Abstract:
This invention relates to novel compounds useful for controlling mites which are represented by the following formula: ##STR1## wherein R 1  is alkyl of 12-14 carbon atoms either branched, cyclic or straight chain; and 
     R 2  is alkyl of 1-17 carbon atoms either branched or straight chain, alkenyl of 2-17 carbon atoms, cycloalkyl of 3-6 carbon atoms, alkoxy of 1-4 carbon atoms, --CH 2  OCH 3 , --CH 2  OCH 2  CH 3  or --CH═CH--CO 2  H.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a continuation-in-part of our copending application Ser. No. 613,553 filed Sept. 15, 1975 U.S. Pat. No. 4,055,661 which in turn is a continuation-in-part of our copending application Ser. No. 531,483, filed Dec. 11, 1974 (now abandoned), which in turn is a continuation-in-part of our copending application 494,294, filed Aug. 2, 1974 (now abandoned), which in turn is a continuation-in-part of our copending application Ser. No. 468,692, filed May 10, 1974 (now abandoned). 
    
    
     BACKGROUND OF THE INVENTION 
     U.S. Pat. Nos. 2,553,647 and 2,553,648 disclose broadly 2-alkyl-3-hydroxy-1,4-naphthoquinones and their corresponding ester derivatives. These compounds are described as having antagonistic action against organism which cause malarial infections. 
     U.S. Pat. No. 2,572,946 discloses the use of nonacylated compounds as miticides; it contains no teaching of acylated compounds. 
     Nakanishi et al. JACS 1952, 3910-3915 discloses the n-undecyl analog of 2-alkyl-3-acetoxy-1,4-naphthoquinone. No use for the composition is disclosed. 
     A need exists for improved miticides; mites are a problem because of the damage they do to valuable crops, e.g., apple trees. 
     SUMMARY OF THE INVENTION 
     This invention relates to novel compounds which are useful for controlling mites; such compounds have the formula: ##STR2## wherein R 1  is alkyl of 12-14 carbon atoms which are branched, cyclic, or straight chain and 
     R 2  is alkyl of 1-17 carbon atoms either branched or straight chain, alkenyl of 2-17 carbon atoms, cycloalkyl of 3-6 carbon atoms, alkoxy of 1-4 carbon atoms, --CH 2  OCH 3 , --CH 2  OCH 2  CH 3  or --CH═CH-CO 2  H. 
     The compounds of Formula I are miticides. That is to say, when an effective amount of such compounds is brought into contact with mites, these pests are killed. The compounds are thus useful for protecting plants and animals from damage caused by mites. 
     The compounds of this invention also have a direct lethal contact action against the eggs of mites. Mite eggs exposed to sprays of these compounds are killed and hatching fails to occur. Rates slightly higher than those used to kill the motile mite forms are generally required for good ovicidal effect. 
     It should be emphasized that it is critical to this invention that R is alkyl of C 12  -C 14 . 
     Preferred for their ease of synthesis are those compounds of Formula I where R 1  is straight chain alkyl of 12- 14 carbon atoms. 
     More preferred for their greater biological activity are those compounds for Formula I where R 1  is straight chain alkyl of 12- 14 carbon atoms, and R 2  is alkyl of 1- 6 carbon atoms, alkenyl of 2 or 3 carbon atoms, methoxy or ethoxy most preferably ethyl or methyl. Specifically, the following compounds are preferred for their superior miticidal activity: 
     3-acetoxy-2-n-tetradecyl-1,4-naphthoquinone; 
     3-acetoxy-2-n-dodecyl-1,4-naphthoquinone; 
     3-propionyloxy-2-n-tetradecyl-1,4-naphthoquinone; 
     2-n-dodecyl-3-propionyloxy-1,4-naphthoquinone; 
     3-butyryloxy-2-n-tetradecyl-1,4-naphthoquinone; 
     2-n-dodecyl-3-methoxycarbonyloxy-1,4-naphthoquinone; 
     2-n-dodecyl-3-ethoxycarbonyloxy-1,4-naphthoquinone; 
     3-butyryloxy-2-n-dodecyl-1,4-naphthoquinone; 
     2-n-dodecyl-3-isobutyryloxy-1,4-naphthoquinone; 
     In a specific embodiment of the instant invention, the compounds of the instant invention are applied in admixture with a superior oil, preferably a minor amount of superior oil, e.g., less than 5% by weight. The resulting miticidal activity is greater than the additive results. Superior oils are discussed in Chapman et al. Selection of a Plant Spray Oil Combining Full Pesticidal Efficiency with Minimum Plant Injury Hazards, Jour. Econ. Ent., 1962, 55:737-43, the disclosure of which is herein incorporated by reference. The resulting mixture of the compound and the superior oil is novel. 
     Combination of the compounds of this invention with other miticides often provides better total mite control than either material alone. Among such products which may be used advantageously with them are chlordimeform (&#34;Galecron&#34;), formetante (&#34;Carzol&#34;), propargite (&#34;Omite&#34;), tetradifon (&#34;Tedion&#34;), and benomyl. Such mixtures are novel. 
     DESCRIPTION OF THE INVENTION 
     Synthesis 
     The compounds of Formula I can be prepared by the procedures described in the previously cited J. Am. Chem. Soc. article and in U.S. Pat. Nos. 2,553,647 and 2,553,648. The final step in the synthesis may be accomplished by treating the corresponding 2-alkyl-3-hydroxy-1,4-naphthoquinone with the appropriate acid chloride or anhydride in the presence of at least an equivalent of an amine such as pyridine or triethylamine, or by treating the salt of the 2-alkyl-3-hydroxy-1,4-naphthoquinone with the appropriate acid chloride or anhydride in an inert solvent. The following examples are given to illustrate the above-described processes. 
    
    
     EXAMPLE 1 
     Preparation of 3-Acetoxy-2-n-dodecyl-1,4-naphthoquinone ##STR3## 
     A mixture of 2.0 parts of 2-n-dodecyl-3-hydroxy-1,4-naphthoquinone, 0.81 parts of triethylamine, 0.63 parts of acetyl chloride and 50 parts of methylene chloride was stirred at room temperature for 30 hours. The resulting mixture was distributed between methylene chloride and water. The methylene chloride layer was separated, dried over magnesium sulfate, then filtered and evaporated under reduced pressure. The residue was crystallized from petroleum ether (b.p. 30°-60°) to give 1.2 parts of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone, m.p. 57°-58° C. 
     EXAMPLE 2 
     Preparation of 2-n-Dodecyl-3-propionyloxy-1,4-naphthoquinone ##STR4## 
     A mixture of 4.0 parts of 2-n-dodecyl-3-hydroxy-1,4-naphthoquinone, 4.4 parts of propionic anhydride, and 50 parts of pyridine was stirred at room temperature for 16 hours. The resulting mixture was evaporated under reduced pressure to remove the pyridine. The residue was crystallized from methanol to give 2.9 parts of 2-n-dodecyl-3-propionyloxy-1,4-naphthoquinone, m.p. 42°-44° C. 
     EXAMPLE 3 
     Preparation of the Sodium Salt of 2-n-Dodecyl-3-hydroxy-1,4-naphthoquinone 
     A dispersion of 1.9 parts of sodium hydride in 250 parts of tetrahydrofuran was added to a solution of 26 parts of 2-n-dodecyl-3-hydroxy-1,4-naphthoquinone in 450 parts of tetrahydrofuran at room temperature. The mixture was stirred at room temperature for 1 hour, then filtered to give a burgundy solution of the sodium salt. 
     EXAMPLE 4 
     Preparation of 2-n-Dodecyl-3-methoxycarbonyloxy-1,4naphthoquinone 
     Sixty parts of the above-mentioned sodium salt solution was stirred with 0.59 parts of methyl chloroformate in 10 parts of tetrahydrofuran at room temperature. The mixture was stirred for 1 hour, then allowed to stand overnight. The resulting suspension was filtered and the filtrate evaporated to dryness. The residue was crystallized from acetonitrile to give 2.0 parts of 2-n-dodecyl-3-methoxycarbonyloxy-1,4-naphthoquinone, m.p. 70°-72° C. 
     By using the appropriate 2-alkyl-3-hydroxy-1,4naphthoquinone and the appropriate acid chloride or anhydride, the following compounds shown in Table I could be similarly prepared by anyone skilled in the art, using the procedure outlined in Examples 1 through 4. 
     
                       Table 1______________________________________ ##STR5##                           Melting                           PointR.sub.1      R.sub.2            (° C.)______________________________________n-C.sub.12 H.sub.25        CH.sub.3          57-58n-C.sub.12 H.sub.25        CH.sub.2 CH.sub.3 42-44n-C.sub.12 H.sub.25        CH.sub.2 CH.sub.2 CH.sub.3                          N.sub.D.sup.25 1.5120n-C.sub.13 H.sub.27        CH.sub.3          58-60 ##STR6##    CH.sub.3          N.sub.D.sup.25 1.5332(CH.sub.2).sub.9CH(CH.sub.3).sub.2         ##STR7##n-C.sub.14 H.sub.29        CH.sub.3          62-63n-C.sub.12 H.sub.25        CH(CH.sub.3).sub.2                          N.sub.D.sup.25 1.5157n-C.sub.14 H.sub.29        CH.sub.2 CH.sub.3 52-53°n-C.sub.14 H.sub.29        CH.sub.2 CH.sub.2 CH.sub.3                          40-41°n-C.sub.14 H.sub.29         ##STR8##         65-67°n-C.sub.12 H.sub.25         ##STR9##         59-61n-C.sub.12 H.sub.25         ##STR10##        50-52n-C.sub.12 H.sub.25         ##STR11##n-C.sub.12 H.sub.25        (CH.sub.2).sub.4 CH.sub.3                          N.sub.D.sup.25 1.5133n-C.sub.12 H.sub.25        C(CH.sub.3).sub.3 N.sub.D.sup.25 1.5133n-C.sub.12 H.sub.25        OCH.sub.3         70-72n-C.sub.12 H.sub.25        OCH.sub.2 CH.sub.3                          42-47n-C.sub.12 H.sub.25         ##STR12##        [IR&gt;=o 1753 cm.sup.-1 ]n-C.sub.12 H.sub.25        CH.sub.2 OCH.sub.3                          69-71n-C.sub.12 H.sub.25        CH.sub.2 OCH.sub.2 CH.sub.3n-C.sub.12 H.sub.25        (CH.sub.2).sub.7 CH.sub.3                          [IR&gt;=o                          1791                          cm.sup.-1 ]n-C.sub.12 H.sub.25        (CH.sub.2).sub.12 CH.sub.3                          51-53n-C.sub.12 H.sub.25        (CH.sub.2).sub.16 CH.sub.3n-C.sub.12 H.sub.25        CHCH.sub.2n-C.sub.12 H.sub.25        CHCHCH.sub.3      43.5-44.5n-C.sub.12 H.sub.25         ##STR13##        N.sub.D.sup.25 1.5202n-C.sub.12 H.sub.25        CHCHCO.sub.2 H    N.sub.D.sup.25 1.5162n-C.sub.12 H.sub.25        CHCH CHCHCH.sub.3 68-74n-C.sub.12 H.sub.25        (CH.sub.2).sub.7 CHCHCH.sub.2        CHCH(CH.sub.2).sub.4 CH.sub.3n-C.sub.12 H.sub.25        (CH.sub.2).sub.5 CH.sub.3                          N.sub.D.sup.25 1.5141n-C.sub.12 H.sub.25        (CH.sub.2).sub.6 CH.sub.3                          54-57______________________________________ 
    
     The method of preparation of the compounds is not critical to the instant invention. 
     Formulation and Use 
     The compounds of Formula I are useful as miticides and can be used to protect both plants and animals from damage caused by these pests. More specifically, fruits, field crops, vegetables, ornamentals, birds and other warm-blooded animals including mean can also be protected. 
     When mites come into contact with the compounds of Formula I, either in the form of direct sprays or by walking over surfaces which have been treated, they rapidly become irritated and leave the area or are killed if they have been exposed to a sufficiently high dosage. While most plants or animals are able to tolerate the presence of very small numbers of mites without apparent adverse effect, the reproductive capacity of these pests is enormous. Generally, mite populations rapidly build up, easily outstripping parasite and predator capabilities for control. Growers noting rapid mite build-up must take immediate action to prevent damage to economically important crops. Thus, a method is needed for immediately reducing mite build-up and thereby preventing damage to important crops. 
     The compounds of this invention also have a direct lethal contact action against the eggs of mites. Mite eggs exposed to sprays of these compounds are killed and hatching fails to occur. Rates slightly higher than those used to kill the motile mite forms are generally required for good ovicidal effect. 
     The compounds of Formula I are most effective for the control of mites. Very small quantities of compounds of Formula I are required for miticidal activity; additionally, the compounds are not rapidly washed from leaves by rain. They do not have any adverse effect on ladybird beetles, which are important mite predators, and the compounds rapidly degrade in the environment. The compounds are also effective against phosphorous-resistant strains of mites. 
     The quantity of compound needed for miticidal activity will vary depending on the specific situation. Among the variables that must be considered in deciding on the quantity of chemical to be used are the specific compound itself, the specific mite to be controlled, weather conditions, the type of crop, the stage of development of the crop, the volume of spray applied, population pressure, and the interval between applications. For plant protection, solutions or suspensions containing as little as 5 ppm of active ingredient in a spray solution may prove effective under a given set of circumstances. For field usage, however, in high-volume applications, aqueous spray preparations containing 40- 4,000 ppm of active ingredient are generally useful. Preferred are suspensions containing 80-1,000 ppm, and most preferred are those containing 150-500 ppm. On an area basis, in general, 0.03 to 15 kilograms of active ingredient per hectare are acceptable, preferably 0.06 to 8 kilograms, and most preferably 0.1 to 4 kg. When applied in an orchard, spraying is continued until run-off is observed. 
     It may be desirable or useful to mix the compounds of this invention with other agricultural pesticides or adjuvants. Such mixtures often increase the effectiveness of the application on mites and broaden the scope of control to embrace other pests such as insects, fungi, nematodes, or bacteria. A mixture with a refined petroleum spray oil or superior oil has been shown to provide greater than additive results on mites. Other pesticides with which the compounds of this invention may be mixed to achieve broader-spectrum activity include: 
     
         ______________________________________diazinon    0,0-diethyl 0-(2-isopropyl-4-       methyl-6-pyrimidyl)phosphorothioatedisulfoton  0,0-diethyl S-2(ethylthio)ethyl-       phosphorodithioatephorate     0,0-diethyl S-(ethylthio)methylphos-       phorodithioateoxamyl      S-methyl 1-(dimethylcarbamoyl)-N-       [(methylcarbamoyl)oxy]thioformimidatemethomyl    S-methyl N-(methylcarbamoyloxy)thio-       acetimidatebenomyl     1-butylcarbamoyl-2-benzimidazole-       carbamic acid, methyl estercaptan      N-trichloromethylthiophthalimide -maneb ethylenebisdithiocarba       mic acid,       manganese saltcarboxin    5,6-dihydro-2-methyl-1,4-oxathiin-       3-carboxanilidestreptomycin       2,4-diguanidino-3,5,6-trihydroxycyclo-       hexyl-5-deoxy-2-o-(2-deoxy-2-       methylamino-α-glycopyranosyl-3-       formylpentofuranosideazinphosmethyl       0,0-dimethyl-5-[4-oxo-1,2,3-benzo-       trazin-3-(4H)ylmethyl]phosphorodi-       thioate.______________________________________ 
    
     The compounds are especially suited for the protection of living plants such as fruit-bearing trees, nut-bearing trees, ornamental trees, forest trees, vegetable crops, horticultural crops (including ornamentals, small fruit and berries) and grain and seed crops. Apple trees, peach trees, cotton, citrus trees, beans and peanuts are particularly susceptible to mite damage and can be protected by application of the compounds of this invention. To assure control throughout the growing season (e.g., June through August in the Northern Hemisphere) multiple applications at desired intervals can be utilized. 
     Many species of mites are controlled by the compounds of this invention. The following is a list of representative susceptible mites along with the types of damage that they can cause: Panonychus ulmi (European red mite) and Tetranychus urticae (two-spotted mite) which are commonly called &#34;orchard mites&#34;, and which attack a great many deciduous trees, such as apple, pear, cherry, plum and peach trees; Tetranychus atlanticus (Atlantic or strawberry mite), T. cinnabarinus (carmine spider mite) and T. pacificus (Pacific mite); which attack cotton and numerous other crop plants; Paratetranchus citri (citrus red mite) and others which attack citus; Phyllocoptruta oleivora which causes citrus rust; Bryobia praetiosa (clover mite) which attacks clover, alfalfa and other crops; Aceria neocynodomis which attacks grasses and other plants; Tetranychus medanieli which attacks deciduous fruit in northwestern U.S.; and Oligonychus pratensis which attacks sorghum and other grasses. 
     Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few pints to several hundred gallons per acre. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 20% surfactant(s) and b) about 5% to 99% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions: 
     
                       Table 2______________________________________       Active    Dilu-     Surfac-       Ingredient                 ent(s)    tant(s)______________________________________Wettable Powders         20-90        0-74     1-10Oil Suspensions,Emulsions, Solutions(including Emulsifi-able Concentrates)          5-50       40-95     0-15Aqueous Suspensions         10-50       40-84     1&#39;20Dusts          1-25       70-99     0-5Granules &amp; Pellets          1-95        5-99     0-15High-strengthCompositions  90-99        0-10     0-2______________________________________ 
    
     Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing. 
     Typical solid diluents are described in Watkins et al. &#34;Handbook of Insecticide Dust Diluents and Carriers&#34;, 2nd Ed., Doland Books, Caldwell, N.J. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, &#34;Solvents Guide&#34;, 2nd End., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. &#34;McCutcheon&#39;s Detergents and Emulsifiers Annual&#34;, Allured Publ. Corp., Ridgewood, New Jersery, as well as Sisely and Wood, &#34;Encyclopedia of Surface Active Agents&#34;, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. 
     The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine, solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Suspensions are prepared by wet-milling (see, i.e., Littler U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, &#34;Agglomeration&#34;, Chemical Engineering, Dec. 4, 1967, pp. 147 ff. and Perry&#39;s Chemical Engineer&#39;s Handbook, 4th Ed., McGraw-Hill, N.Y., 1963, pp. 8-59 ff. 
     For further information regarding the art of formulation, see, for example: 
     J. b. buchanan, U.S. Pat. No. 3,576,834 Apr. 27, 1971, Col. 5, Line 36 through Col. 7, Line 70 and Exs. 1- 4, 17, 106, 123- 140. 
     R. r. shaffer, U.S. Pat. No. 3,560,616 Feb. 2, 1971, Col. 3, Line 48 through Col. 7, line 26 and Examples 3-9, 11-18. 
     E. somers, &#34;Formulation&#34;, Chapter 6 in Torgeson, &#34;Fungicides&#34;, Vol. I, Academic Press, N.Y. 1967. 
     Still another liquid formulation which is particularly convenient for small-scale use is the &#34;aerosol&#34; formulation which is packaged under pressure in a suitable container. The active ingredient may be present in a suspension, emulsion or solution. For simplicity in preparation and use, solutions are preferred. The pressure may be supplied by low-boiling liquids such as propane or chloro-fluoro carbons or by relatively soluble gases such as carbon dioxide or nitrous oxide. The chloro-fluoro carbons are preferred for a combination of good solvent power and lack of flammability. 
     Miticidal ability of the compounds of Formula I is illustrated in the following examples: 
     EXAMPLE 5 
     Test units consisted of plant pots containing two red kidney bean plants in the two-leaf stage per pot. The plants were infested with two-spotted mites and sprayed to run-off with solutions of the compounds of this invention. Solutions were made by dissolving weighed quantities of the active ingredients in 10 ml of acetone and then diluting to volume with water containing 1:3000 of a surfactant, TREM 014®. (TREM 014 is a trade name of the Nopco Chemical Company for a polyhydric alcohol ester.) Mortality was evaulated 2 days after spraying. 
     
                                           Table 3__________________________________________________________________________Compounds ##STR14##          % Mite Mortality at Indicated % Spray ConcentrationR.sub.1  R.sub.2   .005                  .002                      .001                          .0005                              .00025__________________________________________________________________________n-C.sub.12 H.sub.25    CH.sub.3      100 100 100 60n-C.sub.12 H.sub.25    CH.sub.2 CH.sub.3              100 100  99 90  56n-C.sub.12 H.sub.25     ##STR15##              100 100 100 98  44n-C.sub.12 H.sub.25    C(CH.sub.3).sub.3              100 100 --  65n-C.sub.12 H.sub.25    (CH.sub.2).sub.4 CH.sub.3              100 100  99 93  41n-C.sub.12 H.sub.25    (CH.sub.2).sub.5 CH.sub.3              100 100 --  70__________________________________________________________________________ 
    
     EXAMPLE 6 
     Bean plants were sprayed to run-off with the indicated concentrations of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone in TREM 014:water at 1:3000. Sprayed plants were allowed to stand for 3 days prior to infestation with two-spotted mites. Evaluations were made at one and eleven days after infestation. 
     
         ______________________________________% Spray      % Control    % ControlConcentration        After 1 Day  After 11 Days______________________________________.01          99           100.005         90           100.002         58           mites building up______________________________________ 
    
     EXAMPLE 7 
     Bean plants were sprayed to run-off with the indicated concentrations of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone in TREM 014:water at 1:3000. Sprayed plants were allowed to stand for 3 days and then subjected to 7 mm of rain. After drying, the plants were infested with two-spotted mites. Evaluations were made at one and eleven days after infestation. 
     
         ______________________________________% Spray       % Control     % Controlconcentration After 1 Day   After 11 Days______________________________________.01           97            100.005          94             99.002          42            out of control______________________________________ 
    
     EXAMPLE 8 
     Apple seedlings approximately 13 cm in height were infested with European red mites and then sprayed to run-off with the indicated concentrations of 3-acetoxy-2-n-dodecyl 1,4-naphthoquinone in TREM 0.14:water at 1:3000. Evaluations were made 2 days after spraying. 
     
         ______________________________________% Spray Concentration   % Kill______________________________________.005                    100.002                    100.001                    100 .0005                   95______________________________________ 
    
     EXAMPLE 9 
     Red kidney bean plants infested with two-spotted mites were sprayed with 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone alone and in combination with 1% UNICO® spray oil. (UNICO is a trade name of United Co-operatives, Inc., of Alliance, Ohio. It is a refined petroleum distillate containing about 3% inert ingredients and is classified as a superior oil.) Evaluations are averages of three replicates and were made two days after spraying. These results show that greater than additive effects are obtained by using the compounds of the invention in combination with a spray oil. 
     
         ______________________________________             % Spray    %             Concen-    Mortal-Compound          tration    ity______________________________________2-acetoxy-3-      .002       100dodecyl-1,4-naphthoquinone    .001        99             .0005       86             .00025      23             .0001       22-acetoxy-3-      .002       100dodecyl-1,4-naphthoquinone +  .001       1001% UNICO oil inspray solution    .0005      100             .00025      97             .0001       601% UNICO spray oil            0______________________________________ 
    
     EXAMPLE 10 
     Red kidney bean plants in the two-leaf stage were sprayed to run-off with solutions of 2-dodecyl-3-acetoxy 1,4-naphthoquinone at concentrations of 10, 5 and 2.5 ppm. The plants were allowed to dry. Two sets containing two replicates of each rate were formed. One set was infested with normal two-spotted mites and the other with a methyl parathion-resistant strain. The data are set forth below and indicate that phosphorus-resistant strains of mites are equally susceptible as normal mites to the compounds of this invention. 
     
         ______________________________________       % Kill of Mites in 48 HoursConcentration              Phosphorus-of Active                  ResistantIngredient (%)         Normal Mites Mites______________________________________.001          100          100.0005          80           81______________________________________ 
    
     EXAMPLE 11 
     Test units consisting of plant pots containing two red kidney bean plants in the 2-leaf stage were infested with 2-spotted mites and sprayed to run-off with solutions/suspensions of the compounds of this invention. Solutions/suspensions were made by dissolving weighed quantities of the active ingredients in 10 ml of acetone and then diluting to volume with water containing TREM 014 at 1:3000. Mortality was evaluated two days after spraying. 
     
                       Table 4______________________________________Compounds ##STR16##                    % Mortality at .002% R.sub.1   R.sub.2          Spray Concentrations______________________________________n-C.sub.12 H.sub.25  (CH.sub.2).sub.7 CH.sub.3                    96n-C.sub.12 H.sub.25  (CH.sub.2).sub.12 CH.sub.3                    99n-C.sub.12 H.sub.25  CHCHCH.sub.3      100n-C.sub.12 H.sub.25  CHCHCHCHCH.sub.3  98n-C.sub.12 H.sub.25  OCH.sub.3         100n-C.sub.12 H.sub.25  OC.sub.2 H.sub.5  99n-C.sub.12 H.sub.25  CH.sub.2OCH.sub.3 97n-C.sub.12 H.sub.25  CHCHCOOH          100n-C.sub.13 H.sub.27  CH.sub.3          99n-C.sub.12 H.sub.25   ##STR17##        93n-C.sub.12 H.sub.25   ##STR18##        60______________________________________ 
    
     EXAMPLE 12 
     European red mite infestations were monitored on apple trees in an orchard near Newark, Delaware. When counts indicated that the number of mites per leaf had exceeded the grower-acceptable level of 5/leaf, the trees were sprayed with a compound of the invention. Four replicate sets of trees were each sprayed with 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone at 14, 28 and 112 g/400 l concentration levels following grower practices. Sprays were again applied 6 days later. The number of mites present per leaf was rapidly reduced below the economic mite damage level (5 mites/leaf) by all treatments. All treated trees remained healthy, vigorous, and free of observable mite damage until the mite population in the remainder of the orchard collapsed of natural cuses two weeks later. At that time, leaves of untreated trees were badly russeted by the uncontrolled feeding of the mites while leaves on the treated trees had a healthy, dark green coloration. 
     EXAMPLE 13 
     Two-spotted mite eggs oviposited on the leaves of red kidney bean plants were sprayed with aqueous dispersions of 2-acetoxy-3-dodecyl-1,4-naphthoquinone at concentrations of 100, 50, 25 and 12.5 ppm. TREM° 014 was included at 1:3000 in all sprays as a wetting agent. Plants were held in a constant environment room after spraying. Readings on ovicidal activity, recorded at the end of 5 days, are tabulated below: 
     
         ______________________________________Conc. of I           % Ovicidalin ppm               Activity______________________________________ 100                 10050                   10025                   9912.5                 790 (control)          0______________________________________ 
    
     EXAMPLE 14 
     To illustrate the unexpected improvement which is realized by using compounds in which R 1  is C 12  to C 14  the following experiment was conducted. 
     Red kidney bean plants 7-9 days old were infested with mites by placing on the plants leaf sections cut from infested bean plants in a mite culture. The mites transfer to the new plants as the old leaf sections dry out. About 50-100 adult mites per leaf are desired for test use. 
     The naphthoquinones were prepared for testing by dissolving 20 mg of each compound in 10 ml of acetone, then dispersing the acetone solution in water to the desired concentration. Surfactant F (TREM® 014) was added at a concentration of 1:3000 as a wetting agent to the spray solution. 
     The mite-infested plants were sprayed to run-off with the dispersions of the test compounds, using a rotating turntable in a spray hood. The sprayed plants were held in a controlled-environment room for about 48 hours, at which time mortality counts were made. 
     
         ______________________________________ ##STR19##% Mortality at Concentrations ofR.sub.1  .002     .001      .0005    .00025______________________________________C.sub.8 H.sub.17   6       --        --       --C.sub.11 H.sub.23  95        79       19        0C.sub.12 H.sub.25  100      100       56        9C.sub.13 H.sub.27  --       100       47       28C.sub.14 H.sub.29  --        99       68       19______________________________________