DE1941999C3 - Substituted S-containing alkanal and alkanone oxime carbamates, their preparation and use - Google Patents

Description

R ¹ A ¹ CH ₃

R ¹ A ¹ CH,

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 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 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 2 _A 2

= NOCNHR ³

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 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 Nemaiicide and Ir.sekticide.

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

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

ao The new compounds deploy insecticide and nematicide effectiveness. A particularly effective compound is 2-formyl-2,4-dimethyl-1,3-dithiacyclopentanoxime-N-methylcarbamate, which is as strong against houseflies as DDT and against

* 5 that which causes nodule formation 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-methyisulfinylphenyl) 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.

In the production of the new Oxitncarbamate goes one of an oxime of the general formula

Are alkanal and alkanone oxime carbamates with insecticidal, miticidal or nematicidal activity already known, for example, from U.S. Patents 3,299,137 and 3,217,037. In these connections that is α-carbon atom of the alkanal or alkanone part of the oxime carbamate but not bound to two substituted sulfur atoms. Such S, S-substituted 2,2-thio-, sulfinyl- and sulfonyl-alkanal and alkanone oxime carbamates have not yet been described, nor has their use as effective insecticides and nematicids been suggested.

H
R ¹ A ¹ C = NOH

C.
R ² A ² CH ₃

in which A ¹ , A ² , R \ 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 form the corresponding Chloroformate and brings this with an amine of the general formula NH ₂ R ³ , in which R ^{3 is} as defined above, to the reaction or b) it is converted with a substituted isocyanate of the formula R ³ NCO, optionally in the presence of a tertiary amine as Catalyst into the desired oxime carbamate.

The reaction b) must be carried out at temperatures of from about 10 to about 130 "C and is preferably carried out in the range between room temperature and 80 ° C. In general, must be avoided because of the temperature sensitivity of the resulting Oximcarbamat temperatures which are substantially above 130 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 solvent

used, ie solvents that do not contain any groups such as OH or NH ₂ 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 can be used. 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 isocyanate to oxime molar ratio can range from 0.25: 1 to about 2: 1; however, equimolar 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 reaction times of about V2 b ^'s for 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 a conventional manner, e.g. B. by vacuum distillation, through which the solvent and excess isocyanate are driven off, isolated.

Appropriately, in the reaction a) a solution of the oxygen compound in z. B. ethyl ether slowly to a solution of phosgene in toluene or ethyl ether or another suitable organic solvent in the presence of an HCl acceptor, e.g. B. given to an amine such as dimethylaniline. This reaction can be carried out at temperatures from -30 to 40 ° C .; in general, it runs most advantageously between IOC and room temperature. The reaction is slightly exothermic, so that it is usually necessary to cool somewhat 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 this reaction partner such as water, dioxane, toluene or chloroform at temperatures between about -40 and about 80 ^° C., preferably below about 40 ^° C., since the reaction itself occurs at runs smoothly at low temperatures and is so rapid above 40 ° C. that a loss of low-boiling reactants and a certain degree of decomposition can occur.

The compounds of the invention with sulfinyl and sulfonyl bonds are by oxidation of Corresponding oxime ca.bemate with sulfide bond with dilute peracetic acid solution or with sodium metaperiodate receive. If necessary, the oxidation state can also be used with the alkanal, Alkanone or oxime compound products and using the usual selective conditions, in some cases the carbonyl group z. B. is protected by formation of the corresponding acetal or ketal.

The oxo compounds used as Ausgangsmaierial for both above-described alternative methods of synthesis such as potassium acetate may be prepared in an appropriate solvent in ethanol from dan corresponding aldehydes or ketones by reaction with hydroxylamine hydrochloride in the presence of an acid acceptor.

The aldehydes and ketones used as precursors in the production of useful oximes are obtained by processes known per se, z..B. by the reaction of x-ketoaldehydes with mercaptans, described by Tomas L. Fridi η ger, dissertation, University of Maryland, 1967 (it was found that this reaction can also be applied to -diketones) or by formylation or alkanoylation of dithio -substituted carbon atoms in the presence of very strong bases, as described by EJ C o re- j et al., Angewandte Chemie, International Edition, 4, 1075 (1965). If the reaction of α-ketoaldehydes with mercaptans is applied to symmetrical α-diketones, only an iso-animal ketomercaptol can be formed. If this reaction is applied to asymmetrical -diketones, isomeric mixtures of ketomercaptols are formed 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 not stated otherwise. All melting points are given uncorrected.

example 1

λ, χ - bis (methylthio) - propionaldehyde oxime - N - methyl carbamate, 4 drops of triethylamine and 3.8 g of Ä, -x-bis (methylthio) propionaldehyde oxime (23 mmol) were dissolved in 30 cm ^{3 of} chloroform and stirred 5.24 g (92 mol) of methyl isocyanate in 10 cm ^{3 of} chloroform were added. The mixture was heated to reflux temperature, refluxed for 2 hours and then evaporated in vacuo. The remaining oil was stirred with a 5O: 5O mixture of hexane and benzene. This solid residue was crystallized from 50:50 hexane / benzene and then melted at 62 to 65.degree. Its IR and NMR (proton magnetic resonance) spectra were consistent with the structure ascribed to the desired oxime carbamate compound.

Ber. for C ₇ H ₁₄ N ₀ 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:

/ x, - <- Bis- (methy! thio) -propionaldehyde (9.95 g, 55 m-mol), potassium acetaf (6.47 g, 66 mmol) and hydroxylamine hydrochloride (4.58, 66 mmol) were added for 3 hours heated in 80 cm ^{3 of} ethanol 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 ascribed to a, «- bis (methylthio) propionaldehyde oxime.

The aldehyde was made as follows:

11.6 g (0.1 mol) of Ν, Ν, Ν ', Ν'-tetramethylenediamine was added to 71.5 cm ³ of a 1.4 η n-butyl lithium solution in hexane at -2O ⁰ C and this mixture added dropwise with 12 , 2 g (0.1 times) acetaldehyde dimethyldithioacetal 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 washed with 100 cm ^{3 of} 2 ° / _o potassium hydroxide ind 50 cm ³ of water washed twice, evaporated, dried over magnesium sulfate and concentrated in vacuo. The residue weighed 9.95 g. The IR spectrum of the compound agreed with the assigned structure for c \, a-ßis- (methylthio) -propionaldehyde.

Example 2

2-FormyI-2-methyl-1,3-dithiacyclopentane oxime-N-methylcarbamate

To a solution of 81.6 g (0.50 mol) of 2-formyl-2-methyl-1,3-dithiacyclopentane oxime, melting point 104 to 106.5 ° C., 1.0 cm of triethylamine and 50 cm ^{3 of} acetone were added Stirring 30.8 g of methyl isocyanate (0.54MoI) 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, mp 122-124 ° C. The IR spectrum corresponded to the assigned structure.

Ber. for
Found:

C 38.2, H 5.5%;
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-dithiacyclopentanoxy m

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 to 147 ° C

2-formyl-2,4-dimethyl-1,3-dithiacyclopentane oxime
Mp 63 to 65 ° 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

!, j-dithiacyclopentane oxime

·) IR spectrum: absorption at: 2.95-3.4

Ethyl isocyanate n-butyl isocyanate allyl isocyanate methyl isocyanate

Methyl isocyanate

Methyl isocyanate methyl isocyanate

tert-butyl isocyanate

Methyl isocyanate

Methyl isocyanate

- 5.7 - 6.6 - 7.2 2-FormyI-2-methyl-1,3-dithiacyclopentane oxime
N-ethyl carbamate m.p. 122-125 ° C

2-formyl-2-methyl] -l, 3-dithiacyclopentanoxim-Nn-butyl carbamate, mp 67 to 70 ⁰ C.

2-Formyl-2-methyl-1,3-dithiacyclopentane oxime N-allyl carbamate Mp 53 to 54 ° C

2-formyl-2-methyl-1,3-dithiacyclohexane oxime N-methylcarbamate Mp 96 to 99 ° C

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

2-FoΓmyl-2,4,6-trimethyl-1,3-ditniacyclohexanoxime-N-methylcarbamate Mp 45 to 50 ° C

_{2-formyl-2-methyl-cyclohexano-l>} 3-N-dithiacyclopentanoxim inethylcarbamat
Mp 132-134 ° C

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

2-formyl-2,4-dimethyl-l, 3-dithiacyclohexanoxim N-methylcarbamate, mp 106-107 ⁰ C.

2-ethyl-2-foΓmyl-2-methyl-l ₎ 3-dithiacyclopentanoxime-N-methylcarbamate *)

8.1 - 8.95 - 10.3 - 10.8 and 13.1 μΐη.

Example 13

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

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 75 cm ^{3 of} glacial acetic acid was stirred and added dropwise with 18 , 1 g (0.16 mol) of a 30% hydrogen peroxide solution are added. The solution was then heated for 2 '/ ₂ hours under reflux conditions with 75 cm ³ of water and slowly cooled. It secreted from white crystals, which were filtered off, mp 155 ⁰ C (decomposition). The IR spectrum corresponded to the assigned structure.

At s ρ iel 14

2-formyl-2-methyl-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; it had to be cooled 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

7 8

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

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

97 ° C (decomposition) obtained. The IR spectrum of these other components for Sprühmittei compatible zi

Compound agreed with the ascribed structure and may be in the soil, on the seedlings or;

match. 5 grain for application on the roots of plants

Example 15 men, without the seedlings or the plant roots zi

- _. _Λ .,. . , ..,. . . damage; the existing pests on the other hand

2-Formyl-2-methyI-l 3-d, th.acydopentano _X .m- are obtained by immersion or by absorption

N-methylcarbamate-SS-diOMd _{die WuRe | hjn (Jureh killed In addition, di (}

To a cold (0 to 5 ^Ü C) solution of 4.4 g io active substances not to an unacceptable extent for the

(20 liiMoi) 2-formyl-2-methyl-1,3-dithiacyclopentane dangerous for consumers.

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 Wubaer. 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 "C) and then filtered. The filtrate xylene and dispersing the active ingredients in water was concentrated in vacuo to remove the solvent using the usual nonionic, anionic The residue was extracted three times with either conventional surface-active agents such as 50 cm ^{3 of} chloroform; the extracts were dried over magnesium sulphate condensation products of alkylene oxides and phenyl and the chloroform and organic acids, alkylarylsulphonates, were removed in vacuo mixed with plex ether alcohols, quaternary ammonium compound diethyl ether, which was then fertilized in vacuo, produced. Type and amount of the dispersed. Then chloroform and hexane were added to the residue and the emulsifying agent, depending on the active substance, was added and the mixture was 25% substance and the ability of the agent to disperse the heated. The react ionic product to facilitate 2-FormyI-2-methyl active ingredient from. Two: dithiacyclopcntanoxirn-N-methylcarbamate-S.S'-di- is used as little dispersant or emulsifier as oxide with melting point 126C (decomposition), a dark substance possible, so that the dispersion of the active solid was filtered off . When the active filtrate applied to the plant as a spray was cooled, a second build-up of the reaction substance was not emulsified again by rain and was not retained. is washed. In the manufacture of wettable

Powders or dusts or granules will be the

Ber. for CH ^ ¹ A ₁ S ₂ : C Ji, 3 H 4.8 N! 1.1 ⁰ Z ₀ ; Active ingredient in and on a correspondingly finely divided

def .: 33, Ü 4 S, 11.0%. solid support like 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 surface-active agents as well as with With the help of nematodes (Meloidogyne incognita, lignosulphates).

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 larva "tAedes aegypti) be 18601 water as a diluent or approximately

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

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

toxicity. In addition, they have anti-pesticide plants from 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 The invention now relates to substituted S-containing alkanal and alkanone oxime carbamates general formula