CN101558760A - Compound agent of ethyl isothiocyanate and allyl isothiocyanate and application thereof - Google Patents
Compound agent of ethyl isothiocyanate and allyl isothiocyanate and application thereof Download PDFInfo
- Publication number
- CN101558760A CN101558760A CNA2009100850518A CN200910085051A CN101558760A CN 101558760 A CN101558760 A CN 101558760A CN A2009100850518 A CNA2009100850518 A CN A2009100850518A CN 200910085051 A CN200910085051 A CN 200910085051A CN 101558760 A CN101558760 A CN 101558760A
- Authority
- CN
- China
- Prior art keywords
- allyl group
- ethyl isothiocyanate
- composite dose
- group isosulfocyanate
- ethyl
- 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
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a compound agent, which is prepared by performing binary compounding on plant-source compounds of ethyl isothiocyanate and allyl isothiocyanate according to the weight ratio of 1:7-7:1. The compound agent can be prepared into a dissoluble liquid, an aqueous emulsion, an oil solution or a tablet, and is applied to preparing a pesticide fumigant for controlling insect pests and harmful mould fungi in storehouses and soil. The compound agent has the advantages of obvious synergy, high bacteriostatic and insecticidal activity, less relative usage, and obvious fumigation effect on pests of food, tobacco and soil nematodes and the like, and can be used for substituting bromomethane which is forbidden fumigant.
Description
Technical field
The present invention relates to a kind of composition pesticide of preventing and treating pest in warehouse and the soil, specifically, relate to and a kind ofly derive from the compound ethyl isothiocyanate of Cruciferae Armoracia and Brassica plants and composite dose of allyl group isosulfocyanate used the used as pesticides fumigant.
Background technology
Ethyl isothiocyanate (EITC) extensively is present in the plant of Cruciferae with allyl group isosulfocyanate (AITC), and especially Brassicas and Armoracia plant quantum of output are more considerable.Armoracia or brassica plant in fact complete, drying there is no pungent, have only its broken posthydrolysis just to have pungent to produce.This is owing to exist glucosinolate (sulphur glucoside) in the plant, under the effect of hydrolase enzymatic hydrolysis takes place, and discharges the isosulfocyanate compound of highly volatile and produces hot taste.The kind difference of contained isosulfocyanate compound in the different plants, contain allyl group isosulfocyanate in wherein most of plant, ethyl isothiocyanate, the propyl group isothiocyanates, 4-isopentene group isothiocyanates, phenyl isothiocyanates, the benzyl isothiocyanates, 5-first sulfurous base penta isothiocyanates, 6-first sulfurous base hexyl isothiocyanates, 7-first sulfurous base heptyl isothiocyanates or the like.
Isosulfocyanate compound except the seasoning effect, people broad research their various biologically actives.Proved that isothiocyanates has killing or suppresses the ability of bacterium, as comma bacillus, typhoid bacillus, staphylococcus aureus, tulase, Salmonella, diphtheria bacterium, Escherichia coli, bacillus subtilis etc. are had stronger inhibition activity.Fungi such as paecilomyces varioti bacterium, brewer's yeast also there is higher bacteriostasis rate.
CN1124075C discloses a kind of composition and use thereof that contains isothiocyanates, and the bactericidal composition that it contains the polyalcohol of AITC and band aldehyde radical or ketone group is mainly used in the purpose of handling microorganism, fresh-keeping of vegetables and processing perishable commodities.
Once having proposed among inventor's the CN101133739 is several product formulation prescriptions that are respectively applied for soil, grain, textile and tobacco warehouse of main active with the allyl group isosulfocyanate, and the fumigating method very easily to the user is provided, also indicated concrete use object and the dosage of AITC as Pesticidal products.
In extraction to the isosulfocyanate compound in the crucifer, on the basis of separation and purification and evaluation, the inventor to each concrete isosulfocyanate compound carrying out one by one unification compound bioactivity screening and compound screening, find that two or more ITCs combination can produce synergistic effect, complex preparation between two or more the isothiocyanates is not being seen open report as warehouse and soil fumigant, and composite usefulness deals with harmful fungoid and insect and does not also appear in the newspapers and apply for a patent between two or more the isothiocyanates.
Summary of the invention
The purpose of this invention is to provide tangible ethyl isothiocyanate of a kind of synergistic effect and allyl group isosulfocyanate composite dose.
Another object of the present invention provides composite dose of application that is used for preparing in control warehouse and the soil pest fumigant with allyl group isosulfocyanate and ethyl isothiocyanate.
The inventor is when carrying out allyl group isosulfocyanate to the stifling test of large-scale enclosed system such as warehouse and container, find that also there is volatilization in the agent of allyl group isosulfocyanate list not exclusively in the use, fumigation activity such as can not give full play at shortcoming, be necessary by composite, find significantly synergy, drive the combination of allyl group isosulfocyanate volatilization, reach the raising control efficiency, reduce dosing, reduce the purpose of environmental pollution.
For this reason, the inventor has passed through a large amount of tests, utilize the crucifer extract to prepare allyl group isosulfocyanate, ethyl isothiocyanic acid, propyl group isothiocyanates, isopropyl thiocyanates, butyl isothiocyanates, isopentene group isothiocyanates, phenyl isothiocyanates, benzyl isothiocyanates, the agent of 1-phenylethyl isothiocyanates list respectively, and common stored grain insects and disease fungus have been carried out the fumigation activity screening.Screening by single agent and complex preparation, discovery is compared no significant difference with the stifling effect of ethyl isothiocyanic acid composition with the methyl bromide fumigation effect with allyl group isosulfocyanate, but more friendly to environment, to the person poultry safety, can form a kind of desirable biogenic fumigant.
In order to realize purpose of the present invention, the inventor has further carried out the proportioning screening of two kinds of compounds and has found active ingredient allyl group isosulfocyanate and synergistic component ethyl isothiocyanate, the weight ratio of the two is that synergistic effect was all arranged in 1: 7～7: 1, wherein, preferred weight ratio is 1: 5～5: 1, is more preferably 5: 1.
Can make pesticidal preparations well known in the art for composite dose of ethyl isothiocyanate of the present invention and allyl group isosulfocyanate, such as soluble liquid, aqueous emulsion, finish, tablet etc.According to the different application occasion, can be made into different dosage form.
Wherein, when making finish with described composite dose, the component of described finish and weight percentage are:
Allyl group isosulfocyanate 1～60%,
Ethyl isothiocyanate 0.2～20%,
Antioxidant 0.1～2%,
Solvent 10～85.7%,
Vegetable oil polishing to 100%.
Described antioxidant is ascorbic acid class material or gallic acid pentyl ester.
Described solvent is toluene, dimethylbenzene, ethyl acetate or cyclohexanone etc.
Described vegetable oil is thick rapeseed oil, cotton oil or thick soya-bean oil etc.
Its preparation process is: fully mix thoroughly in the mixing mother liquor of ethyl isothiocyanate that the antioxidant input is quantitatively taken by weighing and allyl group isosulfocyanate earlier.Again with the vegetable oil and the abundant mixing of solvent that accurately quantitatively take by weighing.At last above-mentioned two kinds of solution are mixed in preparing tank and continue and stirred 1～3 hour.Product be sub-packed in the dual obstruct plastic bottle or in be coated with in the Aluminum Bottle of barrier layer the sealing storage.Finish generally is applicable to the pest in the control warehouse grain.
The component of described aqueous emulsion and weight percentage are:
Allyl group isosulfocyanate 1～20%,
Ethyl isothiocyanate 0.2～15%,
Emulsifier 12～28%,
Ascorbic acid 0.1～2%,
Solvent 10～30%,
Water polishing to 100%.
Wherein, described emulsifier be 7780, emulsifier such as 7781T, 4103, OP-10, Well201, No. 500,602, Well205 or M30.
Described solvent is ethyl acetate or cyclohexanone.
Its preparation process is: fully mix thoroughly in the mixing mother liquor of ethyl isothiocyanate that the ascorbic acid input is quantitatively taken by weighing and allyl group isosulfocyanate earlier.With emulsifier and the abundant mixing of solvent that accurately quantitatively takes by weighing.At last above-mentioned two kinds of solution are continued to stir 1～3 hour in preparing tank.Product be sub-packed in the dual obstruct plastic bottle vial or in be coated with in the Aluminum Bottle of barrier layer the sealing storage.Described aqueous emulsion generally is used for preventing and treating the pest of grain depot and soil.
The component of described soluble liquid and weight percentage are:
Allyl group isosulfocyanate 1～40%,
Ethyl isothiocyanate 0.2～30%,
Emulsifier 12～28%,
Ascorbic acid 0.3～2%,
Solvent polishing to 100%.
Described emulsifier is 7780,7781T, 4103, OP-10, Well201, No. 500,602, emulsifier such as Well205, M30.
Described solvent is methyl alcohol, ethanol, dimethylbenzene or a line oil, is good with mixed solvent wherein, and dimethylbenzene and a line oil are 1: 1 (V/V), and methyl alcohol and ethanol are 1: 1 (V/V).
Its preparation process is: fully mix thoroughly in the mixing mother liquor of ethyl isothiocyanate that the ascorbic acid input is quantitatively taken by weighing and allyl group isosulfocyanate earlier.With agricultural emulsifier and the abundant mixing of solvent that accurately quantitatively takes by weighing.At last above-mentioned two kinds of solution are continued to stir 1～3 hour in preparing tank.Product is sub-packed in the dual obstruct plastic bottle, the sealing storage.Described soluble liquid generally is used for the pest of stifling grain depot and soil.
The component of described stifling tablet and weight percentage are:
Allyl group isosulfocyanate 1～30%,
Ethyl isothiocyanate 0.2～25%,
Antioxidant 0.5～2.0%,
Vegetable fiber sheet 70～95%.
Described antioxidant is ascorbic acid or gallic acid pentyl ester.
Described vegetable fiber sheet is asbestos fibre sheet, cotton fiber sheet or flaxen fiber sheet.
When needing, also can comprise peppermint essence (or other essence) 0.1～1% (also can face stifling before directly be added on the tablet).
Its preparation process is: earlier antioxidant is dissolved in the mixing mother liquor of allyl group isosulfocyanate and ethyl isothiocyanate, the vegetable fiber sheet of bulk is tiled among the basket, immersed then in the dipper that isothiocyanates is housed about 30 minutes.Basket is promoted, and it is high to leave about ten centimeters of soups, and the soup that allows sheet asbestos not adsorb flows out.Suitably firmly push down sheet asbestos with machine cutting on the platform, with sharp cutting knife sheet asbestos is cut into the piece of different sizes such as 10 grams, 50 grams, 100 grams, 1000 grams, 2000 grams again.Check AITC and EITC content in the sheet asbestos.Certified products are packed in the Nylon Bag.The sheet asbestos of isothiocyanate content deficiency, the composition that can drip a small amount of isothiocyanates is supplied content.Described stifling tablet generally is used for the pest of stifling grain depot.
When being used for fumigating pathogen, component of the present invention composite dose and weight percentage are:
Allyl group isosulfocyanate 0.2～40%,
Ethyl isothiocyanate 1～15%,
Ascorbic acid 1～5%,
With acetic acid or acetum polishing to 100%.
The formulation of this moment is a finish.
Above production process is all finished by machine in confined conditions, the tablet that avoid personnel directly to contact soup and be not cut into.
Allyl group isosulfocyanate of the present invention and ethyl isothiocyanate are used to prepare the agricultural chemicals fumigant of control warehouse and soil pests and harmful mould.
The present invention is the main active that is with allyl group isosulfocyanate, is synergistic component with the ethyl isothiocyanate; Be applicable to the stifling of different occasions such as warehouse, container, warm canopy soil; Have two kinds of biologically actives of insect protected and sterilization; The common insect and the Plant nematode in plurality of cereals warehouse, tobacco leaf warehouse and textile warehouse such as it can the smoked kill corn weevil, lesser grain borer, red flour beetle, booklice, tobacco leaf are chrysomelid; Simultaneously can the smoked kill aspergillus flavus, multiple harmful fungoids such as mould, Neurospora, Mucor, aspergillus oryzae.
Composite dose of synergy of ethyl isothiocyanate of the present invention and allyl group isosulfocyanate is obvious, antibacterial insecticidal activity height, consumption is few relatively, and is obvious to pest fumigating effects such as grain, tobacco, soil nematodess, can be used for substituting disabled fumigant--Celfume.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.Embodiment 1 silo is produced with the potent athomin A of the ethyl isothiocyanate composition finish of 20% allyl group isosulfocyanate and 4%
Accurately quantitatively take by weighing 212 kilograms of the former medicines of 94%AITC, take by weighing ethyl isothiocyanate EITC content again and be 100 kilograms in 4% extraction mother liquor.With two kinds of active ingredient soups at 2M
3Abundant mixing in the blend tank.Accurately take by weighing 10 kilograms in ascorbic acid, drop in the blend tank (1) and abundant once more mixing.In blend tank, accurately drop into 339 kilograms of ethyl acetates and 339 kilograms of vegetable oil again, abundant mixing in blend tank.Continue to stir 1 hour.Preparation obtains the finish product of 1 ton of AITC and EITC composition.
Sampling analysis, wherein the content of AITC is 20.01%, the content of EITC is 4.10%.Scribble in the aluminium pot of barrier material in the product branch packed into, 5 kilograms every jar, amount to 200 jars.The hermetically sealed can mouth, the labelled content that is is 24% the potent athomin A of composition product finish product.
The potent athomin B of embodiment 25% allyl group isosulfocyanate and 1% ethyl isothiocyanate composition soluble liquid produces
Accurately quantitatively take by weighing 53 kilograms of former medicines of 94%AITC and ethyl isothiocyanate content and be 11.1 kilograms of 90% former medicines.With two kinds of active soups abundant mixing in blend tank (1).Accurately take by weighing 15 kilograms in ascorbic acid again, drop into abundant once more mixing in the blend tank (1).In blend tank (2), add 20 kilograms of No. 500, farming breasts, 602 100 kilograms of emulsifier, add 800.5 kilograms in ethyl acetate after the mixing again, fully mixing.920.9 kilograms of materials in the blend tank (2) are all moved in the allotment (1) by pipeline, start agitator behind the hermetically sealed can mouth and stirred 1 hour.Preparation obtains 1000 kilograms of AITC emulsifiable concentrate products.The content of AITC is 5.01% in the sampling analysis product, and ethyl isothiocyanate content is 0.995%, promptly becomes 6% potent athomin B product, the product branch is packed in the plastic bottle of dual obstruct into every bottled medicine 500mL.
The production of embodiment 312% allyl group isosulfocyanate and 1.7% the potent athomin C of ethyl isothiocyanate composition aqueous emulsion
Accurately take by weighing 305 kilograms in the former medicine of AITC of 94% content about 182 kilograms and plant extract mother liquor (AITC content is about 9.5%), 38.2 kilograms of ethyl isothiocyanate content 90% former medicines, 20 kilograms in ascorbic acid stirs four in blend tank.In blend tank, quantitatively add 200 kilograms of agricultural emulsifier TX-10 again, 366 kilograms of ethyl acetates, 350 kilograms of vegetable oil add 539 kilograms of entry, and the limit edged stirs, and after all material adds, continues to stir 1 hour with agitator.
The amount that contains AITC in the sample examination product is 11.98%, and ethyl isothiocyanate content is 1.70%, finally obtains the active princlple total content and be 2 tons of 13.7% products, product with the sealing of 500mL glass bottle bottleneck with embodiment 2.
Embodiment 425% allyl group isosulfocyanate and the potent athomin D of 5% ethyl isothiocyanate composition tablet manufacturing
Accurately quantitatively taking by weighing content is 266 kilograms of the former medicines of 94%AITC, and content is 56 kilograms of 90% ethyl isothiocyanates, drops in the blend tank, adds 2 kilograms in peppermint essence again, and the two is stirred.
Prepare absorption cell.In the hanging basket of absorption cell, put 507 kilograms of loose sheet asbestos earlier into, again the soup in the blend tank is evenly sprayed 169 kilograms by measuring tank to sheet asbestos after paving.Hanging basket is lifted from absorption cell, directly over groove, located to stop 15 minutes for 10 centimeters.Again the sheet asbestos in the hanging basket is moved on to cut and close, be cut into 12.5cm * 20cm side's sheet with cutting knife.The content of AITC is 25.12% in the sampling Detection tablet, and the content of ethyl isothiocyanate is 5.08%, and the active princlple total content is 30.20% in the product.Every tablet is packed and sealed with the double-layer nylon bag film of a 14cm * 22cm.
Embodiment 54% allyl group isosulfocyanate and the potent athomin E of 28% ethyl isothiocyanate composition finish are produced
Accurately quantitatively take by weighing content and be 20% AITC and extract 200 kilograms in mother liquor, take by weighing ethyl isothiocyanate content again and be 312 kilograms of 90% former medicines.With two kinds of active ingredient soups at 2M
3Abundant mixing in the blend tank.Accurately take by weighing 10 kilograms in ascorbic acid, drop in the blend tank (1) and abundant once more mixing.In blend tank, accurately drop into 239 kilograms of ethyl acetates and 239 kilograms of vegetable oil again, abundant mixing in blend tank.Continue to stir 1 hour.Preparation obtains the finish product of 1 ton of AITC and EITC composition.Sampling analysis, wherein the content of AITC is 4.00%, the content of EITC is 27.99%.Scribble in the aluminium pot of barrier material in the product branch packed into, 5 kilograms every jar, amount to 200 jars.The hermetically sealed can mouth, the labelled content that is is 32% the potent athomin E of composition product finish product.
The production of embodiment 64%AITC and the potent athomin F of 4% ethyl isothiocyanate composition soluble liquid
Accurately quantitatively taking by weighing 20%AITC, to extract 200 kilograms in mother liquor and ethyl isothiocyanate content be 44.5 kilograms of 90% former medicines.With two kinds of active soups abundant mixing in blend tank (1).Accurately take by weighing 15 kilograms in ascorbic acid again, drop into abundant once more mixing in the blend tank (1).In blend tank (2), add 20 kilograms of agricultural emulsifier NOs, 100 kilograms of emulsifier op-10s, add 620.5 kilograms in ethyl acetate after the mixing again, fully mixing.740.5 kilograms of materials in the blend tank (2) are all moved in the allotment (1) by pipeline, start agitator behind the hermetically sealed can mouth and stirred 1 hour.Preparation obtains 1000 kilograms of AITC soluble liquid products.The content of AITC is 4.01% in the sampling analysis product, and ethyl isothiocyanate content is 3.99%, promptly becomes 8% potent athomin F product, the product branch is packed in the plastic bottle of dual obstruct into every bottled medicine 500mL.
The production of embodiment 71% allyl group isosulfocyanate and 7% the potent athomin G of ethyl isothiocyanate composition aqueous emulsion
Accurately take by weighing AITC content and be about 222.22 kilograms in 9% plant extract mother liquor, 155.56 kilograms of ethyl isothiocyanate content 90% former medicines, 20 kilograms in ascorbic acid stirs four in blend tank.In blend tank, quantitatively add agricultural emulsifier Well201 again
200 kilograms, 366 kilograms of ethyl acetates, 350 kilograms of vegetable oil add 686.22 kilograms of entry, and the limit edged stirs, and after all material adds, continues to stir 1 hour with agitator.
The amount that contains AITC in the sample examination product is 1.01%, and ethyl isothiocyanate content is 7.01%, finally obtains the active princlple total content and be 2 tons of 8.02% products, product with the sealing of 500mL glass bottle bottleneck with embodiment 2.
Embodiment 8
With the serious soil dress Bowls of Chinese yam fusarium wilt, every Bowls is with native 6 kilograms.Adorn 60 of Bowls altogether, stay 10 Bowls to irritate clear water 300mL as blank, with the bag film bilayer of nylon matter that blank Bowls parcel is tight earlier.Get the potent athomin product B of emulsifiable concentrate that embodiment 2 produces then, dilute 200 times, each Bowls irritates the liquid medicine after the 300mL dilution, earthing.With the bag method of Nylon Bag every Bowls is wrapped up tightly as early as possible by the bag blank.Under the sun, shone above-mentioned basin Bowls 10 days.Remove the film of parcel, spacious gas 5 days.Transplant the watermelon seedling then, every Bowls two strains.Allow the melon seedling grow 40 days under the equal management condition.20 melon seedlings of blank die 17, only dead 3 of 100 melon seedlings on the soil that chemicals treatment of the present invention is crossed.Preventive effect reaches 96%.
Embodiment 9
Select one in small-sized tobacco test warehouse.Long 5.8 meters, wide 3 meters, high 3.2 meters, good sealing effect.Place 500 kilograms on the tobacco leaf of moving in the serious storehouse of chrysomelid generation in the storehouse.2 kilograms in the potent athomin product D tablet of producing with embodiment 5 is contained in the folder tablet device of the axial flow blower air outlet of reequip, and the people started axial flow blower 2 hours after withdrawing from the storehouse, shutdown.Continued the leakage test storehouse 15 days, tobacco leaf was cleared up after 3 days in spacious then storehouse, found chrysomelid adult of tobacco and larva 100% death.
Embodiment 10
One of grain test cabin, long 6 meters, wide 3 meters, high 3.5 meters.Whitewash and carry out sealing in advance.From the serious silo of corn weevil harm, move into 800 kilograms of corns, (without the gunnysack dress) in a huddle in the house.With two 6 commercially available hole water-baths, remove its original annular cover plate, topped up with water is connected power supply and is made water temperature rise to 70 ℃ and stablized 1 hour.With 2 of set stainless steel trays, the ethyl isothiocyanate 150ml of respectively pack into 20%AITC finish 750ml and 4%, its gas composition is equivalent to embodiment 1, with one of pendulum on each water-bath of plate of Sheng medicine.The people withdraws from outside the test cabin, the sealing door.Outside the storehouse, close the power supply of water-bath after 48 hours.Continued the leakage test storehouse 15 days., back pullout (BPO) in 15 days, spacious gas.Get the corn-like inspection at the diverse location of corn heap after three days.Get 5 points altogether, 1 kilogram every, take out 5 kilograms of corns altogether.On inspection, do not see a worm alive.
Embodiment 11
Disinsection mold-proof test in the wardrobe.At the end of spring and the beginning of summer, indoor temperature 24-26 ℃, relative moisture 76%.Gap sealing around one wardrobe is good.In wardrobe, hang 5 in sweater, 2 of pure sheepskin fur clothings (jacket, in regged), totally 10 of textile textile clothing; Folding and putting 5 in sweater, 10 of textile textile clothing.Do not put chemical fibre clothes in the cabinet.Get athomin product A 30mL, in the saucer of packing into, be placed on the wardrobe inner bottom plating.Close the slit of cabinet Men Bingyong single face glue sealed cabinet door periphery immediately.Seal and open the cabinet door after 7 days, in wardrobe, dried 2 hours with electric fan.Allow the room door and window open wide simultaneously 2 hours.After this all recover the daily life present situation.Handle back 10 days, 40 days and 90 days three times and check that clothings damage by worms and mouldy situation.The result does not find any damaging by worms, and does not find any mildew yet.
Embodiment 12
Get 100 of the booklices of collecting from silo, 200 of corn weeviles, 150 of lesser grain borers, booklice special feed 50 grams, corn weevil and lesser grain borer are put into beanbag respectively with whole grain wheat and wheat shorts raising, cloth bag are put into a glass 8L drier again.Embodiment 1 grown place potent athomin product A 0.006ml is equipped with a beaker in the lower floor of drier, coats vaseline on the ground limit with dryer door then, and is again that the lid lid is tight.Checkout facility result after 3 days finds that booklice, corn weevil, lesser grain borer are all dead.
Experimental example 1 unification compound finish is to the bioactive measurement result of pathogen:
The pharmaceutically acceptable part of corresponding plant is pulverized, and through hydrolysis, steam distillation purifying, different colourless or yellow oily isothiocyanates is prepared in rectifying more respectively, and its purity is all greater than 90%.This grease is configured to the finish of different content respectively with a spot of solvent.Measure its stifling biologically active, find that different isothiocyanates has strong fumigation action to common fungi etc. multiple pathogen.Measurement result sees Table 1:
The isothiocyanates of table 1 variable concentrations (thiocyanates) is to pathogen biological activity determination result
The result of last table shows: all have strong to alternaria, Rhizoctonia solani Kuhn, peanut sclerotium rolfsii bacterium, tomato wilt bacterium etc. when single isothiocyanic acid ester concentration is 10ppm, further biologically active is preferably ethyl isothiocyanate, the propyl group isothiocyanates, isopentene group isothiocyanates, and allyl group isosulfocyanate.When the concentration of these four kinds of isothiocyanates was 2ppm, its inhibiting rate to the pathogen mycelial growth promptly reached more than 90%.
Experimental example 2 composition finishes are to the bioactive measurement result of pathogen:
Allyl group isosulfocyanate as above-mentioned separation preparation makes up according to different ratios respectively with ethyl isothiocyanate, and is configured to variable concentrations with acetone, and to the bioactive compound screening of pathogen, it the results are shown in Table 2
Table 2 allyl group isosulfocyanate and ethyl isothiocyanate are to the joint toxicity measuring result of three kinds of germs
The result of table 2 shows, be made up of allyl group isosulfocyanate and ethyl isothiocyanate composite dose in its weight ratio is 1/7～7/1 combination, germ for examination is all had must synergistic effect, and especially the weight ratio with allyl group isosulfocyanate and ethyl isothiocyanate is 5: 1 o'clock, to the peanut sclerotium rolfsii bacterium, the miliary damping-off germ, the CTC value of tomato wilt bacterium is respectively 185.5,172.08,165.94, synergistic effect is remarkable, and the EC50 value significantly reduces.
Experimental example 3 different isothiocyanic acid ester formulations are to the storage pest insecticidal activity:
Prepare different isothiocyanates as above-mentioned separation, and be configured to variable concentrations with acetone, to the bioactive Preliminary screening of storage pest, it the results are shown in Table 3
The isothiocyanates of table 3 variable concentrations is to the bioactive measurement result of three kinds of storage pests
The more excellent isothiocyanates of effect is carried out toxicity test relatively, and it the results are shown in Table 4.
Table 4 isothiocyanates (thiocyanates) is to storage pest 72h toxicity test result
The result of last table shows: when part isothiocyanic acid ester concentration is 20ppm, and to corn weevil, lesser grain borer, red flour beetles etc. all have strong fumigation activity, further biologically active is preferably ethyl isothiocyanate, propyl group isothiocyanates, isopentene group isothiocyanates and allyl group isosulfocyanate.When the concentration of these four kinds of isothiocyanates was 5ppm, its smoked kill rate to three kinds of insects promptly reached more than 80%.
Experimental example 4 ethyl isothiocyanates (EITC) and the mensuration of allyl group isosulfocyanate (AITC) composition to the pest activity
Allyl group isosulfocyanate as above-mentioned separation preparation makes up according to different ratios respectively with ethyl isothiocyanate, and is configured to variable concentrations with acetone, and to the bioactive compound screening of storage pest, it the results are shown in Table 5.
Table 5AITC and EITC complex preparation are to the bioactivity screening of stored grain insects
The result of table 5 shows, be made up of allyl group isosulfocyanate and ethyl isothiocyanate composite dose in its weight ratio is 1/7～7/1 combination, stored grain insects for examination are all had must synergistic effect, and especially the weight ratio with allyl group isosulfocyanate and ethyl isothiocyanate is 5: 1 o'clock, to lesser grain borer, corn weevil, the CTC value of red flour beetle is respectively 307.84,163.39.08,174.82, synergistic effect is remarkable, and the LC50 value significantly reduces.
Experimental example 5 ethyl isothiocyanates and allyl group isosulfocyanate composition are to the bioactive mensuration of corn weevil and lesser grain borer in the real storehouse
The picking growth is consistent, the examination worm (corn weevil, lesser grain borer) that breeding time is approaching, and the preprepared of packing into is made in the cloth bag, and each cloth bag is put into every kind for each 50 of examination worms, and a little grain of packing into is tightened sack.
According to the drier size, the snakeskin pocket of preparing identical size with it is some.Drying wheat is packed in the snakeskin bag, and the cloth bag that examination worm and feed will be housed then divides upper, middle and lower-ranking to put into the snakeskin bag, and every kind of insect is provided with three repetitions for every layer, is spaced apart 6cm between every layer, tightens sack.By single agent AITC, EITC, compound drug (AITC: EITC=5: 1) with and be configured to the variable concentrations gradient with acetone, put into the drier bottom successively, put into the snakeskin bag, hermetically drying device, check result after 72 hours.The results are shown in Table 6.
The result of table 6 shows, composite dose that is made up of allyl group isosulfocyanate and ethyl isothiocyanate is 5: 1 o'clock in its weight ratio, to real storehouse for the stored grain insects of examination all have must synergistic effect, to being in the lesser grain borer of different depth, corn weevil, the CTC value of its simultaneous determination of red flour beetle is not quite similar, wherein to locating corn weevil and the lesser grain borer fumigation activity is obvious, synergy is remarkable, and the LC50 value significantly descends, and the red flour beetle that is in different depth is also had certain synergistic effect.
Experimental example 6 ethyl isothiocyanates and allyl group isosulfocyanate composition are to the tomato root-knot eelworm pot experiment
With EITC, AITC, 1# composition (AITC: EITC 5: 1), 2# composition (AITC: EITC 7: 1) all are provided with concentration of 12.5 μ g/ml, and each handles 4 repetitions, and blank clear water contrast is set.Sandy soil earth basin alms bowl and the sand of having executed medicine are sealed 7 days with plastic membrane of polyvinyl chloride, open wide after 4 days, 21 days tomato seedling of switching growth is in the basin alms bowl.After six weeks, with the harvesting of tomato seedling, wipe out on seedling top, and statistics root root knot quantity is calculated preventive effect, and result of the test sees Table 7.
Table 7EITC and AITC composition are to the tomato root-knot eelworm results from pot experiment test
The result of table 7 shows, composite dose that is made up of allyl group isosulfocyanate and ethyl isothiocyanate is 5: 1 o'clock in its weight ratio, and the fumigation activity of tomato root-knot eelworm is had significant synergistic effect, the malicious factor 68.26 altogether, and synergy is remarkable, the remarkable decline of LC50 value.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. composite dose of ethyl isothiocyanate and allyl group isosulfocyanate, it is characterized in that the weight ratio of allyl group isosulfocyanate and ethyl isothiocyanate is 1: 7～7: 1.
2. composite dose according to claim 1, it is characterized in that the weight ratio of ethyl isothiocyanate and allyl group isosulfocyanate is 1: 5～5: 1.
3. composite dose according to claim 1 and 2, it is characterized in that the weight ratio of ethyl isothiocyanate and allyl group isosulfocyanate is 5: 1.
4. according to any one described composite dose of claim 1-3, it is characterized in that, make soluble liquid, aqueous emulsion, finish or tablet for described composite dose.
5. composite dose according to claim 4, it is characterized in that the component of described finish and weight percentage are:
Allyl group isosulfocyanate 1～60%,
Ethyl isothiocyanate 0.2～20%,
Antioxidant 0.1～2%,
Solvent 10～85.7%,
Vegetable oil polishing to 100%;
Described antioxidant is ascorbic acid class material or gallic acid pentyl ester; Described solvent is toluene, dimethylbenzene, ethyl acetate or cyclohexanone; Described vegetable oil is thick rapeseed oil, cotton oil or thick soya-bean oil.
6. composite dose according to claim 4, it is characterized in that the component of described aqueous emulsion and weight percentage are:
Allyl group isosulfocyanate 1～20%,
Ethyl isothiocyanate 0.2～10%,
Emulsifier 12～28%,
Ascorbic acid 0.1～2%,
Solvent 10～30%,
Water polishing to 100%; Wherein, described emulsifier be 7780,7781T, 4103, OP-10, Well201, No. 500,602, Well205 or M30; Described solvent is ethyl acetate or cyclohexanone.
7. composite dose according to claim 4, it is characterized in that the component of described soluble liquid and weight percentage are:
Allyl group isosulfocyanate 1～40%,
Ethyl isothiocyanate 0.2～30%,
Emulsifier 12～28%,
Ascorbic acid 0.3～2%,
Solvent polishing to 100%; Wherein emulsifier be 7780,7781T, 4103, OP-10, Well201, No. 500,602, Well205, M30; Described solvent is methyl alcohol, ethanol, dimethylbenzene or a line oil.
8. composite dose according to claim 4, it is characterized in that the component of described stifling tablet and weight percentage are:
Allyl group isosulfocyanate 1～30%,
Ethyl isothiocyanate 0.2～25%,
Antioxidant 0.5～2.0%,
Vegetable fiber sheet 70～95%; Wherein said antioxidant is ascorbic acid or gallic acid pentyl ester, and described vegetable fiber sheet is asbestos fibre sheet, cotton fiber sheet or flaxen fiber sheet.
9. composite dose according to claim 4, it is characterized in that when being used for fumigating pathogen, described composite dose component and weight percentage are:
Allyl group isosulfocyanate 0.2～40%,
Ethyl isothiocyanate 1～15%,
Ascorbic acid 1～5%,
With acetic acid or acetum polishing to 100%.
10. described composite dose of the application of claim 1-9 at the agricultural chemicals fumigant that is used for preparing control warehouse and soil pests and harmful mould.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100850518A CN101558760B (en) | 2009-05-20 | 2009-05-20 | Compound agent of ethyl isothiocyanate and allyl isothiocyanate and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100850518A CN101558760B (en) | 2009-05-20 | 2009-05-20 | Compound agent of ethyl isothiocyanate and allyl isothiocyanate and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101558760A true CN101558760A (en) | 2009-10-21 |
| CN101558760B CN101558760B (en) | 2012-07-25 |
Family
ID=41217875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100850518A Active CN101558760B (en) | 2009-05-20 | 2009-05-20 | Compound agent of ethyl isothiocyanate and allyl isothiocyanate and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101558760B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102754644A (en) * | 2011-04-28 | 2012-10-31 | 狮王株式会社 | Smoke insecticide, smoke insect-killing apparatus, and insect-killing method |
| CN103004903A (en) * | 2012-12-21 | 2013-04-03 | 广东省昆虫研究所 | Phyllo treta striolata attractant |
| CN103250525A (en) * | 2012-02-15 | 2013-08-21 | 卢志军 | Method for preventing root-knot nematode by taking brassica crop rapes as raw materials |
| CN106973990A (en) * | 2016-01-19 | 2017-07-25 | 中国科学院上海有机化学研究所 | A kind of fumigating method for being used to prevent and treat grain entomophthora |
| CN107296093A (en) * | 2017-07-07 | 2017-10-27 | 湖北省农业科学院经济作物研究所 | A kind of Chinese yam storage period penicilliosis biological control method |
| CN107385990A (en) * | 2017-06-28 | 2017-11-24 | 常州市奥普泰克光电科技有限公司 | A kind of mask paper and preparation method thereof |
| CN110786193A (en) * | 2019-11-01 | 2020-02-14 | 山东省农业科学院植物保护研究所 | Method for preventing and treating soil-borne diseases by cooperation of biological fumigation and chemical fumigation |
| CN110915339A (en) * | 2019-11-01 | 2020-03-27 | 山东省农业科学院植物保护研究所 | Method for preventing and treating soil-borne diseases by fumigating soil with plants |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006169189A (en) * | 2004-12-17 | 2006-06-29 | Rengo Co Ltd | Chalkbrood disease-controlling agent |
| CN100518512C (en) * | 2006-08-31 | 2009-07-29 | 武汉绿世纪生物工程有限责任公司 | Vermins-proof mildew-proof fumigation product using allyl isosulfocyanate as the active composition and uses thereof |
| CN101253865B (en) * | 2007-11-15 | 2010-12-22 | 华中农业大学 | Emulsions of agricultural chemical composition containing allyl group isosulfocyanate and pyrethroid, preparation and applications |
| CN101171925B (en) * | 2007-11-15 | 2011-04-13 | 华中农业大学 | Effervescence granula of agricultural chemical composition of allyl isosulfocyanate and pyrethroid, method for preparing the same and application thereof |
-
2009
- 2009-05-20 CN CN2009100850518A patent/CN101558760B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102754644A (en) * | 2011-04-28 | 2012-10-31 | 狮王株式会社 | Smoke insecticide, smoke insect-killing apparatus, and insect-killing method |
| CN102754644B (en) * | 2011-04-28 | 2015-05-06 | 狮王株式会社 | Smoke insecticide, smoke insect-killing apparatus, and insect-killing method |
| CN103250525A (en) * | 2012-02-15 | 2013-08-21 | 卢志军 | Method for preventing root-knot nematode by taking brassica crop rapes as raw materials |
| CN103004903A (en) * | 2012-12-21 | 2013-04-03 | 广东省昆虫研究所 | Phyllo treta striolata attractant |
| CN106973990A (en) * | 2016-01-19 | 2017-07-25 | 中国科学院上海有机化学研究所 | A kind of fumigating method for being used to prevent and treat grain entomophthora |
| CN106973990B (en) * | 2016-01-19 | 2019-12-10 | 中国科学院上海有机化学研究所 | fumigation method for preventing and controlling entomophthora in grains |
| CN107385990A (en) * | 2017-06-28 | 2017-11-24 | 常州市奥普泰克光电科技有限公司 | A kind of mask paper and preparation method thereof |
| CN107385990B (en) * | 2017-06-28 | 2019-12-03 | 江苏源清环保科技有限公司 | A kind of mask paper and preparation method thereof |
| CN107296093A (en) * | 2017-07-07 | 2017-10-27 | 湖北省农业科学院经济作物研究所 | A kind of Chinese yam storage period penicilliosis biological control method |
| CN110786193A (en) * | 2019-11-01 | 2020-02-14 | 山东省农业科学院植物保护研究所 | Method for preventing and treating soil-borne diseases by cooperation of biological fumigation and chemical fumigation |
| CN110915339A (en) * | 2019-11-01 | 2020-03-27 | 山东省农业科学院植物保护研究所 | Method for preventing and treating soil-borne diseases by fumigating soil with plants |
| CN110915339B (en) * | 2019-11-01 | 2022-08-05 | 山东省农业科学院植物保护研究所 | Method for preventing and treating soil-borne diseases by fumigating soil with plants |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101558760B (en) | 2012-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101558760B (en) | Compound agent of ethyl isothiocyanate and allyl isothiocyanate and application thereof | |
| US11570986B2 (en) | Antimicrobial compositions and related methods of use | |
| CN100518512C (en) | Vermins-proof mildew-proof fumigation product using allyl isosulfocyanate as the active composition and uses thereof | |
| AU2018200620B2 (en) | Antimicrobial compositions and related methods of use | |
| CN101999345A (en) | Environmentally-friendly, long-acting, bacteriostatic, mildewproof and pesticidal sol preparation | |
| CN104872280A (en) | Cinnamon oil containing grain insecticide | |
| CN106720235A (en) | Kiwi berry and antistaling agent for grape, tin foil and preparation method based on plants essential oil | |
| CN108260603A (en) | A kind of pest of stored grain controlling agent of the repellant containing Java brucea | |
| CN106577804B (en) | A kind of shielding protection type insecticide of repellent natural enemy insect and honeybee | |
| US20230172199A1 (en) | Antimicrobial Compositions and Related Methods of Use | |
| KR20150048479A (en) | Compositions for controlling Sitophilus zeamais comprising pennyroyal oils as active ingredients | |
| KR101463428B1 (en) | Composition for controlling plant diseases comprising mixture of β-sitosterol, campesterol, stigmasterol and brassicasterol as active components and uses thereof | |
| Howard | Insecticides and equipment for controlling insects on fruits and vegetables | |
| NZ750504B2 (en) | Antimicrobial Compositions and Related Methods of Use | |
| Johnson | Insect enemies of house plants and their control |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200420 Address after: 101300 Nansun Lu Liu Ge Zhuang Xing Technology Co., Ltd., Lisui Town, Shunyi District, Beijing Patentee after: Beijing Sino German Star Technology Co., Ltd. Address before: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 501 Patentee before: WUHAN ROCK BIOTECH Co.,Ltd. |
|
| TR01 | Transfer of patent right |