JPH036122B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to insecticides and more particularly to synthetic insecticides of the pyrethrin type, processes for their preparation, compositions containing them and the insecticidal use of these compounds and compositions. For many years, research has been conducted in the field of synthetic analogs of pyrethrins to discover synthetic substitutes that have superior properties to these natural products. Ideally, synthetic analogs of natural pyrethrins should be well comparable to or superior to natural products in terms of insect and animal toxicity levels, insecticide spectrum and knock-down properties; It must be easy to manufacture. Since the discovery that naturally occurring pyrethrins are esters of certain substituted cyclopropanecarboxylic acids and substituted cyclopentenolone, research into synthetic analogs has focused primarily on modifying the alcohol moiety of this ester molecule. Later efforts have focused on modifying the acid portion of the ester molecule, or in some cases both portions of the ester molecule. This naturally occurring ester has the formula It is an ester of chrysanthemum acid or pyrethric acid (wherein X represents a methyl group (chrysanthemum acid) or a carbomethoxy group (pyrethric acid)). In these acids, the substituents on the carbon atoms marked * are believed to be involved in the detoxification of pyrethrin insecticides in insects. The inventors have now discovered that a high level of insecticidal activity and a particularly valuable combination of toxicity and knock-down properties provide esters of 2,2-dimethyl-3-alkenylcyclopropanecarboxylic acids (wherein the 3-alkenyl side chain It has been discovered that the above substituents can be obtained in pyrethrin-like esters (which are different from those of all hitherto known pyrethrin-like esters). Therefore, the present invention provides that the active ingredient has the general formula [In the formula, R ¹ represents hydrogen, R ² represents halogen, R ³ represents hydrogen or a lower alkoxycarbonyl group, and R represents the formula or or or or (In the formula, Z represents -CH ₂ -, Y represents an alkynyl group or phenyl group, R ⁷ and R ⁸ each represent hydrogen, R ⁹ represents hydrogen or a methyl group, R ¹⁰ and R ¹¹ represent Each represents hydrogen, and R ¹² is α to the CH ₂ group to which R ¹² is bonded.
represents an alkenyl group having a carbon-carbon unsaturated bond in the position, ^Z3 represents _-CH2- or -O-, and D represents hydrogen or a cyano group)
The synthetic pyrethroid represented by the group of ] is included as an insecticide. The esters of the invention in which R represents a group of the formula , , or B are insecticidal esters with a valuable combination of toxicity and knockdown properties. Esters in which R represents alkyl are not insecticidal, but they are useful intermediates for the production of insecticidal esters, for example by transesterification. As discussed in more detail hereinafter, this novel alkyl ester of the present invention can be prepared in that form by the Uiteitzg synthesis, and the alkyl ester can be converted to a free carboxylic acid to produce the insecticidal ester of the present invention. There is no need to convert it to . However, if desired, the alkyl ester can be converted to the free carboxylic acid, for example, by hydrolyzing the ester to form a salt and then acidifying the salt. Esters in which R represents alkyl and R ³ is carbalkoxy are useful intermediates in the preparation of insecticidal esters, which can be prepared by converting the carbalkoxy group R using an acid catalyst such as toluene-4-sulfonic acid in benzene. can be converted to the corresponding free carboxylic acid without affecting ³ . As discussed in more detail below, this novel alkyl ester is produced in that form by the Uiteitsig synthesis, and the alkyl ester is converted to the free carboxylic acid to produce the insecticidal ester of the present invention. It is necessary to. This is selectively achieved using tertiary butyl esters (R=tertiary butyl). However, if desired, the tertiary butyl or other alkyl ester can be converted to the free carboxylic acid by partial saponification, but the concomitant carbalkoxy group
It is difficult to prevent saponification of ^R3 . The insecticidal esters of the invention are structurally comprised of 3-substituted 2,2-dimethylcyclopropanecarboxylic acids and alcohols such as benzyl alcohol, furyl methyl alcohol, cyclopentenolone or α-cyanobenzyl or α-cyano-furyl It can be considered an ester with methyl alcohol. Although it is convenient to describe these esters structurally in this way, it is important to note that these esters can be, and often are, prepared by methods other than esterification of acids with alcohols. will be described in more detail below. As far as R ³ is concerned, if this radical contains an alkoxy group, this radical preferably contains up to 6 carbon atoms, especially up to 3 carbon atoms, and carbomethoxy, carboethoxy and Carbopropoxy is of particular interest. When R ² represents a halogen group,
It is preferably fluorine, chlorine or bromine. The ester of the present invention primarily has a substituent R ²
Depending on the nature of and R ³ , it is structurally placed into various subclasses. Another subclass of particular interest are esters where R ¹ and R ³ are each hydrogen and R ² is chlorine or bromine. Another subclass of particular interest are those compounds in which R ² represents hydrogen and R ³ represents a carbalkoxy group. These esters are esters of demethylpyretrinic acid analogs lacking a methyl substituent on the β-carbon atom of the 3-substituent. An interesting subclass that is further halogenated are those esters in which R ¹ represents hydrogen, R ² represents halogen and R ³ represents carbalkoxy. The acid residues in these esters are pyrethric acid analogs in which the methyl substituent on the β-carbon of the 3-substituent is substituted with a halogen, or the carbomethoxy group thereof is
homologues of these acids which are substituted by a carbalkoxy group containing 5 carbon atoms. The halogen is preferably chlorine or bromine and the carbalkoxy group is preferably carbomethoxy, carboethoxy or carbo-n-propoxy. Preferred esters of the present invention have a structure in which the 3-position substituent is Cl-CH=CH- Br-CH=CH- Examples include esters of 2,2-dimethyl-3-substituted cyclopropanecarboxylic acid such as If the ester is structurally derived from furyl methyl alcohol, the furyl methyl alcohol is one of the 3-furyl methyl alcohols described in British Patent No. 1,168,798. It is preferable that In these furyl methyl alcohols and especially 3-furyl methyl alcohols R ⁷ and R ⁸ each represent hydrogen and Y represents a phenyl group. Analogs of these compounds in which D is a cyano group may also be used. Other compounds of interest are those in which Y represents an alkynyl group (eg propargyl) or a furyl group. Specific alcohols in this category from which structurally the esters of the invention can be derived include 5
-benzyl-3-furylmethyl alcohol, 5-
Examples include benzylfurfuryl alcohol and α-cyano derivatives thereof. Cyclopentenolones from which structurally the esters of the invention can be derived are those which are unsubstituted in the 3-position or substituted with a methyl group in the 3-position (R ⁹ =H or CH ₃ ). Cyclopentenolones without substitution in the 3-position are described in British Patent No. 1305025.
Some of these alcohols are 3-demethyl analogs of alcohols from which the natural product pyrethrins are derived. R ¹² is an alkenyl group such as vinyl, prop-1-enyl or but-1,3
- represents a dienyl group. Structurally, the ester of the present invention is a cyclopentenolone substituted with methyl at the 3-position (R ⁹ =
methyl), the ester can be derived from arethrolone (R ¹⁰ = R ¹¹ = H, R ¹² = vinyl), pyrethrolone (R ¹⁰ = R ¹¹ = H, R ¹² = but-1,3-dienyl). ), cinerolon (R ¹⁰ = R ¹¹
-H, ^R12 = prop-1-enyl) or diasmolone ( ^R10 = ^R11 = H, ^R12 = but-1-enyl). When the esters of the invention are phthalimidomethyl esters in which R is a group of the formula, these are 3,
4,5,6-tetrahydrophthalimidomethyl ester. When the esters of the invention are R a radical of the formula, these are 3-benzylbenzyl esters or 3-phenoxybenzyl esters. Other esters of particular interest when R is a group of formula are those in which Z ³ represents O or CH ₂ and D is -CN
such as α-cyano-3-phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohol.
It is an ester of 3-benzyl-benzyl alcohol. The compounds of the invention exhibit geometric and optical isomerism. They can therefore be prepared either as optically active substances which can then be mixed together or as racemic mixtures which can subsequently be resolved into optically active forms. Furthermore, optically active forms or racemic mixtures can be separated into their respective geometric isomers. Furthermore, in addition to the geometric isomerism derived from the coordination of the substituents on the cyclopropane ring with respect to each other and the ring, R ¹ , R ² and R ³ are such that the unsaturated side chains are asymmetrically substituted. In such cases, there is a possibility of geometric isomerism in the side chain at position 3. Further optical isomerism is possible in α-cyano compounds (D is CN), including racemic mixtures and distinct compounds resulting from the asymmetry of the carbon atom bearing the D group. Both isomeric esters are mentioned. The various optical and geometrical isomers of the esters of this invention usually have different insecticidal toxicity and knockdown activities. One of the cyclopropane rings in a trans relationship with each other
Compounds of the invention having hydrogen atoms in the and 3-positions are steric analogs of (+)-trans-chrysanthemum acid and for this reason represent a preferred group of compounds of the invention, but the present invention The invention also encompasses compounds in which the two hydrogen atoms in question are in a cis relationship. The insecticidal esters of the invention include alcohols of formula R-Q or derivatives thereof such as formula, or A
and a cyclopropanecarboxylic acid of the formula or a derivative thereof. In the above formula, Q and COQ ¹ are functional groups or atoms that react together to form an ester bond;
R, ^R1 , ^R2 , ^R3 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 , ^R12
and D, Z, Z ³ and Y are as defined above. In practice, acids or acid halides are reacted with alcohols (COQ ¹ is COOH or CO-halide and Q is OH) or halogen compounds (Q = halogen) are reacted with salts of carboxylic acids (COQ ¹ is It is usually convenient to react with COO M in which M is, for example, a silver or triethylammonium cation. For the reasons stated below, the reaction components are usually initially available in the form of lower alkyl esters (COQ ₁ =COO alkyl) whose alkyl group contains 1 to 6 carbon atoms. That will happen. Therefore, except when R ³ is carbalkoxy, a particularly convenient method of preparing the insecticidal esters of the invention is to transesterify an alkyl ester of formula using, for example, an alcohol ROH in the presence of a basic catalyst. It is to be attached to This alkyl ester has a base-sensitive group such as R ³ =
When containing carbalkoxy, base-catalyzed transesterification is undesirable;
And this can be avoided by producing a tertiary butyl ester, which can then be converted to the free acid by acid-catalyzed decomposition, and then this free carboxylic acid can be directly or Can be esterified via salt or halide. Esters of the invention may also be prepared by reaction between a phosphorane or ylide of formula and an ester of 2,2-dimethylcyclopropanecarboxylic acid having an aldehyde group substitution in the 3-position of formula XI. can. In these formulas and XI, R ¹ , R ² , R ³
is as defined above and R is a group as defined above which does not interfere with the Wittetzg reaction, and Z ⁴ which can in principle represent any organic group is usually a phenyl group. The reason for this is that the stability of the tri-substituted phosphorus oxide produced as a by-product in the reactant is particularly high, and this
This is because it works favorably to complete the reaction between. Esters of the invention in which R ¹ represents hydrogen are:
It can be prepared by reaction with an aldehyde of formula XI. The phosphorane and aldehyde XI are preferably reacted in substantially equimolar ratios, conveniently in the solvent in which the phosphorane itself was prepared. As will be described in more detail below, this may be an aromatic hydrocarbon such as benzene or a polar solvent such as dimethyl sulfoxide or a chlorinated hydrocarbon such as dichloromethane. The product may be improved if the reaction is carried out in an inert atmosphere, for example under nitrogen. The reaction between the phosphorane and the aldehyde or ketone is usually very fast and the desired ester can be recovered from the reaction mixture after a reaction time of up to 1 hour. However, reaction times of up to 24 hours have been used. The desired ester can be recovered from the reaction product by solvent extraction, for example with diethyl ether or petroleum ether. Phosphoranes of the formula can be prepared from the corresponding phosphonium salts, this latter using the following reaction equation Accordingly, it can be prepared by reacting a suitably substituted methyl halide with triorganophosphine. The flexibility of the present synthetic method derives from the fact that the initial starting material is the substituted methyl halide R ³ (R ² )CH hal, and a whole series of such substituted halides are available. This has hitherto been difficult or impossible to manufacture. This makes it possible to prepare a whole series of 2,2-dimethylcyclopropanecarboxylic acids substituted in the 3-position by various groups. In the synthesis of the phosphoranes described above, one starts from a substituted methyl bromide, which is reacted with triphenylphosphine to give the corresponding triphenylphosphonium bromide, and then this phosphonium salt is converted to the phosphorane or ylide represented by the above formula. It is convenient to do so.
Conversion of this phosphonium salt to phosphorane involves converting the phosphonium salt to an alkali metal amide or an alkali metal methylsulfinyl methide ( _CH2 .
This can be done by treatment with SO・CH ₃ M). For example, sodaamide can be prepared by reacting sodium in liquid ammonia, but the reaction is carried out in the presence of excess ammonia as the liquid medium. At the end of the reaction the liquid ammonia is evaporated and the phosphorane is taken up in an organic solvent such as benzene,
The subsequent reaction with aldehyde XI can then be carried out in this organic solvent. Alternatively, dimethyl sulfoxide can be reacted with sodium hydride to give sodium methyl sulfinyl methide, phosphonium salt preparation can be carried out using this reagent, and subsequent reactions with aldehyde XI following phospholane formation can be carried out using this same reagent. It can be carried out in the reaction medium. When R ³ =carbalkoxy, the conversion of the phosphonium salt to phosphorane is carried out by treating the phosphonium salt with an alkali metal amide in liquid ammonia or an aqueous alkali metal hydroxide solution such as 5% NaOH. Can be done. The liberated phosphorane is filtered from the solution and
Subsequently the aldehyde is dissolved in a suitable solvent such as CH ₂ Cl ₂
Can be reacted with XI. Phosphoranes in which R ³ represents carbalkoxy and R ² represents hydrogen can be prepared by the method described above using haloacetate alkyl esters as substituted methyl halides. Phosphorane in which R ² represents halogen is
It can be produced by a simple modification of the above synthetic method. Halogenated phosphoranes can also be prepared by halogenating non-halogenated phosphoranes, which themselves can be prepared by the method described above, using the following reaction sequence: (wherein hal is halogen, R ² is halogen and R ³ is as defined above). The inventors have discovered that in order to achieve the most satisfactory results in the reaction with phosphorane, it is desirable to esterify the carboxyl group in the aldehyde reactant XI as a lower alkyl ester. This means that the alkyl esters of the invention are prepared directly and, except for those containing base-sensitive groups such as R ³ =carbalkoxy, these alkyl esters of the invention can be prepared by a simple base-catalyzed transesterification reaction. It is not necessary to convert the alkyl esters of the invention to the corresponding acids in order to produce insecticidal esters, since they can be converted to insecticidal esters. However, indirect conversion of alkyl esters to insecticidal esters is possible according to the present invention and when operating according to this embodiment the carbalkoxy group in the ester of formula can be converted by conventional hydrolysis. can be converted into the corresponding free carboxylic acid group, for example via an alkali metal or other salt, and this carboxylic acid can be esterified directly as described above, or alternatively first an acid halide, e.g. chloride and this acid halide as described above with the formula
It can be converted into an ester by reacting ROH with a suitable alcohol. When R is a tertiary butyl group, the alkyl ester can be converted to the free acid by heating with a small amount of toluene-4-sulfonic acid. This reaction can be carried out in benzene and the carboxylic acid formed can be converted to the acid chloride in this benzene solution without isolation. In the synthesis method described so far, the alkyl ester of the invention is prepared by a Witteig reaction between phosphorane and the alkyl ester of carbonyl compound XI, and the alkyl ester of the invention produced is prepared by a transesterification reaction. or converted to the insecticidal ester via the free acid and the acid chloride which is then re-esterified with e.g. 5-benzyl-3-furylmethyl alcohol. Although it is usually the most convenient, but not necessarily absolute, to operate in this manner, an alternative practical method is to convert the phosphorane into a phosphorane in which R represents a group of the formula, , or B as defined above. The aim is to directly prepare insecticidal esters by reacting with carbonyl compounds of formula XI. A carbonyl compound such as formula XI can be prepared by converting its R group from an alkyl group to the formula:
, or B can be produced by the above-mentioned synthesis method. Carbonyl compounds of formula XI can be prepared by ozonolysis of the corresponding esters of chrysanthemum acid resulting in oxygenation of the double bond of its isobutyl side chain. That is, if R does not contain any decomposable groups under ozonolysis conditions, the desired carbonyl compound XI for this alternative method can be obtained directly by ozonolysis of chrysanthemum acid esters, and this ozonolysis Tachic acid esters XI can be used in the Uiteitsch reaction to produce insecticidal esters. Certain furan-containing compounds decompose under ozonolytic conditions. Therefore, the 5-benzyl-3-furyl methyl ester of caronaldehyde cannot be obtained from direct ozonolysis of the corresponding chrysanthemum acid ester (which has to be obtained in two steps via the alkyl ester of caronaldehyde). No, but 3-phenoxybenzyl ester can be treated as such. The alcohol and halide formula is covered by British Patent No.
It is described in the specification of No. 1305025. Formula or A when D represents CN
The alcohol can be prepared from the corresponding aldehyde in a conventional manner. i.e. furaldehyde or benzaldehyde, (a) conveniently in situ;
It can be reacted with HCN generated from KCN and acid (forming cyanohydrin if addition of HCN occurs). Formula ROH when R is a group of formula where D=H
The alcohol can be prepared by reducing the corresponding acid or ester with, for example, a hydride or by reducing the corresponding halide with, for example, a hydride or by reacting the corresponding halide with, for example, sodium acetate. esters and then hydrolyzing this ester, or by reacting formaldehyde with a Grignard reagent derived from the corresponding halide. When R is a group of the formula D=H, the halide of the formula R-halogen is a compound Halomethylation of or compounds It can be produced by halogenating the side chain of One or more of the insecticidal esters of the invention can be formulated with an inert carrier or diluent into insecticidal compositions, and these can be used, for example, as powders (dusts) and granular solids, wettable In the form of powders (wettable powders), mosquito coils and other solid preparations or after addition of suitable solvents, diluents and surfactants, emulsions, emulsifiable concentrates, sprays and aerosols and other liquid preparations. It can be prepared as Pyrethrum synergists such as piperonyl butoxide, Sesamex
Or tropital can be added to these compositions. Certain of the insecticidal esters of the present invention exhibit significant superiority in their ability to respond to synergistic agents over structurally similar esters such as chrysanthemum acid esters or pyrethrin esters, and many of the present invention ester has a synergistic factor several times greater than that exhibited by other synthetic esters. Many of the esters derived from the acids of the invention are much more stable to light than those from hitherto known acids, and dihalobinyl esters are particularly preferred in this regard. Additionally, the insecticidal composition may include known synthetic pyrethrins to improve insecticidal and/or knockdown properties or to synergize the activity of known pyrethrins and/or the synthetic pyrethrins of the present invention. . The novel esters of the present invention or insecticidal compositions containing them can be used to kill insects on a domestic or agricultural scale by treating the insects themselves or environments susceptible to insect attack with these compounds or compositions. It can be used to eliminate or control EXAMPLES In order to better understand the present invention, examples will be given and explained below, but the present invention is not limited thereto. Temperatures are given in °C and refractive indices were measured at 20 °C. Unless otherwise specified, the C ₁ and C ₃ hydrogen atoms of the cyclopropane ring are in a trans relationship with each other. Example 1 Chloromethylenetriphenylphosphonium chloride (2.1 g,
0.006 mol) and dry piperidine (0.51 g,
0.006 mol) is treated with 8% n-butyllithium in hexane (4.8 ml [0.388 g, 0.006 mol]) under a stream of nitrogen. The mixture was stirred at room temperature for 1.5 hours and tertiary-butyltrans-caronaldehyde (1.27 g,
0.0064 mol). The mixture is stirred for 3 days, the solution is filtered and the precipitate is washed with dry diethyl ether. _Convert this solution to 10% _H2SO4
and water, dried (Na ₂ SO ₄ ), evaporated the solvent, and then distilled to give a colorless liquid bp 100°/
20mm (70%) is obtained. It is identified by the NMR spectrum as the above ester with the formula where R ² =Cl, R ³ =H, R ¹ =H and R = tertiary-C ₄ H ₉ and n _D 1.4670. The configuration around the double bond αβ for the above ring is 20:80Z:
It is E. Next, the above alkyl ester produced by the method described in Example 1 is converted into the above corresponding 5-benzyl-3-furylmethyl ester by the method described in Example 2 below. Example 2 The tertiary butyl ester described in Example 1 (410
A mixture of toluene-4-sulfonic acid (47.5 mg) and dry benzene (15 ml) is refluxed for 2 hours and then cooled to give a solution of the corresponding carboxylic acid described above. Next, pyridine (163 mg) and thionyl chloride (213 mg) are added and the mixture is left to stand for 2 hours to obtain the above acid chloride. A mixture of the above acid chloride, 5-benzyl-3-furylmethyl alcohol and pyridine in substantially equimolar ratios is prepared in dry benzene, the mixture is cooled and left overnight at room temperature. This mixture was then poured into a neutral alumina column and eluted with benzene to yield a compound of formula (where R ² = Cl, R ₃ = H, R ¹ = H and R = 5-benzyl-3-furylmethyl). can get. This ester, named ester K, has n _D 1.5418. Example 3 Triphenylphosphine (13 g) is dissolved in dry benzene (60 ml) and ethyl bromoacetate (8.3 g) is added dropwise. The solution is heated to 70° for 2 days, then cooled and filtered. The residue is washed with benzene and dried to yield about 16 g of (ethoxycarbonylmethyl)triphenylphosphonium bromide. This phosphonium salt (10 g) is dissolved in water (250 ml) and a 5% aqueous sodium hydroxide solution is added dropwise with stirring until the solution becomes alkaline to litmus. The resulting precipitate is collected, washed with water and dried. Crystallization from ethyl acetate/petroleum ether gives (ethoxycarbonylmethylene)triphenylphosphorane as a colorless solid in about 80% yield. The above phosphorane (3.2 g, 0.0092 mol) in dry dichloromethane (30 ml) was mixed with tert-butyl (+) trans-calonaldehyde (1.5 g,
0.0076 mol) (obtained by ozonolysis of tertiary-butyl(+)-trans-chrysanthemum acid) and continued stirring at room temperature for 2.5 days. Evaporate the solution and transfer the residue to petroleum ether (60-80
Extract at ℃). When this is evaporated and distilled, it becomes a colorless liquid bp112゜/0.7mm, 1.60g (79%), _{n D}
1.4666 is obtained. This product was determined by NMR spectrum and gas phase/liquid phase chromatography to show the formula (wherein R ³ = carboethoxy, R ² = H and R = tertiary
was identified as a compound (compound P19/
B′). Example 4 The procedure described in Example 3 was carried out by using equivalent amounts of methyl bromoacetate and propyl bromoacetate in place of the ethyl bromoacetate described above, and changing the reaction time or reaction temperature as necessary during the production of phosphorane. If the process is repeated, the formula (where R ² = H, R = tertiary butyl and R ³ =
carbomethoxy or carbo-n-propoxy)
compounds, n _D 1.4677 and 1.4723 (compound P19/
A' and P19/C') are obtained, respectively. Example 5 The compound (0.393 g) of the formula described in Example 4 (wherein R ³ = n-propoxycarbonyl, R ₂ = H and R = tertiary butyl) was added to benzene (11.5 ml).
The mixture was refluxed for 2 hours with toluene-4-sulfonic acid (47.2 mg). When this solution is cooled, the generated acid (R ³ = n-propoxycarbonyl, R ₂ = H,
R=H) is precipitated. Dry pyridine (0.127g,
131μ) and thionyl chloride (0.158g, 96μ
) is added and the mixture is left at about 20° for 2 hours to form the corresponding acid chloride described above. A solution of 5-benzyl-3-furyl methyl alcohol (2.75 mg) and pyridine (0.105 g, 108 .mu.) in benzene (8 ml) is added and the solution is left overnight. The solution was passed through a neutral alumina column and evaporated to yield 550 mg of the formula (where R ₃ = n
-propoxycarbonyl, ^R2 =H and R=5
-benzyl-3-furylmethyl) compound, n _D
1.5278 is obtained (compound P19/C). It was confirmed by NMR spectrum and gas/liquid phase chromatography that the structure of the above ester corresponds to the formula. The following esters are prepared in a similar manner. Compounds R ² R ³ n _D P19/A H COOCH ₃ 1.5262 P19/B H COOC ₂ H ₅ 1.5298 P19/C H COO _o −C ₃ H ₇ 1.5278 P19/A to P19/C all have the formula (in the formula R=5-benzyl-3-furylmethyl). Example 6 Triphenylphosphine (13 g) is dissolved in dry benzene (60 ml) and methyl bromoacetate (8.3 g) is added dropwise. The solution is heated at 70° C. for 2 days, then cooled and evaporated. The residue is washed with benzene and dried to yield about 16 g of (methoxycarbonylmethyl)triphenylphosphonium bromide. This phosphonium salt (10
g) is dissolved in water (250 ml) and a 5% aqueous sodium hydroxide solution is added dropwise with stirring until the solution becomes alkaline to litmus. The resulting precipitate is collected, washed with water and dried. Crystallization from ethyl acetate/petroleum ether gives (methoxycarbonylmethylene)triphenylphosphorane as a colorless solid in about 80% yield. (Methoxycarbonylmethyl)triphenylphosphorane (3.34 mL) in methylene chloride (70 ml)
g) was cooled to -70°C and diluted with triethylamine (1.01
g) with stirring followed by chlorine (0.77 g) in CCl ₄ (11 ml). Stirring is continued at this temperature for 30 minutes, and after stirring for an additional hour, the temperature of the reaction mixture rises to room temperature. The reaction mixture is washed with water (3 x 50 ml), dried over Na ₂ SO ₄ and evaporated to give 2.8 g of chlorinated phosphorane/Ph ₃ P=C(Cl)COOMe. Tertiary-butyl-(+)-trans-calonaldehyde (obtained by ozonolysis of the tertiary-butyl ester of (+)-trans-chrysanthemum acid) (0.7
g and the above chlorinated phosphorane (1.3
The mixture of g) is refluxed for 1 hour in 10 ml of dry benzene. After distilling benzene, the resulting product is distilled under reduced pressure to yield tertiary-butyl-2,2-dimethyl-3-(2-chloro-2-carbomethoxyvinyl)-cyclopropylcarboxylate b.
p.110℃ (0.4mm, n ²⁰ _D 1.4749 is obtained. Yield 0.65
g. This compound is named compound P24A'. Example 7 Using ethyl bromoacetate or propyl bromoacetate instead of methyl bromoacetate as described above, or using ethyl bromoacetate instead of methyl bromoacetate and using bromine instead of chlorine in the halogenation of the phosphorane step, Repeating the method described in Example 6 provides the following compound having the formula:

[Table] Example 8 A mixture of the compound P24A' of Example 6 (320 mg) and toluene-4-sulfonic acid (50 mg) is refluxed in dry benzene (10 ml) for about 2 hours and then cooled. 2,
2-dimethyl-3-(2-chloro-2-carbomethoxyvinyl)cyclopropanecarboxylic acid was identified in the solution by NMR. Pyridine (111 mg, 114 microliters) and thionyl chloride (132 mg, 80 microliters)
is added to the solution of the above carboxylic acid and the mixture is left at room temperature for 3 hours. NMR in this solution revealed that 2,2-dimethyl-3-(2-chloro-2-
It was identified as (carbomethoxyvinyl)-cyclopropanecarboxylic acid chloride. 5-benzyl-3-
A solution of furyl methyl alcohol (210 mg) and pyridine (88 mg, 90 microliters) in dry benzene (5 ml) is added and the mixture is left at room temperature overnight. Next, the solution was poured into a neutral alumina column and eluted with benzene, resulting in 200mg of 2,
5 of 2-dimethyl-3-(2-chloro-2-carbomethoxyvinyl)-cyclopropanecarboxylic acid
-benzyl-3-furyl methyl ester n ²⁰ _D
1.5398 is obtained. This compound was named compound P24A. Example 9 Compounds P24B', P24C' and
Repeating the method described in Example 8 using P24D' provides the following compound having the formula: Compound R ³ R ² n ²⁰ _D P24B COOC ₂ H ₅ Cl 1.5404 P24C COO _o −C ₃ H ₇ Cl 1.5332 P24D COOC ₂ H ₅ Br 1.5366 The above three compounds have the formula furylmethyl). The following formulation examples are provided to illustrate the application of the insecticidal compounds of the present invention to insects or environments susceptible to insect attack. Formulation example 1 Oil-based liquid spray against household insects Active compounds 0.015% w/v 25% pyrethrum extract 0.25% Piperonyl butoxide 0.5% Antioxidants 0.1% Odorless light oil solvent (e.g. xylene)
Quantity to make 100 volumes Formulation example 2 Water-based liquid spray concentrate for mosquito control Active compounds 0.25% w/v Piperonyl butoxide 1.0% Non-ionic emulsifier 0.25% Antioxidants 0.1% Water Makes total volume 100 Amount This concentrate is 1:80v/1:80v/water with water before spraying.
should be diluted to v. Formulation example 3 Aerosol Active compound 0.05% w/w 25% pyrethrum extract 0.8% Piperonyl butoxide 1.5% Odorless petroleum distillate (bp 200-265°) 17.338% Propellant (e.g. an equal mixture of trichloromonofluoromethane and dichlorodifluoromethane) ) 80.0% Fragrance 0.2% Antioxidant 0.1% Formulation example 4 Mosquito coil Active compound 0.25% w/w Tab powder (also known as pyrethrum meal)
30.0% Fillers (e.g. wood flour, powdered leaves or nut shells) 68.75% Brilliant Green 0.5% p-Nitrophenol 0.5% Formulation Example 5 Emulsifying concentrate Active compound 1.5% w/w Non-ionic emulsifier 25.0 % Xylene 73.4% Antioxidant 0.1% Before use, add 30ml of this concentrated stock solution to 41% water.
May be diluted at a rate of 2 liters. Formulation example 6 Powder for general purposes such as home, garden, livestock or grain storage Active compound 0.05% w/w Tropital (synergist piperonyl-bis-2-[2'-n-butoxyethoxy)] Ethyl acetal) 0.25% Antioxidants (e.g. butylated hydroxytoluene or hydroxyanisole) 0.03% Fillers 99.67% The insecticidal activity of the esters of the invention was evaluated against house fly and mustard beetle by the following method. Insecticide test against house fly (Musca domestica) Female flies are treated on the thorax with 1 drop of 1 microliter of insecticide dissolved in acetone. 2
A set of 15 flies was used at each dose ratio and six dose ratios were used per compound tested. After treatment, the flies are kept at a temperature of 20°C ± 1° and mortality is assessed 24 and 48 hours after treatment. LD ₅₀ values are calculated in micrograms of insecticide per fly and relative toxicity is calculated from the inverse ratio of the LD ₅₀ values (Bulletin of the World Health Organization).
35, 893, (1966) and EntomoIOgia and Exp.
Appl. 10, 253 (1967)). Insecticidal test against the mustard beetle (Huaedon cochleariae faab) A solution of the test compound in acetone is administered to the abdomen of adult mustard beetles using a microdropper. The treated insects are kept for 48 hours before mortality is assessed. Using two sets of 40 to 50 mustard beetles at different dosage levels,
And three to four dosage levels are used for each compound. Calculate the LD ₅₀ value again and calculate the relative toxicity against the inverse ratio of the LD ₅₀ [J.Sci.
See Food Agric.20, 561 (1969)]. Relative toxicity is calculated by comparison with (+)-trans-chrysanthemum acid 5-benzyl-3-furyl methyl ester. And houseflies and mustard.
It is one of the most toxic chrysanthemum esters known to the beetle, being 24 times more toxic than allethrin to the house fly and 65 times more toxic than allethrin to the mustard beetle. The following relative toxicity was obtained.

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Claims (1)

[Claims] 1. General formula [In the formula, R ¹ represents hydrogen, R ² represents halogen, R ³ represents hydrogen or a lower alkoxycarbonyl group, and R represents 5-benzyl-3-
An insecticide characterized by containing as an active ingredient a synthetic pyrethroid representing a furylmethyl group.