FI57044C - BLANDNING LAEMPLIG FOER BEKAEMPNING AV KVALSTER OCH BLADLOESS - Google Patents

Description

R3BF1 [B] (11) MONTHLY PUBLICATION r? 044 lJ UTLÄGGN INGSSKRIFT 3 un * (51) Kv.ik? / I «.ci.3 A 01 N 31/06 ENGLISH —FINLAND (21) P * t * nttlh * k * mu * —P «** nt» n »eknlnj 7531 ^ 7 (22) Hakamiipllyt - Anattknlngsd ·· 10.11.73 (23) AlkupUvi — Glltlgh * tsdt | 10.11.75 (41) Gotten stuck - Bllvlt offuMlIf 11.05.77

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Patent * och rcgiltcrctyrtlMn Antöktn utlajd och utl.tkrlfttn public · ™! 29.02.80 - (32) (33) (31) Privilege claimed —Begird priorltet (71) E.I. du Pont de Nemours and Company, 1007 Market Street, Wilmington,

Delaware 19898, USA (72) Russell Frank Beilina, Wilmington, Delaware, Dennis Lynn Fost,

Wilmington, Delaware, USA (US) (7 * 0 Oy Kolster Ab (5L) A mixture suitable for the control of mites and aphids - The present invention relates to a mixture suitable for the control of mites and aphids which can be applied to a protected object, which is, for example, apple tree, lemon tree, peach tree, cotton bush, peanut or bean, during the growing season.

The mixture according to the invention is characterized in that it contains a compound of formula

0 S

COC

0 2 57044 having an alkyl group having 8 to 1, preferably 11 to 1 carbon atoms which is either branched, cyclic or straight-chain, and R 1 represents an alkyl group having 1 to 6 carbon atoms which is either branched or straight-chain, preferably a methyl or ethyl group, or a cycloalkyl group containing 3 to 6 carbon atoms, and a paraffin oil.

Some 2-alkyl-3-hydroxy-1,4-naphthoquinone carboxylic acids and their corresponding ester compounds are known from U.S. Patents 2,553,6V7 and 2,553,6U8. These compounds are reported to have anti-malarial activity.

Nakanishi et al., J. Am. Chem. Soc. 1952, 3910-3915 describes the corresponding undecyl compound of 2-alkyl-3-hydroxy-1,1-naphthoquinone. The use of the compound is not described.

It has now been found that the novel compounds of the formula I are acaricides and aphids. This means that when an effective amount of these compounds is contacted with mites or aphids, these pests die. The compounds are therefore useful in protecting plants and animals from damage caused by ticks or aphids.

Preferred due to their ease of synthesis and high mite and aphid killing effect are those compounds of formula I wherein R 1 is an alkyl group having 11 to 1 carbon atoms which is either branched or straight chain, most preferably straight chain, and R 1 is an alkyl group having 1 to 1 carbon atoms. The following compounds are particularly popular due to their high acaricidal and aphidicidal activity: 3-acetoxy-2-n-tetradecyl-1H-naphthoquinone, 3-acetoxy-2-n-dodecyl-1H-naphthoquinone, 3-propionyloxy-2- n-tetradecyl-1H-naphthoquinone, 2-n-dodecyl-3-propionyloxy] -N-naphthoquinone, 3-cyclopropylcarbonyloxy-2-n-tetradecyl-1H-naphthoquinone, 3-butyryloxy-2-n-dodecyl-1 N-naphthoquinone, 2-n-dodecyl-3-isobutyryloxy-N, N-naphthoquinone, 3-cyclopropylcarbonyloxy-2-n-dodecyl-N-naphthoquinone and 3-butyryloxy-2-n-tetradecyl-N-naphthoquinone.

The mixture according to the invention preferably contains 5% by weight of paraffin oil. By paraffin oil is meant a paraffin oil fraction having a Saybolt viscosity of 56-106 sec at 37 ° C (so-called "superior oil", see Chapman et al. J. Econ. Ent., 1962, 55: 737-3).

3,57044

The compounds of the formula I can be prepared as described in J. Am. Chem. Soc. and in accordance with the methods of U.S. Patent Nos. 2,553,6h-7 and 2,553,648. The final step of the synthesis can also be completed by treating the corresponding 2-alkyl-3-hydroxy-1,4-naphthoquinone with an acid chloride or acid anhydride with at least one equivalent of an amine such as pyridine or triethylamine dissolved in the reaction mixture. The following examples are provided to illustrate this method.

Example 1 Preparation of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone O-ch3 "-ciA5

A mixture of 2.0 parts of 2-n-dodecyl-3-hydroxy-1,4-naphthoquinone, 0.81 part of triethylamine, 0.63 part of acetyl chloride and 50 parts of methylene chloride was stirred at room temperature for 30 hours. The resulting mixture was partitioned between methylene chloride and aqueous. The methylene chloride phase was separated, dried over magnesium sulfate and evaporated under reduced pressure. The residue was crystallized from petroleum ether (b.p. 30-60 °) to give], 2 parts of 3-acetoxy-2-n-dodecyl], 4-naphthoquinone, m.p. 57 'at 58 ° C.

Example 2 Preparation of 2-n-dodecyl-3-propionyloxy-1,4-naphthoquinone S ° y \ AY0CCH2CH3 O

A mixture of 4.0 parts of 2-n-dodecyl-3-hydroxy-1,4-naphthoquinone, 4.4 parts of propionic anhydride and 50 parts of pyridine was stirred at room temperature for 16 hours. The resulting mixture was evaporated under reduced pressure to remove pyridine. The residue was crystallized from methanol to give 2.9 parts of 2-n-dodecyl-3-propionyloxy-1,4-naphthoquinone, m.p. 42-44 ° C.

It 57044

The following compounds can be prepared in an analogous manner:

@CC

0 R ^ R2 Melting point or refractive index -n-c8H1T -n-C3H7 -n-c9H19 -C2H5

-η-ΟηΗ23 -CH3 51-53 ° C

-n-C11H23 -CH2CH3 n25 1, 5209 ~ n ~ C11H23 -CH2CH2CH3 n25 ^ 131 131 -n-CnH23 -CH (CH3) 2 n25 1.5155

-n-C12H25 -CH3 57-58 ° C

-n-C12H25 -CH2CH3-n-C12H25 -CH2CH2CH3 n ^ 5 1.5120 -n-C13H27 -CH3 -CH2-CH-C9H19 -CH3 CH3 CH3- (CH2) g-CH (CH3) 2 -CH-CH3 - (CH2) k- <2> -CH2CH3 '“a

-n-O] 1 (H29 -CH3 62-63 ° C

-η-0] 2Η25 -CH (CH3) 2 njp 1.5157 ~ n_C10H21 _CH3

'n ~ ClUH29' CH2CH3 52-53 ° C

-n-ClUH29 CH2CH2CH3 1 + 0-H1 ° C

^ Chp

-n-ClitH29 -CH 2 ^ 65-67 ° C

CH2 5 57044 R R2 Melting point or refractive index o

-n-C H -CH 2 ^ 59-61 C

° ^ ch2

- C, 2H25 - (b) 50-52 ° C

-n-C12H25 ~ (°] -n-C12H25 - (CH2) uCH3 ιξ3 1.5133 _n "C12H25" C ^ CH3 ^ 3 "d5 1.5133" The compounds of the formula I can be used for the control of mites for the protection of both plants and animals. More specifically, fruit, arable crops, vegetables and ornamentals, as well as birds and other warm-blooded animals, including humans, can also be protected.

Upon contact with the compounds of formula I, the mites become immediately irritated and leave the area, or they die if they have received a sufficiently high dose. More plants and animals are able to tolerate a small number of mites without a visible backlash, but the reproductive capacity of pests is usually huge. Often, pink populations grow rapidly, so that their numbers easily exceed their ability to fight cancer and robberies. When they notice a rapid increase in ticks, farmers must take immediate action to prevent damage to economically important crops. In this case, a method for the immediate reduction of pink growth is needed in order to prevent harm to important plants or animals.

Similarly, the compounds of formula I are also useful against aphids and can be used to protect fruits, field and vegetable plants, ornamentals, and other plants from aphid attack. When these are applied to aphids or to an area plagued by aphids, pests die or disappear from the plants.

The composition of the invention is very effective, so very small amounts of active compound are needed to produce mite and aphid killing activity; 6 57044 In addition, the compounds are not immediately washed away from the leaves by rain.

They do not have any detrimental effect on ladybugs, which are important mite and aphid control agents, and the compounds are rapidly degraded in the environment. The compounds are also effective against phosphorus compounds resistant to tick species.

The amount of compound required to produce a mite- or aphid-killing effect depends on the situation. Factors to be considered in determining the amount of chemical to be used include the compound in question, the species of mite to be controlled, the weather conditions, the plant species, the stage of plant development, the amount of material to be sprayed, the population damage, and the time between sprays. In order to protect plants, solutions or suspensions containing as little as 5 ppm of active ingredient in the solution to be sprayed may prove effective under certain conditions. However, when spraying fields and using large amounts, sprayable aqueous solutions containing 000 ppm of active substance are generally useful. Suspensions containing 80-1000 ppm are preferred, and most preferably contain 150-500 ppm. With a starting area, the acceptable amount is generally 0.03-15 kg / ha, preferably 0.06-8 kg / ha, and most preferably 0.1-1 + kg / ha. In garden use, spraying is continued until disappearance is detected.

Mixing the compositions of this invention with other agricultural pesticides or excipients may be desirable or beneficial. Mixtures of this kind often increase the effectiveness of spraying against mites, as well as expand control options to include other pests such as insects, fungi, nematodes, or bacteria. The effectiveness of purified fuel oil or other high quality oil and substance mixture used as spray oil on ticks has been shown to be greater than the combined effect of the ingredients.

Other pesticides to be mixed with the compounds of formula I to provide a broader spectral activity include: "diazinon", i.e. O, O-diethyl-O- (2-isopropyl-1 + -methyl-6-pyrimidyl) -phosphorothioate, "disulfoton", i.e. 0,0-diethyl S-2- (ethylthio) ethylphosphorodithioate, "phorate", i.e. 0,0-diethyl S- (ethylthio) methylphosphorodithioate, "oxamyl", i.e. S-methyl 1- (dimethylcarbamoyl) -N-N-methylcarbamoyl) oxythioimidate , "methomyl", i.e. S-methyl N- (methylcarbamoyloxy) thioacetimidate, "benomyl", i.e. 1-butylcarbamoyl-2-benzimidazolecarbamic acid methyl ester, "captan", i.e. N-trichloromethylthiophthalimide, "maneb", ", i.e. 5,6-dihydro-2-methyl-1H-oxatin-3-carboxanilide, and" streptomycin "i.e. 2,1 + -diguanidino-3,5,6-trihydroxycyclohexyl-5-deoxy-2-O - (2-deoxy-2-methylamino-not-glykopyranosyyli) -3-formyylipentofuranosidi.

7 57044

The compounds are particularly suitable for the protection of live plants, such as fruit-bearing trees, nut-bearing trees, ornamental trees, forest trees, vegetable plants, horticultural plants (ornamental plants, small fruit and berry plants) and cereals and seeds. Apple trees, peach trees, cotton, citrus trees, beans, and peanuts are particularly susceptible to mite and aphid damage, and these plants can be protected using the compounds of this invention. To ensure control for the entire growing season (i.e., from June to August in the northern hemisphere), multiple sprays can be performed periodically.

Several species of mites can be controlled using the compositions of this invention. The following is a list of typical susceptible mites and the types of damage they cause: Panonychus ulmi (European red mite) and Tetranychus urticae (two-spotted mite), commonly referred to as "garden mites", which attack a variety of sensitive tree species such as apple, pear, pear -, plum, and peach trees; Tetranychus atlanticus (Atlantic or strawberry mite), T. cinnabarinus (carmine spider mite) and T. pacificus (Pacific mite); attacking cotton and many other crops Paratetranychus citri (lemon mite) and mites attacking other citrus plants; Phyllocoptruta oleivora, which causes citrus rust; Bryobia praetiosa (clover mite), which attacks clover, alfalfa and other crops; and Aceria neocynodomis, which attacks grass species as well as other plants.

The aphids to be controlled with the compositions of this invention include the black bean aphid, Aphis fabae; green peach aphid, ifyrzus persicae; apple aphid, Aphis pomi; pink apple aphid, Annezphis roseus; potato aphid, Macrosiphum euphorbiae; green lude, Toxoptera graminum; cabbage aphid, Byevicornye byassiere and green citrus aphid, Aphis spiraecola.

The mixtures according to the invention can be prepared by conventional methods. These mixtures include powders, granules, beads, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrated solutions, etc. Several of these can be used as such. Spray preparations can be dissolved in media and used in dilutions ranging from a few liters to several m / ha. Very strong masterbatches are usually diluted before use. The compositions contain from 1 to 99% by weight of active ingredient and at least one of the following: a) about 0.1-20% of surfactant and b) about 5-99% of solid or liquid solvent. More specifically, they contain the following ingredients in approximately the following proportions: 8 57044

table 1

Active Solvent Surfactant component (s) substance (s)

Wettable powders 20-90 0-7 ^ 1-10 Oily suspensions, emulsions (including emulsifiable concentrates, including 5 ~ 50 Ϊ + 0-95 0-15), solutions

Aqueous suspensions 10-50 J + 0-8U 1-20

Powders 1-25 70-99 0-5

Granules & Beads 1-95 5-99 0-15

Very strong compositions 90-99 0-10 0-2

The compositions may, of course, contain a greater or lesser amount of the active ingredient, depending on the intended use, as well as the physical properties of the compound. Higher surfactant to active ingredient ratios are desirable in some cases and are achieved by adding the active ingredient to the original composition or mixing it into a container, already diluted mixture.

Typical solid carriers are described in Watkins et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J. More absorbent solid carriers are used to make moisturizing flours and heavier carriers to make flours. ! ^ wrinkled liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd. Edn., Interscience, New York, 1950. A solubility of less than 0.1% is preferred in the preparation of suspension concentrates; the suspension concentrates are preferably resistant to phase separation at 0 ° C. In "McCutcheon's Detergents and Emulsifiers Annual," Allured Pub. Corp. Ridgewood, New Jersey, as well as Sisley and Wood in "Encyclopedia of Surface Active Agents," Chemical Pub. Col, Inc.,

New York, 196k, lists surfactants and recommends various uses.

The compositions may contain small amounts of other additives to reduce foam, agglomeration, corrosion, microbiological vegetation, and the like. Preferably, the ingredients should be approved by the U.S. Environmental Protection Agency for their intended use.

Methods for preparing the compositions of the invention are well known. Solutions are prepared simply by mixing the ingredients together. The finely divided compositions are prepared by mixing together and usually grinding in a 9,57044 hammer mill or colloid mill. Suspensions are prepared by wet milling (see, e.g., U.S. Patent 3 θ 6θ 081 ·). Granules and beads are prepared by spraying the active ingredient onto an already finished granular carrier or using an agglomeration technique (see J. E, Browning, "Agglomeration, Chemical Engineering, December 1, 1967, page 177, and Perry's" Chemical Engineer's Handbook ", Ith Ed. ., McGraw-Hill, NY, 1963, pp. 8-59).

Reference is further made to the following references: U.S. Patent 3,576,831 (column 5, line 36 to column 7, line 70, and Examples 1-1, 17, 106, 123-110), and U.S. Patent 3,560,6] 6 (column 3, line 18 - column 7 »line 26, and Examples 3-9, 11-18), and E. Somers," Formulation ", Chapter 6, in Torgeson," Fungicides ", Vol. I, Academic Press, New York, 1967.

A further particularly convenient preparation on a small scale is an "aerosol" which is filled under pressure into a suitable container. The active ingredient may be in the form of a suspension, emulsion or solution. The solutions are popular due to their ease of preparation and use. The pressure is provided by the use of liquids with low boiling points, such as propane or chlorinated and / or fluorinated hydrocarbons, or relatively highly soluble gases, such as carbon dioxide or nitric oxide. Chlorine and fluorine substituted hydrocarbons are preferred because they have a strong solubilizing ability and do not ignite.

The mite-like effect of the compounds of formula I is described in the following examples.

Example 3

The experimental units consisted of two flower pots, each containing “two rose beans in the two-leaf stage. The plants were infested with double-spotted mites, and the plants were sprayed with solutions of the compounds of formula I until the solution drained from the leaves. The solutions were prepared by dissolving weighed amounts of the active ingredient in 10 ml of acetone, after which the solution was diluted to its final volume with water containing 1: 3,000 TREM OlU surfactant. (TREM 011+ is a trademark used by Nopco Chemical Company for polyhydric alcohol ester). Mortality was assessed two days after injection. The results are shown in Table 2.

10 57044

Table 2

compounds

O S

oir I | 1 Mortality of ticks {%) 0 R 0.005 0.002 0.001 0.0005 0.00025 # solution n-C12H25 -CH3 100 100 100 60 n "C] 2H25 -ch2ch3 100 100 99 90 56 n-C12H25 -CH2CH2CH3 100 100 99 n "C12H25 -CH (CH3) 2 100 100 99 nC ^ H -CH3. 99 98 98 1 + 5 26 n_C11H23 -CH2CH3 100 92 n_C]] H23 -CH (CH3) 2 100 9¾ 9 * + nC] 2" 25 - <] 100 100 100 98 i + i + nC] 2H25 -c (ch3) 3 100 100 - 65 nC ^ H - (CH2) uCH3 100 100 99 93 Ui n-C12H25 "(CH2) 5CH3 100 100 - 70

Example U

Bean seedlings were sprayed with a solution of TREM 01U (1: 3,000), water and 3-acetoxy-2-n-dodecyl-1,1 + -naphthoquinone. The sprayed seedlings were allowed to stand for 3 days before infection with double-spotted mites. The result was evaluated 1 and 11 days after infection.

Spray solution Power 1 day Power 11 days after active ingredient concentration wedged radiation {%) 0.01 99% dead 100% dead 0.005 90 "100" 0.002 58 "(new mites develop)

Example 5

Bean seedlings were sprayed with a solution of TREM 0.11 (1: 3,000), water and 3-acetoxy-2-n-dodecyl-1,1-naphthoquinone. The sprayed seedlings were allowed to stand for 3 days, after which they were precipitated with 7 mm of water. After drying, the seedlings were infected with double-spotted mites. Mite mortality was assessed 1 and 11 days after infection.

11 57044

Spray solution Power 1 day Power 11 days after active ingredient concentration after ration (#) 0.01 97 # dead 100 # dead 0.005 9b "99" 0.002 k2 "(no dead detected)

Example 6

Approximately 13 cm tall apple seedlings grown from seed were infested with European red mites, after which the seedlings were sprayed with aqueous solutions of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone, also containing 1: 3,000 TREM and water until the solution dripped from seedlings. Mite mortality was assessed 2 days after injection.

Mortality # active substance concentration (#) of the spray solution 0.005 100 0.002 100 0.001 100 0.0005 95

Example 7

Rose beans infected with double-spotted aphids were sprayed with a solution of 3-acetoxy-2-n-dodecyl-1,4-naphthoquinone alone, as well as a mixture of said solution and 1 # UNICO 2 spray oil. Evaluations are the averages of 3 experiments and were performed 3 days after wedging from spraying. The results showed that when the compounds of formula I were used in combination with a spray oil, a result was obtained which was better than the combined effect of the ingredients.

Compound Concentration Mortality- # 2-acetoxy-3-dodecyl-1,1 * - 0,002 100 naphthoquinone. 0.001 99 0.0005 86 0.00025 23 0.0001 2 2-Acetoxy-3-dodecyl-1,1 * -naphtho-0.002 100 quinone + 1 # UNICO11 oil Q 0Q1 100 in spray solution '0.0005 100 0.00025 97 0.0001 60 1 # UNIC01) spray oil 0 1 ^ UNIC0 is a trademark used by United Co-operatives in Alliace, Ohio. The product is a refined petroleum distillate containing 3% of inert ingredients.

57044

Example 8

The bean rose beans were sprayed with 2-dodecyl-3-acetoxy-1,1-naphthoquinone solutions at concentrations of 10, 5, and 2.5 ppm until the solution drained from the plants. Two sets of experiments, each with two specimens for each solution, were performed. In one set of experiments, test plants were infected with normal double-spotted ticks, and in another set, plants were infected with a methyl parathion-resistant tick species. The results are presented below and show that methyl parathion-resistant mite species are as susceptible as normal mites to the mixtures of this invention.

Mite mortality after U8 hours (%)

Normal mites of the active ingredient Mites resistant to methyl parathion concentration (%) 0.001 100 100 0.0005 80 81

The aphid killing properties of the compounds of formula I are described in the following examples.

Example 9

Nasturtium seedlings planted in pots were infected with black bean aphids and sprayed with 2-acetoxy-3-dodecyl-1,1-naphthoquinone at concentrations of 100, 50 and 25 ppm while standing on a rotating medium. Mortality calculations were performed 72 hours after injection, and the results are shown below.

Mortality # concentration {%) of the spray solution 0.01 100

0.005 JOO

0.0025 89

Example 10

Solutions of compounds of formula I were sprayed at concentrations of 150 ppm on potted nasturtium plants infected with black bean aphids. Spraying was performed until the solution was drained from the plants with a hand-held "Son-of-a-Gun" syringe (reg.). The spray solution contained Du Pont L-1J * U-EDG as a wetting agent in a ratio of 1: 2,000. Mortality calculations were performed After 2k hours. The results are shown in the following table.

13 57044 o ^ X X-Ro o R ^ R ^ Aphid mortality- ^ ° 12H25 -CH3 100 C1UH29 “CH3 99 C12H25 -CH2CH3 98 C] ltH29 -CH2CH3 99 C12H25 / -fH2 ° -CH | 97 ^ ch2

= CH

C1UH29 - ° H I 93 ^ ch2 c] 2h25 -ch2ch2ch3 98 C1 * 9 -ch2ch2ch3 87

Example 11

The green peach aphids on the plates cut from Chinese cabbage leaves were sprayed with acetone solutions of the compounds of formula I with the leaf plates on a rotating spraying pad. The leaf plates were kept under unchanged environmental conditions for 2k h, after which the mortality calculation was performed. The concentrations used and the percentage mortality of aphids "are shown in the table below.

lit 57044 oo “Λ \ R1 O Aphid mortality- # ^ Rg OjJ 0.05 0.01 0.005 # solution C ^ H -CH3 100 100 90 86 C11 + H29 -CH3 100 89 85 69 C12H25 -CH2CH3 100 100 91 + 81+ C ^ H 'CH2CH3 100 100 98 83 ^ ψ2 CH -CH I 100 100 88 71 5 ^ ch2

= CH

Cl1 + H29 "Ci ^ CH 97 66 80 25 C12H25 -CH2CH2CH3 100 100 83 75 C ^ H -CH2CH2CH3 100 100 93 79

Example 12

Golden Delicious dwarf apple trees were sprayed with an aqueous emulsion containing 2-acetoxy-3-dodecyl-1,10-naphthoquinone using commercial spraying equipment. Spraying was performed U times every week, starting on May 8, at a concentration of 3.91, 7.82 and 31.28 ml of 25 # commercial product / 100 l of water. The calculation performed three days after the last spray showed that the control was excellent, as shown below. In non-sprayed control trees, the average number of aphids was 573 (per branch).

Concentration of spray solution Mortality rate of apple aphids # (ml / 100 1) 3.91 93.7 7.82 97.6 31.28 99.8

Claims (3)

15 57044 A mixture suitable for controlling mites and aphids which can be applied to a protected object, such as an apple tree, a lemon tree, a peach tree, a cotton bush, a peanut or a bean, during the excavation period, characterized in that it contains a compound of the formula An alkyl group having 8 to 1, preferably 11 to 11 carbon atoms, which is either branched, cyclic or straight-chain, and is an alkyl group having 1 to 6 carbon atoms which is either a branched or straight-chain, preferably a methyl or ethyl group, or 3 A cycloalkyl group containing -6 carbon atoms, and a paraffin oil. A mixture according to claim 1, characterized in that said compound is 3'-ethoxy-2-n-dodecyl-1, U-naphthoquinone. Mixture according to Claim 1, characterized in that the compound is 3-propionyloxy-2-n-dodecyl-1,1-naphthoquinone. A mixture according to claim 1, characterized in that the compound is 3-butyryloxy-2-n-dodecyl-1,1-naphthoquinone.