DE2031311A1 - Pesticides, processes for their manufacture and their use - Google Patents

Description

PATENT LAWYERS MONKS 2
TAU 33
TEL. »11/226394
295051 '.
_ CABLES: THOPATENT
"j TELEX: TO FOLLOW Dipi.-chem. Dr. D. Thomsen Dipi.mg. H. Tiedtke
Dipichem. G.Bühling 203131 FRANKFURT (MAIN) 50
FUCHSHOHL 71
TEL. MH / SIMM Dipwng. W.Weinkauff

Answer requested to:

Plea »· reply to». . '

8000 Munich 2 June 24, 197Q case PP.22003 / T 3682

Imperial Chemical Industries Limited London / Great Britain

Pesticides, processes for their manufacture

and their use

The invention relates to organic compounds, to processes for their preparation and to pest control preparations containing such compounds. In particular, the invention relates to new substituted quinones and pest control preparations containing them.

The compounds according to the invention have the general formula: ο

ίο "
R ITN-COQ

wherein R ^{1 is} a hydrogen atom or a hydrocarbon group

2 ^:

dar »madt, R represents a hydrocarbon group and Q a Naphthachinonyl- or Anthraquinonylreat represents.

. 009882/2250

According to a preferred embodiment of the invention compounds are provided with the formula:

. . ' ... ■. ■■■ ".. - - ■■■ - ■ o ■ ■ - · ■. · ■■ -, - ■, - ■ --- __ .; ■.

R ¹ R ² NCOQ

wherein R ^{1 represents} a hydrogen atom or an AJky! group

2 ■. ■■■ · -. ■■■■

and R represents an alkyl group and Q either (a) represents a l _# 4-naphthaquinon-2-yl radical / which is optionally substituted with one or more alkyl groups or with halogen atomsf or
(b) represents a 9,10-anthraquinon-1-yl radical.

12th
When R and R represent alkyl groups and Q represents

1,4-naphthaquinon-2-yl radical which bears alkyl groups as substituents, these alkyl groups are preferably ^{lower than 1} alkyl groups having 1 to 6 carbon atoms, for example methyl, ethyl and n-buty groups.

According to a preferred embodiment are therefore

according to the invention compounds of the formula:

OR ¹ R ² NCOQ

provided, wherein R is a hydrogen atom or an alkyl

represents a group having 1 to 6 carbon atoms, R represents an alkyl group having 1 to 6 carbon atoms and Q represents either
(a) represents a 1,4-naphthaquinone-2-y! radical which is given

009812/2210 '

optionally with one or more alkyl groups with 1 to 6 Is substituted with carbon atoms or with halogen atoms

(b) represents a 9,10-anthraquinon-1-yl radical.

According to a further preferred embodiment of the Invention, a quinone derivative is provided, which either

η Ii

(a) the formula H QC-KH ¹ A ² .

represents wherein R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R represents an alkyl group having 1 to 6 carbon atoms and X represents an alkyl group having 1 to 6 carbon atoms or a halogen atom, or the
(b) the formula _Λ λ-C-NR ¹ If

has, wherein R and R alkyl groups with 1 to 6 carbon atoms represent.

00 9 88 27 2 250

Specific compounds according to the invention are those whose structural formulas are listed in Table I below along with the melting point (expressed as ⁰ C) for each compound *

Connection no,

Table I.

Structural formula

Melting point C.

• ζχ .91 O Ci 187-189 197 Λ

003S82 / 22E0

Table t (continued)

Compound No. Structural Formula Melting Point

009882/2250

ORIGINAL INSPECTED

2631311

e Ϊ (continued ^

Connection no. Structural formula Melting point C.

A particularly valuable compound for pest control is compound no. 1 in Table I above.

The invention therefore comprises according to a particular aspect leadership fonri the compound of the formula "

009382/2250

ORIGINAL INSPECTED

CH,

The numbering of the ring atoms in the naphthaquinone ring (I) and in the anthraquinone ring (II). corresponds to the illustration in the formulas below:

(D

(II)

The compounds of the invention can by a Number of different methods can be produced. For example, the compounds can have the structural form

O
QOC-NH-R ²

009882/2250

wherein Q represents a 1,4-naphthaquinonyl radical which is connected to the adjacent oxygen atom on any of the carbon atoms which have the positions numbered 2, 3, 5, 6, 7 or 8 in the naphthaquinone ring and optionally in .the remaining positions are substituted, or represents a 9,10-anthraquinonyl radical which is bonded to the oxygen atom on any of the carbon atoms corresponding to the positions numbered 1 to 8 in the anthraquinonyl ring.

gen, and wherein R is a hydrocarbon group represents, by reacting the corresponding quinone, which has a hydroxyl group in a suitable position, with an isocyanate of the formula

wherein R has the meaning given, are obtained,

Compounds of the invention having the formula:

12 ". ITR ^ N-C-O-Q.

1 2
wherein Q, R and R have any of the meanings defined above, can be prepared by reacting the corresponding quinone, which carries a hydroxyl group in a suitable position, with a carbamoyl halide of the formula:.

O HaI-C-NR ¹ R ²

. 009882/2250

wherein Hal represents a chlorine, bromine or iodine atom and R as well as R have any of the meanings listed » can be obtained.

The compounds of the invention can also be prepared by using a quinonyl chloroformate of Formula _Q

Q-C-Cl

wherein Q and X have any of the meanings listed above , with an AmIn of the formula:

"1

R ² -1 2

wherein R and R have any of the meanings listed above, for the production of compounds of the formula: Q according to the invention

12th

wherein Q, R and R have any of the meanings listed own, implements.

The above reactions can be carried out in the presence of a solvent and, if appropriate, in the presence of a base . . ·

The chi used in the above reactions

nonylchloroformate can be produced by

009801/2250

the corresponding quinone, which carries a hydroxyl group, converts phosgene in a suitable solvent and, if necessary, in the presence of a base »

. Suitable solvents .. for all of the above reactions are solvents without hydroxyl groups such as ethers, e.g. Diethyl ether, dioxane; Ketones, e.g., acetone, cyclohexanone; Esters such as ethyl acetate and hydrocarbons such as benzene and cyclohexane. Other suitable solvents are aprotic nitrogenous solvents, e.g. pyridine and Dimethylformamide.

Suitable bases for the above reactions are aprotic nitrogen-containing compounds, e.g. pyridine, triethylamine, N-methylmorpholine and salts of weak inorganic acids, such as carbonic acid, with metals, in particular the alkali and alkaline earth metals. Particularly useful bases for these reactions are sodium and potassium carbonates. . ,

The reactions are expediently carried out at temperatures in a range in which the solvent is in the liquid state, ie between its melting point and its boiling point under ambient pressure. The compounds of the invention are usually used at temperatures in the range from 0 ° to ISO ⁰ C and preferably in the range of

009882/2250

10 ° to 100 ° C.

ι ·

In a further embodiment, the invention thus comprises a method for producing a connection

of the formula: O _n

R ² NH-COQ

wherein Q is a quinonyl radical and R is a hydrocarbon group in which a quinone, which is a Carries hydroxyl group in a suitable position, with an isocyanate of the formula;

R ² -N = C «0

is implemented.

In a further embodiment of the invention is a process for the preparation of a compound of the formula: Q

R ¹ R ^ NCOQ

l 2
provided »in which Q, R and R have any of the meanings listed above, in which a quinone which carries a hydroxyl group in a suitable position with

a carbamoyl halide of the formula:

12 "

R ¹ R ^ NC-Hal

where Hai represents a chlorine, bromine or iodine atom will*

009882/2250

According to a preferred embodiment of the invention a method of the type described above is provided, which in the presence of a solvent or a diluent and a base is executed.

The compounds and preparations according to the invention, which contain these compounds are very toxic to spider and insect pests, including for example following:

Tetranychus telarius (spider mites)

ι.

Aedes aegypti (yellow fever mosquitoes)

In particular, Compound No. 1 of Table I and preparations containing this compound are very valuable in spider mite control and provide excellent control of strains which have become resistant to the toxic agents normally used against them. This compound is also very beneficial in use because of its remarkably low mammalian toxicity, which makes it safer to use than many of the spider mite containments currently available. This is illustrated in Table II below, in which the value for the acute oral toxicity LD ₅₀ ^for rats of compound No. 1 from Table I with such values for various acaricides

009882/22 50

currently used in spider mite containment will be compared. The connections are named with their usual British Standard designations, and the toxic data were taken from "The Pesticide Manual" (I. Edition, 1968), edited by H. Martin and published from the British Crop Protection Council. ·

Table II

link

acute oral toxicity to rats ^ld 5q

No. 1 from Table I Dicofol Binapacryl Azinphos-methyl Dinobutone Demetonmethyl Carbophenothion Parathion Methidathion Dioxathione

> 4OOO 684 120

16 140

65

32 3.6

25th

23

Further advantages of compound no. 1 from Table I. is their rapid action in comparison with some other acaricides and the specificity of their action. In the case of d Reviews used in spider mite containment seem no adverse effects on beneficial insects to lie. '

The compounds of the invention and which contain them-009882/2250

preparations are also toxic to nematode pests, including, for example, Meloidogyne incognita (Root-knot nematodes) and are very active against various fungal diseases, including, for example, the following specific diseases:

Puccinia recondita Phytophthora infestans Sphaerotheca fuliginea Podosphaera leucotricha Uncinula necator Piricularia cryzae Plasmopara viticola Venturia inaequä-is Rhizoctonia solani Fusarium culmorum Pythium ultimum

(Rust) on wheat (tuber rot) on tomatoes "(powdery dust), on cucumbers (melted dust) on apples (melted dust) on wine (fire) on rice
(Vine peronospora) on wine (scab) on apples (wound stalk) on cotton (meltau) on wheat

(Rot of young plants) on peas

A particularly valuable feature of the activity of the compounds according to the invention is their ability to act as intrapeutic pesticides, ie their ability to migrate in the plant to avoid an infestation. or infection to it remote from the site of original compound application. fight. Thus, connection can of the invention or a preparation containing these are applied to the roots of a plant surrounding soil and are taken up by the plant through their roots, to combat pests on the plant according to. .

009882/2250

The invention also includes pest control preparations, which as an active ingredient is a compound of the formula:

12 "
R ¹ R ⁴⁴ NCOQ

contain, in which R is a hydrogen atom or a hydrocarbon " represents a carbon group, R represents a hydrocarbon group and Q represents a naphthaquinonyl or anthraquinonyl radical represents.

According to a preferred embodiment of the invention The invention includes pest control preparations which, as active ingredient, contain a compound of the formula;

12 "

R R ^ N-C-O-Q

contain, where R is a hydrogen atom or an alkyl

represents a group, R represents an alkyl group and Q represents either

(A) represents a 1,4-naphthaquinonyl-2-yl radical which, if appropriate, has one or more alkyl groups or has halogen atoms is substituted, or

(b) represents a 9,10-anthraquinon-1-yl radical.

According to a further preferred embodiment, the invention comprises pest control preparations, which as

00988 2/2250

Active ingredient a compound of the formula

12 "R- ¹ R ^ NCOQ

• 1

contain, where R is a hydrogen atom or an alkyl

represents a group with 1 to 6 carbon atoms, R is an Al-

represents kylgruppe having 1 to 6 carbon atoms and Q ent · W neither

(A) represents a 1,4-naphthaquinon-2-yl radical, which optionally with one or more alkyl groups with 1 to 6 Carbon atoms or substituted by halogen atoms, or

(b) represents a 9,10-anthraquinon-1-yl radical.

According to a further preferred embodiment of the invention, this includes pest control preparations which contain a quinone derivative as an active ingredient, which either
(a) the form || ο-ί-ΗΗ ¹ & ²

wherein R is a hydrogen atom or an alkyl group

2 represents 1 to 6 carbon atoms, R represents an alkyl group represents with 1 to 6 carbon atoms and X represents an alkyl group with 1 to 6 carbon atoms or an Ilalogenatom, or which one

.0098 ^ 2/2250

(b) the formula:

-NB ¹ E ²

I- 2

wherein R and R are alkyl groups of 1 to 6 carbon atoms represent.

A particularly valuable pest control preparation is one which has the compound as an active ingredient No. 1 from Table I above.

According to a further particularly preferred embodiment the invention therefore comprises a pest control preparation, which as active ingredient is the compound of the formula:

contains.

In use, the compounds according to the invention or the preparations containing them can be applied or applied in various ways. Thus, their application can be directed in a suitable manner to the foliage of the plant or to the infected and / or affected areas of the foliage; alternatively, the soil surrounding the plant

00988272250

with the compounds according to the invention or those containing them Preparations are treated. If desired, the seeds themselves can be treated in a corresponding manner will.

According to a further feature, according to the invention, there is therefore a method for controlling undesired pests provided on plants, which consists in the fact that one has a connection or this on the location of the plant containing preparation as defined above, brings up.

According to a further embodiment of the invention a method for controlling pests on plants is provided, which consists in that one on the plants or the seeds of which are a compound or a preparation as above are defined, applies. The invention also includes a method of treating agricultural Ground, which consists in being connected to the ground or applies a preparation of the type defined above.

■ According to a further embodiment, the invention includes a method of controlling pests, which consists in touching the pest © or 'on the spot the occurrence of the pest a compound or a preparation

0Q98 82/2 2 50

of the type defined above.

The compounds and preparations of the invention can are used for agricultural or horticultural purposes, and which are used in the respective case The compound or type of preparation depends on the specific purpose for which it is to be used.

Preparations containing the compounds according to the invention can be in the form of dusty powders or granules in which the active ingredient is mixed with a solid diluent or carrier. Suitable solid diluents or carriers can be, for example, kaolinite (china clay), montmorillonite, attapulgite, talc, pumice stone, silicon dioxide, calcium carbonate, gypsum, powdered magnesium oxide, fuller's earth, Hewitt ¹ see earth and diatomaceous earth. Preparations for the finishing of seeds can for example contain an agent which supports the adhesion of the preparation to the seed, for example a mineral oil.

The preparation can also be in the form of dispersible Powders or granules are present which, in addition to the active ingredient, contain a wetting agent to facilitate dispersion of the powder or the grains contained in liquids. Such powder

009882/2250

2D313

or granules may contain fillers, suspending agents, and the like.

The preparations can also be in the form of liquid preparations which are used as immersion baths or sprays are to be and are generally aqueous dispersions or emulsions that the active ingredient in the presence of a or more wetting agents, dispersants, emulsifiers or suspending agents.

Wetting agents, dispersants and emulsifiers can be of the cationic, anionic or nonionic type be. Suitable agents of the cationic type are, for example quaternary ammonium compounds, for example cetyltrimethylammonium bromide. Suitable agents of the anionic type are, for example, soaps, salts of aliphatic Monoesters of sulfuric acid, for example sodium lauryl sulfate, Salts of sulfonated aromatic compounds, for example sodium dodecylbenzenesulfonate, sodium, calcium or ammonium lignosulfonate, butyl naphthalene sulfonate and a Mixture of the sodium salts of diisopropyl and triisopropyl naphthalenesulfonic acids.

Suitable Miitel of the non-ionic type are, for example, the condensation products of ethylene oxide with Fatty alcohols, such as oleyl alcohol or cetyl alcohol or with

009882/2250

Alky! Phenols such as octyl phenol, nony! Phenol and octyl cresol. Other non-ionic agents are the partial esters derived from long chain acids and hexitol anhydrides are the condensation products of these partial esters with ethylene oxide, the lecithins and block copolymers of ethylene oxide and propylene oxide.

Suitable suspending agents are, for example, bentonites, pyrogenic silicon dioxide and hydrophilic colloids, for example Polyvinylpyrrolidone and sodium carboxymethyl cellulose and the vegetable gums, for example acacia and tragacanth.

The aqueous solutions, dispersions or emulsions can be prepared by dissolving the active ingredient or the active ingredients in an organic solvent which contains one or more wetting agents, dispersants or emulsifiers, and through subsequent addition of the mixture thus obtained to water, which is also one or more wetting, dispersing or Emulsifying agents can be prepared. Suitable organic solvents are ethylene dichloride, isopropyl alcohol, Propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichlorethylene.

The compounds of the invention can also be formulated into preparations in the form of capsules or microcapsules , which contain either the active ingredient itself or the

-OD98B272250

Active ingredient-containing preparation contained and by any of the known encapsulation or microencapsulation techniques getting produced.

The preparations to be used as sprays can be in the form of aerosols, in which the approach in one Container kept under pressure in the presence of a propellant such as fluorotrichloromethane or dichlorodifluoromethane will.

By including suitable additives, for example to improve distribution and adhesion of the powder; and for resistance to rain on treated surfaces the various preparations can be better adapted to the various uses for which they are intended. ·

The compounds of the invention can expediently can also be prepared by mixing with fertilizers. A preferred preparation of this type contains fertilizer granules, which contain a compound according to the invention incorporated, for example coated therewith. That For example, fertilizers can contain nitrogen or phosphate » containing substances. ,

According to a further embodiment of the invention

2011111

a pest control product is therefore provided that contains a compound according to the invention of the type defined above in admixture with a fertilizer.

Those in the form of aqueous dispersions or emulsions Preparations to be used are generally supplied in the form of a concentrate, which has a high proportion of the active ingredient or ingredients, the concentrate being diluted with water before use.

These concentrates are often required to survive storage for long periods of time and after such storage can be diluted with water to form aqueous preparations which are suitable for a remain homogeneous for sufficient time to enable their application by a conventional spray device. The concentrates can expediently 10 to 85 wt .-% of the active ingredient or the active ingredients and generally contain 25 to 60% by weight of the active ingredient or active ingredients. In case of Dilution to form aqueous preparations, such preparations can contain varying amounts of the active ingredient or the Depending on the purpose for which they are to be used, active ingredients contain, however, an aqueous preparation, which between 0.001 and 1.0 wt .-% of the active ingredient or the Containing active ingredients, are used.

009882/2250

Of course, the pest control preparations of the invention can be used in addition to a compound according to the invention.

A -

one or more other compounds with biological Activity included.

An example of such a preparation of the invention consists of a composition other than one according to the invention Compound the compound O, O-dimethyl-O-4 (2-diethylamino-6-methylpyrimidinylthiophosphate contains, also known under the general name pirimiphos-methyl according to British Standard.

The invention is illustrated in more detail by the following examples.

example 1

This example illustrates the preparation of 2-methyl-1-4 -naphthaquinone-s-yldimethylcarbamate (Compound no. From Table I) of the structural formula:

009882/2250

To a solution of 2.5 g of 2-hydroxy-3-methy1-1,4-naphthaquinone in 30 cm of pyridine there was 1.5 cm of methylcarbamoyl chloride added. After the solution was kept at 75 ° C. for 4 hours, the pyridine was removed by evaporation under reduced pressure and the residue distributed between 100 cm of water and 100 cm of chloroform. the Chloroform layer was separated and sequentially with 4%

3 3

aqueous hydrochloric acid (2 × 100 cm), water (1 × 200 cm), 4% aqueous sodium hydroxide solution (3 χ 100 cm} and water (2 × 100 cm) washed. The chloroform solution was then dried over anhydrous sodium sulfate, filtered, and dried the filtrate was evaporated to a solid residue which, upon recrystallization from alcohol, 2-methyl-1,4'-naphthaquinon-3-yl dimethyl carbamate as a buff crystalline solid with a melting point of 91 ° C.

Example 2

The following compounds were prepared by a procedure similar to that explained in Example 1, but using the appropriate reaction components;

2'-Bromo-1,4-naphthaquinone "· 3-yldimethylcarbamate (Compound No. 4 / Table I)

9 ₄ 10 ~ Anthrach: U * on-l * yldiinethylearbamate (Compound No. 5, Table I).

0098 32/22 50

Example 3

This example illustrates the preparation of 3-methyl-l _r 4-naphthaquinon-2-yl-n-butylcarbamate (Compound No.

from Table I) of the formula: "-.

To a solution of 2.0 g of 2-hydroxy-3-methyl-l, 4-

naphthaquinone in 40 cm dimethylformamide in a conical

3

100 cm flasks were 3 drops of N-methylmorpholine and 1.5 cm n-Butyl isocyanate given at 15 ° C. The flask was then closed with a cork and kept at ambient temperature Held for 5 days, whereupon the constituents of the iris in 250 cm cold water was poured and vigorously stirred for 2 minutes. The precipitated solid was collected by filtration collected, washed with cold water and finally air-dried, whereby 3-methyl-l, 4-naphthachinon-3-yl <-n-butyl * carbamate resulted as a yellow microcrystalline solid with a melting point of 120 ° to 122 ° C.

Example 4

Through a working method according to that in Bei

game 3 described, but under VerweB & img der

OOBSS yes / 2250

The following reaction components were used manufactured:

1 ^ -Naphthachlnon-Z-ylinethylcarbamate (Compound No. 2, Table I) "

S-bromo-1 ^ -naphthaquinone ^ -ylinethylcarbamate (Compound No. 3, Table I).

3-methyl-1,4-naphthaquinon-2-ylmethyl carbamate (compound no.

6, table I)

ι.

S-methyl-1 ^ -naphthachihon ^ -yläthylcarbamat (compound no.

7, Table I) <

S-bromo-1 ^ -naphthaquinone ^ -ylethyl carbamate (compound no. 9, Table I) <

3-Bromo-1,4-naphthaquinon-2-yl-n-butylcarbamate (Compound No. 10, table I)

Example 5

This example illustrates an atomizable liquid, speed from a mixture consisting of 25 wt .-% of the compound No. 1 from Table I and 75% by weight of xylene,

Example 6

This example illustrates a dusty powder that can be applied directly to plants or other surfaces can be brought and 1 wt .-% of the compound No. 1 from Table I and 99% by weight talc.

0 0 9 8 8 2/2250

Example 7 '

25 parts by weight of the product described in Example 1, 65 parts by weight of xylene and 10 parts of an alkylaryl polyether alcohol ("Triton" X-100; "Triton" is a trademark) were mixed in a suitable mixer. In this way, an emulsion concentrate was obtained which was mixed with water to prepare an emulsion suitable for use in agricultural applications.

Example 8

5 parts by weight of the product described in Example 1 were carefully mixed with a suitable mixer 95 parts by weight of talc mixed. In this way, a dusty powder was obtained.

Example 9

10 parts by weight of the product described in Example 1, 10 parts of an ethylene oxide-octylphenol condensate ("Lissapol" NX; "Lissapol" is a trademark) and 80 parts by weight Diacetone alcohol was mixed thoroughly. In this way a concentrate was obtained which when mixed

00988 2/2250

with water resulted in an aqueous dispersion that was used as a spray in pest containment. '

Example IO

This example illustrates a concentrated liquid formulation in the form of an emulsion. The ingredients listed below were mixed together in the indicated proportions, and the whole was stirred until the ingredients were dispersed. _G _ _%

Compound No. 4 (Table I) 20

"LUBROL" L ("Lubrol" is a trademark) 17

Calcium dodecylbenzenesulfonate 3

Ethylene dichloride ·. 45

¹¹ AROMASOL "H (" Aromasol "is a trademark) · 15

100%

Example 11

The ingredients listed below were mixed together in the specified proportions for the preparation of a powdered mixture, which is easy in liquids

is dispersible, grind.

% By weight . Compound No. 5 (Table I) 50

Diepersol T ("Dispersed ¹ · is a trademark .5

China Clay 45

009882/2 250 ' 7cm

Example 12

A preparation in the form of grains, which are easily dispersible in a liquid (e.g. water) are, were made by marrying the. first four of the ingredients listed below in the presence of water prepared, whereupon the sodium acetate was mixed in. The mixture was dried and passed through a British Standard mesh screen, Mesh size 44 to 100, passed to get the desired grain size.

Wt% Compound No. 10 (Table I) 5Q Dispersol T 12.5 Calcium lignosulfonate 5 Sodium dodecylbenzenesulfonate 12.5 Sodium acetate 20th

100%

Example 13

A preparation suitable for use as a seed finish was made by all three of the below listed ingredients mixed in the specified parts became. .

Compound No. 1 (Table I) 80 Mineral oil 2

1.00%

Example 14

It became a preparation in the form of granules by dissolving the active ingredient in a solvent, spraying the obtained solution on the granules of pumice stone and evaporation let sen of the solvent produced.

Weight% Compound No. 5 (Table I) 5

Pumice granules 95

100%

Example 15

An aqueous dispersion formulation was prepared by adding the ingredients listed below to the specified Proportions were mixed and ground.

Wt%

Compound No. 10 (Table I) 40 calcium gnosulfonate. 10

Water 50

An explanation is given below for the preparations or substances that are identified by the various trademarks and trade names were designated in the above examples.

009882/2250

"LUBROL" L is a condensate of 1 mole of nonylphenol

with 13 molar proportions of ethylene oxide.

"AROMASOL" H is a mixed solvent of alkyl

benzenes.

"DISPERSOL" T is a mixture of sodium sulfate and

a condensate of formaldehyde with the sodium salt of naphthalenesulfonic acid.

"LUBROL" APN 5 is a condensate of 1 mole of nonylphenol

with 5 1/2 moles of naphthalene oxide.

"LISSAPOL" NX is a condensate of 1 mole of nonylphenol

with 8 moles of ethylene oxide.

"TRITON" X-100 is an alkylaryl polyether alcohol.

Example 16

The toxicity of a number of the compounds according to the invention to various insects and others invertebrate pests were studied, the running Experiments and the results obtained are shown below. The compounds of the invention were described in used in each case in the form of a liquid preparation containing 0.1% by weight of the compound (1000 parts per million (ppm)}. The preparations were made by dissolving each of the Compounds in a solvent mixture, consisting of 4 parts by volume of acetone and 1 part by volume of diacetone alcohol, produced »The solutions were then diluted with water containing 0.01% by weight of a product sold under the trade name" Lissapol " NX to be obtained wetting agent contained until the liquid preparations reached the required concentrations of the compound ("Liesapol" is a trademark).

009882/2 2-50. original inspected

In the case of the use of the preparations in the tests against Aedes aegypti and Meloldogyne Incognita, these were further diluted until they contained 100 ppm of test compound.

The test procedure used was in principle the same for each type of test and consisted of placing a number of the insects on some medium, which may be a host plant or any food on which insects feed, and either the insect or the medium or treated both with the preparations. The mortality of the insects was then examined in time periods which varied from 1 to 3 days after the treatment.

In the chemotherapeutic sterilization test with Tetranychus te- {larius the operation was as follows: 3 days after spraying plants green beans which were infested with the pest, all living adult pests were transferred from the plants removed and fresh untreated plants. After a further period of 3 days, the adult pests were removed again and all the eggs laid on the plants were transferred to transparent adhesive tape, and after a further period of 3 days the viability of the eggs was examined / )

'00988272250. '. '

In the table HZA below, the columns from left to right indicate the specific designation and the general name of the test species, the host plant or the medium to which these were transferred and the number of days that passed after treatment elapsed before determining the mortality of the pest or other effects, for example when the pest (by the pests). was disturbed (time interval T).

Table IXlA
Carrier Mediura /

^spe2les SS5S. ■ »-»

Tetranychus spider mite green beans. 3 teiarius (fully grown) ' ^J ~

Tetranychus spider mite _grfine ^ _{n 3}

Tetranychus spider mite

telarius (chemoster - green beans -

lization

effect)

Aedes aegypti mosquito '

(waxed plywood I

sen)

Meloidogyne root _{kno- Wa} ~ seT "'ι incognita tennematod © water · ι

The respective © 2ifü®It <s2a <gsi l ^ gebsiiss © mind in the table below

0 means less than 30% kill

1 means 30 to 49% kill

2 means 50 to 90% kill

3 means over 90% kill

Table IHB

species

Liaison men from Table I. 1 6 8 9

Tetranychus telarius
(mature)

Tetranychus telarius
(Egg) -

Tetranychus telarius
(Chemosterilization
test) O 0 2 0 Aedes aegypti
(mature) 0 3 O 3 Meloidogyne incognita 3 O 3 0 example 17th

Preparations according to the invention were prepared in the following ways and in different ways versus different ones fungal diseases arising from the foliage were tested. The working method used for each test will be described below.

An aqueous solution or suspension containing parts per million (ppm) of the test compound which is either

009882/2250

suitable for soaking the soil surrounding the germinating plants or for spraying the leaves of cucumber, vine or apple plants is obtained by adding water to a solution of 200 mg of the compound in 1 ml of acetone until the total volume of the mixture is 400 ml is. An aqueous solution or suspension which is suitable for spraying the leaves of wheat, barley or rice plants is prepared in a similar manner, but instead of water a 1% (v / v) aqueous solution of polyoxyethylene sorbitan monolaurate -Wetting agent "Tween" 20 is used ("Tween" is a trademark).

A. Spray Application Protection Test (P.S.A.)

A suspension or solution containing 500 ppm of the active compound was applied directly to the leaves of plants sprayed using a wetting agent when the plant was wheat, barley or rice. After 24 hours it was inoculate the plant with the test mushroom, and after a suitable period of time (time interval A- see below Table) depending on the particular plant or fungus, the extent of the infection was determined visually.

B. Potion Application Protection Test (P.R.B.)

A suspension or solution containing 500 ppm of the

active compound was applied to those surrounding the test plant

009882/2250

Soil was applied and the fungus was inoculated 48 hours later. The extent of the infection was determined visually after a period of time (time interval B - see below Table) depending on the plant and the Fungus noted.

C. Spray Application Eradication Test (E.S.A.)

The plants were inoculated with the test fungus, and 24 hours later, the liquid preparation became containing 500 ppm of the active compound, sprayed onto the leaves of the plants as described under A. above. After a further period of time (time interval C - see table below), again depending on the specific Plant and the special mushroom that became the extent of the Infection detected visually.

Disease and plant Time interval A
and B (Taqe) Time interval C
(Days) 6th Puccinia recondita
(Wheat) 10 \ 9 Phytophthora infestans
(Tomato) 3 9 Sphaerotheca fuliginea
(Cucumber) 7th -. · Podosphaera leucotricha
(Apple) 10 Uncinula necator
(Wine) 10 Plasmopara viticola
(Wine) 7th

Piricularia oryzae

(Rice) 7 β

Venturia inaequaliÖ 0 9 8 8 2/2250

(Apples). 21. 20th

The results of the tests are shown in the table below, with the extent of the disease in a Graduation is expressed which is the percentage Amount of illness indicating:

Graduation percentage of the
illness until 100 -r until 60 O 61 until 25th 1 26th until 5 2 6th 3 O

OO

co O CM

Table IV

Connection
No.
(Table I) «Puccinia
recondita
(Rust) PRD Phytophthora
infestans
(Tubers
rot) PRD Sphasrotheca
fuliginea
tstaubmel-
dew) PRD ESA ' I. Podosphaera
leucotricha
(Dust reporting
dew). PRD Uncinula
necator
fetaubmel
dew). PRD Plasmopara
viticola
(Rebenje-
ronospora] PRD Firicularia
oryisae
(Fire) ¹ PRD Venturia.
inaequalia
(Schoz H PRD O - PPE 0 PPE PPE 3 PPE 3 PPE 3 PPE 0 PPE 0 PPE OI
CM 1 0 1 0 0 3 0 - 0 3 - 3 0 0 0 0 CS
ar 3 0 0 - «Μ- ■ 0 0 .0 1 0 - - - 2 0 - 0 - OO 4th '~ 3 0 3 0 2 0 0 2 1 - 3 0 3 2 - O 5 3. 0 3 0 0 3 0 0 3. - 3 0 0 1 * * 6 1 - 1 - - 0 - 0 - - - 2 - 0 Μ » % 7th 1 - 0 - - 0 0 - 0 around - - 0 - 8th 0 - 0 - - 0 0 - 0 - - - 0 - 1 9 1 - 0 - - 0 0 2 - - - 0 - 0 10 0 3 - 0 3 - 0 3

- 40 Example 18

The compounds of the invention have also been

compared to various fungal diseases arising from the soil tested by the working methods listed below. ·.,

Test procedure against Fusarium culmorum

The culture Fusarium culmorum was maintained at a 2% Malznährboden in an inclined test-tube at 20 ⁰ C. Thirteen to 17 days prior to testing the chemical, the culture was transferred to ground cornmeal, which consisted of 400g of 5% cornmeal in John Innes seed compost contained in a 1/2 pint bottle . The corn flours were plugged with cotton and sterilized in an autoclave for 2 hours before inoculation, 2 days before the chemical test the seeds and soil were prepared. The soil was prepared by mixing the corn flours with John Innes Compost in a ratio of 2 buckets of corn flour to 3 buckets of compost (capacity of 9 liters, corresponding to 2 gallons). The seeds were prepared by placing 10 grams of wheat seeds in a 20% china clay formulation of the chemical (where the chemical was a powder) or a 12.5% china clay formulation (where the chemical was a liquid ), rolled in a ratio of 1000 ppm (w / w), for example 40 mg of a 25% mixture on 10 g of seeds. To test the chemical, approximately 100 g of des

009882/2250

- Al -

mixed soil placed in a fiber pot, 20 seeds applied to the surface, and about 100 g more des Soil were placed on top of the seeds. This was repeated three times, with a total of 4 reproductions were made. The pots were kept in a greenhouse between 16 ° and 20 ° C. After 10 days the The number of seeds germinated was recorded, and after 17 days the roots were taken out and the number of healthy recorded. These records were made with untreated seeds and compared to seeds with Mercury (Agrosan) and calculations were made to obtain a disease control rating. The results are in the following Table V listed.

Test procedure against Pythium ultimum |

The Pythium ultimum culture was kept on a 2% malt medium in inclined test tubes at 20 ° C. 13 to 17 days before testing the chemical, the culture was transferred to ground cornmeal, which was made from 400 g of a 5% cornmeal in John Innes seed compost, contained in a 1/2 pint bottle, passed. The corn flours were plugged with cotton and sterilized in an autoclave for 2 hours before inoculation. Two days prior to testing the chemical, the seeds and soil were prepared. The soil was groomed by using the corn flours

009882/2250

John Innes-Saatkoropast to 3 1/2 compost pots in a ratio of 2 tubs corn flour (the bucket capacity? 9 1, corresponding to 2 gallons) were mixed. The seeds were prepared by placing 25 grams of peas in a 25% china clay formulation of the chemical (where the chemical was a powder) or in a 12.5% china clay formulation (where the chemical was a liquid ) were rolled in a ratio of 500 ppm (w / w), for example 50 mg of a 25% mixture per 25 g of seed. To test the chemical, about 100 grams of the mixed soil was placed in a fiber pot, 10 seeds were placed on the surface, and an additional 100 g of the soil was placed on top of the seeds. This was repeated five times, making a total of 6 reproductions. The pots were kept between 16 ° and 20 ° C. in a greenhouse. After 10 days the number of seeds germinated was recorded and after 17 days the roots, if any, were removed and recorded as healthy and unhealthy, respectively. These records were compared to untreated crops and crops treated with thiram and drazoxalone, and recalculations were made to grade disease containment. The results are shown in Table V below.

Test procedure against Miizoctonia solani,

The culture Rhlaoetonia solani was based on ground corn flours 0098 ^ 2/22

held »which consisted of 400 g of a 5% corn meal in John Innes seed compost contained in a 1/2 pint bottle. The corn meal was plugged with cotton and placed in an autoclave for 2 hours sterilized before inoculation. 9 days before the chemical was tested, the soil was prepared by mixing the cornmeal with John Innes seed compost in a ratio of 1 bucket of cornmeal λ to 1 1/2 buckets of compost (bucket capacity: 9 liters, equivalent to 2 gallons). 4 days before the chemical test, it was mixed with 400 g of the soil in a 1.14 liter bottle (quart bottle) in a ratio of 100 ppm (w / w). About J.00 grams of John Innes seed compost was placed in a fiber pot, 8 cottonseeds were placed on the surfaces, and 100 grams of the mixed soil was placed on top of the seeds. This was repeated three times, making a total of 4 reproductions. After 13 days, the seedlings were examined for disease. These studies were compared to untreated seeds and seeds treated with pentachloronitrobenzene (PCNB) and calculations were made to obtain a disease control rating. The results are shown in Table V below.

OKGiNAL IHSPECTEO 00988.2 / 2250

Table V

Connection no.
(Table I) Fusariua
culmorum Pythium
ultra space Bhizoctonia
solani 2 3 O 0 . 3 0 3 0
t 4th 3 1 2 '5 0 0 2 6th 3 O 10 2 0 ο

0098Q2 / 2250

Claims (1)

Claims ./ Compound of the general formula: O ' 12 "
R ¹ R ^ NCOQ wherein R is a hydrogen atom or a hydrocarbon group means R represents a hydrocarbon group and Q is naphthaquinonyl or anthraquinonyl. • 2. A compound according to claim 1, characterized in that in the general formula R is a hydrogen atom or an alkyl group with 1 to 6 carbon atoms 2
represents, R represents an alkyl group having 1 to 6 carbon atoms and Q represents either (A) represents a 1,4-naphthaquinon-2-yl radical, which optionally is substituted with one or more alkyl groups with 1 to 6 carbon atoms or with halogen atoms, or (b) represents a 9,10-anthraquinon-1-yl radical. 3. quinone derivative according to claim 2, characterized through either (a) the formula .0-6-NR ¹ R ² 0098-8.2 / 2250 INSPECTED wherein R is a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, R represents an alkyl group with represents to 6 carbon atoms and X represents an alkyl group with Represents 1 to 6 carbon atoms or halogen atoms, or by 0 (b) the formula: P PC-NB ¹ B ² 1 2 wherein R and R are alkyl groups of 1 to 6 carbon atoms represent. 4. A compound according to claim 3, characterized the formula: -C-N CIi, 5. Process for the preparation of a compound according to one of the preceding claims, characterized in that a quinone which bears a hydroxyl group in a suitable position is mixed with a carbamic acid halide of the formula 12 "R ¹ R ^ NC-Hal ORJGINAL INSPEGTiD 00993.2 / 2250 where Hal represents / converts a chlorine, bromine or iodine atom. 6. Pest control product, labeled by containing a compound according to any one of the preceding claims. 7. Pest control preparation according to claim 6, characterized in that it is the compound according to claim and the compound 0 _# 0-dimethyl-0-4 (2-diethylamino-6-methylpyrimidinyl) thiophosphate contains. 8. Use of the compounds or preparations according to one of the preceding claims for combating undesirable pests on plants by applying the . bonds or preparations on the plant or the location of the plant. 00988'2 / 22E0