DE2033454C3 - 1-oxa- or 1-thia-3-aminocarbonyloximino-cyclopentane or cyclohexane, process for their preparation and their use - Google Patents

Description

35

R ⁵ R ⁶ R ⁷ R ⁸

NOC-NH-R ⁹ (IH)

il ο

in which X is an oxygen or sulfur atom and η has the value O or I. R ¹ to R "are hydrogen atoms or C, -C ₂ -alk> l radicals, the mercaptomethyl radical or

represent the carbomethoxy radical and R ^{9 is} a C ₁ -C ₃ -

Denotes alkyl or alkenyl radical.

Specific examples of preferred carbamic acid esters of the invention are:

se

Carbamates with insecticidal properties have been around since ! 947 known. In many cases the hydroxyl containing component is in these carbamates a substituted phenol, a naphthol or a heterocyclic hydroxy compound. From US Pat. No. 3,223,585, substituted carbamic acid esters of oximes of cyclic ketosulfides and substituted carbamic acid esters of cyclic thiohydroxanoic acids of the following general formulas are knows:

R ³ R ⁴ R ¹ R ²

N — O — C — N

R ⁵ R ⁶ R ⁷ R ⁸

(D

10

I-Thia-3-methylaminocarbonyl-oximino-

cyclopentane, l-Tnia- ^ methoxycarbonyl ^ -mnethylamino-

carbonyl-oximino-c) clopentane, l-thia-2-methoxycarbonyl-3-methylamino-

earbonyl-oximino-cyciopentane, l-Thia ^. + ^ limethyl-S-methylaminocarbonyl-

oximino-cyclopentane, l-Thia ^ HlimethylO-ethylaminocarboayl-

o \ imino-cyclopentane. l-thia-2,2-dimethy] -4-methylaminocarbonyl-

oximino-cyclopentane. l-Thta ^^^ trimethyM-methylaaimocarbonyl-

oximino-cyclopeiitan, l-Thia-3-methyiamiLnocarbonyl-oximino-cyclo-

hexane, 1 -Thia-S ^ -diäthyM-metliy laminocarbon yl-

oximino-cycloperitane, 1 -Thia ^ melhyM-ethyl-3-methylamino-

carbonyl-oximino-cyclopentane, l-Thia ^^^ - trimethyl ^ -methylaminocarbonyl-

oximino-cyclopeflitan,

I.TIiia ^ -n-propylOJ-dirnethyM-methylamino-

carbonyl-oximino-cyclopentane, j_Thia-2-isopropyl-3,3-dimethyl-4-methylamino-

carbonyl-oxiniino-cydopentane, iSthlSmethylmercapt

I-TbiaSinethylSypme

anjinocarbonyl-oximino-cyclojwntane. l-Tnia-3 ^ nethyi-3-äthylrnerc, vpto-4-rnethyl-

afflinocarbonyl-oximino-cyclopentane. | .0 »-33- <iiniethyl-4-methylaminocarbonyl-

oxinino-cyclopentane,
| / niia-3-methyl-3-methylmercapto-4-methyl-

aminocarbonyl-oximino-cyclonentane, J-Tliia-4,4- <iiniethyl-3-methylaminocarbonyl-

oximino-cydohexane,
1 -Thia-3,3-diniethyl-4-aüylaminocarbon y I-

oximino-cyclopentane,
l_Thia-2 ⁴ 4-triniethyl-3-aIlyIaminocarbonyl-

oximino-cyclopentane,
j-Thia ^ meUiyl-S-methylaminocarrionyl-

oxiaaino-cyciopentane,
I-thia-4-raethyl-3-methylaminocarbon \ I-oximino-cyclohexane.

IO ger esters, addition products of long-chain mercaptans and ethylene oxide, sodium alkylbenzene sulfates with 14 to 18 carbon atoms, alkylphenol-ethylene oxide adducts, which are ζ. B. of p-lsooctylpheno! derive, and soaps. Sodium stearate and sodium oleate.

The solid and liquid biocidal agents can be produced by conventional methods.

The compounds of the invention of the general formula in which the radical R ^{9 is} an alkyl radical can be prepared either by reacting a lower alkyl isocyanate with the corresponding oxime or by reacting the corresponding oxime with phosgene and then reacting the chlorocarbonic acid ester obtained with the corresponding primary amine .

The oximes used according to the process are made from corresponding cyclic ketones Reaction made with hydroxylamine. The ketones themselves are made by Dieckmann condensation or > by thermal decomposition of the barium salts of the corresponding obtained aliphatic dicarboxylic acids.

The examples illustrate the invention.

The compounds of the invention have biocidal activity, ie they are suitable for killing and / or controlling insects. Nematodes. Mites and other pathogens causing plant diseases The compounds of the invention can be applied in undiluted form to the plants or other substances to be protected. Often it is desirable. _{J0 to use} the compounds mixed with either solid or liquid inert auxiliaries, ζ Β as a spray in the form of dispersions, in water or organic solvents. The choice of the suitable solvent depends primarily on the concentration of the active ingredient. in which this is to be used, the required volatility of the solvent, the cost of the solvent and the type of material treated. Typical examples of solvents that can be used are hydrocarbons, such as benzene, toluene and xylene. Kerosene diesel oil. Heating oil, petroleum. Naphtha. Ketones such as acetone, methyl ethyl ketone and cyclohexanone, chlorinated hydrocarbons such as carbon tetrachloride, chloroform, trichlorethylene, perchlorethylene, esters such as ethyl acetate, amyl acetate and butyl acetate, the monoalkyl ethers of ethylene glycol. z. B. Äthylenulykolmonoäthyläther, the monoalkyl ethers of diethylene glycol, such as diethylene glycol monoethyl ether alcohols such as ethanol, isopropanol and amyl alcohol. _S o

The compounds of the invention can be applied to plants and other substances also together with a inert solid carriers are applied, such as talc, Pyrophyllite, attapulgite, kieselguhr, chalk, diatomaceous earth, calcium carbonate, bentonite. Fuller's earth. Cottonseed husks, Wheat flour, soybean flour, pumice stone, tripoli. Sawdust, walnut shell flour and

'Often contain pesticides with compounds of the invention also includes a surfactant. These surface active agents are preferred used in both solid and liquid preparations. The surfactant can be anionic, cationic or nonionic. Typical surfactants are the alkyl sulfonates, Alkyl sulfonates, alkyl sulfates, alkyl amide sulfonates, Alkylaryl polyether alcohols, fatty acid esters of polyhydric alcohols, ethylene oxide adducts such as these game 1

1-thia-S-oximino-cyclopentane 5 g, 0.043 mol) l-thia-S-oximino-cyclopentane (prepared according to the regulation given in Helvetica Chimica Acta 27, p. 1285 [1944]) are with Brought 20 ml of methyl isocyanate to implement. Once the initial exothermic reaction subsided the mixture is refluxed for 5 hours, then cooled and removed from volatiles freed. 9.3 g of 1-thia-4,4-dimethyl-3 - methylaminocarbonyl - oximino - cyclopentane obtained as an amber colored liquid: n £ = 1.5528.

Example 2

A mixture of 5.3 g (0.03 mol) of 1-thia-3-oximinocyclopentane (prepared according to the given in Journal of Organic Chemistry 18, p. 138 [1953] Regulation) and 25 ml of methyl isocyanate are refluxed for 5 hours. Then become volatile Shares stripped off. 8.5 g of 1-thia-3-methylaminocarbonyl are obtained - oximino - cyclopentane as a dark brown viscous liquid.

Confirm the IR absorption spectrum and analysis the structure

C ₈ H ₁₂ N ₂ O ₄ S.

Calculated .
found ..

C 41.4. H 5.2%; C 41.5, H 4.8%.

Example 3

A solution of 20 g (0.125 mol) of 1-thia-2-methoxycarbonyl-cyclopentan-3-one and 20 g (038 mol) of hydroxylamine hydrochloride in 300 ml of methanol 22.9 g (0.29 mol) of pyridine were added and the mixture was heated under reflux for 16 hours. Thereafter, the solvent is distilled off and the residue between ethyl acetate and water distributed. The organic solution is separated off, dried and evaporated. Man receives 14.3 g of l-thia ^ -methoxycarbonyl-S-oximinocyclopentane as a dark brown liquid. The IR absorption spectrum confirms the structure.

A mixture of 5.3 g (0.03 mol) of the oxime obtained and 25 ml of methyl isocyanate is used for 5 hours heated under reflux and then freed from volatile components. There are 9.0 g of 1 -Thia-2-methoxycarbo-

nyl -i 3 - methoxycarbonyl - oximino - cyclopenlan obtained as a dark brown viscous liquid. The IR absorption spectrum confirms the structure.

"; Example 4

a) A solution of 32.6 g (0.25 mol) of l-thia-4,4-dimethyl-cyclopentan-3-one (prepared according to the in Journal of the Chemical Society [1961], p. 650, specified procedure), 34.8 g (0.5 mol) of hydroxylamine hydrochloride and 68 g (0.5 mol) of sodium acetate trihydrate in 200 ml of ethanol and 100 ml of water Heated under reflux for 4 hours. Thereafter, the reaction mixture is concentrated in a rotary evaporator and the residue between ethyl acetate and Water distributed. The ethyl acetate solution is washed with aqueous sodium bicarbonate solution, dried and evaporated. 26 g remain 1 - thia - 4,4 - dimethyl - 3 - oximino - cyclopentane in the form of pink crystals from F. 53 to 54 C. Das IR absorption spectrum confirms the structure.

b) A mixture of 14.5 g (0.1 mol) of the oxime obtained, 7 ml of methyl isocyanate, three drops of triethylamine and 50 ml of diethyl ether is _{refluxed for 3V for 2} hours and then left to stand for 16 to 18 hours. Volatile components are then distilled off. 20.7 g of a yellowish solid remain. The IR absorption analysis shows that the product still contains starting material. 7 ml of methyl isocyanate, three drops of triethylamine and 50 ml of diethyl ether are therefore added to the product and the mixture is heated for a further 3 hours. After the volatile substances have evaporated, 20gl-thia-4.4-dimethyl-3-methylaminocarbonyl-oximino-cyclopentane remain as a yellowish-brown solid with a melting point of 64 to 66 ° C. The IR absorption spectrum confirms the assumed structure

Example 5

A solution of 7.3 g (0.05 mol »1-thia-4,4-dimethyl - 3 - oximino - cyclopentane. 4.1 g (0.05 mol) AHyl isocyanate in 100 ml of anhydrous diethyl ether is refluxed for 16 hours and then evaporated in a rotary evaporator. There are 11.5 g of l-Thia ^ A-dimethylO-aHylaminocarbonyl-oximino-cydopentane as a viscous yellow oil received: n? = 1.5276. Yield 100% of theory.

Example 6

A mixture of 7.3 g (0.05 mol) of 1-thia-4,4-dimethyl-3-oximino-cyclopentane (prepared according to Example 4), 3.9 g (0.05 mol of ethyl isocyanate, three drops of triethylamine and about 60 ml of anhydrous diethyl ether is 24 Heated to reflux for hours, then cooled and evaporated in an env The product awakens at 87 ° C.

Example 7

a) A 50 ml three-necked flask which is marked with equipped with a reflux condenser and heating jacket, net 23.2 g (0.2 mol) of 1-thia-4-methyl-yciopentan-3-one (produced according to the in Svensk Kcmisk Tidskrift 57, p. 24 [1945]. specified regulation). 172 ml of 95% ethanol 27.8 g (0.4 mol) of hydroxylamine hydrochloride in 45 ml of water and 20.1 g (0.19 mol) charged anhydrous sodium carbonate in 45 ml of water. The solution is refluxed for 6V2 hours, and then the ethanol is in a Rotary evaporator evaporated. The two layers of the residue are washed three times with ethyl acetate

; extracted. The combined ethyl acetate extracts are dried over anhydrous magnesium sulfate and then evaporated in a rotary evaporator. It 24.6 g of l-thia ^ -methyl-S-oximino-cyclopentane remain as an orange-colored, moist solid. That IR absorption spectrum confirms the assumed structure.

b) F. in a dried, 200 ml flask equipped with a reflux condenser with a drying tube and is equipped with a heating jacket, 10.5 g (0.08 mol) of the oxime obtained according to a), 100 ml of anhydrous diethyl ether, 5 g (0.088 mol) of methyl isocyanate and four drops of triethylamine were charged The pale yellow solution is refluxed for 6 hours and then placed in a rotary evaporator evaporated 5.8 g of an amber-colored viscous liquid are obtained, which in 50 ml of anhydrous Dissolve diethyl ether and add another 2.6 g (0.04f> Mol) methyl isocyanate and three drops of triethylamine are added and refluxed for 24 hours "vird.

The reaction mixture is then evaporated in a rotary evaporator. There are 6.2 g of 1-thia-4-methyl-3 - methylaminocarbonyl - oximino - cyclopentane as viscous amber liquid obtained. The IR absorption spectrum confirms the assumed one

Structure n £ "= 1.5321.

Example 8

a) A suspension of sodium ethylate in benzene, made from 64 g (1.5 mol) of a 56.2% sodium

hydride dispersion. 69 g (1.5 mol) of anhydrous ethanol and 300 ml of benzene, is over a period of 20 minutes with a solution of 162 g (1.35 mol) Ethyl 2-mercaptoacetate is added in 100 ml of benzene, the mixture being refluxed gently

cooks. The resulting slurry is for 25 minutes in a solution of 179 g (1.4MoI) Ethyl 3,3-dimethyl acrylate in 50 ml of benzene are added and the mixture is then refluxed for 75 minutes heated. The brown colored reaction mixture is with

four portions of ice water extracted. The combined aqueous extracts are immediately acidified with cold concentrated hydrochloric acid and in three portions Benzene extracted. The combined benzene extracts are evaporated and the residue is distilled lates. 198 g of l-thia-4-carbäthoxy-5,5-di- Hiethyl-cyclopentan-3-one in three fractions with refractive indices from nv '= 1.4850 to 1.4850 and with Boiling points from 69 Q0.08 Torr to 77 CO.55 Torr obtain. The IR absorption spectra confirm the

assumed structure.

b) A mixture of 151.7 g (0.75MoI) of 1-thia-4-carbethoxy-5.5-dimethyl-cydopentan-3-one. 200 ml of acetic acid. 105 ml of concentrated sulfuric acid and 750 ml of water is heated and stirred under reflux for 8 hours. After that, the mixture cooled, extracted with two portions of benzene, the combined benzene extracts are washed with 10% sodium hydroxide solution and dried over anhydrous magnesium sulfate. After that the solution is through

a microcolumn with the Aesgen 2.54 χ 15 cm distilled. 79 g of l-Thia-S, 5-dimethvl-cyck> -pentan-3-one are produced as a colorless liquid in two fractions with the refractive indices ni ¹ = 1.4926 to 1.4929

keep. The IR absorption spectra confirm the assumed structure.

■ c) A solution of 32.6 g (0.25 mol) of 1-thia-5,5-dimethyi-cyclopentan-3-one, 34.8 g (0.5 mol) of hydroxylamine hydrochloride and 68 g (0 , 5 mol) sodium acetate trihydrate in 200 ml of 95% ethanol and 110 ml of water is refluxed for 6 hours. Then we <d the reaction mixture under reduced pressure; evaporated and the residue partitioned between ethyl acetate and water. The ethyl acetate solution is washed with aqueous sodium bicarbonate solution, dried and evaporated. 33.5 g of 1-thia-3-oximino-cyclopentane are obtained as a clear, orange-red colored liquid; n? ~ 1.5292. The IR absorption spectrum confirms the assumed structure.

d) A solution of 14.5 g (0.1 mol) of the oxime obtained and 10 ml of methyl isocyanate in 60 ml of benzene three drops of triethylamine are added. An exothermic reaction ensues. Thereafter, the reaction mixture Heated under reflux for 5 hours and then evaporated in a rotary evaporator. There are 23 g of 1-thia-5,5-dimethyl-3-methylaminocarbonyl-oximino-cyclopentane obtained as a red-brown viscous liquid. The IR absorption spectrum confirms the assumed structure: n? = 1.5310.

Example 9

a) A solution of 21.6g (0.15MoI) 1-thia-2,4,4-trimethyl-cyclopentan-3-one (prepared according to that in Journal of the Chemical Society [1961], p. 650. specified regulation). 20.9 g (0.3 mole) hydroxylamine hydrochloride and 24.6 g (0.3MoI) sodium acetate trihydrate in 200 ml of 95% ethanol and 110 ml of water is refluxed for 4 hours and then evaporated in a rotary evaporator. The crystal slurry obtained is filtered off, with Washed with water and dried over sodium hydroxide in a vacuum desiccator. It will be 19.5 g of the corresponding oxime in the form of colorless crystals with a melting point of 81 to 83 ° C.

b) A solution of 9.6 g (0.06 mol) of the oxime obtained, 5 ml of methyl isocyanate and four drops of triethylamine in 150 m! Diethyl ether is refluxed for 6 hours, then left to stand and evaporated in a rotary evaporator. 12.5 g of a cloudy liquid are obtained, which turns into a pasty solid on standing. The IR absorption spectrum confirms the assumed structure for the 1-thia ^ Atrirnethyl ^ -methylarninocarbonyl-oxitnmo-cyclopentane. F. 73 to 76 C Example 10

A solution of 4.0 g (0.025 methyl - 3 - oximino - cyclopentane Example 9), 2 g (0.025MoI) AlIyIi drops of triethylamine in 40 ml ether becomes 5 1/2 hours under then in a Drehverdan.

6.0 g (100% of theory) I-

ethyl-3-allylaminocarbonyl-oximino-cydopentane as get clear yellow oil: n? = 1.5242. Example Il

a) A solution of 132 g (0.68 mol) of 2-bromomethyl-2-methyibutyric acid (prepared according to French patent 1231163) in 35OmI 95 ° iigem ethanol and 980 ml of water and a solution of 28 g (0.7 mol) of sodium hydroxide in 265 ml of water are added in a ratio of 2: 1 within a period of 2 hours to a solution of 69 g (0.75 mol) of mercaptoacetic acid in 400 ml of water.

which contains 66 g sodium hydroxide. The addition takes place over 45 minutes at room temperature carried out, for the remainder of the time under reflux conditions. The resulting mixture is 6 hours heated under reflux, stand 16 to 18 hours

left, the ethanol was distilled off and the residue poured into ice and hydrochloric acid. The acidic mixture is extracted with 4 parts of diethyl ether. The combined ether extracts are then in 4 parts 10% aqueous sodium carbonate solution ex-

watered. The combined sodium carbonate extracts are acidified and extracted with diethyl ether. After the ether extract has been dried and evaporated, 79 g of 2-ethyl-2-methyl-4-lhiaadipic acid are obtained obtained as a light yellow viscous liquid.

20. b) A mixture of 79 g (0.38 mol) of the obtained Thiaadipic acid and 3.0 g of barium hydroxide are placed in a 100 ml three-necked flask, the is equipped with a stirrer, thermometer, distillation attachment, reflux condenser and receiver flask.

While stirring, the mixture is heated to 200 to 310 ° C. in a metal bath until the distillation has ended is. The organic solution of the distillate is separated from the aqueous layer with the aid of ether. The ether solution is dried over magnesium sulfate.

net and evaporated. The residue is through a Vigreux column with the dimensions 13 χ 1.6 cm, which is equipped with a Claisen attachment, distilled. After a short forerun, the following fractions of 1-thia ^ methyW-ethyl-cyclopentan-3-one are collected:
First faction:

Bp _q : 81.5 C: 5.5 g yellow liquid: nV = 1.4967.

Second faction:

Kp ^ g: 80 to 81.5 C: 5.5 g yellow liquid: η >"- 1.4960.

Third parliamentary group:

and bp ^ ₅ : 81.5 C: 3.0g almost colorless liquid: η · .- = 1.4975.

The IR absorption spectrum confirms the assumed Structure.

c) A solution of 28.0 g (0.2 mol) of 1-thia-4-methyl-4-ethyl-cyclopentan-3-one in 172 ml of 95% ethanol is mixed with 27.8 g (0.4 mol) of hydroxylamine hydrochloride in 45 ml of water and 21.2 g (0: 2 mol) of sodium carbonate in 45 ml of water and refluxed for 6 hours in a 500 m SS flask be free. The residue obtained, consisting of two layers, is taken up in ethyl acetate, the ethyl acetate solution is dried and evaporated. 29.5 g of 1-thia-4-methyl-4-ethyl-3-oximino cyclopentane are obtained as a viscous liquid n'J = 1, 5290.

d) A solution of 11.2 g (0.07 mol) of the according to c) er

65 hold oxime in 50 ml of anhydrous diethyl ether

is reacted with 4.4 g (0.077MoI) of methyl isocyanate

four drops of triethylamine are added and 6 hours

heated to reflux. Then the reaction;

509608 / 1-

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mixture evaporated in a rotary evaporator under reduced pressure. 14.7 g of 1-thia-4-methyl -4-ethyl-3-methylaminocarbonyl-oxittiinocyclopentene remain as an amber-colored viscous liquid; h $ - 1.5282. The IR absorption spectrum confirms the acceptable structure.

Example 12

a) A solution of 42.4 g (0.6 mol) of sodium carbonate in 450 ml of water is mixed with 160 g (0.77 mol!) of 1-bromomethyl-2-ethylbutyric acid, the preparation of which is described in French patent 1,231,163 is. A water-insoluble upper layer is formed. This mixture is added to a solution of 78.3 g (0.85 mol) of mercaptoacetic acid in 175 ml of water which contains 52.2 g of potassium hydroxide. The resulting mixture is refluxed _{and stirred for 13V for 2} hours, then cooled and poured into ice and hydrochloric acid. The mixture is extracted with diethyl ether and the ether extract is then extracted with saturated aqueous sodium bicarbonate solution. The sodium bicarbonate solution is acidified and extracted with diethyl ether. The ether extract is dried and evaporated. 68 g of 2,2-diethyl-4-thiaadipic acid are obtained as an almost colorless viscous liquid.

b) A mixture of 67 g (0.3 mol) of 2.2-diethyl anhydrous diethyl ether was added. The resulting solution is stirred for a further hour at 0 to 5 ° C., then freed from the solvent and distilled through a Vigreux column measuring 2.5 × 18 cm. There are 186 g (83% of theory) of 2-methyl-2-methylmercapto-3-chloropropionic acid methyl ester as a pale yellow liquid iii two fractions with a boiling point of 76 to 77 ° C. / 5.3 b ^; s 5.5 torr (n? = 1.4850) and boiling point 76 to 77 "C / 5.1 to 5.3 torr (ni? = 1.4850).

b) A solution made from 16.1 g (0.7 gram atom) sodium and 600 ml anhydrous methanol of sodium methylate is mixed with 74.3 g (0.7 mol) of methyl mercaptoacetate, a trace of sodium iodide and 128 g (0.7 mol) of 2-methyl-2-methylnlercapto-3-chloropropionic acid methyl ester added under nitrogen.

After refluxing for 4 hours, the reaction mixture is filtered and the filtrate under reduced pressure Freed from the pressure of methanol. The residue is taken up in chloroform, the chloroform solution washed with water, dried and evaporated. There are 123 g (70% of theory) 2 - methyl - 2 - methylmercapto - 4 - thiaadipic acid dimethyl ester obtained as an amber liquid; = 1.4963.

20th

b) tin oemiscn from υ / gv «.. ·.« "., <.. <.- ^. , .- c) A reaction of 16.6 g (0.52 mol)

4-thiaadipic acid and 2.1 g of barium hydroxide are simplified in ethanol with 22.3 g (0.52 mol) of 56.2% sodium hygienic Distillation device in a drid dispersion in 1100 ml of anhydrous toluene.

einiacnen ucsiuiauui »» u "". "« »« e ■■ · —- ■■ · _r —— ~ .. «-., · j

Metal bath heated to 220 to 240 C until the slurry is made of sodium methylate

«. ·" ... 1 1 .. *: "# A i, t- sIaiyi P ^ üctilliat jUQ u) inn ^ rhaiH i» in # »c 7i» itraiimf »c vnn" ΧΠ minutes hei 37

35

Distillation has ended. A layer of water (4.5 g) is separated from the distillate (33.9 g). The organic solution is dried and then distilled. 11.4 g of a distillate are obtained in two fractions with a boiling point of 93 to 97 C 7.3 to 9 Torr (“ ■: ■ = 1.4965 to n ' _B · = 1.4994). The IR absorption spectrum confirms the structure of 1-thia-4,4-diethyl-cyclopentan-3-one.

c) A solution of 11.0 g (0.07 mol) of l-Tliia-4.4-diethyl-cyclopentan-3-one in 60 ml of 95 ° ethanol within a period of 30 minutes at 37 to 42 ° C. with a solution of 118.5 g (0.47 Mol) 2 - methyl - 2 - methylmercapto - 4 - thiaadipic acid dimethyl ester in 200 ml of toluene are added. The mixture is heated to 48 to 52 ° C. for 5 hours, then cooled and poured into a mixture of ice and hydrochloric acid. The organic solution is combined with the ether extract of the aqueous solution, dried, freed from solvent and distilled. There are 52 g (50% of theory) 1-thia-2-carbomethoxy - 4 - methyl -4 - mercaptomethyl - cyclopentan-3-one as a yellow liquid in four fractions from the boiling range 70 to 82 C 0.9 Torr (n ^! = 1.5009 to 1.5035). The IR absorption spectrum confirms the assumed structure.

d) A mixture of 48 g (0.22 mol) of l-thia-2-carbomethoxy - 4 - methyl 1 - 4 - methyl mercapto - cyclopentan-3-one and 384 ml of 10% aqueous sulfuric acid is refluxed and stirred for 4 hours. To

-4 _Λ ™. λ L1.::Li ._ ■ _ jj τ * ν. ■ · _ <_ .- * rvi_

is with 9.8 g (0.14 mol) of hydroxylamine hydrochloride
in 15 ml of water and 7.4 g (0.07 mol) of sodium carbonate in 16 ml of water and in a 2 (M) ml
full flask with a reflux cooler and
Heating mantle fitted, refluxed. 45
After 15 ' ₂ hours the clear yellow solution is in
a rotary evaporator on the water jet pump
evaporated and the residue filtered off with suction. The yellow crystals are in a Va- «..."".. * ..." ^ -

Kuum-Fxsikkator dried over calcium chloride. After cooling, the reaction mixture will yield with di 10.4 g of l-thia-4,4-diethyl-3-oximino-cyc1o- äthytäther extracted, the ether solution dried nentane The yellow crystals melt at 69 to 75 C. evaporated and the residue is distilled d) A solution of 7 g (0.04MoI) of the according to c) he 21 g (43% of theory) of 1-thia-4-methy1-3-methyl

"'" "" mercapto-cvclopentan-S-on as a light yellow liquid wedge

obtained from the boiling point 70 C / 9.1 Torr; η = 1.50W e) A solution of 11.7g (0.072MoI) I-Thia 4 - methyl - 4 - methylmercapto - cyclopentane - 3 - one 10 g (0.14 mol) hydroxylamine hydrochloride and 7.6 j (0.072Mol | sodium carbonate in 62 ml of ethanol to 32 ml of water is _{refluxed for 5V for 2} hours and then freed from the solvent.The residue is taken up in ethyl acetate, the ethyl acetate solution is washed with water, dried and <

_{a |} u ". _f » _u _., _ ..,. ..... ... ^ ...._ .. evaporated. It contains 12.2 g of I-thia-4-methyl

acrylic acid methyl ester in 400 ml of anhydrous diethyl 6s 4 - methyl mercapto - 3 - oximino - cyclopentane as dark ether turns into a light brown solid within a period of time, which melts at 40 to 50 C. Hour at 0 to 5T while stirring with a solution f) A dried. 100 ml flask, de

of 108.7 g (1.3 mol) Methanesulfenyichlorid in 330 ml with a reflux condenser with attached dry

hold oxime in 50 ml of anhydrous diethyl ether with Z5g (0.044 mol) of methyl isocyanate and four Drops of TriäthyUmin added. The mixture is refluxed in an oil bath for 6 hours and then evaporated under reduced pressure in a rotary evaporator. 8.5 g of 1-thia-M-diethyl-3 remain - methylaminocarbonyl - oximino - cyclopentane as a light amber viscous liquid; n? = 1.5252.

Example 13 u) A cooled solution of 131g (1.3 mol) meth-

tube and heating jacket is provided, with 5.3 g (0.03 mol) of the oxime obtained according to e), 50 ml of anhydrous Diethyl ether, 1.9 g (0.033 mol) of methyl isocyanate and three drops of triethylamine as a catalyst offset. The mixture is refluxed for 6 hours and then on a rotary evaporator evaporated under reduced pressure. There are 7.6 g of 1-thia ^ -methyl- ^ methylmercaptoO-methylaminocarbonyl - oximino - cyclopentane obtained as a dark amber-colored, viscous liquid. The IR absorption spectrum confirms the assumed structure; »! ^ = 1.5435.

Example 14

A solution of 7.9 g (0.06 mol) of 1-thia-3-oximinocyclohexane (prepared according to the instructions given in Journal of the American Chemical Society 74, p. 917 [1952]), 5 ml of methyl isocyanate, three drops of triethylamine and 50 ml of anhydrous diethyl ether is refluxed for 3 hours, left to stand for 16 to 18 hours and then freed of volatile substances in a rotary evaporator. 12.5 g of l-thia-3-methylaminocarbonyl-oximino-cyclohexane remain as a yellow, viscous, cloudy liquid; n " = 1.5495. The IR absorption spectrum confirms the assumed structure.

In an analogous manner, 1.9 g of 1 - thia - 4 - methyl - 3 - oximino - cyclohexane are obtained from 4.4 g (0.03 mol) (0.033 mol) of methyl isocyanate and four drops of triethylamine in 100 ml of diethyl ether l-thia-4-methyl-3 - methylaminocarbonyl - oximino - cyclohexane from F. 59 to 6OX '.

Example 15

a) A solution of 14.4 g (0.1 mol) of l-thia-4,4-dimethyl-cyclohexan-3-one (prepared according to the specification given in Tetrahedron 22. p. 285 [1966].) in 100 ml of 95% ethanol is with a solution of 14 g (0.2 mol) of hydroxylamine hydrochloride in 35 ml of water and a solution of 10.6 g (0.1 mol) of sodium carbonate in 35 ml of water are added.

The 1-thia-3-oximino-4,4-dimethyl-cyclohexane separates practically immediately in the form of colorless crystals. The crystals are filtered off, washed thoroughly with water and allowed to air dry. Yield 12.5g. F. 147 to 149 C. Another 2.4 g are obtained from the filtrate: F. 145 to 147 C. The infrared absorption spectrum shows the absence of a carbonyl group and the presence from

OH and - C = N groups

bj A solution of 4.8 g (0.03 mol) of that obtained according to a) Oxime, 1.8 g (0.031 mol) of methyl isocyanate and three drops of triethylamine in 200 ml of anhydrous Triethyl ether is refluxed for 17 hours. The reaction mixture is evaporated in a rotary evaporator. There are 6.6 g of 1-thia-4,4-dimethyl-3-diethylaniinocarbonyl-oxinnino-cydohexane ah clear liquid residue which solidified to a colorless, semi-solid mass on standing that IR absorption spectrum confirms the assumed structure

(-NH at 2.9u and -C = O at 5.85 The compound is initially liquid, but crystallizes on standing; F. 58 to 60 ⁰ C.

C ₉ H ₁₆ N ₂ O ₂ S:

Calculated .
found ..

C 50.0, H 7.5%; C 50.7, H 7.7%.

Example 16

A solution of 6.9 g (0.054 mol) of 1-oxa-4,4-dimethyl-3-oximino-cyclopentane (prepared according to the instructions given in Bulletin de la Societe Chimique de France 19t> 7, p. 1909), 3.9 g (0.068 mol) of methyl isocyanate and four drops of triethylamine in 30 ml of anhydrous diethyl ether is refluxed for 6 hours and then evaporated in a rotary evaporator. 10 g of 1-oxa ^^ - dimethyl-S-methylaminocarbonyl-oximino-cyclopentane are obtained as a colorless viscous liquid: n " = 1.4740.

The experiments below illustrate the killing uses of the compounds of the invention and / or control of insects, mites. Bacteria, viruses and nematodes.

Attempt 1

In this experiment, the insecticidal activity of the compounds to be investigated against black Bean aphids (Aphis fabae) examined. Stock solutions are prepared, each 500 ppm of the compound to be investigated. For this, 0.05 g of the test compound or 0.05 ml if the compound is a liquid.

4.0 ml of acetone, which is 0.25 percent by volume of a wetting agent (Trade name: TritonX-155) and 96.0ml contains desalinated water. The stock solutions become the appropriate ones you want Concentrations diluted. The bean aphids are grown on Nasturtium var. Tall Single plants. Insects of various ages are used in these experiments. There will be individuals Nasturtium test plants in 5.7 cm flower pots infected with populations of 100 to 200 bean aphids.

When used as a spray, 50 ml of the stock solution or the diluted solution are evenly distributed splashed on the plants. When used as a systemic agent, 11.2 ml of the stock solution or the diluted solution applied to the earth. A dose of 11.2 ml of the drug since; Containing 500 ppm of the test compound corresponds to a dose of 18 kg / ha.

A moisture resistant piece of a thermo

ss plastic film with the dimensions 10 χ 10 cn is cut open to the center and derar attached to the base of the stem of the test plant that a funnel forms. This test plant egg are watered under fluorescent lamps during the trial period from the bottom of the flower pots Dead bean aphids fall into the funnel so that they can be easily counted. The percentage Mortality is determined 3 days after treatment.

The commercially available pesticide 0.0-diethyl-S-2- <äthylthio) -äthylphosphoi dithioat is used as a comparison compound.
In Table 1 the results are compiled

13th

033 454

14th

Table I.

fixed connection

Use as a spntowuel

percent mortality at concentration in tpm

128 64 100 100 100 100 100 100 100 100 100 100 82 0 100 93 - iOO 100 - 100 100 100 100 100 100 100 61 100 100

32

Use as a systemic malet

percentage mortality at concentration in kg'ha

April 9

452

l-Thui-3-ynethylamioocarbonyloximino-cyclopentane

I-? Hia-4-meÜjoxyearbonyl-3-öiethyIandnocarbonyl-oximino- <gpclopentane

t-T & ia-4,4-cBmethyl-3-methylaminocarbcnyl-oximino-cyclo-

^! pen dew.

i-Tbia-2 ^ - (aimethyl-4-methylaminocarbonyl-oximino-cyclo-, peatane

l-thia-3-methylaaiiBocarbonyloximino-cyclohexane

1-Thia-33-dimethyl-4-allylaminocarbonyl-oximino-cydopentane .

l-Tma ^ 4-dimethyl-3-ethylaminocarbonyl-oximino-cyclopentane .

yy amino-carbonyl-oximino-cyclopentane

-Oxa-S ^ -dimethyM-methylaminocarbonyl-oximino-cyclopentane ..

-Thia-S-methyl-S-methylmercapto-4-methylaminocarbonyl-oximinocyclopencan

l-thia-4 methyl-3-methylamino-

carbonyl-oximino-cyclopentane .. -

yy aminocarbonyl-oximino-cyclohexane

l-thia [2A4-trimethyl -] - 3-allylaminocarbonyl-oximino-cyclohexane

O, O-diethyl-S-2- (ethylthio) ethylphosphorodithioate

100 100

91

100

100

100

100

87 100

90

100 100

85 66

100 100

100

100
100

100

90

100
100

100
59

76

78 100

100 29

83 100

100

0 100

81

38 68

300

63 78

100 100

43

1 (X!

iOO

Attempt 2

In this experiment, the residual insecticidal activity of the compound under investigation will be black Bean aphids (Aphis fabae) determined. The procedure described in Experiment 1 is repeated, if not the readings are taken on the third and seventh day after spraying or soaking. the The results are summarized in Table II:

Tabel!! Test connection

concentration Use as a sprint means
Mortality. ⁰ O 7 days concentration TpM 95 (kg / ha) 3 days 60 256 100 49 9.04 128 100 41 4.52 64 100 42 2.26 32 100 1.13 16 83

use

as a systemic agent

Mortality,%

1-thia-4,4-dimethyl-3-methylamino-carbonyloximino-cyclopentane

Experiment 3 ⁶ 5 spider mites (Tetranychus sp.) Determined. It will

TJ- "..j ,. according to experiment 1 stock solutions prepared the

In this experiment, the acancidic effect of 500 ppm of the test compound will be included. This trunk

Compounds to be investigated versus red solutions are used both as sprays as well

3 days 7 days 100 100 76 47 81 56 25th 46

40

16

used as a systemic agent. A stock culture the spider mill is carved on the leaves of scarlet firebeans. About 18 to 24 hours before 4fiEB attempt, the spinning nails are on the primary Leaves of Lima beans (var. Sieva) transferred to flower pots with a diameter of 5.7 cm to be pulled.

According to Verasch J, the experimental preparations used as systemic agents and sprays.

After 3 days, two of the four leaves treated are examined and the mortality determined. If a test compound is an effective acaricide, the the other two sheets are available to determine the residual S activity of the preparation.

The commercial pesticide 0,0-diethyl-S-2- (äthyUbio) -äthylphosphordithioat is used as a comparison compound

The results are summarized in Table HI / JIt Table IH Test vei bond

J-Tbia-3-Biethylamino-carbonyl- oximino-cyclopentane

l-thia-4,4-dimethyl-3-methyl aminocarbonyl-oximino-cyclopentane

1 -Thia ^ -diraethyl- ^ melhy laminocarbonyl-oximino-cyclo- pentane

1 -Thia-3-methyIaminocarbonyl- oximino-cyclohexane

l-ThiaO ^ -dimethyM-allylaminocarbonyl-oximino-cyclopentane ..

1 -Thia ^^ - dimethyl-S-äthylaminocarbonyl-oximino-cydopentan ..

l-Thia- ^ methyl-i-äthylO-methylaminocarbonyl-oximino-cyclo- pentane

l-Thia ^ -methyl- ^ methylmercapto-3-methylaminocarbonyl-oximino- cyclopentane

l-Thia ^ -mnethyl-S-methylaminocarbonyl-oximino-cyclopentane '..

l-thia-4,4-dimethyl-3-methylaminocarbonyl-oximino-cyclo- hexane

l-thia-2,4,4-trimethyl-3-methylamino-carbonyl-oximino-cyclo- pentane

Q, O-diethyl-S-2- (ethylthio) .äthyI- phosphorodithioate

Use as fuel percent mortality at concentration TpM

SOO

100 100

100 100 100 100

97

97 97

_25O 15

100

100

100

43

73

85 81

100 91 128 100

0 98

78

0 Π

100

58 100

64

100

55

99

100

Use as a systemic agent

percentage mortality at concentration in kg ha

April 9

100

99

100

4.52

100

lOO

95

2.26

100

100

70

1.13

43

86

25th

attempt

In this experiment, the residual acaricidal activity of the compound to be investigated against red Spider mites (Tetranychus sp.) Determined. The experiment is carried out according to experiment 3, but the Readings taken on the 3rd and 7th days after the application of the means. The results are in Table IV compiled:

Table IV

Test connection Concentration
(TpM) Use as an anti-fungal agent!
Mortality. % 7 days Concentralization
(kg / ha) use
as a syslemische! Vl Kiel
Mortality. % 7 days 3 days 100 3 days 100 l-thia-4,4-dimethyl- 128 100 89 9.04 100 100 3-methylaminocarbonyl- 64 100 26th 4.52 100 100 oximino-cyclopentane 32 100 11th 2.26 100 39 16 98 7th 1.13 43 8th 99 5 4th 23

Attempt 5

In this attempt the acaricidal activity of the Compound to be investigated compared to a strain of the red spider mite investigated, the opposite Organophosphoric acid esters is resistant, as well as against another strain that against Organophosphoric acid esters is sensitive.

The experiment is carried out according to experiment 3, however, the readings are taken on the 3rd and 7th day after application. As a comparison compound the commercial pesticide O.O-diethyl-S-2-föthylthio) -äthyIphosphordithioat used.

The results are shown in Table V.

Table V

concentration

(kg ha)

O, O-diethyl-S-2- (ethylthio) ethyl phosphorodjthioate

Application as a systemic means

9.04

4.52

sensitive 3 days | 7 days

Mortality. %

1.13
0

Trial 6

resisteni 3 days _t 7 days

0 1

0 0 0

Test connection

I -Thia-4,4-dimethy 1-3-methylaminocarbonyl-oximino-cyclopentane

Use as a Sprilonitlel Mortality. %

20th

Application as a systemic M. Mortality. % 7 days resis Conc sensitive 100 3 days ι tration 3 days 98 100 (kg ha) 100 68 94 O, O-diethyl 9.04 95 71 50 S-2- (ethylthio) - 4.52 50 43 ethylphosphorus 2.26 6th dithioate 1.13

7 days 100

100 88 83 J ₅ In this experiment, the insecticidal activity of the compounds to be investigated against adult houseflies (Musca domestica) is determined. According to experiment 1, stock solutions are prepared which contain 500 ppm of the test compound. These stock solutions are diluted to the appropriate concentrations.

Ten adult houseflies are placed in a cylindrical cage measuring 3.8 χ 10 cm introduced, which is made of mosquito nets with a mesh size of 0.83 mm. Then be the flies were sprayed with 50 ml of the stock solution or the diluted preparations. The flies will Food and water are offered from a glucose solution so that they can eat as they please. The percentage mortality is determined three days after the treatment.

Ais comparison connection is the customary one Pesticide O, O-Diethy! -S-2- (ethylthio) -ethylphosphorodithioate used.

The results are summarized in Table VI:

Table VI Test connection

l-Thia-S-methylaminocarbonyl-oximino-cyclo-

pentane

l-thia ^ methoxycarbonyl-S-methylaminocarbonyl-

oximino-4-carbomethoxycyclopentane

1 -Thia ^ Adimethyl-S-methyla minocarbonyl-

oximino-cyclopentane

l-thia ^ -dimethyl- ^ methylaminocarbonyl-

oximino-cyclopentane

1-Thia-S-methylaminocarbonyl-oxirnino-cyclohexane l-Thia-S ^ -dimethyM-allylaminocarbonyl-oximino-

cyclopentane

l-Thia ^ -dimethyl-S-ethylaminocarbonyl-oximino-

cyclopentane

l-Thia ^ -methyl- ^ äthyl-S-methylaminocarbonyl-

oximino-cyclopentane

l-Thia-S-methyl-S-methylmercapto ^ -methylamino-

carbonyl oximino cyclopentane

i-Thia ^ -methyl ^ -methylaminocarbonyl-oximino-

cyclopentane

l-Thia ^^^ - trimethyl-S-methylaminocarbonyl-

oximino-cyclopentane

l-Thia ^^ - dirnethyl-S-methylaminocarbonyl-

oximino-cyclohexane

O, O-diethyl-S-2- (ethylthio) ethylphosphorodithioate

J (X)

90 100

100 100 70 100 100 mortality. %. at concentration TpM 250

100

30th

100

70
100

100

100

100

100

100

70

I2K 64 100 100 100 100 90 30th 100 10 100 100 100 100 100 100 100 50 50 100 0

90

100

60

100 100

Trial 7

In this experiment, the insecticidal activity of the compounds to be investigated against Argyrotaenia velutinana definitely

Freshly hatched larvae of the insect are used. Paired, fully spread out primary leaves of winter beans are placed in a water culture and sprayed with 50 ml of the stock solution or the wr-thinned preparation into a rotatable spray hood. The stock solution containing 1000 ppm of ga the test compound and it is manufactured in accordance with Experiment 1, except that 0.1 g instead of "one 0.05 g of the test compound used. The stem solutions are diluted in the same way to produce preparations with a correspondingly lower concentration

As soon as the solvent of the preparations on the leaves has evaporated, the paired leaves become separated from each other. One leaf is placed on a 1.5% water agar in a Petri dish. Ten newly hatched larvae are on the Leaf is applied and the petri dish is covered. The larvae are kept at 22 ° C. for 3 days. Thereafter mortality is determined. The results are summarized in Table VII:

Table VII Test connection

I -Thia-3-meth ylaminocarbonyl-oximinocyclopentane

Mortality,%, at Concentration TPM

• 00 »

IOD

SOO

70

250 _I0

Test connection

1 -Thia-4-methoxycarbonyl-3-methylaminocarbonyl-oximinocydopentane

1-thia-4,4-dimethyl-3-methylaminocarbonyl-oximino-cydopentane

1 -Thia-3-methylaminocarbonyl-oximinocydohexane

1 -Thia - ^^ trimethyl-3-methylaminocarbonyl-oximino-cydopentane

Mortality,%. at concentration TpM

500 ί 250

lOOO

80 62

Trial 8

70 In this experiment, the insectidde activity of the compounds to be investigated compared to the Mexican bean beetle (Epilachna varivestis

certainly. The experiment is carried out as in Experiment 7, but one-day-old larvae of the Beetle used. The larvae are kept at 22 ° C. for 3 days. After that there is mortality and inhibition determined by food intake. The Hem

Food intake is an indication that the compound being investigated is a repulsive one Has an effect

As a comparison compound, the commercially available “pesticide O, O-diethyl-S-2- (ethylthio) ethylphosphorus dithioate used.

The results are summarized in Table VIII:

Table VIII Test connection

1 -Thia-3-methylaminocarbonyloximino-cyclopentane

1-Thia-4-methoxycarbonyl-3-methylaminocarbonyl-oximino-cydopentane

1-Hia-4,4-dimethy! -3-methylaminocarbonyl-oximino-cyclopentane

1-Thia ^ -dimethyl- ^ methylaminocarbonyl-oximino-cyclopentane

l-thia-3-methylaminocarbonyl-

oximino-cyclohexane

l-thia-3,3-dimethyl-4-allylamino-

carbonyl oximino cyclopentane

l-thia - ^ - dimethyl-S-ethylamino-

carbonyl oximino cyclopentane

l-thia-2,4,4-trimethyl-3-methylamino-

carbonyl oximino cyclopentane

l-thia-2,4,4-trimethyl-3-ally] amino-

carbonyl-oximino-cyclopentane

l-thia- ^ methyM-ethyl-S-methylamino

carbonyl-oximino-cyclopentane

*) Inhibition of food intake.

Mortality. %. at concentration TpM

tOOÜ 100 *) ¹ I.
80 *)

500

100 *)

100 *)
100 *)
100 *)
100 *)
100 *)

100 *)
100 *)

250

100 *)

100 *)

100 *)
100 *)

100 *)
100 *)

100 *)
90

128 (A. 100 *) 80 *) 100 *) 100 *) 100 *) 100 *) 100 *) 100 *) 100 *) 100 *) 100 *) 30th 80 *) 0 80 0

J ² 10

continuation

Test connection

Mortality,%. at concentration TpM

1000

500

- Oxa - ^ - dimethyl-S-methylamino carbonyl oximino cyclopentane.

-Thia- ^ methyl- ^ methylmercapto 3-methylaminocarbonyl-oximino cyclopentane

1-thia- ^ methyl-S-methylaminocarbonyl-oximino-cyclopentane.

-Thia- ^^ dimethyl-S-methylamine carbonyl-oximino-cyclohexane ..

O, O-diethyl-S-2- (ethylthio) -ethyl- phosphorodithioate

*) Inhibition of food intake

Attempt 9

The compounds are being examined for their ability to combat the "Southern Bean Mosaic" virus on pinto beans and Maize Dwarf virus on corn (Golden Bantam) jo. Stock solutions of 1000 ppm of each compound are prepared according to Experiment 1, except that the compound is used in an amount of 0.1 g instead of 0.05 g. The leaves are both sprayed and the earth soaked. 1 to \ s 2 hours before the treatment, the leaves with silicon carbide are - sandpaper rubbed and infected with the virus.

When used as a spray, 67 ml of the stock solution are sprayed evenly onto the plants at 1000 ppm. For systemic use, the stock solution is applied to the surface of the soil of each flower pot before spraying at a dose of 72.4 and 36.2 kg / ha, respectively. 10 days after the infection, the plants are examined on the symptoms and a virosis. The results are summarized in Table IX:

100 *)

100 *)

250 12R 64 ^ 2 100 *) 80 *) 30th - ■ 100 *) 100 ») 100 *> 50 100 *) 100 *) 40 - 100 80 40 100 40 0

Table IX Tea connection

1-Thia-5.5-dimethyl-3-ethylenocarbonyl-oxmiHwxvdohexane

Kon7cntralton

(kg 1 »!

72.4

(TpMI

[Beans

1000

Injection pressure

100

Corn

Attempt 10

In this experiment, the effectiveness of the compounds to be investigated against the injection by root knot nematodes iMeloidegyne spp. » certainly.

Composted greenhouse soil diluted one third with clean washed sand. will infected with about 2 g of tomato roots per flower pot. Then be Put 25 ml of the preparation to be investigated on the infected soil. The preparation contains 0.056 g the compound to be examined. 1.0 ml of an emulsifier stock solution (0.25% emulsifier with the Trade names: "Triton X-155" in acetone) and 24. ~ m desalinated water. The concentration is 2240 ppm. Lower concentrations are allowed Receive dilution. ,

After the treatment with the preparation, the soil, the inoculum and the active ingredient are gently mixed, put back into the flower pot, and the mixture is incubated for 7 days at 20 ° C. and constant humidity. After incubation with the V ». In the first test compound in Table X, two seedlings of tomato plants (Rutgers) and three Windsorbean seeds (Vicia foba) are placed in each flower pot. When incubated with the remaining secns test compounds in Table X, two seedlings «S- of tomato plants and three Nasturtium spp. Are placed in each pot. After three weeks of growth, the roots are removed from the earth and examined for root knot formation. The roots of the Windsor beans or the nasturtium plants are only examined if the tomato host plant showed necrosis and the extent of the infection is determined on a scale from 0 to 10. 0 means no root galls or complete suppression, and 10 means strong SS root knot formation, which is comparable to the control plants. Every root system becomes? «° ^η *; ^{Examines π} and the average is multiplied by TO and subtracted from 100. In this way the percentage suppression of the nematodes is obtained. ^. ι

The »» naeis Usual pesticide 0.0-Diithyl-S- <äthylthiolhmethyl

phosphorodithioate. the usual ^ 'f ^ f? of O, O-diethyl-O-2- (äthytthio) -äthylp * osphor thioat and O, O-diethyl-S-2- (äthyltliio) _: ethylphosphorthioat and the commercial Pestiad O-Athyi SS-dipropylpnosphoTdithioat used.

The results are shown in Table X below Table X

24

Test connection

Suppression,%, at concentration, kg / ha 36.2 I 18.1 I 9.05 | 4.52 | 2.26

l-thia-3-methylarninocarbonyl-oximino-

cydopentane

l-Thia ^^ dimethyl-S-methylaminocarbonyl-

oximino-cyclopentane -

l-TWa-4,4-dime & yl-3-ethylaminocarbonyl-

oximino-cyclopentane

l-thia-4,4-dimethyl-3-allylaminocarbonyl-

oximino-cyclopentane

l-thia-lA ^ trimethyl-S-methylamino-

carbonyl-oximino-cyclopentane

l-thia ^ -methyl- ^ thyl-S-methylamino-

carbonyl-oximino-cyclopentane

i-Thia - ^ - methyl ^ methylmercapto-S-methylaminocarbonyl-oximino-cyclo- pentane

O, O-diethyl-S- (ethylthio) -methyl-phosphor- dithioate

Mixture of O, O-diethyl-O-2- (ethylthio) -äthylphosphorthioat and O, O-diethyl- S-2- (ethhykhio) -ethylphosphorthioate

O-ethyl S.S-dipropyl phosphorodithioate

100 100 100 100 100 100

95 100 100

40 100

80

85 100

70 100

0 100

0 40

0 30

70 80

50 100

100

100

90

50 90

0 97

50

0 60

0 30

Attempt 11

Young tomato plants in flower pots with a diameter of 9 cm are treated by soaking the ^{earth egg} with the test compound given in the table below and a P ° P ulatl ° «!? ⁿ Exposure to whiteflies for 7 days in the greenhouse. The plants are treated with the test compound in an amount of 9.05 kg / ha or less. Stock solutions containing 500 IpM of the test compound are prepared according to Experiment 1 and diluted to the desired concentration. After 7 days, numerous eggs could be found on the plants examined. All plants were placed in a holding room. 15 days after treatment was up the total number of living larvae on the third and fourth leaves is determined and the percentage Suppression calculated. The results are shown in Table XI.

Table XI

Test connection Conc
tration
(kg / ha) Under
depression
(%) l-thia-3-methylaminocarbo-
nyl-oximinoA ^ diinethyl-
cydopentane 9.05
2.26
0.565 99
64
41

Attempt 12

Adult cotton boll cheeses ^ ^ grandis) are formed in cylindrical feathers in experiment 6 kept the type described and int Sner SLpensk *, which apply in T.beUeXH verbiiidragbespräbt Then ^ ^ J Sugar washer offered as food «· d

is collected 3 days after the treatment. Master solutions which contain 500 ppm of the test method are prepared according to experiment 1 ma aefdj: ge wished konaotration diluted. The results are shown in Table XII.

Table XlI Tesi connection

I -Thia-3-meth ylaminocarbonyi-oxasnio-4,4-dkaethytcydopentane

concentration

(TpMI

243

81

27

For this purpose 2 sheets of drawings mortality

1 (X)

100

100

60

509608/146

Claims (3)

Patent claims: I. 1 -jOxa "or I - Tfaia - 3 - aminocarbonyloximino ^ yclopentane or -cyclohexane of the all- mean formula • Vhf. R ^ R ⁶ R ⁷ R ' Ν — Ο — C-N t! ' O i \ R ¹ R * R ^J R y> = N — Ο — C — NH- R ⁹ (111) * R * R ⁷ in which X is an oxygen or sulfur atom and η has the value 0 or 1, R ¹ to R ^{8 represent} hydrogen atoms or Q-Ca-AUcyl radicals, the mereaptomethyl radical or the methoxycarbonyl ^{radical and R 9 represents} a Q-Cj-alkyl or alkenyl radical . 2. Process for the preparation of the compounds according to claim 1, characterized in that one in a known manner the corresponding Ox im (A) for the preparation of compounds of the general formula HI in which the radical R * is a Q-Cr-alkyl or alkenyl radical means either (1) with a corresponding alkyl or alkenyl isocyanate or (2) reacted with phosgene and the chlorocarbonate thus obtained with the corresponding primary amine or (b) for the preparation of compounds of the general formula III in which the radical R "is a means other than the hydrogen atom, either (1) reacted with phosgene and the chlorocarbonate thus obtained with the corresponding secondary amine or (2) with the corresponding carbamyl chloride. 3. Use of the compounds according to claim I and 2 as pesticides. in which the radicals R ¹ to R * are hydrogen atoms or lower alkyl radicals, η has the value 0 or I, ίο R ⁹ because hydrogen atom or a lower alkylresi and R ^{10 is} a lower alkylresi. In these compounds, the sulfur atom in the ring is in the o- or γ-separation to the carbonyl group. In terms of the relationship between the structure and the biodden activity of the AUcyJcarbamate and the Activity of the cyclic compounds known from the USA patent should not be expected that compounds which these groupings in a position other than the 1,2- or 1,4-position to one- others have high biocidal activity. However, it has been found that N-alkyl carbamates of oximes of cyclic ketosulfides in which the ring-containing sulfur atom is in the / ^ position to the carbamyl carbon atom, d. i.e. in which this Groups are separated from one another by a carbon atom, surprisingly an excellent one develop biocidal activity The invention relates to I-oxa- or 1-thia-3-aminocarbonyl-oximino-cyclopentane or cyclo- hexanes of the general form!