DE2029079A1 - Pesticides and preparations and their use - Google Patents

Description

PATENT LAWYERS MONKS 2
VAL 33
TEL Mil 172! ZV.
2353 SJ
CABLES: THOPATEMT
TELEX: FOi-ST Dipi.-chem. Dr. D. Thomsen üipi.-ng H. Tfedtke
OiPU-ChBfTuGaBUhHrIg? N? Qn7Q FRANKFURT (UAiN) 50
FUCHSHOHL 71
TEL. "It / Si" ti Dipi.-ing. W.Weinkauff

Reply requested to: Pleas reply to:

8000 Munich 2 June 12, 1970 case PP 21976 / T 3655

Imperial Chemical Industries Limited London / Great Britain

Pesticides and preparations and their use

The invention relates to new chemical compounds having valuable pest control properties pfung, pesticides containing such compounds and processes for their preparation and on methods of controlling plant pests.

The pest control preparations according to the invention contain as active ingredient a compound of the general formula

NO,

00988A / 2225

BATH ORIGINAL

2 - - ^J 7

wherein R is a halogen atom, a kydroxy group or one of them derived ether, a mercapto group or one of them derived thioether, a sulfenylthio group, eir.e unsubstituted or substituted amino group, a ϊί-containing heterocyclic group connected via the nitrogen atom the pyridine ring is attached; . or either (a) a quaternary salt of this compound the general formula:

"1 ■ ■

I ₁ J-

2.

in which R has one of the meanings given above, R is a hydrocarbon group (hydrocarbyl group) and A ^{n is} an anion of valence η, where η is an integer from 1 to 3 inclusive;

or (b) an N-alkylated tautomer of this compound of general formula:

wherein R is a hydrocarbon group and X is oxygen or Represent sulfur atom.

According to a preferred embodiment of the invention 009854/2225

232-3379

pest control preparations are provided, which as Active ingredient a compound of the general formula

contain »where R is a halogen atom, an unsubstituted one or substituted hydrocarbon thio group, one not substituted or substituted alino group, an acylamino group or an N-containing heterocyclic group, which is bound to the pyridine ring via the nitrogen atom.

According to a particularly preferred embodiment of the Invention, a pest control preparation is provided which, as an active ingredient, is a compound of the general formula

contains, where R is a chlorine tone, an alkylthio, arylthio, Aralkylthio, alkarylthio, alkoxycarbonylalkylthio, Amino-, Alkylaiaino-, Dialkylamino-, All-.oxycarbonylalkylaisino-, Cyanoalkylarcino-, Arylaiaino-, Kalocenarylanino-, Benzanido-, Represents calogenbenzaisido or pyrrolidino group.

00986-1 / 2225

BATH ORIGINAL

The term "pest control" used in the present context excludes the ability to destroy vegetation, i.e., herbicidal activity.

Specific compounds which can be used as active ingredients in the preparations according to the invention are listed in Table I below; these all correspond to the general formula

Table I shows the nature of the substituent designated as R and the melting point, expressed as C, given for each compound.

Table I.

(O OO OO

Connect
application no. & • Cl Melting point 1 KKC ₂ H ₅ 118-119 2 MHCK ₃ 152-15 * 3 SH ₂ 173-175 U. . H (CH ₃ ) ₂ 242-2W 5 K (C ₂ H.), 161-162 ό HHCH ₂ COOC ₂ H ₅ 79-80 7th ¹ KKC ₆ H ₅ 127-12 * 8th -N 175-176 9 155-157 10 -SH -f ~ \ 1 * -1 * 6 T

- 5 Table I (port setting)

Connect
application no. <$ - Melting point
( ⁰ C) 11 , Cl 12th 252-253 13th ° / ΓΛ 222-4 14th -NH-CH ₂ -CH ₂ -CN 236 15th -SCH (CH) ₂ 1S3-4 16 · -SCH ₂ CH 107-8 17th -S (CH ₂ ) ₃ CH ₃ 94-5 18th -SCH ₂ CO ₂ C ₂ H ₅ 71-3 19th 100-1 20th 128-9

00988A / 2225

BATH ORIGINAL

Table I (port setting)

Connect
application no. a ^ CH, Melting point 21st ο. 115-0 22nd • a
-SCH ₃
-SH 123-, • -> - Xj 141-2
217-8 25th - / Λ 24S-S 26th ■ O «: 27 .Cl 138-140 ■ ° ~ Ö 28 Cl ^^ 136-138 y
ι • 29 111-113

009884/2225

BATH ORIGINAL

Other specific compounds within the scope of the invention have the structural formulas and melting points set out in Table II below.

Table II

Connect
application no. R. Melting point 30th I _m - 31 ■ γγ - I.
299 I.
C ₂ K ₅

The compounds of Tables ι and II except for compound no. .1 have not yet been described, so new compounds.

In a further embodiment, the invention comprises the connections numbered 2 through 29 inclusive . 00 9 6: - / 2225

fertilize from Table I and the compounds numbered 30 and 31 from Table II.

The compounds according to the invention of the formula:

wherein R has any of the meanings given above can be prepared by reacting a 2-halo-5-nitronicotinnitrile, for example the 2-chloro derivative, and the appropriate amine or alkali salt of the thiol or the phenol with one another. The nitrile is preferably dissolved in an organic solvent, for example ethanol, and the amine is added at room temperature. The resulting solution is then heated under reflux for 2 hours and then ^{cooled to 0} ° C. in order to obtain crystals of the product which can then, if desired, be recrystallized, for example using ethyl alcohol.

The preparations and compounds of the invention are active against fungal diseases from the soil, including the following:

Pythium ultimum (germ drop) - on peas Fusarium culmorum (seedling dry rot) on Wei: Rhizoctonia solani (wound stalk) on cotton Verticillium albo-atrum (wilt) on cotton

0 0 9 e: -i / 2 2 2 5

2029Ö7§

-9 - ■ - ';■■; ■ -. ■ ^:

Compound No. 1 of Table I is particularly valuable against soil fungal diseases, especially versus the first three of the above.

The preparations of the invention also have activity against various foliage-related fungal diseases including, for example, the following special diseases: ■.

Puccinia recondita (rust) on wheat

Podosphaera leucotricha (powdery mildew) on apples

Phytophthora infestans (late blight) on tomatoes

Plasmopara viticola (Meltau vine) on wine

Sphaerotheca fuliginea (Meltau dust) on cucumber

Uncinula necator (powdery mildew) on wine

Piricularia oryzae (fire) on rice

Venturia inaequalis (scab) on apples

Some of the compounds of the invention also have insecticidal activity. For example, Compound No. 9 at 100 ppm (parts per million) gave 100% kill against aphids (Aphis fabae and Megoura viciae), and at 125 ppm, Compounds No. 2, 7 and 13 had a chemosterilizing effect on spider mites on.

A particularly valuable feature of the activity of the compounds according to the invention is peculiar to their ability as internal therapeutic pest control

00 98 34/22 25

to act as agents, that is, their ability to migrate in the plant to combat infection or infestation thereon away from the site of original compound application. Such a compound of the invention or a preparation containing this compound can be ^v applied to the soil around the roots of a plant and taken up by the plant through its roots, to combat pests on the plant.

The compounds according to the invention or the preparations containing them can be used in various ways Way to be applied. So their application can be done in a suitable manner on the foliage of the plant or on the infected and / or infested areas of the plant are addressed; alternatively, the one surrounding the plant Soil are treated with the compounds according to the invention or the preparations containing them. If so desired the seeds themselves can be treated in a similar way.

According to a further feature, a method for controlling undesirable pests on plants is therefore provided, which consists in that, on the location of the plant, a preparation or a compound of those defined above Kind of brings up.

009834/2225

According to a further embodiment of the invention is a method of controlling pests on-plant

zen provided, which consists in applying a preparation or a compound to the plants or their seeds, as defined above. The invention also includes a method of treating agricultural land, which consists in that one on the Soil applies a preparation or a compound of the type defined above.

According to a further embodiment, the invention comprises a method for controlling pests which consists in applying a preparation or a Compound as defined above, applies.

The preparations and compounds of the invention can be used for agricultural and horticultural purposes, and the compound or type of preparation employed in each case depends on the particular purpose for which they are intended.

Preparations containing the compounds according to the invention can be in the form of dusty powders or Granules are present in which the active ingredient with a solid

0 0 SSJ i, 2 2 2.5

Diluent or carrier is mixed. Suitable solid diluents or carriers, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fuller's earth, gypsum, Hewitt ¹ See earth, diatomaceous earth and china clay '(China Clay) be. Preparations for the finishing of seeds can, for example, contain an agent that supports the adhesion of the preparation to the seed, for example a mineral oil.

The preparations can also be in the form of dispersible powders or granules, which in addition to the active ingredient contain a wetting agent to facilitate dispersion of the powder or granules in liquids. Such Powders or granules can contain fillers, suspending agents, and the like.

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

009884/2225

wise quaternary ammonium compounds, e.g. cetyltrimethylammonium bromide. Suitable agents of the anionic type are, for example, soaps, salts of aliphatic monoesters of sulfuric acid, e.g. sodium lauryl sulfate, salts of sulfonated aromatic compounds, e.g. sodium dodecylbenzenesulfonate, sodium *, calcium or ammonium lignosulfonate, Butyl naphthalene sulfonate or a mixture of the sodium salts of diisopropyl and triisopropyl naphthalene sulfonic acids.

Suitable agents of the non-ionic type are, for example, the condensation products of ethylene oxide with ' Fatty alcohols, such as oley alcohol or ceryl alcohol or with Alkyl phenols such as octyl phenol, nonyl phenol and octyl cresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides are the condensation products of the partial esters mentioned with ethylene oxide and the lecithins.

Suitable suspending agents are, for example, hydrophilic Colloids such as polyvinylpyrrolidone and sodium carboxymethyl cellulose and vegetable gums such as acacia and gum tragacanth.

The aqueous solutions, dispersions or emulsions can be prepared by the active ingredient or the

00988-4 / 2226

Dissolves active ingredients in an organic solvent that contain one or more wetting agents / dispersants or emulsifiers can »and then add the resulting mixture to water that in corresponding catfish one or more wetting, dispersing or may contain emulsifiers. Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichlorethylene,

The preparations of the invention can also be used as capsules or microcapsules which contain either the active ingredient itself or a preparation containing the active ingredient and can be replaced by any of the well-known encaps * or microencapsulation techniques. .

The preparations to be used as sprays can also are in the form of aerosols, in which the batch is kept in a container under pressure in the presence of a propellant, such as fluorotrichlonnethane or dichlorodifluoromethane

By incorporating suitable additives, for example to improve distribution, to ensure powder adhesion and resistance to rain on treated Surfaces, the different preparations can be better for

009884/2225

- 15 - '. ■' ■■ V ■■. "'.:

the different uses for which they are intended are to be adjusted.

The preparations and compounds of the invention can also be expediently mixed with fertilizers be set. A preferred preparation of this type consists of granules of fertilizer material with the incorporation of a preparation or compound of the invention for example by coating with it. The fertilizer material can comprise substances containing nitrogen or phosphate, for example.

According to a further embodiment of the invention are therefore pest control preparations or compounds of the type defined above in admixture with one Fertilizer material provided.

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

These concentrates are often required to survive storage for extended periods of time

009B.fc / 2225

and diluted with water after such storage can to form aqueous preparations which remain homogeneous for a sufficiently long time to enable that they are applied by a conventional spray device. The concentrates can expediently contain 10 to 85% by weight of the active ingredient or ingredients and in general 25 to Contain 60 wt. T of the active ingredient or ingredients. In the case of dilution to form aqueous preparations Such preparations can contain varying amounts of the active ingredient or ingredients depending on the purpose for which they are to be used, but an aqueous preparation containing 0.001 to 1.0% by weight of the active ingredient or the Containing active ingredients.

Of course, the pest control preparations of the invention may contain one or more active compounds having biological activity other than those which have been listed above.

The invention is further illustrated by the following examples explained.

example 1

This example illustrates a sprayable liquid containing a mixture consisting of 25 parts by weight of one

009884/2225

Compound no. 1 from Table I and 75% by weight xylene. Example 2

This example illustrates a dusty powder which can be applied directly to plants or other surfaces and 1% by weight of compound no. 1 Table I and 99 wt% talc. .

Example 3

25 parts by weight of the product described in Example 12, 65 parts by weight of xylene and 1p parts of alkylaryl ^{polyether alcohol ("Triton 11} X-100;" Triton ¹ * is a trademark) were mixed in a suitable mixer. In this way there was obtained an emulsion concentrate which can be mixed with water to form an emulsion which is useful for use in agricultural applications. ·

Example 4

5 parts by weight of the product described in Example 12 were carefully mixed in with a suitable mixer 95 parts by weight of talc mixed. In this way, a dusty powder was obtained.

009884/2225

Example 5

10 parts by weight of the product described in Example 12, 10 parts of an ethylene oxide-octylphenol condensate ("Lissapol" NX; "Lissapol" is a trademark) and 80 parts by weight of diacetone alcohol were mixed thoroughly. on a concentrate was obtained in this way, which when mixed * See with water an aqueous dispersion resulted which for Application as a spray in the control of pests is suitable.

Example 6

This example illustrates a concentrated liquid formulation in the form of an emulsion. The ingredients listed below were mixed together in the proportions listed and stirred until the ingredients were

"8 parts were dispersed.

Wt%

Compound No. 1 (Table I) 20

"Lubrol" L ("Lubrol * is a

Trademarks) 17

Calcium dodecylbenzenesulfonate 3 ethylene dichloride 45

"Aromasol" H ("Aromasol" is a

Trademarks) 15

100%

009884/2225

Example 7

The ingredients listed below were mixed together in the proportions listed to achieve to produce a powdered mixture that is easily dispersible in liquids.

Weight l Compound No. 1 (Table I) 50

Dispersol T ("Dispersol" 1st a

. Trademarks) 5

Porcelain clay (China-Clay) * 45

100%

Example 8

A preparation in the form of granules, which are easily dispersible in a liquid (e.g. water), was prepared by grinding the first four of the ingredients listed below in the presence of water, with the sodium acetate then being mixed in. The mixture was dried and passed through a British standard mesh screen, dimensions 44 to 100, passed through to obtain the desired grain size.

Weight% Compound No. 1 (Table I) 50

Dispersol T 12.5 Calcium lignosulfonate 5 Sodium dodecylbenzenesulfonate 12.5 Sodium acetate 20

009864/2225 ■ '■ ^l00%

- 20 -

Example 9

A preparation suitable for use as a seed finish was made by following all three of the following the listed ingredients mixed in the listed proportions

6% by weight

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

China clay 18

100% example OK

A granulated preparation was prepared by dissolving the active ingredient in a solvent, spraying the resulting solution on granules of pumice stone, and allowing the solvent to evaporate.

Weight% Compound No. 1 (Table Z) 5

Pumice granules 95

100%

Example 11

An aqueous dispersion was made by mixing and grinding the ingredients listed below manufactured in the specified proportions.

00988 A / 2225

- 21 - 2029079 Weight ~% Compound No. 1 (Table I) 40 Calcium lignosulfonate 10 water 50 100%

The following is an explanation of the preparations or substances that are identified by the various trademarks and Trade names are given in the preceding examples. ·

"Lubrol" L

"Aromasol" H.

"Dispersol" T

"Lubrol" APN 5

"Lissapol" NX

is a condensate of nonylphenol with ethylene oxide.

is a mixed solvent of alkylbenzenes.

is a mixture of sodium sulfate and a condensate of formaldehyde with the Sodium salt of naphthalenesulfonic acid.

is a condensate of nonylphenol with naphthalene oxide.

is a condensate of nonylphenol with ethylene oxide.

Example 12

This example explains the production of the compound of the structural formula:

CJi

(Compound No. 1 from Table I)

009884/2225

16.5 g of 3-cyano-5-nitro-2-pyridone were refluxed For 3 hours with 41.6 g of phosphorus pentachloride and 30 cm Phosphorus oxychloride heated. The solvents were then removed in vacuo and the residue was cooled on ice, whereupon small portions were added to 100 cm of ice-cold water. Then concentrated sodium hydroxide was added with cooling added to bring the pH to 6. The precipitated material thus obtained was filtered off and air-dried. It was recrystallized using aqueous ethanol: melting point 118 ° to X19 ° C.

The compound of the formula:

Fe · used in the above method became as follows manufactured:

4 cm of a 40% strength aqueous solution of benzyltrimethylammonium hydroxide became a well-stirred solution of 31.4 g sodium nitromalondialdehyde and 16.4 g cyanoacetamide given in 400 ml of water at 20 ° C. The solution turned deep red and solidified into a mass of fine needles, when the temperature rises to 30 ° C in the following 15 minutes was left. It lasted for another 5 minutes

009884/2225

left to stand and then cooled to 5 ° C, whereupon it means The pump was filtered. The crude yellow solid was dissolved in 200 ml of water at 75 ° C and concentrated with 20 ml Treated hydrochloric acid with vigorous stirring. It formed a pale yellow precipitate. The mixture was cooled to 5 ° C and filtered into a chilled Buchner flask. That Product was air dried.

Example 13

This example explains the preparation of the compound with the structural formula:

* ^ _K xSiECHjCOOCjH- (Compound No. 7

from table I)

2.5 g of 2-chloro-3-cyano-5-nitropyridine, 2.0 g of glycine ethyl ester hydrochloride and 2.3 g of sodium acetate were mixed, dissolved in 100 cm of aqueous ethanol, and the solution was heated under reflux for 2 hours. The solvent was then removed in vacuo and the residue dissolved in hot methanol (150 cm ³ CH ₃ OH + 80 cm ³ hot water), filtered and cooled to give pure crystals, m.p.

009884/2225

Example 14

By a procedure similar to that of Example 13, but replacing the glycine ester with the corresponding amines were compounds No. 2 up to and including 6 and 8 through 12 from Table I inclusive.

Example 15

This example illustrates a general procedure for preparing a compound of the general formula

where R is an alkyl, aryl, alkaryl or aralky group.

Potassium carbonate was added in a 10% excess to 0.025 mol of the corresponding thiol in 40 ml of acetone. The mixture was stirred under nitrogen at 30 ° to 35 ° C. for half an hour. Compound No. 1 from Table I. (0.25 mol, prepared by the method of Example 12 above) in 50 ml of acetone was added portionwise, and the mixture was refluxed under nitrogen for 2 hours. The solution was cooled, filtered, and

009884/2225.

the solvent stripped off leaving the product behind, which was recrystallized from methanol or ethanol.

By this procedure, Compounds No. 16 through 18 and 20 through 23 inclusive made from Table X.

Example 16 .

This example illustrates the preparation of 2-carbethoxymethylthio-5-nicotinic nitrile {Compound No. 19 from Table I) of the structural formula:

S-CH ₂ -CO ₂ C ₂ H ₅

Sodium (10% excess) in 100 ml of ethanol was added to 0.025 mol of ethyl thioglycolate in 100 ml of ethanol. The mixture was left under nitrogen at room temperature Stirred for half an hour and the ethanol was stripped off. To the resulting gold-colored oil (ethyl thioglycolate sodium salt), which was partially dissolved in 100 ml of toluene, 0.025 mol of the compound No. 1 from Table I in 100 ml of toluene was added dropwise and the mixture was refluxed under nitrogen for 3 hours. The solution was cooled, filtered, and the solvent

0098 847 222 5

was stripped off, leaving the product behind, v / which was recrystallized from ethanol to give yellow needles, melting point 100-101 ° C.

Example 17

This example illustrates the preparation of Compound No. 24 in Table I, which can be considered as a product with the following two possible t automeren structural formulas.:

X Λ ^mä XX

258 g of mucobromic acid was converted to sodium nitromalondialdehyde by the method listed in “Organic Syntheses Coll. Volume IV, page 844, edited by J. Wiley & Sons, New York) , 2 g of cyanothioacetamide dissolved, and 8 ml of Triton B (technical grade trimethylbenzylammonium hydroxide) were added with vigorous stirring. A temperature rise of 21/2 ° C. was found in half an hour, while a solid formed. The solution was dissolved It was cooled to 5 ° C. and the solid was filtered off and dissolved in 400 ml of warm water . 40 ml of concentrated hydrochloric acid was added with stirring

009 884/2 22 5

added, and an orange immediately formed Mass, the color of which turned yellowish-green when the acid was completely added. The product was in kept the cold and the solid filtered off and boiled with 500 ml of water. After it cooled down, it was the end product is filtered off and recrystallized from water,

ο which resulted in reddish-brown needles, melting point 217 to 218 ° C (decomposition).

Example 18

This example illustrates the preparation of bis (3-cyano-5-nitropyrid-2-yl) disulfide (Compound No. 25 from Table I) with the structural formula:

KC

'2

5 g of the compound obtained in Example 17 above were added to a solution of 1.3 g of sodium hydroxide in 150 ml of water were added and the mixture was stirred until complete solution had occurred. This mixture then became a Solution of 4 g of iodine in 25 ml of ethanol is added dropwise. After the addition was completed, the precipitate was removed by filtration collected »washed with cold, aqueous alcohol and recrystallized from benzene to give a light brown product

0 0988W2225

arose, melting point 248 ° to 249 ° C.

Example 19

This example illustrates the preparation of benzyl 3-cyano-5-nitropyrid-2-yl disulfide (Compound No. 26 from Table I) with the structural formula:

To 0.0125 mol of N-chlorosuecinimide in 50 ml of dry

Benzene, 0.0125 moles of benzyl mercaptan in 25 ml of benzene were

ο °

give, keeping the temperature between 0 and 10 C. The mixture was stirred under nitrogen for half an hour and filtered off. The filtrate became the Product of Example 17 (0.0125 mol) in 50 ml of benzene given at room temperature under nitrogen for one hour stirred and refluxed for a further hour. After it was cold the solvent was stripped off and the remaining solid dissolved in 250 ml of chloroform. The product was made in equal proportions by volume a 5% NaOH solution until the aqueous layer was pale yellow and then dried over CaCl. That Solvent was stripped off and the product was recrystallized from ethanol to give yellow crystals,

0098 8 ^ / 2225

Melting point 140 ° C.

Example 20

This example illustrates the preparation of 2-amino-3-cyano-5-nitropyridine (Compound No. 4 from Table I) with the formula:

0.1 mol of compound No. 1 (Table I) and 0.3 mol of ammonia solution (specific dish 0.9) in 400 ml of ethanol were refluxed for 2 hours with continuous stirring. The solution was cooled and washed of settling solids with water and dried, m.p. 255 ° C bis.256 ^0;

Example 21

This example illustrates the preparation of 2-benzamido-5-nitronikotinnitri1 (Compound No. 13 from Table I) with the structural formula:

009884/2225.

BATH ORIGINAL

A mixture of 0.0125 mol of the compound of Example 20 and 0.0125 mol of benzoyl chloride in 100 ml of pyridine was refluxed for 18 hours. The pyridine was stripped off and the solid that remained was shaken with 250 ml of water and recrystallized from ethanol to give brown needles, melting point 224 ° to 225 ° C.

Example 22

This example illustrates the preparation of 2 (4-chlorobenzamido) -5-nitronicotin nitrile . (Compound No. 14 from Table I) with the structural formula

fc The procedure of Example 21 was followed, from

ser that the reflux was continued for 37 hours and p-chlorobenzoyl chloride used instead of benzoyl chloride became. The product has a melting point of 236 ° C.

Example 23

This example illustrates the preparation of 3-cyano-1-methyl-5-nitropyrid ™ 2-one (Verblraörang Mr. 3O from table II) with the

009

t.A.

129 g of mucobromic acid was converted to sodium nitromalondialdehyde. The wet cake was poured into 200 ml of water dissolved at room temperature with 8.2 g of N-methylcyanoacetamide, and 2 ml of Triton B were added with stirring. The solution changed its color to deep red with an increase in temperature of 5 ° C in the course of 15 minutes. The solution was acidified with concentrated hydrochloric acid, whereby gave a yellow solid which was recrystallized from water to produce colorless needles, melting point 166 ° C.

Example 24

This example illustrates the preparation of 2-chloro-S-cyano-1-ethyl-S-nitropyridinium fluoroborate (Compound no. From Table II) with the structural formula:

Cl

0 C ζ S -. i / 2 2 2 5

202907

0.025 mol of compound no. 1 from Table I and 0.025 mol of freshly prepared triethytoxonium fluoroborate were dissolved in 100 ml of nitromethane. The solvent was evaporated under reduced pressure at about 50 ° C. 100 ml of CH ₂ Cl- was added to the residue and heated on a steam bath for a quarter of an hour. When the volume of the solvent was reduced to about 10 ml, the solution was cooled and a white solid separated out. This was recrystallized from acetonitrile, giving colorless crystals, melting point 229 ° C. (decomposition).

Example 25

Preparations according to the invention were made up and tested against various fungus diseases arising from the soil. The procedure * used in these tests and the results obtained in each of these tests are shown below.

Test procedure against Pythium ultimum

Portions of about 1 g of a culture of Pythium ultimum, which were kept on a 2% agarose Malznährboden in inclined test tubes at 20 ⁰ C, is transferred to about 400 g sterilized soil containing 5% corn flour in a 0.29 1 bottle ( half pint bottle). After 10 to

009884/2225

For 14 days the inoculated soil was covered with sterile John Innes seed compost mixed in a ratio of 2 bottles to 3 1/2 pails having a capacity of approximately 9 liters (2 gallons). The mixture is moistened and covered and after 3 days used as follows. About 100 g of the mixture are put in a fiber pot, and IO pea seeds, which had been coated 2 days previously with the test chemical in an amount of 500 ppm are on the surface of the floor speckled. Another 100 g of the mixed soil is then placed on top of the seeds, and the pot is placed in e S ^ greenhouse at 16 to Held at 22 C. A first emergent seedling count is taken after 10 days and a suppurative count is made Allow a week to elapse before making a second visual assessment by pulling out the seedlings and inspecting of their roots takes place. Perform six repetitions (reproductions) and the number of healthy seedlings as well as the number of unhealthy seedlings determined. The number of non-germinated seeds is 10 less than the number of emerging seedlings. Comparative tests in which untreated seed is used, as well as standard experiments in which thiram-treated seeds are used executed at the same time. Then calculations are made by which a graduation for disease control is obtained.

0098 84/2225

- 34 Test procedure against Fusarium culmorum

A culture of Fusarium culmorum grown on a mixture of soil and wheat flour is mixed with the Test John Innes seed compost, and the total mixture is then poured into brown paper and inoculated in a glass greenhouse for 48 hours. The inoculated soil is placed in pots. Then the seeds (20 per pot) which have been treated with china clay containing the compound according to the invention in a concentration of 1000 parts per million are sown in the pots. Quecksilbersaatappretur treated "are then made counts of emerging seedlings IO day after seeding and the results to a percentage" rate of sown seeds converted. disease investigations be made 16 days after seeding "

Test procedure against Rhizoctonia solani

In this test, an inoculation of Rhizoctonia solani is placed in a partially sterilized clay soil ', around the latter with a 1% (w / w) content of the inoculation to provide. The clay soil is then left to stand for a week in order to protect it from the pathogens

0098 84/222

to be colonized. Then the connection with the clay soil mixed in an amount of 100 parts per million parts of soil (on a weight basis). After standing during 4 days to let the chemical work, plastic pots are half filled with untreated, partially sterilized clay soil and cottonseed on the surface sown, whereupon the pots are covered with the treated clay soil will. A comparison test with P.C.N.B. (Pentachloronitrobenzene) carried out. The pots are then inspected and examined for disease 13 days later.

In Table III below, the numbers in the right column denote the compounds tested in the corresponding numbering (see Tables I and II above), and the number of graduation below it is in Brackets. The particular disease is listed in the left column, and the concentration of the one used Compound listed in brackets under the disease name.

The results are in the following graduation

expressed

009884/22 2.5

BATH ORIGINAL

Graduation O

Meaning of the graduation

No activity or up to 20% of that given by the standard experiment Disease control.

20 to 75% of the disease control given by the standard experiment.

75 to 99% of the disease control given by the standard experiment .

Extent of control equal to or better than the standard experiment.

Table III

illness

Connection number and graduation

Pythius: ultisuo 1 .8th '(O • ¹ \ · 16. 19th 21st (joo ppa .; (3) '(3) . 9. • (O * (Ο * (O ' (O Fusariuc culsorus 1 . 5 . 7th 10 .11 .18 (tOOO ppz ..) (8) '(1) (O '(1 ) '(O ■ Rhizoctonia aolani 1 . 6th (100 ppc.) (3) '(1) Verticilliua albo- 30th atrua
(100 ppa.) (2)

Example 26

Compounds according to the invention were prepared in the following way and in various ways against various fungal diseases arising from the foliage '

009884/2225

units tested. The following is the one used for each test Function described.

An aqueous solution or suspension containing 500 parts per million (ppm) of the test compound which is either to water the surrounding the growing plants Soil or suitable for spraying the leaves of cucumber, vine or apple plants is obtained by adding water a solution of 200 mg of the compound in 1 ml of acetone is added until the total volume of the mixture is 400 ml. An aqueous solution or suspension suitable for spraying onto the leaves of wheat, barley or rice plants is suitable, is prepared in a similar manner, but instead of water a 0.1% (v / v) aqueous Solution of the wetting agent polyoxyethylene sorbitan monolaurate, "Tween" 20, is used ("Tween" is a trademark).

A. Spray Application Protection Test

A suspension or solution containing 50,000 ppm of the active compound was applied directly to the leaves of plants sprayed using a wetting agent if the plant was wheat, barley, or rice. After 24 hours, the plant was inoculated with the test mushroom, and after another suitable length of time, (time interval A - see Table IV below) - depending on the particular plant

00988A / 222S

2023079

and the respective Pils ~ was the extent of the infection visually determined.

B. Potion Application Shutatest

^H A suspension or solution containing 500 ppm of the active compound was applied to the area surrounding the test plant w soil, and 43 hours later, the plant was inoculated with the fungus. The extent of the infection was determined visually after a period of time (time interval B - see Table IV below) - depending on the plant and the fungus.

C.

The plants were inoculated with the Testpils, and 24 hours later the liquid preparation, which 500 ppra of the active compound contained on the leaves of the plants, as described above under A., sprayed. After a further period of time (time interval C. see Table IV below) - again depending on from the respective Pf! ans © and ö <gm respective mushroom - became the extent of the infection was determined visually. '

The results of these tests are given in Table V, before Table TW follows:

983A./2225

division expressed, which is the percentage of the Illness indicates:

Graduation Percentage of the disease 10 - O 61 to 100
1 26 to 60
2 6 to 25
3 0 to 5
Table IV 3 , ^ V "» **. * ■■ ,, time intervals
Illness and time interval
Plant ' ^A ₍ £ f <^ e> 7th - Puccinla O recendita 10 S. (Wheat} Phytcjshthora 9 (Tomato]_ 10 Sphaarotheea - (Cucumber) 7th 6th Podosnhaera 20th leueotricha 7th (Apple) Unc i mil a * (Wine) ■ Pl & smcpara vitLcola (Wine) Piricularia cryzae
(Rice) V «r.tari * LTAt CUiIiS (Apple)

OOSS: 4/22 2 5

Table V

illness

Spray application root protection test soak protection test

Spray application eradication test

(Tea A) (Test B) « (Test C) Puccinia 13 .27 .30
(2) '(2)' (1) (O ^; (1) recondite
(Wheat) 2 .16 .23
(1) '(3) · (3) 2. 5 .28
(2) '(3)' (1) Phyto ^ hthora 2. 3 .15 .29
(2) '(2)' (1) '(1) 2
(3) 1.2.3
(2) '(1)' (1) infestans 14 .16 .19 .20.
(3) '<2)><2)' (1) '
22 .2Ir .25 *
(2) '(2)' (2) (Tomato) 13 .14 .23 .31
(3) '(2)' (3) '(3) Sphaerotheca * . 3 / Λ .29
(Ο (Ο (Ο (2) fuli ^ inea 13 .14 .15 .16
(1) '(1)' (3) '(2) (Cucumber) '20 .23,
(3) / (2) Plasaopara ▼ iticola (Wine) Uncinula necator (Wine) Piricularia
cryzae
(Rice) Podcsphaera. leucotrieha
(Apple) Venturia Inaecjualih (Apple)

009884/2225

BAD ORlGIHAU

Claims (7)

Patent claims 1. Pest control preparations, characterized that it is a compound of the general formula as an active ingredient ~, CN contain, wherein R is a halogen atom, a hydroxy group or an ether derived therefrom, a mercapto group or a thioether derived therefrom, a sulfenylthio group, an unsubstituted or substituted amino group or an N-containing heterocyclic group which via the nitrogen atom is attached to the pyridine ring represents; or either (a) a quaternary salt thereof with the general Formula: NO, where R has one of the meanings given above, R is a hydrocarbon group and A ⁿ ~ is an anion of valence η, where η is an integer from 1 to 3 inclusive? or (b) an N-alkylated tautomer thereof having the general formula 009884/2225 ^ X E ² wherein R represents a hydrocarbon group and X represents an oxygen or sulfur atom, "optionally mixed with a fertilizer. 2. pest control preparation according to claim 1, characterized in that it is a compound of the general formula as active ingredient contains, in which R is a halogenated *, an unsubstituted or substituted hydrocarbon thio group, an unsubstituted or substituted telßo group, an acylaraino group or an H-containing lieteroeyelis group which is bonded to the pyrldine ring via the nitrogen atom. 3. Pest control preparation according to one of the preceding claims, characterized ^ that it as an active ingredient a compound of the * formula 0038 34 / 222S original, erected - 43 - Contains where R is a chlorine atom or an alkylthio, arylthio, aralkylthlo, alkarylthio, alkoxycarbonylalkylthio, _r amino, alkylamino, dialky, amino, alkoxycarbonylalkylamino, cyanoaikylamino, arylamino, haloarylamino, benzamldo-, halobenzene - Or represents a pyrrolidino group. 4. Pest control preparation according to one of the ■ preceding claims for use as a fungicide, characterized in that it is a compound as active ingredient the formula contains. OC3 8 IU / 2225 2029073 5. Use of the preparations according to one of the preceding claims for combating undesirable "" Pests on plants by application to the location of the plant. 6. Use of the preparations according to one of the preceding claims for combating pests to plants by application to the plants or their seeds. 7. Use of the preparations according to one of the preceding claims for combating pests by Application to the pests or to the site of occurrence of the pests. . » 009884/2225