NL8400567A - NEW CHINAZOLINES. - Google Patents

Description

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New ochinazolines

The present invention relates to non-4-alkylaminoquinazoline compounds of 4-alkylaminoquinazolines and their use as acaricides is known, inter alia, from U.S. Patent No. 3,541,094. The use of compounds of this structural class to control ticks is known from U.S. Patent 4,331,667.

It has now been found that compounds of the formula I in which R is 2-decyl or 2-decyl have very valuable pesticidal properties.

Are the compounds of formula I new? they have not been specifically mentioned in any publication so far.

The compound of the formula I wherein R is 2-decyl {i.e. CH (CH ^} - (CH ^ 1} is hereinafter referred to as compound 15A) and the compound of the formula I, wherein R2 is undecyl {i.e. CH ( CH_) - (CH-} 0-CH-} is hereinafter referred to as compound o Zoo B,

The invention also relates to a process for preparing the compounds of the formula I, wherein a compound of the formula II, wherein X is halogen, is reacted with an amine of the formula III, wherein R has the above meanings.

-X is preferably Cl or Br, especially Cl.

The process of the invention can be carried out in a manner known per se for the preparation of 4-alkylaminoquinazoline compounds. The reaction can be carried out well in the presence of an acid-binding agent, such as ^ 200 ^.

The compounds of formula I can be recovered from the reaction mixture in which they are formed by operating in the usual manner. Acid addition salts of the compounds of the formula I can be converted into the free base form in the usual manner and vice versa.

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The compounds of formulas II and III are known or can be prepared in analogy with known methods or with the examples given here.

The compounds of the formula I have a surprisingly strong anti-tick-acting action, in particular against stems which are resistant to phosphoic acid esters having anti-tick-acting action, such as the Mt Alfordstara of the bovine tick Boophilus.

The beneficial anti-inflammatory activity of the compounds of the invention is illustrated in Table A wherein Compound C 10 is 4- (n-C 1 H 3 NH) quinazoline and Compound D is 4- (n-C 2 H 3 NHN) quinazoline.

TABLE A; Effect against the bovine tick, Boophilus microplus Mt Alford, on resistant strain

15_dpn active substance_% E

Compound A 2000 100 500 100 125 0 20 B 2000 100 500 100 125 11 C 2000 11 25 500 2 125 0 D 2000 78 500 0 30 125 0% E = inhibition propagation power in%

Field test results also indicate a very favorable acaricidal activity of the compounds of the formula I. Represents 9400567 Active results of field tests on acaricidal activity are shown in the following table: TABLE B; Acaricidal action on apple trees (Golden delicious) against the European red mite, Panonychus ulmi, 8 days 5 after application (spray volume 1200 1 / ha). Elaboration in% (% E) according to the formula of Henderson% Tilton.

Quantity in

% active ingredient% E

Compound A 0.100 100 10 0.050 100 0.025 97 B 0.100 100 0.050 100 15 0.025 96 C 0.100 98 0.050 95 0.025 91 20 D 0.100 91 0.050 97 0.025 82 25 Furthermore, it was surprisingly found that differences of the 4-alkylaminocomazolines also have insecticidal activity, including insecticidal / ovicidal action. In particular, the compounds of formula IV including n-nonyl, n-decyl, 2-decyl or 2-undecyl, hereinafter referred to as compounds of the invention, have an interesting spectrum of activity because, in addition to a valuable acaricidal activity, they have a have an interesting insecticidal effect.

The compounds of the invention may exist in free base form or in the form of freeze addition salts with inorganic or organic acids (eg BC1, acetic acid, methane-sulfonic acid), but they are preferably used in free base form.

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The insecticidal activity of the compounds of the invention has been demonstrated in laboratory tests with test concentrations of 20 to 500 ppm of Jlhaedon cochleariae and of 60 to 1000 ppm against leaf lice such as Myzus persicae and Aphis fabae. The activity of the compounds of the invention against sucking insects is confirmed by field tests against the pear psylla,

Psylla pyri, with test concentrations from 0.025% to 0.1% (spray volume: 1200 l / ha).

Representative test results from the last field trials are shown in the following table: TABLE C: Insecticidal activity on pear trees (Williams), against the pearpsylla, Psylla pyri, 3 days after application spraying volume: 1200 l / ha).

Effect in percent (% E) according to the formula of

Abbott.

15 Quantity in

_% active substance_% E

Compound A 0.100 93 0.050 96 0.025 93 20 B 0.100 98 0.050 93 0.025 88 25 C 0.100 90 0.050 87 0.025 85 D 0.100 97 30 0.050 86 0.025 86

Laboratory tests with the 4-alkylaminoquinazolines, in particular with the compounds of the invention, also show an interesting insecticidal activity against the eggs of 8400567 * t -5- including Spodoptera littoralis, Spodoptera exigua, Anagasta kuehniella, Diabrotica balteata, Epilachna varivestis and Phaedon cochleariae. An indication of the relative strength of ovicidal activity is given in the following table.

5 TABLE D: Ovicidal action against insect eggs.

Dose causing 95% mortality (LC 95) (yg active substance / 2, αα).

Anagasta Spodoptera Phaedon _kuehniella_littoralis cochleariae 10 Compound A 2.2 1.4 1.7 B 5.9 2.9 1.5 C 1.2 1.9 0.2 D 1.8 5.3 0.6

Chlordine form 2.7 0.2 26.8 15 Amitraz 81.9 3.6 24.9

Good ovicidal activity of the compounds of the invention was also found in field trials against the eggs of the grape moth, Lcöesia botrana.

TABLE E: Ovicidal activity against grape moth eggs, Lobesia botrana (third generation), 33 days after application (spray volume: 180 l / ha).

Effect in% (% È) according to the Abbott formula. Quantity in

__% active substance% E

^ Compound A 0.20 85 0.10 67 0.05 63 B 0.20 75 30 0.10 59 0.05 34 C 0.20 87 0.10 70 35 0.05 53 3400 567 • * -6- D 0.20 52 0.10 52 0.05 37 5 Amitraz 0.20 26 0.10 46 0.05 35

The spectrum of action of the compounds of formula I against plant harmful organisms is similar to that of Amitraz and their potency is generally greater than that of Amitraz. The compounds of the invention are relatively nontoxic and are well tolerated by crop plants, such as green beans, tomatoes, grapes, corn, fruit trees, cotton, peanuts, cabbage plants and lettuce, under greenhouse conditions and field conditions.

In view of their beneficial acaricide (including tick control) and insecticide (including insecticide / ovide) activity, the compounds of formula I can be used to control harmful organisms, such as animal parasites in animals, for example, in livestock such as in cattle and sheep) phytophagus, mites and insects in harvest plants.

Thus, the invention provides a method for controlling harmful organisms, wherein a pesticide is applied to its location an effective amount of a compound of the formula I in free base form or in pesticide-acceptable acid addition salt form.

An aspect of this method is a method of controlling ectoparasites in the herd, wherein an ectoparasite is applied locally to the animal, effective amount of compound of the formula I.

The compounds of the invention are applied to ectoparasites or to a site in free base form or in agriculturally acceptable form. acid addition salt form, for example as hydrochloride or acetate, by topical treatment of animals, for example by spraying by dipping or by spraying 8400567 forms just diluted with water. The compounds of the formula I are preferably used in free base form. The degree of dilution can vary within relatively wide limits. A suitable concentration of the use form is 0.01 to 5.0%, in particular 0.02 to 1.1%, calculated as the weight of the active substance, for example 350 grams / 1000 liters of immersion liquid or 2 grams, respectively. 5 g / 10 1 spray liquid. The treatment is preferably repeated at 7 to 21 day intervals.

For economic use, the compounds of formula I can be well processed into a sprayable powder, a sprayable powder concentrate, wettable powder, emulsifiable concentrate or into a solution with conventional solid or liquid additives, especially as liquid concentrates, especially as liquid concentrates concentrates containing 3.0 to 50% by weight, for example, 20 to 35% by weight of the compound of formula I, which concentrates are diluted with water before use. Such a liquid concentrate preferably contains an emulsifying agent, such as a polyglycol ether, which is derived from a high molecular weight alcohol, mercaptan or alkyl phenol and alkylene oxide, as well as a diluent, such as a liquid aromatic hydrocarbon or mineral oil.

The parasites against which the compounds of the formula I are active include ticks and flesh flies. Tken, against which the use of the compounds of the formula I is indicated, include the family Ixodidae, for example, the bovine tick, such as Boophilus decoloratus and Boqphilus annulatus, Rhipicephalus spp such as Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalert pulushiphalipulus pulhipus Hyalorana truncatum, Hyalcmma rufipes, Hyalonma detritum, 20 Hyalcmma marginatum, Hyalorma drcmedarri and Hyalcmma anatolicum excavatum, Anblycmma spp such as Amblycnma variegatum, Anblycrana hébraeura, Jbtcmlyfraynumsese macroanmamase macroonmarose macartum for example, Otdbius spp. such as Otobius 25 megnini and Omithodoros spp. such as Grnithodoros savignyi, Omithodoros lahorensis and Omithodoros tholozani, the family Psoroptidae 8400567 * * -8- for example Psoroptes oyis and Psoroptes bovis Sarcoptidae bovis. Flesh flies, against which the use of the compounds of the formula I are indicated, include the Lucilla spp., Such as Lucilia cuprina and Lucillia sericata 5 in sheep.

The excellent acaricidal activity of compounds of the formula I against phytophagous mites in combination with their insecticidal activity is an important advantage of these compounds over many pyrethroids, which, although they have insecticidal activity, tend to increase the mite population in plants.

Another aspect of the method of controlling harmful organisms is a method of controlling phytophagous mites and / or insects in harvest plants, wherein a miticide and / or insecticide effective amount of compound of the formula I is applied in the cultivation area. In addition, the invention relates to the insecticide use of compounds of the invention in crop plants, wherein an insecticidally effective amount of the compounds * of the invention is applied in the cultivation area.

In the case of miticide and / or insecticide use of a compound of formula I or insecticide use of the compounds of the invention, the amount to be applied for achieving the desired effect varies with the crop plants concerned and other standard variables, such as the compound used, method of application, treatment conditions, etc.

Appropriate application rates can be determined by routine testing by those skilled in the art, or by comparing the action of the compounds of the invention with standards whose application rates are known, for example, greenhouse tests. In general, however, satisfactory results are usually obtained when the compound is used in concentrations from 0.01 to 1%, preferably from 0.02 to 0.2%, based on the weight of the active substance, with treatment as necessary 35 repeated. For crop protection, the spray volume in 8400567-9 generally ranges from 500 to 1000 l / ha harvest. The concentration of the spray liquid strongly depends on the method of application and the spray volume. In general, the relationship between spray concentration and spray volume is chosen such that the active substance 5 is administered in an amount of 100-1000 g, preferably of 200-500 g per hectare of cultivation area.

Cultivated plants, for which the miticide use of the compounds of the formula I is indicated, are fruit harvests (for example stone fruit harvests, such as almonds, apricots, peaches, 10 raisins and plums, citrus fruit harvests, such as squash, limes, lemons, tangerines, oranges and tangerines, harvests from apple-like fruits, such as apples, pears and quinces and vineyards), cotton and vegetables (for example, tomatoes, egg plants, peas, beans, kcmkoitmers).

15 Mites against which the compounds of the formula I

as particularly effective are indicated for example: TETRANYCHYS UKTICAE **, two-spotted spider mite, T. PACIFICUS, passive spider mite, 20 t. MLamcüS, T. VIENNEMSIS, BOO®3] RaNXCiiüS CARPINI, PANONYCHUS ÜIMI European red mite, P. CPERI, red lemon mite, 25 ΤΟΟΟΡΈΒΙΠΆιΤΟΟΟΡΈΒΙΠΆ OTEIVORA., Lemon rust mite, including strains resistant to phosphoric acid esters.

Harvest plants in which the insecticidal use of the compounds of the formula I and of the compounds C and D, respectively, are indicated:

Cotton Apple-like fruit

Corn stone fruit

Soybeans Grapes

Potatoes Citrus fruit 35 Tabac Vegetables, for example tool plants 3400567 »* -10-

Harmful insects, against which the compounds of the invention are indicated as particularly effective, are for example: in cotton, corn and vegetables: Lepidoptera, in particular SFODOFTERA spp. (especially eggs) such as: S. LITTORALIS, S. LITURA, S. FRUGIPERDA, S * EXIGUA, HELIQTHIS spp. (especially eggs) such as: H. ARMIGERA, Η. ZEA,

H. VIRESCENS

DIABROTICA spp. (Maize root forms), Coleoptera, (especially eggs) such as: D. ÜM3ECIMEUNCTAEA. for potatoes: IEFIINOTARSA DECEMLINEATA, Coleoptera, (in particular eggs and young larvae)., for apple-like fruits: PSYLLA PYRI, Hornoptera (in particular young pupae), IASPEYRESIA PQMQNELIA, Lepidoptera (in particular 20 eggs).

with grapes: Lepidoptera such as LOBESIA FOTRANA (especially eggs) and EQPOECILIA AMBIGÜELLA (especially eggs). in cabbage plants: Lepidoptera such as PIERIS spp. (especially eggs), ELUTELLA XYLOSTELLA (especially eggs), Coleoptera such as FHAEDON COCHLEARIAE (especially eggs).

for rice: Lepidoptera such as CNAFHALÖCROCIS MEDINALIS, rice leaf roller (especially larvae),

Hornoptera, such as NEPHDi'ETilX CINCTICEPS, green rice-30 leaf roller (especially pupae and adults); and NILAPRAVATA LUGENS, brown rice plant grasshopper (especially peppers and adults).

and NILAPARAVATA LUGENS, brown rice plant grasshopper (especially pupae and adults).

The compounds of the invention can and should preferably be used as j-Disticide preparations (in particular against 8400567 ticks, mites and insects) in combination with agriculturally acceptable diluents. Suitable compositions contain 0.01 to 99 wt% compound of the invention, 0 to 30% agriculturally acceptable surfactant and 1 to 99.99% diluent. Higher surfactant to active ingredient ratios are desirable and are obtained by incorporation into the composition by mixing in a tank. Uses of the composition generally contain 0.01 to 25% by weight of the invention. Lower or higher levels of active ingredient 10 may, of course, be present depending on the intended use and the physical properties of the compound. Concentrate forms of the composition intended for dilution for use generally contain from 2 to 90, and preferably from 10 to 80, weight percent compound of the invention.

Good formulations of the compounds of the invention are sprayable powders, pellets, suspension concentrates, wettable powders, dispersible concentrates, etc. They are obtained in the usual manner, for example, by mixing the compounds of the invention with the diluents.

Liquid preparations are in particular obtained by mixing the components, finely divided solid preparations by mixing and usually grinding, suspensions by wet grinding and granules and pellets by impregnation or coating (of preformed) granular carriers with the active ingredient or by agglomeration methods.

Optionally, the compounds of the invention, for example the compounds of formula I, can be used in microcapsule form.

Agricultural acceptable additives can be used in the pesticidal formulations, for example, to improve the active agent process and / or to reduce moulting, caking and corrosion.

Surfactant is here understood to mean an agriculturally acceptable substance which imparts emulsifiability, extensibility, wettability, dispersibility, or other surface modifying properties. Examples of $ 400 567 -12 surfactants include sodium \ llllisisiS ^ iiffi? RSS};:; and lauryl sulfate.

Diluents are here understood to mean liquid or solid agglomerated substances that are used to dilute a concentrated substance to a useful or desired strength. In the case of sprayable powders or granules, this can for instance be talc, kaolin or diatomaceous earth and for liquid concentrate forms, for example, a hydrocarbon, such as xylene or an alcohol, such as isopropanol, and for liquid application forms, inter alia, water or diesel oil.

The above-mentioned pesticidal preparations, which contain a compound of the formula I as active substance, also form part of the invention.

The compositions of the invention may also contain other compounds with biological activity, for example compounds with similar or complementary activity against ticks, mites or insects or compounds with fungicidal or herbicidal activity.

Some specific examples of pesticidal (tick / mite / insect) active preparations will now be described.

EXAMPLE A; Wettable powder.

25 parts of the compound of the formula I, for example compound B, are mixed with 25 parts of synthetic finely divided silica, two parts of sodium lauryl sulfate, 3 parts of sodium lignin sulfonate and 45 parts of finely divided kaolin, until the average particle size is 5 microns. The resulting wettable powder is diluted with water to a spray of the desired concentration before use.

EXAMPLE B: Emulsifiable concentrate.

20 parts of compound of the formula I, for example compound B, 40 parts of xylene, 30 parts of dimethylformamide and 10 parts of emulsifier (for example ATLOX 4851 B, a mixture of Ca-alkylarylsulfonate and a polyethoxylated triglyceride from Atlas 35 Chemistry QtbH) are thoroughly mixed until has obtained a homogeneous solution. The resulting emulsifiable concentrate is diluted with water before use.

EXAMPLE C; Granules

5 kg of the compound of the formula I, for example compound B, are dissolved in 25 l of methylene chloride. The solution is then added to 95 kg of granular attapulgite (sieveate 24/28 iresh / inch) and mixed thoroughly. The solvent is then evaporated under reduced pressure.

The invention is now further illustrated by the following examples in which temperatures in ° C, pressures in Torr and Rf are values on silica gel unless otherwise indicated.

EPOEBQDUCTEN.

Example I: 4- (Decyl-2-amino) -quinazoline

To a mixture of -165.5 g of 4-chloro-quinazoline and 700 ml of water, 64 g of soda are added portionwise with stirring and then 160 g of 2-aminodecane in one go. The reaction temperature rises slightly and the solid flask contents become soft and ointment-like. The reaction mixture is stirred vigorously, first without heating for 1 hour and then at 80 ° for 3 hours. The reaction mixture is then cooled to 25 ° and stirred until the ointment-like flask contents solidify so that it can be aspirated. The product thus obtained is washed thoroughly with water and dried under water jet vacuum at 50 ° C to yield the relatively pure title product, mp 96 °. Recrystallization from vinegar vacuum nitrile gives the title product, m.p. 100 °.

Example 12 4- (Uhdecyl-2-amino) -quinazoline

The title compound is obtained in analogy to the procedure of Example I using 174.5 g of 2-aminoundecane instead of 160 g of 2-aminodecane.

Melting point 102 ° (from acetic acid nitri!).

35 8400567 -14- ♦ ** INTERMEDIATE PRODUCTS.

Example BS: 2-Amino-decane.

184 g of liquid ammonia and 150 g of Raney-Ni are added to a mixture of 1100 g of mathyl octyl ketone in 2000 ml of ethanol. The mixture is hydrogenated in an autoclave at 80 ° below 100 bar. The hydrogenation is completed after 15 hours. The Raney-Ni is then filtered off, the excess ammonia is evaporated (reflux for 1 hour), the reaction mixture is cooled, 1000 ml (10 mol) of concentrated HCl are acidified and the mixture is evaporated to dryness under water jet vacuum. The residue is treated with 100M-30% NaOH and 400 g of ice and the title compound is partitioned from the aqueous phase and distilled. Boiling point 91-93 ° / 20 mm. The title compound thus obtained, containing about 10% impurities, is used as such in the method of Example I.

15 Example Mi 2-Aminoundean.

The title compound is obtained in analogy with the procedure of Example 10 by hydrogenation of methyl nonyl ketone in the presence of liquid anonia and Raney-Ni. The distillation is carried out at 105-107 ° / 18 mm.

8400567

Claims (11)

Method for controlling insects in a harvesting area, characterized in that an effective amount of a compound of the formal IV, in which R 2 n-nonyl, n-decyl, 2-decyl or 2-decyl or 2, is applied in the harvesting area is undecyl in free base form or in the form of an agriculturally acceptable acid addition salt. 2. A plasticization process for preparing a 4-alkylamino-quinazoline compound is characterized in that a compound of the formula I, wherein R is 2-decyl or 2-undecyl, is in free form or in. acid addition salt form prepared by agitating a compound of the formula II, wherein-X is halogen, with an amine of the formula III wherein R has the same meaning as in the formula I and the compound of the formula I thus obtained in free form or in acid addition salt form. The method of claim 2 substantially as described herein by way of example. Product obtained according to a method of claim 2 or 3. A compound of the formula I as defined in claim 2, in free form or in acid addition salt form. Compound according to claim 5, characterized in that R is 2-decyl. Compound according to claim 5, characterized in that R is 2-undecyl. A method for controlling harmful organisms, characterized in that a pesticide effective amount of a compound of the formula I as defined in claim 2, in free base form or in agriculturally acceptable zinc addition salt form, is applied to the plastered location. A method according to claim 8, characterized in that the harmful organisms are ectoparasites. Soaking method according to claim 9, characterized in that the affected area is an eye area. 11. A pesticidal preparation is carbon black characterized in that it contains a 8400567 ΓΛ ¥ * -ΐβ compound of the formula I as defined in claim 2 in free form or in agriculturally acceptable vacuum salt addition form, optionally in caribination with agriculturally acceptable diluent. t 8400557% * - * = * NH-R r ^ YS NH-X f ^ r ^ N kjl ') II H, NR III NH-R, IV SANDOZ A.G. Basel, Switzerland 8400567