CH629651A5 - Acaricide and aphicide - Google Patents

Description

The invention relates to acaricidal and aphicidal agents.

U.S. Patents 2,553,647 and 2,553,648 describe 2-A1-alkyl-3-hydroxy-l, 4-naphthoquinone carboxylic acid and their corresponding ester derivatives. These compounds are said to have an antagonistic effect against organisms which 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 analogue of 2-alkyl-3-hydroxy-l, 4-naphthochi-

nons. Nothing is said in this publication about the use of this connection.

The acaricidal and aphicidal agent according to the invention is characterized in the preceding patent claim 1.

Combinations of the compounds of the formula I with other acaricides, in particular with chlorodime form (“Ga-lecron”), formetanate (“Carzol”), propargite (“Omite”), tetradifone (“Tedion”) and benomyl have a better overall effect than the compounds taken alone. Such mixtures are also new.

If an effective amount of the agent according to the invention is brought into contact with mites or aphids, the pests are killed. The agents according to the invention can therefore be used to protect plants and animals against the action of mites or aphids.

Preferred because of the simple preparation are agents which contain, as an active ingredient, compounds of the formula I in which Rj denotes a straight-chain alkyl group having 8 to 14 carbon atoms.

Because of their biocidal action, agents are particularly preferred which contain, as active ingredient, compounds of the formula I in which R 1 denotes a straight-chain alkyl group having 12 to 14 carbon atoms. Mite eggs treated with these agents die. A little higher doses than those used to combat the mobile forms show a good ovicidal effect.

Preference is given to compositions which contain, as active ingredient, a compound of the formula I in which R2 is Cr-Cg-alkyl, particularly preferably straight-chain Q-Cg-alkyl, C2-C3-alkenyl, methoxy or ethoxy, in particular ethyl or methyl. Because of their extremely high acaricidal and aphicidal activity, agents with the following compounds are particularly preferred: 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-l, 4-naphthoquinone;

3-butyryloxy-2-n-tetradecyl-1,4-naphthoquinone; 2-n-dodecyl-3-methoxycarbonyloxy-1,4-naphthoquinone;

2-n-dodecyl-3-ethoxycarbonyloxy-l, 4-naphthoquinone;

3-butyryloxy-2-n-dodecyl-1,4-naphthoquinone;

2-n-dodecyl-3-isobutyryloxy-l, 4-naphthoquinone;

3-acetoxy-5-chloro-2-dodecyl-l, 4-naphthoquinone.

According to a preferred embodiment of the present invention, the compounds of formula I are mixed with a superior oil, preferably with a smaller amount of superior oil, e.g. less than 5 wt .-% applied. The acaricidal effect obtained is greater than the sum effect. Superior oils are described in Chapman et al. Selection of a Plant Spray Oil Combining Full Pesticidal Efficiency with Minimum Plant Injury Ha-zards, Jour. Econ. Ent., 1962, 55: 737-43. The mixture of the compound with the superior oil obtained is new.

The compounds of the formula I can be prepared by the procedures described in the article from J. Am. Chem. Soc. and U.S. Patents 2,553,647 and 2,553,648. The final stage of the synthesis can also be carried out by treating the corresponding 2-alkyl-3-hydroxy-l, 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 treating the salt of 2-alkyl-3-hydroxy-l, 4-naphthoquinone with a suitable acid chloride or anhydride in an inert solvent.

2nd

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

3rd

629 651

The compounds can either (a) from appropriately substituted naphthol according to DE-OS 2 520 739,

(11/9/75), or (b) from 4-phenyl-3-oxobutyric acid ester according to Fieser et al., US Pat. No. 2,553,647:

(a)

(b)

0 n

CH2CCH2C02CH2CH3

■ V '

0

n

CH2CCHC02CH2CH3 R *

The following explanations illustrate the manufacturing process.

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

H

OC-CH-z n ~ C12H25

A mixture of 2 parts of 2-n-dodecyl-3-hydroxy-1,4-naphthoquinone, 0.81 part of triethylamine and 0.63 part of acetyl chloride and 50 parts of methylene chloride are stirred at room temperature for 30 hours. The mixture obtained is partitioned 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 from petroleum ether (boiling point 30 to 60 ° C.) and gives 1.2 parts of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone with a melting point of 57 to 58 ° C.

Manufacturing 2

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

0

1t

OCCH2CH3

55

60

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-l, 4-naphthoquinone with a melting point of 42 to 44 ° C.

Manufacturing 3

Preparation of 2-n-dodecyl-3-hydroxy-l, 4-naphtho-quinone-Na

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

Manufacturing 4

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

T = parts.

60 T. of the salt solution obtained according to Ex. 3 are stirred with 0.59 T. methyl chloroformate in 10 T. tetrahydrofuran for 1 hour 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-l, 4-naphthoquinone, mp. 70-72 ° C.

Using a suitable 2-alkyl-3-hydroxy-l, 4-naphtho-quinone and acid chloride or anhydride, the compounds listed below can be prepared in accordance with Ex. 1-4.

629651

4th

Table 1

OCR,

Ri

Sp.fC)

—N-CgHj 7

n-C9H ^ 9 -11-C11H23 -11-C11H23 -11-C11H23 - ^ n-Ci1H23

-N-c12h25 -n-ci2h25

—N "Ci2H25 -I1-CI3H27

-ch-ch2-c9h19

ch3

- (ch2) 9-ch (ch3) 2

- (ch2) 3- / s

-11-C14H29 -n-C12H25

—N-C10H2i

-N.-C14H29

-n-C14H29 -n-C14.H29

-n-C12H2 5

-n-C ,, H2

-11-C12H25

-n-C12H25 -n-Ci2H25 -n-Ci2H2S -n-C] 2H25

-11-C3H7

-c2h5

-ch3

-ch2ch3

-ch2gh2ch3

-ch (ch3) 2

-ch3

-CH2CH3

-ch2ch2ch3

-ch3

-ch3

ch3

I.

-ch-CH3

-ch.,

-ch,

-ch3

-ch (ch3) 2

-ch3 ch2ch3

CH2CH2CH3

^ CH2 -ch i ^ ch2 ^ ch2 -ch 1 ^ CH2

- (ch2) 4ch3 -c (ch3) 3 -och3 -och2ch3 ch3

51-53

ND25 1.5209 Nd25 1.5131 Nd2S 1.5155

57-58 42-44

Nd25 1.5120

58-60

Nd25 1.5332

72-74

62-63

Nd2S 1.5157

52-53 40-41

65-67

59-61

50-52

Nd2s 1.5133 Nd2S 1.5133 70-72 42-47

-n-ci2H25

-o-chch2ch,

[IR> = 0 1753 cm-1]

5

Table 1 (continued)

629651

Rt

R2

Sp. (° C)

-N-C12H25

-N-Ci2H25 -n-Ci2H25 -n-Ci2H25

-n-C12H2s

—N-Ci2H25

—N-ci2h25

-N-Cj2H2s -n-Ci2H25 -n-C12H25 -n-C12H2S

-ch ^ ch

2 2

n-C12H25 n-C12H25

-ch2-

-n-C,? II?

-ch2och3

-ch2och2ch3

- (ch2) 7ch3

- (ch2) 12ch3

- (ch2) 16ch3

-ch = ch2 -ch = chch3 ch3

I.

-c = ch2 -ch = ch-co2h

-ch = ch-ch = ch-ch3

- (ch2) 7ch = chch2ch = ch (ch2) 4ch3

-ch3

- (CH2) 5CH3 - (CH2) 6CH3

-CH,

69-71

[IR]> = o 1791 cm-1 51-53

43.5-44.5

Nd25 1.5202 Nd25 1.5162 68-74

68-69

Nd25 1.5141 54-57

91-93

- (CH2) 7-CH = CH- (CH2) 7CH3

Manufacturing 5

Preparation of 2-acetyl-4- (2-methylphenyl) -3-oxobut-tersäureäthylester

ÇH-

0 n

0

It

7 ^ j) -CH2CCHC0CH2CH3 CCH,

n 3

0

According to M. Viscontini and N. Merckling, Helvetica Chimica Acta, 35.2280 (1952), 2.65 T. Magnesium chips with 15 T. abs. Ethanol at room temperature and 0.5 T. carbon tetrachloride. After the reaction has subsided, 100 T. dry ether are added. The mixture is then stirred without cooling until the reaction has stopped, and then 19.6 parts of ethyl 3-oxobutyric acid ester in 20 parts of dry ether are added with ice-cooling and the mixture is stirred well. The precipitate obtained is dissolved, the solution is then cooled in an ice-salt bath and slowly mixed with 16 T. 2-methylphenylacetyl chloride, after which it is left overnight at room temperature and finally combined with ice and H2S04. The ether layer is separated, washed with H20, dried with Na2S04 and finally distilled, whereby the title compound is obtained as a crude oil.

Manufacturing 6

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

O

CH,

3 0

chocch

0

2coch2ch3

According to Hunsdiecher reports, 75, 454 (1942), 26 parts of ethyl 2-acetyl-4- (2-methylphenyl) -3-oxobutyrate-35 ester were stirred for 10 hours at room temperature with 100 T. ethanol and 6.8 T. Na ethoxide. The mixture is diluted with H20 and extracted with ether. The solvent is finally evaporated to give the title compound.

40 Production 7

Preparation of 2 - [(2-methylphenyl) acetyl] tetradecane

acid ethyl ester.

45

50

55

0 0

-CHoCCHC0CH ~ CH

(CH,

2W13

2) i1CH3

3 T. 4- (2-methylphenyl) -3-oxobutyric acid ethyl ester, 1 T. Na methoxide, 4.6 T. 1-bromo-dodecane, 0.5 T. NaJ and 50 T. abs. Ethanol are heated under reflux conditions for 4 hours and then stirred at room temperature for 18 hours. The mixture is then concentrated strongly, diluted with 100 T. water and extracted with ether. The ether extract is washed with saturated NaHC03 and saturated NaCl solution and dried with MgS04. Evaporation of the ether gives 6 T. crude ethyl-2 [(2-methylphenyl) acetyl] tetradecanoic acid ethyl ester as an oil which is not further purified.

Preparation 8 Preparation of 2-dodecyl-3-hydroxy-5-methyl-1,4-naphthoquinone. Q

pr-Z I2H25

65

629 651

6

4 T. raw 2 - [(2-methylphenyl) acetyl] tetradecanoic acid ethyl ester according to Example 7 are concentrated with 12 T. cold. H2S04 combined and stirred at room temperature for 66 hours. The mixture is then poured into ice water and made slightly alkaline with 50% aqueous sodium hydroxide solution. Then sufficient ethanol is added to the solution of 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 extracted again 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, column 92-93 ° C.

Production 9 Production of 3-acetoxy-2-dodecyl-5-methyl

1,4-naphthoquinone.

OCCH.

CH-

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

Preparation 10 Preparation of l- (5-chloro-l-hydroxynaphthalin-2-yl) -1-dodecanone. n

Cl

16.6 T. 5-chloro-1-naphthalenol (Erdmann and Kirchoff, Liebig's Ann., 247, 372 (1888), 19.2 T. dodecanoic acid and 132 T. BF3 ether complex (48% BF3) are added Nitrogen was stirred in a steam bath for 6 hours, then 114 parts of H 2 O were added, and the ether was stripped off by further heating, the mixture was cooled in ice, and the yellow-brown solid obtained was filtered and recrystallized (from ethanol), the 18 parts of the yellow Title compound, Col. 86-87 ° C, gives.

Preparation 11 Preparation of 5-chloro-2-dodecyl-l-naphthalenol

OH

A solution of 17.4 T. l- (5-chloro-l-hydroxynaphthalen-2-yl) -1 -dedecanone and 107 T. 37% HCl in 2.5 T. ethanol is refluxed for 26 hours stirred with 40 T. zinc powder, which was amalgamated by treatment with 3 T. HgCl2 and 53 T. 2.1% hydrochloric acid with subsequent washing with ethanol. The zinc amalgam is added in small portions throughout the reaction. After cooling, the solid is separated off. Then it is dissolved in ethanol, the zinc amalgam is filtered, and after cooling, 0.5 T. of 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 eluent give 12 parts of the title compound, column 68-70 ° C.

Production 12 Production of 5-chloro-2-dodecyl-l, 4-naphthoquinone.

0

5.4 T. 5-chloro-2-dodecyl-l-naphthalenol, 18 T. 96% sulfuric acid, 71.5 T. glacial acetic acid and 29 T. water were stirred at 70 ° C. and added dropwise with 8.85 T. cold 30% H202 added over 8 hours. The mixture is then stirred at 70 ° for a further 17 hours, 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, which gives 2 T. of the title compound, Col. 57.5-58.5 ° C.

Preparation 13 Preparation of 5-chloro-2-dodecyl-3-hydroxy-l, 4-naphthoquinone.

OH

Cl 0

1.7 T. 5-chloro-2-dodecyl-l, 4-naphthoquinone, 25 T. ethanol, 0.626 T. anhydrous Na2C03 and 6.3 T. water were mixed with 1.13 T. 30% hydrogen peroxide at 32 ° C. brought into contact and treated for 10 minutes under reflux conditions. The resulting mixture is then cooled to 50 ° C, after which it is mixed with a solution of 1.56 T. KOH in 49.5 T. ethanol. 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 T. 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, 1.4 T. of the title compound, column 102-104 ° C.

Preparation 14 Preparation of 3-acetoxy-5-chloro-2-dodecyl-l, 4-naphthoquinone.

s

10th

15

20th

25th

30th

35

40

45

50

55

60

65

7

629 651

Then the mixture is mixed with a solution of 0.275 T. acetyl chloride in 30 T. tetrahydrofuran and stirred for 5 hours. The tetrahydrofuran is distilled off under reduced pressure, and the residue is taken up in methylene chloride and then with water, 10% HCl, four times with water washed, dried with Na2S04 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 T. of the title compound, column 57-59 ° C.

With a suitable 2-alkyl-3-hydroxy-l, 4-naphtho-quinone and acid chloride or anhydride can be prepared according to Ex. 5 to 14 of the compounds listed in Table 2.

Table 2

0

0.95 T. 5-chloro-2-dodecyl-3-hydroxy-l, 4-naphthoquinone in 20 T. anhydrous tetrahydrofuran are mixed under N2 with a mixture of 0.0635 T. NaH in 40 T. tetrahydrofuran with stirring for 45 min added at room temperature.

—N-CgHi7

-ch2ch2ch3

Cl

H

-

—N-CgH ^

ch3

ch3

H

-

-s-C8H17

-ch3

Cl

Cl

-

- (CHj) - (i

") -CH3

Cl

H

-

-n-CnH23

-ch3

Cl

H

_

-n-CnH23

-ch2ch2ch3

Cl ch3

-

-n-CiiH23

-och3

och3

H

-

-n-C12H25

-ch2och3

Br

H

-

—N-Ci2H25

-ch3

Cl och3

-

-n-C12H25

-ch2och2ch3

H

Cl

-

^ ch2

-s-Ci2H25

-CH |

Cl

Br

-

ch2

r-

-tch3

- (CHj) 6- <S

J -och3

Cl

H

-

-n-C12H25

-0

Br

H

-

-n-Ci2H25

- (ch2) 4ch3

F

H

-n-Ci2H25

-c (ch3) 3

Cl

F

-

-n-Ci3H27

-och2ch3

ch3

ch3

-

ch3

-n-C12H25

-o-chch2ch3

Cl

H

_

-n-C12H25

- (ch2) 16ch3

Cl

H

-

-n-C12H25

-ch = ch2

Br ch3

-

-n-Ci2H25

-ch = chch3

Br

F

ch3

-n-C12H2J

-ch = ch2

och3

Br

-n-Ci2H25

-ch = chco2h

Cl

H

-n-C12H25

- (ch2) 7ch = chch2ch = ch (ch2) 4ch3

Cl

H

-

629651

8th

Table 2 (continued)

Ri R2 X Y Sp. (° C)

-n-C12H25

- (ch2) 7ch = (ch2) 7ch3

Cl

H

-

—N-Ci4.H29

-ch3

och3

och3

-

—S-C14H29

-ch2ch3

H

ch3

-

- (ch2> 8 <d

-ch = chch3

Cl

H

-

—N-Ci0H2i

-ch3

Cl

H

_

-n-C12H25

-ch3

Br

Br

_

-N-C12H25

-ch3

H

F

_

—N-c12h25

-ch3

H

och3

-

—N-ci2h25

-ch3

H

Br

_

-n-C12H25

-ch3

Br

H

-

As mentioned, the compounds of the formula I are used as active ingredients in acaricides and serve to protect plants and animals against the harmful action of these pests. In particular, fruits, crops, vegetables, ornamental plants, birds and other warm-blooded animals, including humans, can be protected.

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 the formula I, irritating them and leaving or killing this area if they are effective Dose have been suspended. Most plants or animals can tolerate the presence of a very small number of acarines without an obviously harmful effect, but the rate of reproduction of these pests is enormous. In general, the acarine populations multiply very quickly, so that they can often no longer be controlled using the usual methods for combating parasites. If a rapid proliferation of acarines is found, measures must be taken immediately to avoid damage to economically important crops. There is therefore a need for a method of immediately reducing the proliferation of acarines and thus preventing damage to important crops.

Mites eggs can also be killed with these compounds in the form of sprays, using somewhat stronger doses than is necessary to combat the mobile forms.

Even very small amounts of compounds of the formula I have an acaricidal action. In addition, the compounds to be used according to the invention are not washed off the foliage by rain too quickly. In addition, they have no harmful effects on ladybugs, which are important natural enemies for mites. Furthermore, the connections in the surrounding area are quickly cleared. The compounds are also active against phosphorus-resistant acarine strains.

The acaricidally effective amount depends on the specific situation. The variables that must be taken into account when selecting the amount of the substance include the respective compound itself, then the respective mite to be controlled, the weather conditions, the type of crop, its stage of development, the volume of the spray to be applied, the population pressure and the Intervals between the individual application steps. Under certain circumstances, solutions or suspensions with 5 ppm active ingredient in a spray solution can be effective for crop protection. When used outdoors,

20th

25th

30th

35

mean however higher volumes, i.e. aqueous spray preparations with 40 to 4000 ppm of active ingredient are advantageous. 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, spraying takes place until drops form.

It may be desirable or even expedient to mix the compounds proposed according to the invention with other agricultural pesticides or additives. Such mixtures often increase the effectiveness of the application on acarines and expand the control area by including other pests, such as insects, fungi, nematodes or bacteria. A mixture with pesticide oil (refined petroleum) or superior oil has a greater effect on acarines than the pure sum effect. Other pesticides which can be mixed with the compounds proposed according to the invention to broaden the spectrum of action are the following:

Diazonon

40

Disulfoton Phorat 45 Oxamyl

Methomyl so benomyl

Captan Maneb

55 carboxin

Streptomycin

60

Azinphosmethyl

- 0.0-diethyl-0- (2-isopropyl-4-methyl-6-pyrimidyl) phosphorothioate

- 0.0-diethyl-S-2- (ethylthio) ethyl phosphorodithioate

- 0.0-Diethyl S- (ethylthio) methyl phosphorodithioate

- S-methyl-l- (dimethylcarbamoyl) -N - [(methylcarbamoyl) -oxy] thio-formimidate

- S-methyl-N- (methylcarbamoyloxy) thioacetimidate

- Methyl l-butylcarbamoyl-2-benzimidazole carbamate

- N-trichloromethylthiophthalimide

- Ethylene bisdithiocarbamic acid manganese salt

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

- 2,4-Diguanidino-3,5,6-trihydroxycyclo-hexyl-5-deoxy-2-o- (2-deoxy-2-methyl-amino-a-glycopyranosyl) -3-formyl-

, pentofuranoside

- 0.0-Dimethyl-5- [4-oxo-1,2,3-benzotriazin-3- (4H) ylmethyl] phosphorodithioate.

65 The compounds are particularly suitable for protecting living plants, such as fruit-bearing trees, nut-bearing trees, ornamental trees, forest trees, vegetable crops, garden crops (including ornamental

9

629 651

gardens, small fruits and berries), grain fruits and seeds. Apple trees, peach trees, cotton, citrus trees, beans and peanuts are particularly sensitive to mite infestation and can be protected by using the compounds according to the invention. To ensure protection during the growing season (e.g. from June to August in the northern hemisphere), multiple use should be made at the desired intervals.

Many species of mites can be controlled by the compounds according to the invention. The following is a list of representative combatable mites with the type of damage they cause:

Panonychus ulmi and Tetranychus urticae, commonly known as "orchard mites" and which infest many deciduous trees, such as apple, pear, cherry, plum and peach; Tetranychus atlanticus, T. cinnabarinus and T. pacificus, which infest cotton and numerous other plants; Paratetranychus citri and others that infest citrus fruits; Phyllocoptruta oleivora, which causes citrus rust; Bryobia praetiosa, which affects clover, alfalfa and other plants, and Aceria neocynodomis, which affects grasses and other plants; Tetranychus medanieli, which infests fruit falling away in the northwestern United States, and Oli-gonychus pratensis, which infests sorghum and other grasses.

Useful agents containing the compounds of formula I can be prepared in a conventional manner. These are dusts, granules, tablets, solutions, suspensions, emulsions, mesh powder, emulsion concentrates and the like. Many of these types of applications can be used directly. Spray agents can be stretched through suitable media and applied in spray volumes from a few to several hundred liters per hectare. Concentrated agents are primarily used as semi-finished products for other formulations. Such semi-concentrates generally contain about 1 to 99% by weight of active ingredients) and at least one additive a) with about 0.1 to 20% by weight of surfactant (s) and b) with about 5 to 99% solid or liquid diluents). In particular, these agents contain the components in the following approximate proportions:

Table 3

Active ingredient surfactant (s)

Fabric thinning

medium

Mesh powder

20-90

0-

-74

1-10

Oil suspensions, emul

5-50

40-

-95

0-15

sions, solutions (a

finally emulsions

concentrates)

Aqueous Suspen

10-50

40-

-84

1-20

sions

Dusts

1-25

70-

-99

0-5

Granules or

1-95

5-

-99

0-15

Tablets

High proof

90-99

0-

-10

CS

1

O

Concentrates

Higher or lower levels of active ingredient can of course be present depending on the intended use and the physical properties of the compound. Higher surfactant to drug ratios are sometimes desirable 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, N.J.

More absorbent diluents are preferred for mesh powders, denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, “Solvent Guide”, 2nd. Edn., Interscience, New York, 1950. A solubility below 0.1% is preferred for suspension concentrates, solution concentrates should preferably be stable against phase separation at 0 ° C. "McCutcheon's Detergents and Emulsifiers Annual", Al-lured Pubi. Corp., Ridgewood, New Jersey, as well as Sise-ly and Wood, "Encyclopedia of Surface Active Agents", Chemical Pubi. Co., Inc., New York, 1964, lists surfactants and the 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 mixtures should be approved for use by the U.S. Environmental Protection Agency.

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

As a further source of information for the production of the agents according to the invention, reference is made to the following references:

J.B. Buchanan, U.S. Patent 3,576,834.27. April 1971, column 5, line 36 to column 7, line 70 and examples 1-4, 17, 106, 123-140.

R.R. Shaffer, U.S. Patent 3,560,616.2. Feb. 1971, column 3, line 48 to column 7, line 26 and examples 3-9, 11-18.

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

Another type of liquid application that is particularly suitable for small consumption is the aerosol form, which is packed under pressure in a suitable container. The active ingredient can be in a suspension, emulsion or solution. Solutions are preferred for ease of manufacture and use. The pressure can be generated by low-boiling liquids, such as propane or chlorofluorocarbons, or by relatively soluble gases, such as carbon dioxide or nitrogen dioxide. The chlorofluorocarbons are preferred because they combine good solubility and low flammability.

The agents according to the invention and their effects are illustrated by the following examples.

example 1

Test units from pots with two red haricot beans in a two-leaf state per pot are used for this experiment. The plants are infected with mites of the Tetranychus urticae species and sprayed with solutions of the compounds according to the invention until drops form. 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: 3000 of a tenside, namely TREM 014 *. The degree of killing was determined two days after spraying.

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

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

629 651

10th

Table 4

O

Mortality in%

% Spray concentration

Ri R2 0.005 0.002 0.001 0.0005 0.00025

n-c12h25

-ch3

100

100

100

60

n-ci2h25

-ch2ch3

100

100

99

90

56

n-c12h25

-CH2CH2CH3

100

100

99

n-ci2h25

-ch (ch3) 2

100

100

99

n-C12H25

<3

100

100

100

98

44

n-Cj2H25

-c (ch3) 3

100

100

-

65

n-ci2h25

- (ch2) 4ch3

100

100

99

93

41

n-C12H25

- (CH2) 5ch3

100

100

-

70

Example 2

Bean plants were sprayed with the stated concentrations of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone in TREM 014: water as 1: 3000 until drop formation occurred. The sprayed plants were left to stand for 3 days and then infected with mites of the Tetranychus urticae species.

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

Spray concentration,%

Mortality after the first day,%

Mortality after 11 days,%

0.01

0.005

0.002

99 90 58

100 100

Mites reproduce

Spray concentration,%

Mortification after one day,%

Mortality after 11 days,%

0.01

0.005

0.002

97 94 42

100 99

no killing

Example 4

Apple seedlings approximately 13 cm high are infected with mites of the Panonychus ulmi species and then until the formation of drops with the indicated concentrations of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone in TREM

014: water sprayed as 1: 3000. The evaluation was made two 30 days after spraying.

Spray concentration,

%

35

40

Example 3

Bean plants were sprayed with the specified concentrations of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone in TREM 014: water at 1: 3000 until drop formation occurred. The sprayed plants were left for 3 days and then irrigated with 7 mm of rain. After drying, the plants were infected with mites of the species Tetranychus urticae. Evaluation was made the day after infection and 11 days after.

Degree of killing,%

0.005 0.002 0.001 0.0005

100 100 100 95

so

Example 5

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

* UNICO is a trademark of the United Co-operatives, Inc. Alliance, Ohio. It is a refined petroleum distillate with approximately 3% inert ingredients and classified as an upper oil.

55 connection

Concentration killing,

60

65

%

2-acetoxy-3-dodecyl-l, 4-

0.002

100

naphthoquinone

0.001

99

0.0005

86

0.00025

23

0.0001

2nd

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

0.002

100

naphthoquinone + 1% UNICO-

0.001

100

Ö1 in the spray solution

0.0005

100

0.00025

97

0.0001

60

1% UNICO pesticide oil

0

11

629 651

Example 6

Red kidney beans in the two-leaf stage were treated with solutions of 2-dodecyl-3-acetoxy-1,4-naphthoquinone at concentrations of 10, 5 and 2.5 ppm until drops formed. The plants were allowed to dry. 5 Two rows of each concentration with two repetitions were made. A series was made with normal ones

Mites of the species Tetranychus urticae infected and the other with a methylparathione-resistant strain. The results are shown below and show that the resistant mite strains were sensitive to treatment with the compounds according to the invention in the same way as the normal mites.

Active substance concentration,%

Degree of kill in 48 hours,% normal resistance

Mites mites

0.001 0.0005

Example 7

Test units made from pots with two red kidney beans at the two-leaf stage per pot are used for this experiment. The plants are infected with mites of the species Tetranychus urticae and treated with solutions / suspensions of the compounds according to the invention until drops form.

100 100

80 81

sprays. The solutions / suspensions are prepared by dissolving weighed amounts 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 killing was determined two days after spraying.

Table 5

links

0

0 n o-c-fl

R2

Kill in% at 0.002% spray concentration n-C12H25

- (ch2) 7ch3

96

n-cj2h25

- (ch2) 12ch3

99

n-Ci2H25

-ch = chch3

100

n-C12H25

-ch = chch = chch3

98

n-Ci2H25

-och3

100

n-Ci2H25

-oc2h5

99

n-C12H25

-ch2-o-ch3

97

n-Ci2H25

-ch = chcooh

100

n-Ci3H27

-ch3

/ mm

99

n-ci2h25

- <F>

93

n-Ci2H25

-ochch2ch3

60

CH3

Example 8

Apple trees in an orchard near Ne-55 wark in the state of Delaware were sprayed with a compound according to the invention in the case of an infestation of more than five specimens with Pano-nychus ulmi, four groups each with 3-acetoxy-2-n- dodecyl-l, 4-naphthoquinone at a concentration of 14.28 and 112 g / 4001. Spraying was carried out again after 60 6 days. The number of mites quickly fell below the economically harmful level of 5 mites per leaf. All treated trees were healthy and strong and free from mite damage. The mites in the rest of the orchard finally died 65 weeks later due to natural causes. While the leaves of the treated trees were dark green, those of the control were a deep rust brown.

Example 9

Leaves of the red haricot bean populated with eggs from Tetranychus urticae were treated with aqueous dispersions of 2-acetoxy-3-dodecyl-l, 4-naphthoquinone (100, 50.25 and 12.5 ppm) with TREM 014 in a ratio of 1: 3000 sprayed as a wetting agent. After 5 days in constant environmental conditions, the following degree of killing was found:

Concentration of egg kill in% Compound I in ppm

100 100

50 100

25 99

12.5 79

0 (control) 0

629651

12

Example 10

To demonstrate the surprising improvement in activity by using compounds with Rt == C12-Ci4, 7-9 day old red kidney bean plants were infected with adult mites (50-100 / leaf) in such a way that leaf pieces from bean plants infected with mites, that had already dried up.

The required naphthoquinones were prepared by dissolving 20 mg of each compound in 10 ml of acetone and dispersing the acetone solution in H20 to the desired concentration with TREM 014 at a concentration of 1: 3000 as a wetting agent.

After spraying the test plants until dripping using a rotating spray system under constant environmental conditions for approximately 48 hours, the following degree of killing is determined:

c8h17

c11h23 c12h25 c13h27 c14h29

6

95 100

79 100 100 99

19 56 47 68

0 9 28 19

Example 11

Nasturtium in pots is infected with aphis fabae and sprayed on a rotating table with 2-acetoxy-3-dodecyl-l, 4-naphthoquinone at concentrations of 100, 50 and 25 ppm. The degree of killing is carried out 72 hours after spraying. The results are shown below.

Spray concentration,

%

Killing,

%

0.01

0.005

0.0025

100 100 89

Example 12

Solutions of the compounds according to the invention are sprayed in concentrations of 150 ppm onto nasturtium plants in pots which were infected with aphids of the species Aphis fabae. The spray solutions are applied with a hand-held “Son-of-a-Gun” ® sprayer. Du Pont L-144-WDG was present at a 1: 2000 ratio in the spray as a wetting agent. The degree of killing is determined after 24 hours.

10th

15

20th

Ri

R2

Degree of killing,%

R1 killing in% / concentration of (in%)

0.002 0.001 0.0005 0.00025

ci2h25 25 c14h29 ci2h25 ci4H29

Ci 2H2

30th

c14h29

c12h25

35 c14h29

-ch3 -ch3 -ch2ch3 -ch2ch3 _ch2

-ch i ch2 ^ ch2 -CH ^ I

ch2 -ch2ch2ch3 -ch2ch2ch3

100 99

98

99

97

93

98 87

Example 13

Aphids of the species Myzus persicae on slices, cut out of Chinese cabbage leaves, are sprayed on a rotating table with acetone solutions of the compounds according to the invention. The leaf disks 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 destruction are listed below.

Table 6

Connections r,

% Kill at% spray concentration 0.1 0.05

0.01

0.005

Ci2H25

c14h29 c12h25

Ci4H29 C12H7 5

c14h29 c12h25

Ci4H29

-ch3 -ch3 -ch2ch3 -ch2ch3, ch2

-ch i ^ ch2 ^ ch2 -ch i ch2 -ch2ch2ch3 -ch2ch2ch3

100 100 100 100

100

97

100 100

100 89 100 100

100

66

100 100

90 85 94 98

80

83 93

86 69 84 83

71

25th

75 79

13

629 651

Example 14

Test units from pots with two red haricot beans in a two-leaf state per pot are used for this experiment. 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 prepared by dissolving weighed amounts 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 killing was determined two days after spraying. The results are shown below:

Active substance concentration (ppm)

% Kill (24 h)

500 50 20 10 5

2.5

100 100 100 100 100

Example 15

Plants of the red kidney bean in the two-leaf stage were infected with mites to lay their eggs. After approximately 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-naphtho-quinone until drops 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: 3000 of a surfactant, namely TREM 014. After 5 days, the degree of kill of the eggs was determined:

Active substance concentration (ppm)

% Killing the eggs

10th

15

100 50 25 12.5

0 (control)

100 100 98 79 1

Example 16

Mite-infected bean plants were treated with a 25% emulsifiable composition of 2-acetoxy-3-dodecyl-l, 4-naphthoquinone (I), with a 50% emulsifiable composition of chlorodime form (II) or with a until drop formation Combination of both substances sprayed. After 48 hours or 8 and 14 days, the degree of killing 25 was determined, a surprising synergistic effect between I and II being found (table below). 0.0005% I alone and 0.01% chlorodime form had no practical effect after 1 to 2 weeks, while the mites were almost completely destroyed by the combined sprays. Plants that were sprayed with I and II alone showed a strong mite infestation, while conversely with the combined sprays no or only a vanishing mite infestation was found.

Compound% active ingredient% kill Live mites / leaf after concentration (48 hours) 8 days 14 days

2-acetoxy-3-dodecyl-l, 4-naphthoquinone (I) 0.005 85 210> 500

Chlorodime form (II) 0.01 1> 500> 500

I and II 0.005 \ 99 7 1

0.01 /

In the primary leaf stage, mite-infected bean plants were dripped with a 25% emulsifiable composition of 2-acetoxy-3-dodecyl-1,4-naphtho-quinone (I), with the 50% commercial mesh powder benomyl (II) or sprayed with a combination of both substances. After 8 to 14 days, the killing

Example 17

degree found, whereby a surprising synergistic effect between I and II was found (table below). Plants that were sprayed with I and II alone showed a strong mite infestation, while conversely only a vanishing mite infestation was found in the combined sprays.

Compound% active ingredient% kill Live mites / leaf after concentration (48 hours) 8 days 14 days

2-acetoxy-3-dodecyl-1,4-naphthoquinone (I) 0.0005 94 272 135

Benomyl (II) 0.03 2 324> 500

I and II 0.005 \ 93 3 3

0.03 /

Example 18

Mite-infected bean plants were sprayed until a combination of the two substances. After 8 days of fen formation with a 25% emulsifiable composition, the degree of killing was determined, a high level of 2-acetoxy-3-dodecyl-l, 4-naphthoquinone (I) being found with the synergistic effect between I and II (after 12.2% commercially available tetradifone (II) or with the following table).

629651

14

Compound% active ingredient% killing 8-day values concentration (48 hours) Living infestation *

Mites / leaf

2-acetoxy-3-dodecyl-1,4-naphthoquinone (I)

0.0005

80

261

3rd

Tetradifon (II)

0.002

4th

99

9.8

0.001

0

117

9.7

I and II

0.0005 \ 0.002 /

85

6

3rd

I and II

0.0005 \ 0.001 /

85

4th

1.5

* 0 = no infestation 10 = plant died s

Claims (8)

629651 1. ACARICIDAL AND APHICIDAL AGENT, characterized in that it is an inert carrier and as an active ingredient at least one compound of formula (I) X O 0-C0-R2 Y 0 contains, wherein Rj is a straight-chain, branched or cyclic alkyl radical with 8 to 14 carbon atoms, R2 an alkenyl radical with 2 to 17 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, the methoxymethyl radical, the ethoxymethyl radical, the 2-carboxyethene radical , a straight or branched chain alkyl group having 1 to 17 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, and X and Y, which are the same or different, are hydrogen, fluorine, chlorine, bromine, methyl or methoxy. 2. Composition according to claim 1, characterized in that it is an active ingredient a compound of formula (I), wherein Rx is a straight-chain alkyl group having 12 to 14 carbon atoms and R2 is an alkyl group having 1 to 6 carbon atoms, where X and Y does not both mean hydrogen. 3. Means according to claim 1, characterized in that it also contains a "superior oil". 4. Composition according to claim 1, characterized in that it also contains at least one of the following agrochemically active substances: chlorodime form, formetanate, propargite, tetradifone and benomyl. 5. Use of the agent according to claim 1 for the protection of animals and plants against the infestation of mites or aphids, characterized in that an acaricidal or aphicidal effective amount of the agent is applied to the object to be protected. 6. Use according to claim 5, characterized in that the pesticide is used to treat apple, citrus or peach trees, cotton, peanuts or beans. 7. Use according to claim 6, characterized in that apple trees are treated at certain intervals in the growing season. 8. Use according to claim 5, characterized in that 0.03 to 15 kg of active ingredient per hectare, in particular 0.06 to 8 kg, preferably 0.1 to 4 kg per hectare.