NL8402990A - Prodn. of insecticidal pyrethroid ester(s) - namely 3-alkenyl-2,2-di:methyl-1-cyclopropane-carboxylate ester(s) - Google Patents

Abstract

Prodn. of pyrethroids of formula (I) and insecticidal compsns contg. them is claimed: In (I), R1 = H or Me; R2 = H or alkyl; R3 = H or alkoxycarbonyl with at least 2C in the alkoxy gp. when R2 = Me; provided that (a) R2 and R3 are both H only when R1 = Me, and (b) R2 contains at least 2C when R1 = R3 = H and R2 = alkyl; R = a gp. of formula (II)-(V): Z = O, S, CH2 or CO; Y = H, alkyl, alkenyl, alkynyl, or aryl or furyl opt. ring-substd. by alkyl, alkenyl, alkoxy or halogen; R7 and R8 = H, alkyl or alkenyl; R9 = H or Me; R10 and R11 = H or alkyl; R12 = an organic gp. with C-C unsatn. in the posn. alpha to the CH2 gp. to which R12 is attached; A/S = an aromatic ring or a di- or tetrahydro analogue thereof; X1-X4 = H, Cl or Me; Z3 = CH2, O, CO or S; D = H, CN or CCH; Z1 and Z2 = H, Cl or Me; n = 0-2.

Description

VO 6441 Insecticides

The invention relates to insecticides and more particularly to synthetic insecticides of the pyrethrin type, to their preparation, to compositions containing them and to the use of the compounds and compositions as insecticides.

For many years, research has continued in the field of synthetic analogues of the pyrethrins to discover synthetic substitutes having properties superior to those of the natural products. Ideally, synthetic analogues of the naturally occurring pyrethrins 10 would be comparable or even better than the natural products in terms of toxicity, insect and mammal, insecticide spectrum and anesthetic properties ("Knock down") preparation.

Since the discovery that the naturally occurring pyrethrins were esters of certain substituted cyclopropanoic acids and substituted cyclopentenols, research on synthetic analogs has initially focused on modifying the "alcohol" portion of the ester molecule and later on modifying the "acid" portion of the ester molecule or in some cases modifying both parts of the ester molecule. The naturally occurring esters are esters of chrysanthemum or pyrathric acids of formula 1 of the formula sheet, wherein X represents a methyl group (chrysanthemic acid) or a cafbomethoxy group (pyrethric acid). In these acids, it is believed that the substituents on the carbon atom marked with a star are involved in detoxifying the pyrethrin insecticides in the insect.

It has now been found that a high degree of insecticidal activity and a particularly valuable combination of toxicity and anesthetic properties can be obtained in esters of 2,2-dimethyl-5-alkenylcyclopropanecarboxylic acid in which the substitution on the 3-alkenyl side chain differs from that of all hitherto known pyrethrin-like esters.

8402990 * i - 2 -

The invention therefore provides esters of the general formula II of the formula sheet wherein R * represents hydrogen or a methyl group 2 3? R hydrogen or a halogen or alkyl group; R hydrogen or 2 2 a halogen, alkyl (which is different from R when R represents an alkyl group) or a carboalkoxy group containing at least 2 carbon 2 2 3 atoms in the alkoxy residue when R is methyl or R and R together with the carbon atom to which they are attached a cycloalkylene ·. . proposing a ring having at least one endocyclic carbon-carbon-2 2 double bond; with the proviso that (a) R and R each represent hydrogen only when R * represents methyl and (b) R 1 at least 2 contains at least 2 carbon atoms when R and R each represent hydrogen; and R represents (a) hydrogen (or a salt or acid halide derivative of the acid) or an alkyl group, or (b) a group of formulas 3, 4, 5, β, 6A or 6B of the formula sheet, wherein 20 ', S , CH 2 or CO represents, Y represents hydrogen or an alkyl, alkenyl or alkynyl group or an aryl or furyl group unsubstituted or ring-substituted by • one or more alkyl, alkenyl, alkoxy or halogen groups 7 8 R and R which may be the same or different, each represent hydrogen g or an alkyl or an alkenyl group, R is hydrogen or a methyl group, R 1 and which may be the same or different, 12 are each hydrogen or an alkyl group, R is an organic radical with a carbon-carbon unsaturation. in a position a relative to the CH 2 group to which R 1 ^ is attached (A / s) denotes an aromatic ring or a di-12 3 4 hydro or tetrahydro analog thereof, X, X, X and X, 25 which . may be the same or different, each represent hydrogen, chlorine, or a methyl group, - CH - or -O- or -S- or CO-, represents DN, HRT or -C = CH, Z1 and Z, which are the same or can be the same, each represents chlorine or a methyl group and n = 0.1 or 2, with the proviso that R does not represent hydrogen (or an acid chloride derivative of the acid) or an ethyl or allethronyl group 1 2 3 when R represents hydrogen , R and R each represent chlorine and the compound is racemic.

The esters of the invention in which R represents a group of formulas 3, 4,5,6,6A or 6B of the formula sheet are insecticidal stars which have a valuable combination of toxicity and anesthetic properties. The insecticidal activity level of the 8402990-3 * h = tfi new compounds is amazingly high, with the 5-benzyl-3-fuzylmethyl esters of (+) '- trans-3- (but-1-enyl) - and 3- (2,2-dichloro-vinyl} -2,2-dimethylcyclopropanecarboxylic acid, respectively, about 1.7 and 2.5 times more toxic to houseflies than those of the corresponding (+) - trans chrysanthemum .

The esters of the invention in which R represents alkyl are not insseticides but useful intermediates for the preparation of the insecticidal esters, e.g., by transesterification. As will be discussed in more detail below, the novel alkyl esters of the invention may be prepared in that form by a Wittig synthesis and it is not necessary to convert the alkyl ester to the free carboxylic acid to produce the insecticidal esters of the invention to shape. However, if desired, the alkyl esters can be converted to the free carboxylic acid, e.g. by hydrolyzing the ester to form a salt and then acidifying the salt.

The esters of the invention in which R represents alkyl 2 and R = carboalkoxy are useful intermediates in the formation of the insecticidal esters which can be converted by acid catalysis, e.g. using toluene-4-sulfonic acid in benzene, in 2

The corresponding free carboxylic acid without the carbalkalkoxy group R.

to affect. As will be discussed in more detail below, the new alkyl esters of the invention in that form are prepared by a Wittig synthesis and it is necessary to convert the alkyl ester to the free carboxylic acid to form the insecticidal esters of the invention . This is best achieved selectively using a t-butyl ester (R - ^ t-butyl),

However, if desired, a t-butyl or other alkyl ester can be converted to the free carboxylic acid by partial saponification, but it is difficult to prevent saponification of the carboalkoxy group at the same time.

The insecticidal esters of the invention can be structurally considered as esters of a 3-substituted-2,2-dimethylcyclopropanecaronic acid and an alcohol, e.g. a benzyl alcohol, a furylmethyl alcohol, a cyclopentenols or an α-cyano or Q-ethynyl-benzyl or α-cyano or α-ethynyl-fuzylmethyl alcohol. While the esters can be structurally described in this manner for the sake of convenience, it will be appreciated that in more detail 8402990 * 'MT' 4 - 4 - hereinafter, it is explained that the esters can be prepared by methods other than. esterifying it. acid with the alcohol and that they are usually prepared in practice. As for the 12 different substituents R, R and R, it is preferred that when these groups represent alkyl or alkoxy groups these groups contain up to 6 carbon atoms and more particularly up to 3 carbon atoms, where methyl, ethyl, propyl , methoxy, ethoxy and propoxy are of particular interest. When R and / or R represents a halogen group, this group is preferably fluorine, chlorine or bromine.

2 3 10 When R and R each represent a halogen, they are preferably, but not necessarily, the same halogen.

The esters according to the invention structurally fall into different subclasses, mainly depending on the nature of the substituents R and R. A subclass of particular interest are those compounds wherein R 1 and R 2 each represent hydrogen and R represents an alkyl group of at least 2 carbon atoms. It has now been found that in this subclass the highest toxicity to houseflies and mustard beetles is shown by the 5-benzyl-3-furylmethyl esters of 3-B-alkylvinyl-2,2-dimethylcyclopropanecarboxylic acid when the alkyl group is ethyl.

Other subclasses of particular interest are those esters 13 2 in which R and R are each hydrogen and R is chlorine or bromine and 8402990 2 3

those compounds in which R is a methyl and R is hydrogen and R.

hydrogen or an alkyl group containing up to 6 carbon atoms, such as methyl, ethyl or propyl.

2

All of the above subclasses of esters are those in which the carbon atom in the B position in the -3 substituent is directly bound to at least one hydrogen atom. Another subclass of the esters of the invention is that in which the substitution at the star-labeled carbon differs from that of any of the previous compounds in that it is an unsympathetic dialkyl substitution and of this class of compounds are those in which 23 2 R and R methyl and the other ethyl are of interest. When R and 3 R together with the carbon atom to which they are attached form a cyclic group, it is preferred that the ring contains 5 carbon atoms and 1 or 2 endocyclic carbon-carbon double bonds.

. = w - 5 -

Another subclass of particular interest is formed by those compounds wherein R hydrogen and R represent a carboalkoxy group. These esters are esters of a demethylpyrethric acid analog which has no methyl substituent on the 3 »carbon rod atom of the 3 substituent. Another subclass of considerable interest is formed by those esters in which R methyl and R represent a carbon-alkoxy group in which the alkoxy residue contains at least 2 carbon atoms. These esters are esters of pyrethric acid analogs which do not contain a carbomethoxy substituent on the S-carbon bridle of the 3 substituent.

Further subclasses of particular interest are those esters in which R 1 represents an alkyl group having at least 2 carbon atoms; again, these esters are esters of a pyrethric acid homolog that does not contain a methyl substituent on the star 2-labeled carbon of formula 1. In these esters, R may represent the carbomethoxy group (which is present in pyrethric acid) or a higher homologue thereof.

The most effective of the insecticidal esters according to the

The invention are those esters in which R represents hydrogen and R

3 and R each are a halogen group, the 5-benzyl-3-furylmethyl esters of the different isomers, 2,2-dimethyl-3- (2,2-dichloro-vinyl) -cyclopropane carboxylic acids being up to 2 times as toxic to houseflies as the corresponding ester of (+) - trans-chrysanthemic acid, which in itself is 50 times more toxic compared to normal houseflies 25 than naturally occurring pyrethrin I. The esters of these 3-dihalovinyl acids are also of particular interest because of their greater light stability than the corresponding Chrysanthemums.

Another halogenated subclass of interest is formed by those esters in which R represents hydrogen, R halogen and R carbon-30 alkoxy. The acid residues in these esters are analogues of pyrethric acid whose methyl substituent on the 3-carbon atom of the 3 substituent is replaced by halogen and homologues of these acids in which the carbomethoxy group is replaced by a carboalkoxy group containing at least 3 carbon atoms. The halogen is preferably chlorine or bromine and the carboalkoxy group is preferably carbomethoxy, ethoxy or n-propoxy.

Preferred esters of the invention are 8402990

* '' "V

Those esters which are structural esters of a 2,2-dimethyl-3-substituted cyclopropanecarboxylic acid whose 3 substituent is represented by one of the groups of formulas I-XIV of the formula sheet.

When the esters of the invention are alkyl esters, it is preferred that the alkyl group contains up to 6 carbon atoms and it has been found that methyl, ethyl and tert-butyl esters can be readily prepared according to the synthetic methods described.

When the ester is structurally derived from a furylmethyl alcohol, it is preferred that the furylmethyl alcohol be one of the 3-1 furylmethyl alcohols described in British Patent No.

1,168,798. In the furylmethyl alcohols and in particular in the 7-8 3-furylmethyl alcohols it is preferred that R and R each represent hydrogen or groups of up to 4 carbon atoms, especially without a methyl group and that Y represents a phenyl group which is unsubstituted or the ring is substituted with a group containing up to 4 carbon atoms, hv methyl, or methoxy, or by chlorine, and Z = CE2 and D-H. Analogs of these compounds in which Z * 0, S or CO and D are CN or C-CH can also be used. Other compounds of interest are those compounds in which Y represents a hydrogen atom, an alkyl group of up to 4 carbon atoms, an alkylene group of up to 4 carbon atoms, e.g. vinyl an alkadienyl group with up to 4 carbon atoms or an alkyl-yl group, e.g. propargyl or a furyl group ..

Particular alcohols of this category, the esters of which are structurally derivable according to the invention, include 5-benzyl-3-furylmethyl alcohol, 5-benzyl-2-methyl-3-furylmethyl alcohol, 5-benzylfurfuryl alcohol, 4-benzyl-5-methyl- furfuryl alcohol, 5-J-xylyl-furfuryl alcohol, 2,4,5-trimethyl-3-furylmethyl alcohol, 4,5-30 dimethyl-furfuryl alcohol, 5-phenoxy- and 5-benzoyl-3-furylmethyl alcohol and α-cyano and a -ethynyl-5-benzyl-5-benzoyl- and 5-phenoxy-3-furyl-methyl alcohol.

The cyclopentenolones whose esters according to the invention are structurally derivable are those which do not have substituents in the 3-position or which are substituted in the 3-position 9 with a methyl group (R = H or CH 2).

The cyclopentenolones unsubstituted at 8402990 § $ 7 - the 3-position are described in British Patent 1,305,025.

Some of these alcohols are the 3-demethy1 analogues of the alcohols from which the naturally occurring pyrethrins are derived.

In the invention, it is preferred that and R 1 each represent hydrogen, 12 methyl or ethyl and R 1 represents an aryl group such as a phenyl group or a phenyl group substituted by a halogen or alkyl or alkoxy substituent of 1-4 carbon atoms, e.g.

12 tolyl-xylyl, 1-chlorophenyl or 1-methoxyphenyl. R can also represent a 2- or 3-furyl group or an alkenyl group such as a vinyl, prop-1-enyl or buta-1,3-dienyl group.

When the esters of the invention are structurally deducible from the cyclopentenolones substituted in the 3-position by the methyl group, (R 1 methyl), the esters can be derived from allethroles (R ^ = R ^ * - H, R ~ 2 - vinyl), pyrethroles 15 (R * ^ * R ** = H, R * 2 = buta-1,3-dienyl), cinerolone (R1 ^ = R11-H, R * 2 * prop-1-enyl) , jasmill (R10 = R ^ = H, R ^ 2 = but-1-enyl) or furethroles (R ^ = R11 = H, R12-2-furyl).

When the esters of the invention are phthalimidomethyl esters, wherein R is of formula 5, they may be phthalimido, dihydrophthalimido, or tetrahydrophthalimid o-methyl esters in which the phthalimid o-dihydrophthalimido or tetrahydrophthalimid o residue is described in British Patents 985,006 , 1,052,119 or 1,058,309.

Of special interest are the 3,4,5,6-tetrahydrophthalimidomethyl esters.

When the esters of the invention are those, wherein R in R is of formula 6, it is preferred that they be 3-benzyl-benzyl esters, 3-benzoyl-benzyl esters or 3-phenoxybenzyl esters although each of the rings may be substituted with up to 3 chlorine and / or methyl groups. Other esters of particular interest where R is of formula 6 are those wherein 7? 0 or CH 2 and D 30 -CM or C = CH e.g. esters of a-cyano or a-ethynyl-3-phenoxybenzyl alcohol and of a-cyano or a-ethynyl-3-benzyl and 3-benzoylbenzyl alcohols.

The compounds of the invention have geometric and optical isomers and, therefore, they can be prepared in optically active forms which can then be mixed or as a racemic mixture which can then be cleaved. optically active forms. Also, the optically active forms or the racemic mixtures can be separated into the individual geometric isomers. In addition to the geometric isomerism resulting from the configurations of the substituents on the cyclopropane ring relative to each other and the ring, there is also the possibility of geo- • 12 3

metric isomerism in the side chain at position 3 when R, R and R.

* such that the unsaturated side chain is asymmetrically substituted. In the α-cyano and α-ethynyl compounds (D = CN or C - CH) there is the further possibility of optical isomerism and the intended compounds include esters of both the racemic mixture and of the individual isomers that result due to the asymmetry of the carbon atom carrying the D group. The different optical and geometric isomers of the esters of the invention usually have different insecticidal toxicity and anesthetic properties.

The compounds of the invention wherein the hydrogen atoms in the 1 and 3 positions of the cyclopropane ring are in trans configuration relative to each other are stereo analogues of (+) -trans-chrysanthemic acid and for this reason they represent a preferred class of compounds of the invention for but the invention also includes compounds wherein the two hydrogen atoms are in the cis configuration.

The insecticidal esters of the invention can be prepared by esterification involving the reaction of an alcohol or derivative thereof of the formula R-Q, e.g. according to formulas 7, 8 or 8A of the formula sheet, and a cyclopropanecarboxylic acid or derivative thereof according to formula 9, wherein Q and COQ are functional groups or. are atoms that react directly with each other under 1 2 3 7 8 9 1G 11 forming an ester bond and R, R, R, R, R, R, R, R, R, 12 12 3 30 R and D, Z, Ζ , Ζ, Ζ, Υβηη are as defined above.

In practice, it is usually suitable to either react the acid or acid halide with the alcohol (COQ ^ = COOH or ÓQ-halide and Q - OH) or to react a halogen compound (Q = halo ~ 1 geen © none) with a salt of the carboxylic acid (COQ = COO M 35 in which M is eg a silver or triethylammonium cation).

For reasons as described below, reactant 9 is usually initially available in the form of a lower 8402990 tf 3 ... 9 -alkyl ester (COQ * = COO alkyl) in which the alkyl group contains 1-6 carbon atoms and thus a particular suitable way to prepare the insecticidal esters according to the invention, except when R is a carbosylkoxy, to transesterify the alkyl ester of formula 9 using an alcohol ROH, eg

in the presence of a basic catalyst. When the alkyl ester 2 contains a base sensitive group, e.g. R * carboalkoxy, a base-catalyzed transesterification is undesirable and can be avoided by preparing a jt-butyl ester which can then be converted to the free acid by an acid catalyzed decomposition and the free carbonic acid group directly or via a salt or halide can be esterified.

The esters of the invention may also be prepared by the reaction between a phosphoran or ylide of formula 10 and an ester of 2,2-dimethylcyclopropanecarboxylic acid substituted in the 3 "position by an acetyl group or an aldehyde group of formula 11 of the formula sheet. In formulas 10 and 11, R * -, 2 3 R, R are as defined above and R is a group, as defined above, which will not disturb the Witti reaction and Z which can in prxn-20 cipe any organic group will usually be a phenyl radical since the stability of the tri-substituted phosphorus oxide formed as a by-product in the reaction is particularly high, favoring the completion of the reaction between the phosphorane 10 and the aldehyde or ketone 11.

Esters according to the invention in which R 1 represents hydrogen can be prepared by reaction with an aldehyde of formula 11, while esters according to the invention in which R represents methyl can be prepared by reaction of a 3-acetyl compound of formula 11. The phosphorane 10 and the aldehyde or ketone 11 are preferably reacted in substantially equal amounts, conveniently in the solvent in which the phosphorane itself is prepared.

As will be explained 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 can be improved when the reaction is carried out in an inert atmosphere, e.g. under nitrogen. The reaction between the phosphoran and aldehyde or ketone is usually very fast and the desired ester can be recovered from the reaction mixture after a reaction time of less than 1 hour, although reaction times of up to 24 hours have been used to be. The desired ester can be recovered from the reaction product by solvent extraction, e.g. with diethyl ether or petroleum ether.

2 3

The phosphorane of formula 10 wherein neither R or R represents halogen can be prepared from the corresponding phosphonium salt, which in turn can be prepared by reacting the appropriately substituted methyl halide with a triorganophosphine according to the reaction scheme A of the formula sheet.

The pliability of the present synthesis results from the. fact, that the starting material is the substituted 3 2 methyl halide R (R) CH that hall. and the availability of whole arrays of such substituted halides allows the formation of whole arrays of 2,2-dimethylcyclopropanecarboxylic acids substituted in the 3-position by various groups that have hitherto been difficult or impossible to prepare.

In the above synthesis of the phosphoran, it is convenient to start from a substituted methyl bromide which is reacted with triphenylphosphine to give the corresponding triphenylphosphonium bromide and subsequently convert the phosphonium salt to the phosphoran or ylide which may be indicated by the above formula . The conversion of the phosphonium salt to the phosphoran can be accomplished by treating the phosphonium salt with an alkaline amide or an alkaline methylsulfinylmethide. 50..

E.g. sodamide can be prepared by reacting sodium in liquid ammonia and carrying out the reaction in the presence of excess ammonia as the liquid medium. At the end of the reaction, the liquid ammonia is allowed to evaporate and the phosphoran 30 is taken up in an organic solvent, such as benzene, and the following reaction is carried out with aldehyde or ketone according to formula 11 in this organic solvent. Alternatively, the dimethyl sulfoxide can be reacted with sodium hydride to give sodium methyl sulfinyl methide, and the preparation of the phosphonium salt can be carried out using this reagent and following the formation of the phosphorane, the following reaction with the aldehyde or ketone of formula 11 in the same reaction medium 8402990-2; > - 11 - are executed.

When R * carboalkoxy, the conversion of the phosphonium salt to the phosphoran can be effected by treating the phosphonium salt with an alkaline amide in liquid ammonia from an aqueous alkaline hydroxide de-cloyment, e.g. 5% NaOH. The liberated phosphoran can be filtered from the solution and then reacted with the aldehyde of formula 11 in a suitable solvent, e.g. CH.C10.

3 * 2

Phosphoranes in which F carboalkoxy and R represent hydrogen or 10 methyl can be prepared by the procedures described above using a haloacetate or an α-halopropionate alkyl ester as the substituted methyl halide, but this synthesis is not quite sufficient for the preparation of phosphoranes 2 of this type wherein R represents an alkyl group having 2 or more carbon atoms. For such higher homologues, a phosphorus, wherein R hydrogen and R represent the desired alkyl group, is first prepared as an intermediate by the above-described procedure starting from an alkyl halide of at least 3 carbon atoms and this phosphorus intermediate is then reacted with the passene alkyl. Chloroformate ester under entering the desired carboalkoxy group.

2 3

Phosphoranes in which R and / or R represent halogen can be prepared by a simple modification of the above-described synthesis.

When R and R each represent halogen, a carbon tetrahalide can be used in place of the substituted methyl halide and the reaction proceeds according to reaction scheme B of the formula sheet, with the dehydrohalogenation of the quaternary phosphonium halide proceeding spontaneously.

Halogenated phosphoranes can also be prepared by halogenating a non-halogenated phosphoran, obtained by itself by the procedures described above, in accordance with the reaction scheme C of the formula sheet, wherein hal = halogen is R = halogen and R is as defined above.

It has been found that it is desirable that the carboxyl group in the aldehyde or ketone reactant 11 be esterified as 8402990-12 - a lower alkyl ester to achieve the most satisfactory results in the reaction with the phosphorane. This means that the alkyl esters of the. invention and since it is possible to convert these alkyl esters to the insecticide esters of. the invention, except those containing 2 a base sensitive group, e.g. Carboalkoxy, by a simple base-catalyzed transesterification reaction, it is not necessary to convert the alkyl esters of the invention to the corresponding acids to form the insecticidal esters.

However, an indirect conversion of the alkyl esters to the insecticidal esters is possible in accordance with the invention, when working according to this embodiment the carboalkoxy group in the ester of formula 2 can be converted by conventional hydrolysis to the corresponding free carboxylic acid group. e.g. going through the alkaline or other salt, and this carboxylic acid can be directly esterified as described above or otherwise it can first be converted into an acid halide, e.g. the chloride and this acid halide can be converted to an ester by reaction with an appropriate alcohol of the formula ROH as described above.

In the case where R is a t-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 resulting carboxylic acid can be converted to the acid halide in the benzene solution without isolation.

In the syntheses described so far, the alkyl esters of the invention are prepared by a Wittig reaction between a phosphoran 10 and an alkyl ester of a carbicyl compound 11 and the resulting alkyl ester of the invention is converted into an insecticidal ester by transesterification or via the free acid and acid chloride which is subsequently re-esterified eg.

with 5-benzyl-3-furylmethyl alcohol. It is usually very easy to proceed in this way, but it is not essential to do so, and a practical alternative is to prepare the insecticide ester directly by reacting the phosphorane with a carbonyl compound of formula II, wherein R represents a group of formula 3, 4, 5, 6, 6a or 6b as defined above.

8402990 'ψ * - 13 -

Such carbonyl compounds of formula 11 can be prepared by synthesis methods as described above but converting the group R from an alkyl group to a group of formula 3, 4, 5, 6, 6a or 6b, prior to the Wittig-5 reaction instead of or after the Wittig reaction as described above.

Carbonyl compounds of formula 9 can be prepared by ozonolysis of the corresponding ester of the chrysanthematic acid when oxygenation of the double bond occurs in the isobutenyl side chain. Provided that R does not contain a group that degrades under ozonolysis conditions, the required carbonyl compound 11 can be obtained directly by this alternative method by ozonolysis of the chrysanthemum hemate and the ozonized chrysanthemate 11 can be used in the whitish reaction to form the insecticide ester to deliver. Some furan-containing compounds IS are degraded under ozonolysis conditions so that the 5-benzyl-3-furyl methyl ester of caronaldehyde cannot be obtained by direct ozonolysis of the corresponding chrysanthemate hemate (it must be obtained in two stages via an alkyl ester of caronaldehyde), but a 3-phenoxybenzyl ether can thus be treated.

Acids of the general formula 9 (COQ = COOH) wherein 12 3 R = R = H and R = an alkyl group containing at least two carbon atoms can be prepared by reaction between 2-ethynyl-1,3,3-dimethyl-cyclopropanecarboxylic acid and appropriate alkyl halide in the presence of an alkali metal followed by a catalytic semi-hydrogenation.

Alcohols and halides of formula 8 are described in British Patent 1,305,025.

Alcohols of formula 7 or 8A wherein D represents CN or C * C 8 'can be conventionally prepared from the corresponding aldehydes. Thus, a furaldehyde or benzaldehyde can be reacted with (a) HCN, which can conveniently be obtained in situ from HCN and acid, when addition of HCN takes place to form the cyanohydrin or (b) an alkali metal acetylide in liquid ammonia.

Alcohols of the formula rOS, wherein R is a group of formula 6 wherein D represents hydrogen, may be prepared by reduction of the corresponding acids or esters, e.g. with a hydride, or by converting the corresponding halides to 8402990 i. c - 14 - an ester, e.g. by reaction with sodium acetate, followed by hydrolysis of the ester, or by reaction of formaldehyde with a Grighard reactant derived from the corresponding halide. The halide of the formula R-halogen wherein R is a group 5 of formula 6 wherein D represents hydrogen can be prepared by halomethylation of the compound of formula 12 of the formula sheet, or as a side chain halogenation of a compound of formula 13 of the formula sheet.

One or more of the insecticidal esters of the invention can be formulated with an inert carrier or diluent to give insecticidal preparations, e.g. are prepared in the form of powders or granular solids, wettable powders, mosquito coils and other solid preparations or as emulsions, emulsifiable concentrates, sprays and aerosols and other liquid preparations after the addition of suitable solvents, diluents and surfactants .

Pyrethrum synergists, such as piperonyl butoxide or trepital, can be added to these preparations. Certain insecticidal esters of the invention exhibit significant superiority over structurally similar esters, e.g. Chrysanthemates or pyrethrates, in their ability to respond to synergists, and many esters of the invention have a synergistic factor several times greater than that exhibited by other synthetic esters. Many of the esters derived from acids of the invention are much more stable to light than those of heretofore known acids, and dihalovinyl esters are particularly preferred in this regard.

The insecticidal compositions may also include known synthetic pyrethrins to enhance the dying and paralysis activities or to increase the activity of known pyrethrin and / or that of the synthetic pyrethrins of the invention.

The new esters of the invention or the insecticidal compositions containing them can be used for killing insects or controlling the concentration of insects in the home or in agriculture by the insects themselves or an environment susceptible to to treat insect attacks with the compounds or preparations.

8402990 5 Jt - 15 -

The following examples illustrate the invention, with temperatures indicated in ° C and refractive indices measured at 20 ° C. Unless otherwise indicated, the hydrogen atoms at and from the cyclopropane ring are in the trans configuration relative to

5 each other.

Example I

n-Pentyltriphenylphosphonium iodide (9.5 g, 0.02M), prepared by reaction of n-pentyl iodide with triphenylphosphine, was slowly added to sodamide [0.7 g sodium] under nitrogen.

10 (0.03M) in liquid ammonia (130 ml)]. The mixture was stirred for 0.5 hours and the ammonia was allowed to evaporate (2 hours). Benzene (130ml) was added and the mixture was refluxed under nitrogen for 0.5 h, cooled and the supernatant containing it. phosphoran was decanted under nitrogen. The phosphoran solution was added dropwise, under nitrogen, to a stirred solution of methyl transcarbonaldehyde (1.0 g, 0.0064 M) (from the ozonolysis of the methyl ester of (-B-trans-chysysantheoic acid in dry benzene (15 ml) The addition was completed in 10 min and the solution was stirred for a further 0.5 h The solution was evaporated, the residue dissolved in diethyl ether, the organic solution washed with water and dried Evaporation provided a colorless mixture , which was further extracted with petroleum ether (60-80 °), after evaporation of which a colorless liquid with a melting point of 107-109 ° / 5 mm was obtained, in a yield of 1.07 g (8%), n ^ of 1.4622, which was identified by NMR spectroscopy as 2,2-dimethyl-3- (hex-1-enyl) -cyelo-propane-carboxylic acid methyl ester (compound Cr).

Example II

The procedure described in Example I was repeated replacing n-pentyliodide with equivalent amounts of n-propyl iodide or n-butyl bromide to give the alkyl esters of the invention of formula 2 with a refractive index as indicated below: 8402990. - - - 16 - 3 2 1

Connection R R R R nQ

A 'C2H5 η ff CH3 1.4581 B' n ~ C3H7 H 3 CH ^ 1.4572

In compound A ', the 3-but-1-enyl substituent is in the trans configuration relative to the cyclopropane ring. The (+) - cis- (. R, 3S1 isomer (in free acid) was prepared by the following procedure.

(In both compounds A 'and its cis isomer, the ethylenic double bond configuration in the 3-substituent is cis) o 10 n-Propylidene phosphoran (prepared by reacting the corresponding phosphonium iodide (7 g) with sodamide, (sodium (0.7 g) / liquid ammonia (150 ml)] in dry benzene (100 ml) was added dropwise with stirring to a solution of the internal hemiacylal of cis-3-formyl-2,2-dimethyl- cyclopropanecarboxylic acid (0.7 g) (French Patent 1,580,475) in benzene (10 ml) under nitrogen. The benzene was evaporated and the residue dissolved in methylene chloride (75 ml) and washed with water and sodium carbonate solution. acidification of the carbonate extract gave an acid which was extracted with methylene chloride, dried (Na 2 SO 4) and evaporated to give 11 R, cis] 3-but-1-2,2-dimethyl cyclopropanecarboxylic acid (0.7 g) (compound A 'cis).

Example III

The procedure described in Example I was repeated replacing the methyl transcaronaldehyde with an equivalent weight of ethyl (±) -cis-trans-3-acetyl-2,2-dimethylcyclopropane carboxylate and replacing of n-pentyl iodide by methyl iodide, ethyl iodide, n-propyl iodide, or n-butyl bromide to give the alkyl esters of formula 2 with the refractive indices shown below: 3 2 1

30 Connection R R R R nD

F 'Η H Cïï, CH- 1.4469 3 2 5 G' (1) CH3 3 CH3 C2H5 1.4570 H '(2) C2H5 H CH3 C2H5 1.4570 I' n “C3H7 9 ^ 3 C2H5 i-4573 8402990 t - 17 - ( 1) (2) the stereochemistry of these esters about the double bond <x & to the cyclopropane ring is (1) 40.60 and (2) 80:20 Z: E.

Example IV

A suspension of sodium hydride in oil (0.50 g. Approximately 0.009SMNaH) was washed with dry diethyl ether (20 ml) under nitrogen. Dry dimethyl sulfoxide (DMSO) (3.5 ml) was added and the mixture heated at 30 ° C for 0.5 hour. After cooling, a slurry of n-butyltriphenylphosphonium bromide (3.80 g, 0.0104 m) (prepared by reaction of n-butyl bramide with triphenylphosphine) in DMSO (9 ml) was added with stirring, leaving the residue of the slurry was washed with diethyl ether (10 ml). The mixture was stirred for 0.5 hours and ethyl 3-acety 1-2,2-dimethylcyclopropanecarboxylate (1.0 g, Q.0054M) was added. The mixture was shaken thoroughly and stirred under nitrogen for 24 hours. Ice was added and the mixture was acidified with aqueous potassium hydrogen sulfate.

After extraction with diethyl ether, the organic solution was washed with water, saturated with sodium chloride solution and evaporation of the dried solution (Na 2 SO 4) gave a solid which, after extraction with petroleum solvent (60-80 ° C) and evaporation gave a colorless liquid with a melting point of 112-188 ° / 20 mm, 0.52 g, (43%), n ^ 1,457.3 '. This liquid was identified by NMR spectroscopy as the compound of the formula II wherein - n-C, H, R 2r H, R 1; rCH, and R-C 3 (compound I ').

3 7 3 3 3 25 Example V '

The procedure described in Example IV was repeated but replacing the n-butyl bromide with an equivalent weight of 2-bromobutane and replacing the ethyl 3-acety 1-2,2-dimethylcyclopropane carboxyate with an equivalent weight of methyl trans- caronaldehyde, whereby the compound of formula 2 was obtained 3 · 2 1 in which RR "CR-1" R -3 and R 1 CH 2 with nD 1.4643 (compound E1).

Example VI

Chloromethylenetriphenylphosphonium chloride (2.1 g, 0.06M) 35 and dry piperadine (0.51 g, 0.006M) in dry diethyl ether (15 ml) 8.4 0 2 9 8 0 L v - 18 - was treated with 8% under nitrogen - ig n-butyl lithium in hexane (4.8 ml, (0.3.38 g, Q, Q06M]) The mixture was stirred at room temperature for 1.5 hours and t-butyl trans-caronaldehyde (1.27 g, 0 0.0064M) in dry benzene (5ml) was added The mixture was stirred for 3 days after which the solution was filtered and the residue washed with dry diethyl ether The filtrate was washed with 10% H 2 SO 2 water and evaporation of the dried (Na2 SO4) solvent followed by distillation gave a colorless liquid with melting point 100 ° / 20 mm (70%), which was identified by NMR-3 2 10 spectroscopy as the ester of formula 2 wherein R - Cl, R ^ H, R ffH and S tt-C „H ,. with n 1.4670 The stereochemistry around the double - 4 9 p bond dff relative to the ring was 20: R0 Z: E.

The alkyl esters the preparation of which is described above in Examples I-VI were then converted to the corresponding 5-benzyl-3-furyl-methyl esters by procedures as described below in Examples VII-IX.

Example VII

0.2 mol of sodium were slowly added to a. 2 mole solution. 5-benzyl-3-furylmethyl alcohol in toluene.

When the reaction between the sodium and the alcohol was complete to form the sodium fluteal alcoholate, a solution containing about 1 molar amount of the alkyl ester of formula 2 in toluene was added and the mixture was refluxed to separate the methanol or ethanol formed in the transesterification reaction. After the solution was cooled, the desired 5-benzy1-3-furylmethyl ester was recovered in 50-70% yields, based on the weight of the alkyl ester by chromatography on alumina. NMR spectroscopy confirmed that the structure of the esters was in accordance with Formula 2 as well as by gas / liquid chromatography.

8402990 - 19 -

The following insecticidal esters were prepared: 3 2 1

Connection R K S

A C_H_ Η Η 1.5174 (trans isomer) A cis C_H_ Η H 1.5347 ....... 2 j * [IR, cis] isomer 5 B aC, H, Η H 1.5177 J / C nC .H. E a 1.5128 4 9 'E C2H5 CH3 H 1.5090 P Η H CH 1.5157 G CH-. H CS- 1.5206 10 H C2H5 3 CH3 1.5130 I n "C3H7 H ^ 3 * 1.5118

Compounds A - I are all compounds of formula 2 wherein K- - S-benzyl-3-furylmethyl. * These compounds are a mixture of (±) -cis-trans isomers.

Compound A cis was prepared from A 'cis by treatment with thionyl chloride in benzene to convert A' cis into the acid chloride and then reacting the acid chloride with 5-benzyl-3-furyX-methyl alcohol in benzene in the presence of pyridine.

Example VXIX

Methyl 2,2-dimethyl-3- (but-1-enyl) -cyclopropanecarboxylate (prepared as described in Example II) (2.8 g) was refluxed with 1.8 g NaOH in 70 ml methanol for 1 hour. . The reaction mixture was then diluted with water, acidified and extracted with diethyl ether to obtain 2.01 g of 2,2-dimethyl-3- (but-1-enyl) -25 cyclopropanecarboxylic acid with nQ 1.4719. The acid was then converted to the acid chloride by reaction with thionyl chloride and the acid chloride then esterified by reaction in benzene with an equimolar amount of (_ +) -allethrolone, (+) -pyrethrolone, 3-benzylbenzyl alcohol or 3-phenoxybenzyl alcohol in the presence of an equimolar amount of pyridine. The reaction mixture was then chromatographed on neutral alumina and the solvent evaporated to give the desired ester. The following insecticidal esters were prepared:, 8402990 S * - 20 - 3 2 1

Compound RRRR n ^ Q C2H5 Η H (±) -allethronyl 1,5009 R C2H5 Η H (±) -pyrethronyl 1,5159 S C2H5 ηH 3-ben zy lb enzyl 1,5488 5 T ® H '3-phenoxybenzyl 1.5439

Example IX

A mixture of the tertiary butyl ester as described in Example VI (410 mg), toluene-4-sulfonic acid (47.5 mg) and dry benzene (15 ml) was refluxed for 2 hours to give a solution of the corresponding carboxylic acid. pyridine (163 mg) and thionyl chloride (213 mg) were then added, and the mixture was allowed to stand for 2 hours to form the acid chloride. A mixture of substantially equimolar amounts of the acid chloride, 5-benzyl-3-furylmethyl alcohol and pyridine was prepared in dry benzene and the mixture was cooled and left at room temperature overnight. The mixture was then poured through a column of neutral alumina and eluted with benzene to give a 3 2 compound of formula 2 wherein R = C 1, R * H, R * = H and R = 5-benzyl-3-furylmethyl. This ester, designated K, 20, had an hD of 1.5418.

Example X.

Triphenylphosphine (13 g) was dissolved in dry benzene (60 ml) and ethyl bromoacetate (8.3 g) was added dropwise. The solution was heated at 70 ° C for 2 days and then cooled and filtered. The residue was washed with benzene and dried to obtain about 16 g of (ethoxycarbonylmethyl) triphenylphosphonium bromide. The phosphonium salt (10 g) was dissolved in water (250 ml) and a 5% aqueous sodium hydroxide solution was added dropwise with stirring until the solution became alkaline to litmus.

The resulting precipitate was filtered off, washed with water and dried. Crystallization from ethyl acetate / petroleum solvent gave (ethoxycarbonylmethylene) triphenylphosphoran as a colorless solid in about 80% yield. The phosphoran (3.2g, 0.0092M) in dry dichloromethane (30ml) was added to t-butyl trans-35 caronaldehyde (at 1.5g, 0.QQ76M) (from the ozonolysis of t-butyl (+ - 8402990-21 - trans-chrysanthemic acid) in dichloromethane (30 ml) with stirring under nitrogen; stirring was continued at room temperature for 2.5 days. The solution was evaporated and the residue was extracted with petroleum solvent (60-80 °) to obtain a colorless liquid with a melting point of 112 ° / 0.7 mm after evaporation and distillation in a yield of 1.60 g (79 %), with one of 1.4666 which was identified by NMR spectroscopy and gas / liquid chromatography as a compound of formula 2 wherein R s is carbo-3 ethoxy, R * H and R t-butyl (compound P19 / B *).

10 Example .XI '

The procedure of Example X was repeated but replacing the bromoacetic acid ethyl esters with an equivalent weight of the bromoacetic acid methyl ester and by the bromoacetic acid propyl ester and making necessary variations in the reaction time or temperature during the formation of phosphorane to obtain 3 compounds according to formula 2 wherein R - H, R = t-2 butyl and R »carbomethoxy or carbon-n-propoxy, nQ 1,4677 and 1,4723, respectively. (compounds P19 / A and P19 / C).

Example XII

The procedure described in Example X was repeated replacing the bromoacetic acid ethyl ester with an equivalent weight of α-bromopropionic acid ethyl ester and propyl ester. Esters of formula 2 were obtained in which R 2 methyl, R = t-butyl 2 and R 3 carbonethoxy and carbon-n-propoxy, nQ 1.4658 and 1.4712, respectively.

25 "(compounds P19 / D1 and P19 / E1).

Example XIII

n-Propyltriphenylphosphonium iodide was prepared by the procedure described in Example X replacing the ethyl bromoacetate with n-propyl iodide. The phosphonium iodide (9.5 g) 30 was then treated under nitrogen with the NaNH 2 obtained from 0.5 g MA in 100 ml liquid NH 2, the NH 2 being allowed to evaporate for 2 hours. Benzene (120 ml) was then added, the mixture was refluxed for 15 min and 1.08 g of methyl chloroformate in 50 ml of dry benzene was added dropwise. The mixture was further refluxed for 10 min, filtered and the henzene removed to leave a phosphorane of the formula C.He CrH_ 2 5 5 5 ^ C = p / c, H.

/ \ '5 CH300C CqB5 as residue.

The phosphorane was then reacted with t-butyl caronaldehyde in dichloromethane as described in Example X to give a compound melting point 130 ° / 3mm, nQ

. 10 of 1.4714, which was identified as in Example X, have formula 2 2 3 1, wherein R - COOCH 4, R = C 25 S 5, R - H and R = t-butyl (compound P19 / F1).

The above procedure was also repeated replacing the methyl chloroformate with ethyl and n-propyl-15 chloroformate grater. whereby the following compounds of formula 2 were obtained.

3 2 · 1

R R R R b.p. nD

P19 / G1 C00C2Hs C2Hs H t.-butyl 114-116 ° /! mm. 1.4682 P19 / H1 COOn-C ^ H ^ C2H5 H t.-butyl 120 ° / l mm 1.4683 1 2 3 4 5 6 7 8 9 10 11 8 402 990

Example XIV

The compound of formula · 2 wherein R = 3 n-propoxycarbonyl, R 2 = CH 2 and R = t-butyl (0.393 g) described in Example XII was refluxed with toluene-4-sulfonic acid for 2 hours (47.2 mg) in benzene (11.5 ml). The solution was cooled and the resulting acid (R = n-propoxycarbonyl, R = CH2,7 R = H) crystallized out. Dry pyridine (0.127 g, 131 µg ·) and 8 thionyl chloride (0.158 g, 96 µl) was added and the mixture was allowed to stand at about 20 ° C for 2 hours to form over 1 acid chloride.

11

A solution of 5-benzyl-3-furylmethyl alcohol (275 rag) and pyridine (0.105 g, 108 µl) in benzene (8 ml) was added and the solution was left overnight. The resulting solution was passed through a column of neutral alumina and then evaporated to yield 550 mg of a compound of formula 23-23 wherein R = n-propoxycarbonyl, R = CH-2 and R = 5-benzyl-3- furylmethyl with an n ^ of 1.5125 (compound P19 / Ê). The structure of the ester was confirmed to be consistent with NMR spectroscopy and gas / liquid chromatography. formula 2.

The following esters were prepared in similar ways.

3 2 *

Connection R R nQ

P19 / AH COCCH3 1.5262 P19 / BH COOC2S5 1.5298 1 ^ 278 10 P19 / CH COOn-C3H7 P19 / D CH3 COOC2H5 1.5235 219 / E CH3 C00n-C3H7 1.5125 P19 / P C2Hs C00CH3 1.5228 P19 / G C2S5 COOC2ff5 1.5193 IS P19 / H C2H5 COCn-C3H7 1.5190

Compounds Ρ19 / Ά-Ρ19 / Η are all compounds of formula 2, wherein R = 5-benzyl-3-furylmethyl.

Example XV

t-butyl-trans-caronaldehyde (1.0 g) (obtained by ozonolysis of the t-butyl ester of (+) - trans-chrysanthemic acid) and triphenylphosphine (2.65 g) dissolved in dry carbon tetrachloride (10 ml) were heated under nitrogen with stirring at 60 ° C for 7 hours. The reaction mixture was evaporated under reduced pressure and the residue extracted with diethyl ether (30ml). The organic extract was washed with water, dried (over Na 2 O 4) and evaporated. The residue was extracted with petroleum ether (40-60 °) and the solution evaporated and distilled to yield a crude product (0.77 g) (melting point IQQVimm), which was purified by crystallization to give t-butyl-ClR, trans] -2,2-dimethyl-3- (2,2-dichlorovinyl) ** -1 cyclopropanecarboxylate, mp 52-3 ° (compound P21 / A ').

Example XVI

Triphenylphosphine (1.32 g) was added to a well-stirred solution of carbon tetrabroride (0.84 g) in dry dichloromethane (15 ml). t-butyl - (+) - trans-caronaldehyde (0.5 g) was added and the solution was stirred overnight at 8402590

«« I

- 24 - * temperature- After work-up as described in example XV, the crude product was distilled to yield two fractions (1) melting point 83-90 ° / 0.7 mm, (0.15 g), nD 1.4749 (2) mp 90-107 ° / 0.7 mm, (0.24 g), nQ 1.4910. The second fraction was found to contain (glc) about 95% of the desired 5 t-buty 1- {1R, trans] -2,2-dimethyl 1-3- (2,2-dibromoviny 1) cv l-propane carboxylate (compound P21 / B ').

Example XVII

The t-butyl ester described in Example XV (280 mg) was refluxed with toluene-4-sulfonic acid (55 mg) in dry benzene (10 ml) for 1.5 hours and cooled to a solution of the corresponding acid. Pyridine (108.5 mg) and thionyl chloride (125 mg) were added and the mixture was allowed to stand at room temperature for 2 hours. A solution of pyridine (83.5mg) and 5-benzyl-3-furylmethyl alcohol (P19mg) in dry benzene (5ml) was added and the mixture was left overnight. After chromatography on neutral alumina, the solution was evaporated to give 296 mg of a. [IR, trans compound of formula 3 2 1 2, wherein R - Cl, R = Cl, R = H and R = 5-benzyl-3-furylmethyl.

This ester, designated as ester P21 / A, has an nQ of 1.5403.

The above procedure was repeated with ester P21 / B ', as described in Example XVI, to form ClR, trans] 2 3 ester P21 / B wherein R = R = Br, N1 = · H, R = 5-benzyl- 3-furylmethyl and nD 1.5462.

Example XVIII.

The conversion of the acid to the acid chloride and the subsequent esterification using 5-benzyl-3-furylmethyl alcohol as described in Example XVII was repeated replacing the (+) trans acid with other isomers of the acid and in certain experiments using 3-phenoxybenzyl or 3-benzyl-30 benzyl alcohol or (f) -allethrolone or (+) - pyrethrolone as the alcohol to give the following esters of formula 2.

8402990 + * - 25 -

Ships »? r3 R2 r1 configuration amp ° nQ

P21C Cl Cl 3 C ±) -trans 61 1/5518 P21D Cl Cl H (±) -cis 43 1,5485 P21E Cl Cl 3 (±) -cis-trans 48,58 1,5445 5 P21F Cl Cl 3 (± ) -trans 1.5607 P21G Cl Cl 3 (±) -cis 1.5654 P21H Cl Cl 3 (±) -cis-trans 1.5694 P21I Cl Cl 3 (±) -trans 1.5633 P21J Cl Cl 3 (±) ) -cis 1.5654 10 P21K Cl Cl 3 (i) -cis-trans 1.5701 P21L Cl Cl 3 (±) -trans 1.5136 P21M Cl Cl 3 (±) -trans 1.5324

In compounds C, D and S, R is 5-benzyl-3-furylmethyl, in compounds F, G and H, R is 3-phenoxybenzyl, in compounds I, J and K, r is 3-benzylbenzyl, in compound L is R ( ±) -allethronyl and in M R (+) - is pyrethronyl.

The starting acid was prepared by a variant of the conventional chrysanthemic acid synthesis using ethyl diazn acetate in which in this case 1,1-dichloro-4-methyl-1,3-pentadienes were reacted with ethyl diazoacetate in the presence of the copper catalyst and the resulting ethyl (±) -cis-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylate was hydrolyzed to the free acid. The cis and trans isomers can be separated from each other by selective crystallization from n-hexane in which the cis-25 isomer is soluble. The isomer mixture was dissolved in hexane at room temperature and cooled to 0 ° or -20 ° C, precipitating the trans isomer. This precipitate was ground, washed with a small volume of hexane at room temperature and the residue recrystallized from hexane at 0 ° or -20 ° C again, yielding 30 net trans isomer as a residue. The cis isomer is recovered from the hexane solution.

840 29 9.0 ~ 26 -

Example XIX

a) 5-benzyl-3-furylaldehyde

Chromium trioxide (3/00 g) was added to a stirred solution of pyridine (4.75 g) in dry methylene chloride 5 (75 ml) and stirring was continued for 15 min. 5-Benzyl-3-fury Methyl alcohol (0, 94 g) was added and the mixture was stirred for 15 min. The mixture was filtered and the residue washed with ether (100ml ·). The filtrate and washings were combined and washed with a 5% sodium hydroxide solution (3 x 50ml), 2.5N chlorine hydrochloric acid (50ml) and a 5% sodium carbonate solution (50ml) and dried (Na2 SO4). The yield was 0.53 g. melting point 116 ° / 0.8 mm Hg, nQ = 1.5652.

b) (±) α-cyano-5-benzyl-3-furylmethyl alcohol

The aldehyde (1) (0.53 g) was added to a solution of potassium cyanide (0.3 g) in water (3 ml) and dioxane (5 ml) was added to effect dissolution. stirred for 15 min at 15 ° C, after which 40% sulfuric acid (1 ml) was added dropwise, stirring being continued for a further 10 min. The mixture was extracted with carbon tetrachloride 20 (50 ml) and dried (Na 2 SO 4). Evaporation gave the product (0.53 g), 1.5377. (The structure was confirmed by NMR).

c) (a) -a-cyano-5-benzyl-3-furylmethyl- (±) -cis-trans-3- (2 *, 2 * -dichlorovinyl) -2,2-dimethylcyclopropane carboxylate (Compound P21 / N ).

A mixture of the alcohol (265 mg) prepared as described above and 80 mg of pyridine in 10 ml of dry benzene was added to 227 mg of (+) - cis-trans-3- (2,2-dichlorovinyl) -2.2 dimethyl cyclopropane carboxylic acid chloride in 10 ml dry benzene. The resulting mixture was left overnight and chromatographed with neutral alumina. Evaporation of the solvent gave 0.31: g of compound P21 / N, n of 1.5428 (structure confirmed by NMR).

8402990 φ - 27 -

Example. XX

a) 3-phenoxybenzaldehyde

Chromium trioxide (3.00 g) was added to a stirred solution of pyridine (4.75 g) in dry methylene chloride (75 ml) and stirring was continued for a further 15 min. 3-phenoxybenzyl alcohol (1 g) in methylene chloride (5 ml) was added, the mixture was stirred for a further 15 min, decanted and the residue washed with diethyl ether (100 ml). The filtrate was washed with a 5% sodium hydroxide solution (3 x 50ml), 2.5 NHCl (50ml) and S% -10% sodium carbonate solution (50ml) and dried over Na 2 SO 4 to give 3-phenoxy benzalaehyde. Yield (0.80 g), melting point 126 ° / 0.8 ma Hg, nD 1.5984.

b) (±) - (g-cyano) -3-phenoxybenzyl alcohol 3-Phenoxybenzaldehyde (0.8 g) was added to a solution of potassium cyanide (0.3 g) in water (1 ml) at 15 ° C . A 40% sulfuric acid solution (1 ml) was slowly added dropwise over 10 min, stirring continued for a further 15 min. The mixture was extracted with carbon tetrachloride (40 a1), dried (Na2 SO4) and evaporated to yield 0.64 g of 20 (_ +) -α-cyano- (3-cyano- (3-phenoxy) - benzyl alcohol - 1.5832 (structure confirmed by NMR).

c) The above-described α-cyanoalcohol (247 mg), pyridine (79 mg) and (+) -cis / trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylic acid chloride (227 mg), was reacted at 20 ° C in a benzene (20 ml) solution for 18 hours, after chromatography on a neutral alumina and evaporation of the solvent (+) -a-cyano-3-phenoxybenzyl - (+) -cis-trans- 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate was obtained (compound P21 / P) (260 mg), nQ 1.5561 (structure confirmed by NMR).

30 Example XXI

a) 3-benzylbenz: aldehyde

Benzybenzylalcoho 1 (1 g) was oxidized using the chromium trioxide / pyridine complex described in Example XXa) to give the aldehyde (0.67 g), melting point 124 ° C / 0.2 mm, 35 nD 2 O = 1.6010 .

8402990 - 28 - b) (+) - (ct-cyano) -O-benzylbenzyl alcohol

The prepared aldehyde (0/67 g) underwent the reactions described in Example XXb) to form the required cyanohydrin. (0.41 g), nD 2 O = 1.5703. .

5 c) (+ H <i-cyano) -3-benzylbenzyl- (+) -cis- / trans- (2,2-dl chlorovinyl) -2,2-dimethylcyclopgopanecarboxylate

Link. P21 / Q with n ^ 1.5462 was prepared from the alcohol of b) above and the acid chloride according to the procedure of Example XXc) -

Example XXII

a) 31-phenoxybenzy 1-3-formyl-2,2-dimethylcyclopropanecarboxylate 3-phenoxybenzyl - (+) - trans-chrysanthemate (2.0 g) in methanol (500 g) at -70 ° C was subjected to a flow of ozone for 30 min. Nitrogen was passed through the solution and dimethyl sulfide (1.5 g) was added. The mixture was allowed to warm to room temperature with stirring overnight. The solvent was evaporated and acetone (30 ml) and 30% acetic acid (20 ml) were added, leaving the solution at 80 ° C for 30 min. The solution was poured onto water (200 ml) and extracted with ether (200 ml). After washing with sodium carbonate, the organic solution was dried (Na 2 SO 4) and evaporated to yield the above aldehyde. Yield 1.69 g, nD 2 O = 1.5558.

b) The procedure described in Example XV repeated using 3-phenoxybenzyl-3-formyl-2,2-dimethylcyclopropanecarboxylate instead of t-butylcaronaldehyde to directly obtain compound P21F (see Example XVT1I).

Example XXIII

Triphenylphosphine (13 g) was dissolved in dry benzene (60 ml) and methyl bromoacetate (8.3 g) was added dropwise.

The solution was heated at 70 ° C for 2 days and then cooled and filtered. The residue was washed with benzene and dried to provide about 16 g of (methoxycarbonylmethyl) triphenylphosphonium bromide.

The phosphonium salt (10 g) was dissolved in water (250 ml) and a 5% aqueous sodium hydroxide solution was added dropwise with stirring 8 4 2 2 9 9 £ t t - 29 - until the solution became alkaline to litmus. .

The resulting precipitate was filtered off, washed with water and dried. Crystallization from ethyl acetate / petraleum solvent gave (methoxycarbonylmethylene) triphenylphosphoran as a colorless solid in a yield of about 80%.

Methoxycarbonylmethyl) triphenylphosphoran (3.34 g) in methylene chloride (70 ml) was cooled to -70 ° C, triethylamine (1.01 g) was added with stirring followed by chlorine (0.77 g) in CCl 4 (11 ml). Stirring was continued at this temperature for 30 min and for 1 h while the reaction mixture warmed to room temperature. The reaction mixture was washed with water (3 x 50 ml), dried over Na 2 SO 4 and evaporated to give 2.8 g of the chlorinated phosphorane / PhF = c (Cl) COOMe.

A mixture of t-butyl-trans-caronaldehyde (from the ozonolysis of t-butyl ester of (+) - trans-chrysanthemic acid) (0.7 g) and chlorinated phosphorane (1.3 g) in 10 ml dry benzene was refluxed for 1 hour. After distillation of the benzene, the product obtained was distilled under reduced pressure to give t-butyl-2,2-dimethyl-3- (2-chloro-2-carbomethoxyvinyl) -cyclopropylcarboxylate, mp 110 ° C / 0.4 mm, 1 ^ 20 1.4749 (yield 0.65 g). This compound was designated as compound P24A '.

Example XXIV

The procedure described in Example XXIII was repeated replacing the methyl bromoacetate with ethyl bromoacetate or propyl bromoacetate and replacing the methyl bromoacetate with ethyl bromoacetate and replacing chlorine with bromo in the halogenation of the phosphorus step. The following compounds of formula 2 were obtained:

Compound RR ^ R ^ melting point nQ 20 30 P24B * t-butyl COOC ^ Hg Cl 110-112 ° C / 0.4 mm 1.4883 P24C t-butyl COOn-C ^ Cl 160-180 ° C / 0.8 mm .1,4688 P24D 't-butyl COOC ^ Br 120-124 ° C / 0.04 mm 1.4830 8402990 • «- - 30 -

Example XXV

A mixture of compound P24A 'of Example XXIII (320mg) and toluene-4-sulfonic acid (50mg) in dry benzene (10ml) was refluxed for approximately 2 hours. 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) were added to the carboxylic acid solution and the mixture was allowed to stand at room temperature for 3 hours. 2,2-dimethyl-3- (2-chloro-2-carbo-10-methoxyvinyD-cyclopropanecarboxylic acid chloride was identified in the solution by NMR. A solution of 5-benzy1-3-furylmethyl alcohol (210 mg) and pyridine (BS mg (90 microliters) in dry benzene (5 ml) was added and the mixture was left overnight at room temperature The solution was then passed through a column of neutral alumina and eluted with benzene to give 200 mg of the 5- benzyl-3-furylmethyl ester of 2,2-dimethyl-3- (2-chloro-2-carbomethoxy-vinyl) -cyclopropane carboxylic acid, nD1,55398. This compound was designated as compound P24A.

example XXVI

The procedure described in Example XXV was repeated using the compounds P24B ', P24C' and P24D 'according to Example XXIV to give the following compounds of formula 2.

Connection nQ 20 25 P24B COOC2S5 Cl 1.5404 P24C COOn-C ^ H ^ Cl 1.5332 P24D COOC2H5 Br 1.5366

The three compounds described above are compounds of formula 2 wherein R represents 5-benzy1-3-furylmethyl.

The following compositions illustrate the manner in which the insecticide compounds of the invention may be applied to insects or environments susceptible to attack by insects.

8402990 »- 31 -

Composition 1

Liquid spray material for oil-based house insects Active compound 0.015% w / v 25% pyrethrum extract 0.25% piperonyl butoxide 0.5% antioxidant 0.1% odorless, light oil solvent e.g. xylene up to 100 vol.%

Composition 2

Liquid spray concentrate. water-based for mosquito control 10 Active compound 0.25% w / v piperonyl butoxide 1.0% non-ionic emulsifier 0.25% antioxidant 0.1% water up to 100 vol.% IS This concentrate should be diluted 1-80 v / v water before spraying.

Composition 3 Aerosol

Active compound 0.05% w / w 20 25% pyre thrum extract 0.8% piperonyl butoxide 1.5% odorless petroleum distillate (sp 200-265eC) 17,338% propellant, e.g. a mixture of equal amounts of trichloronofluoromethane and 25 dichlorodifluoromethane 80.0 % perfume ^ 0.2% antioxidant 0.1%

Composition 4 Mosquito oil 30 Active compound 0.25% w / w

Tabu powder (also known as pyrethrum mare) 30.0% fillers, e.g. wood flour, powdered leaves or nut peels 68.75% brilliant green 0.5% 35 p-nitrophenol 0.5% 8402990 «- 32 - * <«.

Composition 5 Emulsifiable concentrate

Active Compound 1.5% w / w Nonionic Emulgatar 25.0% Xylene 73.4% Antioxidant 0.1%.

This concentrate can then be diluted with 30ml to 4i liters of water before use.

Composition 6 10 General powder for household, garden, livestock or grain storage Active compound 0.05% w / w tropital (the synergist piperonyl-bis-2- [2'-n-butoxyethoxy] ethyl acetal) 0.25% antioxidant , e.g. butylhydroxytoluene or 15-butylhydroxyaniso1 0.03% filler 99.67%

The insecticidal activity of the esters of the invention was determined against houseflies and mustard beetles using the following techniques: Houseflies (Musea domestica)

Female flies were treated on the thorax with a microliter drop of an insecticide dissolved in acetone. Two replicates of 15 flies were used for each dose amount and 6 dose amounts were used for each test compound. After the treatment, the flies were kept at a temperature of 20 ° C ± 1 ° and dying was observed 24 and 48 hours after the treatment. Praise values were calculated in micrograms of insecticide per fly and the relative toxicity was calculated from the inverse ratios of LDf values (see Sawicki et al, Bulletin of the Word Health 30 Organization, 35, 393, (1966) and Sawicki et al, Entomologia and Exp.

Appl. JO, 253 (1967)).

Mustard beetles (Phaedon cochleariae Fab.)

Acetone solutions of the test compound were applied to adult mustard beetles using a micro-drop applicator.

8402990 * - 33 -

The treated insects were kept for 48 hours, after which the α dying time was measured. Two replicates of 40 to 50 mustard kevars were used for each dose level and 3-4 dose levels were used for each compound. LD values were recalculated and 50 relative toxicity was calculated from the inverse ratios of LD <.q (see Elliott et al, J. Sci. Food Agric, 20, 561, (19693).

Relative toxicity was calculated by comparison with 5-benzyi-3-furylmethyl (+) trans-chrysanthemum which is one of the most toxic Chrysanthemum-10 testers compared to houseflies and mustard beetles, the toxicity of which is approximately 24x that of allethrin and 65 x that of allethrine compared to mustard beetles.

The following relative toxicities were obtained.

Relative toxicity 15 Compound Houseflies Scarab beetles 5-benzyl-3-furylmethyl 1000 1000 (+) - trans-chrysanthemate pyrethrin I 12 1600 bioallethrin 60 20 20 A 1700 2000 B 630 890 C 270 420 E 470 670 P 21 - 25 G 18 H 10 I <10 K 1300 1600 Q 60 69 30 R 30 300 3 120 170 T 240 300 8402990 -34- f »β continued table. "Houseflies Mo8terd beetles P1 $ A 91 100 P19B 67 320 P190 '24 40 5 P19H 290' 440 P19E 290 500 P192. 130 36Ο P19G. 300 500 P19E 20 50 10 P21A 2500 λ 2700 P213 - 1100 1900 P11C 1000 2200 P? 1d 1200 1700 P21E - .700 1800 15 P21F 400 790 P210 680 - 780 P21H '660 740

P21X. - I7O / 42O

P21J 360.35Ο 20 Ρ21Γ. 340 350 P21X. 72 '.73 P21M 19 370 Ρ21ΪΓ 100 2000 P21P 130Q at least 5000 25 P24A 82 310 P24B ISO 310 P24C 23 120 P24B 450 29Ο

The toxicity to mammals of certain esters according to ^. the invention was determined in rats with the following results:

Compound LD ^ Q (mg / kg) for rats.

oral intravenous pyrethrine I 260-420 2-5 5-Venzyl-3-fttrylmethyl (+) - trans chrysanthemate 8000 · 340 A 800-1000 120 35 840 2 δ 9Ό -55- P21A 40 5 P210 '>> 400 - 26- 53

The synergistic activity of "certain esters of the invention" has been determined in experiments in which the LD ^ q of the insecticide 5 in ^ back per female fly was determined by the above-described methods in untreated flies and flies previously treated with 2 µug per fly of the synergist sesamex (2- (3'-4'-ethyl-1-dioxyphenosy) -3,6 ', trioxa-undecane). The following results were obtained :.

"Active compound LD - active compound · synergistic" »0 - active + synergist factor in compound _; _ approach elleea '5-benzyl-3-furyl methyl (+) - trans-' • J5 chrysanthemum 0.0054 0, 00057-9-4 5-b enzyme 1-3 furyl. methyl (+) - cis-transchrysanthemate 0.010 0.00079 15 20 "P21-C 0.0065 · 0.00033 19 P21D 0.0058 0.00046 12. P21P, '0.013 0.00033 39 P210 0.0083 0.0003 7 22 +) - trans- (3-'25 cis-but-1-enyl) - isomer_7 0.0042 0.00033 15 +) - cis- (3-cis-but-1-enyl) -iomer 0.0074 - 0.0012 6 1 8402990.

Claims (2)

9. A method for preparing an insecticidal composition in which a synthetic pyrethroid is mixed with a carrier or a diluent, characterized in that as a pyrethroid a compound of formula 2 is used, wherein R1 hydrogen or a methyl group 2 3 5, R represents hydrogen or alkyl; R represents hydrogen or carboalkoxy 2 with at least 2 carbon atoms in the alkoxy group when R is methyl, 2 3; provided that (a) R and R both both represent hydrogen 1 13 when R represents methyl, and (b) when R 1 represents R 1 -hydrogen 2 and R is alkyl, this alkyl group contains at least 2 carbon-10 atoms, and R represents a group of formulas 3, 4, 5 or 6 of the formula sheet, wherein Z0, S, CH2 or CO represents Y, hydrogen, alkyl, alkenyl, alkynyl or -ene, aryl or furyl group unsubstituted or is substituted in the ring by one or more alkyl, alkenyl, alkoxy or halo groups, 8 represents R and R, which may be the same or different, each representing 9 hydrogen, alkyl or alkenyl, R represents hydrogen or methyl , and which may be the same or different, each represent hydrogen or 12 alkyl, R represents an organic group with a carbon-carbon unsaturation at a position α relative to the CH ^ group to which R ^ is attached, (R / s ) represents an aromatic ring or a dihydro or 12 3 4 20 tetrahydro analog thereof, X, X, X and X, which may be the same or different, each represent hydrogen, chlorine or methyl, represents 3 Z -CH_-, -0-, -CO- or -S-, D, H, CN or -C = CH, 8402990 22 · 2 Z and Z being the same or different, each representing hydrogen, chlorine or methyl and n · = 0,1 or 2. 2. Process for preparing a synthetic pyrethroid in a manner known for analogous compounds, characterized in that a compound of formula 2 is prepared in which the symbols have the meanings set out in claim 1. f * - 0 * 3 ('X) C * - CH - CH - CH - COOH / \ 0¾ CH3 P7 1 3 2 IRR (R) C = * C - CH-CH - GOOR -CH-) “" 1- -ZY r8 // <0 / ^ χΐ 5 i 9 IR n ~ - D. / Λ M 6 T *. CB C.CH, - ZXn - Zn -Z. 7 R o -%. ~. «R- * y? - ~ Rö Jl ii O Z ^ n Z2n 8. Q 2 9 9 ö NATIONAL RESEARCH DEVELOPMENT CORPORATION »^ '* 1 R3 (R2). C = C - CH - CH - COQ1 / \ CH3 CHj H3 E z4 Ri JL \' S * I> = pf- z4 + O = c —CH - CH - CO OR yx * v / c \ ch3 ch3 1 11 zï T3 2 * J “f £ ·} | ^ C * c - CH - CH - COQ1 O * C - CH-CH-COQ1 R3 ^ V / \ / A / c \ •; ch3 ch3 ch3 ch3 r1 I JL f _ 2 Q = C - CH-CH - COQ 2 \ / Rt. C> CH - CH ^ CH3 R3NATIOHAL RESEARCH DEVELOPMENT CORPORATION 8402990 ï £ c2i ^ -cb = ch- γ = 2¾. = CH-3 'CHf Cl-CR = CH-4' Br-CK = CH-5 'CH 3 OOC-CH = CH-gi C 2 H SOOC-cb = ch-7 Λ I 8' -. CH3 CH «OOC — C = CH” 3 | 3 'C2% CULOOC-C = CH ~ 2 ^ | 10 * ° A CH ^ OOC-OC »- ^ | IV Cl C-H- OOC — C = CH- 2. I 12 'ci C1 \ c = ch- 131 er B ^ c = ch- 14 * Br NATI03AL RESEARCH DEVELOPMENT CORPORATION 8402990 REACT1ESCBEMA A R3 [r3 Π e e -' '' Ns hall —3. \ · Ra3 ba! \ jT YY, dehydrohalogenation with base z * \ c = P ^ -Z4 rV7 \ z4 REACTION SCHEDULE B 2 Γ ~ 2 * 4 RR ^ Z * \ as \ / 4 O halogen, + ΖΨΖ2 — A 'C = P — z - κ ^ z4 4 + Z ^ P halogenoL REACT1 SCHEME C Γ * Π · ö R2C ^ hal + PZ4—) R2CH2.PZJ hall 4 / dehydrohalogenation with base LI 3J. * V ^ dehydrohalogenation with base R \ c = p -—z * K * / ^ z4 8 4 ö 2 9 9 ö v NATIONAL F ^ SSMOI DEVELOPMENT CORPORATION