CN102321694B - Application of chiral (R, S) fluvalinate in control of bee mites - Google Patents
Application of chiral (R, S) fluvalinate in control of bee mites Download PDFInfo
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Abstract
The invention discloses an application of a chiral (R, S) fluvalinate to the control of bee mites, and belongs to the field of the synthesis of chiral compounds. The method comprises the following steps of: a, catalyzing S-cyanohydrin acetate by using lipase in an organic system, and stirring for 5 to 72h at the temperature of between 10 and 35 DEG C to obtain S-cyanohydrin; and b, condensing the S-cyanohydrin and R-chrysanthemic acid at the temperature of between 0 and 20 DEG C in an nonpolar organic system by a dicyclohexylcarbodiimide (DDC) method and an acyl chloride method to obtain the chiral (R, S) fluvalinate. The chiral (R, S) fluvalinate prepared by the method is applied to killing of the bee mites in honeycombs, the method for synthesizing the chiral (R, S) fluvalinate is simple and high in yield, the effect of controlling the bee mites is remarkable, the using amount of pesticides is small, and the environmental pollution caused by useless antipodes can be avoided.
Description
Technical field
The invention belongs to the synthetic field of chipal compounds, be specifically related to a kind of chirality (R, the S) application of taufluvalinate on control honeybee mite.
Background technology
The general Fluvalinate by name of taufluvalinate also is referred to as Mavrik, horse pounces on Garrick etc.The pyrethroid insecticides that belongs to non-cyclopropane carboxylic-acid, comprise two isomer compositions, i.e. (RS)-alpha-cyano-3-phenoxy benzyl N-(2-chloro-α, α-α-three fluoro-is right-tolyl)-D-(R) L-valine ester, wherein effective constituent is (S)-alpha-cyano-3-phenoxy benzyl N-(2-chloro-α, α-α-three fluoro-is right-tolyl)-D(R)-and Xie Ansuan, be called for short (R, S) taufluvalinate.
Taufluvalinate is mainly used in the primary pest control that comprises lepidopteran, Coleoptera, Homoptera, Diptera and Thysanoptera on the crops such as cotton, fruit tree, vegetables, corn, tealeaves, tobacco, and is also effective to sanitary insect pest such as housefly, culex pipiens pollens, Groton bug etc.Compare with other chrysanthemum ester, significant acaricidal action is arranged.The honeybee mite is the parasite of honeybee, the growth of energy remarkably influenced honeybee, and it is the major cause that bee colony quantity reduces, and brings bigger financial loss to the beekeeper.As the taufluvalinate of control honeybee mite, significantly miticidal effect has very low bee venom simultaneously, has obtained widespread use in Apiculture.But along with a large amount of uses of taufluvalinate, the resistance problem of honeybee mite constantly increases the weight of, and usage quantity continues to increase, and causes the pesticide residue of honey to strengthen.
(R, S) taufluvalinate is synthetic, needs use S-cyanalcohol and R-chrysanthemumic acid to obtain by the method for ester condensation for chirality.Wherein S-cyanalcohol synthetic has several different methods, mainly contains the asymmetric synthesis method, chemical resolution method and enzyme Split Method.For example traditional S-cyanalcohol prepares the cyanalcohol that adopts racemization, through resolving agent as (R)-1-(1-naphthalene)-ethyl isocyanic acid under nitrogen gas protection, form (R, S)-cyano group-(3-phenoxy phenyl)-(R)-N-1-(1-naphthalene)-ethyl carbamate, through column chromatography for separation, obtain the S-cyanalcohol through hydrolysis again; Perhaps use enzymatic hydrolysis racemization cyanalcohol, remaining R-cyanalcohol is again through racemization, again through the enzyme selectivity hydrolysis, needs just can obtain the S-cyanalcohol through recirculation repeatedly, and its ee% only can reach 95% usually.
Summary of the invention
The present invention is intended to solve traditional synthesis of chiral, and (R S) in the process of taufluvalinate, prepares various, the complicated operation of intermediate S-cyanalcohol operation, the problem that ee% is on the low side.
The present invention is achieved through the following technical solutions: chirality (R, the S) synthetic method of taufluvalinate mainly may further comprise the steps:
The a.S-cyanalcohol acetate by lipase-catalyzed, stirs 5～72h under 10 ℃～35 ℃ temperature in organic system, obtain the S-cyanalcohol;
The b.S-cyanalcohol generates chirality (R, S) taufluvalinate with the R-chrysanthemumic acid by DDC method and chloride method condensation under 0 ℃～20 ℃ conditions in nonpolar organic system.
Wherein, nonpolar organic system described above is that alcohol, ethers or sulfoxide, benzene and the alkyl of the carboxylicesters of alkanes, halogen-containing alkane, lipid, 1～5 carbon, 1～10 carbon or in the nitro substituted benzene any one or more mix.
Wherein, lipase described above is one or more in antarctic candidia lipase, candida cylindracea lipase, porcine pancreatic lipase, lipase PS, the Pseudomonas fluorescens lipase.
Wherein, lipase described above and the mass ratio of S-cyanalcohol are 0.0001 ︰, 1～0.1 ︰ 1.Preferred proportion is 0.02 ︰, 1～0.05 ︰ 1
Wherein, the condensing agent of condensation is N described in the above-mentioned b step, any or several mixtures in N-dimethyl-carbodiimide, thionyl chloride, the N-methyl-pyridine.
Wherein, the mol ratio of R-chrysanthemumic acid and S-cyanalcohol is 0.9 ︰, 1～1.5 ︰ 1 in the b step described above.Be preferably 1.05 ︰, 1～1.20 ︰ 1.
Another purpose of the present invention is the big problem of pesticide residue that solves the honey that causes owing to control honeybee mite, and its technical scheme is: chirality (R, the S) application of taufluvalinate on control honeybee mite.
Wherein, (R, S) working concentration of taufluvalinate is the above solution of 2.5mg/L to chirality described above.
Wherein, (R S) is added with emulsifying agent during taufluvalinate solution to the preparation chirality.
Wherein, (R, S) taufluvalinate solution need be coated with on PP or PE sheet described chirality, makes the extension bar behind super-dry, last powder craft, hangs in the beehive.
The invention utilize chirality (R, S) taufluvalinate be used for to kill the honeybee mite, obtained beyond thought effect, and consumption is few, toxicity is low, effectively prevents because a large amount of use causes the resistance of honeybee mite, and residual few in the honey.
The present invention compared with prior art has the following advantages and beneficial effect:
(1) this synthetic method can one the step make intermediate S-cyanalcohol, effectively save synthesis of chiral (R, the S) operation of taufluvalinate, and synthetic chirality (ee% reaches more than 99% for R, S) taufluvalinate.
(2) this synthetic method is simple to operate, is applicable to suitability for industrialized production.
(3) chirality that makes of this synthetic method (R, S) taufluvalinate has the effect of killing the honeybee mite, and hypotoxicity, dosage are few, the effect of control honeybee mite is remarkable.
(4) can effectively avoid useless enantiomorph to the pollution of environment.
Embodiment
Be described in further detail below in conjunction with the present invention of embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1 preparation chirality (R, S) taufluvalinate
Earlier in triangular flask, add 0.5g(1.88mmol) the S-cyanalcohol acetate, add 87ul(0.94mmol again) BuOH, 0.05mg antarctic candidia lipase (NOVO 435) and 10ml isopropyl ether, place 10 ℃ of shaking tables 72h that vibrates.After then reaction solution being concentrated oven dry, mixing solutions (being formed by 6ml water, 14ml methyl alcohol, 6ml benzene) dissolving with 20ml, separatory takes off a layer solution, mixed solution (benzene and methyl alcohol volume ratio are 7:3) extraction secondary with 10ml benzene and methyl alcohol, steam part methyl alcohol, add EA and remove water layer, the EA layer dry dense do S-cyanalcohol 0.06g.
With 1.31g(0.00444mol) chrysanthemumic acid earlier with an amount of EA dissolving, joins 1.0g(0.00444mol with its mixing solutions again) ice bath stirring in the cyanalcohol.Add 0.90g(0.00444mol more successively) DCC, 0.05g(0.00444mol * 10%) DMAP ice bath stirring 4h.Filter, add EA in the filtrate to be diluted to 50ml, respectively wash three times with 5%NaOH, 3%HCl successively after, be washed to neutrality with saturated common salt, use the anhydrous sodium sulphate drying again, precooling CH is used in filtration at last
2Cl
2Dense the doing in washing back can obtain 1.66g chirality (R, S) taufluvalinate.
Embodiment 2 preparation chirality (R, S) taufluvalinates
Earlier in triangular flask, add 0.5g(1.88mmol) the S-cyanalcohol acetate, add 87ul(0.94mmol again) BuOH, 0.05g lipase PS and 10ml isopropyl ether, place 35 ℃ of shaking tables 5h that vibrates.After then reaction solution being concentrated oven dry, mixing solutions (being formed by 6ml water, 14ml methyl alcohol, 6ml benzene) dissolving with 20ml, separatory takes off a layer solution, mixed solution (benzene and methyl alcohol volume ratio are 7:3) extraction secondary with 10ml benzene and methyl alcohol, steam part methyl alcohol, add EA and remove water layer, the EA layer dry dense do S-cyanalcohol 0.04g.
With 0.65g(0.00222mol) chrysanthemumic acid earlier with an amount of EA dissolving, joins 0.5g(0.00222mol with its mixing solutions again) ice bath stirring in the cyanalcohol.Add 0.4g (0.00222mol) DCC, 0.03g(0.00233mol * 10% more successively) DMAP ice bath stirring 4h.Filter, add EA in the filtrate to be diluted to 30ml, respectively wash three times with 5%NaOH, 3%HCl successively after, be washed to neutrality with saturated common salt, use the anhydrous sodium sulphate drying again, precooling CH is used in filtration at last
2Cl
2Dense the doing in washing back can obtain 0.9g chirality (R, S) taufluvalinate.
Embodiment 3 preparation chirality (R, S) taufluvalinates
Earlier in triangular flask, add 0.5g(1.88mmol) the S-cyanalcohol acetate, add 87ul(0.94mmol again) BuOH, 0.005g antarctic candidia lipase (NOVO 435) and 10ml isopropyl ether, place 20 ℃ of shaking tables 48h that vibrates.After then reaction solution being concentrated oven dry, with mixing molten (being made up of 6ml water, 14ml methyl alcohol, the 6ml benzene) dissolving of 20ml, separatory takes off a layer solution
,With the mixed solution (benzene and methyl alcohol volume ratio are 7:3) of 10ml benzene and methyl alcohol extraction secondary, steam part methyl alcohol, add EA and remove water layer, the EA layer dry dense do S-cyanalcohol 0.06g.
With 1.31g(0.00444mol) chrysanthemumic acid dissolves with an amount of benzene earlier, again its mixing solutions joined 1.0g(0.00444mol) 20 ℃ of stirring in water bath in the cyanalcohol.Add 0.90g (0.00444mol) DCC, 0.05g(0.00444mol * 10% more successively) DMAP20 ℃ stirring in water bath 4h.Filter, add EA in the filtrate to be diluted to 50ml, respectively wash three times with 5%NaOH, 3%HCl successively after, be washed to neutrality with saturated common salt, use the anhydrous sodium sulphate drying again, precooling CH is used in filtration at last
2Cl
2Dense the doing in washing back can obtain 1.66g chirality (R, S) taufluvalinate.
Embodiment 4 chiralitys (R, S) method of taufluvalinate control honeybee mite
With chirality (R, S) taufluvalinate is mixed with the solution of concentration 2.5mg/L, add a certain amount of methyl alcohol and tween 80 during preparation, the amount of methyl alcohol and tween 80 is with chirality (R, S) taufluvalinate all be dissolved as suitable, then with the chirality for preparing (R, S) taufluvalinate solution is coated with on the PP sheet, behind super-dry, last powder craft, make the extension bar, hang in the beehive and can effectively prevent and treat the honeybee mite.
The application of chirality chirality (R_S) taufluvalinate on control honeybee mite
(new drug described in the following example is chirality (R_S) taufluvalinate, and the basis medicine was taufluvalinate in described day, achirality.）
1. test objective
Chirality (R_S) taufluvalinate has been measured the LC of new drug to the toxicity test of the parasite varoa mite on the honeybee and chalcid fly mite
50And LC
90Simultaneously, contrast with achiral taufluvalinate drug effect.
2. test conditions
2.1 for the examination target
Supplying the examination mite is varoa mite (formal name used at school Ya Shi watt mite
Varroa iacobsoni) and chalcid fly mite (the bright hot laelaps of formal name used at school
Tropilelaps clareae), all from the test bee farm honeybee on one's body with the groove spleen on.
2.2 culture condition
The big chalcid fly mite that the consistent quantity in worm age is equated is put in respectively in 10 beehives, and the bee-keeping measure is with usually the same, allows honeybee mite self-sow.
2.3 test apparatus
Constant incubator, stereoscopic microscope, slide glass, double faced adhesive tape, electronic balance
3. test design
3.1 reagent
3.1.1 test medicine
Chirality (R_S) taufluvalinate, thick liquid, synthetic in the laboratory.
3.1.2 contrast medicament
Achiral taufluvalinate (fluvalinate), the former medicine of Japanese import, content are 92.6%.
3.1.3 other reagent
1% methyl alcohol, 0.1% tween 80, water are distilled water
3.2 test is handled
3.2.1 dosage setting
New drug and a day basis medicine all are provided with 7 groups of dosage, are respectively 200 mg/L, 100 mg/L, 50 mg/L, 20 mg/L, 10 mg/L, 5 mg/L and 2.5 mg/L.
3.2.2 test repeats
Test repeats 5 times, each 20 mites, and every group of dosage is totally 100 mites.
3.3 processing mode
3.3.1 treatment time and number of times
Use the medication of slide pickling process once, dipping 5s.
3.3.2 administrated method
After adopting slide pickling process dipping soup around the polypide is blotted with thieving paper.
4. test method
According to the agricultural chemicals indoor bioassay test rule (sterilant) in " People's Republic of China's agricultural industry criteria ", the 12nd part: tetranychid slide pickling process.
4.1 the examination material is prepared
Select honeybee to grow the female one-tenth mite of physiological status unanimity on one's body with on the groove spleen.
Double faced adhesive tape is cut into 2cm length, and card is chosen healthy female one-tenth mite then in an end of slide glass, its back is sticked on the double faced adhesive tape, and every 20, to put into and be lined with the wet sponge container, cover lid places under 35 ℃ of conditions.Microscopy behind the 2h is rejected dead and injured individuality, supplies every 20.
4.2 medicament preparation
New drug and the medicinal dissolve with methanol of day basis are mixed with mother liquor, are mixed with above-mentioned series concentration with 0.1% the tween 80 aqueous solution again.Methanol usage generally is 3-5ml, as long as can not produce precipitation just passable with being mixed with the aqueous solution after the dissolving of former medicine, dissolve the former medicinal methyl alcohol of how many ml, add same amount in the control group, the amount of methyl alcohol and tween 80 does not require, when testing a plurality of former medicine just the methanol usage with that former medicine of using the methyl alcohol maximum be as the criterion, prepare the mother liquor of other former medicines, make the amount of the methyl alcohol of all groups (comprising contrast) of experiment and tween the same.
4.3 chemicals treatment
Take out after slide is dipped in the 5s that vibrates gently in the soup, inhale with thieving paper and remove unnecessary soup, place the ceramic whiteware dish that is lined with wet sponge, use the good plastics film of light transmission to cover.
Every processing repeats 5 times, makes blank with the processing that does not contain medicament (only containing organic solvent and tween 80).
4.4 raise and observe
It is 35 ℃ that the container that fills processing examination worm is placed temperature, raises under the dark condition and observes.
5. data survey and statistical study
5.1 investigation method and death standard
Examine under a microscope the survival condition of mite.Flip feeler and the belly of mite with dissecting needle, motionless with mite is death standard.The standard of big mite and little mite is the same.
5.2 control time and number of times
Observe behind the 12h, record total borer population and dead borer population respectively.
5.3 data statistic analysis
Use SPSS13.0 software to carry out statistical study.
6. result and discussion
6.1 new drug is to the toxic action of varoa mite
As can be seen from Table 1, this new chirality (R_S) taufluvalinate is 4.10 mg/L to the LC50 of varoa mite, and 95% fiducial interval is 0.60-6.76 mg/L, and LC90 is 29.42 mg/L, and 95% fiducial interval is 24.92-36.61 mg/L.And the LC50 of day basis medicine is 25.86 mg/L, and 95% fiducial interval is 10.13-43.08 mg/L, and LC90 is 81.71 mg/L, and 95% fiducial interval is 58.85-146.00 mg/L.The mortality ratio of new drug under the concentration of 100 mg/L is 100%, and the mortality ratio of day basis medicine pilot scale worm is 90.91%, and new drug is higher by 9.09% than day mortality ratio of basis medicine.The mortality ratio of new drug under 20 mg/L concentration is 80.891%, and be close with mortality ratio under the concentration of day basis medicine 50 mg/L.And under the lower concentration of 2.5 mg/L, new drug still still has 38.39% killing rate to big mite.This shows that the general taufluvalinate of big mite energy force rate that kills of new drug improves about 3 times.
The LC of table 1 new drug and day varoa mite of basis medicine 12h
50And 95% fiducial interval
6.2 new drug is to the toxic action of chalcid fly mite
As can be seen from Table 2, new drug also has the stronger ability of killing to little mite.New drug is 10.95 mg/L to the LC50 of chalcid fly mite, and 95% fiducial interval is 6.34-15.00 mg/L, and LC90 is 53.07 mg/L, and 95% fiducial interval is 45.40-64.61 mg/L.And the LC50 of day basis medicine is 31.59 mg/L, and 95% fiducial interval is 13.40-53.95 mg/L, and LC90 is 88.39 mg/L, and 95% fiducial interval is 62.58-168.35 mg/L.Under 5 mg/L concentration, the corrected mortality of new drug is 41.94%, and day mortality ratio of basis medicine under this concentration only is 19.35%.This shows that new drug kills little mite ability and also is better than a day basis medicine, virulence has improved about 2 times.
The LC of table 2 new drug and day chalcid fly mite of basis medicine 12h
50And 95% fiducial interval
7. conclusion
The taufluvalinate tool is tagged and stomach poison function, is the Insecticidal and acaricidal agent that high-efficiency broad spectrum is used.Obtained a kind of chirality (R_S) taufluvalinate in the test, this test has detected this new chirality taufluvalinate and at present general taufluvalinate in the difference of killing on the honeybee mite ability.Test basis " People's Republic of China's agricultural industry criteria ", experimental technique has feasibility and standardization.Carry out in strict accordance with experimental procedure in the test.The mortality ratio of control group is less than 20%, and experimental data is effective.
Experimental result proves that this taufluvalinate that has changed chirality has the stronger ability of killing to varoa mite and chalcid fly mite.Wherein, kill big mite ability a little more than killing little mite ability, this point is identical with day basis medicine.With day the basis medicine compare, change chirality after, the virulence of taufluvalinate can improve at least 2 ~ 3 times.New drug not only has the stronger big mite ability of killing, and kill little mite ability and also significantly improve, so this new drug has broad application prospects.
Claims (4)
1. chirality (R, the S) application of taufluvalinate on control honeybee mite.
2. (it is characterized in that: (R, S) concentration of taufluvalinate is more than the 2.5mg/L to described chirality to chirality according to claim 1 for R, the S) application of taufluvalinate on control honeybee mite.
3. (R, the S) application of taufluvalinate on control honeybee mite is characterized in that: (R S) is added with emulsifying agent during taufluvalinate solution to the preparation chirality to chirality according to claim 2.
4. chirality (R according to claim 3, S) application of taufluvalinate on control honeybee mite is characterized in that: and described chirality (R, S) taufluvalinate solution need be coated with on PP or PE sheet, behind super-dry, last powder craft, make the extension bar, hang in the beehive.
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Non-Patent Citations (6)
| Title |
|---|
| Anderson Richard J et al,.Synthesis and insecticidal activity of the stereoisomers ofα-cyano-3-phenoxybenzyl 2-[2-chloro-4-(trifluoromethyl)anilino]-3-methylbutanoate (fluvalinate) and related analogs.《Journal of Agricultural and Food Chemistry》.1985,第33卷(第3期),第508-514页. |
| Minoru Inagaki et al.One-Pot Synthesis of Optically Active Cyanohydrin Acetates from Aldehydes via Lipase-Catalyzed Kinetic Resolution Coupled with in Situ Formation and Racemization of Cyanohydrins.《J. Org.chem》.1992,第57卷(第21期),第5643-5649页. |
| One-Pot Synthesis of Optically Active Cyanohydrin Acetates from Aldehydes via Lipase-Catalyzed Kinetic Resolution Coupled with in Situ Formation and Racemization of Cyanohydrins;Minoru Inagaki et al;《J. Org.chem》;19921231;第57卷(第21期);第5643-5649页 * |
| Synthesis and insecticidal activity of the stereoisomers ofα-cyano-3-phenoxybenzyl 2-[2-chloro-4-(trifluoromethyl)anilino]-3-methylbutanoate (fluvalinate) and related analogs;Anderson Richard J et al,;《Journal of Agricultural and Food Chemistry》;19851231;第33卷(第3期);第508-514页 * |
| 氟胺氰菊酯的合成;祝捷等;《农药》;20110731;第50卷(第7期);第487-488、491页 * |
| 祝捷等.氟胺氰菊酯的合成.《农药》.2011,第50卷(第7期),第487-488、491页. |
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Effective date of registration: 20180122 Address after: 620860 Pengshan District, Meishan City, Sichuan Province, the central development area of Cheng Mei Industry (Pengshan District Qinglong Town) Patentee after: Sichuan Pengshan Wangshi animal health Co. Ltd. Address before: 610207 Shuangliu County Airport Economic Development Zone, Chengdu, Sichuan Patentee before: Sichuan Wang's Animal Health Co., Ltd. |