CH657847A5 - 2- (1-OXIMINO-BUTYL) -5- (2-AETHYLTHIOPROPYL) -3-OXY-2-CYCLOHEXENONE, HERBICIDE COMPOSITIONS THAT CONTAIN AND METHOD FOR CONTROLLING WEEDERS. - Google Patents

Description

The present invention relates to substituted 2- (l-oxi-mino-butyl) - 5- (2-ethylthiopropyl) -3-oxy-2-cyclohexenones. These new compounds have a herbicidal activity and they can be used as an active ingredient in herbicidal compositions.

Cyclohexane-1,3-diones, which have a herbicidal activity, are described in the US Pat. No. 4,011,256 and in the Swiss Pat. No. 648,547, which do not belong to the prior art.

io It has now surprisingly been found that new

2- (l-oximino-butyl) -5- (2-ethylthiopropyl) -3-oxy-2-cyclohexenones which are substituted with a haloalkenyl group or a halogenaryl group are particularly well suited to combating grass-like weeds , both before

15 occurrence, i.e. in the preliminary process, as well as after their occurrence, i.e. in the follow-up process. The new compounds according to the invention also have excellent resistance in the soil.

The present invention therefore relates to 20-substituted 2- (l-oximino-butyl) -5- (2-ethylthiopropyl) -

3-oxy-2-cyclohexenones, which are characterized in that they have the following formula I

25th

30th

35

V / 0

-R1

(I)

have in which R is a propyl radical, 40 R1 is a trans-3-chloroallyl radical or 4-chlorobenzyl radical, one of the two radicals R2 and R3 denotes a hydrogen atom and the other of these two radicals is a 2-ethyl-thiopropyl radical, and

R5 is a hydrogen atom, a cation or a grouping of the formula

O

-CR6

50

is what

R6 is an alkyl group with 1-6 carbon atoms, a phenyl radical or a naphthyl radical, where, when R5 is a hydrogen atom or a cation, the compound of the formula I can also be present in the tautomeric dione form.

The present invention furthermore relates to herbicidal compositions which are characterized in that they comprise, as active ingredient, a 2- (1-ox-6o imino-butyl) -5- (2-ethylthiopropyl) -3-oxy-2-cyclohexenone according to the invention Formula I included.

The present invention further relates to a method for controlling weeds, which is characterized in that a herbicidally effective amount of a compound of the formula I according to the invention is applied to the plants or to the point where the plants grow or will grow.

The inventive have been particularly advantageous

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Compounds for combating grass-like weeds have been proven, for example for combating finger grass with the Latin name Digitarla sanguinalis, for wild oats with the Latin name Avena fatua and in particular for controlling water grass with the Latin name Echinochloa crusgalli.

Of the compounds of the formula I, those in which the R1 radical is a trans-3-chloroallyl radical are particularly preferred because these compounds have particularly desirable phytotoxic properties.

The salts of the compounds according to the invention, i.e. those compounds of formula I in which R5 is a cation are of interest because they have good solubility and are particularly easy to formulate.

Those compounds according to the invention which are esters, in which the radical R5 is for a grouping of the formula

O

II

-CR6

5 is of interest because it then hydrolyzes outdoors and forms the corresponding starting compound in which R5 is a hydrogen atom.

Typical examples of groups R5 in the compounds according to the invention are the following groupings: io a hydrogen atom, the cations ammonium, sodium, potassium and calcium, and the acyl radicals acetyl, propionyl, butyryl, isobutyryl, isovaleryl, 3,3-dimethylbutyryl, benzoyl , 1-naphthoyl and 2-naphthoyl. The preferred meaning for the radical R5 is a hydrogen atom. 15 The compounds of formula I according to the invention can be prepared according to the following reaction scheme:

(II)

0

+ RCX

0

OCR

+ HX (1)

(IIa)

(III)

R 0

\ / •

III

A1C1.

Oli

(2)

R2 V

(purple)

Illa + H ^ OR1 • HCl

(IV)

OH- H ~ 0

+ (3)

HCl

(Ia)

In the starting materials of the formula IIa which are used to carry out the first reaction stage, X denotes a halogen atom. In the third reaction stage, purple starting materials of the formula IV are required to convert the ketone of the formula. These can be prepared according to the following reaction scheme:

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4th

NOH + R Cl

-r

NOR1 + HCl

(4)

(V)

(Va)

(VI)

VI

Hydrazine

2. HCl

H2NORJ

HCl

(5)

(iv;

In the third stage of the above-mentioned reaction scheme, compounds of the formula Ia are obtained as the end product, in which the radical R5 is therefore a hydrogen atom.

If it is desired to prepare compounds of the formula I in which the radical R5 has a different meaning than that of a hydrogen atom, this can be carried out using customary working methods. If, for example, a hydroxy compound of the formula Ia is treated with a suitable basic salt, corresponding compounds of the formula I in which R5 is a cation are obtained, for example Na +, NH4 +, Ca ++, etc. In the same way, the hydroxy compounds of the formula Ia acylate by treating them with a suitable compound introducing the acyl radical, for example with a corresponding acid halide, and compounds are then obtained in which the radical R5 has the meaning of an acyl radical of the formula

O

II

-CR6

having.

In the reaction scheme mentioned above, the first reaction step can be carried out by operating at room temperature and using essentially equimolar amounts of the dione of formula II and the acid halide of formula IIa. The corresponding acid chloride, in which X is a chlorine atom, is preferably used as the acid halide. The reaction can be carried out in an organic solvent, such as in halogenated hydrocarbons, ethers or glycols. Preferably a base is present, such as an organic amine or an alkali metal carbonate salt. This base serves to bind the hydrogen halide formed in the reaction. Preferred organic amines used for this purpose are pyridine and trialkylamines, such as triethylamine. Pressure conditions are critical and atmospheric pressure is commonly used.

The second reaction stage can be carried out in an inert organic solvent, for example in halogenated hydrocarbons or ethers. At least two moles of aluminum chloride are used per mole of the ester of formula III used in this stage. When working up, the crude product must be decomposed with a proton-providing substance, that is to say a protonator, preferably a mineral acid, such as, for example, hydrochloric acid, so that the trion of the formula purple forms.

The third stage is a common condensation

in which an oxime forms. Since the 2o hydrochloride salt of the compound of formula IV is used as the starting material, this is first neutralized with a base, preferably an alkali metal alkoxide, before this mixture is carried out with the trione. It is also possible to use directly the base which is formed in the corresponding stage 5 25 of the production process for the starting product of the formula IV in the reaction with the hydrazine. The third reaction stage can be carried out in an inert organic solvent, preferably in a lower alcohol.

30 In the preparation of the starting material of the formula IV, reaction stage 4 is a conventional alkylation. This can be carried out in inert organic solvents, such as, for example, in dimethyl sulfoxide, acetic acid, ethers, glycol ethers or hydrocarbons. The reaction is carried out in the presence of a base, such as potassium carbonate. It runs at room temperature.

The reaction stage 5 40 used in connection with the preparation of the starting material of the formula IV can be carried out at elevated temperatures, preferably at temperatures in the range from 30-100 ° C. The phthalimide of the formula VI obtained as an intermediate is preferably heated to the reflux temperature at atmospheric pressure with a small molar excess of hydrazine in an inert organic solvent. A lower alcohol may be mentioned as an example of an inert solvent. The crude mixture is then cooled and it is optionally decomposed with a mineral acid, preferably with hydrochloric acid, so that the product of the formula IV thus obtained is in the form of its salt. However, it is possible to use the free base that has formed directly in reaction stage 3 of the above-mentioned reaction scheme.

Instead of producing the trione of formula lilac according to reaction stages 1 and 2 described above, this trion can also be produced in a single reaction stage by preferably using the dione of formula II with the acid halide of formula IIa in a halogenated hydrocarbon as solvent Carbon tetrachloride, treated in the presence of trifluoromethylsulfonic acid. Typically, the reaction is typically carried out at an elevated temperature, for example in the range of 30-150 ° C., and is complete within 90 hours, but gives a mixture on products. Since the total reaction time for reaction stage 1 and reaction stage 2 6S is about 24 hours and leads to purer products, the two-stage reaction procedure via reaction stage 1 and reaction stage 2 is preferred over the one-stage alternative reaction procedure.

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The starting materials of the formula II can be prepared according to the compounds of the known working processes or obvious modifications required as starting product.

NEN of working processes are prepared, for example, be prepared by the following, illustrated by the following by substitution of certain starting materials by reaction equations:

suitable other starting materials. 5

R-

O

0

II

C = CHC-CH3 + H9C (COR4 ') 9)

'"(l:

ir

(A)

(B)

IIa base

2)

(C)

COH

y

(3)

O

O

fr

R- R "5

11 b

In the reaction scheme given above, R4 'is an alkyl radical with 1-3 carbon atoms and the radicals R2 and R3 have the same meaning as in formula I.

These reactions are well known types of reactions and they can be carried out in the usual way. The first reaction step of this manufacturing process described above can typically be carried out by contacting the compound of formula A with the compound of formula B and a base, for example an alkali metal alkoxide, using conditions under which the reaction proceeds. It is preferable to work in an inert solvent, for example an alkanol, such as ethanol. Typically, the reaction is carried out at a temperature in the range of 60-110 ° C by adding about 0.5 to about 1.5 moles, preferably 0.9 to 1.1 moles, of the compound of formula A and the base per mole of Compound of formula B uses.

In the second reaction step, the ester grouping of the compound of formula IIa is hydrolyzed with a base, the corresponding free carboxylic acid being formed. This hydrolysis can be carried out, for example, by contacting the compound of the formula IIa with metallic sodium in an alkanol, for example ethanol, or by treating with alkali metal hydrogen at temperatures in the range from 60-110 ° C. By combining the reaction steps 1 and 2 can be carried out together.

In the third reaction step, the compounds C can be decarboxylated by carrying out a treatment with a strong inorganic acid, such as, for example, hydrochloric acid or sulfuric acid. This reaction step is typically carried out at temperatures in the range from 25-110 ° C. and it can advantageously be carried out in situ after the basic hydrolysis, that is to say process step 2, has been completed.

The compounds of the formula purple can also be prepared by using the compounds of the formula II

30 an appropriate acid anhydride in the presence of an organic base, preferably using an excess of anhydride or using an inert solvent. Typically, this reaction can be carried out at temperatures ranging from about 35 to about 50-100 ° C using about 5 to 0.5 moles of anhydride per mole of the compound of formula II.

The respective products that form in the reactions described above can be isolated and purified by conventional procedures, for example by chromatography, by distillation, by crystallization and similar procedures, where appropriate.

Those compounds of the formula I according to the invention in which R5 is a hydrogen atom or a cation 45, as already mentioned, can also be present in the tautomeric ion form, which is illustrated by the following formula:

50

55

60

65

-R1

Other tautomeric forms in which these compounds can exist are as follows:

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H- 0

All of these tautomeric forms of the compounds of formula I have a total of three double bonds, one or two of which are carbonyl groups.

In the present description, under the term "oxyaminobutylidene" and under the term "oxyimino-butyl" is a radical of the following formula

CH3- (CH2) 2-C = N-O-R1

to understand, wherein in this formula R1 can be a trans-3-chloro-lylrest. In this case, the residue shown above can be referred to as the “l- (3-chloroallyloxyamino) butylidene residue” or as the “l- (3-chloroallyloxyimino) butyl residue”.

As is well known to a person skilled in the art in the case of compounds of the formula I in which the radical R5 is a hydrogen atom, these compounds are generally referred to as “cyclohexane-1,3-dione” and not as “3 -Hydroxycyclohex-2-en-l-one ».

The invention will now be explained in more detail by means of examples.

example 1

Preparation of trans-2- [l- (3-chloroallyloxyimino) butyl] -5- (2-ethylthiopropyl) cyclohexane-1,3-dione

Process stage (a)

86.6 g of crotonaldehyde was added dropwise to a mixture containing 64.0 g of ethanethiol and 2 ml of triethylamine in 500 ml of acetic acid nitrile. The addition took place at room temperature, i.e. about 20-25 ° C. The resulting mixture was stirred at room temperature overnight, namely for about 15 hours, and then evaporated on a rotary evaporator to remove the acetic acid nitrile. The residue was dissolved in 300 ml of dry diethyl ether, washed twice with water, dried over magnesium sulfate and then concentrated by evaporation. This gave a yellow, liquid concentrate on the ß-ethyl-thiobutyraldehyde.

Process stage (b)

A mixture containing 15.9 g of the β-ethylthiobutyraldehyde and 38.2 g of triphenylphosphoranylidene-2-propanone in 300 ml of methylene chloride was refluxed overnight and then evaporated to give a thick residue. This residue was mixed with hexane and filtered. The filtrate was evaporated in vacuo and the residue was then distilled in vacuo to give the 6-ethylthio-3-hepten-2-one.

Process stage (c)

2.53 g of metallic sodium was added to 100 ml

Add ethanol at room temperature. 17.6 g of diethyl malonate were then added to this material, with stirring, and then 17.2 g of 6-ethylthio-3-hepten-2-one. The mixture thus obtained was then refluxed for four for 5 hours, and then an aqueous sodium hydroxide solution containing 9.5 g of sodium hydroxide in 75 ml of water was added. The mixture was then refluxed for a further two hours.

The mixture was then cooled to 50 ° C and then acidified by adding concentrated hydrochloric acid. The mixture was then heated until the decarboxylation was complete and then evaporated off, leaving a liquid residue. This residue was mixed with diethyl ether, washed with water and then evaporated to give a brown liquid. The liquid was basic, and extraction with acid gave the 5- (2-ethylthiopropyl) cyclohe-xan-1,3-dione.

20th

Process stage (d)

0.2 g of metallic sodium was dissolved in 1 ml of methanol and then 3.2 g of 5- (2-ethyl-thiopropyl) cyclohexane-1,3-dione was added. Then 25 20 ml of butyric anhydride were added and the mixture was refluxed for three hours.

Then the mixture was evaporated and the residue was mixed with methylene chloride and then shaken with an aqueous sodium hydroxide solution containing 30 5% by weight of sodium hydroxide. The basic extract was then washed with methylene chloride, then acidified with concentrated hydrochloric acid and the product extracted into methylene chloride. The methylene chloride was then evaporated to give 2-buty-35 ryl-5- (2-ethylthiopropyl) cyclohexane-1,3-dione.

Process stage (s)

0.38 g of sodium methoxide in 10 ml of methanol and 1.0 g of 3-chloroallyloxyamine hydrochloride of the formula 40 H2NOCH2CH = CHC1 were mixed together and then stirred for 10 minutes at room temperature. 2 g of the 2-butyryl-5- (2-ethylthiopropyl) cyclohexane-1,3-dione were added and the resulting mixture was stirred at room temperature for about two days. This mixture was then concentrated by evaporation and the concentrate mixed with 60 ml of diethyl ether and 40 ml of water. The ether layer was shaken with 40 ml of a 2% by weight aqueous sodium hydroxide solution, washed with 20 ml of water, dried over anhydrous magnesium sulfate and then evaporated to give a smaller amount of the compound mentioned in the form of the trans isomer.

The extract obtained using the 2% sodium hydroxide solution was acidified using 6 nor-55 maier hydrochloric acid until a pH of about 1 was reached. The mixture was then shaken with 100 ml of methylene chloride. The organic layer was washed with 40 ml of water, dried over magnesium sulfate and then evaporated to give the trans-isomer of the compound mentioned in title 60 as a residue. This compound is Compound 1, which is given in Table A below. Most of the compound mentioned in the title was obtained from the sodium hydroxide extract.

65

Example 2

This example explains the preparation of acyloxy compounds according to the invention.

7 657 847

To a reaction mixture which produces 3.0 g (0.01 mol) of the liquid fruit in various fruit trees.

2- [l- (3'-Chloroallyloxyimino) butyl] -5- (2-ethylthiopropyl) - to call.

cyclohexane-1,3-dione and 0.87 g (0.011) mol) of pyridine in The compounds according to the invention can be in any

Containing 20 ml of methylene chloride and which are used at a temperature of a variety of compositions, stirred from 0 ° C, 0.89 g (0.011 mol) of acetic acid are added. In general, these compounds can be added with a tra-acid chloride. The mixture is then stirred at room temperature material of the type used and more usually for 2 hours. The wise man will then be used in this field, diluted and worked up by washing it with water, over which, and as examples of carrier materials, inert solid anhydrous magnesium sulfate should be dried and filtered. This is called fil- tics, water and organic liquids.

stepped is evaporated under vacuum, the product i0 The compounds according to the invention are contained in such i-das 3-acetyloxy-2- [l- (3'-chloroallyloxyimino) butyl] - 5- (2- gene compositions in sufficient quantity ethyl thiopropyl ) -cyclohex-2-en-1-one receives. so that they have their herbicidal effects or their growth

In a similar way, the second would be able to exert a regulatory effect. Usually, the compounds given in Table A are converted into the corresponding 3-acetone from 0.5 to 95% by weight, based on the total weight of oxyderivate, in accordance with the compounds according to the invention in a set of working processes described. of the formulations.

Solid compositions can be made using Example 3 of inert powders. The composition

Based on this example, the production of salt tongues can accordingly be homogeneous powder, which explains the compounds according to the invention. 20 as such or diluted with inert solids, in the form of

To 3.0 g (0.01 mole) of the 2- [1- (3'-chloroallyloxyimino) dust, or they can be in any suitable butyl] -5- (2-ethylthiopropyl) cyclohexane-1,3 -dione are suspended in 10 ml of liquid medium in order to then add 0.4 g (0.01 mol) of sodium hydroxide, in the form of egg-acetone, to a spray. The powder contains dissolved in 2 ml of water. The solvents are mixed under vacuum with the active ingredient being evaporated under a reduced vacuum, the sodium salt being used in relation to the 25 quantities of conditioning agents. Natural keys,

3-Hydroxy group of 2- [l- (3'-chloroallyloxyimino) butyl] -3- which are either absorbent, such as attapulgite, or rather hydroxy-5- (2-ethylthiopropyl) cyclohex-2-en-l-ones receives. are not absorbent, like china clay, diatomaceous earth,

Similarly, using the same synthetic materials containing fine silica, working process, the sodium salt of the second of the compounds listed in, for example, silica, calcium silicate and other inert Table A below, became solid support materials of the type which they normally hold. can be used in appropriate powdered

The usefulness of the herbicidal compositions according to the invention will subsequently be used. These connections explained in more detail. active ingredient is usually between 0.5

The compounds according to the invention are very general% by weight to 90% by weight, based on the total weight of the herbicidally active compounds, both in the case of 35 powder compositions. The solids should usually be used in finely divided form before the weeds appear, ie in the advance loan. For the conversion process, as well as for use after the appearance of the powder in dusts, talc, pyrophyllite, weeds are usually used, that is to say in the wake process. or the like used.

When used in the pre-process to control unwanted plant growth, the herbicidal 40 liquid compositions containing the active compounds according to the invention in a herbicidal amount as described above active compounds are applied at the location or on the growth medium where can be prepared by to grow the connective in question-the plants, ie on the soil that is fertilized with seed fertilized with a suitable liquid diluent or seedlings of such plants. Mixed by one. Typical examples of liquid media which are used to inhibit growth or which are normally used are methanol, benzene, toluene seeds, the germinating seeds and the seedlings are stripped and the like. The active ingredient lies in such river-killed. compositions usually in an amount of

When used in the after-run process, the herbicides are about 0.5 to about 50% based on these liquid compound active compounds directly on the leaves or preparations. Some such compositions have applied to their plant parts. 50 are intended for use as such and others

In general, the herbicides according to the invention are to be diluted particularly effectively against grass-like compounds before use with large amounts of water-active compounds.

Weeds and, by appropriately adjusting the dosage compositions in the form of wettable powders, they can be safely applied to or compositions in the form of liquids,

Combating grasses and the occurrence of grasses in wide 55 can be used as further components to prevent one or more leafy crop plants. The agents active according to the invention, such as, for example, wetting agents, show outstandingly good ingredients, dispersants and emulsifiers. The surface activity in the floor. This is particularly advantageous where agents cause wettable powders or liquids to be used in the preliminary process. can be easily dispersed or emulsified in water.

60 NEN, then using aqueous, sprayable materials If you get the compounds of the invention at.

plants growing above ground in such a way The surfactants that are applied

The amount that these compounds use, the useful plants cannot kill those of the anionic type, the cationic type, then they also show the active, the plant or the non-ionic type. These include growth-regulating or delaying effects and, for example, the sodium salts of long-chain carboxylic acids, Al compounds can, for example, be used with advantage alkyl-aryl-sulfonates, sodium-lauryl sulfate, polyethylene oxides, lignin sulfonates and the growth of the secondary buds in plants other surfactants, to prevent or delay and to thinning out- If you want to do a preliminary treatment,

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then it is desirable to include a fertilizer, an insecticide, a fungicide or another herbicide.

The amount of active compound or herbicidal agent used depends on the particular part of the plant or plant growth medium with which this active compound is to be contacted and also on the general place of application. This is to be understood as whether it is, for example, protected areas, such as a greenhouse, or areas exposed to the weather, such as fields. Furthermore, the amount also depends on the type of control desired.

In general, both for weed control in the preliminary process and in the subsequent process, the compounds according to the invention are applied in amounts which are in the range from 0.2 kg / ha to 60 kg / ha, preferred amounts in the range from 0.5 kg / ha ha up to 40 kg / ha.

If you want to achieve a plant growth regulating or retarding effect, then it is essential to use the compounds in a concentration that is not so great that they would kill the plants. Therefore, in general, if one wishes to achieve a regulation of plant growth or a delay in plant growth, the application rates will be lower than the application rates used to kill the plants. In general, such amounts regulating or delaying plant growth will be in the range from 0.1 to 5 kg / ha and preferably in the range from 0.1 to 3 kg / ha.

Herbicidal tests were carried out using typical examples of compounds according to the invention, the following working methods being used.

Herbicidal test before emergence

An acetone solution of the compound to be tested was prepared by mixing the following components:

500 mg of the compound to be tested,

158 mg of a non-ionic surfactant and 20 ml of acetone.

20 ml of this solution was then added to 80 ml of water, and the test solution was thus obtained.

Seeds of the test plants were placed in a pot of soil and the test solution was uniformly sprayed onto the surface of the soil at a dose of 27.5 micrograms / cm 2. The pots were watered and taken to a greenhouse. The pots were watered again and again afterwards and the development of seedlings, the health of the developing seedlings and similar phenomena were observed over a period of 3 weeks. At the end of this time, the herbicidal activity of the compounds was graded based on the physiological observations.

For this purpose, a grading scale ranging from 0-100 was used, in which the grading 0 indicated that no phytotoxicity could be detected, and the value 100 indicated that complete mortality had occurred. The results of these tests are summarized in Table I.

Table 15 below lists the 15 compounds tested. The compounds tested corresponded to Formula Ia

R

20th

/

NO R

(Ia)

35

wherein in this formula Ia R is a group of the formula

CH3CH2CH2-

means

R2 was a hydrogen atom and 40 R3 the meaning of a grouping of the formula

-CH2CHSCH2CH3

I.

CH3

45

exhibited.

The compounds tested in Table A were oils.

50

Table A

Compounds of formula Ia

Connection No.

1

R1

-CH2CH = CHCl (trans)

-CH2

O

-ci

Results of the elementary analysis H

N

Ber.

Gef.

Ber.

Gef.

Ber.

Gef.

57.82

57.03

7.55

7.42

3.76

3.72

62.32

61.54

7.13

7.14

3.30

2.93

In the following tests, the herbicidal activity of the compounds listed in Table A was also tested in a preliminary process by spraying these compounds in the form of dilute solutions on the earth's surface in various dosages. The results of these tests are summarized in Table II.

Follow-up herbicide tests

In these tests, the compounds to be tested were formulated in the same manner as mentioned above for the tests in the preliminary process. The formulations in question were evenly sprayed onto two similar flower pots containing 24-day-old plants. Here

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there were approximately 15-25 plants per pot, and the no phytotoxicity and 100 meant complete dosing was in the plants killed together in Table I. Results of these tests are in the simulated tests 27.5 micrograms / cm2. After compiling the following table I In subsequent plants were dry again after this spraying process, this procedure was repeated, placing them in a greenhouse and then pouring 5 diluted test solutions that were used on top of them again and again at the bottom of the plants, depending on the tests - The surface of the pots sprayed in different doses as needed. The plants have been periodic. The results of these tests are checked in Table II for phytotoxic effects and also the physiological compilation.

see response and morphological response to these. In Table I, the percent control treatment was determined. After three weeks, the 10 ben, namely the value in the preliminary process and besides herbicidal activity of the compounds was rated, namely the value in the subsequent process, separated by a slant based on these observations. stroke. In both cases, the application amount was 27.5

A grading scale was also micrograms / cm2 in the follow-up procedure.

turns that ranged from 0-100. In this case, 0 meant

Table I

Herbicidal activity and percentage control

dungNo. L M P C W

1 0/40 0/20 0/0 100/100 100/100

2 0/30 0/10 0/18 100/100 100/100

O

100/100 100/100

The weeds tested in Table I were the following:

L = Lambsquarter, white goose foot, Chenopodium album

M = mustard, mustard, Brassica arvensis P = pigweed, foxtail, Amaranthus retroflexus C = crabgrass, finger grass, Digitaria sanguinalis W = watergrass, watergrass, Echinochloa crusgalli

25 O = Wild oats, wild oats, Avena fatua

Table II below again shows the values for the herbicidal activity in the preliminary process and behind the slash the corresponding values in the subsequent process.

30 The second column of Table II shows the dosage in micrograms / cm2 in which the compound in question was used.

Table II

Herbicidal activity% control pre / post

Connect

dosage

soy

rice

L

M

p c

W

O

manure No.

beans

1

4.4

2/0

100/100

0/0

0/0

0/0

94/97

100/100

99/100

1.8

0/0

100/100

0/0

0/0

0/0

95/90

100/100

96/100

0.7

0/0

99/100

0/0

0/0

0/0

73/58

98/98

85/100

0.28

0/0

73/82

0/0

0/0

0/0

13/15

58/90

73/87 '

2nd

4.4

5/0

98/100

0/0

0/0

0/0

93/75

100/100

99/100

1.8

2/0

87/100

0/0

0/0

0/0

33/58

100/100

92/100

0.7

0/0

57/97

0/0

0/0

0/0

0/15

98/98

77/98

0.28

0/0

0/62

0/0

0/0

0/0

0/0

10/92

62/82

In Table II, the abbreviations used for many modifications and variations with regard to the herbicidal weed species controlled have the same meaning as in active compounds and with regard to their use

Table I. are possible.

It is clear to those skilled in the art that

C.

Claims (10)

657 847 PATENT CLAIMS 1. Substituted 2- (l-oximino-butyl) - 5- (2-ethylthiopropyl) - 3-oxy-2-cyclohexenones, characterized in that they have the following formula I R \ ^ ° ~ r1 ° X / ^ / 0R " © have in which R is a propyl radical R1 represents a trans-3-chloroallyl radical or 4-chlorobenzyl radical, one of the two radicals R2 and R3 represents a hydrogen atom and the other of these two radicals is a 2-ethyl-thiopropyl radical, and R5 is a hydrogen atom, a cation or a grouping of the formula O II -CR6 ( is what R6 represents an alkyl group with 1-6 carbon atoms, a phenyl radical or a naphthyl radical, where, when R5 is a hydrogen atom or a cation, the compound of the formula I can also be present in the tautomeric dione form. 2. A compound according to claim 1, characterized in that R5 is a hydrogen atom. 3. A compound according to claim 1, characterized in that R5 is a cation. 4. A compound according to any one of claims 1-3, characterized in that R1 is the trans-3-chloroallyl radical. 5. A compound according to claim 4, characterized in that the radical R5 represents a hydrogen atom or a cation. 6. Herbicidal composition, characterized in that it contains a 2- (l-oximinobutyl) - 5- (2-ethyl-thiopropyl) -3-oxy-2-cyclohexenone of the formula I as the active ingredient. 7. Herbicidal composition according to claim 6, characterized in that it contains a compound of formula I as active ingredient according to one of claims 2-5. 8. A method of combating weeds, characterized in that a herbicidally effective amount of a compound of the formula I according to claim 1 is applied to the plants or to the place where the plants grow or will grow. 9. The method according to claim 8, characterized in that fingergrass, Digitaria sanguinalis; Wild oats, Avena fatua; and particularly preferably water grass, Echi-nochloa crusgalh with the compounds of the formula I fought. 10. The method according to claim 8 or 9, characterized in that one uses a connection according to one of claims 2 to 5.