DE1941999B2 - Substituted S-containing alkanal and alkanone oxime carbamates, their manufacture and use - Google Patents

Description

= NOCNHR ³

in which A ¹ and A "each stand for a thio, sulfinyl or sulfonyl group, R ¹ and R ² either each represent the methyl group or together a ring-forming, optionally methyl or ethyl-substituted ethylene or propylene group or a cyclohexylene group which is adjacent to 2 C atoms is bonded to the sulfur atoms, and R ^{3 is} the methyl, ethyl, butyl or allyl group.

2. 2-Formyl-2,4-dimethyl-1,3-dithiacyclopentane oxime N-methylcarbamate.

3. Process for the preparation of the compounds according to claim 1, characterized in that one is an oxime of the general formula

R ¹ A ¹

R ² A ²

C = NOH

CH ₃

in which A ¹ , A ² , R ¹ and R ^{2 have} the meaning given in claim 1, in a manner known per se in an inert solvent either a) reacts with phosgene to give the corresponding chloroformate and this with an amine of the general formula H ₂ NR ³ . in which R ^{3 has} the meaning given in claim 1, reacts it or b) ^{converts it into the desired oxicarbamate with a substituted isocyanate of the formula R 3} - N = C = O, optionally in the presence of a tertiary amine as a catalyst.

4. Use of the compounds according to claim 1 as nematicides and insecticides.

The invention now relates to substituted S-containing alkanal and alkanone oxime carbamates general formula

R ¹ A ¹ CH ₃

H
R ² A ² C = NOCNHR ³

in which A ¹ and A ² each represent a thio, sulfinyl or sulfonyl group, R ¹ and R ^a either each represent the methyl group? or together a ring-forming,

optionally methyl or ethyl substituted ethylene or prop '' one group or a cyclohexylene group which is bonded to the sulfur atoms with 2 adjacent carbon atoms and R ^{3 is} the methyl, ethyl, butyl or allyl group.

The new compounds develop insecticidal and nematicidal activity. A particularly effective one Compound is 2-formyl-2,4-dimethyl-1,3-dithiacyclopentanoxime-N-methylcarbamate, which is just as effective against houseflies as DDT and against that which causes nodules in tomato roots Nematodes have a much stronger effect than the known active ingredients 2-methylthio-2-methylpropionaldehyde oxime - methyl carbonate and O, O-diethyl-O- (p-methylsulfinylphenyl) thiophosphate.

Compared to the very stable DDT, the use of which has already been banned in some countries and is subject to severe restrictions in other countries, this is what makes the new connections stand out from the fact that they degrade quickly and into non-toxic products in the soil.

The production of the new oxime carbamates is based on an oxime of the general formula

R ¹ A ¹

R ² A ²

H
C = NOH

CH ₃

Are alkanal and alkanone oxime carbamates with insecticidal, miticidal or nematicidal activity already z. Known from U.S. Patents 3,299,137 and 3,217,037. In these connections that is «-Carbon atom of the alkanal or alkanone part of the oxime carbamate but not substituted on two Sulfur atoms bound. Such S.S-substituted 2,2-thio, sulfinyl and sulfonyl alkanal and alkanone oxime carbamates have not been described, nor has their use as effective insecticides been disclosed and Nematicide suggested.

in which A ¹ , A ² , R ¹ , R ^{2 are} as defined above, and sets this in a manner known per se (for example from Belgian patent 674 792) in an inert organic solvent either a) with phosgene to the corresponding chloroformate and brings this to reaction with an amine of the general formula NH ₂ R ³ , in which R ^{3 is} as defined above, or b) it is converted with a substituted isocyanate of the form! R ³ NCO, optionally in the presence of a tertiary amine as a catalyst, into the desired oxime carbamate.

The reaction b) must be carried out at temperatures of from about 10 to about 130 ⁰ C and is preferably carried out in the range between room temperature and 8O ⁰ C. General must because of the temperature sensitivity of the resulting Oximcarbamat temperatures significantly above 130 ⁰ C, can be avoided. The working pressure can be from about 1 atm to about 10 am and is preferably from 1 to 3 atm; it depends on the concentration and the vapor pressure of the volatile isocyanate at the reaction temperature. Suitable inert organic solvents in this reaction the ^r we generally isocyanates solvent inert

used, ie solvents that do not contain any groups such as OH or ΝΗ., - groups. Aliphatic ketones such as acetone, aliphatic and aromatic hydrocarbons such as hexane, heptane, octane, benzene, toluene and other solvents such as diethyl ether and ethyl propyl ether are suitable. Generally, an amount of tertiary amine catalyst of from about 0.1 to about 1.0 percent by weight of the starting material consisting of an isocyanate and the oxime will suffice. Aliphatic and / or aromatic tertiary amines such as dimethylaniline and triethylamine can be used for these purposes. The mole ratio of cocyanate to oxime can range from 0.25: 1 to about 2: 1; however, equivalent amounts or a slight excess of isocyanate are preferably used in order to ensure that the oxime is completely converted. The reaction time can vary from about 5 minutes to about 7 days; usually suffice when operating in the preferred temperature range Ii nsetzungszeiten of about ¹ Z ₂ to about 5 hours for complete reaction.

The oxime carbamate formed falls either as a solid or as an oily liquid and becomes from the reaction mixture in the usual way, e.g. B. by vacuum distillation, through which the solution ^ medium and excess isocyanate are driven off, isolated.

Appropriately, a solution of the oxime compound in z. B. ethyl ether slowly to a solution of phosgene in toluene or ethyl ether or another suitable organic solvent in Geges.wart .ines HCl acceptor, z. B. given to an amine such as di-diethyianiline. This reaction can be carried out at temperatures from -30 to 40 ° C .; in general, it runs most advantageously between -10 C and room temperature. 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 mixture is washed with water to remove the amine hydrochloride formed as a by-product, and the organic layer containing the chloroformate is used for further reactions. The addition of the amino compound z. B. a primary or secondary amine or substituted hydroxylamines takes place in the presence of solvents for these reactants such as water, dioxane, toluene or chloroform at temperatures between about -40 and about 80 ⁰ C, preferably below about 40 ° C, since the reaction itself at runs smoothly at low temperatures and is so fast above 40 "C that a loss of low-boiling reactants and a certain decomposition can occur.

The compounds of the invention with sulfinyl and sulfonyl bonds are by oxidation of corresponding oxime carbamates with sulfide bond with dilute peracetic acid solution or with sodium metaperiodate obtain. If necessary, the oxidation state can also be achieved using the alkanal, Alkanone or oxime intermediates and carried out using the usual selective conditions be, in some cases the carbonyl group e.g. B. by forming the appropriate Acetals or Ketals is protected.

Those used as starting materials for both of the alternative synthetic methods described above Oxo compounds can be obtained from the corresponding aldehydes or ketones by reaction with Hydroxylamine hydrochloride in the presence of an acid acceptor such as potassium acetate in a corresponding one Solvent can be made in ethanol.

The aldehydes and ketones used as precursors in the manufacture of useful oximes are after obtained methods known per se, e.g. B. by the implementation of> -Ketoaldehydes with mercaptans, described by Tomas L. Fridinger, Dissertation, University of Maryland, 1967 (it, - / urde stated, that this implementation also applies to \ -Dikeione can apply) or by formylation or alkanoylation of dithio-substituted carbon atoms in the presence of very strong bases, as described by E.J.Corey et al .. Angewandte Chemie, Inter-

i; national Edition, 4, 1075 (1965). Is the implementation of Λ-ketoaldehydes with mercaptans Applied to symmetrical diketones, only an isomeric ketomercaptol can be formed. If this reaction is applied to asymmetrical Λ-diketones, isomeric mixtures are formed of ketomercaptols, which have to be separated.

The invention is explained in more detail with reference to the following examples. All parts are parts by weight if

* 5 not stated otherwise. All melting points are given uncorrected.

example 1

λ,. \ - bis (methylthio) - propionaldehyde oxime - N - methyl carbamate, 4 drops of triethylamine and 3.8 ga, it-bis (methylthio) propionaldehyde oxime (23 mmol) were dissolved in 30 cm ^{3 of} chloroform and stirred with 5.24 g (92 mol) of methyl isocyanate in 10 cm ^{3 of} chloroform were added. The C-mix was heated 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 recrystallized from hexane / benzene 50:50 and then melted at 62 to 65 ^s C. Its IR and NMR spectra (proton magnetic resonance) agreed with the structure ascribed to the desired oxime carbamate compound.

Ber. for C ₇ H ₁₄ N ₂ O ₂ S ₂ : C 37.8, H 6.3, N 12.6%;

found:

38.1, 6.1, 12.4%.

The oxime used was obtained as follows:

_t v \ -Bis- (methylthio) -propionaldehyde (9.95 g, 55 mol), potassium acetate (6.47 g, 66 mmol) and hydroxylamine hydrochloride (4.58, 66 mmol) were in 80 cm ^{3 for 3 hours} Ethanol heated under reflux conditions. The potassium chloride was filtered off and the filtrate was evaporated almost to dryness. A creamy solid was precipitated by adding ice, which was collected on the filter. The IR spectrum agreed with the structure assigned to "," - bis (methylthio) propionaldehyde oxime.

The aldehyde was made as follows:

11.6 g (0.1 mol) Ν, Ν, Ν ', Ν'-tetramethylenediamine were added to 71.5 cm ^{3 of} a 1.4 η n-butyllithium ^{solution in hexane at -20 0} C and this mixture was added dropwise with 12 , 2 g (0.1 mol) of acetaldehyde dimethyldithioacetal are added. After 2 hours, 8.05 g of dimethylformamide (0.11 mol) were added dropwise. The temperature of the reaction mixture

rose to room temperature and the mixture was stirred overnight and then ^{poured into 200 cm 3 of} water; it was acidified and extracted three times ^{with 75 cm 3 of hexane.} The combined extracts were ³ 2 ° / ₀ potassium hydroxide solution and 50 cm ³ of water twice, dried over magnesium sulfate, evaporated to 100 cm and in vacuo. The residue weighed 9.95 g. The IR spectrum of the compound agreed with the assigned structure for .v, x-bis (methylthio) propionaldehyde.

Example 2

2-formyl-2-methyl- ^{1,3-t 1-} thiacyclopentane oxime N-methylcarbamate

To a solution of 81.6 g (0.50 mol) of 2-Forrnyl-2 - methyl -1,3 -. Dithiacyclopentanoxim, mp 104 to 106.5 ⁰ C, 1.0 cm of triethylamine and 50 cm ³ of acetone were Stirring 30.8 g of methyl isocyanate (0.54 mol) in 50 cm ^{3 of} acetone. The reaction mixture was refluxed for 12 hours, cooled and filtered *. The volume of the solution was reduced to about 250 cm ³ in vacuo. The compound was obtained as a white solid and was recrystallized from acetone, melting point 122 to 124 ^° C. The iR spectrum corresponded to the assigned structure.

IO Ber. for C ₇ H ₁ ^ K-OoS.,: C 38.2, H 5.5 ° / ₀ ;
Found: 38.0, 5.4%.

According to this procedure, those in the following Compounds listed in the table obtained using commercially available isocyanates as reactants. The oximes were according to Example 1 manufactured.

example

Oxime

Isocyanate reaction product

2-formyl-2-methyl-1,3-dithiacyclopentane oxime

2-formyl-2-methyl-1,3-dithiacyclopentane oxime

2-formyl-2-methyl-1,3-dithiacyclopentane oxime

2-Formyl-2-methyl-1,3-dithiacyclohexane oxime, m.p. 145-147 ° C

2-formyl-2,4-dimethyl-l, 3-dithiacyclopentanoxim mp 63 to 65 ⁰ C.

2-formyl-2,4,6-trimethyl-1,3-dithiacyclohexane oxime

2-formyl-2-methylcyclohexano-1-4 -dithiacyclopentane

2-formyl-2-methyl-1,3-dithiacyclopentane oxime

2-formyl-2,4-dimethyl-1,3-dithiacyclohexane oxime

4-ethyl-2-formyl-2-methyl-1,3-aithiacyclopentane oxime

Ethyl isocyanate n-butyl isocyanate Allyl isocyanate Methyl isocyanate

Methyl isocyanate

Methyl isocyanate methyl isocyanate:

tert-butyl isocyanate

Methyl isocyanate

Methyl isocyanate *) IR spectrum: absorption at: 2.95 - 3.4 - 5.7 - f 6 - 7.2 - 2-formyl-2-methyl-1,3-dithiacyclopentanoxime
N-ethyl carbamate m.p. 122-125 ° C

2-Formyl-2-methyl-1,3-dithiacyclopentane oxime N-n-butyl carbamate Mp 67 to 70 ° C

2-formyl-2-methyl-1,3-dithiacyclopentanoxiir.-N-allylcarbamate Mp 53 to 54 ° C

2-ForniyI-2-methyl-1,3-dihiacyclohexanoxime-N-methylcarbamate Mp 96 to 99 ° C

2-formyl-2,4-dimethyl-1,3-dithiacyclopentane oxime N-methylcarbamate Mp 73 to 76 ° C

2-formyl-2,4,6-trimethyl-l, 3-dithiacyclohexanoxim N-methylcarbamate, mp 45 to 50 ⁰ C.

2-formyl-2-methyl-cyclohexano-1,3-dithiacyclopentanecxime-N-methylcarbamate
Mp 132-134 ° C

2-Formyl-2-methyl-1,3-dithiacyclopentane oxime N-tert-butyl carbamate Mp 84 to 86 ° C

l-formyl ^^ - dimethyl-lS-dithiacyclohexanoxim N-methylcarbamate, mp 106-107 ⁰ C.

2-ethyl-2-formyl-2-methyl-1,3-dithiacyclopentanoxime-N-methylcarbamate *)

!, 1 - 8.95 - 10.3 - 10.8 and 13.1 μm.

Example 13

2-formyl-2-methyl-1,3-dithiacyclopentane oxime-N-methylcarbamate-S, S'-bisdioxide

A cold (0 to 5 ^D C) solution of 4.4 g (0.02 mol) of 2-formyl-2-methyl-1,3-dithiacyclopentanoxime-N-methylcarbamate in 75 cm ^{3 of} glacial acetic acid was stirred and added dropwise with 18 , 1 g (0.16 mol) of a 30 ° / _o by weight WasserstofTperoxidlösung added. The solution was then heated under reflux St'.niden 2V _2, with 75 cm ³ of water and slowly cooled. It separated out white crystals, which were filtered off wun'tn, mp 155 ⁰ C (decomposition). The IR spectrum corresponded to the assigned structure.

Oj

65

Example 14

2-Formyl-2-metl ^ yl-1,3-dithiacyclopentane oxime-N-methylcarbamate-S-oxide

4.3 g were added to a cold (0 to 5 ° C.) solution of 4.4 g (0.02 mol) of 2-formyl-2-methyl-1,3-dithiacyclopentanoxime-N-methylcarbamate in 100 cm ^{3 of methanol} (0.2 mol) of sodium metaperiodate added to 50 cm ^{3 of} water; cooling had to be carried out from the outside in order to keep the temperature at 0 to 5 ^° C. The mixture was stirred for 4 hours, then the temperature was allowed to rise to room temperature. The white solid precipitate was filtered off. The filtrate turned in vacuo to an oil that slowly decomposes

solidified, constricted. Still damage when recrystallising from ethyl burning. The active ingredients are

acetate / benzene 1: 1, beige crystals mp 96 were sufficiently chemically inert to with practically all

97 ° C (decomposition) obtained. The IR spectrum of these other ingredients is too spray-compatible

Compound agreed with the attributed structure and can be in the ground, on the seedlings or

match. 5 for application on the roots of plants

B e i s ρ i e! 15 men without the seedlings or the plant roots

_ ". «,. ,. - ..... . ,. damage; the existing pests, however

2-Formyl-2-methyi-l 3-d.thmcyciopentanoxim- are obtained by immersion or by ingestion

N-methyl carbamate-S, S _{-dioxide the root} , _{killed by it} . _{In addition, they} are

To a cold (0 to 5 ⁰ C) solution of 4.4 g io active ingredients not in an unacceptable degree for the

(20 mmol) 2-formyl-2-methyl-1,3-dithiacyclopentane consumer dangerous.

oxime-N-methylcarbamate in 150 cm ^{3 of} methanol was used together in the usual way

with stirring dropwise over 15 minutes with a carrier or diluent which

a solution of 9.0 g (42 mmol) sodium metaperiodate is either liquid or solid.

given in 100 cm ^{3 of} water. A white precipitate fell out. The mixture was stirred for 45 minutes cold active ingredients in a solvent such as acetone or (5 to 10 ⁰ C) and then filtered. The filtrate xylene and dispersing the active ingredients in water were concentrated in vacuo in order to remove the solvent with the help of the usual nonionic, anionic. The residue was extracted three times with each or with cationic surfactants, such as 50 cm ^{3 of} chloroform; the extracts were ao condensation products of alkylene oxides and Phe dried over magnesium sulfate, and the chloroform and organic acids, alkylarylsulfonates, were removed in vacuo. The residue was mixed with plex ether alcohols, quaternary ammonium compound diethyl ether, which was then fertilized in vacuo. The type and amount of the dispersing was drawn. Then chloroform and hexane and emulsifying agents were added to the residue, depending on the active ingredient, and the mixture was agitated and the agent's ability to disperse the warmed. The reaction product to facilitate the 2-formyl-2-methyl active ingredient. Appropriately!, S-dithiacyclopentanoxime-N-methylcarbamate-S.S'-di- we. ·, As little dispersant or emulsifier as oxide with mp 126 ° C (decomposition), a dark yellow possible used, so that the dispersion of the active solid body , was filtered off. When the active filtrate applied to the plant as a spray was cooled, a second crop of reaction material was not emulsified again by rain and waste was obtained. is washed. In the manufacture of wettable

Powders or dusts or granules will be the

Ber. for C ₇ H ₁₃ N ₂ O ₄ S ₂ : C 33.3 H 4.8 N 11.1%; Active ingredient in and on a correspondingly finely divided

Found: 33.0 4.8, 11.0%. solid carriers such as clay, talc, bentonite, diatom

35 earth, coal, corn cob granules or fuller's earth

The insecticidal and nematicidal properties of the dispersed. Netable dusts are combined with the above-new Compounds were made in the usual way with said surfactants as well as with Help from mi; Nematodes (Meloidogyne incognita, lignosulfates attached.

var. acrita) infected roots of tomato plants The required amount of

and using house flies (Musca 40 active ingredients per treated hectare in 9.3 to

domestica) and mosquito larvae (Aedes aegypti) 1860 1 water as a diluent or about

it's correct. 5.6 to 5650 kg inert solid support or ver

The active ingredients according to the invention prevent the fertilizer from being applied. The concentration in

Infestation of plants or other substances by liquid concentrate usually varies between

Insects and nematodes and have a high residual 45 about 5 to 30 percent by weight and in the solid

toxicity. They also have pesticide plants of about 2 to about

have a high margin of safety, since they, in from 80 percent by weight. The approaches are in quantities

A sufficient amount is applied to the insects, corresponding to about 0.28 to 18.6 kg / ha of active ingredient

kill or reject, the plants are not used.

Claims (1)

Patent claims: 1. Substituted S-containing alkanal and alkanone oxime carbamates the general formula R ¹ A ¹ RA ² CH ₁