DE1962408A1 - Pest repellants - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 6627 / E

Pesticides

The present invention relates to new phenyl carbamates of the formula I, their preparation and their Use alone or in agents for controlling pests.

009829/1866

The new compounds of the formula I 0- GO - KHGH "

wherein the substituents R 1 and FU are independent of one another denote an alkyl group with 1-4 carbon atoms or in which one of the two substituents is also a Η atom can be made by reacting a phenol of the formula

DH

with Me thy Ii so cy ana t, an N-methylcarbamic acid halide or obtained with N-methyl-phenylcarbamate or else by initial conversion with COCIp to the corresponding halogen formic acid phenyl ester or carbonic acid bis-phenyl ester and further reaction with methylamine.

These new carbamates have a wide range of biocidal properties.

They are particularly effective as insecticides and acaricides, primarily against harmful orthoptera, coleoptera, Rhynchotes, Diptera and Lepidoptera. You point against

009829/1866

A surprising range of uses for pests in storage and household hygiene: cockroaches, meal beetles, but especially the difficult to control Sitophilus species (Grain weevils) are destroyed with very low application rates.

Those representatives of the formula I in which one of the substituents should be emphasized in terms of their effect R, or R "is hydrogen, a methyl, ethyl or isopropyl group and the other is a methyl, ethyl, propyl or isopropyl group.

The two compounds are particularly effective

0 - CO - NHOH., 0- CO - HHCH-

ι 3 j 3

CH-C = C-CH

When applied in higher amounts, the compounds of the formula (i) have monocotyledon or dicotyledon against various representatives Plant genera have a growth-suppressing or growth-retarding effect.

When applied at a concentration that does not allow phytotoxic symptoms to occur, they show in crop protection an excellent effect against harmful microorganisms, e.g. against fungi, such as Alternaria solani,

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Phytophthora infestans and Septoria apii, as well as against harmful nematodes and their eggs or larvae.

Furthermore, the new agents are generally useful as microbicides, for example against Aspergillus species. she are also effective against mollusks.

The new means 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 ribbons - soaked with a solution of the active ingredients - applied as is familiar to any person skilled in the art and of which the present invention provides some examples. See also U.S. Patent 3,329,702 or Brit.P. 1,047,644 or Swiss Patent No. 424,359.

In many cases, such as in the control of soil insects, the use of granules is useful even release of active ingredients over a longer period of time is an advantage. These can be removed by solving the Active ingredient in an organic solvent, absorption of this solution by granulated mineral, e.g. attapulgite or SiOp or by adsorptive organic high polymers and removing the solvent. They can also be produced in such a way that the active ingredients of the formula I be mixed with polymerizable compounds, whereupon

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a polymerization is carried out, of which the Active substances remain unaffected, and granulation is still carried out during the polymerization.

In the form of one or the other application, such agents can also be applied by distributing them over a large area (Spraying, dusting, etc.) can be carried out with the aid of airplanes.

The concentration of the means used can vary widely depending on the type of Application fluctuate. It is generally from 0.01 percent by weight to 20 percent by weight for more dilute ones Medium, more concentrated, on the other hand, have 20 percent by weight to 98 percent by weight of active ingredient.

The effect of the carbamates according to the invention can be further increased by synergists. Suitable for it e.g. Sesamin, Sesamex, Piperonyl cyclonene, Piperonyl butoxide, piperonal bis [2- [2-butoxyethoxy) ethyl] acetate, sulfoxides, propyl isome, N- (2-ethylhexyl) -r-norbornene-2,3-dicarboxamide, Octachlorodipropyl ether, 2-nitrophenyl propargyl ether, 4-chloro-2-nitrophenylpropargyl ether, 2,4,5-trichlorophenyl propargyl ether.

The various forms of application of such agents can be carried out in the usual way by adding substances which the

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'Distribution, the adhesive strength, the rain resistance and possibly improve the penetration capacity, e.g. fatty acids, resins, wetting agents, glue, casein or alginates, can be adapted more closely to the purposes of use.

The agents according to the invention can for themselves

alone or together with common pesticides, such as herbicides, insecticides, acaricides, nematocides, bactericides, fungicides or molluscicides can be used.

In the following, parts are parts by weight and the temperatures are given in degrees Celsius;

example 1

2-butynyloxyphenol

A solution of 122 parts of 2-butynyl p-toluenesulfate in 150 parts by volume of acetone is added dropwise to a boiling mixture of 66 parts of pyrocatechol, 75 parts of potassium carbonate, 91 parts of potassium iodide and 360 parts by volume of acetone. The suspension is refluxed for 2 hours, cooled, filtered and evaporated. The residue is taken up in ether, washed several times with water and treated in the ice cold with 200 parts by volume of 10 percent. Sodium hydroxide extracted. The alkaline extract is neutralized with hydrochloric acid and the product is taken up with chloroform. After the solvent has evaporated, the product is at a bath temperature of 120 ° at 0.05 mmHg

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distilled. The distillate crystallizes; 43-46 °. 2- (2-butinyloxy) phenyl N-methyl carbamate

56 parts of 2- (2-butyn-1-yl-oxyl) phenol become dissolved in 150 volumes of ethyl acetate, with 0.5 parts Triethylenediamine and in portions with 21 parts of methyl isocyanate offset.

The mixture is kept at 40 ° for 24 hours and then evaporated. The residue is made from chloroform-cyclohexane crystallized. 79-81 °. [Compound no. L]

Example 2

2- (1-butyn-3-yl-oxy) phenol

To a suspension of 110 parts of catechol, 152 parts of anhydrous potassium carbonate and 166 parts Potassium iodide in 100 parts by volume of acetone is 50 a Solution of 247 parts of p-toluenesulfonic acid l-butyn-3-yl ester dripped in 200 parts by volume of acetone. The mixture is refluxed for 2 days, then filtered and evaporated. The residue is taken up in 500 parts by volume of ether, with water and with 450 parts by volume 20 percent. Caustic soda washed. The alkaline extract, together with the partially precipitated sodium salt of the product, is frozen in the cold acidified with semi-diluted hydrochloric acid. The product

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is obtained by extraction with chloroform and evaporation of this solution. It is cleaned in a high vacuum distilled.

Bp. 63-66 ° / 0.07 mm Hg. The distillate crystallizes; M.p. 52-5 ^ °. '

2- (1-butyn-3-yl-oxy) phenyl-N-methylcarbamate

45.5 parts of 2- (l-butyn-3-yl-oxy) phenol and 0.1 part of triethylenediamine are dissolved in 150 parts by volume of carbon tetrachloride, and 19 parts of methyl isocyanate are added. The mixture is stirred at 40 ° for 14 hours. The product which has crystallized out is filtered off and crystallized once from toluene. M.p. 88-9I ⁰ . [Connection 2]

The following connections are established in this or a similar manner:

1) 2- (2-butinyloxy) phenyl-N-methylcarbamate

2) 2- (l-butyn-3-yl-oxy) phenyl-N-methylcarbamate,

3) 2- (2-Pentin-4-yl-oxy) phenyl-N-methylcarbamate,

4) 2- (2-penty-1-yl-oxy) phenyl-N-methylcarbamate _i

5) 2- (l-Pentin-3-yl ~ oxy) phenyl-N-methylcarbamate _i

6) 2- (2-methyl-4-pentin-3-yl-oxy) phenyl-N-methylcarbamate.

009829/1956

Formulation examples

Dust

Equal parts of an active ingredient according to the invention and precipitated silica are finely ground. By mixing it with kaolin or talc, it can be used to produce dusts with an active ingredient content of preferably 1-6 $ will.

Wettable powder

To produce a wettable powder, for example, the following components are mixed and 'fine marry:

50 parts of active ingredient according to the present invention 20 parts of Hisil (highly adsorptive silica) 25 parts of Bolus alba (kaolin) 3 * 5 parts of reaction product from p-tert. Ootyl

phenol and ethylene oxide

1.5 parts (1-benzyl-2-stearyl-benzimidazole-6,3'-disulfosaures Sodium). Emulsion concentrate

Easily soluble active ingredients can also be formulated as an emulsion concentrate according to the following rule: 20 parts active ingredient
70 parts of xylene

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- ίο -

10 parts of a mixture of a reaction product of an alkylphenol with ethylene oxide and caleium dodecylbenzenesulfonate

are mixed. When diluting with water to the desired concentration, a sprayable emulsion is created. Granules

7.5 g of one of the active ingredients of the formula I are dissolved in 100 ml of acetone and the acetone solution thus obtained is poured onto 92 g of granulated attapulgite (mesh size: 24/48 meshes / inch). The whole thing is mixed well and the solvent is drawn off in a rotary evaporator. Granules with a 7.5 % active ingredient content are obtained.

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- li -

Example 3

To test for their action against various pests in storage, 2 g of compound 2 were mixed with J> 8 g of talc and the whole thing was finely ground. A very effective dust powder was obtained with which. the following results were obtained: -

Test species Minimum concentration
Killing in 2k p
time (mg active ingredient
Connection no. 2 tion of the lOO ^ igen
hours exposure
ff per m ² )
Connection number 1 German cockroach
(Phyllodromia germanica) 3 6th American cockroach
(Periplaneta americana) 1.5 25th Russian cockroach
(Blatta orientalis) 6th 25th Flour beetle imago
(Tenebrio molitor) larva 50
200 100
200 Bacon beetle Imago
(Dermestes frischii)
larva 100
50 50
100.
I.

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Sitophilus granarius 25th 200 Fur beetle larva
(Attagenus piceus) 200 100 House barbecue
(Acheta domestica) 12th 25th

Example 4

Lucilia sericata (Blow fly).

Freshly hatched maggots are fed with minced horse meat in small glass vessels, which has been treated with an aqueous emulsion of the test substance. The determination of the limit concentration of the active substance is carried out in 3 test series on different days, with new generations of flies and new dilution series of 100, 48, 24, 12, 6, 3 and 1.5 ppm. It turned out the following limit values for 100% death after 24 hours:

Compound # 1 at 3 ppm Connection no. 2 at 3

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Example 5
Action against mosquito females (Aedes aegypti).

In Petri dishes with a diameter of 11 cm, female mosquitoes are covered with a coating for 6 hours exposed to the substance being tested. To produce this topping, 1 ml of acetone is added to the bottom of the dish beforehand Treated substance solution and dried for one hour. Solutions with 1000, 100, 10 and 1 ppm are used, which corresponds to a concentration of 1, 0.1, 0.01 and 0.001 mg / cup. The mosquitoes are cooled in ice and each 10 females counted in the bowls. Do 4 repetitions per concentration.

The following percentage mortalities were achieved after 9 ° min:

Application rates i-l 0.1 0.01 0.001 mg / cup Connection no. 1
Connection no. 2 $ 100 $ 100 $ 100
$ 100 Z

Example 6 Cimex Lectularius (bed bug).

In a similar test as described in Example 5, in which the active ingredient on filter paper is used in plastic dishes (1 mg per dish is

009829/1966

*1

speaks 1 g per 6 m), and the one in 2 repetitions Ä 10 bugs runs, results for active ingredient no. 2 at a concentration of 10, 1 and 0.1 mg / dish 100% death each time.

Example 7

Contact effect on Ceratitis capitata.

1 half of a Petri dish was mixed with 1 ml of an acetone solution of one of the substances No. 1 and 2 treated, which contained a certain amount of the active ingredient. After evaporation of the solvent, supercooled Put fruit flies in the prepared Petri dishes and put the lid halves on top. Every bowl contained 10 test animals. After 1 hour, a series of dilutions was made with various concentrations Killing controlled.

Conc. [Ppm] Connection no. 1 Verb.Nr, 2 1000 100 # 100 # 100 100 # 100 # 10 $ 100 100 # 5 100 # 100 # 2.5 100 # 100 # 1.25 100 # 50 #

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19624Q8 - 15 -

Example 8

Eating and contact effects against Orgyia gonostigma and Epilachna varivestis.

Potted, young mallow plants (Malva sylvestris) with about 6 leaves are immersed in an active ingredient solution of a certain concentration and left to dry. A cellophane cap containing larvae of Orgyia gonostigma in the L, stage is then put over each plant and fastened with a rubber band. The insecticidal eating and contact effect is tested 2 and 5 days later. If a mortality of $ 100 is determined the first time, the plant will be repopulated so that the effect of the aged preparation is also recorded at the same time.

The experiment with larvae of Epilachna varivestis in the Lu stage is carried out in the same way with Phaseolus as Active plant carried out.

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a) Action against Orgyia

Conc. [ppm] 2 T. Connection no. 1 Connection no. 2 5 d. 100 * 2 T. 100 # 800 $ 100 80 * 100 # 400 8056 8θ $ 100 # 200 60% 8θ # - 100 - 5 τ. $ 100 80 pounds 1005g 100 *

b) Effect against Epilachna after 5 days:

Conc. [Ppm] Connection no. 1 Connection no. 2 800 100 # ^! 100 ^ 400 100 # 100 # 200 100 # 60 ^ 100 80 ^ -

00.9829 / 1956

Claims (1)

Claims Process for the preparation of compounds of formula 0-CO-NHCH, 0- CH-C = C- R ₂ R-, wherein the substituents R and Rp are independent of one another denote an alkyl group with 1-4 C atoms or in which one of the two substituents can also be an H atom Reaction of a phenol of the formula OH 0-CH-CSC-R ₂ with methyl isocyanate, an N-methylcarbamic acid halide or with N-methyl-phenylcarbamate or by initial Conversion with COCIp to the corresponding phenyl haloformate or to the carbonic acid bis-phenyl ester and further reaction with methylamine. . 009829/1956 Compounds of the formula 0- CO - NHCH ₃ in which the substituents R and R ₂ independently of one another denote an alkyl group with 1- · ^ C atoms or in which one of the two substituents can also be a Η atom. 3. The compound of the formula 0- CO - NHCH, 0 - CH ₂ - C = C - The compound of the formula 0- CO - NHCH, 0 - CH - C = CH CH. The compound of the formula 0- CO - NHCH, 0 - CH - C ~ C - CH- OH, 009829/1966 6. Pesticides which contain at least one compound of the general formula as the active substance 0 - CO - NHCH ₅ O ^- - CH - C = C - R ₂ ^R l contain, in which the substituents R- and Rp independently ' denote one another an alkyl group with 1-4 C atoms or in which one of the two substituents is also an H atom can be together with at least one of the following additions: Carriers, solvents, diluents, dispersions, Emulsifiers, wetting agents, adhesives, binders or thickeners or other pesticides. 7. A pesticide according to claim 6, the compound mentioned in claim 3 as the active substance contain. 8. A pesticide according to claim 6, the compound mentioned in claim 4 as the active substance contain. 9 · Pesticide according to claim 6, the active substance being the compound mentioned in claim 5 contain. 009829/1956 1962400 -'20 - 10 »Use of the claims 2 to 5 , compounds mentioned for controlling insects and pests of the order Akarina. 008829/1168