DK142113B - PYRIDINE DERIVATIVES FOR USE IN INSECTICES - Google Patents

Description

OD PUBLICATION NOTICE 142113

(D

DENMARK <5,> ln, c | S I ^ Dh2I7 / i8 § (21) Application No. 636l / 74 (22) Filed on Dec. 6. 1974 (24) Lobed ag 6. deC. 1974 (44) The application submitted and _

the petition published on 'seP · i yOU

DIRECTORATE OF THE PATENT AND TRADEMARKET (30) Priority granted from the

Dec 10 1973s 2361438, DE

(72) HOECHST MTIENGESELLSCHAFT, Brueningstraese 45, D-6230 Frankfurt / "Main 80, DE.

Inventor: Adolf Studeneer, Kelkheim / Taunus, FI ache land 18, DE: Gerhard Salbeck, KeTkhelm / Taunus, Glogauer Strasse 8, DE: Ludwig Emmel, Bergen-Enkheim, Borngasse 1, DE: Werner Knanf, Eschbor n / Taunus, Bre = mer Strasse 8, DE.

(74) Plenipotentiary in the proceedings:

The engineering company Budde, Schou & Co.

(54) Pyridine derivatives for use in insecticides.

The present invention relates to novel pyridine derivatives for use in insecticides.

The pyridine derivatives of the invention are peculiar in that they have the general formula I

R3 j2 \ 1

R R

12 2

in which one of the groups R, R, preferably R, means a group of formula II

2 142113 O CEL · it s

-O-C-N ^ II

ch 3 and the other means hydrogen or (C 1 -C 4) -alkyl, R 2 and R 4 together represent tetramethylene or a group of the formula -CH = CH - 01 = 01 - where these groups may be substituted by halogen, (C 3) -alkoxy, trifluoromethyl or 1-2 (C1-3) alkyl groups, or R3 and R4 together represent a group of the formula χ .... χκ H2Cv / W-CH2

The compounds of formula I may be prepared. 13 from compounds of formula IIa or mb wherein R, R and R4 or R2, R3 and R4 have the meanings of formula I, however, T 2 R or R does not mean the group of formula II: OH R2

Ok RkA

I I Hib

In Ilia II

R X ^ N / ^ R1 R4X ^ nX ^ 0H

The compounds of formula IIla and Hib may also be present in the tautomeric pyridone form:

OH P

r1No rVS

I Illa v -----------: ------- * [I IIIa 'R ^^ nX ^ R1 r ^^ nX ^ R1

H

R2 R2

RKA. rVs - I Illb -------- .. s I j IIIb

R ^^ NX ^ OH r4X ^ N ^ O

H

In each case, there is thus obtained by the action of bases "ambient" anions, e.g.

* 3 X <x VS - * Vj [rV ^ n / Nr1 rV '' \ n / "^ r1 Θ which, with alkylating or acylating agents, can form both O- and N-alkylation or acylation products, or mixtures thereof.

By selecting suitable reaction conditions, we manage to steer the reaction towards the desired ønskede-acylation products of formula I.

1) According to a variant for the process of the present invention, the compounds of formula IIa or Hib are reacted in a manner known per se to reaction with carbamoyl halides of formula IV

0. CH

t? / J

Hal-C-NT IV

Xch3 wherein Hal represents a halogen atom, especially chlorine or bromine, at least stoichiometric amounts.

However, the halide of formula IV is suitably used in an excess of 10-100 #. For carrying out the reaction, the compounds of formula IIla or Hib are dissolved or suspended in an anhydrous, inert solvent or diluent such as chloroform, an aliphatic ketone, acetone / tril or dimethylformamide, and an organic base such as e.g. triethylamine, pyridine, quinoline or an inorganic basic compound such as e.g. sodium, potassium or calcium carbonate is added in at least stoichiometric amount. Then, at temperatures between 0 and 80 ° C, the N, N - dialkylcarbamoyl halide is added.

In order to achieve the desired 0-acylation of the ambient anions obtained after the addition of bases, it is often advantageous to choose the most polar solvents and lowest possible reaction temperatures. Reaction temperatures above 30 ° C certainly accelerate the reaction, but in some cases with increasing temperature, the proportion of N-acylation product is increased at the expense of the 0-acylation product.

4 142113

The reaction time varies according to the base used and depending on the nature of the substituents R - R. The reaction time usually lasts between four and twelve hours.

2) In yet another variant of the present process, the compounds of formula IIa and b can also be reacted with phosgene or chloroformic acid esters in place of carbamic acid halides, and the resulting intermediates can be reacted with dimethylamine, conveniently in the presence of a solvent or a suitable base.

3) The compounds of formula I wherein R and R form a saturated alkylene ring may also be prepared from the corresponding unsaturated compounds by hydrogenation.

The isolation of the compounds of formula I from the reaction mixture is carried out by methods (1) and (2) in the usual manner by filtration of the separated amine hydrohalides and alkali or alkaline earth metal halides and evaporation of the filtrate containing the reaction product. By the addition of a reduction step (process 3), the catalyst is then removed in the same way. For further purification of the crude products, these may be distilled in vacuo or recrystallized from the usual organic solvents if necessary.

The compounds of formula I are available as colorless to slightly yellowish crystalline solids or high viscous liquids. In most organic solvents, they are readily soluble, yet water soluble. The aqueous solutions react slightly alkaline.

The starting compounds used in the processes of (1) and (2) of compounds of formula III may be prepared in known manner or may be prepared by analogy methods.

The preparation of such suitable starting compounds is e.g. disclosed in the following literature sites: U.S. Patent No. 1,147 · 760 (June 15, 1966), German Publication No. 2,058,002 (June 24, 1971), German Publication No. 1,620,066 (February 12, 1970), German Publication No. 2,105 .728 (IO.8.1972), Chem. Rev. 4j3, 45-68 (1948), J. Am. Chem. Soc. 68, 2685 (1946), 68, 2686 (1946), 6g, 565 (1947), 6g, 571 (1947), £ 6, 574 (1947), Monatshefte fur Chemie 100, 152-155 (1969).

142113 5

The compounds of the invention of formula I are characterized by a very good selective insecticidal effect especially against aphids and excellent systemic properties. They work both when uptake over the green part of the plant and uptake over the root system. Therefore, hidden living aphids within the vegetation and other inaccessible plant parts can also be safely combated. Also phosphorus ester resistant aphids can be effectively combated with the compounds.

Examples of aphids which can be successfully combated with the compounds of the invention are Brevicoryne brassicae,

Myzaphis rosarium, Aphis sehneideri, Eriosoma lanigerum (anemia), bile aphids such as Pemphigus spec, as well as Myzodes persicae. Utility animals within the car group, such as. ladybugs, butterflies, retweets, twins, yearlings, e.g. sponge wasps, and predatory mites, on the other hand, are not eradicated even after using high concentrations of active substance. Likewise, the effect of the compounds on aquatic organisms is poor. Only in high concentration do the compounds in water have an effect on fish.

Dutch Patent Publication No. 66.06695 and Danish Patent Application No. 6105/69 disclose compounds which are closely related to the compounds of the invention and are also insecticidal. However, the compounds of the invention exhibit a significantly stronger insecticidal effect than the compounds known from the Dutch disclosure, as is also apparent from biological example I below. Furthermore, the compounds of the invention have a significantly weaker effect on beneficial insects than the compounds known from the Danish patent application, as shown in biological example VI below.

The compounds of the invention or compositions containing these compounds can be used in many ways. The treatment can be directed to the leaves and / or affected parts thereof or also to the soil surrounding the plant.

Compositions containing these compounds may consist of atomizers, powders or granules in which the active substance is mixed with solid extenders or carriers, such as e.g.

inert substances, are available in powder or granular form. The content of the compounds in these agents is usually 3-75 # · As solid extenders or carriers, e.g. kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, powdered magnesium (chalk), full earth, gypsum, diatomaceous earth and clay are used. The compositions may also be used in the form of spray powders which contain, in addition to the active substance in a known manner, wetting agents and / or dispersants and, optionally, also fillers and / or emulsifiers.

The compositions may also be liquid preparations in the form of emulsion concentrates for spray solutions which normally contain the active substance in the presence of one or more wetting agents, dispersing aids or emulsifiers. Organic solvents can also be used to obtain liquid preparations.

The wetting, dispersing and emulsifying aids can be cationic, anionic or non-ionic in nature.

The compounds of formula I may also be active ingredients in scavenger preparations.

The present invention is further illustrated in the following Examples.

PREPARATION EXAMPLES Example 1 COON (CH 2) o in P 1 CTi 3 2-Methyl-4-dimethylaminocarbonyloxyquinoline a) To a suspension of 75 g, 0.47 mol, 2-methyl-4-hydroxy-quinoline in ca. 1 liter of acetonitrile is added at room temperature to 0 g of anhydrous potassium carbonate and heated under vigorous stirring for approx. two hours to reflux temperature (~ 8 ° C). After cooling to room temperature, 76 * 7 g, 0.71 mole, dimethylcarbamic acid chloride is added and the reaction mixture is stirred well for approx. 8 hours at room temperature. Then, by thin layer chromatography, no 2-methyl-4-hydroxyquinoline is detected in the reaction mixture. The reaction mixture is then freed by separation on suction filters for the inorganic salts and the filter cake washed with acetonitrile. The filtrate and washing liquid are mixed and the acetonitrile removed in water jet vacuum.

U2113

The residual oil is fractionated in vacuo. At 158-168 ° C (0.05 mm), 100 g of colorless, high viscous liquid distills over, whose elemental analysis values correspond to the theoretical values of 2-methyl-4- (dimethylaminocarbonyloxy) quinoline and which are found to be uniform according to thin layer chromatogram and NMR spectrum. In addition to the NMR spectrum, IR spectroscopic data confirm the presence of carbamate.

b) Dissolve 24 g, 0.15 mol, 2-methyl-4-hydroxyquinoline in 200 ml of dimethylformamide (anhydrous and amine-free), add 23 g, 0.22 mol, triethylamine, and then 24 g, 0.22 mol, dimethylcarbamine acid chloride is dropped. The reaction mixture is heated to 60 ° C (approx. 8 hours) so long that, in a thin-layer chromatography sample, starting material is no longer detected. The reaction mixture cooled to 0-10 C is extracted from the separated amine hydrochloride, the filtrate is mixed with the washing solution obtained by washing the filter cake (with slightly cold dimethylformamide) and the solvent is removed in vacuo. The oily residue is distilled fractionally.

21 g of colorless, high-viscous liquid are obtained which pass at 145 ° C (0.01 mm).

Example 2 ocon (ch5) 2 αχ 2-Methyl-4-dimethylaminocarbonyloxy-5,6,7,8-tetrahydroquinoline a) hydroxy-5,6,7 '8-tetrahydroquinoline. To this solution are added successively 267 g, 2.64 mole, triethylamine, and 284.5 S * 2.63 mole, dimethylcarbamine boric chloride.

The mixture is now heated to an internal temperature of 50 ° C until a sample taken from the reaction mixture (approximately after 6 hours) according to thin layer chromatogram no longer contains starting compound.

After cooling to room temperature, ca. One liter of ice water is stirred into the reaction mixture, whereby the amine hydrochloride secreted by the reaction dissolves and forms two liquid phases. After separating the chloroform phase from the aqueous phase, the organic phase is washed with a little water, dried and evaporated.

8 142113

After distilling off a few ml of oily, ester-like odor by-product at a bath temperature of 10 ° C and approx. 2-J mm pressure, the residual oily residue is dissolved in boiling n-hexane. From the cooled solution, g colorless product is crystallized with m.p. 89 ~ 90 ° C. According to the thin layer chromatogram, this product is uniform and provides the elemental analysis values expected for the 2-methyl-4-dimethylaminocarbonyloxy-5,6,7 * 8-tetrahydroquinoline. IR and NMR spectroscopic data confirm the formation of the expected 0-acylation product.

b) In 150 ml of chloroform (anhydrous and alcohol free), dissolve 16.3 g, 0.1 mol, 2-methyl-4-hydroxy-5,6,7,8-tetrahydroquinoline and drop this solution into a pre-prepared solution of approx. 20 g, 0.2 mol, phosgene in 100 ml of chloroform at maximum 10 ° C. After 2 hours at 10 ° C, the mixture reacts for an additional 1 hour at room temperature. Unreacted phosgene is then blown out of the solution with dry nitrogen and the solvent removed in vacuo at room temperature. The semi-solid residue is redissolved in dry, non-alcoholic chloroform, the solution is cooled to 10 ° C and at this temperature dimethylamine is passed into excess. After standing for two days at room temperature, the chloroform is distilled off in vacuo, at the same time removing excess amine. The residue is digested with ice water, decanted from the water and dissolved in toluene. Upon drying and evaporation of the toluene solution, 7 g of residue is obtained, which is crystallized by rubbing off with n-hexane. Recrystallization from n-hexane gives 4 g of uniform crystalline product with m.p. 88-89 ° C. It turns out to be identical to the product obtained according to Example 2 a).

c) To a solution of 20 g of substance according to Example 1 in 1 liter of toluene is added 5 g of "Nickel contact 55/5" (Ruhrchemie, 50% by weight nickel on diatomaceous earth) and with stirring the mixture is heated in a 2 liter steel autoclave with 100 ato hydrogen to 100 ° C. After 20 hours, the mixture is cooled, the catalyst is filtered off, washed with toluene and the filtrate is evaporated. The residue is distilled off and 11 g of product are obtained (bp 0.1 130 ° -142 ° C). This product crystallizes and turns out to be identical to the product of Example 2 (a).

U2113 9 The following table lists other compounds prepared analogously to Examples 1-2, with column 1 indicating the number of the example, in column 2 of the compound of formula concerned, in column 3 the base and solvent used, in column 4 the reaction temperature and the reaction time and in column 5 the melting point, as well as the solvent from which it is recrystallized, and the boiling point and the associated pressure.

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FORMULATION EXAMPLES Example A

A water-dispersible wettable powder is prepared by grinding 12 g of 2-methyl-4- (dimethylaminocarbonyloxy) quinoline as an active substance with 5 g of silica silica (or absorbing it in 5-5 g of silica silica) and mixing it with additional

g of a premix consisting of 10 g of lignin sulfonic acid potassium salt 49 g of Sillitin Z

8 g Silcasil (Ga-Mg silicate and Al silicate) 7 g P 750: Silcasil (= 1: 1) 1 g Hostapon 75 g premix.

Thus, 60 g of this spray powder contains

20% by weight of active substance 49% by weight Sillitin Z

16.5% by weight Silcasil 5.5% by weight palypropylene oxide (- 750) 1% by weight Hostapon 10% by weight lignin sulfonic acid potassium salt.

Example B

An emulsifiable concentrate consists of: 1.5 g (15%) of 2-methyl-4-dimethylaminocarbonyloxy-5,6,7,8-tetrahydroquinoline 6 * 5 g (65%) of cyclohexane as solvent and 2.0 g (20%) of ethoxylated nonylphenol (10 Eto) as an emulsifier.

BIOLOGICAL EXAMPLES Example I

Pot beans (Vicia faba) inserted in pots are infected with every 200 black bean lice (Doralis fabae) and sprayed, after stabilizing the stock with decreasing concentrations of active substance, an aqueous dilution of the emulsion concentrate of the compound of Example 1) until it drips off. After 3 days, the degree of extinction is determined by counting live and dead animals.

In the table below, the mortality thus obtained is shown depending on the concentration of active substance (AS) in the aqueous dilution and is compared with the effect of two compounds of similar structure or comparable efficiency.

Table I

Weight percent AS in AS spray liquid% Mortality

Compound of 0.00019 100 Example # 1 0.000095 98 0.000048 80 0.000024 50 2 0.000375 99 0.00019 84 3 0.0006 100 0.000375 90 4 0.0015 100 0.00075 90 5 0.00019 98 0.000095 70 6 0.000375 100 0.00019 90 7 0.000375 100 0.00019 85 8 0.0015 100 0.00075 95 10 0.00075 100 0.00019 95 0.000095 90 16 0 , 00019 98 0.000095 60 20 0.00019 99 0.000095 85 22 0.00075 100 0.000375 95 24 0.0015 100 0.00075 95 29 0.0015 98 0.00075 95 0.000375 81 20 142113

Table I

AS Weight percent AS in% Mortality _ spray the liquid _____________

Compound of Example No.

27 0.0015 100 30 0.000375 100 0.00019 98 0.000095 92 00 0.006 100 0C0N (CH,) o 0.003 p * 0.0015 60 known from Dutch Publication No. 6,606,695 Comparative Compound i) o '52 0.005 100 η λ 0025 96 (0¾) 2Ν-0-0-4 / θ', 0012 60> \ 0.0006 20 H CH 3

Isolan known (Comparative Compound II)

Example II

About the stem of a ca. A 25 cm high field bean plant in pot is wrapped in cotton (cotton) and covered with cellophane. In the cotton pad, 2 ml of aqueous syringe powder suspension of the compound of Example 1 at the indicated concentration of active substance is evenly distributed evenly by means of a syringe. The aphids present on the leaves of the plant are eradicated after 3 days of observation by the amounts of active substance used as follows:

weight percent AS

1 spray liquid__0.25 0.125__0.06 0.03 0.015 io mortality 100 100 86 ^ 70 <20

This proves that the active substance is capable of penetrating plant tissue and then transported within the conduction pathways. This ability also has the other compounds mentioned in Example I.

21 t Λ 2113

Example HI

An effect on beneficial insects, such as the wasp (Coccygominus turionellae (L.)) cannot be detected at concentrations used to control aphids.

island

A rectangular filter paper (150 cm) is evenly dripped using a pipette with an acetone solution of the active substance in decreasing concentrations. After drying, the filter paper is pushed into a glass tube so that its total interior wall area is covered by the filter paper. Next, in each of the glass tubes 10 thus treated is inserted? wheezing, and after closure with a pierced cork plug, a constant flow of air (10 liters of air / hour) is passed through (exclusion of a possible gas phase, mimic air movement in the open air). Thereby, £ ex. using the compound of Example 1) after 24 hours following mortality. For better comparison with prior art, concentrations of an aqueous spray liquid which, using 600 liters / ha, lead to the same density of active ingredient per column are listed in column 5 of the table below. unit area.

mg AS on weight percent AS

_________ filter_in the spray liquid% mortality

Compound According to 0.012 0.2 100 Example 1 0.006 0.1 40 0.003 0.05 0. 0.0012 0.02 0.0006 0.01 0

Carbaryl (known) 0.0006 0.01 100 (Comparative 0.0003 0.005 100 Compound III) 0.00015 0.0025 40 0.000075 0.0012 0

Isolan (known) 0.003 0.05 100 (Comparative 0.0012 0.02 80 Compound II) 0.0006 0.01 0

The compositions mentioned in biological example I give similar or the same favorable results as the compound of Preparative Example 1.

Example IV

Also, no effect is found on ladybugs (Coccinel lidae), which predominantly feed on aphids, at concentrations used for aphid control. In the above example, this is shown in fully developed individuals of the species Coccinella septempunctata: 22 142113 On a petri dish coated with a pet paper, 10 animals of the above species are placed, upon which an aqueous dilution of the emulsion concentrate of the compound of Example 1 is sprayed (corresponding to to 600 liters / ha). The following mortality values are obtained after 24 hours:

mg AS on the filter weight percent AS

Spraying liquid_% mortality_ 0.003 0.05 10 0.0015 0.025 0 0.0006 0.01 o 0.0003 0.005 o 0.00015 0.0025 o

As to the meaning of slot (2), see Example I.

Example V

The characterization of the compounds in question as environmentally friendly products is proved, among other things. also by their favorable fish toxicity.

3-week-old pup pups are exposed to increasing concentrations of aqueous dilution of the emulsion concentrate for 48 hours in 2-liter glass containers. The following toxicities are obtained: concentration _ppm active substance_% mortality

Compound 100 100. according to Example 1 50 70 30 10 10 0

Carbaryl (known) 100 100 (Comparative 50 100 Compound III) 30 100 10 100 5 100 3 80 1 20

All other compounds of Example I of this group exhibit a similar fish toxicity.

23 142113

Example VI

Investigation of the contact poison effect on bees.

In glass containers, batches of 30 bees for droplet wetness are sprayed with 0.02% aqueous emulsions of the tested compounds and then placed in wooden boxes closed with wire mesh. The bees are then left to themselves at 20-24 ° C. At regular intervals, mortality is determined. Bees sprayed with water serve for control. The results are summarized in the following Table II.

Table II

Compound prepared according to Example No. 15 min. 30 min. Ih 4 h 24 h 48 h 72 h 4 0 0 0 0 3 43 53 1 0 0 0 0 27 33 37 2 3 - 3 33 43 43 43 0-C0-N (CH3) 2 3 23 70 100 - (Danish ans No.

6105/69)

Check 0

The experiment shows that the comparative compound, known from Danish Patent Application No. 6105/69, is highly toxic to bees. Already after 4 hours, all the test animals have died. In contrast, the toxicity of the compounds of this invention is substantially inferior. After 72 hours, mortality has stabilized at around 40-50%.