JP2001151612A - Herbicidal 1,3,5-triazines - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a triazine compound exhibiting high activity as an active ingredient for herbicides. SOLUTION: This triazine compound is shown by the formula (wherein, R1 is a haloalkyl or the like; R2 is amino, an alkylcarbonylamino or the like; R3 and R4 are each H or an alkyl; R5 is a halogen, alkyl, alkoxy or the like; m is an integer of 1-4; and n is an integer of 0-5).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to novel triazines and their use as herbicides. The present invention further relates to a method for producing the herbicidal triazine.

[0002]

It is already known that certain triazines act as herbicides (WO 97/3).
1904, WO 97/08156, WO 97/290
95 etc.).

[0003]

However, known triazine derivatives are generally not sufficiently satisfactory in terms of their effect as herbicides and safety.

[0004]

Means for Solving the Problems The present inventors have conducted research to create a novel compound having higher efficacy as a herbicide and higher safety. As a result,
Novel triazines represented by the following formula (I) having excellent biological activity have been found.

[0005]

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Where R¹Is C_1-5Alkyl, C_3-7Cyclo
Alkyl, C_1-4Haloalkyl, optionally halogen
Exchange or C_1-4Benzi optionally substituted with alkyl
Or optionally halogen-substituted or C_1-4Archi
R represents phenyl which may be substituted;^TwoIs Ami
No, C_1-4Alkylamino, formylamino, C_1-4Al
Kill-carbonylamino, C_3-6Cycloalkyl-carbo
Nilamino, C_1-4Haloalkyl-carbonylamino, field
Halogen substitution or C_1-4Alkyl substituted
Optionally benzylcarbonylamino, optionally C
_1-4Alkyl substitution, C_1-4Alkoxy substituted or halogenated
Optionally substituted phenylcarbonylamino, C
_1-4Alkyl-carbonylacetylamino or di (C
_1-4Alkyl) amino-C_{1- Four}Shows alkylideneamino
Then R^ThreeOr R^FourIs independently a hydrogen atom or C_1-4A
Denote R, and R^FiveIs halogen, C_1-4Alkyl, C_1-4
Haloalkyl, C_1-4Alkoxy, C_{1- Four}Haloalkoki
Si, C_1-4Alkylthio, C_1-4Haloalkylthio, C
_1-4Alkylsulfinyl, C_1-4Alkylsulfonyl,
Halogen substitution or C_{1 -Four}Alkyl substituted
Optionally substituted phenyl, optionally halogen substituted
Kuha C _1-4Phenoxy optionally substituted with alkyl,
Represents nitro or cyano, m represents an integer of 1 to 4,
Is an integer of 2 or more,^ThreeAre the same or different
N represents an integer of 0 to 5, and n represents
When indicating an integer of 2 or more, R^FiveAre the same or different
May be.

The compound of the above formula (I) of the present invention can be synthesized, for example, by any of the following production methods (a) to (e). Production method (a) When R ² represents amino: Formula

[0008]

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In the formula, R ³ , R ⁴ , R ⁵ , m and n are as defined above, and X represents a halogen, preferably chloro or bromo, and a compound represented by the formula R ¹ CO ₂ R ⁶ (III) wherein R ¹ is as defined above, R ⁶ is C _1-4 alkyl,
A method of reacting with a carboxylic acid ester represented by the following, which preferably represents methyl or ethyl. Production Method (b) R ² is formylamino, C _1-4 alkyl-carbonylamino, C _3-6 cycloalkyl-carbonylamino, C _1-4 haloalkyl-carbonylamino, optionally substituted with halogen or C _1-4 alkyl. Benzylcarbonylamino, or optionally phenylcarbonylamino, optionally C _1-4 alkyl-substituted, C _1-4 alkoxy-substituted or halogen-substituted:

[0010]

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[0011] In the formula, in ^{R 1, R 3, R 4} , R 5, m and n are defined as above, a compound represented by the formula _{^{R 7 CO 2 R 6 (IV}} ) Equation, R ⁶ is As defined above, R ⁷ is a hydrogen atom, C _1-4
Alkyl, C _3-6 cycloalkyl, C _1-4 haloalkyl,
If the case halogen-substituted or C _1-4 alkyl optionally substituted benzyl or an C _1-4 alkyl-substituted, C _1-4 phenyl which is alkoxy-substituted or halogen-substituted with, in represented carboxylic A method of reacting with an acid ester. Production method (c) When R ² represents C _1-4 alkyl-carbonylacetylamino: The compound of the above formula (Ia) is

[0012]

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Wherein R ⁸ is C _1-4 alkyl, preferably C
A method of reacting with a compound represented by _1-3 alkyl. Process (d) When R ² represents di (C _1-4 alkyl) -C _1-4 alkylideneamino: The compound of the above formula (Ia) is converted to a compound of the formula (Ia)

[0014]

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In the formula, R ⁶ is as defined above, and R ⁹ is C
A method of reacting with a compound represented by _1-4 alkyl, preferably C _1-3 alkyl, and R ¹⁰ represents a hydrogen atom or C _1-3 alkyl, preferably a hydrogen atom, methyl or ethyl. Production method (e) When R ² represents C _1-4 alkylamino: Formula

[0016]

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In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , m and n are as defined above, and R ¹¹ represents C _1-4 alkylidene, preferably C _1-3 alkylidene. A compound to be subjected to a reduction reaction.

The triazines of the formula (I) provided by the present invention exhibit a stronger herbicidal action than the compounds described in the above-mentioned prior art documents.

In the present specification, "halogen" represents fluoro, chloro, bromo or iodo, preferably fluoro, chloro or bromo.

“Alkyl” can be straight-chain or branched and can represent, for example, C _1-4 alkyl, specifically methyl, ethyl, n- or iso.
-Propyl, n-, iso-, sec- or ter
T-butyl and the like can be exemplified.

Examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

[0022] "Haloalkyl" is a straight-chain or branched alkyl halogen substituted, for example, illustrate one to nine fluorine, chlorine and / or alkyl C _1-4 which is substituted by bromine And specifically,
Fluoromethyl, fluorochloromethyl, fluorobromomethyl, fluorodichloromethyl, fluorodibromomethyl, difluoromethyl, difluorochloromethyl,
Difluorobromomethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, 1-fluoroethyl, 2-fluoroethyl, 2,
2,2-trifluoroethyl, 1,2,2,2-tetrafluoroethyl, perfluoroethyl, 1-chloroethyl, 1,2-dichloroethyl, 1-bromoethyl, perfluoropropyl, 1-fluoro-1-methyl ethyl,
1-chloro-1-methylethyl, 1-bromo-1-methylethyl, 1- (trifluoromethyl) -2,2,2-
Trifluoroethyl, 2-chloro-1,1,2-trifluoroethyl, 3-fluoropropyl, 3-chloropropyl, 2,2,3,3,3-pentafluoropropyl,
1,2,2,3,3,3-hexafluoropropyl, perfluorobutyl and the like.

"Alkoxy" is alkyl-O- in which the alkyl moiety has the above-mentioned meaning, and can be, for example, C _1-4 alkoxy, specifically methoxy, ethoxy, n- or iso-. Propoxy, n-, is
o-, sec- or tert-butoxy can be exemplified.

"Alkylthio" is alkyl-S- having an alkyl moiety having the above-mentioned meaning, and may be, for example, C _1-4 alkylthio, and specifically, methylthio, ethylthio, n- or iso-. Propylthio,
Examples thereof include n-, iso-, sec- or tert-butylthio.

"Alkylsulfinyl" is alkyl-SO- in which the alkyl moiety has the above-mentioned meaning, and can be, for example, C _1-4 alkylsulfinyl,
Specifically, methylsulfinyl, ethylsulfinyl, n- or iso-propylsulfinyl, n
-, Iso-, sec- or tert-butylsulfinyl and the like.

"Alkylsulfonyl" has an alkyl moiety
Alkyl-SO having the above meaning _Two-And
If C_1-4Alkylsulfonyl can be represented by
Physically, methylsulfonyl, ethylsulfonyl, n-
Or iso-propylsulfonyl, n-, iso
-, Sec- or tert-butylsulfonyl, etc.
Examples can be given.

"Alkylamino" is alkyl-NH- where the alkyl moiety has the meaning described above, for example, C
_1-4 alkylamino can be shown, specifically,
Methylamino, ethylamino, n- or iso-propylamino, n-, iso-, sec- or te
rt-butylamino and the like can be exemplified.

"Alkyl-carbonylamino" is alkyl-CONH- having an alkyl moiety having the above-mentioned meaning. For example, it can represent C _2-5 alkyl-carbonylamino in total. Examples thereof include carbonylamino, ethylcarbonylamino, n- or iso-propylcarbonylamino, n-, iso-, sec- or tert-butylcarbonylamino and the like.

"Cycloalkyl-carbonylamino" is cycloalkyl-CONH- in which the cycloalkyl moiety has the above-mentioned meaning. For example, it can represent a C _4-7 cycloalkyl-carbonylamino in total. Includes cyclopropylcarbonylamino, cyclobutylcarbonylamino, cyclopentylcarbonylamino,
Cyclohexylcarbonylamino and the like can be exemplified.

"Haloalkyl-carbonylamino" refers to haloalkyl-C wherein the haloalkyl moiety has the meaning described above.
ONH-, for example, a total of C _2-5 haloalkyl-
Can be carbonylamino, specifically, fluoromethylcarbonylamino, difluoromethylcarbonylamino, difluorochloromethylcarbonylamino, difluorobromomethylcarbonylamino, trifluoromethylcarbonylamino, 1-fluoroethylcarbonylamino, Fluoromethylcarbonylamino, 2,2,2-trifluoroethylcarbonylamino, 1,2,2,2-tetrafluoroethylcarbonylamino, perfluoroethylcarbonylamino, perfluoropropylcarbonylamino, perfluorobutylcarbonylamino, etc. Can be illustrated.

The halogen moiety in “benzyl optionally substituted with halogen or alkyl” and “benzylcarbonylamino optionally substituted with halogen or alkyl” have the same meaning as the above “halogen”. And the alkyl moiety has the same meaning as “alkyl” above. Thus, specific examples of "benzyl optionally substituted with halogen or alkyl" include benzyl, 2- (3- and 4-) fluorobenzyl, 2- (3
-And 4-) chlorobenzyl, 2- (3- and 4-) methylbenzyl, 2,3- (2,4-, 2,5-, 2,6
-, 3,4-, 3,5-) difluorobenzyl and the like. Specific examples of "benzylcarbonylamino optionally substituted with halogen or alkyl" may be benzylcarbonylamino. 2-, 3- or 4-fluorobenzylcarbonylamino, 2-, 3- or 4-chlorobenzylcarbonylamino, 2-, 3- or 4-methylbenzylcarbonylamino, 2,3-, 2,4-, 2,5-,
2,6-, 3,4- or 3,5-difluorobenzylcarbonylamino and the like can be exemplified.

The halogen moiety in “phenyl optionally substituted with halogen or alkyl” has the same meaning as the above “halogen”, and the alkyl moiety has the same meaning as the above “alkyl”. Have. Thus, specific examples of "phenyl optionally substituted with halogen or alkyl" include 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, 2,
3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenyl and the like can be exemplified.

In "phenylcarbonylamino optionally substituted with alkyl, alkoxy or halogen", the alkyl moiety has the same meaning as the above "alkyl", and the alkoxy moiety has the same meaning as the above "alkoxy". It has the same meaning, and the halogen moiety has the same meaning as the above “halogen”. Thus, specific examples of "optionally alkyl-substituted, alkoxy-substituted or halogen-substituted phenylcarbonylamino" include phenylcarbonylamino,
2-, 3- or 4-fluorophenylcarbonylamino, 2-, 3- or 4-chlorophenylcarbonylamino, 2-, 3- or 4-methylphenylcarbonylamino, 2-, 3- or 4-methoxyphenylcarbonylamino , 2,3-, 2,4-, 2,5-,
2,6-, 3,4- or 3,5-difluorophenylcarbonylamino, 2,3-, 2,4-, 2,5-,
2,6-, 3,4- or 3,5-dichlorophenylcarbonylamino, 2,3-, 2,4-, 2,5-,
2,6-, 3,4- or 3,5-dimethylphenylcarbonylamino and the like can be exemplified. The alkyl moiety in “alkylcarbonylacetylamino” has the same meaning as the above “alkyl”, and specific examples of “alkylcarbonylacetylamino” include acetoacetylamino, propionylacetylamino, butyrylacetylamino, isobutyiamino Rylacetylamino, valerylacetylamino, isovalerylacetylamino, pivaloylacetylamino and the like can be exemplified.

"Dialkylaminoalkylideneamino"
Has the same meaning as the above-mentioned `` alkyl '', and the above-mentioned alkylidene portion can be linear or branched, and can represent, for example, a C _1-4 alkylidene. . Thus, examples of “dialkylaminoalkylideneamino” include dimethylaminomethylideneamino, 1- (dimethylamino) ethylideneamino, 1- (dimethylamino) (n-propylidene) amino, 1- (dimethylamino) (n -Butylidene) amino, 1- (dimethylamino) (iso-butylidene) amino, diethylaminomethylideneamino, di (n-propyl) aminomethylideneamino, di (n-butyl) aminomethylideneamino, (N-methyl- Examples thereof include (N-ethylamino) methylideneamino and (N-methyl-N- (n-propyl) amino) methylideneamino.

A preferred group of compounds according to the invention is that in formula (I), R ¹ is C _1-4 alkyl, C _3-5 cycloalkyl, C _1-3 haloalkyl, optionally fluoro-substituted, chloro-substituted or C _1-3 alkyl optionally substituted benzyl, or optionally fluoro substituted showed phenyl which is chloro substituted or C _1-3 alkyl substituted, R ² is amino, C _1-3 alkylamino, formyl Amino, C _1-3 alkyl-carbonylamino, C _3-5
Cycloalkyl-carbonylamino, C _1-3 haloalkyl
- carbonylamino, optionally fluoro substituted, chloro-substituted or C _1-3 alkyl substituents on these benzylcarbonyl amino optionally, optionally C _1-3 alkyl-substituted, C _1-3 alkoxy-substituted, are fluoro substituted or chloro-substituted Phenylcarbonylamino, C
_1-3 alkyl-carbonylacetylamino or di (C
_1-3 alkyl) amino-C _1-3 alkylideneamino, R ³ or R ⁴ each independently represent a hydrogen atom or C _1-3 alkyl, and R ⁵ represents fluoro, chloro, bromo, methyl, ethyl, n -Propyl, iso-propyl, ter
t-butyl, C _1-3 haloalkyl, C _1-3 alkoxy, C
_1-3 haloalkoxy, C _1-3 alkylthio, C _1-3 haloalkylthio, C _1-3 alkylsulfinyl, C _1-3 alkylsulfonyl, optionally substituted with fluoro, chloro or C _1-3 alkyl Good phenyl,
Optionally represents phenoxy, nitro or cyano which may be substituted by fluoro, chloro or C _1-3 alkyl, wherein m is an integer of 2 to 4, wherein R ³ may be the same or different , N represents an integer of 0 to 4, and when n represents an integer of 2 or more, compounds wherein R ⁵ may be the same or different.

Further, as a further preferred group of compounds, in the compounds of the above formula (I), R ¹ is methyl, ethyl, n-propyl, iso-propyl, tert-butyl, cyclopropyl, cyclobutyl, fluoromethyl, fluoromethyl, Chloromethyl, fluorobromomethyl, fluorodichloromethyl, fluorodibromomethyl, difluoromethyl, difluorochloromethyl, difluorobromomethyl, trifluoromethyl, chloromethyl, trichloromethyl, bromomethyl, 1-fluoroethyl,
2,2,2-trifluoroethyl, 1,2,2,2-tetrafluoroethyl, perfluoroethyl, 1-chloroethyl, 1,2-dichloroethyl, 1-bromoethyl,
Perfluoropropyl, 1-fluoro-1-methylethyl, 1-chloro-1-methylethyl, 1-bromo-1-
Methylethyl, 1- (trifluoromethyl) -2,2,
2-trifluoroethyl, benzyl optionally substituted with fluoro or methyl, or phenyl optionally substituted with fluoro, chloro or methyl, wherein R ² is amino, methylamino, ethylamino , Formylamino, acetylamino, ethylcarbonylamino, cyclopropylcarbonylamino, fluoromethylcarbonylamino, trifluoromethylcarbonylamino, 1-fluoroethylcarbonylamino, perfluoroethylcarbonylamino,
Benzylcarbonylamino optionally chloro-substituted or methyl-substituted; phenylcarbonylamino optionally fluor-substituted, chloro-substituted, methyl-substituted or methoxy-substituted, acetoacetylamino, or dimethylaminomethylideneamino , R ³ or R ⁴ each independently represent a hydrogen atom, methyl or ethyl, and R ⁵ represents fluoro, chloro, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl Represents methylsulfonyl, phenyl optionally substituted with fluoro or methyl, phenoxy optionally substituted with fluoro or methyl, nitro or cyano,
m represents an integer of 3 to 4, wherein R ³ may be the same or different, and when n represents an integer of 0 to 3 and n represents an integer of 2 or 3, R ⁵ is the same Alternatively, compounds which may be different from each other are mentioned.

In the production method (a), as a raw material, for example,
When using 2-benzylcyclopentylbiguanide hydrochloride and methyl α-fluoro-α-methylpropionate, it is represented by the following reaction formula.

[0038]

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In the production method (b), for example,
2-amino-4- (2'-benzylcyclopentylamino) -6- (α-fluoroisopropyl) -1,3,5
When using triazine and ethyl acetate, it is represented by the following reaction formula.

[0040]

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In the production method (c), as a raw material, for example,
2-amino-4- (2'-benzylcyclopentylamino) -6- (α-fluoroisopropyl) -1,3,5
-When using triazine and acetylmerdrum acid,
It is represented by the following reaction formula.

[0042]

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In the production method (d), as a raw material, for example,
2-amino-4- (2 '-(2-fluorobenzyl) cyclopentylamino) -6- (α-fluoroethyl)-
When 1,3,5-triazine and N, N-dimethylformamide dimethyl acetal are used, they are represented by the following reaction formula.

[0044]

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In the production method (e), as a raw material, for example,
2-ethylideneamino-4- (2'-benzylcyclopentylamino) -6- (α-fluoroisopropyl)-
When 1,3,5-triazine is used, it is represented by the following reaction formula.

[0046]

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In the above production method (a), the compound of the formula (II) as a raw material is a novel compound which has not been described in the conventional literature and is described in, for example, JP-A-1-246279 and JP-A-63-264465. Gazette, JP-A-63-22216
No. 6, JP-A-63-146876, JP-A-63-146876
Methods described in JP-A-3-51379, for example,

[0048]

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In the formula, R ³ , R ⁴ , R ⁵ , m and n have the same meanings as described above, and X represents a halogen. A compound represented by the formula: is substituted with cyanoguanidine and a suitable diluent, for example, n- It can be produced by reacting in decane.

The compound of the above formula (VIII) includes the following compounds including some novel compounds:

[0051]

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Wherein R ³ , R ⁴ , R ⁵ , m and n have the same meanings as defined above, and can be produced by reacting the compound with an appropriate hydrohalic acid such as hydrochloric acid. it can.

The compound of the above formula (IX) is a novel compound, a part of which is not described in the conventional literature.
nic Reaction, Vol.5, p.301 (1962), John Wiley &
The method described in Sons, INC., Ie, the formula

[0054]

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In the formula, R ³ , R ⁴ , R ⁵ , m and n have the same meanings as defined above, and can be produced by subjecting the compound to Leuckart reaction using formamide and formic acid.

The compound of the above formula (X) is a novel compound, a part of which is not described in the conventional literature, and includes, for example, a generally known decarboxylation reaction of β-ketoester.
That is, the expression

[0057]

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Wherein R ³ , R ⁴ , R ⁵ , m and n are as defined above, and R ⁶ represents C _1-4 alkyl. It can be easily produced using hydrobromic acid.

The compound of the formula (XI) is a novel compound, a part of which is not described in the conventional literature. For example, the method described in "Precise Organic Synthesis", Nankodo, p. 160, 1983, ,formula

[0060]

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In the formula, R ³ and m are as defined above, and R ⁶
_{Represents a} C _1-4 alkyl, a compound represented by the formula

[0062]

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In the formula, R ⁴ , R ⁵ and n have the same meanings as described above, and X ¹ represents a halogen, and a suitable condensing agent such as an aqueous sodium hydroxide solution.
It can be easily obtained by reacting in a suitable diluent, for example, dichloromethane, in the presence of a phase transfer catalyst, for example, tetrabutylammonium hydrogen sulfate.

The compounds of the above formula (XII) are partially new compounds which have not been described in conventional literatures.
ganic Reaction, Vol.15, p.1 (1967), John Wiley & S
ons, INC. Can be easily produced.

The compound of the above formula (XIII) is a known compound and is described, for example, in "New Experimental Chemistry Course", edited by The Chemical Society of Japan, vol. 14, (I), p. 331, published in 1962, Maruzen. It can be easily manufactured by any method.

Representative examples of the compound of the formula (II) used as a raw material in the above production method (a) include the following.

2-benzylcyclopentyl biguanide hydrochloride, 2- (2'-fluorobenzyl) cyclopentyl biguanide hydrochloride, 2- (3'-fluorobenzyl) cyclopentyl biguanide hydrochloride, 2- (3'-methylbenzyl) cyclopentyl biguanide Hydrochloride, 2-benzylcyclohexylbiguanide hydrochloride, 2- (2'-fluorobenzyl) cyclohexylbiguanide hydrochloride, 2-
(3'-fluorobenzyl) cyclohexylbiguanide hydrochloride, 2- (3'-methylbenzyl) cyclohexylbiguanide hydrochloride and the like.

The compound of the formula (III) is a known compound, and a commercially available product may be used or EP-A-8509
It can also be easily produced by the method described in No. 11.

Representative examples of the compound of the formula (III) used as a raw material in the above production method (a) include the following.

Ethyl fluoroacetate, ethyl fluorochloroacetate, ethyl fluorobromoacetate, ethyl difluorochloroacetate, ethyl dibromofluoroacetate, ethyl trifluoroacetate, methyl pentafluoropropionate, α-fluoropropionic acid Ethyl ester, α-fluoro-α-methylpropionic acid ethyl ester, ethyl acetate, propionic acid ethyl ester, n-butyric acid ethyl ester, isobutyric acid ethyl ester, cyclopropanecarboxylic acid ethyl ester, cyclopentanecarboxylic acid ethyl ester, cyclohexane Carboxylic acid ethyl ester and the like.

In the above processes (b) to (d), the compound of the formula (Ia) as a raw material is a part of the compound of the formula (I) of the present invention and is easily produced by the above process (a). be able to.

In the above production method (b), the compound of the formula (IV) means a compound based on the definition of R ⁶ , wherein R ⁷ is a hydrogen atom, C _1-4 alkyl, C _3-6 cycloalkyl, C
_1-4 show haloalkyl, halogen-substituted or C _1-4 alkyl optionally substituted benzyl, or C _1-4 alkyl substituted, phenyl which may C _1-4 is alkoxy-substituted or halogen-substituted. Preferably, it means based on the preferable definition of the above R ⁶ , wherein R ⁷ is a hydrogen atom,
C _1-3 alkyl, C _3-5 cycloalkyl, C _1-3 haloalkyl, fluor-substituted, chloro-substituted or C _1-3 alkyl-substituted benzyl, or C _1-3 alkyl-substituted, C _1-3 The phenyl which may be substituted with alkoxy, fluoro, or chloro is shown.

The compound of the formula (IV) is a known compound, and may be used as a commercial product, or for example, as described in EP-A-
The compound can also be easily synthesized by the method described in 850911.

Representative examples of the compound of the formula (Ia) used as a raw material in the above production methods (b) to (d) include the following compounds included in the formula (I).

2-amino-4- (2'-benzylcyclopentylamino) -6- (α-fluoroisopropyl)
-1,3,5-triazine, 2-amino-4- (2'-
(Benzylcyclopentylamino) -6- (α-fluoroethyl) -1,3,5-triazine, 2-amino-4-
(2 ′-(2-fluorobenzyl) cyclopentylamino) -6- (α-fluoroisopropyl) -1,3,5
-Triazine, 2-amino-4- (2 '-(2-fluorobenzyl) cyclopentylamino) -6- (α-fluoroethyl) -1,3,5-triazine, 2-amino-
4- (2 '-(2-fluorobenzyl) cyclopentylamino) -6- (trifluoromethyl) -1,3,5-
Triazine, 2-amino-4- (2 ′-(3-fluorobenzyl) cyclopentylamino) -6- (α-fluoroisopropyl) -1,3,5-triazine, 2-amino-4- (2 ′-( 3-fluorobenzyl) cyclopentylamino) -6- (α-fluoroethyl) -1,3,3
5-triazine, 2-amino-4- (2 '-(3-fluorobenzyl) cyclopentylamino) -6- (trifluoromethyl) -1,3,5-triazine, 2-amino-4- (2'- (3-methylbenzyl) cyclopentylamino) -6- (α-fluoroisopropyl) -1,
3,5-triazine, 2-amino-4- (2 '-(3-
Methylbenzyl) cyclopentylamino) -6- (α-
Fluoroethyl) -1,3,5-triazine, 2-amino-4- (2 ′-(3-methylbenzyl) cyclopentylamino) -6- (α-fluoroisopropyl) -1,
3,5-triazine, 2-amino-4- (2'-benzylcyclohexylamino) -6- (α-fluoroisopropyl) -1,3,5-triazine, 2-amino-4-
(2′-benzylcyclohexylamino) -6- (α-
Fluoroethyl) -1,3,5-triazine, 2-amino-4- (2 ′-(3-fluorobenzyl) cyclohexylamino) -6- (α-fluoroisopropyl)-
1,3,5-triazine, 2-amino-4- (2'-
(3-fluorobenzyl) cyclohexylamino) -6
-(Α-fluoroethyl) -1,3,5-triazine,
2-amino-4- (2 '-(3-methylbenzyl) cyclohexylamino) -6-isopropyl-1,3,5-
Triazine, 2-amino-4- (2 '-(3-methylbenzyl) cyclohexylamino) -6-ethyl-1,
3,5-triazine and the like.

Typical examples of the compound of the formula (IV) used as a raw material in the above-mentioned production method (b) include the following.

Ethyl acetate, ethyl propionate, ethyl n-butyrate, ethyl isobutyrate, ethyl pivalate, ethyl cyclopropanecarboxylate, ethyl cyclopentanecarboxylate, ethyl cyclohexanecarboxylate, phenylacetic acid Ethyl ester, benzoic acid ethyl ester, 3-methylbenzoic acid ethyl ester, 2-chlorobenzoic acid ethyl ester, trifluoroacetic acid ethyl ester and the like.

In the above production method (c), the compound of the formula (V) as a raw material is a known compound, for example, Ch
em. Pharm. Bull. (1987), 35
(5) It can be easily manufactured by the method described in 1860-1870.

Representative examples of the compound of the formula (V) used as a raw material in the above production method (c) include the following.

5-acetyl-2,2-dimethyl-1,3
-Dioxane-4,6-dione, 5-propionyl-
2,2-dimethyl-1,3-dioxane-4,6-dione, 5-butyryl-2,2-dimethyl-1,3-dioxane-4,6-dione, 5-isobutyryl-2,2-dimethyl- 1,3-dioxane-4,6-dione, 5-cyclopropylcarbonyl-2,2-dimethyl-1,3-
Dioxane-4,6-dione, 5-cyclohexylcarbonyl-2,2-dimethyl-1,3-dioxane-4,
6-dione, 5- (2-fluorobenzoyl) -2,2
-Dimethyl-1,3-dioxane-4,6-dione and the like.

In the above production method (d), the compound of the formula (VI) as a raw material is a known compound and can be easily produced, for example, by the method described in JP-A-8-277251.

Typical examples of the compound of the formula (VI) used as a raw material in the above production method (d) include the following.

N, N-dimethylformamide dimethyl acetal, N, N-diethylformamide dimethyl acetal, N, N-dipropylformamide dimethyl acetal, N-methyl-N-ethylformamide dimethyl acetal, N-methyl-N-propylformamide Dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-diethylformamide diethyl acetal, N, N-dimethylacetamidodimethylacetal, N, N-diethylacetamidodimethylacetal and the like.

In the above production method (e), the compound of the formula (VII) as a raw material is a novel compound which has not been described in the conventional literature, and is, for example, a method described in JP-A-63-51379. The compound of the formula (Ia) can be produced by reacting with a C _1-4 aliphatic aldehyde or aliphatic ketone represented by the formula O ケ ト ン R ¹¹ (XIV).

The compound of the formula (XIV) is a known compound, and a commercially available compound can be used.

As typical examples of the compound of the formula (VII) used as a raw material in the above production method (e), the following compounds can be exemplified.

2-methylideneamino-4- (2'-benzylcyclopentylamino) -6- (α-fluoroisopropyl) -1,3,5-triazine, 2-ethylideneamino-4- (2'-benzylcyclopentylamino)
-6- (α-fluoroisopropyl) -1,3,5-triazine, 2-propylideneamino-4- (2′-benzylcyclopentylamino) -6- (α-fluoroisopropyl) -1,3,5- Triazine, 2-isopropylideneamino-4- (2'-benzylcyclopentylamino) -6- (α-fluoroisopropyl) -1,3,3
5-triazine, 2-methylideneamino-4- (2'-
Benzylcyclopentylamino) -6- (α-fluoroethyl) -1,3,5-triazine, 2-ethylideneamino-4- (2′-benzylcyclopentylamino)-
6- (α-fluoroethyl) -1,3,5-triazine, 2-propylideneamino-4- (2′-benzylcyclopentylamino) -6- (α-fluoroethyl)-
1,3,5-triazine, 2-methylideneamino-4-
(2′-benzylcyclohexylamino) -6- (α-
Fluoroisopropyl) -1,3,5-triazine, 2
-Ethylideneamino-4- (2'-benzylcyclohexylamino) -6- (α-fluoroethyl) -1,3,
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) -1,3, 5-triazine, 2-ethylideneamino-4- (2'-benzylcyclopentylamino) -6-isopropyl-1,3,5-triazine and the like.

According to the above production method (b), the compound represented by the formula (IV)
In place of the compound of formula (II), a compound represented by the formula R ¹² -X ¹ (XV), wherein R ¹² represents C _1-4 alkyl and X ¹ represents halogen, can also be used to prepare the above-mentioned production method (e Wherein R ² is C
Compounds of formula (I) of the present invention representing _1-4 alkylamino can be prepared.

The reaction of the above-mentioned production method (a) can be carried out in a suitable diluent. Examples of the diluent used in this case include ethers such as ethyl ether and methyl ethyl ether. Isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like; alcohols such as methanol, ethanol and isopropanol; , Butanol, ethylene glycol and the like; acid amides such as dimethylformamide
(DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA) and the like; sulfones, sulfoxides, such as dimethyl sulfoxide (DMSO ), Sulfolane and the like; bases such as pyridine and the like can be mentioned.

The production method (a) can be carried out in the presence of an acid binder. In this case, the acid binder usable as an inorganic base includes hydrides and hydroxides of alkali metals and alkaline earth metals. , Carbonates, bicarbonates and the like, for example, sodium hydride, lithium hydride, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like; Inorganic alkali metal amides, for example,
Lithium amide, sodium amide, potassium amide and the like; also, as organic bases, alcoholates, tertiary amines, dialkylaminoanilines and pyridines such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, triethylamine,
1,1,4,4-tetramethylethylenediamine (TMEDA), N, N-
Dimethylaniline, N, N-diethylaniline, pyridine,
4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo
[2,2,2] octane (DABCO), 1,8-diazabicyclo [5,4,0]
Undec-7-ene (DBU) and the like.

Process (a) can be carried out within a substantially wide temperature range, but generally from about 0 to about 100
C., preferably between about 20 and about 80.degree. C., is suitable. The reaction is desirably performed under normal pressure, but may be operated under increased or reduced pressure in some cases.

In carrying out the production method (a), for example, 0.8 to 2.2 mol of a compound of the formula (III) in a diluent such as methanol is added to 1 mol of the compound of the formula (II). By reacting in the presence of a few moles of sodium methoxide, the desired compound of formula (I) can be obtained.

In the production method (a), the compound of the formula (IX) is converted from the compound of the formula (IX) via the compound of the formula (VIII).
The reaction for producing the compound of formula (I) can also be carried out continuously.

The reaction of the above production method (b) can be carried out in a suitable diluent. Examples of the diluent used in this case include water; aliphatic, alicyclic and aromatic hydrocarbons. (Optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,
Chlorobenzene, dichlorobenzene and the like; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether ( Ketones such as acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (MIBK);
Nitriles, for example, acetonitrile, propionitrile, acrylonitrile and the like; alcohols, for example, methanol, ethanol, isopropanol, butanol,
Esters such as ethyl acetate and amyl acetate; acid amides such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone and 1,3-dimethyl-2-imidazo; Lydinone, hexamethylphosphoric triamide (HMPA) and the like; sulfones, sulfoxides such as dimethyl sulfoxide (D
MSO), sulfolane and the like; bases such as pyridine and the like.

The production method (b) can be carried out in the presence of a base. In this case, as a base which can be used, hydrides of alkali metals and alkaline earth metals as inorganic bases,
Hydroxide, carbonate, bicarbonate, etc., for example, sodium hydride, lithium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide Calcium and the like; inorganic alkali metal amides, for example, lithium amide, sodium amide, potassium amide and the like; also, as organic bases, alcoholates, tertiary amines,
Dialkylaminoanilines and pyridines, for example,
Triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N, N-dimethylaniline, N, N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP),
1,4-diazabicyclo [2,2,2] octane (DABCO) and 1,8-
Diazabicyclo [5,4,0] undec-7-ene (DBU) and the like; organolithium compounds such as methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium,
Phenyllithium, dimethylkappa-lithium, lithium diisopropylamide, lithium cyclohexylisopropylamide, lithium dicyclohexylamide, n-
Butyllithium / DABCO, n-butyllithium / DBU, n-butyllithium / TMEDA and the like can be mentioned.

Process (b) can be carried out within a substantially wide temperature range, but generally from about 0 to about 150.
C., preferably between about 40 and about 80.degree. C., is suitable. The reaction is desirably performed under normal pressure, but may be operated under increased or reduced pressure in some cases.

In carrying out the production method (b), for example, 2 to 20 mol of the compound of the formula (IV) is added to 1 to 2 mol of sodium methoxide per 1 mol of the compound of the formula (Ia). The target compound of formula (I) can be obtained by reacting under the following conditions.

The reaction of the above process (c) can be carried out in a suitable diluent. Examples of the diluent used in this case include water; aliphatic, alicyclic and aromatic hydrocarbons. (Optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,
Chlorobenzene, dichlorobenzene and the like; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether ( Ketones such as acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (MIBK);
Nitriles, for example, acetonitrile, propionitrile, acrylonitrile and the like; alcohols, for example, methanol, ethanol, isopropanol, butanol,
Esters such as ethyl acetate and amyl acetate; acid amides such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone and 1,3-dimethyl-2-imidazo; Lydinone, hexamethylphosphoric triamide (HMPA) and the like; sulfones, sulfoxides such as dimethyl sulfoxide (D
MSO), sulfolane and the like; bases such as pyridine and the like.

Process (c) can be carried out within a substantially wide temperature range, but generally from about 20 to about 18
Temperatures of 0 ° C, preferably between about 60 and about 120 ° C, are suitable. The reaction is desirably performed under normal pressure, but may be operated under increased or reduced pressure in some cases.

In carrying out the production method (c), for example, the compound 1 of the formula (Ia) is dissolved in a diluent such as benzene.
The target compound of formula (I) can be obtained by reacting the compound of formula (V) in an amount of 1 to 2 moles per mole.

The reaction of the above production method (d) can be carried out in a suitable diluent, and examples of the diluent used in this case include water; aliphatic, alicyclic and aromatic hydrocarbons. (Optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,
Chlorobenzene, dichlorobenzene and the like; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether ( Ketones such as acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (MIBK);
Nitriles, for example, acetonitrile, propionitrile, acrylonitrile and the like; alcohols, for example, methanol, ethanol, isopropanol, butanol,
Esters such as ethyl acetate and amyl acetate; acid amides such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone and 1,3-dimethyl-2-imidazo; Lydinone, hexamethylphosphoric triamide (HMPA) and the like; sulfones, sulfoxides such as dimethyl sulfoxide (D
MSO), sulfolane and the like; bases such as pyridine and the like.

The production method (d) can be carried out in the presence of an acid catalyst. Examples of the acid catalyst which can be used in this case include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid and hydrogen sulfite. Sodium and the like; organic acids such as formic acid, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like; organic amine hydrochlorides such as pyridine hydrochloride, triethylamine hydrochloride and the like; Amine sulfonates, for example, pyridine p-toluenesulfonate, triethylamine p-toluenesulfonate and the like can be mentioned.

Process (d) can be carried out within a substantially wide temperature range, but generally from about 20 to about 18
Temperatures of 0 ° C, preferably between about 60 and about 120 ° C, are suitable. The reaction is desirably performed under normal pressure, but may be operated under increased or reduced pressure in some cases.

In carrying out the production method (d), for example, the compound 1 of the formula (Ia) is dissolved in a diluent such as benzene.
The target compound of formula (I) can be obtained by reacting 2 to 4 moles of the compound of formula (VI) with respect to the mole in the presence of a catalytic amount of p-toluenesulfonic acid.

The reaction of the above production method (e) can be carried out in a suitable diluent. Examples of the diluent used in this case include water; aliphatic, alicyclic and aromatic hydrocarbons. (Optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,
Chlorobenzene, dichlorobenzene and the like; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether ( Ketones such as acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (MIBK);
Nitriles, for example, acetonitrile, propionitrile, acrylonitrile and the like; alcohols, for example, methanol, ethanol, isopropanol, butanol,
Esters such as ethyl acetate and amyl acetate; acid amides such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone and 1,3-dimethyl-2-imidazo; Lydinone, hexamethylphosphoric triamide (HMPA) and the like; sulfones, sulfoxides such as dimethyl sulfoxide (D
MSO), sulfolane and the like; bases such as pyridine and the like.

The production method (e) can be carried out in the presence of a catalyst. Examples of the catalyst which can be used in this case include 10% palladium-carbon.

Process (e) can be carried out within a substantially wide temperature range, but generally from about 0 to about 120.
C., preferably between about 25 and about 80.degree. C., is suitable. The reaction is desirably performed under normal pressure, but may be operated under increased or reduced pressure in some cases.

In carrying out the production method (e), for example, in a diluent such as methanol, 1 to 2 mol of hydrogen gas per 1 mol of the compound of the formula (VII) is added with a catalytic amount of 10% palladium- By reacting in the presence of carbon, the desired compound of formula (I) can be obtained.

The active compounds of the formula (I) according to the invention can be used as herbicides. As used herein, "weed"
Broadly means all plants that grow in undesirable places. The compounds of the present invention act as non-selective or selective herbicides depending on the concentration used. The active compounds of the formula (I) according to the invention can be used, for example, between the following weeds and cultivated plants.

Genus of dicotyledon weeds: mustard (Sinapis), mamegunbinazu (Lepidium), Jaegura kinutasou (Galium), scallop (Stellaria), akaza aritasou (Chenopodium), nettle (Urtica), hangonso novologion (Senecio), Amaran
Thus), Purslane Matsubaboton (Portulaca), Onamomi (Xanthium), Morning Glory (Ipomoea), Willow (Pol)
ygonum), Ragweed (Ambrosia), Nozami (Cirsium), Nogeshi (Sonchus), Eggplant Potato Inuhozuki (Solanum), Inugarashi (Rorippa), Odorikosou (Lamium), Stag Beetle (Ver. onic)
a), Korean morning glory (Datura), Sumirepanji (Vi
ola), Chile maodro (Galeopsis), poppy (Papaver), cornflower (Centaurea), cornflower (Galinsoga),
Rotagal (Rotala), Azena (Lindernia), etc.

A genus of dicotyledonous plants: cotton (Gossypium),
Glycine, soybean and sugar beet (Bet)
a), carrots (Daucus), kidney beans and Aoi imada (P
haseolus), peas (Pisum), eggplant potatoes (Sola)
num), Flax (Linum), Sweet Potato / Asagao (Ipomoe
a), Broad bean Nantenhagi (Vicia), Tobacco (Nicoti)
ana), tomato (Lycopersicon), peanut (Arachi
s), Brassica cabbage cabbage cabbage (Brassic
a), Akinonogeshi (Lactuca), Cucumber melon (Cucu
mis), pumpkin (Cucurbita) etc.

Genus of monocotyledon weeds: Echinochloa, Echinokoro millet (Setaria), millet (Panicum), Meishishiba (Digitaria), ashagaeri timoshi- (Phleum), strawberry jumping tree Po Po, and Oshigonegusa toboshigara (Festuca), Eleusin
e), Lolium, Bromumu inumu (Bromu
s), oats oats (oats) (Avena), cyperaceae papyrus situitui hamasuge (Cyperu
s), Sorghum, Agropyron, Monochoria, Tenbuki (Fimbristylis), Omodaka Kwai (Sagittaria), Harii Krogwi (Eleocha)
ris), fireflies, squirrels (Scirpus), sparrows (Paspalum), platypus (Ischaemum), nukabo (Agrostis), Alpinecurus (Alopecurus), and Cynodon.

Genera of monocotyledon cultivation plants: rice (Oryza), maize hops cone (Zea), wheat (Triticum), barley (Hordeum), oats oats (oat) (Avena), rye (Secale) , Sorghum (Sorghum),
Millet (Panicum), Sugarcane Vaseobana (Saccharu)
m), pineapple (Ananas), asparagus (Asparagu)
s), leek and leek (Allium).

The use of the compound of the present invention is not limited to the above-mentioned plants, and can be similarly applied to other plants. Further, depending on the concentration used, the active compound of the present invention can control weeds non-selectively.For example, it can be used in industrial land such as factories, railway tracks, roads, tree plantations, and non-tree plantations. it can.

Furthermore, the active compounds according to the invention can be used for weed control in perennial plant cultivation,
For example, afforestation, ornamental afforestation, orchard, vineyard, citrus orchard, nut orchard, banana plantation, coffee plantation, tea plantation, rubber plantation, vineyard oil palm plantation,
The present invention can be applied to cocoa cultivation sites, small orchards, hop cultivation sites, and the like, and can also be applied to selective weed control in annual plant cultivation.

The active compounds of the formula (I) according to the invention can be brought into the customary pharmaceutical forms for use. Such forms include, for example, liquids (emulsions, etc.), wettable powders, emulsions, suspensions, powders, hydrated granules, tablets, granules, suspension emulsion concentrates, microcapsules in polymer substances, Jumbo agents and the like can be mentioned.

These preparations can be prepared in a manner known per se, for example, by bringing into association the active compound with a developing agent, ie, a liquid and / or solid diluent or carrier, optionally a surfactant, ie, a surfactant. , Emulsifier and / or dispersant and / or
Alternatively, it can be prepared by mixing with a foam forming agent.

As the liquid diluent or carrier, for example,
Aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [ For example,
Paraffins (eg, mineral oil fractions) such as cyclohexane], and alcohols (eg, butanol, glyco-
And ethers and esters thereof, ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strong polar solvents (eg, dimethylformamide, dimethyl sulfoxide, etc.), water and the like. it can. When water is used as the developing agent, for example, an organic solvent can be used as an auxiliary solvent.

As the solid diluent or carrier, for example,
Ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapull guide, montmorillonite or diatomaceous earth, etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicate, etc.) and the like can be mentioned. it can. Solid carriers for granules include crushed and fractionated rocks (e.g., calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules of inorganic and organic powders, and organic materials (e.g., sawdust, Coconuts include corn cobs and tobacco stems).

Examples of the emulsifier and / or foaming agent include nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (for example, alkyl arylpolyglycol ether).
Ter, alkyl sulfonate, alkyl sulfate, ant
Sulfonate)] and albumin hydrolysis products.

The dispersants include, for example, lignin sulfite waste liquor, methylcellulose and the like.

Fixatives are also used in preparations (powder, granules, jumbo,
Emulsions). Examples of the fixing agent include carboxymethyl cellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol and polyvinyl acetate, etc.). it can.

Coloring agents can also be used, such as inorganic pigments (eg, iron oxide, titanium oxide and Prussian blue), organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and And trace elements such as salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The preparation generally contains the active ingredient in an amount of 0.1%.
%, Preferably in the range of 0.5 to 90% by weight.

The active compounds of the formula (I) according to the invention can be used on their own or in the form of preparations for controlling weeds and also as admixtures with known herbicides. be able to. Such admixtures may be prepared in advance into the final formulation, or they may be tank-mixed for use. Examples of possible combinations as a mixture include a sulfonylurea-based herbicide for paddy fields.

The active compounds of the formula (I) of the present invention also include
Mixtures with safeners are also possible, which allows for a wider application as a selective herbicide.
As a safener for that purpose, for example, 1- (α, α
-Dimethylbenzyl) -3-p-tolylurea.

Surprisingly, some admixtures of the compounds of the invention also exhibit a synergistic effect.

When the active compounds of the formula (I) of the present invention are used, they can be used directly as they are, in the form of the above-mentioned preparations, or in further diluted preparations. For example, waterinjection
g), spraying, atomizing, dusting or granulation can be applied.

The active compounds of the formula (I) according to the invention can be applied both before and after germination of the plants. They can also be incorporated into the soil before sowing.

The application rate of the active compound of the present invention is not strictly limited, and can be varied over a wide range depending on the desired effect, the type of the target plant, the place of application, the time of application, and the like. , When used as a herbicide,
The concentration of the active compound is, for example, in the range of about 0.001 to about 5 kg, preferably about 0.05 to about 2 kg, as an active compound per hectare.

Next, the production and use of the compound of the present invention will be more specifically illustrated by the following examples, but the present invention should not be limited to these. “Parts” are “parts by weight” unless otherwise specified.

[0132]

EXAMPLES Synthesis Example 1

[0133]

Embedded image

2-Benzylcyclopentylamine (3 g) was slowly added dropwise to concentrated hydrochloric acid (3.6 ml) under ice-cooling.
After stirring for 30 minutes as it was, water was distilled off under reduced pressure to obtain 2-benzylcyclopentylamine hydrochloride (3.1 g).

The above 2-benzylcyclopentylamine hydrochloride (3.1 g) and cyanoguanidine (1.23)
g) was suspended in n-decane (30 ml) and heated at 130 ° C. for 4.5 hours. After cooling, the precipitated crystals were collected by filtration, and n
After washing with -hexane and drying under reduced pressure, 2-benzylcyclopentylbiguanide hydrochloride (3 g) was obtained.

To 12 ml of dry methanol was added sodium (0.31 g), and the mixture was stirred for 5 minutes. Then, the above-mentioned 2-benzylcyclopentylbiguanide hydrochloride (2 g) was added, and the mixture was stirred at room temperature for 30 minutes. Next, methyl α-fluoro-α-methylpropionate (1.62 g) was added and the mixture was added at room temperature for 1 hour.
After stirring for 0 hour, 50 ml of water was added, and the mixture was extracted with ethyl acetate. After drying over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (elution solvent: hexane: ethyl acetate = 1: 1) to give 2-amino-4- (2′-benzylcyclopentylamino). ) -6- (α-fluoroisopropyl) -1,
3,5-Triazine (1.65 g) was obtained.

Mp 50-55 ° C.

Synthesis Example 2

[0139]

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Sodium (0.1 g) was added to dry methanol (5 ml), and the mixture was stirred for 5 minutes.
-(2'-benzylcyclopentylamino) -6- (α
(Fluoroisopropyl) -1,3,5-triazine (1 g) was added and stirred at 50 ° C. for 1 hour. After cooling, methanol was distilled off under reduced pressure, and ethyl acetate (10 ml) was added, followed by stirring at 50 ° C for 1 hour. After cooling, water (30 ml) was added, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the ethyl acetate was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (elution solvent: hexane: ethyl acetate =
3: 2) to give 2-acetylamino-4- (2'-benzylcyclopentylamino) -6- (α-fluoroisopropyl) -1,3,5-triazine (0.57 g)
I got n ^D ₂₀ 1.5512.

Synthesis Example 3

[0142]

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2-amino-4- (2'-benzylcyclopentylamino) -6- (α-fluoroisopropyl)
-1,3,5-Triazine (0.5 g) and acetylmeldrum's acid (0.28 g) were dissolved in benzene (20 ml), and the mixture was heated under reflux for 1 hour. After cooling, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (elution solvent: hexane: ethyl acetate = 3: 2) to give 2-acetoacetylamino-4- (2'-benzylcyclopentylamino)- 6- (α-fluoroisopropyl)-
1,3,5-Triazine (0.55 g) was obtained.

N ^D ₂₀ 1.5433.

Synthesis Example 4

[0146]

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2-amino-4- (2 '-(2-fluorobenzyl) cyclopentylamino) -6- (1-fluoroethyl) -1,3,5-triazine (0.3
g), N, N-dimethylformamide dimethyl acetal (0.32 g) and a catalytic amount of p-toluenesulfonic acid monohydrate were dissolved in benzene (20 ml) and heated under reflux for 1.5 hours. After cooling, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (elution solvent: dichloromethane: methanol = 90: 5) to give 2-N ′,
N'-dimethylmethyleneimino-4- (2 '-(2-fluorobenzyl) cyclopentylamino) -6- (1-
Fluoroethyl) -1,3,5-triazine (0.34
g) was obtained. n ^D ₂₀ 1.5776.

The compounds obtained in the same manner as in Synthesis Examples 1 to 4 are shown in Table 1 below together with the compounds synthesized in Synthesis Examples 1 to 4.

[0149]

[Table 1]

[0150]

[Table 2]

[0151]

[Table 3]

[0152]

[Table 4]

[0153]

[Table 5]

[0154]

[Table 6]

[0155]

[Table 7]

[0156]

[Table 8]

[0157]

[Table 9]

[0158]

[Table 10]

[0159]

[Table 11]

[0160]

[Table 12]

[0161]

[Table 13]

[0162]

[Table 14]

[0163]

[Table 15]

[0164]

[Table 16]

[0165]

[Table 17]

[0166]

[Table 18]

[0167]

[Table 19]

[0168]

[Table 20]

[0169]

[Table 21]

[0170]

[Table 22]

[0171]

[Table 23]

[0172]

[Table 24]

In the above production method (b), the compound obtained by carrying out the reaction using methyl iodide, ethyl iodide or propyl iodide instead of the compound of the formula (IV) is shown in Tables 2 and 3 below. The results are shown in Table 3.

[0174]

[Table 25]

[0175]

[Table 26]

Synthesis Example 5

[0177]

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2-benzylcyclopentanone (11.5
A mixture of 1 g) and formamide (44.41 ml) was heated to 140 to 150 ° C., and while maintaining this temperature, formic acid (9.13 g) was slowly added dropwise. After dropping, 15
Heat at 0 ° C. for a further 2 hours. After cooling, water was added, and the mixture was extracted with methylene chloride. The methylene chloride layer was washed with water and dried over anhydrous sodium sulfate. After methylene chloride was distilled off under reduced pressure, concentrated hydrochloric acid (36.85 ml) was added to the residue, and the mixture was heated under reflux for 2 hours. After cooling, water was added, the mixture was made alkaline with sodium hydroxide, and extracted with methylene chloride. After the methylene chloride layer was washed with water and dried over anhydrous potassium carbonate, methylene chloride was distilled off under reduced pressure, and the residue was purified by distillation to obtain 2-benzylcyclopentylamine (5.18 g).
n ^D ₂₀ = 1.5371.

Synthesis Example 6

[0180]

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To 2-benzyl-2-ethoxycarbonylcyclopentanone (23.17 g) was added 48% hydrobromic acid (50 ml), and the mixture was heated under reflux at 120 ° C. for 4 hours.
After cooling, ice (100 g) was added, and the mixture was extracted with diethyl ether. The diethyl ether layer was washed with water, a saturated aqueous solution of sodium hydrogen carbonate and saturated saline, and then dried over anhydrous sodium sulfate. Diethyl ether was distilled off under reduced pressure, and the residue was purified by distillation to give 2-benzylcyclopentanone (11.51).
g) was obtained. n ^D ₂₀ = 1.5288.

Synthesis Example 7

[0183]

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In a solution of 2-ethoxycarbonylcyclopentanone (13.37 g) in methylene chloride (143 ml), tetrabutylammonium hydrogen sulfate (29.1 g) and benzyl iodide (37.37) were used.
g) was added, followed by a solution of sodium hydroxide (6.86 g) in water (143 ml). After stirring the mixture at room temperature for 4 hours, the methylene chloride layer was separated, and the aqueous layer was extracted with methylene chloride (200 ml, three times). The methylene chloride layers were combined, washed with water, a saturated aqueous solution of sodium hydrogencarbonate and saturated saline, and dried over anhydrous sodium sulfate. After the methylene chloride was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography (elution solvent: hexane: ethyl acetate = 9:
1) to give 2-benzyl-2-ethoxycarbonylcyclopentanone (16.8 g). n ^D ₂₀ = 1.5
156.

[Biological test examples] Test example 1: Test of herbicidal effect on paddy field weed Preparation of preparation of active compound Preparation carrier: acetone 5 parts by weight Emulsifier: benzyloxy polyglycol ether 1 part by weight Preparation of active substance Can be obtained as an emulsion by mixing 1 part by weight of the active compound with the above amounts of carrier and emulsifier. A prescribed dose of the preparation is diluted with water and used for the test. Test Method In a greenhouse, three 2.5-leaf (15 cm plant height) rice seedlings (variety: Nipponbare) were planted per pot in 500 cm ² pots filled with paddy soil. Subsequently, various offsprings of Rubitus, Pleurotus japonicus, Fireflies, Konagi, and broadleaf weeds (Azena, Kikasigusa, Mizohakobe, Himemizohagi, Abnomome, etc.) were sowed and watered for about 2 to 3 cm.

Five days after rice transplantation, the surface of the rice was treated with a preparation of each active compound prepared according to the above-mentioned preparation method. After processing, 3
After 3 weeks of spraying, the herbicidal effect was investigated while maintaining an irrigation state of 3 cm. The evaluation of the herbicidal effect was made assuming 100% of complete death to be 0%.
% As no herbicidal effect.

As a result, Compounds 27, 30, and 3 of the present invention
Compounds 2 and 36 each had a dose of 0.25 kg / h.
In a, it showed sufficient herbicidal effect against paddy weeds and safety against transplanted rice.

[Formulation Examples] Formulation Example 1 (granules) 36 (10 parts), bentonite (montmorillonite) (30 parts), talc (talc) (58)
Water) (25 parts) is added to a mixture of the mixture of the lignin sulfonate and the lignin sulfonate (2 parts), and the mixture is kneaded well, formed into granules of 10 to 40 mesh by an extrusion granulator, and dried at 40 to 50 ° C. Agent.

Formulation Example 2 (Granules) Clay mineral particles (95%) having a particle size distribution of 0.2 to 2 mm
Part) was placed in a rotary mixer, and while rotating, the compound of the present invention No. 1 was mixed with a liquid diluent. 27 (5 parts) is sprayed and moistened evenly, and then dried at 40 to 50 ° C. to obtain granules.

Formulation Example 3 (Emulsion) 32 (30 parts), xylene (5
Parts), polyoxyethylene alkylphenyl ether (8 parts) and calcium alkylbenzene sulfonate (7 parts) are mixed and stirred to form an emulsion.

Formulation Example 4 (Wettable powder) 30 (15 parts), a mixture of white carbon (hydrated amorphous silicon oxide fine powder) and powdered clay (1: 5) (80 parts), sodium alkylbenzenesulfonate (2 parts) and sodium alkylnaphthalenesulfonate formalin polymer (3 parts) was powder mixed to obtain a wettable powder.

Formulation Example 5 (hydrated granules) 36 (20 parts), sodium lignin sulfonate (30 parts), bentonite (15 parts) and calcined diatomaceous earth powder (35 parts) were sufficiently mixed, water was added, and the mixture was extruded and dried with a 0.3 mm screen. Hydrated granules.

[0193]

The novel 1,3,5, -triazine tetrazolinone derivative of the present invention has excellent properties as a herbicide, as shown in the above biological test examples.

Continued on the front page (72) Inventor Mark Wilhelm Drebeth Germany Day-40 764 Langenfeld Goethe Strasse 38 (72) Inventor Dieter Voicht Germany-Day 40789 Monheim am Rhein Akerbeek 9 F term (reference) 4H006 AA01 AB04 FC22 FC52 4H011 AB02 BA01 BB09 BC03 BC07 BC20 DA02 DA15 DA16 DC05 DC06 DD01

Claims (5)

[Claims] (1) Formula (1)Where R¹Is C_1-5Alkyl, C_3-7Cycloalkyl, C_1-4Halo
Alkyl, optionally halogen substituted or C_1-4Al
Optionally substituted benzyl, or optionally
Logen substitution or C_1-4May be alkyl-substituted
Represents phenyl, R^TwoIs amino, C_1-4Alkylamino, formylamino,
C_1-4Alkyl-carbonylamino, C_3-6Cycloalkyl
Le-carbonylamino, C_1-4Haloalkyl-carbonyl
Amino, optionally halogen substituted or C_1-4Archi
Benzylcarbonylamino, optionally substituted
If necessary C_1-4Alkyl substitution, C_1-4Alkoxy substitution
Or phenylcarbonyl optionally substituted with halogen
Amino, C _1-4Alkyl-carbonylacetylamino, or
Is di (C_1-4Alkyl) amino-C_{1- Four}Alkylideneami
No, R^ThreeOr R^FourIs independently a hydrogen atom or C_1-4Archi
And R^FiveIs halogen, C_1-4Alkyl, C_1-4Haloalkyl,
C_1-4Alkoxy, C_{1- Four}Haloalkoxy, C_1-4Archi
Lucio, C_1-4Haloalkylthio, C_1-4Alkylsulf
Inil, C_1-4Alkylsulfonyl, optionally halogenated
Substitution or C_{1 -Four}Alkyl-substituted
Phenyl, optionally halogen substituted or C _1-4Archi
Optionally substituted phenoxy, nitro or cyano
M represents an integer of 1 to 4, and when m represents an integer of 2 or more, R^ThreeAre the same or different
N represents an integer of 0 to 5, and n represents an integer of 2 or more
Then R^FiveMay be the same or different,
Triazines represented. 2. R ¹ is C _1-4 alkyl, C _3-5 cycloalkyl, C _1-3 haloalkyl, optionally fluoro substituted,
Chloro substituted or C _1-3 alkyl optionally substituted benzyl, or optionally fluoro substituted showed phenyl which is chloro substituted or C _1-3 alkyl substituted, R ² is amino, C _1-3 alkyl Amino, formylamino,
C _1-3 alkyl-carbonylamino, C _3-5 cycloalkyl-carbonylamino, C _1-3 haloalkyl-carbonylamino, benzylcarbonylamino optionally substituted with fluoro, chloro or C _1-3 alkyl , optionally C _1-3 alkyl-substituted, C _1-3 alkoxy substituted, fluoro substituted or chloro substituents on these phenylcarbonylamino also, C _1-3 alkyl - carbonyl acetylamino, or di (C _1-3 alkyl) Amino-C _1-3 alkylideneamino; R ³ or R ⁴ each independently represents a hydrogen atom or C _1-3 alkyl; R ⁵ is fluoro, chloro, bromo, methyl, ethyl, n
-Propyl, iso-propyl, tert-butyl, C
_1-3 haloalkyl, C _1-3 alkoxy, C _1-3 haloalkoxy, C _1-3 alkylthio, C _1-3 haloalkylthio, C
_1-3 alkylsulfinyl, C _1-3 alkylsulfonyl,
Optionally fluor-substituted, chloro-substituted or C _1-3 alkyl-substituted phenyl, optionally fluor-substituted, chloro-substituted or C _1-3 alkyl-substituted phenoxy, nitro or cyano; And R ³ may be the same or different, and when n is an integer of 0 to 4 and n is an integer of 2 or more, R ⁵ is the same or different The compound of claim 1, which may be present. 3. R ¹ is methyl, ethyl, n-propyl,
iso-propyl, tert-butyl, cyclopropyl, cyclobutyl, fluoromethyl, fluorochloromethyl, fluorobromomethyl, fluorodichloromethyl, fluorodibromomethyl, difluoromethyl, difluorochloromethyl, difluorobromomethyl, trifluoromethyl, chloromethyl, Trichloromethyl, bromomethyl, 1-fluoroethyl, 2,2,2-trifluoroethyl, 1,2,2,2-tetrafluoroethyl,
Perfluoroethyl, 1-chloroethyl, 1,2-dichloroethyl, 1-bromoethyl, perfluoropropyl, 1-fluoro-1-methylethyl, 1-chloro-1
-Methylethyl, 1-bromo-1-methylethyl, 1-
(Trifluoromethyl) -2,2,2-trifluoroethyl, benzyl optionally substituted with fluoro or methyl, or optionally fluoro-substituted,
R ² is amino, methylamino, ethylamino, formylamino, acetylamino, ethylcarbonylamino, cyclopropylcarbonylamino, fluoromethylcarbonylamino, trifluoromethylcarbonylamino , 1
-Fluoroethylcarbonylamino, perfluoroethylcarbonylamino, benzylcarbonylamino optionally substituted with chloro or methyl,
Optionally represents phenylcarbonylamino, acetoacetylamino, or dimethylaminomethylideneamino which may be substituted by fluorine, chloro, methyl or methoxy, wherein R ³ or R ⁴ is each independently a hydrogen atom, methyl or ethyl Wherein R ⁵ is fluoro, chloro, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, methylsulfonyl, and optionally fluoro- or methyl-substituted Phenyl, phenoxy, nitro or cyano which may be optionally substituted by fluorine or methyl; m represents an integer of 3 to 4; R ³ may be the same or different; Indicates an integer of 3 If n is an integer of 2 or 3 Te, R ⁵ may be different identical or different,
A compound according to claim 1. 4. An agricultural chemical comprising the compound according to claim 1 as an active ingredient. 5. A compound of the formula Wherein R ³ , R ⁴ , R ⁵ , m and n have the same meanings as described in claim 1, and X represents a halogen atom.