GB2102408A - 3-phenoxybenzyl cyclopropanecarboxylate esters and their use as pesticides - Google Patents
3-phenoxybenzyl cyclopropanecarboxylate esters and their use as pesticides Download PDFInfo
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- GB2102408A GB2102408A GB08122413A GB8122413A GB2102408A GB 2102408 A GB2102408 A GB 2102408A GB 08122413 A GB08122413 A GB 08122413A GB 8122413 A GB8122413 A GB 8122413A GB 2102408 A GB2102408 A GB 2102408A
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- Prior art keywords
- cis
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- hydrogen
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- phenoxybenzyl
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Classifications
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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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
Abstract
This invention relates to 3- phenoxybenzyl cyclopropanecarboxylate esters. There are provided esters of general formula: <IMAGE> wherein X is hydrogen, or methyl, Y is hydrogen or cyano, and R is methyl or ethyl when Y is hydrogen or is C1-4 alkyl or cyclopropylmethyl when Y is cyano; in the form of one or more 1Rcis-isomers; methods for their manufacture; pesticidal compositions containing them and their use as pesticides. Esters of formula I exhibit insecticidal activity.
Description
SPECIFICATION 3-Phenoxybenzyl cyclopropanecarboxylate esters and their use as pesticides
This invention relates to 3-phenoxybenzyl cyclopropanecarboxylate esters, to their preparation and to compositions containing them for use as pesticides, especially as insecticides.
U.K. Patent Specification No. 1,413,491 describes a broad class of pesticidal cyclopropanecarboxylate esters including inter alia 3-phenoxybenzyl and cY-cyano-3-phenoxybenzyl esters of 3-(2,2-disubstituted-vinyl)-2,2-dimethylcyclopropane carboxylic acids wherein one substituent on the vinyl group may be hydrogen, halo or alkyl and the other substituent may be hydrogen, halo or carboalkoxy. The most active esters are stated to be those wherein both 2-substituents on the vinyl group are halo.
French Patent Application Publication No. 2,384,499 and Belgian Patent Specification No.
851,590 describe a class of parasitical 3-(2,2-disubstituted-vinyl)-2,2-dimethylcyclopropane- carboxylate esters, including inter alia esters of 3-phenoxybenzyl and a-cyano-3-phenoxybenzyl alcohols, wherein one substituent on the vinyl group may be hydrogen, halogen or Cis alkyl and the other substituent may be hydrogen, halogen, Cis alkyl or C28 alkoxycarbonyl or the two substituents together with the interjacent carbon atom form a Cae cycloalkyl group. No examples are given of any esters bearing a C2a alkoxycarbonyl substituent on the vinyl group.
It has now surprisingly been discovered that a limited subclass of 3-(2,2-disubstituted-vinyl)-2,2dimethylcyclopropanecarboxylate esters of 3-phenoxybenzyl and a-cyano-3-phenoxybenzyl alcohols having insecticidal activity has highly effective insect knockdown activity, particularly against flies such as the common housefly.
According to the present invention therefore there are provided 3-phenoxybenzyl cyclopropanecarboxylate esters of general formula
wherein
X is hydrogen, halo or methyl, Y is hydrogen or cyano, and R is methyl or ethyl when Y is hydrogen or is C14 alkyl or cyclopropylmethyl when Y is cyano, in the form of one or more 1 Rcis-isomers.
In formula I there are two possible centres of asymmetry in the cyclopropane ring and when X is cyano there is an additional centre of asymmetry at the a-carbon atom of the benzyl moiety. In the compounds of the invention the sterochemical configuration of the substituted cyclopropane ring is denoted as 1 Rcis-, following the nomenclature of Cahn et al, Agnew. Chem. Int. Ed:, 5, (1 966) Pages 385 et seq. In compounds of the invention there is also E/Z isomerism about the vinyl double bond. Thus a compound wherein configuration about the vinyl double bond is
is a Z-isomer when X is hydrogen or methyl and is an E-isomer when X is halo, and a compound wherein configuration about the vinyl double bond is
is an E-isomer when X is hydrogen or methyl and is a Z-isomer when X is halo.Those skilled in the art will appreciate that the 1 Rcis- compounds of the invention may exist as individual geometrical and optical isomers or as mixtures of isomers.
C34 alkyl moieties in formula I may be straight chain or branched.
Preferred esters of formula I have one or more of the following features:- (i) X is hydrogen, bromo or methyl, and
(ii) R is methyl or ethyl when Y is hydrogen, or is methyl, ethyl, isopropyl or isobutyl when Y is cyano.
The esters of the invention may conveniently be prepared in accordance with the invention by a process which comprises reacting a compound of formula
having 1 Rcis- configuration about the cyclopropane ring with a compound of formula
in an inert solvent, e.g. methylene chloride.
Compounds of formula Ill are either known compounds or may be prepared from known materials in known manner. (See e.g. U.K. Patent Specification No. 1,413,491).
Compounds of formula Il are conveniently prepared as described hereinafter in Examples I and II from 1 Rcis- caronaldehydic acid, which is described, for example, in U.S. Patent No. 3,723,469 and U.K.
Patent Application Publication No. 2,002,377.
The cyclopropanecarboxylate esters according to the invention are of interest as pesticides, especially as insecticides for domestic and agricultural outlets. The invention therefore also provides a pesticidal composition which comprises an ester of formula I as defined above in association with an inert carrier. The invention further provides a method of combating pests, e.g. insect pests, at a locus which comprises applying to the locus an ester of formula I or a composition in accordance with the invention.
A carrier in a composition of the invention may be a solid or a liquid, including a material which is normally gaseous but which has been compressed to form a liquid, inorganic or organic, and of synthetic or natural origin. The active ingredient is suitably formulated with at least one carrier to facilitate its application to the locus, for example plants, seeds or soil, to be treated, or to facilitate storage, transport or handling.
Preferably a composition of the invention contains at least two carriers, at least one of which is a surface-active agent. The surface-active agent may be an emulsifier, a dispersing agent or a wetting agent. It may be non-ionic or ionic. Pesticidal compositions are generally formulated and transported in a concentrated form which is subsequently diluted by the farmer or other user before application. A surface-active agent facilitates this process of dilution.
Any of the carriers commonly used in the formulation of pesticides may be used in the compositions of the invention, and suitable examples of these are to be found, for example, in British patent Specification No. 1,232,930.
The composition of the invention may for example be formulated as a wettable powder, microcapsules, a dust, granules, a solution, an emulsifiable concentrate, an emulsion, a suspension concentrate or an aerosol. The composition may have controlled release properties, or may be suitable for use as a bait.
Wettable powders usually contain 25, 50 or 75% of active ingredient and may contain, in addition to inert solid material, 3-1 0 /Ow of a dispersing agent and, where necessary, 0-10%w of a stabilizer, a penetrant and/or a sticker. A dust is usually formulated as a dust concentrate having a composition similar to that of a wettable powder but without a dispersant, and is diluted in the field with further solid carrier to give a composition usually containing 21 1 0%w of active ingredient.
Granules usually have a size in the range of from 10 to 100 BS mesh (1.676-0.152 mm) and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 1 25% active ingredient and 0-1 0%w of additives, for example a stabilizer, slow release modifier and/or a binding agent.
Emulsifiable concentrates usually contain, in addition to a solvent, and, when necessary, cosolvent, 1 0-50% w/v active ingredient, 2-20% w/v emulsifier and 0-20% w/v of other additives, for example a stabilizer, a penetrant and/or a corrosion inhibitor.A suspension concentrate is a stable, nonsedimenting, flowable product and usually contains 1075%w active ingredient, 0.5-1 5%w of dispersing agent, 0.11 0%w of suspending agent, for example protective colloid and/or a thixotropic agent, and 0-1 0%w of other additives including, for example, a defoamer, a corrosion inhibitor, a stabilizer, a penetrant and/or a sticker, and as dispersant, water or an organic liquid in which the active ingredient is substantially insoluble; certain organic additives and/or inorganic salts may be dissolved in the dispersant to assist in preventing sedimentation or as anti-freeze for water.
The aqueous dispersions and emulsions formed by diluting a wettable powder or an emulsifiable concentrate of the invention with water, also lie within the scope of the present invention. Such dispersions and emulsions may be of the water-in-oil or of the oil-in-water type, and may have a thick "mayonnaise"-like consistency.
A composition of the invention may also contain other ingredients, for example, one or more other compounds possessing pesticidal, herbicidal or fungicidal properties, or attractants, for example pheromones or food ingredients, for use in baits and trap formulations.
The invention will be better understood from the following Examples, of which Examples 1 and 2 relate to the preparation of intermediates and Examples 3 to 16 relate to the preparation of compounds of the invention.
EXAMPLE 1
Preparation of 1 R-cis-3-phenoxybenzyl 2,2-dimethyl-3-formylcyclopropane carboxylate
1 R-cis- caronaldehydic acid (1.4 g, 10 mM), 3-phenoxybenzylbromide (2.65 g, 10 mM) and potassium carbonate (1.5 g, 11 mM) were stirred together in acetone (50 ml) under reflux until reaction was complete (2 hours). The reaction mixture was then diluted with water, and extracted twice with 30 ml portions of diethyl ether. The combined ether extracts were washed with aqueous sodium bicarbonate solution, dried over magnesium sulphate and evaporated to yield 1 R-cis-3-phenoxybenzyl 2,2-dimethyl-3-formylcyclopropanecarboxylate (3.2 g, 99%) as a yellow oil, [a]20 = 36.2O (C2, CHCI3).
C H
Analysis: C20H2004: Calculated 74.0 6.2 Found 74.6 6.9 EXAMPLE 2
Preparation of 1 R-cis-α-cyano-3-phenoxybenzyl 2,2-di methyl-3-formylcyclopropa necarboxylate
1 R-cis- caronaldehydic acid (1.5 g, 10.6 mM), a-cyano-3-phenoxybenzyl bromide (2.9 g, 10 mM) and potassium carbonate (1.4 g, 10 mM) were stirred together in acetone (50 ml) at ambient temperature for two hours. Additional potassium carbonate (1.4 g, 10 mM) was added and the reaction mixture was stirred at ambient temperature for a further hour. The reaction mixture was then diluted with water, and extracted twice with 30 ml portions of diethyl ether.The combined ether extracts were washed with aqueous sodium bicarbonate solution, dried over magnesium sulphate and evaporated to yield 1 R-cis-cr-cyano-3-phenoxybenzyl 2,2-dimethyl-3-formylcyclopropanecarboxylate (3.2 g, 92%) as a yellow oil, [a]O = 32.80 (C2, CHCl3).
EXAMPLES 3 AND 4
Preparation of 1 R-cis-Z- and 1 R-cis-E-3-phenoxybenzyl 2,2-dimethyl-3-(2-methoxyca rbonylvinyl) cyclopropanecarboxylate
3-Phenoxybenzyl 2,2-dimethyl-3-formylcyclopropanecarboxylate (1.62 g, 5 mM) and (methoxycarbonyl methylene)triphenylphosphorane (3.34 g, 10 mM) were stirred together in methylene chloride (30 ml) under reflux for 16 hours. The reaction mixture was evaporated to give a yellow solid residue which was extracted in a Soxhlet extractor using 60/80 petroleum ether as solvent.The solvent was evaporated off to yield a mixture of 1 R-cis-Z- and 1 R-cis-E-isomers of 3-phenoxybenzyl 2,2dimethyl-3-(2-methoxycarbonylvinyl)cyclopropane carboxylate (2.3 g) as a colourless oil (2.3 g) which was chromatographed on silica using 3% v/v acetone in hexane as eluant, yielding, as colourless oils,
(3)1 R-cis-(Z)-3-phenoxybenzyl 2,2-dimethyl-3- (2-methoxycarbonylvinyl) cyclopropanecarboxylate (0.1 g, 5.2%), [25 - +37.8 (C2, CHCl3) and
(4) 1R-cis-(E)-3-phenoxybenzyl 2,2-dimethyl-3-(2-methoxycarbonylvinyl) cyclopropanecarboxylate (0.9 g, 47%), [α]D25 = -43.1 (C2, CHCl3), nD24 = 1.555.
C H
Analysis: C23H240s: Calculated : 72.6 6.4
Found 73.1 6.8
Structural assignment was made on the basis of NMR data as follows:- 3 # 7.6-6.8 (m, 1 OH), 5.95 (d, 1 H, 3JHH = 15.5 Hz, trans), 5.1 (s, 2H), 3.7 (s, 3H), 2.4-1.85 (m,
2H), 1.32 (s, 3H), 1.2 (s, 3H)
4 # 7.5-6.8 (m, 9H), 6.52 (dd, 1H, JHH = 10 Hz, cis), 5.92 (d, 1H, JHH = 11 Hz, cis), 5.07 (s, 2H), 3.68 (s, 3H), 3.27 (dd, 1 H, 3HH = 9Hz), 1.98 (d, 1 H, 3HH = 9Hz), 1.28 (s, 3H), 1.26 (s, 3H)
EXAMPLES 5 TO 16
By processes similar to that described in Examples 3 and 4 there were also prepared the compounds of formula I having X, R and Y as shown in the following Table 1, assignment of isomer structure being made by analysis of NMR data as in Examples 3 and 4.
TABLE I
Analysis C YIELD [α]DT or nDT Compound X R Y isomer (%) (C2, CHCl3) Formula F C H N Br 5 H ethyl H 1R cis E 76% 1.548 -42.2 C24H26O5 C 73.1 6.6 - at T=24 C at T=25 C F 74.4 7.4 6 H methyl CN 1R cis E 62% 1.553 -33.2 C24H23O5N C 71.1 5.7 3.5 at T=21 C at T=25 C F 70.9 6.2 3.5 7 H ethyl CN 1R cis E 60% 1.546 -47.5 C25H25O5N C 71.6 6.0 3.3 at T=21 C at T=25 C F 72.1 6.8 3.6 8 H isopropyl CN 1R cis E 23% - -38.5 C26H27O5N C 72.0 6.3 3.2 at T=25 C F 72.4 6.6 3.2 9 H isopropyl CN 1R cis Z 10% - - C26H27O5N C 72.0 6.3 3.2 F 72.1 6.8 3.3 10 H isobutyl CN 1R cis Z 8% - - C27H29O5N C 72.5 6.5 3.1 F 73.8 6.4 4.0 TABLE 1 (Continued)
Analysis C Yield [α;]DT or Compound X R Y isomer (%) nDT (C2, CHCl3) Formula F C H N Br 11 methyl ethyl H 1R cis 57% - - C25H25O5 C 73.5 6.9 - F 73.9 7.3 - 12 H cyclopro- CN 1R cis Z 8% 1.558 - C27H27O5N C 72.8 6.1 3.1 pylmethyl at T=24 C F 71.5 6.2 3.1 13 H cyclopro- CN 1R cis E 11% 1.553 -48.3 C27H27O5N C 72.8 6.1 3.1 pylmethyl at T=24 C at T=25 C F 71.3 6.6 3.1 14 methyl ethyl CN 1R cis 42% 1.547 -25.8 C26H27O5N C 72.0 6.3 3.2 at T=25 C at T=25 C F 72.3 6.6 2.9 15 Br methyl H 1R cis 35% 1.574 +4.5 C23H23O5Br C 60.1 5.1 - 17.4 at T=24 C at T=25 C F 60.3 5.5 - 17.2 16 Br methyl CN 1R cis 1.570 +1.35 C24H22O5NBr C 59.5 4.6 2.9 at T=24 C at T=25 F 60.2 4.9 2.5 The insecticidal activity of the compounds of the invention were assessed using Egyptian cotton leafworm larvae (Spodoptera litteralis) (s.l.) as follows::
Aqueous test formulations were made up containing 0.2% by weight of the compound to be tested, 0.05% by weight of TRITON X-1 00 (Trade Mark) wetting agent and 1 0% by weight of acetone.
Varying concentrations were obtained by diluting the formulations.
Pairs of leaves were removed from broad bean plants and placed on filter paper inside petri dishes.
The leaves were sprayed on the undersurface with test formulation, left to dry for 2 to 1 hour and each leaf pair was infested with ten Egyptian cotton leafworm larvae (Spodoptera littoralis). After 24 hours the percentages of dead and moribund larvae were recorded.
The results are shown in Table 2 in which the test species are identified by the initials noted above and the activity of the compound is expressed in the form of its Toxicity Index (T.l.) which is calculated from the following equation:- LCso of ethyl parathion (standard)
Toxicity Index (T.l.) = x 100 LCso of test compound
Grades "A" and "B" in Table 2 indicate that 90100% and 30-80% kills respectively were obtained of the relevant test species at the initial test concentration of compound.
The knockdown activity of the compounds according to the invention was assessed employing the common housefly (Musca domestica) (M.d.) by means of the Kearns-March chamber test.
The Kearns-March chamber consists of a 2 foot x 1 foot transparent glass cylinder into which flies can be introduced through a sliding panel at one end. 0.2 ml of a 20% MeCl80% Shellsol K solution containing active material was sprayed for 1- seconds into the chamber at 10 psi and the air supply kept on for a further two seconds to facilitate even distribution of the spray. About 70 flies were used in each treatment and knockdown counts made at 1, 2, 3, 4, 5, 7 and 10 minutes after spraying.
Compounds are classed into six grades according to the concentration of toxicant required to achieve 90% knockdown after ten minutes, that is to say
Grade 0 90% at 10 minutes = concentration 0.025%
Grade 1 90% at 10 minutes = concentration 0.05% Grade 2 90% at 10 minutes = concentration 0.1%
Grade 3 90% at 10 minutes = concentration 0.2%
Grade 4 90% at 10 minutes = concentration 0.4%
Grade 5 < 90% at 10 minutes = concentration 0.4%
Grade 6 No knockdown at 0.4%
Compounds achieving grade 0 are further tested at progressively greater dilutions in order to assess KDso and KDôO values, i.e, the concentrations of toxicant required to achieve 50% and 90% knockdown, respectively, after ten minutes. The results of these tests are also given in Table 2.
(KDso and KDgo concentrations are expressed in units of % x 10-3)
The yields of compounds 9, 10 and 12 were insufficient to enable them to be included in these tests.
TABLE 2
Knockdown activity (M.d.) Compound X R Y isomer Toxicity Index (s.I.) Grade KD50 KD90 3 H CH3 H IR cis Z A 0 1.9 2.9 4 H CH3 H IR cis E 109 0 3.3 5.3 5 H ethyl H IR cis E 59 0 5.2 7.3 6 H methyl CN IR cis E 183 0 1.8 3.0 7 H ethyl CN IR cis E 115 0 2.2 3.6 8 H isopropyl CN IR cis E 28 0 4.0 5.7 11 methyl ethyl H IR cis 18 0 5.8 9.1 13 H cyclopro- CN IR cis E < 21 0 6.8 9.0 pylmethyl 14 methyl ethyl CN 1R cis 23 0 4.5 6.2 15 Br methyl H 1R cis 57 0 4.2 5.7 16 Br methyl CN 1R cis 114 0 3.1 5.2 Comparison A H isopropyl H 1R cis E B 2 - Comparison B cyclopro- H 1R cis E < 21 2 - pylmethyl
Claims (8)
1. A 3-phenoxybenzyl cyclopropanecarboxylate ester of general formula:
wherein
X is hydrogen, halogen or methyl, Y is hydrogen or cyano, and R is methyl or ethyl when Y is hydrogen or is C14 alkyl or cyclopropylmethyl when Y is cyano, in the form of one or more 1 Rcisisomers.
2. An ester according to Claim 1 wherein X is hydrogen, bromo or methyl.
3. An ester according to Claim 1 or 2 wherein R is methyl or ethyl when Y is hydrogen, or is methyl, ethyl, isopropyl, isobutyl or cyclopropylmethyl when Y is cyano.
4. A process for preparing an ester of formula I as defined in any one of Claims 1 to 5, which process comprises reacting a compound of formula:
having 1 Rcis- configuration about the cyclopropane ring with a compound of formula
wherein
X, Y and R are as defined in Claim 1, in an inert solvent.
5. An ester according to Claim 1 substantially as hereinbefore described in any one of Examples 3 to 1 6.
6. A process according to Claim 4 of preparing an ester according to Claim 5 substantially as hereinbefore described in Example 3.
7. A pesticidal composition which comprises an ester of formula I as claimed in any one of claims 1 to 3 and 5 in association with an inert carrier.
8. A method of combating pests at a locus which comprises applying to the locus an ester of formula I as claimed in any one of Claims 1 to 3 and 5 or a composition according to Claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08122413A GB2102408A (en) | 1981-07-21 | 1981-07-21 | 3-phenoxybenzyl cyclopropanecarboxylate esters and their use as pesticides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08122413A GB2102408A (en) | 1981-07-21 | 1981-07-21 | 3-phenoxybenzyl cyclopropanecarboxylate esters and their use as pesticides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2102408A true GB2102408A (en) | 1983-02-02 |
Family
ID=10523381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08122413A Withdrawn GB2102408A (en) | 1981-07-21 | 1981-07-21 | 3-phenoxybenzyl cyclopropanecarboxylate esters and their use as pesticides |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2102408A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3335360A1 (en) * | 1982-09-29 | 1984-03-29 | Roussel-Uclaf, 75007 Paris | NEW PESTICIDE COMPOSITIONS CONTAINING A LIGHT STABILIZER |
| FR2691966A1 (en) * | 1992-06-04 | 1993-12-03 | Roussel Uclaf | Novel process for the preparation of 2,2-dimethyl-3 - [(z) 1-propenyl] cyclopropane carboxylic acid esters and intermediates |
| CN115611774A (en) * | 2022-09-26 | 2023-01-17 | 华南农业大学 | Fenpropathrin hapten, artificial antigen and fenpropathrin detection method |
-
1981
- 1981-07-21 GB GB08122413A patent/GB2102408A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3335360A1 (en) * | 1982-09-29 | 1984-03-29 | Roussel-Uclaf, 75007 Paris | NEW PESTICIDE COMPOSITIONS CONTAINING A LIGHT STABILIZER |
| FR2691966A1 (en) * | 1992-06-04 | 1993-12-03 | Roussel Uclaf | Novel process for the preparation of 2,2-dimethyl-3 - [(z) 1-propenyl] cyclopropane carboxylic acid esters and intermediates |
| EP0573361A1 (en) * | 1992-06-04 | 1993-12-08 | Roussel Uclaf | Process for the preparation of esters of 2,2-dimethyl-3-((Z)-2-(alkoxycarbonyl)ethenyl)cyclopropanecarboxylic acid and intermediates |
| US5312964A (en) * | 1992-06-04 | 1994-05-17 | Roussel Uclaf | Process and intermediates |
| CN1056828C (en) * | 1992-06-04 | 2000-09-27 | 鲁索-艾克勒夫公司 | Preparation process for esters of 2,2-dimethyl 3-{(Z) 1-propenyl} cyclopropane carboxylic acid and intermediates |
| CN115611774A (en) * | 2022-09-26 | 2023-01-17 | 华南农业大学 | Fenpropathrin hapten, artificial antigen and fenpropathrin detection method |
| CN115611774B (en) * | 2022-09-26 | 2024-04-12 | 华南农业大学 | Fenpropathrin hapten, artificial antigen and fenpropathrin detection method |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |