Pesticidal benzodioxole

The present invention relates to heterocyclic compounds having pesticidal, especially insecticidal and acaricidal, activity.
The Applicants have discovered a novel class of heterocyclic compounds which have both insecticidal and acaricidal activity.
In accordance with the present invention there is provided a compound of the general formula: ##STR3## wherein R.sub.1 and R.sub.2 each independently represents a halogen atom or an alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, alkenoxy, cyano or nitro group; R.sub.3 and R.sub.4 each independently represents a hydrogen atom or an alkyl group; R.sub.5 represents a hydrogen atom, or an alkyl, alkoxy or alkoxycarbonylalkyl group; X and Y each independently represents an oxygen or sulphur atom or a group N--R, in which R is a hydrogen atom or an alkyl group; n is 0-3; r is 0 or 1; m is 0-4; and A or B represents a group of the general formula: ##STR4## wherein R.sub.6 represents a hydrogen or halogen atom, or an alkyl group; and R.sub.7 represents a halogen atom or an alkyl group; the other of A and B being a hydrogen atom or as for R.sub.1 or R.sub.2.
When n is greater than 1, each R.sub.1 may be the same or different, and when m is greater than 1, each R.sub.2 may be the same or different.
Preferably, any alkenoxy group, any alkyl group or any alkyl component in any alkoxy, haloalkyl, haloalkoxy or alkoxycarbonyl group has up to 6 carbon atoms.
It is particularly preferred that either (1) R.sub.2 represents a halogen atom, or an alkyl, haloalkyl, alkoxy, haloalkoxy or alkenoxy group; R.sub.3 and R.sub.4 each represents a hydrogen atom; X and Y each independently represents an oxygen or sulphur atom; n is 0; r is 0 or 1; m is 0-2; A represents a group of the general formula II in which R.sub.6 and R.sub.7 each represents a halogen atom; and B represents a hydrogen or halogen atom or an alkyl, haloalkyl or haloalkoxy group, or (2) R.sub.3, R.sub.4 and R.sub.5 each represents a hydrogen atom; X and Y each represents an oxygen atom; n is 0; r is 1; m is 0; B represents a group of the general formula II in which R.sub.6 and R.sub.7 each represents a halogen atom; and A represents a halogen atom or an alkyl group.
In case (1), preferably R.sub.2 represents a fluorine, chlorine or bromine atom, or a methyl, trifluoromethyl or methoxy group; R.sub.6 and R.sub.7 each represents a fluorine atom; and B represents a hydrogen, fluorine or chlorine atom or a methyl, trifluoromethyl or trifluoromethoxy group.
In case (2), preferably R.sub.6 and R.sub.7 each represents a fluorine atom; and A represents a chlorine or bromine atom, or a methyl group.
In accordance with the present invention there is also provided a process for the preparation of a compound of general formula I which comprises hydrogenating a compound of the general formula: ##STR5## to form a compound of the general formula: ##STR6## which is reacted with a compound of the general formula: ##STR7## to form a compound of the general formula I, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, X, Y, n, r and m have the meanings given above; one of R.sub.8 and R.sub.9 represents a nitro group whilst the other represents a hydrogen or halogen atom or an alkyl, haloalkyl or haloalkoxy group; and one of R.sub.10 and R.sub.11 represents an amino group whilst the other represents a hydrogen or halogen atom or an alkyl, haloalkyl or haloalkoxy group.
The hydrogenation of the compound of general formula III is preferably carried out in the presence of a catalyst. Suitable catalysts are platinum or palladium catalysts, particularly a 5% platinum/charcoal catalyst.
The hydrogenation reaction may be carried out in the presence of a solvent or mixture of solvents. Suitable solvents are preferably ethers such as tetrahydrofuran, alcohols such as methanol and ethanol, and hydrocarbons such as toluene. Furthermore, a suitable base may be added as required. Suitable bases are alkali metal carbonates such as anhydrous potassium carbonate.
The reaction is suitably carried out at a temperature in the range 0.degree.-150.degree. C., preferably ambient temperature, and at a pressure of 60 psi or below.
The reaction between compounds of general formulae IV and V is preferably carried out in the presence of a solvent. Suitable solvents are aromatic solvents such as benzene, toluene, xylene or chlorobenzene, hydrocarbons such as petroleum fractions, chlorinated hydrocarbons such as chloroform, methylene chloride or dichloroethane, and ethers such as diethyl ether, dibutyl ether, dioxan and tetrahydrofuran. Mixtures of solvents are also suitable.
Preferably the reaction is carried out at a temperature in the range 0.degree.-110.degree. C., suitably ambient temperature.
Further purification of the product may be achieved by crystallisation from toluene or ethanol, where necessary.
Some compounds of general formula III are themselves novel and constitute a further aspect of the present invention. They may be prepared by reacting a compound of the general formula: ##STR8## with a compound of the general formula: ##STR9## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, X, Y, n, r and m have the meanings given above; Z represents a group --COR.sub.14 in which R.sub.14 represents a hydrogen atom or an alkyl or alkoxycarbonylalkyl group, or represents a group C(alkoxy).sub.3 ; and R.sub.12 and R.sub.13 each independently represents a hydrogen or halogen atom or an alkyl, haloalkyl, haloalkoxy or nitro group, with the proviso that no more than one of R.sub.12 and R.sub.13 can be a nitro group in any reaction and the proviso that when R.sub.3 and R.sub.4 each represents a hydrogen atom, R.sub.12 represents a nitro group, X represents a sulphur atom, Y represents an oxygen atom, n is 0, r is 1 and m is 0, R.sub.13 cannot be a hydrogen atom, and that when neither of R.sub.12 and R.sub.13 is a nitro group, the compound formed is further reacted with nitric acid.
The reaction between compounds of general formulae VI and VII is preferably carried out in the presence of an acid catalyst, which may be any suitable inorganic or organic acid. Suitable acids include sulphonic acids, for example toluene sulphonic acid, carboxylic acids, for example benzoic acid, and mineral acids, for example hydrochloric acid.
The reaction is suitably carried out at a temperature in the range 50.degree.-200.degree. C., particularly 75.degree.-110.degree. C.
The reaction may also be carried out in the presence of a solvent. Suitable solvents include any organic aprotic solvent such as tetrahydrofuran, benzene, hydrocarbons such as toluene, halogenated hydrocarbons, and ethers. Mixed solvents may also be used, such as, for example, toluene with dimethylsulphoxide.
Furthermore, the reaction is suitably carried out under nitrogen, especially when X and/or Y is a sulphur atom.
In the case of further reaction with nitric acid, the temperature of said further reaction is suitably 15.degree.-20.degree. C.
Compounds of general formula I exhibit pesticidal, particularly insecticidal and/or acaricidal, activity. Accordingly the invention also provides a pesticidal composition comprising a compound of general formula I in association with at least one inert carrier therefor. The invention further provides a method of combating pests at a locus, which comprises applying to the locus a pesticidal compound or composition according to the present invention.
A carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may for example be a plant, seed or soil, or to facilitate storage, transport or handling. A carrier may be a solid or a liquid, including a material which is normally gaseous but which has been compressed to form a liquid, and any of the carriers normally used in formulating pesticidal compositions may be used. Preferably compositions according to the invention contain 0.5 to 95% by weight of active ingredient.
Suitable solid carriers include natural and synthetic clays and silicates, for example natural silicas such as diatomaceous earths; magnesium silicates, for example talcs; magnesium aluminium silicates, for example attapulgites and vermiculites; aluminium silicates, for example kaolinites, montmorillonites and micas; calcium carbonate; calcium sulphate; ammonium sulphate; synthetic hydrated silicon oxides and synthetic calcium or aluminium silicates; elements, for example carbon and sulphur; natural and synthetic resins, for example coumarone resins, polyvinyl chloride, and styrene polymers and copolymers; solid polychlorophenols; bitumen; waxes; and solid fertilisers, for example superphosphates.
Suitable liquid carriers include water; alcohols, for example isopropanol and glycols; ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic or araliphatic hydrocarbons, for example benzene, toluene and xylene; petroleum fractions, for example kerosine and light mineral oils; chlorinated hydrocarbons, for example carbon tetrachloride, perchloroethylene and trichloroethane. Mixtures of different liquids are often suitable.
Agricultural compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amounts of a carrier which is a surface-active agent facilitates this process of dilution. Thus preferably at least one carrier in a composition according to the invention is a surface-active agent. For example the composition may contain at least two carriers, at least one of which is a surface-active agent.
A surface-active agent may be an emulsifying agent, a dispersing agent or a wetting agent; it may be nonionic or ionic. Examples of suitable surface-active agents include the sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohol or alkyl phenols, for example p-octylphenol or p-octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkali or alkaline earth metal salts, preferably sodium salts, of sulphuric or sulphonic acid esters containing at least 10 carbon atoms in the molecule, for example sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alkylaryl sulphonates such as dodecylbenzene sulphonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.
The compositions of the invention may for example be formulated as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders usually contain 25, 50 or 75% w of active ingredient and usually contain in addition to solid inert carrier, 3-10% w of a dispersing agent and, where necessary, 0-10% w of stabiliser(s) and/or other additives such as penetrants or stickers. Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and are diluted in the field with further solid carrier to give a composition usually containing 1/2-10% w of active ingredient. Granules are usually prepared to have a size between 10 and 100 BS mesh (1.676-0.152 mm), and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 1/2-75% w active ingredient and 0-10% w of additives such as stabilisers, surfactants, slow release modifiers and binding agents. The so-called "dry-flowable powders" consist of relatively small granules having a relatively high concentration of active ingredient. Emulsifiable concentrates usually contain, in addition to a solvent and, when necessary, co-solvent, 10-50% w/v active ingredient, 2-20% w/v emulsifiers and 0-20% w/v of other additives such as stabilisers, penetrants and corrosion inhibitors. Suspension concentrates are usually compounded so as to obtain a stable, non-sedimenting flowable product and usually contain 10-75% w active ingredient, 0.5-15% w of dispersing agents, 0.1-10% w of suspending agents such as protective colloids and thixotropic agents, 0-10% w of other additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation or as anti-freeze agents for water.
Aqueous dispersions and emulsions, for example compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the invention. The said emulsions may be of the water-in-oil or of the oil-in-water type, and may have a thick `mayonnaise`-like consistency.
The composition of the invention may also contain other ingredients, for example other compounds possessing pesticidal, herbicidal, or fungicidal properties. The compounds of the invention are especially useful when applied in admixture with other insecticides, especially organophosphates and pyrethroids. Mixtures with the commercial products fenvalerate, permethrin, cypermethrin, deltamethrin and alphamethrin are especially useful.

The following Examples illustrate the invention; Examples 1 to 77 illustrate the preparation of intermediates of general formula III, while Examples 78 to 155 illustrate the preparation of compounds of general formula I.
EXAMPLE 1
Preparation of 2-(2-fluorophenyl)-6-nitro-1,3-benzodioxan
An intimate mixture of 2-hydroxy-5-nitrobenzyl alcohol (4.56 g), 2-fluorobenzaldehyde (4.02 g) and benzoic acid (0.2 g) was stirred and heated to 90.degree. C. (.+-.5.degree. C.) under nitrogen for 3% hours. The resulting clear reaction mixture was left to cool for two days whereupon it solidified. This material was dissolved in ethyl acetate (250 ml) and the solution was washed with saturated aqueous sodium bicarbonate, 20% aqueous sodium bisulphite and then with water. The organic phase was dried over sodium sulphate and evaporated to yield the crude product as a solid residue which was purified by suspending briefly in hot ethanol and cooling to 0.degree.-5.degree. C. The pure product was thus obtained as a white crystalline powder (5.3 g, 71%), mp 137.degree.-138.degree. C.
EXAMPLES 2 TO 17
By methods analogous to that of Example 1, further compounds of the general formula III were prepared by reaction of compounds of general formula VI with compounds of general formula VII. Details are given in Table I.
TABLE I______________________________________ ##STR10##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________2 2-Cl 154-155 693 4-Cl 186-187 574 2,4-Cl.sub.2 161-162 435 3,4-Cl.sub.2 148-149 65*6 2,6-Cl.sub.2 140-141 54*7 2-Cl-4-CF.sub.3 127-129 14*8 2,4-F.sub.2 102-103 799 2-Br 149-150 7810 4-CF.sub.3 116-117 4011 2-CN 175-176 912 2-CH.sub.3 136-137 4213 4-CH.sub.3 149-150 5914 4-OCF.sub.3 92-94 5015 2,3-Cl.sub.2 202-203 4416 2-CF.sub.3 93-94 3417 2-OCH.sub.3 159-160 36______________________________________ *used without further purificationyield estimated by nmr
EXAMPLE 18
Preparation of 2-[2-chloro-4-(trifluoromethyl)phenyl]-6-nitro-1,3-benzoxathian
A solution of 2-chloro-4-(trifluoromethyl)-benzaldehyde (5.6 g) and 2-mercaptomethyl-4-nitrophenol (2.0 g) in toluene (80 ml) containing a catalytic amount of p-toluenesulphonic acid monohydrate was stirred at reflux temperature for 1 hour in an atmosphere of nitrogen. Water formed in the reaction was removed by means of a Dean-Stark trap. Removal of the solvent under reduced pressure afforded an off-white solid residue which was purified by suspending briefly in hot ethanol (30 ml) and cooling to 0.degree.-5.degree. C. The pure benzoxathian was obtained as colourless crystals (2.97 g, 73%), mp 121.degree.-122.degree. C.
EXAMPLES 19 TO 26
By methods analogous to that of Example 18, further compounds of the general formula II were prepared by reaction of compounds of general formula VI with compounds of general formula VII. Details are given in Table II.
TABLE II______________________________________ ##STR11##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________19 2-F 86-87 7620 4-Cl 145-146 6821 2,4-Cl.sub.2 97-98 6022 2,6-Cl.sub.2 149-150 5723 2,4-F.sub.2 101-102 5424 2-Br 103-104 5825 4-CH.sub.3 141-143 7926 2-CF.sub.3 135-136 71______________________________________
EXAMPLE 27
Preparation of 6-bromo-2-(4-nitrophenyl)-1,3-benzodioxan
An intimately ground mixture of 5-bromo-2-hydroxybenzyl alcohol (4.06 g), 4-nitrobenzaldehyde (3.93 g) and benzoic acid (0.2 g) was stirred and heated to 85.degree. C. (.+-.5.degree. C.) under nitrogen for 88 hours. The clear melt which formed initially gradually solidified throughout the reaction period. The resulting solidified mass was cooled and dissolved in ethyl acetate (250 ml). The solution was then washed with 20% aqueous sodium carbonate, 20% aqueous sodium bisulphite and finally with brine. After drying over sodium sulphate, the organic phase was evaporated to yield a solid residue which was purified by briefly suspending in hot ethanol (approx. 75 ml) and cooling to 0.degree.-5.degree. C. The pure product was obtained as pale buff-coloured crystals (4.69 g, 70%), mp 163.degree.-164.degree. C.
EXAMPLES 28 TO 30
By methods analogous to that of Example 27, further compounds of the general formula III were prepared by reaction of compounds of general formula VI with compounds of general formula VII. Details are given in Table III.
TABLE III______________________________________ ##STR12##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________28 6-CH.sub.3 140-141 2229 6-Cl 144-145 5130 6,8-Cl.sub.2 169-170 39______________________________________
EXAMPLE 31
Preparation of 2-(4-chlorophenyl)-2-methyl-6-nitro-1,3-benzoxathian
A solution of 2-mercaptomethyl-4-nitrophenol (1.0 g) and 4-chloroacetophenone (1.67 g) in toluene (80 ml) containing a catalytic amount of p-toluenesulphonic acid monohydrate (0.1 g) was stirred at reflux temperature for 70 hours in an atmosphere of nitrogen. Water formed in the reaction was removed by means of a Dean-Stark trap. Removal of the solvent under reduced pressure afforded an oily residue which was redissolved in ethyl acetate (200 ml). The solution was washed with 10% (w/v) aqueous sodium carbonate solution and then evaporated under reduced pressure. The resulting residual oil was subjected to flash chromatography on silica gel using methylene chloride as eluant. The crude benzoxathian was thus isolated as an oil which solidified upon trituration with cold ethanol (.about.5 ml). This material was purified by stirring the suspension at 60.degree. C. for 1 hour and allowing to cool to 0.degree.-5.degree. C. The pure product was obtained as yellow crystals (0.78 g, 45%), mp 163.degree.-164.degree. C.
EXAMPLES 32 TO 33
By a method analogous to that of Example 31, further compounds of the general formula II were prepared by reaction of a compound of general formula VI with a compound of general formula VI. Details are given in Table IV.
TABLE IV______________________________________ ##STR13##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________32 3,4-Cl.sub.2 resin 60*33 2,4-F.sub.2 resin 99*______________________________________ *used without further purificationyield estimated by nmr
EXAMPLE 34
Preparation of 2-(2,4-difluorophenyl)-6-nitro,3,1-benzoxathian
A solution of 2-mercapto-5-nitrobenzyl alcohol (2.2 g) and 2,4-difluorobenzaldehyde (3.37 g) in toluene (80 ml) containing a catalytic amount of p-toluenesulphonic acid monohydrate (0.1 g) was heated under reflux for 2 hours in an atmosphere of nitrogen. Water formed in the reaction was removed by means of a Dean-Stark trap. After removal of the solvent under reduced pressure, the remaining residue was redissolved in ethyl acetate. This solution was then washed successively with 10% aqueous sodium carbonate, 10% aqueous sodium bisulphate and brine. After drying over anhydrous sodium sulphate, the solution was evaporated to yield the crude product as a yellow solid. Crystallisation from ethanol afforded the pure benzoxathian as yellow crystals (2.45 g, 67%), mp 119.degree.-120.degree. C.
EXAMPLES 35 TO 42
By methods analogous to that of Example 34, further compounds of the general formula II were prepared by reaction of compounds of general formula VI with compounds of general formula VII. Details are given in Table V.
TABLE V______________________________________ ##STR14##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________35 H 163-165 49*36 4-Cl 149-150 4837 2,4-Cl.sub.2 174-175 7038 2,6-Cl.sub.2 215-216 4139 2-Br 134-135 3340 2-CH.sub.3 121-122 4241 2-CF.sub.3 136-137 6342 2-Cl-4-CF.sub.3 151-152 40______________________________________ *used without further purificationyield estimated by nmr
EXAMPLE 43
Preparation of 2-(3,4-dichlorophenyl)-2-methyl-6-nitro-3,1-benzoxathian
A solution of 2-mercaptomethyl-4-nitrophenol (1.78 g) and 3,4-dichloroacetophenone (3.83 g) in toluene (80 ml) containing a catalytic amount of p-toluenesulphonic acid monohydrate (0.1 g) was stirred at reflux temperature for 40 hours in an atmosphere of nitrogen. Water formed in the reaction was separated by means of a Dean-Stark trap. Upon cooling to room temperature, some tarry material separated. The supernatant liquor was decanted and washed successively with 10% (w/v) aqueous sodium carbonate solution and brine. After drying over anhydrous sodium sulphate, the solution was evaporated under reduced pressure to leave a mixture of the product and unreacted ketone. This material was subjected to flash chromatography on silica gel using methylene chloride as eluant, whereupon the benzoxathian was isolated as a yellow solid (1.3 g, >95% pure by nmr). Recrystallisation of 0.3 g of this material from ethanol afforded the pure product as yellow crystals (0.27 g), mp 118.degree.-119.degree. C.
EXAMPLES 44 TO 46
By methods analogous to that of Example 43, further compounds of the general formula II were prepared by reaction of compounds of general formula VI with compounds of general formula VII. Details are given in Table VI.
TABLE VI______________________________________ ##STR15##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________44 H 107-108 1845 4-Cl 123-124 3446 4-CF.sub.3 132-133 29______________________________________
EXAMPLE 47
Preparation of 2-(2-fluorophenyl)-5-nitro-1,3-benzodioxole
4-nitrocatechol (3.1 g) and 2-fluorobenzaldehyde (5.0 g) were heated under reflux for 18 hours in toluene (70 ml) containing a catalytic amount (0.2 g) of p-toluenesulphonic acid monohydrate. The water produced in the reaction was separated by means of a Dean-Stark apparatus. The reaction mixture was cooled and some solid material (unreacted catechol) filtered off, washing briefly with methylene chloride. The filtrate was evaporated under reduced pressure and the residue purified by chromatography on silica gel using methylene chloride as eluant. The material thus obtained contained traces of aldehyde which were removed by dissolving in ether and shaking the solution successively with 20% aqueous soldium bisulphite solution, saturated sodium bicarbonate solution and finally with water. The resulting ether solution was dried over anhydrous sodium sulphate and evaporated to yield the pure benzodioxole as pale yellow crystals (4.1 g, 79%), mp 86.degree.-88.degree. C.
EXAMPLES 48 TO 57
By methods analogous to that of Example 47, further compounds of the general formula III were prepared by reaction of compounds of general formula VI with compounds of general formula VII. Details are given in Table VII.
TABLE VII______________________________________ ##STR16##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________48 2-Cl 112-114 5649 3-Cl 80-83 6150 4-Cl 99-101 23*51 2,6-Cl.sub.2 120-122 2752 2,4-Cl.sub.2 resin 1653 3,4-Cl.sub.2 89-91 5954 2-Br 134-136 7055 4-CH.sub.3 100-102 5356 4-CF.sub.3 oil 3157 2,4-F.sub.2 74-76 34______________________________________ *used without further purificationyield estimated by nmr
EXAMPLE 58
Preparation of 2-methyl-2-[4-(trifluoromethyl)phenyl]-5-nitro-1,3-benzodioxole
(i) A solution of catechol (5.5 g) and 4-(trifluoromethyl)acetophenone (10.3 g) in toluene (150 ml) containing a catalytic amount (0.2 g) of p-toluenesulphonic acid monohydrate was heated under reflux for 3 days. Water produced in the condensation was separated by means of a Dean-Stark trap. After removal of the solvent under reduced pressure, the residue was purified by chromatography on silica gel using methylene chloride as eluant. Pure 2-methyl-2-[4-(trifluoromethyl)phenyl]-1,3-benzodioxole was obtained as a colourless oil (10.8 g, 77%).
(ii) A solution of 2-methyl-2-[4-(trifluoromethyl)phenyl]-1,3-benzodioxole (5.6 g) in dichloroethane (15 ml) was added over 10 minutes to vigorously stirred nitric acid (50% w/v, 25 ml) keeping the temperature at 15.degree.-20.degree. C. by means of a cooling bath. The resulting reaction mixture was stirred for a further 1 hour at 20.degree. C., poured into water (200 ml) and extracted with methylene chloride (3.times.100 ml). After drying over anhydrous sodium sulphate, the extract was evaporated under reduced pressure. The residue was purified by chromatography on silica gel using methylene chloride as eluant, affording the pure product benzodioxole as a pale yellow oil (5.3 g, 82%).
EXAMPLES 59 TO 62
By methods analogous to that of Example 58, further compounds of the general formula II were prepared by reaction of compounds of general formula VI with compounds of general formula VII. Details are given in Table VIII.
TABLE VIII______________________________________ ##STR17##Example No. (R).sub.a R mp .degree.C. Yield (%)______________________________________59 4-Cl CH.sub.3 oil 8360 3,4-Cl.sub.2 CH.sub.3 oil 8161 2,4-F.sub.2 CH.sub.3 85-87 9562 H CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 oil 37______________________________________
EXAMPLE 63
Preparation of 2-ethoxy-2-phenyl-5-nitro-1,3-benzodioxole
A solution of 4-nitrocatechol (3.1 g) and triethyl orthobenzoate (6.7 g) in dry toluene (40 ml) was heated under reflux for 21/2% hours. The solvent was then removed under reduced pressure and the resulting residue purified by chromatography on silica gel using methylene chloride as eluant. The pure benzodioxole was obtained as a pale yellow oil (3.8 g, 66%).
EXAMPLE 64
Preparation of 2-(2,4-dichlorophenyl)-5-nitro-1,3-benzoxathiole
2-Mercapto-4-nitrophenol (2.0 g) and 2,4-dichlorobenzaldehyde (2.0 g) were heated under reflux for 6 hours in toluene (70 ml) containing a catalytic amount (0.2 g) of p-toluenesulphonic acid monohydrate. Water formed in the reaction was separated by means of a Dean-Stark apparatus. The resulting reaction mixture was evaporated under reduced pressure, and the residue extracted with cyclohexane. The cyclohexane solution was then evaporated and the residue chromatographed on silica gel using methylene chloride/5% (v/v) methanol as eluant. The material obtained at this stage was contaminated with unreacted aldehyde. This was removed by stirring a methylene chloride solution of the crude product with 30% aqueous sodium bisulphite for 2 hours and then washing the solution successively with saturated sodium bicarbonate solution and water. After drying over anhydrous sodium sulphate, the methylene chloride was removed under reduced pressure. Crystallisation of the residue afforded the pure product as pale yellow crystals (0.7 g, 21%), mp 106.degree.-108.degree. C.
EXAMPLES 65 TO 72
By methods analogous to that of Example 64, further compounds of the general formula II were prepared by reaction of compounds of general formula VI with compounds of general formula VII. Details are given in Table IX.
TABLE IX______________________________________ ##STR18##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________65 2-F 99-101 4766 4-Cl oil 58*67 3,4-Cl.sub.2 112-114 4068 2-Cl-4-CF.sub.3 oil 21*69 2,4-F.sub.2 75-77 8870 2-Br 163-165 5171 4-CF.sub.3 oil 37*72 2-CF.sub.3 oil 34*______________________________________ *used without further purificationyield estimated by nmr
EXAMPLE 73
Preparation of 2-(4-chlorophenyl)-2-methyl-5-nitro-1,3-benzoxathiole
A solution of 2-mercapto-4-nitrophenol (1.7 g) and 4-chloroacetophenone (3.1 g) in toluene (75 ml) containing a catalytic amount of p-toluenesulphonic acid monohydrate (0.2 g) was heated under reflux for 6 hours, removing water formed in the reaction by means of a Dean-Stark trap. The reaction mixture was evaporated under reduced pressure and the resulting residue was purified by chromatography on silica gel using methylene chloride as eluant. The pure benzoxathiole was obtained as pale yellow crystals (1.5 g, 49%), mp 87.degree.-89.degree. C.
EXAMPLES 74 TO 77
By methods analogous to that of Example 73, further compounds of the general formula II were prepared by reaction of compounds of general formula VI with compounds of general formula VII. Details are given in Table X.
TABLE X______________________________________ ##STR19##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________74 3,4-Cl.sub.2 oil 64*75 2,4-Cl.sub.2 oil 21*76 2,4-F.sub.2 oil 26*77 4-CF.sub.3 oil 53*______________________________________ *used without further purificationyield estimated by nmr
Elemental analysis data for the intermediates of general formula III described above, where measured, is set out in Table XI below.
TABLE XI______________________________________Analysis (%)Example C H NNo. Calc. Found Calc. Found Calc. Found______________________________________ 1 61.1 60.9 3.7 3.6 5.1 5.0 2 57.7 57.3 3.5 3.4 4.8 4.6 3 57.7 57.8 3.5 3.6 4.8 5.0 4 51.6 51.6 2.8 3.0 4.3 4.9 8 57.4 56.6 3.1 3.2 4.8 4.6 9 50.0 50.0 3.0 2.9 4.2 3.910 55.4 55.8 3.1 3.2 4.3 4.511 63.8 63.8 3.6 3.5 9.9 9.812 66.4 65.5 4.8 4.6 5.2 5.013 66.4 66.5 4.8 4.9 5.2 5.114 52.8 53.2 3.0 3.2 4.1 4.615 51.6 51.6 2.8 3.0 4.0 4.916 55.4 55.9 3.1 3.3 4.3 4.617 62.7 62.9 4.6 4.5 4.9 5.018 48.0 47.5 2.4 2.6 3.7 3.719 57.7 58.3 3.5 3.7 4.8 4.920 54.6 54.3 3.3 3.3 4.6 4.621 49.1 49.1 2.7 2.8 4.1 4.122 49.1 48.9 2.7 2.7 4.1 4.023 54.4 54.7 2.9 3.0 4.5 4.624 47.7 47.2 2.9 3.0 4.0 3.925 62.7 62.3 4.6 4.5 4.9 4.926 52.8 52.2 3.0 3.1 4.1 3.927 50.0 49.8 3.0 3.0 4.2 4.428 66.4 66.4 4.8 5.1 5.2 5.229 57.7 57.2 3.5 3.6 4.8 5.230 51.6 51.6 2.8 2.6 4.3 4.431 56.0 56.3 3.8 4.0 4.4 4.334 54.4 54.8 2.9 3.3 4.5 4.736 54.6 54.6 3.3 3.5 4.6 4.637 49.1 49.3 2.7 3.0 4.1 4.238 49.1 49.5 2.7 2.8 4.0 4.339 47.7 48.0 2.9 3.0 4.0 4.040 62.7 62.3 4.6 4.5 4.9 4.941 52.8 52.8 3.0 3.1 4.1 4.242 48.0 48.4 2.4 2.7 3.7 3.943 50.6 50.4 3.1 3.4 3.9 4.144 62.7 62.2 4.6 4.5 4.9 4.845 56.0 55.9 3.8 3.8 4.4 4.346 54.1 53.8 3.4 3.5 3.9 3.947 59.8 59.4 3.1 3.4 5.4 5.648 56.2 56.5 2.9 3.4 5.0 5.349 56.2 56.3 2.9 2.9 5.0 5.051 50.0 49.6 2.2 2.0 4.5 4.152 50.0 50.1 2.2 2.5 4.5 4.753 50.0 49.8 2.2 2.9 4.5 5.054 48.4 48.2 2.5 2.3 4.3 4.255 65.4 65.3 4.3 4.6 5.4 5.656 54.0 54.2 2.6 2.8 4.5 4.257 55.9 56.2 2.5 2.6 5.0 5.158 55.4 55.7 3.1 3.3 4.3 4.559 57.6 57.5 3.4 3.6 5.0 4.860 51.5 51.4 2.8 2.9 4.3 4.361 57.3 57.8 3.1 3.3 4.8 4.862 62.0 61.9 4.6 4.6 4.0 4.163 62.7 63.3 4.5 4.6 4.9 4.864 47.6 47.9 2.1 2.6 4.3 4.765 56.3 56.8 2.9 2.2 5.1 5.067 47.6 47.4 2.1 2.3 4.3 4.469 52.9 52.7 2.4 2.7 4.7 4.670 46.1 45.9 2.4 2.3 4.1 4.173 54.6 54.9 3.3 3.4 4.6 4.5______________________________________
EXAMPLE 78
Preparation of 2,6-difluoro-N-[[[2-(2-fluorophenyl)-1,3-benzodioxan-6-yl]amino]carbonyl]benzamide
A suspension of 2-(2-fluorophenyl)-6-nitro-1,3-benzodioxan (2.0 g) in ethanol (250 ml) was hydrogenated at .ltoreq.60 psi hydrogen pressure in the presence of 5% platinum/charcoal (0.3 g) and anhydrous potassium carbonate (0.2 g) at ambient temperature. The resulting reaction mixture was filtered and evaporated under reduced pressure to afford the crude aniline derivative which was dried azeotropically by dissolving in toluene and evaporation under reduced pressure. The dried material was redissolved in dry toluene (20 ml) and treated with 2,6-difluorobenzoyl isocyanate (1.4 g), briefly brought to reflux temperature and left to cool overnight. After cooling to 0.degree.-5.degree. C., the precipitate of product was separated, washed with cold toluene followed by light petroleum and dried under reduced pressure at approx. 60.degree. C. The pure product was thus obtained as a white microcrystalline powder (2.7 g, 87%), mp 203.degree.-206.degree. C.
EXAMPLES 79 TO 126
By methods analogous to that of Example 78, further compounds of the general formula I were prepared from intermediates of the general formula III. Details are given in Tables XII to XVI.
TABLE XII______________________________________ ##STR20##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________79 H 188-190 6380 2-Cl 202-205 8581 4-Cl 225-230 5082 2,4-Cl.sub.2 214-215 5083 3,4-Cl.sub.2 200-203 7384 2,6-Cl.sub.2 203-204 6885 2-Cl-4-CF.sub.3 219-220 4386 2,4-F.sub.2 220-221 5787 2-Br 208-210 7988 4-CF.sub.3 235-236 6489 2-CH.sub.3 198-200 4290 4-CH.sub.3 209-211 6791 4-OCF.sub.3 221-223 7292 2,3-Cl.sub.2 221-222 6493 2-CF.sub.3 201-202 5594 2-OCH.sub.3 205-206 72______________________________________
TABLE XIII______________________________________ ##STR21##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________ 95 2-Cl-4-CF.sub.3 215-216 91 96 2-F 222-224 82 97 4-Cl 209-210 80 98 2,4-Cl.sub.2 217-218 81 99 2,6-Cl.sub.2 229-231 79100 2,4-F.sub.2 228-229 80101 2-Br 223-224 77102 4-CH.sub.3 215-216 55103 2-CF.sub.3 225-226 89104 H 194-195 74______________________________________
TABLE XIV______________________________________ ##STR22##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________105 4-Cl 201-202 66106 3,4-Cl.sub.2 194-195 32107 2,4-F.sub.2 161-163 79______________________________________
TABLE XV______________________________________ ##STR23##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________108 2,4-F.sub.2 242-244 79109 H 221-222 78110 4-Cl 231-233 79111 2,4-Cl.sub.2 222-224 55112 2-CF.sub.3 213-215 25113 2,6-Cl.sub.2 225-226 32114 2-Cl-4-CF.sub.3 210-211 66115 2-Br 215-216 71116 2-CH.sub.3 205-206 75______________________________________
TABLE XVI______________________________________ ##STR24##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________117 H 203-205 61118 4-Cl 237-238 85119 3,4-Cl.sub.2 224-225 66120 4-CF.sub.3 243-244 47______________________________________
EXAMPLE 121
Preparation of N-[[[4-(6-bromo-1,3-benzodioxan-2-yl)phenyl]amino]carbonyl]-2,6,-difluorobenzamide
A suspension of 6-bromo-2-(4-nitrophenyl)-1,3-benzodioxan (2.05 g) in toluene (150 ml) was hydrogenated at .ltoreq.60 psi hydrogen pressure in the presence of 5% platinum/charcoal (0.5 g) and anhydrous potassium carbonate (0.5 g) at ambient temperature. The reaction mixture was filtered and evaporated under reduced pressure, azeotropically removing the water formed in the reaction. The resulting crude aniline derivative was redissolved in dry toluene (25 ml) and treated with 2,6-difluorobenzoyl isocyanate (1.2 g), warming briefly to approx. 60.degree. C. then allowing the stirred reaction mixture to cool overnight. Cooling to 0.degree.-5.degree. C. afforded a precipitate of impure product which was purified by crystallisation from ethanol (0.52 g, 17%), mp 194.degree.-195.degree. C.
EXAMPLES 122 TO 123
By methods analogous to that of Example 121, further compounds of the general formula I were prepared from intermediates of the general formula III. Details are given in Table XVII.
TABLE XVII______________________________________ ##STR25##Example No. (R).sub.a mp .degree.C. Yield (%)______________________________________122 6-CH.sub.3 185-186 32123 6-Cl 185-186 14______________________________________
EXAMPLE 124
Preparation of 2,6-difluoro-N-[[[2-(2-fluorophenyl)-1,3-benzodioxol-5-yl]amino]carbonyl]benzamide
A solution of 2-(2-fluorophenyl)-5-nitro-1,3benzodioxole (2.6 g) in ethanol (150 ml) was hydrogenated at .ltoreq.60 psi hydrogen pressure in the presence of 5% platinum/charcoal (0.2 g) and anhydrous potassium carbonate (0.2 g) at ambient temperature. The resulting reaction mixture was filtered through `Hiflo supercel` (BDH) and the filtrate evaporated under reduced pressure. The residue was dried azeotropically by redissolving in toluene (120 ml) and evaporating under reduced pressure. The crude aniline thus obtained was redissolved in dry toluene (30 ml) and treated with 2,6-difluorobenzoyl isocyanate (2.0 g) at reflux temperature for 1 hour. The acylurea crystallised out on cooling and was filtered off, washing with cold toluene. This material was further purified by chromatography on silica gel, eluting with methylene chloride containing 5% (v/v) methanol. Additional product was recovered from the toluene filtrate by chromatography using the same system. The pure acylurea was obtained as colourless crystals (total yield 3.2 g, 77%), mp 189.degree.-192.degree. C.
EXAMPLES 125 TO 141
By methods analogous to that of Example 124, further compounds of the general formula I were prepared from intermediates of the general formula III. Details are given in Table XVIII.
TABLE XVIII______________________________________ ##STR26##Example No. (R).sub.a R mp .degree.C. Yield (%)______________________________________125 H H 198-200 88126 2-Cl H 234-236 71127 3-Cl H 200-201 68128 4-Cl H 207-209 54129 2,6-Cl.sub.2 H 240-243 67130 2,4-Cl.sub.2 H 211-212 47131 3,4-Cl.sub.2 H 228-230 62132 2-Br H 225-228 55133 4-CH.sub.3 H 171-173 77134 4-CF.sub.3 H 191-193 78135 2,4-F.sub.2 H 202-203 56136 4-CF.sub.3 CH.sub.3 156-157 61137 4-Cl CH.sub.3 102-104 81138 3,4-Cl.sub.2 CH.sub.3 155-156 61139 2,4-F.sub.2 CH.sub.3 138-140 85140 H CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 121-122 73141 H OC.sub.2 H.sub.5 237-239 61______________________________________
EXAMPLE 142
Preparation of N-[[[2-(2,4,dichlorophenyl)-1,3-benzoxathiol-5-yl]amino]carbonyl]-2,6-difluorobenzamide
A solution of 2-(2,4-dichlorophenyl)-5-nitro-1,3-benzoxathiole (0.7 g) in ethanol (100 ml) was hydrogenated at .ltoreq.60 psi hydrogen pressure in the presence of 5% platinum/charcoal (0.2 g) and anhydrous potassium carbonate (0.2 g). The resulting reaction mixture was filtered through `Hiflo supercel` (BDH) and evaporated under reduced pressure. Traces of ethanol and water were removed by redissolving the residue in toluene and evaporating under reduced pressure. The crude aniline thus obtained was then dissolved in dry toluene (70 ml) and treated with 2,6-difluorobenzoyl isocyanate (0.4 g) at reflux temperature for 45 minutes. The product was isolated by removing the solvent under reduced pressure and purifying the residue by chromatography on silica gel using methylene chloride/5% (v/v) methanol as eluant. The pure acylurea was obtained as colourless crystals (0.3 g, 31%), mp 206.degree.-208.degree. C.
EXAMPLES 143 TO 155
By methods analogous to that of Example 142, further compounds of the general formula I were prepared from intermediates of the general formula III. Details are given in Table XIX.
TABLE XIX______________________________________ ##STR27##Example No. (R).sub.a R mp .degree.C. Yield (%)______________________________________143 2-F H 204-206 86144 4-Cl H 196-198 27145 3,4-Cl.sub.2 H 219-221 57146 2-Cl-4-CF.sub.3 H 168-170 36147 2,4-F.sub.2 H 209-211 71148 2-Br H 180-181 46149 4-CF.sub.3 H 235-237 31150 2-CF.sub.3 H 166-168 49151 4-Cl CH.sub.3 130-132 84152 3,4-Cl.sub.2 CH.sub.3 180-182 45153 4-CF.sub.3 CH.sub.3 173-175 45154 2,4-Cl.sub.2 CH.sub.3 203-205 51155 2,4-F.sub.2 CH.sub.3 207-209 43______________________________________
Elemental analysis data for the compounds of general formula I described above is set out in Table XX below.
TABLE XX______________________________________ Analysis (%) C H NExample No. Calc. Found Calc. Found Calc. Found______________________________________78 61.7 60.2 3.5 3.3 6.5 6.379 64.4 64.2 3.9 4.1 6.8 7.180 59.4 60.5 3.4 3.5 6.3 5.881 59.4 59.2 3.4 3.4 6.3 6.282 55.1 55.3 2.9 3.3 5.8 6.283 55.1 55.0 2.9 3.2 5.8 5.784 55.1 55.4 2.9 2.7 5.8 5.385 53.9 53.7 2.7 2.8 5.5 5.886 59.2 60.0 3.2 2.9 6.3 7.587 54.0 53.0 3.1 3.1 5.7 6.688 57.7 56.9 3.2 3.4 5.9 6.289 65.1 65.1 4.3 4.5 6.6 7.490 65.1 62.9 4.3 4.4 6.6 6.691 55.9 56.8 3.1 3.1 5.7 5.692 55.1 55.2 2.9 3.0 5.9 6.193 57.8 58.0 3.2 3.5 5.9 6.094 62.7 62.8 4.1 4.3 6.4 6.495 52.2 52.3 2.7 3.0 5.3 5.296 59.5 59.5 3.4 3.6 6.3 6.497 57.3 57.1 3.3 3.5 6.1 6.098 53.4 53.3 2.9 3.1 5.7 5.699 53.4 53.3 2.9 3.0 5.7 5.7100 57.1 56.8 3.1 3.4 6.1 6.0101 52.3 52.3 3.0 3.2 5.5 5.7102 62.7 62.7 4.1 4.3 6.4 6.4103 55.9 56.1 3.1 3.2 5.7 5.6104 62.0 61.8 3.8 3.8 6.6 6.6105 58.2 58.1 3.6 3.9 5.9 5.8106 54.2 54.4 3.2 3.3 5.5 5.6107 58.0 57.9 3.4 3.6 5.9 5.9108 57.1 56.9 3.1 3.3 6.1 6.0109 62.0 62.2 3.8 3.9 6.6 6.6110 57.3 57.3 3.3 3.4 6.1 6.0111 53.4 53.4 2.9 3.1 5.7 5.3112 55.9 55.7 3.1 3.3 5.8 5.6113 53.4 53.4 2.9 3.0 5.7 5.7114 52.2 52.1 2.7 2.8 5.3 5.3115 52.3 52.4 3.0 3.0 5.3 5.6116 62.7 62.6 4.1 4.1 6.4 6.4117 62.7 62.7 4.1 4.1 6.4 6.4118 58.2 58.5 3.6 3.5 5.9 5.9119 54.2 54.4 3.7 3.4 5.5 5.4120 56.7 56.9 3.4 3.5 5.5 5.5121 54.0 55.4 3.1 3.2 5.7 5.7122 65.1 65.2 4.3 4.3 6.6 6.7123 59.4 59.8 3.4 3.8 6.3 6.2124 60.9 61.1 3.1 3.0 6.8 7.0125 63.6 63.4 3.5 3.7 7.1 7.2126 58.5 57.7 3.0 3.4 6.5 6.7127 58.5 58.4 3.0 3.1 6.5 6.4128 58.5 58.5 3.0 3.4 6.5 6.9129 54.2 53.9 2.6 2.5 6.0 6.0130 54.2 54.5 2.6 2.8 6.0 6.1131 54.2 54.8 2.6 3.0 6.0 6.2132 53.1 52.9 2.7 2.8 5.9 5.8133 64.4 64.3 3.9 3.9 6.8 6.7134 56.9 56.9 2.8 2.6 6.0 5.8135 58.4 58.9 2.8 3.1 6.5 6.5136 57.7 57.9 3.1 3.5 5.9 5.8137 59.4 59.2 3.4 3.6 6.3 6.2138 55.1 55.6 2.9 3.1 5.9 5.9139 59.8 60.1 3.1 3.6 6.3 6.3140 62.2 61.9 4.1 4.4 5.8 5.8141 62.7 62.9 4.1 4.1 6.4 6.3142 52.4 52.1 2.5 2.7 5.8 5.6143 58.6 58.5 3.0 3.3 6.5 6.4144 56.4 56.1 2.9 3.2 6.3 6.1145 52.5 53.0 2.5 2.9 5.8 5.6146 51.3 51.5 2.3 2.5 5.5 5.5147 56.3 55.9 2.7 3.1 6.2 6.1148 51.3 51.0 2.7 2.7 5.7 5.6149 55.0 54.5 2.7 3.0 5.8 5.8150 55.0 54.6 2.7 2.9 5.8 5.8151 57.3 56.8 3.3 3.7 6.1 5.8152 53.3 53.5 2.8 3.0 5.7 5.7153 55.9 55.7 3.0 3.2 5.7 5.6154 53.3 53.6 2.8 3.1 5.7 5.4155 57.1 57.4 3.0 3.0 6.1 6.1______________________________________
EXAMPLE 156
Insecticidal Activity
Insecticidal activity of compounds of general formula I was assessed against the following pests:
Spodoptera littoralis (Egyptian cotton leafworm)
Aedes aegypti (yellow fever mosquito)
Trialeurodes vaporariorum (greenhouse whitefly)
The test methods employed for each species appear below. In each test, unless otherwise stated, solutions or suspensions of test compound were made up over a range of concentrations in water (initially 0.1% w) containing 10% w acetone and 0.025% w "TRITON X-100" (trade mark) surface active agent (the condensation product of ethylene oxide with an alkyl phenol). These solutions were sprayed at a rate equivalent to 340 liters per hectare (3.4.times.10.sup.-5 m.sup.3 /m.sup.2) onto Petri dishes containing either test species per se or diet onto which test species were subsequently introduced, as indicated. In some assays leaf discs infested with test species were sprayed whilst other assays involved the spraying of plants which were infested subsequently with test species after the spray solution had dried. The tests were all conducted under normal insectary conditions (23.degree. C..+-.2.degree. C., fluctuating humidity and light).
Mortality assessments were made as indicated below, in terms of percentage mortality figures. In each test a LC.sub.50 (the dosage of active material required to kill half of the test species) for the compound was calculated from the mortality figures and compared with the corresponding LC.sub.50 for a standard insecticide, ethyl parathion, in the same test. The results are expressed as toxicity indices thus: ##EQU1##
(i) Spodoptera littoralis (7 day) (Sl 7D)
Test solutions were sprayed as indicated above onto Petri dishes containing a nutritious diet for Egyptian cotton leafworm larvae. When the spray deposit had dried, each dish was infested with ten 2nd instar larvae. Mortality assessments were made 7 days after spraying.
(ii) Aedes aegypti (Aa)
Early 4th instar larvae were used, Test solutions were made up to 0.5 ppm of test compound (and progressive half-dilutions) in water containing 0.04% w "TRITON X-100" (trade mark); acetone was initially present to aid solution, but was allowed to evaporate off before introduction of larvae. Ten early 4th instar larvae were placed in 100 ml of test solution held at 28.degree. C., and after 48 hours, larval mortality was recorded. The final mortality was assessed by counting the number of emerged adult mosquitoes after one week.
(iii) Trialeurodes vaporariorum (Tv)
French bean plants (Phaseolus vulgaris) with two fully expanded leaves were placed in a breeding culture of T. vaporariorum, also on French bean plants, which were then disturbed to ensure resettlement on the introduced plants. During the subsequent 24 hour period, eggs were deposited and kept at 27.degree. C., with 14 hours photoperiod. All adult whiteflies were then carefully removed, leaving egg samples of a known age. After eight days the majority of eggs had hatched. Leaf discs containing the newly hatched nymphs were then cut from the leaves and transferred to moist filter paper. The discs were examined under a low-powered microscope to determine the exact number of 1st instar nymphs per disc and to remove any unhatched eggs. On average, 70-100 nymphs were found per disc. The discs were transferred into Petri dishes and sprayed with test solutions as described above. After 6 days percentage mortalities were assessed.
TABLE XXI______________________________________Insecticidal Activity Toxicity IndexCompound of Example No. S.l. A.a. T.v.______________________________________78 550 890 23079 1100 2 400080 30 450 B81 1200 900 B82 1000 620 280083 530 B84 420 180 B85 1400 21086 2100 300 56087 150 1200 B88 560 71 B89 26 890 32090 680 3 13091 570 80 B92 80 21293 4200 268 330094 18 395 220 46 180096 300 170 B97 190 1398 410 57 B99 60 46 B100 280 120 B101 60 90 570102 35 23 B103 320 41 B104 100 31 B105 150 5 160106 490 14108 A109 320 140110 34 58111 210 190112 160 230 B113 A A B114 310 A115 32 A A116 180 150 B121 49 130122 17123 130 21124 100 150 1000125 310 120 B126 94 540 B127 450 240 B128 1800 630 B129 17130 3370 790 1530131 3000 190132 90 490133 19134 3500 130135 790 620 B136 18000 1300 2300137 5700 1100 3200138 12000 1200 1700139 6000 17 1200140 130 9 B141 1700 280142 1000 200 2600143 110 120 B144 460 18 330145 600 18146 1500 330 30147 200 83 2100148 420 400 1400149 420 23150 360 1300 9151 430 53 500152 1200 43 B153 700 2500154 1100 190155 400 170______________________________________
Grades A and B indicate mortalities of 70-100% and 40-69%, respectively, at the initial test concentration of 0.1% w. (1000 ppm).
EXAMPLE 157
Acaricidal Activity (mite life cycle)
Acaricidal activity of some compounds of formula I was assessed, employing adult female glasshouse red spider mites, Tetranychus urticae (T.u.), by the following procedure.
2 cm diameter leaf discs cut from the leaves of French bean plants were placed, underside uppermost, on 5.5 cm diameter filter papers, kept moist by a cotton wool wick dipped in water.
Each leaf disc was infested with 25 to 30 adult female mites which were removed after 6 hours, leaving about 50 eggs on each disc. Within 5 days the eggs hatched. The freshly emerged larvae on the leaf discs were sprayed with solutions of test compound made up as in Example 156 above, at a rate equivalent to 340 liters per hectare (3.4.times.10.sup.-5 m.sup.3 /m.sup.2).
The discs were thereafter kept under normal laboratory conditions (23.degree. C..+-.2.degree. C., fluctuating humidity and 16 hours day length). After 7 days assessment was made of the number of mites emerging as adults.
From the results the LC.sub.50 was calculated, as given in Table XXII below.
TABLE XXII______________________________________Acaricidal Activity LC.sub.50 (% activeCompound of Example No. ingredient in spray)______________________________________82 0.0002384 0.0003685 0.0003187 0.002992 0.08593 0.00022134 0.09142 0.0015145 0.053147 0.05______________________________________

Number	Name	Date
4056540	Buchanan	Nov 1977
4281012	Humbert et al.	Jul 1981
4294845	Humbert et al.	Oct 1981
4611003	Marhold et al.	Sep 1986
4659736	Schluter et al.	Apr 1987
4691027	Yoshiok et al.	Sep 1987
4876277	Burke et al.	Oct 1989
5212171	Anderson et al.	May 1993

Number	Date	Country
23659	Jan 1990	JPX
1583274	Jan 1981	GBX

Pesticidal benzodioxole

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