WO2007128409A1 - Insecticidal despyrrole analogs of lisuride and lysergamides - Google Patents

Abstract

Certain novel despyrrole analogs of lisuride and lysergamides have unexpected insecticidal activity. These compounds are represented by formula (I): where R and R2 are fully described herein. The compounds being particularly useful in compositions comprising an insecticidally effective amount of at least one compound of formula (I), and an insecticidally compatible carrier are also disclosed; along with methods of controlling insects comprising applying said compositions to a locus where insects are present or are expected to be present.

Description

INSECTICIDAL DESPYRROLE ANALOGS OF LISTIRIDE AND LYSERGAMIDES

FIELD OF THE INVENTION

The present invention generally relates to pesticidal compounds and their use in controlling insects and acarids. In particular, it pertains to compositions of pesticidal despyrrole analogs of lisuride and lysergamides and related derivatives and agriculturally acceptable salts thereof, and methods for their use in controlling insects and acarids.

BACKGROUND OF THE INVENTION

It is well known that insects in general can cause significant damage, not only to crops grown in agriculture, but also, for example, to structures and turf where the damage is caused by soil-borne insects, such as termites and white grubs. Such damage may result in the loss of millions of dollars of value associated with a given crop, turf or structures. Thus, there is a continuing demand for new insecticides, and for new acaricides that are safer, more effective, and less costly. Insecticides and acaricides are useful for controlling insects and acarids which may otherwise cause significant damage to crops such as wheat, corn, soybeans, potatoes, and cotton to name a few. For crop protection, insecticides and acaricides are desired which can control the insects and acarids without damaging the crops, and which have no deleterious effects to mammals and other living organisms.

Biogenic amines are important molecules in the central nervous systems of invertebrates as well as vertebrates. In insects biogenic amines such as octopamine and serotonin have effects on numerous systems such as cardiovascular activity, motor control, and feeding behaviour. Functions such as these are vital to insect survival, so it is expected that molecules that interact with these biogenic amine receptors could be useful as insecticides and indeed, some octopamine agonists have been found to be insecticidal.

SUMMARY OF THE INVENTION

In accordance with the present invention, it has now been found that certain novel despyrrole analogs of lisuride and lysergamides and related derivatives are surprisingly active in the control of insects and acarids when used in the insecticidal and acaricidal compositions and methods of this invention. The compounds of formula I are represented by the following general formula I:

wherein R is selected from C(=O)NHC₂H₅ and NH(X=O)R¹, where R¹ is selected from N(C₂Hs)₂, NHC₂H₅, C₂H₅ and n-C₃H₇; and R² is selected from CH₃, CH₂CH=CH₂, (CH₂)₂OCH₃ and CH₂CO₂CH₃. The present invention is also directed to methods of controlling insects, where control is desired, which comprise applying an insecticidally effective amount of the above composition to the locus of crops, or other areas where insects are present or are expected to be present.

DETAILED DESCRIPTION OF THE INVENTION

One aspect of the present invention relates to certain new and useful compounds, namely novel despyrrole analogs of lisuride and lysergamides and related derivatives as depicted in general formula I:

wherein R is selected from C(=O)NHC₂H₅ and NHC(O)R¹, where R¹ is selected from N(C₂H₅)₂, NHC₂H₅, C₂H₅ and n-C₃H₇; and R² is selected from CH₃, CH₂CH=CH₂, (CH₂)₂OCH₃ and CH₂CO₂CH₃.

In addition, in certain cases the compounds of the present invention may possess asymmetric centers, which can give rise to optical enantiomorphs and diastereomers. The compounds may exist in two or more forms, i.e., polymorphs, which are significantly different in physical and chemical properties. The compounds of the present invention may also exist as tautomers, in which migration of a hydrogen atom within the molecule results in two or more structures, which are in equilibrium. The compounds of the present invention may also possess acidic or basic moieties, which may allow for the formation of agriculturally acceptable salts or agriculturally acceptable metal complexes. This invention includes the use of such enantiomorphs, polymorphs, tautomers, salts and metal complexes. Agriculturally acceptable salts and metal complexes include, without limitation, for example, ammonium salts, the salts of organic and inorganic acids, such as hydrochloric acid, sulfonic acid, ethanesulfonic acid, trifluoroacetic acid, methylbenzenesulfonic acid, phosphoric acid, gluconic acid, pamoic acid, and other acid salts, and the alkali metal and alkaline earth metal complexes with, for example, sodium, potassium, lithium, magnesium, calcium, and other metals.

Another aspect of the present invention relates to compositions containing an insecticidally effective amount of at least one compound of formula I with at least one insecticidally compatible carrier therefor.

Another aspect of the present invention relates to compositions containing an insecticidally effective amount of at least one compound of formula I, and an effective amount of at least one second compound, with at least one insecticidally compatible carrier therefor.

Another aspect of the present invention relates to methods of controlling insects by applying an insecticidally effective amount of a composition set forth above to a locus of crops such as, without limitation, cereals, cotton, vegetables, and fruits, or other areas where insects are present or are expected to be present.

The present invention also includes the use of the compounds and compositions set forth herein for control of non-agricultural insect species, for example, dry wood termites and subterranean termites; as well as for use as pharmaceutical agents and compositions thereof.

Lisuride (1) was identified as a lead from a program of screening a collection of biogenic amines for activity against cotton aphids. No lisuride analogs were available for follow-up, but a number of amides of lysergic acid (2) were acquired, and some of these compounds also had modest cotton aphid activity. The removal of the pyrrole ring from these compounds ought to improve their physical properties as field-applied insecticides as well as simplify their synthesis, so we determined to prepare despyrrole analogs using tricyclic ketone 3 described by the Bowman group (Bowman, M.A.E.; Bowman, R.E.; Cavies, R. V.; Haran, G.; Harris, PJ.; Smith, H.J.; Steele, R. W.; Walker, N.; Whiting, K. Journal of Enzyme Inhibition and Medicinal Chemistry, 2002, 17(3), 137-154).

Scheme 1. Preparation of Bowman's ketone 3, part 1

I)Na₂S₂O₅, H₂O, 1h

Ph

I)CICO₂Me, NaHCO₃ I )TFAA, CH₂CI₂, rt, 1h

H₂O, 3 ⁰C, 15 h 2)AICI₃, CH₂CI₂, -15 ⁰C, 5h 2)HCI, 90% 3)HCI, ice, 61%

Scheme 2. Modification to preparation of ketone 3, part 1

I)CICO₂Me, NaHCO₃ I)TFAA₁ CH₂CI₂, rt, 2h

H₂O, rt, 1h 2)AICI₃, CH₂CI₂, O ⁰C₁ 1 h 2)HCI, 80% 3)HCI, ice, 81%

The Strecker reaction with glycine to make compound 4 as described by Bowman and shown in Scheme 1 was not reliable in our hands. Substituting methyl glycine and omitting sodium metabisulfite gave us more consistent results in Scheme 2, but with lower yields of 4. Very slow cooling, with efficient stirring, was critical for the precipitation of clean intermediate 4. A slight modification to the Friedel-Crafts acylation procedure increased the yield of 6 by 20%. Scheme 3 shows the completion of the synthesis of 3 from 6 following the Bowman procedure. However, Bowman reports the isolation of a byproduct A, which could be converted into 3 by treatment with acid. We did not observe A, but we did isolate a new byproduct B. Although it should be possible to convert B to 3 using an aldol reaction, we were unable to find any conditions to accomplish this transformation.

Scheme 2. Preparation of ketone 3, part 2

Byproduct A (14%) 3 (55%) Byproduct B (15%)

pTsOH

Lisuride analogs

Tricyclic ketone 3 was reduced to alcohol 7 following Bowman's procedure. A single diastereomer was formed whose NMR showed a singlet for the H-9 vinyl group. It is presumed that the oc-isomer is formed following hydride approach from the less hindered face of the molecule. Alcohol 7 was converted to the azide with diphenylphosphoryl azide. Although this reaction with DBU is generally presumed to proceed stereoselectively with inversion of configuration, in this case both diastereomers were formed in about equal amounts. All attempts to introduce the azide or other nitrogen containing functional groups via the Mitsunobu reaction failed. After reduction of the azide and carbamate functionalities with DIBAL, amine 9a was able to go on to form the target urea 10. Isomer 9b failed to react when subjected to similar conditions, or any other conditions that were used in an attempt to form a urea, isocyanate, or amide. Scheme 4. Transformation of 3 into lisuride analogs

7 vinyl singlet chromatography

8a fast isomer 8b slow isomer vinyl doublet vinyl singlet

9a vinyl singlet 9b vinyl doublet

No reaction

vinyl singlet

Stereochemical analysis

It is probable that the amino group in 9a is in the less hindered β configuration and that steric constraints account for the lack of reactivity for compound 9b. Zikan and Semonsky report that the pyrrole-containing analog of 9b will react with diethylcarbamoyl chloride and triethylamine in refluxing benzene to give the α analog of 10. We did not try these conditions. The NMR spectrum for 10 shows a broad singlet for H-9, indicating that the dihedral angle between H-8 and H-9 is near 90°. This data is consistent with Ninomiya's analysis of the configuration of the despyrrole analogs of lysergic and isolysergic acid. Therefore, we have actually made a despyrrole analog of isolisυride, as lisuride itself is known to exist in the α configuration and to show a doublet for H-9 in its proton NMR spectrum.

β configuration α configuration φ= 90°, J= 0 Hz φ< 90°, J> 0 Hz

Configuration of nitrogen-containing ring

Lysergic acid analogs

One of the goals for this project was to explore other nitrogen substituents. The sequence described above is only suited for making N-methyl compounds, and all of the procedures that we tried for removing methyl or methyl carbamate groups from compounds 3 through 10 resulted in loss of the substituent at C-8 and formation of multiply unsaturated products. We investigated replacing the methyl carbamate in the synthesis of ketone 3 with trichloroethyl carbamate or CBz groups, but these gave unsatisfactory results. Instead of trying to re-engineer the entire process, we switched our focus to making despyrrole analogs of lysergic acid. Now the substituent at C-8 will not be a leaving group, and if desired, it would be possible to convert lysergic acid to the 8- amino lisuride precursor using the Curtius reaction.

The methyl carbamate was removed from 7 using harsh basic hydrolysis, and replaced with a BOC group after first converting the hydroxyl group to chloride. The Bowman group's procedure was used to introduce the cyano group, which could be hydrolyzed to acid 14 with very little loss of the BOC protecting group. We chose to make the ethyl amide from 14, and then removed the BOC group to give 16 as a common intermediate to be reacted with various alkylating agents. Although the yield of the reaction with methyl iodide was rather modest, yields with other alkylating agents such as methoxyethyl bromide were in the 80% range. The NMR spectra of the intermediates in this procedure up to amine 16 showed both vinyl singlet and doublet in various ratios, indicating that both diastereomers were present. The alkylation of 16 to give 17 or other alkylated products only gave materials with a vinyl doublet in their NMR spectra. By Ninomiya's analysis, these amides are in the α configuration and are derivatives of isolysergic acid. The NMR for dimethyl lysergamide shows a vinyl singlet indicating that the natural configuration is β. This unusual stereochemical outcome could be due to hydrogen bonding between the secondary amide and the ring nitrogen. It would be interesting to repeat the sequence using a tertiary amide in order to see if it is then possible to obtain products with the desired β configuration. Scfaeme 5. Transformation of 7 into lysergic acid analogs

17 vinyl doublet

Biological activity

Compounds made by the methods described above were tested in a cotton aphid foliar assay. The goal was to find compounds with an LC₅₀ below 10 ppm, and to minimize lipophilicity and basicity as much as possible. Compound 10 was the most active on cotton aphid, but its physical properties were not optimal. Compounds 22 and 23 were the least basic and least lipophilic compounds, but they were inactive. We found that the analogs were agonists or partial agonists of a cloned cotton aphid serotonin receptor, except for compounds 22 and 23 which were once again inactive. Table 1. Despyrrole isolisuride analogs

CA = cotton aphid, Aphis gossypii

Table 2. Despyrrole isolysergic acid amide analogs

Bowman's ketone 3 is a useful intermediate for the synthesis of despyrrole isolisuride and isolysergamide analogs. It should be possible to modify the procedure described in Scheme 5 so as to make despyrrole lysergamide analogs with the desired β configuration. While the compounds described here do have some activity against cotton aphids, their poor physical properties precluded the synthesis of more analogs or the further optimization of the synthesis procedures. One skilled in the art will, of course, recognize that the formulation and mode of application of a toxicant may affect the activity of the material in a given application. Thus, for agricultural use the present insecticidal compounds may be formulated as a granular of relatively large particle size (for example, 8/16 or 4/8 US Mesh), as water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as aqueous emulsions, as solutions, or as any of other known types of agriculturally-useful formulations, depending on the desired mode of application. It is to be understood that the amounts specified in this specification are intended to be approximate only, as if the word "about" were placed in front of the amounts specified.

These insecticidal compositions may be applied either as water-diluted sprays, or dusts, or granules to the areas in which suppression of insects is desired. These formulations may contain as little as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight of active ingredient.

Dusts are free flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselgur, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful herein is one containing 1.0 part or less of the insecticidal compound and 99.0 parts of talc.

Wettable powders, also useful formulations for insecticides, are in the form of finely divided particles that disperse readily in water or other dispersant. The wettable powder is ultimately applied to the locus where insect control is needed either as a dry dust or as an emulsion in water or other liquid. Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion. For example, a useful wettable powder formulation contains 80.0 parts of the insecticidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Additional wetting agent and/or oil will frequently be added to a tank mix for to facilitate dispersion on the foliage of the plant.

Other useful formulations for insecticidal applications are emulsifiable concentrates (ECs) which are homogeneous liquid compositions dispersible in water or other dispersant, and may consist entirely of the insecticidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isphorone, or other non-volatile organic solvents. For insecticidal application these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the insecticidal composition.

Flowable formulations are similar to ECs, except that the active ingredient is suspended in a liquid carrier, generally water. Flowables, like ECs, may include a small amount of a surfactant, and will typically contain active ingredients in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the composition. For application, flowables may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.

Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. Surface-active agents, when used, normally comprise 1 to 15% by weight of the composition.

Other useful formulations include suspensions of the active ingredient in a relatively nonvolatile solvent such as water, corn oil, kerosene, propylene glycol, or other suitable solvents.

Still other useful formulations for insecticidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the toxicant is carried on relative coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low-boiling dispersant solvent carrier may also be used. Water-soluble or water-dispersible granules are free flowing, non-dusty, and readily water-soluble or water-miscible. In use by the farmer on the field, the granular formulations, emulsifiable concentrates, flowable concentrates, aqueous emulsions, solutions, etc., may be diluted with water to give a concentration of active ingredient in the range of say 0.1% or 0.2% to 1.5% or 2%.

The active insecticidal compounds of this invention may be formulated and/or applied with one or more second compounds. Such combinations may provide certain advantages, such as, without limitation, exhibiting synergistic effects for greater control of insect pests, reducing rates of application of insecticide thereby minimizing any impact to the environment and to worker safety, controlling a broader spectrum of insect pests, safening of crop plants to phytotoxicity, and improving tolerance by non-pest species, such as mammals and fish.

Second compounds include, without limitation, other pesticides, plant growth regulators, fertilizers, soil conditioners, or other agricultural chemicals. In applying an active compound of this invention, whether formulated alone or with other agricultural chemicals, an effective amount and concentration of the active compound is of course employed; the amount may vary in the range of, e.g. about 0.001 to about 3 kg/ha, preferably about 0.03 to about 1 kg/ha. For field use, where there are losses of insecticide, higher application rates (e.g., four times the rates mentioned above) may be employed.

When the active insecticidal compounds of the present invention are used in combination with one or more of second compounds, e.g., with other pesticides such as herbicides, the herbicides include, without limitation, for example: N-(phosphonomethyl)glycine ("glyphosate"); aryloxyalkanoic acids such as (2,4-dichlorophenoxy)acetic acid ("2,4-D"), (4-chloro-2-methyl- phenoxy)acetic acid ("MCPA"), (+/-)-2-(4chloro-2-methylphenoxy)propanoic acid ("MCPP"); ureas such as N,N-dimethyl-N'-[4-(l-methylethyl)phenyl]urea ("isoproturon"); imidazolinones such as 2-[4,5-dihydro-4-methyl-4-(l-methylethyl)-5-oxo-lH-imidazol-2-yl]-3-pyridinecarboxylic acid ("imazapyr"), a reaction product comprising (+/-)-2-[4,5-dihydro-4-methyl-4-(l-methylethyl)- 5-oxo-lH-imidazol-2-yl]-4-methylbenzoic acid and (+/-)2-[4,5-dihydro-4-methyl-4-(l-methyl- ethyl)-5-oxo-lH-imidazol-2-yl]-5-methylbenzoic acid ("imazamethabenz"), (+/-)-2-[4,5-dihydro-4- methyl-4-(l-methylethyl)-5-oxo-lH-imidazol-2-yl]-5-ethyl-3-pyridinecarboxylic acid

("imazethapyr"), and (+/-)-2-[4,5-dihydro-4-methyl-4-(l-methylethyl>5-oxo-lH-imidazol-2-yl]-3- quinolinecarboxylic acid ("imazaquin"); diphenyl ethers such as 5-[2-chloro-4-(trifluoro- methyl)phenoxy]-2-nitrobenzoic acid ("acifluorfen"), methyl 5-(2,4-dichlorophenoxy)-2-nitro- benzoate ("bifenox"), and 5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitro- benzamide ("fomasafen"); hydroxybenzonitriles such as 4-hydroxy-3,5-diiodobenzonitrile ("ioxynil") and 3,5-dibromo-4-hydroxybenzonitrile ("bromoxynil"); sulfonylureas such as 2- [[[[(4chloro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoic acid

("chlorimuron"), 2-chloro-N-[ [(4-methoxy-6-methyl-l,3,5-triazin-2-yl)amino]carbonyl]benzene- sulfonamide (achlorsulfuron"), 2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]- sufonyl]methyl]benzoic acid ("bensulfuron"), 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carb- onyl]amino]sulfonyl]-l-methy-lH-pyrazol-4-carboxylic acid ("pyrazosulfuron"), 3-[[[[(4-methoxy- 6-methyl-l,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylic acid ("thifen- sulfuron"), and 2-(2-chloroethoxy)-N[[(4-methoxy-6-methyl-l,3,5-triazin-2-yl)amino]carbonyl]- benzenesulfonamide ("triasulfuron"); 2-(4-aryloxyphenoxy)alkanoic acids such as (+/-)-2[4-[(6- chloro-2-benzoxazolyl)oxy]phenoxy]propanoic acid (fenoxaprop"), (+/-)-2-[4[[5-(trifluoromethyl)- 2-pyridinyl]oxy]phenoxy]propanoic acid ("fluazifop"), (+/-)-2-[4-(6chloro-2-quinoxalinyl)oxy]- phenoxy]propanoic acid ("quizalofop"), and (+ /-) -2-[(2,4-dichlorophenoxy)phenoxy]propanoic acid ("diclofop"); benzothiadiazinones such as 3-(l-methylethyl)-lH-l,2,3-benzothiadiazin-4(3H)- one-2,2-dioxide ("bentazone"); 2-chloroacetanilides such as N-(butoxymethyl>2-chloro-N-(2,6- diethylphenyl)acetamide ("butachlor"), 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-l- methylethyl)acetamide ("metolachlor"), 2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methyl- phenyl)acetamide ("acetochlor"), and (ΛS)-2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-l- methylethyl)acetamide ("dimethenamide"); arenecarboxylic acids such as 3,6-dichloro-2- methoxybenzoic acid ("dicamba"); pyridyloxyacetic acids such as [(4-amino-3,5-dichloro-6-fluoro- 2-pyridinyl)oxy]acetic acid ("fluroxypyr"), and other herbicides.

When the active insecticidal compounds of the present invention are used in combination with one or more of second compounds, e.g., with other pesticides such as other insecticides, the other insecticides include, for example: organophosphate insecticides, such as chlorpyrifos, diazinon, dimethoate, malathion, parathion-methyl, and terbufos; pyrethroid insecticides, such as fenvalerate, deltamethrin, fenpropathrin, cyfluthrin, flucythrinate, αjJpAα-cypermethrin, biphenthrin, resolved cyhalothrin, etofenprox, esfenvalerate, tralomehtrin, tefluthrin, cyclo- prothrin, betacyfluthrin, and acrinathrin; carbamate insecticides, such as aldecarb, carbaryl, carbofuran, and methomyl; organochlorine insecticides, such as endosulfan, endrin, heptachlor, and lindane; benzoylurea insecticides, such as diflubenuron, triflumuron, teflubenzuron, chlor- fluazuron, flucycloxuron, hexaflumuron, flufenoxuron, and lufenuron; and other insecticides, such as amitraz, clofentezine, fenpyroximate, hexythiazox, spinosad, and imidacloprid.

When the active insecticidal compounds of the present invention are used in combination with one or more of second compounds, e.g., with other pesticides such as fungicides, the fungicides include, for example: benzimidazole fungicides, such as benomyl, carbendazim, thiabendazole, and thiophanate-methyl; 1 ,2,4-triazole fungicides, such as epoxyconazole, cyproconazole, flusilazole, flutriafol, propiconazole, tebuconazole, triadimefon, and triadimenol; substituted anilide fungicides, such as metalaxyl, oxadixyl, procymidone, and vinclozolin; organophosphorus fungicides, such as fosetyl, iprobenfos, pyrazophos, edifenphos, and tolclofos- methyl; morpholine fungicides, such as fenpropimorph, tridemorph, and dodemorph; other systemic fungicides, such as fenarimol, imazalil, prochloraz, tricyclazole, and triforine; dithiocarbamate fungicides, such as mancozeb, maneb, propineb, zineb, and ziram; non-systemic fungicides, such as chlorothalonil, dichlofluanid, dithianon, and iprodione, captan, dinocap, dodine, fiuazinam, gluazatine, PCNB, pencycuron, quintozene, tricylamide, and validamycin; inorganic fungicides, such as copper and sulphur products, and other fungicides. When the active insecticidal compounds of the present invention are used in combination with one or more of second compounds, e.g., with other pesticides such as nematicides, the nematicides include, for example: carbofuran, carbosulfan, turbufos, aldecarb, ethoprop, fenamphos, oxamyl, isazofos, cadusafos, and other nematicides.

When the active insecticidal compounds of the present invention are used in combination with one or more of second compounds, e.g., with other materials such as plant growth regulators, the plant growth regulators include, for example: maleic hydrazide, chlormequat, ethephon, gibberellin, mepiquat, thidiazon, inabenfide, triaphenthenol, paclobutrazol, unaconazol, DCPA, prohexadione, trinexapac-ethyl, and other plant growth regulators.

Soil conditioners are materials which, when added to the soil, promote a variety of benefits for the efficacious growth of plants. Soil conditioners are used to reduce soil compaction, promote and increase effectiveness of drainage, improve soil permeability, promote optimum plant nutrient content in the soil, and promote better pesticide and fertilizer incorporation. When the active insecticidal compounds of the present invention are used in combination with one or more of second compounds, e.g., with other materials such as soil conditioners, the soil conditioners include organic matter, such as humus, which promotes retention of cation plant nutrients in the soil; mixtures of cation nutrients, such as calcium, magnesium, potash, sodium, and hydrogen complexes; or microorganism compositions which promote conditions in the soil favorable to plant growth. Such microorganism compositions include, for example, bacillus, pseudomonas, azotobacter, azospirillum, rhizobium, and soil-borne cyanobacteria.

Fertilizers are plant food supplements, which commonly contain nitrogen, phosphorus, and potassium. When the active insecticidal compounds of the present invention are used in combination with one or more of second compounds, e.g., with other materials such as fertilizers, the fertilizers include nitrogen fertilizers, such as ammonium sulfate, ammonium nitrate, and bone meal; phosphate fertilizers, such as superphosphate, triple superphosphate, ammonium sulfate, and diammonium sulfate; and potassium fertilizers, such as muriate of potash, potassium sulfate, and potassium nitrate, and other fertilizers.

While this invention has been described with an emphasis upon preferred embodiments, it will be understood by those of ordinary skill in the art that variations of the preferred embodiments may be used and that it is intended that the invention may be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications encompassed within the spirit and scope of the invention as defined by the following claims.

Claims

WHAT IS CLAIMED IS:

1. A compound of formula I:

wherein;

R is C(=O)NHC₂H₅ or NHCC=O)R¹, where R¹ is selected from the group consisting of N(C₂Hj)₂, NHC₂H₅, C₂H₅ and n-C₃H₇; and

R² is selected from the group consisting of CH₃, CH₂CH=CH₂, (CH₂)₂OCH₃ and CH₂CO₂CH₃.

2. A composition containing an insecticidally effective amount of a compound of claim 1 in admixture with at least one agriculturally acceptable extender or adjuvant.

3. The insecticidal composition of claim 2, further comprising one or more second compounds.

4. A method of controlling insects, comprising applying an insecticidally effective amount of a composition of claim 2 to a locus where insects are present or are expected to be present.