CA1090250A

CA1090250A - Pesticidally active compounds and their manufacture and use

Info

Publication number: CA1090250A
Application number: CA271,480A
Authority: CA
Inventors: Hans-Rudolf Kruger; Clemens Kotter; Hartmut Joppien
Original assignee: Schering AG
Current assignee: Bayer Pharma AG
Priority date: 1976-03-04
Filing date: 1977-02-10
Publication date: 1980-11-25
Also published as: JPS574601B2; DE2609280A1; AU2289777A; SU656462A3; JPS52108022A; CS193084B2; DD129611A5; IL51463A; NL7701575A; FR2342661B1; AU508246B2; LU76644A1; DK50977A; IT1143638B; GB1578852A; IE45599B1; IL51463A0; BE852088A; IE45599L; FR2342661A1

Abstract

ABSTRACT OF THE DISCLOSURE
The present invention provides pesticidally active com-pounds of the general formula I

(I) in which R represents a group of the formula

Description

The present invention is concerned with pesticidally active, especially insecticidally and ovicidally active, 2-propynylamine derivatives and with their manufacture and use.
There have already become known as monoamine oxidase inhibitors, compounds which include, for example, trans-2-phenylcyclopropylamine sulphate, 1-isonicotinyl-2-isopropyl-hydrazine phosphate, isonicotinic acid 2-[2-(benzylcarbamoyl)-ethyl]-hydrazide and also a 2-propyny~amine derivative, namely N-benzyl-N-methyl-2-propynylamine.
It has now been found that 2-propynylamine derivatives of the general formula I

¦ (I) . R-CH2-N-CH2-C_CH

in which, R represents a group of the formula X~

in which n represents 0, 1, 2 or 3 and each X represents an alkoxy group or a halogen atom; when n represents 2 or 3 the substituents represented by X may be the same or different; surprisingly exhibit an outstanding action against insect pests as well as against their eggs.
This action is especially surprising and could not have been foreseen, since the other oxidase inhibitors mentioned above do not have such an action.
The action found is effective, in particular, against Lepidoptera, thus, for example, against Spodoptera littoratis ~Egyptian cotton moth), Namestra brassicae (cabbage moth) and Pieris brassicae (large cabbage butterfly).

Moreover the compounds of the general formula I and their salts are distinguished by a slight toxicity towards warm-blooded animals. Thus, for example, the acute LD50-mouse per os is 700 mg/kg in the case of N-benzyl-N-methyl-2-propynylamine, and 305 mg/kg in the case of N-(2-chlorobenzyl)-N-methyl-2-propynylamine.
Furthermore, as these compounds are particularly well tolerated by plants, they can be used advantageously and without danger against pests in vegetable crops.
As such crops there may be mentioned, for example, crops of cotton, tomatoes, cauliflower, cabbage, dwarf beans, Riff beans, sugar beet, maize and rice.
The present invention accordingly provides a method of protecting a living plant against pests, wherein the plant is treated with at least one compound selected from compounds of the general formula I and salts there~f.

.

I (I) R-CH2-N-C~2-C=CH

in which R represents a group of the formula ,~
X~
in which n represents 0, 1, 2 or 3 and each X represents an alkoxy group or a halogen atom; when n represents 2 or 3 the substituents represented by X may be the same or different, and salts thereof.
The present invention also provides for the use of a pesticidal preparation which comprises at least one compound selected from compounds of the general formula I, in which R has the meaning given above, and salts thereof, in admixture or con-junction with a suitable carrier.
The present invention further pro~ides for the use of a

- 2 -5~) pesticidal preparation which comprises at least two compounds selected from compounds of the general formula I, in which R has the meaning given above, and salts thereof.
The present invention further provides a method of pro-tecting a crop against pests, wherein the crop is treated with at least one compound selected from compounds of the general formula I, in which R has the meaning given above, and salts thereof.
The present invention ~urther provides a pack which com-prises at least one compound selected from com~ounds of the general formula I, in which ~ has the meaning given above, and salts thereof, together with instructions for its use as a pesti-cide.
The most favourable application concentration for the compounds used in accordance with the present invention when applied in the form of pesticidal preparations is approximately 0.01% to 1.0%, preferably 0.05% to 0.2%, by weight; when two or more of these active compounds are used these concentration ranges refer o.f course to the total concentrations.
Optimum actions occur in the case of those compounds in which, according to the general formula I, _ represents 0, 1, 2 or 3 and X represents an alkoxy group containing 1 to 3 carbon atoms or a chlorine atom.
The compounds of the general formula I used in accordance with the present invention may be applied, in each case, in the free form or in the form of salts thereof with inorganic or organic acids~
Among the salts, the hydrochlorides are especially suit-able for use in accordance with the present invention.
Specific compounds and salts which may be used in accor-dance with the present invention are, for example, those ~ 3 listed in the following Table:

~BLE I

C _ ound Physical constant_ _ ~-(4-Chlorobenzyl)-N-methyl-2-propynylamine B.p.: 96-106-C/2 torr 4-Chlorobenzyl-methyl-2-propynyl-ammonium chloride M.p.: 216.5~217C

~-Benzyl-N-methyl-2-propynylamine B.p.: 115-120C/25 torr N-(2-Chlorobenzyl)-N-methyl-2-propynylamine B.p.: 92-94DC/2.5 torr N-(3-Chlorobenzyl)-N-methyl-2-propynylamine B,p.: 94-103C/3 torr N-(3,4-Dichlorobenzyl)-N-methyl- 20 2-propynylamine nD = 1.5497 N-(2,4-Dichlorobenzyl)-N~methyl-2- 20 propynylamine nD = 1.5485 N-(3-Methoxybenzyl)-N-methyl-2-propynylamine B.p.: 102-105C/l torr Benzyl-methyl-2-propynyl-ammonium chloride M.p.: 154-155C ~

2-Chlorobenzyl-methyl-2-propynyl- L
ammonium chloride M.p.: 160-160.5C

3-Chlorobenzyl-methyl-2-propynyl-ammonium chloride M.p.: 182-183.5C

; 20 2,4-Dich~orobenzyl-methyl-2-propynyl-ammonium chloride M.p.; 171-172C

3-Methoxybenzyl-methyl-2-propynyl-ammonium chloride ' M.p.: 165-166C

3,4-Dichlorobenzyl-methyl-2-propynyl-ammonium chloride M.p.: 185-186C
F

The free bases are colourless liquids that are readily soluble in organic solvents, for example hydrocarbons, halogenated hydrocarbons, ethers, ketones, alcohols, esters, carboxylic acid amides and carboxylic acid nitriles. Their solubility in water is slight. The 2-propynylamine derivatives can be isolated easily as crystalline bodies in the form of their hydrogen halide salts; the latter are readily soluble in water, 25~) but only sparingly sol~ble in organic solvents.
The compounds used in accordance with the present invention are known per se or may be prepared by processes known per se. They may be prepared, for example, by the process defined below which is also included within the scope of the present invention.
m~ he present invention accordingly further provides a process for the manufacture of a compound of the general Eormula I, in which R has the meaning given above, or a salt thereof, wherein a propargyl halide of the general formula HC C-CH2-~al in which Hal represents a halogen atom, preferably a chlorine or bromine atom, is reacted in the presence of a solvent and of an acid-binding agent with an N-substituted methylamine of the general formula in which R has the meaning given above, and, if desired, the ~-resulting compound of the ~eneral formula I is converted into a salt thereof with an acid.
- 20 In order to synthesize the compounds of the ', general formula I, the reactants are used in approximately ~;
equimolar quantities, Suitable reaction media are solvents ,~
that are inert towards the reactants. The followiny are 'i mentioned as examples of such solvents: halogenated hydrocarbons, for example methylene chloride, chloroform and carbon tetra-chloride, aliphatic and aromatic hydrocarbons, for example petroleum ether, cyclohexane, benzene, toluene and xylene, alcohols, for example methanol and ethanol, and ketones, for example acetone, methyl isobutyl ketone and isophorone.
The reaction takes place between 0 and 100C, but generally between room temperature and the reflux temperature of the reaction mixture in question.

;);250 Tertiary amines~ for example trieth~lamine or N,N-dimethylaniline, pyridine bases or suitable inorganic bases, for example oxides, hydroxides and carbona-tes of alkali ~etals and alkalineearth metals, are used to bind the hydrohalic acids formed.
As a rule, the propargyl halide is added portionwise to the appropriate N-substituted methylamine and the hydrogen halide acceptor, but it is also possible to add the reactants in the reverse order.
After the reaction has taken place, the hydrogen halide salt formed is removed by filtration and washed with the appropriate solvent. After removing the solvent from the filtrate, the residue is subjected to fractional distillation under reduced pressure and the reaction products are obtained as colourless liquids.
The salts of the 2-propynylamine derivatives may, if desired, be obtained by treating the amines with, for example, ethereal solutions of the acids while cooling.
They can be easily recrystallized from a suitable organic solvent., for example a mixture of ethanol and ether.
The compounds used in accordance wi-th the present invention may be applied alone, or in the Eorm of mixtures with one another or with other active substances. If desired, other plant-protecting agents or pest-comhating agents may be added depending on the purpose desired.
The action and speed of action can be enhanced, for example, by action-increasing additives, for example organic solvents, wetting agents and oils. This permits a reduction in the quantity of the actlve substance itself applied.
The active compounds used in accordance with the present invention or mixtures thereof are advantageously applied in the form of pesticidal preparations, for example powders, strewable preparations, yranules, solu-tions, emulsions ~r suspensions, with the additiono~ liquid andtor solid vehicles or diluents and, if desired, of surface;active ag~nts, for example wetting, adherent, emulsifying and/or dispersing agents.
Suitable liquid carriers are, for example, water, aliphatic hydrocarbons, aromatic hydrocarbons, for example benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethylformamide, and also mineral oil fractions.
Suitable solid carriers are, for example? mineral earths, for example tonsil, silica gel, talcum, kaolin, attaclay, limestone and silicic acid, and vegetable products, for example meals.
As surface-active agents there may be mentioned, for ' example, calcium liynin sulphonate, polyoxyethylene alkyl phenyl ethers, naphthalene sulphonic acids and salts thereof, phenol sulphonic acids and salts thereof, formaldehyde condensates, 'fatty alcohol sulphates and also substituted benzene sulphonic acids and salts thereof, l'' The total amount of the active substance or substances 'r in the various pesticidal preparations may vary within wide r limits. For example, the preparations may contain approximately 10 to 80% by weight of active substance(s), approximately 90 ~;
to 20~ by weiqht of li~uid or solid carrier and, if desired, also up to 20~ by weight of surface-active agent(s).
The active compounds may be applied in the usual manner, for example with water as carrier in quantities of spray liquor of about 100 to 1000 litres per hectare. It is also possible to apply the active compounds by the so-called "low-volume" and "ultra-low-volume" methods as well as in the form of'so-called microgranules.
The production of these preparations may be carried out ~30~s() in a manner known per se, for example by mixing or grin~in~
methods. If desired~ the individual components may be mixed together only shortly before they are used, as is the case in practice, for example, in the so-called tank-mix method.
The following Examples illustrate the invention.
Examples 1 and 2 illustrate the manufacture of the compounds of the general formula I and the1r salts, and Examples 3 to 5 illustrate their pesticidal action.
Example 1 N-(4-Chlorobenzyl)-N-methyl-2-propynylamine Cl~j ~CH2-N-CH2-C-CII c 23.8 Grams (0.2 mole) of propargyl bromide were added portionwise at room temperature, while stirring, to a solution of 31.1 grams (0.2 mole) of N-(4-chlorobenzyl)-methylamine and 30.3 grams (0.3 mole) of triethylamine in 150 ml of dry benzene. ~;
The solution was heated for 17 hours under reflux. The mixture was then filtered to remove the sol~id phase, the solvent was distilled off in v cuo, and the residue remaining was subjected .
to fractional distillation under reduced pressure. 30.9 Grams of N-(4-chlorobenzyl)-N-methyl-2-propynylamine(90~ of the theoretical yield) were thus obtained as a colourless li~uid having a boiling point of 96-106C/2 torr.
Example 2 t

4-Chlorobenzyl-methyl-2-propynyl-ammonium chloride C1~ CE12 I C1~2 C-C~I HC1 35 ml of an IICI-saturated ether solution were added at 3

-5~C to a solution of 5 grams (0.0258 mole) of N-(4-chlorobenzyl)-N-methyl-2-propynylamine in 50 ml of ether. It was allowed to :. , - 8 ~

5~) stand overni~ht at room temperature, and -then the thlck, white crystalline magma was xemoved by filtering with suction r washed with ether, and recrystallized from an ethanol-ether mixture.
5.6 Grams (94.5% of the theoretical yield) of 4 chlorobenzyl-methyl-2-propynyl-ammonium chloride having a melting point of 216.5 - 217C were obtained.
Each of the other compounds listed in Table I akove can be prepared ina manner analogous to that descrlbed in Example(s) 1 and/or 2.
Example 3 In a series of tests the compounds used in accordance with the present inventon were applied as aqueous solutions of the salts or as aqueous emulsions of the bases, wh-ich had been formulated as emulsion concentrates, the application being carried out in each case at the concentration indicated in the Table below. The procedure was the same with two of the three agents used for comparison~ namely trans-2-phenyl-cyclopropylamine ^j.
sulphate and l-isonicotinyl-2-isopropyl-hydrazine phosphate; ~, in the case of the other agent used for comparison, namely isonicotinic acid 2-~2-(benzylcarbamoyl)-ethyl]-hydrazi~e, the compound was dissolved in acetone and diluted wi-th water 'r to the concentration indicated in the Table.
Batches of eggs, 2 to 3 days old, of the Egyptian cotton moth, which had been deposited on filter pa~er by fertilized female moths, were immersed in the aforesaid r preparations of active substances until complete wettin~ was achieved and then placed in closed Petri dishes until they were assessed 4 days after the treatment.
The criterion for evaluating the pesticidal action t was the percentage emergence prevention as compared with untreated eggs.
- ` The results obtained are summarized in the following Table.

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Example 4 In a series of tests the compounds used in accordance -with the present invention were applied as aqueous solutions of the salts or as aqueous emulsions of the bases, which had been formulated as emulsion concentrates, the application being carried out in each case at the concentration indicated in the Table below. The procedure was the same with two of the three agents used for comparison, namely trans-2-phenylcyclopropylamine sulphate and l-isonicotinyl-2-isopropylhydrazine phosphate; in the case of the other agent used for comparison, namely isonicotinic acid 2-[2-~benzylcarbamoyl)-ethyl]-hydrazide, the compound was 9 dissolved in acetone and diluted with water to the concentration indicated in the Table.
Batches of eggs, two days old, of the large cabbage butterfly, which had been deposited by fertilized female butter-flies on cauliflower leaves, were immersed in the aforesaid preparations of active substances until complete wettlng was achieved and placed in closed Petri dishes until they were assessed 4 days after the treatment.
The criterion for evaluating the pesticidal action was the percentage emergence pre~ention as compared with untreated eggs.
The results obtained are summarized in the following Table.
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Example 5 In a series of tests the compounds used in accordance with the present invention were applied as an aqueous solution of the salt or as aqueous emulsions of the bases, which had been formulated as emulsion concentrates, the application being carried out at the concentration indicated in the Table below.
The procedure was the same with the agents used for comparison, namely trans-2-phenylcyclopropylamine sulpha~e and l-isonicotinyl-2-isopropylhydrazine phosphate.
Potted mustard seedlings, which had been covered with eggs by female diamond back moths (Plutella maculipennis), were sprayed, until dripping wet, with the aforesaid preparations of active substances. After the treatment, the pots were placed in ventilated glass cylinders for 7 days.
The criterion for evaluating the pesticidal action was the damage on the treated plants caused by eating as compared with such damage on untreated plants.
The results obtained are summarized in the followin~ ~

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method of protecting a living plant against pests, where the plant is treated with at least one compound the general formula (I) in which R represents a group of the formula in which n represents 0, 1, 2 or 3 and each X represents an alkoxy group or a halogen atom or a salt thereof.

2. A method as claimed in claim 1 wherein X represents an alkoxy group containing 1 to 3 carbon atoms or a chlorine atom.

3. A method as claimed in claim 1 or 2 wherein each salt is a salt with an inorganic acid.

4. A method as claimed in claim 1 or 2 wherein each salt is a hydrochloride.

5. A method as claimed in claim 1 or 2 wherein each salt is a salt with an organic acid.

6. A method as claimed in claim 1 wherein the plant is treated with at least one compound selected from N-(4-chlorobenzyl)-N-methyl-2-propynylamine, 4-chlorobenzyl-methyl-2-propynyl-ammonium chloride, N-benzyl-N-methyl-2-propynylamine, N-(2-chlorobenzyl)-N-methyl-2-propynylamine, N-(3-chlorobenzyl)-N-methyl-2-propynylamine, N-(3,4-dichlorobenzyl)-N-methyl-2-propynylamine, N-(2,4-dichlorobenzyl)-N-methyl-2-propynylamine, N-(3-methoxybenzyl)-N-methyl-2-propynylamine, benzyl-methyl-2-propynyl-ammonium chloride, 2-chlorobenzyl-methyl-2-propynyl-ammonium chloride, 3-chlorobenzyl-methyl-2-propynyl-ammonium chloride, 2,4-dichlorobenzyl-methyl-2-propynyl-ammonium chloride, 3-methoxybenzyl-methyl-2-propynyl-ammonium chloride and 3,4-dichlorobenzyl-methyl-2-propynyl-ammonium chloride.

7. A method as claimed in claim 1 in which the plant is treated with a pesticidal preparation which comprises at least one said compound selected from compounds of the general formula I and salts thereof, in admixture or conjunction with a suitable carrier.

8. A process as claimed in claim 7 in which the pesti-cidal preparation comprises at least two said compounds selected from compounds of the general formula I and salts thereof.

9. A method as claimed in claim 7 or 8 in which the preparation is in the form of a powder, a stewable preparation, granules, a solution, an emulsion or a suspension.

10. A method as claimed in claim 7 in which the prepara-tion contains a single compound selected from compounds of the general formula I and salts thereof in an amount of approximately 0.01 to 1.0% by weight.

11. A method as claimed in claim 7 in which the prepara-tion contains a single compound selected from compounds of the general formula I and salts thereof in an amount of 0.05 to 0.2%
by weight.

12. A method as claimed in claim 8, in which the prepara-tion contains two or more compounds selected from compounds of the general formula I and salts thereof in a total amount of approximately 0.01 to 1.0% by weight.

13. A method as claimed in claim 8 in which the prepara-tion contains two or more compounds selected from compounds of the general formula I and salts thereof in a total amount of 0.05 to 0.2% by weight.

14. A method as claimed in claim 7 in which the prepara-tion contains a single surface-active agent in an amount of up to 20% by weight.

15. A method as claimed in claim 7 in which the prepara-tion contains two or more surface-active agents in a total amount of up to 20% by weight.

16. A method as claimed in claim 7 in which the plant is a crop.

17. A method as claimed in claim 16 wherein the crop is a cotton, tomato, cauliflower, cabbage, dwarf bean, Riff bean, sugar beet, maize or rice crop.