JPH05148245A - Triazine derivative, its production and herbicide - Google Patents

Abstract

PURPOSE:To provide a new compound having an excellent herbicidal activity against annual Gramineae weeds, annual broadleaf weeds, etc. CONSTITUTION:A compound of formula I (R<1> is lower alkyl, lower alkenyl, lower alkinyl, etc.; R<2> is H, lower alkyl; R<3> is H, lower alkyl, benzyl; R<4> is lower alkyl, lower alkoxy; X is O, S), e.g. 2-(4,6-dimethoxy-S-triazin-2-yl)oxy-3- ethoxy-3-methylbutanoic acid ethyl ester. The compound of formula I is obtained by reacting a compound of formula II with a compound of formula III in the presence of a base such as potassium carbonate in a solvent such as acetonitrile.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a herbicide containing a novel triazine derivative as an active ingredient.

[0002]

Description of the Prior Art Many herbicides have been developed so far in order to save labor in agricultural work and improve productivity of agricultural products. However, it cannot be said that the conventional herbicides have a sufficient herbicidal effect and sufficiently satisfy the problem regarding the safety to living organisms. Therefore, development of a new herbicide that solves these problems is desired. The triazine derivative of the present invention and the 3-alkoxy-2-mercaptoalkanoic acid compound which is a raw material for producing the triazine derivative are novel compounds, and the herbicidal effect of the triazine derivative of the present invention has not been known.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a novel triazine derivative and 3-alkoxy-
A method for producing a 2-mercaptoalkanoic acid compound, a novel triazine derivative, and a herbicide containing the novel triazine derivative as an active ingredient.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that a novel triazine derivative is superior to annual grass-plant weeds, annual broad-leaved weeds and the like. The present invention has been completed by showing that the herbicidal effect was exhibited and that it was obtained in high yield.
That is, the present invention is as follows. The first invention is represented by the following formula (I):

[0005]

[Chemical 9]

(Wherein R ¹ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a halo lower alkyl group, or a cyano lower alkyl group; R ² represents a hydrogen atom or a lower alkyl group; R ³ Represents a hydrogen atom, a lower alkyl group, or a benzyl group; R ⁴ represents a lower alkyl group or a lower alkoxy group; and X represents an oxygen atom or a sulfur atom.). The second invention is represented by the following formula (II):

[0007]

[Chemical 10]

(Wherein R ¹ , R ² , R ³ and X have the same meanings as described above) and the following formula (II)
I):

[0009]

[Chemical 11]

The present invention relates to a method for producing a triazine derivative represented by the above formula (I), which comprises reacting with a compound represented by the formula (wherein R ⁴ has the same meaning as described above). .. A third aspect of the invention is the following formula (II-
S):

[0011]

[Chemical 12]

(In the formula, R ⁵ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a halo lower alkyl group; R ⁶ represents a hydrogen atom or a lower alkyl group). -2-It relates to a mercaptoalkanoic acid compound. A fourth invention is the following formula (IV):

[0013]

[Chemical 13]

(Wherein R ¹ and R ² have the same meanings as described above; R ⁷ represents a lower alkyl group, an unsubstituted or substituted phenyl group, or a halo-lower alkyl group.) Formula (V):

[0015]

[Chemical 14]

The present invention relates to a process for producing a triazine derivative represented by the above formula (I), which comprises reacting with a compound represented by the formula (wherein R ⁴ has the same meaning as described above). .. The fifth aspect of the present invention is represented by the following formula (IO):

[0017]

[Chemical 15]

(Wherein R ¹ , R ² and R ⁴ have the same meanings as described above, and R ⁸ represents a lower alkyl group), and the compound represented by the formula above is transesterified. The present invention relates to a method for producing a triazine derivative represented by (I). A sixth invention is the following formula (VI):

[0019]

[Chemical 16]

(Wherein R ¹ , R ² and R ⁴ have the same meanings as described above) are hydrolyzed, and the triazine derivative represented by the above formula (I) is characterized. It relates to a manufacturing method of.

The seventh invention relates to a herbicide containing the triazine derivative represented by the formula (I) as an active ingredient. Hereinafter, the present invention will be described in detail. In the novel triazine derivative (I) which is the above-mentioned target compound and the compounds (II) to (IX) which are raw materials for producing the same, R ¹ ,
^{R 2, R 3, R 4} , R 5, R 6, R 7, R 8, R 9, R
¹⁰ , R ¹¹ , R ¹² and X are as follows.

Examples of R ¹ include a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a halo lower alkyl group, a cyano lower alkyl group and the like.

The lower alkyl group for R ¹ is preferably a linear or branched one having 1 to 6 carbon atoms; preferably 1 to 4 carbon atoms; more preferably 1 to 3 carbon atoms (eg, , Methyl group, ethyl group, n-propyl group,
i-propyl group) is preferable.

The lower alkenyl group for R ¹ is
A straight chain or branched chain having 2 to 6 carbon atoms is preferable; preferably 2 to 5 carbon atoms; more preferably 2 to 3
(For example, a propenyl group) is preferable.

The lower alkynyl group for R ¹ is
A straight chain or branched chain having 2 to 6 carbon atoms is preferable; preferably 2 to 5 carbon atoms; more preferably 2 to 3
(For example, a propynyl group) is preferable.

The halo lower alkyl group for R ¹ is preferably a linear or branched one having 1 to 6 carbon atoms (the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like). However, chlorine atom and bromine atom are preferable.);
And more preferably 1 to 3 (eg, chloroethyl group, bromoethyl group, chloropropyl group, etc.).

The cyano lower alkyl group for R ¹ is preferably a linear or branched one having 1 to 6 carbon atoms; preferably 1 to 5; and more preferably 1 to 3 ( For example, a cyanoethyl group) is preferable.

Examples of R ² include a hydrogen atom and a lower alkyl group.

The lower alkyl group for R ² is preferably a linear or branched one having 1 to 6 carbon atoms; preferably 1 to 4 carbon atoms; more preferably 1 to 3 carbon atoms.
(For example, a methyl group or an ethyl group) is preferable.

Examples of R ³ include a hydrogen atom, a lower alkyl group and a benzyl group.

The lower alkyl group for R ³ is preferably a straight or branched one having 1 to 6 carbon atoms; preferably 1 to 4 carbon atoms; more preferably 1 to 3 carbon atoms (eg, , Methyl group, ethyl group, etc.) are preferred.

Examples of R ⁴ include a lower alkyl group and a lower alkoxy group.

The lower alkyl group for R ⁴ is preferably a linear or branched one having 1 to 6 carbon atoms; preferably 1 to 4; and more preferably 1 to 3 (eg, , Methyl group, ethyl group, etc.) are preferred.

The lower alkoxy group for R ⁴ is
A straight or branched chain having 1 to 6 carbon atoms is preferable; one having 1 to 4 carbon atoms is preferable; more preferably 1 to 3
Those (for example, methoxy group, ethoxy group, etc.) are preferable.

Examples of R ⁵ include a lower alkyl group, a lower alkenyl group, a lower alkynyl group, and a halo lower alkyl group; preferably a lower alkyl group [eg, a straight chain having 1 to 6 carbon atoms] Or, branched ones are preferable, those having 1 to 4 are preferable, and those having 1 to 3 are more preferable (for example, methyl group, ethyl group, etc.)
Is good. ] Is good.

Examples of R ⁶ include a lower alkyl group and a hydrogen atom; preferably a lower alkyl group [for example, a linear or branched group having 1 to 6 carbon atoms is preferable, and preferably a lower alkyl group is preferable. It is preferably 1 to 4, more preferably 1 to 3 (eg, methyl group, ethyl group, etc.). ] Is good. R ⁶ , R ⁷ , R ⁸ , R ⁹ , R
^{Examples of 10} , R ¹¹ and R ¹² include lower alkyl groups; preferably linear or branched ones having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, More preferably, those having 1 to 3 (eg, methyl group, ethyl group, etc.) are preferable.

Examples of X include an oxygen atom and a sulfur atom.

As the novel triazine derivative (I) which is the objective compound, optical isomers based on asymmetric carbon atoms can also be mentioned. Compound (I) can be produced, for example, by Production Methods 1 to 4 shown below. (Production method 1)

[0039]

[Chemical 17]

(In the formula, R ¹ , R ² , R ³ , R ⁴ and X have the same meanings as described above.) The compound (I) usually comprises the starting compound (II) and the starting compound (III). Can be produced in the presence of a base in a solvent.

The compound (II-O) in which X represents an oxygen atom in the compound (II) is, for example, [Tetrahed]
ron Letter No. 36 36 3761 (19
1972)] or [Org. Syn. IV p. 459]
The epoxy alkanoic acid ester produced by the method described in 1. can be produced by reacting with an acid catalyst (sulfuric acid, paratoluenesulfonic acid, etc.) in an alcohol as shown below.

[0042]

[Chemical 18]

(In the formula, R ¹ , R ² and R ³ have the same meanings as described above; R ⁹ represents a lower alkyl group.) On the other hand,
The compound (II-S) in which X represents a sulfur atom in the compound (II) is, for example, as shown below.
V) can be prepared by reacting V) with sodium hydrosulfide in a polar solvent.

[0044]

[Chemical 19]

(In the formula, R ¹ , R ² and R ⁷ have the same meanings as described above.) The compound (IV) can be prepared, for example, by subjecting the corresponding 2-hydroxyalkanoic acid and sulfonyl chloride to a solvent in the presence of a base. It can be produced by hydrolyzing 2-sulfonyloxyalkanoic acid obtained by the reaction below.

Examples of the compound (IV) are shown in Table 2
Compounds 4,8,13,17,18,22 shown in 7
Compounds (IV) having respective substituents corresponding to 24, 27, 28, 31, 35, 40 and the like (respectively (IV) ₄ ,
(IV) ₈ , (IV) ₁₃ , (IV) ₁₇ , (IV)
₁₈ , (IV) ₂₂ , (IV) ₂₄ , (IV) ₂₇ ,
(IV) ₂₈ , (IV) ₃₁ , (IV) ₃₅ , (1V)
_It is called ₄₀ . And, for example, compound (IV) ₄ means that R ¹ is CH ₃ , R ² is a hydrogen atom, and R ⁷ is a lower alkyl group (eg, methyl group, ethyl group, etc.)] Can be mentioned.

The compound (II-S ') in which X represents a sulfur atom in the compound (II) is prepared by using the compound (IV) in which R ¹ is R ⁵ and R ² is R ⁶ . Can be synthesized. The compound (IV) used at this time is, for example, a compound (IV) [(IV) _(II-S′-1 ) having each substituent corresponding to the starting compound (II-S ′) shown in Table 7. ₎ , (I
V) _(II-S'-2) , (IV) _(II-S'-3)
And so on. And, for example, (IV)
_(II-S-1) means that R ⁵ and R ⁶ in the compound (IV) are methyl groups. ] Can be mentioned.

The reaction conditions for producing the compound (II-S) are as follows. Sodium hydrosulfide can be obtained as a commercial product. The solvent is not particularly limited as long as it is not directly related to this reaction, for example,
Examples thereof include dipolar aprotic solvents such as N, N-dimethylformamide and dimethyl sulfoxide; nitriles such as acetonitrile.

Examples of the base include sodium hydrosulfide itself, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; and alkali metal alcoholates such as sodium methoxide. The base can be added in a proportion of 0.5 to 1.0 mol with respect to 1 mol of the compound (IV).

The reaction concentration can be 5 to 80%. The ratio of compound (IV) and sodium hydrosulfide used is 1 mol of compound (IV) to 1 mol of sodium hydrosulfide.
-3 mol, preferably 1-1.5 mol. The reaction temperature is not particularly limited as long as it is carried out below the boiling point of the solvent used, but it is usually preferably carried out at 20 to 80 ° C. The reaction time varies depending on the above concentration and temperature, but is usually 1
It can be done in ~ 24 hours.

Examples of the compound (II) are shown in Table 2
Compounds 1, 4, 5, 9, 10, 13, 1 shown in 7
4,17,18,19,22,23,24,25,2
Each compound (II) consisting of the type of each substituent corresponding to 7, 29, 32, 36, 42 [respectively compound (II) ₁ ,
(II) ₄ , (II) ₅ , (II) ₉ , (II) ₁₀ ,
(II) ₁₃ , (II) ₁₄ , (II) ₁₇ , (II)
₁₈ , (II) ₁₉ , (II) ₂₂ , (II) ₂₃ ,
(II) ₂₄ , (II) ₂₅ , (II) ₂₇ , (II)
₂₉ , (II) ₃₂ , (II) ₃₆ , (II) _{42 and the} like. For example, the compound (II) ₁₄ is the compound (I
R ¹ and R ³ in I) are C ₂ H ₅ , R ² is CH ₃ ,
X means O. ] Can be mentioned.

The compound (III-1) in which R ⁴ in the compound (III) is an alkoxy group can be produced, for example, by reacting cyanuric acid with an alkyl alcoholate as shown below.

[0053]

[Chemical 20]

(In the formula, R ¹⁰ represents an alkyl group; M represents an alkali metal.) R ⁴ in the compound (III)
The compound (III-2) in which is represented by an alkyl group can be produced, for example, by reacting cyanuric acid with a Grignard reagent and then reacting with sodium methoxide.

[0055]

[Chemical 21]

(In the formula, R ¹¹ represents an alkyl group; Y represents a halogen atom.) Examples of the compound (III) include compounds 1, 4, 5, 9, 1 shown in Tables 2 to 7.
0, 13, 14, 17, 18, 19, 22, 23, 2
4, 25, 27, 29, 32, 36, 42, etc., each compound (III) consisting of the type of each substituent [each,
Compounds (III) ₁ , (III) ₄ , (III) ₅ ,
(III) ₉ , (III) ₁₀ , (III) ₁₃ , (I
II) ₁₄ , (III) ₁₇ , (III) ₁₈ , (II
I) ₁₉ , (III) ₂₂ , (III) ₂₃ , (II
I) ₂₄ , (III) ₂₅ , (III) ₂₇ , (II
I) ₂₉ , (III) ₃₂ , (III) ₃₆ , (II
I) ₄₂ etc. ] [For example, compound (III)
₁₄ means that R ⁴ in the compound (III) is OCH ₃ . ] Can be mentioned.

The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include water; ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; ketones such as acetone methyl ethyl ketone methyl isobutyl ketone. Nitriles such as acetonitrile; dipolar aprotic solvents such as N, N-dimethylformamide, N, N-dimethyl-2-imidazolidinone and dimethylsulfoxide; mixtures of the above solvents.

Examples of the base include inorganic bases such as sodium amide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride.

The process for producing the compound (I) has a reaction concentration of 5 to 5.
It can be performed at 80%. In the production method, the ratio of the raw material compounds (II) and (III) used is such that the raw material compound (III) is 0.
It can be added in a ratio of 5 to 2 mol, but preferably 1
~ 1.5 mol is preferred. The reaction temperature is not particularly limited as long as it is carried out at a temperature not higher than the boiling point of the solvent used, but usually 10 to
It can be carried out at 50 ° C., but can be heated to shorten the reaction time. The reaction time varies depending on the above-mentioned concentration and temperature, but can be usually 0.5 to 10 hours.

(Manufacturing method 2)

[0061]

[Chemical formula 22]

(In the formula, R ¹ , R ² , R ⁴ and R ⁷ are as defined above.) In the compound (I), R ³ is a hydrogen atom and X is a sulfur atom (I -S ')
Can be obtained in the same manner as in Production Method 1, except that (IV) is used instead of the starting compound (II) and (V) is used instead of the starting compound (III). As the compound (IV), for example, as shown below, a compound (II-O ') in which R ³ in the compound (II-O) is a hydrogen atom and a sulfonyl chloride are present in a suitable solvent in the presence of a base catalyst. It can be produced by reacting under.

[0063]

[Chemical formula 23]

(In the formula, R ¹ , R ² and R ⁷ have the same meanings as described above.) Examples of the compound (IV) include compounds 4, 8, 13, 17 shown in Tables 2 to 7. , 22, 2
4,27,31,35,39,40 and the like, each compound (IV) consisting of the kind of each substituent [compound (IV) ₄ , (IV) ₈ , (IV) ₁₃ , (I
V) ₁₇ , (IV) ₂₂ , (IV) ₂₄ , (I
V) ₂₇ , (IV) ₃₁ , (IV) ₃₅ , (I
V) ₃₉ , (IV) _{40 and the} like. For example, the compound (IV) ₈ is R ¹ CH ₃ in the compound (IV), R ² is a hydrogen atom, and R ⁷ is a lower alkyl group, an unsubstituted or substituted phenyl group, or a halo lower alkyl group. Means that. ] Can be mentioned.

The compound (V) is, for example, the compound (II
I) can be easily prepared by reacting with sodium hydrosulfide in water or alcohol. Examples of the compound (V) include compounds 4, 8, 13, 17, 22, 24, 27, 31, 35, shown in Tables 2 to 7,
Each compound (V) consisting of each substituent type corresponding to 39, 40, etc. [respectively compound (V) ₄ , (V) ₈ , (V)
₁₃ , (V) ₁₇ , (V) ₂₂ , (V) ₂₄ , (V)
₂₇ , (V) ₃₁ , (V) ₃₅ , (V) ₃₉ , (V)
Such as ₄₀ . For example, compound (V) ₈ means that R ⁴ in compound (V) is OCH ₃ . ] Can be mentioned. The solvent, the base, the reaction temperature, and the reaction time may be those described in the production method 1 for the reaction. (Production method 3)

[0066]

[Chemical formula 24]

(In the formula, R ¹ , R ² , R ⁴ and R ⁸ have the same meanings as described above; R ¹² represents a lower alkyl group.) In compound (I), R ³ is benzyl group and X is The compound (VI) represented by an oxygen atom is usually the compound (IO)
In a solvent, using titanium tetraalkoxide as a catalyst,
It can be easily obtained by transesterification with benzyl alcohol. Compound (I-O) can be easily produced, for example, by the above Production Method 1.

Examples of the compound (I-O) are shown in Table 2
Compounds 2, 6, 11, 15, 20, 2 shown in
Each compound consisting of the kind of each substituent corresponding to 6, 30, 33, 37, etc. [respectively compound (IO) ₂ , (I-
O) ₆ , (I-O) ₁₁ , (I-O) ₁₅ , (I-O)
₂₀ , (I-O) ₂₆ , (I-O) ₃₀ , (I-O)
₃₃ , (I-O) _{37 and the} like. For example, compound (I-O) ₁₅ means that R ¹ in compound (VI) is C ₂
It means that H ₅ and R ² are CH ₃ , R ⁴ is OCH ₃ , and R ⁸ is a lower alkyl group. ] Can be mentioned.

The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include aromatic hydrocarbons such as benzenetoluene xylene. Examples of the catalyst include titanium tetraisopropoxide and titanium tetra-n-propoxide. In the method for producing compound (VI), the reaction concentration is 5
~ 80%.

In the production method, the starting compound (IV)
The ratio of benzyl alcohol to the starting compound (IV) 1
The benzyl alcohol may be added in an amount of 1 to 3 moles, preferably 1.5 to 2 moles. The reaction temperature is not particularly limited as long as it is carried out at a temperature not higher than the boiling point of the solvent used, but it can usually be carried out at 70 to 150 ° C. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be 2 to 20 hours. (Production method 4)

[0071]

[Chemical 25]

(In the formula, R ¹ , R ² and R ⁴ have the same meanings as described above.) In the compound (I), R ³ is a hydrogen atom and X is an oxygen atom. ,Normal,
It can be easily obtained by hydrogenating compound (VI) in a solvent at atmospheric pressure using palladium carbon as a catalyst. Compound (VI) can be produced, for example, by the above-mentioned production method 3.
Can be easily manufactured by.

As the compound (VI), for example, Table 2
Compounds 3, 7, 12, 16, 21, 34, shown in 7
Each compound (VI) consisting of the kind of each substituent corresponding to 38, 41, etc. [respectively compound (VI) ₃ , (VI) ₇ ,
(VI) ₁₂ , (VI) ₁₆ , (VI) ₂₁ , and (VI)
₃₄ , (VI) ₃₈ , (VI) _{41 and the} like. For example, compound (VI) ₁₆ means R in compound (VI)
¹ means C ₂ H ₅ , R ² is CH ₃ , and R ⁴ is OCH ₃ . ] Can be mentioned.

The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include chlorinated and unchlorinated aromatic hydrocarbons such as benzenetoluene xylene and chlorobenzene; tetrahydrofuran and the like. Ethers; alcohols such as methanol and ethanol can be mentioned. As a catalyst,
Mention may be made of palladium carbon.

The method for producing the compound (I) has a reaction concentration of 5 to 5.
It can be performed at 80%. The reaction temperature is not particularly limited as long as it is carried out at a temperature not higher than the boiling point of the solvent used, but usually,
It can be performed at room temperature or higher, but is preferably 10 to 80.
C. is good, and more preferably 20 to 50.degree. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be 0.5 to 12 hours. These 1 to 4
As the compound (I) obtained by the production method of, for example, Table 2
To Compounds 1 to 42 shown in [7] [for example, Compound 1 is compound (I) in which R ¹ is C].
H ₃ and R ² are hydrogen atoms, R ³ is C ₂ H ₅ and R ⁴ is C ₂ H
₅ , X means an oxygen atom. ].

A herbicide containing compound (I) as an active ingredient is
It shows an excellent herbicidal effect. That is, the herbicide of the present invention shows an excellent herbicidal effect against annual weeds and perennial weeds that occur in paddy fields, fields, and the like, and the herbicidal effect is particularly that of annual weedy grasses (for example, Meshishiba, Nobie,
It is prominent in annual broadleaf weeds (eg, morning glory, white azalea, dogwood, velvetleaf) and perennial weeds (eg, Johnsongrass, firefly, water lily). Further, although the herbicide of the present invention has an excellent herbicidal effect on the above weeds, some herbicides do not show phytotoxicity to field crops at such a treatment concentration.

The herbicide of the present invention contains at least one compound (I) as an active ingredient. Compound (I)
Can be used alone, but is usually mixed with a carrier, a surfactant, a dispersant, an auxiliary agent, etc. by a conventional method (for example, powders, emulsions, fine granules, granules, wettable powders, oily preparations). It is preferably prepared as a composition such as a suspension or an aerosol).

As the carrier, for example, talc, mica, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, dolomite, zeolite, slaked lime, silica sand, silicic acid anhydride, ammonium sulfate, urea, wood powder,
Solid carriers such as starch and cellulose; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform,
Carbon tetrachloride, etc., ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol) ，
Liquid carriers such as ethylene glycol), polar solvents (dimethylformamide, dimethylsulfoxide, etc.), water; gas carriers such as air, nitrogen, carbon dioxide, and freon (in this case, mixed injection can be performed). It is possible.

Nonionic, anionic, and cationic surfactants can be used to improve the performance of this agent such as adhesion to plants, improvement of absorption, dispersion of agents, emulsification, and spread. , And zwitterionic surfactants (eg alcohol sulfates, alkyl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, etc.). Then, in order to improve the properties of the preparation, carboxymethyl cellulose, polyethylene glycol, gum arabic or the like can be used as an auxiliary agent. In the production of this agent, other pesticides (bactericides, insecticides, etc.), fertilizers, soil conditioners, etc., in addition to the above carriers, surfactants, dispersants, auxiliary agents, etc., depending on their respective purposes, Each can be used alone or in an appropriate combination.

When the compound (I) of the present invention is formulated, the active ingredient concentration is usually 1 to 50% by weight for emulsions, 0.3 to 25% by weight for powders, and 1 to 90% for wettable powders. %, Usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils, and 0.1 to 5% by weight for aerosols. These formulations can be diluted to an appropriate concentration and sprayed on the surface of plant foliage, soil, water surface of paddy fields or directly applied to various applications depending on the purpose.

[0081]

EXAMPLES The present invention will be described below with reference to examples. In addition,
These examples do not limit the scope of the invention. Example 1 [Synthesis of raw material compound (II-S ')] (1) Synthesis of 2-mercapto-3-methoxy-3-methylbutanoic acid [raw material compound (II-S'-1)] N, N-dimethylformamide ( DMF) (10 ml)
3-methoxy-3-methyl-2- (p-toluenesulfonyloxy) butanoic acid (3.02 g, 0.01 mo
l) and 70% sodium hydrosulfide (1.6 g, 0.02 m
ol) was added and the mixture was stirred at 60 ° C. for 3 hours. After stirring, the resulting reaction solution was added with saturated aqueous citric acid solution (30 ml).
Was added, and the mixture was extracted with ethyl acetate, the ethyl acetate layer was washed with saturated brine, dried over sodium sulfate, and the ethyl acetate was evaporated under reduced pressure to give 1. 0 g (yield 61%) was obtained.

(2) 2-mercapto-3-ethoxy-3
Synthesis of methylbutanoic acid [raw material compound (II-S'-2)] N, N-dimethylformamide (DMF) (10 ml)
3-ethoxy-3-methyl-2- (p-toluenesulfonyloxy) butanoic acid (3.16 g, 0.01 mo
l) is dissolved and sodium methoxide (1.9) is added.
3 g, 0.01 mol) and 70% sodium hydrosulfide (0.8 g, 0.01 mol) were added, and the mixture was stirred at 60 ° C. for 3 hours. After completion of stirring, saturated aqueous citric acid solution (30 ml) was added to the obtained reaction solution, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine and dried over sodium sulfate, and the ethyl acetate was evaporated under reduced pressure. By removing, 1.3 g (yield 73%) of the target compound which was a pale yellow oily substance was obtained.

(3) Other starting compounds (II
Synthesis of —S ′) Other raw material compounds (II-S ′) in Table 1 were synthesized in the same manner as in (1) and (2).

[0084]

[Table 1]

Example 2 [Synthesis of compound (I)] (1) 2- (4,6-dimethoxy-S-triazine-2)
Synthesis of ethyl -yl) oxy-3-ethoxy-3-methylbutanoate (Compound 14) The compound (I) of the present invention was synthesized by the method described in (Production Method 1). Ethyl 2,3-epoxy-3-methylbutanoate (14.4 g, 0.1 mol) was dissolved in ethanol (40 ml), and sulfuric acid (0.5 m) was used as a catalyst.
After adding 1), the mixture was stirred at 30 ° C. for 2 hours.

Then, excess ethanol was distilled off under reduced pressure,
The residue was subjected to column chromatography (Wako Gel C-20
0, n-hexane: ethyl acetate = 7: 3 elution) to obtain ethyl 3-ethoxy-2-hydroxy-3-methylbutanoate, which was suspended in sodium hydride (60% dissolved oil 4 g, 0.1 mol). The mixture was added to cloudy tetrahydrofuran (100 ml) at 5 ° C. and stirred for 30 minutes. After completion of stirring, 2-chloro-4,6-dimethoxy-S
-Add a tetrahydrofuran solution (50 ml) in which triazine (17.5 g, 0.1 mol) is dissolved, and add 20 ° C.
It was stirred for 1 hour. The obtained reaction solution was added to water and extracted with ethyl acetate, the ethyl acetate layer was washed with saturated saline,
The residue obtained by drying over sodium sulfate and distilling off ethyl acetate under reduced pressure was isolated by column chromatography (Wakogel C-200, elution with n-hexane: ethyl acetate = 3: 1) to give a colorless oily substance. 26.3 g (yield 80%) of the target compound of

(2) Synthesis of benzyl 2- (4,6-dimethoxy-S-triazin-2-yl) oxy-3-ethoxy-3-methylbutanoate (Compound 15) By the method described in (Production Method 3). , Target compound (I)
Was synthesized. Compound 14 produced in (1) above
(32.9 g, 0.1 mol) and benzyl alcohol (16.2 g, 0.15 mol) were added to toluene (200
ml). Then, titanium tetraisopropoxide (3 ml) was added as a catalyst to the mixture, and the mixture was heated under reflux for 6 hours while removing the ethanol liberated on the way.

Then, the mixture was cooled to room temperature, the toluene layer was washed with water, and the toluene was distilled off under reduced pressure, and the resulting residue was subjected to column chromatography (Wakogel C-200, n-hexane: ethyl acetate = 3: 1 elution). 3) g (yield: 85) of the target compound as a colorless oily substance.
%)Obtained.

(3) Synthesis of 2- (4,6-dimethoxy-S-triazin-2-yl) oxy-3-ethoxy-3-methylbutanoic acid (Compound 16) By the method described in (Production Method 4). The compound (I) of the present invention was synthesized. Compound 15 (39.2 g, 0.1 mol) produced in the above (2) was mixed with ethanol (20
0 ml). Then, palladium carbon (0.5 g) as a catalyst was added thereto, and the mixture was stirred at room temperature (20 ° C.) for 1 hour while blowing hydrogen. Then, the catalyst was filtered and the mother liquor was concentrated to obtain 28.6 g (yield: 95%) of the target compound as a colorless oily substance.

(4) Synthesis of 2- (4,6-dimethoxy-S-triazin-2-yl) thio-3-ethoxy-3-methylbutanoic acid (Compound 16) By the method described in (Production Method 1), Target compound (I)
Was synthesized. 3-Ethoxy-2-mercapto-3-methylbutanoic acid (17.8 g, 0.1 mol) was dissolved in 1N sodium hydroxide. Then, in this, acetone (1
A solution of 2-chloro-4,6-dimethoxy-S-triazine (17.5 g, 0.1 mol) in (00 ml) was added, and the mixture was stirred at room temperature (20 ° C.) for 1 hour.

The resulting reaction solution was added with a 5N hydrochloric acid aqueous solution (100
ml) was added and the mixture was extracted with ethyl acetate, the ethyl acetate layer was washed with saturated brine, dried over sodium sulfate, and ethyl acetate was distilled off under reduced pressure, and the obtained residue was subjected to column chromatography (Wakogel C- 200, n-hexane: ethyl acetate: acetic acid = 1: 1: 0.1 elution).
23.7 g (yield: 75%) of the target compound was obtained as a colorless transparent oily substance.

(5) Synthesis of 2- (4,6-dimethoxy-S-triazin-2-yl) thio-3-methoxy-3-methylbutanoic acid (Compound 8) By the method described in (Production Method 2). Target compound (I)
Was synthesized. 3-Methoxy-3-methyl-2-paratoluenesulfonyloxybutanoic acid (30.2 g, 0.1 m
ol) and 4,6-dimethoxy-2-mercapto-S-triazine (17.3 g, 0.1 mol) were added to N, N, dimethylformamide (150 ml), and potassium carbonate (13.8 g, 0. 1 mol) and add 50
The mixture was stirred at 0 ° C for 2 hours.

5N hydrochloric acid (100 ml) was added to the resulting reaction solution.
Was added and extracted with ethyl acetate, the ethyl acetate layer was washed with saturated brine, dried over sodium sulfate, the ethyl acetate was distilled off under reduced pressure, and the obtained residue was subjected to column chromatography (Wakogel C-200, It was isolated by n-hexane: ethyl acetate: acetic acid = 1: 1: 0.1 elution) to obtain 24.2 g (yield 80%) of the target compound as white crystals.

(6) Other compounds (I) in Tables 2 to 7
The target compound (I) as shown in Tables 2 to 7 was obtained according to any one of the synthetic methods (1) to (5).

[0095]

[Table 2]

[0096]

[Table 3]

[0097]

[Table 4]

[0098]

[Table 5]

[0099]

[Table 6]

[0100]

[Table 7]

Example 3

(1) [Preparation of Granules] 8 parts by weight of compound 8, 30 parts by weight of pentonite, 59 parts by weight of talc, 1 part by weight of neoperex powder (trade name; manufactured by Kao Corporation) and sodium ligninsulfonate. 2 parts by weight were uniformly mixed, and then a small amount of water was added and kneaded, followed by granulation and drying to obtain a granule.

(2) [Preparation of wettable powder] 50 parts by weight of compound 16, 46 parts by weight of kaolin, 2 parts by weight of neoperex powder (trade name; manufactured by Kao Corporation) and demol N (trade name; Kao Corporation) 2 parts by weight) were uniformly mixed and then pulverized to obtain a wettable powder.

(3) [Preparation of emulsion] Compound 17 (30 parts by weight), xylene (60 parts by weight), dimethylformamide (5 parts by weight) and Solpol 3005X (trade name; manufactured by Toho Chemical Industry Co., Ltd.) were added and mixed uniformly. , To obtain an emulsion.

(4) [Preparation of Dust] 5 parts by weight of compound 21, 50 parts by weight of talc and 4 parts of clay
A powder was obtained by uniformly mixing 5 parts by weight.

Example 4 (1) [Paddy field weeding test] A Wagner pot of 1/5000 are was filled with Ube soil (alluvial clay loam soil), and seeds or tubers of weeds (Novier, Firefly, Mizugaya vine) were planted and watered. In addition, the water was flooded to a depth of 3 cm. A wettable powder of the target compound (I) shown in Tables 2 to 7 prepared according to Example 3 was diluted with water to give an effective concentration of the compound (I) in each of these drug solutions at the leaf stage of Novier. Dropping treatment was performed using a pipette so as to obtain 20 g / a. And after controlling for 3 weeks in the glass room of average temperature 25 degreeC, those herbicidal effects were investigated. The evaluation of the drug effect was conducted in 6 levels [0: harmless (normal growth), 1: slight harm, 2: minor harm, 3: moderate harm, compared with the condition of the untreated section.
(4: great damage, 5: complete death). The results are shown in Table 8.

[0107]

[Table 8]

(2) [Field Soil Treatment Test] Ube soil (alluvial clay loam soil) was filled in a 1/5000 ares Wagner pot, and then Nobie, Enocorogusa, Inubiyu,
Shiroza and velvetleaf seeds were sown and covered with soil. The wettable powder of the target compound (I) shown in Tables 2 to 7 prepared according to Example 3 was diluted with water so that the effective concentration of the compound (I) in each of these drug solutions was 20 g / a. Was evenly sprayed on each soil surface layer. And after controlling for 3 weeks in the glass room of average temperature 25 degreeC, those herbicidal effects were investigated.
The evaluation results of the drug effect are shown in Table 9 by the evaluation method described in the paddy field herbicidal effect test (1).

[0109]

[Table 9]

(3) [Field foliar treatment test] A Wagner pot of 1/5000 are was filled with a volcanic ash soil, and seeds of Novie, Enocologsa, Strawberry, Shiroza, and Amaranthus were seeded and covered with soil to grow for 2 weeks. Example 3
The wettable powder of the target compound (I) shown in Tables 2 to 7 prepared according to the above was diluted to 2000 ppm with water containing a spreading agent, neoesterin (manufactured by Kumiai Chemical Co., Ltd.) (500 ppm). Each plant was sprayed uniformly. And after controlling for 3 weeks in the glass room of average temperature 25 degreeC, those herbicidal effects were investigated. The determination results of the drug effect are shown in Table 10 by the evaluation method described in the above-mentioned paddy field herbicidal effect test (1).

[0111]

[Table 10]

[0112]

INDUSTRIAL APPLICABILITY The novel triazine derivative of the present invention has an excellent herbicidal effect on annual weeds, weeds, and so on.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsumasa Harada 5 1978, Ogushi, Ube City, Yamaguchi Prefecture 5 1978, Ube Institute of Industrial Research, Ltd. Ube Institute Co., Ltd.

Claims (7)

[Claims] 1. The following formula: (In the formula, R ¹ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a halo lower alkyl group, or a cyano lower alkyl group; R ² represents a hydrogen atom or a lower alkyl group; and R ³ represents a hydrogen atom. , A lower alkyl group or a benzyl group; R ⁴ represents a lower alkyl group or a lower alkoxy group; X represents an oxygen atom or a sulfur atom.)
The triazine derivative represented by. 2. The following formula: (In the formula, R ¹ , R ² , R ³ and X have the same meanings as described in claim 1.) and a compound represented by the following formula: (In the formula, R ⁴ has the same meaning as described in claim 1.) A method for producing the triazine derivative represented by formula (I) according to claim 1, which comprises reacting with a compound represented by the formula. 3. The following formula: (In the formula, R ⁵ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, or a halo lower alkyl group; R ⁶
Represents a hydrogen atom or a lower alkyl group. ) A 3-alkoxy-2-mercaptoalkanoic acid compound represented by the formula (1). 4. The following formula: (In the formula, R ¹ and R ² have the same meanings as described in claim 1;
R ⁷ represents a lower alkyl group, an unsubstituted or substituted phenyl group, or a halo lower alkyl group. ) And a compound of the following formula: (In the formula, R ⁴ has the same meaning as described in claim 1.) A method for producing the triazine derivative represented by formula (I) according to claim 1, which comprises reacting with a compound represented by the formula. 5. The following formula: (Wherein R ¹ , R ² and R ⁴ have the same meanings as described in claim 1 and R ⁸ represents a lower alkyl group), and the compound is transesterified. A method for producing the triazine derivative represented by the formula (I). 6. The following formula: (In the formula, R ¹ , R ² and R ⁴ have the same meanings as described in claim 1.) The compound represented by formula (I) according to claim 1, which is characterized by subjecting the compound to hydrogenolysis. Method for producing triazine derivative. 7. A herbicide containing the triazine derivative represented by the formula (I) according to claim 1 as an active ingredient.