CN106046197B - A kind of compound and its preparation and application with bacteriostatic activity - Google Patents
A kind of compound and its preparation and application with bacteriostatic activity Download PDFInfo
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- CN106046197B CN106046197B CN201610374518.0A CN201610374518A CN106046197B CN 106046197 B CN106046197 B CN 106046197B CN 201610374518 A CN201610374518 A CN 201610374518A CN 106046197 B CN106046197 B CN 106046197B
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- chitosan
- pyrimethanil
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- bacteriostatic activity
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- 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 marine chemical industry engineering technology, and in particular to a kind of compound and its preparation and application with bacteriostatic activity.Compound is the conjugates of chitosan and pyrimethanil, and general formula is shown in formula I, compound structure novelty provided by the invention, good water solubility, with apparent bacteriostatic activity, and preparation method is simple.
Description
Technical field
The invention belongs to marine chemical industry engineering technology, and in particular to a kind of compound with bacteriostatic activity and its preparation and
Using.
Background technique
Pyrimethanil, chemical name 4,6- Dimethvl-phenyl -2- pyrilamine are a kind of pyrimidine fungicides fungicide.Pyrimethanil
It is the fungicide of a kind of absorbability, has the characteristics that efficient, wide spectrum and low toxicity.Pyrimethanil is for occurring on vegetables and fruit
Gray mold and scab have especially significant control efficiency, it is to phytopathies such as the pathogen of Botrytis cinerea, sclerotinite, Rhizoctonia solani Kuhns
Opportunistic pathogen all has preferable inhibitory activity.Pyrimethanil is by reducing infected crop cell cracking and intracellular fungi
The growth of mycelia reaches fungistatic effect.In addition, pyrimethanil can also inhibit germ by inhibiting the secretion of germ invasive enzyme
Growth.Therefore, pyrimethanil has the function of protection and treatment simultaneously.
Chitosan is a kind of biological polyoses that nature is widely present, and has preferable biocompatibility, and research finds shell
Glycan has the bioactivity such as bactericidal, fungi, antibacterial, disease-resistant growth-promoting, is widely used to agriculture field.However chitosan
When exclusive use, there are certain gaps for other pesticides of activity and commercialization, and which also limits its applications.
Summary of the invention
The present invention is in view of the above-mentioned problems, provide a kind of compound with bacteriostatic activity and its preparation and application.
The technical solution adopted by the present invention to achieve the above object are as follows:
A kind of compound with bacteriostatic activity, compound are the conjugates of chitosan and pyrimethanil, general formula such as Formulas I institute
Show,
The compound is that pyrimethanil molecule is grafted to shell by coupling reaction and is gathered using natural products chitosan as skeleton
It is obtained in glycan molecule.
A kind of preparation method of the compound with bacteriostatic activity, using natural products chitosan as skeleton, by pyrimethanil point
Son is grafted in chitosan molecule by coupling reaction and obtains compound shown in Formulas I.
Reaction equation is as follows:
Step1:
Step2:
Pyrimethanil raw medicine is dissolved in excessive methylene chloride by the first step；Under condition of ice bath, addition chloracetyl chloride,
3- chlorpromazine chloride or 4- (chloromethyl) chloromethane acyl chlorides；And potassium carbonate is added in backward reaction system；After reaction, to reactant
Distilled water is added in system, stratification collects the organic phase of lower layer, and evaporated under reduced pressure, for use；
Wherein, the mass volume ratio of pyrimethanil raw medicine and methylene chloride is 1:10-50；Chloracetyl chloride, 3- chlorpromazine chloride or
The molar ratio of 4- (chloromethyl) chloromethane acyl chlorides and pyrimethanil raw medicine is 1-10:1；The molar ratio of potassium carbonate and pyrimethanil raw medicine is 1:
1-10；
Second step, chitosan are added into excessive chloroform, and mechanical stirring is swollen 30-120min, add hydrogen-oxygen
Change sodium solution and 4- methylamino pyridine is stirred for 4-12h；The product that the first step is prepared is added after being stirred to react, in 50-80
C water bath reacts 4-12h；At the end of reaction, glacial acetic acid is added by pH and is adjusted to 7, filter reactant, solid product is used
The washing of 70%-100% (mass concentration) methanol solution, is dried to obtain compound shown in Formulas I；
Wherein, the molar ratio of chitosan and first step reaction product is 1-10:1；4- methylamino pyridine and chitosan rub
You are than being 1:1-50；The mass volume ratio of chitosan and chloroform is 1:10-50.
The chitosan is that molecular weight is 237Da-4740kDa.
The application of compound with bacteriostatic activity, the compound of formula I is in the application being used to prepare in fungistat.
Principle: containing amino and hydroxyl in chitosan structure, in the product that can be generated with pyrimethanil and acyl chloride reaction
Nucleophilic substitution occurs for active chlorine atom, and then two kinds of substances are coupled together.
First with three classes acyl chlorides acylation reaction occurs for imino group in the present invention in pyrimethanil, later on the position chitosan C2
- NH2And coupling reaction occurs for-the OH on the position C6, ultimately generates chitosan and pyrimethanil conjugates, resulting derivative is through red
External spectrum, which is analyzed, determines its structure, and chitosan and pyrimethanil are effectively combined generation conjugates.
Advantage for present invention:
The present invention is grafted to chitosan molecule by coupling reaction using natural products chitosan as skeleton, by pyrimethanil molecule
In, obtain good water solubility, the apparent conjugates of fungistatic effect.
1. chitosan of the present invention and pyrimethanil coupling gained conjugates have preferable bacteriostatic activity, have in pesticide field
Potential application value.
2, chitosan prepared by the present invention and pyrimethanil conjugates have preferable water-soluble, overcome pyrimethanil water solubility
The disadvantage of difference, convenient for preparing the environment friendly agricultural of organic solvent-free addition.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of chitosan provided in an embodiment of the present invention.
Fig. 2 is the infrared spectrogram of chitosan provided in an embodiment of the present invention and pyrimethanil conjugates (1), infrared signature
Absorb (cm-1): 2879,1750,1630,1590,1556,1497,1337,1246,1027.
Fig. 3 is the infrared spectrogram of chitosan provided in an embodiment of the present invention and pyrimethanil conjugates (2), infrared signature
Absorb (cm-1): 2916,1750,1588,1556,1464,1365,1250,1029.
Fig. 4 is the infrared spectrogram of chitosan provided in an embodiment of the present invention and pyrimethanil conjugates (3), infrared signature
Absorb (cm-1): 2879,1721,1628,1556,1469,1366,778,752,691,660.
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.
The preparation of 1 chitosan of embodiment and pyrimethanil conjugates (1)
The first step weighs 4g pyrimethanil raw medicine, is dissolved in 80ml methylene chloride；Under condition of ice bath, constant pressure funnel is used
0.04mol chloracetyl chloride is added into solution；After acyl chlorides is added dropwise, into reaction system, addition 3.3g potassium carbonate, which is used as, ties up acid
Agent；After reaction, 10ml distilled water is added into reaction system, after pouring into separatory funnel stratification, that collects lower layer has
Machine phase, and evaporated under reduced pressure solvent obtains product.
Second step, weighing 5g molecular weight is that 1,060,000 chitosans are added in there-necked flask, 50ml chloroform is added, machinery stirs
Swelling 30min is mixed, the sodium hydroxide solution of 12ml 10M is added, 0.01g 4- methylamino pyridine stirs 4h.3g the is added later
The product that one step is prepared, 50 C water baths react 4h.At the end of reaction, glacial acetic acid is added by pH and is adjusted to 7, filtering is anti-
Object is answered, solid product is washed with 70%-100% methanol solution, and 60 degrees Celsius are dried to obtain chitosan pyrimethanil conjugates (1).
Structural formula is as follows:
In addition, when preparing the chitosan and pyrimethanil conjugates of different molecular weight, the chitosan that can be 1,060,000 by molecular weight
By microwave degradation, and then the chitosan of different molecular weight is acquired, using the chitosan of different molecular weight as raw material, according to upper
The mode stated, which carries out coupling reaction, can be obtained the chitosan and pyrimethanil conjugates of different molecular weight.
Infrared spectroscopy shows: the infrared spectrum of infrared spectrum (Fig. 2) and chitosan of chitosan pyrimethanil conjugates (1)
(Fig. 1) is compared, in 1500cm-1To 1600cm-1The absorption peak of appearance is the characteristic absorption peak of C-N vibration and phenyl ring, 1750cm-1
To introduce-CH by acyl chlorides2Characteristic absorption peak.Prove that target conjugates 1 synthesize successfully.
The preparation of 2 chitosan of embodiment and pyrimethanil conjugates (2)
The first step weighs 4g pyrimethanil raw medicine, is dissolved in 80ml methylene chloride；Under condition of ice bath, constant pressure funnel is used
0.04mol chlorpromazine chloride is added into solution；After acyl chlorides is added dropwise, into reaction system, addition 3.3g potassium carbonate, which is used as, ties up acid
Agent；After reaction, 10ml distilled water is added into reaction system, after pouring into separatory funnel stratification, that collects lower layer has
Machine phase, and evaporated under reduced pressure solvent obtains product.
Second step, weighing 5g molecular weight is that 1,060,000 chitosans are added in there-necked flask, 50ml chloroform is added, machinery stirs
Swelling 30min is mixed, the sodium hydroxide solution of 12ml 10M is added, 0.01g 4- methylamino pyridine stirs 4h.3g the is added later
The product that one step is prepared, 50 C water baths react 4h.At the end of reaction, glacial acetic acid is added by pH and is adjusted to 7, filtering is anti-
Object is answered, solid product is washed with 70%-100% methanol solution, and 60 degrees Celsius are dried to obtain chitosan pyrimethanil conjugates (2).
Structural formula is as follows:
In addition, when preparing the chitosan and pyrimethanil conjugates of different molecular weight, the chitosan that can be 1,060,000 by molecular weight
By microwave degradation, and then the chitosan of different molecular weight is acquired, using the chitosan of different molecular weight as raw material, according to upper
The mode stated, which carries out coupling reaction, can be obtained the chitosan and pyrimethanil conjugates of different molecular weight.
Infrared spectroscopy shows: the infrared spectrum of infrared spectrum (Fig. 3) and chitosan of chitosan pyrimethanil conjugates (2)
(Fig. 1) is compared, in 1500cm-1To 1600cm-1The absorption peak of appearance is the characteristic absorption peak of C-N vibration and phenyl ring, 1750cm-1
To introduce-CH by acyl chlorides2Characteristic absorption peak.Prove that target conjugates 1 synthesize successfully.
The preparation of 3 chitosan of embodiment and pyrimethanil conjugates (3)
The first step weighs 4g pyrimethanil raw medicine, is dissolved in 80ml methylene chloride；Under condition of ice bath, constant pressure funnel is used
0.04mol 4- (chloromethyl) chloromethane acyl chlorides is added into solution；After acyl chlorides is added dropwise, 3.3g carbon is added into reaction system
Sour potassium is as acid binding agent；After reaction, wet chemical is added into reaction system, pours into separatory funnel stratification
Afterwards, the organic phase of lower layer is collected, and evaporated under reduced pressure solvent obtains product.
Second step, weighing 5g molecular weight is that 1,060,000 chitosans are added in there-necked flask, 50ml chloroform is added, machinery stirs
Swelling 30min is mixed, the sodium hydroxide solution of 12ml 10M is added, 0.01g 4- methylamino pyridine stirs 4h.3g the is added later
The product that one step is prepared, 50 C water baths react 4h.At the end of reaction, glacial acetic acid is added by pH and is adjusted to 7, filtering is anti-
Object is answered, solid product is washed with 70%-100% methanol solution, and 60 degrees Celsius are dried to obtain chitosan pyrimethanil conjugates (3).
Structural formula is as follows:
In addition, when preparing the chitosan and pyrimethanil conjugates of different molecular weight, the chitosan that can be 1,060,000 by molecular weight
By microwave degradation, and then the chitosan of different molecular weight is acquired, using the chitosan of different molecular weight as raw material, according to upper
The mode stated, which carries out coupling reaction, can be obtained the chitosan and pyrimethanil conjugates of different molecular weight.
Infrared spectroscopy shows: the infrared spectrum of infrared spectrum (Fig. 4) and chitosan of chitosan pyrimethanil conjugates (3)
(Fig. 1) is compared, in 1500cm-1To 1600cm-1The absorption peak of appearance is the characteristic absorption peak of C-N vibration and phenyl ring, 700cm-1Extremely
800cm-1For the characteristic absorption peak for introducing the phenyl ring that monosubstituted and contraposition replaces by acyl chlorides.Prove target conjugates 2 synthesis at
Function.
Application examples Antibacterial Activity
Test method
Chitosan shown in Formulas I and pyrimethanil conjugates are obtained as medical fluid using above-described embodiment, and the initial concentration of medical fluid is
Medical fluid is then diluted to 100mg/L with distilled water respectively by 10mg/mL, and 3 concentration of 200mg/L, 400mg/L are as test
Group measures the biocidal property of its Rhizoctonia solani and Gibberella zeae.It tests using the chitosan solution of same concentrations as control,
The culture medium of medical fluid is not added as blank control.
In superclean bench, the test group of above-mentioned setting, positive control and blank control are added into culture medium, and
The bacteria cake of Rhizoctonia solani Kuhn and Gibberella zeae is inoculated on the plate of backward PDA culture medium respectively.Plate is put into constant temperature later
It is cultivated in incubator, the cultivation temperature of incubator is set as 29 DEG C.After cultivating 72 hours under corresponding condition, plate is measured
Upper colony diameter.3 bacterium colonies of each board joint take its maximum gauge (Dmax) of each bacterium colony amount and minimum diameter (Dmin)
Its average value (Dave), and bacteriostasis rate is calculated according to the following formula:
Bacteriostasis rate (%)=(Dmax-Dave)/(Dave-5) × 100
The conjugates that above-described embodiment prepares show good bacteriostatic activity.Experimental result is shown in Table 1
The inhibitory activity of 1 partial Formula of table 1 chitosan and pyrimethanil conjugates Rhizoctonia solani and Gibberella zeae
Claims (5)
1. a kind of substance with bacteriostatic activity, it is characterised in that: substance is the conjugates of chitosan and pyrimethanil, and general formula is such as
Shown in Formulas I,
Formulas I；
Wherein, when R=When, phenyl ring 1 is connected with carbonyl.
2. a kind of preparation method of the substance described in claim 1 with bacteriostatic activity, it is characterised in that: with natural products shell
Glycan is skeleton, and pyrimethanil molecule is grafted in chitosan molecule by coupling reaction and obtains compound shown in Formulas I.
3. the preparation method of the substance as described in claim 2 with bacteriostatic activity, it is characterised in that:
Reaction equation is as follows
；
Wherein when R1=When, phenyl ring 1 is connected with carbonyl；
Pyrimethanil raw medicine is dissolved in excessive methylene chloride by the first step；Under condition of ice bath, chloracetyl chloride, 3- chlorine is added
Propionyl chloride or 4-(chloromethyl) chlorobenzoyl chloride；And potassium carbonate is added in backward reaction system；After reaction, into reaction system
Distilled water is added, stratification collects the organic phase of lower layer, and evaporated under reduced pressure, for use；
Wherein, chloracetyl chloride, 3- chlorpromazine chloride or 4-(chloromethyl) molar ratio of chlorobenzoyl chloride and pyrimethanil raw medicine is 1-10:1；
The molar ratio of potassium carbonate and pyrimethanil raw medicine is 1:1-10；
Second step, chitosan are added into excessive chloroform, and mechanical stirring is swollen 30-120min, add sodium hydroxide
Solution and 4- methylamino pyridine are stirred for 4-12h；The product that the first step is prepared is added after being stirred to react, it is Celsius in 50-80
Spend water-bath 4-12h；At the end of reaction, glacial acetic acid is added by pH and is adjusted to 7, filters reactant, solid product 70%-
The washing of 100% methanol solution, is dried to obtain compound shown in Formulas I；
Wherein, the molar ratio of chitosan and first step reaction product is 1-10:1；The molar ratio of 4- methylamino pyridine and chitosan
For 1:335.14.
4. pressing the preparation method of the substance described in claim 2 or 3 with bacteriostatic activity, it is characterised in that: the chitosan
Molecular weight be 1060KDa -4740kDa.
5. the application of the substance of bacteriostatic activity according to claim 1, it is characterised in that: the substance is being used to prepare inhibition
Application in fungi preparation.
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| 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 |
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