IE43348B1

IE43348B1 - Pyrethroids as insecticides

Info

Publication number: IE43348B1
Application number: IE296/76A
Authority: IE
Original assignee: American Cyanamid Co
Priority date: 1975-02-13
Filing date: 1976-02-13
Publication date: 1981-02-11
Also published as: ATA105676A; ZM2176A1; AR221026A1; CH616313A5; YU40132B; IL49029A0; DK58076A; IT1066095B; GB1490672A; FR2300559A1; YU34276A; IE43348L; KE2882A; NZ180004A; AT343413B; MY7800449A; IL49029A; EG12151A; AU500011B2; NL7601502A

Abstract

The novel phenoxybenzyl esters of spirocarboxylic acids have the formula in which R1 and A have the meanings given in Patent Claim 1. The novel compounds of the formula I are prepared by reacting approximately equimolar amounts of a suitable spirocarboxylic acid halide and of a suitable m-phenoxybenzyl alcohol. The novel compounds of the formula I have an insecticidal and acaricidal activity. They are therefore used for controlling insects and mites. To this end, an insecticidally or acaricidally effective amount of them is brought into contact with the insects or mites, their environment or their diet.

Description

This invention relates to new pyrethroids useful for the control of pests.

The new pyrethroids of this invention ate phenoxybenzyl esters of spirocarboxylic acids of the formulae: (II) wherein R-j is hydrogen, cyano or ethynyl and — represents a single or double bond.

Included within the scope of the present invention are the optical and geometrical isomers of the compounds of formulae I and II.

Pyrethrin-like compounds (pyrethroids) are known in the chemical art. Many such compounds have been shown to possess insecticidal properties, but most have failed to provide entirely satisfactory insect and/or a car id controi. None, to the best of our knowledge, has been suggested for the control of soil-borne insects and, with few exceptions, all have been subject to extremely rapid degradation to non-toxic substances. This latter property has been recognized in the past as 1θ a major deficiency of the pyrethroids. While such compounds have provided excellent knockdown of insects, rapid degradation of said compounds has resulted in lack of residual insect control even for a few days.

In this regard, it is well-known that pyre15 thrins and synthetic pyrethroids are generally too unstable to air and light to be useful for the control of agronomic and forest insects [Y.L. Chen and J.E. Casida, J. Agr. Food Chem., 17, 208 (1969)]. Although this rapid degradation may be desirable for environmental reasons, it is of course obvious that there must be sufficient residual presence of the toxicant to ensure economic control of a particular pest.

The esters of formulae I and II, above, in addition to showing goo:' insecticidal activity, are unexpectedly stable on plant surfaces. This is a sought for but most difficult to find combination of properties. 3 3 18 Unlike the prior art compounds the compounds of this invention do not rely on replacement of essential methyl groups by chlorine atoms to effect greater stability.

Thus it is surprising that the esters of this invention are not susceptible to the immediate light-promoted oxidative degradation which limits the agronomic effectiveness of most of the pyrethroids disclosed to date.

Preferred compounds of the present invention include the following: 3,3 - dimethyl spiro [cyclopropane - 1,1' - inden£] 2 - carboxylic acid, m-phenoxybenzyl ester. 3,3 - dimethylspiro [cyclopropane - 1,1' - inden£J 2 - carboxylic acid, a - cyano - m - phenoxybenzyl ester. 3,3 - dimethylspiro [cyclopropane -1,1' - indane] - carboxylic acid, m - phenoxybenzyl ester. 3,3 - dimethylspiroQcyclopropane -1,1' - indane~J2 - carboxylic acid, a - cyano - m - phenoxybenzyl ester. 2,2 - dimethylspiro Jz,4} hepta - 4,5 - diene - 1 carboxylic acid, m - phenoxybenzyl ester. 2,2 - dimethylspiro j|,4^ hepta - 4,6 - diene - 1 carboxylic acid, a - cyano - m - phenoxybenzyl ester. 2,2 - dimethylspiro [2,4]heptane - 1 - carboxylic acid, m - phenoxybenzyl ester. 2,2 - dimethylspiroJ2,4]heptane - 1 - carboxylic acid, a - cyano - m - phenoxybenzyl ester. 2,2 - dimethylspiro[2,4jheptane - 1 - carboxylic acid, a - ethynyl - m - phenoxybenzyl ester. 2,2 - dimethylspiro j^jijhepta - 4,6 - diene - 1 carboxylic acid, a . ethynyl - m - phenoxybenzyl ester. •ί 3 3 I 8 3,3 -Pdimethylspiro cyclopropane -1,1‘ - indane] - 2 - carboxylic acid, « - ethynyl - m - phenoxybenzyl ester, and 3,3 - dimethylspiro Qcyclopro pane - 1,1' - indene} - 2 5 - carboxylic acid, a - ethynyl - m - phenoxybenzyl ester.

The phenoxybenzyl esters of spirocarboxylic acids, depicted by the formulae I and II above, can be prepared by reacting approximately equimolar amounts of an acid halide, preferably the chloride, of a spirocarboxylic acid (III) and a m-phenoxybenzyl alcohol (IV). The reaction is generally conducted in the presence of a suitable solvent e.g. benzene, toluene or diethyl ether, at a temperature of from about 10°C. to 30°C., and in the presence of an acid acceptor such as an organic tertiaryamine e.g. triethylamine, trimethyl amine or pyridine. The reaction can be graphically illustrated as fol1ows: 3 3 4-8 wherein A is attached by a spiro linkage and is the group R-| is as defined above, and X is halogen, preferably chloro.

The spirocarboxylic acid halide (III) is readily obtained by reaction of the appropriate spirocarboxylic acid VI with a thionyl halide e.g. thionyl chloride, thionyl bromide or thionyl fluoride or a phosphorus halide e.g. phosphorus trichloride or phosphorus oxychloride in the presence of an organic solvent e.g. toluene, benzene or benzene/hexane mixture. This reaction may be conducted at room temperature but is preferably conducted at 60-90°C., and can be illustrated as follows: so2x—> (V) (HI) wherein A and X are as defined above.

It will be understood that various geometric isomers as well as optical isomers of the above-identified compounds result from the preparations described. For example, in the synthesis of the 3,3-dimethylspiro[cyclopropane-1,1'-indene] -2-carboxylic and 3,3-dimethylspiro Rcyclopropane -1,1'-indene]-2-carboxylic and 3,3-dimethylspiro[cyclopropane-1, 1'-indane]-carboxylic acid esters of m-phenoxybenzyl alcohol, d- and 1- isomeric pairs are formed. In the preparation of the α-cyano- and a-ethynyl-m-phenoxybenzyl esters, an additional chiral center is introduced, and this allows for additional d, 1 pairs. Additionally, the above said esters derived from 3,3-dimethylspiro[cyclopropane-1,1'-indene]-2-carboxylic acid and 3,3-dimethylspiro[cyclopropane-1,1'-indane]-2-carboxylic acid will be further complicated by the presence of cis and trans isomers. As previously noted, all such isomers are within the scope of the present invention.

These isomers can be expected, of course, to vary somewhat in the degree of insecticidal and acaricidal activity which they exhibit toward a given pest.

For use as animal systemic insecticidal and acaricidal agents, the compounds of this invention can be administered to the animal host either orally or parenterally. When given orally, it may be in any convenient form designed for oral administration such as a bolus, capsule, tablet or as an oral drench. The active agent may also be incorporated in an edible animal feedstuff such as a nutritionally balanced diet containing from 0.01% to 3.0%, and preferably 0.01% to 1.5% by weight of feed, of the active compound.

If desired, the systemic insecticidal and acaricidal agent may be introduced into the body of the animal by subcutaneous, intramuscular or intraperitoneal injection, such that it may be distributed through the animal's body by the action of the animal's circulatory 3 348 system. In practice, the systemic agent may be dissolved or dispersed in a pharmaceutically acceptable carrier such as water, propylene glycol, vegetable oil or glycerol formal for administration.

Advantageously, the systemic agents have relatively low mammalian toxicity and are effective for protecting a variety of animals, particularly livestock and domestic animals such as cattle, sheep, horses, dogs and cats from attack by such pests as fleas, mosquitoes, flies and ticks.

For the control of insects, including soil insects, which attack growing plants and/or harvested drops, including stored grain, the insecticidal compounds of this invention may be applied to the foliage of plants, the insect's habitat and/or the insect’s food supply. Generally, the active compound is applied in the form of a dilute liquid spray; however, it may also be applied in other forms, e.g. as an aerosil, a dust or wettable powder.

Liquid sprays which are particularly useful are oil sprays and emulsifiable concentrates which can be further diluted for application.

A typical emulsifiable concentrate useful for protecting a variety of crops such as cereals, cole crops, cucurbits, ornamentals and'shrubs, may comprise about 24% by weight of the active agent; 4% by weight of an emulsifying agent, conventionally employed in the preparation of pyrethroid formulations; 4% by weight of a surfactant; 23% by weight of an organic sol30 vent such as cyclohexanone; and about 45% by weight of a petroleum solvent having a minimum aromatic content of about 93 volume °L When applied to the foliage of the plants to be protected, it is generally preferred to apply an amount of active compound sufficient 3 3 18 to provide from 20g to 228g of active compound per acre, more preferably from 28g to 113.4 g of active compound per acre.

The compounds of this invention are highly effective as contact and stomack poisons for ixodide ticks and for a wide variety of insects, particularly Dipterous, Lepidopterous, Coleopterous and Homopterous insects. Moreover, these compounds are advantageous pyrethroids, in that they exhibit extended residual insecticidal activity and are surprisingly effective for the control of soil-borne insects. They do not normally require admixture with a stabilized phenol derivative such as bisphenols, BHT or arylamines, to achieve insecticidal and acaricidal compositions having stabilized effects; however, they may be used in combination with other biological chemicals, for example, pyrethroid synergists such as piperonyl butoxide, sesamex or n-octyl sulfoxide of isosafrole.

The invention is illustrated by the following examples.

Example 1 Preparation of 3,3 -dimethylspiro[cyclopropane-1,l'-indene]-2-carboxylic acid, m-phenoxybenzyl ester To 4.3 g. (0.02 mol) of 3,3-dimethylspiro[cyclopropane-1, 1'-indene]-2-carboxylic acid in either hex9 3 3 4 8 ane/benzene or benzene is added 8 ml. of thionyl chloride. The solution is then stirred for 12 hours at room temperature. The solvent is then removed in vacuo leaving 4.7 g. of an orange liquid (theoretical yield). In5 frared indicates an acid chloride carbonyl at 1790 cm--'·.

The acid chloride and 4.0 g. (0.02 mol) of m-phenoxy benzyl alcohol are dissolved in 20 ml. of ether and 2.1 g. (0.02 mol) of triethylamine dissolved in 8 ml of ether is added dropwise at 20°C. Solids precipitate from solution immediately. The resulting mixture is Stirred for 12 hours at room temperature. The crude product is partitioned in an ether/water mixture, and the ether layer is dried over magnesium sulfate and concentrated in vacuo to yield 7.7 g. (96% theory) of a brown liquid.

The crude product is purified by dry-column chromatography on silica gel using 25% methylene chloride in hexane as a solvent. 4.4 Grams of a pale yellow liquid is obtained. The infrared spectrum shows an ester carbonyl band at 1720 cm-·*·. The nuclear magnetic resonance spectrum (CCl^) shows the following: = 1.41 1.45, 1.58, 1.66 (4S, 6H, methyls), 2.61 (S, IH, cyclopropane H), 4.85-5.10 (m, 2H, O-CH2), 6.12 (d, 0.5H, J = 5.5 Hz, vinyl), 6.66-7.76 (m, 14.5h aromatic and vinyl).

Analyses: Calculated for C27H24°35 C, 81.83; Η, 6.06. Found: C, 82.14; Η, 6.29.

Example 2 Preparation of 3,3-dlmethylspiro[cyclopropane-1,l'-in30 dene]-2-carboxylic acid, a-cyano~!!l~.phenoxybenzyl eater 3 3 4 8 3,3-Dimethylspiro[cyclopropane-1,1 *-indene]-2-carboxylic acid, 3.4 g., is dissolved in 100 ml. of a hexane/benzene (4:1) solution. Thionyl chloride, 15.0 g., is then added and the solution is stirred for 12 hours. Refluxing is carried out for 20 minutes, and the volume is reduced in vacuo to remove solvents and excess thionyl chloride. The acid chloride is used directly without further purification. The acid chloride is taken up in 20 ml. of benzene and is added dropwise to a solution of 3,1 g. of α-oyano-m-phenoxybenzyl alcohol and 1.0 g. of pyridine in’100 ml. of benzene. After 4 hours, the precipitate is filtered, and the filtrate reduced in vacuo to give a viscous oil. Purification by column chromatography on silica gel with elution by chloroform/ hexane (1:2) gives 1.3 g. of pale yellow oil which exhibits the following spectral properties: infrared spectrum (neat film) 1730 cm-1; nuclear magnetic resonance spectrum (CdClg) = 6.8-7.6 (m, 14.5H, aromatic and CN vinyl), 6.37 (m, IH, -C-0), 6.22 (d, 0.5H, vinyl), 2.73 H H 0 (m, IH, /C-C-C-), 1.72-1.43 (m, 6H, methyls). 3 3 18 Example 3 Preparation of 3,3-dimethylspiro[cyclopropane-1,1'-indane] -2-carboxylie acid, jS. .-phenoxybenzyl ester The procedure of Example 1 is followed using 3,3-dimethylspiro[cyclopropane-1,1’-indane]-2-carboxylic acid in place of 3,3- dimethylspiro[oyclopropane-1,1'-indene]-2-carboxylic acid to give the crude product as an oil. The pure ester obtained by chromatography had the following spectral properties: Infrared spectrum (neat film) 1720 cm-·*·; nuclear magnetic resonance spectrum (CC14) J' = 6.7-7.6 (in, 13H, aromatic), 4.8-5.1 (m, 2H, 0-CH2), 1.1-3.2 (m, 11H, CH3, indane CH2, and cyclopropane H).

Example 4 Preparation of 3,3-dimethylspiro[cyclopropane-1,1'-indane] -2-carboxylic acid, a-cyano-W-phenoxybenzyl ester CH3 0 The procedure of Example 2 is followed using 3,3-dimethylspiro[cyclopropane-1,1’-indane]-2-carboxylic acid in place of 3,3-dimethylspiro[cyclopropane-1,1130 -indene]-2-carboxylic acid to give the crude product. 3 3 4 8 Example 5 Preparation of 3, 3-Diiiiethylspiro lcyclopropane-l,l'-indane] -2-carboxylic acid, m-phenoxybenzyl ester Step I To 4.3 g. of 3,3-dimethylspiro[cyclopropane-1,1'-indane]-2-carboxylic acid in 75 ml. of n-hexane is added 10 ml. of thionyl chloride. The solution is then stirred at room temperature for 2 days.

The clear pale orange solution is concentrated under vacuum to yield 4.7 g. (100% theory) of an orange liquid. IR shows a carbonyl stretch at 1780 cm-!, typical for an acid chloride.

Step II To 4.7 g. of the above acid chloride 4.0 g. of m-phenoxybensyl alcohol in 50 ml. of ether is added 2.1 g. of triethylamine in 8.0 ml. of ether, dropwise, with cooling. Solids begin to precipitate immediately. After 3 hours at room temperature, the crude product is worked up in ether and then H20, The resulting crude product is then purified by dry-column chromatography using a silica gel packing and 25% CH2Cl2/hexane as a solvent for development. There is obtained 3.9 g. (49% theory) of a pale yellow viscous liquid. IR shows a carbonyl stretch at 1720 cm"l. NMR Iff = 1.1-3.2 (11 H, (CH3)2, , cyclo- propane Η), 4.8-5.1 (2Η, -OCII2-) , 6.7-7.6 (13 Η, aromatic)! confirms the assigned structure.

Analysis calculated for C, 81.42; H, 6.53. Found: C, 81.57; H, 6.97.

Example 6 Preparation of 3,3-Dimethylspiro[cyclopropane-1,l'-indane]-2-carboxylic acid, α-cyano-m-phenoxybenzyl ester 3,3-Dimethylspiro[cyclopropane-1,11-indane]-215 -carboxylic acid, 4.1 g. is refluxed in 20 ml. of thionyl chloride for 1 hour and then stripped at 50°C. using water aspirator pressure to remove excess thionyl chloride.

The acid chloride thus formed is taken up in 50 ml. of benzene and added to a 50 ml. benzene solution of 3.1 g. of α-cyano-m-phenoxybenzyl alcohol and 1.5 g. of pyridine. Stirring of the solution is then continued for 18 hours. The reaction is worked up by filtration of the precipitate and removal of the solvent in vacuo to give a light yellow oil. Purification by dry-column chromatography on silica gel with elution by ethyl acetate: hexane (1:9) gives 4.1 g. of pale yellow viscous oil. NMR tfl.2-1.45; 2.06; H-rV H ch3 CH CN if 2.3-2.9,- —0—C— , 3 3 4 8 bonyl 1725 cm I.

Analysis calculated for C28H25NO3: C, 79.41; H, 5.95; N, 3.31. Found: C, 78.22; H, 6.06; N, 3.15.

Example 7 Preparation of 2,2-dimethylspiro[2,43heptane-l-carboxylic acid, m-phenoxybenzyl ester CH CH C-O-CIL· The procedure of Example 1 is followed using 2,2-dimethylspiro[2,4]heptane-l-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro{2Xj -hepta-4,6-diene-l-carboxylic acid to give the crude product. The pure ester obtained by chromatography has the following spectral properties: Infrared spectrum (neat film) 1730 cm-·’·; nuclear magnetic resonance spectrum (CCl4) / = 6.8-7.4 (m, 9H, aromatic), 5.0 (s, 2H, O-CH2), 1.4-1.7 (m, 8H, cyclopentane CH2), 1.1 (s, 3H, CII3), 1,2 (s, 3H, CH3) .

Example 8 Preparation of 2,2-Dimethylspiro[2,4]heptane-l-carboxylic acid α-cyano-Jli- phenoxybenzyl ester The procedure of Example 2 is followed using 3 3 4 8 2,2-dimethylspiro[2,4]heptane-l-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid to give the crude product.

It must be recognized that various geometric isomers as well as optical isomers result from these preparations. Thus, in the case of the 2,2-dimethylspiro[2,4]hepta-4,6-diene-l-carboxylic acid and 2,2-dimethylspiro [2,4] heptane-l-carboxylic acid esters of m~' -phenoxybenzyl alcohol d and 1 isomeric pairs will result. Where the α-cyano and α-ethynyl m-phenoxybenzyl esters are formed, an additional chiral center is introduced allowing for additional d, 1 pairs. Although in most instances the separation of these isomers may not be practical, it is recognized that they will differ in the degree of effectiveness and the spectrum of their activity against the many insects and other pests of economic importance. In addition, the subject esters derived from 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-l-carboxylic acid and 2,2-dimethyl-4,5-benzospiro[2,4]-hepta-4-ene-l-carboxylic acid will be further complicated by the presence of cis and trans isomers. These different esters are also expected to show differing degrees of insecticidal activity when separately tested.

Example 9 Preparation of 3,3'-Dimethylspiro[cyclopropane-1,11-indene] -2-carboxylic acid, a-ethynyl-jn.-phenoxybenzyl ester 3 3 4 8 The procedure of Example 1 is followed using α-ethynyl-m-phenoxybenzyl alcohol in place of m-phenoxybenzyl alcohol to give the product as an oil.

Example 10 Preparation of 3,3 -Dimethylspiro[cyclopropane-1,1'-indane] -2-carboxylic acid, g-ethynyl-JE-phenoxybenzyl ester H The procedure of Example 1 is followed using 3,3 -dimethylspiro[cyclopropane-1,1'-indane]carboxylic acid in place of 3,3-dimethylspiro[cyclopropane-1,1'-indene] -2-carboxylic acid and a-ethynyl-m-phenoxybenzyl alcohol in place of m-phenoxybenzyl alcohol to give the product as an oil.

Example 11 Preparation of 2,2-Dimethylspiro[2,4]hepta-4,6-diene-l-carboxylic acid, a.-ethynyl-jsi.-phenoxybenzyl ester Η The procedure of Example 1 is followed using 2,2-dimethylspiro[2,4]hepta-4,6-diene-l-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-l-carboxylic acid and a-ethynyl-m-phenoxybenzyl alcohol in place of m-phenoxybenzyl alcohol to give the product as an oil.

Example 12 15 Preparation of 2,2-Dimethylspiro[2,43 heptane-l-carboxylic acid, g-ethynyl-ia-phenoxybenzyl ester C H The procedure of Example 1 is followed using 2,2-dimethylspiro[2,4]heptane-l-oarboxylie acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-l-carboxylic acid and α-ethynyl-m-phenoxybenzyl alcohol in place of m-phenoxybenzyl alcohol to give the product as an oil.

Example 13 Insecticidal Activity The high degree of effectiveness of the compounds of the invention for controlling insects is demonstrated in the following tests wherein Tobacco budworm, Heliothis virescens (Fabricius),· Cotton Boll Weevil, Anthonomus grandis (Boheman); Western Potato Leafhopper, Empoasca abrupta (Soy) and Bean Aphid, Aphis fabae (Scopoli), are employed as test insect species. Procedures employed are as follows: Tobacco Budworm, Heliothis virescens (Fabricius).

A cotton plant with two true leaves expanded is dipped for 3 seconds with agitation in a test solution (35% water/65% acetone) containing 300, 100 or 10 ppm of test compound. A 1/2 to 3/4-inch square of cheesecloth with about 50 to 100 budworm eggs 0-24 hours old is also dipped in the test solution and placed on a leaf of the cotton plant, all being placed in the hood to dry. The leaf with the treated budworm eggs is removed from the plant and placed in an 8-ounce Dixie cup with a wet 2 piece of dental wick and covered with a lid. The other leaf is placed in a similar cup with a wick and a piece of cheesecloth infested with 50-100 newly hatched larvae is added before covering the cup with a lid. After 3 days at 80°F., 50% r.h., observations of egg hatch are made, as well as kill of newly hatched larvae. Data obtained are reported as percent kill in the table below.

Cotton Boll Weevil, Anthonomus grandis (Boheman).

A cotton plant with cotyledons expanded is dipped for 3 seconds, with agitation, in a 35% water/65% acetone solution containing 1000 ppm. of test compound.

The dipped plants are then placed in a hood to dry. One cotyledon is removed from the plant and placed in a 4-inch petri dish containing a moist filter paper on the bottom and 10 adult boll weevils. After 2 days at 80°F., and 50% r.h., mortality counts are made. Data obtained are reported below.

Western Potato Leafhopper, Empoasca abrupta (Soy) A Siev.-λ lima bean plant with the primary leaf expanded to 3 to 4 inches is dipped into a 35% water/65% 10 acetone solution containing 100 ppm of test compound.

The dipped plant is placed in the hood to dry and then a one-inch piece of the tip of one leaf is cut off and placed in a 4-inch petri dish with a moist filter paper in the bottom. From 3 to 10 second-instar nymphs are placed in the dish and the dish is then covered. Mortality counts are made holding the thus-prepared dishes for 2 days at 80°F. and 50% r.h.

Bean Aphid, Aphis fabae (Scopoli) Two-inch fiber pots, each containing a nastur20 tium plant 2 inches high and infested with 100 to 150 aphids 2 days earlier are placed on a 4 rpm turntable and sprayed with a 35% water/65% acetone solution containing 100 ppm. of test compound for 2 revolutions using a DeVilbiss Atomizer and 20 psi. air pressure. The spray tip is held about 6 inches from the plants and the spray directed so as to give complete coverage of the aphids and the plants. The sprayed plants are laid on their sides on white enamel trays. Mortality estimates are made after 1 day at 70°F., 50% r.h.

In these tests, permethrin and phenothrin, •ι 3 3 4 8 known pyrethroid insecticides, are used as checks for the purpose of evaluation. Data are reported as percent mortality determined at the rate indicated. From the data it can be seen that the test compound^ are substan5 tially more effective than permethrin and phenothrin against the above-named insects. 433 48 3 3 4 8 Example 14 Insecticidal Activity The unique insecticidal activity of the phenoxybenzyl esters of spiro carboxylic acids of the present invention is demonstrated in the following tests wherein a variety of pyrethroid type insecticides are employed as controls. The Confused Flour Beetle, Tribolium confusum and the German Cockroach, Blattella germanica are used for this evaluation.

Confused Flour Beetle - Tribolium confusum The compounds to be tested are formulated as 1% dusts by mixing 0.1 cm. (0.1 ml. if a liquid) with 9.9 cm. of Pyrax ABB talcs, wetting with 5 ml. of acetone, and grinding to dryness in a mortar and pestle. 12.5 Milligrams of this dust is blown into the top of a dust settling tower with a short blast of air at 20 psi, and allowed to settle for 2 minutes on 9 cm. petri dishes (Deposit = .09375 mg/cm2 of 1% dust). 25 Adult Confused Flour Beetles are placed in each dish. Mortality counts are made after 3 days at 80°F. A beetle is alive if it can move 2 or more appendages when prodded.

German Cockroach - Blattella germanica The compounds to be tested are formulated as 1% dusts as described above in the test procedure for the Confused Flour Beetle. 25 Milligrams of the dust is sprinkled manually over the bottom of a 7 1/2 inch diameter dish 2 1/2 inches high. A water bottle with cotton wick is arranged to supply water to the test insects, and 10 male adult German Cockroaches are placed in the dish. A screen cover is placed over the dish to 3 3 4 8 prevent the insects escape. Mortality counts are made after holding the prepared test dishes for 3 days at 80°F.

Data obtained are reported in the table below as percent insect mortality. From the data it can be seen that the compounds of this invention are highly effective insecticidal agents superior to non-halogenated pyrethroids known in the art, and as effective or superior to the halogenated pyrethroids of the art, against the insects mentioned above.

The term pyrethrins is used in the following table and means a mixture of 4 compounds Pyrethrin I and IX and Cinerin I and II shown as follows: Mixture of 4 Compounds CH=CCHq Pyrethrin I: C21H28°3 R1 = ch3 r2 = -ch2ch=chch-ch2 Cinnerin I: c20^28°3 R1 = -CiI3 r2 = -ch2ch=chch.

R1 Pyrethrin II: C22H28°5 R. = -C-OCH·, r2 = -ch2ch=chch=ch2 Cinnerin II: ^21Η28Ο5 R = -C-OCH, 11 J R-> = -CH_CH=CHCH-2 J 3 3 4 8 Insecticidal Actii'ity rman Roach At 0.1¾ 1 o o rd 1 O 100 15 100 80 100 100 1¾ Kill-Ge o'5* rH p Cj «if» * rH 1 1 oo •M- rH O » CM O X3 •rl β fr-« q\« 1 rH © © © © rH Ο O rH rH •rH 1 1 I β rH O rH 1 rH I 1 O X β X O is o rH P 43 t ι O 42 «Η 42 «Η «Η ι is in p O -tO ι ρ υ - β ρ u * x •rt Λ U O UrltJ I H ω is-η ο •Π 0 is-d ϋ p.rt Β υ ή χ ι g u ·η ρ β Β ο·η P ι O rH rH ri >sO X C •η γη ϋ co ΜΗ rt •rt r-v 0 O ν Β XX Ό υ « ο o Ό rH rt Φ Ο tl rH Rl g -•rt Κ N ι β P 1 is Ι-Η • x csti 0 fi! NH UU R Ν fi UH Ο W <—\ N R Url 5—' » Ω O * is-H >. ID - Ο -rt X β Ι-Η « 0 -H !s i cm μ ts CM PrH42 p CM PrH β fiT3H (M PrH β to * rt x 1 Ο X ι O ι Ο X Ο ρ Ρ! 1 O isd 1 CM U K -χ Η Κ M· rH ι—' Η ίΗ Η X 0 Ό μ X M-l /—ν ι O +1 04 0 I U tl Ρ Ο Ο •rl ft! +1 ρ,ο I +1 Ο β —'rH 40 rH X <^H^ β Β Μ 0 ''-'rH 42 CO *—'rH β O p i XJmXU > X β ·η V—/ ι χμ ι ι χ oj <β 3 W 43 rt rH I ut ii ft (Λ fiH in 43 Rl H ω ρ p p O pj P O rH CM (3 Ρ O 0 β·Η β ρ υ x fi! ·Η Ο 1 . p cd 4) o rt ι rt Ο ω β •Hit rt 0 O c4 rt > β SI € e C ' H μ β fi! O β rC ·Η μ S fi p! β o p o PI Rl Γ4 is μ Ρ 1 te ι—1 tp h p » rt ο β Ρ β o * o 1 N ft ι Λ 1) 1 ΓΊ lit POO I CM ΡΩ O 1 .0 H t) WM.O «-^p p tn Μ ο u 0 (-1 ft! WM □ 1 4J W rH U »rl Ή 1 p +1 ID 1/) •rl I 1 β 1 β X«rt •rt ι β lo tn rtp2 XU u|io PjS-' g o U|to p© P Cu U u|to PM 0 u|u u « β β β •rt •rt β β β β «rl 43 42 42 β P P P Λ o 0 O Ρ S a β 'fl β 0 O 0 < Λ o4 P rH <Μ to rt LO id T) • rH υ ρ >!> t: Ki 11 -Tribol ium At j 1 Kill-Geman Roach K oo r·* • mJ K P. υ ι cd > I >1 W Λ. (Ξ 1 >. Ο ·\ 35 Ρ * (· I Ρ &Ό Ρ (J> Ο ·Ή ¢) .—\ g «-Η ') +- + 1 ι ο cd (ii Cl > . Qj ‘—'(JO ~3 <Λ I s'— ·Μ »—J q G I'I rH M > C3 1 >·. >·. 11 ο q Γ-f £ H q Ρ Ρ >, Ο Ο O ΕΞ 1 35 P.33 33 σ Γ/1 P O P > U υ o {m cd *x β P u o Sh Ch © © r-Ί © © t—I ·>; R © o CI O 0 o o r-l 1 r—H 1 c O CJ O Cl Cti S 1 >> ι >> q Or—i o r-i ο φ L-J (D | sq 1_1 Φ P 0 C E3ltD o P 0 w H (D 4i q Φ 0 id Ό « ρ ρ ό ο Ρ £ Ό H CO Ti ·Η W τί Ή S>j rd 1 Ο H rd I Ο N >»- cti >a >s - 33 rd N 33 rd fl) ρ o a © «on Φ rd Ή Θ Φ H »zd >a E 1 H X) E 1 H « •Η Φ >3 >s •H I) hO a p * h q κ q 1 CU o o 1 (COO) - an s *· m ο q cn o q p « q cti 33 . « q « i. mp o a CC a o El οθ tn +j © (Λ ι Φ rd Ή σι T3 ϋ q ΕΞ ο ¢0 d μ ο Ρ <ί Ρ < * •Κ * Example 15 Insecticidal Activity The unique insecticidal activity of the com. pounds of the present invention, over a variety of pyre5 throid type insecticides, is further demonstrated by the following tests.

The test procedures employed for the evaluation against Boll Weevils, Southern Armyworms and Tobacco Budworms are described in the preceding examples. The procedures employed for evaluation against mosquito larvae and Mexican Bean Beetles are as follows.

Malaria Mosquito - Anopheles quodrimaculatus Say Milliliter of a 35% water/65% acetone solution containing 300 ppm. of test compound is pipetted in a 400 ml. beaker containing 250 ml. of deionized water and stirred with the pipette, giving a concentration of 1.2 ppm. A wax paper ring 1/4 inch wide to fit inside the beaker is floated on the surface of the test solution to keep the eggs from floating on the meniscus curve and drying out on the side of the glass. A spoon made of screen is used to scoop up and transfer about 100 eggs (0-24 hours old) into the test beaker. After 2 days at 80°F., 50% r.h., observations of hatching are made.

Mexican Bean Beetle - Epilachna varivestis Mulsant Sieva lima bean plants (2 per pot) with primary leaves 3 to 4 inches long, are dipped in the 300 ppm. test solution and set in the hood to dry. One leaf is removed from a plant and placed in a 4 inch petri dish containing a moist filter paper on the bottom and 3 3 4 8 last-instar larvae (13 days from hatching). The day after treatment, another leaf is removed from the plant and fed to the larvae after removing the remains of the original leaf. Two days after treatment, the third leaf is fed to the larvae, this usually being the last needed. The fourth leaf is used on the third day after treatment if the larvae have not finished feeding. The test is now set aside and held until adults have emerged, usually in about 9 days after treatment began.

After emergence is complete, each dish is examined for dead larvae, pupae or adults; deformed pupae or adults; larval-pupal intermediates or pupal-adult intermediates; or any other interference with normal molting, transformation and emergence of pupae or adults.

Data obtained are reported in the table below.

Southern Armywork - Spodaptera eridania (Cramer Methods: Sieva lima bean plants pruned back to two expanded 3 to 4 inch primary leaves are dipped three sec20 onds with agitation in the treatment solutions and then set in a hood to dry. After the leaves are ary they are excised and each excised leaf is placed in * 4 inch petri dish containing a piece of moist filter paper and ten third-instar southern armyworm larvae approximately 3/8 of an inch long. The petri dishes are covered and placed m a holding room for 2 days at a temperature of 80°F. and 50% relative humidity.

Mortality counts are maae after 2 days. Compounds which produce a larval kill are held for an ex3Γ tra day and counted again. 433 18 No Test 3 4 Example 16 Residual Insecticidal Activity Leaf Dip Test Young cotton plants with 2 or 3 expanded true leaves are dipped into 65% acetone-water solutions to thoroughly wet the leaves. The leaves are allowed to dry before the initial leaf samples are removed for bioassay with southern armyworm, Prodenia eridania (Cramer), tobacco budworm, Heliothis virescens (Fabricius) or cabbage looper, Trichoplusia ni (Hubner). Leaf samples are placed in a standard glass petri dish containing moist filter paper and 10 third instar southern armyworm or cabbage loopers. For the tobacco budworm assay, a single leaf is cut into sections of about 1/2 square inch and placed in individual medicine cups with a moist dental wick and one tobacco budworm larvae. The assay samples are held at a constant temperature of 80°F. for 72 hours when mortality counts are made and the corrected percent mortality determined.

The treatment solutions are prepared by dissolving 100 mg. of test compound in 65 ml. of acetone then making the solution to 100 ml. with deionized water to give a 1000 ppm. concentration of the compound. Ten fold dilutions are prepared by taking 10 ml. of the 1000 ppm. solution and diluting to 100 ml. with 65 % acetone and water for 100 ppm. Then 10 ml. of the 100 ppm. solution is diluted the same way to give a 10 ppm. solution.

After the leaves have dried the plants are removed to the greenhouse section fitted with polymethyl methacrylate panels which permit the penetration of 3 3 4 8 ultra-violet light for determination of the residual insecticidal persistance of the compound. Leaf samples are removed for bioassay over a 9- to 10-day period.

Data obtained are reported in the table below where it can be seen that the compounds of the present invention are effective as insecticidal agents for ah extended period of time when applied to plants as a liquid formulation containing from about 100 ppm. to 1000 ppm. of active compound. 3 3 ί 8 ii •Η •r! Ρ ο rt •σ «Μ Ο •ri pi Ο Φ UJ c ρϊ « Eh o o co cy ω P>i o © rt < Ο σ\ α OQ rrt Φ hi) Ih ο nJ Φ rrt Ώ Cl η o rt o O h4 σ σ (14 co -=r Ui >> o co rt < o ro w Vi rrt φ s· Ml φ a to di rt il IT t*· rt (J rd .« o rt . l r > 3 o © © © rn o cy © x> trt rrt r—I ω >2 O O o © cn <3 σ in © P— u w r-l (rt φ hl) rt > rt Φ o o η a O'© rt rt |—I rt u O >-l ο σ © © rfi o a ©co Ui H rrt r-l r—‘ rt o c © 3 M < o o © O Vi r-l rrt r— σ hl' Sh rt Φ rt rt rt rt rt rt o J Ε C. ,-s >ι Ε Μ < Ε rt rt PQ Ε rt Ο Φ υ Λ ο •ρ Λ 3 Ό ο ο W Ε-1 II II < CQ ν’. ΕΗ 3 3 4 8 Example 17 Residual Insecticidal Activity Foliar Spray Test Young cotton plants with 3 to 4 expanded true 5 leaves and young bean plants are sprayed with an overhead traveling spray apparatus delivering 86 gallons of liquid per acre through a flat fan nozzle. By varying the compound concentration in the spray solution different rates of compound per acre are obtained; hence 84 mg. of compound per 240 ml. of solution will result in the delivery of 4 oz. of compound in 86 gallons of liquid per acre, 42 mg. per 240 ml. of solution will result in the delivery of 2 oz. of compound in 86 gallons of liquid per acre and 21 mg. per 240 ml. of solution will result in 1 oz. of compound in 86 gallons of liquid per acre.

Plants are sprayed and leaves permitted to dry before initial leaf samples are taken for bioassay with southern armyworm and tobacco budworm. Bioassay is done as described for Leaf Dip Test.

Plants are removed to the greenhouse for evaluation of residual persistance of the compounds as described for Leaf Dip Test.

Solutions are prepared by dissolving 84 mg. of compound in 240 ml. of 65% acetone-water (A) for the oz/A rate, 120 ml. of solution A is diluted to 240 ml. with 65 % acetone-water (B) for the 2 oz/A rate, and 120 ml. of solution B is diluted to 240 ml. with 65% acetone-water for the 1 oz/A rate. To each 120 ml. of spray solution is added 0.2 ml. of 3% ’’triton X-100 sur34 *Triton is a trade mark factant.

Data obtained are reported in the table below where it can be seen that the compounds of the present invention demonstrate unusual residual insecticidal ef5 fectiveness as compared to a variety of the known pyrethroid type insecticidal compounds. Only the chlorinated prior art compound permethrin [cyclopropane carboxylic acid, 3-(2,2-dichlorovinyl)-2,2-dimethyl-m-phenoxybenzyl ester] of all pyrethroid types tested, also exhibited extended residual activity. oz. = 28.35 grams oz. = 56.70 grams 4 oz. = 113.40 grams Percent Mortality 1 i 11 Days 1 CQ EH < CO ι ι o cm 1 1 o 1 o o CAO rt 1 o o ca o o o o sr o o o M3 CM ooo rH t»O rH OOO CM O rt 60 100 0 0 90 60 Ί0 0 100 100 80 80 ooo EM CM ZJ OOO T CM ooo ooo rt rt rt OOO ooo rt rt rt V) S ci Q a 3 CQ Eh S w I I o i 1 o CM 1 o o f-oi o o 1 ho rt O O O M3 O rt O O O cm-=t o rt ooo rt Ο O rt rt OOO CAO rt ooo 43 Ο O rt rt OOO sr ο o rt rt OOO >-o o rt rt OOO moo rt rt OOO 43 143 CO OOO OOO rt rt rt OOO CAO O rt rt OOO OOO rt rt rt tn >> nJ σ D tH 3 a: Ό 1 J o AT 1 1 o 1 o o c— σ» I o m uacm o mo CM CM «Ο Ο Ο O CM OcO rt OOO t-c-o rt O O O M3 CAO r-t OOO 43 33 CO OOO x?-a· O rt OOO CAO O rt rt OOO 33 CAO rt ooo CM X> O rt OOO 43 OMJ rt OOO OOO rt rt rt OOO OOO tn >» (ti □ Q W ooo CM o o o CM M3 o o o moo rt rt ooo o o OOO CM CO OOO ST O rt OOO o r-o rt rt Ο O <3 O o rt rt OOO =r Ο o rt rt OOO too rt rt OOO OOO rt rt rt OOO OOO ooo O 43 rt OOO =ί M3 O rt OOO ooo rt rt rt OOO OOO «ai Φ 4J rt 5 N N tf O 0 O rt CM-=T Ν Ν N OOO rt CM-=T Ν Ν N OOO rt CM-=T Ν Ν N OOO rt cm ar j Compound A 0 Ό ’’P «Η 1 « OH Φ rt >» 43 rt UP >, •HON rf a C >iH 0 Η Ό 43 O 1 >5 43 Ύ1 X Jh «Ο rt tn c ο 1 o 0) O 43 C fc o, rt ο ι ftrt El 043 1 Sm o o g.«h c 0 Ό rt rt 1 >» o cm o >» Λ I OCM d fc 1 PJ» 1 o CM 1 rt rt >, fi N 43 β +5 Q> > 1 X cn o C A 0 Ό 43 •H fX O 1 . d el 0 A •H | tl rt >S >» +5 rt 3 O CQ -P rt 1 >5 ο N μ . c cu IS o H? rt 0 o* >> I 2 ϋ cn£ 1_J .1 OJ OrLC H 0)9- •Η β', p, qjEI cn Ό £.% 3-'s a) w1 | Js A cn gx +i * go w m βο φ 1 0 M ai Ο Μ 1, η nj El ϋ ϋ ι thi © un 5 e «—1 t (0 t· Or—i >» Φ ho Ήβ 1 S CUO) d φ U)O__, >.·5'α > 5 I Ή Ν Ο c .5_Γ ο >> r>r « 75.-iS S « ® *22 Ο 43 °Ό.Ρ, ο ο Ο Ο CJ r4 rl Ό <υ £ •rt Ρ α ο ο I >5 4> •rt υ < Ό •rt ς> «rt •μ ο ω tn $4 ΙΟ Ό C Π3 ιη OJ r- Ο ε •sSs C J- Ό 3 < 3 S " •Ρ 3 .Ω S- Ο Ο «τ; ιη ιί- II II •2 3: ca s- Example 18 Soil Insecticidal Activity Southern Corn Rootworm - Diabrotica undecimpuctata howardi (Barber) Ten mg. of compound are diluted to 10 ml. with acetone to make a stock solution. Two ml. of this solution is then diluted to 10 ml. with acetone to make solution B; and 1 ml. of said solution B is further diluted to 10 ml. with acetone to make solution C. Approx10 imately 0.7 g. Pyrax ABB talc is then placed in a 1 oz. wide-mouth jar and 1.25 ml. of the selected solution is added to the talc to produce the following concentrations : 1.25 ml. solution A yields 50 lb/A 1.25 ml. solution B yields 10 lb/A 1.25 ml. solution C yields 1 lb/A The selected test solution is mixed with the talc to wet it evenly before it is dried under an air-jet dryer for 10-15 minutes. Twenty-five ml. of moist sterilized potting soil and approximately 0.6 g. millet seed (food for larvae) are then added to the jars containing test compound. .The jars are capped and the contents mixed on a vibrating mixer. Each jar then receives 10 Southern corn rootworm larvae 6-8 days old. The jars are loosely capped and placed in a holding room at 80°F. and 50% r.h. with constant light. Mortality counts are made after 6 days.

Fj-om the data obtained and reported below, as percent mortality, it can be seen that the m-phenoxybenzyl esters of spirocarboxylic acids of the present invention » J 3 4 8 which are highly effective soil insecticidal agents, when applied to soil at a rate of from 10 pounds to 50 pounds per acre.

Soil Insecticide Activity Compound Southern Corn Rootworm 50 lb/A 10 lb/A 3,3-Dimethylspiro[cyclopropane-1 ,1'-indene]-2-carboxylic acid, m-phenoxybenzyl ester 100 0 3,3-Dimethylspiro[cyclopropane-1 ,11-indene]-2-carboxylic acid, a- cyano -m-phenoxybenzyl ester 100 100 Example 19 Systemic Control of Stable Flies on Mice α-Cyano-m-phenoxybenzyl ester of 2,2-dimethyl-4,5~benzospiro[2,4]hepta-4,6-diene-l-carboxylic acid is dissolved in 10% acetone/90% corn oil and administered orally (by gavage) to two 20 g. Swiss-Webster white female mice at 400 mg/kg. One mouse is dosed with 10% acetone/90% corn oil and used as a control.

One hour after treatment, 9 stable flies (Stomoxys calcitrans) are placed in a cage with each mouse and allowed 4 1/2 hours to feed. With 1 1/2 hours after the flies are placed with the mice, all flies in the treated group are knocked down. The flies are held overnight and mortality measured at 24 hours. 1 Number of Mice Treated Dose (mg/kg) Number Plies on Number Dead After 24 Hour 2 400 18 17 5 1 0 9 2 Example 20 Animal Systemic Insecticidal Activity To determine the effectiveness of the compounds of the invention as animal systemic insecticidal agents, the m-phenoxybenzyl ester of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-l-carboxylic acid; and the α-cyano-m-phenoxybenzyl ester of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-l-carboxyiic acid are mixed in 10% acetone-90% sesame oil and administered by gavage to 2 mice each at 25, 100, 200 and 400 mg/kg of animal body weight.

Adult, one day old, unfed stable flies (Stomoxys calcitrans) are then exposed to the mice for 18 hours to permit them to feed on said mice. Mortality counts are made at 24 hours and data obtained are reported below: mg/kg Flies Dead Flies ο ο σ © © CS CS ts CS CM ooomo © O © Φ ϋ Ό ►Η φ 2 Ρ Φ * Φ μ ίΖ Η cs cs cs CS CS CS CS CS CS CS χτ >1 >1 I X 1 1 ι κ I * 0 * 0 - 0 - 0 Η 3 Η 3 Η 3 Η 3 s Φ * Φ * Φ ·>. φ Η Λ ι—1 >} Η XJ Η ίΧ ι a I υ 1 a 0 Φ I Φ 1 Φ 1 Φ 1 3 ε 3 6 3 ε 3 6 AJ 3 φ Φ Q. » a * λ > a * 0 *0 0 Ό 0 Ό ο τι Li «Η μ ·μ μ η μ ·μ & υ a ο a ο a ο ο φ 0 φ 0 Φ 0 Φ Η r-l μ Η Η μ ο ϋ □ α Φ ϋ ϋ 0 ϋ φ ΐχ·Η ίΧ·μ Ρ >ι·μ >ί·Η Ρ 0 κ 0 Η ω 0 Η 0 Η ω >> — >1 Φ - b ‘Τ' £? φ 0 κ 0 X 0 Λ Ο Μ μ 0 μ oh μ ο μ 0 Η •μ Λ •Η Λ ίχ •μ Λ •Η X >1 & μ α μ Ν a μ a μ Ν W φ ω φ 3 ω φ ω φ 3 Η ϋ μ Η ϋ Φ Η ϋ μ Η ο Φ >1 1 φ >ι 1 X >ι 1 φ >ι ' X Λ cs Ρ Ρ CS >1 X! cs Ρ X cs ίχ •Ρ ! V) -Ρ 1 X Ρ 1 ω Ρ 1 Μ Ό φ η φ φ η 0 φ η Φ φ η 0 β ε φ ε φ 3 ε φ ε φ 3 3 •Η 3 Η •Η 3 Φ μ 3 Η Η 3 Φ 0 Q φ >1 Ω ΦΛ Ο Φ >1 Q Φ XJ & Ό Ν ί Ό Ρ ι τι Ν ό a £ co 3 3 co C 1 CO 3 3 cn β 1 . 0 *·μ Φ *·Η Βι χ Ή Φ -·Η 61 υ co 1 Λ co J I co ι XI C0 11 3 3-4-8 Example 21 Ixodicidal Activity Effective control of acarina larvae is demonstrated in the following tests with larvae of Boophilus microplus, a one-host tick which can remain on a single host through its three life stages, i.e., larvae, nymph and adult. In these tests, a 10% acetone - 90% water mixture contains 3.1, 12.5 or 50 ppm. of test compound. Twenty larvae are enclosed in a pipet sealed at one end with a gauze material and solution containing'the test compound is then drawn through the pipet with a vacuum hose, the whole simulating a spray system. The ticks are then held for 48 hours at room temperature and mortality is determined. The results achieved are set forth below.

Compound 3,3-Dimethylspiro[cyclopropane1,1'-indene]-2-carboxylic acid, m-phenoxybenzyl ester 3,3-Dimethylspiro[cyclopropane1, 1-indene] -2-carboxylic acid, α-cyano-m-phenoxybenzyl ester Mortality Boophilus Microplus larvae 100% at 50 ppm. 100% at 12.5 ppm. 100% at 3.1 ppm. 100% at 50 ppm. 100 % at 12.5 ppm. 80% at 3.1 ppm.

Example 22 Suppression of Fecundity and Chemosterilant Effect in Ixodidae The efficacy of the compounds of the present invention for suppression of fecundity in ticks is dem30 onstrated in the following tests wherein engorged adult female Boophilus microplus ticks which have dropped from cattle are collected and used for testing.

The compound to be tested is dissolved in a 35% acetone/65% water mixture in sufficient amount to provide 15.62, 31.25, 62.5, 125 and 250 ppm. of compound in the test solution. Fifteen ticks per treatment are used and they are immersed in test solution for three to five minutes, then removed and placed in dishes and held in incubators for 2 to 3 weeks at 28°C. Counts of ticks laying eggs are then made and recorded. Eggs which were laid are weighed and placed in containers and kept for one month to observe hatching and to determine chemosterilant effect. For each test, fifteen ethion-resistant ticks are used since they are the most difficult of their kind to control. Results of these tests are given in the tables below.

Efficacy is determined on the percent reduction in weight of egg masses over controls and is reported for each concentration of chemical applied.

The effectiveness of test chemicals for suppressing the fecundity of ixodid ticks is also determined on the basis of the 3 highest rates of application, e.g. 62.5 ppm; 125 ppm and 250 ppm, employing the rating system given below.

Rating System Result Score No oviposition 4 Partial ovipositions, no hatch 3 Total oviposition, no hatch 2 Partial oviposition, viable eggs 1 Normal oviposition and hatch 0 The rating system is based on the summation of scores from all ticks in the above-said tests. Using this rating system the best score possible would be 180 or 45 (the total number of ticks used) x 4 (the highest score). The efficacy is reported as percent of the best possible score.

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Claims

1. A compound having the formula represents a single or double bond.

2. 3. A compound according to Claim 2, 3,3-dimethylspiro [cyclopropane-1,1'-indene]-2-carboxylic acid, m-phenoxybenzyl ester.

3. 4. A compound according to Claim 2, 3,3 -dimethylspiro [cyclopropane-1,1'-indene]-2-carboxylic acid, α-cyano-m-phenoxybenzyl ester.

4. 5. A compound according to Claim 2, 3,3 -dimethylsprio[cyclopropane-1,1 1 -indane]-2-carboxylic acid, m-phenoxybenzyl ester.

5. 6. A compound according to Claim 2, 3,3 -dimethylspiro [cyclopropane-1,1'-indane]-2-carboxylic acid, α-cyano-m-phenoxybenzyl ester.

6. 7 A compound according to Claim 1', 2,2-dimethylspiro[2,4]hepta-4,6-diene-l-carboxylic acid, m-phenoxybenzyl ester.

7. 8. A compound according to Claim 1, 2,2-dimethylspiro[2,4]hepta-4,6-diene-l-carboxylic acid, α-cyano-m-phenoxybenzyl ester.

8. 9. A compound according to Claim 2,2-dimethylspiro[2,4]heptane-l-carboxylic acid, m-phenoxybenzyl ester.

9. 10 A compound according to Claim '> 2,2-dimethylspiro[2,4]hsptane-l-carboxylic acid, a-cyano-m-phenoxybenzyl ester.

10. 11. A compound according to Claim 1, 2,2-dimethylspiro [2,4]heptane-l-carboxylic acid, a-ethynyl-m-phenoxybenzyl ester.

11. 12. A compound according to Claim 1,. 2,2-dimethylspiro[2,4]hepta-4,6-diene-l-carboxylic acid, Λ25

12. 13. A compound according to Claim 2, 3,3 - dimethylspiro [cyclopropane - 1,1' - indane] -2 - carboxylic acid, a ethynyl - m - phenoxybenzyl ester.

13. 14. A compound according to Claim 2, 3,3 - dimethyl spiro ^cyclopropane - 1,1' - indene*] - 2 - carboxylic acid, a ethynyl - m - phenoxybenzyl ester.

14. 15. A process for the manufacture of a compound of the formula wherein A is attached via a spiro linkage and is the group: or wherein R 1 is hydrogen, cyano or ethynyl, and - represents a single or double bond, which comprises reacting approximately equimolar amounts of an acid halide 15 of a spirocarboxylic acid of the formula: 4 3 348 wherein A is as defined above and X is halogen, with a m-phenoxybenzyl alcohol.

15. 16. A method for the control of insects and acarids comprising contacting said insects and acarids their habitat 5 or their food with an insecticidal or acaricidal amount of a compound according to any preceding claim.

16. 17. A method for protecting plants from attack by insects comprising applying to the foliage of the plants or to the soil in which they are growing, an insecticidally 10 effective amount of a compound according to any one of Claimsl-14.

17. 18. A method according to Claim 17, comprising applying the compound to the foliage of the plants in sufficient amount to provide from 28 g. to 228 g. per acre of said compound. 15

18. 19. A method according to Claim 18 wherein the compound is applied at a rate of from 28 g. to 113.4 g. per acre.

19. 20. A method according to Claim 17 wherein the compound is applied to the soil in which plants are growing at a rate of from 10 to 50 pounds per acre. 20

20. 21. An insecticidal or acaricidal composition, comprising a compound according to any one of Claims 1 - 14, and an inert solid or liquid or liquid carrier therefor.

21. 22. An insecticidal or acaricidal composition according to Claim 21, formulated with a liquid carrier and an emulsify2o ing agent for application as a spray.

22. 23. A method for the systemic control of ectoparasites which attack warm-blooded hon-human animals, comprising administering to said warm-blooded animals a systemically effective amount against the ectoparasites of a compound 30 according to any one of Claims 1 - 14.

23. 24. A method according to Claim 23, wherein the compound is administered orally or parenterally to the animal host at a dose level of from

24. 25 mg/kg of animal body weight to 1000 mg/kg of animal body weight. 5

25. A composition for the systemic control of ectoparasites which attack warm-blooded, non-human animals, comprising a compound according to any one of Claims 1-14 and a pharmaceutically acceptable carrier or diluent.

26. A composition according to Claim 1 or Claim 2, 10 substantially as described in any one of Example 1-12 herein.

27. A process for the manufacture of a compound according to Claim 1 or Claim 2, substantially as described in any one of Examples 1-12 herein.

28. A compound according to Clain 1 or Claim 2, whenever 15 prepared by a process according to Claim 15 or Claim 27.

29. A method for the control of insects and acarids, according to Claim 16 and substantially as described in any one of Examples 14-18 herein.

30. A method for the systemic control of ectoparasites 20 which attack warm-blooded, non-human animals, according to Claim 23 and substantially as described in any one of Examples 19-22 herein.