HK1142589A

HK1142589A - Pesticidal diazene oxide carboxylates

Info

Publication number: HK1142589A
Application number: HK10109073.9A
Authority: HK
Inventors: M‧A‧德凯瑟; P‧T‧麦克唐纳
Original assignee: 科聚亚公司
Priority date: 2007-05-16
Filing date: 2008-04-03
Publication date: 2010-12-10

Description

Insecticidal diazene oxide carboxylic acid esters

This application is a continuation-in-part application of U.S. application serial No. 11/804,282 filed on 16.5.2007.

Technical Field

This invention relates to certain diazene oxide carboxylate compounds and compositions useful as pesticides. The present invention also relates to a method of controlling pests such as mites comprising: contacting said pest with a pesticidally effective amount of said diazene oxide carboxylate compound, or applying said diazene oxide carboxylate compound to foliage of a plant susceptible to attack by said pest.

Background

U.S. patent No. 5,438,123 describes certain insecticidal phenylhydrazine derivatives of the general formula:

wherein:

x is a) phenyl; lower phenylalkoxy; phenoxy or benzyl; or b) one substituent selected from group a) and one or more substituents selected from C₁-C₄An alkoxy group; halogen; lower alkyl and lower alkylthio; or c) together with the phenyl group to which it is attached form a multiple fused ring heterocycle such as dibenzofuranyl;

y is H, C₁-C₄Alkanoyl radical, C₁-C₄Haloalkanoyl, dialkoxyphosphoryl, alkylaminocarbonyl, haloalkylsulfonyl or C₁-C₄An alkoxycarbonyl group; and

r is H, C₁-C₆Alkyl radical, C₁-C₆Alkoxy radical, C₃-C₆Cycloalkoxy, haloalkyl, alkoxyalkyl, aralkoxy, alkenyl, alkylthio, alkoxycarbonyl, alkylamino, heteroaryl, aralkyl, haloalkoxy, aryloxy or C₃-C₆A cycloalkyl group; and

z is O or S.

Us patent 5,376,679 discloses a method for combating fungi and/or yeasts and/or bacteria and/or nematodes, which method comprises treating a susceptible plant with a compound of the general formula:

wherein R2 and R3 together, or R3 and R4 together represent optionally substituted by 1-2C_1-6Alkyl radical, C_1-6Haloalkyl, C_1-6Hydroxyalkyl radical, C_1-6Alkoxyalkyl or phenyl, or an alkylene- (CH) optionally bridged over adjacent carbon atoms₂)₄-, or C optionally substituted by a group ═ O_3-4An oxyalkylene or oxyalkylene chain; the ring is optionally substituted at any one or each of the remaining positions R5, R6 and R2 or R4, wherein each of R5, R6 and R2 or R4 is independentlyRepresents a halogen atom or C_1-6Alkyl or C_1-6An alkoxycarbonyl group; x represents a cyano group.

U.S. patent 5,084,448 discloses an antifungal method comprising treating the fungus with a fungicidally effective amount of a compound of the formula:

wherein R represents an optionally substituted aryl group; x represents a hydrogen atom or an amino group or an optionally substituted alkyl, aryl or thienyl group, and Z represents a hydrogen atom or an alkanoyl group.

Mortarini, V.et al (European Journal of Medicinal Chemistry, pp.475-478(1980)) disclose antifungal activity of methyl and ethylphenyldiazonenecarboxylate 2-oxide derivatives. The phenyl group is optionally substituted with halogen, nitro, alkoxy or alkyl.

It is an object of the present invention to provide novel diazene oxide carboxylate compounds and compositions.

It is another object of the present invention to provide a method for controlling pests using the diazene oxide carboxylate compounds and compositions.

Disclosure of Invention

The present invention relates to compounds having the general structural formula:

wherein:

R²is C₁-C₆Branched or straight chain alkyl; c₁-C₄A branched or straight chain haloalkyl; orC₃-C₆A cycloalkyl group;

m is 0, 1 or 2;

x is selected from: c₁-C₆A branched or straight chain alkoxy group; halogen; c₁-C₆Branched or straight chain alkyl, or C₁-C₆A branched or straight chain alkylthio group;

n is 0 or 1;

a is O; CH (CH)₂Or NR ', wherein R' is (C)₁-C₆Alkyl) carbonyl;

y is phenyl; a benzyl group; a thiazolyl group; a thienyl group; pyridyl or tetrahydrofuryl, the aromatic ring of each substituent being optionally substituted by halogen, C₁-C₆Branched or straight chain alkyl, or C₁-C₆One or more of branched or straight chain haloalkyl groups.

The present invention also relates to a method of controlling pests such as mites by contacting the pest with a pesticidally effective amount of at least one compound of the general structural formula:

wherein:

R²is C₁-C₆Branched or straight chain alkyl; c₁-C₄A branched or straight chain haloalkyl; or C₃-C₆A cycloalkyl group;

m is 0, 1 or 2;

x is selected from: c₁-C₆A branched or straight chain alkoxy group; halogen; c₁-C₆Branched or straight chain alkyl; or C₁-C₆A branched or straight chain alkylthio group;

n is 0 or 1;

a is O; CH (CH)₂Or NR ', wherein R' is (C)₁-C₆Alkyl) carbonyl;

In yet another aspect, the present invention relates to a composition comprising:

(A) an insecticidally effective amount of a compound of the general structural formula:

wherein:

m is 0, 1 or 2;

n is 0 or 1;

a is O; CH (CH)₂Or NR ', wherein R' is (C)₁-C₆Alkyl) carbonyl;

y is phenyl; a benzyl group; a thiazolyl group; a thienyl group; pyridyl or tetrahydrofuryl, the aromatic ring of each substituent being optionally substituted by halogen, C₁-C₆Branched or straight chain alkyl, or C₁-C₆One or more of branched or straight chain haloalkyl; and

(B) a suitable carrier.

Detailed Description

The present invention relates to compounds of the general structural formula:

wherein:

m is 0, 1 or 2;

n is 0 or 1;

a is O; CH (CH)₂Or NR ', wherein R' is (C)₁-C₆Alkyl) carbonyl;

y is phenyl; a benzyl group; a thiazolyl group; a thienyl group; pyridyl or tetrahydrofuryl, the aromatic ring of each substituent being optionally substituted by halogen, C₁-C₆Branched or straight chain alkyl, or C₁-C₆One or more of branched or straight chain haloalkyl;

the use of compounds of the general formula I as pesticides, such as insecticides, acaricides and nematicides, and compositions comprising compounds of the general formula I.

Preferably, X is C₁-C₆A branched or straight chain alkoxy group; y is phenyl; r²Is C₁-C₆Branched or straight chain alkyl.

The compounds of formula I are preferably useful as acaricides for controlling mites and other acarines.

More preferably, the present invention relates to a diazene oxide carboxylate compound of the general structural formula:

wherein R is¹And R²Each independently is C_1-6Branched or straight chain alkyl; the use of the diazene oxide carboxylate compounds as pesticides, such as insecticides, acaricides and nematicides, and compositions comprising the diazene oxide carboxylate compounds. Preferably, R¹And R²Each independently is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, or isohexyl. More preferably, R¹And R²Each independently is a lower alkyl group containing 1 to 4 carbon atoms. Most preferably, R¹Is methyl or ethyl, R²Is methyl, ethyl or isopropyl.

The compounds of the invention may be prepared by reacting a suitably substituted compound of formula III:

x, Y, A, R therein²M and n are as defined above,

with an oxidizing agent, such as m-chloroperbenzoic acid or other "peroxy" reagent, in a suitable inert organic solvent, such as a halogenated hydrocarbon, e.g. dichloromethane, at a temperature suitably in the range of-20 to 60 ℃. The compounds of formula (I) are known and can be prepared by the methods described in U.S. Pat. No. 5,438,123, the disclosure of which is incorporated herein by reference in its entirety.

The compositions of the present invention comprise (a) a compound having a structure within formula I or II above, and (b) a suitable carrier. Such suitable carriers may be solid or liquid in nature. The compositions are preferably insecticidally active, more preferably acaricidally active.

Suitable liquid carriers may consist of water, alcohols, ketones, phenols, toluene and xylenes. In such formulations, additives commonly employed in the art, for example, one or more surfactants and/or inert diluents, may be employed to facilitate handling the application of the resulting pesticide composition.

The pesticidal composition may alternatively comprise a solid carrier in the form of a dust, granule, wettable powder, paste, aerosol, emulsion, emulsifiable concentrate and water-soluble solid.

For example, when a powdered solid carrier, such as an inorganic silicate, e.g., mica, talc, pyrophyllite and clay, is admixed with or absorbed onto a surface-active dispersant so as to obtain a wettable powder, the pesticidal compound of the present invention may be applied as dust, and the wettable powder may then be applied directly to the site to be treated. Alternatively, a powdered solid carrier containing the compound admixed therewith may be dispersed in water to form a suspension for administration in such form.

Granular formulations of the compounds, suitable for application by dusting, side application, soil incorporation or seed treatment, are suitably prepared using granular or granulated forms of carriers such as granular clays, vermiculite, charcoal or corn cobs.

Alternatively, the pesticidal compounds may be applied as a liquid or spray when used in a liquid carrier, for example, in solution or dispersed in a suitable non-solvent medium, for example, water, containing a compatible solvent such as acetone, benzene, toluene or kerosene.

Another method of application to the site to be treated is aerosol treatment, for which the compound may be dissolved in an aerosol carrier that is liquid under pressure but gaseous at ambient temperature (e.g., 20 ℃) and pressure. Aerosol formulations can also be prepared as follows: the compounds are first dissolved in a less volatile solvent and the resulting solution is then admixed with a highly volatile liquid aerosol vehicle.

For the pesticidal treatment of plants (which term includes plant parts), the compounds of the invention are preferably applied in an aqueous emulsion containing a surface-active dispersant which may be a nonionic, cationic or anionic surface-active dispersant. Suitable surfactants include those known in the art, such as those disclosed in U.S. Pat. No. 2,547,724 (columns 3 and 4). The compounds of the present invention can be mixed with these surface active dispersants, with or without organic solvents, as concentrates for subsequent addition of water to produce aqueous suspensions in which the compounds are at the desired concentration level.

In addition, the compounds may be employed with carriers which are themselves pesticidally active, for example insecticides, acaricides, fungicides or bactericides.

It will be appreciated that the amount of the pesticidally active compound in a given formulation will depend upon the particular pest to be combated, as well as the particular chemical composition and formulation of the compound intended for use, the method of application and the locus of treatment of the compound/formulation, such that the pesticidally effective amount of the compound may vary widely. In general, however, the concentration of the compounds as active ingredients in pesticidally effective formulations may be from about 0.1 to about 95% by weight. Spray dilutions can be as low as several parts per million, while at the opposite extreme, full concentration concentrates of the compounds can usefully be applied by ultra-low volume techniques. The concentration per unit area when the plants comprise the treatment site may be from about 0.01 to about 50 pounds per acre, with concentrations of from about 0.1 to about 10 pounds per acre being preferred for crops such as corn, tobacco, rice, and the like.

For combating pests, sprays of the compounds can be applied directly to the pests and/or to the plants on which they feed or nest. The pesticidally active formulation may also be applied to the soil or other medium in which the pests are present.

Harmful insects, nematodes and mites attack a wide variety of plants, including ornamental and agricultural plants and cause damage by eating roots and/or leaves, extracting vital juices from the plants, sequestering toxins and often transmitting disease. The compounds of the present invention may be advantageously used to minimize or prevent these impairments. The particular method of application, as well as the selection and concentration of these compounds will, of course, vary depending upon factors such as the geographic region, climate, terrain, plant tolerance, and the like. Suitable compounds, concentrations and methods of administration can be readily determined by one skilled in the art for a particular situation by routine experimentation.

The compounds and compositions of the present invention are particularly useful as acaricides for foliar application.

Examples

The following examples are provided to illustrate the invention.

Example 1

Preparation of 2- (4-methoxy- [1, 1' -biphenyl ] -3-yl) diazoene-carboxylic acid 1-methylethyl ester 2-oxide

(4-methoxy- [1, 1' -biphenyl) in an ice bath]A solution of 1-methylethyl (10.25g) of (3-yl) diazoenecarboxylic acid in dichloromethane (160mL) was cooled and m-chloroperbenzoic acid (14.8g) was added in portions with stirring. Additional dichloromethane (90mL) was added and the solution was kept stirring at room temperature for 3 days. To the mixture was added dichloromethane (200mL) and washed with saturated potassium bicarbonate (300mL), then with saturated sodium sulfite (2 × 200mL) and finally with saturated potassium bicarbonate (200mL), the organic phase was dried over sodium sulfate and evaporated to give the product as a brown-orange solid (9.78 g). Purification by silica gel chromatography (1: 5 ethyl acetate: hexane)The product was obtained. The desired portion was evaporated to give the purified product (6.19g) as an orange solid having a melting point of 102-106 ℃. By NMR (CDCl)₃) And LC/MS analysis of the product, the NMR showed 1.4d (6H), 3.9s (3H), 5.2m (1H), 7.1-7.9m (8H), where d represents a doublet, s represents a singlet, and m represents a multiple peak; the LC/MS showed m/z: 315.8(M + H)⁺，(M)⁺314.7。

Example 2

Preparation of the formulation

The remaining examples relate to the pesticidal use of the compounds of the present invention. In all of these examples, a stock solution of the compound at 3000ppm was prepared as follows: 0.3 grams of the compound to be tested is dissolved in 10mL of acetone and 90mL of distilled water plus four drops of ethoxylated sorbitan monolaurate or similar suitable wetting agent is added. For each example that follows, this stock solution was used and the specified dilution was prepared. All the tests discussed below (including treatment with the compounds of the invention) were always repeated with control samples in which no active compound was provided to allow comparison, and percent control was calculated based on this comparison.

Example 3

Acaricidal imago and acaricidal egg agent/larvicide test

One day before treatment, the "number 8" configuration of the tree tanglefoot was applied to each of two pieces of cowpea primary leaves, one primary leaf of each of the two plants in the crucible. In each number, the circle closer to the stem is designated for the acaricidal egg agent/larvicide test and the circle further from the stem is designated for the acaricidal adult test.

Groups of adult mites (Tetranychus urticae Koch) were transferred into ovicide circles one day prior to treatment and the females were allowed to lay eggs until one hour prior to treatment, at which time they were removed. Plants were sprayed with 1000ppm solution diluted from 3000ppm stock solution to rinse out.

One day after treatment, groups of approximately 25 adult mites were transferred into the adulticide circle. After 5 days, the circles were examined for residual live mites on the leaves. Percent control was estimated based on the number of mites surviving on the test plants.

Nine days after treatment, the ovicide/larvicide circles were examined for hatched eggs and live larvicides. Percent control was estimated based on detecting the number of eggs hatched and young mites surviving on the plants. When the treatment effect is egg, the control is named as ovicidal (O); when the effect of the treatment was larval, the control was named larvicidal (L).

The results of the miticidal adult (MI) and ovicide/larvicide (MIOVL) assays on compound 1 are as follows: MI 100% control, MIOVL (L) 100% control.

Claims

1. A compound having the general structural formula:

wherein:

m is 0, 1 or 2;

n is 0 or 1;

a is O; CH (CH)₂Or NR ', wherein R' is (C)₁-C₆Alkyl) carbonyl;

y is phenyl; a benzyl group; a thiazolyl group; a thienyl group; pyridyl or tetrahydrofuryl, the aromatic ring of each substituent being optionally substituted by halogen, C₁-C₆One or more of a branched or straight chain alkyl group, or a branched or straight chain haloalkyl group.

2. A compound according to claim 1, wherein R²Is C₁-C₆Branched or straight chain alkyl; x is C₁-C₆A branched or straight chain alkoxy group; y is phenyl.

3. A compound having the general structural formula:

wherein R is¹And R²Each independently is C_1-6Branched or straight chain alkyl.

4. A compound according to claim 3, wherein R¹And R²Each independently is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, or isohexyl.

5. A pesticidal composition comprising:

A) a pesticidally effective amount of a compound according to claim 1; and

B) an acceptable carrier.

6. A pesticidal composition comprising:

A) a pesticidally effective amount of a compound according to claim 3; and

B) an acceptable carrier.

7. A method for the control of undesirable pests which comprises applying to the locus to be protected a pesticidally effective amount of a compound according to claim 3.

8. A method for controlling undesirable pests which comprises applying to the locus to be protected a pesticidally effective amount of a composition according to claim 3.