WO2001017977A1 - 1,3,5-triazines as herbicides - Google Patents

Abstract

The invention relates to novel 1,3,5-triazine derivatives represented by general formula (I) wherein R?1, R2, R3, R4¿, m, n and R5 are defined as described in the specification, and multiple processes and intermediates for their preparation as well as their use as herbicides.

Description

1,3,5-TRIAZINES AS HERBICIDES

The present invention relates to novel 1,3,5-triazines, to multiple processes and intermediates for their preparation and to their use as herbicides.

It has been already known that certain kinds of triazines show herbicidal activity (cf. WO 97/31904, WO 97/08156, WO 97/29095 etc.).

There have now been found novel 1,3,5-triazines ofthe formula (I)

wherein

R¹ represents C₁.₅ alkyl, C_3-7 cycloalkyl, C].₄ haloalkyl, benzyl which may be optionally halogen-substituted or C_M alkyl-substituted, or phenyl which may be optionally halogen-substituted or C alkyl-substituted,

R² represents amino, C alkylamino, formylamino, C_M alkyl-carbonylamino, C _₆ cycloalkyl-carbonylamino, C_M haloalkyl-carbonylamino, benzyl- carbonylamino which may be optionally halogen-substituted or C_M alkyl- substituted, phenylcarbonylamino which may be optionally C_M alkyl- substituted, C_M alkoxy-substituted or halogen-substituted, C_M alkyl- carbonylacetylamino, or di(C_1-4 alkyl)amino-CM alkylideneamino,

R³ or R⁴ each independently represent hydrogen atom or C_M alkyl, R⁵ represents halogen, C alkyl, CM haloalkyl, C alkoxy, CM haloalkoxy,

CM alkylthio, CM haloalkylthio, CM alkylsulfinyl, C_M alkylsulfonyl, phenyl which may be optionally halogen-substituted or Cι_-4 alkyl-substituted, phenoxy which may be optionally halogen-substituted or C_M alkyl - substituted, nitro or cyano,

m represents an integer of 1-4, and

the R³ substituents may be identical or different, in case m represents an integer of 2 or more,

n represents an integer of 0-5, and

the R⁵ substituents may be identical or different, in case n represents an integer of 2 or more.

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

a) in case R² represents amino:

compounds by the formula (II)

R³

wherein R³, R⁴, R⁵, m and n have the same definitions as aforementioned, and

X represents halogen, preferably chlorine or bromine,

are reacted with compounds ofthe formula (III)

R^,CO₂R⁶ (HI)

wherein

R¹ has the same definition as aforementioned, and

R⁶ represents C_M alkyl, preferably methyl or ethyl,

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

or

b) in case R² represents formylamino, C_M alkyl-carbonylamino, C_3-6 cycloalkyl- carbonylamino, C haloalkyl-carbonylamino, benzylcarbonylamino which may be optionally halogen-substituted or C_M alkyl-substituted, or phenylcarbonylamino which may be optionally C_1-4 alkyl-substituted, C_M alkoxy-substituted or halogen-substituted:

compounds ofthe formula (la)

wherein

R¹, R³, R⁴, R⁵, m and n have the same definitions as aforementioned,

are reacted with compounds ofthe formula (IV)

R⁷CO₂R⁶ (IV)

wherein

R⁶ has the same definition as aforementioned,

R⁷ represents hydrogen atom, C_1-4 alkyl, C_3-6 cycloalkyl, C_M haloalkyl, benzyl which may be optionally halogen-substituted or C_M alkyl-substituted, or phenyl which may be optionally C_M alkyl-substituted, C_M alkoxy- substituted or halogen-substituted,

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

or

c) in case R »2 represents C_M alkyl-carbonylacetylamino: the compounds of the formula (la) are reacted with compounds of the formula (V)

wherein

R _>s represents C_M alkyl, preferably Cι_-3 alkyl,

in the presence of an inert solvent,

or

d) in case R² represents di(C_1-4 alkyl)-C_1-4 alkylideneamino:

the compounds ofthe formula (la)

are reacted with compounds ofthe formula (VI)

I (VI)

(R⁹)₂N-C(OR⁶)₂

wherein

R has the same definition as aforementioned,

R⁹ represents C_M alkyl, preferably Cj_-3 alkyl, and

R¹⁰ represents a hydrogen atom or Cι-₃ alkyl, preferably hydrogen atom, methyl or ethyl, in the presence of an inert solvent, and if appropriate, in the presence of an acid catalyst,

or

e) in case R represents C_1- alkylamino:

compounds ofthe formula (VII)

wherein

R¹, R³, R⁴, R⁵, m and n have the same definitions as aforementioned, and R^{1 1} represents Cι-₄ alkylidene, preferably Cι- alkylidene,

are reduced in the presence of an inert solvent, and in the presence of catalyst.

The triazines of the formula (I), according to the present invention show stronger herbicidal action compared with the compounds described in the aforementioned prior art literature.

In the formulae:

"Halogen" represents fluorine, chlorine, bromine or iodine, and preferably represents fluorine, chlorine or bromine. "Alkyl" can be straight chain or branched chain and can represent, for example, C_M alkyl, and there can be mentioned specifically methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl.

As "cycloalkyl" there can be mentioned, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

"Haloalkyl" is halogen-substituted straight chain or branched chain alkyl and there can be mentioned, for example, C_M alkyl substituted with 1 - 9 fluorine, chlorine and/or bromine atoms, specifically fluoromethyl, fluorochloromethyl, fluoro- bromomethyl, fluorodichloromethyl, fluorodibromomethyl, difluoromethyl, difluoro- chloromethyl, difluorobromomethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, l-fluoroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 1,2,2,2-tetrafiuoroethyl, perfluoroethyl, 1-chloroethyl, 1,2-dichloroethyl, 1-bromo- ethyl, perfluoropropyl, 1-fluoro-l-methylethyl, 1-chloro-l-methylethyl, 1-bromo-l- methylethyl, l-(trifluoromethyl)-2,2,2-trifluoroethyl, 2-chloro-l,l,2-trifluoroethyl, 3- fluoropropyl, 3-chloropropyl, 2,2,3,3, 3-pentafluoropropyl, 1,2,2,3,3,3-hexafluoro- propyl or perfluorobutyl.

"Alkoxy" is alkyl-O-, of which the alkyl part has the above-mentioned meaning, and can represent, for example, C_1-4 alkoxy. There can be mentioned specifically methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec- or tert-butoxy.

"Alkylthio" is alkyl-S-, of which the alkyl part has the above-mentioned meaning, and can represent, for example, C_1-4 alkylthio. There can be mentioned specifically methylthio, ethylthio, n- or iso-propylthio, n-, iso-, sec- or tert-butylthio.

"Alkylsulfinyl" is alkyl-SO-, of which the alkyl part has the above-mentioned meaning, and can represent, for example, CM alkylsulfinyl. There can be mentioned specifically methylsulfinyl, ethylsulfinyl, n- or iso-propylsulfinyl, n-, iso-, sec- or tert-butylsulfinyl.

"Alkylsulfonyl" is alkyl-SO₂-, of which the alkyl part has the above-mentioned meaning, and can represent, for example, C alkylsulfonyl. There can be mentioned specifically methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, n-, iso-, sec- or tert-butylsulfonyl.

"Alkylamino" is alkyl-NH-, of which the alkyl part has the above-mentioned meaning, and can represent, for example, CM alkylamino. There can be mentioned specifically methylamino, ethylamino, n- or iso-propylamino, n-, iso-, sec- or tert- butylamino.

"Alkyl-carbonylamino" is alkyl-CONH-, of which the alkyl part has the above- mentioned meaning, and can represent, for example, C_2-5 alkyl-carbonylamino in total. There can be mentioned specifically methylcarbonylamino, ethylcarbonyl- amino, n- or iso-propylcarbonylamino, n-, iso-, sec- or tert-butylcarbonylamino.

"Cycloalkyl-carbonylamino" is cycloalkyl-CONH-, of which the cycloalkyl part has the above-mentioned meaning, and can represent, for example, C_4- cycloalkyl- carbonylamino. There can be mentioned specifically cyclopropylcarbonylamino or cyclobutylcarbonylamino, cyclopentylcarbonylamino, cyclohexylcarbonylamino.

"Haloalkyl-carbonylamino" is haloalkyl-CONH-, of which the haloalkyl part has the above-mentioned meaning, and can represent, for example, C₂-₅ haloalkyl-carbonylamino. There can be mentioned specifically fluoromethylcarbonylamino, difluoro- methyl-carbonylamino, difluorochloromethylcarbonylamino, difluorobromo-methyl- carbonylamino, trifluoromethylcarbonylamino, 1-fluoroethylcarbonylamino, 2- fluoromethylcarbonylam.no, 2,2,2-trifluoroethylcarbonylamino, 1 ,2,2,2-tetrafluoro- ethylcarbonylamino, perfluoroethylcarbonylamino or perfluoropropylcarbonylamino, perfluorobutylcarbonylamino. In "benzyl which may be optionally halogen-substituted or alkyl-substituted" and "benzylcarbonylamino which may be optionally halogen-substituted or alkyl- substituted" the halogen atoms are the same as mentioned above for "halogen" and the alkyl part has the same meaning as the above-mentioned "alkyl". As specific examples of "benzyl which may be optionally halogen-substituted or alkyl- substituted" there can be mentioned benzyl, 2-(3- and 4-)fluorobenzyl or 2-(3- and 4-)chlorobenzyl, 2-(3- and 4-)methylbenzyl, 2,3-(2,4-, 2,5-, 2,6-, 3,4-, 3,5-)- difluorobenzyl and as specific examples of "benzyl carbonylamino which may be optionally halogen-substituted or alkyl-substituted" there can be mentioned benzylcarbonylamino, 2-, 3- or 4-fluorobenzylcarbonylamino, 2-, 3- or 4-chlorobenzyl- carbonylamino, 2-, 3- or 4-methylbenzylcarbonylamino, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-difluorobenzylcarbonylamino.

In "phenyl which may be optionally halogen-substituted or alkyl-substituted" the halogen atoms are the same as mentioned above for "halogen" and the alkyl part has the same meaning as the above-mentioned "alkyl". As specific examples of "phenyl which may be optionally halogen-substituted or alkyl-substituted" there can be mentioned phenyl, 2-, 3- or 4-fluorophenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4- methylphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-difluorophenyl, 2,3-, 2,4-, 2,5-, 2,6-,

3,4-, or 3,5-dichlorophenyl or 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-dimethylphenyl.

In "phenylcarbonylamino which may be optionally alkyl-substituted, alkoxy- substituted or halogen-substituted " the alkyl part has the same meaning as the above- mentioned "alkyl", the alkoxy part has the same meaning as the above-mentioned

"alkoxy" and the halogen atoms are the same as mentioned above for "halogen". As specific examples of "phenylcarbonylamino which may be optionally alkyl substituted alkoxy-substituted or halogen-substituted" there can be mentioned phenylcarbonylamino, 2-, 3- or 4-fluorophenylcarbonylamino, 2-, 3- or 4-chlorophenyl- carbonylamino, 2-, 3- or 4-methylphenylcarbonylamino, 2-,3- or 4-methoxyphenyl- carbonylamino, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-difluoro phenylcarbonylamino, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-dichlorophenylcarbonylamino or 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3 , 5 -d imethylphenylcarbony 1 amino .

In "alkylcarbonylacetylamino" the alkyl part has the same meaning as the above- mentioned "alkyl" and as specific examples of "alkylcarbonylacetylamino" there can be mentioned acetoacetylamino, propionylacetylamino, butyrylacetylamino, iso- butyrylacetylamino, valerylacetylamino, isovalerylacetylamino or pivaloylacetyl- amino.

In "dialkylaminoalkylideneamino" the alkyl part has the same meaning as the above- mentioned "alkyl" and the above-mentioned alkylidene part can be straight chain or branched chain and can represent, for example, C_M alkylidene. As examples of "dialkylaminoalkylidene-amino" there can be mentioned dimethylaminomethylidene- amino, 1 -(dimethylamino)ethylideneamino, 1 -(dimethylamino)(n-propylidene)amino_J l-(dimethylamino)(n-butylidene)amino, l-(dimethylamino)(iso-butylidene)amino, diethylaminomethylideneamino, di(n-propyl)aminomethylideneamino, di(n-butyl)- aminomethylideneamino, (N-methyl-N-ethylamino)methylideneamino or (N-methyl- N-(n-propyl)amino)methylideneamino.

As a preferable group of compounds of the present invention there can be mentioned compounds which in the formula (I)

R¹ represents Cι_-4 alkyl, C_3-5 cycloalkyl, Cι- haloalkyl, benzyl which may be optionally fluoro-substituted, chloro-substituted or Cι- alkyl-substituted, or phenyl which may be optionally fluoro-substituted, chloro-substituted or Cι_-3 alkyl-substituted,

R² represents amino, C_1-3 alkylamino, formylamino, Cι_-3 alkyl-carbonylamino,

C₃.₅ cycloalkyl-carbonylamino, Cι_-3 haloalkyl-carbonylamino, benzyl- carbonylamino which may be optionally fluoro-substituted, chloro-substituted or Cj-₃ alkyl-substituted, phenylcarbonylamino which may be optionally Cι_-3 alkyl-substituted, Cι_-3 alkoxy-substiruted, fluoro-substituted or chloro- substituted, Cι_-3 alkyl-carbonylacetylamino, or di(Cι_-3 alkyl)amino-Cι_-3 alkylideneamino,

R³ or R⁴ each independently represent hydrogen atom or C_1-3 alkyl,

R⁵ represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, tert- butyl, Cι-3 haloalkyl, C1.3 alkoxy, Cι_-3 haloalkoxy, Cι_-3 alkylthio, Cι_-3 haloalkylthio, Cι_-3 alkylsulfinyl, Cι_-3 alkylsulfonyl, phenyl which may be optionally fluoro-substituted, chloro-substituted or C₁.₃ alkyl-substituted, phenoxy which may be optionally fluoro-substituted, chloro-substituted or Ci. ₃ alkyl-substituted, nitro or cyano,

m represents an integer of 2-4, and

the R³ substituents may be identical or different,

n represents an integer of 0-4, and

the R substituents may be identical or different, in case n represents an integer of 2 or more.

And as a more preferable group of compounds there can be mentioned compounds which in the compounds ofthe aforementioned formula (I)

R¹ represents methyl, ethyl, n-propyl, isopropyl, tert-butyl, cyclopropyl, cyclo- butyl, fluoromethyl, fluorochloromethyl, fluorobromomethyl, fluorodi- chloromethyl, fluorodibromomethyl, difluoromethyl, difluorochloromethyl, difluorobromomethyl, trifluoromethyl, chloromethyl, trichloromethyl, bromo- methyl, l-fluoroethyl, 2,2,2-trifluoroethyl, 1,2,2,2-tetrafluoroethyl, perfluoro- ethyl, 1-chloroethyl, 1,2-dichloroethyl, 1-bromoethyl, perfluoropropyl, 1- fluoro-1-methylethyl, 1-chloro-l-methylethyl, 1-bromo-l-methylethyl, 1- (trifluoromethyl)-2,2,2-trifluoroethyl, benzyl which may be optionally fluoro- substituted or methyl-substituted, or phenyl which may be optionally fluoro- substituted, chloro-substituted or methyl-substituted,

R represents amino, methylamino, ethylamino, formylamino, acetylamino, ethylcarbonylamino, cyclopropylcarbonylamino, fluoromethylcarbonylamino, trifluoromethylcarbonylamino, 1 -fluoroethylcarbonylamino, perfluoroethyl- carbonylamino, benzylcarbonylamino which may be optionally chloro- substituted or methyl-substituted, phenylcarbonylamino which may be optionally fluoro-substituted, chloro-substituted, methyl-substituted or methoxy-substituted, acetoacetylamino, or dimethylaminomethylideneamino,

R³ or R⁴ each independently represent hydrogen atom, methyl or ethyl,

R , 5 represents fluoro, chloro, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, methylsulfonyl, phenyl which may be optionally fluoro-substituted or methyl- substituted, phenoxy which may be optionally fluoro-substituted or methyl- substituted, nitro or cyano,

m represents an integer of 3 or 4, and

the R³ substituents may be identical or different,

n represents an integer of 0-3, and

the R⁵ substituents may be identical or different, in case n represents an integer of 2 or 3. The aforementioned preparation process (a), in case, for example, 2-benzylcyclo- pentylbiguanide hydrochloride and methyl α-fluoro-α-methylpropionate are used as the starting materials, can be illustrated by the following reaction scheme.

The aforementioned preparation process (b), in case, for example, 2-amino-4-(2'- benzylcyclopentylamino)-6-(α-fluoroisopropyι)- 1,3,5-triazine and ethyl acetate are used as the starting materials, can be illustrated by the following reaction scheme:

The aforementioned preparation process (c), in case, for example, 2-amino-4-(2'- benzylcyclopentylamino)-6-(α-fluoroisopropyl)-l ,3,5-triazine and acetyl-Meldrum's acid are used as the starting materials, can be illustrated by the following reaction scheme:

The aforementioned preparation process (d), in case, for example, 2-amino-4-(2'-(2- fluorobenzyl)cyclopentylamino)-6-(α-fluoroethyl)-l,3,5-triazine and N,N-dimethyl- formamide dimethylacetal are used as the starting materials, can be illustrated by the following reaction scheme:

The aforementioned preparation process (e), in case, for example, 2-ethyideneamino- 4-(2'-benzylcyclopentylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine is used as the starting material, can be illustrated by the following reaction scheme:

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 and can be prepared according to the process described in, for example, Japanese Laid-open Patent Application Nos. 246279/1989, 264465/1988, 222166/1988, No. 146876/1988, No. 51379/1988 by reacting, for example, a compound ofthe formula (VIII)

R³

wherein

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

X represents halogen,

with cyanoguanidine in an appropriate diluent, for example, n-decane. The compounds of the above-mentioned formula (VIII) can be prepared by reacting compounds ofthe formula (IX),

R³

(CH),

wherein

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

with an appropriate hydrogen halide acid, such as hydrochloric acid.

The compounds of the above-mentioned formula (IX), a part of which is novel and not described in the literature, can be prepared according to the process, (Leuckart's reaction) described in, for example, Organic Reaction, Vol.5, p.301 (1962), John Wiley & Sons, INC., by reacting compounds of the formula (X)

R³

wherein

R³, R⁴, R⁵, m and n have the same definitions as aforementioned, with formamide and formic acid. The compounds of the above-mentioned formula (X), a part of which is novel and not described in the literature, can be easily prepared by reacting, for example, in the commonly well known decarboxylation of β-ketoesters, namely, compounds represented ofthe formula (XI)

wherein

R , 3 , R , R , m and n have the same definitions as aforementioned, and

R⁶ represents Cι_-4 alkyl,

with an appropriate mineral acid, for example, hydrobromic acid.

The compounds of the above-mentioned formula (XI), a part of which is novel and not described in the literature, can be easily obtained by, for example, the process described in "SEIMITSU YXJKI GOSEI" (Precise organic syntheses), Nankodo, p.160, 1983, namely, by reacting compounds ofthe formula (XII)

R³

C0₂R⁶

wherein R and m have the same definitions as aforementioned, and

R⁶ represents C_M alkyl,

with compounds ofthe formula

wherein

R , R and n have the same definitions as aforementioned, and

X¹ represents halogen,

using an appropriate acid binding agent, for example, an aqueous solution of sodium hydroxide in an appropriate diluent, for example, dichloromethane in the presence of a phase transfer catalyst, for example, tetrabutylammonium hydrogen sulfate.

The compounds of the above-mentioned formula (XII), a part of which is novel and not described in the literature, can be easily prepared according to the process described in, for example, Organic Reaction, Vol.15, p.l (1967), John Wiley & Sons, INC.

The compounds of the above-mentioned formula (XIII) are known compounds and can be easily prepared according to the process described in, for example, "SHIN JIKKEN KAGAKU KOZA" (New experimental chemistry lectures), edited by the Chemical Society of Japan, Vol. 14(1), p.331, 1962, published by Maruzen.

As compounds of the formula (II) used as the starting materials in the above- mentioned preparation process (a) there can be mentioned the following: 2-benzylcyclopentylbiguanide hydrochloride, 2-(2'-fluorobenzyl)cyclopentylbiguanide hydrochloride, 2-(3'-fluorobenzyl)cyclopentylbiguanide hydrochloride, 2-(3 '-methylbenzyl)cyclopentylbiguanide hydrochloride, 2-benzylcyclohexylbiguanide hydrochloride,

2-(2'-fluorobenzyl)cyclohexylbiguanide hydrochloride, 2-(3'-fluorobenzyl)cyclohexylbiguanide hydrochloride and 2-(3 '-methylbenzyl)cyclohexylbiguanide hydrochloride.

The compounds of the formula (III) are known compounds and can be commercially obtained. They can also be easily prepared according to the process described in EP-A-850911.

As compounds of the formula (III) used as the starting materials in the above- mentioned preparation process (a) there can be mentioned the following: ethyl fluoroacetate, ethyl fluorochloroacetate, ethyl fluorobromoacetate, ethyl di fluorochloroacetate, ethyl dibromofluoroacetate, ethyl trifluoroacetate, methyl pentafluoropropionate, ethyl α-fluoropropionate, ethyl α-fluoro-α-methylpropionate, ethyl acetate, ethyl propionate, ethyl n-butyrate, ethyl isobutyrate, ethyl cyclopropanecarboxylate, ethyl cyclopentanecarboxylate and ethyl cyclohexanecarboxylate. The compounds of the formula (la) used as the starting materials in the above- mentioned preparation processes (b) - (d) are a part of the compounds of the formula (I) of the present invention and can be easily prepared by the above-mentioned preparation process (a).

In formula (IV) according to the above-mentioned preparation process (b) R⁷ preferably represents a hydrogen atom, Cι_-3 alkyl, C_3-5 cycloalkyl, Cι_-3 haloalkyl, benzyl which may be fluoro-substituted, chloro-substituted or Cι_-3 alkyl-substituted, or phenyl which may be Cι_-3 alkyl-substituted, Cι_-3 alkoxy-substituted, fluoro- substituted or chloro-substituted.

The compounds of the formula (IV) are known compounds and can be obtained as commercially available. Or they can be easily synthesized according to the process described in, for example, EP-A-850911.

As compounds of the formula (la) used as the starting materials in the above- mentioned preparation processes (b) - (d) which are included in the formula (I), there can be mentioned the following: 2-amino-4-(2'-benzylcyclopentylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine,

2-amino-4-(2'-benzylcyclopentylamino)-6-(α-fluoroethyl)-l,3,5-triazine, 2-amino-4-(2'-(2-fluorobenzyl)cyclopentylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine, 2-amino-4-(2'-(2-fluorobenzyl)cyclopentylamino)-6-(α-fluoroethyl)-l,3,5-triazine_J 2-amino-4-(2'-(2-fluorobenzyl)cyclopentylamino)-6-(trifluoromethyl)-l,3,5-triazine, 2-amino-4-(2'-(3-fluorobenzyl)cyclopentylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine,

2-amino-4-(2'-(3-fluorobenzyl)cyclopentylamino)-6-(α-fluoroethyl)-l,3,5-triazine, 2-amino-4-(2'-(3 -fluorobenzyl)cyclopentylamino)-6-(trifluoromethyl)- 1 ,3 ,5 -triazine, 2-amino-4-(2'-(3-me ylbenzyl)cyclopentylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine, 2-amino-4-(2^,-(3-methylbenzyl)cyclopentylamino)-6-(α-fluoroethyl)-l,3,5-triazine, 2-amino-4-(2'-(3-memylbenzyl)cyclopenrylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine,

2-amino-4-(2'-benzylcyclohexylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine, 2-amino-4-(2'-benzylcyclohexylamino)-6-(α-fluoroethyl)-l,3,5-triazine, -amino-4-(2^,-(3-fluorobenzyl)cyclohexylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine, 2-amino-4-(2'-(3-fluorobenzyl)cyclohexylamino)-6-(α-fluoroethyl)-l,3,5-triazine, 2-amino-4-(2'-(3-methylbenzyl)cyclohexylamino)-6-isopropyl-l,3,5-triazine and 2-amino-4-(2'-(3-methylbenzyl)cyclohexylamino)-6-ethyl-l,3,5-triazine.

As compounds of the formula (IV) used as starting materials in the above-mentioned preparation process (b) there can be mentioned the following: as follows: ethyl acetate, ethyl propionate, ethyl n-butyrate, ethyl isobutyrate, ethyl pivalate, ethyl cyclopropanecarboxylate, ethyl cyclopentanecarboxylate, ethyl cyclohexanecarboxylate ethyl phenylacetate, ethyl benzoate, ethyl 3-methylbenzoate, ethyl 2-chlorobenzoate and ethyl trifluoroacetate.

The compounds of formula (V), used as the starting materials in the above-mentioned preparation process (c) are known compounds and can be easily prepared according to the process described in, for example, Chem. Pharm. Bull. (1987), 35(5), 1860- 1870.

As compounds of the formula (V) used as starting materials in the above-mentioned preparation process (c) there can be mentioned the following:

5-acetyl-2,2-dimethyl-l,3-dioxan-4,6-dione, 5-propionyl-2,2-dimethyl-l,3-dioxan-4,6-dione, 5-butyryl-2,2-dimethyl-l,3-dioxan-4,6-dione, 5-isobutyryl-2,2-dimethyl-l,3-dioxan-4,6-dione, 5-cyclopropylcarbonyl-2,2-dimethyl-l,3-dioxan-4,6-dione, 5-cyclohexylcarbonyl-2,2-dimethyl-l,3-dioxan-4,6-dione and

5-(2-fluorobenzoyl)-2,2-dimethyl-l,3-dioxan-4,6-dione.

As compounds of formula (VI), used as the starting materials in the above-mentioned preparation process (d), are known compounds and can be easily prepared according to the process described in, for example, Japanese Laid-open Patent Application No.

277251/1996.

The compounds of the formula (VI) used as the starting materials in the above- mentioned preparation process (d) there can be mentioned the following: N,N-dimethylformamide dimethylacetal,

N,N-diethylformamide dimethylacetal,

N,N-dipropylformamide dimethylacetal,

N-methyl-N-ethylformamide dimethylacetal,

N-methyl-N-propylformamide dimethylacetal, N,N-dimethylformamide diethylacetal,

N,N-diethylformamide diethylacetal,

N,N-dimethylacetamide dimethylacetal and

N,N-diethylacetamide dimethylacetal.

The compounds of the formula (VII) used as the starting materials in the above- mentioned preparation process (e) are novel and not described in the literature and can be prepared according to the process described in, for example, Japanese Laid- open Patent Application No. 51379/1988, for example, by reacting the compounds of the aforementioned formula (la) with aliphatic aldehydes or aliphatic ketones with in total 1 to 4 carbon atoms in the aliphatic groups ofthe formula (XIV) O=R^u (XIV)

wherein R , π means the remaining aliphatic group forming the aliphatic aldehydes/ketones.

The compounds of the formula (XIV) are known compounds and can be commercially obtained.

As compounds ofthe formula (VII) used as starting materials in the above-mentioned preparation process (e) there can be mentioned the following:

2-methylideneammo-4-(2'-benzylcyclopentyl-mιino)-6-(α-fluoroisopropyl)-l,3₎5-triazine, 2-ethylideneamino-4-(2^,-benzylcyclopentylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine, 2-propylideneamino-4-(2^,-benzylcyclopentylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine, 2-isopropyUdeneammo-4-(2'-benzylcyclopentylammo)-6-(α-fluoroisopropyl)-l,3,5-m^'azine, 2-methylideneamino-4-(2'-benzylcyclopentylamino)-6-(α-fluoroethyl)-l,3,5-lriazine,

2-ethylideneamino-4-(2'-benzylcyclopentylamino)-6-(α-fluoroethyl)- 1 ,3 ,5-triazine, 2-propylideneamino-4-(2'-benzylcyclopentylamino)-6-(α-fluoroethyl)-l,3,5-triazine, 2-methylideneamino-4-(2'-benzylcyclohexylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine, 2-ethylideneamino-4-(2'-benzylcyclohexylamino)-6-(α-fluoroethyl)-l,3,5-triazine, 2-ethylideneamino-4-(2^,-(3-fluorobenzyl)cyclopentylamino)-6-(α-fluoroisopropyl)-

1,3,5-triazine,

2-ethylideneamino-4-(2'-(3-methylbenzyl)cyclopentylamino)-6-(α-fluoroethyl)-l,3,5- triazine and 2-ethylideneamino-4-(2'-benzylcyclohexylamino)-6-isopropyl-l,3,5-triazine.

As another alternative to the preparation according to process (e) compounds of formula (I) can also be prepared according to process (b), if, instead of compounds of the formula (IV) compounds ofthe formula (XV)

R^,2-X" (XV) wherein

R¹² represents C_1- alkyl, and

X¹ represents halogen,

are used.

The reaction of the above-mentioned preparation process (a) can be conducted in an appropriate diluent. As examples of such diluents used in that case there can be mentioned ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) or diethylene glycol dimethyl ether (DGM); alcohols, for example, methanol, ethanol, isopropoanol, butanol or ethylene glycol; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, l,3-dimethyl-2-imidazolidinone or hexamethylphosphoric triamide (HMPA); sulfones and sulfoxides, for example, dimethyl sulfoxide (DMSO) or sulfolane; bases, for example, pyridin.

The preparation process (a) can be conducted in the presence of an acid binding agent. As an acid binding agent usable in that case there can be mentioned, as inorganic bases, hydrides, hydroxides, carbonates or bicarbonates of alkali metals and alkaline earth metals, for example, sodium hydride, lithium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide; inorganic alkali metal amides, for example, lithium amide, sodium amide or potassium amide; and as organic bases, alcoholates, tertiary amines, dialkyl- aminoanilines and pyridines, for example, sodium methoxide, sodium ethoxide, potassium tert-butoxide, triethylamine, 1,1,4,4-tetramefhylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylamino- pyridine (DMAP), l,4-diazabicyclo[2,2,2Joctane (DABCO) or 1,8-diazabicyclo- [5,4,0]undec-7-ene (DBU). The preparation process (a) can be conducted at various of temperatures. Suitable temperatures are in the range of generally about 0 - about 100°C, preferably about 20 to about 80°C. Said reaction may be 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 objective compound of the formula (I) can be obtained, for example, by reacting 1 mole of a compound of the formula (II) with 0.8-2.2 moles of a compound of the formula (III) in a diluent, for example, methanol, in the presence of 2-3 moles of sodium methoxide.

Further, in the preparation process (a) the reaction to produce the compound of the formula (II) from a compound of the formula (IX) through the intermediate compound ofthe formula (VIII) can be also conducted continuously.

The reaction of the above-mentioned preparation process (b) can be conducted in an appropriate diluent. As examples of such diluents used in that case there can be mentioned water; 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, dichlorobenzene etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) or diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone or methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile, propionitrile or acrylonitrile; alcohols, for example, methanol, ethanol, isopropanol, butanol or ethylene glycol; esters, for example, ethyl acetate or amyl acetate; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, l,3-dimethyl-2-imidazolidinone or hexamethyl- phosphoric triamide (HMPA); sulfones and sulfoxides, for example, dimethyl sulfoxide (DMSO) or sulfolane; bases, for example, pyridine. The preparation process (b) can be conducted in the presence of an acid binding agent. As an acid binding agent usable in that case there can be mentioned, as inorganic bases, hydrides, hydroxides, carbonates or bicarbonates of alkali metals and alkaline earth metals, for example, sodium hydride, lithium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide; inorganic alkali metal amides, for example, lithium amide, sodium amide or potassium amide; and as organic bases, alcoholates, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethyl- ethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4- dimethylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO) or 1,8- diazabicyclo[5,4,0]undec-7-ene (DBU); organolithium compounds, for example, methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, phenyl lithium, dimethyl copper lithium, lithium diisopropylamide, lithium cyclohexylisopropyl- amide, lithium dicyclohexylamide, n-butyl lithium-DABCO, n-butyllithium-DBU or n-butyl lithium-TMEDA.

The preparation process (b) can be conducted at various temperatures. Suitable temperatures are in the range of generally about 0 - about 150°C, preferably about 40

- about 80°C. Said reaction may be 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 objective compound of the formula (I) can be obtained, for example, by reacting 1 mole of a compound of the formula (la) with 2-20 moles of a compound of the formula (IV) in the presence of 1-2 moles of sodium methoxide.

The reaction of the above-mentioned preparation process (c) can be conducted in an appropriate diluent. As examples of such diluents used in that case there can be mentioned water; 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 or dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) or diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone or methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile, propionitrile or acrylonitrile; alcohols, for example, methanol, ethanol, isopropanol, butanol or ethylene glycol etc.; esters, for example, ethyl acetate or amyl acetate; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methyl-pyrrolidone, l,3-dimethyl-2-imidazolidinone or hexa- methylphosphoric triamide (HMPA); sulfones and sulfoxides, for example, dimethyl sulfoxide (DMSO) or sulfolane; bases, for example, pyridine.

The preparation process (c) can be conducted at various temperatures. Suitable temperatures are in the range of generally about 20 - about 180°C, preferably about 60 - about 120°C. Said reaction may be 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 objective compound of the formula (I) can be obtained, for example, by reacting 1 mole of a compound of the formula (la) with 1-2 moles of a compound of the formula (V) in a diluent, for example, benzene.

The reaction of the above-mentioned preparation process (d) can be conducted in an appropriate diluent. As examples of such diluents used in that case there can be mentioned water; 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 or dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofiiran (THF) or diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone or methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile, propionitrile or acrylonitrile; alcohols, for example, methanol, ethanol, isopropanol or butanol, ethylene glycol; esters, for example, ethyl acetate or amyl acetate; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methyl-pyrrolidone, l,3-dimethyl-2-imidazolidinone or hexamethyl- phosphoric triamide (HMPA); sulfones and sulfoxides, for example, dimethyl sulfoxide (DMSO) or sulfolane; bases, for example, pyridine.

The preparation process (d) can be conducted in the presence of an acid catalyst. As examples of such acid catalysts usable in that case there can be mentioned mineral acids, for example, hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid or sodium hydrogen sulfite; organic acids, for example, formic acid, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, p- toluenesulfonic acid; organic amine hydrochlorides, for example, pyridine hydrochloride or triethylamine hydrochloride; amine sulfonates, for example, pyridine p- toluenesulfonate or triethylamine p-toluenesulfonate.

The preparation process (d) can be conducted at various temperatures. Suitable temperatures are in the range of generally about 20 - about 180°C preferably about 60 - about 120°C Said reaction may be 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 (d) the objective compound of the formula (I) can be obtained, for example, by reacting 1 mole of a compound of the formula (la) with 2-4 moles of a compound of the formula (VI) in a diluent, for example, benzene in the presence of a catalytic amount of p-toluenesulfonic acid. The reaction of the above-mentioned preparation process (e) can be conducted in an appropriate diluent. As examples of such diluents used in that case there can be mentioned water; 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 or dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofiiran (THF) or diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone or methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile, propionitrile or acrylonitrile; alcohols, for example, methanol, ethanol, isopropanol, butanol or ethylene glycol; esters, for example, ethyl acetate or amyl acetate; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methyl-pyrrolidone, l,3-dimethyl-2-imidazolidinone or hexamethyl- phosphoric triamide (HMPA); sulfones and sulfoxides, for example, dimethyl sulfoxide (DMSO) or sulfolane; bases, for example, pyridine.

The preparation process (e) can be conducted in the presence of a catalyst. As examples of such catalysts usable in that case there can be mentioned 10% palladium-carbon.

The preparation process (e) can be conducted at various temperatures. Suitable temperatures are in the range of generally about 0 - about 120°C, preferably about 25 - about 80°C. Said reaction may be 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 (e) the objective compound of the formula (I) can be obtained, for example, by reacting 1 mole of a compound of the formula (VII) with 1-2 moles of hydrogen gas in a diluent, for example, methanol in the presence of a catalytic amount of 10% palladium-carbon. The active compounds of the formula (I) , according to the present invention 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 of the present invention act as total or selective herbicides depending upon the applied concentration. The active compounds of the formula (I) of the present invention can be used, for example, for the following weeds and cultures.

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipomoea,

Polygonum, Ambrosia, Cirsium, Sonchus, Solanum, Rorippa, Lamium, Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Galinsoga, Rotala, Lindemia 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.

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 organis 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 compostions containing them directly to the plants or plant parts or to this 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 layer.

The active compounds of the present invention can, depending upon the applied concentration, non-selectively control weeds and may 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.

The active compounds of the formula (I), according to the present invention, can be made into the customary formulations in case of using. As such formulations there can be mentioned, for example, liquids (emulsifiable concentrates etc.), wettable powders, emulsions, suspension concentrates, powders, water-dispersible granules, tablets, granules, suspension-emulsion concentrates, microcapsules in polymeric substances or jumbo formulations.

The formulations can be prepared according to known methods, for example, by mixing the active compounds with extenders, namely liquid and/or solid diluents or carriers, and optionally with surface-active agents, namely emulsifiers 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 or alkylnaphthalene), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides or methylene chloride), aliphatic hydrocarbons [for example, cyclohexane or paraffins (for example, mineral oil fractions)], alcohols (for example, butanol or glycol) and their ethers, esters etc., ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), strongly polar solvents (for example, dimethylformamide or dimethyl sulphoxide) or 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 or diatomaceous earth), ground synthetic minerals (for example, highly dispersed silicic acid, alumina or silicates) etc. As solid carriers for granules there can be mentioned, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite or dolomite) or synthetic granules of inorganic and organic meals or particles of organic materials (for example, sawdust, coconut shells, maize cobs and tobacco stalks).

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 or arylsulphonates)] or albumin hydrolysis products. As dispersants there are included, for example, ligninsulphite waste liquor or methyl cellulose etc.

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

Colorants may also be used. As said colorants there can be mentioned inorganic pigments (for example, iron oxide, titanium oxide and Prussian Blue) 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 or molybdenum or zinc.

Said formulations can contain in a range of generally 0.1-95 % by weight, preferably 0.5-90 % by weight of the aforementioned active components.

The active compounds of the formula (I) of the present invention can be used as such or in form of formulations for controlling weeds. They can be used also as a mixed agent with known herbicides. Such a mixed agent can be previously prepared in a final formulation form or can be prepared by tank-mixing on the occasion of the application. As a mixing partner for a possible combination there can be mentioned, for example, sulfonylurea type herbicides for paddy field use.

Furthermore, the active compounds of the formula (I) of the present invention can be also mixed with a safener and their application as a selective herbicide may be broadened by such a mixing. As an example of the safener for that purpose l-(α,α- dimethylbenzyl)-3-p-tolylurea can be mentioned. Surprisingly, some of the mixing partners ofthe compounds of the present invention show synergistic effects.

In case of using the active compounds of the formula (I) of the present invention they can be directly employed as such or in the aforementioned forms of formulation or applied in the application forms prepared by further dilution. They can be applied by means of, for example, watering, spraying, atomizing, dusting or granule application.

The active compounds of the formula (I) of the present invention can be applied at any stages before and after germination of plants. They may also be taken into the soil before sowing.

The application rate of the active compounds of the present invention is not strictly restricted but may be varied in a wide range according to the desired effect, kind of objective plant, location and period of application. In case of herbicidal use, as the application rate there can be mentioned, for example, ranges of about 0.001 to about 5 kg, preferably about 0.05 to about 2 kg ofthe active compounds per hectare.

Then the preparations and applications of the compounds of 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. "Parts" are "parts by weight", unless specified.

Synthesis Example 1

2-Benzylcyclopentylamine (3 g) was slowly added drop by drop to concentrated hydrochloric acid (3.6 ml) under ice cooling. After stirring of the mixture for 30 minutes, water was distilled off under reduced pressure to obtain 2-benzylcyclo- pentylamine hydrochloride (3.1 g).

The above-mentioned 2-benzylcyclopentylamine hydrochloride (3.1 g) and cyano- guanidine (1.23 g) were suspended in n-decane (30 ml) and heated at 130°C for 4.5 hours. After cooling, the deposited crystals were filtered, washed with n-hexane and dried under reduced pressure to obtain 2-benzylcyclopentylbiguanide hydrochloride

(3 g).

After adding sodium (0.31 g) in 12 ml of dry methanol and stirring for 5 minutes, the above-mentioned 2-benzylcyclopentylbiguanide hydrochloride (2 g) was added and the mixture stirred at room temperature for 30 minutes. Then methyl α-fluoro-α- methylpropionate (1.62 g) was added to the mixture, which was stirred at room temperature for 10 hours. Thereafter 50 ml of water were added and the reaction product was extracted with ethyl acetate. After drying with anhydrous sodium sulfate, the ethyl acetate was distilled off under reduced pressure and the residue was treated by silica gel column chromatography (eluent: hexane: ethyl acetate = 1:1) to obtain 2-amino-4-(2'-benzylcyclo-pentylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine (1.65 g). mp 50-55°C. Synthesis Example 2

After adding sodium (0.1 g) in dry methanol (5 ml) and stirring for 5 minutes, 2- amino-4-(2'-benzylcyclopentylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine (1 g) was added and the mixture was stirred at 50°C for 1 hour. After cooling, methanol was distilled off under reduced pressure. Then ethyl acetate (10 ml) was added and the mixture was stirred at 50°C for 1 hour. After cooling, water (30 ml) was added and the reaction product was extracted with ethyl acetate. After drying with anhydrous sodium sulfate, the ethyl acetate was distilled off under reduced pressure and the residue was treated by silica gel column chromatography (eluent: hexane : ethyl acetate = 3:2) to obtain 2-acetylamino-4-(2'-benzylcyclopentylamino)-6-(α-fluoroiso- propyl)- 1,3,5-triazine (0.57 g). n^D ₂₀ 1.5512.

Synthesis Example 3

2-Amino-4-(2'-benzylcyclopentylamino)-6-(α-fluoroisopropyl)-l,3,5-triazine (0.5 g) and acetyl-Meldrum's acid (0.28 g) were dissolved in benzene (20 ml) and refluxed for 1 hour upon heating. After cooling, the solvent was distilled off under reduced pressure and the residue was treated by silica gel column chromatography (eluent: hexane : ethyl acetate = 3:2) to obtain 2-acetoacetylamino-4-(2'-benzylcyclopentyl- amino)-6-(α-fluoroisopropyl)- 1,3,5-triazine (0.55 g). n^D ₂₀ 1.5433.

Synthesis Example 4

2-Amino-4-(2'-(2-fluorobenzyl)cyclopentylamino)-6-(l-fluoroethyl)-l,3,5-triazine (0.3 g), N,N-dimethylformamide dimethylacetal (0.32 g) and a catalytic amount of p- toluenesulfonic acid monohydrate were dissolved in benzene (20 ml) and refluxed for

1.5 hours upon heating. After cooling, the solvent was distilled off under reduced pressure and the residue was treated by silica gel column chromatography (eluent: dichloromethane : methanol = 90:5) to obtain 2-N',N'-dimethylmethyleneimino-4-(2'- (2-fluorobenzyl)cyclopentylamino)-6-(l-fluoroethyl)-l,3,5-triazine (0.34 g). n^D ₂₀ 1.5776.

The compounds, which can be obtained in the same manner as the above-mentioned Synthesis Examples 1 to 4, are shown in the following Table 1, together with the compounds synthesized according to the Synthesis Examples 1 to 4. Table 1

Compound

No. R¹ R² R⁴ (R⁵)n mp or n D ₂₀

1. CH₃ NH₂ H H

2. C₂H₅ NH₂ H H

3. C₃H₇-n NH H H

4. C₃H₇-iso NH₂ H H

5. C₄H₉-n NH₂ H H

6. C Hg-sec NH₂ H H

7. C H₉-iso NH₂ H H

8. C₄H₉-tert NH₂ H H

9. C₅H,,-n NH₂ H H

12. ^→® NH₂ H H

13. A^> NH₂ H H

14.

15. C -H₂Θ NH₂ H H

F NH₂ H H

16. CH₂C1 NH₂ H H

Table 1 (continued)

Compound

No. R¹ R² R⁴ (R⁵)_n mp or n^D ₂₀

89. (CH₃)₂CF NH₂ H 2,4-Ch

90. (CH₃)₂CF NH₂ H 3,4-Cl₂

91. (CH₃)₂CF NH₂ H 3,5-Cl₂

92. (CH₃)₂CF NH₂ H 2,4-(CH₃)₂

93. (CH₃)₂CF NH₂ H 3,4-(CH₃)₂

94. (CH₃)₂CF NH₂ H 3,5-(CH₃)₂

95. (CH₃)₂CF NH₂ H 3,5-(CF₃)₂

96. (CH₃)₂CF NH₂ H 3,4-(OCH₃)₂

97. (CH₃)₂CF NH₂ H 2,3,4-Cl₃

98. (CH₃)₂CF NH₂ H 2,4,6-(CH₃)₃

99. (CH₃)₂CF NHCHO H H

100. (CH₃)₂CF NHCOCH₃ H H 1.5512

101. (CH₃)₂CF NHCOC₂H₅ H H

102. (CH₃)₂CF NHCOC₃H₇-n H H

103. (CH₃)₂CF NHCOC₃H₇-iso H H

104. (CH₃)₂CF NHCOC₄H₉-ter t H H

106. (CH₃)₂C NHCO - in] H H

107. (CH₃)₂CF ^NHC0 —Qj) H H

108. (CH₃)₂CF NHCOCH₂F H H Table 1 (continued)

Compound No. R¹ R² R⁴ (R⁵)_n mporn^D ₂₀

109. (CH₃)₂CF NHCOCF₃ H H

110. (CH₃)₂CF NHCOCHFCH₃ H H

111. (CH₃)₂CF NHCOCF₂CF₃ H H

112. (CH₃)₂CF NHCOCH₂ -O H H

113. (CH₃)₂CF NHCOCH₂ ^{H H}

Cl

114. (CH₃)₂CF NHCOCH₂ — ^~S ^H H

115. (CH₃)₂CF NHCO-<ζ H H

116. (CH&CF _N NH_HCC_OO ^ H H

117. (CH₃)₂CF NHCO ~ ζj H H

118. (CH₃)₂CF NHCO - r-OCH_{3 H H}

Table 1 (continued)

Compound No. R¹ R R⁴ (R⁵)π mp or n ₂₀

121. (CH₃)₂CF NHCOCH₂COCH₃ H H 1.5433

122. (CH₃)₂CF N=CHN(CH₃)₂ H H

123. (CH₃)₂CC1 NH₂ H H

124. (CH₃)₂CBr NH₂ H H

125. C1CH₂C1CH₂ NH₂ H H

126. CH₂CF₃ NH₂ H H

127. CHFCF₃ NH₂ H H

128. CH₂CF₃ NH₂ H H

129. CF₂CF₂CF₃ NH₂ H H

130. (CF₃)₂CH NH₂ H H

131. CF₂CF₂CF₂CF₃ NH₂ H H

132. CH -O NH₂ H H

Table 1 (continued)

Compound No. R^l R² R⁴ (R⁵)π mp or n^D ₂₀

135. -o NH₂ H H

.Cl

137. — ^NH2 H H

138. - V- CH_{3 N}H₂ H H

141. CF₃ NH₂ CH₃ H

142. CF₃ NH₂ CH₃ 3-F

143. CF₃ NH₂ CH₃ 3-CH₃

144. CF₃ NH₂ CH₃ 3,5-F₂

145. CF₃ NH₂ CH₃ 3,5-(CH₃)₂

146. CH₃CHF NH₂ CH₃ H Table 1 (continued)

Compound

No. R¹ R² R⁴ (R⁵)n mp or n^D ₂₀

147. CH₃CHF NH₂ CH₃ 3-F

148. CH₃CHF NH₂ CH₃ 3-CH₃

149. CH₃CHF NH₂ CH₃ 3,5- F₂

150. CH₃CHF NH₂ CH₃ 3,5-(CH₃)₂

151. (CH₃)₂CF NH₂ CH₃ H

152. (CH₃)₂CF NH₂ CH₃ 3-F

153. (CH₃)₂CF NH₂ CH₃ 3-CH₃

154. (CH₃)₂CF NH₂ CH₃ 3,5- F₂

155. (CH₃)₂CF NH₂ CH₃ 3,5-(CH₃)₂

156. CF₃ NH₂ C₂H₅ H

157. CF₃ NH₂ C₂H₅ 3-F

158. CF₃ NH₂ C₂H₅ 3-CH₃

159. CH₃CHF NH₂ C₂H₅ H

160. CH₃CHF NH₂ C₂H₅ 3-F

161. CH₃CHF NH₂ C₂H₅ 3-CH₃

162. (CH₃)₂CF NH₂ C₂H₅ H

163. (CH₃)₂CF NH₂ C₂H₅ 3-F

164. (CH₃)₂CF NH₂ C₂H₅ 3-CH₃

165. CF₃ NH₂ C₃H₇-n H

166. CH₃CHF NH₂ C₃H₇-n H

167. (CH₃)₂CF NH₂ C₃H₇-n H

Table 1 (continued)

Compound

No. R¹ R² R⁴ (R⁵)n mp or n^D ₀

186. CH₃CHF NH₂ H 3-F

187. CH₃CHF NH₂ H 4-F

188. CH₃CHF NH₂ H 2-C1

189. CH₃CHF NH₂ H 3-C1

190. CH₃CHF NH₂ H 4-C1

191. CH₃CHF NH₂ H 3-Br

192. CH₃CHF NH₂ H 3-CF₃

193. CH₃CHF NH₂ H 2-CH₃

194. CH₃CHF NH₂ H 3-CH₃

195. CH₃CHF NH₂ H 4-CH₃

196. CH₃CHF NH₂ H 2-OCH₃

197. CH₃CHF NH₂ H 3-OCH₃

198. CH₃CHF NH₂ H 4-OCH₃

199. CH₃CHF NH₂ H 3-SCH₃

200. CH₃CHF NH₂ H 3,5-F₂

201. CH₃CHF NH₂ H 3,5-(CH₃)₂

202. (CH₃)₂CF NH H H

203. (CH₃)₂CF NH₂ H 2-F

204. (CH₃)₂CF NH₂ H 3-F

205. (CH₃)₂CF NH₂ H 4-F

206. (CH₃)₂CF NH₂ H 2-C1

207. (CH₃)₂CF NH₂ H 3-C1

208. (CH₃)₂CF NH₂ H 4-C1

209. (CH₃)₂CF NH₂ H 3-Br

210. (CH₃)₂CF NH₂ H 3-CF₃

Table 1 (continued)

R¹

Compound

No. R¹ R² R⁴ (R⁵)n mp or n ₂₀

232. CF₃ NH₂ H H

233. CF₃ NH₂ H 3-F

234. CF₃ NH₂ H 3-CH₃

235. CF₃ NH₂ H 3,5-F₂

236. CF₃ NH₂ H 3,5-(CH₃)₂

237. CH₃CHF NH₂ H H

238. CH₃CHF NH₂ H 3-F

239. CH₃CHF NH₂ H 3-CH₃

240. CH₃CHF NH₂ H 3,5-F₂

241. CH₃CHF NH₂ H 3,5-(CH₃)₂

242. (CH₃)₂CF NH₂ H H

243. (CH₃)₂CF NH₂ H 3-F

244. (CH₃)₂CF NH₂ H 3-CH₃ Table 1 (continued)

Com- pound No. R¹ R² R⁴ (R⁵)π mp or n ₂₀

245. (CH₃)₂CF NH₂ H 3,5-F₂

246. (CH₃)₂CF NH₂ H 3,5-(CH₃)₂

247. CF₃ NH₂ CH₃ H

248. CF₃ NH₂ C₂H₅ H

249. CH₃CHF NH₂ CH₃ H

250. CH₃CHF NH₂ C₂H₅ H

251. (CH₃)₂CF NH₂ CH₃ H

252. (CH₃)₂CF NH₂ C₂H₅ H

Table 1 (continued)

R<

Compound No. R¹ R R⁴ (R⁵)π mp or n^D ₂Q

253. CH₃ NH₂ H H

254. C₂H₅ NH₂ H H

255. C₃H₇-n NH₂ H H

256. C H -iso NH₂ H H

257. C₄H₉-n NH₂ H H

258. C₄H₉-sec NH₂ H H

259. C₄H₉-iso NH₂ H H

260. C H₉-tert NH₂ H H

261. C₃H₇-n NH₂ H H

262. -<] NH₂ H H

263. ^~ NH₂ H H

co co co CO co O CO co CO CO co CO CO co CO co co CO ) co T3 to to to t to to to t to to »— - »—* o Z O o o H t-> O 00 ^J ON Ui 42. CO to o VO 00 _^α Ui ^ co to o 3 3 3 r

P- n

_^-^ ^-_{^ ^}— _^ ,. — _^ ^ _^-^ ,_^- , — _*-_N ^- ^ _*- ,— _s ,— _N o- / -— _N s~- _s

O O O o O o O o o O o O o o o O O O o *L

53 53 33 33 33 33 53 53 33 u 3>3 33 u 3»3 33 33 33 53 u 5

^-_^ »3 53 33 53 «^ 'w' *~s ^— _^-^ o t

Tl o to to

O

TJ o Tl TJ o Tl o O O O

Tl TJ o TJ o TJ o TJ o O

TJ TJ TJ T o O J TJ TJ Tl o 41 o TJ o TJ o a

3

*> 3 O-

33 ffi W K W W W ffi ffi HH hC ffi K MS HH HM W K 5«

Table 1 (continued)

Compound No. R¹ R² R⁴ (R⁵)_n mporn^D ₂₀

352. (CH₃)₂CF NHCOC₃H₇-iso H H

353. (CH₃)₂CF NHCOC₄H₉-tert H H

354. (CH₃)₂CF NHCO— <] H H

355. (CH₃)₂CF HCO-^H] _{H H}

356. (CH₃)₂CF NHCO -Q ^H H

357. (CH₃)₂CF NHCOCH₂F H H

358. (CH₃)₂CF NHCOCF₃ H H

359. (CH₃)₂CF NHCOCHFCH₃ H H

360. (CH₃)₂CF NHCOCF₂CF₃ H H

NHCOCH,— ^~\

361. (CH₃)₂CF \=/ H H

Cl

362. (CH₃)₂CF NHCOC_r^-^ H H

363. (CH₃)₂CF NHCO- _{R R}

F

364. (CH₃)₂CF NHCO-^ H H

365. (CH₃)₂CF _mco_ ^~( H H Table 1 (continued)

Compound No. R¹ R² R⁴ (R⁵)n mp or n ₂₀

366. (CH₃)₂CF NHCO - ^~ - OCH₃ H H

369. (CH₃)₂CF NHCOCH₂COCH₃ H H

370. (CH₃)₂CF N=CHN(CH₃) ₂ H H

371. (CH₃)₂CC1 NH₂ H H

372. (CH₃)₂CBr NH₂ H H

373. CH₂C1CH₂C1 NH₂ H H

374. CH₃CF₃ NH₂ H H

375. CHFCF₃ NH₂ H H

376. CF₂CF₃ NH₂ H H

377. CF₂CF₂CF₃ NH₂ H H

378. (CF₃)₂CH NH₂ H H

379. CF₃ NH₂ CH₃ H

380. CF₃ NH₂ CH 3-F

381. CF₃ NH₂ CH₃ 3-CH₃

382. CF₃ NH₂ CH₃ 3,5-F₂

383. CF₃ NH₂ CH₃ 3,5-(CH₃)₂

384. CH₃CHF NH₂ ^' CH₃ H

385. CH₃CHF NH₂ CH₃ 3-F Table 1 (continued)

Compound

No. R¹ R² R⁴ (R⁵)n mp or n^D ₂₀

386. CH₃CHF NH₂ CH₃ 3-CH₃

387. CH₃CHF NH₂ CH₃ 3,5-F₂

388. CH₃CHF NH₂ CH₃ 3,5-(CH₃)₂

389. (CH₃)₂CF NH₂ CH₃ H

390. (CH₃)₂CF NH₂ CH₃ 3-F

391. (CH₃)₂CF NH₂ CH₃ 3-CH₃

392. (CH₃)₂CF NH₂ CH₃ 3,5-F₂

393. (CH₃)₂CF NH₂ CH₃ 3,5-(CH₃)₂

394. CF₃ NH₂ C₂H₅ H

395. CF₃ NH₂ C₂H₅ 3-F

396. CF₃ NH₂ C₂H₅ 3-CH₃

397. CH CHF NH₂ C₂H₅ H

398. CH₃CHF NH₂ C₂H₅ 3-F

399. CH₃CHF NH₂ C₂H₅ 3-CH₃

400. (CH₃)₂CF NH₂ C₂H₅ H

401. (CH₃)₂CF NH₂ C₂H₅ 3-F

402. (CH₃)₂CF NH₂ C₂H₅ 3-CH₃

403. CF₃ NH₂ C₃H₇-n H

404. CH₃CHF NH₂ C₃H₇-n H

405. (CH₃)₂CF NH₂ C₃H₇-n H Table 1 (continued)

R¹

pound

No. R¹ R² R⁴ (R⁵)n mp or n ₀

406. CF₃ NH₂ H H

407. CF₃ NH₂ H 2-F

408. CF₃ NH₂ H 3-F

409. CF₃ NH₂ H 4-F

410. CF₃ NH₂ H 2-C1

41 1. CF₃ NH₂ H 3-C1

412. CF₃ NH₂ H 4-C1

413. CF₃ NH₂ H 3-Br

414. CF₃ NH₂ H 3-CF₃

415. CF₃ NH₂ H 2-CH₃

416. CF₃ NH₂ H 3-CH₃

417. CF₃ NH₂ H 4-CH₃

418. CF₃ NH₂ H 2-OCH₃

419. CF₃ NH₂ H 3-OCH₃

420. CF₃ NH₂ H 4-OCH₃

421. CF₃ NH₂ H 3-SCH₃

Table 1 (continued)

Compound

No. R¹ R² R⁴ (R⁵)π mp or n^D ₂₀

447. (CH₃)₂CF NH₂ H 3-Br

448. (CH₃)₂CF NH₂ H 3-CF₃

449. (CH₃)₂CF NH₂ H 2-CH₃

450. (CH₃)₂CF NH₂ H 3-CH₃

451. (CH₃)₂CF NH₂ H 4-CH₃

452. (CH₃)₂CF NH₂ H 2-OCH₃

453. (CH₃)₂CF NH₂ H 3-OCH₃

454. (CH₃)₂CF NH₂ H 4-OCH₃

455. (CH₃)₂CF NH₂ H 2-SCH₃

456. (CH₃)₂CF NH₂ H 3,5-F₂

457. (CH₃)₂CF NH₂ H 3,5-(CH₃)₂

458. CF₃ NH₂ CH₃ H

459. CF₃ NH₂ C₂H₅ H

460. CH₃CHF NH₂ CH₃ H

461. CH₃CHF NH₂ C₂H₅ H

462. (CH₃)₂CF NH₂ CH₃ H

463. (CH₃)₂CF NH₂ C₂H₅ H

Table 1 (continued)

Compound

No. R¹ R² R⁴ (R⁵)π mp or n^D ₂o

507. (CH₃)₂CF NH₂ H 2-CH₃

508. (CH₃)₂CF NH₂ H 3-CH₃

509. (CH₃)₂CF NH₂ H 4-CH₃

510. (CH₃)₂CF NH₂ H 2-OCH₃

511. (CH₃)₂CF NH₂ H 3-OCH₃

512. (CH₃)₂CF NH₂ H 4-OCH₃

513. (CH₃)₂CF NH₂ H 3-SCH₃

514. (CH₃)₂CF NH₂ H 3,5-F₂

515. (CH )₂CF NH₂ H 3,5-(CH₃)₂

516. CF₃ NH₂ CH₃ H

517. CF₃ NH₂ C₂H₅ H

518. CH₃CHF NH₂ CH₃ H

519. CH₃CHF NH₂ C₂H₅ H

520. (CH₃)₂CF NH₂ CH₃ H

521. (CH₃)₂CF NH₂ C₂H₅ H

Table 1 (continued)

Compound

No. R¹ R² R⁴ (R⁵)n mp or n 2₀

541. (CH₃)₂CF NH₂ CH₃ H

542. (CH₃)₂CF NH₂ C₂H₅ H

The compounds, obtained by using methyl iodide, ethyl iodide or propyl iodide, instead of the compounds of the formula (IV) in the aforementioned preparation process (b), are shown in the following Tables 2 and 3.

Table 2

Compound

No. R¹ R² R⁴ (R⁵)n mp or n ₂₀

543. (CH₃)₂CF NHCH₃ H H

544. (CH₃)₂CF NHC₂H₅ H H

545. (CH₃)₂CF NHC₃H₇-n H H Table 3

R¹

Compound No. R¹ R² R⁴ (R⁵)n mp or n ₀

546. (CH₃)₂CF NHCH₃ H H

547. (CH₃)₂CF NHC₂H₅ H H

548. (CH₃)₂CF NHC₃H₇-n H H

Synthesis Example 5

A mixture of 2-benzylcyclopentanone (11.51 g) and formamide (44.41 ml) was heated at 140-150°C. Then formic acid (9.13 g) was slowly added to the mixture drop by drop at the given temperature. After finishing the addition, the mixture was heated at 150°C for further 2 hours. After cooling, water was added to the mixture and the reaction product was extracted with methylene chloride. The methylene chloride layer was washed with water and dried with anhydrous sodium sulfate.

After the methylene chloride was distilled off under reduced pressure, concentrated hydrochloric acid (36.85 ml) was added to the residue and refluxed for 2 hours by heating. After cooling, water was added, alkalized with sodium hydroxide and the product was extracted with methylene chloride. The methylene chloride layer was washed with water and dried with anhydrous potassium carbonate. After the methylene chloride was distilled off under reduced pressure, the residue was purified by distillation to obtain 2-benzylcyclopentylamine (5.18 g). n^D2o = 1.5371.

Synthesis Example 6

O

48% hydrobromic acid (50 ml) was added to 2-benzyl-2-ethoxycarbonylcyclo- pentanone (23.17 g) and refluxed at 120°C for 4 hours by heating. After cooling, ice (100 g) was added to the mixture and the reaction product was extracted with diethyl ether. After washing the diethyl ether layer with water, a saturated aqueous solution of sodium hydrogen carbonate and a saturated aqueous solution of sodium chloride, it was dried with anhydrous sodium sulfate. After the diethyl ether was distilled off under reduced pressure, the residue was purified by distillation to obtain 2-benzylcyclopentanone (11.51 g). n^D ₂o = 1.5288.

Synthesis Example 7

To a solution of 2-ethoxycarbonylcyclopentanone (13.37 g) in methylene chloride (143 ml), tetrabutylammonium hydrogen sulfate (29.1 g), benzyl iodide (37.37 g) was added and then a solution of sodium hydroxide (6.86 g) in water (143 ml) was added. After the mixture was stirred at room temperature for 4 hours, the methylene chloride layer was separated and the water layer was extracted with methylene chloride (200 ml, 3 times). The methylene chloride layers were put together, washed with water, saturated aqueous solution of sodium hydrogen carbonate and saturated aqueous solution of sodium chloride, and dried with anhydrous sodium sulfate. After the methylene chloride was distilled off under reduced pressure, the residue was treated by silica gel column chromatography (eluent: hexane : ethyl acetate = 9:1) to obtain 2-benzyl-2-ethoxycarbonylcyclopentanone (16.8 g). n^D ₂₀ = 1.5156.

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 emulsion by mixing 1 part by weight of the active compound with the above-mentioned amount of carrier and emulsifier. A prescribed amount of said solution of active ingredients is diluted with water and used for the test.

Test method

In a greenhouse 3 seedlings of paddy rice (cultivar: Nihonbare) of 2.5 leafstage

(15 cm tall) were transplanted in a 500 cm² pot filled with paddy field soil. Then seeds of barnyard grass, smallflower, bulrush, monochoria and broad-leaved weeds (common false pimpernel, Indian toothcup, long stemmed waterwort, Ammannia multiflora Roxb., Dopatrium junceum Hammilt etc.) were sown and water was poured to a depth of about 2-3 cm.

5 days after the paddy rice transplantation a solution of each active compound prepared according to the aforementioned preparation method was applied to the surface of the water. The herbicidal effect was examined on the day 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 death and as 0% in the case of no herbicidal effect.

As a result, the compounds of the present invention No. 27, 30, 32 and 36 showed at the application rate of 0.25 kg/ha of active compound a sufficient herbicidal effect against paddy field weeds and showed safety to the transplanted paddy rice.

Formulation Example 1 (Granule)

To a mixture of the compound No. 36 of the present invention (10 parts), bentonite (montmorillonite) (30 parts), talc (58 parts) and ligninsulphonate salt (2 parts), water (25 parts) is added. The mixture is well kneaded, made in granules of 10-40 mesh by 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. 27 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 a granule. Formulation Example 3 (Emulsifiable concentrate)

The compound No. 32 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. 30 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 alkylnaphthalenesulfonate- formalin-polymer (3 parts) are mixed in powder form and made into a wettable powder.

Formulation Example 5 (Water-dispersible granule)

The compound No. 36 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.

Claims

Claims

1. A compound ofthe general formula (I)

wherein

R¹ represents Cι_-5 alkyl, C_3-7 cycloalkyl, Cι_-4 haloalkyl, benzyl which may be optionally halogen-substituted or C_M alkyl-substituted, or phenyl which may be optionally halogen-substituted or C_M alkyl- substituted,

R represents amino, C_M alkylamino, formylamino, Cι- alkyl-carbonylamino, C -6 cycloalkyl-carbonylamino, C haloalkyl-carbonylamino, benzylcarbonylammo which may be optionally halogen-substituted or

CM alkyl-substituted, phenylcarbonylamino which may be optionally C_M alkyl-substituted, Cι_-4 alkoxy-substituted or halogen-substituted, CM alkyl-carbonylacetylamino, or di(Cι_-4 alkyl)amino-C_M alkylideneamino,

R³ or R⁴ each independently represents hydrogen atom or C_M alkyl,

R⁵ represents halogen, C alkyl, C_1-4 haloalkyl, C alkoxy, Cι_-4 haloalkoxy, CM alkylthio, C_1-4 haloalkylthio, C_M alkylsulfinyl, CM alkylsulfonyl, phenyl which may be optionally halogen-substituted or C_M alkyl-substituted, phenoxy which may be optionally halogen- substituted or C alkyl-substituted, nitro or cyano,

m represents an integer of 1 -4,

the R substituents may be identical or different, in case m represents an integer of 2 or more,

n represents an integer of 0-5, and

the R substituents may be identical or different, in case n represents an integer of 2 or more.

2. A compound according to Claim 1 wherein

R¹ represents Cι_-4 alkyl, C_3-5 cycloalkyl, Cι_-3 haloalkyl, benzyl which may be optionally fluoro-substituted, chloro-substituted or Cι_-3 alkyl- substituted, or phenyl which may be optionally fluoro-substituted, chloro-substituted or Cι- alkyl-substituted,

R² represents amino, Cι_-3 alkylamino, formylamino, Cι- alkyl-carbonylamino, C _-5 cycloalkyl-carbonylamino, Cj_-3 haloalkyl-carbonylamino, benzylcarbonylammo which may be optionally fluoro-substituted, chloro-substituted or Cι_-3 alkyl-substituted, phenylcarbonylamino which may be optionally Cι_-3 alkyl-substituted, Cι_-3 alkoxy-substi- tuted, fluoro-substituted or chloro-substituted, C_1- alkyl-carbonyl- acetylamino, or di(Cι_-3 alkyl)amino-Cι_-3 alkylideneamino,

R or R each independently represents hydrogen atom or Cι_-3 alkyl, R⁵ represents fluoro, chloro, bromo, methyl, ethyl, n-propyl, isopropyl, tert-butyl, C|.₃ haloalkyl, Cι_-3 alkoxy, Cι- haloalkoxy, Cι_-3 alkylthio,

Cι_-3 haloalkylthio, Cι- alkylsulfinyl, Cι. alkylsulfonyl, phenyl which may be optionally fluoro-substituted, chloro-substituted or Cι_-3 alkyl- substituted, phenoxy which may be optionally fluoro-substituted, chloro-substituted or Cι- alkyl-substituted, nitro or cyano,

m represents an integer of 2-4, wherein the R³ substituents may be identical or different,

represents an integer of 0-4, and

the R , 5 substituents may be identical or different, in case n represents an integer of 2 or more.

A compound according to Claim 1 wherein

R represents methyl, ethyl, n-propyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, fluoromethyl, fiuorochloromethyl, fluorobromomethyl, fluorodichloromethyl, fluorodibromomethyl, difluoromethyl, difluoro- chloromethyl, difluorobromomethyl, trifluoromethyl, chloromethyl, trichloromethyl, bromomethyl, l-fluoroethyl, 2,2,2-trifluoroethyl, 1,2,2,2-tetrafluoroethyl, perfluoroethyl, 1-chloroethyl, 1,2-dichloro- ethyl, 1-bron oethyl, perfluoropropyl, 1 -fluoro- 1-methylethyl, 1- chloro- 1-methylethyl, 1 -bromo- 1-methylethyl, 1 -(trifluoromethyl)-

2,2,2-trifluoroethyl, benzyl which may be optionally fluoro-substituted or methyl-substituted, or phenyl which may be optionally fluoro- substituted, chloro-substituted or methyl-substituted,

R represents amino, methylamino, ethylamino, formylamino, acetylamino, ethylcarbonylamino, cyclopropylcarbonylamino, fluoromethyl- carbonylamino, trifluoromethylcarbonylamino, 1 -fluoroethylcarbonyl- amino, perfluoroethylcarbonylamino, benzylcarbonylammo which may be optionally chloro-substituted or methyl-substituted, phenylcarbonylamino which may be optionally fluoro-substituted, chloro- substituted, methyl-substituted or methoxy-substituted, acetoacetyl- amino, or dimethylaminomethylideneamino,

R³ or R⁴ each independently represents hydrogen atom, methyl or ethyl,

R⁵ represents fluoro, chloro, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, methylsulfonyl, phenyl which may be optionally fluoro- substituted or methyl-substituted, phenoxy which may be optionally fluoro-substituted or methyl-substituted, nitro or cyano,

m represents an integer of 3-4, wherein the R³ substituents may be identical or different,

n represents an integer of 0-3, and

the R⁵ substituents may be identical or different, in case n represents an integer of 2 or

3.

4. A process for the preparation of the compounds ofthe formula (I)

wherein

R¹ represents C₁.₅ alkyl, C .₇ cycloalkyl, Cι_-4 haloalkyl, benzyl which may be optionally halogen-substituted or C_M alkyl-substituted, or phenyl which may be optionally halogen-substituted or C_M alkyl- substituted,

R represents amino, Cι_-4 alkylamino, formylamino, C alkyl-carbonyl- amino, C_3-6 cycloalkyl-carbonylamino, C_M haloalkyl-carbonylamino, benzylcarbonylamino which may be optionally halogen-substituted or C_M alkyl-substituted, phenylcarbonylamino which may be optionally C_1-4 alkyl-substituted, CM alkoxy-substituted or halogen-substituted, CM alkyl-carbonylacetylamino, or di(C_M alkyl)amino-Cι- alkyl- ideneamino,

R³ or R⁴ each independently represents hydrogen atom or C alkyl,

R⁵ represents halogen, C alkyl, Cι_-4 haloalkyl, CM alkoxy, C_M haloalkoxy, C_M alkylthio, C_M haloalkylthio, Cι_-4 alkylsulfinyl, C alkylsulfonyl, phenyl which may be optionally halogen-substituted or Cι_-4 alkyl-substituted, phenoxy which may be optionally halogen- substituted or Cι_-4 alkyl-substituted, nitro or cyano,

m represents an integer of 1-4,

the R³ substitutents may be identical or different, in case m represents an integer of 2 or more,

n represents an integer of 0-5, and the R⁵ substituents may be identical or different, in case n represents an integer of 2 or more,

charactrized in that

a) in case R² represents amino:

compounds by the formula (II)

R³

(CH), NH NH

CH

HC NH₂ HX (II)

H H

wherein

R³, R⁴, R⁵, m and n have the same definition as aforementioned, and

X represents halogen, preferably chloro or bromo,

are reacted with compounds ofthe formula (III)

wherein

R has the same definition as aforementioned,

R represents C_M alkyl, preferably methyl or ethyl, in the presence of an inert solvent, and if appropriate, in the presence of an acid binding agent,

or

b) in case R² represents formylamino, C alkyl-carbonylamino, C_3-6 cycloalkyl-carbonylamino, C_M haloalkyl-carbonylamino, benzylcarbonylammo which may be optionally halogen-substituted or Cι_-4 alkyl-substituted, or phenylcarbonylamino which may be optionally

C_M alkyl-substituted, C_1-4 alkoxy-substituted or halogen-substituted:

compounds ofthe formula (la)

wherein

R¹, R³, R⁴, R⁵, m and n have the same definitions as aforementioned,

are reacted with compounds ofthe formula (IV)

R⁷CO₂R⁶ (IV)

wherein

R has the same definition as aforementioned, R⁷ represents hydrogen atom, C_M alkyl, C _-6 cycloalkyl, C_M haloalkyl, benzyl which may be optionally halogen-substituted or C_M alkyl-substituted, or phenyl which may be optionally C_M alkyl-substituted, C_1-4 alkoxy-substituted or halogen- substituted,

in the presence of an inert solvent, and if appropriate, in the presence of an acid binding agent, or

c) in case R represents C_M alkyl-carbonylacetylamino:

the compounds of the formula (la) are reacted with compounds of the formula (V)

wherein

R represents C_M alkyl, preferably Cι- alkyl, in the presence of an inert solvent, or

d) in case R² represents di(CM alkyl)-CM alkylideneamino:

the compounds of the formula (la) are reacted with compounds of the formula (VI)

I (VI)

(R⁹)₂N- C(OR⁶)₂

wherein

R⁶ has the same definition as aforementioned,

R⁹ represents Cι_-4 alkyl, preferably C].₃ alkyl and

R¹ represents a hydrogen atom or Cι_-3 alkyl, preferably hydrogen atom, methyl or ethyl,

in the presence of an inert solvent, and if appropriate, in the presence o f an acid catalyst, or

e) in case R² represents C_M alkylamino:

compounds ofthe formula (VII)

wherein R¹, R³, R⁴, R⁵, m and n have the same definitions as aforementioned, and

R¹¹ represents Cι_-4 alkylidene, preferably Cι_-3 alkylidene,

are reduced in the presence of an inert solvent, and in the presence of catalyst.

5. A herbicidal composition, characterized in that they contain at least one compound ofthe formula (I) according to claim 1.

6. A process for combating weeds, characterized in that a compound of the formula (I) according to claim 1 is allowed to act on weeds and/or their habitat.

7. Use of a compound of the formula (I) according to claim 1 for combating weeds.

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

9. A compound ofthe general formula (II)

R³

wherein

R , R⁴, R^D, m and n have the same definitions as described in Claim 1, and

X represents halogen.