CN105601684A - Glucoside of dehydroabietic acid hydroxyl derivatives as well as preparation and application of glucoside - Google Patents
Glucoside of dehydroabietic acid hydroxyl derivatives as well as preparation and application of glucoside Download PDFInfo
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- CN105601684A CN105601684A CN201510967664.XA CN201510967664A CN105601684A CN 105601684 A CN105601684 A CN 105601684A CN 201510967664 A CN201510967664 A CN 201510967664A CN 105601684 A CN105601684 A CN 105601684A
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- dehydroabietic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/20—Carbocyclic rings
- C07H15/24—Condensed ring systems having three or more rings
- C07H15/256—Polyterpene radicals
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- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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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
Abstract
The invention provides glucoside of dehydroabietic acid hydroxyl derivatives. The structural formula of glucoside is shown in formula (I), wherein R represents an oligosaccharide group which is one of an alpha-glucosyl group, a cellobiose group, a maltose group and a xylobiose group. A preparation method of the dehydroabietic acid hydroxyl derivatives comprises steps as follows: peracetylated protection is performed on hydroxyl of oligosaccharide through acetic anhydride, oligosaccharide in peracetylated protection and 12,14-dyhydroxyl dehydroabietic acid are subjected to a condensation reaction to form glucoside, acetyl protection groups are removed, and glucoside of the dehydroabietic acid hydroxyl derivatives is obtained. The glucoside of the dehydroabietic acid hydroxyl derivatives has an excellent control effect on Bursaphelenchus xylophilus pests, has the advantages of high efficiency, low toxicity, few residues, good environmental compatibility and the like and can meet the demands for efficient and safe insecticides and bactericides for protection of pinaceae plants.
Description
Technical field
The invention belongs to technical field of pesticide, be specifically related to one and can be used as pest control agent active componentThe glucosides and preparation method thereof of dehydroabietic acid hydroxy derivatives.
Background technology
Due to the attention of the mankind to environmental protection, the toxicity to agricultural chemicals and more and more tighter to the requirement of ambient influnenceLattice, efficient, low toxicity, selectively good, safe, Environmental compatibility becomes well the target of pesticide research exploitation.In recent years, part botanical pesticide efficient, low toxicity be used to substitute halogenated hydrocarbon, thiocarbimide ester class,The high-toxic pesticide such as carbamates and organic phosphates, the glucosides of dehydroabietic acid hydroxy derivatives is wherein oneClass.
Agricultural chemicals comes from plant, is mainly to utilize the secondary metabolites in plant to carry out killing pests and suppressing bacteria. According to the study,Secondary metabolites in plant, mainly comprises alkaloid, flavonoids, terpenes, polyyne class, phenols and fatAcid etc., all have anti-nematicide effect. Botanical pesticide use cost is low, and Environmental compatibility is good, from protectionThe new method that the angle of environment seeks to control nematode is the common recognition of Chinese scholars, research, exploitation botanical pesticideIt is the development trend of control nematode.
Rosin is the mixture of various kinds of resin acid and a small amount of aliphatic acid and neutral substance, and wherein resin acid is mainWant composition, stable in properties, has good biologically active. Dehydroabietic acid (dehydroabietic acid), have antibacterial,Antiviral, antifeedant activity, the active isoreactivity of slowly-releasing. Rosin can obtain dehydrogenation pine easily by disproportionated reactionFragrant acid, therefore cheap and easy to get. Utilize that dehydroabietic acid is multiple for raw material can synthesize has bioactive chemical combinationThing, hydroxylating dehydroabietic acid has significant effect at aspects such as antibacterial, desinsections. Dehydroabietic acid chemical constitutionAs follows:
Dehydroabietic acid is carried out to simple structural modification, on phenyl ring, increase phenolic hydroxyl group quantity and improve and kill nematodeAbility.
In the disease-resistant inducible factor of current research plant, compound sugar because of its wide material sources, induce resistance height alsoThe advantages such as energy coordinate plant growth become the focus of domestic and international concern. Compound sugar elicitor can excite rapidly plantDefense response, starts system of defense, makes plant produce tocopherols compound, lignin, protective plant protecting agent, the course of diseaseThe disease-resistance substances such as GAP-associated protein GAP, and raising defensive ferment and the Active oxygen eliminating enzyme system system relevant to disease-resistant metabolism livedProperty.
Summary of the invention
First object of the present invention is to provide has good prevention effect to loose nematode pests, has height simultaneouslyThe glucosides of one class dehydroabietic acid hydroxy derivatives of the feature such as effect, low toxicity, low residual, Environmental compatibility are good,Protect the demand to highly effective and safe desinsection, bactericide to meet pinaceae plant.
The glucosides of one class dehydroabietic acid hydroxy derivatives, its molecular structural formula is suc as formula shown in (I):
In formula (I), R be oligomeric glycosyl (compound sugar refers to contain the compound that 2-10 glycosidic bond is polymerized,Glycosidic bond is that certain monohydroxy of a monose and certain monohydroxy dehydrating condensation of another monose form).
As preferably, described glycosyl is the one in cellobiose base, malt-base and xylobiose base.
Second object of the present invention is to provide a kind of preparation method of above-claimed cpd, and described preparation method comprisesFollowing steps:
(1) the full acetylated protection of compound sugar hydroxyl
By adding in reaction vessel after catalyst and compound sugar mixing grinding, add acetic anhydride, be heated to50-70 DEG C is stirred until after reactant liquor is clear solution, continue reaction 1-2h, pours while hot reactant into iceIn water, rapid stirring, after suction filtration, washing, then with 95% hexanol recrystallization 2-3 time, takes off through active carbonLook, after dry full acetylated compound sugar;
(2) the selective bonding of full acetylated compound sugar and aglycon
Add reaction to hold compound sugar full acetylated step (1) gained and 12,14-dihydroxy dehydroabietic acidIn device, add solvent toluene, in 100-120 DEG C of stirring, then add BF3Et2O, continues to stir lower reaction0.5-1.5h, then decompression extracts toluene, is cooled to after room temperature, adopts chloroform extraction, combining extraction liquid, waterWash rear dry with anhydrous calcium chloride, then through the full acetylated glucosides that is recrystallized to obtain;
(3) deprotection
In reaction vessel, add the full acetylated glucosides of step (2) gained and solvent absolute methanol, in 40-50 DEG CBe stirred to reactants dissolved, add sodium methoxide-methanol solution, after insulation reaction 1-2 hour, be cooled to room temperature,Filter, filtration cakes torrefaction obtains the glucosides of dehydroabietic acid hydroxy derivatives.
As preferably, catalyst described in step (1) is the one in acid, pyridine and sodium acetate.
More preferably, described acid is acetic acid.
As preferably, described in step (1), compound sugar is the one in cellobiose, maltose and xylobiose.
As preferably, described in step (1), the mol ratio of catalyst and acetic anhydride is 1:0.9-1.1, described secondThe amount of substance of acid anhydrides is 1.1-1.3n times of compound sugar amount of substance, and described n is hydroxyl in oligosaccharides moleculeNumber.
As preferably, full acetylated compound sugar and 12,14-dihydroxy dehydroabietic acid described in step (2)Mol ratio be 1:1.1-1.3, described full acetylated compound sugar and BF3Et2The mol ratio of O is 0.8-1.5 times.
As preferably, the concentration of sodium methoxide-methanol solution amount of substance described in step (3) is 0.2-0.4mol/L,The amount of substance of described sodium methoxide is 0.9-1.1n times of compound sugar amount of substance, and described n is in oligosaccharides moleculeHydroxyl number.
Taking glucose as example, the synthetic route of the glucosides of dehydroabietic acid hydroxy derivatives is:
The present invention is used 12, and 14-dihydroxy dehydroabietic acid is that laboratory makes, and concrete synthetic route is:
Described 12, the concrete preparation process of 14-dihydroxy dehydroabietic acid is:
(a) dehydroabietic acid of 5g is dissolved in the acetic acid of 20ml, adds the dense HNO of 20ml3,At 60 DEG C, magnetic agitation, reaction 3h, after reaction, imports reactant liquor in 100ml water, separates out yellow solidBody, suction filtration, obtains intermediate A;
(b) 3.5g intermediate A is dissolved in methyl alcohol, adds 0.8g zinc powder, and the 1g ammonium formate aqueous solution,Magnetic agitation 2h, after reaction, filtering mixt, gets filtered fluid, removes organic layer with revolving to steam, with chloroform againDissolve, add saturated NaCl solution, extraction (upper strata), gets upper strata liquid, removes chloroform with revolving to steam, and must consolidateBody intermediate B;
(c) get 3.1g intermediate B and be dissolved in methyl alcohol, add 2g dilute sulfuric acid aqueous solution, be chilled to 0 DEG C with frozen water,Drip 0.12g sodium nitrite in aqueous solution, magnetic agitation stirs 30min, after reaction, puts into immediately 60 DEG C of oil bathsHeating, and add 2g dilute sulfuric acid aqueous solution magnetic agitation, after reaction 1h, filter, get filtrate, treat that solvent is certainlySo volatilization, obtains product yellow solid 12,14-dihydroxy dehydroabietic acid.
The 3rd object of the present invention is to provide the application of the glucosides of dehydroabietic acid hydroxy derivatives, with dehydrogenation pineThe glucosides of fragrant sour hydroxy derivatives is active component, adds insecticides adjuvant to make the aqueous emulsion of desinsection, sterilization, micro-Emulsion or emulsion.
The glucosides of the dehydroabietic acid hydroxy derivatives shown in formula (I) is to loose ends worm and carry pathogenic bacteria and haveGood prevention effect, therefore can be used as desinsection, the bactericide of the pinaceae plants such as protection agricultural, gardening, canUse separately, or use the dehydroabietic acid as shown in formula (I) in the mode of desinsection, bactericidal compositionThe glucosides of hydroxy derivatives is active component, adopts the conventional insecticides adjuvant in this area to be processed into aqueous emulsion, micro emulsionAgent, emulsion and wettable powder.
Conventional insecticides adjuvant comprises: liquid-carrier, as water; Organic solvent as toluene, dimethylbenzene, cyclohexane,Methyl alcohol, butanols, ethylene glycol, propyl alcohol, dimethyl formamide, ether, methyl-sulfoxide, animal and plant oil orAliphatic acid; Conventional surfactant, as emulsifying agent and dispersant, comprises anion surfactant, cationSurfactant, non-ionic surface active agent or amphoteric surfactant; Other auxiliary agents, as wetting agent or thickeningAgent.
The glucosides of the dehydroabietic acid hydroxy derivatives shown in formula (I) becomes as the activity in desinsection, bactericideTimesharing, the content in described pesticide can be selected in 0.1% to 99.5% scope, and can basisDosage form and application process are determined suitable active component content. Conventionally, in aqueous emulsion, containing 5-50% (weighsAmount percentage, lower same) described active component, preferably its content is 20-50%; In microemulsion, contain 5-50%Active component, preferably its content is 20-40%; In missible oil, contain the active component of 1-90%, preferably itsContent is 20-90%.
Described aqueous emulsion, microemulsion, can be using compound (I) and solvent and surface-active as active componentThe auxiliary agents such as agent evenly mix and make, and when use, dilutable water is to prescribed concentration. Described wettable powder,Can will pulverize and make as mixing such as compound (I), solid carrier and the surfactants of active componentBecome, when use, water dilutes. The processing method of preparation is absolutely not limited to foregoing, the technology of this areaPersonnel can, according to described active component and application target etc., select suitable method.
Except the glucosides of the dehydroabietic acid hydroxy derivatives shown in the formula as active component (I), the present inventionDescribed desinsection, bactericide also can comprise other pesticides, bactericide, insect growth regulator, IGR, plant growthAny applicable active component such as conditioning agent and soil conditioner.
Desinsection containing compound shown in formula (I) of the present invention, the using method of bactericide, can select normalWith application method, as sprinkling, seed dressing, stem brush, execute pesticide-clay mixture etc. For example, in the time adopting cauline leaf to spray, adoptThe aqueous emulsion, microemulsion or the missible oil that are 1-1000ppm with active component content, preferably active component content is1-500ppm。
Beneficial effect of the present invention is:
1, the glucosides of novel dehydroabietic acid hydroxy derivatives provided by the present invention has good to loose ends parasitosisPrevention effect, can be used for preparing desinsection, the bactericide in the field such as agricultural chemicals, gardening, have efficient, low toxicity,Eco-friendly advantage.
2, be that raw material is prepared dehydroabietic acid hydroxy derivatives by dehydroabietic acid cheap and easy to get and compound sugarGlucosides, method is simple, easy and simple to handle, and raw material is cheap and easy to get, is applicable to suitability for industrialized production.
Detailed description of the invention
Below in conjunction with specific experiment embodiment, the present invention is described in further detail, but the present invention is not implementedExample restriction.
The preparation (glycosyl is cellobiose base) of the glucosides of embodiment 1 dehydroabietic acid hydroxy derivatives
Synthesizing of (1) eight acetyl fibre two sugar esters
After being mixed to grinding, the 4.84g anhydrous sodium acetate cellobiose dry with 2.50g (0.0073mol) proceed toIn the there-necked flask of 250ml, add 6.53g (0.064mol) acetic anhydride, be heated to 50 DEG C, and stir until anti-Answer thing to become clear solution. Continue heating 1h, reactant poured into while hot and filled in 100ml frozen water beaker,Rapid stirring, suction filtration, after twice of a small amount of cold water washing, with the hexanol recrystallization twice of 10.00ml95%, andAdd a small amount of activated carbon decolorizing, after being dried, obtain 4.83g eight acetyl fibre two sugar ester white crystals, yield is 53.4%,Purity is 96.6%.
Synthesizing of (2) eight acetyl fibre disaccharides-dihydroxy dehydroabietic acid glucosides
Get eight acetyl fibre two sugar ester 4.80g (0.0072mol) and 12,14-dihydroxy dehydroabietic acids2.52g (0.0079mol) adds in reaction vessel, adds solvent toluene, in 100 DEG C of stirrings, then adds BF3Et2O1.6g, continues to stir lower reaction 0.5h, and then decompression extracts toluene, is cooled to after room temperature, adopts chloroform extraction,Combining extraction liquid, washing, dry with anhydrous calcium chloride, obtain white crude product, 6.63g white needles is recrystallized to obtainCrystallization, is eight acetyl fibre disaccharides-dihydroxy dehydroabietic acid glucosides, and yield is 90.6%, and purity is 95.2%.
(3) cellobiose-dihydroxy dehydroabietic acid glucosides is synthetic
In 100ml flask, add 6.30g (0.0068mol) eight acetyl fibre disaccharides-dihydroxy dehydroabietic acidsGlucosides and 30.00ml absolute methanol, in 40 DEG C of heating for dissolving, add 12.0ml (0.20mol/L) sodium methoxide-Methanol solution, insulated and stirred reaction 1h, cooling cellobiose-dihydroxy dehydroabietic acid glucosides white of separating outCrystal, quality is 4.30g, and yield is 45.1%, and purity is 95.8%.
Cellobiose-dihydroxy dehydroabietic acid glucosides structural formula is:
1H-NMR data:1HNMR(DMSO/TMS)δ：6.37(1H,s),5.63(1H,s),5.23(1H,d),4.67(1H,d),4.51(1H,d),3.65(1H,dd),3.32(1H,dd),3.29(1H,dd),3.22(1H,dt,J＝13.5),2.95(1H,m,J＝6.9),2.92(1H,ddd,J＝16.5,J＝12.3andJ＝6.3),2.75 (1H,dd,J＝16.5andJ＝4.8),2.21(1H,d,J＝12),1.70(6H,m),1.42(1H,m),1.36(3H,s),1.31(3H,s),1.23(3H,d,J＝6.3),1.21(3H,d,J＝6.3)ppm.
The preparation (glycosyl is malt-base) of the glucosides of embodiment 2 dehydroabietic acid hydroxy derivatives
Synthesizing of (1) eight acetyl Maltose Ester of Fatty Acid
After being mixed to grinding, the 5g anhydrous sodium acetate maltose dry with 2.50g (0.0069mol) proceeds to 250mlThere-necked flask in, add 6.2g (0.061mol) acetic anhydride, be heated to 60 DEG C, and stirring until reactant becomeFor clear solution. Continue heating 1.5h, reactant is poured into while hot and filled in 100ml frozen water beaker, fastStir, suction filtration, after twice of a small amount of cold water washing, with the hexanol recrystallization twice of 10.00ml95%, and adds fewCarbon content active decolouring, obtains 4.75g eight acetyl Maltose Ester of Fatty Acid white crystals after being dried, and yield is 54.6%, purityBe 93.1%.
Synthesizing of (2) eight acetyl maltose-dihydroxy dehydroabietic acid glucosides
Get eight acetyl Maltose Ester of Fatty Acid 4.70g (0.0067mol) and 12,14-dihydroxy dehydroabietic acid2.33g (0.0073mol) adds in reaction vessel, adds solvent toluene, in 110 DEG C of stirrings, then adds BF3Et2O1.2g, continues to stir lower reaction 1h, and then decompression extracts toluene, is cooled to after room temperature, adopts chloroform extraction,Combining extraction liquid, washing, dry with anhydrous calcium chloride, obtain white crude product, 6.35g white needles is recrystallized to obtainCrystallization, is eight acetyl maltose-dihydroxy dehydroabietic acid glucosides, and yield is 90.3%, and purity is 98.2%.
(3) maltose-dihydroxy dehydroabietic acid glucosides is synthetic
In 100ml flask, add 6.30g (0.0066mol) eight acetyl maltose-dihydroxy dehydroabietic acid sugarGlycosides and 30.00ml absolute methanol, in 45 DEG C of heating for dissolving, add the first of 12ml (0.20mol/L) sodium methoxideAlcoholic solution, insulated and stirred reaction 1.5h, cooling maltose-dihydroxy dehydroabietic acid glucosides white crystalline substance of separating outBody, quality is 4.30g, and yield is 45.6%, and purity is 96.2%.
Maltose-dihydroxy dehydroabietic acid glucosides structural formula is:
1H-NMR data:1HNMR(DMSO/TMS)δ：6.41(1H,s),6.13(1H,d),5.95(1H,d),5.73(1H,s),5.46(1H,dd),5.40(1H,dd),5.12(1H,dd),5.10(1H,dd),4.90(1H,q),4.88(1H,q),4.50(1H,d),4.48(1H,d),4.20(1H,d),4.18(1H,d),4.02(1H,dd),3.98(1H,dd),3.12(1H,dt,J＝13.5),2.95(1H,m,J＝6.9),2.90(1H,ddd,J＝16.5,J＝12.3andJ＝6.3),2.74(1H,dd,J＝16.5andJ＝4.8),2.21(1H,d,J＝12),1.71(6H,m),1.45(1H,m),1.35(3H,s),1.32(3H,s),1.25(3H,d,J＝6.3),1.22(3H,d,J＝6.3)ppm.
The preparation (glycosyl is xylobiose base) of the glucosides of embodiment 3 dehydroabietic acid hydroxy derivatives
Synthesizing of (1) six acetyl xylobiose ester
After being mixed to grinding, the 4.84g anhydrous sodium acetate xylobiose dry with 2.50g (0.0089mol) proceed to 250In the there-necked flask of ml, add 6.00g (0.059mol) acetic anhydride, be heated to 70 DEG C, and stirring is until reactantBecome clear solution. Continue heating 2h, reactant is poured into while hot and filled in 100ml frozen water beaker, fastStir, suction filtration, after twice of a small amount of cold water washing, with the hexanol recrystallization twice of 10.00ml95%, and adds fewCarbon content active decolouring, obtains 4.62g six acetyl xylobiose ester white crystals after being dried, and yield is 54.4%, purityBe 95.9%.
Synthesizing of (2) six acetyl xylobiose ester-dihydroxy dehydroabietic acid glucosides
Get six acetyl xylobiose ester 4.60g (0.0088mol) and 12,14-dihydroxy dehydroabietic acid 3.19G (0.0100mol) adds in reaction vessel, adds solvent toluene, in 120 DEG C of stirrings, then adds BF3Et2O1g，Continue to stir lower reaction 1.5h, then decompression extracts toluene, is cooled to after room temperature, adopts chloroform extraction, mergesExtract, washing, dry with anhydrous calcium chloride, obtain white crude product, the 6.80g white, needle-shaped crystals that is recrystallized to obtain,Be six acetyl xylobiose ester-dihydroxy dehydroabietic acid glucosides, yield is 87.3%, and purity is 96.8%.
(3) xylobiose-dihydroxy dehydroabietic acid glucosides is synthetic
In 100ml flask, add 6.80g (0.0087mol) six acetyl xylobiose ester-dihydroxy dehydroabietic acidsGlucosides and 30.00ml absolute methanol, in 50 DEG C of heating for dissolving, add 12ml (0.20mol/L) sodium methoxideMethanol solution, insulated and stirred reaction 2h, cooling xylobiose-dihydroxy dehydroabietic acid glucosides white crystalline substance of separating outBody, quality is 5.02g, and yield is 50.7%, and purity is 94.8%.
Xylobiose-dihydroxy dehydroabietic acid glucosides structural formula is:
1H-NMR data:1HNMR(DMSO/TMS)δ：6.42(1H,s),5.69(1H,s),4.58(1H,d),4.43(1H,d),4.02(1H,d),3.95(1H,d),3.76(1H,q),3.61(1H,q),3.53(1H,dd),3.44(1H,dd),3.35(1H,d),3.31(1H,d),3.26(1H,dd),3.24(1H,dd),3.11(1H,dt,J＝13.5),2.93(1H,m,J＝6.9),2.89(1H,ddd,J＝16.5,J＝12.3andJ＝6.3),2.69(1H,dd,J＝16.5andJ＝4.8),2.25(1H,d,J＝12),1.73(6H,m),1.45(1H,m),1.37(3H,s),1.30(3H,s),1.26(3H,d,J＝6.3),1.23(3H,d,J＝6.3)ppm.
The following example is described the formulation example taking the compounds of this invention as active component, and described preparation can be used as agricultureDesinsection, the bactericide in industry, gardening and flower culture field. But, embodiments of the present invention do not limit toLower content.
Embodiment 4 aqueous emulsions
20 parts, the glucosides of dehydroabietic acid hydroxy derivatives, 10 parts of toluene, epoxy ethane-epoxy propane block5 parts of copolymers, 5 parts of xanthans, ethylene glycol/propylene glycol meets 8 parts of antifreezing agents, 0.9 part of organosilicon, water45 parts, be evenly mixed to get together active component and be 20% aqueous emulsion.
Embodiment 5 microemulsions
20 parts, the glucosides of dehydroabietic acid hydroxy derivatives, 10 parts of triphenylethylene phenol APEOs, alkyl5 parts of benzene sulfonic acid calcium salts, 5 parts, acetone, isopropyl alcohol 10 examples, 3 parts of APEO formamides, 47 parts, water,Evenly be mixed to get together active component and be 20% microemulsion.
Embodiment 6 missible oil
10 parts, the glucosides of dehydroabietic acid hydroxy derivatives is dissolved in by 40 parts of dimethylbenzene and 35 parts of dimethyl methylsIn the mixed solvent of acid amides composition, then add 15 parts of POLYSORBATE 80 emulsifying agents, stir and be evenly mixed to get workThe missible oil that property composition is 10%.
The desinsection taking the compounds of this invention as active component, the test example of bactericide by narration below. But, thisWorking of an invention mode is not limited to following content.
The insecticidal test of embodiment 7 pine wood nematodes
Get withered loose diseased wood, thinly slice, separate and obtain nematode by the graceful funnel method of shellfish, confirm through microscopy, putIn covering with on the potato dextrose agar flat board of the pathogen of Botrytis cinerea Botrytiscinerea, 25 DEG C of constant temperatureIn case, cultivate. Substantially eaten after mycelia until nematode, more further expanded and cultivate. Finally will cultivate with sterilized waterNematode on Botrytis cinerea flat board is washed down, and being mixed with concentration is the nematode suspension of 5000-6000 bar/ml, suppliesTest for subsequent use.
Adopt laboratory (suspension+agricultural chemicals directly tag method) to carry out insecticidal effect test. To real with pure waterDesinsection, the bactericide missible oil of executing example 6 gained dilute, and dilute 10 times, and 20 times, 30 times. At culture dishInside add pesticide and the lml nematode suspension of 1mL test concentrations simultaneously, after vibrations mix, place 1h. ?The situation that survives of test under microscope nematode, statistics nemic death rate, evaluates its insecticidal effect. According to calculating knotFruit must table 1.
The insecticidal effect of the glucosides of table 1 dehydroabietic acid hydroxy derivatives to pine wood nematode
| Raw material glucosides kind | The median lethal dose (μ g/ml) of 1h |
| Cellobiose | 29.6 |
| Maltose | 21.3 |
| Xylobiose | 19.2 |
The BA of embodiment 8 to pathogenic bacteria
Scraps of paper disperse method extracorporeal bacteria inhibitor test is surveyed sterilizing ability, is separate in the strain of Zhejiang Province, China worm excellent for examination bacterial classificationGesture bacterium is the Pantoeatoletana of general Pseudomonas, the bacterial strain of Jiangsu Province, China Lishui isolation and another JapanBacterial strain is same, i.e. enterobacter cloacae (Enterobactercloacae), nematode stain of Pantoea agglomerans (Pantoeaagglomerans)。
In super-clean bench, open dry strain tube, strain transfer, in nutrient broth, is put at 28 DEG C and cultivated24h. After 24h, take out nutrient solution, centrifugal and remove supernatant, with BS Eddy diffusion bacterial classification, andBacterial classification is evenly placed in respectively to the nutrient solution of 3 the same terms, puts at 28 DEG C and cultivate 24h. After 24h, get 2mlEmbodiment 6 pesticides, drip in the middle of culture dish, cultivate 10min, observed result.
The bactericidal effect of the glucosides of table 2 dehydroabietic acid hydroxy derivatives
Below only enumerated the preferred embodiments of the invention, protection scope of the present invention is not restricted to this, thisAny change that those skilled in the art do within the scope of the claims in the present invention all falls into protection domain of the present inventionIn.
Claims (10)
1. the glucosides of a class dehydroabietic acid hydroxy derivatives, its molecular structural formula is suc as formula shown in (I):
In formula (I), R is oligomeric glycosyl.
2. the glucosides of a class dehydroabietic acid hydroxy derivatives as claimed in claim 1, is characterized in that:Described oligomeric glycosyl is the one in cellobiose base, malt-base and xylobiose base.
3. the glucosides of preparation dehydroabietic acid hydroxy derivatives as claimed in claim 1, is characterized in that:Described preparation method comprises the steps:
(1) the full acetylated protection of compound sugar hydroxyl
By adding in reaction vessel after catalyst and compound sugar mixing grinding, add acetic anhydride, be heated to50-70 DEG C is stirred until after reactant liquor is clear solution, continue reaction 1-2h, pours while hot reactant into iceIn water, rapid stirring, through suction filtration, washing after, then with 95% hexanol be recrystallized 2-3 time, through activated carbon decolorizing,After dry, obtain full acetylated compound sugar;
(2) the selective bonding of full acetylated compound sugar and aglycon
Add reaction to hold compound sugar full acetylated step (1) gained and 12,14-dihydroxy dehydroabietic acidIn device, add solvent toluene, in 100-120 DEG C of stirring, then add BF3Et2O, continues to stir lower reaction0.5-1.5h, then decompression extracts toluene, is cooled to after room temperature, adopts chloroform extraction, combining extraction liquid, waterWash rear dry with anhydrous calcium chloride, then through the full acetylated glucosides that is recrystallized to obtain;
(3) deprotection
In reaction vessel, add the full acetylated glucosides of step (2) gained and solvent absolute methanol, in 40-50 DEG CBe stirred to reactants dissolved, add sodium methoxide-methanol solution, after insulation reaction 1-2 hour, be cooled to room temperature,Filter, filtration cakes torrefaction obtains the glucosides of dehydroabietic acid hydroxy derivatives.
4. preparation method as claimed in claim 3, is characterized in that: described in step (1), catalyst isOne in acid, pyridine and sodium acetate.
5. preparation method as claimed in claim 4, is characterized in that: described acid is acetic acid.
6. preparation method as claimed in claim 3, is characterized in that: described in step (1), compound sugar isOne in cellobiose, maltose and xylobiose.
7. preparation method as claimed in claim 3, is characterized in that: catalyst described in step (1) withThe mol ratio of acetic anhydride is 1:0.9-1.1, and the amount of substance of described acetic anhydride is compound sugar amount of substanceDoubly, described n is hydroxyl number in oligosaccharides molecule to 1.1-1.3n.
8. preparation method as claimed in claim 3, is characterized in that: full acetylated described in step (2)Compound sugar and the mol ratio of 12,14-dihydroxy dehydroabietic acid be 1:1.1-1.3, described full acetylated oligomericSugar and BF3Et2The mol ratio of O is 0.8-1.5 times.
9. preparation method as claimed in claim 3, is characterized in that: sodium methoxide described in step (3)-Methanol solution amount of substance concentration is 0.2-0.4mol/L, and the amount of substance of described sodium methoxide is compound sugar sugar substanceAmount 0.9-1.1n doubly, described n is hydroxyl number in oligosaccharides molecule.
10. the application of dehydroabietic acid hydroxy derivatives glucosides as claimed in claim 1, is characterized in that: withDehydroabietic acid hydroxy derivatives glucosides claimed in claim 1 is active component, adds insecticides adjuvant to make and killsAqueous emulsion, microemulsion or the emulsifiable concentrate of worm, sterilization.
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