KR20010052014A - Herbicidal N-Cyclohexadienyl Heteroaryloxyacetamides - Google Patents

Abstract

PURPOSE: To obtain a herbicide that has the high herbicidal action with retention of needed selectivity and the increase in the soil degradation by using readily available isophorone as a starting material in order to overcome the inconvenience of the known heteroaryloxy acetamide that this conventional herbicide can manifest a considerable level of the activity against a plurality of weeds, but shows unsatisfactory selectivity and undesirable persistency to the environment. CONSTITUTION: This invention provides a novel compound represented by formula I, wherein Het represents the nitrogen atom including a 5-or 6-membered heteroaromatic group which may be substituted or may be benzo-condensed; R1 is an alkyl, an alkoxyalkyl or cycloalkyl group; R2s are independently from each other alkyl or alkenyl groups; m is 0 or an integer of 1-6, provides herbicidal composition containing the novel compound as an active ingredient and the resultant herbicidal composition can be used in a variety of agricultural methods.

Description

Herbicide N-cyclohexadienyl heteroaryloxyacetamide {Herbicidal N-Cyclohexadienyl Heteroaryloxyacetamides}

The present invention relates to certain novel heteroaryloxyacetic acid N-alkenylamides, the preparation of such compositions, herbicide compositions containing these compounds and methods of using these compounds to inhibit unwanted plant growth.

U.S. Patent 4,585,471 discloses compounds having the following formulas useful as herbicides.

European Patent Application EP 0 005 501 discloses herbicides benzofused oxazol-2-yl and thiazoles in which amido nitrogen atoms are hydrogen atoms and / or optionally substituted with alkyl, alkenyl, alkynyl, cycloalkyl or aryl groups. 2-yl-oxyacetamide is disclosed.

European Patent Application EP 0 165 537 discloses benzofused oxazoles in which amido nitrogen atoms are substituted with one or two aryl groups, one cyclohex-1-enyl, one cyclohex-3-enyl or one vinyl group- 2-yl and thiazol-2-yl-oxyacetamides are disclosed. This compound is taught as being useful as a herbicide.

International patent application WO 97/08160 discloses N- (1-isopropyl-2-methyl-1-propenyl) -heteroaryloxyacetamide useful as a herbicide.

International patent application WO 99/25702 discloses a herbicide heteroaryloxyacetamide in which amido nitrogen atoms are substituted with cyclohexenyl groups.

None of these documents, however, discloses heteroaromatic oxyacetamides in which amido nitrogen atoms are attached to the cyclohexadienyl moiety.

While many of the known heteroaryloxyacetamides exhibit significant activity against various weeds, they lack the selectivity or disadvantageously remain in nature. N-3,3,5-trimethylcyclohexadienyl heteroaryloxyacetamide of the present invention overcomes these disadvantages and has the advantage that it can be prepared from isophorone which is a readily available starting material. The compounds according to the invention combine high herbicidal activity with the required selectivity and improved soil degradability.

The present invention relates to novel compounds of formula (1).

<Formula 1>

In the above formula,

Het represents an optionally substituted, optionally benzofused nitrogen containing 5 or 6 membered heteroaromatic group,

R ¹ represents an alkyl, alkoxyalkyl or cycloalkyl group,

R ² independently represents an alkyl or alkenyl group,

m represents 0 or the integer of 1-6.

Accordingly, the present invention provides a method for controlling unwanted plant growth by contacting a plant with a novel compound of formula (1), an effective amount of a new compound, a selective herbicide composition containing the new compound as an active ingredient, and a novel preparation of the new compound To provide.

This compound has higher selectivity to crops than the compounds disclosed in the preceding patent application and also shows good herbicidal activity at low doses. This compound exhibits good selective herbicidal activity and improved soil degradability for certain crops (eg, rice, corn, grains, beans, beets, canola, sugar cane or potatoes).

These and other objects and features of the present invention will become more apparent from the following detailed description.

Surprisingly, it has been found that the novel compounds of formula (1) show good herbicidal activity against a wide range of weeds and exhibit a high degree of selectivity.

"Optionally benzofused nitrogen containing 5 or 6 membered heteroaromatic group" means a heteroaryl or heteroaryl group having 1 to 3 nitrogen, oxygen or sulfur atoms, such as azole (e.g., pyrrole, para Sol and imidazole, oxazole, thiazole, taadiazole), azine (eg, pyridine, pyrimidine, pyrazine, pyridazine and triazine). Of these, optionally benzofused azoles are preferred. Het represents a thiadiazolyl, benzoxazolyl or benzthiazolyl group which may be substituted with one or more halogen atoms or an alkyl or phenyl group.

If any group is optionally substituted, the optionally present substituent may be any compound commonly used for modification and / or improvement of herbicide compounds, especially to maintain or improve herbicidal activity associated with the compounds of the invention Or substituents that affect the duration of action, soil or plant penetration, or any other desired property of such herbicide compounds.

Each part of the molecule may have one or more substituents, identical or different.

With respect to the moieties defined above as containing optionally substituted heteroaryl groups, such optional substituents include halogens (especially fluorine, chlorine and bromine) and nitro, cyano, amino, hydroxyl, C _1-4 -alkyl , C _1-4 -alkoxy, C _1-4 -haloalkyl, C _1-4 -haloalkenyl, C _1-4 -haloalkoxy, C _1-4 -haloalkylthio and aryl groups (e.g. phenyl ) And 1 to 5 substituents may be used, but 1 to 2 substituents are preferable, and most preferably, 1 substituent is used.

Het preferably represents the following formulas (2) and (3).

In the above formula,

R ³ represents hydrogen or a halogen atom or an alkyl or haloalkyl group, preferably a C _1-4 -alkyl or C _1-4 -fluoroalkyl group, in particular a trifluoromethyl group,

X represents O or S,

Y independently of one another is a halogen atom or an optionally substituted alkyl group, preferably a fluorine or chlorine atom or C _1-4 -alkyl, C _1-4 -fluoroalkyl, C _1-4 -alkoxy or C _1-4 -fluor A ralkoxy group, in particular a chlorine atom or a methyl atom,

n is an integer of 0 to 4, preferably 0 or 1.

Particularly preferred are thiadiazole derivatives (2) and benzoxazole derivatives (3) of formula (1), wherein X is oxygen.

If any part of the moiety contains an alkyl or alkenyl group, unless otherwise stated, such a group may generally be straight or branched, and may contain up to 6, preferably 1 to 4 carbon atoms. Examples of such alkyl or alkenyl groups include methyl, ethyl, propyl, (1) -butyl, isobutyl, t-butyl and prop-1-en-2-yl groups. The alkyl moiety of haloalkyl, haloalkoxy, haloalkylthio, alkylthio or alkoxy groups is suitably having from 1 to 4, preferably 1 to 2 carbon atoms.

If any of the above moieties contain an alkoxyalkyl group, these groups may generally be straight or branched unless otherwise indicated and may contain 2 to 12, preferably 3 to 5 carbon atoms. Examples of such groups include methoxymethyl, 2-methoxyethyl, 3-methoxypropyl, 2-methoxy-1-methylethyl and methoxybutyl.

"Halogen" means a fluorine, chlorine, bromine or iodine atom, but preferably a fluorine, chlorine or bromine substituent.

When any part of the moiety comprises a haloalkyl group, such group can be generally straight or branched unless otherwise indicated, and may contain 1 to 6, preferably 1 to 4 carbon atoms. Such groups include halomethyl, haloethyl, halopropyl, haloisopropyl, halobutyl, haloisobutyl and halo tert-butyl groups.

The haloalkyl portion of any group in the definitions used herein may contain one or more halogen atoms, preferably fluorine, chlorine or bromine. Haloalkyl is preferably a mono-, di-, tri- or perfluoroalkyl group, in particular trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl or 1,1,1-trifluoro Although it is shown the rope-rope-2-yl group, trifluoromethyl is the most preferable.

R ¹ preferably represents a C _1-4 -alkyl, C _1-6 -alkoxy-C _1-6 -alkyl or C _{3-7 -haloalkyl} group, but methyl, ethyl, propyl, isopropyl, cyclopropyl And 2-methoxyethyl group is most preferred.

R ² each independently preferably represents a C _1-4 -alkyl or C _2-4 -alkenyl group, most preferably a methyl group or prop-1-en-2-yl group. m preferably represents 1, 2 or 3, most preferably 3.

Especially preferred are compounds of formula (4).

In the above formula, Het, R ¹ and R ² are as defined above, and the curve shows the presence of two conjugated bonds at one or the other position relative to the point of attachment of the nitrogen atom.

Especially preferred are compounds of the formulas (5) and (6).

In the formula, R ¹ represents an alkyl or alkoxyalkyl group.

Het is a group selected from formulas (2) and (3).

<Formula 2>

<Formula 3>

In the above formula,

X represents O or S,

Y represents a halogen atom or a methyl group,

n is 0 or 1,

R ³ represents a C _1-4 -alkyl or C _1-4 -fluoroalkyl group.

Compounds of formula (1) can be prepared or used as isomeric mixtures of compounds of formula (4), differing only in the position of the double bond. The present invention therefore preferably relates to mixtures of isomeric compounds of formula (1), in particular mixtures of compounds of formula (4), differing only in double bond positions. Most preferred are mixtures of formulas (5) and (6), wherein formula (5) is the main component.

Representative compounds of the invention are the following compounds:

2- (5-Trifluoromethyl- [1,3,41-thiadiazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1, 3-dienyl ) -Acetamide,

2- (5-trifluoromethyl- [l, 3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-die Nil) -acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-die Nil) -acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-die Nil) -acetamide,

2- (5-ethyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl)- Acetamide,

2- (5-ethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl)- Acetamide,

2- (5-ethyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl)- Acetamide,

2- (5-ethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl)- Acetamide,

2- (5-pentafluoroethyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-die Nil) -acetamide,

2- (5-pentafluoroethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-die Nil) -acetamide,

2- (5-pentafluoroethyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-die Nil) -acetamide,

2- (5-pentafluoroethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-die Nil) -acetamide,

2- (5-t-butyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl ) -Acetamide,

2- (5-t-butyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-l, 3-dienyl ) -Acetamide,

2- (5-t-butyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-l, 5-dienyl ) -Acetamide,

2- (5-t-butyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl ) -Acetamide,

2- (5-Trifluoromethyl- [l, 3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3- Dienyl) -acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohexa-1,5- Dienyl) -acetamide,

2- (5-ethyl- [l, 3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) Acetamide,

2- (5-ethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) Acetamide,

2- (5-pentafluoroethyl- [l, 3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3- Dienyl) -acetamide,

2- (5-pentafluoroethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1,5- Dienyl) -acetamide,

2- (5-t-butyl- [l, 3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-die Nil) -acetamide,

2- (5-t-butyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohexa-1,3-diene Nil) -acetamide,

2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohexa -1,3-dienyl) -acetamide,

2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohexa -1,5-dienyl) -acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-cyclopropyl-N- (3,5,5-trimethylcyclohexa-1,3- Dienyl) -acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-cyclopropyl-N- (3,3,5-trimethylcyclohexa-1,5- Dienyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1,5-dienyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide,

2- (benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-triethylcyclohexa-1,5-dienyl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (6-Chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1,5-dienyl) -acetamide

2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (5-Chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -aceta mid,

2- (5-chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3.3,5-trimethylcyclohexa-1,5-dienyl) -acetamide,

2- (6-Chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -aceta mid,

2- (6-Chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -aceta mid,

2- (5-methyl-benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (5-methyl-benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide,

2- (5-methyl-benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (5-methyl-benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide,

2- (5-methyl-benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (5-methyl-benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide,

2- (5-Methyl-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -aceta mid,

2- (5-Methyl-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -aceta mid,

2- (benzothiazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-enyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-enyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,5-dienyl) -acetamide,

2- (benzothiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide,

2- (benzothiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide.

The compound of formula 1 is an oil, gum or crystalline solid substance. This compound is excellent due to its valuable herbicidal properties. For example, this compound can be used for the control of unwanted plants in agriculture or related fields. The compounds of formula (1) according to the invention have high herbicidal activity in a wide range of concentrations and at low doses, and in particular pre emergence and post emergence in certain crops (eg corn, rice) Undesired plants by application [eg, Alopecurus myosuroides, Echinochloa crusgalli, Setaria viridis, Gallium aparine, Stella Stellaria media, Veronica persica, Digitaria sanguinalis, Lolium perenne, Lamium purpureum, Viola arvensis, Abu Any difficulties in agriculture for the selective regulation of Abutilon theophrasti, lpomoea purpurea and Amaranthus retroflexus] This may be used.

The compounds according to the invention can be prepared by conventional methods.

Suitable methods for the preparation of compounds of formula (1) include reacting a compound of formula (7) with a compound of formula (8).

Wherein R ¹ , R ² and m are as defined above.

Het-L ²

Wherein Het is as defined above, one of L ¹ and L ² represents a hydroxy group and the other represents a leaving group.

The reaction can be carried out in the presence or absence of a solvent that does not accelerate or at least interfere with the reaction. Among these are polar solvents, protonic solvents or aprotic solvents (e.g., N, N-dimethylformamide, dimethylsulfoxide, sulfolane, acetone, acetonitrile, methyl ethyl ketone), or ethers (e.g. tetra Hydrofuran or dioxane), or alcohol or water or mixtures thereof. The reaction is carried out between ambient temperature and the reflux temperature of the reaction mixture, preferably at elevated temperature, in particular at reflux temperature. Preference is given to using almost equivalents of reactant.

The reaction may be carried out with a basic compound (eg alkali hydroxide), carbonate or bicarbonate (eg sodium hydroxide or potassium hydroxide), alkali alkoxide (eg sodium ethoxide) or organic base (eg tri Ethylamine). In a particularly preferred embodiment, the process according to the invention is carried out in the presence of a phase transfer catalyst, preferably tetraalkyl-ammonium halides, in particular tetraethyl-ammonium bromide.

Suitable leaving groups L ¹ or L ² are, for example, alkyl- and arylsulfonyl (particularly methylsulfonyl), alkyl- and arylsulfonyloxy or perfluoroalkylsulfonyloxy groups and halogen atoms (particularly fluorine, Chlorine and bromine).

Compounds used as starting materials are particularly known and some are novel. The compounds according to the invention also relate to novel intermediates, in particular compounds of formula (7).

<Formula 7>

Wherein R ¹ , R ² and m are as defined above and L ¹ represents a hydroxy group or a leaving group selected from alkyl- and arylsulfonyl, alkyl- and arylsulfonyloxy and perfluoroalkylsulfonyloxy groups.

Most preferred are the compounds of the formula (9) below.

In the above formula,

R ¹ represents an alkyl, cycloalkyl or alkoxyalkyl group,

L ¹ represents a hydroxy group or a halogen atom,

The curve shows the presence of two conjugated bonds at one or the other position relative to the point of attachment of the nitrogen atom.

The compound of formula (7) is reacted with 2-chloroacetyl chloride and then with alkali acetate or by direct reaction with 2-acetoxyacetyl chloride and deacylated with an aqueous solution of alcoholic alkali hydroxide. It is prepared from the corresponding cyclohexenimine.

Wherein R ¹ , R ² and m are as defined in formula (1).

Compounds of formula (10) can be prepared by condensing primary amines and the corresponding cyclohexenes. When using asymmetric ketones, the double bonds produced in the corresponding compounds of formulas (1) and (7) can be formed at two different positions. The reaction product may then contain a mixture of isomeric compounds of formulas (1) and (7) that differ only in the position of the conjugated double bond. Commercially readily available cyclohexenes such as cyclohex-2-enone, 3-methylcyclohex-2-enone, carbon and 3,5,5-trimethylcyclohex-2-enone (isophorone) Most preferred as starting material, most preferred is isophorone. Condensation reaction of cyclohexenone and amine can be carried out by removing the produced water by a known method, for example, azeotropic distillation. Removal of water can be accomplished by addition of an acid or acid catalyst (eg hydrochloric acid, para-toluenesulfonic acid or ammonium sulfate), or basic compounds (eg sodium hydroxide or potassium hydroxide) and alkali carbonates, or dehydrating agents (eg For example, TiCl ₄ or molecular sieves). In a preferred method of preparing the imine of formula (10), cyclohexenone is treated with a mixture of primary alkylamines in the presence of the corresponding alkylammonium halide and then with a basic compound, most preferably potassium hydroxide.

The invention also relates to a process for using the compound of formula (1) as herbicide. Thus, the present invention typically inhibits the growth of unwanted plants in the locus by treating any locus with an effective amount of a compound of formula (1), which is typically incorporated in the herbicide composition. Provide a method.

Particularly interesting activities have been found for grass and broad leaf weeds, including both pre and post emergence. It has also been found that the main crop species (eg wheat, barley, corn, rice and soybeans) are selective. Since the useful action is by side spray application, the locus is best suited for plants in the crop area (the crop is typically grain, corn, soy, sunflower or cotton). However, it is also possible to apply it to soil for compounds with preemergence herbicidal action or to water for crops such as rice. An effective amount of the active ingredient for weeding may be, for example, 0.005 to 3 kg / ha, preferably 0.01 to 1 kg / ha.

Furthermore, the present invention provides a herbicide composition comprising an active ingredient which is at least one compound of formula (1) as defined above and at least one carrier. In particular, at least one of the carriers is a surfactant. Also provided is a method of preparing such a composition comprising combining a compound of formula (1) as defined above with a carrier (s). Such compositions may contain a single active ingredient or a mixture of several active ingredients of the present invention. In addition, it is contemplated that other isomers or mixtures thereof may have different levels or ranges of activity, so that the compositions may comprise individual isomers or mixtures thereof to broaden the herbicidal activity of the compositions.

The composition according to the invention preferably contains from 0.5 to 95% by weight (w / w) of at least one active ingredient.

Agriculturally acceptable carriers in the compositions according to the invention may be formulated to facilitate application to the locus (eg plant, seed or soil) to which the active ingredient is to be treated or to facilitate storage, transport or handling. Any material that can be. The carrier may be a liquid or a solid, and may comprise a substance which is usually gaseous or compressed to form a liquid.

The compositions are prepared in well-established methods such as emulsion concentrates, solutions, water-based emulsions, wet powders, soluble powders, suspension concentrates, dusts, granules, water dispersible granules, microcapsules, gels and other formulations. Can be. This method involves the active ingredient thoroughly with other substances (eg, fillers, solvents, solid carriers, surfactants, and optionally solid and / or liquid auxiliaries and / or adjuvants). Mixing and / or milling are included. The form of use (eg, spraying, automating, dispersing or pouring) can be selected according to the desired subject and given environment of use.

Solvents used are aromatic hydrocarbons (e.g., Solvesso 200), substituted naphthalenes, phthalic esters (e.g. dibutyl or dioctyl phthalate), aliphatic hydrocarbons (e.g. cyclohexane or Paraffin), alcohols and glycols, ethers and esters thereof (e.g. ethanol, ethylene glycol mono- and dimethyl ether), ketones (e.g. cyclohexanone), strong polar solvents (e.g., N-methyl- 2-pyrrolidone, γ-butyrolactone), higher alkyl pyrrolidones (eg n-octylpyrrolidone or cyclohexylpyrrolidone), epoxidized plant oil esters (eg methylated coconut or Soybean oil ester) and water. Mixtures of other solvents are also often suitable as carriers.

Solid carriers usable as dust, wet powder, water dispersible granules or granules may be inorganic acid additives (eg calcite, talc, kaolin, montryloniite or aperpulzite). Physical properties can be improved by adding highly disperse silica gel or polymer. The granular carrier may be a porous material such as pumice, kaolin, sepiolite, bentonite, and the non-hygroscopic carrier may be calcite or sand. A number of pre-granulated inorganic or organic materials, such as dolomite or ground plant residues, can further be used.

Herbicide compositions are often formulated and delivered in concentrated form, which concentrate is diluted by the user before use later. Dilution is facilitated even when only a small amount of the carrier, which is a surfactant, is present. Thus, at least one carrier in the composition according to the invention is preferably a surfactant. For example, the composition may comprise two or more carriers, one of which is a surfactant.

The surfactants used may be nonionic, cationic or amphoteric ions having good dispersing, emulsifying and wetting properties depending on the nature of any compound of formula (1) to be formulated. "Surfactant" here also includes a mixture of two or more surfactants.

The compositions of the present invention can be formulated, for example, as wet powders, water dispersible granules, dusts, granule solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wet granules usually contain from 5 to 90% by weight (w / w) of active ingredient, in addition to the usual solid inert carriers, 3 to 10% (w / w) dispersants and wetting agents, if necessary 0 to 10% (w / w) stabilizer (s) and / or other additives (eg, penetrants or residual enhancers (adhesives)). The dust has a composition similar to the wet powder, but is usually formulated as a dust concentrate without dispersant, which is further diluted in the field with a solid carrier and usually contains 0.5 to 10% by weight (w / w) of the active ingredient. The composition can be provided. Water dispersible granules and granules are conventionally prepared to have a size of 0.15 mm to 2.0 mm, and can be prepared by various techniques. Granules of this type will contain from 0.5 to 90% by weight of active ingredient and from 0 to 20% by weight of additives (eg stabilizers, surfactants, sustained release modifiers and binders). So-called "dry flowables" consist of relatively small granules having a relatively hard furnace active ingredient. Emulsifiable concentrates, in addition to solvents or solvent mixtures, contain from 1 to 80% (w / v) of active ingredient, from 2 to 20% (w / v) emulsifier and from 0 to 20% (w / v) of other additives (e.g. For example, stabilizers, penetrants and corrosion inhibitors). Suspension concentrates are typically milled to obtain a stable, non-precipitated flowable product, 5 to 75% (w / v) of active ingredient, 0.5 to 15% (w / v) of dispersant, 0.1 to 10% (w) / v) suspending agents (e.g. protective colloids and thixotropic agents), 0-10% (w / v) of other additives [e.g. antifoams, corrosion inhibitors, stabilizers, penetrants and residual improvers ( Pressure-sensitive adhesive)] and an organic liquid which is almost soluble to water or the active ingredient. Any organic solid or inorganic salt may prevent precipitation and crystallization, or in the case of water, may be present in dissolved form in the formulation as an antifreeze agent.

Aqueous dispersants and emulsions, for example compositions prepared by dilution of the formulation products according to the invention with water, are also within the scope of the invention.

Of particular interest in improving the persistence of the protective activity of the compounds of the invention is the use of a carrier which will release slowly around the plant to be protected with the herbicide compound.

The biological activity of the active ingredient can also be increased by including auxiliary actives in the spray diluent. As used herein, an auxiliary activator can be used to increase the biological activity of an active ingredient, but by itself defines to mean a substance that does not have significant biological activity. Auxiliary active agents can be included in the formulation as coformulants or carriers or can be added to the spray tank together with the formulation containing the active ingredient.

As a product, the composition is in concentrated form, but it is common for the end user to use the diluted composition. The composition may be diluted to an active ingredient concentration of 0.001% or less. Doses typically range from 0.01 to 10 kg a.i./ha.

Examples of formulations according to the invention are as follows:

Emulsion Concentrate (EC) Active ingredient Compound of Example 1 30% (w / v) Emulsifier (s) Trademark Attlox 4856 B / registered Trademark Atrox 4858 B (commercially available from ICI Spectrum; mixtures containing calcium alkyl aryl sulfonates, fatty alcohol ethoxylates and light aromatics / calcium alkyl aryl sulfonates, Fatty alcohol ethoxylates and mixtures containing light aromatics) 5% (w / v) menstruum Trademark Shellsol A [Commercially available from Deutsche Shell AG; Mixture of C ₉ -C ₁₀ aromatic hydrocarbons] 1,000 ml or less

Suspension Concentrate (SC) Active ingredient Compound of Example 1 50% (w / v) Dispersant Trademark: Soprophor FL (commercially available from Long-Pullang; polyethylene polyaryl phenyl ether phosphate amine salt) 3% (w / v) Antifoam Trademark: Rhodorsil 422 (commercially available from Long-Plan; nonionic aqueous emulsion of polydimethylsiloxane) 0.2% (w / v) Salvage Trademark Kelzan S (available from Kelco; Xanthan Gum) 0.2% (w / v) Antifreeze Propylene glycol 5% (w / v) Biocides Proxel® Aqueous dipropylene glycol containing 20% 1,2-benisothiazolin-3-one 0.1% (w / v) water 1000 ml or less

Wet Powder (WP) Active ingredient Compound of Example 2 60% (w / w) Humectant Trademark Atrox 4995 (available from ICI Spectrum; Polyethylene Alkyl Ether) 2% (w / w) Dispersant Trademark Witcosperse D-60 (available from Witco; mixture of sodium salt of condensed naphthalene sulfonic acid and alkylarylpolyoxy acetate) 3% (w / w) Carriers / Fillers kaoline 35% (w / w)

Water Dispersible Granules (WG) Active compound Compound of Example 2 50% (w / w) Dispersant / Binder Trademark Witcosparse D-450 (available from Witco; mixture of sodium salt of condensed naphthalene sulfonic acid and alkyl sulfonate) 8% (w / w) Humectant Trademark Morwet EFW (available from Witco; formaldehyde condensation product) 2% (w / w) Antifreeze Trademark Rordorcil EP 6703 (available from Long-Plan; encapsulated silicone) 1% (w / w) Disintegrant Trademark Agrimer ATF (available from International Specialty Products; cross-linked homopolymer of N-vinyl-2-pyrrolidone) 2% (w / w) Carriers / Fillers kaoline 35% (w / w)

The compositions of the present invention may also include other compounds with biological activity, for example compounds with similar or supplemental pesticidal activity or compounds with plant growth regulation, fungal or pesticidal activity. This mixture typically has a broader activity than the single compound of formula (1). Furthermore, other components can be selected to exert a synergistic effect on the pesticidal activity of the compound of formula (1).

Combinations of two or more herbicides may be included as a single formulation or added in a suitable form later in the process of preparing the tank mixture. Representative herbicides that can be used in such mixtures are amitydione, metabenztidazurone, metamitrone, metribuzin, 2,4-D, 2,4-DB, 2,4-DP, alarcler, alkoxy Dim, Asulam, Atrazine, Bensulfuron, Ventazone, Biphenox, Bromosinyl, Butacler, Carpentratone, Chloridazone, Chlorimuron, Chlorprofam, Chlorsulforon, Chloroluron, Cynmethyline , Clopyralide, cyanazine, cycloate, cyclosulfamuron, cycloxydim, diclobenyl, diclopov, dimethenamid, EPTC, ethiozin, phenoxaprop, flamprop, fluazipope, Plumethuron, pluridone, fluoroxypyr, pomesapene, glufosinate, glyphosate, haloxypope, hexazinone, amizamethabenz, amazametaphyr, amazimox, amazapyr, amazaquin , Amazetapyr, oxynyl, isoproturon, isoxaplutol, lactofen, MCPA, MCPP, mefenacet, Zacler, Metorlaccler, Metsulfuron, Molinate, Norflurazon, Orizalin, Oxyfluorophene, Fendimethalin, Piccloram, Pretilacller, Propacler, Pyridate, Quizalopope, Cetoxy Dim, simethrin, terbutryn, thiobencarb, triallate, trifuralline, diflufenican, propanyl, triclopyr, diccarba, dicamba, desmedipharm, acetochlor, fluoroglosses Lycopene, halosafen, trakcockdim, amidosulfonon, cynosulfuron, nicosulfuron, pyrazolfuron, sulfentrazone, thiamethuron, thifensulfuron, triasulfuron, tribenuron, esprocarb , Prosulfocarb, terbutylazine, benfuresate, clomazone, dimethazone, dithiopyr, isoxaben, quinclolac, quumelac, and sulfosate.

Mixtures with other active ingredients such as fungicides, insecticides, acaricides and nematicides are also possible.

A formulation containing a compound according to the invention consists of 100 g of the active ingredient (compound of formula (1)), 30 g of dispersant, 3 g of antifoam, 2 g of structuring agent, 50 g of antifreeze agent, 0.5 g of biocide and 1000 ml of water. Can be. Before using this composition, dilution with water gives the desired concentration of the active ingredient.

To more clearly understand the present invention, specific examples are described below. These examples are merely exemplary and should not in any way be intended to limit the scope of the invention or to represent the principles of the invention. Various modifications of the invention in addition to those described and shown below will be apparent to those skilled in the art based on the following examples or the above description. Also, such modifications are intended to fall within the scope of the appended claims.

The structure of the present invention prepared in the following examples was additionally confirmed by NMR (nuclear magnetic resonance) and MS (mass spectrometer).

Example 1

2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N-3,3,5-trimethyl-cyclohexa-1,5-die Nil) -acetamide

1A ethyl- (3,5,5-trimethyl-cyclohex-2-enylidene) -amine:

Ethylamine (42 ml of a 70% solution in water, 530 mmol) is slowly added to a stirred mixture of isophorone (9.67 g, 70 mmol) and ethylamine hydrochloride (0.29 g, 3.5 mm) at -7 ° C. After the addition is complete, the temperature of the mixture is allowed to warm to room temperature and the mixture is stirred for 72 additional hours. The mixture is then cooled to 10 ° C. and potassium hydroxide (44.9 g, 800 mm) is added several times. After 45 minutes, ice is added and the mixture is stirred. The organic phase is then separated, dried over sodium sulphate and evaporated in vacuo to give the crude product (11.0 g, 95%) as a yellow oil which is used in the next step without further purification.

1 B 2-Acetoxy-N-ethyl-N- (3,3,5-trimethyl-cyclohexa-1,5-dienyl) -acetamide:

2-Ethoxyacetyl chloride (6.42 g, 4.7 mmol) is added slowly to the mixture of the material of step 1A (7.62 g, 4.2 mmol) and toluene (50 ml) and cooled to -5 ° C. After the addition is complete, the mixture is further stirred at −5 ° C. for 1 hour, then warmed to room temperature and stirred for another 1.5 hours. The reaction mixture is then cooled to −3 ° C. and a mixture of triethylamine (6.5 ml, 4.7 mmol) and toluene (25 ml) is slowly added to the mixture. The mixture is stirred for another 16 hours, at which time the temperature is gradually raised to room temperature. The mixture is filtered, the filtrate is washed three times with water, dried over sodium sulfate and evaporated in vacuo to give the prepared product (12.0 g, 89%) in oil. A portion of the prepared material (4 g) was flash chromatographed with a mixture of ethyl acetate and petroleum ether (1: 4), flash chromatography to give pure product (2.3 g, equivalent to 51% total yield, mp 38-40 ° C.) Get Analysis of this by NMR showed that the product had a purity of about 88 mol% and the impurities consist mainly of two isomeric products.

1C 2-hydroxy-N-ethyl-N- (3,3,5-trimethyl-cyclohexa-1,5-dienyl) -acetamide:

A mixture of potassium hydroxide (0.47 g, 8.3 mmol) and water (5 ml) is added to the Step 1 B product (2.2 g, 8.3 mmol) in ethanol (10 ml) and the mixture is stirred at room temperature for 3 hours. The solvent is evaporated in vacuo and the resulting residue is dissolved in dichloromethane. The organic solution is washed twice with a small amount of water, dried over sodium sulfate and evaporated in vacuo to give the product (1.6 g, 86%) in beige crystals (m. P. 53-56 ° C.). Analysis by NMR revealed that the product had a purity of 84 mol% and the main pollutant was another diene isomer.

1D 2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N-3,3,5-trimethyl-cyclohexa-1,5- Dienyl) -acetamide:

Sodium hydroxide (0.15 g, 60% suspension in oil, 3.8 mmol) is added to a stirred mixture of the product of step 1C (0.78 g, 3.5 mmol) and THF (tetrahydrofuran) (10 ml) and the mixture is stirred for 30 minutes. Then, a mixture of 2-methanesulfonyl-5-trifluoromethyl- [1,3,4] -thiadiazole (0.81 g, 3.5 mmol) and THF (5 ml) was added to the stirred suspension, and the mixture was allowed to come to room temperature. Stir for another 16 hours. The solvent is removed by vacuum evaporation, and the resulting oil is flash chromatographed, eluting with a mixture of ethyl acetate and petroleum ether (1: 4) to give the product (0.45 g, 34%) as a yellow oil. As a result of NMR analysis, the structure of the product was confirmed to be consistent.

Example 2

Preparation of 2- (benzoxazol-2-yloxy) -N-ethyl-N-3,3,5-trimethyl-cyclohexa-1,5-dienyl) -acetamide

Sodium hydroxide (0.15 g, 60% suspension in oil, 3.8 mmol) is added to a stirred mixture of step 1C (0.78 g, 3.5 mmol) and THF (10 ml) and the mixture is stirred for 30 minutes. Then, a mixture of 2-chlorobenzoxazole (0.54 g, 3.5 mmol) and THF (5 ml) is added to the stirring suspension, and the mixture is further stirred at room temperature for 16 hours. The solvent is removed by vacuum evaporation and the solid residue is recrystallized from diisopropyl ether to give the product (0.58 g, 49%) as beige crystals (m. P. 97-99 ° C.). As a result of NMR analysis, the structure of the product was confirmed to be consistent.

Example 3-15

Additional compounds of the invention are prepared according to the general methods of Examples 1 and 2 and listed in Tables 1 and 2 (for simplicity, the table shows the 3,3,5-trimethylcyclohexa-1,3-dienyl moiety). Only the main product containing, the substituents being for the following formula).

Example number R ¹ R ³ 3 methyl Trifluoromethyl m.p. 54-57 ℃ 4 Isopropyl Trifluoromethyl oil 5 methyl ethyl oil 6 ethyl ethyl oil 7 methyl Pentafluoroethyl oil 8 ethyl Pentafluoroethyl m.p. 55 ℃ 9 methyl t-butyl oil 10 ethyl t-butyl 11 Isopropyl ethyl oil 12 Isopropyl Pentafluoroethyl 13 Isopropyl t-butyl 14 2-methoxyethyl Trifluoromethyl 15 Cyclopropyl Trifluoromethyl

Example 16-34

Additional examples are prepared according to the general preparation methods of Examples 1 and 2 and listed in Table 2 (substituents for which the formulas are below).

Example number Y X R ¹ 16 H O methyl mp. 77-81 ℃ 17 H O i-profile oil 18 H O 2-methoxyethyl 19 5-Cl O methyl 20 5-Cl O ethyl 21 5-Cl O Isopropyl 22 6-Cl O methyl 23 6-Cl O ethyl 24 6-Cl O Isopropyl 25 5-Cl O 2-methoxyethyl 26 6-Cl O 2-methoxyethyl 27 5-methyl O methyl 28 5-methyl O ethyl 29 5-methyl O Isopropyl 30 5-methyl O 2-methoxyethyl 31 H S methyl 32 H S ethyl 33 H S Isopropyl 34 H S 2-methoxyethyl

Example 35-43

Additional examples are prepared according to the general preparation methods of Examples 1 and 2, and the results are listed in Table 3.

Herbicide activity

Compounds of the present invention are tested for pre and post emergent herbicidal activity. Species included in the test are listed below.

TRZAW Triticum aestivum Winter wheat HORVW Hordeum vulgare Winter barley ZEAMX Zea mays corn GLXMX Glycine max bean ORYSA Orvza sativum rice AMATA Amaranthus tuberculatus Waterhemp GALAP Gallium aparine Clever ALOMY Alopecurus myosuroides Blackgrass APESV Apera spica venti Bentgrass ECHCG Echinochloa crus-galli Barnyardgrass SETVI Setaria viridis Green foxtail LOLPE Lolium perenne Eavers

Each pollen is assessed 3 weeks after treatment and phytotoxicity is assessed according to the following evaluation system:

Evaluation system % Difference between growth versus untreated control 0-no effect 0 1-minor effect 1-5 2- slight effect 6-15 3-moderate effect 16-29 4-damage 30-44 5-limited damage 45-64 6-herbicide effect 65-79 7-excellent herbicidal effect 80-90 8-almost complete removal 91-99 9-complete removal 100

Pre-emergence herbicidal evaluation of test compounds

Preemergence herbicidal activity of the compounds of the present invention is exemplified by the following test, in which various monocotyledonous and dicotyledonous plants are mixed separately with the detrimental soil and planted about 1 inch above the soil in each pollen. The shim is then sprayed with the selected aqueous acetone solution containing the test compound in an amount sufficient to provide the test compound in pollen sugar equivalents of about 0.8 to 0.1 kg per hectare. The treated pots are then placed in greenhouse pots, watered and managed according to conventional greenhouse methods. The results are shown in Table 4 below.

Post-emergence herbicide evaluation of the test compound

Post-emergence herbicidal activity of the compounds of the present invention is a test compound solution in acetone in which various monocotyledonous and dicotyledonous plants contain 0.4% by weight of an alkylphenol / ethylene oxide condensate (available under the trade name Triton X-155). This is demonstrated by the following test treated with the formulation prepared from: The acetone solution is diluted with water and the resulting formulation uses the test compound per pollen at a dose level of about 0.4 to about 0.1 kg per hetar. After spraying, the plants are placed in greenhouse pots and managed in a conventional manner according to conventional greenhouse practices. The results are shown in Table 5 below.

The compounds according to the invention combine high herbicide activity with the required selectivity and improved soil degradability.

Claims (16)

A compound of formula (1) <Formula 1> In the above formula, Het represents an optionally substituted, optionally benzofused nitrogen containing 5 or 6 membered heteroaromatic group, R ¹ represents an alkyl, alkoxyalkyl or cycloalkyl group, Each R ² independently represents an alkyl or alkenyl group, m represents 0 or the integer of 1-6. 2. The compound of claim 1, wherein each R ² independently represents a C _1-4 alkyl or C _2-4 alkenyl group, and m is 1, 2 or 3. 3. The compound of claim 1, wherein Het represents a thiadiazolyl, benzoxazolyl or benzothiazolyl group which may be substituted with one or more halogen atoms or an alkyl, haloalkyl, haloalkoxy or phenyl group. 4. A compound according to claim 3, wherein Het represents a group selected from formulas (2) and (3): <Formula 2> <Formula 3> In the above formula, R ³ represents hydrogen or a halogen atom or an alkyl or haloalkyl group, X represents O or S, Y independently of each other represents a halogen atom or an optionally substituted alkyl group, n is an integer of 0-4. The compound of claim 1, wherein R ² represents a methyl group and m is 3. The compound of claim 1, wherein R ¹ represents a C _1-5 alkyl, cyclopropyl or 2-methoxyethyl group. A compound of formula (4) <Formula 4> Wherein Het, R ¹ and R ² are as defined in claim 1, and the curve shows the presence of two conjugated double bonds at one or the other with respect to the point of attachment of the nitrogen atom. Indicates. 8. A compound according to claim 7, selected from formulas (5) and (6): <Formula 5> <Formula 6> Wherein R ¹ represents an alkyl or alkoxyalkyl group, Het is a group selected from formulas (2) and (3) <Formula 2> <Formula 3> (Wherein X is as defined above, Y represents a halogen atom or a methyl group, n is 0 or 1, and R ³ represents a C _1-4 -alkyl or C _1-4 -fluoroalkyl group). Isomer mixtures of two compounds of formula (4) according to claim 7 differing only in the position of double bonds. The compound of claim 1 selected from the group consisting of: 2- (5-Trifluoromethyl- [1,3,41-thiadiazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1, 3-dienyl ) -Acetamide, 2- (5-trifluoromethyl- [l, 3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-die Nil) -acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-die Nil) -acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-die Nil) -acetamide, 2- (5-ethyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl)- Acetamide, 2- (5-ethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl)- Acetamide, 2- (5-ethyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl)- Acetamide, 2- (5-ethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl)- Acetamide, 2- (5-pentafluoroethyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-die Nil) -acetamide, 2- (5-pentafluoroethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-die Nil) -acetamide, 2- (5-pentafluoroethyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-die Nil) -acetamide, 2- (5-pentafluoroethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-die Nil) -acetamide, 2- (5-t-butyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl ) -Acetamide, 2- (5-t-butyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-l, 3-dienyl ) -Acetamide, 2- (5-t-butyl- [1,3,4] -thiadiazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-l, 5-dienyl ) -Acetamide, 2- (5-t-butyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl ) -Acetamide, 2- (5-Trifluoromethyl- [l, 3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3- Dienyl) -acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohexa-1,5- Dienyl) -acetamide, 2- (5-ethyl- [l, 3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) Acetamide, 2- (5-ethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) Acetamide, 2- (5-pentafluoroethyl- [l, 3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3- Dienyl) -acetamide, 2- (5-pentafluoroethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1,5- Dienyl) -acetamide, 2- (5-t-butyl- [l, 3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-die Nil) -acetamide, 2- (5-t-butyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohexa-1,3-diene Nil) -acetamide, 2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohexa -1,3-dienyl) -acetamide, 2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohexa -1,5-dienyl) -acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-cyclopropyl-N- (3,5,5-trimethylcyclohexa-1,3- Dienyl) -acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-cyclopropyl-N- (3,3,5-trimethylcyclohexa-1,5- Dienyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1,5-dienyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide, 2- (benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-triethylcyclohexa-1,5-dienyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (6-Chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1,5-dienyl) -acetamide 2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (5-Chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -aceta mid, 2- (5-chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3.3,5-trimethylcyclohexa-1,5-dienyl) -acetamide, 2- (6-Chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -aceta mid, 2- (6-Chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -aceta mid, 2- (5-methyl-benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide, 2- (5-Methyl-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -aceta mid, 2- (5-Methyl-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -aceta mid, 2- (benzothiazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohexa-1,5-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohexa-1,5-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohexa-1,5-dienyl) -acetamide, 2- (benzothiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohexa-1,3-dienyl) -acetamide, 2- (benzothiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohexa-1,5-dienyl) -acetamide. A process for preparing a compound according to claim 1 comprising reacting a compound of formula (7) with a compound of formula (8): <Formula 7> (Wherein R ¹ , R ² and m are as defined in claim 1), <Formula 8> Het-L ² (Wherein Het represents an optionally substituted, optionally benzofused nitrogen containing 5 or 6 membered heteroaromatic group, one of L ¹ and L ² represents a hydroxy group and the other represents a leaving group). A compound of formula (7) <Formula 7> Wherein R ¹ represents an alkyl, alkoxyalkyl or cycloalkyl group, Each R ² independently represents an alkyl or alkenyl group, m represents 0 or an integer from 1 to 6, L ¹ represents a hydroxy group or leaving group selected from alkyl- and arylsulfonyl, alkyl- and arylsulfonyloxy and perfluoroalkylsulfonyloxy groups. A herbicide composition comprising at least one compound according to claim 1 and at least one agriculturally acceptable carrier. The composition of claim 13, comprising two or more carriers, at least one of which is a surfactant. A method of inhibiting unwanted plant growth at a site, comprising applying the compound of claim 1 to a locus in an amount effective for weeding. A method of inhibiting unwanted plant growth at a site comprising applying the compound of claim 13 in an amount effective for herbicidal use.