CN106046197A - Compound having bacteriostatic activity and preparation and application thereof - Google Patents
Compound having bacteriostatic activity and preparation and application thereof Download PDFInfo
- Publication number
- CN106046197A CN106046197A CN201610374518.0A CN201610374518A CN106046197A CN 106046197 A CN106046197 A CN 106046197A CN 201610374518 A CN201610374518 A CN 201610374518A CN 106046197 A CN106046197 A CN 106046197A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- compound
- pyrimethanil
- bacteriostatic activity
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC(*)(*)CCN Chemical compound CC(*)(*)CCN 0.000 description 5
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
Abstract
The invention belongs to an ocean chemical engineering technology and particularly relates to a compound having bacteriostatic activity and preparation and application thereof. The compound is a conjugate of chitosan and pyrimethanil, and a general formula of the compound is shown in a formula I. The compound is novel in structure and good in water solubility and has obvious antibacterial activity, and the preparation method is simple.
Description
Technical field
The invention belongs to marine chemical industry engineering, be specifically related to a kind of compound with bacteriostatic activity and preparation and
Application.
Background technology
Pyrimethanil, chemical name 4,6-Dimethvl-phenyl-2-pyrimidinamine, is a kind of pyrimidine fungicides antibacterial.Pyrimethanil
It is the antibacterial of absorption in a class, has efficiently, the feature such as wide spectrum and low toxicity.Pyrimethanil is for occurring on vegetable and fruit
Gray mold and scab have especially significant prevention effect, and it is to phytopathies such as the pathogen of Botrytis cinerea, sclerotinite, Rhizoctonia solani Kuhns
Former bacterium the most all has preferable inhibitory activity.Pyrimethanil cracks by reducing infected crop cell, and intracellular fungus
The growth of mycelia reaches fungistatic effect.Additionally, pyrimethanil can also suppress pathogenic bacteria by the secretion of suppression infection process enzyme
Growth.Therefore, pyrimethanil has protection and the effect for the treatment of simultaneously.
Chitosan is the class biological polyoses that nature is widely present, and has preferable biocompatibility, and research finds shell
Polysaccharide has the biological activitys such as bactericidal, fungus, antibacterial, disease-resistant growth-promoting, is widely used to agriculture field.But chitosan
When being used alone, there is certain gap with other pesticide of commercialization in its activity, which also limits its application.
Summary of the invention
The present invention is directed to the problems referred to above, it is provided that a kind of compound with bacteriostatic activity and preparation thereof and application.
The technical solution used in the present invention is for achieving the above object:
A kind of compound with bacteriostatic activity, compound is the conjugates of chitosan and pyrimethanil, its formula such as Formulas I institute
Show,
Described compound is with natural product chitosan as skeleton, by coupling reaction, pyrimethanil molecule is grafted to shell and gathers
Glycan molecule obtains.
The preparation method of a kind of compound with bacteriostatic activity, with natural product chitosan as skeleton, divides pyrimethanil
Son is grafted in chitosan molecule obtain compound shown in Formulas I by coupling reaction.
Reaction equation is as follows:
Step1:
Step2:
The first step, is dissolved in former for pyrimethanil medicine in the dichloromethane of excess；Under condition of ice bath, addition chloracetyl chloride,
3-chlorpromazine chloride or 4-(chloromethyl) chloromethane acyl chlorides；And backward reaction system adds potassium carbonate；After reaction terminates, to reactant
System adds distilled water, stratification, collects the organic facies of lower floor, and evaporated under reduced pressure, stand-by；
Wherein, the former medicine of pyrimethanil is 1:10-50 with the mass volume ratio of dichloromethane；Chloracetyl chloride, 3-chlorpromazine chloride or
4-(chloromethyl) chloromethane acyl chlorides is 1-10:1 with the mol ratio of the former medicine of pyrimethanil；Potassium carbonate is 1 with the mol ratio of the former medicine of pyrimethanil:
1-10；
Second step, chitosan adds to the chloroform of excess, and the swelling 30-120min of mechanical agitation adds hydrogen-oxygen
Change sodium solution and 4-methylamino pyridine is stirred for 4-12h；The product that the first step prepares is added, in 50-80 after stirring reaction
C water bath reacts 4-12h；At the end of reaction, add glacial acetic acid by pH regulator to 7, filtration reactant, solid product use
70%-100% (mass concentration) methanol solution washs, and is dried to obtain compound shown in Formulas I；
Wherein, chitosan is 1-10:1 with the mol ratio of first step product；4-methylamino pyridine rubs with chitosan
That ratio is 1:1-50；Chitosan is 1:10-50 with the mass volume ratio of chloroform.
Described chitosan be molecular weight be 237Da-4740kDa.
Having the application of the compound of bacteriostatic activity, described compound of formula I is for preparing the application in antifungal.
Principle: containing amino and hydroxyl in chitosan structure, in its product that can generate with pyrimethanil and acyl chloride reaction
Active chlorine atom generation nucleophilic substitution, and then two kinds of materials are coupled together.
In the present invention imino group in pyrimethanil first with three class acyl chlorides generation acylation reactions, afterwards with on chitosan C2 position
-NH2And-the OH on C6 position occurs coupling reaction, ultimately generating chitosan and pyrimethanil conjugates, the derivant of gained is through red
External spectrum analysis determines that its structure, chitosan and pyrimethanil are effectively combined generation conjugates.
Advantage for present invention:
Pyrimethanil molecule, with natural product chitosan as skeleton, is grafted to chitosan molecule by coupling reaction by the present invention
In, it is thus achieved that the obvious conjugates of good water solubility, fungistatic effect.
Chitosan the most of the present invention and pyrimethanil coupling gained conjugates have preferable bacteriostatic activity, have at pesticide field
Potential using value.
2, chitosan prepared by the present invention and pyrimethanil conjugates have preferable water solublity, overcome pyrimethanil water solublity
The shortcoming of difference, it is simple to prepare the environment friendly agricultural that organic solvent-free adds.
Accompanying drawing explanation
The infrared spectrogram of the chitosan that Fig. 1 provides for the embodiment of the present invention.
The chitosan that Fig. 2 provides for the embodiment of the present invention and the infrared spectrogram of pyrimethanil conjugates (1), its infrared signature
Absorb (cm-1): 2879,1750,1630,1590,1556,1497,1337,1246,1027.
The chitosan that Fig. 3 provides for the embodiment of the present invention and the infrared spectrogram of pyrimethanil conjugates (2), its infrared signature
Absorb (cm-1): 2916,1750,1588,1556,1464,1365,1250,1029.
The chitosan that Fig. 4 provides for the embodiment of the present invention and the infrared spectrogram of pyrimethanil conjugates (3), its infrared signature
Absorb (cm-1): 2879,1721,1628,1556,1469,1366,778,752,691,660.
Detailed description of the invention
Below in conjunction with Figure of description, the invention will be further described, and protection scope of the present invention is not only limited to
Following example.
Embodiment 1 chitosan and the preparation of pyrimethanil conjugates (1)
The first step, weighs the former medicine of 4g pyrimethanil, is dissolved in 80ml dichloromethane；Under condition of ice bath, use constant pressure funnel
0.04mol chloracetyl chloride is added in solution；After acyl chlorides dropping, in reaction system, add 3.3g potassium carbonate as tiing up acid
Agent；After reaction terminates, in reaction system, add 10ml distilled water, after pouring separatory funnel stratification into, collect having of lower floor
Machine phase, and evaporated under reduced pressure solvent obtains product.
Second step, weighing 5g molecular weight is that 1,060,000 chitosans add in there-necked flask, adds 50ml chloroform, and machinery stirs
Mix swelling 30min, add the sodium hydroxide solution of 12ml 10M, 0.01g 4-methylamino pyridine stirring 4h.Add 3g the afterwards
The product that one step prepares, 50 C water bath react 4h.At the end of reaction, addition glacial acetic acid, by pH regulator to 7, filters anti-
Answering thing, solid product 70%-100% methanol solution washs, and 60 degrees Celsius are dried to obtain chitosan pyrimethanil conjugates (1).
Structural formula is as follows:
During it addition, prepare chitosan and the pyrimethanil conjugates of different molecular weight, can be the chitosan of 1,060,000 by molecular weight
By microwave degradation, and then acquire the chitosan of different molecular weight, using the chitosan of different molecular weight as raw material, according to upper
The mode stated carries out coupling reaction can obtain chitosan and the pyrimethanil conjugates of different molecular weight.
Infrared spectrum shows: the infrared spectrum (Fig. 2) of chitosan pyrimethanil conjugates (1) and the infrared spectrum of chitosan
(Fig. 1) compare, at 1500cm-1To 1600cm-1The absworption peak occurred is C-N vibrations and the characteristic absorption peak of phenyl ring, 1750cm-1
For by acyl chlorides introducing-CH2-characteristic absorption peak.Prove that target conjugates 1 synthesizes successfully.
Embodiment 2 chitosan and the preparation of pyrimethanil conjugates (2)
The first step, weighs the former medicine of 4g pyrimethanil, is dissolved in 80ml dichloromethane；Under condition of ice bath, use constant pressure funnel
0.04mol chlorpromazine chloride is added in solution；After acyl chlorides dropping, in reaction system, add 3.3g potassium carbonate as tiing up acid
Agent；After reaction terminates, in reaction system, add 10ml distilled water, after pouring separatory funnel stratification into, collect having of lower floor
Machine phase, and evaporated under reduced pressure solvent obtains product.
Second step, weighing 5g molecular weight is that 1,060,000 chitosans add in there-necked flask, adds 50ml chloroform, and machinery stirs
Mix swelling 30min, add the sodium hydroxide solution of 12ml 10M, 0.01g 4-methylamino pyridine stirring 4h.Add 3g the afterwards
The product that one step prepares, 50 C water bath react 4h.At the end of reaction, addition glacial acetic acid, by pH regulator to 7, filters anti-
Answering thing, solid product 70%-100% methanol solution washs, and 60 degrees Celsius are dried to obtain chitosan pyrimethanil conjugates (2).
Structural formula is as follows:
During it addition, prepare chitosan and the pyrimethanil conjugates of different molecular weight, can be the chitosan of 1,060,000 by molecular weight
By microwave degradation, and then acquire the chitosan of different molecular weight, using the chitosan of different molecular weight as raw material, according to upper
The mode stated carries out coupling reaction can obtain chitosan and the pyrimethanil conjugates of different molecular weight.
Infrared spectrum shows: the infrared spectrum (Fig. 3) of chitosan pyrimethanil conjugates (2) and the infrared spectrum of chitosan
(Fig. 1) compare, at 1500cm-1To 1600cm-1The absworption peak occurred is C-N vibrations and the characteristic absorption peak of phenyl ring, 1750cm-1
For by acyl chlorides introducing-CH2-characteristic absorption peak.Prove that target conjugates 1 synthesizes successfully.
Embodiment 3 chitosan and the preparation of pyrimethanil conjugates (3)
The first step, weighs the former medicine of 4g pyrimethanil, is dissolved in 80ml dichloromethane；Under condition of ice bath, use constant pressure funnel
0.04mol 4-(chloromethyl) chloromethane acyl chlorides is added in solution；After acyl chlorides dropping, in reaction system, add 3.3g carbon
Acid potassium is as acid binding agent；After reaction terminates, in reaction system, add wet chemical, pour separatory funnel stratification into
After, collect the organic facies of lower floor, and evaporated under reduced pressure solvent obtains product.
Second step, weighing 5g molecular weight is that 1,060,000 chitosans add in there-necked flask, adds 50ml chloroform, and machinery stirs
Mix swelling 30min, add the sodium hydroxide solution of 12ml 10M, 0.01g 4-methylamino pyridine stirring 4h.Add 3g the afterwards
The product that one step prepares, 50 C water bath react 4h.At the end of reaction, addition glacial acetic acid, by pH regulator to 7, filters anti-
Answering thing, solid product 70%-100% methanol solution washs, and 60 degrees Celsius are dried to obtain chitosan pyrimethanil conjugates (3).
Structural formula is as follows:
During it addition, prepare chitosan and the pyrimethanil conjugates of different molecular weight, can be the chitosan of 1,060,000 by molecular weight
By microwave degradation, and then acquire the chitosan of different molecular weight, using the chitosan of different molecular weight as raw material, according to upper
The mode stated carries out coupling reaction can obtain chitosan and the pyrimethanil conjugates of different molecular weight.
Infrared spectrum shows: the infrared spectrum (Fig. 4) of chitosan pyrimethanil conjugates (3) and the infrared spectrum of chitosan
(Fig. 1) compare, at 1500cm-1To 1600cm-1The absworption peak occurred is C-N vibrations and the characteristic absorption peak of phenyl ring, 700cm-1Extremely
800cm-1For being introduced the characteristic absorption peak of the monosubstituted phenyl ring with para-orientation by acyl chlorides.Prove that target conjugates is 2-in-1 to become into
Merit.
Application examples Antibacterial Activity
Test method
Obtaining chitosan and pyrimethanil conjugates shown in Formulas I using above-described embodiment as medicinal liquid, the initial concentration of medicinal liquid is
10mg/mL, is then 100mg/L with distilled water diluting by medicinal liquid respectively, and 3 concentration of 200mg/L, 400mg/L are as test
Group, measures the biocidal property of its Rhizoctonia solani and Gibberella zeae.Test using the chitosan solution of same concentrations as comparison,
Be not added with medicinal liquid culture medium as blank.
In superclean bench, the test group of above-mentioned setting, positive control and blank are added to culture medium, and
The bacterium cake of Rhizoctonia solani Kuhn and Gibberella zeae is inoculated respectively on the flat board of backward PDA culture medium.Afterwards flat board is put into constant temperature
Cultivating in incubator, the cultivation temperature of incubator is set to 29 DEG C.After cultivating 72 hours under corresponding conditions, measure flat board
Upper colony diameter.3 bacterium colonies of each board joint, to each its maximum gauge of bacterium colony amount (Dmax) and minimum diameter (Dmin), take
Its meansigma methods (Dave), and according to following formula calculating bacteriostasis rate:
Bacteriostasis rate (%)=(Dmax-Dave)/(Dave-5) × 100
The conjugates that above-described embodiment prepares shows good bacteriostatic activity.Experimental result is shown in Table 1
Table 1 partial Formula 1 chitosan and pyrimethanil conjugates Rhizoctonia solani and the inhibitory activity of Gibberella zeae
Claims (6)
1. a compound with bacteriostatic activity, it is characterised in that: compound is the conjugates of chitosan and pyrimethanil, and it leads to
Formula shown in formula I,
2. the compound with bacteriostatic activity as described in claim 1, it is characterised in that: described compound is with natural product
Chitosan is skeleton, is grafted in chitosan molecule obtain by coupling reaction by pyrimethanil molecule.
3. the preparation method of the compound with bacteriostatic activity described in a claim 1, it is characterised in that: with natural product
Chitosan is skeleton, is grafted in chitosan molecule obtain compound shown in Formulas I by coupling reaction by pyrimethanil molecule.
4. the preparation method of the compound with bacteriostatic activity as described in claim 3, it is characterised in that:
Reaction equation is as follows
Step1:
Step2:
The first step, is dissolved in former for pyrimethanil medicine in the dichloromethane of excess；Under condition of ice bath, add chloracetyl chloride, 3-chlorine
Propionyl chloride or 4-(chloromethyl) chloromethane acyl chlorides；And backward reaction system adds potassium carbonate；After reaction terminates, in reaction system
Add distilled water, stratification, collect the organic facies of lower floor, and evaporated under reduced pressure, stand-by；
Wherein, chloracetyl chloride, 3-chlorpromazine chloride or 4-(chloromethyl) chloromethane acyl chlorides are 1-10:1 with the mol ratio of the former medicine of pyrimethanil；
Potassium carbonate is 1:1-10 with the mol ratio of the former medicine of pyrimethanil；
Second step, chitosan adds to the chloroform of excess, and the swelling 30-120min of mechanical agitation adds sodium hydroxide
Solution and 4-methylamino pyridine are stirred for 4-12h；The product that the first step prepares is added after stirring reaction, Celsius in 50-80
Degree water-bath 4-12h；At the end of reaction, add glacial acetic acid by pH regulator to 7, filtration reactant, solid product 70%-
100% methanol solution washing, is dried to obtain compound shown in Formulas I；
Wherein, chitosan is 1-10:1 with the mol ratio of first step product；4-methylamino pyridine and the mol ratio of chitosan
For 1:1-50.
5. the preparation method of the compound with bacteriostatic activity as described in claim 3 or 4, it is characterised in that: described shell gathers
Sugar is 237Da-4740kDa for molecular weight.
6. the application of the compound of the bacteriostatic activity as described in claim 1, it is characterised in that: described compound is prepared being used for
Application in suppression fungi preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610374518.0A CN106046197B (en) | 2016-05-31 | 2016-05-31 | A kind of compound and its preparation and application with bacteriostatic activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610374518.0A CN106046197B (en) | 2016-05-31 | 2016-05-31 | A kind of compound and its preparation and application with bacteriostatic activity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106046197A true CN106046197A (en) | 2016-10-26 |
| CN106046197B CN106046197B (en) | 2019-02-15 |
Family
ID=57172225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610374518.0A Active CN106046197B (en) | 2016-05-31 | 2016-05-31 | A kind of compound and its preparation and application with bacteriostatic activity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106046197B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124633A (en) * | 2022-06-24 | 2022-09-30 | 广东粤威制药有限公司 | Preparation method and application of thymol composition |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4574150A (en) * | 1985-02-19 | 1986-03-04 | University Of Delaware | Dry free-flowing water-soluble complexes of chitosan |
| US5734031A (en) * | 1995-09-25 | 1998-03-31 | The United States Of America As Represented By The Secretary Of Agriculture | Cation exchange resin |
| US20050214255A1 (en) * | 2004-03-25 | 2005-09-29 | Chitogenics, Inc. | N-acylated chitinous polymers and methods of use thereof |
| CN101054397A (en) * | 2007-04-27 | 2007-10-17 | 大连中科格莱克生物科技有限公司 | N-nicotinoyl chitosan oligosaccharide and preparation method thereof |
| CN101553119A (en) * | 2006-12-12 | 2009-10-07 | 拜尔农科股份有限公司 | Pesticidal composition comprising a synthetic compound useful as nodulation agent of leguminous plants and an insecticide compound |
| CN101816305A (en) * | 2010-05-09 | 2010-09-01 | 海南正业中农高科股份有限公司 | Bactericide pesticide composite containing oligochitosan |
| CN104788587A (en) * | 2015-04-22 | 2015-07-22 | 中国科学院海洋研究所 | Chemical compound with insecticidal activity, as well as preparation and application of chemical compound |
-
2016
- 2016-05-31 CN CN201610374518.0A patent/CN106046197B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4574150A (en) * | 1985-02-19 | 1986-03-04 | University Of Delaware | Dry free-flowing water-soluble complexes of chitosan |
| US5734031A (en) * | 1995-09-25 | 1998-03-31 | The United States Of America As Represented By The Secretary Of Agriculture | Cation exchange resin |
| US20050214255A1 (en) * | 2004-03-25 | 2005-09-29 | Chitogenics, Inc. | N-acylated chitinous polymers and methods of use thereof |
| CN101553119A (en) * | 2006-12-12 | 2009-10-07 | 拜尔农科股份有限公司 | Pesticidal composition comprising a synthetic compound useful as nodulation agent of leguminous plants and an insecticide compound |
| CN101054397A (en) * | 2007-04-27 | 2007-10-17 | 大连中科格莱克生物科技有限公司 | N-nicotinoyl chitosan oligosaccharide and preparation method thereof |
| CN101816305A (en) * | 2010-05-09 | 2010-09-01 | 海南正业中农高科股份有限公司 | Bactericide pesticide composite containing oligochitosan |
| CN104788587A (en) * | 2015-04-22 | 2015-07-22 | 中国科学院海洋研究所 | Chemical compound with insecticidal activity, as well as preparation and application of chemical compound |
Non-Patent Citations (1)
| Title |
|---|
| 杨龙强等: "新型壳聚糖双季铵盐的制备及其抗氧化活性", 《应用化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124633A (en) * | 2022-06-24 | 2022-09-30 | 广东粤威制药有限公司 | Preparation method and application of thymol composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106046197B (en) | 2019-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107746433A (en) | A kind of preparation method of cellulose base antibacterial material dialdehyde cellulose lysine | |
| CN106905443B (en) | The preparation method and applications of guanidinated chitosan | |
| CN102276757A (en) | Method for preparing chitin quaternary ammonium salt | |
| CN107216411B (en) | One kind quaternary ammonium salt of Acetylated Chitosans containing ureas and its preparation method and application | |
| CN105968217B (en) | A kind of acetylated starch quaternary phosphonium salt and its preparation method and application | |
| CN107163160A (en) | A kind of Ascorbic acid chitosan quaternary ammonium salt and its preparation method and application | |
| CN101440072B (en) | 4-tertiary butyl-6-aryl-2-6H-1,3-thiazine or salt thereof, as well as preparation method and application thereof | |
| CN105801722A (en) | Marine organism polysaccharide copper compound and preparation method and application thereof | |
| CN106046197A (en) | Compound having bacteriostatic activity and preparation and application thereof | |
| CN108864324B (en) | Triazole-based chitosan biquaternary ammonium salt and preparation method and application thereof | |
| CN106749760A (en) | A kind of season phosphine chitosan quaternary ammonium salt and its preparation method and application | |
| CN103755841B (en) | A kind of Aminopyridine type acetyl synanthrin and preparation method thereof | |
| CN107998686A (en) | A kind of extractant and its extracting method and application for being used to extract high bacteriostatic activity humate | |
| CN110003364A (en) | A kind of synanthrin derivative and its preparation method and application containing schiff bases | |
| CN109776623B (en) | Preparation method and application of fluorine-containing oxamide homonuclear/heteronuclear compound | |
| CN107602726A (en) | Low molecule amount C6 carboxy chitins and preparation method thereof | |
| CN101284836B (en) | Rotenone oxime ether, preparation method and applications thereof | |
| CN102718885B (en) | Novel 1,2,3-triazole derivative of chitosan and preparation method thereof | |
| CN101343277B (en) | Carbamic tubatoxin oxime ester, preparation and application thereof | |
| CN107216410A (en) | A kind of chitosan derivatives and its preparation method and application | |
| CN108863909A (en) | A kind of novel halogen amine structure compound and preparation method thereof and the application of antibacterial field | |
| CN103664844A (en) | N-(2-phenoxy benzene) furoylamide compounds and preparation method and bactericidal activity thereof | |
| CN107501358B (en) | Heterocyclic chitosan oligosaccharide derivative and synthesis method thereof | |
| CN104788587A (en) | Chemical compound with insecticidal activity, as well as preparation and application of chemical compound | |
| CN101195617A (en) | 2-thiazolyl-3-pyridinyl vinyl cyanide compounds and production and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |