DE1806197A1 - Pesticidal compns contng alkoxy or thio alkyloxy or - Google Patents

Abstract

Pesticidal compositions contng. carbamates:- The group -X-A-Y-R2 is an o-, or m-position to the carbamoyl residue; R1 = H or lower alkyl; X = -O or -S; A = branched alkylene (C3-6); Y = -O or -S, R2 = alkyl, alkenyl or alkinyl; R3 = H, halogen or lower alkyl. (I) have insecticidal- and acaricidal activity against all development stages of harmful organisms. Esp against Phyllodromia germanica, Periplaneta americana, Blatta orientalis, Acheta domestica and Rhodnius prolixus. In large doses (I) has growth-inhibitory or -retarding effect on many mono- or dicotyledonous plants. In non-phytotoxic doses they show excellent activity against harmful micro-organisms such as fungi or against nematodes and their eggs and larvae. They are generally useful as microbiocides, useful against Molluscs.

Description

Pesticides The present invention relates to pesticides which, as an active component, contain at least one compound of the formula with the proviso that the radical -XAY-R2 in these compounds is in o- or m-position to the carbamoyloxy radical, and where R1 is hydrogen or a lower alkyl radical, X is oxygen or sulfur, A is a branched alkylene radical with 3-6 C- Atoms, Y is oxygen or sulfur, R2 is a lower alkyl, alkenyl or alkynyl radical and R3 is hydrogen, halogen or a lower alkyl radical.

In a narrower sense, the present invention relates to pesticides which contain at least one of the compounds of the formula included, in which R1, R2, X, A and Y have the meaning given above.

Of these, those of the formula (III) are to be particularly emphasized in which R1, R2, X, A and Y have the meanings given above, especially those in which R1 is hydrogen and X and Y are oxygen.

The new carbamates can be used for making this body class common methods - e.g. by reacting corresponding phenols with methyl isocyanate, Alkyl or dialkylcarbamic acid chlorides or by reacting the corresponding Phenyl carbonates or phenyl chlorocarbonates with methylamine or methylalkyl amines be won. One can also, if R3 means halogen, proceed in such a way that one first the carbamate grouping produces and then subsequently R introduced by post-halogenation.

The invention also relates to the new carbamates of the general formula in which the radical -XAY-R2 is in the o- or m-position to the carbamoyloxy radical, und.worin R1 is hydrogen or a lower alkyl radical, X is oxygen or sulfur, A is a branched alkylene radical with 3-6 carbon atoms, Y is oxygen or sulfur , R2 is a lower alkyl, alkenyl or alkynyl radical and R3 is hydrogen, halogen or a lower alkyl radical.

These carbamates act as insecticides and acaricides against all stages of development these pests, especially strong against houseflies, aphids, caterpillars, ticks, Bedbugs and beetles, such as grain beetles and colorado beetles, without this listing Claim to be complete.

In the contact effect they are the well-known active ingredient 1? Carbarylff (N-methyl-a-naphthylcarbamate) strongly superior.

Particularly noteworthy is the powerful effect against phyllodromia germanica, Periplaneta americana, Blatta orientalis, Acheta domestica and Rhodnius prolixus.

The advantage of these carbamates of formula (I) is an obvious one Long-term effect that still remains in the dry surface 5 months no impairment reveals. After the application is therefore a complete for this period Protection against household pests, for example.

The new carbamates are therefore well suited for combating Pests in the hygiene sector, in storage, but also in crop protection.

Particularly effective representatives are the o-rl-methoxy-2-propoxy] -phenyl-N-methylcarbamate, the o- [l-allyloxy-2-propoxy} phenyl-N-methylcarbamate and the o- [l-propargyloxy-2-propoxy] -phenyl-N-methylcarbamate.

In a higher application rate, the compounds of formula (I) have against different representatives of monocotyledonous or dicotyledonous plant genera a growth-suppressing one or growth retarding effect.

They show applied at a concentration that is not phytotoxic Can appear phenomena, an excellent effect against in plant protection harmful microorganisms, e.g. against fungi, such as Alternaria solani, Phytophthora infestans and Septoria apii, as well as against harmful nematodes and their eggs or Larvae.

Furthermore, the new agents are generally used as microbicides, e.g. Aspergillus species useful. They are also effective against mollusks.

The new funds can be used in the most varied of ways and in various forms, e.g. in the form of sprays, dust powders, so-called fly plates or tapes - soaked with a solution of the active ingredients - can be applied, such as it is familiar to any person skilled in the art and what the present invention is for provides some examples. See also U.S. Patent 3,329,702 or Brit. Patent 1,047,644 or Swiss Patent No. 424,359.

The agents according to the invention can be used alone or together with common pesticides such as herbicides, insecticides, acaricides, Nematocides, bactericides, fungicides or molluscicides can be used.

In the following, parts mean parts by weight, which are temperatures given in degrees Celsius.

Example 1 1-Methoxy-2-propyl-p-toluenesulfonate To 216 parts of 1-methoxy-2-propanol 420 parts of p-toluenesulfonyl chloride are added in portions at Oo. Then; send 324 parts of pyridine are added dropwise to the mixture with stirring at 0 ° and it is still held 16 hours at this temperature.

After diluting with 1000 parts of ice water, the product is with 1000 parts by volume of ether extracted. The ethereal solution is repeated several times with 2n Hydrochloric acid, saturated sodium bicarbonate solution, and water, washed over anhydrous Dried sodium sulfate and evaporated. The product remains as an oil.

O- (L-methoxy-2-proyloxy -) - phenol To the solution of 110 parts of pyrocatechol and 244 parts of 1-methoxy-2-propyl-p-toluenesulfonate in 500 parts by volume of dimethyl sulfoxide 90 parts of 44.5 percent strength are added dropwise under nitrogen. Sodium hydroxide solution given, whereby the temperature rises to 420. The mixture is 14 hours at room temperature stirred, poured into 2000 parts of water and three times 250 parts by volume of toluene extracted. The toluene solution is washed twice with 200 parts of water and evaporated. The residue is distilled in a high vacuum. Boiling point 70-820 / 0.04 mmHg.

O- (1-Metlioxy-2-propox.yX -phenyl-N-methyl-carbamate (Comp. 1) 38 parts o- (l-methoxy-2-propoxy) -pheno1 are dissolved in 250 parts by volume of dry toluene, 0.3 parts of triethylenediamine and 13 parts of methyl isocyanate are added in portions.

The solution is held at 350 for 14 hours and then evaporated. The product gradually crystallizes: mp 57 °. It can be made from carbon tetrachloride cyclohexane be recrystallized.

Example 2 m- (1-Methoxy-2-propoxy) phenol To the boiling slurry of 110 parts of resorcinol, 149 parts of potassium carbonate, 179 parts of potassium iodide in 200 Parts by volume of acetone are added dropwise to 268 parts of 1-methoxy-2-propyl-ptoluenesulfonate. The mixture is refluxed for 20 hours, filtered and evaporated. 250 parts of water and 500 parts by volume of ether are added to the residue. The separated ether is extracted twice with 300 parts by volume of 30% sodium hydroxide solution. The alkaline solution is neutralized with hydrochloric acid and the product with ether extracted. The extract is dried over anhydrous sodium sulfate, filtered and evaporated. The residue is distilled in a high vacuum. Bp 1050 / 0.1 mmHg.

m- (l-methoxy-2-propoxy) -phenyl-N-methylcarbamate (compound no.2) 37 parts of m- (l-methoxy-2-propoxy) phenol are in 200 parts by volume of dry toluene dissolved, with 0.25 parts of triethylenediamine and dropwise with 14 parts of methyl isocyanate offset. The solution is held at 350 for 14 hours and then evaporated. as Oily m- (1-methoxy-2-propoxy) -phenyl-N-methylcarbamate is obtained.

Example 3 o- (1-Methoxy-2-propylthio) phenol To the stirred mixture of 138 parts of potassium carbonate, 166 parts of potassium iodide and 500 parts by volume of acetone 126 parts of o-mercaptophenol are added in portions in a nitrogen atmosphere with cooling given. The mixture is then heated to the boil and 268 parts of 1-methoxy-2-propyl-p-toluenesulfonate are added dropwise to. The mixture is refluxed for 24 hours, filtered and evaporated. The residue is taken up in 750 parts by volume of toluene, with water and then washed twice with 250 parts by volume of 15% sodium hydroxide solution.

The alkaline extract is immediately neutralized with hydrochloric acid and extracted with toluene. The toluene solution is poured over anhydrous sodium sulfate dried, filtered and evaporated. The residue is distilled in a high vacuum.

O- (1-Methoxy-2-propylthio) -phenyl-N-methylcarbamate [Comp. No. 3] 45 Parts of o- (l-methoxy-2-propylthio) phenol are in 250 parts by volume of dry toluene dissolved, with 0.2 parts of diethylenetriamine and dropwise with 17 parts of methyl isocyanate offset.

The solution is kept at 3035O for 14 hours. The oily product will obtained by evaporating the solution in vacuo.

Example 4 o- (1-Methoxy-2-propylthio) -phenyl-N, N-dimethylcarbamate [Compound No. 4] 45 parts of o- (l-methoxy-2-propylthio) phenol become 150 parts by volume dry dioxane, 30 parts of triethylamine and, in portions, with 32 parts of dimethylcarbamic acid chloride offset. The mixture is stirred at 900 for 14 hours. The precipitated triethylamine hydrochloride is filtered off.

The filtrate is evaporated, dissolved in 250 parts by volume of toluene and washed in the presence of ice with twice 200 parts by volume of 10% sodium hydroxide solution. The solution is dried over anhydrous sodium sulfate, filtered and evaporated. Oily o- (l-methoxy-2-propylthio) -phenyl-N, N-dimethylcarbamate is used as residue obtain.

The following compounds are prepared analogously: 5) o- [1-ethoxy-2-propoxy] -phenyl-N-methylcarbamate, 6) o- [1-Allyloxy-2-propoxy] -phenyl-N-methylcarbamate, 7) o- [1-propargyloxy-2-propoxy] -phenyl-N-methylcarbamate, 8) o- [1-methylthio-2-propoxy] -phenyl-N-methylcarbamate, 9) o- [1-methylthio-2-propylthio] -phenyl-N-methylcarbamate, 10) o- [1-ethoxy-2-propylthio] -phenyl-N-methyl-carbamate, 11) o-rl-ethylthio = 2-propoxy] -phenyl-N-methylcarbamate, 12) o-rl-ethylthio-2-propylthio] -phenyl-N-methylcarbamate, 13) o- [1-methoxy-2-butoxy] -phenyl-N-methylcarbamate, 14) o- [1-methylthio-2-propoxy] -phenyl-N, N-dimethylcarbamate, 15) o- [1-methylthio-2-propylthio] phenyl-N, N-dimethylcarbamate, 16) o {l-ethylthio-2-propylthio] -phenyl-N, N-dimethylcarbamate, 17) o- [1-Methoxy-2-propoxy] -4-methylphenyl-N-methylcarbamate, 18) .o- [1-Methoxy-2-propoxy] -5-chlorophenyl-N-methylcarbamate, 19) m- [1-ethoxy-2-butoxy] -5 methylphenyl-N-methylcarbamate Formulation examples Dusts Equal parts of an active ingredient according to the invention and precipitated silica are finely ground. Mixing it with kaolin or talc can turn it into dust are produced with preferably 1-6% active ingredient content.

Spray powder To produce a spray powder, for example the following components mixed and finely ground: 50 parts of active ingredient according to present invention 20 parts of Hisil (highly adsorptive silica) 25 parts of bolus alba (kaolin) 3.5 parts of reaction product from p-tert. Octylphez and Ethy-1 enoxide 1.5 parts (1-benzyl-2-stearyl-benzimidazole-6,3'-disulfo acid sodium).

Emulsion concentrate Easily soluble active ingredients can also be used as an emulsion concentrate are formulated according to the following rule: 20 parts of active ingredient 70 parts of xylene 10 Parts of a mixture of a reaction product of an alkylphenol with ethylene oxide and calcium dodecylbenzenesulfonate are mixed. When diluted with water on the desired concentration results in a sprayable emulsion.

Example 5 To test for their action against various pests the storage 2 g of compound 1 were mixed with 38 g of talc and that Finely grind the whole thing.

In this way a highly effective dust powder was obtained, with which the following results were achieved: Limit concentration of 100% waste killing in 24 hours exposure Test animals time mg of active ingredient per m² German cockroach 3 (Phyllodromia germanica) American cockroach 3 (Periplaneta americana) Russian cockroach 25th (Blatta orientalis) Rhodnius blood bug 25th (Rhodnius prolixus) House barbecue 25th (Acheta domestica) Example 6 Action against female mosquito (Aedes aegypti).

40 female mosquitoes are placed in Petri dishes with a diameter of 11 cm 6 hours exposed to a deposit of the substance to be tested. To make this The bottom of the dish is covered beforehand with 1 ml of acetone solution of Wrb.Nr. treated and dried for one hour. Solutions come with the application 1000, 100, 10 and 1 ppm, representing a concentration of 1, 0.1, 0.01 and 0.001 mg / cup is equivalent to. The mosquitoes are cooled in ice and 10 females each in the bowls counted. For each concentration, 2 parallel tests run on 2 days. Consistent 100% kill after 45 minutes at one concentration was found in all 4 experiments of 0.001 mg / cup achieved.

Example 7 Effect against bedbugs.

Rhodnius prolixus. As described in Example 6, acetone Active ingredient solutions in Petri dishes with all diameters applied so that concentrations of 1 mg, 0.1 mg, 0.01 mg and 0.001 mg per dish 2 can be guaranteed. (1 mg per bowl corresponds to 1 g per 9.4 m 10 bugs become in the L3 stage after one hour Drying the prepared dishes exposed to the active ingredient coating for 24 hours. The effect will be felt after 45 minutes, 90 minutes, 3 hours, 6 hours and 24 hours, checked.

One-time repetition with a new dilution series.

The following mortalities were achieved: Connection no. mg / cup After After After 45 min. 6 hrs. 24 hrs. 1 0.01 100% 100% 100% 1 0.001 - 80% 100% Compounds 3 to 7, 11-15 and 18 show similar effects.

Cimsx lectularius (bed bug). In a similar test in which the active ingredient is applied to filter paper in plastic trays 2 (1 mg per tray corresponds to 1 g per 6 m and which runs in 2 repetitions of 10 bugs results in for active ingredient no. 1 at a concentration of a) 1 mg / dish according to 45 Minutes 100% destruction b) 0.1 mg / dish after 6 hours 100% destruction.

Example 8 Action against Acarina.

Rhipicephalus bursa. 5 hungry adult ticks are placed in a glass tube counted and for 1-2 minutes in 2 ml of an aqueous emulsion with 100, 10 or 1 ppm test substance immersed. The tube is then covered with a standardized cotton ball closed and turned upside down so that the active ingredient emulsion from the cotton wool is recorded. The evaluation takes place after 1 and 2 weeks.

Do two repetitions for each attempt.

Compound No. 1 achieved the following values: At 100 ppm after 1 week 100% kill at 100 ppm after 24 hours 100% kill at 10 ppm after 2 weeks 100% destruction Example 9 Action against Diptera Lucilia sericata (larvae) With the emulsifiable preparation of the active ingredient no. 1, a dilution series is made.

2 ml solution of a certain concentration are in a 10 ml glass vessel mixed with 2 g minced horse meat.

20-30 freshly hatched in these vessels? Larvae transferred. The evaluation takes place after 24 hours. An active ingredient concentration of 3 ppm was achieved 100 kill.

Similar results are obtained with compounds No. 3, 5-11, 17 and 19 received.

Claims (12)

Claims 1. Pesticides which contain at least one compound of the general formula as the active component with the proviso that the radical -XAY-R2 in these compounds is in the o- or m-position to the carbamoyloxy radical, and in which R1 is hydrogen or a lower alkyl radical, X is oxygen or sulfur, A is a branched alkylene radical of 3-6 C. -Atoms, Y is oxygen or sulfur, R2 is a lower alkyl, alkenyl or alkynyl radical and R3 is hydrogen, halogen or a lower alkyl radical, and optionally one or more of the following additives: solvent, diluent, dispersant, wetting agent , Emulsifiers, thickeners and other pesticides. 2. A pesticide according to claim 1, which contains at least one compound of the formula as the active component with the proviso that the radical -XAY-R2 is in the o- or m-position to the carbamoyloxy radical and in which R1, R2, X, A and Y have the meaning given in claim 1. 3. A pesticide according to claim 1 or 2, containing at least one compound of the formula as active component wherein R1, R2, X, A and Y have the meaning given in claim 1. 4. Pesticides according to Claims 1 to 3, containing as the active component at least one compound of the formula given in claim 3, in which R1 is hydrogen and X and Y are oxygen, A is a branched one An alkylene radical with 3 - 6 carbon atoms and R2 is a lower alkyl, alkenyl or Means alkynyl radical. 5. Pesticides according to claims 1 to 4, containing the compound of the formula as active component 6. Use of the active compounds mentioned in claims 1 to 5 for combating of insects, nematodes and pests of the order Acarina in all their stages of development. 7. The active compounds mentioned in claim 1. 8. The active compounds mentioned in claim 2. 9. The active compounds mentioned in claim 3. 10. The active compounds mentioned in claim 4. 11. The active compound mentioned in claim 5. 12. Process for the preparation of compounds of the formula where the radical - X ~ A - Y - R2 is in the o- or m-position to the carbamoyloxy radical and R1 is hydrogen or a lower alkyl radical, X is oxygen or sulfur, A is a branched alkylene radical with 3-6 carbon atoms, Y is oxygen or sulfur , R2 is a lower alkyl, alkenyl or alkynyl radical and R3 is hydrogen, halogen or a lower alkyl radical a) by reaction of a phenol of the formula with methyl isocyanate or an alkyl or dialkyl carbamic acid chloride of the formula or b) by reaction of a phenyl carbonate or a phenyl chlorocarbonate of the formula with methylamine or with a methylalkylamine, where X stands for chlorine or any alcoholic, easily cleavable radical -ORt.