IL43593A - Stereoisomeric derivatives of e-3-(2-alkoxymethyl-1-propenyl)-2,2-dimethyl-cyclopropanecarboxylic acid,process for preparing them and insecticidal compositions containing them - Google Patents

Description

STEREOISOMERIC DERIVATIVES OF ECARBOXYLIC PROCESS FOR PREPARING THEM AND INSECTICIDAL COMPOSITONS CONTAINING THEM s m m j The present vention has as subject the various c that 1s the of the compounds of formula in which the double bond of the side chain fixed in the 3 position 1s of structure E and in which X represents radical a double bond at any position in the or a radical of the 1n which and being the same or represent an alkenyl or al radical and represents an alkyl alkenyl alkadienyl or phenyl radical or a in ch Z represents an and Y represents an alkyl radical containing from to 6 carbon as wel l as the salts of these forms when X and esters corresponding to this general formula have already been described French Patent by the Sumitomo Although patent has taken these latter into by specifying that they could exist not only 1n the but also in the form of stereoi somers no process has been indicated for the preparation of such a fortiori none of them has 1n actual fact been The various esters which are the subject of the invention can display an vity much greater than the corresponding esters of Patent the stry of which i s indetermi Thus it for that a concentration of of permits one to in four a mortality rate of 100 with regard to whereas for the corresponding compound in the Sumitomo of the same but of indeterminate steric a concentration of only permits one to obtain a mortality rate of is indicated in the said Sumitomo the trans compound of the present invention confesses to having a lethal activity upon more than twenty times superior to that of the corresponding compound in the Sumitomo Amongst the compounds dealt with the one may in those described in the The different stereoisomeric forms of the esters of formula I endowed with interesting insecticidal which make them able to be used in the agricultural and domestic fields in the fight against harmful They remarkable knock down properties as well as high lethal activity which may be made evident especially by tests on the house Examples of such tests are given further The invention also comprises a process for preparing the different stereoisomeric forms of the compounds of formula as well as their salts when X illustrated by the attached diagram and essentially selecti ve erized in that one reacts a agent with the ester function of a carbonyl acid of or resulting reacts with a strong then with an esterifying and etherifying agent to obtain a of having the one saponifies the ester functio by the action of a basic agent to obtain a or one of its functional derivatives with an alcohol or a functional derivative of this alcohol to obtain the corresponding compound in one of the stereoisomeric forms of the same configuration at positions 1 and as that of the starting acid of formula The agent which one reacts with the acid II is preferably lithium aluminium The reduction is conveniently carried out in preferably around The strong base which one reacts with the acid III in metal metal raetal an alkaline or an The eoterifying or etherifying agent which one reacts with the nlkali an fication and carried out in organic solvent like dimethyl To obtain the ester starting from the acid I it is convenient to react the chloride of the acid I with the alcohol in the presence a tertiary such as pyridine or as amine in an organic solvent benzene or The chloride of the acid I is easily obtained by the action metal of oxalyl chloride with an salt of this acid such as the metal potassium This salt of the acid I is itself metal easily obtained by the action of an methylate or of an in stoichiometric on the acid I To carry out the esterification leading to compounds one can also use as functional derivative of the acid I the anhydride or a mixed The esters I can also be prepared by reacting a halide Hal representing a a silver salt or with a triethylamine salt of acid I One can also obtain the esters I by reacting the chloride of the acid I with an alkali metal derivative of the alcohol The invention also relates to insecticidal compositions the stereoisomeric forms of of formula IV in which Y has the meaning and in particular methyl carboxylate and methyl Tho following illustrate the giving it any limiting NMR The NMR spectrum presents the following characteristics peaks at hz corresponding to the hydrogens of the methyls at 2 peaks at corresponding to the hydrogen at 1 at hz corresponding to hydrogens of the methyl at on the propenyl chain peaks at hz corresponding to the hydrogen at peak at 5 hz corresponding to the hydrogens of the methyl of the ether peak at 219 hz corresponding to the hydrogens of the methyl of methoxycarbonyl peak at 226 hz corresponding to the hydrogens at on the propenyl chai peaks at hz corresponding to the at of propenyl hydroxide To of 2N aqueous sodiun solution one in an inert g agitates for fifteen extraction eliminates the neutral fraction by with acidifies the aqueous solution by adding an aqueous solution of hydrochloric extracts with methylene washes ethereal solution with dries concentrates it to dryness by under reduced the residue on silica eluting with a mixture of flthyl cyclohexane and acetic acid and obtains g of NMR Spectrum The NMR spectrum presents the following characteristics peaks at hz corresponding the hydrogens of the methyls at 2 peaks at hz corresponding to the hydrogen at 1 peaks at hz corresponding to the hydrogens of the methyl at peak at 227 hz corresponding to the hydrogens at of the chain peaks at corresponding to the hydrogen at of the propenyl chain peak at 621 hz corresponding to the hydrogen of the Example acid A To a suspension of g of lithium aluminium hydride 100 of ether one at g of caibonyl eyelopro pyrethric agitates two hours at brings the temperature back to o 0 slowly adds 180 of 2N aqueous solution of hydrochloric extracts with methylene washes the disti l l ati on with dries eliminates the solvent by under reduced chromatographs the residue on silica eluting with a mixture of ethyl and acetic acid hydroxymethyl and obtains S of Analysis Calculated C II Found To a suspension of 2 of sodium hydride in baseline oil in of one slowly at ambient g 3 acid in solution in of brings the reaction mixture to keeps it there for three brings the temperature adds 12 of methyl agitates for dryness by under reduced pressure and obtains g of crude methyl 2 containing one uses as is for the following 3 sodi um ydroxyde one Into 125 of N in an inert g of methyl agitates for fifteen eliminates the extracti on neutral fractions by e with acidifies the aqueous phase i by adding an aqueous solution of hydrochloric extracts the aqueous phase with methylene washes the organic solution with di sti l ati on dries eliminates the solvent by under reduced pressure and f obtains g of 2 Spectrum The spectrum presents the following characteristics peaks at hz corresponding to the hydrogens of the methyls at 2 peaks at hz corresponding to the hydrogens of the methyl at the propenyl chain methoxy peak at 195 corresponding to the hydrogens of the methyl of the o peak at 229 hz corresponding to the hydrogens at of the propenyl chain of of the methoxymet peaks at hz corresponding to tho hydrogen nt of propenyl chain peak at hz corresponding to the hydrogen of the Example To a solution of g of 2 2 acid in 20 of one in an inert a normal solution of methanolic potash s a n by under reduced pressure and obtains the potassium salt of carboxylic acid used as is for the following Acid chloride to 15 of benzene and 7 cm O In of pyridine one at 5 of oxalyl in an inert the potassium salt previously agitates for one hour at ambient eliminates excess oxalyl chloride and the benzene by disti ll ati on distilling under reduced adds of by the precipitate washes it with concentrates di l l ati on the filtrate to dryness by under reduced and obtains carboxylic acid chloride used as it is for the following The acid chloride previously obtained is dissolved in a mixture of 20 of benzene and of one slowly at in an inert g of methanol in 3 solution in 10 of agitates for fifteen hours at normal pours the reaction mixture into a 2 aqueous solution of hydrochloric extracts with washes the organic solution with with aqueous solution of sodium then with eliminates the ether by distilling under reduced the residue on silica eluting with a mixture of ethyl acetate and cyclohcxane and obtains g of tetrahydrophthalimido methyl Analysis Calculated C H N Found al lethronyl Example methyl lic adds to the acid chloride 15 of benzene and 7 of of dl allethroafe in solution hours at ambient pours the reaction mixture into a 2N aqueous solution of hydrochloric extracts with washes the ethereal phase with with an aqueous solution of sodium bicarbonate water eliminates the ether by under reduced chromatographs the residue on silica eluting cyclohexane and obtains Oalculated C H Found Spectrum The spectrum presents the following characteristics peaks at hz corresponding to the hydrogens of the methyls at 2 peak at 103 corresponding to the hydrogens of the methyl at of propenyl chain peak at 120 hz corresponding to the methyl on the cyclopcntenone ring peak at hz corresponding to the methyl of the peak at hz corresponding to the hydrogens at the propenyl chain mass at 288 to Ο hz corresponding to the vinylic hydrogens of allo the cyclopentenone 1 dime thy 2 One prepared the potassium and acid chloride in the manner as in Example starting with g of adds to the acid chloride 15 cm of benzene and of in agitates for one night at normal pours the reaction into a 2N aqueous solution of hydrochloric extracts with washes the organic phases with with an aqueous solution of sodium then with dries concentrates them to on dryness by under reduced the residue on silica eluting with a mixture of ethyl acetate and cyclohexane and obtains of methyl Calculated C Found The NMR spectrum presents the following characteristics peaks at hz corresponding to the hydrogens of the methyls at 2 peak at 102 hz corresponding to the hydrogens of the methyl at of the propenyl chain methoxy peak at hz corresponding to the hydrogens of the methyl of the peak at 225 hz corresponding to the at of the propenyl to peak at hz corresponding to the hydrogens of M o the carboxyl peaks at corresponding to the hydrogen at of the propenyl chain peak at 6Ο hz corresponding to the hydrogen at position of the f ring peak at hz corresponding to the benzene hydrogens peak at hz corresponding to the hydrogen at position 2 of the u l methyl 3 One dissolves of in an inert a solution of potash until the phcnolphthalein turns eliminates the methanol by under reduced three benzene one evaporates under reduced pressure and obtains the potassium salt of acid used as is for the following To a solution of of oxalyl chloride in 15 of benzene and of one at in an inert allows it the potassium salt previously to agitate for one hour at normal eliminates the excess oxalyl chloride and the benzene distillation by under reduced adds by the precipitate washes it with eliminates the benzene by distilling under reduced pressure and obtains acid which one uses as is for the following Esterification One dissolves the acid chloride previously obtained in 20 of 2 benzene and of drop by an inert o at a solution of 2 g of methyl alcohol in 10 of agitates for fifteen hours at normal pours the reaction mixture into a 2 aqueous solution hydrochloric washes the organic solution with with a solution of then with distillation eliminates the ether by distilling under reduced chromatographs the residue on silica eluting with a mixture of ethyl acetate and cyclohexane and obtains 2 g of methyl Calculated C 7 66 7 Spec rum chloro peaks at corresponding to the hydrogens at 1 and at peaks at corresponding to the hydrogens of methyl at 2 of the propcnyl chain methoxy peak hz corresponding to the hydrogens of the methyl of the peak at hz corresponding to the hydrogens at 3 of the propenyl chain of the of the ether peak at hz corresponding to the hydrogens of the of the benzyl peak at hz corresponding to the hydrogens of the a the carboxyl peaks at hz corresponding to the hydrogen at of the propenyl chain peak at 359 hz corresponding to the hydrogen at position of the c ring peak at hz corresponding to the hydrogens of the benzene ring peak at hz corresponding to the hydrogen ut position 2 of the Dl The potassium salt and the acid chloride prepared in the same manner as in 6 starting with g of 2 2 1 one adds to the acid chloride 15 of 2 of in an inert a solution of g of dl allethrolone in 10 of agitates for eighteen hours at ambient by the precipitate it with pours the filtrate a 2 aqueous solution of hydrochloric washes the ethereal phase with an aqueous solution of sodium with an dries aqueous solution of sodium then with concentrates it to dryness by distilling under reduced chromatographs the residue on silica cluting with a mixture of cyclohexane and ethyl al ethronyl acetate obtains g of dl 2 1 Calculated C Found 72 Will Spectrum The spectrum presents the following characteristics peaks at 7 hz corresponding to the hydrogens of the methyls at 2 peak at 103 hz corresponding to the hydrogens of the methyl at 2 of the propenyl chain at 120 hz corresponding to the hydrogens of the at 3 of the cycl opentenyl ring methoxy peak at hz corresponding to the hydrogens of the methyl of the peak at hz corresponding to the hydrogens at of the propenyl chain of the GH of the ether peaks at hz corresponding to the hydrogens of the vinylic peaks at hz corresponding to the hydrogen at the propenyl chain peak around corresponding to the ethylenic hydrogen of the vinyl peak at hz corresponding to the hydrogen at position of the pentenyl al l ethronyl Example 8 This compound is prepared in the same as the ester Example but replacing the racemic allethrolone with al l ethronyl One obtains 2 2 1 1 carbon Calculated C H 9 Found of the insect of thyl th oxy 1 pro eye late of 2 the knock down time to knock down of the The test insects arc female days One operates by direct spraying in a Kearns and March using as solvent a mixture in equal volumes of acetone and kerosene of i solution used One uses about insects per One carries out and fifteen minutes then hours allethronyl er The reference product is e d trans chrysanthemate the carries out a series of tests products and a series of tests in the presence of piperonyl butoxide the proportion of 10 of nyl butoxide to 1 of the compound to The experimental results are summarised in the following tables C and D a knock down clearly superior to that of d male female house by topically acetone applying 1 of solution of the product to be tested on the dorsal thorax of the One uses about 50 insects per One carries out the mortality count four hours after One carries out a series of tests with pure products and a series of tests in the presence of piperonyl The experimental results are summarized in the following tables Table 5 compound Doses in or mortality Ί0 in hours Compound A 100 100 10 50 100 5 Compound A piperonyl butoxide 100 7 25 100 ί 10 8 Conclusion Compounds C and D havo good activity on the house Compound the methyl trans has particularly insufficientOCRQuality

Claims (8)

1. 43593/2 as the salts of these sterol somerlc forms when X = H.

2. 5-benzyl-3-furylmethyl 2,2-diιτlethy^-3R-(2, -methyl -3'- methoxy-1 ' (E)-propenyl )-cyclopropane-l R-carboxylate;

3. 3,4,5,6-tetrahydrophthal1m1do-methyl 2, 2-dl methyl -3R- (2* -methyl 3'-methoxy-l ' (E)-propenyl )-cyclopropane-l R-carboxyl ate;

4. 5-benzyl-3-furylmethyl 2,2-dimethyl-3S-(2' -methyl -3' -methoxy- 1 ' (E)-propenyl)-cyclopropane-l R-carboxylate;

5. Dl allethronyl 2, 2-d1 methyl -3R-(2* -methyl -3' -methoxy-1 "(E)- propenyl )-cycl opropane-1 R-carboxyl ate.

6. Dl allethronyl 2 ,2-dimethyl-3S-(2' -methyl -3-methoxy-l ' (E)- propenyl)-cyclopropane-lR-carboxylate.

7. D allethronyl 2, 2-dimethyl-3R-(2' -methyl -3' -methoxy-1 '(E)- propenyl )-cycl opropane-1 -carboxyl ate .

8. A process for preparing the products defined in claim 1, characterised in that one reacts a reducing agent with the ester function of a 2,2-d1methyl-3(2'-methoxycarbonyl-l 1 (E)-propenyl)- cyclopropane-l-carboxylic add, of (1R.3R) (1S.3S) (1R,3S) (1S.3R) structure, reacts the resulting 2,2-d1methyl-3-(2'-hydroxymethyl-l (E)-propeny^-cyclopropane-l-carboxylic add with a strong base, then with an esterlfylng and etherlfying agent to obtain a 2,2-dimethyl- 3-(2,-methyl-3'-0Y-l,(E)-propenyl)-cyclopropane-l-carboxylate of Y (Y representing an alkyl radical containing from 1 to 6 carbon atoms) of which one saponifies the ester function by the action of a basic agent, to obtain the corresponding 2,2-dimethyl -3-(2' -methyl -3' -0Υ-Γ (E)- propenyl )-cyclopropane-l-carboxyl1c acid which one possibly converts into a salt by means of a base, or possibly converts It Into one of its functional derivatives, then reacts the said add, I, (X = H) or one of Its functional derivatives, with an alcohol X-OH (X f H) or a functional derivative of this alcohol to obtain the desired I, in one of the stereoi someri c forms (1R,3R) V ) of the same configuration at positions 1 and 3