Novel tetrazole derivatives

[0001] 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.

[0002] 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. Pat. Specifications Nos. 5,834,402, 5,846,906, DE-A-19846792, WO 99/10327 etc.).

[0003] There have now been found novel tetrazole derivatives of the formula (I)

[0004] wherein

[0005] R1 represents halogen, methyl, ethyl, halomethyl, methoxy, ethoxy, C1-2 haloalkoxy, methylthio, ethylthio, C1-3 alkylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, nitro or cyano,

[0006] R2 represents C1-6 alkyl or C3-6 cycloalkyl which may be optionally substituted with halogen or C1-3 alkyl, or represents C1-4 haloalkyl, C2-6 alkenyl, or phenyl which may be optionally substituted with halogen, C1-3 alkyl, C1-2 haloalkyl or nitro,

[0007] m represents 0, 1 or 2,

[0008] and the two R1 substituents may be identical or different, in case m represents 2,

[0009] n represents 1 or 2,

[0010] Q represents one of the following groups

[0011] wherein

[0012] R3, R4, R5, R6, R7 and R8 are identical or different and each represents a hydrogen atom or methyl,

[0013] R9 represents a hydrogen atom, halogen, C1-3 alkyl, halomethyl, methoxy or nitro,

[0014] R10 represents C1-6 alkyl,

[0015] R11 it represents halogen, and

[0016] k represents 1 or 2.

[0017] The compounds of the formula (I), according to the invention, can be obtained by a process wherein

[0018] a) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-1) or (Q-2):

[0019] compounds of the formula (II)

[0020] wherein

[0021] R1, R2, m and n have the same definition as aforementioned, and

[0022] T1 represents one of the following groups

[0023] wherein

[0024] R3, R4, R5, R6, R7 and R8 have the same definition as aforementioned,

[0025] 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,

[0026] or

[0027] 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:

[0028] compounds of the formula (Ib)

[0029] wherein

[0030] R1, R2, m and n have the same definition as aforementioned, and

[0031] Qb represents one of the following groups

[0032] wherein

[0033] R3, R4, R5, R6, R7 and R8 have the same definition as aforementioned,

[0034] are reacted with a halogenating agent in the presence of inert solvents,

[0035] or

[0036] c) in case of preparing a compound of the formula (I) wherein Q represents groups (Q-3), (Q-4) or (Q-S):

[0037] compounds of the formula (Ic)

[0038] wherein

[0039] R1, R2, m and n have the same definition as aforementioned, and

[0040] Qc represents one of the following groups

[0041] wherein

[0042] R3, R4, R5, R6, R7 and R8 have the same definition as aforementioned,

[0043] R11c represents chloro or bromo,

[0044] are reacted with compounds of the formula (III)

R12—SH (II)

[0045] wherein

[0046] R12 represents the following group

[0047] R10

[0048] wherein

[0049] R9, R10 and k have the same definition as aforementioned,

[0050] in the presence of inert solvents, and if appropriate, in the presence of an acid binding agent.

[0051] 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.

[0052] In the formulae:

[0053] “Halogen” represents fluoro, chloro, bromo or iodo, and preferably represents fluoro, chloro or bromo.

[0054] “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.

[0055] “Cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. These cycloalkyls may be optionally substituted with halogen (for example, fluoro, chloro, bromo etc.), C1-3 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, 1-methyl-2-fluorocyclopropyl, 2-methylcyclopropyl, 2-fluorocyclopropyl, 1-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.

[0056] As “alkenyl” there can be mentioned, for example, vinyl, allyl, 1-methylallyl, 1,1-dimetylallyl and 2-butenyl.

[0057] “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, C1-4 alkyl substituted with 1-6 fluoro and/or chloro, specifically difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, dichloromethyl, 2-chloro-1,1,2-trifluoroethyl, 3-fluoropropyl, 3-chloropropyl, 2,2,3,3,3-pentafluoropropyl and 1,2,2,3,3,3-hexa-fluoropropyl.

[0058] 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.

[0059] “Alkylsulfonyl” represents an alkyl-SO2-group, wherein the alkyl part has the above-mentioned meaning, and includes specifically methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl.

[0060] As preferred definitions in the formula (I) there can be mentioned:

[0061] R1 preferably represents fluoro, chloro, bromo, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, C1-2 haloalkoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, nitro or cyano.

[0062] R2 preferably represents C1-3 alkyl, cyclopropyl which may be optionally substituted with fluoro, chloro, methyl or ethyl, C1-3 haloalkyl, C2-4 alkenyl, or phenyl which may be optionally substituted with fluoro, chloro, methyl, ethyl, trifluoromethyl or nitro.

[0063] m preferably represents 1 or 2.

[0064] n preferably represents 1 or 2.

[0065] R9 preferably represents a hydrogen atom, fluoro, chloro, methyl, ethyl or tri-fluoromethyl.

[0066] R10 preferably represents methyl or ethyl.

[0067] R11 preferably represents chloro or bromo.

[0068] k preferably represents 1.

[0069] As more preferred definitions in the formula (I) there can be mentioned:

[0070] R1 more preferably represents chloro, bromo, methyl or methylsulfonyl,

[0071] R2 more preferably represents methyl, ethyl, n-propyl, isopropyl or cyclopropyl,

[0072] 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.

[0073] n more preferably represents represents 1.

[0074] In a most preferred group of the inventive compounds the group

[0075] bonds to the 3-position (according to formula (I)) of the benzene ring.

[0076] In another most preferred group Q represents one of the following groups

[0077] The substituents among the different ranges of preference can be combined without limitation among each other.

[0078] limitation among each other.

[0079] 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.

[0080] The aforementioned preparation process (a) can be illustrated by the following reaction formula, in case of using, for example, 3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate as the starting material.

[0081] The aforementioned preparation process (b) can be illustrated by the following reaction formula, in case of using, for example, 2-{2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}cyclohexane-1,3-dione as the starting material, and, for example, oxalyl dichloride as chlorinating agent.

[0082] 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-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-2-cyclohexen-1-one and thiophenol as the starting materials.

[0083] It is further mentioned that the group (Q-1) defined for Q in the above-mentioned formula (I) can also exist in the following two tautomeric forms

[0084] 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

[0085] 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-1a), (Q-1b), (Q-2a) or (Q-2b) as group Q-1 or Q-2 respectively. In 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).

[0086] 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)

[0087] wherein

[0088] R1, R2, m and n have the same definition as aforementioned, and

[0089] M represents halogen,

[0090] with compounds of the formula (V)

Qa-H (V)

[0091] wherein

[0092] Qa represents one of the following groups

[0093] wherein

[0094] R3, R4, R5, R6, R7 and R8 have the same definition as aforementioned,

[0095] in an appropriate diluent, for example, dichloromethane, in the presence of an appropriate condensing agent, for example, triethylamine.

[0096] The compounds of the formula (IV) 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)

[0097] wherein

[0098] R1, R2, m and n have the same definition as aforementioned,

[0099] with a halogenating agent, for example, phosphorus oxychloride, phosphorus-oxy-bromide, phosphorus trichloride, phosphorus tribromide, phosgene, oxalyl dichloride, thionyl chloride, thionyl bromide.

[0100] 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).

[0101] 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)

[0102] wherein

[0103] R1, R2, m and n have the same definition as aforementioned, and

[0104] T2 represents C1-4 alkoxy, preferably methoxy or ethoxy,

[0105] in an appropriate diluent, for example, aqueous dioxane, in the presence of an appropriate base, for example, sodium hydroxide.

[0106] 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)

[0107] wherein

[0108] R2 has the same definition as aforementioned

[0109] with compounds of the formula (IX)

[0110] wherein

[0111] R1, m and n have the same definition as aforementioned,

[0112] T2 represents C1-4 alkyl, preferably methyl or ethyl, and

[0113] M represents halogen,

[0114] in an appropriate diluent, for example, N,N-dimethylformamide, in the presence of an appropriate condensing agent, for example, potassium carbonate.

[0115] The compounds of the above-mentioned formula (VIII) 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.

[0116] 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.

[0117] 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.

[0118] 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:

[0119] 3-Oxo-1-cyclohexenyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0120] 3-oxo-1-cyclohexenyl 2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-fluorobenzoate,

[0121] 3-oxo-1-cyclohexenyl 4-chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0122] 3-oxo-1-cyclohexenyl 4-chloro-2-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0123] 3-oxo-1-cyclohexenyl 4-chloro-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,

[0124] 3-oxo-1-cyclohexenyl 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0125] 3-oxo-1-cyclohexenyl 4-bromo-2-{[(1-phenyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0126] 3-oxo-1-cyclohexenyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluorometh-ylbenzoate,

[0127] 3-oxo-1-cyclohexenyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylbenzoate,

[0128] 3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,

[0129] 3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]meth-yl}benzoate,

[0130] 3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-(2-chlorophenyl)-1H-tetrazol-5-yl)thio]-methyl}benzoate,

[0131] 3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-meth-ylsulfonylbenzoate,

[0132] 3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoate,

[0133] 3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-(n-pentyl)-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoate,

[0134] 3-oxo-1-cyclohexenyl 2-chloro-3-{[(1-(3-difluoromethylphenyl)-1H-tetrazol-5-yl)-thio]methyl}-4-methylsulfonylbenzoate,

[0135] 3-oxo-1-cyclohexenyl 4-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-meth-ylsulfonylbenzoate,

[0136] 3-oxo-1-cyclohexenyl 2,4-dimethylsulfanyl-3-{[(1-methyl-1H-tetrazol-5-yl)thio]-methyl}benzoate,

[0137] 3-oxo-1-cyclohexenyl 4-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-meth-ylsulfonylbenzoate,

[0138] 3-oxo-1-cyclohexenyl 2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0139] 3-oxo-1-cyclohexenyl 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-methoxybenzoate,

[0140] 3-oxo-1-cyclohexenyl 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-methylsulfonyloxybenzoate,

[0141] 3-oxo-1-cyclohexenyl 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitrobenzoate,

[0142] 3-oxo-1-cyclohexenyl 4-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-2-nitrobenzoate,

[0143] 5,5-dimethyl-3-oxo-1-cyclohexenyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoate,

[0144] 4,4-dimethyl-3-oxo-1-cyclohexenyl 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]-methyl}benzoate,

[0145] 4,4-dimethyl-3-oxo-1-cyclohexenyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)-thio]methyl}benzoate,

[0146] 4-{4-chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyloxy}-bicyclo[3.2.1]-3-octen-2-one,

[0147] 4-{2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoyloxy}bi-cyclo[3.2.1]-3-octen-2-one,

[0148] 4-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyloxy}bicyclo[3.2.1]-3-octen-2-one.

[0149] 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:

[0150] 4-Chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,

[0151] 4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,

[0152] 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoyl chloride,

[0153] 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,

[0154] 2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,

[0155] 2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl chloride,

[0156] 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl chloride,

[0157] 2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,

[0158] 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl chloride,

[0159] 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitro-benzoyl chloride,

[0160] 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl bromide,

[0161] 2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl bromide,

[0162] 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl bromide.

[0163] 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:

[0164] 4-Chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,

[0165] 4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,

[0166] 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoic acid,

[0167] 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,

[0168] 2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,

[0169] 2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoic acid,

[0170] 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoic acid,

[0171] 2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoic acid,

[0172] 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thiolmethyl}benzoic acid,

[0173] 4-{[(1-methyl-1H-tetrazol-5-yl)thiolmethyl}-2-nitro-benzoic acid.

[0174] 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.

[0175] Methyl 4-chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0176] methyl 4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,

[0177] methyl 2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethyl-benzoate,

[0178] methyl 2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,

[0179] methyl 2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoate,

[0180] methyl 2chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}4-methylsulfonylbenzoate,

[0181] methyl 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoate,

[0182] methyl 2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0183] methyl 2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0184] methyl 4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitro-benzoate,

[0185] ethyl 2,4-dichloro-3-{(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoate,

[0186] ethyl 2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-4-methylsulfonylbenzoate,

[0187] ethyl 2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoate.

[0188] The compounds of the formula (Ib), 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).

[0189] As typical examples of the compounds of the formula (Ib) used as the starting materials in the aforementioned preparation process (b), the followings, included in the formula (I), can be mentioned:

[0190] 2-{4Chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,

[0191] 2-{4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,

[0192] 2-{2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethyl-benzoyl}cyclo-hexane-1,3-dione,

[0193] 2-{2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,

[0194] 2-{2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}cyclo-hexane-1,3-dione,

[0195] 2-{2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl}-cyclohexane-1,3-dione,

[0196] 2-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl}cyclohexane-1,3-dione,

[0197] 2-{2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,

[0198] 2-{2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-cyclohexane-1,3-dione,

[0199] 2-{4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-2-nitrobenzoyl}-cyclohexane-1,3-dione,

[0200] 3-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl}bicyclo[3.2.1]-octane-2,4-dione

[0201] As a halogenating agent used for the reaction with the compounds of the formula (Ib) in the preparation process (b) there can be mentioned, for example, thionyl chloride, thionyl bromide, oxalyl dichloride, oxalyl dibromide etc.

[0202] 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).

[0203] 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:

[0204] 3-Chloro-2-{4-chloro-2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclohexen-1-one,

[0205] 3-chloro-2-{4-bromo-2-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclohexen-1-one,

[0206] 3-chloro-2-{2-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-trifluoromethylbenzoyl}-2-cyclohexen-1-one,

[0207] 3-chloro-2-{2,4-dichloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclohexen-1-one,

[0208] 3-chloro-2-{2,4-dichloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-2-cyclohexen-1-one,

[0209] 3-chloro-2-{2-chloro-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoyl}-2-cyclohexen-1-one,

[0210] 3 -chloro-2-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoyl}-2-cyclohexen-1-one,

[0211] 3-chloro-2-{2-chloro-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclo-hexen-1-one,

[0212] 3-chloro-2-{2-bromo-4-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}-benzoyl}-2-cyclohexen-1-one,

[0213] 3-chloro-2-{4-{[(1-methyl-1H-tetrazol-5 -yl)thio]methyl}-2-nitrobenzoyl}-2-cyclohexen-1-one,

[0214] 4-chloro-2-{2-chloro-3-{[(1-cyclopropyl-1H-tetrazol-5-yl)thio]methyl}-4-methyl-sulfonylbenzoyl}bicyclo[3.2.1]-3-octen-2-one.

[0215] 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:

[0216] Methyl mercaptan,

[0217] ethyl mercaptan,

[0218] thiophenol,

[0219] 4-fluorothiophenol,

[0220] 4-chlorothiophenol,

[0221] 2-methylthiophenol,

[0222] 4-ethylthiophenol,

[0223] 4-trifluoromethylthiophenol etc.

[0224] 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)

[0225] wherein

[0226] W represents T1, hydroxy or T2, wherein

[0227] R1, R2, m, n, T1, T2 and M have the same definition as aforementioned.

[0228] 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).

[0229] 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 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU).

[0230] 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.

[0231] 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.

[0232] In conducting the preparation process (a) the target compounds of the afore-mentioned 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 1 to 4 moles of triethylamine in a diluent, for example, acetonitrile, in the presence of 0.01 to 0.5 moles of acetone cyanohydrin.

[0233] 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 (I) and (II).

[0234] 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, 1,3-dimethyl-2-imidazolidinone and hexamethyl-phosphoric triamide (HMPA).

[0235] 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.

[0236] In conducting the preparation process (b) the target compounds of the afore-mentioned formula (I), in case that Q represents groups (Q-6) or (Q-7), wherein R11 in said group represents chloro or bromo, can be obtained, for example, by reacting 1 mole of a compound of the formula (Ib) with 1 to 5 moles of oxalyl dichloride in a diluent, for example, dichloromethane.

[0237] 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.

[0238] 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 (MAP), 1,4-diazabicyclo[2,2,2]octane (DABCO) and 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU).

[0239] 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.

[0240] In conducting the preparation process (c) the target compounds of the afore-mentioned 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.

[0241] 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, according 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.

[0242] 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.

[0243] Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita etc.

[0244] 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.

[0245] Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium etc.

[0246] 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.

[0247] 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.

[0248] 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.

[0249] 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.

[0250] 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 emulsifiers and/or dispersants and/or foam-forming agents.

[0251] As liquid diluents or carriers there can be mentioned, for example, aromatic hydro-carbons (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.

[0252] 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.

[0253] 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.

[0254] Dispersants include, for example, ligninsulphite waste liquor, methyl cellulose etc.

[0255] 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.).

[0256] 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.

[0257] Said formulations can contain the active compounds of the formula (I) in a range of generally 0.1 to 95% by weight, preferably 0.5 to 90% by weight.

[0258] 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.

[0259] Acetamide type herbicides, for example, pretilachlor, butachlor, tenylchlor, alachlor etc.;

[0260] amide type herbicides, for example, clomeprop, etobenzanid etc.;

[0261] benzofuran type herbicides, for example, benfuresate etc.;

[0262] indanedione type herbicides, for example, indanofan etc.;

[0263] pyrazole type herbicides, for example, pyrazolate, benzofenap, pyrazoxyfen etc.;

[0264] oxazinone type herbicides, for example, oxaziclomefone etc.;

[0265] sulfonylurea type herbicides, for example, bensulfuron-methyl, azimsulfuron, imazosulfuron, pyrazosulfuron-ethyl, cyclosulfamron Ethoxysulfuron, Halosulfuron (-methyl) etc.;

[0266] thiocarbamate type herbicides, for example, thiobencarb, molinate, pyributycarb etc.;

[0267] triazine type herbicides, for example, dimethametryn Simetryn etc.;

[0268] triazole type herbicides, for example, cafenstrole etc.;

[0269] quinoline type herbicides, for example, quinclorac etc.;

[0270] isoxazole type herbicides, for example, isoxaflutole etc.;

[0271] dithiophosphate type herbicides, for example, anilofos etc.;

[0272] oxyacetamide type herbicides, for example, mefenacet, flufenacet etc.;

[0273] tetrazolinone type herbicides, for example, fentrazamide etc.;

[0274] dicarboxyimide type herbicides, for example, pentoxazone etc.;

[0275] trione type herbicides, for example, sulcotrione, benzobicyclon etc.;

[0276] phenoxypropinate type herbicides, for example, cyhalofop-butyl etc.;

[0277] benzoic acid type herbicides, for example, pyriminobac-methyl etc.;

[0278] diphenylether type herbicides, for example, chlomethoxyfen, oxyfluorfen etc.;

[0279] pyridinedicarbothioate type herbicides, for example, dithiopyr etc.;

[0280] phenoxy type herbicides, for example, MCPA, MCPB etc.;

[0281] urea type herbicides, for example, dymron, cumyluron etc.;

[0282] naphthalenedione type herbicides, for example, quinoclamine etc.;

[0283] isoxazolidinone type herbicides, for example, clomazone etc.

[0284] diphenylether type herbicides, for example, chlomethoxyfen, oxyfluorfen etc.;

[0285] pyridinedicarbothioate type herbicides, for example, dithiopyr etc.;

[0286] phenoxy type herbicides, for example, MCPA, MCPB etc.;

[0287] urea type herbicides, for example, dymron, cumyluron etc.;

[0288] naphthalenedione type herbicides, for example, quinoclamine etc.;

[0289] isoxazolidinone type herbicides, for example, clomazone etc.

[0290] In addition to the above mentioned herbicides, the following herbicides, shown in common names, for example, Acetochlor, Acifluorfen (-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, Inazaquin, Imazethapyr, Iodosulfuron (-methyl, -sodium), Ioxynil, 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, Pelargonsäure, Pendimethalin, Pendralin, Pethoxamid, Phenmedioham, 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, Triasulfiuron, Tribenuron (-methyl), Triclopyr, Tridiphane, Trifloxy-sulfuron, Trifluralin, Triflusulfuron (-methyl), Tritosulfuron.

[0291] The above-mentioned herbicides are known herbicides mentioned in “Pesticide Manual” 2000, published by The British Crop Protect Council.

[0292] The weight ratios of the groups of active substances in the mixed compositions can vary within relatively wide ranges.

[0293] For instance, per part by weight of (1) the compounds of the formula (I),

[0294] 0.2 to 14 parts by weight of acetamide type herbicides,

[0295] preferably 0.66 to 5 parts by weight;

[0296] 2 to 40 parts by weight of amide type herbicides,

[0297] preferably 3.96 to 16 parts by weight;

[0298] 0.2 to 20 parts by weight of benzofuran type herbicides,

[0299] preferably 1.00 to 6 parts by weight;

[0300] 0.2 to 8 parts by weight of indanedione type herbicides,

[0301] preferably 0.49 to 2 parts by weight;

[0302] 0.06 to 4 parts by weight of oxazinone type herbicides,

[0303] preferably 0.20 to 0.8 parts by weight;

[0304] 0.02 to 4 parts by weight of sulfonylurea type herbicides,

[0305] preferably 0.07 to 1.2 parts by weight;

[0306] 1 to 100 parts by weight of thiocarbamate type herbicides,

[0307] preferably 2.47 to 40 parts by weight;

[0308] 0.6 to 12 parts by weight of triazine type herbicides,

[0309] preferably 1.32 to 4.5 parts by weight;

[0310] 0.1 to 8 parts by weight of triazole type herbicides,

[0311] preferably 0.33 to 3 parts by weight;

[0312] 0.2 to 10 parts by weight of dithiophosphate type herbicides,

[0313] preferably 1.00 to 4 parts by weight;

[0314] 0.2 to 50 parts by weight of oxyacetamide type herbicides,

[0315] preferably 1.00 to 12 parts by weight;

[0316] 0.02 to 10 parts by weight of tetrazolinone type herbicides,

[0317] preferably 0.17 to 3 parts by weight;

[0318] 0.1 to 12 parts by weight of dicarboxyimide type herbicides,

[0319] preferably 0.33 to 4.5 parts by weight;

[0320] 0.2 to 12 parts by weight of phenoxypropinate type herbicides,

[0321] preferably 0.4 to 1.8 parts by weight;

[0322] 0.6 to 20 parts by weight of diphenylether type herbicides,

[0323] preferably 1.65 to 7.5 parts by weight;

[0324] 0.02 to 14 parts by weight of pyridinedicarbothioate type herbicides,

[0325] preferably 0.20 to 5 parts by weight;

[0326] 0.2 to 10 parts by weight of phenoxy type herbicides,

[0327] preferably 0.66 to 4parts by weight,

[0328] and

[0329] 2 to 80 parts by weight of urea type herbicides,

[0330] preferably 4.95 to 25 parts by weight,

[0331] are used.

[0332] 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.

[0333] As an example of the safener, the following safeners can be mentioned;

[0334] 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.

[0335] The above-mentioned safeners are known safeners mentioned in “Pesticide Manual”, 2000, published by The British Crop Protect Council.

[0336] The weight ratios of the groups of active substances in the mixed comositions can vary within relatively wide ranges.

[0337] For instance, per part by weight of (1) the compounds of the formula (I),

[0338] 0.05 to 50 parts by weight of Dichlormid,

[0339] preferably 0.1 to 1 0 parts by weight;

[0340] 0.05 to 50 parts by weight of Dymron,

[0341] preferably 0.1 to 10 parts by weight;

[0342] 0.05 to 50 parts by weight of Fenclorim,

[0343] preferably 0.1 to 10 parts by weight;

[0344] 0.05 to 50 parts by weight of Mefenpyr (-diethyl),

[0345] preferably 0.1 to 10 parts by weight;

[0346] and

[0347] 0.05 to 50 parts by weight of Naphthalic anhydride,

[0348] preferably 0.1 to 10 parts by weight,

[0349] are used.

[0350] 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.

[0351] Surprisingly, some of the mixed compositions, according to the present invention show synergistic effects.

[0352] 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.

[0353] 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.

[0354] 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.

[0355] 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

[0356]

[0357] 3-Oxo-1-cyclohexenyl 2-chloro-3-{[(1-ethyl-1H-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-{[(1-ethyl-1H-tetrazol-1-yl)thio]methyl}-4-methylsulfonylbenzoyl}cyclohexane-1,3-dione (0.75 g). mp: 67-71° C.

Synthesis Example 2

[0358]

[0359] To a solution of 2-{2-chloro-4-methylsulfonyl-3-{[(1-methyl-1H-tetrazol-5-yl)thio]-methyl}benzoyl}cyclohexane-1,3-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-chloro4-methylsulfonyl-3-{[(1-methyl-1H-tetrazol-5-yl)thio]methyl}benzoyl}-2-cyclohexen-1-one (0.71 g). IR (NaCl):=1662, 1310, 1279, 1150 cm−1.

Synthesis Example 3

[0360]

[0361] 3-Chloro-2-{2-chloro-4-methylsulfonyl-3-{[(1-methyl-1H-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 tetrahydro-furan (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.

[0362] 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-{[(1-methyl-1H-tetrazol-5-yl)thio]meth-yl}benzoyl}-3-phenylthio-2-cyclohexen-1-one (0.61 g). mp: 76-87° C.

[0363] 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.

[0364] Examples of the compounds in case the compound of the formula (I) of the present invention is represented by the formula

[0365] are shown in Table 1,

[0366] examples of the compounds in case they are represented by the following formula

[0367] are shown in Table 2, and

[0368] examples of the compounds in case they are represented by the following formula

[0369] are shown in Table 3.

[0370] In Tables 1, 2 and 3,

[0371] Q1a a represents the group

[0372] Q1b represents the group

[0373] Q1c represents the group

[0374] Q2 represents the group

[0375] Q3a a represents the group

[0376] Q3b represents the group

[0377] Q3c represents the group

[0378] Q3d represents the group

[0379] Q3e represents the group

[0380] Q3f represents the group

[0381] Q3g represents the group

[0382] Q3h represents the group

[0383] Q3i represents the group

[0384] Q3j represents the group

[0385] Q3k represents the group

[0386] Q3l represents the group

[0387] Q3m represents the group

[0388] Q3n represents the group

[0389] Q3o represents the group

[0390] Q3p represents the group

[0391] Q3q represents the group

[0392] Q3r represents the group

[0393] Q3s represents the group

[0394] Q3t represents the group

[0395] Q3u represents the group

[0396] Q3v represents the group

[0397] Q3w represents the group

[0398] Q3x represents the group

[0399] Q3y represents the group

[0400] Q3z represents the group

[0401] Q3za represents the group

[0402] Q3zb represents the group

[0403] Q3zc represents the group

[0404] Q3zd represents the group

[0405] Q4a represents the group

[0406] Q4b represents the group

[0407] Q4c represents the group

[0408] Q4d represents the group

[0409] Q5a represents the group

[0410] Q5b represents the group

[0411] Q5c represents the group

[0412] Q5d represents the group

[0413] Q5e represents the group

[0414] Q5f represents the group

[0415] Q6a represents the group

[0416] Q6b represents the group

[0417] Q7 represents the group

[0418] 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, SO2Et represents ethylsulfonyl, SO2n-Pr represents n-propylsulfonyl, OSO2Me represents methyl-sulfonyloxy, OSO2Et represents ethylsulfonyloxy and Ph represents phenyl.

1TABLE 1

Com-poundmelting pointNo.YZRnQ(mp) or nD20I-1 HHMe1Q1aI-2 HHMe2Q1aI-3 HHMe1Q2I-4 OMeHMe1Q1aI-5 ClHMe1Q1aI-6 MeHMe1Q1aI-7 HFMe1Q1aI-8 HFMe1Q2I-9 HFMe1Q3aI-10HFMe1Q5aI-11HFMe1Q6aI-12HFEt1Q1aI-13HF

Q1aI-14HClMe1Q1aI-15HClMe2Q1aI-16HClMe1Q2I-17HClMe1Q3aI-18HClMe1Q5aI-19HClMe1Q7I-20HClEt1Q1aI-21HCl

1Q1aI-22HBrMe1Q1a1.6212I-23HBrMe1Q2I-24HBrMe1Q3aI-25HBrMe1Q5aI-26HBrMe1Q6aI-27HBrEt1Q1aI-28HBr

1Q1aI-29HIMe1Q1aI-30HIMe1Q2I-31HIMe1Q3aI-32HIMe1Q5aI-33HIEt1Q1aI-34HI

1Q1aI-35HMeMe1Q1aI-36HCF3Me1Q1aI-37HCF3Me1Q2I-38HCF3Me1Q3aI-39HCF3Me1Q5aI-40HCF3Me1Q6aI-41HCF3Me1Q7I-42HCF3Et1Q1aI-43HCF3

1Q1aI-44HOMeMe1Q1aI-45HOMeMe1Q2I-46HOMeMe1Q3aI-47HOMeMe1Q5aI-48HOMeMe1Q6aI-49HOMeEt1Q1aI-50HOMe

1Q1aI-51HOSO2MeMe1Q1aI-52HOSO2MeMe1Q2I-53HSMeMe1Q1aI-54HSMeMe1Q2I-55HSO2MeMe1Q1aI-56HSO2MeMe1Q2I-57HSO2MeMe1Q3aI-58HSO2MeMe1Q5I-59HSO2MeMe1Q6aI-60HSO2MeEt1Q1aI-61HSO2Me

1Q1aI-62HNO2Me1Q1aI-63HNO2Me1Q2I-64HNO2Me1Q3aI-65HNO2Me1Q5aI-66HNO2Et1Q1aI-67HNO2

1Q1aI-68HCNMe1Q1aI-69HCNMe1Q2I-70HCNMe1Q3aI-71HCNMe1Q5aI-72HCNEt1Q1aI-73HCN

1Q1aI-74HOCHF2Me1Q1aI-75HOCHF2Me1Q2I-76HOCHF2Me1Q3aI-77HOCHF2Me1Q5aI-78HOCHF2Me1Q6aI-79HOCHF2Et1Q1aI-80HOCHF2

1Q1aI-81HOCF3Me1Q1aI-82HOCF3Me1Q2I-83HOCF3Me1Q3aI-84HOCF3Me1Q5aI-85HOCF3Et1Q1aI-86HOCF3

1Q1a

[0419]

2

TABLE 2

Compound No.
X
Z
R
n
Q
melting point (mp) or nD20

II-1
H
H
Me
1
Q1a

II-2
H
H
Me
2
Q1a

II-3
H
H
Me
1
Q2

II-4
OMe
H
Me
1
Q1a

II-5
OMe
H
Me
1
Q2

II-6
OSO2Me
H
Me
1
Q1a

II-7
OSO2Me
H
Me
1
Q2

II-8
NO2
H
Me
1
Q1a

II-9
NO2
H
Me
1
Q2

II-10
F
Cl
Me
1
Q1a
66-72

II-11
F
Cl
Me
1
Q2

II-12
F
Cl
Me
1
Q3a

II-13
F
Cl
Me
1
Q5a

II-14
F
Cl

1
Q1a

II-15
F
Cl

1
Q2

II-16
F
Cl

1
Q3a

II-17
F
Cl

1
Q5a

II-18
Cl
Cl
Me
1
Q1a
1.6010

II-19
Cl
Cl
Me
2
Q1a

II-20
Cl
Cl
Me
1
Q1b

II-21
Cl
Cl
Me
1
Q1c

II-22
Cl
Cl
Me
1
Q2

II-23
Cl
Cl
Me
1
Q3a

II-24
Cl
Cl
Me
1
Q3b

II-25
Cl
Cl
Me
1
Q3d

II-26
Cl
Cl
Me
1
Q4a

II-27
Cl
Cl
Me
1
Q4b

II-28
Cl
Cl
Me
1
Q5a

II-29
Cl
Cl
Me
1
Q5c

II-30
Cl
Cl
Me
1
Q6a

II-31
Cl
Cl
Me
1
Q7

II-32
Cl
Cl
Et
1
Q1a

II-33
Cl
Cl
Et
2
Q1a

II-34
Cl
Cl
Et
1
Q1b

II-35
Cl
Cl
Et
1
Q1c

II-36
Cl
Cl
Et
1
Q2

II-37
Cl
Cl
Et
1
Q3a

II-38
Cl
Cl
Et
1
Q3f

II-39
Cl
Cl
Et
1
Q4a

II-40
Cl
Cl
Et
1
Q4b

II-41
Cl
Cl
Et
1
Q5a

II-42
Cl
Cl
Et
1
Q5d

II-43
Cl
Cl
Et
1
Q6a

II-44
Cl
Cl
Et
1
Q7

II-45
Cl
Cl
n-Pr
1
Q1a

II-46
Cl
Cl
n-Pr
1
Q2

II-47
Cl
Cl
n-Pr
1
Q3a

II-48
Cl
Cl
n-Pr
1
Q5a

II-49
Cl
Cl
i-Pr
1
Q1a

II-50
Cl
Cl
i-Pr
1
Q2

II-51
Cl
Cl
i-Pr
1
Q3a

II-52
Cl
Cl
i-Pr
1
Q5a

II-53
Cl
Cl

1
Q1a

II-54
Cl
Cl

1
Q1b

II-55
Cl
Cl

1
Q1c

II-56
Cl
Cl

1
Q2

II-57
Cl
Cl

1
Q3a

II-58
Cl
Cl

1
Q3e

II-59
Cl
Cl

100

1
Q4a

II-60
Cl
Cl

101

1
Q4b

II-61
Cl
Cl

102

1
Q5a

II-62
Cl
Cl

103

1
Q6a

II-63
Cl
Cl

104

1
Q7

II-64
Cl
Cl

105

1
Q1a

II-65
Cl
Cl

106

1
Q1a

II-66
Cl
Cl

107

1
Q1a

II-67
Cl
Cl

108

1
Q2

II-68
Cl
Cl
—CH═CH2
1
Q1a

II-69
Cl
Cl
—CH═CH2
1
Q1b

II-70
Cl
Cl
—CH═CH2
1
Q1c

II-71
Cl
Cl
—CH═CH2
1
Q2

II-72
Cl
Cl
—CH═CH2
1
Q3a

II-73
Cl
Cl
—CH═CH2
1
Q4a

II-74
Cl
Cl
—CH═CH2
1
Q4b

II-75
Cl
Cl
—CH═CH2
1
Q5a

II-76
Cl
Cl
—CH═CH2
1
Q6a

II-77
Cl
Cl
—CH2CH═CH2
1
Q1a

II-78
Cl
Cl
—CH2CH═CH2
1
Q2

II-79
Cl
Cl
—CH2CH═CH2
1
Q3a

II-80
Cl
Cl
—CH2CH═CH2
1
Q5a

II-81
Cl
Cl
Ph
1
Q1a

II-82
Cl
Cl
2-Cl-Ph
1
Q1a

II-83
Cl
Cl
2-Me-Ph
1
Q1a

II-84
Cl
Cl
3-CF3-Ph
1
Q1a

II-85
Cl
Cl
CH2CH2F
1
Q1a

II-86
Cl
Cl
CH2CH2F
1

II-87
Cl
Cl
CH2CH2F
1
Q3a

II-88
Cl
Cl
CH2CH2F
1
Q5a

II-89
Cl
Cl
CH2CH2F
1
Q6a

II-90
Cl
Cl
CH2CH2Cl
1
Q1a

II-91
Cl
Cl
CH2CH2Cl
1
Q2

II-92
Cl
Cl
CH2CH2Cl
1
Q3a

II-93
Cl
Cl
CH2CH2Cl
1
Q5a

II-94
Cl
Cl
CH2CF3
1
Q1a

II-95
Cl
Cl
CH2CF3
1
Q1b

II-96
Cl
Cl
CH2CF3
1
Q1c

II-97
Cl
Cl
CH2CF3
1
Q2

II-98
Cl
Cl
CH2CF3
1
Q3a

II-99
Cl
Cl
CH2CF3
1
Q4a

II-100
Cl
Cl
CH2CF3
1
Q4b

II-101
Cl
Cl
CH2CF3
1
Q5a

II-102
Cl
Cl
CH2CF3
1
Q6a

II-103
Cl
Cl
CH2CF3
1
Q7

II-104
Cl
Cl
CH2CF2CF3
1
Q1a

II-105
Cl
Cl
CH2CF2CF3
1
Q2

II-106
Cl
Cl
CH2CF2CF3
1
Q3a

II-107
Cl
Cl
CH2CH2CH2F
1
Q5a

II-108
Cl
Cl
CH2CH2CH2F
1
Q1a

II-109
Cl
Cl
CH2CH2CH2F
1
Q2

II-110
Cl
Cl
CH2CH2CH2F
1
Q3a

II-111
Cl
Cl
CH2CH2CH2F
1
Q5a

II-112
Cl
SMe
Me
1
Q1a

II-113
Cl
SMe
Me
1
Q2

II-114
Cl
SMe
Et
1
Q1a

II-115
Cl
SMe

109

1
Q1a

II-116
Cl
SMe
—CH═CH2
1
Q1a

II-117
Cl
SO2Me
Me
1
Q1a
78-84

II-118
Cl
SO2Me
Me
1
Q1a

II-119
Cl
SO2Me
Me
1
Q1b

II-120
Cl
SO2Me
Me
1
Q1c

II-121
Cl
SO2Me
Me
1
Q2
60-63

II-122
Cl
SO2Me
Me
1
Q3a
76-87

II-123
Cl
SO2Me
Me
1
Q3c
210-211

II-124
Cl
SO2Me
Me
1
Q3

II-125
Cl
SO2Me
Me
1
Q4a
79-82

II-126
Cl
SO2Me
Me
1
Q4b

II-127
Cl
SO2Me
Me
1
Q5a

II-128
Cl
SO2Me
Me
1
Q5f

II-129
Cl
SO2Me
Me
1
Q6a

II-130
Cl
SO2Me
Me
1
Q7

II-131
Cl
SO2Me
Et
1
Q1a
67-71

II-132
Cl
SO2Me
Et
2
Q1a

II-133
Cl
SO2Me
Et
1
Q1b

II-134
Cl
SO2Me
Et
1
Q1c

II-135
Cl
SO2Me
Et
1
Q2

II-136
Cl
SO2Me
Et
1
Q3a

II-137
Cl
SO2Me
Et
1
Q3b

II-138
Cl
SO2Me
Et
1
Q4a

II-139
Cl
SO2Me
Et
1
Q4b

II-140
Cl
SO2Me
Et
1
Q5a

II-141
Cl
SO2Me
Et
1
Q5b

II-142
Cl
SO2Me
Et
1
Q6a

II-143
Cl
SO2Me
Et
1
Q7

II-144
Cl
SO2Me
n-Pr
1
Q1a
142-145

II-145
Cl
SO2Me
n-Pr
1
Q2

II-146
Cl
SO2Me
n-Pr
1
Q3a

II-147
Cl
SO2Me
n-Pr
1
Q5a

II-148
Cl
SO2Me
i-Pr
1
Q1a
69-73

II-149
Cl
SO2Me
i-Pr
1
Q2

II-150
Cl
SO2Me
i-Pr
1
Q3a

II-151
Cl
SO2Me
i-Pr
1
Q5a

II-152
Cl
SO2Me

110

1
Q1a
79-84

II-153
Cl
SO2Me

111

1
Q1b

II-154
Cl
SO2Me

112

1
Q1c

II-155
Cl
SO2Me

113

1
Q2

II-156
Cl
SO2Me

114

1
Q3a

II-157
Cl
SO2Me

115

1
Q3d

II-158
Cl
SO2Me

116

1
Q4a

II-159
Cl
SO2Me

117

1
Q4b

II-160
Cl
SO2Me

118

1
Q5a

II-161
Cl
SO2Me

119

1
Q6a

II-162
Cl
SO2Me

120

1
Q7

II-163
Cl
SO2Me

121

1
Q1a

II-164
Cl
SO2Me

122

1
Q2

II-165
Cl
SO2Me

123

1
Q1a

II-166
Cl
SO2Me

124

1
Q1a

II-167
Cl
SO2Me

125

1
Q2

II-168
Cl
SO2Me
—CH═CH2
1
Q1a

II-169
Cl
SO2Me
—CH═CH2
1
Q1b

II-170
Cl
SO2Me
—CH═CH2
1
Q1c

II-171
Cl
SO2Me
—CH═CH2
1
Q2

II-172
Cl
SO2Me
—CH═CH2
1
Q3a

II-173
Cl
SO2Me
—CH═CH2
1
Q4a

II-174
Cl
SO2Me
—CH═CH2
1
Q4b

II-175
Cl
SO2Me
—CH═CH2
1
Q5a

II-176
Cl
SO2Me
—CH═CH2
1
Q6a

II-177
Cl
SO2Me
—CH2CH═CH2
1
Q1a
63-68

II-178
Cl
SO2Me
—CH2CH═CH2
1
Q2

II-179
Cl
SO2Me
—CH2CH═CH2
1
Q3a

II-180
Cl
SO2Me
—CH2CH═CH2
1
Q5a

II-181
Cl
SO2Me
Ph
1
Q1a

II-182
Cl
SO2Me
4-F-Ph
1
Q1a

II-183
Cl
SO2Me
2-Cl-Ph
1
Q1a
84-90

II-184
Cl
SO2Me
3-Et-Ph
1
Q

II-185
Cl
SO2Me
4-NO2-Ph
1
Q1a

II-186
Cl
SO2Me
CH2CH2F
1
Q1a

II-187
Cl
SO2Me
CH2CH2F
1
Q2

II-188
Cl
SO2Me
CH2CH2F
1
Q3a

II-189
Cl
SO2Me
CH2CH2F
1
Q5a

II-190
Cl
SO2Me
CH2CH2Cl
1
Q1a

II-191
Cl
SO2Me
CH2CH2Cl
1
Q2

II-192
Cl
SO2Me
CH2CH2Cl
1
Q3a

II-193
Cl
SO2Me
CH2CH2Cl
1
Q5a

II-194
Cl
SO2Me
CH2CF3
1
Q1a
82-87

II-195
Cl
SO2Me
CH2CF3
1
Q1b

II-196
Cl
SO2Me
CH2CF3
1
Q1c

II-197
Cl
SO2Me
CH2CF3
1
Q2

II-198
Cl
SO2Me
CH2CF3
1
Q3a

II-199
Cl
SO2Me
CH2CF3
1
Q4a

II-200
Cl
SO2Me
CH2CF3
1
Q4b

II-201
Cl
SO2Me
CH2CF3
1
Q5a

II-202
Cl
SO2Me
CH2CF3
1
Q6a

II-203
Cl
SO2Me
CH2CF3
1
Q7

II-204
Cl
SO2Me
CH2CF2CF3
1
Q1a

II-205
Cl
SO2Me
CH2CF2CF3
1
Q2

II-206
Cl
SO2Me
CH2CF2CF3
1
Q3a

II-207
Cl
SO2Me
CH2CH2CH2F
1
Q5a

II-208
Cl
SO2Me
CH2CH2CH2F
1
Q1a

II-209
Cl
SO2Me
CH2CH2CH2F
1
Q2

II-210
Cl
SO2Me
CH2CH2CH2F
1
Q3a

II-211
Cl
SO2Me
CH2CH2CH2F
1
Q5a

II-212
Cl
SO2Et
Me
1
Q1a
70-74

II-213
Cl
SO2Et
Me
1
Q2

II-214
Cl
SO2Et
Me
1
Q3a

II-215
Cl
SO2Et
Me
1
Q5a

II-216
Cl
SO2Et
Me
1
Q6a

II-217
Cl
SO2Et
Me
1
Q7

II-218
Cl
SO2Et
Et
1
Q1a

II-219
Cl
SO2Et
Et
1
Q2

II-220
Cl
SO2Et

126

1
Q1a

II-221
Cl
SO2Et

127

1
Q2

II-222
Cl
SO2Et

128

1
Q1a

II-223
Cl
SO2Et
—CH═CH2
1
Q1a

II-224
Cl
SO2Et
—CH═CH2
1
Q2

II-225
Cl
SO2n-Pr

129

1
Q1a

II-226
Br
Br
Me
1
Q1a
72-179

II-227
Br
Br
Me
1
Q1b

II-228
Br
Br
Me
1
Q1c

II-229
Br
Br
Me
1
Q2

II-230
Br
Br
Me
1
Q3a

II-231
Br
Br
Me
1
Q3c

II-232
Br
Br
Me
1
Q3f

II-233
Br
Br
Me
1
Q4a

II-234
Br
Br
Me
1
Q4b

II-235
Br
Br
Me
1
Q5a

II-236
Br
Br
Me
1
Q5e

II-237
Br
Br
Me
1
Q6a

II-238
Br
Br
Me
1
Q7

II-239
Br
Br
Et
1
Q1a

II-240
Br
Br
Et
1
Q2

II-241
Br
Br
Et
1
Q3a

II-242
Br
Br
Et
1
Q3d

II-243
Br
Br
Et
1
Q5a

II-244
Br
Br
n-Pr
1
Q1a

II-245
Br
Br
n-Pr
1
Q2

II-246
Br
Br
i-Pr
1
Q1a

II-247
Br
Br
i-Pr
1
Q2

II-248
Br
Br

130

1
Q1a

II-249
Br
Br

131

1
Q1b

II-250
Br
Br

132

1
Q1c

II-251
Br
Br

133

1
Q2

II-252
Br
Br

134

1
Q3a

II-253
Br
Br

135

1
Q4a

II-254
Br
Br

136

1
Q4b

II-255
Br
Br

137

1
Q5a

II-256
Br
Br

138

1
Q1a

II-257
Br
Br
—CH═CH2
1
Q1a

II-258
Br
Br
—CH═CH2
1
Q2

II-259
Br
Br
—CH═CH2
1
Q3a

II-260
Br
Br
—CH═CH2
1
Q5a

II-261
Br
Br
—CH2CH═CH2
1
Q1a

II-262
Br
Br
—CH2CH═CH2
1
Q2

II-263
Br
Br
Ph
1
Q1a

II-264
Br
Br
2-Cl-Ph
1
Q1a

II-265
Br
Br
2-CF3-Ph
1
Q1a

II-266
Br
Br
CH2CH2F
1
Q1a

II-267
Br
Br
CH2CH2F
1
Q2

II-268
Br
Br
CH2CH2Cl
1
Q1a

II-269
Br
Br
CH2CH2Cl
1
Q2

II-270
Br
Br
CH2CF3
1
Q1a

II-271
Br
Br
CH2CF3
1
Q2

II-272
Br
Br
CH2CF3
1
Q3a

II-273
Br
Br
CH2CF3
1
Q5a

II-274
Br
Br
CH2CF2CF3
1
Q1a

II-275
Br
Br
CH2CH2CH2F
1
Q1a

II-276
Br
SO2Me
Me
1
Q1a
87-90

II-277
Br
SO2Me
Me
1
Q2

II-278
Br
SO2Me
Et
1
Q1a

II-279
Br
SO2Me

139

1
Q1a

II-280
Br
SO2Me

140

1
Q1a

II-281
Br
SO2Me
—CH═CH2
1
Q1a

II-282
OMe
Cl
Me
1
Q1a
1.6131

II-283
OMe
Cl
Me
1
Q1b

II-284
OMe
Cl
Me
1
Q1c

II-285
OMe
Cl
Me
1
Q2

II-286
OMe
Cl
Me
1
Q3a

II-287
OMe
Cl
Me
1
Q4a

II-288
OMe
Cl
Me
1
Q4b

II-289
OMe
Cl
Me
1
Q5a

II-290
OMe
Cl
Me
1
Q6a

II-291
OMe
Cl
Et
1
Q1a

II-292
OMe
Cl
Et
1
Q2

II-293
OMe
Cl
Et
1
Q3a

II-294
OMe
Cl
Et
1
Q5a

II-295
OMe
Cl
Et
1
Q7

II-296
OMe
Cl
n-Pr
1
Q1a

II-297
OMe
Cl
n-Pr
1
Q2

II-298
OMe
Cl
i-Pr
1
Q1a

II-299
OMe
Cl
i-Pr
1
Q2

II-300
OMe
Cl

141

1
Q1a

II-301
OMe
Cl

142

1
Q1b

II-302
OMe
Cl

143

1
Q1c

II-303
OMe
Cl

144

1
Q2

II-304
OMe
Cl

145

1
Q3a

II-305
OMe
Cl

146

1
Q4a

II-306
OMe
Cl

147

1
Q4b

II-307
OMe
Cl

148

1
Q5a

II-308
OMe
Cl

149

1
Q1a

II-309
OMe
Cl

150

1
Q1a

II-310
OMe
Cl
—CH═CH2
1
Q1a

II-311
OMe
Cl
—CH═CH2
1
Q2

II-312
OMe
Cl
—CH═CH2
1
Q3a

II-313
OMe
Cl
—CH═CH2
1
Q5a

II-314
OMe
Cl
—CH2CH═CH2
1
Q1a

II-315
OMe
Cl
—CH2CH═CH2
1
Q2

II-316
OMe
Cl
Ph
1
Q1a

II-317
OMe
Cl
2-Cl-Ph
1
Q1a

II-318
OMe
Cl
CH2CH2F
1
Q1a

II-319
OMe
Cl
CH2CH2F
1
Q2

II-320
OMe
Cl
CH2CH2Cl
1
Q1a

II-321
OMe
Cl
CH2CH2Cl
1
Q2

II-322
OMe
Cl
CH2CF3
1
Q1a

II-323
OMe
Cl
CH2CF3
1
Q2

II-324
OMe
Cl
CH2CF3
1
Q3a

II-325
OMe
Cl
CH2CF3
1
Q5a

II-326
OMe
Cl
CH2CF2CF3
1
Q1a

II-327
OMe
Cl
CH2CH2CH2F
1
Q1a

II-328
OCHF2
Cl
Me
1
Q1a

II-329
OCHF2
Cl
Me
1
Q2

II-330
OCHF2
Cl
Me
1
Q3a

II-331
OCHF2
Cl
Et
1
Q1a

II-332
OCHF2
Cl

151

1
Q1a

II-333
OCHF2
Cl
—CH═CH2
1
Q1a

II-334
OCH2CF3
Cl
Me
1
Q1a

II-335
OCH2CF3
Cl
Me
1
Q2

II-336
OCH2CF3
Cl
Et
1
Q1a

II-337
SMe
Cl
Me
1
Q1a

II-338
SMe
Cl
Me
1
Q2

II-339
SMe
Cl
Et
1
Q1a

II-340
SMe
Cl

152

1
Q1a

II-341
SMe
Cl
—CH═CH2
1
Q1a

II-342
SMe
SMe
Me
1
Q1a

II-343
SMe
SMe
Me
1
Q2

II-344
SMe
SMe
Et
1
Q1a

II-345
SMe
SMe

153

1
Q1a

II-346
SMe
SMe
—CH═CH2
1
Q1a

II-347
SO2Me
Cl
Me
1
Q1a

II-348
SO2Me
Cl
Me
1
Q2

II-349
SO2Me
Cl
Et
1
Q1a

II-350
SO2Me
Cl

154

1
Q1a

II-351
SO2Me
Cl
—CH═CH2
1
Q1a

II-352
SO2Me
SO2Me
Me
1
Q1a

II-353
SO2Me
SO2Me
Me
1
Q2

II-354
SO2Me
SO2Me
Et
1
Q1a

II-355
SO2Me
SO2Me

155

1
Q1a

II-356
SO2Me
SO2Me
—CH═CH2
1
Q1a

II-357
Me
SO2Me
Me
1
Q1a
69-71

II-358
Me
SO2Me
Me
2
Q1a

II-359
Me
SO2Me
Me
1
Q1b

II-360
Me
SO2Me
Me
1
Q1c

II-361
Me
SO2Me
Me
1
Q2

II-362
Me
SO2Me
Me
1
Q3a

II-363
Me
SO2Me
Me
1
Q3c

II-364
Me
SO2Me
Me
1
Q3d

II-365
Me
SO2Me
Me
1
Q4a

II-366
Me
SO2Me
Me
1
Q4b

II-367
Me
SO2Me
Me
1
Q5a

II-368
Me
SO2Me
Me
1
Q5c

II-369
Me
SO2Me
Me
1
Q6a

II-370
Me
SO2Me
Me
1
Q7

II-371
Me
SO2Me
Et
1
Q1a

II-372
Me
SO2Me
Et
1
Q2

II-373
Me
SO2Me
Et
1
Q3a

II-374
Me
SO2Me
Et
1
Q3b

II-375
Me
SO2Me
Et
1
Q5a

II-376
Me
SO2Me
n-Pr
1
Q1a

II-377
Me
SO2Me
n-Pr
1
Q2

II-378
Me
SO2Me
i-Pr
1
Q1a

II-379
Me
SO2Me
i-Pr
1
Q2

II-380
Me
SO2Me

156

1
Q1a

II-381
Me
SO2Me

157

1
Q1b

II-382
Me
SO2Me

158

1
Q1c

II-383
Me
SO2Me

159

1
Q2

II-384
Me
SO2Me

160

1
Q3a

II-385
Me
SO2Me

161

1
Q4a

II-386
Me
SO2Me

162

1
Q4b

II-387
Me
SO2Me

163

1
Q5a

II-388
Me
SO2Me

164

1
Q1a

II-389
Me
SO2Me

165

1
Q1a

II-390
Me
SO2Me

166

1
Q1a

II-391
Me
SO2Me
—CH═CH2
1
Q1a

II-392
Me
SO2Me
—CH═CH2
1
Q2

II-393
Me
SO2Me
—CH═CH2
1
Q3a

II-394
Me
SO2Me
—CH═CH2
1
Q5a

II-395
Me
SO2Me
—CH2CH═CH2
1
Q1a

II-396
Me
SO2Me
—CH2CH═CH2
1
Q2

II-397
Me
SO2Me
Ph
1
Q1a

II-398
Me
SO2Me
2-Cl-Ph
1
Q1a

II-399
Me
SO2Me
4-NO2-Ph
1
Q1a

II-400
Me
SO2Me
CH2CH2F
1
Q1a

II-401
Me
SO2Me
CH2CH2F
1
Q2

II-402
Me
SO2Me
CH2CH2Cl
1
Q1a

II-403
Me
SO2Me
CH2CH2Cl
1
Q2

II-404
Me
SO2Me
CH2CF3
1
Q1a

II-405
Me
SO2Me
CH2CF3
1
Q2

II-406
Me
SO2Me
CH2CF3
1
Q3a

II-407
Me
SO2Me
CH2CF3
1
Q5a

II-408
Me
SO2Me
CH2CF2CF3
1
Q1a

II-409
Me
SO2Me
CH2CH2CH2F
1
Q1a

II-410
CN
SO2Me
Me
1
Q1a
54-60

II-411
CN
SO2Me
Me
1
Q2

II-412
CN
SO2Me
Me
1
Q3a

II-413
CN
SO2Me
Et
1
Q1a

II-414
CN
SO2Me

167

1
Q1a

II-415
CN
SO2Me

168

1
Q5a

II-416
Cl
SEt
Me
1
Q1a

II-417
Cl
SO2Me
Me
1
Q3g

II-418
Cl
SO2Me
Me
1
Q4c

II-419
Cl
SO2Me
Me
1
Q4d

II-420
Cl
SO2Me
Me
1
Q6b

II-421
Cl
SO2Me
n-Bu
1
Q1a

II-422
Cl
SO2Me
n-Hex
1
Q1a

II-423
Cl
SO2Me
—CH2CH═CHCH3
1
Q1a

II-424
Cl
SO2Me
—(CH2)4CH═CH2
1
Q1a

II-425
Cl
SO2Me
4-(n-Pr)-Ph
1
Q1a

II-426
Cl
SO2Me
4-(CH2CH2Cl)-Ph
1
Q1a

II-427
Cl
SO2Me
—(CH2)4Cl
1
Q1a

II-428
OEt
Cl
Me
1
Q1a

II-429
OSO2Me
Cl
Me
1
Q1a

II-430
OSO2Et
Cl
Me
1
Q1a

II-431
Et
SO2Me
Me
1
Q1a

II-432
Cl
SO2Me
Me
1
Q3h

II-433
Cl
SO2Me
Me
1
Q3i
128-131

II-434
Cl
SO2Me
Me
1
Q3j

II-435
Cl
SO2Me
Me
1
Q3d
85-91

II-436
Cl
SO2Me
Me
1
Q3k

II-437
Cl
SO2Me
Me
1
Q3l

II-438
Cl
SO2Me
Me
1
Q3m

II-439
Cl
SO2Me
Me
1
Q3n

II-440
Cl
SO2Me
Me
1
Q3o

II-441
Cl
SO2Me
Me
1
Q3p

II-442
Cl
SO2Me
Me
1
Q3q

II-443
Cl
SO2Me
Me
1
Q3r

II-444
Cl
SO2Me
Me
1
Q3s

II-445
Cl
SO2Me
Me
1
Q3t

II-446
Cl
SO2Me
Me
1
Q3u

II-447
Cl
SO2Me
Me
1
Q3v

II-448
Cl
SO2Me
Me
1
Q3w

II-449
Cl
SO2Me
Me
1
Q3b

II-450
Cl
SO2Me
Me
1
Q3x

II-451
Cl
SO2Me
Me
1
Q3y
208-209

II-452
Cl
SO2Me
Me
1
Q3f

II-453
Cl
SO2Me
Me
1
Q3z

II-454
Cl
SO2Me
Me
1
Q3za

II-455
Cl
SO2Me
Me
1
Q3zb

II-456
Cl
SO2Me
Me
1
Q3zc

II-457
Cl
SO2Me
Me
1
Q3zd

[0420]

3

TABLE 3

169

Com-

pound

melting point

No.
X
Y
R
n
Q
(mp) or nD20

III-1
H
H
Me
1
Q1a

III-2
H
H
Me
2
Q1a

III-3
H
H
Me
1
Q2

III-4
H
OMe
Me
1
Q1a

III-5
H
NO2
Me
1
Q1a

III-6
F
H
Me
1
Q1a

III-7
F
H
Me
1
Q2

III-8
F
H
Et
1
Q1a

III-9
F
H

170

1
Q1a

III-10
F
H
—CH═CH2
1
Q1a

Ill-11
Cl
H
Me
1
Q1a

III-12
Cl
H
Me
2
Q1a

III-13
Cl
H
Me
1
Q2

III-14
Cl
H
Me
1
Q3a

III-15
Cl
H
Me
1
Q5a

III-16
Cl
H
Me
1
Q6a

III-17
Cl
H
Et
1
Q1a

III-18
Cl
H

171

1
Q1a

III-19
Cl
H
—CH═CH2
1
Q1a

III-20
Br
H
Me
1
Q1a

III-21
Br
H
Me
1
Q2

III-22
Br
H
Me
1
Q3a

III-23
Br
H
Me
1
Q5a

III-24
Br
H
Me
1
Q7

III-25
Br
H
Et
1
Q1

III-26
Br
H

172

1
Q1a

III-27
Br
H
—CH═CH2
1
Q1a

III-28
I
H
Me
1
Q1a

III-29
I
H
Me
1
Q2

III-30
I
H
Me
1
Q3a

III-31
I
H
Me
1
Q5a

III-32
I
H
Me
1
Q6a

III-33
I
H
Et
1
Q1a

III-34
I
H

173

1
Q1a

III-35
I
H
—CH═CH2
1
Q1a

III-36
CF3
H
Me
1
Q1a

III-37
CF3
H
Me
1
Q2

III-38
CF3
H
Me
1
Q3a

III-39
CF3
H
Me
1
Q5a

III-40
CF3
H
Me
1
Q6a

III-41
CF3
H
Et
1
Q1a

III-42
CF3
H

174

1
Q1a

III-43
CF3
H
—CH═CH2
1
Q1a

III-44
OMe
H
Me
1
Q1a

III-45
OMe
H
Me
1
Q2

III-46
OMe
H
Me
1
Q3a

III-47
OMe
H
Me
1
Q5a

III-48
OMe
H
Et
1
Q1a

III-49
OMe
H

175

1
Q1a

III-50
OMe
H
—CH═CH2
1
Q1a

III-51
OSO2Me
H
Me
1
Q1a

III-52
OSO2Me
H
Me
1
Q2

III-53
OSO2Me
H
Me
1
Q3a

III-54
OSO2Me
H
Me
1
Q5a

III-55
OSO2Me
H
Et
1
Q1a

III-56
OSO2Me
H

176

1
Q1a

III-57
OSO2Me
H
—CH═CH2
1
Q1a

III-58
SMe
H
Me
1
Q1a

III-59
SMe
H
Me
1
Q

III-60
SMe
H
Me
1
Q3a

III-61
SMe
H
Et
1
Q1a

III-62
SMe
H

177

1
Q1a

III-63
SMe
H
—CH═CH2
1
Q1a

III-64
OSO2Me
H
Me
1
Q1a

III-65
OSO2Me
H
Me
1
Q2

III-66
OSO2Me
H
Me
1
Q3a

III-67
OSO2Me
H
Me
1
Q5a

III-68
OSO2Me
H
Et
1
Q1a

III-69
OSO2Me
H

178

1
Q1a

III-70
OSO2Me
H
—CH═CH2
1
Q1a

III-71
NO2
H
Me
1
Q1a
82-87

III-72
NO2
H
Me
2
Q1a

III-73
NO2
H
Me
1
Q1b

III-74
NO2
H
Me
1
Q1c

III-75
NO2
H
Me
1
Q2

III-76
NO2
H
Me
1
Q3a

III-77
NO2
H
Me
1
Q4a

III-78
NO2
H
Me
1
Q4b

III-79
NO2
H
Me
1
Q5a

III-80
NO2
H
Me
1
Q6a

III-81
NO2
H
Me
1
Q7

III-82
NO2
H
Et
1
Q1a

III-83
NO2
H
Et
1
Q2

III-84
NO2
H
Et
1
Q3a

III-85
NO2
H
Et
1
Q5a

III-86
NO2
H
Et
1
Q6a

III-87
NO2
H
n-Pr
1
Q1a

III-88
NO2
H
n-Pr
1
Q2

III-89
NO2
H
i-Pr
1
Q1a

III-90
NO2
H
I-Pr
1
Q2

III-91
NO2
H

179

1
Q1a

III-92
NO2
H

180

1
Q2

III-93
NO2
H

181

1
Q3

III-94
NO2
H

182

1
Q5a

III-95
NO2
H

183

1
Q1a

III-96
NO2
H
—CH═CH2
1
Q1a

III-97
NO2
H
—CH═CH2
1
Q2

III-98
NO2
H
—CH═CH2
1
Q3a

III-99
NO2
H
—CH═CH2
1
Q5a

III-100
NO2
H
—CH2CH═CH2
1
Q1a

III-101
NO2
H
Ph
1
Q1a

III-102
NO2
H
2-Cl-Ph
1
Q1a

III-103
NO2
H
CH2CH2F
1
Q1a

III-104
NO2
H
CH2CH2Cl
1
Q1a

III-105
NO2
H
CH2CF3
1
Q1a

III-106
NO2
H
CH2CH2F
1
Q1a

III-107
NO2
H
CH2CF2CF3
1
Q1a

III-108
NO2
H
CH2CH2CH2F
1
Q1a

III-109
CN
H
Me
1
Q1a

III-110
CN
H
Me
1
Q2

Ill-111
CN
H
Me
1
Q3a

III-112
CN
H
Me
1
Q5a

III-113
CN
H
Et
1
Q1a

III-114
CN
H

184

1
Q1a

III-115
CN
H
—CH═CH2
1
Q1a

Synthesis Example 4

[0421]

185

[0422] 2-Chloro-3-{[(1-ethyl-1H-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-1-cyclohexenyl 2-chloro-3-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonylbenzoate (0.83 g). mp: 122-123° C.

Synthesis Example 5

[0423]

186

[0424] To a solution of methyl 2-chloro-3-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-4-meth-ylsulfonylbenzoate (0.83 g) in dioxane (15 ml), a 10N 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 10N 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-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-4-methyl-sulfonylbenzoic acid (0.80 g). mp: 193-195° C.

Synthesis Example 6

[0425]

187

[0426] 1-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-{[(1-ethyl-1H-tetrazol-5-yl)thio]methyl}-4-methylsulfonyl-benzoate (0.88 g), mp: 109-1 10° C.

Test Example 1

[0427] Test for Herbicidal Effect Against Paddy Field Weeds

[0428] Preparation of a Formulation of the Active Compound

4Carrier:Acetone 5 parts by weightEmulsifier:Benzyloxypolyglycolether 1 part by weight

[0429] 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.

[0430] Test Method

[0431] In a greenhouse 3 seedlings of paddy rice (cultivar: Nipponbare) of 2.5 leafstage (15 cm tall) were planted in a 500 cm2 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 junceum Hammilt etc.) and Japanese ribbon wapato were inoculated and water was poured to a depth of about 2-3 cm.

[0432] 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.

[0433] As a result, the compounds No. H-18, II-117, II-122, II-131, II-194, II-212 and III-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

[0434] Test of Pre-Emergence Soil Treatment Against Field Weeds

[0435] Test Method

[0436] In a greenhouse, on the surface layer of a 120 cm2 pot filled with field soil, and then seeds of barnyardgrass, 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.

[0437] Effects:

[0438] The compounds No. II-117, II-122 and II-194 showed at application rate of 2.0 kg/ha herbicidal activities of more than 90% against objective weeds (barnyardgrass, foxtail, common amaranth and knotweed).

Test Example 3

[0439] Test of Post-Emergence Foliage Treatment Against Field Weeds

[0440] Test Method

[0441] In a greenhouse, seeds of barnyardgrass, 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.

[0442] Results:

[0443] The compounds No. II-18, II-117, II-122, II-131, II-194, II-212 and II-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

[0444] Test for Synergistic Action by Foliar Spray Application

[0445] Preparation of the Test Solution

5Carrier:acetone, 5 parts by weightEmulsifier:benzyloxypolyglycol ether, 1 parts by weight

[0446] 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.

[0447] Test Method

[0448] In a greenhouse, paddy soil was filled in pots (250 cm2), and seeds of weed (barnyardgrass, bulrush, monochoria and falspimernel) 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).

[0449] Test results of test example 4 are shown in Table 4.

Test Example 5

[0450] Test for Synergistic Action by Water Sureface Application

[0451] Test Method

[0452] In a greenhouse, paddy soil was filled in pots (250 cm2), and seeds of weed (barnyardgrass, bulrush, monochoria, falspimernel, 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 the test method of Test Example 4.

[0453] Test results of test example 5 are shown in Table 5.

[0454] Synergistic action of Test Example 4 and Test Example 5 were evaluated by Colby's equation.

Colby : E = X + [Y \times \frac{(100 - X)}{100}]

[0455] E: expected herbicidal activity at p+q g/ha

[0456] X: the percentage of herbicidal activity at p g/ha

[0457] Y: the percentage of herbicidal activity at q g/ha.

[0458] The following abbreviations are used in Table 4 and Table 5:

6CYPSErepresents Cyperus serotinus (flatstage),ECHSSrepresents Echinochloa spp. (barnyardgrass),ELTTPreprerstnts Elatine triandra (waterwort),LIDPYrepresents Lindernia pyridaria (flasepimpernel),MOOVPrepresents Monochoria vaginalis (monochoria),ROTINrepresents Rotala indica (indian toothcup),

[0459] Compounds (1) in Table 4 and Table 5 are listed by the compound numbers previously used in Tables 1, 2 and 3.

[0460] In Table 4 and Table 5 other known herbicides are represented by the capital letters as shown in the following list:

[0461] A: 4-(2-chlorophenyl)-N-cyclohexyl-N-ethyl-4,5-dihydro-5-oxo-1H-tetrazole-1-carboxamide (fentrazamide),

[0462] B: 3,′4′-dichloropropionanilide (propanil),

[0463] C: N,N-diethyl-3-mesitylsulfonyl-1H-1,2,4-triazole-1-carboxamide (cafenstrole),

[0464] D: 3-[1-(3,5-dichlorophenyl)-1-methylethyl]-2,3-dihydro-6-methyl-5-phenyl-4H-1,3-oxazin-4-one (oxaziclomefone),

[0465] E: 2-chloro-2′,6′-diethyl-N-(2-propoxyethyl) acetamide (pretilachlor),

[0466] F: 2-(1,3-benzothiazol-2-yloxy)-N-methylacetanilide (mefenacet),

[0467] G: (RS)-2-[2-(3-chlorophenyl)2,3-epoxypropyl]-2-ethylindan-1,3-dione (indanofan).

[0468]

7

TABLE 4

Herbicidal efficacy (%) by foliar spray application

Herbicidal efficacy (%)

known
compound(1) +
Expected activ-

Test
compound(1)
herbicide
known herbicide
ity E according

plant
(g a.i./ha)
(g a.i./ha)
(g a.i./ha)
to Colby (%)

1st run:
II-131
A
II-131 + A
II-131 + A

(125)
(135)
(125 + 135)

SCPSS
70
60
90
88

MOOVP
70
60
95
88

LIDPY
50
50
80
75

2nd run:
II-131
B
II-131 + B
II-131 + B

(125)
(750)
(125 + 750)

ECHSS
40
30
80
58

SCPSS
70
10
80
73

MOOVP
70
30
90
79

LIDPY
50
40
80
70

[0469]

8

TABLE 5

Herbicidal efficacy (%) by water surface application

Herbicidal efficacy (%)
Expected

known
compound(1) +
activity

Test
compound(1)
herbicide
known herbicide
E According to

plant
(g a.i./ha)
(g a.i./ha)
(g a.i./ha)
Colby (%)

1st run:
II-117
A
II-117 + A
II-117 + A

(75)
(100)
(75 + 100)

LIDPY
75
50
100
87.5

ROTIN
50
70
95
85

ELTTP
50
80
95
90

2nd run:
II-117
C
II-117 + C
II-117 + C

(75)
(100)
(75 + 100)

LIDPY
70
60
90
88

3rd run:
II-122
D
II-122 + D
II-122 + D

(60)
(40)
(60 + 40)

ECHSS
0
80
85
80

SCPSS
60
30
80
72

LIDPY
70
40
90
82

4th run:
II-18
E
II-18 + E
II-18 + E

(60)
(300)
(60 + 300)

MOOVP
80
60
100
92

LIDPY
60
60
95
84

CYPSE
50
40
80
70

5th run:
III-71
F
III-71 + F
III-71 + F

(125)
(500)
(125 + 500)

LIDPY
80
40
95
88

ROTIN
70
40
90
82

run6:
III-71
G
III-71 + G
III-71 + G

(125)
(75)
(125 + 75)

LIDPY
80
60
98
92

ROTIN
70
60
95
88

Test Example 6

[0470] Test for Safening Action on Rice by Water Surface Application

[0471] Test method

[0472] 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).

[0473] Test result of test example 6 are shown in Table 6.

[0474] Safening action of Test Example 6 were evaluated by Colby's equation.

Colby : E = X + [Y \times \frac{(100 - X)}{100}]

[0475] E: expected phytotoxicity at p+q g/ha

[0476] X: expected phytotoxicity at p g/ha

[0477] Y: expected phytotoxicity at q g/ha

[0478] Compounds (1) in Table 6 are listed by by the compound numbers previously uesd in Tables 1, 2 and 3.

[0479] In Table 6 the known safeners are represented by the capital letters as shown in the following list:

[0480] a: N,N-diallyl-2,2-dichloroacetamide (dichlormid),

[0481] b: 4,6-dichloro-2-phenylpyrimidine (fenclorin),

[0482] c: diethyl (RS)-1-(2,4-dichlorophenyl)-5-methyl-2-pyrazoline-3,5-dicarboxylate (mefenpyr-diethyl),

[0483] d: N-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea (dymron),

[0484] e: 2-(dichloroacetyl)-2,2,5-trimethyl-oxazolidine (R-29148),

[0485] f: 1H,3H-naphtho [1,8-cd]pyran-1,3-dione(naphthalic anhydride).

9TABLE 6Safening efficacy (%) by water surface applicationExpectedcompound (1) +phytotoxcity (E)compound (1)Phytotoxicitysafenerphytotoxicitysafenerphytotoxicityaccording to(g a.i./ha)(%)(g a.i./ha)(%)(g a.i./ha)(%)Colby (%)II-27640a (200)0II-276 + a540(400)(400 + 200)b (400)0II-276 + b2040(400 + 400)c (400)20II-276 + c2552(400 + 400)II-13140d (400)0II-131 + d1040(400)(400 + 400)b (400)0II-131 + b1540(400 + 200)e (200)0II-131 + e2040(400 + 200)II-12230d (400)0II-122 + d1030(600)(600 + 400)a (200)0II-122 + a1030(600 + 200)b (400)0II-122 + b530(600 + 400)f (400)0II-122 + f030(600 + 400)II-11760d (400)0II-117 + d3060(400)(400 + 400)a (200)0II-117 + a4060(400 + 200)f (400)0II-117 + f3060(400 + 400)III-7130a (200)0III-71 + a1030(600)(600 + 200)c (400)20III-71 + c2044(600 + 400)II-19450d (400)0II-194 + d2550(400)(400 + 400)b (400)0II-194 + b3050(400 + 400)f (400)0II-194 + f2050(400 + 400)

Formulation Example 1 (Granule)

[0486] To a mixture of the compound No. II-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)

[0487] 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. II-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)

[0488] The compound No. II-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)

[0489] The compound No. II-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)

[0490] The compound No. II-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, extruded using a 0.3 mm screen and dried to obtain a water-dispersible granules.

Number	Date	Country	Kind
2000-204914	Jul 2000	JP
2001-143072	May 2001	JP

Novel tetrazole derivatives

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