DE1912294C - Oxime Carbamates and Their Use as Akaricides - Google Patents

Description

ft ³ -

Elated hydrocarbons such as carbon tetra- be and a thick mayonnaise-like consistency

tidilorid, including liquefied ones, usually have. ...

Gaseous compounds; The invention is illustrated by means of the following examples

Sf iniische various liquid substances suitably explained in more detail. ψ The surfactant can be a wetting agent, 5

P «in emulsifier or a dispersant and not Example 1

S? be ionic or ionic. All when preparing i- (2-CyanoäthyIthio) -acetaldoxime-N-methylcarbamate

Ii herbiciden or insecliciden common upper small approach

II surface-active agents can be used for ^a) *** "*** ^Approach .

ί men. Examples of this are the sodium or calcium io 16.8 triethylamine were added to one with stirring

fi salts of polyacrylic acids, the condensation products - 10 ⁰ C held solution of 15.5 g of l-chlorine

* of fatty acids or aliphatic amines or acetaldoxime added to ether and the solution

f "Amides with at least 12 carbon atoms if at -10 ⁰ C with 14.4 g 3-Mercaptopropionitnl

"Molecule with ethylene oxide and / or propylene oxide, added. It was stirred, while the temperature

oartieile esters of said fatty acids with glycerol, 15 rose to room temperature. Then there was water

ί ^Α Sorbitan, sucrose or pentaerythritol, condensate and dichloromethane added and the organic

cation products of alkylphenols !! like p - () ctyl- "layer separated, dried and evaporated.

ohenol or p-octyl cresol with ethylene oxide and / or it left the crude oxime, its melting point

Propylene oxide, sulfates or sulfonates of these condensates - after recrystallization from benzene at 82 bis

sail · ^ products as well as alkali salts, preferably Na-20 84 "C.

triuiii ^ alze of sulfuric acid esters or sulfonic acid- Calculated

esters with at least 10 carbon atoms in for CH ₈ N ₂ SO. .C 41.6, H 5.6, N 19.4, S 22.2%;

Molecule such as sodium lauryl sulfate, sodium sec-aikyl- found C 41.6, H 5.8, N 19.3, S 22.7%.

sulfates, sodium salts of sulfonated! Castor oil and ^B. ₃ . Sodium alkylarylsulphonates such as sodium dodecylbenzene- 25 The oxime obtained (2.1 g) was m lOücm ui-

_su ti., nat chloromethane dissolved and with 1 drop of Tnathylamiη

D- pest control according to the invention * - and 4 cm ^{3 of} methyl isocyanate added. The Remisen

Means can be used as wettable powders, dusts, and boiled under reflux for 1 hour

Gr.nulate, solutions, emulsifiable concentrates, and then evaporated to dryness. It behind Diieo Emulsions and pastes are prepared. Wettable 30 a product which, when recrystallized from benzo /

PuWr generally contain 25. 50 or 75 · /. Active ingredient 60 to 80 petroleum ether ^^^ 1 * ») ^.

and generally, in addition to the solid support, 3 to 10 ° / ₀ · doxime-N-methylcarbamate, m.p. 83 to 84 c, ergao.

Dispersant and optionally K up to 10% Stabili- Calculated

sawr (en) and / or other additives such as penetration for C ₇ H _n N ₃ SOj .. C 41.8, H 5.5, S 15.9%;

agents and adhesives. Dusts are all found C 42.1, H 5.5, S 15.9%.

Geinein set up as a dust concentrate, the same thing

Composition like a wettable powder, ^ Larger approach

but does not contain a dispersant; at M _a , _r i " _m hir _n rhonat

the application in the open field with further solid 11 mol Acetaldox.m, 22 mol ^ numb ^ carrier for a means with 0.5 to 10% active ingredient 40 and 41 water were in a m, t R "h ™ ^Erk > Ther

thinned. Granules are generally in a grain- mometer and gases ^ ™ & ™ ^h * ™? £ ^e ™ _k J ° j \

size from 0.15 to 1.68 mm given by agglomerating flask and stirring on OC jbjekuML

or impregnate. Se usually contain ¹ ^ moles of chlorine in the course of wn

wise 0 5 to 25% active ingredient and 0 to 25% additives _{initiated 1V 4} hours. During the chlorination

w Stabilizers, release retarders, binders 45 w ^ die ^ ktion.tcnineratwB ^ O ^ - ^ C

i.a. m. Emulsifiable concentrates contain in general terms. After the chlorination has ended; was erne

in addition to the solvent and optionally a solution of 10 mol of Mercaotopropontolm 1 ^ Me

Co-solvent 10 to 50% w / v Active ingredient, m thylenchlond with vigorous Ruhreni Verlaut

2 to 20% w / v Emulsifiers and 0 to 20% addition of 45 minutes to the solution and the

acids such as stabilizers, penetrants and _S o reaction temperature thereby «rad, erι CMond -10 C

Corrosion inhibitors. Pastes are considered permanent, held. The HCyanoathylthioVacetaldoxu

flowable product and generally contain the course of the reaction1 as because *

10 to 60% active ingredient, 2 to 20% corresponding to an additional hour at 1> <-

Sä: ä iSeSSsSSSS

latine, glue, casein, vegetable resins and polyvinyl · dries. ^Da * ^Οε ™ 7riä _t hvlamin and then in alcohol, sodium polyphosphate, cellulose ether, rod, - 60 cools and with If m ^^^ ylhocy «-»

lizers such as ethylenediaminetetraesstgsaure other J ^. ^^ J '^^ throw the temperature

Pesticides and adhesives, e.g. offset, wah «nd d ^^ g ^ ^^ ^^" ^

non-volatile oils. . . _T then let stand and then

The active compounds can also be an aqueous dispersants ^ ^c ht be, Raumtemperai ^ _ngee depends and the

colorless crystals with a melting point of 90 to 92 ° C. were obtained.

Example 2

HS-CyanopropylthioJ-acetaldoxime-N-methylcarbamate

4.6 g of sodium were dissolved in 150 cm ^{3 of} methanol and hydrogen sulfide was introduced into this solution at 0 ° C. for 1 hour. A solution of 9.3 g of 1-chloroacetaidoxime in 100 cm ^{3 of} ether was then added dropwise and the mixture was stirred for 2 hours. The solution was then evaporated to a thick slurry, which was washed with 3 times 100 cm = ether and, after decanting off the ether, evaporated to dryness.

The solid substance obtained was dissolved in 150 cm ^{3 of} water and acidified to pH 6 with concentrated hydrochloric acid. The reaction mixture was then ^{extracted with 2 times 200 cm 3 of} ether, the extract was dried over magnesium sulfate and evaporated to dryness. An oil remained which was dissolved in 35.5 cm ^{3 of} ether and treated with 5.0 cm ^{3 of} triethylamine; then 4-bromobutyronitrile was added dropwise with cooling. The mixture was stirred for 15 minutes, ^{treated with 30 cm 3 of} acetone in order to decompose the triethylamine hydrochloride, and filtered and the filtrate was evaporated to dryness. H3-cyanopropylthio) -acetaidoxime remained, melting point 94 to 95 ° C. Calculated

for C ₆ H ₁₀ N ₂ SO .. C45.5, H6.6, N17.7, S20.3%; found C 46.2, H 6.6, N 17.4.519.9%

The oxime was dissolved in 70 cm ^{3 of} dichloromethane and treated with 1 drop of triethylamine and 3.5 cm ^{3 of} methyl isocyanate. The mixture was kept under reflux conditions for 2 hours and then evaporated vigorously; an oil remained which was purified by chromatography on a silica gel column; A mixture of 60% dichloromethane and 40% ether was used as the eluent. The desired compound,! - (S-CyanopropylthioJ-acetaldoxime-N-methylcarbamate, melted at 43 to 45 ° C.

Calculated

for C ₈ H ₁₃ N ₃ SO ₂ .. C 44.6, H 6.1, S 14.9%; found ........ C 44.4, H 6.1, S 15.2%.

In a similar manner, the following were each given the melting point and the result of the elemental analysis connections listed:

connection M.p. C analysis
C. C ₈ H _n N ₃ SO ₂ H N 1- (2-cyanoethylthio) acetaldoxime carbamate 110 to 120 Calculated 38.5% Found 38.7% 4.8% 22.5% C ₇ H _n N ₃ SO ₂ 5.1% 22.7% 1-Q-CyanopropylthioJ-acetaldoxime carbamate 102 to 103 Calculated 41.8% Found 41.6% 5.5% 20.9% C ₁₀ H ₁₇ N ₃ SO ₂ 5.7% 21.1% l- (3-Cyanopropylthio) -isobutyraldoxime-N-methyl- 50 to 52 Calculated 49.3% carbamate Found 49.7% 7.1% 17.3% C ₉ H ₁₆ N ₃ SO ₂ 7.3% 17.3% 1-W-CyanobutylthioJ-acetaldoxime-N-methylcarbamate 43 to 45 Calculated 47.1% Found 47.3% 6.6% 18.3% 6.7% 18.7%

Example 3 «

The insecticidal and acaracid effectiveness of the compounds obtained in the previous examples were checked as follows:

A 1.0 percent by weight solution of the compound to be tested in acetone was prepared and drawn up into a small syringe with micrometer graduation. 2 to 3 day old adult female house flies (Musca domestica, Md) were _{anesthetized with CO 2} and a Ι μΙ drop of the solution to be tested was brushed onto the ventral side of each fly. The treated flies were placed in jars containing a few grains of sugar for food; after 24 hours the dead and dying flies were counted.

In a beaker, 0.1 cm ^{3 of} a 1 percent strength by weight solution of the compound to be tested in acetone were ^{mixed with 100 cm 3 of} water. Twenty 5 to 6 day old mosquito larvae (Acdcs aegypli - A. a., Fourth stage of development) were added and the glasses were left to stand for 24 hours. The dead and dying larvae were then counted.

III. The compounds were prepared as solutions or suspensions in water which contained 20 percent by weight acetone and 0.05 percent by weight condensation product of octylphenol and ethylene oxide (Triton X 100) as wetting agents and each 0.7 percent by weight of the compound to be tested. Beet and broad bean plants were cut to a leaf each and sprayed with the solution or suspension on the underside of the leaf; for this purpose, the plants were led past a spray device on a conveyor belt, which delivered 44.8 l / m ² . Ten 8-day-old cabbage moth larvae (Plutella maculipennis - P. m., Fourth stage of development), ten wingless 6-day-old shrimp aphids (Megoura viciae - M. v.) And ten adult 1 to 2 week old mustard beetles (Phaedon cochlcariae - P. c.) placed on the sprayed leaves; each plant was then placed in a glass cylinder which was sealed at one end with a gauze cap. The mortality rate was determined after 24 hours.

IV. For the experiments with red greenhouse spider mites (Tetranychus telarius — T.t) Leaf disks cut out from green bean plants, sprayed in the same way as in III and 1 hour after spraying with ten adult mites occupied. The mortality was determined 24 hours later V. For the experiments with cabbage whites (Pieris brassica - P. b.) were cabbage leaves according to III sprayed. Then 8 to 10 day old larvae (third stage of development) were exposed to the the sprayed leaves set cut-out slices and the leaf disks between two Petri dishes held. The dead and dying larvae were counted after 24 hours

The results are summarized in the table below. A means 100% destruction, B partial destruction and C complete survival of the test animals. For all compounds with a rating of A, the toxicity index (TI) of the compound to be tested was also determined by determining the LD _M value of the compound and comparing it with the LD ^ value of parathion as a reference substance according to the equation

_. . . »_». . LD ₅₀ test connection ""

Toxicity index = - - x 100 LD ₆₆ parathion

is determined and given in brackets.

R * O

I!

CN- (CH ^ -SC = NOC-NHR ¹

connection R M.d. AWAY. Insecticidal effectiveness (T.].) P.m. P.b. M. v. T.t. (CH ₁ ), R * CH, A (I) A (I) P.c. C. A (4) A (20) A (250) (CH,), CH, CH, B. C. A (4) C. A (I) A (4) A (200) (CH ₁ ), CH, H A (3) B. C. B. A (I) A (15) A (ISO) (CHJ ₂ CH, CH, B. A (I) C. C. B. A (12) A (150) (CHO, iC, H ₇ H B. C. C. C. B. B. A (150) (CH ₁ ), CH, CH, C. A (I) C. C. C. A (I) A (150) (CHJ ₄ CH, C.

Comparative experiments

bonds that are most effective against the insects listed in Example 3 (Dipteria and The toxicity index (T-I) Lepidoptera was shown in Example 3) and mites are in dei all summarized in the British patent specification 1090 986 following table and the ent written connections with parathion as reference 4 »speaking widths for the registration according to substance determines The values for those compounds compared

Connection (state of the art) CH, R. R, M-d. A.9. Insecticide effectiveness (T.I.) P.m. P.b. M. ν. T.t. X R. C ₁ H ₆ CH, CH, 50 B. P.c. 1.3 6.5 40 40 O i-QH ₇ CH, CH, 120 1 2 1 8th 70 15th O CH _t = CH-CH, CH, CH, 70 7th 2 B. 8th 10 35 O CH, CH, CH, 60 1 2 2.7 B. 40 11th O CH, CH, CH, 12th B. 2 100 9 45 S. C.H, CH, H 25th C. B. 2.7 20th 20th 45 S. iC, H ₇ CH, CH, 30th 1 B. B. 33 5.5 40 S. CH, CH, CH, 6th 3 1.5 B. 50 4.5 40 S. C ₁ H ₈ QH _S CH, 8th 2 5 B. 50 6.5 20th S. CN-CH ₁ - C ₁ H ₅ CH, 8th 10 B. U 50 18th 23 S. CN- (CHJ, CH, CH, 60 1 2 B. 7th 10 80 S. CN- (CH ₁₆ ), CH, CH, 1 1 B. C. 4th 20th 250 S. CN- (CHJ, CH, H 3 B. 4th B. 1 15th 150 S. CN- (CH ₁ J, CH, H B. C. C. C. B. B. 150 S. CN (CH ₁ ), CH, CH, B. C. C. C. 1 4th 200 S. . CN (CHJ ₄ i-QH, CH, B. 1 C. C. B. 12th 150 S. CII, CH, C. 1 C. C. Γ 4th 150 S. V

partial eradication
C germ 'extinction

M. d. Mtnca damcstia A. a. Aedes acpypti

P c Placdon cncMcariac

P. m. Plntcfla maculpcnm M. v. Mcgoura viciac T. t. Tcirsnychus tclariu.

The compounds are according to the general formula

R _t O

I Il

R ₁ -XC = NOC-NHR

characterized by their substituents; the test animals were as in the table of Example 3 with the Abbreviation of their Latin names. The evaluation B and C again means partial Extermination or complete survival.

The comparison shows the following:

i. All connections according to the state of the art 'are against houseflies (M. d.) And / or strongly effective against cabbage white butterflies (P. b.), while the compounds according to the invention these ao both species show only lower activity.

2. The aearic effectiveness of the compounds according to the state of the art (T.I. <100) never reaches the value of the reference substance Parathion, while the compounds according to the invention increase the activity of parathion by at least Exceed 50%.

3. The known compound 1-cyanomethylthioacetyldoxime-N-methylcarbamate, which differs from the compounds according to the invention only in the length of the carbon chain in the cyanoalkylthio group, achieves only 80% of the acaricidal activity of parathion. The similar structure compound according to Example 1, however, the 1-Cyanoäthylthio N-methylcarbamate acts, 2 ¹ ^ aI stronger than parathion: Based on this compound has only one group CHj more, is the efficacy of the known 1-Cyanomethylthioacetaldoxim- N-methyl carbamate only 30%; based on the least effective compounds according to the invention, its effectiveness is only about 50%.

Claims (5)

1 2 isocyanate of the Foungl R1NCO or with a patent claim: carbamyl halide, of the formula 1. Oxime carbamates of the general formula 0 5! ^R2 ° R ¹ HN-C-HaI St. NC - (CH ₄ ). - S - C = NO - C - NHR ^1, optionally in the presence of a base, preferably an organic base, e.g. 8. a trialkylanMn, wherein η - 2, 3 or 4 and R ^{1 is} a hydrogen io is reacted, where n, R ¹ and R * in these formulas atom or a methyl group and R ^s a methyl have the meaning given above and Hai group or when η = 3 and R ^{1 is} a halogen atom The reaction with the iso- A methyl group is also an isopropyl group; cyanate or carbamyl chloride is preferred can - in the presence of a liquid organic reaction - 2. I-te-CyanoäthylthioJ-acetaldoxime-N-methyl mediums like methylene chloride or benzene by carbamate. guided; the implementation with phosgene, however, can 3. 10-CyanopropylthioJ-acetaldoxime-N-methyl- can also be carried out in an aqueous medium. In some carbamate. Cases it is advantageous to use the isocyanate R ¹ NCO in 4. Use of the compounds according to claim to allow the course of the reaction itself to arise, for. B. 1 to 3 as Akaricide. ao by thermal decomposition of an acid azide or, if R ¹ - H, by thermal decomposition of cyanuric acid. The 1 -Cyanoal kylthioaldoxime of the formula 11 can by reacting the corresponding 1-halooxime »5 with the corresponding mercaptan in an organ- From British patent specification 1090 986 ruffled reaction mediums such as etha.iol or ether are known pest control agents which contain S-containing oxime carbamates as active ingredients or substances obtained in a basic aqueous medium. You can also use the appropriate halogen and especially against insects and nematodes. aldoxime with an alkali metal, e.g. B. Sodium or It has now been shown that a group of 3 »potassium and hydrogen sulfide to the salt of the thio-specific way substituted, also S-containing hydroxamic acid and this salt then convert with the ent-oxime carbamate a completely different spectrum of activity speaking halonitrile,
has and primarily a surprisingly strong It is generally known that oximes unfold in two stereo-effectiveness against mites, while isomeric forms, the cis and trans form, the known compounds can only moderately acaricid 35; the same stereoisometry occurs at the are effective. Oxime carbamates according to the invention, and the invention relates to oxime carbamates of the invention therefore includes both stereoisomeric forms of the general formula oxime carbamates and mixtures thereof. _R2 Q The 1-cyanoalkylthiooxime carba- s 40 mate are used in pesticides m <~ ir> u \ c f-_Ki r> η mudi usual way, optionally together with a NL- (t_H ₂ ) "- b - l_ Ν - υ - L- NHR carrier material and / or a surface-active I means formulated. The usual where η = - 2, 3 or 4, R ^{1 is} a hydrogen atom 45 organic or organic synthetic or or a methyl group and R * a methyl group natural substances in question with which the active ingredient or when η = 3 and R ^{1 is} a methyl group mixed or added to its application can also be an isopropyl group. on the plants, the seeds, the soil or others The compounds to be treated according to the invention and its storage, are characterized by their strong acaricidal effectiveness 50 to facilitate transport and handling. The carrier that of the well-known remedy perathion can be solid or liquid. All when preparing significantly exceeds. Common pesticides can be particularly effective the compounds l- (2-Cyanoäthylthio) -acetaldoxini- are used. N-methylcarbamate and l- (3-cyanopropylthio) -acet- Examples of suitable solid carriers are silicates, aldoxime-N-methylcarbamate, which is therefore preferred for clays such as kaolinite, synthetic hydrated silicon Control of these pests are used. oxides, synthetic calcium silicates. Elements like In addition, the compounds also have insecticidal carbon and sulfur, natural and synthetic Effectiveness, which, however, is not as pronounced. Resins such as coumarone resins, rosin, copai, The new connections are in z. B. from Shellac, Dammar, polyvinyl chloride and styrene poly Belgian Auslegeschrift 674 792 known manner 60 merisates and copolymers, solid chlorophenols, produced by adding the corresponding 1-cyanoalkylthio bitumen, asphaltite, waxes such as beeswax, paraffin aldoxime of the formula fin wax, montan wax and chlorinated mineral waxes R ² as well as solid fertilizers such as superphosphates. I Examples of liquid carriers are water, NC - (CH ₂ ) ,, - S - CN OH II ⁶ S alcohols such as isopropanol, ketones such as acetone, Methyl ethyl ketone, methyl isobutyl ketone and cyclo- with phosgene and ammonia or the corresponding hexanone, ether, aromatic hydrocarbons such as substituted amine of the formula H ₂ NR ¹ or with a benzene and toluene, petroleum fractions such as kerosene,