GB2053188A - Furylmethyloxime ether derivatives and their use as pesticides - Google Patents
Furylmethyloxime ether derivatives and their use as pesticides Download PDFInfo
- Publication number
- GB2053188A GB2053188A GB7924142A GB7924142A GB2053188A GB 2053188 A GB2053188 A GB 2053188A GB 7924142 A GB7924142 A GB 7924142A GB 7924142 A GB7924142 A GB 7924142A GB 2053188 A GB2053188 A GB 2053188A
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- compound
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- general formula
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- 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
- A01N43/06—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 five-membered rings
- A01N43/08—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 five-membered rings with oxygen as the ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Furylmethyloxime ether derivatives of the general formula: <IMAGE> wherein R<1> represents an unsubstituted or substituted aryl or alkyl group and R<2> represents a lower alkyl group, in the form of E-isomer or Z-isomer or mixtures thereof exhibit insecticidal activity.
Description
SPECIFICATION
Furylmethyloxime ether derivatives and their use as pesticides
The present invention relates to furylmethyloxime ether derivatives, to their preparation, to their use as pesticides and to pesticidal compositions containing them.
The invention provides a compound of the general formula:
wherein R1 represents an unsubstituted or substituted aryl or alkyl group and R2 represents a lower alkyl group, in the form of either its E-isomer or its Z-isomer or mixtures thereof.
An aryl group represented by R1 is preferably a naphthyl group, or a phenyl group which may be unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms and alkyl and alkoxy groups preferably having from 1 to 4 carbon atoms, for example fluorine, chlorine and bromine atoms and methyl, ethyl, t-butyl and methoxy groups. Preferably a phenyl group R1 is mono- or di-substituted, preferably having a subsfituent in the 4-position.
An alkyl group represented by R1 may be straight-chain or branched and may, for example, be substituted by one or more of the same or different substituents selected from halogen atoms, alkoxy groups and aryl groups, for example chlorine, fluorine and bromine atoms and methoxy and phenyl groups. The alkyl moiety preferably contains from 1 to 10 carbon atoms.
The group R2 preferably represents a lower alkyl group of up to 6 carbon atoms, more preferably of 2 to 6 carbon atoms, e.g. an ethyl, propyl or butyl group, and more advantageously R2 is a branched alkyl group of 3 to 6 carbon atoms, e.g. an isobutyl or tertiary butyl group, or, especially, an isopropyl group.
Especially preferred compounds of the general formula I are those in which R1 represents a phenyl group, mono-substituted in the 4-position by a fluorine, chlorine or bromine atom or an alkyl or alkoxy group having up to 4 carbon atoms, and R2 represents an isopropyl group.
The compounds according to the invention exhibit geometric isomerism about the oximic double bond, and, as stated above, the present invention extends to the individual E- and Z-isomers and to mixtures thereof. Substituents in R1 and R2 may lead to further isomerism, and in such a case the invention extends to all geometric and/or optical isomers and mixtures thereof.
The invention also provides a process for the preparation of a compound of the general formula I, which comprises reacting an alkali metal salt of a ketoxime of the general formula
wherein R1 and R2 have the meanings given for formula I, with a compound of the general formula
wherein X represents a chlorine, bromine or iodine atom, preferably a chlorine or a bromine atom, especially a chlorine atom.
The reaction is preferably carried out in the presence of a polar aprotic solvent; particularly suitable solvents are anhydrous acetonitrile, dimethylformamide in toluene, ortetrahydrofuran. Reaction temperatures are generally in the range 60-1 50"C preferably in the range 70-11 0,C and reaction times of 2 to 10 hours may be used. Alternatively, the reaction may be carried out in a two-phase organic/inorganic system in the presence of a phase transfer catalyst. The phase transfer catalyst may be any reagent which will accelerate interphase reactions in organic/inorganic two-phase systems. The alkali metal salt of the ketoxime of formula II may be prepared by the reaction of an alkali metal hydride, for example sodium hydride, with the ketoxime, or by reaction of aqueous potassium or sodium hydroxide with the ketoxime.The alkali metal salt of the ketoxime is preferably prepared in situ.
The compound of the general formula Ill may be prepared bythe reaction of 2-benzyl-4 hydroxymethylfuran with a suitable halogenating agent, for example thionyl chloride, suitably in an inert solvent in the presence of a base, for example pyridine.
The compounds of the invention have exhibited pesticidal, especially insecticidal, activity. The invention therefore provides a pesticidal composition which comprises as active ingredient a compound of the general formula I, in association with a suitable carrier. The invention also provides a method of combating pests at a locus, which comprises applying to that locus a compound of the general formula I or a pesticidal composition according to 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% w of active ingredient and may contain, in addition to inert solid material, 3-10% w of a dispersing agent and, where necessary, 0-10% w of a stabiliser, 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 1/2-10% w of active ingredient.
Granules usually have a size in the range offrom 10 to 100 BS mesh (1.676-0.152 mm) and may be manufactured by aggolomeration or impregnation techniques. Generally, granules will contain 1/2-25% w active ingredient and 0-10% w of additives, for example a stabiliser, slow release modifier and/or a binding agent.
Emulsifiable concentrates usually contain, in addition to a solvent, and, when necessary, co-solvent, 10-50% w/v active ingredient, 2-20% w/v emulsifier and 0-20% w/v of other additives, for example a stabiliser, a penetrant and/or a corrosion inhibitor.A suspension concentrate is a stable, non-sedimenting, flowable product and usually contains 10-75% w active ingredient, 0.5-15% w of dispersing agent, 0.1-10% w of suspending agent, for example protective colloid and for a thixotropic agent, and 0-10% w of other additives including, for example, a defoamer, a corrosion inhibitor, a stabiliser, 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 illustrative Examples, of which Examples 2 to 4 relate to the preparation of compounds of the invention, and Example 1 relates to the preparation of the intermediate, 2-benzyl-4-chloromethylfuran.
EXAMPLE 1 Preparation or of2-benzyl-4-chlorom eth ylfuran
Asolution of 13 g (0.11 mol) thionyl chloride in toluene was added dropwise over 15 minutes to a mixture of 15.8 g (0.2 mol) pyridine and 18.8 g (0.1 mol) 2-benzyl-4-hydroxymethylfuran, in toluene, at a temperature of 0-5"C. The mixture was slowly warmed to 80"C and stirred for 11/2 hours, and then cooled in an ice-bath, poured into ice and filtered. The resulting solution was extracted with diethyl ether, washed with water and then with sodium bicarbonate solution, and dried over magnesium sulphate.The solution was then stripped of solvent, yielding 13.4 g of a brown oil, which was chromatographed over silica gel using toluene as eluent to give 7.2 g of 2-benzyl-4-chloromethylfuran as a brown oil.
EXAMPLE 2
Preparation of4-chlorophenyl isopropyl ketoxime 2-benzyl-4-furyl-methyl ether
A solution of 2.0 g (0.01 M) of4-chlorophenyl isopropyl ketoxime in 20 ml of 20% by volume dimethylformamide/toluene was added dropwise over 15 minutes to 1.0 g of a 50% suspension of sodium hydride in oil dispersed in 10 ml of 20% by volume dimethylformamide/toluene (0.02 M of NaH), at a temperature of 60"C. A solution of 2.3 g (0.011 M) of 2-benzyl-4-chloromethylfuran in 20 ml of 20% by volume dimethylformamide/toluene was then added, and the resulting mixture was stirred at 80-900C for 2 hours.
The mixture was then cooled to room temperature and ethanol was added to destroy excess sodium hydride. The mixture was poured into ice in dilute hydrochloric acid, filtered through diatomaceous earth, extracted with diethyl ether, washed with water and with sodium bicarbonate solution (4 times) and dried over magnesium sulphate. The solvent was evaporated off to give 3.2 g of crude product as a dark brown oil, which was purified by chromatography on a silica column, eluting with 1:1 dichloromethane/60-80 petroleum ether. The title product was obtained in the form of an oil, (Yield = 0.5 g, 14%), n92 = 1.579, about 40% being in the form of the E-isomer.
Analysis:
C H N
Calculated for C22H22N02CI 71.9 6.0 3.8
Found 71.5 5.9 3.0
EXAMPLES 3 AND 4
By methods similar two that of Example 2 there were also prepared the following compounds: lEJ-lsopropyl-4-mefhoxyphenyl ketoxime 2-benzyl-4-furylmethyl ether
95% E-isomer, ng2 = 1.568
Analysis:
C H N
Calculated for C23H25N03 76.1 6.9 3.9
Found 76.2 7.0 3.5 Isoprop yl-4-methylphen y/ ketoxime 2-benzyl-4-furylmethyl ether about 40% E-isomer, nD2 = 1.566
Analysis:
C H N
Calculated for C23H25N02 79.5 7.2 4.0
Found 79.0 7.5 3.9
Pesticidal Tests
The insecticidal activity of the compounds according to the present invention was assessed employing the following insect pests::
Musca domestica (m.d.)
Spodoptera littoralis (s.l.)
Aphis fabae (a.f.)
The test methods employed for each species appear below:
(i) Musca domestica (m.d.) A 0.4% by weight solution in acetone of the compound to be tested was prepared and taken up in a micrometer syringe. Two to three day old adult female houseflies (Musca domestica) were anaesthetised with carbon dioxide, and 1 ssl of the test solution was applied to the ventral side of the abdomen of each fly, 20 flies being tested. The treated flies were held in glass jars covered with paper tissue held by an elastic band. Cotton-wool pads soaked in dilute sugar solution were placed on top of the tissue as food. After 24 hours the percentage of dead and moribund flies were recorded.
(ii) Spodoptera littoralis (s.l.)
Pairs of leaves were removed from broad bean plants and placed on filter paper inside plastic petri dishes.
The leaves were sprayed on the undersurface with an aqueous formulation containing 20% by weight of acetone, 0.05% by weight of TRITON X-100 (Trade Mark) as wetting agent and 0.4% by weight of the compound to be tested. Varying concentrations were obtained by diluting the formulation. After spraying the leaves were left to 1/2-1 hour drying period and then each leaf pair was infested with ten larvae of the
Egyptian cotton leafworm (Spodoptera littoralis). After 24 hours the percentage of dead and moribund larvae were recorded.
(iii) Aphis fabae (A.f.)
Tests were carried out on adult aphids (Aphis fabae) bysimllarmethods to that used for Spodoptera littoralis in (ii) above.
The results are shown in Table I 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:
Toxicity Index (T.l ) = LCso of ethyl parathion (standard) LLCSO of test compound
The knockdown activity of the compounds according to the invention was assessed employing the common housefly (Musca domestica) 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 o MeCI2 80 o Shellsol K solution containing active material was sprayed for 1/2 seconds into the chamber at 10 psi and the air supply kept on for a further two seconds to facilitate even treatment and knockdown counts made at 1,2,3,4,5,7 and 10 minutes after spraying.Compounds are graded into six classes according to the concentration of toxicant required to achieve 90 < O knockdown after ten minutes, that is to say
Class 0 90 O at 10 minutes = concentration 0.025# Class 1 90 O at 10 minutes = concentration 0.05 Class 2 90 at 10 minutes = concentration 0.1# Class 3 9050 at 10 minutes = concentration 0.2No Class 4 90 at 10 minutes = concentration 0.4 O Class 5 90b at 10 minutes = concentration 0.4o Class 6 No knockdown at 0.4 -O The results of these tests are also given in Table I.
TABLE I
Compound Toxicity Index Knockdown
of
Example m.d. s.l. a.f. Class
2 25 27 4
3 71 35 7 2
4 30 8 B + not yet tested.
Grade "B" in Table I indicates that 30 "O to 80% kill was obtained of the relevant test species at the initial test concentration of compound.
Claims (13)
1. Acompound of the general formula
wherein R1 represents an unsubstituted or substituted aryl or alkyl group and R2 represents a lower alkyl group, in the form of either its E-isomer or its Z-isomer or mixtures thereof.
2. A compound as claimed in Claim 1, wherein R1 represents a naphthyl group, or a phenyl group which may be unsubstituted or substituted by one or more of the same or different substituents selected from halogen atoms and alkyl and alkoxy groups having from 1 to 4 carbon atoms.
3. A compound as claimed in either Claim 1 or Claim 2, wherein R1 represents a mono- or di-substituted phenyl group having a substituent in the 4-position.
4. A compound as claimed in any one of Claims 1 to 3, wherein R2 represents a lower alkyl group having from 2 to 6 carbon atoms.
5. A compound as claimed in Claim 4, wherein R2 represents a branched alkyl group.
6. A compound as claimed in Claim 5, wherein R2 represents an isopropyl group.
7. A compound as claimed in Claim 1, wherein R' represents a phenyl group which is mono-substituted in the 4-position by a fluorine, chlorine or bromine atom or an alkyl or alkoxy group having up to 4 carbon atoms, and R2 represents an isopropyl group.
8. A compound as claimed in Claim 1, substantially as described in any one of Examples 2 to 4.
9. A process for the preparation of a compound as claimed in any one of Claims 1 to 8, which comprises reacting an alkali metal salt of a compound of the general formula
R2 R1 - C = NOH (II) wherein R' and R2 have the meanings given in Claim 1, with a compound of the general formula
wherein X represents a chlorine, bromine or iodine atom.
10. A process as claimed in Claim 11, carried out substantially as described with reference to any one of
Examples 2 to 4.
11. A compound as claimed in Claim 1, whenever prepared by a process as claimed in either Claim 9 or
Claim 10.
12. A pesticidal composition which comprises a compound as claimed in any one of Claims 1 to 8and 11 in association with a suitable carrier.
13. A method of combating pests at a locus, which comprises applying to the locus a compound as claimed in any one of Claims 1 to 8 and 11 or a pesticidal composition as claimed in Claim 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7924142A GB2053188A (en) | 1979-07-11 | 1979-07-11 | Furylmethyloxime ether derivatives and their use as pesticides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7924142A GB2053188A (en) | 1979-07-11 | 1979-07-11 | Furylmethyloxime ether derivatives and their use as pesticides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2053188A true GB2053188A (en) | 1981-02-04 |
Family
ID=10506435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7924142A Withdrawn GB2053188A (en) | 1979-07-11 | 1979-07-11 | Furylmethyloxime ether derivatives and their use as pesticides |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2053188A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07506097A (en) * | 1992-04-22 | 1995-07-06 | ヘキスト・シェーリング・アグレボ・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Acaricidal, insecticidal and nematicidal substituted (hetero)arylalkylketone oxime O-ethers, processes for their preparation, drugs containing them and their use as pest control agents |
-
1979
- 1979-07-11 GB GB7924142A patent/GB2053188A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07506097A (en) * | 1992-04-22 | 1995-07-06 | ヘキスト・シェーリング・アグレボ・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Acaricidal, insecticidal and nematicidal substituted (hetero)arylalkylketone oxime O-ethers, processes for their preparation, drugs containing them and their use as pest control agents |
| JP2931407B2 (en) | 1992-04-22 | 1999-08-09 | ヘキスト・シェーリング・アグレボ・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Acaricidal, insecticidal and nematicidal substituted (hetero) arylalkylketone oxime O-ethers, their preparation, medicaments containing them and their use as pesticides |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |