NL8601900A - Weed control agents based on 2-1- (3-CHLOROALLYLOXYAMINO) -ALKYLIDES-5-ALKYLTHIOALKYL-1,3-CYCLOHEXANE. - Google Patents

Description

N.0. 33,940 Weed control products based on 2- [1- (3-CHLOQRALLYLOXYAMINQ) -ALKYLIDES] -5-ALKYLTHIQAUCYL-1,3-CYa0HEXAANDI0N.

Background of the invention

The invention relates to certain trans-2- [1- {3-chloro-allyloxyamino) propylidene} -5- (alkylthioalkyl) -1,3-cyclohexanediones and salts thereof and to the use of such compounds as herbicides .

U.S. Patent 4,440,566, published April 3, 1984, discloses compounds of formula 1, wherein R is preferably an alkyl group containing 1-3 carbon atoms, most preferably ethyl or propyl; Most preferably R * is 3-trans-chloroallyl or 4-chlorobenzyl; R2 and R2 preferably each are an alkyl group with 1-3 carbon atoms or one of the groups R2 and R2 is a hydrogen atom and the other is an alkylthioalkyl group with 2-8 carbon atoms and most preferably R1 and R2 each are methyl or one of the groups R2 and R2 is hydrogen and the other 2 is 2-ethylthiopropyl.

This patent also teaches that these compounds have herbicidal activity against grasses and are safe for broadleaf crops.

Summary of the invention

It has been found that some of the compounds included in U.S. Patent 4,440,556 (ie, of Formula 2} exhibit surprisingly better herbicidal activity than others. Although the compounds of Formula 1 generally have very good herbicidal activity, the excellent herbicidal activity of the present compounds is rare and cannot be predicted in advance.

The present compounds have both pre-emergence and post-emergence phytotoxicity to grasses and have excellent, especially post-emergence herbicidal activity against hand grass, sew there, finger grass, spontaneously emerging corn, spontaneously emerging sorghum, chicken leg, broad-leaf signal grass, sticky herb, red rice, sprangletop, safflower chaff and seed rhizome.

The compounds of formula II exhibit excellent phyto-35 toxicity to grasses even at very low amounts used and can be safely used in those amounts over broadleaf crops. Thus, the compounds are especially useful for controlling grassy weeds in broadleaf crops and especially useful for controlling grassy weeds in soy crops.

The compounds of the present invention can be represented by formula 2, wherein R * is 3-trans-chloroallyl and 2-methylthiopropyl or 2-propylthioethyl.

The invention also includes suitable salts of the compounds of formula 2.

As is known, compounds of the type of formula 2 exist as 10 tautomers. The compounds also have two asymmetric carbon atoms and can also exist as optical isomers. Formula 2 is intended to include the various tautomeric forms and the individual optical isomers as well as mixtures thereof and the various tautomeric and optical isomers as well as mixtures thereof are part of the invention.

The invention also relates to a herbicidal composition comprising a suitable carrier and an amount of the compound (s) according to the invention or mixtures thereof effective for the weed eradication.

The invention also relates to a method for preventing or controlling the growth of undesired grassy plants, which method of treating the growing medium and / or the foliage of such plants with an amount of the compound (s) effective for pest-killing according to the invention or mixtures thereof.

The invention further relates to a method of regulating plant growth which treats the growing medium and / or the foliage of such plants with an amount of the compound (s) effective to control plant growth in deviation from the normal growth pattern. according to the invention or mixtures thereof.

The invention furthermore relates to intermediates and processes for the preparation of the compounds according to the invention.

The invention is further described below.

35

FURTHER DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENTS

The compounds of formula II can be readily prepared by the process shown in Tiet scheme of Figure 1, wherein R1 and r2 are as defined above.

This process can be easily carried out by contacting compound (3) 8601900 * 3 with 3-trans-chloroallyloxyamine (4), preferably in an inert organic solvent.

Typically, this process is performed at temperatures between about 0 and 80 ° C, preferably from about 20 to 40 ° C, for X 5 to 48 hours, preferably about 4 to 12 hours using 1-2, preferably 1 0.05-1.2 moles of 3-trans-chloroallyloxyamine (4) per mole of compound (3). Suitable inert organic solvents that can be used are, for example, lower al channels such as methanol, ethanol; ethers such as diethyl ether; and dichloromethane. Two-phase systems with water and an immiscible organic solvent (eg hexane) and suitable mixtures thereof can also be used as the reaction medium.

Trans-chlorallyloxyamine is a known compound and can be prepared by known methods, for example as described in US patent 4,440,566. A hydrochloride of transchloroallyloxyamine can be used in which the salt is neutralized in situ with an al potassium alkoxide.

The starting materials of formula III can also be prepared according to the general method described in US patent 4,440,566.

The suitable salts of compound 2 can be prepared by conventional methods, for example, by reacting a compound of formula 2 with a base such as, for example, sodium hydroxide, potassium hydroxide and the like with the desired cation. Other variations in the cation of the salt can also be brought about by ion exchange with an ion exchange resin with the desired cation.

GENERAL PROCESS CONDITIONS The reaction product can be prepared in any suitable separation and Method such as, for example, chromatography, is recovered from the reaction mixture. Suitable separation and purification methods are illustrated in the examples below.

Generally, the above-described reactions are conducted as liquid phase reactions and therefore the pressure is irrelevant except for the temperature (boiling point) when reactions are conducted at reflux. Therefore, these reactions are typically conducted under pressures of about 300 to 3000 mm of mercury and are conveniently conducted under about atmospheric or field prevailing pressures.

8601900

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It is noted that if typical or preferred process conditions (eg reaction temperatures, times, mole ratios of reactants, solvents, etc.) are stated, other process conditions could also be adhered to. »Optimal reaction conditions (eg temperature, reaction time, mole ratios, solvents, etc.) ) may vary according to the particular reagents or organic solvents used, but may be determined by ordinary optimization methods.

When mixtures of optical isomers are obtained, the individual optical isomers can be obtained by conventional separation procedures. Geometric isomers can be separated by conventional separation methods depending on differences in physical properties between the geometric isomers. In general, however, it is preferable to allow the reaction to proceed with the desired isomeric starting material.

Definitions

The following terms have the following meanings in this document unless expressly stated otherwise.

The term "2-methylthiopropyl" refers to the group of the formula: CH3 25 -CH2-CH-S-CH3

The term "2-propylthioethyl" refers to the group of the formula 30 -CH2-CH2-S-CH2CH2CH3

The term "suitable salts" refers to salts which do not significantly adversely affect the herbicidal properties of the parent compound. Eligible salts include cation salts such as, for example, the cation salts of lithium, sodium, potassium, alkaline earth metals, copper, zinc, ammonia, quaternary ammonium ions, and the like.

The term "room temperature" refers to 20-25 ° C.

40 Application 19 0 0 * £ wr

The compounds of formula II and their salts have both a pre-emergence and a post-emergence herbicidal activity and especially show good herbicidal activity against grasses. In particular, the compounds exhibit good phytotoxicity towards sewing there, hand grass, finger grass, rhizome-rye corn and spontaneously emerging corn.

These weeds are generally difficult to control and therefore the present compounds offer an important advantage in controlling such weeds.

Generally, the post-emergence herbicidal compounds are applied directly to the leaves or other plant parts. For pre-emergence applications, the herbicidal compounds are applied to the growth medium or to the expected growth medium for the plant. The optimum amount of herbicidal compound or composition varies according to the particular plant species and the degree of plant growth if present and the particular part of the plant to be contacted and the degree of contact. The optimal dosage can also vary with the general location or environment (for example, protected areas such as greenhouses versus open areas such as fields) and the desired type and degree of control. In general, the present compounds are used both before and after emergence control in amounts of from about 0.02 to 60 kg / ha, preferably from about 0.02 to 10 kg / ha.

Although the compounds can theoretically also be used undiluted, they are usually used in practice as a composition or formulation comprising an effective amount of the compounds and an acceptable carrier. An acceptable or suitable carrier (acceptable from an agricultural point of view) is a carrier which does not significantly adversely affect the desired biological effect of the active compounds, except for diluting it.

Traditionally, the composition contains about 0.05 to 95% by weight of the compound of formula 2 or mixtures thereof. Concentrates of high concentrations can also be made for dilution before application. The carrier can be a solid, liquid or aerosol. The actual compositions can be in granular, powder, dust, solution, emulsion, slurry, aerosol form and the like.

Suitable solid carriers that can be used are, for example, natural clays (such as kaolin, attapulgite, montmoril lonite, etc.), talc, pyrophyllite, diatomaceous earth, synthetic silica, calcium aluminosilicate, tricalcium phosphate and the like.

Organic carriers such as, for example, walnut husk flour, cotton seed husks, wheat flour, wood flour, wood bark flour and the like can also be used as carriers. Suitable liquid diluents that can be used include, for example, water, organic solvents (for example, hydrocarbons such as benzene, toluene; dimethyl sulfoxide, kerosene, diesel oil, fuel oil, naphtha, etc.) and the like. Suitable aerosol carriers that can be used include conventional aerosol carriers such as halogenated greaves, etc.

The composition may also contain various auxiliaries and surfactants that increase the rate of transport of the active compound to the plant tissue, such as, for example, organic solvents, wetting agents and oils, and in the case of compositions intended for the pre-emergence application , agents which decrease the leachability of the compound or otherwise increase the stability in the soil. Crop oils such as, for example, soybean oil, paraffin oils and olefinic oils are particularly advantageous as carriers or additives in that they increase phytotoxicity.

The composition may also contain various suitable adjuvants, stabilizers, conditioners, insecticides, fungicides and, if desired, other herbicidal compounds.

A suitable concentrate composition that can be used includes 23 to 27% by weight of the active herbicide of the invention, 2 to 4% by weight of an emulsifier, for example, calcium alkyl benzene sulfonate, octyl phenol ethoxylate, etc .; or mixtures thereof and about 70-75% of an organic solvent, for example xylene etc. The concentrate is mixed with water before use, preferably a crop oil and used as a water emulsion containing about 0.5 to 2% of a crop oil , for example, soybean oil, and paraffinic oils and olefinic oils. Advantageously, the herbicide is used as a water emulsion containing about 0.02-0.6 wt%, preferably 0.07-0.15 wt% of the herbicide of the invention, about 0.001-0.01 wt. % of an emulsifier, about 0.08-2.5% by weight of an organic solvent and about 95 to 99% by weight of water. Preferably, the composition also contains about 0.25 to 2% by weight of a crop oil. The composition can be easily prepared by mixing the concentrate composition with about 1/4 to 1/2 of the desired amount of water, then adding the crop oil and finally the remaining amount of water. If no crop oil is used, the water and the concentrate composition are simply mixed together.

260 1 9 0 0 i 7

Further insight into the invention can be obtained with the following non-limiting preparation (s) and examples, in which, unless expressly stated otherwise, all temperatures and temperature ranges are indicated in degrees Celsius and the term "room temperature" refers to 20-25 ° C. The term "percent" or refers to weight percent and the term "mole" or "mill" refers to gram moles. The term "equivalent" refers to an amount of reagent in moles equal to the number of moles of the previous or next reactant mentioned in the relevant example in terms of final moles or final weight or volume. Examples are also repeated where necessary to provide additional starting material for subsequent examples.

EXAMPLES 15 Example I

2--1- (3-Trans-chloroallyloxyami no) propylidene] -5- (2-methylthropropyl) - 1,3-cyclohexanedione (a) To a cooled solution of 48 g (1.0 mol) of methanethiol (methyl mercaptan in 250 ml of dichloromethane, 82.4 g of crotonaldehyde solution containing 15¾ water and 85¾ crotonaldehyde (1.0 mol) was added, followed by addition of 2 ml of triethyl amine. Due to the resulting exothermic reaction, the mixture boiled for about 2 min. The mixture was stirred at room temperature overnight (about 18 hours) and then dried over magnesium sulfate and filtered. The filtrate was evaporated to yield 142.4 g of concentrate containing 78% by weight of methyl-thiobutyraldehyde and 22% by weight of methylene chloride.

(b) 71.2 g (0.5 mole) of O-methylthiobutyraldehyde was dissolved in 500 ml of dichloromethane. 159.18 g (0.5 mol) of triphenylphosphoranylidene-2-propanone was then added and the mixture was stirred at room temperature overnight (about 18 hours). The dichloromethane was evaporated to leave a solid residue. The residue was stirred in hexane and filtered. The residual solid was washed thoroughly with hexane and filtered. The combined filtrates were evaporated to dryness, yielding 70.6 g of 6-methyl-3-hepten-2-one as oil. (On a large scale, this product can also be readily prepared by the general methods described in U.S. Patent 4,355,184 and U.S. Patent Application 655,776, filed September 27, 1984).

(c) To a solution of 27 g (0.5 mole) of sodium methanolate in about 300 ml of methanol, 66.0 g of 360 µl were first added dropwise at 0-5 ° C.

Kr 8 (0.5 mol) diethyl malonate and then 79.5 g (0.5 mol) 6-methylthio-3-hepten-2-one were added. The mixture was then stirred at room temperature overnight (about 18 hours). The mixture was evaporated to dryness and the residue was mixed with 300 ml of water. The resulting aqueous solution was washed with diethyl ether, then acidified to pH 2 with concentrated hydrochloric acid and extracted with dichloromethane. The dichloromethane extract was dried over magnesium sulfate and evaporated to yield 4-methoxycarbonyl-5- (2-methylthiopropyl) -1,3-cyclohexanedione.

(D) A mixture of 129 g (0.5 mole) of 4-methoxycarbonyl-5- (2-methylthiopropyl) -1,3-cyclohexanedione and 65 g of 85 wt% aqueous potassium hydroxide (1 mole ) in 300 ml of water was refluxed for 2 hours and then stirred at room temperature overnight (about 18 hours). The mixture was evaporated to dryness and the residue dissolved in water. The aqueous solution formed was washed with 100 ml of diethyl ether and then acidified with 6N hydrochloric acid to pH 1 and extracted twice with dichloromethane. The combined dichloromethane extract was washed with water, dried over magnesium sulfate and evaporated to dryness, yielding 60 g of 5- (2-methylthiopropyl) -1,3-cyclohexanedione 20 as an oil which solidified after 3 or 4 days.

(e) To a mixture of 16.0 g (0.08 mole) of 5- (methylthiopropyl) -1,3-cyclohexanedione in 200 ml of toluene were slowly added over 5 min.

8.8 g (0.088 mol) of triethylamine and then 2.4 g (0.02 mol) of dimethyl aminopyridine. To this mixture was added 7.7 g of 25 (0.084 mol) propionyl chloride over 20 min. The mixture was kept at 65-70 ° C for 3 hours, then cooled and kept at room temperature overnight (about 18 hours). The mixture was first washed with water and then with 10¾s hydrochloric acid. The water layer and the toluene layer were separated. The aqueous layer was extracted with toluene and the extract was combined with the previously separated toluene layer. The entire toluene phase was extracted with 1% aqueous sodium hydroxide. The extract was washed with dichloromethane, then acidified to pH 1 with hydrochloric acid and extracted with dichloromethane. The dichloromethane extract was dried over magnesium sulfate and evaporated to dryness to give 2-propionyl-5- (2-methylthiopropyl) -1,3-cyclohexanedione.

(f) A solution of 4.2 g (0.0117 mol) of 2-propionyl-5- (2-methyl-thiopropyl) -1,3-cyclohexanedione and 2.7 g of 3-trans-chlorallyloxyamine in 50 ml of ethanol was added stirred at room temperature for about 2-1 / 2 days and then evaporated to dryness. The residue was dissolved in dichloromethane and extracted twice with 1¾ sodium hydroxide in water. The water extract was washed with diethyl ether, then acidified to pH 1 with hydrochloric acid and extracted with dichloromethane. The dichloromethane extract was dried over magnesium sulfate and then evaporated to dryness to yield 2.1 g of the title compound as an oil. Elemental Analysis: Carbon: Calc. 55.56%, found. 55.96%; hydrogen: ber. 6.99%, found. 7.32%; nitrogen: ber. 4.05%, found. 4.2%.

Example II

2- [1-f3-Trans-chloroalkyl oxyamlno) propylidene] -5- (2-propylthloeth.yl) - 1,3-cyclohexanedione

A solution of 42.3% by weight of the hydrochloride of trans-chloroalloxyamine in dilute hydrochloric acid was treated with dilute aqueous sodium hydroxide to pH 8-10 to release the amine. The solution was then extracted twice with diethyl ether, the combined ether extracts were washed twice with a saturated aqueous sodium chloride solution and dried over magnesium sulfate; after evaporation chloroallyloxyamine was obtained as a pale yellow liquid.

A mixture of 3.2 g of 2-propionyl-5- (2-propylthioethyl) -1,3-cyclohexanedione and 1.3 g of trans-chloroallyloxyamine in 20 ml of ethanol was left overnight (about 15 to 18 hours) stirred at room temperature and then evaporated and mixed with 50 ml diethyl ether. The pH of the mixture was adjusted to pH 11-12 by adding a solution of 5% sodium hydroxide in water. The water layer was separated and treated with 10% hydrochloric acid to pH 2 and then extracted twice with diethyl ether. The combined ether extracts were washed twice with aqueous sodium chloride solution, dried over magnesium sulfate and evaporated to a yellow liquid. The yellow liquid was chromatographed on a silica gel column eluting with dichloromethane to give 3.1 g of the title compound as an oil.

Example III

2- [1- (3-Trans-chloro-alloxyamino) propylidene] -5- (2-ethylthioropyl) -35 1,3-cyclohexanedione

In this example, 17.2 g (0.0636 mole) of 2-propionyl-5- (2-ethylthiopropyl) -1,3-cyclohexanedione, 0.9 g (0.0153 mole) of acetic acid and 10.9 g (0 .0757 mol) 3-trans-chloroallyloxyamine in 35 ml water was added to 20 ml hexane and stirred. Then in about 15 min.

40 slowly added a solution of 5 wt% sodium hydroxide in water 88019 * 0 yr 10 until 3.0 g (0.0757 mol + small excess) of sodium hydroxide was added and the pH of the reaction mixture was about 6. The mixture was heated and kept at 40 ° C for about 2.5 hours and then cooled back to room temperature. The organic layer (i.e., hexane layer) was separated and washed with 10 ml of 5% hydrochloric acid, then 6.25 wt% aqueous sodium hydroxide was added to pH 12. The water layer was separated and mixed with 25 ml of hexane; the pH was adjusted to 5.4 by the dropwise addition of 36 wt% hydrochloric acid in an ice bath. The organic phase was separated, dried over magnesium sulfate and then evaporated to yield 18.0 g of crude product. The crude product was purified by column chromatography over silica gel with hexane: dichloromethane as eluent to afford the purified title compound as an oil.

Elemental Analysis: Carbon: Calc. 56.73%, found. 56.63%; Hydrogen: calc. 7.28%, found. 7.55%; nitrogen: ber. 3.89%, found. 3.55%.

Example IV

Sodium 2- [1- (3-trans-chloro-1-yloxyamino) propylidene] -5- (2-methylthiopropyl) -3-oxo-1-yl ohexen-1-olate In this example, illustrated a method that can be used for the preparation of the title compound.

A solution of 0.01 mole of sodium hydroxide in 2 ml of water was added at room temperature to a solution of 0.01 mole of 2- [1- (3-trans-chloroallyloxyamino) propylidene] -5- (2-methylthio-propyl) -1 3-cy-25 clohexanedione. When the reaction was completed, the solvents were evaporated under reduced pressure to yield the 1-hydroxy sodium salt of 2- [1- (3-trans-chloroallyloxyamino) propylidene] -5- (2-methylthiopropyl) 3-oxo-1-cyclohexene-1- ol was obtained.

Example V

In this example, the title compounds of Examples 1 - III, i.e., 2- [1- (3-trans-chloro-alloxyamino) propylidene] -5- (2-methylthiopropyl) -1,3-cyclohexanedione (1); 2- [1- (3-trans-chloro-alloxy-amino) propylidene] -5- (2-propylthioethyl) -1,3-cyclohexanedione (2) and 2- [1- (3-trans-chloro-alloxyamino) propylidene ] -5- (2-ethylthiopropyl) -35 1,3-cyclohexanedione (3) tested for pre-emergence and post-emergence phytotoxic activity against a variety of grasses and broadleaf plants including a cereal and a broadleaf according to the method described below crop.

Pre-emergence herbicide test 40 The pre-emergence herbicide activity was determined in the following manner. 86 0 1 9 0 0 11.

Test solutions of the respective compounds were prepared as follows: 355.5 mg Test compound was dissolved in 15 ml of acetone. 2 ml of Ace-5 tons containing 110 mg of a non-ionic surfactant were added to the solution. 12 ml of this stock solution was then added to 47.7 ml of water containing the same nonionic surfactant at a concentration of 625 mg / l. Seeds of the test crop were planted in a pot of soil and the test solution was uniformly sprayed over the soil surface at a dose of 27.5 micrograms per cm 2 unless otherwise specified in the following tables. The pot was poured and placed in a greenhouse. The pot was watered from time to time and examined for three weeks for the emergence of seedlings, the health of the emerging seedlings, etc. At the end of this period, the herbicidal activity of the compound was rated based on the physiological observations. A scale from 0 to 100 was used, with 0 corresponding to no phytotoxicity and 100 corresponding to complete death. The results of these tests are summarized in Table A.

20 Post-emergence herbicide trial

The test compound was formulated in the same manner as described above for the pre-emergence test. This formulation was applied evenly on two similar pots with plants 5 to 7.5 cm high (except wild oats, soybeans and water grass, which were 7.5 to 10 cm high) (about 15 to 25 plants per pot) at a dosage of 27.5 micrograms of test compound per cm 3 unless otherwise noted in the following tables. After the plants dried, they were placed in a greenhouse and then poured from time to time at the base as needed. The plants were periodically examined for phytotoxic effects and physiological and morphological responses to treatment. After three weeks, the herbicidal activity of the compound was evaluated based on these observations. A scale of 0 to 100 was used, with 0 referring to no phytotoxicity and 100 referring to complete death. The results of these tests are summarized in Table B.

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Example VI

In this example, the title compounds of Examples I-III were tested for post-emergence herbicidal activity at a very low dose in addition to 2- [1- (3-trans-chloroallyloxyamino) butylidene] -5- (2-ethyl-5 thiopropyl) -1,3-cyclohexanedione ("Cl") and the commercially available herbicide Sethoxydim ("C-2") being 2- [1- (ethoxyamino) butylidene] -5- (2-ethylthiopropyl) -1,3- cyclohexanedione against a range of unwanted grasses and two cultivated crops.

The tests were carried out in the same manner as described in Example V10, except that the dosages listed in Table C were used and four repetitions were made per test. The results of these tests are summarized in Table C, where 0 indicates no phyto-toxicity and 100 indicates complete death. Generally, a photoxicity below about 20 to 30¾ is not considered meaningful because the plant can usually grow over such an amount of damage.

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Table C shows that all compounds at this dosage were ineffective against almond (Cyperus esculentus). With this one exception, compounds 1-3 were better than compound C-1 over the other weeds in the test and significantly better than compound C-2.

In terms of the dosages required for Calibrated Responses, an application amount of compound 1 or 2 of 0.05 // cm2 was equivalent or better than an application amount of compound Cl of 0.28 // cm2 to control finger grass and chaff . An application amount of 0.05 // cm2 of compound 1 or 2 corresponded to an application amount of 0.11 // cm2 of compound C-1 for combating coot. With regard to wild oats and yellow needle, an application amount of 0.11 / cm2 of compound 1 or 2 gave better control than an application amount of 0.28 / cm2 of compound C-1. As indicated above, compound C-1 was better than compound C-2 and the dosing benefits of compounds 1 and 2 were even greater over compound C-2.

Of course, many modifications and variations to the invention described above and below are possible without departing from the core and its scope.

8601900

Claims (18)

1. Compounds of formula 2, wherein R 1 is 3-trans-chloroallyl and 5 R 2 is 2-methylthiopropyl or 2-propylthioethyl, and suitable salts thereof. The compound of claim 1 wherein R2 is 2-methylthiopropyl. 3. A compound according to claim 2, characterized in that the compound is 2- [1- (3-trans-chloro-alloxyamino) propylidene] - 5- (2-methylthiopropyl) -1,3-cyclohexanedione. Compound according to claim 1, characterized in that R2 is 2-propylthiomethyl. 5. A compound according to claim 4, characterized in that the compound contains 2- [1- (3-trans-chloro-lyloxyamino) propylidene] -5- (2-propylthioethyl) -1,3-cyclohexanedione is. A herbicidal composition comprising an herbicidal effective amount of a compound according to claim 1 and a suitable carrier. Herbicidal composition comprising an herbicidal effective amount of the compound of claim 2 and a suitable carrier. 8. Herbicidal composition comprising an effective weed killing amount of the compound of claim 4 and a suitable carrier. A herbicidal composition comprising an herbicidal effective amount of the compound of claim 1 and a wash oil. 10. A method of controlling grassy plants comprising the use of an herbicidal effective amount of a compound of claim 1 on the foliage or habitats of those plants. 11. A method of controlling grassy plants comprising the use of an herbicidal effective amount of the compound of claim 2 or mixtures thereof on the foliage or habitats of those plants. A method of controlling grassy plants comprising the use of an herbicidal effective amount of the compound of claim 4 or mixtures thereof on the foliage 40 or habitats of those plants. 8601900> «\ _ -1β 19 13. Method for combating the grasses sewing thread, hand grass, spontaneously emerging sorghum, broad-leaf signal grass, cleavers, red rice, sprouting bud, rye corn or spontaneously emerging maize, which use an amount of weed-killing effective compound according to claim 1 on said grasses or the living space thereof. Herbicidal composition comprising 0.02-0.6 wt% of a compound according to claim 1; 0.001-0.15 wt% of an emulsifier; 0.08-2.5 wt% of an organic solvent and about 95 to 99 wt% water 10. Composition according to claim 14, characterized in that the composition comprises about 0.25 to 2% by weight of a crop oil. A herbicidal concentrate composition comprising 23-27 wt% of a compound of claim 1, 2-4 wt% of an emulsifier and about 70-75 wt% of an organic solvent. A process for the preparation of the compound of claim 3 comprising the step of contacting 2-propionyl-5- (2-methylthiopropyl) -1,3-cyclohexanedione with 3-trans-chloroallyl-oxyamine under reactive conditions yield the corresponding compound of formula 2. Process according to claim 17, characterized in that the process is carried out in an inert organic solvent at temperatures from about 0 to 80 ° C. ? i) r; 'V "-w R NO-R1 / ORl \ / / c ch3ch2c I Λ 1 Q ^^ v ^ OR5 0Tl ^ 0H / V r4 / \ r2 r3 HR% CH, CH- .0 ° Y ^ V ^ 0H I + H2NOR1 -> I Λ, - HR ^ 3,860 1 9 0- ^