DE2027058B2 - N-acylated carbamates, processes for preparing the same and pesticides containing these compounds - Google Patents

Description

15th

wherein R is ethyl or n-propyl.

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

(a) S-Isopropyl-S-methylphenyl-N-methylcarbamate with an anhydride of the formula

R-CO-O-CO-R,

wherein R is as defined in claim 1 in the presence of a small amount of sulfuric acid reacts at temperatures up to the reflux temperature of the mixture or

(b) S-Isopropyl-S-methylphenyl-N-methylcarbamate reacted at room temperature and in an inert solvent with an excess of sodium hydride and then the resulting Product with a halide of the formula R — CO — X, where R is the definition of Claim 1 possesses and X denotes chlorine or bromine jn, converts or

(c) S-Isopropyl-S-methylphenyl-N-methylcarbamate in the presence of an inert solvent and a polar solvent with a Reacts excess sodium hydride and j-, then the product obtained with a halide of the formula R — CO — X, in which R is the Definition of claim 1 and X is chlorine or bromine, converts or

(d) S-isopropyl-S-methylphenyl-N-methylcarbamate with a halide of the formula R — CO — X, in which R is as defined in claim 1 and X is chlorine or bromine, at temperatures in the range from 50 to 150 ° C implements or vi

(e) S-Isopropyl-S-methylphenyl-N-methylcarbamate with a halide of the formula R — CO — X, where R is the definition of Claim 1 has and X is chlorine or bromine, in the presence of a base at Tempe- w temperatures in the range of 80 to 130 ° C.

3. Pesticides, characterized in that there is one in addition to the usual auxiliaries The compound of claim 1 contains. τ>

It is well known that carbamates are useful as insect control agents. So is for example the compound 3-isopropyl-5-methylphenyl-N-methylcarbamate (Promecarb) a well-known insecticide with a wide range of activities. However this compound, like other carbamates, suffers from the disadvantage that it is relatively high Has toxicity to mammals. μ

It has now been found that the new N-acylated described in claim 1 above Carbamates have been used effectively as pesticides and especially as tick control agents that they are effective against resistant tick strains and that they are effective against cattle have a significantly lower toxicity than Promecarb.

These compounds can be prepared in the manner as set out in claim 2 above is

The invention thus relates to N-acylated carbamates, processes for producing the same and Pesticides containing these compounds according to the preceding claims.

In the preparation according to variant (a), the molar ratio of the anhydride mentioned to 3-isopropyl-5-methylphenyl-N-methylcarbamate is required only 1: 1, but an excess of the anhydride, for example a ratio of 2: 1, is preferred Completion of the reaction, the sulfuric acid can be reacted with anhydrous sodium acetate to remove the To eliminate mineral acidity, whereupon any excess anhydride present by distillation is removed and the desired product by known measures, such as. B. distillation, from the Reaction mixture is obtained.

In the preparation according to variant (b) or (c), the sodium halide formed as a by-product can be from separated from the reaction mixture and the desired product by known measures, such as. B. Evaporation or distilling off the solvent.

Even in the case of the preparation according to variant (d) or (e), the reaction product is known per se Measures, for example removing the solvent by distillation, isolated.

The compounds according to the invention are valuable pesticides and, in particular, germicides. They can be used in their pure state for this purpose. However, they will normally as a mixture with inert carriers or diluents and, if appropriate, other auxiliaries used. By an inert carrier is meant a diluent that is used to: achieve the desired concentration of active ingredient and facilitate handling.

One pest that is particularly difficult to eradicate or control is the beef tick (Boophilus microplus). The new compounds and compositions have been found to be effective in combating the beef tick on animals are better than the previously known carbamates.

The compounds according to the invention have a high contact activity against the most diverse Strains of Boophilus microplus in the adult state, in the larval state and in intermediate states. Both "sensitive" and "resistant" strains can be combated. The simultaneous effectiveness against both sensitive and resistant strains of Boophilus microplus is not just one considerable and growing economic importance, as will be explained in more detail below, it is also a remarkable and highly selective trait, as it appears to affect very few members a large number of the previously known carbamates is limited. It could be shown that many known analogs with similar structure, even closely related compounds and / or isomers, not these superior effect against resistant ticks

demonstrate.

The compounds of the invention have very low mammalian toxicity. The middle lethal oral dose of S-isopropyl-S-methylphenyl-N-methylcarbamate in rats is 35 mg / kg body weight. The compounds of the invention possess in contrast, surprisingly low mammalian toxicity. So the mean is lethal oral dose in mice for both compounds greater than 1500 mg / kg body weight When the invention Compounds on 14 consecutive days at a dose of 100 mg / kg orally on rats were administered, there were no deaths. Dermal applications in rats up to 4000 mg / kg remained without effect. In addition, when the active ingredients of the invention are applied in an amount to cattle are used, which showed an effective control of the beef tick, then showed in the Cattle have no symptoms of poisoning. So the control can be carried out in the usual way be, for example by spraying or by immersing the animals, without any harmful toxic effects occur.

Another advantage of the compounds according to the invention is that they can easily be converted into stable aqueous compounds Emulsions can be transferred. They are in many of the common non-toxic organic solvents, such as B. toluene or xylene, which are used for the production of emulsifiable concentrates, soluble or mixable with it. They are practically insoluble in water. As a result, it can be relatively high Concentrated emulsifiable concentrates are made that are kept at low temperatures in the presence of water are stable for many weeks without solid deposits being formed. Likewise, they are final aqueous emulsions made from these concentrates over a wide temperature range stable without the formation of deposits.

This is important in the case of dipping agents for cattle, which are often left to stand for many days, and their concentrations not allowed to lose.

The known non-acylated carbamates, such as. B. S-methyl-S-isopropyl-N-methylcarbamate, are far more difficult to process into preparations. So is the latter compound in organic solvents less soluble than their acylated derivatives. If they are made in the form of an aqueous formulation that called as an emulsion or as an emulsifiable concentrate, then they tend to form crystalline deposits, even after they have stood for a few hours. Compare the differences in solubility and the Stability of emulsifiable concentrates demonstrating this behavior are in Example 5 specified.

Emulsifiable solutions or suspensions of the active compound can be prepared by that the active compound in a solvent or a solvent mixture which is non-toxic to the animals on which they are to be used, dissolves or suspends, adding an emulsifier and / or a wetting agent and optionally adding some water. A typical one could emulsifiable concentrate approach of this type for use in the inventive method 60% by weight active ingredient, 35% by weight of a high-boiling point consisting largely of aromatics Petroleum solvent and 5 wt .-% of a nonionic Emuieators contain. This concentrate is then made before

after application, diluted with water to the desired concentration.

The compounds according to the invention can also be used as dispersible powders, with the active ingredient is mixed with an inert solid carrier such as e.g. B. with powdered chalk, Talc, clay, kieselguhr, bentonite and dispersants. Suitable emulsifiers and dispersants are in known in the art. Anionic, cationic and nonionic agents can be used. A a suitable nonionic emulsifier is, for example, a condensation product of nonylphenol with Ethylene oxide. Suitable dispersants are e.g. B. the disodium salt of dinaphthyl methanedisulfonate, sodium lauryl sulfate and a condensation product of an alkylphenol with ethylene oxide.

Control of resistant tick infestations in cattle is like any other in Australia Countries a problem of considerable economic importance. In the past there have been many Tick strains called "sensitive" or "non-resistant" strains by spraying or dipping agents containing insecticides as active ingredients, such as. B. organophosphates, chlorinated hydrocarbons (e.g. DDT and BHC) and carbamates.

Recently, however, certain beef ticks have appeared, which are now in Australia and are widespread and still spreading elsewhere, such as B. the "Biarra" tribe, the unaffected by the broad spectrum insecticides normally used for this purpose will. These tick strains cannot be combated by the known insecticides unless they are not be used in concentrations that are either overly toxic or very expensive, or both. These strains are known as "resistant" strains of the bovine tick and they currently represent the Australian cattle breeding is a serious problem.

A typical "sensitive" strain is the "Yeerongpilly" strain, which is widespread and easy to use conventional tick control agents can be combated, such as 1-naphthyl-N-methylcarbamate, chlorinated hydrocarbons (such as DDT and BHC) and a wide variety of organophosphorus insecticides. This strain is used by the authorities as a "sensitive" reference standard against the the degree of resistance of resistant strains is measured. A typical resistant strain is the »Biarra« - Tribe, also known as the "Esk" or "Aderson" tribe, and in 1966 in the Esk district in Queensland, Australia. Various authorities, such as B. the Commonwealth Scientific and Industrial Research Organization, have found that this strain is against nearly most of the known Tick control agent is extremely resistant, which is therefore no longer economical and safe Concentrations can be used.

When determining the effectiveness of tick control substances against resistant tick strains it is common practice to reduce the concentration of active Component that is necessary to kill 50% of a tick infestation by the »Biarra« strain (LC50B) the concentration required to kill 50% of a tick infestation by the »Yeerongpilly« strain (LC50Y) is necessary to compare. The ratio LC50B: LC50Y is used as the resistance factor of the tick control substance designated. It is desirable that

the resistance factor is as low as possible and that it is preferably in the range of 1. Of the Resistance factor of some of the commonly used insecticides was determined by Commonwealth Scientific and Industrial Research Organization determined. She has established that the resistance factor is organophosphorus compounds is very high. For example, the following compounds should be mentioned here:

Carbophenothione (chemical name see Table I):

Resistance factor 39

CoumaphosO.O-diethyl-O.S-chloro ^ -methyl-7-coumarinylphosphorothioate):

Resistance factor 25 ethione (chemical name see table I):

Resistance factor 19

Carbaryl (= 1-naphthyl-N-methylcarbamate) has a resistance factor of 8, which is better than that of the organophosphorus compounds listed above, but still for practical purposes is too high.

In contrast to this, the compounds according to the invention have resistance factors which are essential are closer to 1 than is the case with the known compounds. Because you own Resistance factors of about 2.6 or less. This is a significant commercial advantage. For example possesses the compound S-isopropyl-S-methylphenyl-N-propionyl-N-methylcarbamate a resistance factor of approximately 2.3.

This reduced resistance factor and the low toxicity of the compound of the invention is due to the Treatment of animals to control beef ticks both the sensitive and the resistant strains are highly desirable.

The fact that the N-propionyl according to the invention or butyryl carbamates are far more effective than the non-acylated compounds was not at all to foresee. It is generally accepted in the art that the acylated N-alkyl carbamates, though they may have some beneficial properties, are almost invariably less active than that corresponding non-acylated compounds. There is no known case that an acylated N-alkyl carbamate represents a stronger poison against mites or insects than the non-acylated starting compound. When a Tick control agent is not active against both resistant and sensitive strains, then results long-term treatment in a specific treatment area does not control ticks, but merely an increase in the population of the resistant strain in relation to the sensitive one Tribe.

The doses for tick control in cattle are not very critical. With external Application of sprays to the skin of cattle, using aqueous approaches in an amount of 3.31 per 100 kg body weight of the animal were used, were concentrations of the invention Connections between 0.03% (w / v) and 1% (w / v) are useful. Concentrations above 0.05% (w / v) resulted in effective control. The practically usable concentrations are therefore 0.03 to 1% (w / v). The preferred concentrations are 0.05 to 0.15% (w / v). With external application of Injection compositions are suitable in amounts of 0.01 to 0.3 g / kg of body weight and amounts between 0.015 and 0.05 g / kg body weight are preferred.

However, the compounds according to the invention are not only highly active in cattle ticks proven, but they are also active against a wide variety of other pests.

One example is Lucilia cuprina (sheep blow fly). It can be both sensitive and resistant Tribes can be controlled by these compounds. The simultaneous! Effectiveness against both sensitive

iü before as well as resistant strains of Lucilia cuprina not only of considerable and growing economic value, as explained below, but it is also a remarkable and highly selective property, as it appears to be very In contrast, it is general known that the organophosphates and carbamates of the prior art at practically useful and Non-toxic concentrations against the resistant strains are not effective.

As with ticks, the infestation of sheep by Lucilia cuprina is also a problem of considerable economic importance. To date, susceptible or non-resistant strains of Lucilia cuprina fights with pesticides or dipping agents, insecticides as active ingredients contained, such as B. organophosphates, chlorinated organic compounds such as DDT, BHC and Deldrin, carbamates and boric acid compounds. However, chlorinated hydrocarbons can no longer be used for The treatment of cattle can be used because they are retained in adipose tissue. Furthermore could recently from various agencies such as B. from the Commonwealth Scientific Industrial Research Organization, It can be shown that a similar resistance has developed in individual strains as in the Ticks. These strains are now widespread in Australia and continue to spread. you will be not affected by the broad spectrum insecticides normally used for this purpose, and they can therefore not be controlled by the known insecticides unless they are in Concentrations are used that are either overly toxic, or very expensive, or both. These tribes are known as the resistenle strains of Lucilia cuprina and are extremely popular in Australian sheep farming serious problem.

In determining the effectiveness of insecticidal agents against resistant strains of Lucilia

so cuprina it is customary to compare the behavior in the same way as it was above for the tick happened.

The CSIRO has found that the resistance factor in most compounds to Lucilia cuprina is very high. For example, the resistance factor for the commercially available Diazinon is 15.

In contrast to this, the compounds according to the invention have a considerably lower resistance factor. For example, the compound has S-isopropyl-S-methylphenyl-N-propionyl-N-methylcarbamate against Lucilia cuprina a resistance factor of about 3 to 4. The reduced resistance factor and the low toxicity of the compounds of the invention is useful in the treatment of animals Control of sensitive and resistant strains of Lucilia cuprina is extremely desirable.

Here, too, as in the case of ticks, the fact that the N-propionyl or N-buty-

ryl carbamates are far more potent than similar non-acylated compounds, completely unexpected. In technology it is well known that the acylated N-alkyl carbamates have certain advantages, but almost without exception they are less active than them corresponding non-acylated compounds. There is no known case of an acylated N-alkyl carbamate which has a stronger effect against mites or insects than the corresponding non-acylated starting compound, in

If an insecticide isn't effective against both resistant and sensitive strains, then If the treatment in a certain area does not result in the long-term control of Lucilia cuprina, but merely an increase in the population of the resistant strain in relation to the population of the sensitive trunk.

The doses for controlling an infestation in sheep by Lucilia cuprina are not very critical. When using external sprays on the skin and wool of the sheep, with aqueous approaches in one Amounts of 2.41 per 10 kg of body weight of the animal were applied, concentrations were the Compounds according to the invention between 0.02% (w / v) and 1% (w / v) can be used. Concentrations above> 5 0.05% (w / v) gave effective control. Practically usable concentrations are therefore 0.02 to 1% (w / v). The preferred concentrations are 0.05 to 0.15% (w / v). An external spray application between 0.05 and 2.25 g / kg of body weight is suitable and amounts between 0.10 and 0.40 g / kg will be preferred.

Finally, it has also been found that the compounds according to the invention are effective against gastropods are effective, such as B. against snails, and that they are therefore used to combat infestation by gastropods Can be used in horticulture and agriculture. This activity is surprising since similar, non-acylated carbamates, e.g. B. 3-isopropyl-5-methyl-N-methylcarbamate, were completely ineffective at concentrations of the active ingredient, the 10% for the compounds according to the invention Mortality resulted.

The following examples illustrate the preparation of the compounds and compositions according to the invention as well as their biological effects.

example 1

S-isopropyl-S-methylphenyl-N-propionyl-

N-methyl carbamate

A mixture of 0.2 moles of S-isopropyl-S-methylphenyi-N-methylcarbamate, 0.2 mol of propionyl chloride, 0.2 mol of pyridine and 75 ml of toluene were added with stirring to 18 Heated under reflux conditions for hours. After cooling to room temperature, the pyridine hydrochloride became was filtered off and the toluene was removed by distillation under reduced pressure. That liquid product was identified by infrared and nuclear magnetic resonance spectroscopy. The yield exceeded 85%. t> o

The MKR spectrum ") (CDCb solution) showed signals at ό 6.95 (1 H, Ar-CH), 6.84 (2 H, Ar-CH), 3.35 (3 H, singlet, N- CH ₃ ), 2.95 (quartet, J = 7 Hz,

'·) All MKR spectra in this description have been marked with a Varian AöO spectrometer measured. The positions are all given in the ppm downfield of tetramethylsilane used as the internal reference.

COCH ₂ ), 2.8-2.9 (multiples obscured by the 2.95 CH band of isopropyl), 2.34 (3 H, singlet, Ar-CH ₃ ), 1.24 (6 H, doublet , CH ₃ of isopropyl) and 1.15 (triplet, terminal CH ₃ ).

A similar yield of this material was obtained by the procedure of Example 2 when the Butyryl chloride of that example was replaced by propionyl chloride.

Example 2

S-isopropyl-S-methylphenyl-N-butyryl-N-methylcarbamate

A mixture of 0.1 mol S-isopropyl-S-methylphenyl-N-methylcarbamate, 0.15 mol of butyryl chloride and 40 ml of toluene were refluxed for 30 hours held while purging with dry nitrogen.

The toluene and the unreacted butyryl chloride were removed by distillation under reduced pressure eliminated, the product remaining in a yield of 85%. The identity of the product was made through Infrared and MKR spectroscopy confirmed.

The MKR spectrum (CDCI ₃ ) showed signals at ό 6.92 (1 H, Ar-CH), 6.82 (2 H, Ar-CH), 3.31 (3 H, singlet, N-CH ₃ ) , 2.80-2.90 (1H, multiplet, J = 7 Hz, CH of isopropyl), 2.85 (2H, quartet, J = 7 Hz, COCH ₂ ), 2.31 (3 H, singlet , Ar-CH ₃ ), 1.64 (2 H, multiplet, J = 7 Hz, C-CH ₂ -C), 1.23 (6 H, doublet, J = 7 Hz, CH ₃ of isopropyl), 0, 94 (3 H, triplet, J = 7 Hz, closed CH ₃ ).

A similar yield of this material was obtained by the procedure of Example 1 when the Propionyl chloride of that example was replaced by butyryl chloride.

Example 3

S-isopropyl-S-methylphenyl-N-butyryl-N-methylcarbamate

A mixture of 0.2 moles of S-isopropyl-S-methylphenyl-N-methylcarbamate, 0.4 mol of butyric anhydride and 0.2 ml of concentrated sulfuric acid were kept at reflux temperature for 1 hour. Anhydrous Sodium acetate was added to neutralize the sulfuric acid and the excess anhydride was removed by distillation under reduced pressure. Vacuum distillation of the residue resulted S-isopropyl-S-methylphenyl-N-butyryl-N-methylcarbamate in a yield of about 60%.

Example 4

S-isopropyl-S-methylphenyl-N-propionyl-N-methylcarbamate

A solution of 0.2 moles of S-isopropyl-S-methylphenyl-N-methylcarbamate in xylene was held at reflux temperature for 10 hours with 0.2 mol of sodium hydride. 0.2 mol of propionyl chloride was added to the cold reaction mixture with stirring. The unusual one Sodium chloride was separated by filtration and the solvent was removed under reduced pressure evaporated, S-isopropyl-S-methylphenyl-N-propionyl-N-methylcarbamate was obtained.

Example 5

S-methyl-S-isopropylphenyl-N-methylcarbamate was processed into an emulsion which was stable for more than 24 hours. There have been more than 50 approaches made to optimize the quality of the emulsion. The maximum concentration of a usable turnover

zes was the following 20% (w / v) emulsifiable concentrate:

S-methyl-S-isopropylphenyl-N-methylcarbamate 20.0 g

Nonionic, surface-active agent · *) 5.1g Anionic, surface-active agent ·) 2.1g of cationic, surface-active agent Medium * *) 0.3 g 10% (V / V) n-butanol in xylene, ad. 100 ml

*) An anionic, surface-active agent, which consists of a 70% solution of calcium dodecylbenzenesulfonate consists in a non-aqueous solvent. ··) A non-ionic, surface-active agent that is obtained by condensation of nonylphenol with approximately 13 moles of ethylene oxide.

***) A cationic, surface-active agent, which by Condensation of stearylamine with about 20 moles of ethylene oxide is obtained.

When 1 ml of this solution is added to 100 ml of water and the mixture is shaken well, an emulsion is then obtained, although in this case, after standing for 24 hours, crystals of des active ingredient were deposited.

With dipping agents it is very desirable that the emulsion remain stable for much longer times. the Acylated carbamates of the invention form such stable emulsions, even at much higher concentrations.

A typical 60% (w / v) emulsifiable concentrate is given below:

3- isopropyl-5-methylphenyl- 60.0 g N-butyryl-N-methyl carbamate Non-ionic, surfaces 4.85 g active agent **) Anionic, surfaces 4.85 g active agent *) Non-ionic, surfaces 0.30 g active agent **) 100 ml Toluene, ad.

*) See above.

**) A non-ionic, surface-active agent that is obtained by condensation of nonylphenol with ethylene oxide and propylene oxide. ***) A nonionic, surface-active agent, which by condensation of nonylphenol with 15 mol Ethylene oxide is obtained.

If 1 ml of this solution is added to 100 ml of water and the mixture is shaken, then an excellent emulsion is obtained. This emulsion also separates for 3 months no crystals sticking out for a long time. The concentration of the active ingredient can be increased up to 85% without a loss of quality and stability of the emulsion.

Example 6

The approach of S-isopropyl-S-methylphenyl-N-butyryl-N-methylcarbamate Example 5 was used to control an infestation of calves by the cattle tick Boophilus microplus.

The compositions were emulsified in water, with various concentrations of the active Components were made, for example 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.5% and 1.0% (w / v) .

The emulsions thus obtained were sprayed onto 2 year old calves weighing approximately 135 kg weighed. 4.51 per calf were used. For comparison, various known compositions were used used in the same way. The calves were at various stages of development sensitive "Yeerongpilly" strain of Rinderzekke heavily infested. The effect of the active ingredient the ticks were determined in different ways:

1. All adult female ticks that were fully sucked at the time of spraying were collected within 24 hours from the isolated calves

Vi had fallen off. They were then placed in a Petri dish in an incubator to determine mortality, based on their ability to lay eggs, and, if eggs were laid, based on egg viability, as evidenced by hatching of live larvae. This result is given in Table I as "Mortality of fully sucked adult ticks".

2. At daily intervals, certain sample • Γ) areas of each calf on the effect of the chemical on the other stages of development, which were present at the time of spraying, examined. The result was a final Obtained a determination showing the percent kill of these stages of development. The classification was as follows:

Estimated percentage kill 0 1-24 25-49 50-74 75-94 95-99 100 Mortality Education 0 1 2 3 4th 5 6th

These determinations are shown in Table I as "Mortality of nymphs" and "Mortality of undersucked adult ticks ”.

The results shown in Table I show that the compounds according to the invention are effective in combating of sensitive beef ticks is very effective.

A similar approach was made in which S-isopropyl-S-methylphenyl-N-butyryl-N-methylcarbamate by S-isopropyl-S-methylphenyl-N-propionyl-N-methylcarbamate was replaced. This approach was followed in the same way.

Example 7

Example 6 was repeated, but using the sensitive "Yeerongpilly" strain of the beef tick was replaced by the resistant »Biarra« strain.

The results shown in Table I clearly show the unexpected fact that the compounds of the invention are effective against the resistant strain an activity of the same order of magnitude as that of the sensitive strain of the ticks

own. The agents according to the invention can therefore be used to control ticks both the resistant and can also be used for the sensitive trunk. in the

In contrast, the known compounds are relatively ineffective against the resistant strain.

Table I.

Effect on beef ticks (a) sensitive strain and (b) resistant strain

Active component

S-isopropyl-S-methylphenyl-N-propionyl-N-methylcarbamate (according to the invention)

S-Isopropyl-S-methyl-phenyl-N-butyryl-N-methylcarbamate (according to the invention)

0.1 +

0.1 +

Carbaryl-1-naphthyl-N-methylcarbamate according to the state of the art

Ethione = O, O, O> -Tetraethyl-S, S'-methylenebis-phosphorodithioate

according to the state of the art

Trithione = O, O-diethyl-S-p-chlorophenyl-thiomethyl-phosphorodithioate

according to the state of the art

3-isopropyl-5-methylphenyl-N-methylcarbamate according to the prior art

') = sensitive trunk.

² ) - resistant strain ("Biarra" strain).

♦) = the concentration used commercially.

+ = slightly above the standard concentration.

- = experiment was not carried out at this concentration.

% more active Mortality from R ² ) Mortality from mortality R. Nymphs R. component soaked 100 not soaked the 6th (Classification) 6th in the spray adult 100 adult 6th 6th middle Ticks 100 Ticks 6th S. 6th (G / V) (%) 90 (Classification) 6th 6th 6th S ¹ ) - S. - 6th - 0.3 100 - 6th - 6th - 0.2 100 - 6th - - - 0.1 100 100 6th 6th 5 6th 0.08 - 100 - 6th 5 6th 0.05 100 90 6th 6th 3 6th 0.04 100 75 6th 4th 6th 4th 0.03 80 - 5 - 6th - 0.3 100 - 6th - 5 - 0.2 100 - 6th - - - 0.1 100 - 6th - 5 - 0.08 - - - - 5 - 0.07 - 15th 6th 4th 4th 4th 0.05 80 - 6th - 5 - 0.04 80 - 6th - 6th - 0.03 80 6th 6th 0.4 100 6th 6th 0.3 *) 93 6th 6th 0.2 47 6th 0.1 15th 5

100

100

0.15 100 100 6th 6th 6th 6th 0.1 100 - 6th 5 6th 4th 0.075 100 - 6th - 5 0.05 50 - 6th - 2

The above test results are averages of 6 tests. Since these are in-vivo and in-vitro tests, they represent an essential statement about the usefulness of the compounds under the conditions in the open field.

Example 8

The biological effects of various compounds of the invention on adult females and larval beef ticks were tested as follows.

Using the procedure outlined in Example 6, aqueous compositions were prepared which contained active ingredients in the concentrations given in Tables 2 and 3. 20 soaked adult female beef ticks of both the sensitive "Yeerongpilly" strain and the resistant "Biarra" strain were treated individually with a micro-syringe technique.

A microdroplet (free falling) from a microsyringe, which had a carefully cleaned needle with an inner diameter of 0.15 mm and an outer diameter of 0.4 mm, was dropped on the abdomen of each tick to be treated. After 14 days the Mortality rate of adult ticks is determined by the number of eggs laid by them and the Percentage of eggs hatched was counted.

In addition, nearly 100 tick larvae became short immersed in similar preparations as described above, and the mortality number of tick larvae. ven was determined after 48 hours. The control obtained is shown in Tables 2 and 3 as a percentage Mortality reported.

Table II

Adult beef ticks - mortality after 14 days

link

Concentration of
active ingredient%
(G / V)

% Mortality

S ¹ )

R ² )

S-Isopropyl-S-methylphenyl-N-propionyl-N-methylcarbamate 1.0

(according to the invention) 0.1

S-Isopropyl-S-methylphenyl-N-butyryl-N-N-methyl carbonate 1.0 (according to the invention)

2-Isopropyl-5-methylphenyl-N-acetyl-N-methylcarbamate 1.0

(according to the state of the art) 0.1

2,3,5-trimethylphenyl-N-butyryl-N-methylcarbamate 1.0

(according to the state of the art) 0.1

3,4,5-trimethylphenyl-N-butyryl-N-methylcarbamate 1.0

(according to the state of the art) 0.1

S-tert-butylphenyl-N-propionyl-N-methylcarbamate 0.1 (according to the state of the art)

') = sensitive strain; ² ) = resistant strain. 100 25

40

20th

0 0 0 0 0 0 0 0 0 0 0 0

Table III

Bovine tick larvae - mortality after 48 hours

link

Concentration of% mortality

active ingredient%

(G / V)

S ¹ )

S-isopropyl-S-methylphenyl-N-propionyl-N-methylcarbarnate (according to the invention)

S-Isopropyl-S-methylphenyl-N-butyryl-N-methylcarbamate (according to the invention)

2,3,5-trimothylphenyl-N-methylcarbamate
(according to the state of the art)

') - sensitive mute; ² ) = rcsistcntcr mute. 1.0
0.1
0.01

1.0
0.1
0.01

1.0
0.1
0.01

100 100 100 100 100 100 100 100 100 100 100 100 100 100 65 15th 0 0

Example 9

A dispersible powder was prepared from the following ingredients.

3-isopropyl-S-methylphenyl- 50% by weight N-propionyl-N-methyl carbamate Non-ionic, surfaces 1% by weight active agent *) 44 wt% volume 5% by weight water

*) A non-ionic, surface-active agent that obtained by condensation of nonylphenol with approximately 8.5 moles of ethylene oxide.

The powder was dispersed in water so that the active ingredient concentrations described in Examples 6 and 7 were obtained. When these approaches were applied to tick infested calves according to Examples 6 and 7, examples similar to Examples 6 and 7 were obtained.

Example 10

A spray that contains 0.05% (w / v)
ethyl phenyl N-propionyl-N-methylcarbamate and prepared by the procedure described in Example 6 was applied to Calandra granaria. A count was made 3 days after the spraying, which showed that the mortality of Calandra granaria was 85%.

Example 11

Injectables containing 0.1% (w / v) and 0.05% (w / v) α-Isopropyl-S-methylphenyl-N-butyryl-N-methylcarbamate and prepared by the procedure of Example 6 were reappeared Stepped adult Musca domestica (house fly) applied. Mortality counts among the Flies 24 hours after spraying showed that 100% and 10% of the flies, respectively, after treatment with the spraying agents listed above were used.

Example 12

Injectables containing 0.05% (w / v) and 0.025% (w / v) S-isopropyl-S-methylphenyl-N-propionyl-N-methylcarbamate and prepared by the procedure of Example 6 were on applied to certain areas of the back of sheep that carried approximately 5 cm of wool up to this Area was soaking wet. The sheep were run in pens under natural conditions. 6 weeks after spraying, larvae of a sensitive strain of Lucilia cuprina were exposed to the treated areas by a procedure known as a larval implantation test to which the skin of the treated area is scratched, a number of larvae are applied, and these are sewn under a damp cotton pad under the wool in order to have a natural infestation Simulate Lucilia cuprina. In these experiments, both of the above concentrations of des active ingredient killed the larvae of Lucilia cuprini, and an infestation could occur in the treated Areas do not develop. In identical experiments in which untreated sheep are implanted with larvae an artificial infestation of Lucilia cuprina developed.

Example 13

Example 12 was repeated, except that the in treated areas implanted larvae larvae de! resistant strain of Lucilia cuprina. It was found that the larvae of Lucilia cuprina were killed by the sprays containing 0.1% (w / v) and 0.05% ( (W / v) of the active ingredient.

Example 14 (comparative example)

The procedure of Example 12 was repeated except that the active ingredient was the commercially available one chemical substance Oiätriyl-2-isopropyl-6-methyl-4-pyri midinyl phosphorol thionate was used. It was found that the sensitive larvae at Konzen active ingredient concentrations of 0.02% (w / v killed.

Example 15 (comparative example)

The procedure of Example 13 was repeated except that the active ingredient in Example 14 The commercially available chemical used has been used. It was found that 100% Killing of the resistant larvae could not be obtained until a concentration of active one Component of 0.1% (w / v) was used.

Example 16

A mixture of the following ingredients was made:

Bran 20% by weight

Water 20% by weight

Molasses 1% by weight S-isopropyl-S-methylphenyl-

N-propionyl-N-methylcarbamate 10% by weight

The mixture was diluted with further bran, with concentrations of active ingredients of 1%, 2 ° / c and 4% (w / v) in the composition. E: Similar compositions were still made in which 3-isopropyl-5-methylphenyl-N-butyryl-N-methylcarbamate was the active ingredient. For Ver Similar compositions were prepared in which 3-isopropyl-5-methylphenyl-N methyl carbamate was the active ingredient. The compositions described above and a ver Equivalent compositions containing no active ingredient were applied to snails. 3 days Mortality counts were taken after the supplements were applied, and the results are given in Table IV below.

809 524/11:

Table IV

Snail mortality after 3 days

Active component

Active Ingredient Concentration% (w / v)

mortality

S-isopropyl-S-methylphenyl-N-propionyl-N-methylcarbamate

S-isopropyl-S-methylphenyl-N-butyryl-N-methylcarbamate

B-Isopropyl-S-methylphenyl-N-methylcarbamate
(Connection according to the state of the art)
Nothing (comparison)

Example 17

S-isopropyl-S-methylphenyl-N-methylcarbamate was at room temperature with excess sodium hydride in the presence of dry diethyl ether and treated with a small amount of dry dimethylformamide. After about 10 hours it became propionyl chloride added to the mixture and the ingredients were allowed to stir for an additional 10 hours at room temperature implemented together. The precipitated sodium chloride was filtered off and the solvents were removed evaporated, leaving a product as

S-isopropyl-S-methylphenyl-N-propionyl-N-methylcarbamate was identified.

Example 18

S-isopropyl-S-methylphenyl-N-methylcarbamate was at room temperature with excess sodium hydride in the presence of dry dimethylformamide treated. After about 10 hours, butyryl chloride was added to the mixture and the Components were reacted for a further 10 hours at room temperature. The precipitated sodium chloride was filtered off and the dimethylformamide was evaporated leaving a product which was known as S-isopropyl-S-methylphenyl-N-butyryl-N-methylcarbamate was identified.

4.0 2.0 1.0

4.0
2.0
1.0

4.0
2.0
1.0
0.0

Example 19

100 70 50

100 80 60

0 0 0 0

Young rough lemon seedlings covered with ripe Aonidiella aurantii (Mask.) (California red scale insect) were infected were sprayed with the compositions shown in Table V until they were were dripping wet. The sprays were prepared by the method described in Example 6 and contained 0.1% (w / v) active ingredient. The active ingredients used were 3-isopropyl-S-methylphenyl-N-propionyl-N-methylcarbamate and 3-isopropyl-5-methylphenyl-N-butyryl-N-methylcarbamate. The percentage of death obtained was determined 6 weeks after spraying. The results are in Table V summarized.

Table V

Active component

Percentage kill of animal scale insect

β-Isopropyl-S-methylphenyl-N-propionyl-N-methylcarbamate

S-isopropyl-S-methylphenyl-N-butyryl-N-methylcarbamate

Nothing (comparison)

91

Claims (1)

Patent claims:
1. N-acylated carbamates of the general formula O-CO-N-CO-R CH ₃ -CH
CH ₃ lü