DE2641343A1 - ACARICIDE AND APHICIDE EFFECTIVE 2-HIGH ALKYL-3-HYDROXY-1,4-NAPHTHOQUINONE CARBONIC ACID ESTER - Google Patents

Description

Priorities: September 15, 1975, USA, 613 553 March 29, 1976, USA, 671 044 April 29, 1976 U.S. 681 594

Acaricide and aphicide v / irksame 2-higher alkyl-5-hydroxy-1,4-naphthoquinone carboxylic acid ester

The invention relates to acaricidally and aphicidally active 2-higher alkyl-3-hydroxy-1,4-naphthoquinone-carboxylic acid esters.

U.S. Patents 2,553,647 and 2,553,648 disclose the 2-alkyl-3-hydroxy-1,4-naphthoquinonecarboxylic acid and their corresponding ester derivatives. These connections are said to have an antagonistic effect against organisms that cause malaria infections.

U.S. Patent 2,572,946 deals with the use of non-acylated compounds as acaricides.

Nakanishi et al. JACS 1952, 3910-3915 describes the n-undecyl analog of 2-alkyl-3-hydroxy-1,4-naphthoquinone,

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Nothing is said in this publication about the use of this compound.

The present invention relates to acaricidally and aphicidally active compounds, processes for their preparation, compositions, containing these compounds and methods of using the same for the protection of plants and animals against mites and aphids, the formula X

R ₁ = straight, branched or eyclic

C _8-14 alkyl;
Rp ⁼ straight or branched C 1 -C 7 -alkyl, C

Alkenyl, C ₃ Cg-Cycloalkyl, C ₁ -Qf-Alkoxy,

-CH ₂ OCH ₃ , -CH ₂ OCH ₂ CH ₃ or -CH = CH-COOH;

and
X and Y = H, F, Cl, Br, methyl or methoxy.

The compounds in which at least one of the symbols X and Y have a meaning other than hydrogen are new.

Connections with
also new.

= Are alkyl of 12-14 carbon atoms

Combinations of the compounds according to the invention with other acaricides, in particular with Chlordimeform ("Galecron"), Formetanate ("Carzol"), Propargit ("Omite"), Tetradifon ("Tedion") and benomyl show a better overall effect than the compounds taken alone. Such mixtures are also new.

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⁵ "2S41343

The compounds of the formula I are acaricides and aphicides. An effective amount of these compounds is brought into contact with mites or aphids, these pests are killed. The connection proposed according to the invention. fertilizers can therefore be used to protect plants and animals against the action of mites or aphids.

Because of their ease of preparation, compounds with R ₁ meaning straight C ₃ -C ₁ ^ -alkyl are preferred.

Because of their biocidal effect, compounds with R ₁ meaning straight C ^ -C ^ -alkyl are particularly preferred. Mite eggs sprayed with these compounds die off. Somewhat higher effective doses than those used to combat the mobile forms show a good ovicidal effect.

Preference is given to R _{2 in the meaning of C 1} -C 6 -alkyl, particularly preferably straight-chain C 1 -C 6 -alkyl, C 2 -C 4 -alkenyl, methoxy or ethoxy, in particular ethyl or methyl. Due to their extremely high acaricidal and aphicidal effectiveness, the following compounds are preferred:

3-acetoxy-2-n-tetradecyl-1,4-naphthoquinone; 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone; S-propionyloxy-Z-n-tetradecyl-1,4-naphthoquinone; 2-n-dodecyl-3-propionyloxy-1,4-naphthoquinone; 3 * -butyryloxy-2-n-tetradecyl-1,4-naphthoquinone; 2-n-Ibdecyl-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; 3-acetoxy-5-chloro-2-dodecyl-1,4-naphthoquinone.

According to a preferred embodiment of the present invention, the compounds according to the invention are mixed with a superior oil, preferably with a lower one

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Amount of superior oil, e.g. less than 5% by weight, applied. The acaricidal effect obtained is greater than the total effect. Superior oils are 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 obtained mixture of the compound with the superior oil is new.

The compounds of the formula I can be prepared by the procedures as cited in the introduction Article from J.Am.Chem.Soc. and U.S. Patents 2,553,647 and 2,553,648. The last stage of the_ synthesis can also be carried out by mixing the corresponding 2-alkyl-3-hydroxy-1,4-naphthoquinone (III) with a suitable Acid chloride or anhydride in the presence of at least one equivalent of amine, such as pyridine or triethylamine or the salt of 2-alkyl-3-hydroxy-1,4-naphthoquinone treated with a suitable acid chloride or anhydride in an inert solvent.

The compounds can either (a) from appropriately substituted Naphthol according to DT-OS 2 520 739, (11/9/75), or (b) from 4-phenyl-3-oxobutyric acid ester according to Fieser, et al., US-PS 2,553,647 produced:

, χ Y OH Y OH

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- «ίΓ-

CH ₂ CCH ₂ CO ₂ CH ₂ CH, ->

CH ₀ CCHCO ₀ CH ₀ Ch, 2, ι 2 2 3

^R 1

The following examples illustrate the manufacturing process.

example 1

Preparation of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone

A mixture of 2 parts of 2-n-dodecyl-3-hydroxy-1,4-naphthoquinone, 0.81 parts and 0.63 parts Triäthylarain Acetylchlo- chloride and 50 parts of methylene chloride are stirred for 30 hours hei room temperature. The mixture obtained is distributed between methylene chloride and water. The methylene chloride layer is separated, dried over magnesium sulfate, then filtered and evaporated under reduced pressure. The residue is crystallized ais petroleum ether (b.p. 30 to 60 ° C) to yield 1.2 parts of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone having a melting point of 57-58 ⁰ C.

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Example 2

Preparation of 2-n-dodecyl-3-propionyloxy-1,4-naphthoquinone

OCCH ₂ CH

A mixture of 4 parts of 2-n-dodecyl-3-hydroxy-1,4-naphthoquinone, 4.4 parts of propionic anhydride and 50 parts of pyridine is stirred at room temperature for 16 hours. The resulting mixture is then evaporated under reduced pressure to remove the pyridine. The residue is recrystallized from methanol, so that 2.9 parts of 2-n-dodecyl-3-propionyloxy-1,4-naphthoquinone with a melting point of 42 to 44 ^° C. are obtained.

Example 3

Production of 2-n-dodecyl-3-hydroxy-1,4-naphthoquinone-Na

A dispersion of 1.9 parts of NaOH in 250 parts of tetrahydrofuran becomes a solution of 26 parts of 2-n-dodecyl-3-hydroxy-1,4-naphthoquinone added in 450 parts of tetrahydrofuran at room temperature, then stirred for 1 hour and finally filtered, whereby the wine-red solution of the sodium salt is obtained.

Example 4

Preparation of 2-n-dodecyl-3-methoxycarbonyloxy-1,4-naphthoquinone

T = parts.

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Λ '

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T. 60 of the salt solution obtained according to Ex. 3 are stirred with 0.59 T. methyl chloroformate in tetrahydrofuran T. 10 1 St. at room temperature. After standing overnight , the suspension is filtered and the filtrate is evaporated to dryness. After recrystallization of the residue from acetonitrile, 2.0 T. 2-n-dodecyl-3-methoxycarbonyloxy-1-4-naphthoquinone, bp. 70-72 ° C., is obtained.

With a suitable 2-alkyl-3-hydroxy-1,4-naphthoquinone and acid chloride or anhydride, the compounds listed below can be prepared in accordance with Examples 1-4.

Table 1

OCR,

Sp. ( ⁰ C)

-SC ₃ H ₇

C ₂ H ₅ 51-53 5209 CH ₃ Njp 1. 5131 CH ₀ CH, N ²⁵ 1 CHpCHpCH,

-CH (CH ₃ ) ₂

1.5155

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Table 1 (continued)

R ₁ R ₂ Sp. ( ⁰ C)

-SC ₁₃ H ₂₇

CH ₃

- (CH ₂ ) _g -CH (CH ₃ ) ₂

-CH ₃ 57-58 -CH ₂ CH ₃ 42-44 -CH ₂ CH ₂ CH ₃ N ^ ⁵ 1.5120 -CH ₃ 58-60 -CH ₃ NJp 1.5332 CH ₃
ι
-CH-CH ₃ -CH ₃ 72-74

-CH ₃ CH ₃

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-CH (CH ₃ ) ₂ Nq ⁵ 1.5157

/ Γ

Table 1 (continued)

264-343

.Sp, - ( ⁰ C)

CH ₂ CH ₃

-CH

-CH

CH, CH ₂

CH. 52-53 °

65-67 °

59-61

50-52

1.5133

C (CH ₃ ) 3

OCH ₃

OCH ₂ CH ₃ | 1.5133 70-72 1I2-1J7

CH ₃ -0-CHCH ₂ CH ₃ *

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[IR> o 1753 cm " ¹ ]

OBiQlNAL IHSPEGTED

Table 1 (continued) 'Sv "

nC ₁₂ H ₂₅ -CH ₂ OCH ₃ 69-71

<< D

-CH ₂ OCH ₂ CH ₃

1791cm " ¹ ]

5I.53

- & - ° 12 ^H 25 -CH = CH ₂ -UC ₁₂ H ₂₅ -CH = CHCH ₃ CH ₀
tj -nC _az H ₂₅ -C = CH ₂ 'Λ DD -CH = CH-COgH -HC ₁₂ H ₂₅ -CH = CH-CH = CH-CH ₃

Nj ^ 1.5202

25th
N _D 1.5162

68-74

- (ch ₂ ) ₇ ch = chch ₂ ch = ch (ch ₂ j

-CH ₃ 68-69

nC ₁₂ H ₂₅ - (CH ₂ J ₅ CH ₃ N ^ ⁵ 1.51m

HC ₁₂ H ₂₅ - (CH ₂ J ₆ CH ₃ 511-57

-CH ₃ 91-93

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- (CH ₂ J ₇ -CH = CH- (CH ₂ J ₇ CH ₃

OBlGSNAL INSPECTED

Example 5

Production of 2-acetyl-4- (2-mathylphenyl) -3-oxobutter-

acid ethyl ester

ο O ti η

, -Ch ₂ CCHCOCH ₂ CH ₃ CCH,

Il ->

According to M. Viscontini and N. Merckling, Helvetica Chimica Acta , 35 t 2280 (1952), 2.65 T. magnesium shavings with 15 T. abs. Ethanol at room temperature and 0.5 T. carbon tetrachloride added. After the reaction has subsided, 100 T. dry ether are added. The mixture is then stirred without cooling until the reaction has ceased and then mixed with 19.6 parts of ethyl 3-oxobutyric acid ester in 20 parts of dry ether while cooling with ice and stirred well. The resulting precipitate is dissolved, the solution is then cooled in an ice-salt bath and 16 parts of 2-methylphenylacetyl chloride are slowly added, after which it is left to stand overnight at room temperature and finally combined with ice and H ₂ SO. The ether layer is separated off, _{washed with H 2} O, with Na ₂ SO. dried and finally distilled to give the title compound as a crude oil.

Example 6

Production of ethyl 4- (2-methylphenyl) -3-oxobutyrate.

CH,

0 0

CH ₂ CCH ₂ COCH ₂ CH ₃

According to Hunsdiecher reports. 75, 454 (1942), 26 parts of ethyl 2-acetyl-4- (2-methy! Phenyl) -3-oxobutyric acid were stirred for 10 hours at room temperature with 100 parts of ethanol and 6.8 parts of sodium ethoxide. The mixture is _{diluted with H 2} O and extracted with ether. The solvent is finally evaporated to give the title compound.

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Example 7

Production of 2-A2-methylphenyl) acetyl / tetradecanoic acid

ethyl ester.

CH,

⁵ O 0

π η

-CH ₂ CCHCOCH ₂ Ch ₃

3 parts of ethyl 4- (2-methylphenyl) -3-oxobutyrate, 1 T. Na methoxide, 4.6 parts 1-bromododecane, 0.5 parts NaI and 50 parts abs. Ethanol is refluxed for 4 hours and then stirred for 18 hours at room temperature. After that, that will Mixture strongly concentrated, diluted with 100 parts of water and extracted with ether. The ether extract is saturated with NaHCO, - and saturated NaCl solution and washed with MgSO / dried. Evaporation of the ether gives 6 T. crude ethyl-2 / "(2-methylphenyl) -acetyl / tetradecanoic acid ethyl ester as oil that is not further purified.

Example 8

Preparation of 2-dodecyl-3-hydroxy-5-methyl-1,4-naphthoquinone.

~ ^C 12 ^H 25

4 T. raw 2 - / (2-methylphenyl) acetyl / tetradecanoic acid ethyl ester according to Example 7 are concentrated with 12 T. HpSQr combined and stirred at room temperature for 66 hours. It is then poured into ice water and made slightly alkaline with 50% aqueous sodium hydroxide solution. Then sufficient ethanol is added to dissolve the organic substance and the solution is aerated for 3 hours. Then it is extracted twice with 100 T. petroleum ether, acidified with hydrochloric acid and again

709814/1088

extracted with ether. The ether extract is washed with saturated NaCl solution, dried with magnesium sulfate and evaporated. The residue is taken up in acetonitrile and filtered. The filtrate is evaporated to dryness. This residue is triturated with petroleum ether, giving 0.2 g of the title compound, bp. 92-93 ° C.

Example 9

Preparation of 3-acetoxy-2-dodecyl-5-methyl-1,4-naphthoquinone.

3 »8 parts of 2-dodecyl-3-hydroxy-5-methyl-1,4-naphthoquinone, 8 parts of acetic anhydride and 32 parts of pyridine are stirred at room temperature for 16 hours. The mixture is evaporated under reduced pressure to remove the pyridine. The residue is recrystallized (from methanol) to give 2.5 of the title compound T., Sp. 69-75 ⁰ C is obtained.

Example 10

Preparation of 1- (5-chloro-1-hydroxynaphthalen-2-yl) -1-

dodecanon.

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to 2541343

16.6 T. 5-chloro-i-naphthalenol (Erdmann and Kirchoff, Liebig's Ann., 247, 372 (1888), 19.2 T. dodecanoic acid and 132 T. BF, -ether complex (48 % BF,) are stirred under nitrogen in the steam bath for 6 hours. Then 114 T. HpO are added, and the ether is driven off by further heating. The mixture is cooled in ice, and the yellow-brown solid obtained is filtered and recrystallized (from ethanol), which is 18 T. of the yellow title compound, bp. 86-87 °.

Example 11

Manufacture of 5-chloro-2-dodecyl-1-naphthalenol

OH

A solution of 17.4 parts of 1- (5-chloro-1-hydroxynaphthalen-2-yl) -1-dedecanone and 107 parts of 37 % HCl in 2.5 parts of ethanol is refluxed for 26 hours with 40% T. zinc powder stirred, which was _{amalgamated by treatment with 3 T. HgCl 2} and 53 T. 2.1 % hydrochloric acid followed by washing with ethanol. The zinc amalgam is added in small portions during the entire reaction period. After cooling, the solid is separated off. Then it is dissolved in ethanol and the zinc amalgam is filtered _; and after cooling, 0.5 T. starting material is obtained, which is filtered. Concentration of the filtrate, purification by recrystallization from ethanol and column chromatography on silica gel with 1-chlorobutane as the eluent give 12 parts of the title compound, sp. 68-70 ° C.

Example 12

Preparation of 5-chloro-2-dodecyl-1,4-naphthoquinone.

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5.4 T. S-chloro ^ -dodecyl-i-naphthalenol, 18 T. 96 % sulfuric acid, 71.5 Τ »glacial acetic acid and 29 T. water were stirred at 70 ° and added dropwise with 8.85 T. cold 30 % H ₂ O _{2 added} for 8 hours. The mixture is then stirred for a further 17 hours at 70 °, cooled, the orange-colored solid is taken up in methylene chloride, and the extract is washed with water, dried and distilled. The tan solid is purified by column chromatography from 1-chlorobutane on silica gel, yielding the title compound 2 T., Sp. 57.5 to 58.5 C ^0.

Example 13

Preparation of 5-chloro-2-dodecyl-3-hydroxy-1,4-naphthoquinone.

OH Cl O

1.7 T. 5-chloro-2-dodecyl-1,4-naphthoquinone, 25 T. ethanol, 0.626 T. anhydrous Na ₂ CO, and 6.3 T. water with 1.13 T. 30% hydrogen ercradbei 32 ⁰ C brought into contact and treated for 10 min. under reflux. The mixture obtained is then cooled to 50 °, after which a solution of 1.56 parts of KOH in 49.5 parts of ethanol is added. The deep red mixture is ^{heated to 50 °} C. for 25 minutes, after which it is kept at this temperature for 45 minutes. After cooling to 10 ^° C., the mixture is contacted with 251 parts. 2.72% HCl. The yellow crystals are filtered, dried and purified by column chromatography on silica gel using 1-chlorobutane as the eluent. After removal of the solvent, 102-104 ⁰ C. T., 1.4 of the title compound, Sp.

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Example 14

Preparation of 3-acetoxy-5-chloro-2-dodecyl-1,4-naphthoquinone.

0.95 T. 5-chloro-2-dodecyl-3-hydroxy-1,4-naphthoquinone in 20 T. anhydrous tetrahydrofuran are under N ₂ a mixture of 0.0635 T. NaH in 40 T. tetrahydrofuran with stirring for 45 Added min. At room temperature. Then a solution of 0.275 parts of acetyl chloride in 30 parts of tetrahydrofuran is added and the mixture is stirred for 5 hours. The tetrahydrofuran is distilled off under reduced pressure, and the residue is taken up in methylene chloride and then washed with water, 10% HCl, four times with water , with Na ₂ SO. dried and distilled. The yellow solid obtained is purified by column chromatography on silica gel using 1-chlorobutane as the eluent. After removal of the solvent, 0.9 parts of the title compound, bp. 57 ° -59 ° C., are obtained

With a suitable 2-alkyl-3-hydroxy-1,4-naphthoquinone as well as acid chloride or acid anhydride, the compounds listed in Table 2 can be used in accordance with Examples 5 to 14 getting produced.

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el el el el el el el el ei γ γ «, | ,,,,,,

7098U / 108S

to X iH X O it O ι X ι *! X O X O iH O H CVJ χ ο O I. I. he" μλΊ CVJ CO '- = r * "- rH Oj

The compounds of the formula I are used as acaricides and serve to protect plants and animals against the harmful effects of these pests. In particular, can thus fruit, field crops, vegetables, ornamental plants, birds and other warm-blooded animals including humans are protected will.

The acarines come into contact with the compounds to be used according to the invention either in the form of sprays or by walking over surfaces which have been treated with a compound of formula I, whereby they are irritated and leave that area or be killed if exposed to an effective dose. Most Plants or animals can recognize the presence of a very small number of acarins without one tolerate harmful effect, but the rate of reproduction of these pests is enormous. Generally multiply the acarine populations very rapidly, so that they often no longer use the usual methods of combating parasites can be brought under control. If a rapid increase in acarines is found, measures must be taken immediately taken to avoid harm to economically important crops. So there is a need for a method to immediately reduce the multiplication of acarines and thus to prevent damage to important ones Cultures.

Even mite eggs can with these compounds in the form of Sprays are killed, with somewhat stronger doses being used than for combating the moving forms is required.

Even very small amounts of compounds of the formula I are acaricidal. In addition, according to the invention connections to be used not too quickly from the sheet

709814/1085

work washed off by rain. In addition, they have no harmful effects on ladybugs, which are important for mites are natural enemies. Furthermore, the connections in the surrounding area are quickly broken down. The connections are also effective against phosphorus-resistant acarine strains.

The acaricidally effective amount depends on the specific situation. Among the variables that need to be considered When choosing the amount of the substance, the particular compound itself belongs, then the particular one to be combated The mite, the aging conditions, the type of crop, its stage of development, the volume of the plant to be applied Sprays, the population pressure and the intervals between the individual application steps. For crop protection can Under certain circumstances, solutions or suspensions with 5 ppm active ingredient in a spray solution can be effective. When used outdoors, however, higher volumes are generally required, i.e. aqueous spray preparations with 40 to 4,000 ppm Active ingredient beneficial. Suspensions with 80 to 1000 ppm and in particular those with 150 to 500 ppm are preferred. Based on the area, 0.03 to 15 kg / ha are generally sufficient, in particular 0.06 to 8 kg, preferably 0.1 to 4 kg. In fruit growing, it is sprayed until drops form.

It may be desirable or expedient to carry out the process according to the invention proposed links with other agricultural Mixing pesticides or additives. Such mixtures often increase the effectiveness of the application to acarins and expand the control range by including other pests such as insects, fungi, nematodes or bacteria. A mixture with pesticide oil (refined petroleum) or superior oil shows a greater effect on acarines than the pure Cumulative effect. Other pesticides that use the compounds proposed according to the invention for broadening of the spectrum of activity can be mixed are the following:

Diazinon - 0,0-diethyl-0- (2-isopropyl-4-methyl-6-

pyrimidyl) phosphorothioate 7098U / 108S

Disulfoton Fhorat

Oxamyl Hethomyl Benomyl Captan

Maneb

Carboxin streptomycin

Azihpho smethyl

0 _f O-diethyl-S-2- (äthylthio) äthylphosphor-

dithioate

0, O-diethyl-S- (ethylthio) methylphosphorus

dithioate

S-methyl-1 - (dimethylcarbamoyl) -N - / "(methylcarbamoyl) oxy / thioformimidate

S-methyl-N- (methylcarbamoyloxy) thioacetimidate

i-Butylcarbamoyl ^ -benzimidazole carbamic acid methyl ester

N-trichloromethylthiophthalimide Ethylenebisdithiocarbamic acid manganese salt

5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide

2,4-diguanidino-3,5,6-trihydroxycyclohexyl-5-deoxy-2-o- (2-deoxy-2-methylaminoiX-glycopyranosyl) -3-iormylpentofuranoside.

0,0-dimethyl-5 .- / "4-oxo-1,2,3-benzotriazin-3- (4H) ylmethyl / phosphorodithioate.

The connectors are particularly suitable for protecting living Plants such as fruit-bearing trees, nut-bearing trees, ornamental trees, forest trees, vegetable plantations, garden cultuations (including ornamental gardens, small fruits and berries), grain fruits and seeds. Apple trees, peach trees, Cotton, citrus trees, beans, and peanuts are special sensitive to mite infestation and can be protected by using the compounds according to the invention. Umeinen Ensure protection during the growing season (e.g. June to August in the northern hemisphere) multiple applications can be made at the desired intervals.

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Many types of mites can be controlled by the compounds according to the invention. The following is a list representative manageable mites with the type of damage they are causing:

Panonychus ulmi and Tetranychus urticae, ■ those in general are called "orchard mites" and attack many deciduous trees, such as apple, pear, cherry, plum and peach trees; Tetranychus atlanticus, T. cinnabarinus and T. pacificus, which attack cotton, and numerous other plants; Paratetranychus citri and others, the citrus fruits infested; Phyllocoptruta oleivora, which causes citrus rust; Bryobia praetiosa, the clover, alfalfa and other plants infested, and Aceria neocynodomis, the grasses and others Plants infested., Tetranychus medanieli, which infects sloping fruit in the northwestern United States, and Oligonychus pratensis, which attacks sorghum and other grasses.

Useful agents containing the compounds of the formula I- can be prepared in a customary manner. These are dusts, granulates, tablets, solutions, suspensions, emulsions, wetting powder, emulsion concentrates and the like. Many of these types of application can be used directly. Sprays can be stretched through suitable media and applied in spray volumes of a few to several hundred liters per hectare. Concentrated products are primarily used as semi-finished products for further formulations. Such semi-concentrates generally contain from about 1 to 99 wt .-% of active ingredient (s) and at least one additive a) with about 0.1 to 20 wt -.% Surfactant (s) and b) with about 5 to 99% of solid (s ) or liquid diluent (s). In particular, these agents contain the components

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in the. following approximate ratios:

Table 3

Active ingredient dilution surfactant (s)

middle

Mesh powder 20-90 0-74 1-10

oil suspensions, emulsions, Solutions (including emulsion

concentrates) 5-50 40-95 0-15 Aqueous suspensions 10-50 .40-84 1-20 Dusts 1-25 70-99 0-5 Granules or tablets 1-95 5-99 0-15

High percentage concentrates 90-99 0-10 0-2

It goes without saying that higher or lower contents of active ingredient can be used depending on the intended use and physical Properties of the connection must be present. Higher surfactant to active ingredient ratios are sometimes used are desired and are obtained by incorporation into the composition or by mixing in the tank.

Typical solid diluents are described by Watkins et al. in the "Handbook of Insecticide Dust Diluents an Carriers", 2nd Ed., Dorland Books, Caldwell, NJ. More absorbent diluents are preferred for wetting powders, denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd. Edn., Interscience, New York, 1950. A solubility below 0.Λ% is

7098U / 108S

30 - .. 26A1343

"preferred for suspension concentrates, with solution concentrates preferably being stable against phase separation at ⁰ ° C."McCutcheon's Detergents and Emulsifiers Annual ¹¹ , Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents" , Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All of these agents can contain minor amounts of additives to prevent foaming, caking, corrosion, microbiological growth, etc. Preferably, the ingredients of the blends should be approved for use by the US Environmental Protection Agency.

The manufacturing processes for the mixtures are known. Solutions are made by simply mixing the ingredients. Fine solids are made by mixing and usual grinding in a hammer mill or Jet mill. Suspensions can be prepared by wet milling (see e.g. U.S. Patent 3,060,084). Granules and tablets can be prepared by spraying the active ingredient onto preformed granulated carriers or by agglomeration. See J.E. Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp. 147 ff and Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, N.Y., 1963, pp. 8-59 ff.

As a further source of information for the production of the invention Means are based on the following references ▼ proven:

J.B. Buchanan, U.S. Patent 3,576,834, April 27, 1971, column 5, line 36 through column 7, line 70 and Examples 1-4, 17, 106, 123-140.

7098U / 1085

a.R. Shaffer, U.S. Patent 3,560,616, Feb. 2, 1971, column 3, line 48 to column 7, line 26 and examples 3-9, 11-18.

S. Somers, "Formulation," Chapter 6 in Torgenson, "Fungicides," Volume I, Academic Press, New York, 1967. *

Another liquid application, especially for small consumption is suitable is the aerosol form, which is packaged under pressure in a suitable container. The active substance can be in a suspension, emulsion or solution. Solutions are made for ease of manufacture and use preferred. The pressure can be caused by low boiling liquids such as propane or chlorofluorocarbons or by relative soluble gases such as carbon dioxide or nitrogen dioxide are generated. The chlorofluorocarbons are preferred because they combine good solvability and low flammability.

The acaricidal activity of the compound of the formula I is illustrated by the following examples

Example 15

Test units from pots are used for this experiment two red kidney beans in the two-leaf stage per pot »The plants are infected with mites of the species Tetranychus urticae and with solutions of the compounds according to the invention to sprayed to form droplets. The solutions are prepared by dissolving weighed amounts of active ingredient in 10 ml of acetone and diluting with water to a volume containing 1: 3,000 of a surfactant, namely TREM 014 *. The degree of mortification was determined two days after spraying.

* TREM 014 is a trademark of Nopco Chemical Company for a polyhydric ester.

70981 kl 1085

Table 4

links

^R 1

-CH

CH ₂ CH ₃ CH ₃ CH ₂ CH ₂ ) ₂ CH (CH ₃ < 3 C (CH ₃ )

- (CHg) ₅ CH

0.005

Destruction in%% Spray Concentration

Q 002 Q 001 Q 0005 0.00025

100

100

100

100 100 99 90 100 100 99 100 100 99 100 100 100 98 100 100 - 65 100 100 99 93 100 100 mm 70

60 56

44

41

33 * -. 2541343

Example16

Bean plants were treated with the specified up to droplet formation Concentrations of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone in TREM 014: water as 1: 3,000 sprayed. The sprayed Plants were left to stand for 3 days and then with mites of the species Tetranychus urticae. infected.

The assessment was made on the day after infection and 11 days after it.

Spray conc
tration, % Mortification after
first day, % Mortification after
eleven days, % 0.01 99 100 0.005 90 100 0.002 58 Mites multiply
themselves Example 17

Bean plants were treated with the specified up to droplet formation Concentrations of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone in TREM 014: water as 1: 3,000 sprayed. The sprayed Plants were left to stand for 3 days and then sprinkled with 7 mm of rain. After drying, the plants were covered with mites of the species Tetranychus urticae. The assessment was made on the day after infection and 11 days after it.

Spray concentration kill after kill after tration, % one day, % 11 days, %

0.01-97 100

0.005 94 99

0.002 42 no killing

7098U / 1085

- 9Br-

Example 18

Apple seedlings about 13 cm high are infected with mites of the species Panonychus ulmi and then until droplets are formed with the indicated concentrations of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone in TREM 014: water sprayed as 1: 3,000. The evaluation was made two days after the spraying.

Spray concentrate Example 19 Degree of mortification tion, % # 0.005 100 0.002 100 0.001 100 0.0005 95

Red kidney beans are infected with mites of the species Tetranychus urticae and with 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone alone and sprayed in combination with 1? o UNICO * pesticide oil. the Ratings are averages from 3 replicates and are taken two days after spraying. The results show that the values are greater than the sum values when using compounds according to the invention in combination with a spray oil.

link concentration Kill, % 2-acetoxy-3-dodecyl-1,4- 0.002 100 naphthoquinone 0.001 99 0.0005 86 0.00025 23 0.0001 2

♦ ÜKICO is a trademark of United Co-operatives, Inc. Alliance, Ohio. It is a refined petroleum distillate with approximately 3% inerts and inhaled as a top oil.

7098U / 108S

- * & ■ -

link

<■ - 2641-343 concentration Kill, % 0.002 100 0.001. 100 0.0005 100 0.00025 97 0.0001 60 0

2-acetoxy-3-dodecyl-1,4-naphthoquinone + 1 # UNICO oil in the spray solution

UNICO pesticide oil

Example 20

Red kidney beans at the two-leaf stage grew to form droplets treated 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 of two replicates were made of each concentration. A number became infected with normal mites of the species Tetranychus urticae and the other with a methyl parathion-resistant strain. the Results are given below and show that the most resistant strains of mites when treated with the compounds of the invention were just as sensitive as the normal mites.

Concentration of Äbtötungsgrad in 48 hours,% active ingredient,% Normal mites resistant MII ben

0.001 100 100

0.0005 80 81

Example 21

Test units consisting of pots with two red kidney beans in the two-leaf stage per pot are used for this experiment. the Plants' are infected with mites of the species Tetranychus urticae and with solutions / suspensions of the invention Connections sprayed until droplets form. The solutions / suspensions are prepared by dissolving weighed

7098 U / 108 5

Amount active ingredient in 10 ml of acetone and dilute with water to a volume containing 1: 3,000 of a surfactant, namely TREM 014. The degree of destruction was determined two days after spraying.

Tabel links

O-C-R,

Killing in % at 0.002 % spray concentration

SC ₁₂ H ₂₅
SC ₁₂ H ₂₅
SC ₁₂ H ₂₅
SC ₁₂ H ₂₅
SC ₁₃ H ₂₇

SC ₁₂ H ₂₅

- (CH ₂ ) ₇ CH ₃ - (CH ₂ ) ₁₂ CH

-CH-CHCH

-CH = CHCH = CHCH

-OCH ₃

-OC ₂ H ₅

-CH ₀ -O-CH, ^ 3

-CH = CHCOOH -CH,

-OCHCHoCH CH

₂ CH ₃

96 99

100 98

100 99 97

100 99

93 60

70981 kl 1085

Example 22 ³ .

Apple trees in an orchard near Newark in the State of Delaware were infected with Panonychus ulmi of over five specimens per leaf with an inventive Compound sprayed, namely four groups each with 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone at one concentration of 14, 28 and 112 g / 400 1. In each case after 6 days, spraying was carried out again. The number of mites fell very quickly below the economically harmful level of 5 mites per leaf. All trees treated were healthy and vigorous and free from mite damage. The mites in the rest of the orchard eventually died of natural causes 2 weeks later. While the leaves of the treated trees were dark green, those of the control were very rusty brown.

Example 23

Leaves of the kidney bean covered with eggs of Tetranychus urticae were treated with aqueous dispersions of 2-acetoxy-3-dodecyl-1,4-naphthoquinone, (100, 50, 25 and 12.5 ppm ) j with TREM 014 in a ratio of 1: 3000 sprayed as a wetting agent. After 5 days under constant environmental conditions, the following degree of destruction was determined:

Conc. V. Compound I. Kill of eggs in % in ppm 100 100 50 100 25th 99 12.5 79 0 (control) 0 Example 24

To demonstrate the surprising improvement in the effect through the use of compounds with R ₁ = C-i2 ~ ⁱ "'i4, 7-9-day-old plants of the kidney bean were grown with adults

70.9814 / 1085

Mites (50-100 / leaf) are infected in such a way that leaf pieces of bean plants infected with mites that had already dried out.

The required naphthoquinones were prepared by dissolving 20 mg of each compound in 10 ml of acetone and dispersing the acetone solution in H ₂ O to the desired concentration with TREM 014 at a concentration of 1: 3,000 as a wetting agent.

Use after spraying the test plants to drain a rotating spray system under constant environmental conditions for approx. 48 hours, the following degree of destruction is achieved established:

O-C-CH ₃

Kill in % / concentration of (in %)

^R 1 0.002 0.001 0.0005 0.00025 ^C 8 ^H 17 6th - - ^C 11 ^H 23 95 79 19th 0 C ₁₂ H ₂₅ 100 100 56 9 C ₁₃ H ₂₇ - 100 47 28 Cj. /.Hon 99 68 19th

7098U / 1085

Example 25

Nasturtium in pots is infected with aphids of the species Aphis fabae and placed on a rotating table with 2-acetoxy-3-dodecy 1-1,4-naphthoquinone sprayed at concentrations of 100, 50 and 25 ppm. The degree of destruction is 72 hours after carried out spraying. The results are shown below.

Spray Concentration Kill%%

0.01 100

0.005. . 100

0.0025 89

Example 26

Solutions of the compounds according to the invention are sprayed in concentrations of 150 ppm onto nasturtium plants in pots which have been infected with aphids of the Aphis fabae species. The spray solutions are applied with a hand- "Son-ofa Gun lf ® -sprayer applied Du Pont L-144-TOG was in a ratio of 1: 2,000 in the spray as a wetting agent. The ^{degree of destruction is determined after 24 hours""}

R ₂ degree of destruction,

-CH ₃ 100

7098U / 1085

R ₂ * degree of destruction,

C ₁₄ H ₂₉ -CH ₃ 99

-CH ₂ CH ₃ 98

..- CH ₂ CH ₃ 99

-CH I -97

C ₁₄ H ₂₉

-CH j 93

-CH ₂ CH ₂ CH ₃ 98

C ₁₄ H ₂₉ -CH ₂ CH ₂ CH ₃ 87

Example 27

Aphids of the species Myzus persicae on discs, cut out of Chinese cabbage leaves, are sprayed on a rotating table with acetone solutions of the compounds according to the invention. The leaf discs are kept under constant environmental conditions for 24 hours, after which the degree of destruction is determined. The concentrations used and the percentage of aphid exposure are given below.

70981 kl 1085

Table 6 links

'-C-R,

% Kill at

56 Spray Concentration

^R 1 R ₂ αϊ 0.05 0.01 0.005 ^C 12 ^H 25 -CH, .too. 100 90 86 C ₁₄ H ₂₉ -CH ₃ 100 89; 85 69 ^C 12 ^H 25 -CH ₂ CH ₃ 100 100 94 84 C ₁₄ H ₂₉ -CH ₂ CH ₃ 100 100 98 .83 C ₁₂ H ₂₅ CE ₅
CH ₂ 100 100 88 71 C ₁₄ H ₂₉ I.
-CH ^
\
I. 97 66 80 25th C ₁₂ H ₂₅ 100 100 83 75 C ₁₄ H ₂₉ -CH ₂ CH ₂ CH ₃ 100 100 93 79 Example 28 -CH ₂ CH ₂ CH ₃

Is used for this test test units from plugs with two Red kidney beans in a two-leaf stage per pot. The plants are infected with mites of the species Tetranychus urticae and sprayed with various amounts of dispersions of 3-acetoxy-5-chloro-2-dodecyl-1,4-naphthoquinone until drops form. The dispersions are produced by

.7098H / 1085

dissolving weighed quantities of active ingredient in 10 ml of acetone and diluting with water to a volume containing 1: 3000 of a surfactant, namely TREM 014. The degree of destruction was determined two days after the spraying. The results are shown below:

Concentration of % Kill Active substance (ppm) (24 St.) 500 100 50 100 20th 100 10 100 5 100 2.5 88

Example 29

Plants of the kidney bean in the two-leaf stage were infected with mites for the purpose of oviposition. After about 24 hours, the leaves were immersed in a tetraethyl pyrophosphate solution to kill the mites. After drying, the plants were sprayed with various amounts of dispersions of 3-acetoxy-5-chloro-2-dodecyl-1,4-naphthoquinone until droplets were formed. The dispersions are prepared by dissolving weighed amounts of active ingredient in 10 ml of acetone and diluting with water to a volume containing 1: 3,000 of a surfactant, namely TREM 014. After 5 days, the degree of destruction of the eggs was determined:

Concentration of % kill of eggs

Active substance (ppm)

100 100 50 100 25th 98 12.5 79 0 (control) 1

709814/1085

Example 50

Bean plants infected with mites were treated with a 96% emulsifiable composition of 2-acetoxy-3-dodecyl-1,4-naphthoquinone (i), with a 50% emulsifiable composition of Chlordimeform (II) or " ^m ^ After 48 hours or 8 and 14 days, the degree of destruction was determined, whereby a surprising synergistic effect between I and II was found (table below): 0.0005 % I alone and 0.01 % chlorodimeform resulted after 1 to 2 weeks there was no practical effect, while the combined sprays almost completely destroyed the mites. Plants that were sprayed with I and II alone showed a strong mite infestation, while conversely with the combined sprays no or only one vanishing mite infestation was observed.

Compound % active ingredient % kill living mites / leaf

concentr. (48 St.) after

_t ___________ 8 days 14 days

2-acetoxy-3-0.005 85 210> 500

dodecyl-1,4-

naphthoquinone

Chlordimeform 0.01 1> 500> 500

(H)

I and 0.005n 99 7 1

II 0.01 ^;

70981 4/1085

Example 51

Bean plants infected with mites were in the primary leaf stage until the droplets formed with a 25% emulsifiable composition of 2-acetoxy-3-dodecyl-1,4-naphthoquinone (j) _t with the 50% commercially available wetting powder Benomyl (II) or sprayed with a combination of both substances. The degree of destruction was determined after 8 to 14 days, a surprising synergistic effect between I and II being found (table below). Plants that were sprayed with I and II alone showed a strong mite infestation, while conversely with the combined sprays only a vanishing mite infestation was found.

link

2-acetoxy-3-dodecyl 1,4-naphthoquinone

Benomyl (II)

I and
II

% Active ingredient- % kill live mites / leaf concentr. (48 hours) after 8 days 14 days

0.0005

0.03

0.005? 0.03 j

94

2 93

272

324
3

135

> 500 3

Example 32

Bean plants infected with mites were treated with a 25% emulsifiable composition of 2-acetoxy-3-dodecyl-1,4-naphthoquinone until droplets were formed (I), with the 12.2% strength commercially available Tetradifon (II) or with a combination of both Fabrics sprayed. After 8 days, the degree of destruction was determined, with a high synergistic effect between I and II (table below).

7098U / 1085

link % Effective
fabric conc. 0.002
0.001 % Kill
(48 St.) 8-day values
Live mites / leaf Infestation * 2-acetoxy-O.0005
3-dodecyl-1,4-
naphthoquinone
(I) 0.0005?
0002 J 80 261 3 Tetradifon
(II) 0.0005)
0.001 y 4th
0 99
117 9.8
9.7 I and
II 85 6th 3 I and
II 85 4th 1.5

* 0 = no infestation 10 = plant dead

709814/1085

Claims (1)

Claims Λ 1. Compound of the formula I. 0. wherein Rj = straight, branched or cyclic - Straight or branched CjC ^ "- alkyl, C ₂ -C ^ - alkenyl, Cg-Cg-cycloalkyl, C ₁ -C ^ -AlkOXy, -CH ₂ OCH ₃ , -CH ₂ OCH ₂ CH ₃ or -CH = CH -COOH; with the exception that alkyl may not be C ₁ -Cg and cycloalkyl may not be C ₃ -Cg when X and Y are H, X and Y = H, F, Cl, Br, methyl or methoxy, where, when R _{1 is} Cg- Is C ₁₁ -alkyl, at least one of the symbols X and Y has a meaning other than H. 2. A compound according to claim 1, characterized in that R _{2 is} Oj-Cg-alkyl, C ₂ -C ₃ -alkenyl, methoxy or ethoxy . 7098U / 1085 41343 3. A compound according to claim 1, characterized net gekennzeich that R ₂ is methyl or ethyl. 4. 3-Acetoxy-2-n-tridecyl-1,4-naphthoquinone. 5. 3-acetoxy-2-n-tetradecy 1-1, 4-naphthoquinone. 6. A compound according to claim 1, characterized I gekennze net that at least one of X and Y has a similar meaning as H. 7- A compound according to claim 6, characterized I gekennze net that Rj means straight or branched Cj ^ -C ^ alkyl. 8. A compound according to claim 6, characterized in that I ■ net that R _{2 is} alkyl with 1-6 carbon atoms, alkenyl with 2 or Means 3 carbon atoms, methoxy or ethoxy. 9. A compound according to claim 6, characterized I gekennze net that X or Y is H. 10. A compound according to claim 6, characterized net- gekennzeich that R ₁ is straight C ₁ -C ^ ₁ ^ alkyl. 11. A compound according to claim 6, characterized in that R ₂ is methyl or ethyl. 7088U / 1088 12. A compound according to claim 6, characterized in that R _{1 is} straight or branched alkyl with 11-14 carbon atoms, Rp is alkyl with 1-6 carbon atoms, alkenyl with 2-3 carbon atoms, methoxy or ethoxy. 13. A compound according to claim 12, characterized in that g e k e η η - shows that R _{1 is} straight alkyl having 11-14 carbon atoms. 14. A compound according to claim 12, characterized in that R _{2 is} methyl or ethyl. 15. A compound according to claim 6 _f, characterized in that R _{1 is a} straight C ₁₁ -C ₁ ^ alkyl, R _{2 is} methyl or ethyl and YH. 16. 3-Acetoxy-5-chloro ^ -n-dodecyl-1,4-naphthoquinone. 17. Process for the protection of plants against acarines and aphids, characterized in that the former is treated with an effective amount of a compound according to claims 6-16 . 18. Acaricidal and aphicidal agents, consisting of at least one surfactant (a), a solid or liquid diluent and a compound according to claims 6 to 16. 9. A method for protecting plants from acarines and aphids, characterized in that the former is treated with an effective amount of a compound of the formula 7098U / 1085 wherein R ₁ = straight, branched or cyclic Cq-C ₁ ^ alkyl;
R = straight or branched C ₁ -C ₁ y-alkyl, Alkenyl, C ₁ -C ^ -alkoxy, -CH ₂ OCH ₃ , -CH ₂ OCH ₂ CH ₃ or -CH = CH-COOH, treated. 20. Process for the preparation of a compound of formula I. before in β straight, branched or cyclic C ₈ -C ₁ ^ alkyl; .-CH - = straight or branched C ₁ -C ₁ "alkyl, C ₂ -C ₁ ^ alkenyl, C ^ Cg-cycloalkyl, _C1 ^ -alkoxy, ₂ OCH _3, -CH ₂ OCH ₂ CH ₃ or -CH = CH-COOH; with the exception that alkyl may not be C ₁ -Cg and cycloalkyl may not be C ₃ -Cg when X and Y are H, X and Y = H, F, Cl, Br, methyl or methoxy, where, when R _{1 is} C ₃ -C ₁₁ alkyl, at least one of X and Y is other than H hatj 7 0 9 8 14/1085 - Mr- characterized in that a substituted naphthol is used as the starting point Y OH where X and Y have the abovementioned meaning in a known manner alkylated eu of a compound of the formula IH where Y, X and R ,. have the meaning given above, the se · compound oxidizes to a compound of the formula ' (in) where X, Y and R ^ have the meaning given above and this compound is then esterified in a known manner or into a compound of a 4-phenyl-3-oxobutyric acid ester of the formula 709814/1085 CH ₂ CCH ₂ CO ₂ CH ₂ CH ₃ in a known manner to a compound of the formula implements and then closes the ring in a known manner. 7098U / 108S