CA1080743A - Spiroheptenyl carboxylate - Google Patents

Abstract

Abstract of the Disclosure The spiroheptenyl carboxylate of the formula

Description

~ he present invention relates to the spiroheptenyl carboxylate of the formula C~i CH
~,CH ~3~ 3 0 CH C - ~t'H C-O-CH~ O~

~ ~H2 to prooesses for produci.n~ it, and to its use for combating pests~
The compound of the formula I is produced by methods known per se, for example as follows: .
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~,CH \3 / 3 1) CT- ~ ~ C \ Q acid-binding C ~ C / CH-C-OH ~ x CEI ~ ~ agent lII) . (III~

CH~ ~ ~C n acid-binding

2 ) CH C----\CH-C-X ~HO-CH ~0~
CN ~ ~ a~ent CH \ ~C~ " -H20

3 ~C'~ ~ CH - C -OH ~ H-CHl~l-~ - ~
CN ~ ~J water-bindi.ng (II~ lV) agent .... . . .. .. . . . .

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CH3 C~i ~,c ~ \ / o -~OH

4 ) C C ----CH-C-OR + E10--CH-~-O~

., (VI) ~V) In the formulae III and IV, X represents a halogen atom particularly chlorine or bromine, and in the formula VI, R
represents Cl-C~-alkyl, especially methyl or ethyl. Suitable as an acid-binding agent ror the processes 1 and 2 are, in particular, tertiary amines such as trialkylamines and pyridine, also hydroxides, oxides, and carbonates and bicarbon2tes or alkali metals and alkaline-earth me~als as well as alkali metal alcoholates such as potassium-t.bu~ylate and sodium methylate.
As the water-billding agent for the process 3, it is poss~ble ~o use, e.g., dicyclohexylcarbodiimîde. The processes 1 to 4 are p~rformed at a reaction temperature of between -10 and 100C, usually between 20 and 80C, at normal or elevated pressure and preferably in an inert solvent or diluent. Suitable solvents or diluents are, e.g.: ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, dimethoxyethane and tetrahydrofuran; amides such as N,N-dialkylated carboxylic acid amides; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, toluene, xylene, chlo~oform and chloro-benzene; nitriies such as acetonitrile; dimethylsulphoxide and ketones such as acetone and methyl ethyl ketone. The process 2 can be performed also in an aqueous solutlon.

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7~ 3 The starting materials of the formulae III to VI are known or can be produced by methods analogous to known methods.
A me-~hod ~or producing the novel compound of the ~ormula II
is described in Example 1.
The compound of the formula I is obtained as a mix~ure of various op~ically active isomers, unless the s~arting materials used to produce the said compound are homogeneous optically act~ve materialsO The different stable isomeric mixtures can be separated by known methods into the individual isor.lers. It is understood that the term compound of the formula I em~races both the separate isomers and the mixtures thereo~.
The compound of the formula I is suitable for combating animal and plant pes~s. I~ can thus be used for combating members of the order Acarina, such as phytopathogenic mites, for example of the genus Tetranychus and Panonychus, and also ticks of the f~nilies Dermanyssidae and Ixodidae. It is particularly suitable however for combating ~nsects, for example of the families: Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, ~eduviidae, PyrrhocoridaP, Cimici~ae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabacidae, Dermes~id2e, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae 3 Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae.
The compound o~ the formulà I is especially suitable ~or . . ,: , combating insects whîch damage plants, particularly insects which darnage plall~s by eatiltg~ in crops of ornamental plants and useful plants, especially in cotton crops (e.g. against Spodoptera littoralis and Heliothis virescens) and in crops of vege~ables (e.g. agai.nst Leptinotarsa decemlineata and Myzus persicae). The active substance of the formula I exhibits 2 very favourable action also against flies~ such as Musca domes~ica, and a~ainst mosquito larvae.
The acaricidal and insecticidal action can be substantially broadened and adap~ed to suit given circumstances b-y the addition of other insecticides and/or acaricides~ Suitable additives are, e.g. organic phosphorus compounds, nitrophenols and derivatives thereof; formamidines, ureas, other pyrethrin-like compounds, as well as carbamates and chlorinated hydro-carbons.
The compound of the formula I ls combined particularly advantageously also with substances which have a synergistic or intensifying effect on pyrethroids. Examples of such compounds are, inter alia: piperonylbutoxide, propynyl ethers, propynyl oximes, propynyl carbamates and propynyl phosphonates, 2-(3,4-methylened~oxyphenoxy)-3,6,9-trioxaundecane, ~Sesamex or Sesoxane), S,S,S-tributylphosphorotrithioates, 1,2 methylene dioxy-4-(~-octylsulphonyl)~propyl)-benzene.

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7~3 The compolr-cl of the formula 1 Call be used or its o~n vr toc,ether ~l~tll 5U~ table carriers and/or aclditives. Suitable addi.tives can be colid or liquid and they correspond to the subst:ances co~lr.lon in orrnulaticn practice, such as na~ural 3 regenerated substances, so].vents, dispersing agents, we~t ng agen~s, adhesives, thickeners, binders and/or fertilisers.
The composi.ti.ons according to the invention are produced in a manner kno~.n per se by the intimate mixing an~l/or grinding OL' the active substance of the formula I ~7i',-h su;.taDle carrie~s, optionally with the addition O,c dispersing agents or solvents ~hich are inert to Lhe active substances. The active substance can be obtainecl and used in the following forms:

olici pree~ ons: d~sts, sca~tering agents, granules (coated granules, impregnated ~ranules and homogeneous granules);
liguid ~ arations:
) water-dispersible concen~rates of active substance:
wettable powders, pas~es or emulsions;
b~ solutions.
The content of active substance in ~he described co~positions i~ between 0.1 and 95%; it is to be mentioned here that with application from an aeroplane, or from other suitable devices, concentrations of up to 99.5% or even the pure active substance can be used~
The active substance of the formula I can be formulated ~or example as follo~s: (parts are ~y weight):

'7~3 s ~s __ The ~ollo~i.ng substances are used to produce a) a 5% dust and b~ a 2% dust:
a) 5 parts of active substance, parts of ~alcum;
b) 2 ~arts of ac~ive substance, 1 part of highly dispexsed silicic acid, 97 parts o talcl~.
The active substance is mix2d and ground with the carriers.
~ranula~e _~ .
The following ingredients are used to produce a 5V/o granula~e:
parts of active substance, 0.~5 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 30~0 parts of polyethylene glycol, 91 par~s o kaolin (particle size 0.3 - 0.8 ~m)~
The aetive substance is mi~ed with epichlorohydrin and dissolved wi.th 6 parts of acetone; ~he polyethylene glyccl and ee~yl polyglycol ether are then added. The solution obtained is sprayed onto kaol.in and the acetone i5 evaporated of in vaeuo.
Wetta~le ~owder The following constit.uents are used to produce a) a 40%~
b) and e) a 25%, and d~ a 10% wettable powder:
a) 40 parts o active subs~ance, parts of sodium lignin sulphonate~

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1 part of sod-um dibu~ naphthalene suiphonateg ~ 4 parts of silicic acid;
b) 25 par~s of active substance, 4 . 5 par~s of calcium lignin sulphonate~
1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl-naphthalene sulphonate, 19.5 parts o~ silicic acid, l9.S parts of Charnpagne chalk, 28.1 parts of kaolin;
c) 25 parts of active subs~ance, 2.5 parts of isooctylphenoxy-polyo~yethylene~ethanol, 1.7 par~s OI Champagne chalk/hydroxyethyl cellulose mix~ure ~1:1), `
8.3 parts of sodi.um aluminium silicate, 16.5 pa~ts of kieselguhr, 46 parts of kaolin;
d) ~0 parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcoho] sulphates, S parts of naphthalenesulphonic acid/~ormaldehyde condensate, 82 parts o~ kaolin.
The active substance is intimately mixed in suitable mi~ers with the additives, and the mixt~lre is then ground in the appropriate mills and rollers to obtain wettable powders which . . . ~
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~ ~ ' can be diluted with water to give suspensions of the desired concentration.
Emulsifiable concentrates _ The following substances are used to produce a) a 10%, b) a 25%, and c) a 50% emulsifiable concentrate:
a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylaryl sulphonate calcium salt, 40 parts of dimethylfoImamide 43.2 parts of xylene;
b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, lO parts of alkylarylsulphonate/fatty alcohol poly-glycol ether mixture3

5 parts of dimethylformamide, 57.5 parts of xylene;
c) 50 parts of active substance, 4.2 parts of tributylphenol-polyglycol ether, 5.8 parts of calcium-dodecylbenzenesulphonate, 20 parts of cyclohexanone, 20 par~s of xylene.
Emulsions of the required concentration can be prepared from these concentrates by dilution with water.

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The folio~qing constituents are used to produce a) a 5~O
spray and b) a 95% spray:
a~ 5 parts of active substance, 1 part of epichlorohydrin, 94 parts of ligroin (boiling limits 160-190C);

b~ 95 parts of ac~ive substance, par~s of epichlorohydrin.

The invention is further illustrated by the ollowing Ex~mp].es.

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Production o ~-cyano-3-phenoxybenzyl-2',2'-dimethylspiro-(~,4)-hept-4-~ene-carboxylate a) Produc~ion of 2~2-dimethylspiro (2,4)-hepta-4,6-diene l-carboxylic acid.
To a solution, cooled to ~C, of 310.5 g (1.35 moles) of carbethoxymethyl-dimethyl-sulphonium bromide in 1075 ml of chloroform are quickly added 1310 ml of saturated aquec,us potassium carbonate solution and 107.5 ml of 12.5N aqueous sodium hydroxide solution. The reaction mixture is stirred ~or 15 minutes at room temperature, filtered and the chloroform phase is separa~ed~ The chloroform solution is dried over potassium carbonate and heated to 40C. After the slow dropwi.se addition of 143.7 g (1.35 moles) of 6,6-dimethylfulvene, the reaction mixture is held at 40C for 16 hours. The chloroform solution is washed once with saturated sodium chloride solution, dried over sodium sulphate and distilled off. To th~ residu2, dissolved in 900 ml of ethanol, there is added dropwise at 10C 182 g o~ potassium hydroxide in ~50 ml of water. The reaction mixture is refluxed for 2 hours and stirred ror 14 hours at room temperature. For processing, the reaction mîxture is concentrated under reduced pressure, poured into ice water and extracted wlth ether. The ether phase is waqhed neu~ral with saturated sodium chloride solution~ dried over sodium 11 - ' - ' , . : - ... .
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sulphate and concentrated under reduced pressure. Recrystal-lisation of the solid residue from ethanol/water yie]ds the compound of the formula Cll = Cl~
~C -- CH - COOH
CH = C~l ~ C

having a melting point of 130-132C.
b) Production of 2,2-dimethylspiro-~2,4) hept-4-ene-1-carboxylic acid:
5 g (0.031 mole) of 2~2-dimethylspiro-(2,4)-hepta-4,6-diene in 150 ml of methanol/water = 2:1 is hydrogenated using 0.1 g of palladium on charcoal (5%) as catalyst at normal pressure.
After fil~ration of the reaction mixture and removal of the solvent~ the residue is taken up in etherl washed with saturated sodium chloride solution, dried (Na2S04) and concentrated by evaporation. Recrystallisation from petroleum ether yields the compound of the formula CH C~3 CH3 CH2 C ~ CHCOOH

in the form of a diastereomeric mixture having a melting point of 88~93C.
c) Production of ~-cyano-3-phenoxybenzyl-2',2'-dimethyl-spiro-(2,4)-hept-4-ene-1-carboxylate.

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After the dropwise addition of 6 rnl of oxalyl chloride to a solution of 1.9 g ~0.0114 mole~ of 2,2 dimethylspiro-~2,4) hept-4-ene-1-carboxylic acid in 50 ml of benzene, the reaction mixture is stirred for 4 hours at room temperature.
The reaction mixture is subsequently freed from the solvent, and the residue is dissolved in 50 ml of benzene. To the solution, cooled to 0C, there is added dropwise within 15 minu~s 2.47 g (0.0110 mole) of a-cyano-3-phenoxybenzyl alcohol dissolved in 4 ml of pyridine. The reac~ion mix~ure is stirred for 12 hours at room temperature. For processing, the mixture is diluted with ether, washed three times with water, three times ~lith 0.5N hydrochloric acid and twice with saturated ~odium chloride solution. The organic phase is separated, dried over sodium sulphate and concentrated by evaporation. The crude product is chromatographed with ether/hexane = 1:~ as eluant through silica gel. There is obtained the compo~nd of the formula CH CH
~ / 3 C C - C~-C-0-CH ~ 1i-~
C~2 as a diastereoisomeric mixture having a refractive index of nD = 1.5~78.

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7~3 Example Z
A) Insecticidal stomach-poison action Tobacco and potato plants were sprayed with a 0.05%
aqueous active-substance emulsion ~obtained from a 10% emul-sifiable concentrate~.
After drying of the coating, caterpillars of Spodoptera littoralis in the L3-stage and of Heliothis virescens in the L3-stage were placed onto the tobacco and potato plants. The test was carried out at 24C with 60% relative humidity.
The compound according to Example 1 exhibited in the above test a good insecticidal stomach poison action against Spodoptera littoralis and Heliothis virescens caterpillars.
B) Insecticidal contact action . _ One day before application of the active-substance emulsion, broad beans (Vicia faba) grown in pots were infested with about 200 bean aphids ~Aphis fabae) per plant. The spray emulsion at a concentration of lOOO ppm (prepared from a 25% wettable powder) was applied by means of a compressed-air sprayer to the leaves infested with aphids. An evaluation was made 24 hours after application.
The compound according to Example 1 exhibi~ed in the above test a good contact ac~ion against Aphis fabae.

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. The compound of the formula

2, Process for producing the compound according to claim 1, which process comprises reacting a compound of the formula wherein X represents a halogen atom, in the presence of an acid-binding agent, with the compound of the formula

3. A method for combating animal and plant pests at a locus, which methodcomprises applying to the locus the compound of claim 1.

4. A method according to claim 3 wherein the pests are of the class Insecta.