AU2001274401A1

AU2001274401A1 - Novel tetrazole derivatives

Info

Publication number: AU2001274401A1
Application number: AU2001274401A
Authority: AU
Inventors: Toshio Goto; Shinichi Narabu; Shinichi Shirakura; Chieko Ueno; Akihiko Yanagi
Original assignee: Bayer CropScience KK
Current assignee: Bayer CropScience KK
Priority date: 2000-07-06
Filing date: 2001-06-25
Publication date: 2002-04-11
Anticipated expiration: 2021-06-25

Description

NOVELTETRAZOLEDERIVATIVES

The present invention relates to novel tetrazole derivatives, to processes for their preparation, to their intermediates, to their use as herbicides and to novel herbicidal compositions for use in paddy fields.

It has been already known that certain kinds of tetrazole derivatives show a herbicidal activity (cf. Japanese Laid-open Patent Application No. 12275/1999, No. 21280/1999 etc.). Furthermore, it has been known that certain kinds of heterocyclic derivatives show a herbicidal activity (cf. U.S. Patent Specifications No. 5834402, No. 5846906, DE-A- 19846792, WO 99/10327 etc.).

There have now been found novel tetrazole derivatives of the formula (I)

wherein

R- represents halogen, methyl, ethyl, halomethyl, methoxy, ethoxy, Cι_₂ haloalkoxy, methylthio, ethylthio, Cι- alkylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, nitro or cyano,

R² represents Cι.₆ alkyl or C .₆ cycloalkyl which may be optionally substituted with halogen or Cι_₃ alkyl, or represents C haloalkyl, C₂.₆ alkenyl, or phenyl which may be optionally substituted with halogen, Cι.₃ alkyl, Cι_₂ haloalkyl or nitro,

m represents 0, 1 or 2, and the two R¹ substituents may be identical or different, in case m represents 2,

n represents 1 or 2,

represents one of the following groups

or

wherein

"\ A f. H Q

R , R , R , R , R and R are identical or different and each represents a hydrogen atom or methyl, R⁹ represents a hydrogen atom, halogen, .₃ alkyl, halomethyl, methoxy or nitro,

R¹⁰ represents -₆ alkyl,

R¹¹ represents halogen, and

k represents 1 or 2.

The compounds of the formula (I), according to the invention, can be obtained by a process wherein

a) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-l) or (Q-2):

compounds of the formula (II)

wherein

R , R , m and n have the same definition as aforementioned, and

T¹ represents one of the following groups

or

wherein

R >3 , τ R4 , τ R_>5 , r R,6 , τ R,7 and R have the same definition as aforementioned,

are reacted to a rearrangement in the presence of inert solvents, and if appropriate, in the presence of a base and a cyanide, and if appropriate, in the presence of a phase-transfer catalyst, or

b) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-6) or (Q-7) and R »π in said groups represents chloro or bromo:

compounds of the formula (lb)

wherein

R ,ι , R , m and n have the same definition as aforementioned, and

represents one of the following groups

or

wherein

R >3 , R , R , R , R and R have the same definition as aforementioned, are reacted with a halogenating agent in the presence of inert solvents,

or

c) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-3), (Q-4) or (Q-5):

compounds of the formula (Ic)

wherein

R ,ι , R , m and n have the same definition as aforementioned, and

represents one of the following groups

or

wherein

R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the same definition as aforementioned,

R^Uc represents chloro or bromo,

are reacted with compounds of the formula (III)

R¹²-SH (III)

wherein

R¹² represents the following group

or

_Rιo

wherein

R , R and k have the same definition as aforementioned,

in the presence of inert solvents, and if appropriate, in the presence of an acid binding agent.

The tetrazole derivatives of the formula (I) provided by the present invention show stronger herbicidal activity than with the compounds described in the aforementioned prior art references. In the formulae:

"Halogen" represents fluoro, chloro, bromo or iodo, and preferably represents fluoro, chloro or bromo.

"Alkyl" can be straight chain or branched chain and there can be specifically mentioned, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-, iso-, neo-, or tert-pentyl and n- or iso-hexyl.

"Cycloalkyl" includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. These cycloalkyls may be optionally substituted with halogen (for example, fluoro, chloro, bromo etc.), Cι-₃ alkyl (for example, methyl, ethyl, n- or iso-propyl etc.) and in case that a plurality of substituents exist, they may be identical or different. As specific examples of such substituted cycloalkyls there can be mentioned 1-methylcyclo- propyl, 1-ethylcyclopropyl, 1-n-propylcyclopropyl, l-methyl-2-fluorocyclopropyl, 2- methylcyclopropyl, 2-fluorocyclopropyl, l-methyl-2,2-difluorocyclopropyl, 1- methyl-2,2-dichlorocyclopropyl, 2,2difluorocyclopropyl, 2-methylcyclopentyl, 1- methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,6-dimethylcyclohexyl and 2,5-dimethylcyclohexyl.

As "alkenyl" there can be mentioned, for example, vinyl, allyl, 1-methylallyl, 1,1- dimetylallyl and 2-butenyl.

"Haloalkyl" represents straight chain or branched chain alkyl, of which at least one hydrogen is substituted with halogen, and there can be mentioned, for example, Cμ alkyl substituted with 1-6 fluoro and/or chloro, specifically difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, dichloromethyl, 2-chloro-l,l,2-trifluoroethyl, 3- fluoropropyl, 3-chloropropyl, 2,2,3,3,3-pentafluoropropyl and 1, 2,2,3, 3,3-hexa- fluoropropyl.

The Haloalkyl part in "haloalkoxy" can have the same definition as the afore- mentioned "haloalkyl" and as "haloalkoxy" there can be specifically mentioned, for example, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2- bromoethoxy, 2,2,2- trifluoroethoxy and 3-chloropropoxy.

"Alkylsulfonyl" represents an alkyl-SO₂- group, wherein the alkyl part has the above- mentioned meaning, and includes specifically methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl.

As preferred definitions in the formula (I) there can be mentioned:

R¹ preferably represents fluoro, chloro, bromo, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, Cι.₂ haloalkoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, nitro or cyano.

R² preferably represents d.₃ alkyl, cyclopropyl which may be optionally substituted with fluoro, chloro, methyl or ethyl, Cμ₃ haloalkyl, C₂.₄ alkenyl, or phenyl which may be optionally substituted with fluoro, chloro, methyl, ethyl, trifluoromethyl or nitro.

m preferably represents 1 or 2.

n preferably represents 1 or 2.

R⁹ preferably represents a hydrogen atom, fluoro, chloro, methyl, ethyl or trifluoromethyl.

R¹⁰ preferably represents methyl or ethyl.

R^{1 l} preferably represents chloro or bromo.

preferably represents 1. As more preferred definitions in the formula (I) there can be mentioned:

R¹ more preferably represents chloro, bromo, methyl or methylsulfonyl,

R² more preferably represents methyl, ethyl, n-propyl, isopropyl or cyclopropyl,

m more preferably represents 2, and in this case the two R¹ substituents are bond respectively to the 2-position and 4-position of a benzene ring and the two R¹ substituents may be identical or different.

n more preferably represents represents 1.

In a most preferred group of the inventive compounds the group

R²

- (CH₂)_n-S- \ _^ 11

bonds to the 3-position (acccording to formula (I)) of the benzene ring. In another most preferred group Q represents one of the following groups

or

The substituents among the different ranges of preference can be combined without limitation among each other. limitation among each other.

However, as a preferred group of compounds there may be explicitly mentioned the compounds of the formula (I) wherein the substituents have the preferred meaning as described above, and as a more preferred group of compounds there may be explicitly mentioned the compounds of the formula (I) wherein the substituents have the more preferred meaning as described above.

The aforementioned preparation process (a) can be illustrated by the following reaction formula, in case of using, for example, 3-oxo-l-cyclohexenyl 2,4-dichloro- 3-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoate as the starting material.

The aforementioned preparation process (b) can be illustrated by the following reaction formula, in case of using, for example, 2-{2,4-dichloro-3-{[(l-methyl-lH- tetrazol-5-yl)thio]methyl}benzoyl}cyclohexane-l,3-dione as the starting material, and, for example, oxalyl dichloride as chlorinating agent.

The aforementioned preparation process (c) can be illustrated by the following reaction formula, in case of using, for example, 3-chloro-2-{2,4-dichloro-3-{[(l- methyl-lH-tetrazol-5-yl)thio]methyl}benzoyl}-2-cyclohexen-l-one and thiophenol as the starting materials.

It is further mentioned that the group (Q-l) defined for Q in the above-mentioned formula (I) can also exist in the following two tautomeric forms or

It is also mentioned that the group (Q-2) defined for Q in the above-mentioned formula (I) can also exist in the following two tautomeric forms

or

Thus, the compounds of the formula (I) of the present invention include the compounds of the formula (I) wherein Q represents the above-mentioned tautomeric groups (Q-la), (Q-lb), (Q-2a) or (Q-2b) as group Q-1 or Q-2 respectively. the present specification, however, it should be understood that these tautomeric groups are represented, unless specified, by the illustration of group (Q-1) or group (Q-2).

The compounds of the formula (II), the starting materials in the above-mentioned preparation process (a), are novel compounds which were not described in the literature up to the present and can be prepared according to the process described in various publications (e.g., Japanese Laid-open Patent Publications No. 222/1990, No. 173/1990, No. 6425/1990 etc.) by reacting compounds of the formula (IV)

wherein

R¹, R², m and n have the same definition as aforementioned, and

M represents halogen,

with compounds of the formula (N)

Q_a-H (N)

wherein

represents one of the following groups or

wherein

R , 3 , R , R , R , R and R have the same definition as aforementioned,

in an appropriate diluent, for example, dichloromethane, in the presence of an appropriate condensing agent, for example, triethylamine.

The compounds of the formula (IN) used in the above-mentioned reaction are also novel compounds which were not described in the literature up to the present and can be prepared, for example, by reacting compounds of the formula (VI)

wherein

R , 1 , T R> 2 , m and n have the same definition as aforementioned,

with a halogenating agent, for example, phosphorus oxychloride, phosphorus^'oxy- bromide, phosphorus trichloride, phosphorus tribromide, phosgene, oxalyl dichloride, thionyl chloride, thionyl bromide.

The compounds of the formula (V) used as the starting materials in the preparation of the compounds of the above-mentioned formula (II) are per se known and commercially available or can be easily prepared according to the processes described in various publications (e.g., Japanese Laid-open Patent Publications No. 6425/1990, No. 265415/1998, No. 265441/1998).

The compounds of the formula (VI) used for the preparation of the compounds of the above-mentioned formula (IV) are also novel compounds which were not described in the literature up to the present and can be easily prepared, for example, by hydrolyzing compounds of the formula (VII)

wherein

R¹, R², m and n have the same definition as aforementioned, and

T² represents Cμ alkoxy, preferably methoxy or ethoxy,

in an appropriate diluent, for example, aqueous dioxane, in the presence of an appropriate base, for example, sodium hydroxide.

The compounds of the above-mentioned formula (VII) are also novel compounds and can be easily obtained, for example, by reacting compounds of the formula (VIII) R^<

wherein

R has the same definition as aforementioned

with compounds of the formula (IX)

I (CH₂)_n- M (LX)

wherein

R¹, m and n have the same definition as aforementioned,

T² represents C_M alkyl, preferably methyl or ethyl, and

M represents halogen,

in an appropriate diluent, for example, Ν,Ν-dimethylformamide, in the presence of an appropriate condensing agent, for example, potassium carbonate.

The compounds of the above-mentioned formula (NIII) are known compounds described, for example, in Berichte Vol. 28, p. 74-76 (1895) and can be easily prepared according to the process described in said publication.

On the other hand, the compounds of the above-mentioned formula (IX), a part of which are novel compounds which were not described in the literature up to the present, can be easily prepared according to the process described, for example, in Japanese Laid-open Patent Publication No. 173/1990.

The compounds of the formula (II), the starting materials in the above-mentioned preparation process (a), can also be easily prepared from compounds of the aforementioned formula (VI) according to the process described, for example, in WO93/18031.

As typical examples of the compounds of the formula (II) used as the starting materials in the aforementioned preparation process (a), the followings can be mentioned:

3-Oxo-l-cyclohexenyl 2-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoate,

3-oxo-l-cyclohexenyl2-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-4-fluorobenzoate,

3-oxo-l -cyclohexenyl 4-chloro-2- {[(1 -methyl-lH-tetrazol-5-yl)thio]methyl}benzoate,

3-oxo-l-cyclohexenyl 4-chloro-2-{[(l-ethyl-lH-tetrazol-5-yl)thio]methyl}benzoate,

3 -oxo- 1 -cyclohexenyl 4-chloro-2- { [( 1 -cyclopropyl- lH-tetrazol-5 -yl)thio]methyl} - benzoate,

3-oxo-l-cyclohexenyl 2-bromo-4-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoate,

3-oxo-l-cyclohexenyl -bromo-2-{[(l-phenyl-lH-tetrazol-5-yl)thio]methyl}benzoate,

3-oxo- 1 -cyclohexenyl 2- { [( 1 -methyl- 1 H-tetrazol-5-yl)thio]methyl } -4-trifluorometh- ylbenzoate,

3-oxo-l -cyclohexenyl 2- {[(1 -methyl- lH-tetrazol-5-yl)thio]methyl} -4-methylbenzoate,

3-oxo- 1 -cyclohexenyl 2,4-dichloro-3 - { [(1 -methyl- 1 H-tetrazol-5 -yl)thio]methyl} - benzoate,

3 -oxo- 1 -cyclohexenyl 2,4-dichloro-3 - { [( 1 -cyclopropyl- 1 H-tetrazol-5 -yl)thio]meth- yl}benzoate,

3-oxo-l -cyclohexenyl 2,4-dichloro-3-{[(l-(2-chlorophenyl)-lH-tetrazol-5-yl)thio]- methyl}benzoate,

3-oxo-l -cyclohexenyl 2-chloro-3 - { [( 1 -methyl- 1 H-tetrazol-5-yl)thio]methyl} -4-meth- ylsulfonylbenzoate, 3 -oxo- 1 -cyclohexenyl 2-chloro-3-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-4- methylsulfonylbenzoate,

3-oxo- 1 -cyclohexenyl 2-chloro-3 - { [( 1 -(n-pentyl)- lH-tetrazol-5 -yl)thio]methyl} -4- methylsulfonylbenzoate,

3-oxo-l-cyclohexenyl 2-chloro-3-{[(l-(3-difluoromethylphenyl)-lH-tetrazol-5-yl)- thio]methyl}-4-methylsulfonylbenzoate,

3-oxo-l-cyclohexenyl 4-chloro-3-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-2-meth- ylsulfanylbenzoate,

3 -oxo- 1 -cyclohexenyl 2,4-dimethylsulfanyl-3 - { [( 1 -methyl- 1 H-tetrazol-5 -yl)thio] - methyl}benzoate,

3-oxo- 1 -cyclohexenyl 4-chloro-3 - { [( 1 -methyl- 1 H-tetrazol-5 -yl)thio]methyl} -2-meth- ylsulfonylbenzoate,

3-oxo-l-cyclohexenyl 2-chloro-4-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoate, 3-oxo-l-cyclohexenyl 4-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-2-methoxybenzo- ate,

3 -oxo- 1 -cyclohexenyl 4- { [( 1 -methyl- 1 H-tetrazol-5 -yl)thio]methyl} -2-methylsulfon- yloxybenzoate,

3-oxo-l-cyclohexenyl 4- {[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-2-nitrobenzoate, 3-oxo- 1 -cyclohexenyl 4- { [( 1 -ethyl- 1 H-tetrazol-5-yl)thio]methyl} -2-nitrobenzoate, 5,5-dimethyl-3-oxo-l-cyclohexenyl 2-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-4- trifluoromethylbenzoate,

4,4-dimethyl-3 -oxo- 1 -cyclohexenyl 2-bromo-4-{[(l-methyl-lH-tetrazol-5-yl)thio]- methyl}benzoate,

4,4-dimethyl-3 -oxo-1 -cyclohexenyl 2,4-dichloro-3- {[(1 -methyl- lH-tetrazol-5-yl)- thio]methyl}benzoate,

4- {4-chloro-2- { [( 1 -methyl- 1 H-tetrazol-5 -yl)thio]methyl} benzoyloxy } -bicyclo [3.2.1]- 3-octen-2-one,

4- {2,4-dichloro-3-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-benzoyloxy} bicyclo [3.2.1 ] -3 -octen-2-one,

4-{2-chloro-3-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl- benzoyloxy}bicyclo[3.2.1]-3-octen-2-one. As typical examples of the compounds of the formula (IV) used as the starting materials in the preparation of the compounds of the aforementioned formula (II), the followings can be mentioned:

4-Chloro-2-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoyl chloride,

4-bromo-2- { [( 1 -cyclopropyl- 1 H-tetrazol-5 -yl)thio]methyl}benzoyl chloride,

2- {[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoyl chloride,

2,4-dichloro-3-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoyl chloride,

2,4-dichloro-3-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}benzoyl chloride,

2-chloro-3-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl chloride,

2-chloro-3-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl chloride,

2-chloro-4- { [(1 -methyl- 1 H-tetrazol-5-yl)thio]methyl} benzoyl chloride,

2-bromo-4- {[(1 -methyl-lH-tetrazol-5-yl)thio]methyl}benzoyl chloride,

4- {[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-2-nitro-benzoyl chloride,

2,4-dichloro-3-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoyl bromide,

2-chloro-3 - { [( 1 -methyl- 1 H-tetrazol-5-yl)thio]methyl} -4-methylsulfonyl-benzoyl bromide,

2-chloro-3 - { [( 1 -cyclopropyl- lH-tetrazol-5 -yl)thio]methyl} -4-methylsulfonylbenzoyl bromide.

As typical examples of the compounds of the formula (VI) used as the starting materials in the preparation of the compounds of the aforementioned formula (IV), the followings can be mentioned:

4-Chloro-2- {[(1 -methyl- lH-tetrazol-5-yl)thio]methyl}benzoic acid, 4-bromo-2-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}benzoic acid, 2-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoic acid, 2,4-dichloro-3- {[(1 -methyl-lH-tetrazol-5-yl)thio]methyl}benzoic acid, 2 ,4-dichloro-3 - { [( 1 -cyclopropyl- 1 H-tetrazol-5 -yl)thio]methyl} benzoic acid, 2-chloro-3 - { [( 1 -methyl- 1 H-tetrazol-5 -yl)thio]methyl} -4-methylsulfonyl-benzoic acid, 2-chloro-3-{[(l-cycloρropyl-lH-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoic acid,

2-chloro-4-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoic acid, 2-bromo-4-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoic acid, 4-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-2-nitro-benzoic acid.

As typical examples of the compounds of the formula (VII) used as the starting materials in the preparation of the compounds of the aforementioned formula (VI), the followings can be mentioned.

Methyl 4-chloro-2-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoate, methyl 4-bromo-2-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-benzoate, methyl 2-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-4-trifluoromethyl-benzoate, methyl 2,4-dichloro-3-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-benzoate, methyl 2,4-dichloro-3-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-benzoate, memyl 2-cUoro-3-{[(l-me yl-lH-te1razol-5-yl)thio]methyl}-4-methylsulfonylbenzoate, methyl 2-chloro-3-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl- benzoate, methyl 2-chloro-4-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoate, methyl 2-bromo-4-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoate, methyl 4- {[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-2-nitro-benzoate, ethyl 2,4-dichloro-3-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoate, ethyl 2-chloro-3-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-4-4-methylsulfonylbenzoate, ethyl 2-chloro-3- { [( 1 -cyclopropyl- 1 H-tetrazol-5-yl)thio]methyl} -4-methylsulfonyl- benzoate.

The compounds of the formula (lb), starting materials in the aforementioned preparation process (b), are a part of the compounds of the formula (I) of the present invention and can be easily prepared according to the above-mentioned preparation process (a).

As typical examples of the compounds of the formula (lb) used as the starting materials in the aforementioned preparation process (b), the followings, included in the formula (I), can be mentioned:

2-{4-Chloro-2-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-l,3- dione,

2-{4-bromo-2-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane- 1,3-dione,

2- {2- {[(1 -methyl- lH-tetrazol-5-yl)thio]methyl} -4-trifluoromethyl-benzoyl} cyclo- hexane-l,3-dione,

2-{2,4-dichloro-3-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane- 1,3-dione,

2-{2,4-dichloro-3-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-benzoyl}cyclo- hexane-l,3-dione,

2- {2-chloro-3- {[(1 -methyl- lH-tetrazol-5-yl)thio]methyl} -4-methylsulfonylbenzoyl} - cyclohexane- 1 ,3-dione,

2-{2-chloro-3-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl- benzoyl} cyclohexane- 1 ,3-dione,

2-{2-chloro-4-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-l,3- dione,

2-{2-bromo-4-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-l,3- dione,

2- {4- {[(1 -methyl- lH-tetrazol-5-yl)thio]methyl} -2-nitrobenzoyl} -cyclohexane- 1 ,3- dione,

3-{2-chloro-3-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl- benzoyl}bicyclo[3.2.1]-octane-2,4-dione

As a halogenating agent used for the reaction with the compounds of the formula (lb) in the preparation process (b) there can be mentioned, for example, thionyl chloride, thionyl bromide, oxalyl dichloride, oxalyl dibromide etc.

The compounds of the formula (Ic), the starting materials in the aforementioned preparation process (c), are a part of the compounds of the formula (I) of the present invention and can be easily prepared according to the above-mentioned preparation process (b).

As typical examples of the compounds of the formula (Ic) used as the starting materials in the aforementioned preparation process (c), the followings, included in the formula (I), can be mentioned:

3-Chloro-2-{4-chloro-2-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-benzoyl}-2- cyclohexen- 1 -one,

3-chloro-2-{4-bromo-2-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-benzoyl}-2- cyclohexen- 1 -one,

3 -chloro-2- {2- { [( 1 -methyl- 1 H-tetrazol-5-yl)thio]methyl} -4-trifluoromethylbenzoyl} - 2-cyclohexen- 1 -one,

3-chloro-2-{2,4-dichloro-3-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-benzoyl}-2- cyclohexen- 1 -one,

3-chloro-2-{2,4-dichloro-3-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}benzoyl}- 2-cyclohexen- 1 -one,

3-chloro-2-{2-chloro-3-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl- benzoyl} -2-cyclohexen- 1 -one,

3 -chloro-2- {2-chloro-3- { [( 1 -cyclopropyl- lH-tetrazol-5 -yl)thio]methyl} -4- methylsulfonylbenzoyl} -2-cyclohexen- 1 -one,

3-chloro-2- {2-chloro-4- {[(1 -methyl-lH-tetrazol-5-yl)thio]methyl} -benzoyl} -2-cyclohexen- 1 -one,

3-chloro-2-{2-bromo-4-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-benzoyl}-2- cyclohexen- 1 -one, 3-chloro-2-{4-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}-2-nitrobenzoyl}-2- cyclohexen- 1 -one,

4-chloro-2-{2-chloro-3-{[(l-cyclopropyl-lH-tetrazol-5-yl)thio]methyl}-4-methyl- sulfonylbenzoyl}bicyclo[3.2.1]-3-octen-2-one.

The compounds of the formula (III), the starting materials in the above-mentioned preparation process (c), are thiol compounds well known in the field of organic chemistry and as typical examples of the compounds of the formula (III) the followings can be mentioned:

Methyl mercaptan, ethyl mercaptan, thiophenol,

4-fluorothiophenol,

4-chlorothiophenol,

2-methylthiophenol,

4-ethylthiophenol,

4-trifluoromethylthiophenol etc.

Each compound of the formulae (II), (IV), (VI) and (VII), starting material or intermediate product in the aforementioned processes (a)-(c) for the preparation of the compounds of the formula (I) of the present invention is a novel compound which was not described in the literature up to the present. The compounds can be illustrated collectively by the following general formula (X)

wherein

W represents T , hydroxy or T , wherein R¹, R², m, n, T¹, T² and M have the same definition as aforementioned.

The reaction of the aforementioned preparation process (a) can be conducted in an appropriate diluent. As examples of such diluents there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, toluene, dichloromethane, chloroform and 1,2-dichloroethane; ethers, for example, ethyl ether, dimethoxyethane (DME) and tetrahydrofuran (THF); ketones, for example, methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile; esters, for example, ethyl acetate; acid amides, for example, dimethylformamide (DMF).

The preparation process (a) can be conducted in the presence of a cyanide and a base. As a cyanide usable in that case there can be mentioned, for example, sodium cyanide, potassium cyanide, acetone cyanohydrin and hydrogen cyanide. As a base there can be mentioned, for example, as inorganic bases, hydroxides and carbonates of alkali metals and alkaline earth metals, for example, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; and as organic bases, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, pyridine, 4-dimethylaminopyridine (DMAP), 1,4- diazabicyclo[2,2,2]octane (DABCO) and l,8-diazabicyclo[5,4,0]undec-7-ene (DBU).

The aforementioned preparation process (a) can be conducted also in the co-existence of a phase-transfer catalyst. As examples of the phase-transfer catalyst usable in that case there can be mentioned crown ethers, for example, dibenzo-18-crown-6, 18- crown-6 and 15-crown-5.

The reaction of the preparation process (a) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about -10 to about 80°C, preferably about 5 to about 40°C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure. In conducting the preparation process (a) the target compounds of the aforementioned formula (I), in case that Q represents groups (Q-1) or (Q-2), can be obtained, for example, by reacting 1 mole of a compound of the formula (II) with lto 4 moles of triethylamine in a diluent, for example, acetonitrile, in the presence of 0.01 to 0.5 moles of acetone cyanohydrin.

In conducting the preparation process (a) it is possible to obtain the compounds of the formula (I) by conducting reactions starting from the compounds of the aforementioned formula (VI) continuously in one pot without isolating the compounds of the formulae (IV) and (II).

The reaction of the aforementioned preparation process (b) can be conducted in an appropriate diluent. As examples of such there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chloro- benzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone and methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile and propionitrile; esters, for example, ethyl acetate and amyl acetate; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, l,3-dimethyl-2-imidazolidinone and hexamethyl- phosphoric triamide (HMPA).

The reaction of the preparation process (b) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about -20 to about 100°C, preferably about 0 to about 50°C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure. In conducting the preparation process (b) the target compounds of the aforementioned formula (I), in case that Q represents groups (Q-6) or (Q-7), wherein Rⁿ in said group represents chloro or bromo, can be obtained, for example, by reacting 1 mole of a compound of the formula (lb) with 1 to 5 moles of oxalyl dichloride in a diluent, for example, dichloromethane.

The reaction of the aforementioned preparation process (c) can be conducted in an appropriate diluent. As examples of such diluents there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone and methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile, propionitrile and acrylonitrile; esters, for example, ethyl acetate and amyl acetate; acid amides, for example, dimethyl- formamide (DMF), dimethylacetamide (DMA) and N-methylpyrrolidone; sulfones and sulfoxides, for example, dimethyl sulfoxide (DMSO) and sulfolane; bases, for example, pyridine.

The preparation process (c) can be conducted in the presence of a condensing agent. As a usable condensing agent there can be for example mentioned, as inorganic bases, hydrides and carbonates of alkali metals, for example, sodium hydride, lithium hydride, sodium carbonate and potassium carbonate; and as organic bases, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4- tetramethylethylenediamine (TMEDA), pyridine, 4-dimethylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO) and l,8-diazabicyclo[5,4,0]undec-7-ene (DBU).

The reaction of the preparation process (c) can be conducted in a substantially wide range of temperatures. Suitable temperatures are in the range of generally about -20 to about 140°C, preferably about 0 to about 100°C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure.

In conducting the preparation process (c) the target compounds of the aforementioned formula (I), in case that Q represents groups (Q-3), (Q-4) or (Q-5) can be obtained, for example, by reacting 1 mole of a compound of the formula (Ic) with 1 to 5 moles of thiophenol in a diluent, for example, tetrahydrofuran in the presence of 1 to 5 moles of triethylamine.

The active compounds of the aforementioned formula (I), according to the present invention, show, as shown in the biological test examples to be described later, excellent herbicidal activities against various weeds and can be used as herbicides. In the present specification weeds mean, in the broadest sense, all plants which grow in locations where they are undesired. The compounds, acoording to the present invention, act as total or selective herbicides depending upon the applied concentration. The active compounds, according to the present invention, can be used , for example, between the following weeds and cultures.

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Cheno- podium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipomoea, Polygonum, Ambrosia, Cirsium, Sonchus, Solanum, Rorippa, Lamium, Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Galinsoga, Rotala, Lindernia etc.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita etc.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis, Alopecurus, Cynodon etc.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium etc.

The use of the compounds, according to the present invention, is not restricted to the above-mentioned plants, but may be applied to other plants in the same manner. The active compounds, according to the present invention, can, depending upon the applied concentration, non-selectively control weeds and can be used, for example, on industrial terrain, rail tracks, paths, places with or without tree plantings. Moreover, the active compounds, according to the present invention, can be used for controlling weeds in perennial cultures and applied in, for example, afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings, hopfields etc. and can be applied also for the selective controlling of weeds in annual cultures.

According to the invention all plants and plant parts can be treated. The term plants includes all plants and plant populations, such as desired or undesired wild plants and cultivated plants (including naturally occurring cultivated varieties). Cultivated plants can be plant varieties that were obtained by conventional breeding and optimizing processes or by biotechnological and genetic engineering methods or a combination of such processes and methods, including transgenic plants and including plant varieties that cannot or can be protected by plant patents or plant variety rights. Plant parts are all parts and organs of plants occurring above or below the surface of the soil, e.g. shoots, leaves, needles, stalks and stems, trunks, flowers, fruits and seeds as well as roots, tubers, bulbs and rhizomes. The term plant parts also includes harvested crops and propagation material, e.g. cuttings, tubers, bulbs, rhizomes, shoots and seeds. According to the invention the plants and plant parts are treated using the usual methods by applying the active ingredients or compositions containing them directly to the plants or plant parts or to their surroundings (including the soil) or storeroom, e.g. by dipping, spraying, dusting,^' fogging, spreading and in the case of propagation material also by coating using one or multiple layers.

The active compounds, according to the present invention, can be made into the customary formulations. As such formulations there can be mentioned, for example, solutions, wettable powders, emulsions, suspensions, powders, water-dispersible granules, tablets, granules, suspension-emulsion concentrates, microcapsules in polymeric substances, jumbo formulations etc.

These formulations can be prepared according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid or solid diluents or carriers, and optionally with surface-active agents, namely emulsifϊers and/or dispersants and/or foam-forming agents.

As liquid diluents or carriers there can be mentioned, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride etc.), aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions etc.)], alcohols (for example, butanol, glycol etc.) and their ethers, esters etc., ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc.), strongly polar solvents (for example, dimethylformamide, dimethyl sulphoxide etc.) and water. In case of using water as extender, for example, organic solvents can be used as auxiliary solvents.

As solid diluents or carriers there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates etc.) etc. As solid carriers for granules there can be mentioned, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite etc.), synthetic granules of inorganic and organic meals, particles of organic materials (for example, sawdust, coconut shells, maize cobs and tobacco stalks etc.) etc.

As emulsifiers and/or foam-forming agents there can be mentioned, for example, nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates etc.)], albumin hydrolysis products etc.

Dispersants include, for example, ligninsulphite waste liquor, methyl cellulose etc.

Tackifiers can also be used in formulations (powders, granules, emulsions). As said tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate etc.).

Colorants can also be used. As said colorants there can be mentioned inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue etc.) and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further trace nutrients such as salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum, zinc etc.

Said formulations can contain the active compounds of the formula (I) in a range of generally O.lto 95 % by weight, preferably 0.5 to 90 % by weight.

The active compounds of the formula (I), according to the present invention, can be used as such or in their formulation forms for controlling weeds. They can be used also as a mixed agent with known herbicides. Such a mixed agent can be previously prepared as a final formulation form or can be prepared by tank-mixing on occasion of application. As herbicides usable in combination with the compounds of the formula (I), according to the present invention, as a mixed agent there can be specifically mentioned, for example, the following herbicides shown in common names.

Acetamide type herbicides, for example, pretilachlor, butachlor, tenylchlor, alachlor etc.; amide type herbicides, for example, clomeprop, etobenzanid etc.; benzofuran type herbicides, for example, benfuresate etc.; indanedione type herbicides, for example, indanofan etc.; pyrazole type herbicides, for example, pyrazolate, benzofenap, pyrazoxyfen etc.; oxazinone type herbicides, for example, oxaziclomefone etc.; sulfonylurea type herbicides, for example, bensulfuron-methyl, azimsulfuron, imazosulfuron, pyrazosulfuron-ethyl, cyclosulfamron Ethoxysulfuron, Halosulfuron

(-methyl) etc.; thiocarbamate type herbicides, for example, thiobencarb, molinate, pyributycarb etc.; triazine type herbicides, for example, dimethametryn Simetryn etc.; triazole type herbicides, for example, cafenstrole etc.; quinoline type herbicides, for example, quinclorac etc.; isoxazole type herbicides, for example, isoxaflutole etc.; dithiophosphate type herbicides, for example, anilofos etc.; oxyacetamide type herbicides, for example, mefenacet, flufenacet etc.; tetrazolinone type herbicides, for example, fentrazamide etc.; dicarboxyimide type herbicides, for example, pentoxazone etc.; trione type herbicides, for example, sulcotrione, benzobicyclon etc.; phenoxypropinate type herbicides, for example, cyhalofop-butyl etc.; benzoic acid type herbicides, for example, pyriminobac-methyl etc.; diphenyl ether type herbicides, for example, chlomethoxyfen, oxyfluorfen etc.; pyridinedicarbothioate type herbicides, for example, dithiopyr etc.; phenoxy type herbicides, for example, MCPA, MCPB etc.; urea type herbicides, for example, dymron, cumyluron etc.; naphthalenedione type herbicides, for example, quinoclamine etc.; isoxazolidinone type herbicides, for example, clomazone etc. diphenylether type herbicides, for example, chlomethoxyfen, oxyfluorfen etc.; pyridinedicarbothioate type herbicides, for example, dithiopyr etc.; phenoxy type herbicides, for example, MCPA, MCPB etc.; urea type herbicides, for example, dymron, cumyluron etc.; naphthalenedione type herbicides, for example, quinoclamine etc.; isoxazolidinone type herbicides, for example, clomazone etc.

In addition to the above mentioned herbicides, the following herbicides, shown in common names, for example, Acetochlor, Acifiuorfen (-sodium), Aclonifen, Alloxydim (-sodium), Ametryne, Amicarbazone, Amidochlor, Amidosulfuron, Amitrole, Asulam, Atrazine, Azafenidin, Beflubutamid, Benazolin (-ethyl), Bentazon, Benzfendizone, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bispyribac -(sodium), Bromacil, Bromobutide, Bromofenoxim, Bromoxynil, Butafenacil -(allyl), Butenachlor, Butralin, Butroxydim, Butylate, Carbetamide, Carfentrazone (-ethyl), Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulf- uron, Chlorthiamid, Chlortoluron, Cinidon (-ethyl), Cinmethylin, Cinosulfuron, Clefoxydim, Clethodim, Clodinafop (-propargyl), Clopyralid, Cloransulam (-methyl), Cyanazine, Cybutryne, Cycloate, Cycloxydim, 2,4-D, 2,4-DB, Desmedipham, Diallate, Dicamba, Dichlobenil, Dichlorprop (-P), Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl), Difenopenten (-ethyl), Difenzoquat, Diflufenican, Diflufenzopyr, Dikegulac (-sodium), Dimefuron, Dimepiperate, Dimethachlor, Dimethenamid (-P), Dimexyflam, Dinitramine, Diphenamid, Diquat (-dibromide), Diuron, Epropodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethiozin, Ethofumesate, Ethoxyfen, Fenoxaprop (-P-ethyl), Flamprop (-M-isopropyl, -M-methyl), Flazasulfuron, Florasulam, Fluazifop (-P-butyl), Fluazolate, Flucarbazone (-sodium), Fluchloralin, Flumetsulam, Flumiclorac (-pentyl), Flumiox- azin, Flumipropyn, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, Flurpyrsulfuron (-methyl, -sodium), Flurenol (-butyl), Fluridone, Fluroxypyr (-butoxypropyl, -meptyl), Flurprimidol, Flurtamone, Fluthiacet (-methyl), Fomesafen, Foramsulfuron, Glufosinate (-ammonium), Glyphosate (-ammonium, -isopropylammonium), Halosafen, Haloxyfop (-ethoxy- ethyl, -P-methyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imaza- mox, Imazapic, Imazapyr, Imazaqύin, Imazethapyr, Iodosulfuron (-methyl, -sodium), loxynil, Isopropalin, Isoproturon, Isouron, Isoxaben, Isoxachlortole, Isoxadifen (-ethyl), Isoxapyrifop, Ketospiradox, Lactofen, Lenacil, Linuron, Mecoprop (-P), Mesotrione, Metamitron, Metazachlor, Methabenzthiazuron, Methyldymron, Metobenzuron, Metobromuron, (S-) Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Monolinuron, Naproanilide, Napropamide, Neburon, Nicosulfuron, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Paraquat, Pelargonsaure, Pendimethalin, Pendralin, Pethoxamid, Phenmedipham, Picolinafen, Piperophos, Primisulfuron (-methyl), Profluazol, Profoxydim, Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propoxycarbazone (-sodium), Propyzamide, Prosulfocarb, Prosulfuron, Pyraflufen (-ethyl), Pyrazogyl, Pyribenzoxim, Pyridafol, Pyridate, Pyridatol, Pyriftalid, Pyrithiobac (-sodium), Quinmerac, Quizalofop (-P-ethyl, -P-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Sulfosulfuron, Tebutam, Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thiazopyr, Thidiazimin, Thifensulfuron (-methyl), Tiocarbazil, Tralkoxydim, Triallate, Triasulfuron, Tribenuron (-methyl), Triclopyr, Tridiphane, Trifloxy- sulfuron, Trifluralin, Triflusulfuron (-methyl), Tritosulfuron.

The above-mentioned herbicides are known herbicides mentioned in "Pesticide Manual " 2000, published by The British Crop Protect Council.

The weight ratios of the groups of active substances in the mixed compositions can vary within relatively wide ranges.

For instance, per part by weight of (1) the compounds of the formula (I),

0.2 to 14 parts by weight of acetamide type herbicides, preferably 0.66 to 5 parts by weight;

2 to 40 parts by weight of amide type herbicides, preferably 3.96 to 16 parts by weight;

0.2 to 20 parts by weight of benzofuran type herbicides, preferably 1.00 to 6 parts by weight;

0.2 to 8 parts by weight of indanedione type herbicides, preferably 0.49 to 2 parts by weight;

0.06 to 4 parts by weight of oxazinone type herbicides, preferably 0.20 to 0.8 parts by weight;

0.02 to 4 parts by weight of sulfonylurea type herbicides, preferably 0.07 to 1.2 parts by weight;

1 to 100 parts by weight of thiocarbamate type herbicides, preferably 2.47 to 40 parts by weight;

0.6 to 12 parts by weight of triazine type herbicides, preferably 1.32 to 4.5 parts by weight;

0.1 to 8 parts by weight of triazole type herbicides, preferably 0.33 to 3 parts by weight;

0.2 to 10 parts by weight of dithiophosphate type herbicides, preferably 1.00 to 4 parts by weight;

0.2 to 50 parts by weight of oxyacetamide type herbicides, preferably 1.00 to 12 parts by weight;

0.02 to 10 parts by weight of tetrazolinone type herbicides, preferably 0.17 to 3 parts by weight;

0.1 to 12 parts by weight of dicarboxyimide type herbicides, preferably 0.33 to 4.5 parts by weight;

0.2 to 12 parts by weight of phenoxypropinate type herbicides, preferably 0.4 to 1.8 parts by weight;

0.6 to 20 parts by weight of diphenylether type herbicides, preferably 1.65 to 7.5 parts by weight;

0.02 to 14 parts by weight of pyridinedicarbothioate type herbicides, preferably 0.20 to 5 parts by weight; 0.2 to 10 parts by weight of phenoxy type herbicides, preferably 0.66 to 4parts by weight, and

2 to 80 parts by weight of urea type herbicides, preferably 4.95 to 25 parts by weight,

are used.

Furthermore, the active compounds of the formula (I) , according to the present invention, can be mixed also with a safener and their application as a selective herbicide can be broadened to reduce phytotoxicity and to provide wider weed- control spectrum by such a mixing.

As an example of the safener, the following safeners can be mentioned; AD-67, BAS-145138, Benoxacor, Cloquintocet (-mexyl), Cyometrinil, 2,4-D, DKA- 24, Dichlormid, Dymron, Fenclorim, Fenchlorazol (-ethyl), Flurazole, Fluxofenim, Furilazole, Isoxadifen (-ethyl), MCPA, Mecoprop (-P), Mefenpyr (-diethyl), MG- 191, Naphthalic anhydride, Oxabetrinil, PPG-1292, R-29148.

The above-mentioned safeners are known safeners mentioned in "Pesticide Manual", 2000, published by The British Crop Protect Council.

The weight ratios of the groups of active substances in the mixed comositions can vary within relatively wide ranges.

For instance, per part by weight of (1) the compounds of the formula (I),

0.05 to 50 parts by weight of Dichlormid, preferably 0.1 to 10 parts by weight; 0.05 to 50 parts by weight of Dymron, preferably 0.1 to 10 parts by weight; 0.05 to 50 parts by weight of Fenclorim, preferably 0.1 to 10 parts by weight;

0.05 to 50 parts by weight of Mefenpyr (-diethyl), preferably 0.1 to 10 parts by weight; and

0.05 to 50 parts by weight of Naphthalic anhydride, preferably 0.1 to 10 parts by weight, are used.

And furthermore, the above-mentioned combinations of the compounds of the formula (I), according to the present invention, and the above-mentioned herbicides can be mixed with also the above-mentioned safeners and their application as selective herbicidal compositions can be broadened to reduce phytotoxicity and to provide wider weed - control spectrum by mixing safeners and/or other selective herbicides.

Surprisingly, some of the mixed compositions, according to the present invention show synergistic effects.

In case of using the active compounds of the formula (I) and their mixed compositions, according to the present invention, they can be directly used as such or used in formulation forms such as ready-to-use solutions, emulsions, tablets, suspensions, powders, pastes, granules or used in the use forms prepared by further dilution. The active compounds of the present invention can be applied by means of, for example, watering, spraying, atomizing, granule application etc.

The active compounds of the formula (I) and their mixed compositions, according to the present invention, can be used at any stages before and after germination of plants. They can also be taken into the soil before sowing.

The application amount of the active compounds of the formula (I) and their mixed compositions, according to the present invention, can be varied in a substantial range and are fundamentally different according to the nature of the desired effect. In case of using as herbicides, as the application amount there can be mentioned, for example, ranges of about 0.01 to about 3 kg, preferably about 0.05 to about 1 kg of the active compounds per hectare.

The preparations and applications of the compounds and their mixed compositions according to the present invention, will be described more specifically by the following examples. However, the present invention should not be restricted to them in any way.

Synthesis Example 1

3-Oxo-l-cyclohexenyl 2-chloro-3-{[(l-ethyl-lH-tetrazol-5-yl)thio]methyl}-4-meth- ylsulfonylbenzoate (0.83 g) was dissolved in acetonitrile (20 ml), to which triethylamine (0.34 g) and acetone cyanohydrin (10 mg) were added and the mixture was stirred at room temperature for 5 hours. After distilling off the solvent, the mixture was acidified by addition of diluted hydrochloric acid and extracted with dichloromethane (150 ml). The organic layer was washed with a saturated aqueous solution of sodium chloride and dried with anhydrous magnesium sulfate. Dichloromethane was distilled off to obtain the objected 2-{2-chloro-3-{[(l-ethyl- lH-tetrazol-l-yl)thio]methyl}-4-methylsulfonylbenzoyl}cyclohexane-l,3-dione (0.75 g). mp: 67-71°C. Synthesis Example 2

To a solution of 2-{2-chloro-4-methylsulfonyl-3-{[(l-methyl-lH-tetrazol-5-yl)thio]- methyl}benzoyl}cyclohexane-l,3-dione (1.0 g) in dichloromethane (100 ml), oxalyl chloride (0.91 g) and 2 drops of N,N-dimethylformamide were added dropwise and the mixture was refluxed for 3 hours. The residue obtained by distilling off the solvent after the reaction was purified by silica gel column chromatography (eluant: ethyl acetate : hexane = 7 : 3) to obtain the objective 3-chloro-2-{2-chloro-4- methylsulfonyl-3-{[(l-methyl-lH-tetrazol-5-yl)thio]methyl}benzoyl}-2-cyclohexen- 1-one (0.71 g). IR (NaCl): =1662, 1310, 1279, 1150 cm^"1.

Synthesis Example 3

3-Chloro-2-{2-chloro-4-methylsulfonyl-3-{[(l-methyl-lH-tetrazol-5-yl)thio]meth- yl}benzoyl} -2-cyclohexen- 1 -one (0.75 g) and thiophenol (0.19 g) were dissolved in tetrahydrofuran (7 ml), to which a solution of triethylamine (0.19 g) in tetrahydrofuran (3 ml) was added dropwise at 5°C and the mixture was stirred at room temperature for 4 hours. After the reaction cold water was added to the mixture, extracted with ethyl acetate (50 ml) and dried with anhydrous magnesium sulfate. The residue obtained by distilling off the ethyl acetate was purified by silica gel column chromatography (eluant: ethyl acetate : hexane = 7 : 3) to obtain the objective 2-{2-chloro-4-methylsulfonyl-3-{[(l-methyl-lH-tetrazol-5-yl)thio]meth- yl}benzoyl}-3-phenylthio-2-cyclohexen-l-one (0.61 g). mp: 76-87°C.

The compounds, obtained in the same manner as the above-mentioned Synthesis Examples 1-3, are shown in the following Tables 1-3, together with the compounds synthesized in the Synthesis Examples 1-3.

Examples of the compounds in case the compound of the formula (I) of the present invention is represented by the formula

are shown in Table 1,

examples of the compounds in case they are represented by the following formula

are shown in Table 2, and examples of the compounds in case they are represented by the following formula

are shown in Table 3.

In Tables 1, 2 and 3,

Qla a represents the group

Qlb represents the group

Qlc represents the group

Q2 represents the group

Q3a a represents the group

Q3b represents the group

Q3c represents the group

Q3d represents the group

Q3e represents the group

Q3f represents the group

O

Q3g represents the group

Q3h represents the group

Q3i represents the group

Q3j represents the group

Q3k represents the group

Q31 represents the group

Q3m represents the group

Q3n represents the group

Q3o represents the group

Q3p represents the group

Q3q represents the group

Q3r represents the group

Q3s represents the group

Q3t represents the group

Q3u represents the group

Q3v represents the group

Q3w represents the group

Q3x represents the group

Q3y represents the group

Q3z represents the group

Q3za represents the group

Q3zb represents the group

Q3zc represents the group

Q3zd represents the group

Q4a represents the group

Q4b represents the group

Q4c represents the group

Q4d represents the group

Q5a represents the group

Q5b represents the group

Q5c represents the group

Q5d represents the group

Q5e represents the group

Q5f represents the group

Q6a represents the group

Q6b represents the group

Q7 represents the group

Me represents methyl, Et represents ethyl, n-Pr represents n-propyl, i-Pr represents isopropyl, n-Bu represents n-butyl, t-Bu represents tert-butyl,n-Hex represents n- hexyl, OMe represents methoxy, OEt represents ethoxy, SMe represents methylthio, SEt represents ethylthio, SO₂Me represents methylsulfonyl, SO Et represents ethylsulfonyl, SO₂n-Pr represents n-propylsulfonyl, OSO₂Me represents methyl- sulfonyloxy, OSO Et represents ethylsulfonyloxy and Ph represents phenyl.

Table 1

tom- pounc i melting point

No. Y Z R n 0 (mp) or n_D ²⁰

1-1 H H Me 1 Qla

1-2 H H Me 2 Qla

1-3 H H Me 1 Q2

1-4 OMe H Me 1 Qla

1-5 CI H Me 1 Qla

1-6 Me H Me 1 Qla

1-7 H F Me 1 Qla

1-8 H F Me 1 Q2

1-9 H F Me 1 Q3a

1-10 H F Me 1 Q5a

1-11 H F Me 1 Q6a

1-12 H F Et 1 Qla

1-13 H F - Qla

1-14 H CI Me 1 Qla

1-15 H CI Me 2 Qla

1-16 H CI Me 1 Q2

1-17 H CI Me 1 Q3a

1-18 H CI Me 1 Q5a

1-19 H CI Me 1 Q7

1-20 H CI Et 1 Qla

1-22 H Br Me 1 Qla 1.6212

1-23 H Br Me 1 Q2 Com- pounc I melting point

No. Y Z R n Q (mp) or n_D ²⁰

1-24 H Br Me 1 Q3a

1-25 H Br Me 1 Q5a

1-26 H Br Me 1 Q6a

1-27 H Br Et 1 Qla

1-28 H Br - 1 Qla

1-29 H Me 1 Qla

1-30 H Me 1 Q2

1-31 H Me 1 Q3a

1-32 H Me 1 Q5a

1-33 H Et 1 Qla

1-34 H I < 1 Qla

1-35 H Me Me 1 Qla

1-36 H CF₃ Me 1 Qla

1-37 H CF₃ Me 1 Q2

1-38 H CF₃ Me 1 Q3a

1-39 H CF₃ Me 1 Q5a

1-40 H CF₃ Me 1 Q6a

1-41 H CF₃ Me 1 Q7

1-42 H CF₃ Et 1 Qla

1-44 H OMe Me 1 Qla

1-45 H OMe Me 1 Q2

1-46 H OMe Me 1 Q3a

1-4-7 H OMe Me 1 Q5a

1-48 H OMe Me 1 Q6a

1-49 H OMe Et 1 Qla

1-50 H OMe < 1 Qla

1-51 H OSO₂Me Me 1 Qla

1-52 H OSO₂Me Me 1 Q2

1-53 H SMe Me 1 Qla

1-54 H SMe Me 1 Q2

1-55 H SO₂Me Me 1 Qla

1-56 H SO₂Me Me 1 Q2

1-57 H SO₂Me Me 1 Q3a

1-58 H SO₂Me Me 1 Q5

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Compound melting point

No. X z R n (mp) or no 20

11-59 CI CI Q4a

π-60 CI CI - Q4b

π-6i CI CI Q5a

C₂H_S π-64 CI CI - ] ⁱ Qla

π-68 CI CI -CH=CH₂ Qla π-69 CI CI -CH=CH₂ Qlb π-70 CI CI -CH=CH₂ Qlc π-7i CI CI -CH=CH₂ Q2 π-72 CI CI -CH=CH₂ Q3a π-73 CI CI -CH=CH₂ Q4a π-74 CI CI -CH=CH₂ Q4b

11-75 CI CI -CH=CH₂ Q5a

11-76 CI CI -CH=CH₂ Q6a π-77 CI CI -CH₂CH=CH_; 1 1 Qla

O O O O O gCD gCD SCD HO HC?D;

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^pnou^d Compound melting point

No. X z R n Q (mp) or n_D ²⁰

11-185 CI SO₂Me 4-Nθ₂-Ph 1 Qla π-186 CI SO₂Me CH₂CH₂F 1 Qla π-187 CI SO₂Me CH₂CH₂F 1 Q2 π-188 CI SO₂Me CH₂CH₂F 1 Q3a

II- 189 CI SO₂Me CH₂CH₂F 1 Q5a π-190 CI SO₂Me CH CH C1 Qla π-i9i CI SO₂Me CH₂CH₂C1 1 Q2

11-192 CI SO₂Me CH₂CH₂C1 1 Q3a

II- 193 CI SO₂Me CH₂CH₂C1 1 Q5a π-194 CI SO Me CH₂CF₃ 1 [ Qla 82-87

II- 195 CI SO₂Me CH₂CF₃ 1 Qlb

II- 196 CI SO₂Me CH₂CF₃ 1 Qlc π-197 CI SO₂Me CH₂CF₃ 1 L Q2 π-198 CI SO₂Me CH₂CF₃ ] I Q3a

II- 199 CI SO₂Me CH₂CF₃ 1 L Q4a π-200 CI SO₂Me CH₂CF₃ 1 L Q4b π-2oι CI SO₂Me CH₂CF₃ 1 L Q5a π-202 CI SO₂Me CH₂CF₃ 1 I Q6a

11-203 CI SO₂Me CH₂CF₃ ] I Q7

11-204 CI SO₂Me CH₂CF₂CF₃ 1 L Qla π-205 CI SO₂Me CH₂CF₂CF₃ 1 L Q2

II-206 CI SO₂Me CH₂CF₂CF₃ ] I Q3a

11-207 CI SO₂Me CH₂CH₂CH₂F ] [ Q5a

II-208 CI SO₂Me CH₂CH₂CH₂F 1 L Qla

11-209 CI SO₂Me CH₂CH₂CH₂F ] L Q2 π-210 CI SO₂Me CH₂CH₂CH₂F 1 L Q3a π-211 CI SO₂Me CH CH CH₂F I Q5a π-212 CI SO₂Et Me L Qla 70-74 π-213 CI SO₂Et Me I Q2

II-214 CI SO₂Et Me 1 Q3a

11-215 CI SO₂Et Me [ Q5a π-216 CI SO₂Et Me I Q6a

II-217 CI SO₂Et Me 1 Q7

II-218 CI SO₂Et Et I Qla

11-219 CI SO₂Et Et 1 Q2

II-220 CI SO₂Et -< 1 Qla

11-221 CI SO₂Et -<\ 1 Q2 ©

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Compound melting point

No. X R n (mp) or n_D ²⁰

11-350 SO₂Me CI <\ 1 Qla

11-351 SO₂Me CI -CH= =CH₂ 1 Qla

II-352 SO₂Me SO₂Me Me 1 Qla π-353 SO₂Me SO₂Me Me 1 Q2

11-354 SO₂Me SO₂Me Et 1 Qla

11-356 SO₂Me SO₂Me -Cff =CH₂ 1 Qla

II-357 Me SO₂Me Me 1 Qla 69-71

11-358 Me SO₂Me Me 2 Qla

11-359 Me SO₂Me Me 1 Qlb

11-360 Me SO₂Me Me 1 Qlc π-361 Me SO₂Me Me 1 Q2

11-362 Me SO₂Me Me 1 Q3a

11-363 Me SO₂Me Me 1 Q3c

II-364 Me SO₂Me Me 1 Q3d

11-365 Me SO₂Me Me 1 Q4a

11-366 Me SO₂Me Me 1 Q4b

11-367 Me SO₂Me Me 1 Q5a

11-368 Me SO₂Me Me 1 Q5c

11-369 Me SO₂Me Me 1 Q6a

II-370 Me SO₂Me Me 1 Q7

II-371 Me SO₂Me Et 1 Qla

11-372 Me SO₂Me Et 1 Q2

II-373 Me SO₂Me Et 1 Q3a

II-374 Me SO₂Me Et 1 Q3b

IΪ-375 Me SO₂Me Et 1 Q5a

11-376 Me SO₂Me n-Pr 1 Qla

II-377 Me SO₂Me n-Pr 1 Q2

11-378 Me SO₂Me i-Pr 1 Qla

II-379 Me SO₂Me i-Pr 1 Q2

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11-380 Me S 1 Qla

11-381 Me SO₂Me 1 Qlb

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11-382 Me SO Me 1 Qlc

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Synthesis Example 4

2-Chloro-3- { [( 1 -ethyl- 1 H-tetrazol-5 -yl)thio]methyl} -4-methylsulfonyl-benzoic acid (0.77 g) and thionyl chloride (0.49 g) were added to 1,2-dichloroethane (30 ml) and the mixture was, after addition of 2 drops of N,N-dimethylformamide, refluxed for 3 hours. After cooling, the residue obtained by distilling off the solvent was dissolved in dichloromethane (10 ml) and the mixture was added dropwise to a solution of 1,3- cyclohexanedione (0.28 g) and triethylamine (0.28 g) in dichloromethane (10 ml) at 5°C and stirred at room temperature for 6 hours. After the reaction the mixture was extracted with dichloromethane (100 ml), washed with diluted hydrochloric acid and an aqueous dolution of sodium hydrogen carbonate, and dried with anhydrous magnesium sulfate. The residue obtained by distilling off the dichloromethane was purified by silica gel column chromatography (eluant: ethyl acetate : hexane = 3 : 7) to obtain the objective 3-oxo-l-cyclohexenyl 2-chloro-3-{[(l-ethyl-lH-tetrazol-5- yl)thio]methyl}-4-methylsulfonylbenzoate (0.83 g). mp: 122-123°C.

Synthesis Example 5

To a solution of methyl 2-chloro-3-{[(l-ethyl-lH-tetrazol-5-yl)thio]methyl}-4-meth- ylsulfonylbenzoate (0.83 g) in dioxane (15 ml), a ION aqueous solution of sodium hydroxide (1.0 ml) and water (2 ml) were added and the mixture was stirred at room temperature for 3 hours. Water (30 ml) is added. Then, after concentration under reduced pressure, a ION aqueous solution of sodium hydroxide (1.0 ml) was added to the concentrate and the concentrate is washed with ethyl acetate (100 ml). The aqueous layer was acidified with hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with saturated aqueous solution of sodium chloride and dried with anhydrous magnesium sulfate. Ethyl acetate was distilled off to obtain the objected 2-chloro-3-{[(l-ethyl-lH-tetrazol-5-yl)thio]methyl}-4-methyl- sulfonylbenzoic acid (0.80 g). mp: 193-195°C.

Synthesis Example 6

l-Ethyl-5-mercaptotetrazole (0.31 g) and methyl 3-bromomethyl-2-chloro-4-methyl- sulfonylbenzoate (0.80 g) were suspended in acetonitrile (20 ml) and the suspension was, after addition of potassium carbonate (0.32 g), refluxed for 3 hours. After addition of cold water upon the completion of the reaction, the mixture was extracted with ethyl acetate (100 ml) and dried with anhydrous magnesium sulfate. The residue obtained by distilling off the ethyl acetate was recrystallized from dichloromethane-hexane to obtain the objected methyl 2-chloro-3-{[(l-ethyl-lH- tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoate (0.88 g). mp: 109-110°C. Test Example 1 : Test for herbicidal effect against paddy field weeds

Preparation of a formulation of the active compound

Carrier: Acetone 5 parts by weight

Emulsifier: Benzyloxypolyglycolether 1 part by weight

A formulation of the active substance is obtained as an emulsion by mixing 1 part by weight of the active compound with the above-mentioned amount of carrier and emulsifier. A prescribed amount of the formulation is diluted with water.

Test method

In a greenhouse 3 seedlings of paddy rice (cultivar: Nipponbare) of 2.5 leafstage (15 cm tall) were planted in a 500 cm pot filled with paddy field soil. Then seeds or tubers of smallflower, bulrush, monochoria, broad-leaved weeds (common false pimpernel, Indian toothcup, long stemmed water wort, Dopatrium juncevm Hammilt etc.) and Japanese ribbon wapato were inoculated and water was poured to a depth of about 2-3 cm.

5 Days after the rice transplantation a formulation of each active compound prepared according to the aforementioned preparation method was applied to the surface of the water. The herbicidal effect was examined after 3 weeks from the treatment during which period the water depth of 3 cm was maintained. The herbicidal effect was rated as 100% in the case of complete extiinction and as 0% in the case of no herbicidal effect.

As a result, the compounds No. 11-18, II-l 17, 11-122, 11-131, 11-194, 11-212 and 111-71 showed at the application rate of 0.25 kg/ha a herbicidal effect of more than 90% against paddy field weeds and showed safety to the transplanted paddy rice. Test Example 2: Test of pre-emergence soil treatment against field weeds

Test method

In a greenhouse, on the surface layer of a 120 cm pot filled with field soil, and then seeds of bamyardgrass, foxtail, common amaranth and knotweed were sown and covered with soil. The prescribed amount of chemicals prepared in the same manner as in the above-mentioned Test Example 1 was spread uniformly on the soil surface layer of each test pot. The herbicidal effect was examined after 4 weeks from the treatment.

Effects:

The compounds No. 11-117, 11-122 and 11-194 showed at application rate of 2.0 kg/ha herbicidal activities of more than 90% against objective weeds (bamyardgrass, foxtail, common amaranth and knotweed).

Test Example 3: Test of post-emergence foliage treatment against field weeds

Test method

In a greenhouse, seeds of bamyardgrass, foxtail, common amaranth and knotweed were sown in 120 cm² pots filled with field soil and covered with soil. After 10 days after the sowing and soil covering (weeds were 2-leafstage in average) the prescribed amount of chemicals prepared in the same manner as in the above-mentioned Test Example 1 was spread uniformly on the foliage of the test plants in each test pot. The herbicidal effect was examined after 3 weeks from the treatment.

Results:

The compounds No. 11-18, 11-117, 11-122, 11-131, 11-194, 11-212 and 11-276 showed at the chemical amount of 2.0 kg/ha herbicidal activities of more than 90% against barnyardgrass, foxtail, common amaranth and knotweed.

Test Example 4: Test for synergistic action by foliar spray application

Preparation of the test solution

Carrier: acetone, 5 parts by weight

Emulsifier: benzyloxypolyglycol ether, 1 parts by weight

One part of an active compound and the above amounts of carrier and emulsifier are mixed to obtain a formulation of the active substance as an emulsion. A prescribed amount of this formulation is diluted with water to prepare testing solutions.

Test method

In a greenhouse, paddy soil was filled in pots (250 cm²), and seeds of weed (bamyardgrass, bulrush, monochoria and falsepimpemel) were inoculated in the surface layer of the soil in the pots under wet conditions and covered with soil. All of the weed species were individually inoculated in each pot. Each pot was watered to 2 cm in depth. When the weeds grew up to 1.5-2.2 leaf stage (or pair), a predetermined amount of the compound as a testing solution prepared in the above was applied to the weeds in pots by foliar spray after draining the water in the pot. On the day following the application, the pots were irrigated again to 2 cm of water depth. The herbicidal effect was evaluated at 4 weeks after the application on a scale of 0(not active) to 100(complete damage).

Test results of test example 4 are shown in Table 4. Test Example 5: Test for synergistic action by water sureface application

Test method

In a greenhouse, paddy soil was filled in pots (250 cm²), and seeds of weed (bamyardgrass, bulrush, monochoria, falsepimpernel, indian toothcup, waterwort and flatstage) were inoculated in the surface layer of the soil in the pots under wet conditions and covered with soil. All of the weed species were individually inoculated in each pot. Each pot was watered to 2 cm in depth and the depth was kept during the test period. When the weeds grew up to 1.5-2.2 leaf stage (or pair), a predetermined amount of the compound as a testing solution prepared in the same manner as the above-mentioned Test Example 4 was applied to the pots by water surface treatment method. The herbicidal effect was evaluated at 4 weeks after the application on the same scale as in thetest method of Test Example 4.

Test results of test example 5 are shown in Table 5.

Synergistic action of Test Example 4 and Test Example 5 were evaluated by Colby's equation.

Colby : E = X + [ Y x (100-X) ]

100 E : expected herbicidal activity at p+q g/ha X : the percentage of herbicidal activity at p g/ha Y : the percentage of herbicidal activity at q g/ha

The following abbreviations are used in Table 4 and Table 5 :

CYPSE represents Cyperus serotinus (flatstage),

ECHSS represents Echinochloa spp. (bamyardgrass),

ELTTP reprerstnts Elatine triandra (waterwort),

LIDPY represents Lindemia pyridaria (flasepimpernel), MOOVP represents Monochoria vaginalis (monochoria),

ROTIN represents Rotala indica (indian toothcup),

Compounds (1) in Table 4 and Table 5 are listed by the compound numbers previously used in Tables 1, 2 and 3.

In Table 4 and Table 5 other known herbicides are represented by the capital letters as shown in the following list:

A: 4-(2-chlorophenyI)-N-cyclohexyl-N-ethyl-4,5-dihydro-5-oxo-lH-tetrazole -l- carboxamide (fentrazamide),

B : 3 , ' 4 ' -dichloropropionanilide (prop anil),

C: N,N-diethyl-3-mesitylsulfonyl-lH-l,2,4-triazole-l-carboxamide (cafenstrole),

D: 3-[l-(3,5-dichlorophenyl)-l-methylethyl]-2,3-dihydro-6-methyl-5-phenyl-4H-

1 ,3-oxazin-4-one (oxaziclomefone), E: 2-chloro-2',6'-diethyl-N-(2-propoxyethyl) acetamide (pretilachlor),

F: 2-(l,3-benzothiazol-2-yloxy)-N-methylacetanilide (mefenacet),

G: (RS)-2-[2-(3-chlorophenyl)2,3-epoxypropyl]-2-ethylindan-l,3-dione (indanofan). Table 4: Herbicidal efficacy (%) by foliar spray application

Table 5: Herbicidal efficacy (%) by water surface application

Table 5: (Continued)

Test Example 6: Test for safening action on rice by water surface application

Test method

In a greenhouse, paddy soil was filled in pots (1,000 cm²), and seeds of rice (cv. Nipponbare) were sown in the surface layer of the soil in the pots under wet conditions. 7 days after seeding, at the one leaf stage of the rice seedlings, the pots were watered to 3 cm in depth and the depth was kept during the test period. When the rice seedlings grew up to 1.5 leaf stage during the 9 days after seeding, a predetermined amount of the compound as a testing solution prepared in the same manner as the above-mentioned Test Example 4 was applied to the pots by water surface treatment method. The phytotoxicity to rice seedlings was evaluated at 3 weeks after the application on a scale of 0 (no damage) to 100 (complete deth).

Test result of test example 6 are shown in Table 6.

Safening action of Test Example 6 were evaluated by Colby's equation.

Colby : E = X + [ Y x (100-X) ]

100

E expected phytotoxicity at p + q g/ha X expected phytotoxicity at p g/ha Y expected phytotoxicity at q g/ha

Compounds (1) in Table 6 are listed by by the compound numbers previously uesd in Tables 1, 2 and 3.

In Table 6 the known safeners are represented by the capital letters as shown in the following list:

a : N,N-dialιyl-2,2-dichloroacetamide (dichlormid), b : 4,6-dichloro-2-phenylpyrimidine (fenclorin), c : diethyl (RS)-l-(2,4-dichlorophenyl)-5-methyl-2-pyrazoline-3,5-dicarboxylate (mefenpyr-diethyl),

N-(4-methylphenyl)-N' -(1 -methyl- 1 -phenylethyl)urea (dymron), 2-(dichloroacetyl)-2,2,5-trimethyl-oxazolidine (R-29148), lH,3H-naphtho [ 1,8-cd ] pyran-l,3-dione (naphthalic anhydride). Table 6: Safening efficacy (%) by water surface application

Table 6 : (Continued)

Formulation Example 1 (Granule)

To a mixture of the compound No. 11-18 of the present invention (2.5 parts), bentonite (montmorillonite) (30 parts), talc (65.5 parts) and ligninsulphonate salt (2 parts), water (25 parts) is added. The mixture is well kneaded, made in granules of 10-40 mesh by an extrusion granulator and dried at 40-50°C to obtain a granule.

Formulation Example 2 (Granule)

Clay mineral particles having particle size distribution of 0.2-2 mm (95 parts) are put in a rotary mixer. While rotating it, the compound No. 11-117 of the present invention (5 parts) is sprayed together with a liquid diluent into the mixer wetted uniformly and dried at 40-50°C to obtain granules.

Formulation Example 3 (Emulsifiable concentrate)

The compound No. 11-122 of the present invention (30 parts), xylene (5 parts), poly- oxyethylenealkyl phenyl ether (8 parts) and calcium alkylbenzenesulfonate (7 parts) are mixed and stirred to obtain an emulsion. Formulation Example 4 (Wettable powder)

The compound No. 11-194 of the present invention (15 parts), a mixture of white carbon (hydrous amorphous silicon oxide fine powders) and powder clay (1:5) (80 parts), sodium alkylbenzenesulfonate (2 parts) and sodium alkylnaphthalene- sulfonate-formalin-polymer (3 parts) are mixed in powder form and made into a wettable powder.

Formulation Example 5 (Water-dispersible granule)

The compound No. 11-18 of the present invention (20 parts), sodium ligninsulfonate (30 parts), bentonite (15 parts) and calcined diatomaceous earth powder (35 parts) are well mixed, added with water, extmded using a 0.3 mm screen and dried to obtain a water-dispersible granules.

Claims

1. A compound of the formula (I)

5 wherein

R¹ represents halogen, methyl, ethyl, halomethyl, methoxy, ethoxy, Cι- haloalkoxy, methylthio, ethylthio, C₁-₃ alkylsulfonyl, methyl- sulfonyloxy, ethylsulfonyloxy, nitro or cyano,

R² represents Cι-₆ alkyl, C₃. cycloalkyl which may be optionally substituted with halogen or C₁.₃ alkyl, C₁-₄ haloalkyl, C₂.₆ alkenyl, or phenyl which may be optionally substituted with halogen, C₁.₃ alkyl, Cι-2 haloalkyl or nitro,

m represents 0, 1 or 2,

the two R¹ substituents may be identical or different, in case m represents 2,

n represents 1 or 2,

Q represents one of the following groups

or

wherein

R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are identical or different and each represents a hydrogen atom or methyl,

R ,9 represents a hydrogen atom, halogen, C₁.₃ alkyl, halomethyl, methoxy or nitro,

R . 10 represents Cι-6 alkyl,

R represents halogen, and k represents 1 or

2.

A compound of the formula (I) according to Claim 1 wherein

R¹ represents fluoro, chloro, bromo, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, Cι-₂ haloalkoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, nitro or cyano,

R² represents Cι_₃ alkyl, cyclopropyl which may be optionally substituted with fluoro, chloro, methyl or ethyl, Cι-₃ haloalkyl, C₂.₄ alkenyl, or phenyl which may be optionally substituted with fluoro, chloro, methyl, ethyl, trifluoromethyl or nitro,

m represents 1 or 2,

the two R substituents may be identical or different, in case m represents 2,

n represents 1 or 2,

Q represents one of the following groups

or

wherein

R⁹ represents a hydrogen atom, fluoro, chloro, methyl, ethyl or trifluoromethyl

R¹⁰ represents methyl or ethyl,

R¹¹ represents chloro or bromo, and

k represents 1.

3. The compounds of the formula (I) according to in Claim 1 wherein

R¹ represents chloro, bromo, methyl or methylsulfonyl,

R² represents methyl, ethyl, n-propyl, isopropyl or cyclopropyl, m represents 2, and in this case the two R¹ substituents are bond respectively to the 2-position and 4-position of a benzene ring and the two R¹ substituents may be identical or different,

n represents 1,

the group

R²

- (CH₂)_n- S-<\ I I

bonds to the 3 -position of the benzene ring, and

Q represents one of the following groups

or

4. A process for the preparation of the compounds of Claim 1

characterized in that

a) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-1) or (Q-2): compounds of the formula (II)

wherein

R , ι , R , m and n have the same definition as mentioned in Claim 1, and

T¹ represents one of the following groups

or wherein

R , R , R , R , R and R have the same definition as mentioned in Claim 1,

are reacted to a rearrangement in the presence of inert solvents, and if appropriate, in the presence of a base and cyanide, and if appropriate, in the presence of a phase-transfer catalyst, or

b) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-6) or (Q-7) and R¹¹ in said groups represents chloro or bromo:

compounds of the formula (lb)

wherein

R , R , m and n have the same definition as mentioned in Claim 1, and

Q_b represents one of the following groups or

wherein

R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the same definition as mentioned in Claim 1,

are reacted with a halogenating agent in the presence of inert solvents, or c) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-3), (Q-4) or (Q-5):

compounds of the formula (Ic)

wherein

R . 1 , r R>2 , m and n have the same definition as mentioned in Claim 1, and Q_c represents one of the following groups

or

wherein

R^{1 lc} represents chloro or bromo,

are reacted with compounds of the formula (III)

R¹²-SH (III)

wherein

R¹² represents the group or

R 10 wherein

R , R and k have the same definition as mentioned in Claim 1,

5. A herbicidal composition, characterized in that it contains at least one compound according to Claim 1.

6. A method for combating weeds, characterized in that a compound according to Claim 1 is allowed to act on weeds and / or their habitat.

7. Use of a compound according to Claim 1 for combating weeds.

8.. A process for the preparation of herbicidal compositions, characterized in that a compound according to Claim 1 is mixed with extenders and / or surface active agents.

9. A compound represented by the formula (X)

wherein R ,ι , R , m and n have the same definition as mentioned in Claim 1,

W represents halogen, hydroxy, C_M alkoxy or one of the following groups

or

wherein R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the same definition as mentioned in Claim 1.

10. A Herbicidal composition, characterized in that it contains an acitive substance combination comprising one tetrazole derivative of the formula (I) according to Claim 1 and at least one known active ingredient selected from the group consisting of acetamide type herbicides, amide type herbicides, benzofuran type herbicides, indanedione type herbicides, pyrazole type herbicides, oxazinone type herbicides, sulfonylurea type herbicides, thio- carbamate type herbicides, triazine type herbicides, triazole type herbicides, quinoline type herbicides, isoxazole type herbicides, dithiophosphate type herbicides, oxyacetamide type herbicides, tetrazolinone type herbicides, dicarboxyimide type herbicides, trione type herbicides, phenoxypropinate type herbicides, benzoic acid type herbicides, diphenylether type herbicides, pyridinedicarbothioate type herbicides, phenoxy type herbicides, urea type herbicides, naphthalenedione type herbicides and isoxazolidinone type herbicides.

11. A herbicidal composition, characterized in that it contains an active substance combination comprising one tetrazole derivative of formula (I) according to Claim 1 and at least one known safener selected from the group consisting of AD-67, BAS-145138, Benoxacor, Cloquintocet (-mexyl), Cyometrinil, 2,4-D, DKA-24, Dichlormid, Dymron, Fenclorim, Fenchlorazol (-ethyl), Flurazole, Fluxofenim, Furilazole, Isoxadifen (-ethyl), Mefenpyr (-diethyl), MG-191, Naphthalic anhydride, Oxabetrinil, PPG-1292, R-29148.

12. A Herbicidal composition, characterized in that they contain an active substance combination comprising one tetrazole derivative of the formula (I) according to Claim 1 together with at least one active ingredient selected from the group consisting of acetamide type herbicides, amide type herbicides, benzofuran type herbicides, indanedione type herbicides, pyrazole type herbicides, oxazinone type herbicides, sulfonylurea type herbicides, .thio- carbamate type herbicides, triazine type herbicides, triazole type herbicides, quinoline type herbicides, isoxazole type herbicides, dithiophosphate type herbicides, oxyacetamide type herbicides, tetrazolinone type herbicides, di- carboxyimide type herbicides, trione type herbicides, phenoxypropinate type herbicides, benzoic acid type herbicides, diphenylether type herbicides, pyridinedicarbothioate type herbicides, phenoxy type herbicides, urea type herbicides, naphthalenedione type herbicides and isoxazolidinone type herbicides, and at least one known safener selected from the group consisting of AD-67, BAS-145138, Benoxacor, Cloquintocet (-mexyl), Cyometrinil, 2,4- D, DKA-24, Dichlormid, Dymron, Fenclorim, Fenchlorazol (-ethyl), Flur- azole, Fluxofenim, Furilazole, Isoxadifen (-ethyl), Mefenpyr (-diethyl), MG- 191, Naphthalic anhydride, Oxabetrinil, PPG- 1292, R-29148.

13. A process for combating weeds, characterized in that an active substance combination according to any of Claims 10, 11 or 12 is allowed to act on the weeds and/or their habitat.

14. Use of an active substance combination according to any of Claims 10, 11 or 12 for combating weeds.

15. A process for the preparation of a herbicidal composition, characterized in that an active substance combination according to any of Claims 10, 11 or 12 is mixed with extenders and/or surface-active agents.