KR20010032160A - Herbicidal n-alkenyl heteroarylyloxyacetamides - Google Patents

Abstract

Novel compounds of formula (I) and herbicide compositions containing these compounds as active ingredients can be used in a number of agricultural methods.

Formula I

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 represents a hydrogen atom and R ³ represents an alkyl group or R ² and R ³ taken together represent a single bond or a methylene group:

R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independently represent a hydrogen atom or a C ₁ -C ₄ alkyl group, provided

At least two of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ must represent an alkyl group: 2- (5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy)- N-methyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide is excluded.

Description

Herbicidal en-alkenyl heteroarylyloxyacetamide {HERBICIDAL N-ALKENYL HETEROARYLYLOXYACETAMIDES}

Surprisingly, the present inventors have found that the novel compounds of formula (I) show good herbicidal activity even at low contents and have improved selectivity in crops than those described in the aforementioned patents.

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 represents a hydrogen atom, R ³ represents an alkyl group, or R ² and R ³ are taken together to form a single bond or methylene group;

R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independently represent a hydrogen atom or a C ₁ -C ₄ alkyl group, provided

a) at least two of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ must represent an alkyl group;

b) 2- (5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohex-1-enyl)- Acetamide is excluded.

Accordingly, the present invention relates to a novel compound of formula (I), a method of weeding an undesirable plant by contacting the plant with a herbicidally effective amount of a compound of formula (I), an optional herbicide composition containing a compound of formula (I) as an active ingredient, and a compound of formula (I) It provides a novel manufacturing method of.

The compounds of formula I have good selective herbicidal activity and improved soil degradability in certain crops such as rice, corn, cereals, soybeans, sugar beets, canola, sunflower or potatoes. Many objects and features of the present invention will become more apparent from the following detailed description.

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

For example, U.S. Patent 4,585,471 has the formula

It describes a compound of.

European patent application EP 0 005 501 discloses benzofused oxazol-2-yl- and thiazol-2-yl-oxyacetamides wherein the amido nitrogen atom is a hydrogen atom and / or an optionally substituted alkyl, alkenyl, Alkynyl, aralkyl, cycloalkyl or aryl groups). However, no alkenyl-substituted compounds or cycloalkenyl compounds in which the 1-position to the nitrogen atom is a double bond are not described.

European patent application EP 0 165 537 discloses benzofused oxazol-2-yl- and thiazol-2-yl oxyacetamides, wherein the amido nitrogen atom has one or two allyl groups, one cyclohex-1 A process for preparing enyl, one cyclohex-3-enyl or one vinyl group) is described. However, side chain alkenyl compounds or alkyl substituted cycloalkenyl compounds are not described.

International patent application WO 97/08160 describes N- (1-isopropyl-2-methyl-1-propenyl) -heteroaryloxyacetamide. However, heteroaromatic oxyacetamides, wherein amido nitrogen atoms form and form enamines derived from ketones having different alkyl chains and / or have seven or more carbon atoms, are not described.

While many known heteroaryloxyacetamides show significant activity against many weeds, they are not completely satisfactory in terms of selectivity or persistence.

The compounds of the present invention show high herbicidal activity with the required selectivity and improved soil degradability.

Surprisingly, it has been found that the novel compounds of formula I show good herbicidal activity and high selectivity against a large number of weeds.

As used herein, the term ″ optionally benzofused nitrogen-containing 5- or 6-membered heteroaromatic group refers to azoles such as pyrrole, pyrazole, imidazole, oxazole, thiazole and thiadiazole, pyridine, pyrimidine, pyrazine Azines such as pyridazine and triazine. Preference is given to optionally benzofused azoles.

The term ″ Het ″ preferably denotes a thiadizolyl, benzoxazolyl or benzthiazolyl group which may be substituted with one or more halogen atoms or alkyl, haloalkyl or phenyl groups.

Where any group is named as optionally substituted, the optionally present substituent groups may be those conventionally used in the modification and / or development of pesticide compounds, in particular herbicidal activity, or soil or plant infiltration with the compounds of the present invention. And substituents that maintain or enhance other desirable properties of these herbicide compounds.

One or more identical or different substituents may be present in each portion of the molecule.

With respect to the residues defined above comprising an optionally substituted heteroaryl group, the optional substituents are halogen, in particular fluorine, chlorine and bromine atoms, and nitrogen, cyano, amino, hydroxyl, C _1-4 -alkyl, C _1-4 -alkoxy, C _1-4 - include aryl groups, such as haloalkylthio and phenyl -haloalkyl, C _1-4 - alkenyl, halo, C _1-4 - haloalkoxy, C _1-4. One to five substituents, preferably one to two substituents, most preferably one substituent may be used.

In particular, the term ″ Het ″ refers to a group selected from compounds of Formula 1 and Formula 2.

In the above formula,

R ⁹ represents hydrogen or a halogen atom or a haloalkyl group;

X represents O or S;

Y independently of one another, represents a halogen atom or an optionally substituted alkyl group;

n is an integer of 0-4.

Y is preferably a fluorine or chlorine atom or C _1-4 alkyl, C _1-4 fluoroalkyl, C _1-4 alkoxy or C _1-4 fluoroalkoxy groups, in particular chlorine atoms.

The variable n is preferably 0, 1 or 2, most preferably 0 or 1.

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

In general, if the aforementioned moieties include alkyl groups, these groups may be straight or branched unless otherwise specified and may contain 1 to 6, preferably 1 to 4 carbon atoms. Examples of such groups are the methyl, ethyl, propyl, butyl, isobutyl and tert-butyl groups. The alkyl moiety of haloalkyl, haloalkoxy, haloalkylthio, alkylthio or alkoxy groups preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms.

In general, if the aforementioned moieties comprise alkoxyalkyl groups, these groups may be straight or branched and contain 2 to 6, preferably 3 to 5 carbon atoms, unless otherwise specified. Examples of such groups are methoxymethyl, 2-methoxyethyl, 3-methoxypropyl, 2-methoxy-1-methylethyl and methoxybutyl.

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

In general, if the aforementioned moieties include haloalkyl groups, these groups may be straight or branched and contain 1 to 6, preferably 1 to 4 carbon atoms, unless otherwise specified. Examples of such groups are halomethyl, haloethyl, halopropyl, haloisopropyl, halobutyl, haloisobutyl and halo tert-butyl groups. Haloalkyl residue groups within 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-tri Fluoroprop-2-yl group, most preferably trifluoromethyl.

R ¹ is preferably a C _2-4 alkyl, C _2-6 alkoxyalkyl or C _3-7 cycloalkyl group, most preferably ethyl, propyl, isopropyl, cyclopropyl and 2-methoxyethyl group.

When R ² and R ³ together form a single bond, the resulting ring system is a substituted cyclopent-1-enyl group. When R ² and R ³ together form a methylene group, the resulting ring system is a substituted cyclohex-1-enyl group such as 3,3,5-trimethylcyclohex-1-enyl or 3,5, 5-trimethylcyclohex-1-enyl group.

When R ² represents a hydrogen atom and R ³ represents an alkyl group, in particular a methyl group, the resulting branched alkenyl group preferably contains a formula containing 8 to 12 carbon atoms, more preferably 9 or 10 carbon atoms.

Is a group. Most preferred are 2,6-dimethylhept-3-en-1-yl groups.

R ⁴ to R ⁸ independently represent preferably hydrogen or a C _1-4 alkyl group, in particular a hydrogen atom or a methyl group, provided that at least two of these substituents are C _1-4 alkyl groups. R ⁴ represents a hydrogen atom; Most preferred are compounds of formula I, wherein R ⁵ and R ⁷ are methyl groups, one of R ⁶ and R ⁸ is a methyl group and the other is a hydrogen atom.

Particular preference is given to compounds of the formula IA.

In the above formula,

R ¹ represents an alkyl or alkoxyalkyl group, in particular a C _2-3 alkyl or 2-methoxyethyl group,

Het represents a group selected from Formula 1 and Formula 2.

Formula 1

Formula 2

(In the above formula,

X represents O or S;

Y represents a halogen atom, in particular a chlorine atom, or a methyl group;

n is 0 or 1;

R ⁹ represents a C _1-4 fluoroalkyl group, in particular a trifluoromethyl group.)

Furthermore, compounds of formula (IB) are also preferred.

In the above formula,

R ¹ represents a C _1-5 alkyl or C _3-5 alkoxyalkyl group, in particular an ethyl, isopropyl or 2-methoxyethyl group,

Het represents a group selected from formulas (1) and (2), provided that when R1 represents a group of formula (1) R ¹ represents a C _2-5 alkyl or C _3-5 alkoxyalkyl group.

Formula 1

Formula 2

(In the above formula,

X represents O or S;

Y represents a halogen atom, in particular a chlorine atom, or a methyl group;

n is 0 or 1;

R ⁹ represents a C _1-4 fluoroalkyl group, in particular a trifluoromethyl group;

Two lines indicate the presence of a double bond in one or the other positions.)

Particular preference is given to compounds of the formulas IB1 to IB4.

In the above formula,

R ¹ represents an ethyl or isopropyl group,

X represents O,

R ¹ represents a C _1-5 alkyl group, or a methoxy-C _1-4 alkyl group, in particular a methyl, ethyl, isopropyl, methoxymethyl, 2-methoxyethyl or 2-methoxy-1-methylethyl group Indicates,

n is 0 or 1;

Preferably, the compounds of formula I are obtained and used as isomeric mixtures of compounds of formula I which differ only in the position of the double bond. Thus, the invention preferably relates to isomeric mixtures of compounds of formula I, in particular only mixtures of compounds of formula IB, differing only in the position of the double bond.

The invention is illustrated by the compounds described below.

2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1-enyl)- Acetamide,

2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohex-1-enyl)- Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,4-trimethylcyclopent-1-enyl)- Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,4,4-trimethylcyclopent-1-enyl)- Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,4-trimethylcyclopent-1-enyl) Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,4,4-trimethylcyclopent-1-enyl) Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclopent-1-enyl)- Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (2,4,4-trimethylcyclopent-1-enyl)- Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclopent-1-enyl) Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (2,4,4-trimethylcyclopent-1-enyl) Acetamide,

2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (2,6-dimethylhept-3-en-4-yl) Acetamide,

2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (2,6-dimethylhept-3-en-4-yl ) -Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohex -1-enyl) -acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohex -1-enyl) -acetamide,

2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2yloxy) -N- (2-methoxyethyl) -N- (2,6-dimethylhept-3-ene -4-yl) -acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-cyclopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-cyclopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) Acetamide,

2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-cyclopropyl-N- (2,6-dimethylhept-3-en-4-yl ) -Acetamide,

2- (benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

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

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

2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,3,4-trimethylcyclopent-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,4,4-trimethylcyclopent-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,4-trimethylcyclopent-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,4,4-trimethylcyclopent-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclopent-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-ethyl-N- (2,4,4-trimethylcyclopent-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclopent-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-isopropyl-N- (2,4,4-trimethylcyclopent-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-ethyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide,

2- (benzoxazol-2-yloxy) -N-isopropyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide,

2- (benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

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

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

2- (5-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (5-chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (6-chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

2- (5-methyl-benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (5-methyl-benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

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

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

2- (5-methyl-benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (5-methyl-benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

2- (5-methyl-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (5-methyl-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

2- (5-methyl-benzoxazol-2-yloxy) -N-ethyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide,

2- (5-methyl-benzoxazol-2-yloxy) -N-isopropyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide,

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

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

2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-ethyl-N- (3,3,4-trimethylcyclopent-1-enyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-ethyl-N- (3,4,4-trimethylcyclopent-1-enyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,3,4-trimethylcyclopent-1-enyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,4,4-trimethylcyclopent-1-enyl) -acetamide,

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

2- (benzothiazol-2-yloxy) -N-ethyl-N- (2,4,4-trimethylcyclopent-1-enyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclopent-1-enyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-isopropyl-N- (2,4,4-trimethylcyclopent-1-enyl) -acetamide,

2- (benzothiazol-2-yloxy) -N-ethyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide,

2- (benzothiazol-2-yloxy) -N-isopropyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide,

2- (benzothiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide,

2- (benzothiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide,

2- (5-chloro-benzothiazol-2-yloxy) -N-ethyl-N- (3,3,4-trimethylcyclopent-1-enyl) -acetamide,

2- (5-Chloro-benzothiazol-2-yloxy) -N-ethyl-N- (3,4,4-trimethylcyclopent-1-ethyl) -acetamide.

Compounds of formula (I) are oils, gums or mainly crystalline solid materials. They are superior by their valuable herbicidal properties. For example, they can be used in agriculture or related fields for the control of undesirable plants. Compounds of formula (I) exhibit good herbicidal activity at low concentrations within a wide concentration range and are particularly difficult in certain crops such as corn and rice, especially Alopecurus myosuroides, Echinoloa cros-Gali (Echinochloa crus-galli), Setaria viridis, Gallium aparine, Stellaria media, Veronica persica, Digitaria sanguinalis ), Lolium perenne, Lamium purpureum, Viola arvensis, Abutilon theophrasti, Ipomoea purpurea and Amaranthus retro It can be used in agriculture by pre- and post-germination spraying for selective weeding of undesirable plants such as Amaranthus retroflexus.

Compounds of formula (I) can be prepared by conventional methods.

Particularly suitable methods for preparing compounds of formula (I) include the reaction of compounds of formula (II) with compounds of formula (III):

Het-L ²

In the above formula,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above,

Het is as described above,

One of L ¹ and L ² represents a hydroxyl group and the other represents a leaving group.

The reaction can be carried out in the absence or presence of a solvent that does not promote or at least interfere with the reaction. Polar, aprotic or protic solvents are preferred, ethers such as N, N-dimethylformamide, dimethylsulfoxide, sulfolane, acetone, acetonitrile, methyl ethyl ketone, or tetrahydrofuran or dioxane, or Alcohols, or water, or mixtures thereof are suitable. The reaction is carried out at ambient temperature to reflux, preferably at elevated temperatures, in particular at reflux temperature of the reaction mixture. Substantially the same amount of reactant is commonly used.

The reaction is in the presence of an alkali hydroxide, a bicarbonate or carbonate, for example sodium or potassium hydroxide, a bicarbonate or carbonate, an alkali alkoxide, for example sodium ethoxide, or an organic base such as triethylamine. Can be run under the following conditions. In a particularly preferred embodiment, the process of the invention is carried out in the presence of a phase transfer catalyst, preferably tetraalkyl-ammonium halides, most preferably tetraethyl-ammonium bromide.

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

The specific compounds used as starting materials are known and the rest are new compounds. The present invention also relates to novel intermediates of formula (II).

Formula II

In the above formula,

R ¹ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above,

R ² represents a hydrogen atom,

R ³ represents an alkyl group,

L ¹ represents a hydroxy group or leaving group selected from alkyl- and arylsulfonyl, alkyl- and arylsulfonyloxy or perfluoroalkylsulfonyloxy groups and halogen atoms. Most preferred are compounds of formula IIA.

In the above formula,

R ¹ represents an alkyl or alkoxyalkyl group,

L ¹ represents a hydroxy group or a halogen atom.

Compounds of formula (II) are obtained by reaction with 2-chloroacetyl chloride from the imine corresponding to formula (IV), followed by subsequent reaction with alkali acetate and deacylation with aqueous -alkali alkali hydroxide solution. The imine of formula IV can be prepared by the condensation of a primary amine with the corresponding ketone.

In the above formula,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above for the compound of formula (I).

When asymmetric ketones are used, the resulting double bonds in the compounds corresponding to Formula I and Formula II may be formed at two different positions. The reaction product then contains a mixture of isomeric compounds of formula (I) and formula (II), differing only in the position of the double bond.

Commercially available ketones such as 3,5,5-trimethylcyclohexanone, 2,2,4-trimethylcyclopentanone, 2,4,4-trimethylcyclopentanone and di- (2-methylpropyl) -ketone This is preferable. The condensation reaction between the ketone and the amine can be carried out by azeotropic distillation of the resulting water, according to known methods. Removal of water is by addition of acid or acid catalysts such as hydrochloric acid, p-toluenesulfonic acid or ammonium sulfate, or basic compounds such as sodium or potassium hydroxide and alkali carbonates, or by dehydrating agents such as TiCl ₄ or molesieve. Can be promoted.

The invention also relates to the use of the compounds of formula (I) as herbicides. Thus, the present invention provides a method of inhibiting the growth of undesirable plants in the locus by treating the locus with an herbicidally effective amount of the compound of formula I, which is typically mobilized into the herbicide composition. Since a useful task is spraying leaves, locus is most suitable for crop growing, usually for grain, corn, soybean, sunflower or cotton growing plants. However, such compounds with pre-germination herbicidal activity can be applied to the soil or to water for crops such as paddy rice.

The present invention also provides a method of inhibiting the growth of undesirable plants in the locus, which includes spraying such compounds or compositions. In particular, the desired activity was found for grass and broad leaf weeds both before and after germination. Selectivity has also been found in important crop species such as wheat, barley, corn, rice and soybeans.

In the process of the invention, the effective amount of the active ingredient of the compound of the invention is, for example, 0.05 to 10 kg / ha, preferably 0.01 to 4 kg / ha, especially 0.05-3 kg / ha, most preferably 0.1 to May be 1 kg / ha. The locus can be an agricultural or horticultural locus, including for example plants or soil. In a preferred method the locus includes the growth of undesirable plants and the treatment is spraying the leaves.

Compounds of formula I exhibit herbicidal activity. Accordingly, the present invention further provides a herbicidal composition comprising at least one active ingredient which is a compound of formula (I) and at least one carrier. The process for the preparation of such a composition also includes the step of compounding the compound of formula I described above with the carrier (s). Such compositions may contain a single active ingredient or a mixture of multiple active ingredients of the present invention. It has also been observed that different isomers or mixtures of isomers have different levels or spectra of activity, so that the composition may eventually include a range of herbicidal activities of the composition, including each isomer or mixture of isomers.

The composition according to the invention preferably contains from 0.5% to 95% by weight (w / w) of one or more active ingredients.

Agronomically acceptable carriers in the compositions according to the invention are substances which can be formulated to facilitate spraying on the locus to be treated, for example plants, seeds or soil and to facilitate storage, transport or treatment. The carrier may be a solid or liquid, and typically includes a material that is a gas that is compressed to form no liquid.

The compositions are well-known methods, for example, emulsions, emulsifiable concentrates, solutions, oil-in-water emulsions, wettable powders, soluble powders, suspension concentrates, dusts, granules, granules in which water is dispersed, microcapsules, gels, aerosols and It may be prepared in other dosage forms. Such methods include milling the active ingredient and other substances such as strong mixing and / or fillers, solvents, solid carriers, surface active compounds (surfactants), and optionally solid and / or liquid auxiliaries and / or adjuvants. Spreading forms such as spraying, powdering, atomizing or pore can be selected according to the desired purpose and spreading environment.

Solvents used are aromatic hydrocarbons such as Solvesso ^R 200, substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffin, alcohols and glycols and ethers thereof And esters such as ethanol, ethylene glycol mono- and dimethyl ether, ketones such as cyclohexanone, N-methyl-2-pyrrolidone, γ-butyrolactone, higher alkyl pyrrolidones such as n- Strong polar solvents such as octylpyrrolidone or cyclohexylpyrrolidone, epoxidized vegetable oil esters such as methylated coconut or soybean oil esters and water. Often different solvent mixtures are suitable as carriers.

Dust, wetting powders, granules in which water is dispersed, or solid carriers that can be used for granulation can be mineral fillers such as calcite, mica, kaolin, montmorillonite or attapulgite. Physical properties can be improved with the addition of highly disperse silica gels or polymers. The carrier for granulation may be a porous material, for example a non-adsorbent carrier such as pumice, kaolin, sepiolite, bentonite or calcite or sand. In addition, a number of pre-granulated inorganic or organic materials can be used, such as dolomite or milled plant residues.

Herbicide compositions are often prepared and delivered in concentrated form, which is subsequently diluted by the user before sparging. The presence of small amounts of the carrier, which is a surfactant, facilitates this dilution process. Thus, preferably at least one carrier in the composition according to the invention is a surfactant. For example, the composition may comprise two or more carriers, at least one of which is a surfactant.

The surfactants used may be nonionic, anionic, cationic or zwitterionic materials which have good dispersion, emulsifying and wetting properties depending on the nature of the particular compound of formula I prepared. The term "surfactant" is also intended to include mixtures of two or more surfactants.

Wettable powders typically contain from 5 to 90% w / w of active ingredient, and in addition to solid inert carriers, typically contain from 3 to 10% w / w of dispersant and wetting agent, and zero stabilizer (s) if necessary. To 10% w / w and / or other additives such as penetrants or retention enhancers (stickers). Dust can be formulated as a powder concentrate, typically having a composition similar to the wettable powder, without a dispersant, and diluted outdoors with an additional solid carrier to give a composition which typically contains 0.5 to 10% w / w of the active ingredient. Granules and granules in which water is dispersed are typically prepared to have a size of 0.15 mm to 2.0 mm and can be prepared by various techniques. Generally, this type of granules will contain from 0.5 to 90% w / w of active ingredient and will contain additives such as stabilizers, surfactants from 0 to 20% w / w and will slowly release the modifiers and binders. . So-called "drying fluids" consist of relatively hardeners having a relatively high concentration of the active ingredient.

Emulsifiable concentrates typically contain a solvent or solvent mixture, 1 to 80% w / v of active ingredient, 2 to 20% w / v of emulsifier and 0 to 20% w / v of other additives such as stabilizers, penetrants and corrosion inhibitors. . Suspension concentrates are typically milled to give a stable, non-precipitated flowable product and are usually suspended in active agents such as active ingredients 5 to 75% w / v, dispersants 0.5 to 15% w / v, protective colloids and thixotropic agents. 0.1 to 10% w / v, antifoaming agents, corrosion inhibitors, stabilizers, penetrants and other additives such as retention enhancers (stickers) 0 to 10% w / v, and organic liquids in which water or the active ingredient is substantially insoluble. Certain organic solids or inorganic salts are dissolved in the formulation to prevent precipitation and crystallization or, in the case of water, serve as cryoprotectants.

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

Particular object to extend the duration of the protective activity of the composition of the present invention, among certain objects, is achieved by the use of a carrier which will provide a slow release of the pesticide composition into the environment of the plant to be protected.

The biological activity of the active ingredient will also be enhanced by including an adjuvant in the spray diluent. Adjuvant is defined herein as a substance capable of enhancing the biological activity of the active ingredient, but is substantially not itself biologically active. Adjuvants may be included in the formulation as a co-formulation or carrier, or may be added to the spray tank with a formulation containing the active ingredient.

As a commodity, the composition is preferably in concentrated form but the end user generally uses the diluted composition. The composition may be diluted to a concentration of up to 0.001% active ingredient. The spreading rate is usually 0.01 to 10 kg a.i./ha.

Examples of formulations according to the invention are as follows.

The compositions of the present invention may also comprise other compounds having biological activity, for example compounds having similar or complementary pesticidal activity or compounds having plant growth inhibitory, fungicidal or pesticidal activity. Such mixtures typically have a broader spectrum of activity than the compounds of formula (I) alone. In addition, other ingredients may be selected to produce synergistic effects on the pesticidal activity of the compound of formula (I).

At least two herbicide combinations may be included in a single formulation or later added in a suitable form during the preparation of the tank mixture. Examples of herbicides that can be used in such mixtures are: ammethyldione, viranaphos, metabenzthiazuron, metamitrone, metrizin, 2,4-D, 2,4-DB, 2,4-DP, Alacler, Aloxydim, Asuram, Atrazine, Bensulfuron, Ventazone, Biphenox, Bromozainyl, Butacler, Carpentraton, Chloridazone, Chlorimuron, Cloprofam, Closulfuron, Clotorru Lone, Cynmethinine, Cropyride, Cyanazine, Cycloate, Cyclosulfaeuron, Cyclozydim, Diclobenyl, Diclopop, Dimethenamid, EPTC, Ethiozine, Phenoxaplop, Flamprop, Prolua Zippop, Fluomethuron, Flulidone, Flurooxypyr, Pomsaphene, Glufosinate, Glyphosate, Halozaipop, Hexazinone, Imazametabenz, Imazamataphyr, Imazamax, Imazaphyr , Imazaquin, imazetapyr, oxynyl, isoproturon, isoflulutol, lactofen, MCPA, MCPP, mefenacet , Metazaclo, metolacler, metsulfuron, mololinate, noflurazone, oryzarine, oxyfluorophene, pendimethalin, picloram, frtylacler, propacler, pyridate, quizaropop, Cetoxydim, simethrin, terbutrin, thiobencap, trialate, trifluurine, diflufenican, propanyl, triclopyr, dicamba, desmedimaph, acetochlor, fluoroglycopene, halosafene , Tracocosidim, amidosulfuron, cynosulfuron, nicosulfuron, pyrazosulfuron, sulfentrazone, thiamethuron, thifensulfuron, triasulfuron, trivenuron, esprocap, prosulfocap, Terbutylrazine, benfurate, clomazone, dimethazone, dithiopyr, isobenzone, quinclolac, quinmerak, sulfosate. Mixtures with other active ingredients such as fungicides, insecticides, acaricides and nematicides are also possible.

Typical formulations containing a compound according to the invention are 100-500 g of active ingredient (compound of formula I), 30 g of dispersant, 2 g of antifoam, 2 g of structuring agent, 50 g of cryoprotectant, 0.5 g of fungicide and 1000 ml of water ad. It may contain. Dilution with water prior to use gives the active ingredient in the desired concentration.

For a clear understanding of the invention, certain examples are described below. Such embodiments are merely illustrative and should not be understood as limiting the scope and principle of the invention in any way. Many modifications of the invention and those described below will become more apparent to those skilled in the art from the following examples and the following description. Such modifications should also be within the scope of the appended claims.

The structure of the compound prepared according to the following example is additionally confirmed by NMR and Zeelang spectrometer.

Example 1:

N- (3,3,5-trimethylcyclohex-1-enyl) -N-ethyl-2-hydroxyacetamide and N- (3,5,5-trimethylcyclohex-1-enyl) -N-ethyl Preparation of 2-hydroxyacetamide

1A N-ethyl-N- (3,3,5-trimethylcyclohexylidene) amine

A total of 140 g (about 3.1 mol) of gas ethylamine was stirred with a mixture of 3,3,5-trimethylcyclohexanone (42 g, 0.3 mol), p-toluene sulfonic acid (0.5 g) and toluene (150 mL) Froth at room temperature over about 2 days at. The progress of the reaction is periodically monitored by removing small samples of the reaction mixture for mass spectrometer analysis. When no more water is produced and p-toluenesulfonic acid is completely dissolved, about 1/2 of ethylamine is added, followed by anhydrous sodium sulfate (about 30 g) to the mixture. After stirring for a few minutes, the solid material is filtered off and an additional fraction of p-toluenesulfonic acid (0.5 g) is added. The addition of ethylamine is then continued. When the ratio of product to starting material is about 70:30, concentrated hydrochloric acid (0.5 mL) is added to the reaction mixture and the remaining ethylamine is then bubbled. The reaction mixture is then diluted with approximately equal volume of petroleum ether and sodium hydroxide pellets (50 g) are added as a cloudy solution. The mixture is shaken several times and the supernatant is subsequently evaporated in vacuo to yield crude product 1A (40 g) as a yellow oil. Its analysis by NMR and mass spectrometer indicates that the product content is about 75%. It is used without further purification in the next step.

1B N- (3,3,5-trimethylcyclohex-1-enyl) -N-ethyl-α-chloroacetamide and N- (3,5,5-trimethylcyclohex-1-enyl) -N-ethyl -α-chloroacetamide

A solution of 2-chloroacetyl chloride (22.3 g, 0.19 mol) in toluene (100 mL) is added dropwise to a stirred mixture of 1A (40.0 g, about 0.18 mol) in toluene (400 mL) at 0 ° C. over 30 minutes. During the addition, a light-colored precipitate forms. The mixture is slowly warmed to room temperature and stirred for a further 16 hours. The mixture is then cooled back to about 0 ° C. and a solution of triethylamine (21.0 g, 0.205 mol) in toluene (100 mL) is added dropwise. After the addition is complete, the mixture is warmed to room temperature and stirred for an additional 5 hours, at which time analysis of the sample by thin layer chromatography indicates that the reaction is complete. The precipitate which formed was removed by filtration and the filtrate was washed five times with water (200 mL), dried over sodium sulfate and evaporated in vacuo. The resulting brown oil (46 g) was distilled on a Vigreux column under reduced pressure to give product 1B (33 g, 75%) as colorless oil (boiling point 118-123 ° C./0.01 mmHg). NMR analysis shows that this consists of about 42:58 mixtures of 3,3,5- and 3,5,5-trimethylcyclohex-1-enyl isomers.

1C N- (3,3,5-trimethylcyclohex-1-enyl) -N-ethyl-2-acetoxyacetamide and N- (3,5,5-trimethylcyclohex-1-enyl) -N- Ethyl-2-acetoxyacetamide

A mixture of sodium acetate (11.1 g, 0.135 mol), 1B (33.0 g, 0.135 mol) and crystalline acetic acid (40 mL) is refluxed for 16 hours and then cooled to room temperature. The precipitate is filtered off and the filtrate is evaporated in vacuo. The residue is azeotroduced twice with toluene (100 mL) to remove the acetic acid residue. The resulting oil (about 42 g) was dissolved in dichloromethane (250 mL) and the solution washed three times with water (100 mL), dried over sodium sulfate, filtered over a plug of silica gel, evaporated in vacuo and the 1C ( 29.0 g, 81%) is obtained as a pale brown oil. It is used without further purification in the next step.

1D N- (3,3,5-trimethylcyclohex-1-enyl) -N-ethyl-2-hydroxyacetamide and N- (3,5,5-trimethylcyclohex-1-enyl) -N- Ethyl-2-hydroxyacetamide

A mixture of a solution of potassium hydroxide (6.17 g, 0.11 mol) and 1C (29.0 g, 0.109 mol) in water (11 mL) and ethanol (44 mL) was refluxed for 24 hours, then cooled and evaporated in vacuo to give the crude product. (21 g) is obtained as a brown oil. It was purified by flash chromatography eluting with petroleum ether / ethyl acetate (4: 1) to give 1D (16.8 g, 69%) as a yellow oil.

Example 2

2- (5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy) -N- (3,5,5-trimethylcyclohexen-1-yl) -N-ethylacetamide and Of 2- (5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy) -N- (3,3,5-trimethylcyclohexen-1-yl) -N-ethylacetamide Produce

Potassium carbonate (13.8 g, 100 mmol) was added to a stirred solution of 1D (16.8 g, 75 mmol) in acetone (450 mL), followed by 2-methyl-sulfonyl-5-trifluoromethyl-1,3 , 4-thiadiazole (16.9 g, 73 mmol) is added followed by tetraethyl ammonium bromide (2 g). The mixture is stirred at rt for 30 h. The precipitate is filtered off and the filtrate is evaporated in vacuo. The residue is dissolved in dichloromethane (250 mL) and the solution is washed twice with water (50 mL), then dried over sodium sulfate and evaporated in vacuo to afford the crude product (21 g) as a brown oil. Purification by flash chromatography eluting with toluene / ethyl acetate (9: 1) gave 2 (11.9 g, 43%) as pale brown oil. Identification and purity of the product was confirmed by ¹ H NMR spectrometer and also shows that the isomer ratio is approximately 1: 1.

¹⁹ F NMR (CDCl ₃ /TFA)δ-17.8 ppm

Example 3-16:

Additional compounds of the invention are prepared by the conventional methods of Examples 1 and 2 and shown in Table 1.

Two lines of 3,3,5-trimethylcyclohexenyl groups indicate that the corresponding examples are mixtures of isomeric compounds that differ only in the position of the double bond.

Example 17:

2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide and 2- (benzoxazol-2-yloxy) -N Preparation of -ethyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide

A 1D (3.6 g, 16 mmol) solution in dry tetrahydrofuran (THF) (25 mL) is added dropwise to a stirred suspension of sodium hydride (0.66 g, 16.5 mmol) in dry THF (50 mL). After approximately 30 minutes, when there is no further hydrogen evolution, a solution of 2-chlorobenzoxazole (2.3 g, 15 mmol) in dry THF (40 mL) is added dropwise to the stirred mixture and the reaction mixture is stirred overnight at room temperature. Water (about 2.0 mL) is added to the mixture and then evaporated in vacuo. Dichloromethane (150 mL) is added to the residue and the organic phase is washed with water (4 x 100 mL), dried over sodium sulfate and evaporated in vacuo. The residue is triturated with petroleum ether (5 mL) to give 2 (3.9 g, 77%) as a beige waxy solid. Identification and purity of the product was confirmed by ¹ H NMR photometer and also shows that the isomer ratio is approximately 1: 1.

Examples 18-59:

Additional compounds of the invention are prepared by the conventional methods of Examples 1 and 17 and shown in Table 2.

Two lines of 3,3,5-trimethylcyclohexenyl groups indicate that the corresponding examples are mixtures of isomeric compounds that differ only in the position of the double bond.

Examples 60-75:

Additional compounds of the invention are prepared by the conventional methods of Examples 1, 2 and 17 and shown in Table 3.

Herbicide activity

The compounds of the present invention are tested before and after germination using the species in the table below.

Plant species used TRZAWZEAMXGLXMXHORVWORYSAALOMYAMARUAPESVDIGSAECHCGLOLPESETVISETFA Triticum aestivumZea maysGlycine maxHordeum vulgareOryza sativumAlopecurus myosuroidesAmaranthus rudisApera spica ventiDigitaria sanguinalisEchinochloa crus-galliLolium perenneSetaria viridisSetaria faberi Winter wheat corn soybean winter barley rice black grass

Three weeks after the treatment of each pollen was tested and the extent to which the plant is harmful is expressed in the range of 0-100% meaning 0 = no effect and 100 = all deaths.

Assessment of herbicidal activity before germination of test compounds

The pre-germination herbicidal activity of the compounds of the present invention is exemplified by the testing of the seeds of a number of monocotyledonous and dicotyledonous plants, respectively, mixed with pollen soil and planting in a separate pollen about 1 inch above the soil. After planting, the pollen is sprayed with an aqueous solution of selected acetone containing a sufficient amount of the test compound to provide about 0.8 to 0.1 kg per hectare of test compound per pollen. The treated pots are then placed on a greenhouse bench, watered, and cared for in a conventional greenhouse process. The results are shown in Tables 4, 6 and 8.

Assessment of herbicidal activity after germination of test compounds

The herbicidal activity after germination of the compounds of the present invention is a formulation prepared from a solution of a test compound in acetone containing 0.4 wt% of an alkylphenol / ethylene oxide condensate sold under the trade name TRITON X-155 for a number of monocotyledonous and dicotyledonous plants. It is described as a test that is processed with. The acetone solution is diluted with water and the test compound per pollen is applied in an amount of about 0.4 to 0.2 kg per hectare. After spraying, the plants are placed on a greenhouse bench and taken care of by conventional methods and measured by conventional greenhouse practices. The results of the test are shown in Tables 5, 7 and 9.

Example A

2- (5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy) -N- (3,5,5-trimethylcyclohexene-1 of the prior art (US Pat. No. 4,585,471) -Yl) -N-methylacetamide and 2- (5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy) -N- (3,3,5-trimethylcyclohexene-1 Compared to the mixture of -yl) -N-methylacetamide (Compound B), the compounds of the present invention, ie the compounds of Examples 3 and 2, were found in wheat, corn, soybean and rice as shown in Table 4 below. It clearly demonstrates having better crop resistance than compound B.

This is especially true for wheat and soybeans below the highest content of 800 g / ha and below 400 g / ha in rice, and with this content in turfgrass such as Allopecurus, Digitaria, Echinocloe and Setaria. This is illustrated by the compound of Example 3, which shows good crop selectivity. However, Compound B, which exhibits low growth of wheat at a minimum content of 100 g / ha, has insufficient activity against allopelus, an important grass species in European crops, which is wheat selective herbicide against allopelus compared to Example 3. Indicates that is not achieved by Compound B. In maize, the compound of Example 3 exhibits excellent selectivity in corn and complete herbization of the Setaria parberry at 200 g / ha, whereas the standard is 100 g / ha, which is selective only in corn and in this content Insufficient activity for. The compound of Example 2 also shows significantly better selectivity in maize than compound B, which gives a high level of turfgrass weed activity, including cetaria, with up to 400 g / ha of total selectivity in maize and selective content in maize. .

Pre-germination spray: Compound Content g / ha T Z G OR E L RZ A X YA M M SW X A A A D E SL I C EO G HTM S C FY A G A Example 2 800 Example 2 400 Example 2 200 30 50 20 9 530 0 5 50 20 0 0 15 100 100 100 100 100 100 100 100 90 100 100 100 Example 3 800 Example 3 400 Example 3 200 10 55 0 405 20 0 00 0 0 0 99 100 100 100 95 100 100 100 75 100 97 100 B 800B 400B 200B 100 65 75 30 9 545 45 20 9 225 45 0 4525 0 0 10 100 100 100 10095 100 100 10092 100 99 10075 100 98 80

Example B

2- (5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy) -N- (3,5,5-trimethylcyclohexene-1 of the prior art (US Pat. No. 4,585,471) -Yl) -N-methylacetamide and 2- (5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy) -N- (3,3,5-trimethylcyclohexene-1 Compared with the mixture of -yl) -N-methylacetamide (Compound B), the compound of Example 3 clearly shows better selectivity in wheat and rice than Compound B, which is sufficient in these crops with a maximum content of 400 g.ha or less. Because it is optional. However, compound B is not selective enough in wheat at 400 g / ha and only slightly selectable in wheat at 200 g / ha.

Spray after germination compound Content g / ha T OR RZ YA ZW A A D SL I EO GTM S VY A I Example 3 Example 3 400200 0 00 0 95 90 90 70 80 60 BB 400200 35 2020 0 95 90 90 85 90 70

Example C

In addition, the compounds of the inventive example 8 were tested before and after germination and tested in the prior art (international patent application WO 97/08160) with compound C, 2- (5-trifluoromethyl-1,3,4-thia Compare to diazol-2-yloxy) -N- (2,4-dimethylhept-2-en-3-yl) -N- (2-methoxyethyl) acetamide. Three weeks after the treatment of each pot, the test is carried out and the harm is assessed according to the following grading system.

% Growth rate difference with untreated control 0-No Effect 01-Slight Effect 1-52-Slight Effect 6-153-Medium Effect 16-294-Damage 30-445-Definite Damage 45-646-Herbal Effect 65-797-Excellent Herbicide Effect 80-908-Complete Proximity to Weed 91-999-100 Weed Complete

The compound of Example 8 clearly shows better crop resistance in wheat, corn, soybeans and rice than Compound C, as shown in Tables 6 and 7 below.

Pre-germination spray compound g / ha T OR RZ YA SW A A S E A GL E C M AO T H A LM V C R AY I G U P C 80040020010050 7 75 51 20 00 0 9 9 9 8 28 8 9 7 08 8 8 0 05 4 5 0 02 0 2 0 0 Example 8 80040020010050 4 22 02 00 00 0 9 9 9 8 79 9 9 8 38 8 8 6 07 8 7 0 05 6 4 0 0

The compound of Example 8 clearly shows better selectivity in both wheat and rice than compound C of PCT WO 97/08160. The compounds of the present invention are sufficiently selective in wheat at 400 g / ha and show good selectivity in rice with a maximum content of 800 g / ha, while compound C is resistant to both crops even with a reduced content of 200 g / ha. . In addition, the compounds of the present invention were significantly more active in monocotyledonous weeds (Allopecurus, Cetaria, Echinocloe) and dicotyledonous weeds (Amaranthus, Gallium).

Spray after germination compound g / ha T H ZR O EZ R AA V MW W X A AL PO EM SY V Compound C 400200 4 4 52 0 3 8 64 4 Example 8 400200 2 0 30 0 0 8 87 5

The compound of Example 8 is sufficiently selective in maize at 200 g / ha in wheat and barley with a maximum content of 400 g / ha. Compound C is certainly less selective in these crops than the compounds of the present invention. In addition, the compounds of the present invention are considerably more active in allopecurus myosoids and Apera spica-Venti, both of which are important grass weeds in European cereals. Both grasses are controlled by the compounds of the present invention in wheat and barley at an optional content of 400 g / ha. Compound C does not show a sufficient level of activity in the apera at any content and allopecurus control is not achieved in wheat and barley at an optional content.

Example D

In the following tests, the compounds of Examples 17 and 19 of the present invention were shown to show excellent selectivity in wheat, barley, soybean and rice as the results shown in Tables 8 and 9. When sprayed at an optional content in crops before or after germination, all of the compounds of Examples 17 and 19 are allopecurus, brachiaria, digitaria, echinoloa, setaria parberry and S. viridis. Shows high activity.

Pre-germination spray Example number g / ha T H O GR O RY LZA RV S YW W A MA A B DI E S SL R G C E EO A S H T TM P A C F VY P G A I 17 400200 0 1 3 10 1 1 0 8 8 9 8 9 88 7 9 8 8 8 19 400200 1 0 0 00 0 0 0 8 8 9 8 8 87 5 9 8 8 8

The compounds of Examples 17 and 19 of the present invention show good selectivity in wheat, barley, soybeans and rice. In addition, allopecurus, digitaria, in selective content in crops. High activity is recorded in Echinoloa, Setaria parberry and S. viridis.

Spray after germination Example number g / ha T H OR O RZ R YA V SW W A A D E S SL I C E EO G H T TM S C F VY A G A I 17 400200 3 2 10 0 0 8 8 9 8 86 8 9 7 8 19 400200 0 0 00 0 0 7 8 8 8 86 8 8 7 7

Example E

In the following test, the compound of Example 21 of the present invention was tested by post-germination spraying and the compound D, 2- (6-chlorobenzoxazol-2-yloxy)-of the prior art (European patent application EP 0 165 537)- Compare with N- (Cylohex-1-enyl) -N-methyl-acetamide. The compound of Example 21 clearly shows better selectivity in barley than Compound D of the prior art, as shown in the results of Table 10.

Spray after germination compound g / ha HORVW A L AL O PO L EM P SY E V Compound d 400200100 3550 95 70 9590 60 9085 55 70 Example 21 400200100 1550 98 90 9596 85 9085 60 85

The compounds of the present invention are certainly more active in allopecurus, loriben and apera, which are more resistant in barley and important grass in cereals than compounds of the prior art. The compounds of the present invention are sufficiently resistant to barley up to 400 g / ha, while the maximum resistance by prior art compounds is 200 g / ha. While selective compounds of 400 g / ha in crops show good control of allopecurus and apera (98 and 95%, respectively) in the crops, the compounds of the prior art are surely resistant to barley in such grasses. Control effect seems less.

Claims (16)

Compound of Formula (I). Formula I 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 represents a hydrogen atom, R ³ represents an alkyl group, or R ² and R ³ are taken together to form a single bond or methylene group; R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independently represent a hydrogen atom or a C ₁ -C ₄ alkyl group, provided a) at least two of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ must represent an alkyl group, b) 2- (5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohex-1-enyl)- Acetamide is excluded. The compound of claim 1, wherein R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independently represent hydrogen or methyl. 3. Compounds according to claim 1 or 2, wherein Het represents a thiadiazolyl, benzoxazolyl or benzothiazolyl group which may be substituted with one or more halogen atoms or alkyl, haloalkyl or phenyl groups. 4. A compound according to claim 3, wherein Het represents a group selected from formulas (1) and (2). Formula 1 Formula 2 In the above formula, R ⁹ represents hydrogen or a halogen atom or a haloalkyl group; X represents O or S; Y independently represents a halogen atom or an optionally substituted alkyl group with one another; n is an integer of 0-4. The compound of claim 1, wherein R ² and R ³ are taken together to form a single bond or methylene group. 6. The compound of claim 1, wherein R ¹ represents a C _2-5 alkyl, cyclopropyl, or 2-methoxyethyl group. 7. The compound of formula IA according to claim 1. Formula IA Formula 1 Formula 2 In the above formula, R ¹ represents an alkyl or alkoxyalkyl group; Het represents a group selected from formulas (1) and (2); X represents O or S; Y represents a halogen atom or a methyl group; n is 0 or 1; R ⁹ represents a C _1-4 fluoroalkyl group. The compound of formula IB according to claim 1. Formula IB Formula 1 Formula 2 In the above formula, R ¹ represents a C _2-5 alkyl or alkoxyalkyl group; Het represents a group selected from formulas (1) and (2); X represents O or S; Y represents a halogen atom or a methyl group; n is 0 or 1; R ⁹ represents a C _1-4 fluoroalkyl group; Line 2 indicates the presence of a double bond at one or more positions. Isomer mixtures of two compounds of formula (IB) of claim 8 differing only in the position of the double bond. 10. A compound according to any one of claims 7 to 9 selected from the following groups. 2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1-enyl)- Acetamide, 2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohex-1-enyl)- Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,4-trimethylcyclopent-1-enyl)- Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,4,4-trimethylcyclopent-1-enyl)- Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,4-trimethylcyclopent-1-enyl) Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,4,4-trimethylcyclopent-1-enyl) Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclopent-1-enyl)- Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (2,4,4-trimethylcyclopent-1-enyl)- Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclopent-1-enyl) Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (2,4,4-trimethylcyclopent-1-enyl) Acetamide, 2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-ethyl-N- (2,6-dimethylhept-3-en-4-yl) Acetamide, 2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-isopropyl-N- (2,6-dimethylhept-3-en-4-yl ) -Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohex -1-enyl) -acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohex -1-enyl) -acetamide, 2- (5-Trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N- (2-methoxyethyl) -N- (2,6-dimethylhept-3- En-4-yl) -acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-cyclopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-cyclopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) Acetamide, 2- (5-trifluoromethyl- [1,3,4] -thiadiazol-2-yloxy) -N-cyclopropyl-N- (2,6-dimethylhept-3-en-4-yl ) -Acetamide, 2- (benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,3,4-trimethylcyclopent-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,4,4-trimethylcyclopent-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,4-trimethylcyclopent-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,4,4-trimethylcyclopent-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclopent-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-ethyl-N- (2,4,4-trimethylcyclopent-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclopent-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-isopropyl-N- (2,4,4-trimethylcyclopent-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-ethyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide, 2- (benzoxazol-2-yloxy) -N-isopropyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide, 2- (benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5, -trimethylcyclohex-1-enyl) -acetamide, 2- (benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N-ethyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N-isopropyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (6-chloro-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-methyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-methyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-ethyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide, 2- (5-methyl-benzoxazol-2-yloxy) -N-isopropyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide, 2- (benzoxiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-ethyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-ethyl-N- (3,3,4-trimethylcyclopent-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-ethyl-N- (3,4,4-trimethylcyclopent-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,3,4-trimethylcyclopent-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,4,4-trimethylcyclopent-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-ethyl-N- (3,3,5-trimethylcyclopent-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-ethyl-N- (2,4,4-trimethylcyclopent-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-isopropyl-N- (3,3,5-trimethylcyclopent-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-isopropyl-N- (2,4,4-trimethylcyclopent-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N-ethyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide, and 2- (benzothiazol-2-yloxy) -N-isopropyl-N- (2,6-dimethylhept-3-en-4-yl) -acetamide, 2- (benzothiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,3,5-trimethylcyclohex-1-enyl) -acetamide, 2- (benzothiazol-2-yloxy) -N- (2-methoxyethyl) -N- (3,5,5-trimethylcyclohex-1-enyl) -acetamide, 2- (5-chloro-benzothiazol-2-yloxy) -N-ethyl-N- (3,3,4-trimethylcyclopent-1-enyl) -acetamide, 2- (5-Chloro-benzothiazol-2-yloxy) -N-ethyl-N- (3,4,4-trimethylcyclopent-1-enyl) -acetamide. A process for preparing a compound according to any one of claims 1 to 10, comprising the reaction of a compound of formula II with a compound of formula III. Formula II Formula III Het-L ² In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined in claim 1; Het has a given meaning; ^One of L ¹ and L ² represents a hydroxy group and the other represents a leaving group. Compound of Formula II. Formula II In the above formula, R ¹ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined in claim 1, R ² represents a hydrogen atom, R ³ represents an alkyl group, L ¹ represents a hydroxy group or leaving group selected from alkyl- and arylsulfonyl, alkyl- and arylsulfonyloxy, perfluoroalkylsulfonyloxy group and halogen atoms. A herbicide composition comprising at least one compound according to any one of claims 1 to 10 and at least one agriculturally acceptable carrier. The composition of claim 13, wherein at least one of the carriers comprises at least two carriers that are surface-active agents. A method of controlling undesirable plants in a locus, comprising spraying the locus with a herbicidally effective amount of the compound according to any one of claims 1 to 10. A method for controlling undesirable plants in a locus, comprising spraying a locus with a herbicidally effective amount of the composition according to claim 13.