 109021033A CN 201810810737 A CN201810810737 A CN 201810810737A CN 109021033 A CN109021033 A CN 109021033A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H5/00—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
- C07H5/04—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to nitrogen
- C07H5/06—Aminosugars
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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 invention belongs to marine chemical industry engineering technology, and in particular to a kind of chitosan oligosaccharide derivative and preparation method thereof containing thiocarbamide and diethoxy phosphinylidyne amine structure.Containing thiocarbamide and diethoxy phosphinylidyne hydrazine structural shell oligosaccharide derivative as shown in formula I, wherein n=2-20.In the present invention, first by chitosan oligosaccharide and 1, the reaction of 2- Bromofume generates bromoethyl chitosan oligosaccharide derivative, then ammonium thiocyanate is added, it is reacted with bromoethyl and generates isothiocyanic acid ethyl chitosan oligosaccharide derivative, isothiocyanate group further with hydration hydrazine reaction, obtains the aminothio Asia urea ethyl chitosan oligosaccharide derivative containing thiourea group, it is finally reacted with diethyl chloro-phosphate, obtains the chitosan oligosaccharide derivative containing thiocarbamide and diethoxy phosphinylidyne amine structure.Gained derivative determines its structure through infrared spectrum analysis, and the group of chitosan oligosaccharide and access, which is effectively combined, generates the chitosan oligosaccharide derivative containing thiocarbamide and diethoxy phosphinylidyne amine structure, improves the bioactivity of chitosan oligosaccharide.
Description
Technical field
The invention belongs to marine chemical industry engineering technology, and in particular to a kind of shell containing thiocarbamide and diethoxy phosphinylidyne amine structure
Oligosaccharide derivative and preparation method thereof.
Background technique
Chemical pesticide has indispensable meaning for the development of modern agriculture, is prevention and treatment corps diseases, insect pest
Main means of prevention.However, most of toxicity of pesticide are stronger, while killing germ, disease pest and weeds, also bring more
Serious environmental hazard, remaining pesticide are shifted with water and soil, are caused to the health of non-target plant, the animal even mankind
It threatens.Therefore, reducing its phytotoxicity while guaranteeing its drug effect is the task of top priority.
From the chitin that chitosan is widely present in nature is deacetylated, chitosan oligosaccharide is the catabolite of chitosan.
Shell is poly-/and oligosaccharides is nontoxic, and Environmental compatibility is good, and has many activity, such as antibacterial, degeneration-resistant, growth promotion, immunological regulation, soil
Earth improvement etc., thus agriculturally having relatively broad application.But for its bioactivity compares traditional pesticide, there are still one
Determine gap./ oligosaccharides poly- to shell carries out structural modification, enhances its bioactivity, is the hot spot studied both at home and abroad.
Organophosphorus pesticide and Thiourea pesticide are two kinds of important types of modern, mainly as insecticide, fungicide
Applied to agricultural production, significant effect.But as most of pesticides, problem of environmental pollution caused by component residue is difficult to solve
Certainly.
Summary of the invention
It is an object of that present invention to provide a kind of good water solubility, structure novel contain thiocarbamide and diethoxy phosphinylidyne amine structure
Chitosan oligosaccharide derivative and preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of chitosan oligosaccharide derivative containing thiocarbamide and diethoxy phosphinylidyne amine structure contains thiocarbamide and diethoxy phosphinylidyne hydrazine knot
Structure chitosan oligosaccharide derivative as shown in formula I,
In formula, n=2-20.
A kind of preparation method of the chitosan oligosaccharide derivative containing thiocarbamide and diethoxy phosphinylidyne amine structure: it is deposited in acid binding agent pyridine
Under, aminothio Asia urea ethyl chitosan oligosaccharide derivative and the diethyl chloro-phosphate 30-60min under microwave action obtain I institute of formula
Showing the chitosan oligosaccharide derivative containing thiocarbamide and diethoxy phosphinylidyne amine structure --- the thio sub- urea ethyl shell of diethoxy phosphamide is few
Sugar derivatives.Wherein, diazanyl and diethyl chloro-phosphate molar ratio are 1:1-3 in aminothio Asia urea ethyl chitosan oligosaccharide derivative.
Further, in the presence of acid binding agent, aminothio Asia urea ethyl chitosan oligosaccharide derivative and diethyl chloro-phosphate
In solvent n,N-Dimethylformamide, using the microwave power of 500-600W, microwave treatment reacts 30- at 45-60 DEG C
60min is added dehydrated alcohol dilution, filters after reaction, filter cake washs with dehydrated alcohol, be dried to obtain shown in formula I containing thiocarbamide and
The chitosan oligosaccharide derivative of diethoxy phosphinylidyne amine structure；Wherein, diethyl chloro-phosphate and acid binding agent molar ratio are 1:1-1.5, ammonia
The thio sub- urea ethyl chitosan oligosaccharide derivative of base and N,N-dimethylformamide mass volume ratio are 1:40-50 (g:mL).
The acquisition of the aminothio Asia urea ethyl chitosan oligosaccharide derivative be in the presence of acid binding agent triethylamine, chitosan oligosaccharide with
1,2- Bromofume reacts 12-18h at 50-60 DEG C, obtains bromoethyl chitosan oligosaccharide derivative；Gained bromoethyl chitosan oligosaccharide is spread out
Biology and ammonium thiocyanate, using reacting under microwave action, react 20- under microwave power 500-600W in the presence of acetonitrile
30min controls 45-60 DEG C of microwave reaction temperature, obtains isothiocyanic acid ethyl chitosan oligosaccharide derivative；Gained isothiocyanic acid ethyl shell
Oligosaccharide derivative reacts 18-20h at 60-80 DEG C of 85% hydrazine hydrate, obtains aminothio Asia urea ethyl chitosan oligosaccharide derivative.
The chitosan oligosaccharide and 1,2- Bromofume exist in solvent n,N-Dimethylformamide, and in acid binding agent triethylamine
Lower reaction, filters after reaction, and filter cake is washed with dehydrated alcohol, dry at 60 DEG C；Wherein chitosan oligosaccharide and glycol dibromide mole
Than for 1:2-5；Chitosan oligosaccharide and N,N-dimethylformamide mass volume ratio are 1:10-20 (g:mL), triethylamine and N, N- diformazan
Base formamide volume ratio is 1:10-15.
The bromoethyl chitosan oligosaccharide derivative passes through microwave condition in the solution that acetonitrile and acetone mix with ammonium thiocyanate
Reaction, filters after reaction, and filter cake is dry at 60 DEG C with acetone washing；Wherein, acetonitrile in the solution that acetonitrile and acetone mix
And acetone, volume ratio 1:1, bromoethyl chitosan oligosaccharide derivative and mixed solvent mass volume ratio are 1:20-40 (g:mL), bromine second
Bromoethyl and ammonium thiocyanate molar ratio are 1:1-6 in base enclosure oligosaccharide derivative.
The isothiocyanic acid ethyl chitosan oligosaccharide derivative and 85% hydrazine hydrate are in excessive N,N-dimethylformamide or nothing
It reacts in the presence of water-ethanol, is precipitated after reaction with dehydrated alcohol, filtered, filter cake is washed with dehydrated alcohol, dry at 60 DEG C；
Wherein, isothiocyanic acid ethyl chitosan oligosaccharide derivative and solvent quality volume ratio are 1:20-40 (g:mL), and isothiocyanic acid ethyl shell is few
Isothiocyanic acid ethyl and hydrazine hydrate molar ratio are 1:2-9 in sugar derivatives.
A kind of application of the chitosan oligosaccharide derivative containing thiocarbamide and diethoxy phosphinylidyne amine structure contains thiocarbamide shown in the formula I
It is applied in the drug as controlling plant diseases with the chitosan oligosaccharide derivative of diethoxy phosphinylidyne amine structure.
Principle: in the presence of acid binding agent, 1,2- Bromofume can be with-OH and-NH on chitosan oligosaccharide2Substitution reaction occurs,
Bromine atom is easy to leave away on bromoethyl, and substitution reaction can further occur with ammonium thiocyanate, and N=C=S cumulated double bond is unstable
It is fixed, addition reaction can occur with hydrazine hydrate, then in the presence of acid binding agent pyridine, diethyl chloro-phosphate and diazanyl generation are acylated anti-
It answers.
Advantages of the present invention: organophosphorus pesticide and Thiourea pesticide are the sterilization, insecticide pesticide that agriculturally two classes are important, two
Ethyoxyl phosphamide and thiourea group bioactivity with higher, the present invention is using chitosan oligosaccharide as parent, successively by thiourea group
It is grafted on chitosan oligosaccharide molecule with diethoxy phosphoamide groups, there is the reaction of 2 steps to carry out under microwave action in the reaction, reduce
Reaction temperature and reaction time have been arrived, reaction progress is greatly accelerated, original conventional heating needs to react 10h or more, and microwave is anti-
The reaction time foreshortens within 20-60min under the conditions of answering.New derivatives improve shell on the basis of guaranteeing water-soluble
The bioactivity of oligosaccharides itself, and there is synergy between nontoxic degradable chitosan oligosaccharide and two class pesticide activity groups
Effect, provides new way for the exploitation of new type of green pesticide.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of chitosan oligosaccharide provided in an embodiment of the present invention, and infrared signature absorbs (cm-1): 3175,
2874,1632,1538,1403,1152,1019.
Fig. 2 is the infrared spectrogram of bromoethyl chitosan oligosaccharide derivative provided in an embodiment of the present invention, and infrared signature absorbs
(cm-1): 3284,2880,1633,1556,1374,1024,859.
Fig. 3 is the infrared spectrogram of isothiocyanic acid ethyl chitosan oligosaccharide derivative provided in an embodiment of the present invention, infrared spy
Sign absorbs (cm-1): 3271,2880,2050,1632,1538,1373,1025.
Fig. 4 is the infrared spectrogram of urea ethyl chitosan oligosaccharide derivative in aminothio Asia provided in an embodiment of the present invention, red
Outer characteristic absorption (cm-1): 3280,2876,2054,1633,1555,1374,1024,894.
Fig. 5 is the infrared spectrogram of urea ethyl chitosan oligosaccharide derivative in aminothio Asia provided in an embodiment of the present invention, red
Outer characteristic absorption (cm-1): 3272,2876,2052,1633,1555,1373,1253,1025.
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
1) preparation of bromoethyl chitosan oligosaccharide derivative
It taking 3.0g chitosan oligosaccharide to swell in 30mL n,N-Dimethylformamide, 3mL triethylamine is added, stirring is swollen 12h,
3mL 1 is added, 2- Bromofume is warming up to 50 DEG C, is stirred at reflux reaction 12h, filters, and filter cake is rinsed with dehydrated alcohol, and 60 DEG C
Lower drying obtains Tan solid, as bromoethyl chitosan oligosaccharide derivative.
Infrared spectroscopy shows: the infrared spectrum (Fig. 2) of bromoethyl chitosan oligosaccharide derivative and the infrared spectrum (Fig. 1) of chitosan oligosaccharide
It compares ,-NH2Absorption peak from 1538cm-1It is transferred to 1556cm-1Place, and obvious decrease, explanation-NH2It is reacted,
1024cm-1Place's C-O absorption peak is transferred to 1019cm-1Place, and peak type comes to a point, and illustrates to be reacted on C-OH, in 1374cm-1
There is the absorption peak of methylene C-H in place, it was demonstrated that bromoethyl chitosan oligosaccharide derivative is successfully prepared.
2) preparation of isothiocyanic acid ethyl chitosan oligosaccharide derivative
2.0g bromoethyl chitosan oligosaccharide derivative is taken to be added to 40mL acetonitrile/acetone (v:v=20:20) stirring swelling overnight,
2.2g ammonium thiocyanate is added, reacts 20min in microwave power 500W, controls 45 DEG C of reaction temperature, filter, filter cake is washed with acetone
It washs, it is dry at 50 DEG C, obtain brown solid, as isothiocyanic acid ethyl chitosan oligosaccharide derivative.
Infrared spectroscopy shows: the infrared spectrum (Fig. 3) of isothiocyanic acid ethyl chitosan oligosaccharide derivative spreads out with bromoethyl chitosan oligosaccharide
The infrared spectrum (Fig. 2) of biology is compared, in 2050cm-1There is apparent N=C=S characteristic peak in place, it was demonstrated that bromoethyl chitosan oligosaccharide
Derivative is successfully prepared.
3) preparation of aminothio Asia urea ethyl chitosan oligosaccharide derivative
It takes 1.5g isothiocyanic acid ethyl chitosan oligosaccharide derivative to swell in 40mL dehydrated alcohol, 85% water of 0.68mL is added
Hydrazine is closed, is warming up to 60 DEG C, reaction 18h is stirred at reflux, filters, and filter cake is rinsed with dehydrated alcohol, drying at 60 DEG C obtains pale yellow
Color solid, as aminothio Asia urea ethyl chitosan oligosaccharide derivative.
Infrared spectroscopy shows: the infrared spectrum (Fig. 4) and isothiocyanic acid second of aminothio Asia urea ethyl chitosan oligosaccharide derivative
The infrared spectrum (Fig. 3) of base enclosure oligosaccharide derivative is compared, 2054cm-1The N=C=S characteristic peak at place obviously weakens, and illustrates N=C=
S is reacted, and 1538cm-1- the NH at place2Absorption peak is transferred to 1556cm-1Place, illustrates itself the and-NH in the diazanyl being introduced into2
It is had occurred with it be overlapped, it was demonstrated that aminothio Asia urea ethyl chitosan oligosaccharide derivative is successfully prepared.
4) preparation of derivatives I shown in formula I
0.5g aminothio Asia urea ethyl chitosan oligosaccharide derivative, 0.4mL diethyl chloro-phosphate is taken to be added to 20mL N, N- bis-
In methylformamide, 0.2mL pyridine is added, 30min is reacted under microwave power 500W, controls 45 DEG C of reaction temperature.It is added a small amount of
Dehydrated alcohol dilution, filters, and filter cake is washed three times with dehydrated alcohol, dry at 60 DEG C, obtains hazel-color solid, as contains thiocarbamide
With the chitosan oligosaccharide derivative of diethoxy phosphinylidyne amine structure, as derivatives I shown in formula I.
Infrared spectroscopy shows: the infrared spectrum (Fig. 5) of derivatives I shown in formula I spreads out with aminothio Asia urea ethyl chitosan oligosaccharide
The infrared spectrum (Fig. 4) of biology is compared ,-NH2Absorption peak is transferred to 1538cm again-1Place, illustrates to be reacted on diazanyl, and
1253cm-1There is P=O characteristic peak in place, it was demonstrated that aminothio Asia urea ethyl chitosan oligosaccharide derivative is successfully prepared.
Application examples Antibacterial Activity
Using growth rate method measurement sample to the bacteriostatic activity of black and white verticillium sp.It tests under 3 sample concentrations i.e.:
100 μ g/ml, 200 μ g/ml, 400 μ g/ml, to the inhibitory effect of black and white verticillium sp.
Experiment is using distilled water as blank control.Culture medium is uniformly poured into the culture dish that 2 diameters are 9cm, to complete
After solidification, the bacteria cake that 3 pieces of diameters are 5mm is inoculated in each culture dish.After cultivating 72 hours at 27 DEG C, measurement bacterium colony is straight
Diameter calculates the bacteriostasis rate of sample.2 culture dishes of setting per treatment, every ware are inoculated with 3 bacterium colonies, maximum to each Detection of colony
Diameter (Dmax) and minimum diameter (Dmin), are averaged as sample antibacterial circle diameter D sample, and total Test is repeated once.Root
Bacteriostasis rate is calculated according to 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, the I chitosan oligosaccharide derivative to black and white verticillium sp
As described in table 1, the activity of the chitosan oligosaccharide derivative containing thiocarbamide and diethoxy phosphinylidyne amine structure described in formula I,
It is substantially better than chitosan oligosaccharide raw material, and to compose oligosaccharides well 20 percentage points strong for the antibacterial agent than being commercialized at present.
Therefore the chitosan oligosaccharide derivative of the present invention containing thiocarbamide and diethoxy phosphinylidyne amine structure has preferable suppression
Bacterium activity.
The present invention is successively grafted thiocarbamide and phosphoamide groups using chitosan oligosaccharide as skeleton, and being promoted, chitosan oligosaccharide itself is active
Meanwhile synergistic function is generated between chitosan oligosaccharide molecule and both active groups, enhance the control efficiency to plant disease,
New type of green pesticide to develop environmental-friendly provides a kind of new approaches.
Claims (8)
1. a kind of chitosan oligosaccharide derivative containing thiocarbamide and diethoxy phosphinylidyne amine structure, it is characterised in that: contain thiocarbamide and diethoxy
Base phosphinylidyne hydrazine structural shell oligosaccharide derivative as shown in formula I,
In formula, n=2-20.
2. a kind of preparation method of the chitosan oligosaccharide derivative described in claim 1 containing thiocarbamide and diethoxy phosphinylidyne amine structure,
It is characterized by: aminothio Asia urea ethyl chitosan oligosaccharide derivative and diethyl chloro-phosphate are micro- in the presence of acid binding agent pyridine
Wave acts on lower 30-60min, obtains chitosan oligosaccharide derivative --- the diethyl containing thiocarbamide and diethoxy phosphinylidyne amine structure shown in formula I
The thio sub- urea ethyl chitosan oligosaccharide derivative of oxygroup phosphamide.Wherein, in aminothio Asia urea ethyl chitosan oligosaccharide derivative diazanyl with
Diethyl chloro-phosphate molar ratio is 1:1-3.
3. the preparation method of the chitosan oligosaccharide derivative as described in claim 2 containing thiocarbamide and diethoxy phosphinylidyne amine structure,
Be characterized in that: in the presence of acid binding agent, aminothio Asia urea ethyl chitosan oligosaccharide derivative and diethyl chloro-phosphate are in solvent N, N-
In dimethylformamide, 30-60min is reacted using microwave treatment at 45-60 DEG C of microwave power of 500-600W, is added after reaction
Dehydrated alcohol dilution, filters, and filter cake is washed with dehydrated alcohol, is dried to obtain shown in formula I containing thiocarbamide and diethoxy phosphamide knot
The chitosan oligosaccharide derivative of structure；Wherein, diethyl chloro-phosphate and acid binding agent molar ratio are 1:1-1.5, aminothio Asia urea ethyl shell
Oligosaccharide derivative and N,N-dimethylformamide mass volume ratio are 1:40-50 (g:mL).
4. the preparation method of the chitosan oligosaccharide derivative described in claim 2 or 3 containing thiocarbamide and diethoxy phosphinylidyne amine structure is pressed,
It is characterized by: the acquisition of the aminothio Asia urea ethyl chitosan oligosaccharide derivative is in the presence of acid binding agent triethylamine, shell is few
Sugar reacts 12-18h at 50-60 DEG C with 1,2- Bromofume, obtains bromoethyl chitosan oligosaccharide derivative；Gained bromoethyl shell is few
Sugar derivatives and ammonium thiocyanate, using reacting under microwave action, react 20- under microwave power 500-600W in the presence of acetonitrile
30min controls 45-60 DEG C of microwave reaction temperature, obtains isothiocyanic acid ethyl chitosan oligosaccharide derivative；Gained isothiocyanic acid ethyl shell
Oligosaccharide derivative reacts 18-20h at 60-80 DEG C of 85% hydrazine hydrate, obtains aminothio Asia urea ethyl chitosan oligosaccharide derivative.
5. the preparation method of the chitosan oligosaccharide derivative according to claim 4 containing thiocarbamide and diethoxy phosphinylidyne amine structure,
Be characterized in that: the chitosan oligosaccharide and 1,2- Bromofume are deposited in solvent n,N-Dimethylformamide, and in acid binding agent triethylamine
It is filtered after lower reaction, reaction, filter cake is washed with dehydrated alcohol, dry at 60 DEG C；Wherein chitosan oligosaccharide rubs with glycol dibromide
You are than being 1:2-5；Chitosan oligosaccharide and N,N-dimethylformamide mass volume ratio are 1:10-20 (g:mL), triethylamine and N, N- bis-
Methylformamide volume ratio is 1:10-15.
6. the preparation method of the chitosan oligosaccharide derivative according to claim 4 containing thiocarbamide and diethoxy phosphinylidyne amine structure,
Be characterized in that: the bromoethyl chitosan oligosaccharide derivative passes through microwave condition in the solution that acetonitrile and acetone mix with ammonium thiocyanate
Reaction, filters after reaction, and filter cake is dry at 60 DEG C with acetone washing；Wherein, acetonitrile in the solution that acetonitrile and acetone mix
It is 1:1 with acetone volume ratio, bromoethyl chitosan oligosaccharide derivative and mixed solvent mass volume ratio are 1:20-40 (g:mL), bromine second
Bromoethyl and ammonium thiocyanate molar ratio are 1:1-6 in base enclosure oligosaccharide derivative.
7. the preparation method of the chitosan oligosaccharide derivative according to claim 4 containing thiocarbamide and diethoxy phosphinylidyne amine structure,
Be characterized in that: the isothiocyanic acid ethyl chitosan oligosaccharide derivative and 85% hydrazine hydrate are in solvent N,N-dimethylformamide or anhydrous
It reacts in the presence of ethyl alcohol, is precipitated after reaction with dehydrated alcohol, filtered, filter cake is washed with dehydrated alcohol, dry at 60 DEG C；Its
In, isothiocyanic acid ethyl chitosan oligosaccharide derivative and solvent quality volume ratio are 1:20-40 (g:mL), isothiocyanic acid ethyl chitosan oligosaccharide
Isothiocyanic acid ethyl and hydrazine hydrate molar ratio are 1:2-9 in derivative.
8. a kind of application of the chitosan oligosaccharide derivative described in claim 1 containing thiocarbamide and diethoxy phosphinylidyne amine structure, special
Sign is: the chitosan oligosaccharide derivative containing thiocarbamide and diethoxy phosphinylidyne amine structure shown in the formula I is as controlling plant diseases
Drug in apply.
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| CN112010722A (en) * | 2020-09-14 | 2020-12-01 | 南通大学 | Synthesis method of E-type beta-thiocyanatelamide derivative |
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| CN109824799A (en) * | 2019-01-25 | 2019-05-31 | 佛山市海力盈生物科技有限公司 | A kind of chitosan derivatives and preparation method thereof of sulfur-bearing urea structure |
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| CN112010722B (en) * | 2020-09-14 | 2023-01-06 | 南通大学 | Synthesis method of E-type beta-thiocyanatelamide derivative |
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