DE2420068A1 - N, N-DIMETHYL-0- SQUARE CLAMP ON 1-ISOPROPYL-5-N, N-DIMETHYLCARBAMINYLTHIO1,2,4-TRIAZOL (3) YL SQUARE CLAMP ON CARBAMIC ACID ESTER, THE PROCESS FOR ITS MANUFACTURING AND USING ITS USE - Google Patents

Description

Bayer Aktiengesellschaft 2 4. “* ■

Central area patents, trademarks

and i

. 509 Leverkusen. Bayerwerk

Rt / As

IJ, N-dimethyl-O-Zl-isopr opyl-5-N, N-dimethy 1-carbaminylthio-1, 2,4-triazol (3) yi7- ^{car1 :)} amino acid ester, process for its preparation and its use as an insecticide

The present invention relates to the new N, N-dimethyl-0- / T-isopropyl-5-N, II-dimethylcarbaminylthio- _1,2-t 4-triazol (3) yl / carbamic acid ester, a process for its preparation and its Use as an insecticide.

It is already known that the N, N-dimethyl-0- / 1-phenyl-3-methyl-pyrazol (5) yl7-carbamic acid ester has insecticidal properties (see Swiss patent specification 282,655).

It has been found that the new UjN-dimethyl-O-Zl-isopropyl-5-N, N-dimethylcarbaminylthio-1,2,4-triazole (3 ^! / - carbamic acid ester of the formula

S-CO-N (GH ₅ )

has an excellent insecticidal effect. Le A 15 653 - 1 -

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It has also been found that the new ΙΓ, Ιί-dimethyl-Op.-isopropyl ~ 5-N _i N-dimethylcarbaminylthio-l, 2,4_triazol (3) yl) - 'carbamic acid ester of constitution (i) is obtained when l -iso-propyl-J-hydroxy ^ -mercapto-1,2,4-triazole of the formula

SH

(II)

-G ₃ H ₇ -Lo

optionally in the presence of an acid acceptor or in the form of the alkali, alkaline earth or ammonium salts with at least 2 moles of NyN-dimethylcarbamic acid chloride of the formula

(CH ₃ ) ₂ N-CO-Cl (III)

optionally in the presence of a solvent or diluent implements.

Surprisingly, the ΪΓ, Ν-dimethy according to the invention shows ΙΟ- [l-isopropyl-5-NjN-aimethylcarbaminylthio-l, 2,4-triazol (3) -ylj-carbamic acid ester (i) a better insecticidal effect than the previously known Ν, ΪΤ-dimethyl-O- [l-phenyl-3-methylpyrazol- (5) yl] -carbamic acid ester analogous constitution and the same direction of action. The substance according to the invention thus represents a real asset to technology.

If you use l-iso-propyl ^ -hydroxy-S-mercapto-l, 2,4-triazole and NjN-dimethylcarbamic acid chloride as starting materials,

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the course of the reaction can be shown by the following equation be reproduced:

SH - HTeT- ,, S-OOJ (OB.),

(CH ₃ ) ₂ B-C0-01 ^gate . (CH.), H-CO-OI

The i-iso-propyl-3-hydroxy-5-mercapto-1,2,4-triazole which can be used as starting material and the Ν, Ν-dimethylcarbamic acid chloride are unambiguous by the formulas (II) and (III) Are defined.

The N, N-dimethylcarbamic acid chloride to be used as the starting material is known from the literature and can be prepared by generally customary processes, as is the 1-iso— Propyl-3-hydroxy-5-mercapto-1,2,4-triazole, e.g. Implementation of

a) ethyl chlorocarbonate with potassium thiocyanate and then is made with iso-propylphenylhydrazone, or by implementing

b) Carbonic acid ethyl ester hydrazide and acetone and then catalytic hydrogenation, reaction with hydrogen rhodanide and cyclization in the presence of alcoholate can be produced according to the following formula scheme »

a) CH = O-CO-Cl + KSCN> C ₂ H ₅ O-CO-NCS +

-KCl

Water + HCl N ^ /

C ₂ H ₅ O-CO-NH-CS-NN = C (CH ₃ ) ₂ > HO- (χ J

C ₃ H ₇ iso

(H)

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SH
NNG ₃ H ₇ -ISO

b) C ₂ H ₅ O-GO-NH-NH ₂ + (GHG) ₂ GO) G ₂ H ₅ 0-CO-NH-N = C (CH _3);

^ _n + HSCN

⁺ ^ ² _x C ₂ H ₅ O-GO-NH-NH-C ₃ E ₇ -IsO} C ₂ H ₅ O-CO-NH-N-CS-NH ₂

7 τ

C ₃ H ₇ iso

+ Alcoholate _ϋΓι /

SH
N-

F- ^ TC ₃ H ₇ -ISO
(ID

The process for making the compound of the present invention is preferably carried out with the use of suitable solvents and diluents. As such, come in handy all inert organic solvents in question. These include in particular aliphatic and aromatic, if appropriate chlorinated hydrocarbons such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, or ethers, e.g. diethyl and dibutyl ethers, dioxane, also ketones; for example acetone, methylethyl-, methylisopropyl- and methyl isobutyl ketone, as well as nitriles such as aceto- and propionitrile.

All customary acid binders can be used as acid acceptors find »Alkali carbonates and alcoholates such as sodium and potassium carbonate and methylate have proven particularly effective or ethylate, also aliphatic, aromatic or heterocyclic Amines, for example triethylamine, trimethylamine, Dimethyl aniline, dimethylbenzylamine and pyridine.

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The reaction temperature can be varied within a relatively wide range. Generally one works between ο and 12o ° C, preferably at 5o to 9o ° G.

The reaction is generally allowed to proceed at normal pressure,

To carry out the process, 1 mol of the hydroxytriazole component is generally employed in 2 mol of N, N-dimethylcarbamic acid chloride. The reaction is preferably carried out in the presence of one of the abovementioned solvents, if appropriate in the presence of an acid acceptor, at the temperatures indicated. After a reaction time of one to several hours, usually at elevated temperature, the batch is cooled, any solids present are suctioned off, the solvent is evaporated off in vacuo and the residue is dissolved in a little water. The aqueous phase is extracted with an organic solvent, for example chloroform. After drying the organic phase _; the solvent is distilled off and the residue solidifies. It can be purified by recrystallization, for example from an ethyl acetate / ligroin mixture. The substance is crystalline with a sharp melting point.

As already mentioned several times, the N, N-dimethyl-O- [l-iso-propyl-S-NjNTdimethylcarbaminylthio-1,2,4-triazol (3) yl] carbamic acid ester according to the invention is distinguished characterized by an excellent insecticidal effectiveness. With low phytotoxicity, it has both a good effect against sucking as well as biting insects.

For this reason, the connection according to the invention can with Success in crop protection can be used as a pesticide.

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The sucking insects mainly include aphids
(Aphidae) such as the green peach aphid (Myzus persleae),
the black bean (Doralis fabae), oat (Rhopalosiphum
paal) " Pea (Macrosiphum pisi) and potato mouse (Macrosiphum solanifolii), furthermore the currant gall (Cryptomyzus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black cherry aphid (Myzus cerasi), also shield - and mealybugs (Coccina), for example the ivy shield louse (Aspidiotus hederae) and cup lice (Lecanium hesperidum) and the mealybug (Pseudococcus maritimus);
Bladder feet (Thysanoptera) such as Hercinothrips femoralis and
Bed bugs, for example beet bugs (Piesma quadrata), cotton bugs (Dysdercus intermedius), bed bugs (Cimex lectularius), predatory bugs (Rhodnius prolixus) and chaga bugs (Triatoma infestans),
also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

Among the biting insects, butterfly caterpillars (Lepidoptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar) and golden juices should be mentioned in particular
(Euproctis chrysorrhoea) and Ringelspinner (Malacosoma neustria) to continue the cabbage (Mamestra brassicae) and the turnip moth (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae) _# small Prost tensioner (Cheimatobia brumata), green oak (Tortrix viridana), the army - (Laphygma frugiperda) and Egyptian baaai woolworm (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestia kühniella) and large ones
Wax moth (Galleria mellonella),

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Furthermore, the biting insects include beetles (Coleoptera) e.g. grain (Sitophilus granarius = Calandra granaria), Potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), raspberry (Byturus tomentosus), table bean (Bruchidius = Acanthoscelides obtectus), Bacon (Dermestes frischi), khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), corn (Calandra or Sitophilus zeamais), bread (Stegobium paniceum), common meal (Tenebrio molltor) and grain beetle (Oryzaephilus surinamensis), but also species living in the ground such. B. wireworms (Agriotes spec.) And white grubs (Melolontha melolontha); Cockroaches like that German (Blattella germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia maderae), Oriental (Blatta orientalis), giant cockroach (Blaberus giganteus) and black cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; also Orthoptera e.g. the cricket (Gryllus domesticus); Termites such as the terrestrial termites (Reticulitermes flavipes) and Hymenoptera such as ants, for example the meadow ant (Lasius niger).

The Diptera essentially comprise flies like the Tau (Drosophila msianogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domestica), small room (Fannia canicular is), gloss fly (Phormia regina) and blowfly (Calliphora erythrocephala) as well as the calf gnaw (Stomoxys caloitraris); also mosquitoes, e.g. mosquitoes such as the yellow fever (Aedes aegypti), house mosquito (Culex pipiens) and malaria mosquito (Anepheles Stephens!) "

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The active compounds according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granulates. These are in known - produced, "e.g. by mixing the active ingredients with extenders, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In the case of using tob. Water as an extender can also be organic, for example Solvents can be used as co-solvents. The main liquid solvents that can be used are: Aromatics such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons such as chlorobenzenes, chloroethylene or Methylene chloride,

aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutylene ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, soio.Q water ; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons, for example freon; as a solid carrier, natural rock powder, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomeenerae and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates; as emulsifying and / or foam-forming agents, nonionic and anionic emulsifiers, such PoIyoxyäthylen fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl ₀ polyglycol ethers, alkylsulfonates, alkyl sulfates> Ary sulfonate and protein hydrolysates;! as dispersants, for example, lignin, sulphite waste liquors and methyl cellulose. The active ingredients according to the invention can be present in the formulations as a mixture with other known active ingredients.

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The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90 %.

The active ingredients can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, emulsions, foams, suspensions, powders, pastes, soluble powders, dusts and granules be applied. It is used in the usual way, e.g. by spraying, atomizing, atomizing, dusting, Scattering, smoking, gasifying, pouring, pickling or encrusting.

The active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. In general they are between 0.0001 and 10 %, preferably between 0.01 and 1 %.

The active ingredients can also be used with good success in the ultra-low-volume process (ULV), where it is possible to apply formulations of up to 95% or even the 100% active ingredient alone.

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Example A.

Myzus test (contact effect)

Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified Amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired Concentrate *

Cabbage plants (Brassica oleracaa), grows strongly from the peach aphid (Myzus persicae) are infected, sprayed to runoff.

After the specified times, the degree of destruction is determined in%. 100 % means that all aphids have been killed ;, O % means that none of the aphids have been killed

Active ingredients ₉ active ingredient concentrations, evaluation times and results g & h & n from the following table 1 »

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Table 1

(plant damaging insects)

Myzus test

Active ingredients

Active ingredient concentration in $>

Degree of destruction in $> by day

'Ϊ ii il ³

(known)

0.1 0.01

98 0

O (CH, JoN-C- (

0.1 0.01

100 98

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Example B.

Doralis test (systemic effect)

Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the production of an appropriate preparation of the active substance 1 part by weight of active ingredient is mixed with the stated amount of solvent and the stated amount of emulsifier and dilutes the concentrate with water to the desired concentration.

The preparation of the active compound is used to produce bean plants (Vicia faba) which are strongly influenced by the black bean louse (Doralis fabae) are infected, poured on, so that the preparation of active compound penetrates the bed without the leaves of the bean plants to wet. The active ingredient is absorbed from the soil by the bean plants and thus reaches the infected ones Scroll"

After the specified times, the degree of destruction is determined in % . 100% means that all aphids have been killed, 0 % means that none of the aphids have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 2 below

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Tabel

(plant damaging insects)

Doralis test (sjst. Effect)

Active ingredients

Active ingredient concentration in

Degree of destruction in io after

4 days

HC - C-CH,

(CH,) ^ NCOC ^{5 ά}

(known)

0.1 0.01 100 0

_N SCN (CH ₃ ).

(CH,) ₂ NC-0- ( _x

^X N- ^ fC, H _r ,

0.1 0.01 100 100

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Manufacturing example

S-GO-N (OH ₃ ) ₂

44 g (0.4 mol) of N, N-dimethylcarbamic acid chloride and 41 g of iriethylamine. The mixture is refluxed for 8 hours, any pest bodies present are filtered off with suction and the solvent is evaporated off in vacuo. The residue is dissolved in a little water and extracted with chloroform. The organic phase is dried, evaporated in vacuo and the solidified residue is recrystallized from an ethyl acetate-ligroin mixture. 26 g (43 ° / ° of theory) Ν, Ν-dimethyl-O- [l-iso-propyl-S-N, N-dimethylcarbaminylthio-l, 2,4-triazol (3) ylj-carbamic acid ester with a melting point of lo5 are obtained ° C.

The production of the "used as a starting material" l-iso-propyl ^ -hydroxy-S-mercapto-l ^^ - triazoles (II) can E.g. in the following way:

a) CjJiH ₅ 0-CO-NH-NH-C ₃ H ₇ -iso

A solution of ethyl carbonate hydrazone (C ₂ H ₆ O-CO-NH-N = G-CH ₃ made from ethyl carbonate hydrazide and acetone) with a melting point of 70 ° C in 500 ml of ethanol is treated with 10 g of a 5 $> platinum-carbon catalyst Hydrogenated ^{at 60 °} C. under high pressure. The reaction mixture is then filtered,

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the solvent was evaporated and the residue was distilled at 87 ° C./6 torr. Ho 'g (76 ^l / ° of theory) of N-iso-propyl-carbonic acid ethyl ester hydrazide with a refractive index of 1.4362 is obtained.

_t ) C ₂ H ₅ O-CO-IIIH-N-CS-NH ₂

t
C ₃ H ₇ iso

To 73 g (e, 5 mol) of the product obtained described under a) 45 ml of concentrated hydrochloric acid and then 50 g of potassium rhodanide are added to 200 ml of water. The reaction mixture is briefly boiled, evaporated in a vacuum of 30 mm and heated then 2 hours at 100 ° C. It is then cooled and recrystallized from water. The product is available in $ 68 Yield obtained with a melting point of 168 ° C.

SH

a ₂ ) ΗΟ-ς j

N-N-i

C ₃ H ₇ -ISO

1 mol of sodium methylate solution is added to 205 g (1 mol) of the product obtained described under a _x ) in 400 ml of methanol and the mixture is refluxed for 8 hours. The reaction solution is then evaporated and the residue is suspended in a little water. It is acidified with 80 ml of pure concentrated hydrochloric acid, the precipitate is filtered off with suction, washed and recrystallized from methanol. This gives 96 g (6o ° / o of theory) of l-isopropyl-3-hydroxy-5-mercapto-triazole (l, 2,4) having a boiling point of 228 ⁰ C.

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Claims (6)

Claims J. 1. The compound N, N-dimethyl-0- / i "-isopropyl-5-1, N-dimethylcarbaminylthio-1,2,4-triazole (3 ^ / - carbamic acid ester. 2. Process for the preparation of the K, N-dimethyl-0- / T-isopropyl-5-lJ, N-dimethylcarbaniinylthio-1,2,4-triazole (3 ^! / - carbamic acid ester, characterized in that i-isopropyl-3-hydroxy-5-mercapto-1,2,4-triazole in the presence of an acid acceptor or in the form of the alkali, alkaline earth or ammonium salt with at least 2 mol Ν, Ν-dimethylcarbamic acid chloride, optionally in the presence of a solvent or diluent implements. 3. Insecticidal agents, characterized by a content to N, F-dimethyl-0- / T-isopropyl-5-N ", li-dimethylcarbaminylthio-1,2,4-triazol (3) yl7-carbamic acids ster. 4. A method for combating insects, characterized in that ΪΓ, Ιί-dimethyl-O- / T-isopropy 1-5-N, H-dimethylcarbaminylthio-1,2,4-triazol (3) yl7-carbamic acid ester can act on insects and / or their habitat. 5. Use of UjN carbaminylthio-1,2,4-triazol (3) yl7-carbamic acid ester for the control of insects. 6. Process for the preparation of insecticidal compositions, thereby characterized in that υ, Ν-dimethyl-O- ^ T-isopropyl-5-N, H-dimethyl-carbaminylthio-1,2,4-triazol (3) yl7-carbamine acid esters mixed with extenders and / or surfactants. Le A 15 653 - 16 - 509846/1027