CA1070321A - Miticidal and aphicidal method utilizing 2-higher alkyl-3-hydroxy-1, 4-naphthoquinone carboxylic acid esters - Google Patents

Abstract

ABSTRACT
This invention relates to a novel pesticidal, e.g., miticidal and aphicidal method utilizing an active ingredient which is represented by the following formula:
I
wherein R1 is alkyl of 8-14 carbon atoms either branched, cyclic or straight chain; and R2 is alkyl of 1-6 carbon atoms either branched or straight chain or cycloalkyl of 3-6 carbon atoms.

Description

10703'~1 BACKGROUND OF THE INVENTION
-mi8 inventlon relates to mltlcidal and aphl-cldal methods using 2-hydroxy-3-higher alkyl-1,4-naphtho-quinone carboxylic acld ester~.
U.S. Patents 2,553,647 and 2,553,648 dlsclose broadly 2-alkyl-3-hydroxy-1,4-naphthoquinone carboxylic acids and their corresponding ester derivatives. me~e compounds are de~cribed as having antagonistic action against organisms which cause malarlal in~ections.
Nakanishi et al. JACS 1952, 3910-3915 dlsclose~
th~ n-undecyl analog o~ 2-hydroxy-3-aIk~1-1,4-naphtho-quinone. No use ror the composition i8 disclo~ed.
SUMMARY OF THE INVENTION
Thi~ invention 1~ a method for controlling mites or aphid~ by applying to a locus to be protected, pre~erably a plant, a miticidal or aphicidal amount or a compound or the ror~ula:

~O~-R2 ~herein Rl iB alk~l 0~ 8-14 carbon atoms which are branched, cyclic, or straight chain and R2 i8 alkyl Or 1-6 carbon atoms either branched or straight chain or cycloalkyl of 3-6 carbon atoms.

` ` `~07Q32:~
m e compound~ Or Formula I are mitlcldes and aphicldes. m at is to say, when an ef~ective amount of such compound~ i8 brought into contact with mites or aphids, these pests are ~ ed. me compounds are thus useful for protecting plants and animals from damage ;~
caused by mites or aphids.
The inventi~n include~ miticidal and aphicidal compositions which contain at lea~t one compound o~ ;
Formula I a~ actlve ingredient.
Preferred because oi their ease of synthesis and greater miticldal and aphicidal activity are those compounds of Formula I wherein: ;
Rl 18 alkgl Or 11-14 carbon atoms, either branched or straight chain, most preferably straight chain, and R2 is alkgl of 1-4 carbon atoms.
; Specifically, the following compounds are pre~erred for thelr hlghest miticidal and aphicidal activity: -

2-acetoxy-3-n-tetradecyl-1,4-naphthoquinone;
2-acetoxy-3-n-dodecyl-1,4-naphthoquinone, ~i 20 2-propionyloxy-3-n-tetradecyl-1,4-naphthoquinone, ,~ 2-propionglQxy-3-n-dodecyl-1,4-naphthoquinone;
2-cyclopropylcarbonyloxy-3-n-tetradecyl-1,4-naphthoquinone, 2-butyryloxy-3-n-dodecyl-1,4-naphthoquinone;
2-iso~utyryloxy-3-n-dodecyl-1,4-naphthoquinone;
2 cyclopropylcarbonyloxy-3-n-dodecyl-1,4-naphthoquinone; ;-2-butyryloxy-3-n-tetradecyl-1,4-naphthoquinone.
In a speciflc embodiment of the instant lnvention, ~!~`; the compounds of the instant invention are applted in ~, '.1 .
admlxture with a superior oll, preferablg a mlnor amount of superior oil, e.g., less than 5% by weight. The resulting !
~` miticldal activity is greater than the additive results.
... .
Superior oils are discus~ed in Chapman et al.

- 3 -~t -.

~ .

``` ~ 10703Zl Selection o~ a Plant S~ray Oil Combining Full Pestlcldal Efficiency with Minimum Plant InJu~y Hazards, Jour. Econ.
Ent., 1962, 55:737-43. me re~ulting mixture of the compound and the superior oil is novel.
DESCRIPTION OF THE INVENTION
S~nthesi3 The compound~ of Formula I can be prepared by the procedure~ de~cribed in the previousl~ cited J. A~. Chem.
Soc. article and in U.S. Patent Nos. 2,553,647 and '648. `~
m e final ~tep in the synthesi~ may also be accomplished by treating the corresponding 2-hgdroxy-3-alkyl-1,4-naphtho-quinone with the appropriate acid chloride or anhydrlde in the presence of at lea~t an equivalent of an amine such as pyridine or triethylamine. The following examples are given to lllustrate the above-described proces~

Example 1 ~ ;
Preparation of 2-Aceto~-3-n-dodeeyl-1,4-naphthoquinone O
[~-GI~3 A mixture of 2.0 parts of 2-hydroxy-3-n--dodecyl-1,4-naphthoquinone, 0.81 part~ of triethylamine, 0.63 parts of acetyl chloride and 50 parts of methylene chloride was ~tirred at room temperature for 30 hours. me re~ulting mixture wa~ distributed between methylene chlorlde and .... . . .. . . .

` ` 10703Zl water. The methylene chloride layer was separated, dried over magnesium sulfate, then filtered and evaporated under reduced pressure. me residue was crystallized from petrol-eum ether ~b.p. 30-60) to give 1.2 parts of 2-acetoxy-3-n-dodecyl-1,4-naphthoquinone, m.p. 57-58C.
-Example 2 Preparation_of 2-propionyloxy-3-n-dodecyl-1,4-naphthoquinone O O

nC12H5 ;, O

~ A mixture of 4.0 parts of 2-hydroxy-3-n-dodecyl-6 10 1,4-naphthoqulnone, 4.4 parts of propionic anhydride, and 50 parts of pyridine was stirred at room temperature for 16 hours. me resulting mixture was evaporated under re-duced pressure to remove the pyridine. The residue was crystalllzed ~rom methanol to give 2.9 parts of 2-propionyl-oxy-3-n-dodecyl-1,4~naphthoquinone, m.p. 42-44C.
; By using the approprlate 2-hydroxy-3-alkyl-1,4-naphthoquinone and the appropriate acid chloride or anhydrlde, the following compounds shown in Table I could be similarly prepared by anyone skilled in the art, using the procedure outlined ln 1 and 2.
;
, "~

~'' .. ;.. "j .

.

10703Zl Table 1 ..... . . - Meltin~ ~ ~
- - -- P~rlt . :
Rl, . ., . R2 (~C. ) . ~- :
-n-C8H17 -n-C3H7 ~ .
-n-CgHlg -C2H5 -~-C11~23 -CH3 51-53 - -n-CllH23 -~H2CH3 N25 1.5209 .-n-CllH23 -CH2CH~CH3 ND5 1.513i ~:. *
-n-CllH23 -CH(CH3)2 N25 1.5155 - .
-n-C12H25 -CH3 57-58 -n-C12H25 C~2CH3 . 42-44 -n-C12H25 . .-CH2CH2CH3 N25 1.5120 .
. -n-C13~27 CH3 -cH2-cH-c9Hl9 CH3 ! CN3 C,H3 -(CH2)g-CH~CH3)2 -CH C 3 -(CH2)4 ~ -CH2CH3 . ~

, 3 . :

-n-C14~l29 -CH3 62-63 -n-C12H25 -CH(CH3)2 ND 1.5157 -n-C.10~21 -CH3 ~07Q321 Table 1 (contlnued) O

- ~leltlng Point Rl ~2 _ . _ - -n-~14H2g CH2C}~3 - - 52-5 3 -n-C~H29 CH2CH2CH3 40-41 . .
-n-C14}~2g C~, IH2 6~-670 ~.
~ C~2 ' _n-Cl~N25 -CH ¦ ~ 59-61 ~

-n-C12~25 {~3 50-52 ~;

~ "~
-n-C12N25 ~ . .

-n=C12H25 - -(CH2)4CH3 N25 1. 5133 -n-C12H25 -C (CH3) 3- . ND5 ~ - 5133 - :
~ :.

" ~07~32~

The method of preparation o~ the compounds 18 not critical to the instant invention.
Formulation and Use m e compounds of Formula I are useful as miticides and can be used to protect both plants and animal ~rom damage caused by these pests. More spec~fically, frults, field crops, vegetables, ornamentals, birds and other warm-blooded animals including man can also be protect~d. ~ .*
The mites come into contact wlth the compound~ of Formula I, either in the form o~ direct sprays or by walking over surfaces which have been treated with ang of the compounds of For~ula I, they rapidly become ~rritated and leave the area or are killed if they have been expo~ed to an erfective dosage. While most plants or animals are able to tolerate the presence of very small numbers of mites l without apparent adverse effect, the reproductive capacity of -~ these pe8ts i8 enormous. Generally, mite populations rapidly build up, ea~ily outstripping parasites and predator capabilities for control. Growers noting rapid mlte-build-up must take immediate action to prevent damage to economically important crops. mus, a method i8 needed for immediately reducing mite build-up and therebg preventing damage to important crops or animals.
Similarlg the compounds of Formula I are also useful as aphicides and can be used to protect fruits, ~ield and vegetable crops, ornamentals, and other plants from aphid attack. When applied to aphid~ or to the locus of aphld infe~tation, these pests are killed or driven from the plants~
The method of this lnventlon, namely, contacting mites or aphids with a miticidally or aphicidally effectlve ~0~03Z~

concentration of Formula I, i~ a most desirable method for control of these pests. For in~tance, very small quantities of compound~ of Formula I are required ~or miticidal or aphicidal actlvity; additionally, the compounds are not rapidly wa~hed from leaves by rain.
They do not have ang adverse effect on ladybird beetles, whlch are important mite and aphtd predators, and the compounds rapidlg degrade in the environment. The com-pound~ are also effective against phosphorous-reslstant ~trains of mites.
The quantity of compound needed for miticidal or aphicldal activity will vary depending on the ~pecific ~ituation. Among the variables that must be con~idered in decid~ng on the quantity of chemical to be used are the speclfic compound ltself, the specific mite or aphid to be controlled, w~ather conditions, the ~y.pe of crop, the ;
stage of development of the crop, the volume of spray applied, population pre~sure, and the interval between applications.
For plant protection, solutions or suspensions containing as little as 5 ppm of active in OEedient ln a spray solutiQn may prove effectlve under a given set of circumstance~. For - -field usage, however, ln high-volume applications, aqueous spray preparations containlng 40-4,000 ppm of active ingredient are generally useful. Preferred are suspension~ containing 80-1,000 ppm, and most preferred are tho~e containing 150-500 pp~. On an area basis, in general, .03 to 15 kilograms o~ actlve ingredient per hectare are acceptable, preferably .o6 to 8 kilograms, and most preferably~ .1 to 4 kg. When applied in an orchard, spraying i8 continued untll run-off i9 observed.

_ 9 _ -` 10~032'1 It may be de~irable or useful to mix the compound~
of this invention with other agricultural pe~ticide~ or adJuvants. Such mixtures o~ten increase the effectivene~s of the application on mites and broaden the scope of control to embrace other pests such as insects, ~ungl, nematode~, or bacteria. A mixture with a reiined petroleum spray oil or ~uperior oil has been shown to provide greater than additive result~ on mites. Other pesticides wlth which the compounds of thi~ in~entlon may be mlxed to achieve broader-spectrum activity include:
diazinon - O,O-diethyl-0-(2-i~opropyl-4-meth~1-6-pyrimidyl)phosphorothioate disul~oton - O,O-diethyl S-2-(ethylthio)ethylphosphoro-dithioate phorate - O,O-diethyl S-(ethylthio)methylphosphoro-dithioate oxamyl - S-methyl l-(dimethylcarbamoyl)-~- ~methyl-carbamoyl)o ~ thio~ormimidate methomyl - S-methyl N-(methylcarbamoyloxy)thioacet-imidate benomyl - l-butylcarbamoyl-2-benzimidazolecarbamlc acid, methyl e~ter captan - N-trichloromethylthiophthallmide ~1 maneb - ethylenebisdithiocarbamic w ld, mangane~e ~alt .

~0703Zl :
,~
carboxin - 5,6-dihydro-2-methyl-1,4-oxathiln-3-carboxanilide streptomycin - 2,4-diguanidino-3,5, 6-trihgdroxycyclo-hexyl-5-~eoxy-1-o- (2-deoxy-2-methyla~ino--glycopyranosyl)-3-formglpentofuranoside e compounds are especiallg sulted for the ;
protection of living plants ~uch a~ ~ruit-bearing tree~
nut-bearing tree~, ornamental trees, forest tree~, vegetable crop~, horticultural crop8 (including ornamentals, small fruit and berries) and graln and ~eed crop~. Apple trees, peach tree~, cotton, citru~ tree~, beans and peanuts are partl-cularly susceptible to mite or aphid damage and can b~ protected by appllcation of the compounds Or this inventlon. To assure control throughout the growing ~eason (e.gO, June throu~h Au~ust in the Northern Hemisphere) multiple applications at ~ -desired interval~ can be utilized.
Mang species of mltes are controlled by the com-pounds of this invention. ffl e following i~ a li~t of representative su~ceptible mites along with the type~ of damage that they can cause: Panonychus ulmi (European red mite) and tranrchus urticae (two-spotted mite) whlch are commonly called "orchard mites", and which attack a great m~ny decidu~us treesJ suGh as apple, pear, cherry, plum and peach trees; Tetrangchus atlanticus (Atlantlc or strawberry mite), T. cinnabarinus (carmine spiaer mite~ and T. pacificus ~ 7~321 (Pacific mite); whlch attack cotton and numerou~ other crop plants; Paratetranychu~ citri (citrus red mite) and other~ -;
whlch attach citru~; Phylloco~truta oleivora whlch cause~
citru~ ru~t; Bryobia ~ (clover mite) ~hich attack~
cloVer, al~al~a and other crops; and Aceria ~ which attac~s gra~ses and other plants.
Aphids controlled b~ the compounds of thi~ ln-vention lnclude but are not limited to the bl~ck bean aphid, Aphis fabae; the green peach aphid, ~ ~_slcae3 the apple aphid, A~his pomi; the rosy apply aphid, Annezphis roseue; the pstato aphid, Macrosi~hum eu~horbiae; the green bug, Toxo~tera grAminum; cabbage aphid, Byevicor,yne byassiere and green citrus aphid, Aphis splraecola.
Useful formu~tions of the compounds o~ Formula I
can be prepared in conventional ways. mey include dusts, granules, pellets, ~olutions, suspensions, emulsion~, wettable pcwders, emul~lflable concentrates and the llke. Many of these may be applied directly. Sprayable ~ormulation~ can be extended ln 3uitable medla and used at spray volumes o~
~rom a ~ew pints to several hundred gallons per acre. High strength compo~ition~ are primarlly used as intermediates ~or ~urther formulation. The formulatlons, broadly, contain about 1~ to 99~ by weight of actlve ln OE edlent(s) and at least one o~ a) about 0.1% to 20% surfactant~s) and - : ... , ., ....... i .. .

` iO7~3Zl b) about 5~ to 99~ solid or ~quid dilient(s). More ~pecl-~ically, they will contain these ingredients in the followinæ
approxlmate proportions:
Table 2 Active Dilu- Sur~ac-Ingredient ent(s) tant(s) ~ettable Powders 20-90 0-74 1-10 Oil Suspensions -~
Emulsion~, ~olution~
(including Emulsifi-able Concentrates) 5-50 40-95 0-15 ~ -;
Aqueou~ Suspen~ions10-50 40-84 1-20 Dusts 1-25 70-99 O- 5 Granules & Pellet~1-95 5-99 0-15 High-strength ~ ~-Compo8ition~3 90-99 0-10 0- 2 Lower or hi~her levels o~ actlve ingredient can, of cour~e, be present depending on the intended u3e and the phgsi~
cal properties of the co~pound. Higher ratlos of surfactant to active lngredi~nt are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
Typical solid diluents are described in Watkins et aL , ~ -1'Handbook o~ Insecticlde Du~t Dlluents and Carriers"J 2nd Ed., Dorland ~ooks, Caldwell, N.J. The more absorptlve diluents are pre~erred for wettable powders and the den~er ones ~or du~s.
TM ic~l liquid diluents and solvents are descrlbed in Marsden, "Solvents Guide'', 2nd Edn., Interscience, New York, ~950~
Solubility under 0.1% iB preferred for ~uspen~ion concentrates;
solution concentrate~ are preferably stable against phase 1070~Z~

separation at 0C. "McCutcheon's Detergents and Emulslfier~
Annual", Allured Publ. Corp., Rideewood, New Jer~ey, as well as Si~ely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ. Co., Inc~, New York7 1964, li~t ~ur~actant~ and recommended uses. All formulations can contaln minor amounts of add~tlves to reduce foam, c~k~ng, corrosion, microbiologicai growth, etc. Preferably, ingredients ~hould be approved by the U.S. Environmental Protection Agency ~or the u~e intended.
The methods of maklng ~uch compositions are uell known. Solutions are pre~errea by 8imply mixing the lngredlents.
Fine, solid co~positions are made by blend~ng and, usually, grind-lng as in a hammer mill or fluid energy mill. Suspensions are prepared by wet-~illing ~see, i.e., Littler U.S. Patent 3,o60,084).
aranules and pellets may be made by ~praying the active material upon pre~ormed granular carrier~ or by agglomeration techniques.
~ee J. E. Browning, "Agglomeration", Chemical Engineerlng, December 4, 1967, pp. 747 ~. and Perry'~ Chemical Eneineer'3 en k, 4th Ed., McGraw-Hlll, N.Y., 1963, pp. 8-59 ~f.
For further in~ormation regarding the art oP ~ormu-lation, ~ee ror example:
! J. B. Buchanan, U.8. Patent 3 576,834, April 27, 1971, Col. 5 Ilne 36 through Col. 7 Iine 70 and Ex. 1-4, 17, 106, 123-140.
R. R. Sha~er, U.S. Patent 3,560,616, Feb. 2, 1971, Col. 3 Line 48 through Col. 7 Line 26 and Example~ 3-9, 11~18.

- 14 _ 10703Zl E. Somers, ~Formulation", Chapter 6 in Torgeson, "Fungicides", Vol. IJ
Academlc Pre~s, New Yor~, 1967.
Still another li~uid formulatlon which 18 particularly -convenient for small-scale use i~ the "aerosol" formulation which 1~ packaged under pressur~ in a suitable container. m e active ingredient may be present in ~ suspension, emulsion or -~
301ution. For simpllcity in preparat~on ana use, solution~ are prererred. The pra~sure may be ~upplied by low-bolling liqulds such as propane or chlor~-rluoro carbons or by relati~ely ~luble ga~e~ ~uch as carbon dioxide or nitrou~ oxide. me chloro-fluoro carbon~ are preferred for a combination of good solvent p~wer ~nd lack of flammabilit~.
Miticidal ability of the compound3 of Formula I is illu~trated in the following example~. '! ' E~ample 3 Te~t units consi3ted of plant pots contalning two red kidney bean plant~ in the two-leaf stage per pot. The plant~
were infest~d with two-~potted mites and eprayed to run-off with ~olution~ of the compound~ of thi~ invention. Solutions were made by dis~olving weiehed quantities of the active ingredient~ ln 10 ml o~ acetone and then diluting to volume with water col~aining 1:3000 o~ a surfactant, TRE~ 014*.
Mortality wa~ evaluated two day~ after ~praylng.
.

*TREM 014 is a trade mark of the Hopco Chemical Company for a polyhydric alcohol ester.

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... ... . ` ' 1~)7(~321 Example 4 Bean plant~ were sprayed to run-off with the indicated concentrations of 2-acetoxy-3-n-dodecyl-1,4-naphthoquinone in TREM 014:water at 1:3000. Sprayed plants were allowed to stand for 3 day~ prior to infestation with two-spotted mite~.
Evaluations were made at one and eleven day3 after infestation.
% Spray % Control % Control Concentration After 1 ~ayAfter 11 Da,v9 . 01 99 100 .005 90 1~0 .002 58 mites building up Example 5 Bean plants were ~prayed to run-of~ with the indicated concentrations of 2-acetoxy-3-n-dodecyl-1,4-naphthoquinone in TREM 014:~ater at 1:3000. Sprayed plants were allowed to stand for 3 day~ and then subJected to 7 mm of rain. After drying, the plant~ were infested with two-spotted mites. Evaluatlons were made at 1 and 11 days after infe~tation. -~
% Spr~y ~ Control % Control ConcentrationArter 1 DayAfter 11 Days _ .01 97 100 .005 94 99 .002 42 out of control `~

Example 6 Apple 3eedlings approximatelg 13 cm in helght were lnfe~ted wlth European red mite~ and then sprayed to run-off with the indicated concentrations of 2-acetoxy-3-~-dodecyl-1,4-naphthoquinone in TREM 014:water at 1:3000. Evaluations were made two dag~ after sprayi~g.

~,~
~1 .
......... , Spray Concentration %_Kill .0~5 100 .00~ 100 ''"
. 001 100 .0005 95 '' "', '' Example 7 Red kidney bean plants infested with two-spotted mltes ~`
were spraged wlth 2-acetoxy-3-n-docecyl-1,4-naphthoquinone alone -~
and in combination with 1% UNICO* spray oil. Evaluation~ are averages of three replicate~ and were made two days after spraying. mese result~ ~how that greater than additive effects are obtained bg using the compounds of the invention in com~ina-tion with a spray oil.
: ~"
Compound Concentration % Mortality 2-acetoxy-3-dodecyl-1,4-naphthoquinone .002 100 . 001 99 ",~
.0005 86 ~ -.00025 23 ;
.0001 2 2-acetoxy-3-dodecyl-1,4-naphthoquinone 1% UNICO* oil ~n ~pary solution .002 100 .001 100 ,~
.0005 100 ~-.00025 97 .0001 60 1% UNICO* spray oil O
*U~ICO is a trade mark of United Co-operatives, Inc., of Alllance, Ohlo. It is a refined petroleum distillate containing about 3~ inert ingredients and is clas~ifled as a ~uperior oil.

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Example 8 Red kidney bean plants ln the two-leaf stage were sprayed to run-off with ~olutions o~ 2-acetoxy-3-dodecyl-1~4-naphthoquinone at concentrations o~ 10, 5 and 2.5 ppm.
The plants were allcwed to dry. Iwo sets containing two replicates of each rate were formed. One set was infested with normal 2-spotted mltes and the other with a methyl parathion-resistant ~train. me date are ~et forth below and indicate that phosphorus-resistant ~tralns of mites are equally susceptible as normal mites to the compound3 o~ this invention.
~ Klll of Mites in 48 Hour~
Concentration Phos~orus-of Active Re~istant Ingredient (~) Normal Mites Mites . 001 100 100 .000~ 80 81 Aphicidal propertie~ o~ the compound~ o~ Formula I
are illu~trated in the following examples.

'~t : ~

` ' ' ' ~~ 10703Z~
Exs~ple 9 Potted nasturtium plants ~nfested with the black bean aphld were sprayed on a rotating turntable ~lth 2-acetoxg-3-dodecyl-1,4-naphthoquinone at concentration~ of 100, 50, and 25 rpm. Mortalit~ counts were made 72 hours a~ter spraying, with the re~ult~ indicated below.
Sprag Concentration ~ Xill . 01 10~ ' .0025 89 ExamDle 10 801utlons of the compounds of this in~ention were ~prayed at a concentratlon o~ 150 ppm on potted na~turtium plant~ infested with the black bean aphid. Spray~ were applied to run-o~f with a hand-held "Son-of-a-Gun"~ sprayer.
DU Pont l-144-WDG wa~ included at 1:2000 in the ~pray~ a~ a wetting agent. Mortal~tY counts were made at the end of 24 hours.
OR

o R
R R % Aphid 1 2 Mortality "

O

C12X25 -C-CH2C~I3 98 ~.
O

`` 107~3Zl % Aphid Rl R2 ~:

C12H25 -C-CH l 97 O ~ CH2 Cl~ 29 -C-CH ¦ 93 ~-~l2H25 C-CH2C~2SH3 98 o C14H29 C-CH2CH2CH3 87 : ~

Example 11 :~ ;
Green peach aphid~ on dl~c~ cut from Chinese cabbage leaves were sprayed on a turn-table ~pray rig with acetone ~olution~ of the co~pounds of thi3 invention.
The leaf discs were held under con~t~nt environmental conditions ~or 24 hour~ at which time mortallty counts were made. me concentratlons used and percent aphid klll are tabulated below.

iQ703Z~ ~ ~

: .
Compounds - O ., ~Rz 0 1 S Aphld Mortality at % Spra~ Concentratlon Or Rl R2 .1 _. 05. 01 005 .~
C H 0 .
12 25 --C--CH3 100 100. 90 86 O . ..
C14H29 -C-CH3 100 89 85 69: : .
, O
.. .
C12 25 --C--CH2CH3 100 100 g4 84 O . ..
C14H29 -C-CH2CH3 100 100 . 98 83 C12H25 -C-CH ¦ - 100 100 88 71 :, . ~CH2 ` '.

~:H2 66 80 25 O : :
"
C12H25 C-C~[2C~I2 3 100 100 83 75 :~ ~
: O
.. ..
C14H29 C-CH2CH2C 3 100 100 93 79 ~ ~

' :

, . ~.

: . , ;.. , .. ,, . . . ,... .. .. , - ,.

~0703Z~
Example 12 A 25% emul~ifiable composition of 2-acetoxy-3-dodecyl-1,4-naphthoquinone was applied with commerclal equ~pment to dwar~ Golden Deliclous apple trees ln a Del~ware orchard. Application was made four t~me~ at .
weekly interval8, starting May 8, at rateæ o~ 0.5, 1, and 4 o~/100 eallons. Counts made 3 days after the last ~pray showed excellent control o~ the apple aphid as indicated below. There wa~ an average o~ 573 aphid~ per terminal in unsprayed control trees.

Spray Concentration ~ Control o~
92/100 gal~. A~ple Aphid 0.5 93.7 1 97.6

4 99.8 - .. -. ., .. . : .

10703Z~

SUPPLEMENTARY DISCLOSURE

It has now been found that preferred embodiments of the present invention are particularly efflcaciou~ for the control of mites and aphids. Thus in a preferred embodiment of thls invention there is provided novel mlticidal and aphicidal compounds o~ the following formula and proce~ses ~or preparing them: O
O
~ OC-R2 ' ~ ~ ' O ' "' where Rl = stralght chaln alkyl of 12-14 carbon atoms; ~;
R2 = alkyl of 1-6 carbon atoms either branched or or ~traight chained, or cycloalkyl of 3-6 -~
carbon atoms.
Combinations o~ the compounds of this invention with othar miticides o~ten provlde~ better total mite control than either material alone. Among such products which may be u~ed advantageously with them are chlordimeform ("Galecron"*), formetanate ("Carzol"*), propargite ("Omite"*), tetradifon ("Tedion"*), and benomyl. Such mixtures are novel.
Example 13 To illustrate the une~pected lmprovement which 18 realized by using compounds in which Rl is C12 to C14 the followlng experiment was conducted.
Red Kidney bean plant3 7-9 days old were lnfested wlth mites by placing on the plants leaf sectlons cut from * denote~ trade mark A~ ~
. , .

` ` 1070321 lnfested bean plants in a mite culture. The mlte~ transfer to the new plants as the old lea~ section~ dry out. About -~
50-100 adult mites per leaf are desired for test u~e.
The naphthoquinones were prepared for testlng by dissolving 10 m~ of each compound ln 10 ml oi acetone, then disperslng the acetone solution in water to the desired con-centration. Surfactant F ( ~ 014~ was added at a concen-tration of 1:3000 a~ a wetting agent to the spray Rolution.
The mite-infested plants were sprayed to run-off with the disperæions of the test compounds, using a rotating turntable in a ~pray hood. The sprayed plants were held in a controlled-environment room for about 48 hours, at which time mortality counts were made.

O "
RI

Mortality at Concentrations of t, .
~1.002 .001 .0005 0002~ ~
, C8H17 6 - ~ ~
CllH23 95 79 19 C14H29 ~ 99 68 19 Example 14 Mite-infe~ted bean plant3 were ~prayed to run-off with a 25~ emulsifiable composition of 2-acetoxy-3-dodecyl-1,4-naphthoqulnone (I), with a 50% emul~ifiable compo~ition of . - ., - . . . ' `` 1~D7V3Zl chlordimeform (II), or with a combination of the two materlal~
Mite control readings were taken at 48 hours and at 8 and 14 days after spraying. The data tabulated below ~how a surprtsing ~ynergi3tic action between I and II. I at 0.0005~ alone and chlordimeform at .01% alone gave no practical control at the ~nd of 1 or 2 weeks, while nearly complete eradlcation of the mite population resulted from the c~mbined sprays. Severe mlte feeding in~ury was evident on theplants receiving sprays of I
or II alone; there wa~ no or trace feedlng inJury on plants receiving comblned ~prays of I and II.

~ Conc.% E111 Live Mites/Lea~
_reatment Actlve(48 hr~.)8 days 14 days 2-acetoxy-3- 5 85 210 >500 dodecyl-1,4-naphthoguinone chlordlmeform .01 1 >500 ~500 I and .005)99 7 20 II .01 ) Example 15 Mite-lnfested red kidney bean plant~ in the primary leaf stage were ~prayed to run-off with a 25~ emulslfiable compo-sition of 2-acetoxy-3-dodecyl-1,4-naphthoquinone (I), with a commercial 50~ wettable powder of benomyl (II), and with a com-blnation of I and II. Rate~ of application were as shcwn in the table bel~w.
Mite populatlon counts were made 1-2 weeks after ~praylng showed a synergi~tic reduction in mite numbers where a combined appl~cation of I and II were made. Heavy mite feeding inJury occurred in the individual treatments of I and II, but very little ~uch was noted on the plants receivlng the combinatlon 3pray.

: A~`

'' ~L07032~

% Conc. $ Kill T~ve Mite~/Leaf Treatment Active (48 hrs ) 8 days 14 days 2-acetox~-3-dodecyl- .0005 94 272 135 1,4-naphthoq~inone (I) benomyl (II) .03 2 324 ~500 I and .005) 93 3 3 II 3 ) Example 16 .- ~
Mite-infested red kidney bean plant~ were sprayed to run-off wlth 2-acetoxy-3-dodecyl-1,4-naphthoquinone (I), wlth ~-tetradlfon (II), or with a combinatlon of I and II. A 25 emulsifiable composltion of I and a 12.2% commercial formula-tion of II were u~ed.
Counts made 8 day3 a~ter spraying revealed greatly superior mite control and reduced feedin~ inJury when a combined spray was applied.
8-Day Readings % Conc. ~ Klll T~ve Mites/ Feeding 20 Treatment Active (48 hr~.)Leaf In~ury*
2-acetoxy-~- .000580 261 3 dodecyl-l,~-naph-thoquinone (I) tetradifon (II) .002 4 99 9.8 .001 0 117 9.7 I and ~5) 85 6 3 IIi .002 ) I and .0005~85 4 1.5 II .001 ) *Ba~ed on a scale of 0-10, where O = no lnJury and 10 = plant died.

. ~. .

Claims (19)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A method for protecting plants from mites or aphids comprising applying to the plant locus to be protected a miticidally or aphicidally effective amount of a compound selected from compounds of the formula:

wherein R1 is alkyl of 8-14 carbon atoms which are branched, cyclic, or straight chain and R2 is alkyl of 1-6 carbon atoms either branched or straight chain or cycloalkyl of 3-6 carbon atoms.

2. The method of Claim 1 wherein R1 is an alkyl of 11-14 carbon atoms either branched or straight chain and R2 is methyl or ethyl.

3. The method of Claim 1 wherein said compound is 2-acetoxy-3-n-dodecyl-1,4-naphthoquinone.

4. The method of Claim 1 wherein the compound is 2-propionyloxy-3-n-dodecyl-1,4-naphthoquinone.

5. The method of Claim 1 wherein the compound is 2-butyrloxy-3-n-dodecyl-1,4-naphthoquinone.

6. The method of Claim 1 wherein the locus is selected from the group consisting of apple, citrus, and peach trees and cotton, peanuts, and beans.

7. The method of Claim 1 wherein said compound is applied in admixture with a superior oil.

8. A method of any one of Claim 1, Claim 2 and Claim 7 in which said compound is mixed with a compound selected from the group consisting of diazinon, disulfoton, phorate, oxamyl, methomyl, benomyl, captan, maneb, carboxin and streptomycin.

9. 2-Acetoxy-3-n-dodecyl-1,4-naphthoquinone, the compound of the formula where R1 is a straight chain alkyl group of 12 carbon atoms and R2 is methyl.

10. 2-Acetoxy-3-n-tetradecyl-1,4-naphthoquinon, the compound of the formula of Claim 9 wherein R1 is a straight chain alkyl group of 14 carbon atoms and R2 is methyl.

CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE

11. A compound of the formula:

where R1 = straight chain alkyl of 12-14 carbon atoms;
R2 = alkyl of 1-6 carbon atoms either branched or straight chain; or cycloalkyl of 3-6 carbon atoms.

12. The compound of Claim 11 where R2 is alkyl of 1-6 carbon atoms.

13. The compound of Claim 11 where R2 is methyl or ethyl.

14. The compound of Claim 11: 2-acetoxy-3-n-tridecyl-1,4-naphthoquinone.

15. A method for protecting plants from mites or aphids comprising applying to the plant locus to be protected a miticidally or aphicidally effective amount of a compound selected from compounds of the formula where R1 = straight chain alkyl of 12-14 carbon atoms;
R2 = alkyl of 1-6 carbon atoms either branched or straight chain; or cycloalkyl of 3-6 carbon atoms.

16. The method of Claim 15 wherein said compound is 2-acetoxy-3-n-tridecyl-1,4-naphthoquinone.

17. The method of Claim 15 wherein said compound is 2-acetoxy-3-n-tetradecyl-1,4-naphthoquinone.

18. The method of Claim 15 wherein said compound is applied in admixture with a superior oil.

19. The method of Claim 15 or Claim 18 in which said compound is in admixture with a compound selected from the group consisting of chlorodimeform, formetanate, propargite, tetra-difon, and benomyl.