DE2245344A1 - N-sulphenylated n-methylcarbamic acid aryl esters - - insecticides acaricides nematocides - Google Patents

Abstract

Cpds. of gen. form.(I) where X = H or halogen R = opt. alkyl, alkenyl, alkoxy, alkenoxy, alkylmercapto or dioxolanyl-substd. phenyl, naphthyl or dihydrobenzofuranyl; are prepd. by reacting a cpd. (II): with pref. max. 20% excess of a cpd. R-OH in the presence of a diluent and acid-binding agent at pref. 20-40 degrees C. (I) have high insecticidal and acaricidal act. against organisms harmful to plants and hygiene. They have partly fungicidal act. and are active against nematodes and soil insects. (I) have low phytotoxicity and high residual act. on wood and loam as well as high stability on white-washed surfaces.

Description

N-sulfenylated aryl N-netliylcarbamate, process for their Manufacture and their use as insecticides and acaricides ~ The present The invention relates to new N-sulfenylated N-methylcarbamic acid aryl esters, which are insecticidal and have acaricidal properties and a method for their preparation.

It has already become known that trihalomethylsulfenylated Aryl N-methylcarbamate are very good insecticides and the unsubstituted ones Carbamates due to their better insecticidal effectiveness and their lower toxicity to warm blooded animals protrude (DOS 1 922 929).

The disadvantage, however, is that representatives of this series often have one have certain skin-irritating effects, which makes them technically usable in many Areas prevented.

Furthermore, it has already become known that N-substituted aryl carbamates have insecticidal properties (cf.

DOS 1 949 2341 The disadvantage of these compounds is their, especially at low application concentrations, low effectiveness.

It has now been found that the new N-sulfenylated N-methylcarbamic acid aryl ethers of the general formula in which X is H or halogen and R is optionally substituted by alkyl, alkenyl, alkoxy, alkenoxy, alkylmercapto, dioxolanyl, phenyl, naphthyl or dihydrobenzofuranyl radicals have strong insecticidal and acaricidal properties. The compounds according to the invention are also effective against phytopathogenic fungi and resistant aphids.

It has also been found that N-sulfenylated N-methylcarbamic acid aryl esters of the formula I are obtained if substituted carbamic acid fluorides of the formula II in which X has the meaning given above with compounds of the formula III R - OH III in which R has the meaning given above, reacts in the presence of a diluent and an acid-binding agent.

It is extremely surprising that the compounds according to the invention show a higher insecticidal and acaricidal effect than the corresponding non-sulfenylated Carbamates. These substituted compounds are also far less toxic to them Warm-blooded animals. Furthermore, the compounds according to the invention are more skin-friendly than the known trihalomethylsulfenylated carbamic acid esters.

The substances according to the invention thus represent an enrichment of technology represent.

When using N-methyl-N- (3-trifluoromethylphenylmercapto) -carbamic acid fluoride and 2-isopropoxyphenol as starting materials, the course of the reaction can be represented by the following equation: The substituted carbamic acid fluorides required for this can be produced by the following known process (cf. Deutsche Auslegeschrift 1 297 095): The sulfenic acid chlorides which are used as starting materials are b <'can (cf. DOS 2 049 814).

The following N-sulfenylated-N-methylcarbamic acid esters are preferably used, in which X is hydrogen and the radical R is 3,5-dimethyl-4-methylmercapto-substituted Phenyl, also for in the 2-position by lower alkoxy, dioxolanyl and lower Alkenoxy-substituted phenyl, also for naphthyl and for 2,2-dimethyl-2,3-dihydrobenzofuranyl stands.

The compounds in which X stands for chlorine.

N-methyl-N- (3-trifluoromethylphenylmercapto) -carbamic acid, -2-isopropoxyphenyl ester, -3,5-dimethyl-4-methylmercaptophenylester, -2-dioxyloanylphenylester, -1 -naphthylester ,, -7- (2,2-dimethyl-2,3-dihydrobenzofuranyl) ester, N-methyl-N- (4-chloro-3-trifluoromethylphenylmercapto) -carbamic acid phenyl ester, -2-isopropoxyphenyl ester, -3,5-dimethyl-4-methylmercaptophenyl ester, -2-dioxolanylphenyl ester, -4-tolyl ester, -2-methoxy-4-methylphenyl ester, 2-alkyloxyphenyl ester, -2-methylalkyloxyphenyl ester, S2-isopropylphenyl ester, -3-isopropylphenyl ester, -3-t-butylphenyl ester, -1 -naphthyl ester, -7- (2,2-dimethyl-2,3-dihydrobenzofuranyl) ester, -2-isopropyl mercaptophenyl ester.

All inert organic solvents can be used as diluents in question. These include ethers such as diethyl ether, dioxane, tetrahydrofuran and hydrocarbons such as benzene and chlorinated hydrocarbons such as chloroform and chlorobenzene.

To bind the hydrogen fluoride released during the reaction a tertiary base such as triethylamine is added to the reaction mixture, if appropriate also start directly from the alkali salts of the compounds ROH.

The reaction temperatures can be varied within a relatively wide range are generally used between 0 and 1000C, preferably at 20 - 4000.

The process according to the invention is carried out generally in molar amounts. In many cases it has been shown to be beneficial if the compounds of the formula ROH in a slight excess, preferably up to to apply 20 X.

As already mentioned several times, the new N-sulfenylated-N-methylcarbamide-aryl esters stand out due to an excellent insecticidal and acaricidal effectiveness against plant and hygiene pests. They have both a good effect against sucking as well as eating insects and mites. At the same time they have a low phythotoxicity in addition to a partly fungicidal effect.

The sucking insects mainly include aphids (Aphidae) such as the common peach aphid (Myzus persicae), the black bean (Doralis fabae), oat (Rhopalosiphum padi), pea (Macrosiphum pisi) and potato blue lice (Macrosiphum solanifolil), also the currant gall (Cryptomyzu8 korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black Cherry aphid (Myzus cerasi), also scale and mealybugs (Coccina), e.g. the ivy shield (Aspidiotus hederae) and cup scale (Lecanium hesperidum) as well the mealybug (Pseudococcus maritimus); Bladder feet (Thysanoptera) such as Hercinothrips feioralis and bed bugs, for example beetroot (Piesma quadrata), cotton (Dysdercus intermedius), bed bug (Cimex lectularius), predatory bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans), also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

Among the biting insects, butterfly caterpillars should be mentioned above all (Lepidoptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), golden afters (Euproctis chrysorrhoea) and ring moth (Malacosoma neustria), furthermore the cabbage (Mamestra brasslcae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small frostworm (Cheimatobia brumata), Oak moth (Tortrix viridana), the army (Laphygma frugiperda) and Egyptian Cotton worm (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestla kühniella) and large wax moth (Galleria mellonella), Farther are among the biting insects beetles (Coleoptera) e.g. corn (Sitophilus granarius = Calandra granaria), potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed gloss (Meligethes aeneus), Raspberry (Byturus tomentosus), table bean (Bruchidlus = Acanthoscelides obtectus), Bacon (Dermestes frischi), Khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), corn (Calandra or Sitophilus zeamais), bread stegobium paniceum), common flour beetle (Tenebriomolitor) and grain beetle (Oryzaephilus surinamensis), but also species living in the ground e.g.

Wireworms (Agriotes spec.) And white grubs (Melolontha melolontha); Cockroaches like the 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 (Acheta domesticus); Termites like 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 melanogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domestica), small house fly (Fannia canicularis), gloss fly (Phormia regina) and blowfly (Calliphora erythrocephala) and the calf stick (Stomoxys calcitrans); also mosquitoes, e.g. Mosquitoes such as the yellow fever mosquito (Aedes aegypti), house mosquito (Culex pipiens) and malaria mosquito (anopheles stephensi).

The mites (Acari) include the spider mites (Tetranychidae) like the bean (Tetranychus telarius = Tetranychus althaeae or Tetranychus urticae) and the fruit tree spider mite (Paratetranychus pilosus = Panonychus ulmi), gall mites, e.g. the currant mite (Eriophyes ribis) and tarsonemids for example the shoot tip mite (Hemitarsonemus latus) and cyclamen mite (Tarsonemus pallidus); finally ticks like the leather tick (Ornithodorus moubata).

When used against hygiene pests, especially flies and backs, the process products are also characterized by an excellent residual effect on wood and clay as well as good alkali stability on limed substrates.

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 produced in a known manner, e.g. by mixing the active ingredients liquefied pressurized liquids with extenders, i.e. liquid solvents Gases and / or solid carriers, optionally using surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means. In the case of using water as an extender, you can. z.3. also organic Solvents can be used as co-solvents. As a liquid solvent are essentially: aromatics, such as xylene, toluene, benzene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol and their Ethers and esters, ketones9 such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers such liquids are meant which are at normal temperature and under normal pressure are gaseous, e.g. aerosol propellants such as halogenated hydrocarbons, e.g. freon as solid carrier substances, natural rock flour, such as kaolins, clays, talc, Chalk, quartz, attapulgite, montmorillonite, or diatomaceous earth, and synthetic Ground rock, such as finely divided silica, aluminum oxide and silicates; as emulsifying and / or foam-generating agents, nonionic and anionic emulsifiers, such as Polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylryl polyglycol ethers Alkyl sulfates, Aryl sulfonates and protein hydrolyzates as dispersants: e.g. lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be mixed in the formulations present with other known active ingredients.

The formulations generally contain between 0.1 and 95 percent by weight 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, emulsifiable Concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, Dusts and granules are used.

It is used in the usual way, e.g. by splashing, Spraying, atomizing, dusting, scattering, smoking, gasifying, pouring, pickling or encrusting.

The active ingredient concentrations in the ready-to-use preparations can be varied in larger areas. 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) used where possible, formulations up to 95% or even to apply the 100% active ingredient alone.

Example A Residual test test animals: Musca domestica and Aedes aegypti Mesh powder base consisting of: 3% diisobutylnaphthalene-1-sulphonic acid sodium 6 ffi sulphite waste liquor, partially condensed with aniline 40% highly dispersed silica, Contains CaO 51% colloid kaolin For the production of an appropriate active ingredient preparation 1 part by weight of active ingredient is intimately mixed with 9 parts by weight of wetting powder basic substance. The preparation of active compound obtained in this way is suspended in 90 parts of water.

The active ingredient suspension is applied at an application rate of 1 g of active ingredient per m2 sprayed onto substrates made of different materials.

The spray coatings are biological at certain time intervals Effect tested.

For this purpose, the test animals are brought onto the treated documents. A flat cylinder is placed over the test animals, which is at its upper end is closed with a wire mesh to prevent the animals from escaping. To The animals are killed for 8 hours on the support determined in%.

Active ingredients, type of test documents and results are shown in Table 1 below M. O ao II 0 o 1 o c \ oO 0 0 cu PPI O 0 1 2 6 o CU a) 0 00 o Musca plywood s cu r O o O 0 Clll a, poo sW OOO -51 rOr O Aegypti r .- Sw II 0 0 0 0 kD $ OOOO (yg-p Clay Aegypti 100 OOO cVOO 000 r <CPIC DS-r 0 CTP 0011 000 According to the invention: 00 000 CF3 CH plywood MomSestica O 10Q O 100 100 100 100 100 100 100 8h = 8 \ Dor 006 868 006 fl AgdypS 100 OOO CUrr- p- 000 000 Clay Äegypti 100 OOOO rrvrr Y Z P w + a S wz U m AXAUX c) a) @ X o @ @ h @ Pa a) S e Q e QXS e Q e Q > o Q @ Q @ ao @ @ @ @ S. N ZD N o H ç HOX OP m H m 2 h: U h ri k o @ O XX dz ms A @ o uz g Wn n bD O m ov n cz VH bD m t 4 t; ne vQ XY 1a XX Example B Mosquito larvae test Aedes aegypti test animals Solvent: 99 parts by weight acetone Emulsifier: 1 part by weight benzyl hydroxydiphenyl polyglycol ether To prepare an appropriate preparation of active compound, 2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent containing the emulsifier in the amount indicated above. The solution thus obtained is diluted with water to the desired lower concentration.

Lan fills the aqueous active ingredient preparations into glasses and sets then put about 25 mosquito larvae in each glass.

The degree of destruction is determined in% after 24 hours. Thereby means 100 that all larvae have been killed. 0% means that there are no larynx at all have been killed.

Active ingredients, active ingredient concentrations, test animals and results are shown in Table 2 below: Table 2 Mosquito larvae test Active ingredient active ingredient concentration degree of destruction tration of lo- in% solution in ppm known: O-CO-NHCH3 (OH3) 2 0.1 0 According to the invention: 3 \ Qu: 3 OF3 OH 0.1 -N-COO G -SN-COO t known: O-CO-NHCH3 Öci According to the invention: OH OO, 2 1 95 I. CF, CH, 1 80 3-O1H3 - 1 so Ol1S; N-O00, BeisDiel C w 'Tetranychus test (resistant) Solvent: 3 parts by weight of acetone 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 containing the specified amount of emulsifier, and the concentrate is diluted with water the desired concentration.

Bean plants (Phaseolus vulgaris), which have a height of about 10 - 30 cm, sprayed dripping wet. These bean plants are strong with all stages of development of the common spider mite (Tetranychus urticae) infested.

After the specified times, the effectiveness of the active ingredient preparation is determined determined by counting the dead animals. The degree of destruction thus obtained becomes given in%. 100% means that all spider mites have been killed, 0 means that that no spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 3 below: Table 3 (plant-damaging mites) Tetranychus test (resistant) Active ingredients Active ingredient concentration degree of destruction tration in% in ffi 2 days 0 II 5 OC-NH-CH3 -C-NH-CH3 O-CH (CH3) 2 (known) 0 pC-NH-CH3 0.1 0 (known) 9 ' OC-NH-CH 1 3 ; (CH3 (CH3) 2 2 0.1 6 2 (known) CF3 S-CH9 IU 90Q / JI I "3 Q, 01 85 SN-COO s-CIH3 CH3 0.001 40 N-COO- \ c: H3 3 Tab 1 1 e 3 (continued) (plant-damaging mites) Active ingredients active ingredient concentration killing tration in% degree in% tration in degrees in after 2 'pegen CH3 CH3 CF3 H3CHY \ H3 CF ~) L g -SN-COO 0.1 95 Example D Plutella test Solvent: 3 parts by weight of dimethylformamide emulsifier: parts 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 stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Eohl leaves (Brassica oleracea) are sprayed with the preparation of the active compound dewy and populated with caterpillars of the cabbage moth (Plutella maculipennis).

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

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 4 below: Table 4 (plant-damaging insects) Plutella test Active ingredients Active ingredient concentration degree of destruction tration in «in s nach 3 days ßO-C-NH-CH 0.1 100 \ 0- tC 0.01 80 32 H3) 2 0.001 0 (known) NT? CH3 to H3 CF3 CH3 0 '0.1 100 O SN-COO <0.001 85 0.0001 30 Example E Phaedon larvae test 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 stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with 5 water to the desired amount Concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the active ingredient preparation dripping wet and populated with mustard beetle larveh (Phaedon cochleariae).

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

Active ingredients, active ingredient concentrations, times of evaluation and results are shown in Table 5 below: Table 5 (insects which are harmful to plants) Phaedon larvae test Active ingredients active ingredient killing degree centering in; after in ffi 3 days 0 OC "-NH-CH3 0.1 100 - -C-NH-CH3 0.01 0 O-CH (CH3) 2 (known) CF3 H3 -S-CH, O FH3 (\ f> -SN CSHC3H3 \ »SCH o, o1 100 CH3 0.001 100 CF3 OH C1- -O - \ 0.1 1ioOO 0.01 CH CF3 d C1H3? 0.1 100 SN -0-0 0.01 100 0.001 75 T abe 1 1 e 5 (continued) (insects which are harmful to plants) Phaedon larvae test Active ingredients active ingredient killing degree centering in% in 3 days \ F3 CH 1 9 0.1 100 0.01 95 0.00.1 90 example 1 12.7 g of N-methyl-N- (3-trifluoromethylphenylmercapto) carbamic acid fluoride and 8.2 g of 7-hydroxy-2,2-dimethyl-2,3-dihydrobenzofuran are dissolved in 200 ml of benzene. 6 g of triethylamine are added dropwise with stirring at room temperature. The temperature rises slightly here. After 2 hours, the precipitated amine hydrochloride is filtered off with suction and the filtrate is washed several times with water. After drying with Na2SO4, the solvent is distilled off. A yellow oil remains.

Yield: 15 g (75%), nD20 = 1.5349 analogously one obtains: Kp0.08 = 155 - 15800 nD20 = 1.5301 Kp0.6 = 205 - 210 ° C nD20 = 1.5629 Kp0.4 = 198-2000C 20 Mp. = 104 ° C Kp0.18 = 160-1650C nD20 = 1.5376 nD20 = 1.5733 The intermediates required for the preparation of the compounds according to the invention can be prepared as follows: 56 g of 3-trifluoromethylphenylsulfenchloride and 20.4 g of N-methylcarbamic acid fluoride are placed in 250 ml of toluene and 37 ml of triethylamine are added dropwise at 20.degree.-30.degree.

Then the precipitated amine hydrochloride is filtered off and the filtrate constricted.

Vac. least.

Yield: 46 g (70%) bp 0.15 = 94-960C 20 nD = 1.4896 analogously one obtains: Kp0.1 = 108 - 110 ° C nD20 = 1.5145

Claims (9)

Claims t. N-sulfenylated N-methylcarbamic acid aryl esters of the general formula I. in which X represents H or halogen, R represents optionally substituted by alkyl, alkenyl, alkoxy, alkenoxy, alkylm-ercapto, dioxolanyl, phenyl, naphthyl, dihydrobenzofuranyl. 2. N-sulfenylated -N-methylcarbamic acid esters of the formula (I) in claim 1 in which X stands for hydrogen and R for 3,5-dimethyl-4-methylmercaptophenyl, for in the 2-position by alkoxy or alkenoxy with 1-3 carbon atoms or dioxolanyl substituted phenyl, represents naphthyl or 2,2-dimethyl-2,3-dihydrobenzofuranyl and in which, when X is halogen, R is optionally substituted by alkyl, alkenyl, Alkoxy, alkenoxy, alkylmercapto, dioxolanyl, substituted phenyl, naphthyl, dihydrobenzofuranyl stands. 3. N-sulfenylated N-methylcarbamic acid aryl esters of the formula 4. A process for the preparation of N-sulfenylated N-methylcarbamic acid aryl esters of the general formula I, characterized in that N-phenylmercaptocarbamic acid fluorides of the general formula II in which X has the meaning given above with a compound of the general formula III ROH III in which R has the meaning given above, in the presence of a diluting agent and an acid-binding agent. 5. A process for the preparation of N-sulfenylated N-methylcarbamic acid aryl esters of the general formula (I), characterized in that N-phenylmercaptocarbamic acid fluorides of the general formula (II) in which X has the meaning given above with a compound of the general formula (III) ROH (III) in which R has the meaning given in claim 2. 6. Insecticidal and acaricidal agent, characterized by a Content of N-sulfenylated N-methylcarbamic acid esters according to Claim 1. 7. A method for combating insects and mites, characterized in that that one N-sulfenylated N-methylcarbamic acid aryl ester according to claim 1 on insects and allows mites and / or their habitat to act. 8. Use of N-sulfenylated N-methylcarbamic acid aryl esters according to claim 1 for combating insects and mites. 9. Process for the production of insecticidal and acaricidal agents, characterized in that N-sulfenylated N-methylcarbamic acid aryl esters according to Claim 1 mixed with extenders and 7 or surface-active agents.