Abstract:
This invention relates to novel insecticidal compositions comprising a m-phenoxybenzyl ester of a spirocarboxylic acid and an insecticidal agent of chlorinated camphene; O,O-dimethyl-O-p-nitrophenyl phosphorothioate; N&#39;-(4-chloro-o-tolyl)-N,N-dimethylformamidine; 2-(diethoxyphosphinylimino)-4-methyl-1,3-dithiolane; O,O-dimethyl-S-[4-oxo-1,2,3-benzotriazin-3-(4H)-ylmethyl]phosphorodithioate; 1-naphthyl N-methylcarbamate. O,O-dimethylphosphorodithioate of diethylmercaptosuccinate; or mixtures of the latter named chemical insecticidal agents and to the use of the above compositions for protecting agricultural crops from attack by insect pests.

Description:
This is a division, of application Ser. No. 874,305, filed Feb. 2, 1978 now abandoned, which in turn is a division of Ser. No. 623,864 filed Oct. 20, 1975, now U.S. Pat. No. 4,087,523 (1978). 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The field of the invention is pyrethroids in combination with selected insecticidal agents for the control of insect pests, particularly those which are of major economic importance to the cotton industry. 
     2. The Prior Art 
     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 acarina control. None, to the best of our knowledge, has been entirely satisfactory for the control of the complex of insects which ravage growing cotton plants: and, with few exceptions, all have been subject to extremely rapid degradation to non-toxic substances. This latter property has been recognized as a major deficiency of the pyrethroids. While such compounds have provided excellent knockdown of many insects, rapid degradation of said compounds has resulted in lack of residual insect control even for a few days. 
     The pyrethroids useful in my invention are described in the R. W. Addor United States Patent Application Ser. No. 550,105, filed Feb. 13, 1975. now U.S Pat. No. 3,966,959. 
     Heretofore, many conventional insecticidal chemicals have also been employed for the control of insects which ravage growing cotton plants. Many have met with a high degree of acceptance by cotton growers, but virtually all have been found to have their limitations and none has afforded complete protection for the growing cotton plants against the insect complex encountered. 
     It is therefore an object of the present invention to provide an insecticidal composition which is highly effective for protecting crops, particularly cotton crops, from insect attack. 
     It is also an object of this invention to provide a chemical composition which contains (1) a pyrethroid compound that is not subject to immediate degradation and (2) a selected phosphate, N-methylcarbamate, chlorinated camphene or chlorinated formamidine insecticide; and it is a further object of this invention that such composition be more effective for controlling certain Lepidopterous, Hemipterous and Coleopterous insects and more effective for protecting important agronomic crops from attack by the insects, than is the pyrethroid alone or the phosphate, carbamate, chlorinated camphene, chlorinated formamidine or mixtures thereof. 
     Advantageously, the compositions of the invention are useful as contact or stomach posions. They are superior in insecticidal activity or insect repellancy, to the pyrethroid alone or the phosphate, carbamate, chlorinated camphene or chlorinated formamidine insecticides and can be employed as protecting agents for important agronomic crops such as cotton, soybeans, tobacco, cole crops, leafy vegetables, forage crops, corn, snapbeans, and tomatoes. 
     SUMMARY OF INVENTION 
     This invention relates to insecticidal compositions comprising (a) a phenoxybenzyl ester of a spirocarboxylic acid having a formula of: ##STR1## wherein R 1  is hydrogen, cyano or ethylnyl,    represents a single or double bond, and the optical and geometric isomers thereof, and (b) chlorinated camphene; 0,0-dimethyl-0-p-nitrophenyl phosphorothioate; N&#39;-(4-chloro-o-tolyl)-N,N-dimethylformamidine; 2-(diethoxyphosphinylimino)-4-methyl-1,3-dithiolane; 0,0-dimethyl S-[4-oxo-1,2,3-benzotriazin-3-(4H)yl-methyl]phosphorodithioate; 0,0-dimethylphosphorodithioate of diethylmercaptosuccinate; 1-naphthyl N-methylcarbamate, and mixtures thereof. More particularly, this invention relates to novel insecticidal compositions in which the ratio of the conventional insecticide to the pyrethroid is from 5:4 to 40:1 and preferably 5:4 to 20:1. Still more particularly, the compositions of this invention are applied to foliage of plants, which are to be protected from insect attack, in amounts sufficient to provide from about 1.0 to 5.0 oz and preferably 1.6 to 3.2 oz of the pyrethroid and from 0.25 to 4.0 lbs per acre of the conventional insecticide. These most preferred rates are equivalent to 0.11 to 0.22 kg/hectare of the pyrethroid and from 0.28  to 4.48 kg/hectare of the conventional insecticide. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     In accordance with this invention the phenoxybenzyl esters of benzospirocarboxylic acids depicted by formula I, can be prepared by reacting approximately equimolar amounts of an acid halide, preferably the chloride, of a benzospirocarboxylic acid (IV) and m-phenoxybenzyl alcohol (V). The reaction is generally conducted in the presence of a suitable solvent such as benzene, toluene, diethyl ether, or the like, at a temperature between about 10° C. and 30° C., and in the presence of an acid acceptor such as an organic tertiaryamine such as triethylamine, trimethylamine, pyridine, or the like. The reaction can be graphically illustrated as follows: ##STR2## wherein R 1  is hydrogen, cyano, or ethynyl, and X is halogen, preferably chloro. 
     The benzospirocarboxylic acid halide (IV) is readily obtained by reaction of the appropriate benzospirocarboxylic acid (III) with a thionyl halide such as thionyl chloride, thionyl bromide or a phosphorus halide such as phosphorus trichloride or phosphorus pentachloride in the presence of an organic solvent such as toluene, benzene or benzenehexane mixture. This reaction may be conducted at room temperature but is preferably conducted at 60°-90°; and can be illustrated as follows: ##STR3## 
     The formula II phenoxybenzyl esters of spirocarboxylic acids can be prepared in a manner similar to that described above for the preparation of the formula I benzospiro compounds, by substituting the appropriate spirocarboxylic acid (VI) for the above-mentioned benzospirocarboxylic acid (III); converting said acid to its corresponding acid halide (VII) and reacting the thus-formed acid halide with m-phenoxybenzyl alcohol (V), under the conditions mentioned above, to obtain the formula (II) m-phenoxybenzyl ester of the spirocarboxylic acid. This reaction can be graphically illustrated as follows: ##STR4## wherein X is halogen, preferably chloro, and R 1  is hydrogen, cyano, or ethynyl. 
     In accordance with this invention, it should also be understood that various geometric isomers as well as optical isomers of the above-identified compounds do result from the preparations described. For example, in the synthesis of the 2,2-dimethylspiro[2,4]hepta-4,6-diene-1-carboxylic and 2,2-dimethylspiro[2,4]hepta-4-ene-1-carboxylic acid esters of m-phenoxybenzyl alcohol, d and l isomeric pairs are formed. In the preparation of the α-cyano- and α-ethynyl-m-phenoxybenzyl esters, an additonal chiral center is introduced, and this allows for additional d, l pairs. Additionally, the esters derived from 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid and 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-carboxylic acid will be further complicated by the presence of cis and trans isomers. 
     For the control of insects, including soil insects, which attack growing plants and/or harvested crops, including stored grain, the insecticidal compositions of this invention may be applied to the foliage of plants, the insect&#39;s habitat and/or the insect&#39;s food supply. Generally, the active composition is applied in the form of a dilute liquid spray; however, it may also be applied as an aerosol, a dust, wettable powder, or the like. 
     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, shrubs, and the like, may comprise about 24% by weight of the active composition; 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 solvent such as cyclohexanone; and about 45% by weight of a petroleum solvent having a minimum aromatic content of about 93 volume %. 
     Typical compositions of this invention which are highly effective for controlling insect pests and or protecting crops from attack thereby are as follows. 
     
         __________________________________________________________________________Typical Preferred Compositions of the Present Invention        Rate of Chemical                 *Pyrethroid Rate                          Ratio of ChemicalChemical     kg/ha    kg/ha    To Pyrethroid__________________________________________________________________________Chlorinated Camphene        2.24-4.48                 0.11-0.22                          10-1 to 40-1Methyl Parathion        0.28-1.68                 0.11-0.22                          5-4 to 15-1Chlorinated Camphene +        0.56 to 4.48-                 0.11-0.22                          5-4-1 toMethyl Parathion        0.28 to 1.68      40-15-1Chlordimeform        0.56-1.12                 0.11-0.22                          2.5-1 to 10-1Chlorinated Camphene +        2.2-0.14 0.11-0.22                          10-0.625-1 toChlordimeform                  20-1.25-1Chlorinated Camphene +        2.2-0.56- 0.14                 0.11-0.22                          10-2.5-0.625-1Methyl Parathion +Chlordimeform                  to 20-5-1.25-1Carbaryl     1.12-2.8 0.11-0.22                          5-1 to 25-1Azinphos-methyl        0.28-0.56                 0.11-0.22                          5-4 to 5-1Melathion    0.56-2.2 0.11-0.22                          2.5-1 to 20-1__________________________________________________________________________ *Preferred pyrethroids are 2,2Dimethyl-4,5-benzospiro[2,4]hepta4,6-diene-1-carboxylic acid, mphenoxybenzyl ester and 2,2Dimethyl-4,5-benzospiro[2,4]hepta4,6-diene-1-carboxylic acid, cyano-n-phenoxybenzyl ester. 
    
    
    
     The invention is further demonstrated by the non-limiting examples provided below. 
     EXAMPLE 1 
     Preparation of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid, m-phenoxybenzyl ester ##STR5## 
     To 4.3 g (0.02 mole) of 2,2-dimethyl-4,5-benzospiro-2,4-hepta-4,6-diene-1-carboxylic acid in either hexane/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). Infrared indicates an acid chloride carbonyl at 1790 cm -1 . 
     The acid chloride and 4.0 g (0.02 mole) of m-phenoxy benzyl alcohol are dissolved in 20 ml of ether, and 2.1 g (0.02 mole) 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 -1 . The nuclear magnetic resonance spectrum (CCl 4 ) shows the following: δ=1.41, 1.45, 1.58, 1.66 (4S, 6H, methyls), 2.61 (S, 1H, cyclopropane H), 4.85-5.10 (m, 2H, O--CH 2 ), 6.12 (d, 0.5H, J=5.5 Hz, vinyl), 6.66-7.76 (m, 14.5H aromatic and vinyl). 
     Analyses: Calculated for C 27  H 24  O 3  : C, 81.83; H, 6.06. Found: C, 82.14; H, 6.29. 
     EXAMPLE 2 
     Preparation of 2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid, α-cyano-m-phenoxybenzyl ester ##STR6## 
     2,2-Dimethyl-4,5-benzospiro [2,4] hepta-4,6-diene-1-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-cyano-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 (CDCl 3 ) δ= 6.8-7.6 (m, 14.5H, aromatic and vinyl), 6.37 (m, 1H, ##STR7## 6.22 (d, 0.5H, vinyl), 2.73 (m, 1H, ##STR8## 1.72-1.43 (m, 6H, methyls). 
     EXAMPLE 3 
     Preparation of 2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-carboxylic acid, m-phenoxybenzyl ester 
     The procedure of Example 1 is followed using 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-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 as an oil. The pure ester obtained by chromatography had the following spectral properties: Infrared spectrum (heat film) 1720 cm -1  ; nuclear magnetic resonance spectrum (CCl 4 ) δ=6.7-7.6 (m, 13H, aromatic), 4.8-51 (m, 2H, O--CH 2 ), 1.1-3.2 (m, 11H, CH 3 , indane CH 2 , and cyclopropane H). 
     EXAMPLE 4 
     Preparation of 2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-carboxylic acid, α-cyano-m-phenoxybenzyl ester 
     The procedure of Example 2 is followed using 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-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. 
     EXAMPLE 5 
     Preparation of 2,2-Dimethylspiro[2,4]hepta-4,6-diene-1-carboxylic acid, m-phenoxybenzyl ester 
     The procedure of Example 1 is followed using 2,2-dimethyl[2,4]hepta-4,6-diene-1-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. 
     EXAMPLE 6 
     Preparation of 2,2-Dimethylspiro[2,4]hepta-4,6-diene-1-carboxylic acid, α-cyano-m-phenoxybenzyl ester 
     The procedure of Example 2 is followed using 2,2-dimethylspiro[2,4]hepta-4,6-diene-1-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. 
     EXAMPLE 7 
     Preparation of 2,2-Dimethylspiro[2,4]heptane-1-carboxylic acid, m-phenoxybenzyl ester ##STR9## 
     The procedure of Example 1 is followed using 2,2-dimethylspiro[2,4]heptane-1-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. The pure ester obtained by chromatography has the following spectral properties: Infrared spectrum (neat film) 1730 cm -1  ; nuclear magnetic resonance spectrum (CCl 4 ) δ=6.8-7.4 (m, 9H, aromatic), 5.0 (s, 2H, O--CH 2 ), 1.4-1.7 (m, 8H, cyclopentane CH 2 ), 1.1 (s, 3H, CH 3 ), 1.2 (s, 3H, CH 3 ). 
     EXAMPLE 8 
     Preparation of 2,2-Dimethylspiro[2,4]heptane-1-carboxylic acid, α-cyano-m-phenoxybenzyl ester 
     The procedure of Example 2 is followed using 2,2-dimethylspiro[2,4]heptane-1-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-1-carboxylic acid and 2,2-dimethylspiro[2,4]heptane-1-carboxylic acid esters of m-phenoxybenzyl alcohol, d and l 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, l 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-1-carboxylic acid and 2,2-dimethyl-4,5-benzospiro[2,4]-hepta-4-ene-1-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 2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid, α-ethynyl-m-phenoxybenzyl ester 
     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 2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-carboxylic acid, α-ethynyl-m-phenoxybenzyl 
     The procedure of Example 1 is followed using 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid and α-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-1-carboxylic acid, α-ethynyl-m-phenoxybenzyl ester 
     The procedure of Example 1 is followed using 2,2-dimethylspiro[2,4]hepta-4,6-diene-1-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid and α-ethynyl-m-phenoxybenzyl alcohol in place of m-phenoxybenzyl alcohol to give the product as an oil. 
     EXAMPLE 12 
     Preparation of 2,2-Dimethylspiro[2,4]heptane-1-carboxylic acid, α-ethynyl-m-phenoxybenzyl ester 
     The procedure of Example 1 is followed using 2,2-dimethylspiro[2,4]heptane-1-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid and α-ethynyl-m-phenoxybenzyl alcohol in place of m-phenoxybenzyl alcohol to give the product as an oil. 
     EXAMPLE 13 
     Evaluation of Chemical Compositions Against Tobacco Budworm (Heliothis virescens) on Cotton Plants 
     The effectiveness of the compositions of this invention for protecting cotton plants, and/or controlling insects which attack them, is demonstrated by the following tests. 
     In these tests stock solutions of test compounds are prepared by dissolving and/or dispersing a sufficient amount of test compound in 67 ml of acetone and diluting the thus prepared solution with 36 ml of water to yield 100 ml of stock solution with a given concentration of test compound. Thus, 400 mg of N&#39;-(4-chloro-2-methylphenyl)-N,N-dimethylformamidine yields a stock solution containing 4,000 ppm of compound; and this solution, when used with equal parts of three additional stock solutions, provides an insecticidal composition containing 1,000 ppm of the above-said compound. All stock solutions of test compounds are prepared in this manner and solutions are varied in concentration to match the desired ratio among components. 
     To determine the effectiveness of test compositions for controlling the tobacco budworm (Heliothis virescens (Fabricius)) and protecting cotton plants from attack thereby, one-third of a cotyledon of a Stoneville #213 cotton plant, which had been dipped in test solution is placed in a 1 oz plastic medicine cup containing a 1 inch dental wick saturated with water. One third-instar tobacco budworm larva is placed in each cup and the cup capped and held at 26° C. and 30% relative humidity. Ten larvae are used for each concentration tested. After 3 days, mortality counts are made. Data obtained are reported below. 
     For convenience in reporting data obtained in this evaluation and/or evaluations reported in subsequent examples, common names for chemicals other than the pyrethroids are used. Said chemicals are as follows: 
     
         ______________________________________Chemical              Common Name______________________________________Chlorinated camphene  toxapheneO,O-Dimethyl-S-[4-oxo-1,2,3-                 azinphos-methylbenzotriazin-3(4H)-ylmethyl]-PhosphorodithioateN&#39;-(4-Chloro-2-methylphenyl)-                 chlordimeformN,N-dimethylformamidineO,O-Dimethyl-O-p-nitrophenyl                 methyl parathionphosphorothioate2-(Diethoxyphosphinylimino)-                 mephosfolan4-methyl-1,3-dithiolaneO,O-Dimethyl phosphorodithioate                 malathionof diethylmercaptosuccinate1-Naphthyl N-methylcarbamate                 carbaryl______________________________________ 
    
     
                       TABLE I______________________________________Control of Tobacco Budworm Larvae onCotton Plants Expressedas Percent Mortality of Larvae                    Concen-  %                    tration  Mor-   Compound              ppm      tality______________________________________2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-                    15           101-carboxylic acid, m-phenoxybenzyl ester                    30           332,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-                    30           381-carboxylic acid, α-cyano-m-phenoxybenzyl esterChlorinated camphene     100          0Chlordimeform            1000         50Azinphos-methyl          50           0Chlorinated camphene plus - 2,2-Dimethyl-4,5-                    100benzospiro[2,4]hepta-4,6-diene-1-carboxylic                    plus         50acid, m-phenoxybenzyl ester                    30Chlorinated camphene plus 2,2-Dimethyl-4,5-                    60benzospiro[2,4]hepta-4,6-diene-1-carboxylic                    plus         100acid, α-cyano-m-pheoxybenzyl ester                    3Aminophos-methyl plus 2,2 Dimethyl-4,5-                    50benzospiro[2,4]hepta-4,6-diene-1-carboxylic                    plus         80acid, α-cyano-m-phenoxybenzyl ester                    15______________________________________ 
    
     EXAMPLE 14 
     Evaluation of Chemical Compositions Against Cabbage Looper (Trichoplusia ni) larvae on Cotton Plants 
     To determine the effectiveness of test compositions for controlling cabbage looper (Trichoplusia ni (Huber)) on cotton plants true leaves of a Stoneville #213 cotton plant, dipped in test solution and dried, are placed in separate 9.0 cm petri dishes which are fitted with a moist Whatman #1 filter paper. Ten third-instar cabbage looper larvae are placed in each of the dishes which are then covered and held in a room maintained at 26° C. and 30% relative humidity. After 3 days, mortality counts are made and feeding damage is estimated. Data obtained are reported below. 
     
                       TABLE II______________________________________Control of Cabbage Looper Larvae onCotton Plants Expressed as Percent Mortality andPlant Protection Expressed as Percent Feeding Damage             Concen-           %             tration  %        FeedingCompound or Composition             ppm      Mortality                               Damage______________________________________2,2-Dimethyl-4,5-benzospiro [2,4]-             5            20     30hepta-4,6-diene-1-carboxylic acid,             3            15     63m-phenoxybenzyl ester             1.5           0     1002,2-Dimethyl-4,5-benzospiro[2,4]-             1.5          60     10hepta-4,6-diene-1-carboxylic acid,             1            68     16α-cyano-m-phenoxybenzyl esterChlorinated camphene             100           0     100Methyl parathion   10           0     100Chlordimeform     1000         40     100Aminphos-methyl   150           0     1004-(diethoxyphosphinylimino)-4-             100          50     100methyl-1,3-dithiolane2,2-Dimethyl-4,5-benzospiro[2,4]             3hepta-4,6-diene-1-carboxylic acid,             plus         70     10m-phenoxybenzyl ester plus             10methyl parathion2,2-Dimethyl-4,5-benzospiro[2,4]-hepta-4,6-diene-1-carboxylic acid,m-phenoxybenzyl ester             1Plus              PlusMethyl parathion  15Plus              Plus         90     2Chlordimeform     1.875Plus              PlusChlorinated camphene             302,2-Dimethyl-4,5-benzospiro[2,4]-hepta-4,6-diene-1-carboxylic acid,α-cyano-m-phenoxybenzyl ester             1Plus              Plus         100    1Chlordimeform     10002,2-Dimethyl-4,5-benzospiro[2,4]-hepta-4,6-diene-1-carboxylic acid,m-phenoxybenzyl ester             0.25Plus              Plus         70     20Chlordimeform     250Plus              PlusChlorinated camphene             1252,2-Dimethyl-4,5-benzospiro[2,4]-hepta-4,6-diene-1-carboxylic acid,α cyano-m-phenoxybenzyl ester             1.5Plus              Plus         90     5Aminphos-methyl   1502,2-Dimethyl-4,5-benzospiro[2,4]-hepta-4,6-diene-1-carboxylic acid,m-phenoxybenzyl ester             5Plus              Plus         90     5Aminphos-methyl   1502,2-Dimethyl-4,5-benzospiro[2,4]-hepta-4,6-diene-1-carboxylic acid,α-cyano-m-phenoxybenzyl ester             1Plus              Plus         90     52-(diethoxyphosphinylimino)-4-             100methyl-1,3-dithiolane______________________________________ 
    
     EXAMPLE 15 
     Effectiveness of Chemical Compositions Against Adult Boll Weevils (Anthonomus grandis) on Cotyledons of Cotton Plants 
     To determine the effectiveness of test compositions for controlling boll weevils and/or protecting plants from their attack, cotyledons from Stoneville #213 cotton plants are dipped in solutions of test compositions and then permitted to dry. After drying, these treated cotyledons are placed in individual 9.0 cm petri dishes with moist Whatman #1 filter papers on the bottom thereof. Ten adult boll weevils are then placed in each of the dishes and the dishes are covered and placed in a room maintained at 26° C. and 30% relative humidity. After 3 days, mortality counts are made and the amount of feeding is estimated. 
     Data obtained are reported in the Table III below. 
     
                       TABLE III______________________________________Effectiveness of Compositions forControlling Adult Boll Weevilson Cotyledons of Cotton Plants               Concen-  %      %               tration  Mor-   FeedingCompound of Composition               ppm      tality Damage______________________________________2,2-Dimethyl-4,5-benzospiro               300          43   5[2,4]hepta-4,6-diene-1-carboxylic               100          23   3acid, m-phenoxybenzyl esterChlorinated camphene               500          20   10               100           0   152,2-Dimethyl-4,5-benzospiro[2,4]-hepta-4,6-diene-1-carboxylic acid,α-cyano-m-phenoxybenzyl ester               100          32   3Methyl parathion    3            20   25Chlordimeform       1000          0   25Malathion           100          30   30Chlorinated camphene plus 2,2-Dimethyl-4,5-benzospiro[2,4]-               100hepta-4,6-diene-1-carboxylic               Plus         50   0acid, α-cyano-m-phenoxybenzyl               100esterMethyl parathion plus 2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-               3diene-1-carboxylic acid, α-cyano               +            100  5m-phenoxybenzyl ester               100Chlorinated camphene plus methyl               60Parathion plus 2,2-Dimethyl-4,5-               +benzospiro[2,4]hepta-4,6-diene-1-               30           100  0carboxylic acid, m-phenoxybenzyl               +ester               100Chlorinated camphene plus methyl               60parathion plus 2,2-Dimethyl-4,5-               +benzospiro[2,4]hepta-4,6-diene-1-               30           100  0carboxylic acid, α-cyano-m-phenoxy-               +benzyl ester        100Chlordimeform plus 2,2-Dimethyl-4,5-               1000benzospiro[2,4]hepta-4,6-diene-1-               +carboxylic acid, m-phenoxybenzyl               300          90   0water plus chlorinated camphene               +               500Malathion plus 2,2-Dimethyl-4,5-               100benzospiro[2,4]hepta-4,6-diene-1-               +            80   0carboxylic acid, m-phenoxybenzyl               300ester______________________________________ 
    
     EXAMPLE 16 
     Evaluation of Chemical Compositions for the Control of Western Potato Leaf Hopper (Empoasca abrupta Delong) 
     A treated primary leaf of a Sieva lima bean plant is placed in a 9.0 cm petri dish with moist Whatman #1 filter paper on the bottom. Approximately 3 to 10, second-instar nymphs are tapped from the culture plant into the test dish which is then covered. The dish is held at about 26° C. and 30% relative humidity for 3 days and then mortality counts are made. 
     Data obtained are reported in Table IV below. 
     
                       TABLE IV______________________________________Effectiveness of Test Compositions forControlling Western Potato Leaf Hoppers                   Concen-  %                   tration  Mor-Chemical or Composition ppm      tality______________________________________Chlorinated camphene    30           15Methyl Parathion        3            38Azinphos-methyl         5             02,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid, m-phenoxy                   10           46benzyl ester2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid, α-cyano-                   10           52m-phenoxybenzyl esterChlorinated camphene plus 2,2-dimethyl-                   304,5-benzospiro[2,4]hepta-4,6-diene-1-                   +            85carboxylic acid, m-phenoxybenzyl ester                   10Chlorinated camphene plus 2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-                   10carboxylic acid, α-cyano-m-phenoxybenzyl                   +            100ester                   3Chlorinated camphene plus                   15Methyl Parathion plus   +Chlordimeform plus      7.5          1002,2-Dimethyl-4,5-benzospiro[2,4]hepta-                   +4,6-diene-1-carboxylic acid,                   0.94m-phenoxybenzyl ester   +                   5Azinphos methyl plus 2,2-Dimethyl-4,5-                   1.5benzospiro[2,4]hepta-4,6-diene-1-carboxylic                   +            100acid, α-cyano-m-phenoxybenzyl ester                   5______________________________________ 
    
     EXAMPLE 17 
     Evaluation of Chemical Composition for the control of Bean Aphids (Aphid fabae Scopoli) 
     A two-inch square fiber pot containing a nasturtium plant which is infested with approximately 100 aphids 2 days prior to test initiation, is placed on a 4 rpm turntable located in an exhaust hood. The plant and aphids are sprayed directly with the test solution for 2 revolutions of the turntable with a DeVilbiss atomizer at 20 psi air pressure. The spray tip is held 6 to 8 inches from the plant during spraying and after spraying the pot with plant and aphids is laid on its side on a white enamel tray. One day after treatment the plants are examined and mortality counts are made. Data obtained are reported in Table V below. 
     
                                           TABLE V__________________________________________________________________________Effectiveness of Chemical Composition for Controlling Bean Apids (Aphidfabae Scopoli)Chemical or Composition  Concentration ppm                              % Mortality__________________________________________________________________________Chlorinated camphene     30        30Methyl parathion         1         50Chlorodimeform           100        5Azinphos-methyl          1.5       60Carbaryl                 1.0        02,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-                    1.0       51carboxylic acid, m-phenoxybenzyl ester                    0.3        72,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-                    0.1       61carboxylic acid, α-cyano-m-phenoxybenzyl ester                    0.03      12Chlorinated camphene plus the m-phenoxybenzyl                    20ester (identified-above) +         95                    1.0Methyl parathion plus the m-phenoxybenzyl ester                    1.0(identified-above)       +         99                    0.3Methyl parathion plus the α-cyano-m-phenoxybenzyl                    1.0ester (identified above) +         100                    0.03Chlorinated camphene plus                    0.6Methyl parathion plus    +                    0.3       95The m-phenoxybenzyl ester                    +                    1.0Chlorinated camphene plus                    0.6Methyl parathion plus    +                    0.3       95The α-cyano-phenoxybenzyl ester                    +                    0.1Chlorinated camphene plus                    0.6Methyl parathion plus    +                    0.3Chlordimeform plus       +         100                    0.04                    +The α -cyano-m-phenoxybenzyl ester                    0.1Chlorinated camphene plus                    12.5Chlordimeform plus       +                    25        80The m-phenoxybenzyl ester                    +                    0.25Chlorodimeform plus      100                    +         100The m-phenoxybenzyl ester                    1.0Chlorinated camphene plus                    12.5                    +Chlordimeform plus       25        80                    +The α-cyano-m-phenoxybenzyl ester                    0.025Malathion plus           10                    +         95The m-phenoxybenzyl ester                    1.0Malthion plus            10                    +         100The α-cyano-m-phenoxybenzyl ester                    0.1Azinphos-methyl plus     1.5                    +         100The α-cyano-m-phenoxybenzyl ester                    0.05Carbaryl plus            1.0                    +         100The m-phenoxybenzyl ester                    1.0Carbaryl plus            1.0                    +         90The α-cyano-m-phenoxybenzyl ester                    0.1__________________________________________________________________________ 
    
     EXAMPLE 18 
     Evaluation of Test Compositions for the Control of Southern Armyworms (Spodoptera eridania (Cramer)) 
     A treated primary leaf of a Sieva lima bean plant is placed in a 9.0 cm petri dish with moist Whatman #1 filter paper on the bottom and containing 10, third-instar southern armyworm larvae. The dish is covered and held in a room maintained at 26° C. and 30% relative humidity. After 3 days, all petri dishes are examined and mortality counts are made. Data obtained are reported in Table VI below. 
     
                                           TABLE VI__________________________________________________________________________Effectiveness of Test Compositions forControlling Southern Armyworms (Spodoptera eridana)                      %     % FeedingCompound of Composition             Concentration ppm                      Mortality                            Damage__________________________________________________________________________Chlorinated camphene             30       40    100Methyl Parathion  10       40    100Chlordimeform     1000     70    55Chlordimeform     300      40    80Carbaryl          30       0     1002,2-Dimethyl-4,5-benzospiro[2,4]-             6        50    50hepta-4,6-diene-1-carboxylic acid,             3        5     80m-phenoxybenzyl ester             1.5      0     1002,2-Dimethyl-4,5-benzospiro[2,4]hepta-             3        66    124,6-diene-1-carboxylic acid, α-cyano-             1.5      10    15phenoxybenzyl ester             1        0     43Chlordimeform plus             1000The α-cyano-m-phenoxybenzyl ester             +        100   1(identified-above)             1Chlordimeform plus             250The m-phenoxybenzyl ester             +        90    15(identified above) plus             0.75chlorinated camphene             +             25.0Chlorinated camphene plus             30Methyl parathion plus             +             15Chlordimeform plus             +             1.9      100   5The α-cyano-m-phenoxybenzyl ester             +             3Malathion plus    100             +        90    5The α-cyano-m-phenoxybenzyl ester             3Carbaryl plus     30             +        100   10The m-phenoxybenzyl ester             3__________________________________________________________________________ 
    
     EXAMPLE 19 
     Evaluation of Test Compositions for the Control of Tarnished Plant Bug (Lygus lineolaris (Palisot de Beauvois)) 
     A treated primary leaf of a Sieva lima bean plant is placed in an 8 oz waxed cup containing a 2 inch dental wick saturated with water and 10 adult tarnished plant bugs. The cup is covered with a clear plastic lid and held in a room maintained at 26° C. and 30% relative humidity. After 3 days, the leaves in the cups are examined and mortality counts are made. Data obtained are reported in Table VII below. 
     
                                           TABLE VII__________________________________________________________________________Effectiveness of Test Composition for Controlling Tarnished Plant Bugs(Lyrus lincolaris (Palisot de Beauvois))Chemical or Composition Concentration ppm                             % Mortality__________________________________________________________________________Methyl parathion        0.3       40Chlorinated camphene    10        502,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene                   30        421-carboxylic acid, m-phenoxybenzyl ester2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene                   10        471-carboxylic acid, α-cyano-m-phenoxybenzyl esterMethyl parathion plus   0.3The m-phenoxybenzyl ester                   +         100(identified above)      30Chlorinated camphene plus                   1.5Methylparathion plus    +                   0.75      90The α-cyano-m-phenoxybenzyl ester                   +(identified above)      5__________________________________________________________________________