DE2010053A1 - Pesticides - Google Patents

Description

201Ö0SI

CIBA AKTIENGESELLSCHAFT, B AS E L (S C H WE IZ)

Case 6691 / E "

Pesticides

BAD ORIQiNAL

The invention relates to new ones. lo-Dithiolanyloximlno- · carbamates of the formula T, their production: and their use as active substances in pest control agents. In formula I.

R ₁ and R are independently hydrogen or a lower alkyl group, R is hydrogen or a methyl group and R ^ is hydrogen or a lower alkyl group. Under a lower alkyl group here and in the following a CH, -, CL-, nC ^ fL-, iso-CJfr, -, nC ^ H -, sec.-C ₂ ^ H-, iso-C ^ H -, tert .-C ^ H -, n-CJH ^ -, iso-C ₁ -H -, sec.-CH group.

The possible syn (a) or anti (ß) isomers of Oxime carbamates are mil locked in. - It is therefore not particularly in the following pointed out to them.

One of the particularly important groups of act ί ν substances are the dithiolanes of the formula

-NO-CO-HH-R ^ΙΣ

wherein R and Rp are independently hydrogen or a lower alkyl group and R _{5 is} a lower alkyl group.

009838/2306

BAOORfQJNAL

■ · · The production of the new Iy3-Dithiolanyloximinocarbamate of the formula I is carried out by reacting a Qxitns of the formula:

■ --R ₁ - - -. ■■■ · .Ζ

CH _p = CS HI

Y \

R ₂ - + ■ Λ-ΝΟΗ

with an isocyanate PU-NCO or R ₁ . Or with a similar -NCO

Alkyl or methylalkylcarbamic acid halide of the formula Hal-CO-N (P -) (Rj, in which Hal is halogen, preferably chlorine, and R, and R ^ are as defined above.

The compounds of the formula I have a surprising biological breadth of action, which has an effect partly in the comprehensive control of pests, partly in crops of useful plants, in addition to the herbicidal activity in the form of beneficial effects on useful plants.

Furthermore, the compounds of the formula I (j have a molluscicidal effect, which is particularly evident in gastropods, which are schistosome transmitters. The compounds also have good microbicidal activity against bacteria and fungi, especially against phytopathogenic fungi such as Erysiphe cichoracearum, Alternaria tenuis and solani.

009838/230 6.,

'■ ϊ ■ .Ti

centrations, no damage to plants can be detected.

Furthermore, the compounds of the formula I have an effect against nematodes, e.g. Panagrellus redivivus, Meloidogyne sp. and others, as well as a very good insecticidal and acaricidal effect, which are also clearly demonstrated biologically chemo-sterilizing properties, available. ^ For example, these carbamates have a very strong effect

against houseflies, aphids, caterpillars and beetles, e.g. Grain beetles and colorado beetles. In the contact effect they are the well-known active ingredient "Carbaryl" (N-methyl-a-naphthyl-carbamate) strongly superior.

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

The new carbamates are therefore well suited for

fc Control of pests in the hygiene sector and in stockpiling.

Their effectiveness against diptera, coleoptera, rhynochotes and lepidoptera makes them a particularly suitable class of compounds. Ground insects are found in the ground with minor Fights application rates. -. .

009838/2306

BATH ORIGINAL

It is particularly worth mentioning that well-known rice pests like Nephotettix eincticeps, Nilaparvata lugens, Sogatella fureifera or the rice stem borer Chi Ip sup-. pressalis and cotton pests such as Prodenia or Anthonomus effectively combated.

The compounds of the formula I have 10 to 20 times less toxicity to warm blooded animals than the compound 1,3-dithiolanyl oximino-N-methylcarbamate. You are in the ground degradable, there are no regressions, would lag behind in utility floors.

The oximinocarbamates of the formula I can be used alone or with suitable additives. The pesticide formulation is in USP. 3 329 702 or Brit. .P 1 047 644 or Schweizer P. 424 359. '. . . ^:

Generally used as a pesticide contain one or more of the following additives: solvent, diluent, dispersing, emulsifying, wetting, adhesive, binding | or thickeners, but can also contain other active ingredients contain. ,

In addition to use in the form of solutions, emulsions, concentrates, dusts, wettable powders or by spraying is the use of granules for in many cases

^. Uniform release of active ingredients over a longer period of time approx space is an advantage. These can be removed by dissolving the active ingredient

in an organic solvent, absorption of this solution by granulated mineral, e.g. attapulgite or

and removing the solvent. You can also be prepared so that the active ingredients of the formula I in the same way of granules with urea-formaldehyde or Polyacrylonitrile-based are included.

Depending on the application, such agents can also be applied by distributing them over a large area (spraying, dusting etc.) with the help of airplanes.

The different forms of application of such funds

tk can in the usual way by adding substances which improve the distribution, the adhesive strength, the rain resistance and possibly the penetration capacity, such as
Fatty acids, resins, wetting agents, glue, casein or alginates can be adapted to the intended use.

The compounds of the formula I can be used in the inventive Pesticides can be present as the only active ingredient, or together with common ones Insecticides, acaricides, nematocides, bactericides, fungi-P cides, herbicides or with fertilizers.

All organophosphorus compounds, carbamic acid derivatives, chlorinated hydrocarbons, nitrophenyl derivatives, but also natural active ingredients such as Sabadilla, Rotenone, Pyrethrin and others as mixing partners.

009838/2306

■ - Ί -

When fighting representatives of the Order Äearinä let see from the number of known ones Äearieide especially 'the following for the combined Ahwendnahm with the active substances of the formula Ϊ herartzieheriii Dinö <iä | i> Binäpacryl, ^ -seeibutyl ^^ je-dinitropheriylöyGlö-

ape>; Dinobutone, chiobenzides, fluorosurfactants, " fetradifon, Teträsul, ^ -Chlorophenyl-ai ^

lfidi 2 _> 4-I) iG; hiörphenylbenzolsuifönat _J N * - "{k ^ chlöF-Q- ' (j methyiphenyiJ-Niii-dimethylformainidin, formetanate., 2-Süti-nyi-p-chlorocarbahilat, cytilopropanecarboxylic acid-S-nitro- ^ -chloranllide, dicofol.

Gie concentration of the application "'gel · - in the middle *! can vary widely depending on the type of Application fluctuate * It is generally σ ^ ΘΪ (Jewichtsprözertt up to 2Θ percent by weight for more dilute '' Meanwhile, more concentrated titrates, on the other hand, have 20 percent by weight

up to 98 percent active ingredient. Preparations with the highest concentration are produced with the lowest! Amounts of · additives -used? -, · The ti IiV-Te chrii k 'is -with' fdinstzör dusting spray- '

Direction applied -, preferably - with the help of 'aircraft * · - *' · ''"·" ■ "■ -.--- · ^:. · - ...---. i · ..-. . .-, ■ · .. -

BATH ORIGINAL

The effect of the carbamates according to the invention can be further increased by synergists. Sesamini Sesamex, Piperonyl cyclonene, Piperonyl butoxide, Pipe.ronal bis [2- (2-butoxyethoxy) ethyl] acetate, sulfoxides, propyl isome, N- (2-ethylhexyl) -5-norbornene-2,3- are suitable for this. . dicarboxamide, octachlorodipropyl ether, 2-nitrophenyl propargyl ether, 4-chloro-2-nitrophenyl _{propargyl ether and} 2,4,5-trichlorophenyl propargyl ether.

In the following examples, parts by weight are referred to as parts, and the temperatures are in degrees Celsius specified.

009838/2306

Example 1'

At 30-55 ° a mixture of 16 ^ parts potassium .carbonate 125 files ciß-li ^ -Biehlor-S-buten 'and 15OQ Parts by volume of water-free alcohol with stirring 19 ^ parts

registered., '

d the suspension for 14 hours * under ^ ^c: cooled to room temperature and fiitrterfc, Ft It pat is evaporated, taken up in 100 ¥ olumenteilen (III) * filtered ^again and ain-Ber B & afcstand vfird under high vacuum destililerfc · ¹ '

feile a ^ Isopropgrltstino ^ -vlE ^ l ^ l ^^ - äitöiJiolaek be with 100 'Yolifflte & tetien hlte & h®! . vermisehf; and with \ ß Hydroasyleain «Kyäroehlorld * i @ I ^ afe in

Bit MiEotoung is 5 Bfed * under Büakfliass _teile Sistiftsser poured and mife Aether.auf ethereal Ulisung n ^ rö with. l * n lE & troiilftttge extracted * - Alkalisehe Extrc & t '^ tM under liikikluns «life koaa estellt ®ä slt
ig itlrd ife © r »tA
filtered KtM © toge-sfajspft «Da

BATH ORIGINAL

2-methylcarbamoyloximino - ^ - vinyl-ly ^ -dithiolane 20 parts of 2-0ximino-4-vinyl-1,> dithiolane and 0.1 part of triethylenediamine are dissolved in 100 parts by volume of dry toluene and added dropwise at 3O-4o ° with 8 parts of methyl isocyanate offset. The solution is kept at 40 ° for 14 hours and then evaporated. The residue is crystallized from methanol-water and then from toluene-kexane. 114-117 ° (compound 1). A semisolid product (compound Ia) which corresponds to the stereoisomer of the compound is obtained from the combined mother liquors by evaporation.

In this or similar ways, the following are made

Connections, shown.

No. 2 CH ₂ = CH _x S

^ NO-CQ-NH-CH ₃ S

0O983B / 23Q6

Formulation examples ..

Stättbenilt.tel. ,

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

Spray powder *

For the production of a wettable powder xuerden example-r wisely the following components mixed and finely ground:

50 parts of active ingredient according to the present invention 20 parts Hisil (highly adsorptive silica) 25 parts Bolus alba (kaolin)

1.5 parts of 1-benzyl-2-stearyl-benzimidazole-6,3 ^1- disulfonic acid sodium. _;

3.5 parts of reaction product from p-tert-octylphenol and ethylene oxide

Emulsion concentrate _t

Highly soluble active ingredients can also be used as an emulsion concentrate be formulated according to the following rule:

20 parts of active ingredient.

70 parts of xylene ^, .. ■ / f -, "_ 10 parts of a mixture of a reaction product of an alkylphenol with Aethyler.oxyd'und Calciun-nodecylbenzenesulfonat

009838/2306 .,,

BATH ORIGINAL

are mixed. When diluted with water to the desired concentration, a sprayable one is produced Emulsion.

Granules

7.5 S of one of the active ingredients of the formula I are dissolved in 100 ecm 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, the solvent is drawn off in a rotary evaporator. Granules with 7.5 ^c / o active ingredient content are obtained.

f i 9 8 3 8/2 3 0 6

ORIGINAL BATHROOM

Example 2

A dusting agent made according to the above example with 5 $ active ingredient No. 1 and the, isomer la, which was obtained from the mother liquor of compound 1, achieved the following result in the control of stock pests: ■

Test gardens Minimum concentration of 100 fo
lgen killing in 24 hrs. Expo
sition time (mg V / active substance per m ^) Verb. No. La German cockroach
(Phyllodromia germanica) Verb. No. 1 12th American cockroach
(Perlplaneta americana) 12th 12th Russian cockroach
(Blatta orientalis) 12th 50 Flour beetle imago
(Tenebrio rnolitor) larva 25th 50
100 Bacon beetle ■ Imago
(Dermestes frischii) larva > 200
> 200 100
100 Sitophilus granarius 25th
25th ■ 6 Fur beetle larva
(Attagenus piceus) 6- 50 House barbecue
(Acheta domestica > 200 25, ■ 25th

GO9838 / 230 6

BADORIGIi ^ AL Example 3>

Effect against spider mites . Bush bean plants (Phaseolus vulgaris) are infected with spider mites in the two-leaf stage 12 hours before the active substance treatment by placing infested leaf pieces from a cultivation, so that after this time a population in all stages of development is found on the plant. Using a chromatography atomizer, the plants are then sprayed with the emulsified active ingredient until a uniform coating of droplets forms on the leaf surface. An evaluation is carried out after 7 days: the plant parts are inspected under a stereo microscope to calculate the percentage of destruction.

The following table shows the mortality percentages of the normally sensitive species Tetranychus urticae Koch for Connection ur. 1 and the isomer la indicated.

009838/2306

BATH ORIGINAL

Verb. No. Conc. Kill in percent Eggs Larvae Adults (ppm) after 7 days 0 100 100 800 0 100 80 ' 1 Bo 100 100 hoo 8oo 8o 100 100 la • .Ί0 "0

Example 4

• Contact effect on Mus ca domestica (L.) and Gerat i ti s eapltata. Half of each Petri dish was treated with 1 ml of an acetone solution of one of the substances No. 1 and la, which contained 1000, 100, 10, 5 and 2.5 ppm of the active ingredient. After the solvent had evaporated, supercooled houseflies were placed in the Each dish contained 10 test animals. After increasing time intervals, the killing was checked at the various concentrations. The following killing in percent was achieved after 4 hours ·.

·· ■ ■ '* »
Verb. No. Conc.
(ppm) M .., dornestica C, capitata 1000 loo; ΐ 100 fo " 100 100 % 100 % 1 10 100 % 100 % 5 50 * 50 % "2.5 0 %. 50 '' o

009838/2306

BATH ORIGINAL

Verb. Hr. K on 7 ,.
(ppm) M. thornest! Approx C. capitata 1000 100 % 100 % ion 100 pounds 100 # 1 η 10 100; »; 100 % ;;, 50 % 100 5Ä ?. . ^r : 30 Z 100 ^

y'irkunt-; i ^ egen Proc'eni "I itura-Lai'ven. 5 larvae each in J ^ -. '.: 1 PdI ¹¹ IH wooden on oin j'.latt of Malva pilvcstrir, df ::; in a wäSGJj ^ c Lö .vui.i; dor / UrtivKubstanr. Ur. 1 or in ^f h ": J." .: unc the Alctiv. 'substance Ki ^-1 . la was thawed and then placed in an arrodeect Petri dish, ge.se? '..:.; ι. where di. " }, ν.ί '': - ί \ - 'iV-i ^ ity with i'inoin 1; efeuchtetcn WattebauGCli auirrohtci-will keep. Bej this K (H) InI: ', .- and Fi \' i ^,! .r tf .'- t becomes the effect "nr; after 1 and 2 Tog ^ n. yeprnrt, whereby consistently after a T ^ i.- · ine Keubeniedlung before, ^: , enoimnen v / 1 rd.

vi, wurcic i'olr ' ^! '.drr; j, o ::: ijs er "ie]' -:

Verb. 1, 'r

BAD OFHQtNAL

Example 6 '.

A) activity against Rhi picephalus bursa. 5 adult, hungry ticks are counted in a glass tube and immersed for 1-2 minutes in 2 ml of an aqueous emulsion with 100 ppm test substance. The tube is then closed with a standardized cotton ball and turned upside down so that the active ingredient emulsion is absorbed by the cotton wool. The evaluation takes place after 1 and 2 weeks.

■ "■ ■ ■■ ^.: ' T

Do two repetitions for each attempt. Compound No. 1 achieved 10000 kill after 2 weeks, Compound No. 1a "achieved IQOJo kill after 2 weeks.

B) Boophilus microplus (larvae). Using the method given under A), approximately 10-20 larvae are placed in a tube and treated with 50 ppm test substance in an aqueous emulsion. ■

Comp. No. 1 achieved 100 % kill after 2 weeks. i Verb. No. la scored after 2 weeks. 100 fo death.

009838/2306 BADORIOUS

"t € v around

Bei pie l 7

V. Effect against Dipt eren

Lucilia soricata (larvae). A dilution series is made with the emulsifiable preparation of compound 1 and compound la. 2 ml of a concentration are mixed with 2 g of minced horse meat in a 10 ml glass vessel. 20- ^ 0 newly hatched larvae are transferred into these vessels. The evaluation takes place after 24 hours. A concentration of 24 or 12 ppm causes a 100% kill after 24 hours.

Example 8
Effect against soil insects

10 larvae of Diabrotica balteata ("Banded cucumber beetle") , 4-7 days old, are placed in a Petri dish at one end of a 90 cm long filter strip (width 15 cm) soaked with active ingredient solution, at the other end of which 10 germinated Corn kernels are located as a source of food. The dishes are covered and kept at room temperature for 48 hours. During this time the larvae try to cross the length of the filter strip. The experiment is repeated once. The mortality for a 0.005 # solution of compound 1 and compound Ia was $ 100.

009838/2306

bath

Claims (8)

Claims L pesticides containing as active ingredient the syn (a) or anti (β) isomer of a compound the general formula wherein R and R independently of one another are hydrogen or a lower alkyl group, R, hydrogen or a methyl group and Rk are hydrogen or a lower alkyl group, \ together with one or more of the following additives: solvent, diluent, dispersing, emulsifying, wetting, adhesive, Binders or thickeners and other active ingredients. 2. Pesticide according to claim 1, containing as active ingredient a compound of the formula CO-NH-R 5 wherein R, and R_ independently of one another are hydrogen or mean a lower alkyl group and R _ stands for a lower alkyl group. 009838/2306 3. Pesticide according to claim 1, containing the compound of the formula as active ingredient CH ₂ = CH CO-KH-CH 4. Use of active compounds according to any one of claims 1 to 3 for combating insects, pests of the order Acarina, nematodes, bacteria, fungi, undesired plant growth and mollusks. 5. Process for the preparation of 1,3-dithiolanyloximinocarbamates the general formula ⁰ R it / R, N-O-C-N ^? wherein the substituents R., R ₂ , R, and R ^ have the meaning given in claim 1, by reaction of an oxime of the formula _ CB ₂ -C _v S JL X = KOH with an isocyanate of the formula R ^ -NCO or Rk-NCO or with a methyl alkylene carbamic acid halide or alkyl carbamine 009838/2306 • acid halide of the formula _{Halogen-CO-N (R 1} ) (R ^), in which R 1 and R 1 ^ have the meaning given in claim 1. ' 6. The active ingredients mentioned in claim 1. 7. The active ingredients mentioned in claim 2. . 8. The active ingredient mentioned in claim 3. 009838/2306