CA1175350A - Carbamoyloxyisoxazole derivatives, their preparation and insecticidal compositions containing them - Google Patents
Carbamoyloxyisoxazole derivatives, their preparation and insecticidal compositions containing themInfo
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- CA1175350A CA1175350A CA000433518A CA433518A CA1175350A CA 1175350 A CA1175350 A CA 1175350A CA 000433518 A CA000433518 A CA 000433518A CA 433518 A CA433518 A CA 433518A CA 1175350 A CA1175350 A CA 1175350A
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- dimethylcarbamoyloxy
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Abstract
ABSTRACT OF THE DISCLOSURE
Compounds of formula (I):
Compounds of formula (I):
Description
3L~ 3~i~
The present invention relates to insecticidal compositions containing a series o~ new carbamo~loxy isoxazole derivatives and conventional organic phosphate or carbamate insecticides which exhibit a synergistic increase in activity.
This application is a divisional application of co-pending application No. 389,795 filed November 10, 1981.
Insects cause considerable damage to plants and can represent a serious danger to health; ab best, they are a major nuisance. Accordingly, large sums are spent on their destruction. Although many insecticides are available, a large number of these have to be used with considerable care, because they endanger the health of humans or other animals or because of their phytotoxicity. ~oreover, because of their short life cycles, insects can develop immunity to many of the commonly used insecticides and, accordingly, there is always a continuing need for new compounds exhibiting in-secticidal properties.
A number of compounds containing the isoxazole system are known to exhibit insecticidal activity. For example, ~apanese Patent Publication No. 10145/70 discloses carbamoyloxyisoxazole derivatives of formula:
R / Ra - O-CO-N
.: : I 1- ' Rb R '' \ O ~
~in which Ra, Rh and Rd each represents a lower alkyl group and R represents a hydrogen atom or a lower alkyl group)-and discloses that these compounds are useful as insecticides.
3S However, these compounds are potentially toxic to warm-blooded animals, which means that such severe restrictions would have '~' 3~D
to be placed upon their use.that, in practice, they are un-likely ever to be actually used.
We have now discovered a series of carbamoyloxy-isoxazole derivatives which, whilst chemically similar to the known compounds of the aforementioned Japanese Patent Application, surprisingly have very much reduced toxicity to ~arm-blooded animals, but at the same time, equally good or eve.n better.insecticidal activity.
The invention, as claimed in copending application No. 389,795, accordingly, provides compounds of formula (I):
Rl CH3 \ ,,'' - -r O-CO-N (I) R -A-CH2 ~ N
O
1 1 7~35~
in which: Rl represents a hydrogen atom or a halogen atom;
R represents a Cl-C6 alkyl group; and A represents an oxy~en atom, a sulphur atom, a sulphinyl group or a sulphonyl group.
The invention of the copending application No. 389, 795 also provides a process for preparing these compounds in which a compound of formula (III):
~ O-CO N /
O
`: 3Q
' ~ 3 -4 ~ 3~ ~
(wherein R1 is as defined above and X represents a halogen atom) is reacted with an alkoxide or mercaptide of formula (IY):
R2 _ A' - M (IV) (in which R2 jS as defined above, A' represents an oxygen atom or a sulphur atom and M represents an alkali metal atom) to give a compound of formula (II):
1--I --CO--N~CH3 (in which R1, R2 and A' are as defined above) and, if ; 10 necessary~ said compound of formula (II7 in which A' ~: :represents a sulphur atom is oxidized to give a compound of formula (Y):
~CH3 lrl O-CO-N
R -~(O~n-CH2 ~ 3 5.
(wherein R and R2 are as defined above and n is 1 or
The present invention relates to insecticidal compositions containing a series o~ new carbamo~loxy isoxazole derivatives and conventional organic phosphate or carbamate insecticides which exhibit a synergistic increase in activity.
This application is a divisional application of co-pending application No. 389,795 filed November 10, 1981.
Insects cause considerable damage to plants and can represent a serious danger to health; ab best, they are a major nuisance. Accordingly, large sums are spent on their destruction. Although many insecticides are available, a large number of these have to be used with considerable care, because they endanger the health of humans or other animals or because of their phytotoxicity. ~oreover, because of their short life cycles, insects can develop immunity to many of the commonly used insecticides and, accordingly, there is always a continuing need for new compounds exhibiting in-secticidal properties.
A number of compounds containing the isoxazole system are known to exhibit insecticidal activity. For example, ~apanese Patent Publication No. 10145/70 discloses carbamoyloxyisoxazole derivatives of formula:
R / Ra - O-CO-N
.: : I 1- ' Rb R '' \ O ~
~in which Ra, Rh and Rd each represents a lower alkyl group and R represents a hydrogen atom or a lower alkyl group)-and discloses that these compounds are useful as insecticides.
3S However, these compounds are potentially toxic to warm-blooded animals, which means that such severe restrictions would have '~' 3~D
to be placed upon their use.that, in practice, they are un-likely ever to be actually used.
We have now discovered a series of carbamoyloxy-isoxazole derivatives which, whilst chemically similar to the known compounds of the aforementioned Japanese Patent Application, surprisingly have very much reduced toxicity to ~arm-blooded animals, but at the same time, equally good or eve.n better.insecticidal activity.
The invention, as claimed in copending application No. 389,795, accordingly, provides compounds of formula (I):
Rl CH3 \ ,,'' - -r O-CO-N (I) R -A-CH2 ~ N
O
1 1 7~35~
in which: Rl represents a hydrogen atom or a halogen atom;
R represents a Cl-C6 alkyl group; and A represents an oxy~en atom, a sulphur atom, a sulphinyl group or a sulphonyl group.
The invention of the copending application No. 389, 795 also provides a process for preparing these compounds in which a compound of formula (III):
~ O-CO N /
O
`: 3Q
' ~ 3 -4 ~ 3~ ~
(wherein R1 is as defined above and X represents a halogen atom) is reacted with an alkoxide or mercaptide of formula (IY):
R2 _ A' - M (IV) (in which R2 jS as defined above, A' represents an oxygen atom or a sulphur atom and M represents an alkali metal atom) to give a compound of formula (II):
1--I --CO--N~CH3 (in which R1, R2 and A' are as defined above) and, if ; 10 necessary~ said compound of formula (II7 in which A' ~: :represents a sulphur atom is oxidized to give a compound of formula (Y):
~CH3 lrl O-CO-N
R -~(O~n-CH2 ~ 3 5.
(wherein R and R2 are as defined above and n is 1 or
2~.
The invention sti11 further provides an insecti-cidal composition comprising an insecticide and a carrier or diluent, characterized in that the insecticide comprises one or more of the compounds of formula (I) defined above.
In the compounds of formula (I), where R1 represents a halogen atom, it may be a chlorine, bromine, iodine or fluorine atom and is preferably a chlorine, bromine or iodine atom, rnore preferably a chlorine or bromine atom. It is, however, preferred that R1 should represent a hydrogen atom.
.
R2 represents a straight or branched chain Cl-C6 alkyl group, for example a methyl, ethyl, propyl, isopropyl, butyl, t-butyl or pentyl group, preferably a C1-C3 alkyl group and most preferably a methyl or ethyl group.
: .
~;~ A preferably represents a sulphur atom.
.
Representative examples of compounds of the invention are listed below; the numbers appended to the compounds in the following list are used to identify ~ 3 6.
those compounds hereinafter:
1. 3-Dimethylcarbamoyloxy-5-methylthiomethylisoxa-zole 2. 3-Dimethylcarbamoyloxy-5-ethylthiomethylisoxa-zole
The invention sti11 further provides an insecti-cidal composition comprising an insecticide and a carrier or diluent, characterized in that the insecticide comprises one or more of the compounds of formula (I) defined above.
In the compounds of formula (I), where R1 represents a halogen atom, it may be a chlorine, bromine, iodine or fluorine atom and is preferably a chlorine, bromine or iodine atom, rnore preferably a chlorine or bromine atom. It is, however, preferred that R1 should represent a hydrogen atom.
.
R2 represents a straight or branched chain Cl-C6 alkyl group, for example a methyl, ethyl, propyl, isopropyl, butyl, t-butyl or pentyl group, preferably a C1-C3 alkyl group and most preferably a methyl or ethyl group.
: .
~;~ A preferably represents a sulphur atom.
.
Representative examples of compounds of the invention are listed below; the numbers appended to the compounds in the following list are used to identify ~ 3 6.
those compounds hereinafter:
1. 3-Dimethylcarbamoyloxy-5-methylthiomethylisoxa-zole 2. 3-Dimethylcarbamoyloxy-5-ethylthiomethylisoxa-zole
3. 3-Dimethylcarbamoyloxy-5-propylthiomethylisoxa-: zole
4. 3-Dimethylcarbamoyloxy-5-isopropylthiomethylisoxa-zole
5. 3-Dimethylcarbamoyloxy-5-methylsulphinylmethyl-isoxazole :
6. 3-Dimethylcarbamoyloxy-5-ethylsulphinylmethyl-: isoxazole :~ 7. 3-Dimethylcarbamoyloxy-5-methylsulphonylmethyl-: 15 isoxazole 8. 3-Dimethylcarbamoyloxy-5-ethylsulphonylmethyl-isoxazole : 9. 4-Chloro-3-dimethylcarbamoyloxy-5-methylthio-methylisoxazole ~ 3
7.
10. 4-Chloro-3-dimethylcarbamoyloxy-5-ethylthio-methylisoxazole 11. 4-Ch7oro-3-dimethylcarbamoyloxy-5-methylsulphinyl-methylisoxazole 12. 4-Chloro-3-dimethylcarbamoyloxy-5-methylsulphonyl-methylisoxazole 13. 4-Bromo-3-dimethylcarbamoyloxy-5-methylthiomethyl-isoxazole 14. 3-Dimethylcarbamoyloxy-4-iodo-5-methylthiomethyl-~ lO isoxazole : 15. 3-Dimethylcarbamoyloxy-5-methoxymethylisoxazole 16. 3-Dimethylcarbamoyloxy-5-ethoxymethylisoxazole ; 17. 4-Chloro-3-dimethylcarbamoyloxy-5-methoxymethyl-isoxazole ~ .
18. 4-Chloro-3-dimethylcarbamoyloxy-5-ethoxymethyl-isoxazole.
0~ the compounds listed above, particularly preferred compounds are Compounds No. 1, 2, 9 and 13.
Compounds of formula (II):
~--lro--CD--N~ (~
(in which Rl and R2 are as defined above and A' represents an oxygen atom or a sulphur atom), that is to say compounds of ~ormula (1) in which A is an oxygen or sulphur atom, may be prepared by reacting a compound of formula (III):
Rl ,~3 )~0 CO N~CH (11 XCH2 o ~ N
(in which Rl and X are as defined above~ with an alkoxide or mercaptide of formula (IV):
:10 : R2 _ A' - M (IY) ; ~ (in wh.ich R2, A' and M are as defined above)~ The : alkoxide or mercaptide may have been prepared in advance;
alternatively, it may be prepared ln situ in a suitable reaction solvent,by methods well-known in the art.
- ~ ~ '7~3~
9.
The reaction between the compounds of formulae (III) and (IY) is preferably effected in the presence of a solvent, Suitable solvents include: alcohols, such as methanol or ethanol; ethers, such as tetrahydro-furan, dioxan or diethylene glycol dimethyl ether;
dimethylformamide; dimethyl sulphoxide; hexamethyl-phosphoric triamidei and mixtures of any two or more of these solvents. Of these solvents, ethers are parti-cularly preferred. Where the compound of formula (IV~
is a mercaptide, additional suitable solvents include:
water; ketones, such as acetone or methyl isobutyl ketone; and mixtures of any two or more of the solvents.
In the case of a mercaptide, methanol is the preferred solvent.
' The reaction is preferably effected at a temperature greater than 0C but below the reflux temperature of the solvent used; preferably the temperature may range from above O~C to ambient temperature.
:
A~ter completion of the reaction, the desired product of formula (II) may be separated and purified by techniques well-known in the art. For example, the solvent is distilled off under reduced pressure;
the residue is diluted with a solvent such as methylene chloride; the organic solution is washed and dried;
and then the solvent is distilled off. The product ~ 7~;35~
10.
may then be further purified3 if desired, by recrystalli-zation or by various chromatography techniques.
.
Compounds of formula (V3:
Rl C~3 ~T O-cO-N <
R2-S(O1n-CH2 Ct~3 (Y ) ~wherein R1 and R2 are as defined above and n is 1 or 2), that is to say compounds of formula (I) in which A represents a sulphinyl or sulphonyl group, may be ; prepared by oxidizing the corresponding compound of formula (VI):
.
~: Rl ,CH3 , O-~O-N
o ~ ~ 3 ( ~ ~ R2-S-~H~ ~ o ,N
(in which R1 and R2 are as defined above); the compound of formula (YI) may itself have been prepared as described above.~
The oxidizing agent is preferably a peroxide, for example hydrogen peroxide or an organic peroxide (such as benzoyl peroxide or m-chloroperbenzoic acid, 3~
11 .
preferably m-chloroperbenzoic acid).
Where hydrogen peroxide is employed as the oxidizing agent, the reaction is preferably effected in the presence of a solvent, for example an aliphatic carbo~ylic acid, particularly acetic acid9 and the amount of hydrogen peroxide employed is preferably an approximately equimolar amount with respect to the compound of formula (YI).
Where hydrogen peroxide is the oxidizing agent, the reaction is preferably effected at a temperature of from 5C to 25C.
On the other hand, where an organic peroxide, particularly m-chloroperbenzoic acid, is used as the oxidizing agent, the reac~ion is also preferably effected in the presence of a solvent9 the nature of which is not critical~ provided that it has no adverse effect on the reaction; preferred solvents are halogenated hydrocarbons, such as methylene chloride~ carbon tetra-chloride, chloroform, chlorobenzene and o-dichlorobenzene.
In this case, the organic peroxide is preferably employed in an amount greater than equimolar. The reaction will go to completion at a relatively low temperature, which may be below ambient temperature and as low as 0C, within a few hours. However, the reaction can also be performed at the reflux temperature of the solvent employed. In the case where an organic peroxide is used, 7~;3 2.
insolubles, if any, should be filtered off before the desired product is separa~ed from the reaction mixture and purified.
After completion of the reaction, the solvent is preferably distilled off under reduced pressure, after which the residue is diluted with a solvent such as methylene chloride, the organic solution is washed and dried and then the solvent is distilled off. The resulting product may~ if desired, be further purified by recrystallization or chromatography.
Compounds of formula (III) are novel and also form part of the present invention. They may be prepared by reacting a 3-hydroxyisoxazole derivative of formula (VII):
- Rl ,OH
X~H~D'~
(in which R1 and X are as defined above) with a carbamoyl halide of formula (VIII):
~ 7 3.
~H3 Y CO N<CH (~m1 (in which Y represents a halogen atom).
The reaction is preferably effected in the presence of a solvent, the nature of which is not critical, provided that it has no adverse effect upon the reaction. Suitable solvents include: aliphatic and aromatic hydrocarbons, such as hexane, petroleum ether, benzene, toluene or xylene; chlorinated hydrocarbons, such as methylene chloride, chloroform or carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, d;oxan, tetra-hydrofuran or diethylene glycol dimethyl ether; ketones, such dS acetone, methyl ethyl ketone or methyl isobutyl ketone; and amides, such as d;methylformamide, diethyl-acetamide and hexamethylphosphoric triamide.
~ ~ The temperature of the reaction may vary over a wide range and the reaction may, for example~ be effected wi~th ice-cooling or at temperatures up to ambient.
The reagents are preferably emp~oyed in an equimolar or approximately equimolar ratio and the reaction is .
~'7~3~;~
14 .
Preferably effected in the presence of an acid-bind;ng agent, which may be organic (e.g. an organic amine, such as dicyclohexylamine, dimethylbenzylamine, picoline or lutidine) or inorganic (e.g. an alkali metal hydroxide, carbonate or bicarbonate, e.g. the hydroxide, carbonate or bicarbonate of sodium or potassium).
The compounds of formula (YII~ which are used as starting materials in this process may be prepared, where R1 represents a hydrogen atom, by the method described in Tetrahedron Letters 25, 2077 (1965). Compounds in which R1 represents a halogen atom may be prepared by reacting the corresponding compound in which R1 represents a hydrogen atom with a halogenating agent, for example chlorine, bromine~ a sulphuryl halide or an N-halosuccinimideO
For examplé, compounds of formula (VII) in which R1 represents a chlorine atom may be obtained by treating the corresponding compound in which R1 represents a hydrogen atom with sulphuryl chloride, under reflux, in the presence or absence of an inert solYent, or with a calculated amount of gaseous chlorine~ at ambient temperature, in dimethylformamide.
Compounds of formula (VII) in which R1 represents a bromine or iodine atom may be obtained by treating the corresponding compound in which R1 represents a ~ 3 15.
hydrogen atom with N-bromosuccinimide or N-iodosuccinimide in dimethylformamide, with heating to about 60~C.
We have found that the compounds of formula (I) exhibit insecticidal activity against a ~ide variety of insect pests, including many of importance to agriculture, for example the green peach aphid, the green rlce leaf-hopper and the brown planthopper; such activity is comparable with or even higher than that of known compounds but is accompanied by remarkably lo~ toxicity to warm-blooded animals.
~ n order to control effectively harmful insects9the compounds of formula (I) may be formulated with carriers and diluents well-known in this art~ particularly with agriculturally acceptable carriers and diluents, by conventional techniques. The resulting compositions may be in various forms, both solid and liquid and may be used for spraying or soil application to control ; lnsects on leaves and stems of various plants, including rice plants, fruit trees~ vegetables and flowers. The compounds of the invention have the significant advantage of possessing systemic insecticidal activity.
The co~pounds o~ for~ula I in accordance with the present ~nyentio,n may be ~sed in c~ination with y,ariou~.or,~nic ~hos,phate or carbamate insecticides in order to broaden the insecticidal , . .
i3S~
16.
spectrum and the compounds most suprisingly show syner-gistic activity in such combinations. Examples of insecticides which may be used in combination with the compounds of formula (I~ inolude, for example:
0,0-Diethyl 0-(5-phenyl-3-isoxazolyl)phosphoro-thioate (Isoxathion);
S-Methyl N-(methylcarbamoyloxy)thioacetimidate (Methomyl);
0,0-D;methyl 0-~3-methyl-4-nitrophenyl)thiophos-phate (Fenitrothion);
0,0-Dimethyl 0-[2-chloro-1-(2,4-dichlorophenyl)-vinyl]phosphate (Dimethylvinphos);
: 0,0-Dimethyl S-(~-ethoxycarbonylbenzyl)phosphoro-dithioate (Cidial);
Q,0-Dipropyl 0-4-methylthiophenylphosphate (Propaphos);
1-Naphthyl N-methylcarbamate (Carbaryl);
2-Isopropylphenyl N-methylcarbamate (Isoprocarb);
and ~ 3~ ~
3-Tolyl N~methylcarbamate (MTMC).
The synergistic effect obtained by combining one or more of the compounds of formula ~) with one or more organic phospha~e or carbamate insecticides~
such as those mentioned above, will be observed over a very wide range of ratios between the active ingredients.
In general, however, we prefer to employ from o.l to 10 parts by weight of the organic phosphate or carbamate insecticide per one part by weight of the compound of formula (I)o The compounds of the invention may be employed in various types of preparation as is well-known for other insecticides; for example, they may be in the form of dusts, coarse dusts, micro granules, fine granules, wettable powders, emulsifiable concentrates, aqueous solutions or suspensions, water-soluble powders or oil suspensions. The carrier employed may be natural or synthetic and organic or inorganic; it is mixed with the active ingredient to a sist that ingredient to reach the material to be treated~ and to make it easier to store, transport or handle the active ingredient.
Suitable solid carriers include: inorganic substances, such as clays (examples of which are kaolinite, montmorillonite and attapulgite), talc, mica, pyrophyllite, 18.
pumice, vermiculite, gypsum, calcium carbonateJ dolo-mite, diatomaceous earth, magnesium carbonate, apatite, zeolite, silicic anhydride and synthetic calcium sillcate;
organic substances derived from vegetables, such as soybean meal, tobacco powder, walnut powder, wheat flour, wood meal, starch and crystalline cellulose; synthetic or natural high molecular weight polymersS such as cumarone resins, petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums9 copal gum and dammar gum; waxes, such as carnauba wax and beeswax; or urea.
Examples of suitable liquid carriers include:
paraffinic or naphthenic hydrocarbons, such as kerosine, mineral oil, spindle oil and white oil; aromatic hydro-carbons, such as benzene, toluene, xylene, ethylbenzene,.
cumene and methylnaphthalene; chlorinated hydrocarbons, such as carbon tetrachloride, chloroform, trichloro-ethylene, chlorobenzene and o-chlorotoluene; ethers, such as dioxan and tetrahydrofuran; ketones, such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclo hexanone, acetophenone and isophorone; esters, such as ethyl acetate, pentyl acetate, ethylene glycol acetate~
diethylene glycol acetate, dibutyl maleate and diethyl succinate; alcohols, such as methanol, hexanol, ethylene glycol, diethylene glycol, cyclohexanol and benzyl ~S35~
1~.
alcohol; ether alcohols, such as ethylene glycol mono~
ethyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; other polar organic solvents, such as dimethyl-formamide or dimethyl sulphoxide; and water.
The insecticidal compositions of the present invention may contain surface active agents in order to emulsify, disperse, wet, spread, bind, control disinte-gration of~ improve fluidity of or rust-proof the insecti-cidal composition or to stabilize thè active ingredient;although any of the conventional classes of surface active agent, be they non-ionic, anionic, cationic or amphoteric, may be emp7oyed, we prefer to employ non- .
ionic and/or anionic surface active agents. Examples of suitable non-ionic surface active agents include:
. the polymerization adducts of ethylene oxide with higher alcohols~ sush as lauryl alcohol, stearyl alcohol or oleyl alcohol; the polymerization adducts of ethylene oxide with alkylphenols, such as isooctylphenol or nonyl-phenol; the-polymerization adducts of ethylene oxide with alkylnaphthols, such as butylnaphthol or octylnaphthol;
the polymerization adducts of ethylene oxide with higher fatty acids, such as palmitic acid, stearic acid or oleic acid; the polymerization adducts of ethylene oxide with mono-or di- alkylphosphoric acids, such as stearylphosphoric acid 535i~
or d~laurylphosphoric acid; the polymerization adducts of ethylene oxide with amines, such as dodecylamine;
the polymerization adducts of ethylene oxide with higher fatty acid amides, such as stearamide~ the polymerization adducts of ethylene oxide with higher fatty acid esters of polyhydric alcohols, such as sorbitan, and the fatty acid esters themselves, and the polymerization adducts of ethylene oxide with propylene oxide. Examples of suitable anionic surface active agents include: alkyl sulphate salts, such as sodium lauryl sulphate or oleyl sulphate amine salt; alkyl sulphonate salts, such as sodium dioctyl sulphosuccinate or sodium 2-ethylhexene sulphonate; and aryl sulphonate salts, such as sodium isopropylnaphthalene sulphonate, sodi um methylenebis-naphthalene sulphonate, sodium ligninsulphonate or sodi um dodecylbenzene sulphonate~
: Moreover, the insecticidal compositions of the present invention may be used in combination with high : ~ molecular weight compounds or other auxiliary agents, such as casein, gelatin., albumin, glue, sodium alginate, carboxymethylcellulose, methylcellulose, hydroxyethyl-cellulose or polyYinyl alcohol, in order to improve the properties and/or to increase the biological effect of the composition.
~S 3 21.
The above-mentioned carriers and various auxiliary agents may be used alone or in any desired combination, depending upon the type of preparation, the application and other factors.
The concentration of the active ingredient, the compound or compounds of formula (I~, in the composition may vary over a wide range, although it will normally be ~rom 0.1 to 95~ by weight and more preferably from 1 to 90X by weight of the composition, depending upon the type of preparation.
For example, dusts may conveniently contain from 1 to 25% by weight of the active compound, the remainder being a solid carrier.
Wettable powders may conveniently contain, for example, from 25 to 90X by weight of the active compound, the remainder being a solid carrier and a dispersing and wetting agent, if required, together with a protective :
colloidal agent, a thixotropic agent and an anti-foaming agent.
' Granules may conveniently contain from 1 to 35X by weight of the active compound, a major portion of the remainder being a solid carrier. The active compound is preferably homogeneously admixed with the solid carrier or is adhered to or adsorbed onto the 7~3 22 .
çarrier surface; the diameter of each granule is prefer-ably from 0.2 to 1.5 mm.
Emulsifiable concentrates may conveniently contain, for example, from 5 to 50% hy weight of the active compound and from 5 to 20% by weight of an emulsifying agent, the remainder being a liquid carrier, together with, if required, a corrosion inhibitor.
The invention is further illustrated by the following Examples, of which Examples 1 to 3 illustrate the preparation of certain starting materials for preparing the compounds of the invention~ Examples 4 to 18 illustrate the preparation of compounds of the invention, Examples 19 to 22 illustrate insecticidal compositions containing the compounds of the invention and Examples 23 to 27 lS~ illustrate the use of the compounds and compositions of the invention in the contral of insects.
~ ' ~53~;;Q
23 .
EXAMPLE
4-Chloro-5-chloromethyl-3-hy(lroxyisoxazole To a solution of 8.01 9 of 5-chloromethyl-3-hydroxyisoxazole in 50 ml of benzene were added 10 9 of sulphuryl chloride, and then the mixture was refluxed for 10 hours. At the end of this time9 the solvent and the excess sulphuryl chloride were distilled off from the reaction mixture, and the residue was dissolved in S0 ml of diethyl ether and washed five times, each time with 20 ml of water. The washed diethyl ether solution was dried over anhydrous sodium sulphate, the solvent was removed by distillation, and the residue was extracted three times, each time with 30 ml of hot hexane. The hexane was distilled off from the extract and the residue was recrystalli2ed from carbon tetra-chloride, to give 4-chloro-5-chloromethyl-3-hydroxyisoxa zole in the form of colourless crystals melting at 116 - 118C.
~:
4~Bromo-5-chloromethyl-3-hydrox~i_soxazole To a solution of 1.33 9 of 5-chloromethyl~3-hydroxy-isoxazole in 2 ml of dimethylformamide were added 2.0 9 of ~-bromosuccinimide, and then the mixture was heated at 61C for 1.5 hours. The reaction mixture was then - 25 poured into 100 ml of ice-water and extracted with diethyl 24~
ether, after which the ethereal extract was dried over anhydrous sodium sulphate. The solvent was dist~11ed off, leaving crystals, which were recrystallized from a mixture of diisopropyl ether and hexane, giving 4-bromo-5-chloromethyl-3-hydroxyisoxazole, in the form of white crystals melting at 136.5 - 138C (with decomposition)O
Following the same method, 5-chloromethyl-3-hydroxy-4-iodoisoxazole, melting at 147 - 150C (with decomposition), was also prepared.
5-Chloromethyl-3-dimethylcarbamoyloxyisoxazole To a solution of 2.0 9 of 5-chloromethyl-3-hydroxy-isoxazole in 60 ml of benzene were added 1.7 9 of dimethyl-carbamoyl chloride and 108 9 of triethylenediamine (as acid-binding agent), and the mixture was stirred for 1 hour at ambient temperature. The reaction mixture was then washed twice, each time with 20 ml of water, after which the benzene solution was dried over anhydrous sodium sulphateu The solvent was then distilled off and the remaining oil was purified by column chromatography through silica gel eluted w;th a 10 : 1 by volume mixture of hexane and acetone, to give 5-chloromethyl-3-dimethyl-carbamoyloxyisoxazole in the form of a faintly yellow oil n24 5 = 1 4977 Following the same procedure as described above, 25.
the following compounds were also prepared:
5-Chloromethyl-4-chloro-3-dimethylcarbamoyloxy-isoxazole, n23 = 1.5024;
4-Bromo-5-chloromethyl-3-dimethylcarbamoyloxy-isoxazole, nD5 = 1.5166;
5-Chloromethyl-3-dimethylcarbamoyloxy-4-iodo-isoxazole, melting at 69 - 71~C;
5-Bromomethyl-3-dimethylcarbamoyloxyisoxazole, n23-5 = 1.5062;
.
5-Bromomethyl-4-chloro-3-dimethylcarbamoyloxy-: isoxazole, n22 = 1.5179;
and 4-Bromo-5-bromomethyl-3-dimethylcarbamoyloxy-i~soxazole, melting at 153 - 154C.
' 3-Dimethylcarbamoyloxy-5-methylthiomethylisoxazole To 6 9 of a 15% w/v aqueous solution of sodium methanethiolate, diluted with 20 ml of ethanol, was added, with stirring at room temperature, a solution ~ 6.
of 3.07 9 of 5-chloromëthyl 3-dimethylcarbamoyloxyisoxazole in 5 ml of ethanol; stlrring was continued for a further 30 minutes at room temperature.
The ethanol was then distilled from the reaction S mixture and 20 ml of water were added to the residue.
The mixture was extracted with 40 ml of methylene chloride, and the extract was dried over anhydrous sodium sulphate.
The solvent was distilled off, leaving a brown oil, which was caused to crystalli~e by the addition of diiso-propyl ether. The crystals were then recrystallizedfrom dii sopropyl ether, giving 2.62 9 (yield 80.9%) of 3-dimethylcarbamoyloxy-5-methylthiomethylisoxazole, in the form of colourless crystals melting at 40-41C.
EXAMPLES 5 to 11 .
Following the procedures described in Example 4, the following compounds were prepared:
3-Dimethylcarbamoyloxy-5-ethylthiomethylisoxazole, melting at 49 - 50C;
3-Dimethylcarbamoyloxy-5-propylthiomethylisoxazole, ~0 n23 = 1.5078;
D
3-Dimethylcarbamoyloxy-5-isopropylthiomethyl-isoxazole, nD3 = 1.5077;
4-Chloro-3-dimethylcarbamoyloxy-5-methylthiomethyl-isoxazole, nD1 = 1.5221;
4-Chloro-3-dimethylcarbamoyloxy-5-ethylthiomethyl-isoxazole. nD = 1.5162;
4-Bromo-3-dimethylcarbamoyloxy-5-methylthiomethyl-isoxazole, nD4-5 = 1 5352;
3-Dimethylcarbamoyloxy-4-iodo-5-methylthiomethyl isoxazole, n21 = 1.5563.
The procedure described in Example 4 W2S repeated, except that sodium methoxide was used in place of the sodiu~ methanethiolate, to give 3-dimethylcarbamoyloxy-5-methoxymethylisoxazole, n2455 = 1.4720.
:::
;; 15 3-Di~ethylcarbamoyloxy-5-meth~lsulPhin~_methylisoxazole A solution of 757 mg of 3-dimethylcarbamoyloxy-5-methylthiomethylisoxazole In 5 ml of methylene chloride was 3dded dropwise over a period of 30 m;nutes, with stirring~ to an ice-cooled solution of 711 mg of m-chlnro-perbenzoic acid in 15 ml of methylene chloride. The .
. ~ ~7~
2~.
mixture was ~hen stirred for a further 30 minutes, after which it was filtered and the preeipitate was washed with 2 ml of methylene chloride~ The filtrate and the washings were combined, and then the solvent was removed by distillation~ leaving a colourless, crystalline residue, which was recrystallized from diethyl ether, to give 700 mg (yield 86.1X) of 3-dimethylcarbamoyloxy-5-methylsulphinylmethylisoxazole, in the form of colourless needles melting at 84-85C.
EXAMPLES 14 and 15 The procedure described in Example 4 was repeated, to prepare the following compounds:
3-Dimethylcarbamoyloxy;5-ethylsulphinylmethyl-isoxazole, melting at 85-86C;
4-Chloro-3-dimethylcarbamoyloxy-5-methylsulphinyl-methylisoxazole, melting at 7g-81C.
.
:: EXAMPLES 16 - 18 The procedure described in Example 4 was repeated, except that the m-chloroperbenzoic acid was used in an amount of 2 moles per mole of starting isoxazole compound, to prepare the following compounds:
29 .
3-Dimethylcarbamoyloxy-5-methylsulphonylmethyl-isoxazole, melting at 145 146C, 3-Dimethylcarbamoyloxy-5-ethylsulphonylmethyl-isoxazole, melting at 106 - 107C;
4-Chloro-3-dimethylcarbamoyloxy-5-methylsulphonyl-methylisoxazole, melting at 104 - 105C.
Dust 5 parts by weight of Compound No. 1, 50 parts by weight of talc and 45 parts by weight of kaolin were thoroughly blended to give a dust.
: Wettable powder : 50 parts by weight of Compound No. 2, 29 parts ~by wei~ght of c~lay, 10 parts by weight of diatomaceous earth, 5 parts by weight of white carbon, 3 parts by weight of sodlum ligninsulphonate, 2 parts by weight of Newcol 1106 ("Newcol" is a trade mark) and ~ part by weight of polyvinyl alcohol were thoroughly blended : 20 in a mixer and then pulverized three times with a hammer mill to give a wettable powder.
:
~ 7~;35 30 .
Granules 70 parts by weight of Compound No. 1 were finely pulverized, mixed with 30 parts by weight of clay and then blended in a mixer to make a premix. 10 parts by weight of the premix, 60 parts by weight of rlay and 30 parts by weight of bentonite were thoroughly blended in a mixer and then a small amount of water was added to the mixture. The mixture was then compounded in a kneader, extruded through a screen whose apertures were of diameter 0.8 mm and then dried at 50C in a forced air oven. The dried compound was granulated with a sifter to give granules.
Emulsifiable concentrate ~ . _ 20 parts by weight of isoxathion, 5 parts by weight of Compound No. 1, 60 parts by weight of xylene and 15 parts by weight of Paracol PS ("Paracol" is a trade mark) were uniformly blended to give a emulsifiable concentrate.
S35~
Tox1city Test Each of the compounds listed in Table 1 was administered in the form of a suspension, ~o.which 0.5 w/v gum tragacanth had been added, to a group of 5 week old ddY-SLC series mice. Each test group consisted of 10 male and 10 female mice. The LD50 value was calculated, by the method of Litchfield and Wilcoxon [J. Pharmac. Exp. Ther. 96, 99 (1949)], from ~the mortality rate after 7 days. The results are shown in Table 1 .
Table Compound No. LD50 (mg~kg) . 1 . male 110.2 . . female 109.1 : .
: ~ . 2 male 124.7 . female 103.5 3-Dimethylcarbamoyloxy-5- male/female 31.2 methylisoxazole (Con~rol) .
32.
Similar tests were conducted with each of Compounds No. 3 - 15 and in each case9 the LD50 value was greater than lO0 mg/kg~ These results demonstrate the low toxicity of the compounds of the invention to warm-blooded animals.
Control_of qreen peach aphid ~ontact activity A wettable powder was prepared by homogeneously mixing and pulverizing three times in a hammer mill 10 parts by weight of one of the test compounds ind;cated in Tables 2 and 3, 4 parts by weight of sodium dodecyl-benzene sulphonate, 2 parts by weight of polyvinyl alcohol and 84 parts by weight of clay. The wettable powder thus prepared was then diluted with water to the concentration indicated in Table 1, and then 0.01% w/v of Gramin (a spreader) was added.
The resulting diluted solution was then sprayed onto the lea~es of a cabbage bearing green peach aphids (Myzus persicae) in an amount of 10 ml per leaf. The leaf stalk of each leaf was then placed in a 30 ml bottle containing water and the mouth of the bottle was plugged with cotton wool. The bottles were then left in a ~:~'7~3~i~
33 .
room ~aintained at 25C. After 72 hours, the percentage mortality of the aphids was assessed and the results are shown in Tables 7 and 3.
Systemic activit.v Test suspensions were prepared as described above and then diluted to the concentrations indicated in Tables 2 and 3. The suspensions were then poured into 30 ml bottles. Leaves of the Chinese mustard "Komatsuna" bearing green peach aphids were then placed in the bottles and the mouths of the bottles were plugged with cotton wool. The bottles were placed in a room maintained at 25C for 72 hours, after which the percentage mortality of the aphids was assessed. The results are shown in Tables 2 and 3.
.
3~.
Table 2 Percentage mortality of green peach aphid.
Compound No. Contact Systemic . 50 ppm 6.. 25 ppm :
- 2 . 100 100 : 3 86 100 . ~1 96 . 5 86 100
10. 4-Chloro-3-dimethylcarbamoyloxy-5-ethylthio-methylisoxazole 11. 4-Ch7oro-3-dimethylcarbamoyloxy-5-methylsulphinyl-methylisoxazole 12. 4-Chloro-3-dimethylcarbamoyloxy-5-methylsulphonyl-methylisoxazole 13. 4-Bromo-3-dimethylcarbamoyloxy-5-methylthiomethyl-isoxazole 14. 3-Dimethylcarbamoyloxy-4-iodo-5-methylthiomethyl-~ lO isoxazole : 15. 3-Dimethylcarbamoyloxy-5-methoxymethylisoxazole 16. 3-Dimethylcarbamoyloxy-5-ethoxymethylisoxazole ; 17. 4-Chloro-3-dimethylcarbamoyloxy-5-methoxymethyl-isoxazole ~ .
18. 4-Chloro-3-dimethylcarbamoyloxy-5-ethoxymethyl-isoxazole.
0~ the compounds listed above, particularly preferred compounds are Compounds No. 1, 2, 9 and 13.
Compounds of formula (II):
~--lro--CD--N~ (~
(in which Rl and R2 are as defined above and A' represents an oxygen atom or a sulphur atom), that is to say compounds of ~ormula (1) in which A is an oxygen or sulphur atom, may be prepared by reacting a compound of formula (III):
Rl ,~3 )~0 CO N~CH (11 XCH2 o ~ N
(in which Rl and X are as defined above~ with an alkoxide or mercaptide of formula (IV):
:10 : R2 _ A' - M (IY) ; ~ (in wh.ich R2, A' and M are as defined above)~ The : alkoxide or mercaptide may have been prepared in advance;
alternatively, it may be prepared ln situ in a suitable reaction solvent,by methods well-known in the art.
- ~ ~ '7~3~
9.
The reaction between the compounds of formulae (III) and (IY) is preferably effected in the presence of a solvent, Suitable solvents include: alcohols, such as methanol or ethanol; ethers, such as tetrahydro-furan, dioxan or diethylene glycol dimethyl ether;
dimethylformamide; dimethyl sulphoxide; hexamethyl-phosphoric triamidei and mixtures of any two or more of these solvents. Of these solvents, ethers are parti-cularly preferred. Where the compound of formula (IV~
is a mercaptide, additional suitable solvents include:
water; ketones, such as acetone or methyl isobutyl ketone; and mixtures of any two or more of the solvents.
In the case of a mercaptide, methanol is the preferred solvent.
' The reaction is preferably effected at a temperature greater than 0C but below the reflux temperature of the solvent used; preferably the temperature may range from above O~C to ambient temperature.
:
A~ter completion of the reaction, the desired product of formula (II) may be separated and purified by techniques well-known in the art. For example, the solvent is distilled off under reduced pressure;
the residue is diluted with a solvent such as methylene chloride; the organic solution is washed and dried;
and then the solvent is distilled off. The product ~ 7~;35~
10.
may then be further purified3 if desired, by recrystalli-zation or by various chromatography techniques.
.
Compounds of formula (V3:
Rl C~3 ~T O-cO-N <
R2-S(O1n-CH2 Ct~3 (Y ) ~wherein R1 and R2 are as defined above and n is 1 or 2), that is to say compounds of formula (I) in which A represents a sulphinyl or sulphonyl group, may be ; prepared by oxidizing the corresponding compound of formula (VI):
.
~: Rl ,CH3 , O-~O-N
o ~ ~ 3 ( ~ ~ R2-S-~H~ ~ o ,N
(in which R1 and R2 are as defined above); the compound of formula (YI) may itself have been prepared as described above.~
The oxidizing agent is preferably a peroxide, for example hydrogen peroxide or an organic peroxide (such as benzoyl peroxide or m-chloroperbenzoic acid, 3~
11 .
preferably m-chloroperbenzoic acid).
Where hydrogen peroxide is employed as the oxidizing agent, the reaction is preferably effected in the presence of a solvent, for example an aliphatic carbo~ylic acid, particularly acetic acid9 and the amount of hydrogen peroxide employed is preferably an approximately equimolar amount with respect to the compound of formula (YI).
Where hydrogen peroxide is the oxidizing agent, the reaction is preferably effected at a temperature of from 5C to 25C.
On the other hand, where an organic peroxide, particularly m-chloroperbenzoic acid, is used as the oxidizing agent, the reac~ion is also preferably effected in the presence of a solvent9 the nature of which is not critical~ provided that it has no adverse effect on the reaction; preferred solvents are halogenated hydrocarbons, such as methylene chloride~ carbon tetra-chloride, chloroform, chlorobenzene and o-dichlorobenzene.
In this case, the organic peroxide is preferably employed in an amount greater than equimolar. The reaction will go to completion at a relatively low temperature, which may be below ambient temperature and as low as 0C, within a few hours. However, the reaction can also be performed at the reflux temperature of the solvent employed. In the case where an organic peroxide is used, 7~;3 2.
insolubles, if any, should be filtered off before the desired product is separa~ed from the reaction mixture and purified.
After completion of the reaction, the solvent is preferably distilled off under reduced pressure, after which the residue is diluted with a solvent such as methylene chloride, the organic solution is washed and dried and then the solvent is distilled off. The resulting product may~ if desired, be further purified by recrystallization or chromatography.
Compounds of formula (III) are novel and also form part of the present invention. They may be prepared by reacting a 3-hydroxyisoxazole derivative of formula (VII):
- Rl ,OH
X~H~D'~
(in which R1 and X are as defined above) with a carbamoyl halide of formula (VIII):
~ 7 3.
~H3 Y CO N<CH (~m1 (in which Y represents a halogen atom).
The reaction is preferably effected in the presence of a solvent, the nature of which is not critical, provided that it has no adverse effect upon the reaction. Suitable solvents include: aliphatic and aromatic hydrocarbons, such as hexane, petroleum ether, benzene, toluene or xylene; chlorinated hydrocarbons, such as methylene chloride, chloroform or carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, d;oxan, tetra-hydrofuran or diethylene glycol dimethyl ether; ketones, such dS acetone, methyl ethyl ketone or methyl isobutyl ketone; and amides, such as d;methylformamide, diethyl-acetamide and hexamethylphosphoric triamide.
~ ~ The temperature of the reaction may vary over a wide range and the reaction may, for example~ be effected wi~th ice-cooling or at temperatures up to ambient.
The reagents are preferably emp~oyed in an equimolar or approximately equimolar ratio and the reaction is .
~'7~3~;~
14 .
Preferably effected in the presence of an acid-bind;ng agent, which may be organic (e.g. an organic amine, such as dicyclohexylamine, dimethylbenzylamine, picoline or lutidine) or inorganic (e.g. an alkali metal hydroxide, carbonate or bicarbonate, e.g. the hydroxide, carbonate or bicarbonate of sodium or potassium).
The compounds of formula (YII~ which are used as starting materials in this process may be prepared, where R1 represents a hydrogen atom, by the method described in Tetrahedron Letters 25, 2077 (1965). Compounds in which R1 represents a halogen atom may be prepared by reacting the corresponding compound in which R1 represents a hydrogen atom with a halogenating agent, for example chlorine, bromine~ a sulphuryl halide or an N-halosuccinimideO
For examplé, compounds of formula (VII) in which R1 represents a chlorine atom may be obtained by treating the corresponding compound in which R1 represents a hydrogen atom with sulphuryl chloride, under reflux, in the presence or absence of an inert solYent, or with a calculated amount of gaseous chlorine~ at ambient temperature, in dimethylformamide.
Compounds of formula (VII) in which R1 represents a bromine or iodine atom may be obtained by treating the corresponding compound in which R1 represents a ~ 3 15.
hydrogen atom with N-bromosuccinimide or N-iodosuccinimide in dimethylformamide, with heating to about 60~C.
We have found that the compounds of formula (I) exhibit insecticidal activity against a ~ide variety of insect pests, including many of importance to agriculture, for example the green peach aphid, the green rlce leaf-hopper and the brown planthopper; such activity is comparable with or even higher than that of known compounds but is accompanied by remarkably lo~ toxicity to warm-blooded animals.
~ n order to control effectively harmful insects9the compounds of formula (I) may be formulated with carriers and diluents well-known in this art~ particularly with agriculturally acceptable carriers and diluents, by conventional techniques. The resulting compositions may be in various forms, both solid and liquid and may be used for spraying or soil application to control ; lnsects on leaves and stems of various plants, including rice plants, fruit trees~ vegetables and flowers. The compounds of the invention have the significant advantage of possessing systemic insecticidal activity.
The co~pounds o~ for~ula I in accordance with the present ~nyentio,n may be ~sed in c~ination with y,ariou~.or,~nic ~hos,phate or carbamate insecticides in order to broaden the insecticidal , . .
i3S~
16.
spectrum and the compounds most suprisingly show syner-gistic activity in such combinations. Examples of insecticides which may be used in combination with the compounds of formula (I~ inolude, for example:
0,0-Diethyl 0-(5-phenyl-3-isoxazolyl)phosphoro-thioate (Isoxathion);
S-Methyl N-(methylcarbamoyloxy)thioacetimidate (Methomyl);
0,0-D;methyl 0-~3-methyl-4-nitrophenyl)thiophos-phate (Fenitrothion);
0,0-Dimethyl 0-[2-chloro-1-(2,4-dichlorophenyl)-vinyl]phosphate (Dimethylvinphos);
: 0,0-Dimethyl S-(~-ethoxycarbonylbenzyl)phosphoro-dithioate (Cidial);
Q,0-Dipropyl 0-4-methylthiophenylphosphate (Propaphos);
1-Naphthyl N-methylcarbamate (Carbaryl);
2-Isopropylphenyl N-methylcarbamate (Isoprocarb);
and ~ 3~ ~
3-Tolyl N~methylcarbamate (MTMC).
The synergistic effect obtained by combining one or more of the compounds of formula ~) with one or more organic phospha~e or carbamate insecticides~
such as those mentioned above, will be observed over a very wide range of ratios between the active ingredients.
In general, however, we prefer to employ from o.l to 10 parts by weight of the organic phosphate or carbamate insecticide per one part by weight of the compound of formula (I)o The compounds of the invention may be employed in various types of preparation as is well-known for other insecticides; for example, they may be in the form of dusts, coarse dusts, micro granules, fine granules, wettable powders, emulsifiable concentrates, aqueous solutions or suspensions, water-soluble powders or oil suspensions. The carrier employed may be natural or synthetic and organic or inorganic; it is mixed with the active ingredient to a sist that ingredient to reach the material to be treated~ and to make it easier to store, transport or handle the active ingredient.
Suitable solid carriers include: inorganic substances, such as clays (examples of which are kaolinite, montmorillonite and attapulgite), talc, mica, pyrophyllite, 18.
pumice, vermiculite, gypsum, calcium carbonateJ dolo-mite, diatomaceous earth, magnesium carbonate, apatite, zeolite, silicic anhydride and synthetic calcium sillcate;
organic substances derived from vegetables, such as soybean meal, tobacco powder, walnut powder, wheat flour, wood meal, starch and crystalline cellulose; synthetic or natural high molecular weight polymersS such as cumarone resins, petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums9 copal gum and dammar gum; waxes, such as carnauba wax and beeswax; or urea.
Examples of suitable liquid carriers include:
paraffinic or naphthenic hydrocarbons, such as kerosine, mineral oil, spindle oil and white oil; aromatic hydro-carbons, such as benzene, toluene, xylene, ethylbenzene,.
cumene and methylnaphthalene; chlorinated hydrocarbons, such as carbon tetrachloride, chloroform, trichloro-ethylene, chlorobenzene and o-chlorotoluene; ethers, such as dioxan and tetrahydrofuran; ketones, such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclo hexanone, acetophenone and isophorone; esters, such as ethyl acetate, pentyl acetate, ethylene glycol acetate~
diethylene glycol acetate, dibutyl maleate and diethyl succinate; alcohols, such as methanol, hexanol, ethylene glycol, diethylene glycol, cyclohexanol and benzyl ~S35~
1~.
alcohol; ether alcohols, such as ethylene glycol mono~
ethyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; other polar organic solvents, such as dimethyl-formamide or dimethyl sulphoxide; and water.
The insecticidal compositions of the present invention may contain surface active agents in order to emulsify, disperse, wet, spread, bind, control disinte-gration of~ improve fluidity of or rust-proof the insecti-cidal composition or to stabilize thè active ingredient;although any of the conventional classes of surface active agent, be they non-ionic, anionic, cationic or amphoteric, may be emp7oyed, we prefer to employ non- .
ionic and/or anionic surface active agents. Examples of suitable non-ionic surface active agents include:
. the polymerization adducts of ethylene oxide with higher alcohols~ sush as lauryl alcohol, stearyl alcohol or oleyl alcohol; the polymerization adducts of ethylene oxide with alkylphenols, such as isooctylphenol or nonyl-phenol; the-polymerization adducts of ethylene oxide with alkylnaphthols, such as butylnaphthol or octylnaphthol;
the polymerization adducts of ethylene oxide with higher fatty acids, such as palmitic acid, stearic acid or oleic acid; the polymerization adducts of ethylene oxide with mono-or di- alkylphosphoric acids, such as stearylphosphoric acid 535i~
or d~laurylphosphoric acid; the polymerization adducts of ethylene oxide with amines, such as dodecylamine;
the polymerization adducts of ethylene oxide with higher fatty acid amides, such as stearamide~ the polymerization adducts of ethylene oxide with higher fatty acid esters of polyhydric alcohols, such as sorbitan, and the fatty acid esters themselves, and the polymerization adducts of ethylene oxide with propylene oxide. Examples of suitable anionic surface active agents include: alkyl sulphate salts, such as sodium lauryl sulphate or oleyl sulphate amine salt; alkyl sulphonate salts, such as sodium dioctyl sulphosuccinate or sodium 2-ethylhexene sulphonate; and aryl sulphonate salts, such as sodium isopropylnaphthalene sulphonate, sodi um methylenebis-naphthalene sulphonate, sodium ligninsulphonate or sodi um dodecylbenzene sulphonate~
: Moreover, the insecticidal compositions of the present invention may be used in combination with high : ~ molecular weight compounds or other auxiliary agents, such as casein, gelatin., albumin, glue, sodium alginate, carboxymethylcellulose, methylcellulose, hydroxyethyl-cellulose or polyYinyl alcohol, in order to improve the properties and/or to increase the biological effect of the composition.
~S 3 21.
The above-mentioned carriers and various auxiliary agents may be used alone or in any desired combination, depending upon the type of preparation, the application and other factors.
The concentration of the active ingredient, the compound or compounds of formula (I~, in the composition may vary over a wide range, although it will normally be ~rom 0.1 to 95~ by weight and more preferably from 1 to 90X by weight of the composition, depending upon the type of preparation.
For example, dusts may conveniently contain from 1 to 25% by weight of the active compound, the remainder being a solid carrier.
Wettable powders may conveniently contain, for example, from 25 to 90X by weight of the active compound, the remainder being a solid carrier and a dispersing and wetting agent, if required, together with a protective :
colloidal agent, a thixotropic agent and an anti-foaming agent.
' Granules may conveniently contain from 1 to 35X by weight of the active compound, a major portion of the remainder being a solid carrier. The active compound is preferably homogeneously admixed with the solid carrier or is adhered to or adsorbed onto the 7~3 22 .
çarrier surface; the diameter of each granule is prefer-ably from 0.2 to 1.5 mm.
Emulsifiable concentrates may conveniently contain, for example, from 5 to 50% hy weight of the active compound and from 5 to 20% by weight of an emulsifying agent, the remainder being a liquid carrier, together with, if required, a corrosion inhibitor.
The invention is further illustrated by the following Examples, of which Examples 1 to 3 illustrate the preparation of certain starting materials for preparing the compounds of the invention~ Examples 4 to 18 illustrate the preparation of compounds of the invention, Examples 19 to 22 illustrate insecticidal compositions containing the compounds of the invention and Examples 23 to 27 lS~ illustrate the use of the compounds and compositions of the invention in the contral of insects.
~ ' ~53~;;Q
23 .
EXAMPLE
4-Chloro-5-chloromethyl-3-hy(lroxyisoxazole To a solution of 8.01 9 of 5-chloromethyl-3-hydroxyisoxazole in 50 ml of benzene were added 10 9 of sulphuryl chloride, and then the mixture was refluxed for 10 hours. At the end of this time9 the solvent and the excess sulphuryl chloride were distilled off from the reaction mixture, and the residue was dissolved in S0 ml of diethyl ether and washed five times, each time with 20 ml of water. The washed diethyl ether solution was dried over anhydrous sodium sulphate, the solvent was removed by distillation, and the residue was extracted three times, each time with 30 ml of hot hexane. The hexane was distilled off from the extract and the residue was recrystalli2ed from carbon tetra-chloride, to give 4-chloro-5-chloromethyl-3-hydroxyisoxa zole in the form of colourless crystals melting at 116 - 118C.
~:
4~Bromo-5-chloromethyl-3-hydrox~i_soxazole To a solution of 1.33 9 of 5-chloromethyl~3-hydroxy-isoxazole in 2 ml of dimethylformamide were added 2.0 9 of ~-bromosuccinimide, and then the mixture was heated at 61C for 1.5 hours. The reaction mixture was then - 25 poured into 100 ml of ice-water and extracted with diethyl 24~
ether, after which the ethereal extract was dried over anhydrous sodium sulphate. The solvent was dist~11ed off, leaving crystals, which were recrystallized from a mixture of diisopropyl ether and hexane, giving 4-bromo-5-chloromethyl-3-hydroxyisoxazole, in the form of white crystals melting at 136.5 - 138C (with decomposition)O
Following the same method, 5-chloromethyl-3-hydroxy-4-iodoisoxazole, melting at 147 - 150C (with decomposition), was also prepared.
5-Chloromethyl-3-dimethylcarbamoyloxyisoxazole To a solution of 2.0 9 of 5-chloromethyl-3-hydroxy-isoxazole in 60 ml of benzene were added 1.7 9 of dimethyl-carbamoyl chloride and 108 9 of triethylenediamine (as acid-binding agent), and the mixture was stirred for 1 hour at ambient temperature. The reaction mixture was then washed twice, each time with 20 ml of water, after which the benzene solution was dried over anhydrous sodium sulphateu The solvent was then distilled off and the remaining oil was purified by column chromatography through silica gel eluted w;th a 10 : 1 by volume mixture of hexane and acetone, to give 5-chloromethyl-3-dimethyl-carbamoyloxyisoxazole in the form of a faintly yellow oil n24 5 = 1 4977 Following the same procedure as described above, 25.
the following compounds were also prepared:
5-Chloromethyl-4-chloro-3-dimethylcarbamoyloxy-isoxazole, n23 = 1.5024;
4-Bromo-5-chloromethyl-3-dimethylcarbamoyloxy-isoxazole, nD5 = 1.5166;
5-Chloromethyl-3-dimethylcarbamoyloxy-4-iodo-isoxazole, melting at 69 - 71~C;
5-Bromomethyl-3-dimethylcarbamoyloxyisoxazole, n23-5 = 1.5062;
.
5-Bromomethyl-4-chloro-3-dimethylcarbamoyloxy-: isoxazole, n22 = 1.5179;
and 4-Bromo-5-bromomethyl-3-dimethylcarbamoyloxy-i~soxazole, melting at 153 - 154C.
' 3-Dimethylcarbamoyloxy-5-methylthiomethylisoxazole To 6 9 of a 15% w/v aqueous solution of sodium methanethiolate, diluted with 20 ml of ethanol, was added, with stirring at room temperature, a solution ~ 6.
of 3.07 9 of 5-chloromëthyl 3-dimethylcarbamoyloxyisoxazole in 5 ml of ethanol; stlrring was continued for a further 30 minutes at room temperature.
The ethanol was then distilled from the reaction S mixture and 20 ml of water were added to the residue.
The mixture was extracted with 40 ml of methylene chloride, and the extract was dried over anhydrous sodium sulphate.
The solvent was distilled off, leaving a brown oil, which was caused to crystalli~e by the addition of diiso-propyl ether. The crystals were then recrystallizedfrom dii sopropyl ether, giving 2.62 9 (yield 80.9%) of 3-dimethylcarbamoyloxy-5-methylthiomethylisoxazole, in the form of colourless crystals melting at 40-41C.
EXAMPLES 5 to 11 .
Following the procedures described in Example 4, the following compounds were prepared:
3-Dimethylcarbamoyloxy-5-ethylthiomethylisoxazole, melting at 49 - 50C;
3-Dimethylcarbamoyloxy-5-propylthiomethylisoxazole, ~0 n23 = 1.5078;
D
3-Dimethylcarbamoyloxy-5-isopropylthiomethyl-isoxazole, nD3 = 1.5077;
4-Chloro-3-dimethylcarbamoyloxy-5-methylthiomethyl-isoxazole, nD1 = 1.5221;
4-Chloro-3-dimethylcarbamoyloxy-5-ethylthiomethyl-isoxazole. nD = 1.5162;
4-Bromo-3-dimethylcarbamoyloxy-5-methylthiomethyl-isoxazole, nD4-5 = 1 5352;
3-Dimethylcarbamoyloxy-4-iodo-5-methylthiomethyl isoxazole, n21 = 1.5563.
The procedure described in Example 4 W2S repeated, except that sodium methoxide was used in place of the sodiu~ methanethiolate, to give 3-dimethylcarbamoyloxy-5-methoxymethylisoxazole, n2455 = 1.4720.
:::
;; 15 3-Di~ethylcarbamoyloxy-5-meth~lsulPhin~_methylisoxazole A solution of 757 mg of 3-dimethylcarbamoyloxy-5-methylthiomethylisoxazole In 5 ml of methylene chloride was 3dded dropwise over a period of 30 m;nutes, with stirring~ to an ice-cooled solution of 711 mg of m-chlnro-perbenzoic acid in 15 ml of methylene chloride. The .
. ~ ~7~
2~.
mixture was ~hen stirred for a further 30 minutes, after which it was filtered and the preeipitate was washed with 2 ml of methylene chloride~ The filtrate and the washings were combined, and then the solvent was removed by distillation~ leaving a colourless, crystalline residue, which was recrystallized from diethyl ether, to give 700 mg (yield 86.1X) of 3-dimethylcarbamoyloxy-5-methylsulphinylmethylisoxazole, in the form of colourless needles melting at 84-85C.
EXAMPLES 14 and 15 The procedure described in Example 4 was repeated, to prepare the following compounds:
3-Dimethylcarbamoyloxy;5-ethylsulphinylmethyl-isoxazole, melting at 85-86C;
4-Chloro-3-dimethylcarbamoyloxy-5-methylsulphinyl-methylisoxazole, melting at 7g-81C.
.
:: EXAMPLES 16 - 18 The procedure described in Example 4 was repeated, except that the m-chloroperbenzoic acid was used in an amount of 2 moles per mole of starting isoxazole compound, to prepare the following compounds:
29 .
3-Dimethylcarbamoyloxy-5-methylsulphonylmethyl-isoxazole, melting at 145 146C, 3-Dimethylcarbamoyloxy-5-ethylsulphonylmethyl-isoxazole, melting at 106 - 107C;
4-Chloro-3-dimethylcarbamoyloxy-5-methylsulphonyl-methylisoxazole, melting at 104 - 105C.
Dust 5 parts by weight of Compound No. 1, 50 parts by weight of talc and 45 parts by weight of kaolin were thoroughly blended to give a dust.
: Wettable powder : 50 parts by weight of Compound No. 2, 29 parts ~by wei~ght of c~lay, 10 parts by weight of diatomaceous earth, 5 parts by weight of white carbon, 3 parts by weight of sodlum ligninsulphonate, 2 parts by weight of Newcol 1106 ("Newcol" is a trade mark) and ~ part by weight of polyvinyl alcohol were thoroughly blended : 20 in a mixer and then pulverized three times with a hammer mill to give a wettable powder.
:
~ 7~;35 30 .
Granules 70 parts by weight of Compound No. 1 were finely pulverized, mixed with 30 parts by weight of clay and then blended in a mixer to make a premix. 10 parts by weight of the premix, 60 parts by weight of rlay and 30 parts by weight of bentonite were thoroughly blended in a mixer and then a small amount of water was added to the mixture. The mixture was then compounded in a kneader, extruded through a screen whose apertures were of diameter 0.8 mm and then dried at 50C in a forced air oven. The dried compound was granulated with a sifter to give granules.
Emulsifiable concentrate ~ . _ 20 parts by weight of isoxathion, 5 parts by weight of Compound No. 1, 60 parts by weight of xylene and 15 parts by weight of Paracol PS ("Paracol" is a trade mark) were uniformly blended to give a emulsifiable concentrate.
S35~
Tox1city Test Each of the compounds listed in Table 1 was administered in the form of a suspension, ~o.which 0.5 w/v gum tragacanth had been added, to a group of 5 week old ddY-SLC series mice. Each test group consisted of 10 male and 10 female mice. The LD50 value was calculated, by the method of Litchfield and Wilcoxon [J. Pharmac. Exp. Ther. 96, 99 (1949)], from ~the mortality rate after 7 days. The results are shown in Table 1 .
Table Compound No. LD50 (mg~kg) . 1 . male 110.2 . . female 109.1 : .
: ~ . 2 male 124.7 . female 103.5 3-Dimethylcarbamoyloxy-5- male/female 31.2 methylisoxazole (Con~rol) .
32.
Similar tests were conducted with each of Compounds No. 3 - 15 and in each case9 the LD50 value was greater than lO0 mg/kg~ These results demonstrate the low toxicity of the compounds of the invention to warm-blooded animals.
Control_of qreen peach aphid ~ontact activity A wettable powder was prepared by homogeneously mixing and pulverizing three times in a hammer mill 10 parts by weight of one of the test compounds ind;cated in Tables 2 and 3, 4 parts by weight of sodium dodecyl-benzene sulphonate, 2 parts by weight of polyvinyl alcohol and 84 parts by weight of clay. The wettable powder thus prepared was then diluted with water to the concentration indicated in Table 1, and then 0.01% w/v of Gramin (a spreader) was added.
The resulting diluted solution was then sprayed onto the lea~es of a cabbage bearing green peach aphids (Myzus persicae) in an amount of 10 ml per leaf. The leaf stalk of each leaf was then placed in a 30 ml bottle containing water and the mouth of the bottle was plugged with cotton wool. The bottles were then left in a ~:~'7~3~i~
33 .
room ~aintained at 25C. After 72 hours, the percentage mortality of the aphids was assessed and the results are shown in Tables 7 and 3.
Systemic activit.v Test suspensions were prepared as described above and then diluted to the concentrations indicated in Tables 2 and 3. The suspensions were then poured into 30 ml bottles. Leaves of the Chinese mustard "Komatsuna" bearing green peach aphids were then placed in the bottles and the mouths of the bottles were plugged with cotton wool. The bottles were placed in a room maintained at 25C for 72 hours, after which the percentage mortality of the aphids was assessed. The results are shown in Tables 2 and 3.
.
3~.
Table 2 Percentage mortality of green peach aphid.
Compound No. Contact Systemic . 50 ppm 6.. 25 ppm :
- 2 . 100 100 : 3 86 100 . ~1 96 . 5 86 100
8 80 85 ', 9 100 100 ~ ,10 97 100 ~ 1l loo lao 15 . 84 100 :: _ :
3-Dimethylcarbamoyloxy-5- 84 89 methylisoxazole ~Control) . . .
~ 3 35.
Table 3 . ~ . .
. . Percentage mort~lity .. . . of -green peach aphid Compound No. Contact Systemic . . 12.5 ppm 1.56 ppm , _ _ . . 1 ..83 10~
. 9 , go 1~0 l . 13 g9 100 ~ _ - . - . .
3-Dimethylcarbamoyloxy-5 -methylisoxazole (Control~ ~34 74 ._ `
~10 ~ EXAMPLE 25 ActiYity against the green rice leafhopper and the brown planthopper ~ ~ .
~ A lU~ dust was prepared by homogeneously mixing :~ : and pulverizing twice wi~h a pulverizer 2 parts by weight 15~ of each in turn of the test compounds indicated in Table 4 and 98 parts by weight sf clay. The dusts were then ; sprayed onto rice seedlings planted in plastic pots and covered~with a plastic cylinder, in amounts sufficient to provide 10 mg of the 10~ dust per pot (corresponding to 1.4 kg of dust per 10 ares)~ 10-:15 of the final instar larvae of the green rice leafhopper (Naphote$tix cincticeps) or of the brown planthopper (Nilaparvata lugens) of strains known to be resistant 36 .
both to conventional organic phosphorus and carbamate insecticides were released into each pot. After main-tal ni ng the pots at 25C for 72 hours, the percentage mortal ~ty of the 1 arvae was assessed. Each test was carried out twice and the results averaged. The results are shown i n Tabl e 4.
Table 4 :
Percentage mortality Compound No. Green rice Brown : leafhopper planthopper . .
. 1 - 65 100 ; 2 67 95 . 3 68 68
3-Dimethylcarbamoyloxy-5- 84 89 methylisoxazole ~Control) . . .
~ 3 35.
Table 3 . ~ . .
. . Percentage mort~lity .. . . of -green peach aphid Compound No. Contact Systemic . . 12.5 ppm 1.56 ppm , _ _ . . 1 ..83 10~
. 9 , go 1~0 l . 13 g9 100 ~ _ - . - . .
3-Dimethylcarbamoyloxy-5 -methylisoxazole (Control~ ~34 74 ._ `
~10 ~ EXAMPLE 25 ActiYity against the green rice leafhopper and the brown planthopper ~ ~ .
~ A lU~ dust was prepared by homogeneously mixing :~ : and pulverizing twice wi~h a pulverizer 2 parts by weight 15~ of each in turn of the test compounds indicated in Table 4 and 98 parts by weight sf clay. The dusts were then ; sprayed onto rice seedlings planted in plastic pots and covered~with a plastic cylinder, in amounts sufficient to provide 10 mg of the 10~ dust per pot (corresponding to 1.4 kg of dust per 10 ares)~ 10-:15 of the final instar larvae of the green rice leafhopper (Naphote$tix cincticeps) or of the brown planthopper (Nilaparvata lugens) of strains known to be resistant 36 .
both to conventional organic phosphorus and carbamate insecticides were released into each pot. After main-tal ni ng the pots at 25C for 72 hours, the percentage mortal ~ty of the 1 arvae was assessed. Each test was carried out twice and the results averaged. The results are shown i n Tabl e 4.
Table 4 :
Percentage mortality Compound No. Green rice Brown : leafhopper planthopper . .
. 1 - 65 100 ; 2 67 95 . 3 68 68
9 - 100 3-Dimethylcarbamoyloxy-5- 9 22 .. ........... ~ ...... ~.... .
methylisoxazole (Gontrol) ~53 37 .
EXAMPLE ?6 Activity a~ainst the brown planthopper ~mixed formulation) Soll and water were p1aced into plastic pots having inside diameters and heights each of about 10 cm to prepare th~ pots for submerged cultivation, with water to a depth of about 2 cm. Rice seedlings were then planted in the pots and maintained in a greenhouse until they had grown to a height of about 15 cm.
. Dusts were prepared, each containing 0~1% w/w of Compound No. 1 or of the known organic phosphate or carbamate insectic;des listed in Table 5, and these were homogeneously applied, in the amounts specified in the Table, to each pot. 10 - 15 of the final instar larvae of the brown planthopper were then released onto each pot. The pots were then covered and maintained at 25C for 72 hours, after which the percentage mortality of the larvae was assessed. The results are shown in Table 5.
.
The experiments were conducted using the known organic phosphate and carbamate insecticides either alon~ or together with Compound No. 1 (50 mg). The percentage mortality achieved using Compound No~ 1 alone : in an amount of 50 mg was also assessed and found to be OS. The expected percentage mortality of the combination of C~mpound No. 1 with the known organic phosphate and -38 .
~arbamate insecticides was c21culated by the method of C.I. Bliss [Ann. Appl. Biol. 26" 585 (1939)] and i s shown i n p~rentheses i n the Tabl e.
Tabl e 5 Speciës and Amount of Compound 1 0.1~ dust organic phosphate or carbamate insecticide 0 mg 50 mg Dimethylvinphos o.i% dust . _. .._... . (14.7) 100 mg 14.7 54.1 MEP 0.1% dust (37.1 . 100 mg . 37.1 75.8 _ NAC 0.1~ dust (29.2) .
50 mg 29.2 65.4 MIPC 0.1 ~ dust (25.0) : ~ 50 mg 25.Q sa.3 MTMC 0.1% dust ~20.B) 50 mg 20.8 77.8 .
7~3S( i Activity against green peach aphids (mixed formulation) Emulsffiable concentrates containing a total of 25X by weight of active ingredient or ingredients were prepared as described in Example 22 and diluted with water to the concentrations given in the following Table 6. Each emulsion contained as act~ve ingredient Compound No. 1, Compound No. 9 or the known insecticide isoxathion alone or contained a mixture of isoxathion and Compound No. 1 or No. 9. The diluted emulsions were sprayed, in an amount of 10 ml per leaf, onto the leaYes of the Chinese mustard "Komatsuna" bearing green peach aphids of a strain known to be resistant to organic phosphate insecticides. The leaf stalks of the leaves 1~ were placed into 30 ml bottles and the mouths of the bottles were pluqged with cotton wool. After ma;ntaining the leaves at 25C for 7~ hours, the percentage mortality was assessed and the results are shown in Table 6.
: The expected percen,tage mortalities in the case of the ~ 20 mixed formulations are shown in parentheses in the Table.
, ~535~
Tabl e 6 . . . . __ . __ Concentration (ppm) .of active ingredient Percentage _ ._ ._ _ . .
Compound 1 Compound 9 Isoxathion mortality .. .. __ . , ._ .. _ _ 0 . 0 25 0 0 0 25.8 0 0 59.8 ' 0 - 2.5 0 20.1 : 0 ~ 5 0 38.4 0 25 98.9(25.8) 0 S0100 (61.6 0 2.5 12.5gs,~(~2U.l~
_ 5 25100 (~.4) __ : ~
~ ~ ;
:. :
..
.
..~ ., ~753 41 .
The results of the experiments carried out in Examples 26 and 27 illustrate the s~gnificant and unexpected synergy achi eved when the compounds of the invention are used in combination with known organic phosphate and carbamate insecticides.
methylisoxazole (Gontrol) ~53 37 .
EXAMPLE ?6 Activity a~ainst the brown planthopper ~mixed formulation) Soll and water were p1aced into plastic pots having inside diameters and heights each of about 10 cm to prepare th~ pots for submerged cultivation, with water to a depth of about 2 cm. Rice seedlings were then planted in the pots and maintained in a greenhouse until they had grown to a height of about 15 cm.
. Dusts were prepared, each containing 0~1% w/w of Compound No. 1 or of the known organic phosphate or carbamate insectic;des listed in Table 5, and these were homogeneously applied, in the amounts specified in the Table, to each pot. 10 - 15 of the final instar larvae of the brown planthopper were then released onto each pot. The pots were then covered and maintained at 25C for 72 hours, after which the percentage mortality of the larvae was assessed. The results are shown in Table 5.
.
The experiments were conducted using the known organic phosphate and carbamate insecticides either alon~ or together with Compound No. 1 (50 mg). The percentage mortality achieved using Compound No~ 1 alone : in an amount of 50 mg was also assessed and found to be OS. The expected percentage mortality of the combination of C~mpound No. 1 with the known organic phosphate and -38 .
~arbamate insecticides was c21culated by the method of C.I. Bliss [Ann. Appl. Biol. 26" 585 (1939)] and i s shown i n p~rentheses i n the Tabl e.
Tabl e 5 Speciës and Amount of Compound 1 0.1~ dust organic phosphate or carbamate insecticide 0 mg 50 mg Dimethylvinphos o.i% dust . _. .._... . (14.7) 100 mg 14.7 54.1 MEP 0.1% dust (37.1 . 100 mg . 37.1 75.8 _ NAC 0.1~ dust (29.2) .
50 mg 29.2 65.4 MIPC 0.1 ~ dust (25.0) : ~ 50 mg 25.Q sa.3 MTMC 0.1% dust ~20.B) 50 mg 20.8 77.8 .
7~3S( i Activity against green peach aphids (mixed formulation) Emulsffiable concentrates containing a total of 25X by weight of active ingredient or ingredients were prepared as described in Example 22 and diluted with water to the concentrations given in the following Table 6. Each emulsion contained as act~ve ingredient Compound No. 1, Compound No. 9 or the known insecticide isoxathion alone or contained a mixture of isoxathion and Compound No. 1 or No. 9. The diluted emulsions were sprayed, in an amount of 10 ml per leaf, onto the leaYes of the Chinese mustard "Komatsuna" bearing green peach aphids of a strain known to be resistant to organic phosphate insecticides. The leaf stalks of the leaves 1~ were placed into 30 ml bottles and the mouths of the bottles were pluqged with cotton wool. After ma;ntaining the leaves at 25C for 7~ hours, the percentage mortality was assessed and the results are shown in Table 6.
: The expected percen,tage mortalities in the case of the ~ 20 mixed formulations are shown in parentheses in the Table.
, ~535~
Tabl e 6 . . . . __ . __ Concentration (ppm) .of active ingredient Percentage _ ._ ._ _ . .
Compound 1 Compound 9 Isoxathion mortality .. .. __ . , ._ .. _ _ 0 . 0 25 0 0 0 25.8 0 0 59.8 ' 0 - 2.5 0 20.1 : 0 ~ 5 0 38.4 0 25 98.9(25.8) 0 S0100 (61.6 0 2.5 12.5gs,~(~2U.l~
_ 5 25100 (~.4) __ : ~
~ ~ ;
:. :
..
.
..~ ., ~753 41 .
The results of the experiments carried out in Examples 26 and 27 illustrate the s~gnificant and unexpected synergy achi eved when the compounds of the invention are used in combination with known organic phosphate and carbamate insecticides.
Claims (8)
1. An insecticidal composition comprising at least one insecticide compound of formula (I):
(I) wherein: R1 represents a hydrogen atom or a halogen atom;
R2 represents a C1-C6 alkyl group; and A represents an oxygen atom, a sulphur atom, a sulphinyl group or a sulphonyl group;
an organic phosphate or carbamate insecticide;and an insecticide carrier or diluent.
(I) wherein: R1 represents a hydrogen atom or a halogen atom;
R2 represents a C1-C6 alkyl group; and A represents an oxygen atom, a sulphur atom, a sulphinyl group or a sulphonyl group;
an organic phosphate or carbamate insecticide;and an insecticide carrier or diluent.
2. A composition as claimed in claim 1, wherein R1 represents a hydrogen, chlorine or bromine atom.
3. A composition as claimed in claim 1, wherein R2 represents a methyl or ethyl group.
4. A composition as claimed in claim 1, wherein A represents a sulphur atom.
5. A composition as claimed in claim 1, wherein:
R1 represents a hydrogen atom; R2 represents a methyl or ethyl group; and A represents a sulphur atom.
R1 represents a hydrogen atom; R2 represents a methyl or ethyl group; and A represents a sulphur atom.
6. A composition as claimed in claim 1, wherein said insecticide is selected from the group consisting of:
3-Dimethylcarbamoyloxy-5-methylthiomethylisoxazole; 3-dimethylcarbamoyloxy-5-ethylthiomethylisoxazole; 4-chloro-3-dimethylcarbamoyloxy-5-methylthiomethylisoxazole and 4-bromo-3-dimethylcarbamoyloxy-5-methylthiomethylisoxazole.
42 .
3-Dimethylcarbamoyloxy-5-methylthiomethylisoxazole; 3-dimethylcarbamoyloxy-5-ethylthiomethylisoxazole; 4-chloro-3-dimethylcarbamoyloxy-5-methylthiomethylisoxazole and 4-bromo-3-dimethylcarbamoyloxy-5-methylthiomethylisoxazole.
42 .
7. A composition as claimed in claim 6, wherein said organic phosphorus or carbamate insecticide is selected from the group consisting of 0,0-diethyl 0-(5-phenyl-3-isoxazolyl)phosphorothioate; S-methyl N-(methylcarbamoyloxy) thioacetimidate; 0,0-dimethyl 0-(3-methyl-4-nitrophenyl) thiophosphate; 0,0-dimethyl 0-[2-chloro-1-(2,4-dichlorophenyl)-vinyl]phosphate; 0,0-dimethyl S-(.alpha.-ethoxycarbonylbenzyl) phosphorodithioate; 0,0-dipropyl 0-4-methylthiophenylphosphate;
1-naphthyl N-methylcarbamate; 2-isopropylphenyl N-methylcar-bamate; and 3-tolyl N-methylcarbamate.
1-naphthyl N-methylcarbamate; 2-isopropylphenyl N-methylcar-bamate; and 3-tolyl N-methylcarbamate.
8. A composition as claimed in claim 1, wherein said insecticide comprises a mixture or one or more compounds selected from: 3-dimethylcarbamoyloxy-5-methylthiomethylis-oxazole; 3-dimethylcarbamoyloxy-5-ethylthiomethylisoxazole;
4-chloro-3-dimethylcarbamoyloxy-5-methylthiomethylisoxazole and 4-bromo-3-dimethylcarbamoyloxy-5-methylthiomethylisoxazole, together with one or more compounds selected from: 0,0-diethyl 0-(5-phenyl-3-isoxazolyl)phosphorothioate; S-methyl N-(methylcarbamoyloxy)thioacetimidate; 0,0-dimethyl 0-(3-methyl-4-nitrophenyl)thiophosphate; 0,0-dimethyl 0-[2-chloro-1-(2,4-dichlorophenyl)-vinyl]phosphate; 0,0-dimethyl S-(.alpha.-ethoxycarbonylbenzyl)phosphorodithioate; 0,0-dipropyl 0-4-methylthiophenylphosphate; 1-naphthyl N-methylcarbamate;
2-isopropylphenyl N-methylcarbamate; and 3-tolyl N-methyl-carbamate.
4-chloro-3-dimethylcarbamoyloxy-5-methylthiomethylisoxazole and 4-bromo-3-dimethylcarbamoyloxy-5-methylthiomethylisoxazole, together with one or more compounds selected from: 0,0-diethyl 0-(5-phenyl-3-isoxazolyl)phosphorothioate; S-methyl N-(methylcarbamoyloxy)thioacetimidate; 0,0-dimethyl 0-(3-methyl-4-nitrophenyl)thiophosphate; 0,0-dimethyl 0-[2-chloro-1-(2,4-dichlorophenyl)-vinyl]phosphate; 0,0-dimethyl S-(.alpha.-ethoxycarbonylbenzyl)phosphorodithioate; 0,0-dipropyl 0-4-methylthiophenylphosphate; 1-naphthyl N-methylcarbamate;
2-isopropylphenyl N-methylcarbamate; and 3-tolyl N-methyl-carbamate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000433518A CA1175350A (en) | 1980-11-11 | 1983-07-28 | Carbamoyloxyisoxazole derivatives, their preparation and insecticidal compositions containing them |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55158550A JPS5793968A (en) | 1980-11-11 | 1980-11-11 | Carbamic acid ester and insecticide containing the same |
| JP158550/80 | 1980-11-11 | ||
| CA000389795A CA1160236A (en) | 1980-11-11 | 1981-11-10 | Carbamoyloxyisoxazole derivatives, their preparation and insecticidal compositions containing them |
| CA000433518A CA1175350A (en) | 1980-11-11 | 1983-07-28 | Carbamoyloxyisoxazole derivatives, their preparation and insecticidal compositions containing them |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000389795A Division CA1160236A (en) | 1980-11-11 | 1981-11-10 | Carbamoyloxyisoxazole derivatives, their preparation and insecticidal compositions containing them |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1175350A true CA1175350A (en) | 1984-10-02 |
Family
ID=27167168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000433518A Expired CA1175350A (en) | 1980-11-11 | 1983-07-28 | Carbamoyloxyisoxazole derivatives, their preparation and insecticidal compositions containing them |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1175350A (en) |
-
1983
- 1983-07-28 CA CA000433518A patent/CA1175350A/en not_active Expired
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