DE2033454B2 - 1-oxa- or l-thia-3-aminocarbonyloximino-cyclopentane or cyclohexane, process for their preparation and their use - Google Patents

Description

R ^s R * R ⁷ R ⁸

in which X is an oxygen or sulfur atom and η has the value 0 or 1, R ¹ to R ^{x represent} hydrogen alloins or C ₁ -Q-alkyl radicals, the mercaptomethyl radical or the methoxycarbonyl radical and R ″ _{denotes a QC 3} -alkyl or alkenyl radical.

2. Process for the preparation of the compounds according to claim 1, characterized in that the corresponding oxime is used in a manner known per se

(a) for the preparation of compounds of general ² - ^s common formula III in which the radical R ⁴ is a Q-Cj-alkyl or alkenyl group, either

(1) with a corresponding alkyl or alkenyl isocyanate or

(2) reacted with phosgene and the chlorinated carbon dioxide obtained in this way with the corresponding primary amine or

(b) for the preparation of compounds of the general formula III in which the radical R ^q denotes a radical other than the hydrogen atom, either

(1) Reacts with phosgene and the chlorocarbonate thus obtained with the corresponding secondary amine or

(2) with the corresponding carnamyl chloride implements.

3. Use of the compounds according to claims 1 and 2 as pesticides.

R ³ R ⁴ R ¹ R ²

S> = N-O-C-N

R ⁵ R ⁶ R ⁷ R ^K

(Il

(C)

^{4 /}

N — O — C — N

OR ¹⁰

(H)

in which the radicals R ¹ to R ^{8 represent} hydrogen atoms or lower alkyl radicals, η has the value O or 1, R ^{9 is} a hydrogen atom or a lower alkyl radical and R ^{10 is} a lower alkyl radical. In these compounds, the sulfur atom in the ring is in the u or y position to the carbonyl group. In view of the relationship between the structure and the biocidal activity of the alkyl carbamates and the activity of the cyclic compounds known from the U.S. patent, one should not expect that compounds containing these groupings in a position other than the 1,2- or 1 , 4-position to each other, have high biocidal activity.

However, it has been found that N-alkyl carbamates of oximes of cyclic ketosulfides, in which dus ring-shaped sulfur atom in / ^ - position to the carbamyl carbon atom stands, i.e. in which these groups are separated by a carbon atom get rcnη t are, surprisingly, an excellent one develop biocidal activity.

The invention relates to 1-oxa- and 1-thia-3-ammocarbonyl-oximino-cycIopenlane or cyclohexanes of the general formula

R ¹ R ²

(HI)

R ⁵ R ⁶ R ⁷ R ⁸

5 °

Carbamates with insecticidal properties have been known since. In many cases the one that contains hydroxyl groups Component in these carbamates is a substituted phenol, a naphthol or a heterocyclic hydroxy compound. U.S. Patent 3,223,585 discloses substituted carbamic acid esters of oximes of cyclic ketosulfides and substituted carbamic acid esters of cyclic thiohydroxanoic acids the following general formulas known:

in which X is an oxygen or sulfur atom and has the value O or 1, R ¹ to R ^{8 are} hydrogen atoms or C _{1 -C 2} -alkyl radicals. represent the mercaptomethyl radical or the carbomelhoxy radical and R ^{g is} a C ₁ -Cy alkyl or alkenyl radical.

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

l-thia-3-methylaminocarhonyI-oximino-

cyclopentane,
l-thia-i-methoxycarbonylO-methylamino-

carbonyl-oximino-cyclopenlan,
l-thia ^ -methoxycarbonyl-S-methylamino-

carbonyl-oximino-cyclopentane,
l-thia-4,4-dimethyl-3-methylaminocarbonyl-

oximino-cyclopentane,
l-Thia ^^ - dimelhyl ^ -äthylaminocarbonyl-

oximino-cyclopentane,
l-Thia ^^ - dimelhyW-methylaminocarbonyl-

oximino-cyclopentane,
l-Thia-I ^^ - trimethyM-methylaminocarbonyl-

oximino-c \ clopentane,
! -Tliia-3-ynethylaminocarbonyl-oximino-cyclo-

hcxan.
l-Thia-3.3-diii.thy! -4-mcthy! aminocarbonyI-

oximino-cyclopcntane,
l-Thia ^ -melhyM-älhyl-S-mclhylamino-

carbonyl-oximino-cyclopenlan,
l-Thia-2.3.3-trimethyl-4-methhvlarninocarbon \! -

oximino-cyclopenlan.

l-thia-2-n-propy] -3,3-dimethyl-4-methylamino-

carbonyl-oximino-cyclopentane, ] -Thia-2-isopropyl-3,3-dimethyl-4-methylamino-

carbonyl-oximino-cyclopentane, 1 -Thia ^ -methyl-S-methylmercapto- ^ methyl-

aminocarbonyl-oximino-cyclopentane, l-thia-S-methyl-S-ethylmercapto ^ -methyl-

aminocarbonvl-oximino-cyclopentane. l-oxa-3,3-dimethyl-4-methylaminocarbonyl-

oximino-cyclopeman,

1 -Thia ^ -methyl-S-methylmercapto ^ -methyl-

aminocarbonyl-oximino-cyclopentane. l-thia-4,4-dimethyl-3-me: hyIaminocarbonvl-

oximino-cyclohexane,
l-Thia-S ^ -dimethyM-allylaminocarbonyl-

oximino-cyclopenlan,
! -Thia-IA ^ trimethylO-ailylaminocarbonvl-

oximino-cyclopentane,
l-thia-4-methyl-3-methylaminocarbonyloximino-cyclopentane,

1-thia-4-methyl-3-methylaminocarbonyloximino-cyclohexane.

The compounds of the invention have biocidal activity; h., they are suitable for mortification and / or or control of insects, nematodes. Mites and other pathogens causing plant diseases. the Compounds of the invention can be applied in undiluted form to plants or others to be protected Substances are applied. Often it is desirable. the compounds mixed with either solid or to use liquid inert auxiliaries, e.g. B. as a spray in the form of dispersions, in water or organic solvents. Choosing the appropriate one Solvent mainly depends on the concentration; ation of the active ingredient in which it is used should be, from the required volatility d-js solvent, the cost of the solvent and the type of material being treated. Typical examples of usable solvents are Hydrocarbons such as benzene, toluene. 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. Perchloalhylen. tster. such as ethyl acetate, amylacelate and butyl acetate. the monoalkyl ethers of ethylene glycol, e.g. B. Ethylene glycol monoethyl ether, the monoalkyl ethers of diethylene glycol, such as diethylene glycol monoethyl ether. Alcohols such as ethanol, isopropanol and allyl alcohol.

The compounds of the invention can be applied to plants and other substances also together with a inert solid carriers can be applied, such as talc. Pyrophyllite. Attapulgite, diatomite, chalk. Diatomecncrdc, Calcium carbonate, bentonite, fuller's earth. Cottonseed husks, Wheat flour, soybean flour Pumice stone, tripoli, sawdust. Walnut shell flour and Lignin.

Frequently, pesticidal agents with compounds of the invention also contain a surface-active one Middle. These surfactants are preferably used in both solid and liquid Preparations used. The surfactant can be anionic, cationic or non-ionic. Typical surface-active agents are the alkyl (15 sulfonates, alkylarylsulfonates, alkyl sulfates, and alkali sulfonals. Alkylaryl polyether alcohols. Fatty acid esters of polyhydric alcohols. Ethylene oxide Addukic such Esters, addition products of long-chain mercaptans and ethylene oxide, sodium alkylbenzenesulfonates with 14 to 18 carbon atoms, alkylphenol-ethylene oxide adducts, which z. B. derived from p-isooctylphenol, and soaps, sodium leaai and sodium oleate.

The solid and liquid biocidal agents can after customary processes.

The compounds of the invention of the general formula in which the radical R ⁹ denotes an alkyl radical can be prepared either by reacting a lower alkyl cyanate 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 the corresponding cyclic ketones Reaction made with hydroxylamine. The ketones themselves are made by Dieckmann condensation or obtained by thermal decomposition of the barium salts of the corresponding aliphatic dicarboxylic acids. The examples illustrate the invention.

example 1
1 -Thia-3-oximino-cyclopentane

5 g (0.043 mol) of 1-thia-S-oximino-cyclopentane (prepared according to the instructions given in Helvetica Chimica Acta 27. S. 1285 [1944]) are reacted with 20 ml of methyl isocyanate. As soon as the initial exothermic reaction has subsided, the mixture is refluxed for 5 hours, then cooled and freed from volatile constituents. 9.3 g of l-thia-4,4-dimethyI-3-methylaminocarbonyl-oximino-cyclopenta !! echo as an amber liquid; n'o = 1.5528.

Example 2

A mixture of 5.3 g (0.03 mol) of l-thia-3-oximinocyclopentane (prepared according to that 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 l-thia-3-methylaminocarbony are obtained] - oximino - cyclopcnlan as a dark brown viscous liquid.

Confirm the IR absorption spectrum and the analysis the structure.

C ₈ H ₁₂ N ₂ O ₄ S: . C41.4. H 5.2%: Calculated .. . C 41.5. H 4.8%. found . ..

Example 3

A solution of 20 g (0.125 mol) of 1-thia-2-methoxycarbonyl-eyclopentan-3-one and 20 g (0.288 mol) of hydroxylamine hydrochloride in 300 ml of methanol are mixed with 22.9 g (0.29 mol) of pyridine and 16 hours heated to reflux. Thereafter, the solvent is distilled off and the residue between Älhylacctal and water distributed. The organic solution is separated off, dried and evaporated. Man receives 14.3 g of 1-thia ^ -methoxycarbonyl-.Voximinocyclopentane as a dark brown liquid. The IR absorption spectrum eliminates 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. 9.0 g of l-thia-2-methoxycarbo-

r \ -t - »

: 404

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

Example 4

a) i-inc solution of 32.6 g (0.25 mol) of l-thia-4.4-dimethy I - cyclopenta ·; 3-on (prepared according to the protocol given in Journal of the Chcmica! Society ['196I]. P. 650.). 34.8 g (0.5 Mo!) Hydro.wlamin hydrochloride and 68 g (0.5 mole) sodium octate trihydrate. in 2 (KImI ethanol and 100 ml water Heated under reflux for 4 hours. Then that would be Reaction mixture 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 and dried and evaporated. 26g of 1 - thia - 4,4 - dimethyl - 3 - oximino - cyclopentane in Form of pink crystals from F. 53 to 54 C. The IR absorption spectrum confirms the structure.

bl A mixture of 14.5 g (0.1 mol) of the gum obtained. 7ml methyl isocyanate. three drops of triethylamine, ^ J 5Ci ::! r ^ ith \! ua: ^ ·. ; id 3 ¹ hours under reflux and then left to stand for 16 to 15 hours. Volatile constituents are then distilled off. There remain 20.7 g of a yellowish solid. The IR absorption analysis shows that the product still contains starting material. Therefore, the product should be mixed with 7 ml of methyl isocyanate. orei drops of triethylamine and 50 ml of diethyl ether are added and the mixture is heated for a further 3 hours. After the volatile substances have evaporated, 20 g of 1-thia-4.-1 di-neibyl-3-methylaminocarbonyl-oximino-cyelopenlan remain as a yellowish-brown solid at a temperature of 64 to 66 ° C. The IR absorption spectrum confirms the assumed structure

Example 5

A solution of 7.3 g (0.05 mol) of l-thia-4,4-dimethyl - "■■ - oximino - cyclopentane. 4.1 g (0.05 mol) Allyl isocyanate in 100 ml of anhydrous diethyl ether is refluxed for 16 hours and then heated evaporated in a rotary evaporator. E> 11.5g of l-thia - ^ - dimethyl - ^ - allylarninoearbonyl-oximino-cyclopentane obtained as a viscous yellow oil; / i: '= 1.5276. Yield 100% of theory

Example 6

Fm mixture of 7.3 g (0.05MoI)) -Thia-4.4-dimethyi - 3 - oximino - eyelopentane (prepared according to Example 4), 3.9 g (0.05 mol) of ethyl isocyanate. three drops Triethylamine and about 60 ml of anhydrous diethyl ether are refluxed for 24 hours, then cooled and evaporated in a rotary evaporator. 9.5 g of 1-thia-4,4-dimethyl-3-eth} laminocarbonyl-oximino-cyclopentane are obtained obtained as colorless crystals with a temperature of 92 to 94 ° C. The product softens at 87 'C.

Example 7

a) A five-neck flask with a capacity of equipped with a reflux condenser and heating mantle • st. is with 23.2 g (0.2 mol) of l-thia-4-methyl-cycloiVutan-3-one (produced according to the specification given in Svcnsk Kcmisk Titlskrifl 57, pp. 2-4 [1945]). Γ ·. * Ml 95% ethanol. 27. S g (0.4 mole) of hydroxy 1-amine hydrochloride in 45 ml of water and 20.1 g (0.! 9MoI) of anhydrous sodium carbonate in 45 ml of water. The solution is refluxed for 6 1/2 hours. and after that the ethanol becomes in one Rotary evaporator evaporated. The two layers of the residue are washed three times with ethyl acetate extracted. The combined Älhvlacelaiextrakle will be dried over anhydrous magnesium sulfate and then evaporated in a rotary evaporator. 1> 24.6 g! -Thia-4-methyl-3-oximino-c) ck pcnii'.n as an orange-colored moist solid. Da - IR absorption spectrum confirms the assumed structure.

hl A dried. 200ml flask. the one with a reflux condenser with drying tube and is equipped with a heating jacket. is with 10.5 g (0.08 mol) of the oxime obtained according to al, 100 ml of anhydrous Diethyl ether. 5 g (0.088 mole) methyl isocyanate and load four drops of triethylamine! The pale yellow solution is refluxed for 6 hours heated and then in a rotary evaporator

evaporated jo There are 5.8 g of an amber viscous liquid, which is dissolved in 50 ml of anhydrous diethyl ether and again with 2.6 g (0.046 mol Methyl isocyanate and three drops of triethykunin \ replaced and refluxed for 24 hours. Then the reaction mixture is evaporated evaporated. 6.2 g of l-thia-4-melliyi-

3 - mcthylaininocarbonyl - oximino - cyclopenta! '. . ·.! - viscous amber liquid hallen Dms 1R absorption spectrum confirms the assumed Structure, fif - 1.5321.

Example p

a) A suspension of sodium ethylenite in benzene, made from 64 g (1.5 mol of a 56.2% sodium hydride dispersion. 69 g (1.5 moles) of anhydrous ethanol and 300 ml of benzene are added over a period of time a solution of 162 g (35 Moll 2-mcaptoacetic acid ester in 100 ml benzene) the mixture gently refluxing. The resulting slurry is during 25 minutes with a solution of 179 g (! .4MoI) 3.3-Dimethylacrylätliyiester in 50 ml benzene and then refluxed for 75 minutes. The brown colored reaction mixture is with four portions of ice water extracted. The combined aqueous extracts are immediately concentrated with cold Hydrochloric acid acidified and extracted with three portions of benzene. The combined benzene extracts are evaporated, and the residue is distilled

so loosely. There are 198 g of l-thia ^ -carbethoxy-S ^ -dimethyl-cyclopentan-3-one in three fractions with refraction indices from nv "= 1.4850 to 1.4850 and with Boiling points from 69 'CO.OSTorr to 77 C 0.55 Torr obtain. The IR absorption spectra confirm the assumed structure.

b) A mixture of 151.7g (0.75MoI) 1-thia-

4 - carbaldoxy - 5.5 - dimethyl - cyclopentan - 3 - one 200 ml of acetic acid. 105 ml of concentrated sulfuric acid and 750 ml of water is refluxed and stirred for 8 hours. After that, the mixture cooled, extracted with two portions of benzene, the combined Benzolextraktc with 10% sodium hydroxide solution washed and dried over anhydrous magnesium sulfate. After that the solution is through a microcolumn has dimensions of 2.54 * 15cm distilled. There are 79 g of l-thia-5.5-dimethyl-cyclopent ;; n-3-one as a colorless liquid in two fractions with the Brcchuncsindices 11 · '- 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-dimethyl-cyc! topentan-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. The reaction mixture is then evaporated under reduced pressure and the residue is partitioned between ethyl acetal and water. The Athylaeeiatlösung is washed with aqueous sodium bicarbonate solution, dried and evaporated. 33.5 g of 1-thia-3-oximino-cyclopenlan are obtained as a clear, orange-red colored liquid; ni ° - 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 isoeyanate 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 l-thia-S.S-dimethyl ^ -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 21.6 g (0.15 mol) of 1-thia-2,4,4-methyl-cyclopentan-3-one (prepared according to the procedure given in Journal of the Chemical Society [1961]. p. 650.). 20.9 g (0.3 mole) hydroxylamine hydrochloride and 24.6 g (0.3 mol) of sodium acetate trihydrate in 200 ml of 95% ethanol and 110 ml Water is refluxed for 4 hours and then evaporated in a rotary evaporator. the The resulting crystal slurry 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 isoeyanate and four drops of triethylamine in 150 ml of 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 ^ A ^ trimethyl-S-methylaminocarbonyl-oximino-cyclopentane. F. 73 to 76 ^r C.

Example 10

A solution of 4.0 g (0.025 mol) of l-thia-2,4,4-trimethyl-3-oximino-cyclopentane (prepared according to Example 9), 2 g (0.025 mol) of allyl isocyanate and three drops of triethylamine in 40 ml of anhydrous diethyl ether is used Heated under reflux for 5 _1/2 hours and then evaporated in a rotary evaporator. 6.0 g (100% of theory) 1 -Thia ^^ - trimethyl - 3 - allylaminocarbonyl - oximino - cyclopentane are obtained as a clear yellow oil: n? = 1.5242.

Example 11

a) A solution of 132 g (0.68 mol) of 2-bromomethyl-2-methylbutyric acid (manufactured according to French patent 1231163) in 350 ml 95% ipem Ethanol and 980 ml of water and a solution of 28 g (0.7 mol) of sodium hydroxide in 265 ml of water are 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 containing 66 g of sodium hydroxide. While The addition is carried out at room temperature for 45 minutes and under reflux conditions for the remainder of the time. The resulting mixture is refluxed for 6 hours. Left to stand for 16 to 18 hours, the ethanol is distilled off and the residue poured into ice and hydrochloric acid. The acidic mixture is extracted with 4 parts diethyl ether. The combined ether extracts are then in 4 parts 10% aqueous sodium carbonate solution extracted. The combined sodium carbonate extracts are acidified and extracted with diethyl ether. After drying the ether extract and evaporation 79 g of 2-Ättiyl-2-methyl-4-thiaadipic acid are obtained as a pale yellow viscous liquid.

zo 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 with a stirrer, thermometer. Distillation attachment. Is equipped with reflux condenser and receiver flask.

The mixture is heated to 200 to 310 ° C. in a metal bath, while stirring, until the distillation has ended. 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 and evaporated. The residue is passed through a Vigreux column with dimensions 13 χ 1.6 cm. which is equipped with a Claisen attachment. distilled. After a short run, the following fractions of l-thia ^ -methyM-ethyl-cyclopentan-3-one are collected:
First faction:

Bp: 81.5 C; 5.5 g yellow liquid:
ηψ = 1.4967.

Second faction:

Kp. ,,,: 80 to 81.5 ⁰ C: 5.5g yellow liquid wedge:
_n »= 1.4960.

Third parliamentary group:

B.p., ₅ : 81.5 ° C; 3.0 g almost colorless liquid: n? = 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 added with 27.8 g (0.4 mol) of hydroxylamine hydrochloride in 45 ml of water and 21.2 g (0.2 Mo!) of sodium carbonate added in 45 ml of water and refluxed for 6 hours in a 500 ml flask. The clear, light yellow solution is freed from ethanol in a rotary evaporator using a water jet pump. The residue obtained, consisting of two layers, is taken up in ethyl acetate

Ethyl acetate solution dried and evaporated. 29.5 g of 1-thia-4-methyl-4-ethy1-3-oximinocyclopentane are obtained as a viscous liquid: n% = 1.5290.

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

hold Osims in 50 ml of anhydrous diethyl ether with 4.4 g (0.077 mol) of methyl isoeyanate and four drops of triethylamine are added and the mixture is refluxed for 6 hours. Then the reaction

409 526/457

mixture evaporated in a rotary evaporator under reduced pressure. There remain 14.7 g of 1-thia-4-methyl-4-athyi-3-meth \ laminocarbonyl-oximinocyclopenlan as an amber-colored viscous liquid: ii »= 1.5282. The IR absorption spectrum confirms s the adopted 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 2-bromomethyl-2-ethylbuuic acid, the preparation of which is described in French patent 1,231,163. 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 13 ″ for 2} hours, then cooled and poured into ice and hydrochloric acid. The mixture is extracted with diethyl ether and the Atherex- 2c 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 a nearly / 11 colorless viscous liquid.

b) A mixture of 67 g (0.3 mol) of 2,2-diethyl-4-thiaadipic acid and 2.1 g of barium hydroxide is heated in a simple distillation device in a metal bath to 220 to 240 ° C. until the distillation has ended. From the distillate (33.9 g A layer of water is separated off. The organic solution is dried and then distilled. 11.4 g of a desillate are obtained in two fractions with a boiling point of 93 to 97 ° C, 7.3 to 9 Torr (d = 1.4965 to > v- ' - 1.4994) The IR absorption spectrum confirms the structure of 1-thia-4,4-diethylcyclopedia-3-one.

ei a solution u> n 1 i.wg (0.0 " ¹ Moll l-thia-4.4-diethyl-c \ ckipentai! -3-one in 60ml 95% ethanol is mixed with 9.8 g (0.Ϊ4 mol) hydroxylamine- hydrochloride in 15 ml of water and ~ .4 gi () .07 mol) of sodium carbonate in 16 ml of water and refluxed in a 200 ml flask equipped with a reflux condenser and heating jacket For hours the clear yellow solution is evaporated in a rotary evaporator with a water jet pump and the residue is filtered off with suction. The yellow crystals are dried over calcium chloride in a vacuum desiccator . Yield 10.4 g of 1-thia-4,4-diethyl-3- o \ imino-cyc'iopentane. The yellow crystals melt at 69 biv "* 5 i

dl A solution of ~ g (0.04 mol) of the oxime obtained according to the present invention in 50 ml of anhydrous dialheum is mixed with 2.5 g (0.044 mol of methyl cyanide and \ ie: ^ drops of triethylamine. The mixture is refluxed in an oil bath for 6 hours and so :; nn evaporated under reduced pressure in a rotary steamer, leaving 8.5 g of 1-thia-4,4-di; ithyl-3-methylaminocarbonyl-oximino-cyclopentane as a light amber-colored viscous liquid wedge : n? 1.5252

Example 13

a) A cooled solution of 131 g (1.3 mol) of methyl methacrylate in 400 ml of anhydrous diethyl ether is unlzr within a period of one hour at 0 to 5 ° C with stirring with a solution of 108.7 g (1.3 mol) in Methansiilfenylchlorid 330 m! anhydrous diethyl ether 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 with dimensions of 2.5 × 18 cm. There are 186 g (83% of theory) 2 - methyl - 2 - methylmercapto - 3 - ehlotpropionic acid methyl ester as a light yellow liquid in two fractions with a boiling point of 76 to 77 "C / 5.3 to 5.5 Torr (nV = 1.4850) and a boiling point of 76 to 77 ° C 5.1 to 5.3 Torr t / i? = 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 methyl 2-methyl-2-methylmercapto-3-chloropropionate added under nitrogen.

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

c) A suspension of sodium methoxide prepared by reacting 16.6 g (0.52 mol) of methanol with 22.3 g (0.52 mol! 56.2% strength sodium hydroxide dispersion in 100 ml of anhydrous toluene) is heated at 37 to 42 ° C. over a period of 30 minutes with a solution of 118.5 g (0.47 mol) of 2-methyl-2-methylmercapto-4-thiaadipic acid dimethyl ester in 2OtHn / toluene The mixture is heated to 45 ° 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. 52 g (50% of theory I l-Thia-2-carbomethoxx -4-meth \ 'i-4-mercaptometh \ lc \ clopentar.-3-one obtained as a yellow liquid in four fractions from the boiling range 70 to 82 ° C 0.9 Torr | ιΓ ^ - 1.5009 to 1.5035). The IR absorption spectrum determines the assumed structure.

A mixture of 48 g (0.22 Moll of 1-thia-2-carbomethoxx -4-methyl -4-metln! mercapto-cyclopentan-3-one and 384 ml of 10 ° aqueous sulfuric acid is heated under reflux for 4 hours and stirred. After cooling) the reaction mixture is extracted with dietary ether, the ethereal solution is dried, evaporated and the residue is distilled. 2 g of i43 ", the theory of 1-thia-4-nieth-3-mcth-car-cyclopentane-3 -on obtained as a light yellow liquid with a boiling point of 70 C 9.1 Torr: η - 1.5080

c! A solution of 11.7 g (0.072 mol) of 1-thia-4-methyl-4-ynethylmercapio-cyclopentan-3-one. ! 0 g (0:14 mol) of hydroxylamine hydrochloride and ib g (O. () ⁷ 2 Mf> l »sodium carbonate in 62 ml of ethanol and 32 ml of water is 5 _\: heated under reflux and then hours freed from the solvent The residue is. taken up in ethyl acetate, the ethyl acetate solution washed with water, dried and evaporated. 12.2 g of 1-thia-4-methyl-4-methylmercapto-3-oximino-cyclopentane remain as a dark brown solid which melts at 40 to 50 "C.

Γ) A dried one. 100 ml flask, which is equipped with a reflux condenser with attached drying

pipe and heating jacket! is provided. is 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 were added as a catalyst. The mixture is refluxed for 6 hours and then evaporated in a rotary evaporator under reduced pressure. 7.6 g of 1-thia ^ -methyl ^ -methylmercapto-.Vmclhylaminocarbonyl-oximino-cyclopentane are obtained as a dark amber-colored, very viscous liquid. The IR absorption spectrum confirms the assumed structure; / ii ' - 1.5435.

B e ii s ρ i e 1 14

A solution of 7.9 g (0.06 mol) of 1-Tliia-. " ¹ -Mminocyclohexane (prepared according to the instructions given in Join na T the American Chemical Society 74, p. 917 [1952].), 5 ml of methyl isocyanate Three drops of triethylamine and 50 ml of anhydrous diethyl ether are heated under reflux 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 1-thia-3-methylaminoearbonyl-oximino-cyclohexane remain as a yellow, viscous, cloudy liquid: υ "- = 1.5495. The JR absorption spectrum confirms the assumed structure.

In an analogous manner, 4.4 g (0.03 mol) of 1 - thia - 4 - methyl - 3 - oximino - cyelohexane are obtained. 1.9 g «1033 Moll methyl isocyanal and four drops of triethylamine 100 ml of diethyl ether l-thia-4-meilnl-3 - metbylaminocarbonyl · oximino - cyelohexan \ oni F. 59 to 60 C.

Example 15

a) A solution of 14.4g (0.1 mol) l-thia-4.4-dimeth \ l-c \ clohexan-3-oii (prepared according to the specification given in Tetrahedron 22. p. 285 [1966]) 111 100 ml of 95% ethanol is mixed with a solution of 14 2 (0.2 mol) hydroxylamine hydrochloride in 35 ml of water and a solution of 10.6 g (O.i mol) Sodium carbonate is added to 35 ml of water.

The 1 -Thia-3 separates practically immediately - oximino - 4,4 - dimethyl - cyelohexane in the form of colorless crystals. The crystals will film washed thoroughly with water and allowed to air dry. Yield! 2.5g. F. 147 to 149 C. Another 2.4 g are obtained from the filtrate: 1- '. 145 up to ϊ47 C. The IR absorption spectrum shows; the The absence of a carbonyl group and the presence of

OH and - C = - ■ N groups.

b) A solution of 4.8 g (0.03 MoD of the one obtained according to ai Oxims. 1.8g (0.031 Moll Meih \ lisoc> anat and three drops of triethylamine in 200 ml of anhydrous Triethyl ether is refluxed for 17 hours. The reaction mixture is in a rotary evaporator evaporated. 6.6 g of 1-thia-4,4-dimethyl-3-methyIaminocarbonyl-oximino-clohcxane remain as a clear liquid residue that dissolves when standing ? .u solidified into a colorless, semi-solid mass. That IR absorption spectrum confirms the assumed structure

1 ■■ - NH at 2.9 ·.,. and - O- O at 5. * 5

The compound is initially liquid, crystallized but when standing: F. 58 to 60 C.

Calculated ... C 50.0. H 7.5%;
found .... C 50.7. H 7.7'V

Example 16

A solution of 6.9 g (0.054 mol) | -Oxa-4.4-dimeth> l-3-oximino-cyclopenlan (prepared according to the specification given in Bulletin de la Societe Chimique de France 1967, p. 1909). 3.9 g (0.068MoI)

i _S 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 I-oxa-4,4-ilimethyl-3-methylaminocarbonyl-oximino-cyclopentane are obtained as a colorless viscous liquid; ny = ■ 1.4740.

The following experiments illustrate the use of the compounds of the invention for oil removal 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) is investigated. Stock solutions are prepared which each contain 50 ( ¹ ppm of the compound to be investigated). 5ml. If the connection is a liquid.

4.0 ml of acetone, which is 0.25 percent by volume of a Ne ', / - mean (Trade name: Triton X-! 551 and 96.0 ml contains desalinated water. The stock solutions become the appropriate ones you want Concentrations diluted. The bean lice will be on Nasturtium -pflan / s var. Tall Single bred In these experiments, insects of the most varied Age range used. Individual Nasturtium test plants are placed in 5.7 cm large 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 center! will ! 1.2 ml of the stock solution

so simg or the dilute. Solution to earth !. Line dose of Ii.2 ml of the preparation, which contains 500 tpm of the Tesi compound, corresponds to a dose of IS kg ha.

A moisture-proof piece of an ihermo

-, 5 plastic film mn the dimensions 10 ■ in. Cm is cut up to the Mineipiinki and such into the base of the trunk de: \ ersu. ; ispflanze attached :, that a funnel is formed. These comparative plants are used under fluorescent lamps during the

t> o suchsuauer watered from the bottom of the flower pots. Dead bean leaves: -e fall into the funnel, so that they easily counted; \ we can. The percentage Mortality wire! 3 days after the treatment determined;

The customary Pcsiizid Ö.O-Diäihvl-S-2- <äihv! Thio) -äthyIphosphordithioat »Crwcndei.

Table 1 shows the results.

13th

14th

Tabel!

TesUerbindunu

-Thia-3-ynethylaminocarbonyloximino-cyclopentane

-Thia ^ l-methoxycarbonyl-3-methylaminocarbonyl-oxiulinocyclopentane

-Thia ^^ - dimethyl-S-methylaminocarbonyl-oximino-cyclopentane

-Thia-l ^ -dimethyl ^ -methylaminocarbonyl-oximino-cyclopentane

-Thia-S-methylaminocarbonyioximino-cyclohexane

carbonyl-oximino-cyclopentane .. l-Thia - ^ - dimethyi-e-athyiamino-

carbonyl-oximino-cyclopentane .. l-Thia ^^ - trimethyl-S-methylamino-carbonyl-oximino-cyclo-

pentane

l-oxa-3,3-dimethyl-4-methylamino-

carbonyl-oximino-cyclopentane .. l-Thia-3-methyl-3-methylmercapto-4-methylaminocarbonyl-oximino-

cyclopentane

-Thia-4-methyl-3-methylaminocarbonyl-oximino-cyclopenlan ..

-Thia ^^ - dimethyl-S-methylaminocarbonyl-oximino-cyclohexane

l-thiate 2,4,4-trimethyl -] - 3-allylaminocarbonyl-oximino-cyclohexane ·

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

Use as injection agent

percentage morlaliüi
at concentration in tpm

t 64

250 12.S 100 100 100 100 100 100 100 100

100 100 100

100 100

100 100

100 100

91

100

87 100

90

100 100

85 66

100 100

Use as a systemic agent

percentage mortality at concentration in kg ha

April 9

100

100

100 100

100

90

100 100

100 59

4 ^ 52

100

76

78 100

43

100

0 100

126

100

81

38 68

100 100 29 - 83 63 100 78

100

100

Attempt 2

In this experiment, the residual insecticidal activity of the compound to be investigated against black Bean aphids (Aphis fabae) determined. The procedure described in Experiment 1 is repeated, wherein on the third and seventh day after spraying b? .w. readings are taken after soaking. the The results are summarized in Table II:

Tabel!]

Test connect

-Thia ^ A-dimethyl-3-methylaminocarbonyloximino-cyclopentane

son / entition Use ;
Mona Is fuel / medium
it; it. "ο concentration • - ■ - ■■ -
use
as systemic milk 7 1 ag TpM Ikι: hai Mortality. "" 100 • Vague 7 days 3 days 47 256 ! 00 95 April 9 100 56 128 100 60 4.52 76 46 64 100 49 2.26 81 32 100 41 1.13 25th 16 83 42

65 spider mites (Tetranychus sp.) Were identified. It will prepared according to experiment 1 Stamni solutions that 500 ppm of test compound included. This Suunm - /. U investigating compounds versus red solutions are used both as sprays as well

Experiment 3 In this experiment, the acaricidal action is the

15th

used as a systemic agent. A stock culture of the spider mites is made on the leaves of scarlet firebeans held. About 18 to 24 hours before the experiment, the spider mites will be on the primary Leaves of Limabohi ^ n (var.Sieva) transferred to the grown in flower pots with a diameter of 5.7 cm.

According to Verusch 1, the test preparations are used as systemic agents and sprays.

After 3 days, two of the four puff eggs will be treated examined and mortality determined. If a test compound is an effective acaricide, the andaren two sheets available to the residual activity of the preparation.

The commercial pesticide 0,0-diethyi-S-2- (ethylthio) -äthylphosphordithioat is used as a comparison compound used.

The results are shown in Table III.

iestverhmiUaiu

1 -Thia-3-methylamino-carbonyloximino-cyclopentane

1 -Thia-'M-dimethyl-S-methylaminocarbonyl-oximino-cyclopentane

I -Thia ^ I-dimeihyM-methylaminocarbonyl-oximino-cyclopenlan

I -Thia ^ -methylaminocarbonyloximino-cyclohexane

1-thia-3,3-dimethyl-4-allylaminocarbonyl-oximino-cyclopentane . .

l-Thia-4,4-dimethyl-3-ethylamino-carbonyl-oximino-eyclopenlan . .

l-Thia ^ -methyM-ethyl ^ -methylaminocarbonyl-oximino-cyclopentane

1 ^: Thia-4-methyl-4-methylmercapto-3-methylaminocarbonyl-o \ iminoeydopentane

1 -Thia-4-methyl-3-methamino-carbonyl-oximino-cyclo-cyclopentine .

1-'l "hi-4,4-dimethyl-3-methylaminocarbony'l-oximino-cyclohexane

l-Thia ^^^ - trimethylO-methylamino-carbonyl-oximino-cyclopentane

O.O-diethyl-S-2- (ethylthio) aiii vlphosphorodithioate

Table III

Use as Sp'it / mitiel percent mortality at concentration tpm

Application as a systemic: means

percentage mortality at concentration in Κμ Iu

100

100

100

100

100

100

97 9. (M

4.52

2.26

100

55

100

100

100

43

99

100

100

100

100

70

Attempt 4

In this experiment, the residual acaricidal activity of the compound to be examined against dead spider mites (Tetranychus sp.) Is determined. The experiment is carried out as in Experiment 3, but the readings are taken on the 3rd and 7th days after the application of the agents. The results are summarized in Table IV:

Table IV

U '^ erhmdun, bom I- Ki-ii. 'entrain rhia-4.4-dimethyl at 12X 3-methylaminocar 64 oximino-cyelopent 32 ! (> S; 4th

iidiini: .iK Spni / mitti-l ι

MiM'l.llll.M. ",

Ί H) ΌΟ

"" lukewarm
10 (1

ΚοΜ / Ί'ΓιΙΜΙΙ

ik: - hai

April 9
4.52

100 100

4 «

MiIIeI

"I .11'L-

100 100

100 39

409 526/457

AA

Attempt 5

In this experiment the acaricidal activity of the Compound to be investigated compared to a strain of the red spider mite 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, but the readings on the 3rd and 7th day are after the application carried out. The commercially available pesticide O, O-diethyl-S-2- (ethylthio) ethyl phosphorodithioate is used as a comparison compound used.

The results are compiled in T'ibelle V.

use ils systemic MiUeI 0 Trial 6 7 days reäisseni 7 days Kon / cn- Morlaliläi,% 3 days 8th tr.ii ion sensitive 0 Iki! shark J days 1 4th O, O diethyi- </, 04 0 S-2- (ethylthio) - 4.52 0 3 ethylphosphorus 2.26 0 dithioate 1.13

Table V Test connection Use as Spril / millel Mortality, "i resisicnl sensation 3 days Conc lich 100 l-thia-4,4-dimethyl- tration 3 days 100 3-methylaminocarbo- TpM 100 nyl-oximino-cyclo- 64 99 pentane 16

15th

Application as a systemic M. Mortality. % 7 days resis Conc sensitive 100 3 days ι tration 3 days 98 100 (kg ha) 100 68 9d 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 In this experiment, the insecticidal activity of the compounds to be investigated against adults Determined house flies (Musca domestica). According to experiment 1, stock solutions are prepared, which contain 500TpM of the test compound. These

ίο Stock solutions graze at the appropriate concentrations diluted.

Ten adult houseflies are placed in a cylindrical cage measuring 3.8 χ 10 cm brought in the mosquito screen with the clear

2j mesh size 0.83 mm is made. 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.

The commercially available pesticide 0,0-diethyl-S-2- (ethylthio) -äthylphosphordilhioat is used as a comparison compound used.

The results are compiled in Table VI:

Table V

Tesl connection

l-thia-3-methyiaminocarbonyl-uxiinino-cyclo-

pentane

l-thia ^ -methoxycarbonyl-S-methylaminocarbonyl-

oximino-4-carbomethoxycyclopentane

l-Thia ^^ - dimethyl-S-methylaminocarbonyl-

oximino-cyclopentane

l-thia-2,2-dimethyl-4-methylaminocarbonyl-

oximino-cyclopentane

1-Thia-S-methylamino-carbonyl-oximino-cyclohexane l-thia-3,3-dimethyl-4-allylaminocarbonyl-oximino-

cyclopentane

l-Thia ^^ - dimethylO-ethylaminocarbonyl-oximino-

cyclopentane

l-Thia ^ -methyM-ethyl-S-methylaminocarbonyl-

oximino-cyclopentane

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

carbonyi-oximino-cyclopentane

l-Thia ^ -methyl-S-methylaminocarbonyl-oxirnino-

cyclopentane

l-thia-2,4,4-trimethyl-3-methylaminocarhonyloximino-cyclopentane

1-Thia ^ -dimethyl-S-methylaminocarbonyloximino-cyclohexane

€), 0-diethyl-S-2- (äthylihio) -äthylphiisphordiiliioai

S (K) 100
100
100

90
100

100
100

70
100
100

Mortality, " 0. at con / emration TpM 64 25Ü 12H 100 100 100 ._ 30th 100 100 100 70 30th 100 90 10 100 100 100 100 100 0 100 100 100 100 100 100 50 KM) 100

32 90

AROUND)

60

HK) HK)

/ ir

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 expanded primary leaves of winter beans are kept in a water culture and diluted with 50 ml of the stock solution or the Preparation sprayed into a rotating spray hood. The stock solution contains 1000 ppm of the compound to be investigated and it is prepared according to Experiment 1, but 0.1 g is in place of 0.05 g of test compound was used. The stock solutions were prepared in the same way of preparations according to a lower concentration

As soon as the solvent of the preparations on the leaves has evaporated, they become paired. leaves separated from each other. One leaf is on one 1.5% water agar was placed 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

1 -Thia-3-methylaminocarbonyl-oximino-

cyclopentane

Mortality. %. at concentration TpM

1000

100

5 (X)

70

250

70

35

fixed connection

Mentality. %. be \ concentration TpM

25 <i

KXK)

S (H)

25th

65

1 -Thia-4-methoxycarbo-

nyl-3-methylamino-

carbonyl oximino

cyclopentane 80

l-thia-4,4-d; methyl-

3-met hylaminocarbo-

nyl-oximino-cyclo-

pentane! - 80

1 -Thia-3-methylamino-

carbonyl oximino

cyclohexane - 62

l-thia-2,4,4-trimethyl-

3-methylaminocarbo-

nyl-oximino-cyclo-

pentane

Trial 8

In this experiment, the insecticidal activity of the compounds to be investigated against the Determined Mexican bean beetle (Epilachna varivestis). The experiment is carried out according to experiment 7, however, day-old larvae of the beetle are used. The larvae are 3 days at 22 T. held. The mortality and the delay in food consumption are then determined. The inhibition of food intake is an indication that that the compound to be investigated has a repellent effect.

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

The results are summarized in Table VIII:

Table VIII

Tcst connection

I -Thia-3-methylaminocarbony] -

oximino-cyclopentane

l-thia ^ -methoxycarbonyl-S-methyl-

aminocarbonyl-oximino-cyclopentane 1 -Thia-4,4-dime! hyl-3-methylamino-

carbonyl oximino cyclopentane

l-thia-2,2-dimethyl-4-methylamino-

carbonyi-oximino-cyclopentane

1 -Thia-3-methyiaminocarbonyl-

oximino-cyclohexane

1 -Thia ^ S-dimethyl- ^ - allylamino-

carbonyl oximino cyclopentane

1 -Thia ^ A-dimethyl-S-ethylamino-

carbonyl oximino cyclopentane

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

carbonyl oximino cyclopentane

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

carbonyl oximino cyclopentane

Mortality. "/ 0. At concentration IpM

KXX)

500

(..ι: tviivl-oximino-ι /. ■■ 'ο \ ιη <\, η \' 1 I ι. niitiunj 'the V ^; him · - ..!' !! i; / '· ¹ ·' ■

100 *) ¹ I 100 *)

80 *) j 100 *)
100 *)
100 *)
100 *)
K) O *)

250
100 *)

100 *)
0

100 * 1

KX) *)
100 *)
100 *)

KM) *)

12X M. 100 *) 80 *) KX) *) 100 *) 100 *) KX) *) 100 *) 100 *) 100 *) 100 *) KX) *) 30th 80 *) 0

10 KX) *)

30 *) 0 30

TeMveibmdimii

l-Oxa-4,4-dimethyl-3-meth_vlaminocarbonyl-oximino-cyciopentane ..

1-Thia ^ -melhyM-methylmercapto-3-melhylaminocarbonyl-oximinocyclopentane

i-Thia ^ -methyl-S-methylaminocarbonyl-oximino-cyclopentane ..

l-Thia ^^ - dimethylO-methylaminocarbonyl-oximino-cyclohcxane ...

O.O-diethyl-S-2- (ethylthio) -äthylphospiioidithioat

* i Hemmunp der N; ihriinus; iiifn; ihme

continuation

I (XK)

Moilalil.il. "ei. hei Ki> n / cnlr; iiinn VpM

SO (I

KK) *)

HH) * I

KK) *) 25 (1

100 *)

KK) *)

KK) *)

KK)

I2S

SO*)

KK) *)
HX) *)
80
100

30th

KX) *)
40
40
40

50

Attempt 9

The compounds are tested for their ability to combat the "Southern Bean Mosaic" virus on pinto beans and maize dwarf virus on corn (golden bantam) \ o . examined. 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. Both the leaves are sprayed and the earth is soaked. 1 to; s. 2 hours before the treatment, the blue stains are rubbed off with silicon carbide sandpaper and infected with the viruses. ,.

When applying the spray, 67 ml the Siammlösung with 1000 ppm evenly on the to Plants sprayed. With systemic application, the sludge solution is applied to the surface of the earth applied to each flower pot at a dose of 72.4 and 36.2 kg / ha, respectively, before spraying. 10 days after of infection, the plants will respond to symptoms * 5 investigated a virosis. The results are summarized in Table IX:

Table IX

Icstvcrbimluiiu

1-Thia-5,5-dimethyl-3-methylaminocarbonyl-oximino-cyclohexane

ki! Wed (TnMl

72.4! 1000

Beans J.
100 i

55

60

Attempt H)

In this experiment, the effectiveness of the compounds to be tested against the infection determined by root knot nemaioden (Meloidegyne spp.).

Composted greenhouse soil diluted one third with clean washed sand is used infected with about 2 g of tomato roots per flower pot. Then be Put 25 ml of the preparation to be examined on the infected soil. The preparation contains 0.056 g of the compound to be investigated, 1.0 ml of an emulsifier stock solution (0.25% emulsifier with the Trade name: "Triton X-155" in acetone! and 24.0 ml of deionized water. The concentration is 2240 ppm Lower concentrations are obtained by dilution.

After treatment with the preparation, the soil, inoculum and active ingredient are thorough mixed, poured back into the flower pot, and the mixture is incubated for 7 days at 20 ° C. and constant humidity. After incubation with the first test compound in Table X are two seedlings of tomato plants (Rütgers) and three Vindsorbean (Vicia faba) seeds set in each flower pot. When incubated with the remaining six test compounds in Table X, two seedlings of tomalen plants and three nasturlium seeds (Nasturtium spp.) Placed in each pot. After three weeks of growth, the roots will be de: Soil removed and examined for root knuckle formation. The roots of the Windsor beans or the Nasturtium plants are only examined when the tomato host plant showed necrosis. The extent of the infection is measured on a scale from 0 to 10 determined. 0 means no root galls or complete suppression, and 10 means strong root knot formation with the control plants is comparable. Each root system is examined separately and the average is multiplied by ten and deducted from 100. In this way the percent suppression of the nematodes is obtained.

The commercially available Pesticide O, O-diethyl-S- <äthy! Thio) -methylphosphordithioat, the commercial pestkid mixture of O, O - Diälhy] - O - 2 - (ethylthio) - ethylphosphorohioate and 0.0-diethyl-S-2- (ethylthioVäthylphosphorthioat and the commercially available pesticide O-ethyl-S, S-dipropylphosphorodithioate used.

The results are summarized in Table X:

Table X

Tcslverbiiuluni:

l-thia-3-methylaminocarbonyl-oximino-

cyclopentane

l-Thia-M-dimethyl-B-methylaminocarbonyl-

oximino-cyclopentane

l-thia-4,4-dimethy] -3-ethylaminocarbonyl-

oximino-cyclopentane

i-Thia ^ -dimethyl ^ -allylaminocarbonyl-

oximino-cyclopcntane

l-thia-2,4,4-trimethy! -3-methylamino-

carbonyl oximino cyclopentane

l-Thia ^ -methyl ^ -äthyW-methylamino-

carbonyl oximino cyclopentane

l-Thia ^ -methyM-melhylmercapto-3-methylaminocarbonyl-oximino-cyclo-

pentane

0,0-Diiithy1-S - (: ithy1thioUmethyl-phosphor-

dithioate

Mixture of O.O-diethyl-O-2- (ethytthio) -äthylphosphorthioat and O.O-diethyl

S-2- (ethylthio) ethyl phosphorothioate

O-ethyl-S.S-dipropylphosphorodhioate

Oppression.

72.4 i 3 (i.2 IS.I

100

100

100

100

100

100

100

100

90 100 95

100

100

40

100

100

70
100

100

40

30th

70

80

50
100

"<i. at conc 4.05

100

'Cnlration. 4.52

! 00

50
90

0
97

50

0 60

2.2 (i

90

50

0 30

0 0

attempt

Lung tomato plants in 9 cm flower pots Diameters are determined by soaking the soil with the test compound given in the table below treated and a population of whiteflies (whiteflies) for 7 days in the greenhouse exposed. The plants are compounded with the test "in an amount of 9.05 kg ha or treated less. Slamming solutions. that contain 500TpM of the soldered joint are made according to the experiment 1 and diluted to the desired concentration. After 7 days the examined plants numerous eggs are found. All plants were in a holding room brought. Fifteen days after the treatment, the total number of living larvae became the third and fourth leaves are determined and the percentage suppression is calculated. The results are in Table XI compiled.

Table XI

Tcsiverbindting

1-Thia-3-methylaminocarbonyl-oximino ^ / l-dimethyl- cyclopentane

concentration

_ (kg ha)

9.05

2.26 0.565

attempt

Adult cotton boll beetles (Anthonomus grandis) are kept in cylindrical fly cages held in the manner described in Experiment 6 and with a suspension of the test compound mentioned in Table XIl sprayed. Then the insects are offered sugar water as food. The mortality is determined 3 days after treatment. Slamming solutions, "the 500TpM of test compound included. are prepared according to experiment 1 and set to the desired Concentration diluted. The results are shown in Table XII.

Table XIl

Teslvcibiniliint

1-thia-3-methylaminocarbonyl-oximino-4,4-dimethylcyclopcntane

concentration

(TpM)

243

81

27

Unk-r-

99

64 41

mortality

100

100

100

60

10

For this purpose 2 sheets of drawings 409 526/457

Claims (1)

Patent claims: i. 1-oxa- or 1-thia-3-aminocarbonyloximino-cyclopentane or cyclohexanes of the general formula R ¹ R ² R \ yX ^V \ = N-O-C-NH-R ⁹ (III)