JPS63238071A - Triazine derivative, production thereof and herbicide containing said derivative - Google Patents

Abstract

NEW MATERIAL:A triazine derivative expressed by formula I [Z<1> and Z<2> are O, methylene, ethylene, trimethylene, vinylene or oxymethylene as a ring member; R<1> is alkyl; R<2> is halogen, 1-4C alkylthio, 1-4C alkoxy or 1-4C haloalkyl; R<3> is NH2, NHCOR<4>, N-CHR<5> (R<4> is alkyl, cycloalkyl or alkenyl; R<5> is alkyl)]. EXAMPLE:2-Amino-4-chloro-6-[1-(2'-naphthyl)ethylamino]-s-triazine. USE:A herbicide having reduced crop injury. PREPARATION:For example, an alkylamine derivative expressed by formula II is reacted with a dihalogenated aminotriazine expressed by formula III (X<1> and X<2> are halogen) to provide the compound expressed by formula IV which are one of the compound expressed by formula I.

Description

[Detailed description of the invention] [Industrial application field] The present invention is a novel compound, a triazine derivative.

The present invention relates to a method for producing the same and a herbicide containing the same.

[Prior Art and Problems to be Solved by the Invention] Various compounds have been known as triazine herbicides. For example, 2-methylthio-4,6-bis(alkylamino)-S-triazine derivatives have strong herbicidal power and are known to be effective as herbicides.

However, for example 2-methylthio-4,6-bis(
The effectiveness of ethylamino)-S-triazine is highly dependent on soil and temperature conditions. in particular,
In warm regions, even normal application rates may cause chemical damage, and in cold regions, there is a problem that the effect is not fully demonstrated. Therefore, the disadvantage is that the areas where it can be applied as a herbicide are considerably restricted.

In addition, 2-amino-4-benzylamino-6-(trifluoromethyl)-S-)-riazine has also been developed as a herbicide (U.S. Pat. Nos. 3,816,419 and 3,932,167). It has the disadvantage that it does not have a sufficient herbicidal effect when used for paddy rice, and it is also highly harmful to paddy rice.

[Means for Solving the Problems] The present inventors have solved the above-mentioned problems with conventional herbicides, and have achieved almost the same effect under various soil and temperature conditions, while also causing no chemical damage to paddy rice. We conducted intensive research to develop a completely new herbicide that can exhibit excellent herbicide effects against a variety of weeds ranging from annual to perennial weeds. In the course of this research, the present inventors have already developed triazine derivatives as disclosed in JP-A No. 140569/1982, and are conducting intensive research to further develop herbicides with improved herbicidal activity or less phytotoxicity. layered. As a result, the inventors discovered that a specific triazine derivative was suitable for the above purpose, and completed the present invention.

That is, the present invention is based on the general formula [wherein 2' and z2 each represent an oxygen atom, a methylene group, an ethylene group, a trimethylene group, a vinylene group, or an oxymethylene group as ring members, and R1 has 1 to 1 carbon atoms.
4 alkyl group, R2 is a halogen atom, carbon number 1
-4 alkylthio group, C1-4 alkoxy group, or C1-4 haloalkyl group, R3 is N
H2.

NHCOR'AZ IhaN-CHR' (,m,:
Te, R'Gf water 1[child, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, and R5 is an alkyl group having 1 to 4 carbon atoms. It is. ) is shown. ] In addition to providing a triazine derivative represented by the following, the following six methods are provided as efficient methods for producing this triazine derivative. That is, [where zl, z2 and RJt are the same as above. ] and the general formula [where xl and x2 represent halogen atoms]. ] [wherein zl, Z2. R1 and x1 are the same as above. ] A method for producing a triazine derivative (halogen-containing triazine derivative) represented by (hereinafter referred to as "Method 1"), a halogen-containing triazine derivative represented by the above general formula [l-Al, the general formula R'SH...[ IV] [In the formula, R6 represents an alkyl group having 1 to 4 carbon atoms] or an alkyl mercaptan represented by the general formula
(R'S)nM·[V] [Wherein, M represents an alkali metal or an alkaline earth metal, and n represents the valence of M. Moreover, R6 is the same as above. ] [wherein xi, 12. R1 and R6 are the same as above. ] A method for producing a triazine derivative (sulfur-containing triazine derivative) represented by (hereinafter referred to as "Method 2"), a halogen-containing triazine derivative represented by the above-mentioned general formula [■-^], the general formula R'OH... - [■] [Wherein, R6 is the same as above. ] Alcohol represented by the general formula (R'O)nM ... [■] [wherein R', M and n are the same as above. ] [wherein, zl, z2. R1 and R6 are the same as above. A method for producing a triazine derivative (oxygen-containing triazine derivative) represented by (hereinafter referred to as "Method 3"), [wherein zl, Z2 and R' are the same as above,
X represents a halogen atom. ] A salt of an alkylamine derivative represented by the following is reacted with a cyanoguanidine represented by the formula H2N-C-N)l-CN to form a compound having the general formula [where zl, z2. R1 and X are the same as above. ] A salt of a biguanide derivative represented by the formula R'(:OOR'... [IX] [wherein R7 represents a haloalkyl group having 1 to 4 carbon atoms] is prepared. , R8
represents an alkyl group having 1 to 4 carbon atoms], wherein zl, zl, nl and R7 are the same as above. ] A method for producing a triazine derivative (haloalkyl group-containing triazine derivative) represented by (hereinafter referred to as "Method 4").

), general formula [wherein zl, zl, R1 and R2 are the same as above. ] A triazine derivative (amino group-containing triazine derivative) represented by the general formula [r -A1.[I-B
E.

It includes all triazine derivatives represented by [I-C] and [I-Dl, and is a part of the triazine derivatives represented by general formula [I]. ), the general formula R'COX .[X ] [wherein R' and X are the same as above. ] Carboxylic acid halide.

General formula R’C0OH-[XI] [In the formula, R4 is the same as above. ] Carboxylic acid represented by

General formula (R'CO), 0...[X[I] [wherein, R4 is the same as above. ] Carboxylic acid anhydride or general formula R'
GOOR" ・[Xll1] [wherein R4 is the same as above, and R9 represents an alkyl group having 1 to 4 carbon atoms.] where zl, zl, Hl, R2 and R' are the same as above.] A method for producing a triazine derivative (amide group-containing triazine derivative) (hereinafter referred to as "Method 5") and the general formula The amino group-containing triazine derivative represented by [I'] has the general formula R'CHO... [In the formula, R5 is the same as above. Aldehyde represented by or general formula R'CH(OR9) 2 ...[XV
] [In the formula, ns and R@ are the same as above. [wherein zl, zl, ul, R2 and R5 are the same as above]. ] A method for producing a triazine derivative (imino group-containing triazine derivative) represented by (hereinafter referred to as "Method 6") is provided.

Further, the present invention provides the general formula [I] (which corresponds to the general formula [I])
t-A1. [t-B1. [1-cl, [I
-Dl, [I-El.

Including all [IF] and [I']. ) The present invention also provides a herbicide containing a triazine derivative represented by:

The compound represented by the general formula [1] is a novel triazine derivative, where zl, zl, R1゜R
2 and R3 are as described above. In other words, zl,
zl represents an oxygen atom, a methylene group, an ethylene group, a trimethylene group, a vinylene group, or an osymethylene group as a ring member, respectively. therefore,
Depending on the type of zl and zl, there is a formula in general formula [I], for example, when zl and zl are both vinylene groups, it is a group), and when zl and zl are both ethylene groups,
When Zl is a methylene group and zl is an ethylene group, it becomes a ru group). When zl is an ethylene group and zl is an oxygen atom (or when zl is a methylene group and zl is an oxymethylene group, it becomes a benzofuranyl group). When zl is a vinylene group. When zl is a methylene group, it becomes a ru group). When both zl and Zl are an oxymethylene group, it becomes an nzodioxanyl group). When zl is an oxymethylene group, when Zl is an oxygen atom, it becomes an nzodioxolyl group). becomes.

Note that zi and zl represent the groups described above as ring members, but a halogen atom or an alkyl group having 1 to 4 carbon atoms can be further introduced as a substituent into the formed ring.

Next, R1 in the general formula [I] is an alkyl group having 1 to 4 carbon atoms, i.e., a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, 5ec
-Represents a butyl group or a tert-butyl group. Also R
2 is a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom, etc.), an alkylthio group having 1 to 4 carbon atoms (methylthio group, ethylthio group, propylthio group, butylthio group), an alkoxy group having 1 to 4 carbon atoms ( methoxy group, ethoxy group, propoxy group, butoxy group) or carbon number 1 to
4 haloalkyl group (trifluoromethyl group, trichloromethyl group, dichloroethyl group, tetrafluoroethyl group, monochloromethyl group, monobromomethyl group, monofluoromethyl group, difluoromethyl group, chlorofluoromethyl group, dibromoethyl group, (dichloromethyl group, bromofluoromethyl group, heptafluoropropyl group, dibromomethyl group, dibromofluoromethyl group, chlorodifluoromethyl group, bromodifluoromethyl group, dichlorofluoromethyl group, pentafluoroethyl group, difluoroethyl group, etc.) . Furthermore, R3 is N)+2.
NHCOR' or N-C)IR5, where N
) 84 of ICOR' is a hydrogen atom, methyl group, ethyl group,
Alkyl groups with 1 to 4 carbon atoms such as propyl groups, cycloalkyl groups with 3 to 6 carbon atoms such as cyclopropyl groups, cyclobutyl groups, and cyclohexyl groups, or 2 to 5 carbon atoms such as vinyl groups, propenyl groups, and allyl groups. represents an alkenyl group. Further, R5 in N-C)IR' represents an alkyl group having 1 to 4 carbon atoms, similar to R1 above.

There are various specific examples of the triazine derivatives of the present invention, but in addition to the compounds obtained in the production examples described below, 2-
Methoxycarbonylamino-4-methylthio-6-[1
-(2'-naphthyl)ethylamino] -S-triazine, 2-methylthio-4-(1-(2'-naphthyl)ethylamino-6-bropionylamino-5-)-riazine, 2-acryloylamino-4 -methylthio-6-
[1-(2'-naphthyl)ethylamino] -S-triazine, 2-isobutyleneimino-4-[1-(2'-
naphthyl)ethylamino] -6-trifluoromethyl-5-triazine, 2-acetylamino-4-[1-(
2'-naphthyl)ethylaminoco-6-trifluoromethyl-5-)-lyazine, 2-acetylamino-4-methylthio-6-[1-(2'-naphthyl)propylamino]-S-triazine.

2-isobutyleneimino-4-methylthio-6-(1-
(2'-naphthyl)propylamino-S-triazine, 2-acetylamino-4-[1-(2'-naphthyl)
pro-ruamino] -6-)-lifluoromethyl-8-
Triazine, 2-acetylamino-4-methylthio-6
-(1-(indan-5-yl)ethylaminoco-S-
triazine.

2-acetylamino-4-[1-(indan-5-yl)ethylaminoco-6-trifluoromethyl-S-triazine, 2-acetylamino-4-methylthio-6-[
1-(5', 6', 7', 8'-tetrahydro-2'
-naphthyl)ethylamino-S-triazine, 2-acetylamino-4-[1-(5', 6', 7', 8'-
Tetrahydro-2'-naphthyl)ethylaminoco-6-
Trifluoromethyl-S-triazine, 2-acetylamino-4-methylthio-6-(1-(6'-indenyl)ethylamino-S-triazine, 2-acetylamino-4-(1-(6'-indenyl) ) ethylaminoco-6-trifluoromethyl-5-1-riazine, 2-
Acetylamino-4-methylthio-6-[1-(2”,
3'-dihydrobenzofuran-5'-yl)ethylaminoco-S-triazine, 2-acetylamino-4-[1
-(2',3'-dihydrobenzofuran-5'-yl)ethylamino]-6-)lifluoromethyl-5-)
Riazine, 2-acetylamino-4-methylthio-6-
[1-(6'-indenyl)ethylaminoco-S-triazine, 2-acetylamino-4-methylthio-6-[
1-Ni==(1',4'-benzodioxan-6'-yl)ethylamino]-s-triazine, 2-acetylamino-4-methylthio-6-[1-Ni2::(1', 3
'-benzofuran'JEE2-5 '-yl)ethylaminoco-S-triazine, 2-amino-4-ethylthio-6-(1-(2'-naphthyl)ethylamino] -
s-triazine, 2-amino-4-ethoxy-6-(1
-(2'-naphthyl)ethylamino] -s-triazine, 2-amino-4-fluoromethyl-6-[1-(2
'-naphthyl)ethylaminoco-3-triazine, 2-
Amino-4-difluoromethyl-6-[1-(2'-naphthyl)ethylamino-5-triazine, 2-amino-4-[1-(2'-naphthyl)ethylamino]-6-
α,α,β,β-tetrafluoroethyl-S-triazine, 2-amino-4-ethylthio-6-[1-(2'-
naphthyl)propylamino]-S-triazine, 2-amino-4-methoxy-6-[1-(2'-naphthyl)propylamino]-5-) riazine, 2-amino-4-[
1-(2'-naphthyl)propylaminoco-6-trifluoromethyl-5-triazine, 2-amino-4-methoxy-6-[1-(indan-5-yl)ethylamino]-g-triazine, 2-amino-4-[1-(indan-5-yl)ethylaminoco-6-trifluoromethyl-3-triazine, 2-amino-4-methoxy-6-
[1-(5', 6', 7', 8'-tetrahydro-2'
-naphthyl)ethylaminoco-S-triazine.

2-amino-4-[1-(5', 8', 7', 8' -
Tetrahydro-2'-naphthyl)ethylaminoco-6-
Trifluoromethyl-s-triazine, 2-amino-4
-methoxy-6-[1-(8'-indenyl)ethylaminoco-S-triazine, 2-amino-4-(t-(6
'-indenyl)ethylaminoco-6-trifluoromethyl-8-triazine, 2-amino-4-methoxy-6
-[1-(2',3'-dihydrobenzofuran-5'
-yl)ethylamino]-5-)riazine, 2-amino-4-[1-(2',3'-dihydrobenzofuran-5
'-yl)ethylamino]-6-)-lifluoromethyl-S-triazine, 2-amino-4-[1-(6'
-indenyl)ethylamino] -6-)lifluoromethyl-5-)-riazine, 2-amino-4-[1-C:
xx '-benzodioki layer 15'-a) T-choi 6
-trifluoromethyl-5-triazine and the like.

The doriazine derivative of the present invention represented by the above general formula [1] can be produced by various methods. Among them, the above-mentioned methods 1 to 6 are efficient manufacturing methods.
can be given.

According to method 1, the desired triazine of general formula [IA] is produced by reacting an alkylamine derivative represented by general formula [II] with a dihalogenated aminotriazine represented by general formula [III]. A derivative (halogen-containing triazine derivative) is obtained.

Here, the general formula [I! ] The alkylamine derivatives represented by formulas vary depending on the types of zl, z2 and R1 in the formula, but specifically, the alkylamine derivatives represented by the above-mentioned general formula [II (i.e., general formulas [1-A] to [I-Fl)] Compounds corresponding to specific examples of triazine derivatives are listed. This general formula [II]
Although various methods can be considered for producing the alkylamine derivative, the following method is usually used. That is, [where zl, Z2 and R' are the same as above.

] 150 to 200 alkyl ketone derivatives represented by
By reacting ammonium formate or formamide with formic acid under heating at ℃, and further heating and hydrolyzing this reaction mixture in the presence of an acid or alkali, the general formula [
An alkylamine derivative represented by II] is obtained.

Alternatively, an oxime can be produced by reacting the alkyl ketone derivative of the above general formula [XVT] with hydroxylamine or a derivative thereof in place of ammonium formate, and this can be reduced with a reducing agent such as diborane, or catalytic reduction can be carried out. For example, an alkylamine derivative represented by the general formula [1] is obtained.

On the other hand, as the dihalogenated aminotriazine represented by the general formula [III], that is, 2-amino-4,6-dihalogeno-S-triazine, for example, 2-amino-4,
Examples include 6-dichloro-5-triazine. This dihalogenated aminotriazine can be obtained by reacting a cyanuric halide such as cyanuric chloride with ammonia.

In method 1 of the present invention, as described above, an alkylamine derivative represented by the general formula [II] and a general formula [III]
A dihalogenated aminotriazine represented by the following formula is reacted. In this reaction, the same compound may be used in approximately equimolar ratios, and a solvent is not necessarily required, but ketones such as acetone, methyl ethyl ketone, cyclohexanone, n-hexane, etc. , aliphatic hydrocarbons such as n-heptane, cyclic hydrocarbons such as benzene, decalin and alkylnaphthalene, chlorinated hydrocarbons such as carbon tetrachloride and ethylene tetrachloride, and ethers such as tetrahydrofuran and dioxane. Furthermore, it is also effective to add a deoxidizing agent (dehydrohalogenating agent) such as sodium carbonate, sodium hydrogen carbonate, or triethylamine to this reaction system. In addition, the reaction temperature is not particularly limited, and can range from low to high temperatures.
Specifically, the process progresses satisfactorily in the range of 10 to 100°C.

In method 1 of the present invention, the general formula [I-
8] A halogen-containing triazine derivative represented by the following can be obtained with high purity and high yield.

In addition, in method 2 of the present invention, after producing a halogen-containing triazine derivative of the general formula [I-A] according to the above-mentioned method 1 of the present invention or by another method, this triazine derivative is converted into a halogen-containing triazine derivative of the general formula [rV]. By reacting the alkyl mercaptan represented by the formula [I] or the alkyl mercaptide represented by the general formula [V],
-8] is obtained.

Here, examples of the alkyl mercaptan include methyl mercaptan, ethyl mercaptan, and propyl mercaptan. In addition, alkyl mercaptides include sodium methyl mercaptide (CH, 5Na), potassium methyl mercaptide (CHS), magnesium methyl mercaptide ((CHsS) 2Mg),
Sodium ethyl mercaptide (C, lI, 5Na)
, Ethyl mercaptide of potassium (in C, H, S), Ethyl mercaptide of magnesium <(C2)IS
S) 2Mg) etc. In addition, when using an alkyl or mercaptan in the above method 2, it is preferable to carry out the reaction in the presence of a caustic alkali, such as sodium hydroxide or potassium hydroxide.

In method 2 of the present invention, the mixing ratio of the halogen-containing triazine derivative of the general formula [l-Al and the alkyl mercaptan or alkyl mercaptide is not particularly limited, but may be equimolar. Note that this reaction can be performed without a solvent using isopropyl alcohol, dimethylformamide, toluene, xylene, etc. It also proceeds in solvents such as benzene. Further, the reaction temperature is not particularly limited, and the reaction proceeds satisfactorily at a temperature ranging from a low temperature to a high temperature, specifically, from 10 to 150°C.

After the reaction is complete, the resulting solid is washed by cooling and further purified by silica gel column chromatography.
A sulfur-containing triazine derivative represented by the general formula [1-B1] is obtained with high purity and high yield.

Furthermore, in method 3 of the present invention, after producing a halogen-containing triazine derivative of the general formula [l-Al] according to the above-mentioned method 1 of the present invention or by another method, this triazine derivative is converted into a halogen-containing triazine derivative of the general formula [V1]. By reacting the alcohol represented by the formula or the alkoxide represented by the general formula [■], the desired oxygen-containing triazine derivative represented by the general formula [l-Cl] can be obtained.

Here, examples of the alcohol include methyl alcohol, ethyl alcohol, and propyl alcohol. Also,
As the alkoxide, sodium methoxide (CH
3ONa), potassium methoxide (CH,0),
Calcium methoxide ((CH30) zca).

Examples include sodium ethoxide ((:28sONa), potassium ethoxide ((:2H, OK), calcium ethoxide ((C2HsO) 2ca), etc. When alcohol is used in the above method 3, alkali metals, e.g. It is preferable to carry out the reaction in the presence of metallic sodium, metallic potassium, or the like.

In method 3 of the present invention, the mixing ratio of the halogen-containing triazine derivative of the general formula [I-Al and alcohol or alkoxide is not particularly limited, but equimolar ratios may be used as a guide. However, it also proceeds in a solvent, and the solvent in this case is preferably an alcohol such as methyl alcohol, ethyl alcohol, or isopropyl alcohol. Further, the reaction temperature is not particularly limited, and the reaction proceeds satisfactorily at a temperature ranging from a low temperature to a high temperature, specifically, from 10 to 100°C.

After the reaction is completed, the solid produced by cooling is washed, purified by silica gel column chromatography, and dried to obtain an oxygen-containing triazine visiting conductor represented by the general formula [I-Cl with high purity and high yield. .

According to method 4 of the present invention, a salt of an alkylamine derivative represented by the general formula [11'l] is reacted with cyanoguanidine to form a salt of a biguanide derivative represented by the general formula [■], and this is converted into a salt of a biguanide derivative represented by the general formula [■]. By reacting with a halogen-containing ester represented by [IX], the desired haloalkyl group-containing triazine derivative represented by the general formula [1-D] can be obtained.

Here, the salt of the alkylamine derivative represented by the general formula [11'] can be easily obtained by treating the alkylamine derivative represented by the above-mentioned general formula [II] with concentrated hydrochloric acid or hydrobromic acid.

In Method 4 of the present invention, first, the thus obtained salt of the alkylamine derivative represented by the general formula [11'] is reacted with cyanoguanidine. In this reaction, the same compounds may be used in approximately equimolar ratios, and a solvent is not necessarily required, but methanol, ethanol,
Alcohols such as isopropanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, aliphatic hydrocarbons such as n-hexane and n-hebutane, cyclic hydrocarbons such as benzene, decalin, and alkylnaphthalene, carbon tetrachloride, and ethylene dichloride. , chlorinated hydrocarbons such as chlorobenzene and dichlorobenzene, ethers such as tetrahydrofuran and dioxane, and even kerosene. Furthermore, it is also effective to add a deoxidizing agent (dehydrohalogenating agent) such as sodium hydrogen carbonate or triethylamine to this reaction system. In addition, there is no particular restriction on the reaction temperature;
The process progresses satisfactorily at low to high temperatures, specifically in the range of 80 to 200°C.

Through this reaction, a salt of a biguanide derivative represented by the general formula [■] is obtained. In Method 4 of the present invention, the desired haloalkyl group-containing triazine derivative represented by the general formula [1-D] is produced by reacting this with a halogen-containing ester of the general formula [IX].

This reaction usually involves methanol or ethanol.

Alcohols such as isopropanol and various ketones.

Aliphatic hydrocarbons, various ethers, various cyclic hydrocarbons,
In the presence of a catalyst such as a base in a solvent such as a chlorinated hydrocarbon,
It progresses efficiently at about 10 to 100°C.

Here, the halogen-containing ester of general formula [IX] is n8. a? There are various types depending on the type, but specific examples include ethyl fluoroacetate, methyl chloroacetate, ethyl chloroacetate, t-butyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, isopropyl bromoacetate, t-butyl bromoacetate, Methyl dichloroacetate, methyl trichloroacetate, ethyl trichloroacetate, ethyl trifluoroacetate, methyl chlorodifluoroacetate, methyl 2-chloropropionate, ethyl 2-chloropropionate, ethyl 3-chloropropionate, methyl 2-bromopropionate, Methyl 3-bromopropionate.

Methyl 2.3-dichloropropionate, methyl 2.2-dichloropropionate, ethyl 2.3-dibromopropionate, methyl 4-chlorobutyrate, ethyl 4-bromobutyrate, ethyl 2-bromobutyrate, 2- Ethyl bromoisobutyrate,
Examples include ethyl 2-bromovalerate and ethyl 5-bromovalerate.

Subsequently, according to method 5 of the present invention, method 1 of the present invention described above
˜According to Method 4 or otherwise, the general formula [I
'] (triazine derivative containing an amino group) (this is a triazine derivative represented by the general formula [■-^], [1-B
1. [I-C1 and all triazine derivatives represented by [I-[1]] are included. ), the general formula [X]
A carboxylic acid halide of general formula [X11], a carboxylic acid anhydride of general formula [X[I], or a carboxylic acid ester of general formula [XIII] are reacted. This reaction depends on the type of compound used, but when using a carboxylic acid halide, the amount of the above carboxylic acid halide is usually 1 to 3 times per mole of the amino group-containing triazine derivative of general formula [I']. benzene, used in molar proportions, and the solvent is not necessarily required.

Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chloroform and methylene chloride, ketones such as acetone and methyl ethyl ketone, aliphatic hydrocarbons such as hexane and heptane, ethers such as tetrahydrofuran and ethyl ether, or bases such as pyridine. It is preferable to use a neutral solvent or the like. Furthermore, it is also effective to add a base such as triethylamine to this reaction system. Further, the reaction temperature is not particularly limited, but the reaction proceeds satisfactorily from low to high temperatures, specifically in the range of -20°C to 80°C.

Further, when using a carboxylic acid ester of the general formula [XIII], it is sufficient to use at least an equimolar amount of the amino group-containing triazine derivative of the general formula [■'], and a solvent is not necessarily required, but a solvent such as water or benzene may be used.

Aromatic hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, and hexane.

Aliphatic hydrocarbons such as heptane, ethers such as tetrahydrofuran and ethyl ether, and methanol.

It is preferable to use alcohol such as ethanol, dimethylformamide or dimethyl sulfoxide as a solvent. Furthermore, this reaction system contains sodium methoxide,
It is also effective to add bases such as sodium ethoxide, n-butyllithium, sodium hydride, and the like. Further, the reaction temperature is not particularly limited, but the reaction proceeds satisfactorily at a temperature ranging from low to high temperatures, specifically from 10 to IQQ°C.

In addition, carboxylic acid of general formula [XI] and general formula [XII]
When using the carboxylic acid anhydride, it may be carried out in the same manner as when using the above-mentioned carboxylic acid ester.

According to Method 5 of the present invention, the desired triazine derivative (amide group-containing triazine derivative) represented by the general formula [I-El] is obtained by the above reaction.

Further, in Method 6 of the present invention, the general formula [I']
The triazine derivative (amino group-containing triazine derivative) represented by the general formula [)l! An aldehyde of Vl or an acetal of general formula [XV] is reacted. In this reaction, an amino group-containing triazine derivative of general formula [I'] is reacted with an aldehyde of general formula [XV] and an amino group-containing triazine derivative of general formula [I'].
It is sufficient to use approximately equal moles of acetals, and a solvent is not necessarily required; Hydrogen, tetrahydrofuran, ethers such as ethyl ether, etc. can be used as suitable solvents. Furthermore, it is preferable to use a dehydrating agent such as potassium water hydride or a catalyst such as para-toluenesulfonic acid in this reaction system, and the reaction temperature is not particularly limited, and ranges from low to high temperatures, specifically from 10 to 100%. The process progresses satisfactorily in the ℃ range.

According to Method 6 of the present invention, the desired triazine derivative (imino group-containing triazine derivative) represented by the general formula [I-Fl] can be obtained by the above reaction.

In the methods 1 to 6 of the present invention described above, after the reaction is completed, the product is separated and washed to form the general formula [I] (general formula [I-A], [1-8], [I -C].

[r -t+L It -El Oyohi[z -Fl
) Wasalel triazine derivatives can be obtained with high purity and high yield.

Further, the triazine derivative represented by the general formula [I] suppresses the germination and growth of weeds and has high selectivity, so it is suitable as a herbicide. In addition, it not only shows excellent herbicidal effects against weeds such as broad-leaved weeds such as Kikashigusa, Azena, and Nagisa, Cyperaceae weeds such as Cyperus japonicus, and Poaceae weeds such as Nobie, without causing any chemical damage to rice. It also exhibits excellent weeding effects against perennial weeds such as firefly, cypress, and weed, which are currently difficult to control.

In addition, this triazine derivative does not cause any phytotoxicity to corn and sorghum, which are important crops in upland areas.
Shows excellent herbicidal effects against harmful weeds such as Ebisu grass, Maruba morning glory, and Ichibi.

Next, the herbicide of the present invention contains the above-mentioned compound of the invention, that is, a triazine derivative represented by the general formula [I], particularly as an active ingredient, and these compounds are mixed in a liquid form such as a solvent. It can be used by mixing it with a solid carrier such as a carrier or fine mineral powder, and formulating it in the form of a wettable powder, an emulsion, a powder, and the like. Emulsifying properties during formulation.

A surfactant may be added to impart dispersibility, spreadability, etc.

When the herbicide of the present invention is used in the form of a wettable powder, the above-mentioned triazine derivative of the present invention is usually used as an active ingredient.
A composition may be prepared by blending the solid carrier at a ratio of ~55% by weight, the solid carrier at 40-88% by weight, and the surfactant at 2-5% by weight, and then used. In addition, when used in the form of an emulsion,
The triazine derivatives of the present invention are usually used as active ingredients.
50% by weight, 35-75% solvent and 5% surfactant
It may be prepared by blending at a ratio of ~15% by weight.

On the other hand, when used in the form of a powder, it is usually prepared by blending 1 to 15% by weight of the triazine derivative of the present invention as an active ingredient, 80 to 97% by weight of a solid carrier, and 2 to 5% by weight of a surfactant. Bye.

Furthermore, when used in the form of granules, 0.1 to 15% by weight of the triazine derivative of the present invention as an active ingredient.

80-97.9% by weight of solid carrier and 2-5% surfactant
What is necessary is just to mix|blend and prepare in the ratio of weight%. Here, fine mineral powder is used as the solid carrier, and examples of the fine mineral powder include oxides such as diatomaceous earth and slaked lime, phosphates such as apatite, sulfates such as ceracola, talc, and pyroferrite. , clay, kaolin, bentonite, acid clay,
Examples include silicates such as white carbon, quartz powder, and silica powder.

In addition, organic solvents are used as solvents, specifically aromatic hydrocarbons such as xylene, toluene, benzene, etc.
Chlorinated hydrocarbons such as chlorotoluene, trichloromethane, and trichlorethylene, alcohols such as cyclohexanol, amyl alcohol, and ethylene glycol, and isophorone. Ketones such as cyclohexanone, cyclohexenyl-cyclohexanone, ethers such as butyl cellosolve, dimethyl ether, methyl ethyl ether, esters such as isopropyl acetate, benzyl acetate, methyl phthalate,
Amides such as dimethylformamide or mixtures thereof can be mentioned.

Further, as the surfactant, any of anionic, nonionic, cationic, and amphoteric ionic types (amino acids, betaine, etc.) can be used.

The triazine derivative of the novel compound represented by the general formula [11] of the present invention is a highly selective herbicide that has a high herbicidal effect not only on early weeds but also on perennial weeds and has no phytotoxicity on paddy rice. It is extremely useful as a Also,
When used as a field foliar treatment agent for field crops such as corn, wheat, barley, oats, and sorghum, it exhibits better effects than commercially available field end foliage treatment agents.

The herbicide of the present invention has general formula [11
Other herbicidal ingredients can also be used together with the triazine derivative represented by. Examples of such other herbicidal ingredients include conventionally commercially available herbicides, such as phenoxy herbicides, diphenyl ether herbicides, triazine herbicides, urea herbicides, carbamate herbicides, Various herbicides include thiol carbamate herbicides, acid anilide herbicides, pyrazole herbicides, phosphate herbicides, sulfonylurea herbicides, and oxacycin.

Furthermore, the herbicide of the present invention can be used in combination with insecticides, fungicides, plant growth regulators, fertilizers, etc., if necessary.

[Examples] Next, the present invention will be described in more detail based on Examples.

Reference Example 1 (Synthesis of 1-(2-naphthyl)ethylamine) 12.1 g (70.9 mmol) of 2-naphthylmethylketone and 14.3 g (227 mmol) of ammonium formate were placed in a reaction vessel, and heated at 180°C for 5 minutes. Stir for hours.

The reaction mixture was dissolved in 50 ml of benzene, washed with water,
After drying with sodium sulfate, benzene was distilled off under reduced pressure. 25 mj of 35% hydrochloric acid to the product after benzene distillation! was added and heated under reflux for 1.5 hours. After cooling, add 50 m of ethyl acetate.
1' was added, and water N was separated. This aqueous layer was made alkaline with an aqueous sodium hydroxide solution, and the free oil layer was evaporated with 50 mJ of ethyl ether! Extracted with. The ethyl ether layer was washed with water, dried over sodium sulfate, and then the ethyl ether was distilled off under reduced pressure.
mHg) L/t, 1-(2-naphthyl)ethylamine expressed by the formula 6.7
9 g (yield 56%) was obtained.

Reference example 2 (1-(5,6,7,8-tetrahydro-2
-Synthesis of (naphthyl)ethylamine) Same procedure as in Reference Example 1, except that 5,6,7.8-tetrahydro-2-naphthylmethylketone was used instead of 2-naphthylmethylketone. 1-(5,6,7,8-tetrahydro-2
-naphthyl)ethylamine 6.21g (yield 50%)
I got it.

Reference Example 3 (Synthesis of 1-(indan-5-yl)ethylamine) Same procedure as in Reference Example 1 except that indan-5-yl-methyl ketone was used instead of 2-naphthylmethyl ketone. The operation yielded 6.40 g (yield 56%) of 1-(indan-5-yl)ethylamine represented by:

Reference example 4 (1-(5,6,7,8-tetrahydro-2
-Synthesis of (naphthyl)propylamine) The same procedure as in Reference Example 1 was used, except that 5,6,7.8-tetrahydro-2-naphthylethyl ketone was used instead of 2-naphthylmethyl ketone. 1-(5,6,7,8-tetrahydro-
2-naphthyl)propylamine 6.44g (Yield: 448
%) was obtained.

Reference example 5 (1-(1,3-benzodioxole-5-
Synthesis of ethylamine) 1.3-benzodioxol-5-ylmethylketone 2
0 g (122 mmol) was dissolved in 300 ml of methanol, and 11.2 g (122 mmol) of hydroxylamine hydrochloride was dissolved therein.
162 mmol) and 18.8 g (1
58 mmol) was added thereto, and the mixture was mixed and stirred at room temperature for 8 hours.

Thereafter, 100 mj' of water was added to the reaction mixture, and methanol was distilled off under reduced pressure. Then, the precipitated crystals were filtered and washed with water to obtain 18.5 g (yield: 85%) of 1,3-benzodioxol-5-ylmethylketone oxime represented by the formula.

Next, this oxime was dissolved in 400 mA' ethanol and heated in a groove. When it started to boil, heating was stopped and 30.8 g (1330 mmol) of metallic sodium was added while stirring. After dissolving the metallic sodium, cool and
Diluted with 0 mJ of water. The reaction solution was extracted with ethyl ether, the extract was dried over anhydrous sodium sulfate, and the ethyl ether was distilled off under reduced pressure.
7 mmHg) L/, 1-(1,3-benzodioxole-5-
6.8 g (yield: 40%) of ethylamine (yield: 40%) was obtained.

Reference Example 6 (Synthesis of 1-(1,4-benzodioxan-6-yl)ethylamine) 150 ml of a 4-mix ethanol aqueous solution of 10.6 g (153 mmol) of hydroxylamine hydrochloride and 7.98 g (75 mmol) of sodium carbonate! under water cooling, 1.4-
Benzodioxan-6-yl-methylketone 20.6g
(116 mmol) was added dropwise and stirred at room temperature for 24 hours. The reaction was poured into 300ml water and extracted with ethyl ether. After drying the extract over sodium sulfate, ethyl ether was distilled off under reduced pressure to obtain 21.4 g (l11
mmol) in a yield of 96%.

Next, 21.4 g (111 mmol) of this oxime was dissolved in 15 hj of ethanol, 6 g of activated carbon with 5% palladium was added thereto, and the reaction mixture was stirred for 12 hours at room temperature under a hydrogen atmosphere and passed through a furnace. The solution was concentrated under reduced pressure and extracted with ethyl ether. After drying the extract over sodium sulfate, ethyl ether was distilled off under reduced pressure to obtain 1-(1,4
-benzodioxan-6-yl)ethylamine 7.6
g (yield 42%) was obtained.

Reference Example 7 (1-(2,3-dihydrobenzofuran-5-
Synthesis of ethylamine) Same as Reference Example 6 except that 2,3-dihydrobenzofuran-5-ylmethylketone was used instead of 1,4-benzodioxan-6-yl-methylketone. 16.1 g (yield: 78%) of 2,3-dihydrobenzofuran-5-ylmethylketone oxime was obtained, and from this oxime, 1-(2 ,3-dihydrobenzofuran-5
8.65 g (45% yield) of ethylamine (yield: 45%) was obtained.

Reference Example 8 (Synthesis of 1-(6'-indenyl)ethylamine) 7.35 g (48.5 mmol) of 6-acetylindene was dissolved in 100 mA' of methanol, and 35.8 g (465 mmol) of ammonium acetate and cyanohydrogenation were added. 2.04 g (32.5 mmol) of sodium boron was added, and the mixture was mixed and stirred at room temperature for 30 hours. The reaction mixture was concentrated under reduced pressure, acidified with a small amount of concentrated hydrochloric acid, and extracted with ethyl ether and water. The resulting aqueous layer was made alkaline with an aqueous sodium hydroxide solution and extracted with ethyl ether. The ethyl ether layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 1-(6'-indenyl)ethylamine represented by the formula 5.
．． Oz (68% yield) was obtained.

Reference Example 9 (Synthesis of 1-(2-naphthyl)ethylbiguanide hydrochloride) 10.4 g (50 mmol) of 1-(2-naphthyl)ethylamine hydrochloride synthesized in Reference Example 1, 4.2 g of cyanoguanidine ( 50 mmol) and 35 ml of 0-dichlorobenzene were mixed and heated at 140-150°C for 10
The mixture was heated and stirred for hours. Thereafter, the reaction mixture was cooled, and the precipitate deposited was collected in a furnace and washed three times with 5 mi' of toluene. Then, the toluene was distilled off under reduced pressure to obtain solid 1-(2-naphthyl)ethyl biguanide hydrochloride 1.
2.8 g (yield 88%) was obtained.

Reference Example 10 (Synthesis of 1-(5,6,7,11-tetrahydro-2-naphthyl)ethylbiguanide hydrochloride) In Reference Example 9, 1-(5- ,6,7,8-tetrahydro-2
The same operation as in Reference Example 9 was carried out except that 50 mmol of 1-(5,6-naphthyl)ethylamine hydrochloride was used.
, 7,8-tetrahydro-2-naphthyl)ethylbiguanide hydrochloride (14.1 g (yield 95%)) was obtained.

Production example 1 2-amino-4,6-dichloro-s-triazine 1.6
4 g (10 mmol) was dissolved in 5.5 g of acetone, and 1.71 g (10 mmol) of 1-(2-naphthyl)-ethylamine obtained in Reference Example 1 was added thereto, followed by 6.5 g (10 mmol) of water. 0.84g of sodium hydrogen carbonate (
A suspension of 10 mmol) was added at 0-5° C. with stirring. Thereafter, the mixture was gradually warmed to 50° C. over 1 hour.

After heating, the mixture was cooled, the product was separated, washed with water, and recrystallized from ethanol-water. White crystals of 2-amino-4
-Chloro-6-[1-(2'-naphthyl)ethylamino 1-s-triazine (Compound 1) was obtained in an amount of 2.78 g (yield 93%). The structural formula and analysis results of this product are shown in Tables 1 to 3.

Production Examples 2 to 8 In Production Example 1, the same operations as Production Example 1 were performed except that each alkylamine obtained in Reference Examples 2 to 8 was used instead of 1-(2-naphthyl)ethylamine. and the corresponding 2-amino-4-chloro-6-alkylamino-8-triazine (in the order of Reference Examples 2 to 8 of the alkylamines used, Compound 2, Compound 3, Compound 5, Compound 8, Compound 7. Compound 4. Compound 6) was obtained. Their structural formulas and analysis results are shown in Tables 1 to 3.

Production Example 9 9.0 g of isopropanol heated to 50-60°C and sodium methyl mercaptide a, o g at a concentration of 15%
2-amino-4-chloro- obtained in Production Example 1
6-4--[1-(2'-naphthyl)ethylamino]
3.00 g (10 mmol) of -s-triazine was added with stirring. While stirring the resulting reaction mixture,
After heating under reflux for an hour, cool to 10°C and add 100% water to this.
mj! added. Further, extraction was performed three times with 20 mR of ethyl acetate, and the ethyl acetate layer was dried over sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: toluene/ethyl acetate = 8/2) and recrystallized from ethanol-water to give white crystals of 2-amino-4-methylthio-6-
2.61 g (yield 94%) of [1-(2'-naphthyl)ethylamino]-S-triazine (Compound 9) was obtained.

The structural formula and analysis results of this product are shown in Tables 1 to 3.

Production Examples 10 to 16 In Production Example 9, 2-amino-4-chloro-6-(1
-(2'-naphthyl)ethylamino] In place of -s-triazine, each compound 2 obtained in Production Examples 2 to 8 was used.
The same operation as in Production Example 9 was carried out except that 8-8 was used, and the corresponding 2-amino-4-methylthio-6-alkylamino-8-triazine (Compound 10.
1. Compound 12° Compound 13. Compound 14. Compound 15
．． Compound 16) was obtained. Their structural formulas and analysis results are shown in Tables 1 to 3.

Production Example 17 2-Amino-4-chloro-6-[1 synthesized in Production Example 1
-(2'-naphthyl)ethylamino] -s-triazine (compound 1) 3.00 g (10 mmol) in methanol 20 mJ! After dissolving in the solution, 2.31 g (12 mmol) of 28% sodium methylate was added, and the mixture was heated under reflux with stirring for 14 hours. After methanol was distilled off under reduced pressure, it was dissolved in 50 mj of chloroform and washed with water. After drying the chloroform layer over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: toluene/ethyl acetate = 872) and recrystallized from ethanol-water to give white crystals of 2-amino-4-methoxy-6-(1-( 2'-naphthyl)ethylamino]-s-triazine (Compound 17) was obtained in an amount of 2.74 g (yield 93%).The structural formula and analysis results of this product are shown in Tables 1 to 3.

Production example 18 20ml of dry methanol! 0.46g of sodium
(20 mmol) was gradually added to form sodium methoxide, and 2.92 g (10 mmol) of 1-(2-naphthyl)ethyl biguanide hydrochloride obtained in Reference Example 9 was added, and 30 mmol was heated at room temperature. Stir for a minute. Then, 2.38 m1' (20 mmol) of trifluoroacetic acid ethyl ester was added dropwise, and the mixture was stirred at room temperature for 10 hours. After the reaction, the contents were poured into 100 mF of water, and 50 mF of ethyl acetate was added.
Extractions were performed three times with mR. After drying this ethyl acetate layer over sodium sulfate, ethyl acetate was distilled off under reduced pressure. After the residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate = 4/1),
Recrystallized from hexane-ethyl ether to give a white 2-amino-4-(1-(2'-naphthyl)ethylaminocor).
6-trifluoromethyl-8-triazine (compound 18
) was obtained (1.14 g (yield 34%)). The structural formula and analysis results of this product are shown in Tables 1 to 3.

Production Example 19 ″ Production Example except that 5 mmol of 1-(5,6,7,8-tetrahydro-2-naphthyl)ethylbiguanide hydrochloride was used instead of 1-(2-naphthyl)ethylbiguanide hydrochloride. 2-amino-4-
(1-(2'-naphthyl)ethylamino]-6-(α,
α-dichloroethyl) -S-triazine (compound 19
) was obtained. The analysis results and structural formula of this product are shown in Tables 1 to 3.

Production Example 20 2 by replacing trifluoroacetic acid ethyl ester
-Amino-4-[1-(5',6',7',8'-tetrahydro-2'-naphthyl)ethylamino]-6-(α
, α-dichloroethyl)-s-)-riazine (compound 2
0) was obtained. The analysis results and structural formula of this product are
It is shown in Table 3.

Production Example 21 2-Amino-4-chloro-6-[1 obtained in Production Example 1
-(2'-naphthyl)ethylamino]-s-triazine3. oog (10 mmol) to benzene 20mj! Then 1.57 g (20 mmol) of triethylamine was added. To this was added dropwise 2.02 g (20 mmol) of acetyl chloride while stirring under water cooling, followed by stirring at room temperature for 3 hours, and then heating under reflux for 1 hour. After cooling, the benzene layer was washed with water, dried over sodium sulfate, and then benzene was distilled off under reduced pressure.

The residue was subjected to silica gel column chromatography (developing solvent: toluene/ethyl acetate = 8/2) to obtain 0.75 g (yield 22%) of gin (compound 21). The structural formula and analysis results of this product are shown in Tables 1 to 3.

Production Example 22 2-amino-4-methylthio-6- obtained in Production Example 9
[3.11 g (10 mmol) of 1-(2'-naphthyl)ethylaminoco-5-triazine, 1.93 g (10 mmol) of a 28% methanol solution of sodium methoxide and 10 mj of methanol! was added, and after heating to 50°C, methanol was distilled off under reduced pressure. Add 2 methyl acetate to the residue.
0mJ! After adding and heating to 50°C, 20 ml of water was added. After washing the ethyl acetate layer with water, ethyl acetate was distilled off under reduced pressure, and the resulting solid was recrystallized from acetone-water, resulting in white crystals of 2-acetylamino-4-methylthio-6-[
2.58 g (yield 73%) of 1-(2'-naphthyl)ethylamino]-S-triazine (compound 22) was obtained. The structural formula and analysis results of this product are shown in Tables 1 to 3.

Production Example 23 2-amino-4-methoxy-6- obtained in Production Example 17
(2-Cyclopropylcarbonylamino-4-methoxy −
6-[1-(2'-naphthyl)ethylamino]-S-triazine (Compound 23) was obtained. The structural formula and analysis results of this product are shown in Tables 1 to 3.

Production Example 24 2-amino-4-methylthio-6- obtained in Production Example 9
3.11 g (10 mmol) of [1-(2'-naphthyl)ethylamino]-s-triazine was added to 20 ml of benzene.
2.18 g (30 mmol) of isobutyraldehyde and 0.05 g of p-toluenesulfonic acid were added.
The mixture was heated to reflux for an hour. After cooling, the benzene layer was washed with water, dried over sodium sulfate, and then distilled off under reduced pressure. The residue was developed and purified by silica gel column chromatography (developing solvent: toluene/ethyl acetate = 98/2) to give a colorless resinous 2-isobutyleneimino-4-methylthio-6-[1-(2'-naphthyl). ) Ethylaminoco-S-triazine (Compound 24) was obtained in an amount of 2.34 g (yield 64%). The structural formula and analysis results of this product are shown in Tables 1 to 3.

Examples 1 to 16 (1) Preparation of herbicide 97 parts by weight of talc (trade name: Nidicrite) as a carrier, alkylaryl sulfonate (trade name: Nesai Verex, manufactured by Kao Atlas ■) as a surfactant.1. 5 parts by weight and nonionic and anionic surfactants (trade name: Solbol 800A).

1.5 parts by weight (manufactured by Toho Kagaku Kogyo ■) were uniformly ground and mixed to obtain a carrier for wettable powders.

90 parts by weight of this wettable powder carrier and 10 parts by weight of the triazine derivatives obtained in Production Examples 1 to 24 were uniformly ground and mixed to obtain a herbicide.

(2) Biological test (flooded soil treatment test) Paddy soil was filled in a porcelain pot measuring 1,715,500 are.
On the surface layer, weeds, cypress, and broad-leaved weeds (kikashigusa,
Seeds of Japanese cypress (Konagi) and Japanese firefly were sown uniformly, and tubers of Japanese cypress and Japanese cypress were also transplanted, and paddy rice at the two-leaf stage was transplanted.

Thereafter, when the weeds germinated, a predetermined amount of the diluted herbicide obtained in (1) above was uniformly dropped onto the water surface to treat the weeds, and then the pots were left in a greenhouse and watered at appropriate times.

Table 4 shows the results of investigating the herbicidal effect and rice damage after 20 days of chemical treatment. The dosage is 50g of active ingredient.
/10a to 400g/10a. Also, paddy rice chemical damage,
The herbicidal effect was measured for each air-dried product and expressed as follows.

Degree of phytotoxicity Paddy rice phytotoxicity (vs. untreated plot) 0100% 1 95-99% 2 90-94% 3 80-89% 4 60-79% 5 50-69% Degree of herbicidal effect Weeding effect (vs. untreated plot) ratio) 0
100% 1 61~99%2
21-60% 3 11-20%
41N10% 5 0
% Comparative Example 1 In Example 1, 2-methylthio-4,6-bis(ethylamino)-S-)-riazine (represented by the following formula [A]) was used instead of the doriazine derivative produced in Production Example 1. The same operation as in Example 1 was performed except that cymetrine (generic name: cymetrine) was used. The results are shown in Table 4.

Comparative Example 2 In Example 1, 2-amino-4-α-methylbenzylamino-6-trifluoromethyl-S- represented by the following formula [B] was used instead of the triazine conductor produced in Production Example 1. The same operation as in Example 1 was performed except that triazine was used. The results are shown in Table 4.

[Effects of the Invention] As mentioned above, the triazine derivatives of the present invention are novel compounds that can be effectively used as herbicides, and according to methods 1 to 6 of the present invention, the triazine derivatives can be efficiently used. It can be produced with high purity and high yield. Furthermore, the herbicide of the present invention containing this triazine derivative as an active ingredient is characterized in that it has greater efficacy, less phytotoxicity, and a wider herbicidal spectrum than existing herbicides for paddy rice. Specifically, as already mentioned above, it is not only effective against annual weeds such as field weeds and broad-leaved weeds, but also shows remarkable effects against weeds of the Cyperaceae family, such as cypress and bulrush, and perennial weeds, such as weed.

Claims (8)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Z^1 and Z^2 each represent an oxygen atom, methylene group, ethylene group, trimethylene group, vinylene group, or oxymethylene group as ring members. , R^1 represents an alkyl group having 1 to 4 carbon atoms, R^2 is a halogen atom,
It represents an alkylthio group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms,
R^3 is NH_2, NHCOR^4 or N-CHR
^5 (Here, R^4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, and R^5 is an alkyl group having 1 to 4 carbon atoms. ~4
is an alkyl group. ) is shown. ] A triazine derivative represented by. (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Z^1 and Z^2 each represent an oxygen atom, methylene group, ethylene group, trimethylene group, vinylene group, or oxymethylene group as ring members. and R^1 represents an alkyl group having 1 to 4 carbon atoms. ] and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X^1 and X^2 represent a halogen atom. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Z^1, Z^2, R^1 and X^1 are the above-mentioned is the same as ] A method for producing a triazine derivative represented by: (3) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Z^1 and Z^2 each represent an oxygen atom, methylene group, ethylene group, trimethylene group, vinylene group, or oxymethylene group as ring members. , R^1 represents an alkyl group having 1 to 4 carbon atoms, and X^1 represents a halogen atom. ] The halogen-containing triazine derivative represented by the general formula R^6SH [wherein R^6 represents an alkyl group having 1 to 4 carbon atoms]. ] Alkyl mercaptan or general formula (R
^6S)_nM [In the formula, M represents an alkali metal or an alkaline earth metal, and n represents the valence of M. Further, R^6 is the same as above. ] A general formula characterized by reacting an alkyl mercaptide represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Z^1, Z^2, R^1 and R^6 are the same as above It is. ] A method for producing a triazine derivative represented by: (4) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Z^1 and Z^2 each represent an oxygen atom, methylene group, ethylene group, trimethylene group, vinylene group, or oxymethylene group as ring members. , R^1 represents an alkyl group having 1 to 4 carbon atoms, and X^1 represents a halogen atom. ] The halogen-containing triazine derivative represented by the general formula R^6OH [wherein R^6 represents an alkyl group having 1 to 4 carbon atoms. ] An alcohol represented by the general formula (R^6O)_nM [wherein M represents an alkali metal or an alkaline earth metal, and n represents the valence of M. Further, R^6 is the same as above. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting alkoxides represented by ▼ [In the formula, Z^1, Z^2, R^1 and R^6 are the same as above . ] A method for producing a triazine derivative represented by: (5) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, Z^1 and Z^2 each represent an oxygen atom, a methylene group, an ethylene group, a trimethylene group, a vinylene group, or an oxymethylene group as a ring member. , R^1 represents an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom. ] A salt of an alkylamine derivative represented by the formula ▲mathematical formula,
There are chemical formulas, tables, etc. By reacting with cyanoguanidine represented by ▼, the general formula ▲ There are numerical formulas, chemical formulas, tables, etc. It is. ] A salt of a biguanide derivative represented by is produced, and then the salt of the derivative has the general formula R^7COOR^6 [wherein R^7 represents a haloalkyl group having 1 to 4 carbon atoms, and R^8 represents a carbon atom] It represents an alkyl group of numbers 1 to 4. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Z^1, Z^2, R^1 and R^7 are the same as above] It is. ] A method for producing a triazine derivative represented by: (6) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Z^1 and Z^2 each represent an oxygen atom, methylene group, ethylene group, trimethylene group, vinylene group, or oxymethylene group as ring members. , R^1 represents an alkyl group having 1 to 4 carbon atoms, R^2 is a halogen atom,
It represents an alkylthio group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms. ] The amino group-containing triazine derivative represented by the general formula R^4COX [wherein R^4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a cycloalkyl group having 2 to 6 carbon atoms]
5 represents an alkenyl group, and X represents a halogen atom. ] A carboxylic acid halide represented by the general formula R^4COOH [wherein R^4 is the same as above. ] Carboxylic acid represented by the general formula (R^4CO)_2O [wherein R^4 is the same as above. ] Carboxylic acid anhydride or general formula R^4COOR^9 [wherein R^4 is the same as above, R^9 has a carbon number of 1
-4 alkyl group is shown. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting carboxylic acid esters represented by ▼ [In the formula, Z^1, Z^2, R^1, R^2 and R^4
is the same as above. ] A method for producing a triazine derivative represented by: (7) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Z^1 and Z^2 each represent an oxygen atom, methylene group, ethylene group, trimethylene group, vinylene group, or oxymethylene group as ring members. , R^1 represents an alkyl group having 1 to 4 carbon atoms, R^2 is a halogen atom,
It represents an alkylthio group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms. ] The amino group-containing triazine derivative represented by the general formula R^5CHO [wherein R^5 represents an alkyl group having 1 to 4 carbon atoms. ] Aldehyde represented by the general formula R^5CH(OR^9)_2 [wherein R^5 is the same as above, R^9 has a carbon number of 1
~4 alkyl group is shown. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting acetals represented by ▼ [In the formula, Z^1, Z^2, R^1, R^2 and R^5
is the same as above. ] A method for producing a triazine derivative represented by: (8) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Z^1 and Z^2 each represent an oxygen atom, methylene group, ethylene group, trimethylene group, vinylene group, or oxymethylene group as ring members. , R^1 represents an alkyl group having 1 to 4 carbon atoms, R^2 is a halogen atom,
It represents an alkylthio group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms,
R^3 is NH_2, NHCOR^4 or N=CHR
^5 (Here, R^4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, and R^5 is an alkyl group having 1 to 4 carbon atoms. ~4
is an alkyl group. ) is shown. ] A herbicide containing a triazine derivative represented by: