DE1941999A1 - Substituted S-containing alkanol and alkanone oximes and their carbamyl derivatives - Google Patents

Description

concerning

Substituted S-containing alkali metal and alkanone oximes as well as their carbaray derivatives

There are certain alkanal and alkanone oxime carbarates with insecticidal, miticidal or nematocidal activity e.g. from U.S. Patents 3,299,137 and 3,217,037 known. In contrast, compounds in which one WL carbon atom of the alkanal or Alkanonteiles of an oxime is bound to two substituted sulfur atoms and the corresponding carbamate • derivatives not previously described, nor has the use of these compounds been found as effective insecticides, Akaricide and Nematicide. suggested.

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The invention therefore relates to S, S-substituted © 2,2-thio-, sulfinyl- and sulfonyl-alkanal and alkanone oximes and their N-substituted carbamyloximderlvates. These new carbamyloxime derivatives are insecticid, acaricid and nematicid effective.

The compounds according to the invention correspond as oximes the formula

^r i ^a : l y & z

R ₀ A ^ C-NOH
^{2 ά} . · I

or as Carbamylderivate.der formula

R ₀ Ap C = NOCN

² I- B.
■ «ή ο

12th
wherein A and A are independently a thio-, sulfinyl

12 mean T or sulfonyl group, H, B and Br independently from one another denote an alkyl or alkenyl group with up to 4 carbon atoms or R and R together denote one Form alkylene or alkenylene groups with up to 12 carbon atoms, connecting sulfur atoms

Il

Carbon chain contains 2-5 carbon atoms, R is hydrogen or an alkyl group with up to k carbon atoms and R ^ and R each denote hydrogen, an alkyl group, cycloaliphatic group, alkoxy or alkenyl group with up to 10 carbon atoms with the proviso that only one substituent R ^ and R is hydrogen. "...

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In the preferred compounds according to the invention, R- ^{5 is} a methyl or ethyl group, and R and R are added. · Samraen either contain no more than 5 carbon atoms or form an alkylene group with 2 or 3 carbon atoms in the carbon chain between the two sulfur atoms; R stands for hydrogen, R ^ for one

6th
Methyl or ethyl group and R for hydrogen. Such compounds are preferred because they have a stronger neraaticidal activity than the other compounds, which, however, also all have nematicidal activity.

The oxime compounds used as the starting material for both of the alternative synthesis methods described above can from the corresponding aldehydes or ketones by reaction with hydroxylamine hydrochloride in Presence of an acid acceptor such as potassium acetate in an appropriate solvent in ethanol.

As examples of this «! Oximes are the following bindings listed:

CH «NOH CH ₂ CH ₃

yy-4,5-dimethyl-1,3-dithiolene oxime

, CH * NOH CH (CH ₃ ) ₂

CH ₃

dl, ä-Bls (isopropylsulfinyl) propionaldehyde oxime

C-CH «NOH

2 * Pormyl-2, U-diisopropyl-i, 3- d ,, oi-Bi s (allyl thio) propiondithiolanoxime ·· aldehyde oxime

CH ₃ (CHg) ₃ -

CH = NOH

S 'S <

^ rCH = NOH

• Jv. , oUBis (n-butylthio) propion-2-formyl-2-methyl-1, 5-aldehyde oxime dithioloxime

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~? ^S \ ^ ^CH = NOH ^ s -CH-MOH

c. Il

- ^ '(CH ₂ J ₃ CH ₃

2-formyl-2- (η-butyl) -i | - ethyl-1,3-di- 5 - formyl-5-methyl-3-, 6-thiolanoxime tetraoxide »Dithiepinoxime

⁵ V-SC ^ . ^> CH-NOH

2-formyl-2,6-dimethyl-1,3-

dithiene oxime monoxide ^}

The oximes useful as precursors in the manufacture Aldehydes and ketones used are obtained by methods known per se, e.g., by the reaction von (i.-Ketoaldehydes with mercaptans, described by Tomas L. Fridinger, Dissertation, University of Maryland, 1967 (it was found that this implementation is also can be applied to do-diketones) or by formylation or alkanoylation of dithio-substituted carbon atoms in the presence of very strong brooms, as described by E.J. * Corey et al., Angewandte Chemie International Edition, 4, 1075 (1965). is described.

V / ird the implementation νοηΛ -Ketoal deny den with mercaptans Applied to symmetrical ^ -diketones, only an isomeric ketomercaptol is formed. If this reaction is applied to asymmetrical ^ -diketones, "isomers are formed Mixtures of ketomercaptols which are separated have to.

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The carbamyloxime compounds according to the invention can be obtained in various ways from the correspondingly substituted oximes. One possible synthesis is the addition of an isocyanate to a substituted oxime whose substituents R ¹ , R ² , H ^ and R correspond to the desired compound; this way is explained by the following equation, trorin A ¹ , A ² , R ¹ , R ² , R ³ , R and Br have the meaning given above:

1 * * - ■ · f «

C-NOH + R ₅ NCO - * - RC »NOCNHR

³ /

CO

^R i ^R 2 R ₁ V

The isocyanate addition is generally carried out by contacting the Dxim with the isocyanate in an inert organic solvent, and preferably in the presence of a tertiary amine catalyst. ■ The reaction must be carried out at temperatures of about IG "to about 130 ^o C and is preferably carried out in the range between room temperature and 8O ⁰ C. In general, must be avoided because of-the temperature sensitivity of the resulting Carbamyloxims temperatures significantly higher than 13O ⁰ C The working pressure can be about 1 atm to about 10 atm and is preferably 1 to 3 atm; it depends on the concentration and the vapor pressure of the volatile isocyanate at the reaction temperature Isocyanates used versus inert solvents, ie solvents that do not contain any

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Contain groups such as OH or NHg groups. Examples are aliphatic ketones such as acetone, aliphatic and aromatic hydrocarbons such as hexane, heptane, octane, benzene, toluene and others, and other solvents such as diethyl ether, ethyl propyl ether and others. Generally a sufficient amount of tertiary amine catalyst is from about 0.1 to about 1.0 wt -.% Of the starting material consisting of an isocyanate and the oxime. Aliphatic and / or aromatic tertiary amines such as dimethylaniline, triethylamine * or am can be used for these purposes. The molar ratio of isocyanate to oxime can be in the range from 0.2.5: 1 to about 2: 1; Preferably, however, equimolar amounts or a slight excess of isocyanate are used to ensure that the oxime is completely converted. The reaction time can vary from about 5 minutes to about 7 days; When working in the preferred temperature range, reaction times of about 1/2 to about 5 hours are usually sufficient for complete conversion.

The carbamyloxime formed falls either as a solid or as an oily liquid and is made from Reaction mixture in the usual way, e.g. by vacuum distillation, through which the solvent and excess isocyanate are driven off, isolated.

According to another synthesis process, a substituted oxime is reacted with phosgene to chloroformate, in turn with a compound that is a reactive

hige amino group C-IiH) contains, e.g. a primary or secondary amine, substituted hydroxylamines and others for Reaction is brought about, whereby the desired oxime carbamate is formed. This synthesis is represented by the following reaction equation explains where A, A and R to R have the above Have meaning:

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IA-36 652 ^:

* ο C = NOH

COCl

HNR ₁ Rr

In the above step i wi ^ ä ... ^T> 3 "of Oxiraverbindung in eg ethyl ether zweGkmäBigeriielE ng. . ^ s.am added to a solution of phosgene in toluene or ethyl ether or another suitable organic solvent in the presence of an HCl acceptor, e.g. an amine such as diraethylaniline. The reaction can be carried out at temperatures from -30 C to 40 ⁰ C; in general, it runs most advantageously between -10 ° C and Barattemperstür. The reaction is slightly exothermic, so that something usually has to be cooled in order to keep the temperature in the desired range. The reaction gel is washed with water in order to remove the amine hydrochloride formed as a by-product, and the organic layer containing the chloroformate is used for further reactions. D £ _'# e addition of a reactive amino group containing reactant, the above step 2, in the presence of solvents for this reaction partner, for example water, dioxane, toluene or chloroform

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made at temperatures between about -4O ⁰ C and about 80 C; is preferably carried out below about 4O ⁰ C, since the reaction proceeds even at low temperatures and is smooth so quickly 4o ° C, that a loss may occur at low-boiling reactants and some decomposition.

The compounds according to the invention with sulfinyl and sulfonyl bonds are made by using the corresponding carbamyl oxo compounds of the invention with sulfide bond with dilute peracetic acid solution or with "sodium metaperiodate, be oxidized. According to another The form of formation is the oxidation state using the alkanal, alkanone or oxime intermediates r "application of the" usual selective conditions

carried out. In some cases it may be desirable to remove the carbonyl group prior to oxidation protect, e.g. by forming the corresponding acetal or ketals. -

The invention is illustrated in more detail by means of the following examples. All parts are parts by weight $ if not stated otherwise. All melting points are uncorrected specified.

example 1

A »^ ~ ^sis (methylthio-propionaldehyde oxime-K-methylcarbamate, 11.6 g (0.1 Hol) M, N, N ', N ¹ -tetramethylene diamine were added to 71.5 cm of a 1.5 to n-butyllithium solution in hexane at -20 ° C. and 12.2 g (0.1 Hol) of acetaldehyde dimethyldithioacetal were added dropwise to this mixture After 2 hours, 8.05 g of dimethylformamide (0.11 mol) were added dropwise and the temperature of the reaction mixture was allowed to rise to room temperature and the mixture over

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Stirred night. The mixture was poured into 200 cubic centimeters of water, acidified, and extracted three times with 75 cubic centimeters of hexane. The combined extracts were washed twice with 100 cm ^ 2 strength potassium hydroxide solution and 50 cm water, dried over magnesium sulfate and evaporated in vacuo. The residue weighed 9.95 g. The IR spectrum of the compound was consistent with the assigned structure for J. , o6-bis (methylthio) propionaldehyde. · *

Ji , ^ - Bis (methylthio) propionaldehyde (9.95 g, 55 mmoles), potassium acetate (6.47 g, 66 mmoles) and hydroxylamine hydrochloride (4.58 g, 66 mmoles) were in 80 cm ^ ethanol for 3 h Heated to reflux. The potassium chloride was filtered off and the filtrate was evaporated almost to dryness. A cream-like solid was precipitated by adding ice, which was collected on the filter. The IR spectrum agreed with the structure ascribed to si , [/ (- bis (methylthio) propionaldehyde oxime.

4 drops of triethylamine and 3.8 g of J. , / - bis (methylthio) -

'S

Propionaldehyde oxime (23 mmol) were dissolved in 30 cnr chloroform dissolved and mixed with 5.24 g (92 mmol) methyl isocyanate in 10 cm ^ chloroform with stirring. The mixture was warmed to reflux temperature, refluxed for 2 h and then evaporated in vacuo. The remaining oil was stirred with a 50:50 mixture of hexane and benzene. “This solid residue was made from hexane / benzene Recrystallized at 50:50 and then melted at 62-65 ° C. - "- ZIlSeIn" "IR and NIIR spectra (proton magnetic resonance) agreed with that ascribed to the desired carbamyloxime compound Structure over a. ....

Ber. ' for C ₇ H ₁ ^ N ₂ O ₂ S ₂ : C 37.8 H-6.3 N 12.6 % Found: ~ 38.1 6.1 12.4 %

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Following the procedure of Example 1, using commercially available isocyanates as reactants, those in the following Get the summarized "Connections" table.

Table 1

At- ^ · reaction-

game . . Oxime isocyanate product

«, Ι, <cfc-bis (methyl thio) - η-butyl- dl, öt-bis (methylthio) 2 propionaldehyde oxime isocyanate propionaldehyde oxime

N-n-butyl carbamate

Allyliso- ^, 4-bis (methylthio) cyanate propionaldehyde oxime N-allyl carbamate

* l * * Ethyl iso- dv., 4rBis (methyl thio) -

cyanate propionaldehyde oxime. N-ethyl carbamate

5 "Cyclohexyl-A ^ -Bis (methyl thio) -

. ■ ■ isocyanate .propionaldehyde oxime

N-cyclohexyl carbamate

Example 6

2-formyl-2-methyl-1,3-dithiolanoxime-N, N-dimethylcarbamate.

A mixture of 360.3 g of an aqueous solution of methylglyoxal (2.0 hol), 179 g of 1,2-ethanedithiol (90 mol), 600 cm- 'benzene and 2.0 g of p-toluenesulfonic acid hydrate was stirred and heated to reflux for h h, with about 175 cm- ^ water separating out in a Dean-Stark trap. The dark brown solution was stirred for 6 h at room temperature and then ^{poured into 300 cm J} diethyl ether. This solution is vaped with 500 cubic centimeters of a five-quart sodium bicarbonate solution and then with 500 cubic centimeters of water and dried over magnesium sulphate. The dry solution was fractionally distilled in vacuo (water aspirator) and at 105 - 108 ⁰ C over solid fraction examined IR analysis. The spectrum of this fraction agreed with the structure for 2-formyl-2-methy1-1,3-dithiolane.

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Ber. for C ₅ HgOS ₂ : C 40 _f 5 H 5.4 % found : 40.7 5.6 %

In accordance with this general procedure described, known starting materials became the following derivatives vonc (-dicarbonyl compounds produced as intermediates are useful in the preparation of oxira intermediates of the present invention. The connections were identified by their synthesis and by their IR spectra.

2-formyl-2-methylcyclohexane-1,3-dithiolane, 2-formyl-2,4,6-trimethyl-1,3-dithiane, 2-Fprmyl-2-methyl-1,3-dithiane,
2-formyl-2,4-dimethyl-1,3-dithiolane, 2-formyl-2,5-dimethylbenzo-1,3-dithiolane, 2-formyl-2-methyl-4-phenyl-1,3-dithiolane, 2-formyl-2, ij-dimethyl-1 _f 3-dithiane, 4-ethyl-2-f oriiiyl-2-methyl-1,3-cli thiolane, 2-acetyl-2-methyl-l _t 3-dithiolane,
2-acetyl-2,4-dimethyl-i _£ -Oithiolan, 2-ethyl-2-propionyl-l _t 3-dithiolane.

A mixture of 162.4 g of 2-formyl-2-methyl-1,3-dithiolane (1.1 Hol), 83.4 g of hydroxylamine hydrochloride (1,2yNo1), 117/8 g of potassium acetate (1.2 mol) and l _f 0 1 ethanol / water 1: 1 was heated under reflux with stirring for 6 h and then cooled overnight in an ice maker. The white crystals ine 2-formyl-2-methyl-1,3-dithiolanoxime was collected on the filter, washed with a cold 1: 1 ethanol / water solution (200 cm) and dried in vacuo, m.p. 104-106.5 ° C ...

Ber. for G ₅ H ₉ NOS ₂ : C 36.8 H 5.6 N 8.6 %, calc .: 37.0 5.5 8.3. %

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Following this general procedure, the following oxime zwisohen compounds of the present invention were prepared from the above connections described:. .

2-Porroyl-2-methylpyclic-hexano-1,3-dithialanoxime 2-FQrmyl-2, 4, 6-trimethyl-1,3-dithianoxime, E-Porrnyl-Ermethyl-1,3-dithianoxime, 2-pormyl-2, ^ - dimethyl-1,3-dithiolanoxime, 2-formyl-2,5-dimethylbenzo-1,3-dithiolanqxira, 2-formyl-2-methyl-4-phenyl-1,3-dithiolanoxime, 2-formyl-2,4-dimethyl-1,3-dithianoxime, 4-ethyl-2-formyl-2-methyl-1,3-dithiolanoxime, 2-acetyl-2-methyl-1,3-dithiolanoxime,

2 Acetyl-2,4-dimethyl-1,3-dithiolanoxime, 'ZIZ .

2-ethyl-2-propionyl-1,3-dithiolanoxime.

In one, kept under nitrogen and protected by a dry-ice cold (Q <- 5 ° C) soln ^ g from 24 g N, N-Diraethylanilin <O, 2 mol) Ixx 200 cm ^ diethyl ether were g stirring for 22 phosgene · (0 , 22 Hol) initiated. As soon as the solution became cloudy, 32.6 g of 2-formyl-2-methyl-1,3-dithiolanoxime (0.20 Hol) dissolved in 200 cnP of diethyl ether were added dropwise, the reaction temperature being between -5 and + 5 ° C After the addition had ended, the mixture was stirred for a further hour at 0 ° C. and then f
narrowed to 240 cm- '.

0 ⁰ C stirred and then filtered. The colorless piltrate was

9.0 g of dimethylamine (0.20 mol) were added dropwise to an 80 cm × ^{5 portion of this filtrate at 0-5 ° C. with stirring.} This solution was ^{stirred for a further hour at 0} ° C. and the white solid precipitate which had separated out was filtered off. Recrystallization from hexane η-white crystals, mp 75-76 ⁰ C. N-dimethylcarbamate The IR spectrum of this compound corresponded to the structure of 2-Pormyl-2-methyl-1,3-dithiolanoxim-N.

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Example 7

ty-Butyl ^ -formyl ^ -methyl-l ^ -dithlolanoxime-NjN-dimethylcarbamate.

The procedure was as in Example 6 and instead of 2-formyl-2-methyl-1,3-dithiolane / I-butyl-2-.formyl-2-methyl-1,3-dithiolane used as starting material. The desired compound was after recrystallization obtained from η-hexane in the form of white crystals and identified by the IR spectrum.

Example '8

2-formyl-2-methyl-2,3-dithiolanoxime N-methyl carbamate. TO dithiolanbxim 3-a solution of 81.6 g (0.50 mol) of 2-formyl-2-methyl-l, 1,0 cm and 50 cm ^ Triäthylämin ^J g acetone with stirring 30.8 methylisocyanate (0, 5 ^ moles) in 50 cm ^ acetone. The reaction mixture was 12 h heated under reflux off "cooled and filtered, and the volume of the solution was concentrated in vacuo to about 250 cm ^ The compound was obtained as a white solid body and recrystallized from acetone, mp 122 -.. 12 ^ ⁰ G. The IR spectrum corresponded to the assigned structure.

Ber. for C ₇ H ₁₂ N ₂ O ₂ S ₂ : C 38.2 H % 5% found : 38.0 5Λ%

According to this process, the compounds listed in the table below were obtained using commercially available isocyanates as reactants. The oximes were prepared according to Example 6.

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652

Table 2

Bel-
game Oxime Isocyanate 9 2-formyl-2-methyl-
1,3-dithiolanoxime Ethyl-
isocyanate 10 • \
H n-butyl
isocyanai « 11th η Allyl
isoeyanat 12th 2-formyl-2-methyl-
1,3-dithianoxime
Pp 145 toilet Methyl-
is ocyanate

Reaction product

2-porijiyl -2-methyl .1,3-dithiolanoxime N-ethyl carbamate Pp 122-125 C

2-porrayl-2-methyl 1,3-dithiolanoxira N-n-butyl carbaraate Pp 6? -? 0 ° C

2-Pormyl-2-methy1 1,3-dithiolanoxim N-allylcarbaraat mp 53-5 C ^ ⁰

2-Pormyl-2, IF-dimethyl-1,3-methyl-dithiolanoxim Pp 63-65 ⁰ C "isocyanate 2-formyl-2-methyl-1,3-dithianoxim-N-methylcarbaraat Pp 96-99 C

2-formyl-2,4-diraethyl.1,3-dithiolane-oxini-N «methylcarbamate m.p. 73-76 ^D C

2-pormyl-2,4,6-tri-methyl-2-pormyl-2 ', 4,6-trimethyl-1,3-dithianisocyanate methyl-1 ", 3-dithianoxime oxime N-methyl carbamate

Fp 45-5QrG

_ cyclohexanp-l _t 3- aithidlanoxime

16 ·. ' \ 2-Pormyl-2-raethyl-1,3-dithiolanoxime

2-formyl-2,5-di-

methylbenzo-i, 3-di thiolanoxira

,; _! 2-pormyl-2-methylcyclo-

Methyl hexano-1,3-dithiolanoxy isocyanate N-methyloebamate m.p. 132 - "^ ¹ ' ⁰ "

tert-butyl-2-pormyl-2-methyl isocyanate 1,3-dithiolanoxime

. N-tert-butyl carbamate Pp 84-86 ⁰ C t

Methyl isocyanate 2-formyl-2,5-diraethyl- ^ benzo-1,3 "dithiolane" OXiBi- N ~ rae thyl carbama t Pp 125127 ° G - ^r

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Table "2 (Forte et zum)

Example . . , Oxime. ,, Isacyanate reaction product

18 a-Formyl-a-methyl-k-methyl-2-formyl-2-methyl- * J-phenyl-1,3-dithiolane isocyanate phenyl-1-4 -dithiolanoxime \ 'oxira-.N-methyl carbamate

19 2-Formyl-2, ^ - dimethyl-methyl-2-formyl-2, ij-dimethyl-1,3-dlthianoxira isoeyanate 1,3-d.ithiane-oxime-N-

methylcarbamate, mp 106 to 107 ^Q C

20 4-Ethyl-2-fOΓrayl-2-methyl-2-ethyl-2-formyl-2-methyl-1,3-dithioisooyanate methyl-1,3-dithiolane lanoxime oxim-N-methyl carbamate

21 2-Acetyl-2-methyl-methyl-2-acetyl-2-methyl-1 »3-dithiolanoxira 'isocyanate 1,3-dithiolanoxini-

N-methylcarbaraate m.p. 10? - 109 C

22 · 2-acetyl-2, ^ dimethyl- methyl- 2-acetyl-2, ^ - diraethyl-

1,3-dlthiolane oxime isocyanate 1,3-dithiolane oxime

N-methyl carbamate Mp 89-92 ° C

Example 23

2-formyl-2-methyl-1,3-dithiolanoxira-N-methylcarbamate

S ^ '- bisdioxide.

A cold (0 - 5 ° C) solution of 4-, k g (0.02 mol)

* 2-Formyl-2-raethyl-1,3-dithiolanoxime-N-methylcarbamate in 75 cm- 'glacial acetic acid was stirred and added dropwise 18.1 g (0.16 mol) of a 30% strength hydrogen peroxide solution offset. The solution was then refluxed for 2 1/2 hours. 75 cpm of Hasser was then added and the solution slowly cooled. Whites parted

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Crystals from which were filtered off, mp 155 ° C (dec.). The IR spectrum corresponded to the assigned structure.

Example 2k

2-'Pormyl-2-methyl-1,3-di-thiolanoxime-N-methylcarbamate-S-oxide

4, 3 g (0.2 mol) sodium metaperiodate given in 50 cm- ⁷ V / water; it had to be cooled from the outside in order to keep the temperature at 0 - 5 ° C. The mixture was stirred hours, to allowing the temperature to rise to room temperature. The white solid precipitate was filtered off. The piltrate was closed in vacuo. an oil that slowly solidified. Obtained 97 ⁰ C (dec.) - 1- viurden beige crystals, mp 96: Recrystallization from ethyl acetate / benzene. 1 The IR spectrum of this compound was consistent with the assigned structure.

Example 25

2-formyl-2-methyl-1,3-clithiolano'xime-N-methylcarbamate-S, S'-dioxide.

To a cold (0-5 ° C.) solution of 4.4 g (20 mmol) of 2-formyl-2-methyl-1,3-dithiolanoxime-N-methylcarbamate in 150 cnr methanol was added dropwise over 15 min a solution of 9.0 g (42 mmol) of sodium
given metaperiodate in 100 cnr v / water. A white precipitate formed. The mixture vnirde k5 min cold (5 - 10 ° c). Stirred and then filtered ' The filtrate was concentrated in vacuo to remove the solvent. The residue was extracted three times with 50 cnor chloroform each time, the extracts were dried over magnesium sulfate

dried and the chloroform stripped off in vacuo. The ι i

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Biäthyläther was added to the residue, which was then added peeled off in a vacuum. Then chloroform and Hexane was added to the residue and the mixture was heated. The reaction product, 2-formyl-2-methyl-1,3-dithio- «Lanoxime-N-methylcarbamate-S, S'-dioxide with Pp 126 ° C (decomp.), a dark yellow solid was filtered off. Upon cooling the filtrate, a second crop of reaction product was produced obtain.

Ber. for C ₇ H ₁₃ N ₂ O ^ S ₂ : C 33.3 H 4.8 N 11.1 % found : 33, ^v O 4.8 11.0 %

The pest control properties of the carbameyloxime derivatives of the present invention have become more common Way checked. The nematicide effectiveness was determined with the help of Neiiiatoden (Meloidogyne incognita, var. Acrita) infected roots of tomato plants, the acaricide effectiveness with cotton plants infested by Tetranychus telarium and the insecticidal activity using of house flies (Musca domestica) and mosquito larvae (Aedes aegypti) determined.

The following compounds were particularly effective as nematicides, acaricides or insecticides: "

2-formyl-2-methyl-1,3-dithiolanoxime-N-methylcarbamate, ä-Formyl ^ -methyl-l ^ -dithianoxime-N-methylcarbamate, 2-formyl-2,4-aminoethyl-1,3-& ithiolane-oxime-N-methylcarbamate

All carbamyloxime compounds of the above general formula falling within the scope of the invention are in In a certain way nematicid or insecticid effective, of course but some compounds are more effective than

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the others. The compounds listed above are examples of preferred embodiments that have a high Effectiveness, especially as Nematicide.

The compounds according to the invention are used in the customary manner as insecticides, acaricides and nematicides. The pesticides that contain these agents as an active ingredient usually also contain one Carrier or a diluent which is either liquid or solid.

Liquid concentrates. Are made by dissolving one of these . These compounds in a solvent such as acetone or xylene and dispersing the active ingredients in water using Prepared with the help of suitable surface-active agents, e.g. dispersants and emulsifiers. The choice of the dispersing and emulsifying agent as well as the one used Amount depends on the type of pesticide, and the ability of the agent to disperse the agent of the active ingredient to ease off. In general, it is advisable to use as little dispersant or emulsifier as possible to use, in accordance with the desired dispersion of the active ingredient in the spray, so that the on the Active ingredient applied to the plant is not emulsified and washed off again by rain. Non-ionic, anionic or cationic surfactants such as the condensation products of alkylene oxides with phenol and organic acids, alkylarylsulfonates, complex ether alcohols, quaterrial ammonium compounds, etc. the production of wettable powders or dusts or granules is the active ingredient and on a corresponding basis finely divided solid carriers such as clay, talc

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Bentonlt, diatomaceous earth, coal, shark cob granules, Pullerorde and others dispersed. When preparing the networkable The surface-active substances mentioned can be used , Agents and lignosulphates are used.

The required amount of active ingredients according to the invention is applied per treated hectare in 9.3 to 1860 liters V / water as a diluent or in about 5 ^, 6-5,650 kg of inert solid carrier or diluent. The concentration in the liquid concentrate typically ranges from about 5 to 30 wt -.%, And in the solid pesticide from about 2 to about 80 weight "% The batches are kg in amounts corresponding to about 0.28 -.. 18.6 kg / ha Active ingredient applied.

The pesticides according to the invention prevent the infestation of plants or other substances by insects, mites and nematodes and have a high residual toxicity ^x. Compared to plants, they have a high margin of safety because, when applied in sufficient quantities to kill or repel the insects, they neither burn nor damage the plants. The active ingredients are sufficiently chemically inert to be compatible with practically all other components for sprays and can be found in the soil, on the seedlings or on the. Plant roots are used without damaging the seedlings or the plant roots; the existing pests, on the other hand, are killed by immersion or by absorption through the roots. In addition, the properties of the active ingredients are such that they are not unacceptable for the

x. (residual toxicity)

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users are dangerous.

'. Some of the new oximes according to the invention have a dampening effect on the central nervous system, for example as muscle relaxants and sedatives (sedatives). ■

Claims

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Claims (13)

Claims. before Substituted S-containing alkanal and alkanone oximes and their carbamyl derivatives of the general formula R ¹ A ¹ C = NOH 2 ₂ / \ H ¹ A ¹ V / E- bzvi. R ² A ² ^ C = KOCN 0 R 12 · liorin A and A independently chosen thio-, sulfinyl- and sulfonyl bonds, R, R and R- 'are independently selected lower alkyl and lower alkenyl groups 1 2
or R and R together represent an alkylene or alkenylene group with up to 12 carbon atoms, with 2-5 carbon atoms on the carbon chain connecting the sulfur atoms, R denotes hydrogen or a lower alkyl group and Br ~ and R independently of one another denote hydrogen or an alkyl group, a "cycloaliphatic group, alkoxy or Alkenyl groups with up to 10 carbon atoms represent with the proviso that only one »tr / f - the substituents R ^ and R is hydrogen. 2. Compounds according to claim 1, characterized in that g e k e η η - 12th
indicates that A and A are -S- bonds. 3. Compounds according to claim 1 and 2, characterized 12 indicates that 'R, R and E Il
are a methyl group and R is hydrogen. g e each for 009809/1 7 8 4 - ar- iA-36 652 -J ₉₄₁ 999 4. Compounds according to claim 1 to 3, characterized in that R is a methyl group and, if , present, R ^ is hydrogen and R is a methyl group. 5. 2-Formyl-2-methyl-1,3-dithiol ^ jloxime-N-methyΓcarbamate. 6. 2-Formyl-2-methyl-l _, 3-dithianoxime-N-methylcarbamate. 7. 2-Forrayl-2,4-dimethyl-1,3-dithiolane oxime N-methyl carbamate. 8. A process for the preparation of the compounds according to claim 1 to 7 »marked. en
that one is an aldehyde of the formula R ¹ A ¹ CHO 1 2 1 T
wherein A, A and R - R- * have the above meaning with a hydroxylamine salt of a strong acid in water or an organic solvent at a temperature in the range of 0-200 ⁰ C, preferably in the presence of an acid acceptor, whereupon the oxime obtained is reacted either in an inert solvent with phosgene to give the corresponding chloroformate and this in an inert organic solvent with a compound of the formula brings to reaction, in which F. and R have the above meaning 009809/1 78A • -ar- · iA-36 652 _19A1999 "half or with a substituted isocyanate of the formula R ⁵ -N = C = O wherein R is as defined above in an inert organic Solvent converted into the desired oxime carbamate. 9. The method according to claim 8, characterized in that the chloroformate is mixed with a
primary or secondary amine converts. 10. The method according to claim 8, characterized in that the chloroformate with ammonia implements. 11. The method according to claim 8, characterized geke η η - · characterized in that the chloroformate with a
substituted hydroxylamine converts. 12. The method according to claim 8, characterized in that in the reaction with a
Isocyanate a tertiary amine is used as a catalyst. 13. Use of the compounds according to Claims 1 to 7 as ilematicide, acaricide and / or insecticide. 009809/1794