DE2922270A1 - N- (CHLOROACETYL) -1,4OXAZA-HYDROCARBONS DERIVATIVES, THE PROCESS FOR THEIR MANUFACTURING AND PLANT PROTECTION PRODUCTS CONTAINED - Google Patents

Description

DR. STEPHAN G. BESZÜDES PATENT ADVOCATE

-ff-

AUTHORIZED REPRESENTATIVE AT THE EUROPEAN PATENT OFFICE

PROFESSIONAL REPRESENTATIVE ALSO BEFORE THE EUROPEAN PATENT OFFICE

2022270

DACHAU NEAR MÖNCHEN

BOX 1168

MDNCHENER STRASSE 8OA Federal Republic of Germany TELEPHONE: DACHAU 4371 Postal checking account Munich (BLZ 700 100 80)

Account no. 1 368 71

Bank account no. 906 370 at the Kreis- und Stadtsparkasse Dachau-Indersdorf (bank code 700 515 40) (VIA Bayerische Landesbank Girozentrale, Munich)

P 1 227

description

for patent application

eszakmagyarorsz / gi vegyimüvek

Sajobäbony, Hungary

concerning

N - (chloroacetyl) -1,4-oxaza-spiro-hydrocarbon derivatives, processes for their preparation and plant protection products containing them

The invention relates to new N- (chloroacetyl) -1,4-oxaza- -spirocarbon derivatives, a process for their Manufacture and crop protection products containing them.

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Some herbicides are known to be effective on weeds when used in agriculture Quantities in addition to the destruction of the weeds also change the natural development of the cultivated plants and these can harm. This damage can manifest itself in the hindrance or unevenness of development, in reduced yields or in other abnormalities. A better or complete selectivity of the herbicidal agents, that is, improvement or assurance their compatibility with the cultivated plants, can with 2 or more active ingredients containing herbicide mixtures or by the presence of a protective agent or antidote in herbicidal agents or by the common Use of the protective agents and herbicidal agents can be achieved. Such protective means are for example from the German Offenlegungsschrift 2 215 097 known.

The invention is based on the object of providing superior protective agents or antidotes in pesticides useful new compounds, a process for their preparation and crop protection agents containing them to accomplish.

The above has surprisingly been achieved by the invention.

It was found, surprisingly, that new N- (chloroacetyl) -1,4-oxaza-spiro-hydrocarbon derivatives the formula given below, the harmful effect of herbicidal agents on the crop plants, in particular the agents containing thiocarbamates (thiol carbamates) as active ingredients, markedly reduce or cancel and thus increase the selectivity of the herbicidal agents.

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The invention therefore relates to N- (chloroacetyl) - -1,4-oxaza-spiro-hydrocarbon derivatives of the general formula

Cl -

H
I.
σ - 0
Il /
C-N
N O ^ R ₁ Cl ■ R R ₂ ^R 3 '\ \ /

and

stands for a lower alkyl radical,

independently of one another hydrogen "or lower alkyl radicals mean and

Is O or 1.

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The lower alkyl radical for which R _x stands and / or the lower alkyl radical or lower alkyl radicals for which Rp and / or R ^ can or can stand is or have 1 or 2 carbon atoms.

Furthermore, all symbols are preferably R _x . , R ~ and R, alkyl radicals. It is particularly preferred that the N- (chloroacetyl) -1,4-oxaza-spiro hydrocarbon derivatives according to the invention of 3 lower alkyl radicals for which R _x . , Rp and R ^ stand, have 2 in the same position of the spiro-hydrocarbon ring.

According to the invention, N- (dichloroacetyl) -6,6,8- (trimethyl) -1,4-oxaza-spiro [4,4] nonane are very particularly preferred, N- (dichloroacetyl) -7,7j8- (trimethyl) -1,4-oxaza-spiro [4.5] decane and N- (dichloroacetyl) -7,7,9- (trimethyl) -1,4-oxaza- -spiro [4.5] decane.

The subject of the invention is also a method for Preparation of the compounds according to the invention, which is characterized in that a 1,4-oxaza-spirohydrocarbon derivative the general lOrmel

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wherein

^η are defined as above, in

Presence of an acid binding agent, for example
Triethylamine, is reacted with dichloroacetyl chloride.

The 1,4-oxaza-spiro hydrocarbon derivatives used as starting materials in the process according to the invention. general formula II can be used in a manner known per se
by converting a cycloalkanone of the general
formula

90984 9/0897

-X-

2322270

Η- »

III

where R ^, Ep »R * and η are defined as above, with Ethanolamine (J.A.C. p. 75 [1953], 358).

Furthermore, according to the invention, plant protection agents which contain 1 or more compound (s) according to the invention as protective agent (s) or antidote or antidote, optionally together with 1 or several herbicide (s) and / or solid and / or liquid carrier (s) and / or diluent (s) and / or dispersants (s) and / or emulsifying agent (s) and / or other surface-active agent (s), for example wetting agent (s) are marked. The compounds according to the invention namely, as already mentioned, have valuable protective effects on herbicides.

The crop protection agents according to the invention can be used in the customary manner or in or on the

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Ground. Also the direct treatment of the Planting or dressing the grains is possible.

The compounds of the general formula I according to the invention can either be used together with the herbicidal agents or in the form of independent agents (without herbicidal active ingredient), in the latter case before or after the treatment or can be used simultaneously with the herbicidal agents.

The compounds according to the invention reduce as protective agents especially the damaging effect of the thiocarbamates as active ingredients on the crop plants herbicidal agents. The compounds according to the invention also enable the safe use of such Agents containing thiocarbamates as active ingredients, in which the dose effective on the weeds and that on the crop plants are not yet close to each other or overlap with the phytotoxic dose. But it is also to be considered draw that the effectiveness of the herbicidal agents is also influenced by the composition of the soil and by the weather will.

The plant protection agents according to the invention therefore preferably contain Λ or more thiocarbamate derivative (s) as herbicide active ingredient (s).

It is also preferred to spray the plants with crop protection agents according to the invention which do not contain any herbicidal active ingredients before or after the treatment or simultaneously with thiocarbamates as herbicidal active ingredients for reduction or inhibition of the phytotoxic activity of the same to treat.

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49.

The effect of compounds according to the invention as protective agents on herbicidal agents was demonstrated in a greenhouse cultivated plants examined. In 30 cm χ 40 cm χ 10 cm Large parcels of organic matter were filled in with free quartz sand, causing the surface of the soil to settle S-ethyl-N, N-di-n-propylthiocarbamate containing herbicides Agent in an amount of 10 kg active ingredient / ha and at the same time an N- (dichloroacetyl) -6,6,8- (trimethyl) -1,4-oxaza- -spLro [4,4] nonane or N- (dichloroacetyl) -7,7,9- - Plant protection product containing (trimethyl) -i, 4-oxaza-spiro [4,5] decane in quantities of 0.1 kg active ingredient / ha ^ T- (dichloroacetyl) -6,6,8- (trimethyl) ~ 1,4-oxaza- -spiro [4,4] nonane} or 1 kg active ingredient / ha {n- (dichloroacetyl) -7,7,9- (trimethyl) -i, 4-oxaza- -spiro [4,5] decane} sprayed and then worked into the soil became. The grains of the crops and the weeds were grown in the soil thus prepared.

No plant treatment was carried out as a blind test and as comparative experiments, plants with an S-ethyl-NjN-di-n-propylthiocarbamate were used as the active ingredient herbicidal agents or with a mixture of a S-ethyl-NiN-di-n-propylthiocarbamate as active ingredient in an amount of 10 kg / ha containing agent and a NjN-diallyl-dichloroacetamide as protective agent respectively Treated antidote active ingredient in an amount of 1 kg / ha containing pesticides.

The plots were kept at 21 to 32 ^° G in greenhouses and watered according to the favorable development of the plants.

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The evaluation was 3 "to 6 weeks after that treatment in terms of selectivity and phytotoxicity.

The plants examined were as follows: maize (Zea mays), oats (Avena sativa), poppy seeds (Papaver somniferum), Red clover (Trifolium pratense), Sinapis alba, Panicum capillare, Setaria viridis and chicken millet (Echinochloa crus-galli).

The results are compiled in the following table.

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- 10 table

CO

CD οο

CD O

co

CD·

middle Herbicide v
Art fuel
Application rate
in
kg / ha Protective effect
Art ; off
AutWall amount
in
kg / ha Results concerning the plants Green weight
of the corn
in
kg / parcel number of
plants
piece Corn / g Certainly
piece cht
β S-ethyl-N, N-di-
-n-propylthio-
carbamate 10 N- (dichloroacetyl) -6,6,8-
- (trimethyl) -i, 4-oxaza-
-spiro [4.4] nonane 0.1 Healthy
plants 111 91 1.11 80 97 S-ethyl-N, N-di-
-n-propylthi o-
carbamate 10 - (trimethyl) -i, 4-oxaza-
-spiro [4.5] decane 1 100 105 92 1.20 80 95 S-ethyl-N, N-di-
-n-propylthio-
carbamate 10
(Ver _f Sieichsversuch} - 98 103 84 1.09 80 94 S-ethyl-N, N-di-
-n-propylthio-
carbamate
[Mixture ν
N, N-dially 10
on S-ethyl-N, N-
1-dichloroacetai
{Ver ( N, N-diallyl
-dichlor-
acetamide
-di-n-propyl thiocarbamate
nid in weight ratio
; cessation trial} 1
with
from 10: 1] 94 100 88 ' 1.03 80 86 - ^ Blind versi oh [no treatment]} - 97 114 93 1.14 80 97 100

I '

CD to ro ro -j ο

From the data in the table above it can be seen that the compound according to the invention N- (dichloroacetyl) -6,6,8- - (trimethyl) -1 / l - oxaza-spiro [4-, 4-] nonane the cultivated plants at an application rate of 0.1 kg / ha, i.e. in an amount of 1% by weight, based on the herbicide active ingredient, against the damaging effect of the said thiocarbamate containing S-ethyl-NjN-di-n-propylthiocarbamate as an active ingredient herbicidal agent protects, the herbicidal effect is the same. The well-known Ν, Ν-diallyl dichloroacetamide Containing pesticides, on the other hand, still has a somewhat less than equal protective effect only in one Application rate of 1 kg / ha, i.e. in an amount of 10% by weight, based on the same herbicide active ingredient. Even the protective effect of the compound according to the invention N- (dichloroacetyl) -7,7,9- (trimethyl) -1,4-oxaza- -spiro [4,5] decane at an application rate of 1 kg / ha becomes the well-known N, N-diallyl-dichloroacetamide at the same application rate not reached yet.

The compounds according to the invention can also be used in herbicidal agents which contain 2 or more active ingredients are present. One of the components is advantageous here of the herbicidal agent is a thiocarbamate derivative.

When using the compound (s) according to the invention serving as protective agents together with a herbicidal agent it is appropriate to use the former or the former in the same way as the herbicidal agent, wherein the inventive compound (s) with the herbicidal agents mixed in the form of the usual agents of this type is brought to the treatment area or will.

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The amount of the present invention serving as protectants Compound (s) depends, inter alia, on the type of weeds, on the crop plants, on the herbicidal agent and on the desired effect. In general, good results can be achieved if the (s) according to the invention Compound (s) in an amount of 0.001 to 50% by weight, preferably 0.1 to 10% by weight, based on the herbicidal active ingredient, is or are used.

When using the compound (s) of the general formula I according to the invention as a mixture with a herbicidal Medium, the total active ingredient content of the preparation can be advantageous 0.1 to 95% by weight.

When using the compound (s) according to the invention general formula I in the form of an independent agent can or can advantageously be used in this as Compound (s) according to the invention serving as a protective agent are present in an amount of 0.1 to 95% by weight, preferably 0.5 to 70% by weight.

Examples of solid carriers and diluents are talc, silica gel, aluminum silicates, tricalcium phosphate, Kaolin, bentonite and other ground mineral substances.

Examples of liquid carriers and diluents are hydrocarbons and their derivatives, such as toluene, xylene and Acetophenone, polar solvents and mineral, vegetable and animal oils.

The surfactants can be ionogenic or anionic in nature. Examples of surfactants Agents are condensation products of ethylene oxide

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(Ethylene dioxide) with nonyl- or octylphenol, Alkali and alkaline earth salts of sulfonic acid esters and sulfonic acid derivatives and salts of lignosulfonic acid.

The crop protection agents according to the invention can be used in Usually by spraying, atomizing, pickling or dusting in the form of spraying agents, solutions, suspensions, Emulsions, casting agents (abrasives), dusts or Granules are used.

It is generally advantageous to start from a concentrated solution that is available in the field of use can be diluted to the appropriate concentration or mixed with the herbicidal agent.

The invention is explained in more detail by means of the following examples.

example 1

N- (dichloroacetyl) -6,6,8- (trimethyl) -1,4-- -oxaza-spiro [4-, 4-] nonane

It was made by adding 6.21 g (0.1 mol) of ethanolamine to a mixture of 80 cnr benzene and 12.61 g (0.1 mol) of 2,2,4-trimethylcyclopentanone and heating for 3.5 hours of the reaction mixture to boiling with constant removal of the resulting water solution of 6,6,8- (trimethyl) -1,4-oxaza- -spiro [4,4] nonane in benzene 10.12 g (0.1 mol) of triethylamine added at a temperature below 1'5 ⁰ C, whereupon at a temperature of 0 to 15 ° C with cooling and stirring

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or shaking in portions 14.74 g (0.1 mol) Dichloroacetyl chloride were added. The reaction was strongly exothermic. Thereafter, the reaction mixture was at Stirred or shaken for 0.5 hour at room temperature. Water was used to dissolve the obtained salt added and the benzene phase was separated, washed with an aqueous sodium bicarbonate solution and water and dried over anhydrous sodium sulfate. The benzene solution was filtered and washed with a little benzene, whereupon the Solvent was distilled off. The product was 20.4 g (72.9% of theory) N- (dichloroacetyl) -6,6,8- (trimethyl) · -1,4-oxaza-spiro [4,4] nonane was obtained as a yellow liquid with an nj- ° value of 1.4892.

Example 2

N- (dichloroacetyl) -7,7,9- (trimethyl) -1,4- -oxaza-spiro [4.5] decane

There were by adding 6.21 g (0.1 mol) of ethanolamine to a mixture of 80 cm- * benzene and 14.01 g (0.1 mol) of 3 »3» 5-trimethylcyclohexanone and 4.5 hours long heating of the reaction mixture to boiling with constant removal of the water obtained Solution of 7 »7» 9- (trimethyl) -1,4-oxaza-spiro [4.5] decane in Benzene 10.12 g (0.1 mol) of triethylamine was added, whereupon at a temperature of 0 to 15 ° C with cooling and stirring 14.74 g (0.1 mol) of dichloroacetyl chloride were added in portions or by shaking. After that, that became The reaction mixture was stirred or shaken at room temperature for 0.5 hour. To solve the received

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Salt was added to water and the benzene phase was separated with an aqueous sodium bicarbonate solution washed and dried over anhydrous sodium sulfate. The benzene solution was filtered, followed by the solvent was distilled off. After cooling, the product was 22.4 g (76.2% of theory) of N- (dichloroacetyl) -7,7,9- - (trimethyl) -i, 4-oxaza-spiro [4,5] decane in crystalline form Form obtained with a melting point of 121 to 123 ° C.

Claims

909849/0897

Claims (8)

-yC- 2322270 claims 1.) N- (chloroacetyl) -1,4-oxaza-spiro hydrocarbon derivatives the general formula Cl - HO I H c -σ Cl wherein stands for a lower alkyl radical, and E, independently of one another, hydrogen or lower alkyl radicals mean and Is 0 or 1. 9098 49/0897 2522270 2.) N- (chloroacet; yl) -1,4-oxaza-spiro-hydrocarbon derivatives according to. Claim Λ , characterized in that the lower alkyl radical for which H ^ stands and / or the lower alkyl radical or lower alkyl radicals for which Ep and / or R can stand, one or those with 1 or 2 Carbon atoms is or are. ·) N- (Chlorace tyl) -1,4-oxaza-spiro-hydrocarbon derivatives according to claim 1 or 2, characterized in that they of 3 lower alkyl radicals for which E ^, ^ ^ ¹ · ³ · ^R z are 2 in the same Have the position of the spiro-hydrocarbon ring. 4) IT- (dichloroacetyl) -6,6,8- (trimethyl) -1,4-oxaza- -spiro [4.4] nonane. 5.) N- (dichloroacetyl) -7,7,8- (trimethyl) -1,4-oxaza- -spiro [4.5] decane. 6.) N- (dichloroacetyl) -7,7,9- (trimethyl) -1,4-oxaza- -spiro [4.5] decane. 7 «) Process for the preparation of the compounds according to claim 1 to 6, characterized in that one a 1,4-oxaza-spirohydrocarbon derivative of general formula 909849/0897 2322270 H-N wherein R ^, I ^ »^ ^R * ^{1 η} * ^{η r as the Ans} üchen P 1 is set to 3, in the presence of an acid-binding agent with dichloroacetyl chloride is reacted. 8.) Plant protection products, characterized by a content of 1 or more compound (s) according to claim 1 "to 6 as protective agent (s), optionally together with 1 or more Herbicide (s) and / or solid and / or liquid carrier (s) and / or diluent (s) and / or Dispersant (s) and / or emulsifier (s) and / or other surface-active agent (s). 909849/0897 2322270 9) Plant cleaning agents according to claim 8, characterized in that they are used as herbicide (s) Contain 1 or more thiocarbamate derivative (s). 909849/0897