DEN0006135MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: September 25, 1952. Known on July 19, 1956

GERMAN PATENT OFFICE

PATENT APPLICATION

CLASS 451 GROUP 3oi
N 6135 IVaI'451

Johannes Thomas Hackmann, Amsterdam (Netherlands)

has been named as the inventor

N. V. De Bataafsche Petroleum Maatschappij, The Hague

Representative: Dr.-Ing. F. Wuesthoff and Dr. F. Wuesthoff, patent attorneys, Munich 9

Methods for controlling pests, in particular fungi

The invention relates to the use of hydrazine derivatives in pest control and suggests a certain group of derivatives of hydrazine, namely the hydrazidines, the also referred to as acid amide hydrazones, and their derivatives for controlling pests, in particular of fungi, one of which is an organic material or a plant or animal organism is infested to use.

The hydrazidines or, according to their common name, the acid amide hydrazones are known (see e.g. »Traite de Chimie Organiquecc, Grignard [1948], Vol. XV, p. 584) Compounds which are obtained when one in the molecule the amidine replaces the imide radical with an optionally substituted hydrazine radical. The amidines have the general formula

HN = C-R

'NH ₂

where the radical R can be of very different types. So the hydrazidines have the general formula

X ₁ X ₂ NN = CR

NH ₂ wherein X ₁ , X ₂ and R are hydrogen atoms or given

609 · 550/475

N 6135 IVa / 451

if they represent substituted alkyl or aralkyl groups. According to Pinner, »Annalen der Chemie«, 297 [1898], pp. 224 and 225, they can also be used in the tautomeric »imido form « with the above configuration

X ₁ X ₂ N-HN-CR

NH

exist or react. The invention relates to connections of both types of tautomeric configuration. It has been suggested to use certain hydrazine derivatives for similar purposes, however In none of the previously proposed substances can be found for the effectiveness of the agents after registration characteristic group

X ₁ X ₂ NNC

/ or X ₁ X ₂ N-NH-C-

NH,

NH

According to the invention, hydrazidine derivatives of the above general formula are preferably used, in which X _{1 is} a hydrogen atom and X _{2 is} an aryl or aralkyl group, but preferably a phenyl group, while R is preferably a radical in which the valence of a carbon atom is carried, which in turn carries a doubly bonded oxygen atom or a doubly or triple bonded nitrogen atom. Examples of such preferred radicals are acyl groups, aminoacyl groups (carbamide groups) and the cyano group. Hydrazidines of the above general formula, in which X _{1 represents} a hydrogen atom and X _{2 represents} a phenyl group, are called amidrazones (see the passage from "Traite de Chimie Organique" cited above).

Good results are z. B. achieved with acetyl

amidrazone, cyanamidrazone and formamidamidrazone, which have the formulas

ν — N = c — c:

NH,

, 0

XH,

or.

C ₆ H ₆ -NN = CC = N

"V. NH ₂ -

or.

N-N = C-

C = O

^v .., ._ ■■ NH ₂ NH ₂

get.

Without giving a binding theoretical explanation, let us say that most of them the substances to be used according to the invention most likely have an internal chemotherapeutic effect to have. Such an effect is based on the fact that the substances penetrate into the plants spread and make them immune, at least less susceptible to attack by pathogens do. It should be noted, however, in this context that according to the present Invention to use substances in addition to the internal chemotherapeutic effect also an external Have an effect. On the other hand, with some of the substances in question, the internal chemotherapeutic Effect cannot be determined properly. .

It should also be noted that the substances which can be used according to the invention are not only used in combating Plant diseases or their pathogens can be used, but quite generally for Control of pests, particularly fungi, using any predominantly organic material, for example Leather or textiles, or an organism, for example a plant or animal, have infested. The invention extends to these purposes as well.

The substances according to the invention can either individually or in combination with one another or with other fungitoxic, antiviral, insecticidal or acaricidal substances are used, their chemotherapeutic effect can be an internal or an external, with wetting agents and optionally adhesives can also be added. Also combinations with system insecticides and / or Plant nutrients and / or plant hormones are possible. ''

Suitable wetting agents are, for example, alkyl sulfates, Alkylarylsulfonates, sulfosuccinates, ethers from polyethylene glycols and alkylphenols. Quality Results were achieved using a technical mixture of sodium alkyl sulfates in amounts from 0.01 to 0.05 percent by weight. Insofar as the substances are in the form of emulsions or suspensions, z. B. in water, solvents such as oils, emulsifiers, emulsion stabilizers and the like can also be added. Furthermore can substances are also added that enable the use of unusually high doses, without phytotoxic symptoms occurring. Glucose, for example, protects tomato plants against damage caused by certain substances that have a phytotoxic effect in high concentrations, such as B. urea.

The substances according to the invention can be administered in various ways, such as, for example firstly by applying the substances to above-ground or underground parts of the plants or on the seeds, secondly, by introducing the substances into the soil near the roots, and thirdly by directly introducing the substances into the plants, e.g. B. through boreholes or incisions in parts of plants.

The application to above-ground parts of the plants, for example by means of Splash. If the substances are introduced into the ground,

550/475

N 6135 IVaI451

so care must be taken that the solution is introduced as close as possible to the roots or sufficiently • Select high concentrations, as otherwise some of the active substances will be absorbed by the soil components or the substances may be subjected to chemical or microbiological transformation can be before they penetrate the plants.

The plants to be treated are preferably sprayed with aqueous solutions of the active substances that are ο, οΐ to ι percent by weight, preferably 0.1 to 0.5 percent by weight of these substances. Sometimes there are even lower ones Concentrations effective; under certain circumstances, if phytotoxicity does not occur, also higher concentrations can be used. Usually it is precisely with regard to phytotoxicity working with low concentrations is recommended.

Of course, the active compounds according to the invention do not need to be used in pure form get. Inactive admixtures can be present during the technical Manufacture. Mixtures of active compounds can also be used like them are easy to manufacture from technical products.

The effectiveness of the new pesticides extends to very different types of pathogens, some of which are of great practical importance in the following list will:

Latin
name of
Disease
exciter German name
illness Important plants,
where the
Disease before
can come Cladosporium
fulvum Brown spots
illness tomatoes
plant Septoria apii
graveolentis celery
plant Phytophthora
infestans Herb and
Tuber rot
(Potato
illness) potato
plant,
tomatoes
plant Colletotrichum
Lindemuthi-
anum Focal spots
illness Bean plants
(Phaseolus
vulgaris L.) Exobasidium
vexans »Blister blight cc
(English
Surname) Tea plants Erysiphacaea
(different
Species) mildew Different
Plant,
z. B. Apple
trees Uredinales
(different
Species) rust Cereals

Latin German name Important plants, name of illness where the Disease Disease before exciter Wilted sickness can come Fusarium and Cucumber plants Verticillium (different Species) Dutch elm disease Ceratostomella Elm trees ulmi Bacterial cancer Pseudomonas Tomato and (different many other Species, e.g. B. plant Agrobacte rium tume- faciens)

The list is of course not exhaustive: all of the pathogens listed are fungi, with Except for the last one, which is bacteria. . '. ·' ■ - '· ■

In tests, including the tests described in the following examples, the effect of the substances to be used according to the invention was assessed in the following way: After some time, the ratio of the leaf surface attacked by the disease to the total leaf surface in treated and untreated plants was determined. If the quotient of these two numbers is subtracted from 1, a quantity is obtained which is a measure of the degree of suppression of the pathogen. Furthermore, this quantity, expressed as a percentage, is called the degree of suppression. The point in time at which the determination of the degree of suppression, as just defined, was carried out was chosen in each case so that all plants that remained untreated showed clear symptoms of the disease. The leaf surfaces are usually not measured, but estimated with the required accuracy. In this way, a trained person can determine the degree of suppression with an accuracy of about 5 ° / _0. This accuracy is sufficient because, in general, the results obtained in biological experiments can only be reproduced within fairly wide limits. The invention is illustrated below using examples: '

Example I.

2-month-old potato plants or tomato plants were sprayed until they drained off with an 0.5% or 0% aqueous solution of acetylamidrazone and infected with Phytophthora infestans. The degree of suppression achieved was 68 and 82%, while in potato and tomato plants treated with a 0.75 percent suspension of copper oxychloride and infected with Phytophthora, the degree of suppression achieved was 36 and ¹ JO ⁰ I ₀ , respectively.

609 550/475

N 6135 IVa / 451

Rye infected with rust was also treated with an aqueous solution of acetylamidrazone splattered. The degree of suppression achieved was 88%. ■

Example II

A number of apple seedlings (20 cm high) were treated with an aqueous solution of 0.3 percent by weight Cyanamidrazone with an addition of 0.1% by weight

to percent of a technical mixture of sodium alkyl sulphates as a wetting agent. 80 ecm of liquid per m ^{2 were} used. 3 days later, the plants were inoculated with apple powdery mildew spores. After 3 weeks, the infestation of the meanwhile unfolded leaves at the top of the plant was determined. A degree of suppression of 80 ° / ₀ was achieved. ■

Example III

Potato plants infected with Phytophthora infestans were with 0.5 percent aqueous solutions of acetylamidrazone or cyanamidrazone respectively Formamidamidrazon splashed. The degree of suppression achieved was approximate in all cases 80%.

Claims (9)

Patent claims: i. Use of preferably water-soluble Hydrazidine derivatives of the general formula X ₁ X ₂ NN = CR NH, where X ₁ , X ₂ and R represent hydrogen atoms or optionally substituted alkyl or aralkyl groups, for the purpose of combating pests, in particular fungi, by which an organic material or a plant or animal organism is attacked. 2. Use of hydrazidine derivatives according to claim 1, characterized in that X _{1 is} a hydrogen atom and X _{2 is} an aryl or aralkyl group, but preferably a phenyl group, while the radical · R is preferably one in which the with the remainder of the Molecule connected valence is carried by a carbon atom, which in turn carries a double bonded oxygen atom or a double or triple bonded nitrogen atom. 3. Use of hydrazidine derivatives according to claim 2, characterized in that R is a Represents cyano group. 4. Use of hydrazidine derivatives according to claim 2, characterized in that R is a Represents acyl group. 5. Use of hydrazidine derivatives according to claim 2, characterized in that R is a Represents aminoacyl group. 6. Use of acetylamidrazone for the purposes of claim 1.. 7. Use of cyanamidrazone for the purposes of claim 1. 8. Use of formamidamidrazone for the purposes of claim 1. 9. Use of the agent according to claims 1 to 5, individually or mixed with one another.