IL33525A - 2-alkinyloxyphenylcarbamates,their preparation and pesticidal compositions containing them - Google Patents

Description

33525/2 OR33Π ,D»BBIOnp «3B-4031K>»3»P>K-2 2-Alkinyloxyphenylcarba-aates, their preparation and peeticidal compoeitlons containing them CIBA-GEIGT A.G.

C 131759 - 2 - 33525/2 $he present invention relates to two novel phenyl-carbamates of the formula I, processes for their manufacture and their use by themselves or in preparations for controlling pests. he present Invention provides compounds of the formula I in which one of the substituents R^ and R2 represents a hydrogen atom and the other represents a methyl group.

Formula I above covers the two compounds She present invention also provides a process for preparing the compounds of the above formula I, which comprises reacting a phenol of the formula OH in which R^ and R2 have the same meaning as above, with me h lisocyanate, an H-methylcarbamic acid halide or with H-methyl-phenylearbamate, or by first reacting a phenol of the above formula with C0C12 to give the corresponding - 3 - 33525/2 haloformio acid phenyl ester or to give the carbonic acid bisphenyl ester* and then reacting the ester with methylamine These two new carbamates have a wide spectrum of biocidal properties.

They act especially as insecticides and acaricides, primarily against harmful orthoptera, coleoptera, rhynchotes, di tera and lepidoptera. They may be used for controlling a wide variety of storage pests and in domestic hygiene: cockroaches, mealworms, and especially against sitophilus species (corn weevil) which are difficult to control can be destroyed with very small amounts of the active substances.

When used is large amounts, the compounds of the formula I display against various representatives of mono-or dicotyledonous plant types a growth inhibiting or growth delaying activity.

When used in plant protection in a concentration which does not produce any phytotoxic effects they display an outstanding activity against harmful microorganisms, for example against fungi, for example, against Altenaria solani, Phytophthora infestans and Septoria apii, also against harmful nematodes and their eggs or larvae.

Furthermore, the new substances act quite generally as microblcides, for example, against Aspergillus species. They also act against molluscs. 2-Propynyloxyphenyl- ~methyloarbamate is known from British Patent No. 937,897 and U.S. Patent No. 3,202,573, both of which publications also disclose the insectioidal activity of that compound. The compounds of formula Z The' new preparations can be used in a wide varie y of ways and in different forms, for example, in the form of sprays, dusting powders, so-called fly plates or tapes, impregnated with a solution of the active substances, as is generally known to experts and for which applications the present invention provides a few examples. Compare in this connection also U.S. Specification 3,329,702 or British Specification No. 1,047,644 or Swiss Specification Ho. 424,359.

In many cases, as, for example, in combating soil insects, the use of granulates is of advantage to ensure that the active substances are given off uniformly over an extended period of time. Such granulates can be prepared by dissolving the active substance in an organic solvent, absorption of this solution by a granulated material, for example attapulgite or SiOg or by adsorptive organic high polymers and removal of the solvent. The granulates can also be prepared by mixing an active substance of the formula I with a polymerisable compound, then polymerising the mixture, without affecting the active substance, and carrying out the granulation during the polymerisation.

In whatever form such preparations are they may be distributed (by spraying or dusting) over large surfaces with the aid of aircraft.

The concentration in which the preparation is applied may vary within wide limits depending on the purpose in hand and is in general from 0.01 to 20 °> by v/eight for rather dilute preparations, while more concentrated ones contain 20 to 98 f» by weight of active substance.

By admixture of synergists the activity of the carbamates of this invention can be further increased; for this purpose there are suitable, for example, sesamine, sesamex, piperonylcyclonene , piperonylbutoxide , piperonal bis[ 2-[ 2-butoxye hoxy] ethyljacetate, sulphoxides, propyl-isome , N-(2-ethylhexyl}-5-norbornene-2,3-dicarboxamide, octachloro-dipropyl ether, 2-nitrophenyl-propargyl ether, 4-chloro-2-nitrophenyl-propargyl ether and 2,4, 5-trichloro-phenyl-propargyl ether.

The various forms of application of such preparations can be adapted to the individual purpose by admixing with them substances that improve the distribution, the adhesion, the stability towards rain and possibly the penetration, for example, fatty acids, resins, wetting agents, glue, casein or alginates.

The preparations according to this invention may be used by themselves or in conjunction with conventional pest control agents, for example, herbicides, insecticides, acaricides, nematocides, bactericides, fungicides or molluscicides.

The following Examples illustrate the invention.

The parts are by weight unless otherwise indicated and temperatures are shown in degrees centigrade.

E x a m p l e l 2-Butinyloxyphenol A solution of 122 parts of £-toluenesulphonic acid-2-butinyl ester in 150 parts by volume of acetone is dropped into 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 24 hours, then cooled, filtered and evaporated. The residue is take up in ether, repeatedly washed with water and while "being cooled with ice extracted with 200 parts by volume of sodium hydroxide solution of 10 # strength. The alkaline extract is neutralised with hydrochloric acid and the product taken up with chloroform. The solvent is evaporated and the product distilled at a bath temperature of 120°C under 0.05 mm Hg pressure. The distillate crystallises; it melts at 43 to 46°0. 2-( 2-Butinyloxy) pheriyl-N-methylcarbamate A solution of 56 parts of 2-(2-butin-l-yloxy) phenol in 150 parts by volume of ethyl acetate is mixed with 0.5 part of triethylenediamine and then port onwise with 21 parts of methylisocyanate.

The mixture is kept for 24 hours at 40°C and then evaporated. The residue is crystallised from chloroform+ cyclohexane; it melts at 79 "to 81°C (Compound Ho. 1).

E x a m p l e 2 2-( l-Butin-3-yloxy) phenol A solution of 247 parts of jg-toluenesulphonic acid-l-butin-3-yl ester in 200 parts by volume of acetone is dropped at 50°0 into a suspension of 110 parts of pyro-catechol, 152 parts of anhydrous potassium carbonate and 166 parts of potassium iodide in 100 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, washed with water and with 450 parts by volume of sodium hydroxide solution of 20 # strength. The alkaline extract,, together with the partially precipitated sodium salt of the product, is acidified with semidilute 33525/2 hydrochloric acid while being cooled with ioe. The product r is obtained by extracting this solution with chloroform and evaporating the extraot. For purification it is distilled under a high vacuum; Boiling point: 63 to 66°C under 0.07 mm Hg. The distillate •crystallises; it melts at 52 to 54°C 2-(l-Butin-3-yloxy) phenyl-N~me hylcarbamate A solution of 45.5 parts of 2-(l-butin-3-yloxy) phenol and 0.1 part of triethylenediamine in 150 parts by volume of carbon tetrachloride is mixed with 19 parts of methylisocyanate. The mixture is stirred for 14 hours at 40°C. The resulting crystalline produot is filtered off and. once recrystallised from toluene. It melts at 68 to 91°C (Compound No. 2). '; EXAMPLES OP FORMATIO S ' Dusting agent Equal proportions of an active substance of this invention and. of preoipitated silicio aoid are finely ground together. When this powder is mixed with kaolin" or talcum, there result dusting agents preferably having a oontent of Syray powder' .

To manufacture a spray powder, for example, the following ingredients are mixed and finely ground together: 50 parts of an active substance according to this invention parts of HISIL (highly adsorptive silica) parts of bolus alba (kaolin) .5 parts of a reaction product of ^-tertiary octylphenol with ethylene oxide 1.5 parts of sodium salt of l-benzyl-2-stearyl- benzimidazole-6 ,3 * -disulphonic acid .

Emulsion concentrate Readily soluble active substances can' also be formulated as emulsion concentrates in the following manner: parts of active substance 70 parts of xylene parts of a mixture of a reaction product of an alkylphenol with ethylene oxide, with calcium dodecylbenzenesulphonate are mixed together. When this mixture is diluted with water to the desired concentration, a sprayable emulsion results* Granulate A solution of 7.5 g of an active substance of the formula I in 100 ml of acetone is poured over 92 g of granulated attapulgite (mesh width: 24/48 mesh per inch). The whole is thoroughly mixed and the solvent removed in a rotary evaporator. The resulting granulate contains 7.5 # of active substance..

E x a m p l e 3 To test the effect against various storage pests, 2 g of the Compound No. 2 were mixed with 38 g of talcum and the whole was very finely ground. In this manner a dusting powder of good efficacy was obtained, with which the following results were achieved: Organisms tested Minimum concentration needed for 100$ lethal effect within 24- hours' exposure (mg of active substance per square metre) Compound No. 2 Compound No. 1 German cockroach (Phyllodromia germanica) 3 6 American cockroac (Periplaneta americana) 1.5 25 Russian cockroach (Blatta orientalis) 6 25 Yellow mealworm beetle imago 50 100 (Tenebrio molitor) larva 200 200 Bacon beetle imago 100 50 (Dermestes frischii) larva 50 100 Grain weevil (Sitophilus granarius) 25 200 Pur beetle larva (Attagenus piceus) 200 100 House cricket (Acheta domestica) 12 25 E x a m p l e 4 Lucilia sericata (Blowfly) Freshly hatched maggots in small glass vessels were fed horseflesh which had been treated with an aqueous emj&sion of the substance under test. The determination of the limit concentration of the active substance was performed in 3 test series on different days, in which new fly generations and new dilution series of 100, 48, 24, 12, 6, 3 and 1.5 ppm were used. After 24 hours the following limit values for a 100 lethal effect were obtained: Compound No. 1 at 3 ppm Compound No. 2 at 3 ppm E x a m p l e 5 Activity against female mosquitoes (Aedes aegypti) Female mosquitoes were kept for 6 hours in Petri dishes coated with the substance under test. To produce this coating the bottom half of the dish was first treated with 1 ml of an acetonic solution of the substance and then dried for 1 hour. The solutions used contained 1000, 100, 10 and 1 ppm respectively, which corresponds to a concentration of 1, 0.1, 0.01 and 0.001 mg per dish. The mosquitoes were cooled in ice and 10 females were counted into each dish, For every concentration 4 parallel tests were made.

After 0 minutes the following values were recorded: E x a m p l e 6.

Cimex lectularius (Bed bug) In a similar test to that described in Example 5, in which the active substance is tested on filter paper in plastic dishes (1 mg per dish corresponds to 1 g per 6 m2), and which was repeated twice with 10 bugs each, resulted for the active substance No. 2 at a concentration of 10, 1 and 0.1 mg/dish in a 100 fo lethal effect in each case.

E x a m p l e 7 .

Contact effect against Ceratitis capitata The bottom half of each Petri dish was treated with 1 ml of an acetonic solution of the substances Nos. 1 and 2 each, which solution' con ained a specified quantity of active substance. Then the solvent was expelled and deep-cooled fruit flies were placed in the prepared Petri dishes and the lids were then put on. Each dish contained 10 flies. After 1 hour the lethal effect achieved with different concentrations of a dilution series was examined: E x a m p l e 8 Stomach and contact effects against Orgyia gonostigma and Epilachna varivesti8 Young mallow plants (Malva sylvestris) in pots with about 6 leaves were immersed in a solution of the active substance of a specific concentration and allowed to dry.

Over every plant a cellophane hood containing larvae of Or yia gonostigma in the L, stage were then placed and fastened with a rubber band. The insecticidal stomach and contact effects were examined 2 and 5 days later. When at the first examination 100 a/° mortality is found, the plant is reinfested so that at the same time the activity of the aged preparation can be determined.

The test with larvae of Epilachna varivestis in the stage was carried out in an identical manner with Phaseolus as host plant, (a) Effect against Orgyia (b) Effect against Epilachna (after 5 days)

Claims (15)

- 13 - 33525/2

1. Compounds of the general ormula in which one of the eubstituents and R2 represents a hydrogen atom and the other represents a methyl group.

2. · t e compound of the formula

3. · T e compound of the formula

4. * A process for the manufacture of compounds of the formula ∑ in Claim 1, which comprises reacting a phenol of the ormula in which ¾ and ¾ have the same meaning as in Claim 1, with methylisooyanate, an M-meth lcarbamic acid halide or with H-meth l-phenlcarbamate, or by first reacting a phenol - 14 - 33525/2 of the above formula with COC g to form the corresponding haloformic acid phenyl ester or carbonic acid bisphenyl ester respectively and then reacting the ester with methy1-amine.

5. * A process as claimed in Claim 4» conducted substantially as described in Example 1 or 2 herein*

6. A compound as claimed in Claim 1, whenever prepared by a process claimed in Claim 4*

7. A pest control preparation which contains as active ingredient at least one compound of the general formula I in Claim 1, in conjunction with at least one of the following additives: vehicles* solvents, diluents, dispersants, emulsiflers, wetting agents, adheslves, binders or thickening agents or further pest control agents..

8. A pest control preparation according to Claim 7, containing as active Ingredient the compound defined in Claim 2,

9. A pest control preparation according to Claim 7, containing as active ingredient the compound defined in Claim 3.

10. A pest control preparation as claimed in Claim 7, substantially as described in the formulation Example herein.

11. A method of combating insects and harmful organisms of the order Acarina, wherein a compound claimed in any one 1 to of Claims/ or 6 is applied to the locus of the insects and/or the harmful organisms. - 15 - 33525/2

12. A method of combating insects and harmful organisms of the order Acarina, wherein a preparation as claimed in any one of Olaims 7 to 10 is applied to the locus of the insects and/or the harmful organisms.

13. · A method according to Claim 12 , wherein the preparation contains from 0.01 to 20$ by weight of the active ingredien .

14. * A method according to Claim 12, wherein the preparation contains from 20 to 98% of the active ingredient.

15. * method according to Claim 12, conducted substantially as described in any one of Examples 3 to Θ herein. For the Applicants iiD/rb