JPH04342586A - Azine compounds, their production and herbicides containing the same - Google Patents

Abstract

PURPOSE:To provide the subject novel compound as a herbicide. CONSTITUTION:A compound of formula I [R1 is halogen, (halogen-substituted) alkyl, alkoxy, etc.; R2, R3 are H, alkyl; R4 is alkyl; X1, X2 are O, S; Y1, Y2 are methyl, methoxy; Z is =CH-, N). For example, 2-bromo-6-[(4,6- dimethoxypyridin-2-yl)oxy]benzaldehyde ethylene acetal. The compound of formula I is produced by reacting a compound of formula II with a compound of formula III [Q is halogen, alkylsulfonyl, (substituted)benzenesulfonyl].

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD The present invention relates to novel azine compounds, methods for producing them, and herbicides containing them.

0002

[Prior Art] 2-phenoxypyrimidine derivatives useful as active ingredients of herbicides are described in JP-A-63-115870 and JP-A-1-93576, but the chemical structure of the compound of the present invention is Make it different.

0003

DISCLOSURE OF THE INVENTION The present invention relates to general formula (I);

0004

[Chemical formula 1]

(In the formula, R1 is a halogen atom, an alkyl group optionally substituted with a halogen atom, an alkoxy group, or -
PO(OR4) 2 groups, R2 and R3 are each independently a hydrogen atom or an alkyl group, R4 is an alkyl group, X1 and X2 are each independently an oxygen atom or a sulfur atom, and Y1 and Y2 is each independently a methyl group or a methoxy group, and Z is a =CH- group or a nitrogen atom)
The present invention relates to azine compounds represented by the above, methods for producing them, herbicides containing them, and intermediates for producing the compounds.

In the general formula (I), the alkyl group or alkyl moiety contained in R1, R2, R3 and R4 has 1 to 8 carbon atoms, such as a methyl group, an ethyl group,
Examples include propyl group, butyl group, hexyl group, octyl group, etc., and they also include structural isomers of linear or branched aliphatic chains. Further, in the general formula (I), examples of the halogen atom contained in R1 include fluorine, chlorine, bromine, and iodine atoms. The azine compound of the general formula (I) can be produced by the following method.

[A]

[0008]

[C6]

(In the formula, R1, R2, R3, X1, X2,
Y1, Y2 and Z are as described above, and Q is a halogen atom, an alkylsulfonyl group, a benzylsulfonyl group or a substituted benzylsulfonyl group)

In the general formula (III), examples of the substituent of the substituted benzylsulfonyl group represented by Q include a halogen atom, an alkyl group, an alkoxy group, and a nitro group.

The above reaction [A] is usually carried out in the presence of a base and a solvent. Examples of the base include metal hydrides such as sodium hydride and calcium hydride; hydroxides of alkali metals or alkaline earth metals such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, calcium carbonate, and sodium hydrogen carbonate; Examples include carbonates, amines such as monomethylamine, dimethylamine, and triethylamine, and nitrogen-containing heterocyclic compounds such as pyridine and quinoline. Examples of solvents include hydrocarbon solvents such as benzene, xylene, and toluene, halogenated hydrocarbon solvents such as methylene chloride and chloroform, ether solvents such as ether, tetrahydrofuran, and 1,4-dioxane, dimethylformamide, dimethylacetamide, Examples include aprotic polar solvents such as dimethyl sulfoxide and N-methyl-2-pyrrolidone. The reaction temperature of the reaction [A] is usually 0 to 20
The temperature is 0°C, preferably 50 to 150°C, and the reaction time is usually 0.1 to 24 hours, preferably 0.1 to 6 hours.

[B]

[0013]

[C7]

(wherein R1, R2, R3, X1, X2,
Y1, Y2 and Z are as described above)

The reaction [B] is usually carried out in the presence of an acid catalyst and a solvent. Examples of acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and hydrogen bromide, organic acids such as p-toluenesulfonic acid and carboxylic acid, boron trifluoride etherate, acidic ion exchange resins, and zinc chloride. . Examples of the solvent include hydrocarbon solvents such as benzene, xylene, and toluene.

[0016] The reaction temperature of the above reaction [B] is usually 0 to 30
The temperature is 0°C, preferably 50 to 200°C, and the reaction time is usually 0.1 to 100 hours, preferably 0.1 to 48 hours. Furthermore, in the case where both Y1 and Y2 in the general formula (I) are methoxy groups, it can also be produced by the following method.

[C]

[0018]

[Chemical formula 8]

(In the formula, R1, R2, R3, X1, X2 and Z are as described above, and Hal is a halogen atom)

The first step of the reaction [C] is the reaction [C].
B], and the second step is usually carried out in the presence of a base and a solvent. Examples of the base used in the second step include those mentioned in the above reaction [A], and examples of the solvent include methanol in addition to those mentioned in the above reaction [A].

The reaction temperature in the second step of reaction [C] is usually 0 to 150°C, preferably 50 to 100°C, and the reaction time is usually 0.1 to 100 hours, preferably 0.1 to 48 hours. . In the general formula (I), R1 is -CH2R1'
When it is a group (R1' is an alkyl group which may be substituted with a fluorine atom or a chlorine atom, or a hydrogen atom), it can also be produced by the following method.

[D]

[0023]

[Chemical formula 9]

(In the formula, R2, R3, X1, X2, Y1,
Y2, Z, Hal and R1' are as described above, and T is a chlorine atom, bromine atom or iodine atom)

[0025]
The reaction [D] is usually carried out in the presence of a solvent and, if desired, a catalyst. Examples of the catalyst include palladium catalysts such as bis(triphenylphosphine)palladium(II) chloride, and nickel catalysts such as bis(1,3-diphenylphosphinopropane)nickel(II). As a solvent, benzene, toluene,
Examples include hydrocarbon solvents such as xylene, ether solvents such as ether, tetrahydrofuran, and 1,4-dioxane. The reaction temperature of the reaction [D] is usually 0 to
200°C, preferably 0 to 100°C, reaction time usually 0
．． The time is 1 to 100 hours, preferably 0.1 to 48 hours.

[E]

[0027]

[Chemical formula 10]

(In the formula, R1' is as described above, and W is a methyl group, normal butyl group, secondary butyl group,
tert-butyl group or phenyl group)

002
9] The reaction [E] above is usually carried out under a nitrogen atmosphere in the presence of a solvent. Examples of the solvent include ethers and ethers such as tetrahydrofuran. The reaction temperature of the reaction [E] is usually -78 to 50°C, preferably -78 to 25°C, and the reaction time is usually 0.1 to 100 hours.
Desirably it is 0.1 to 48 hours. The general formula (I)
Among them, when R1 is an alkoxy group, it can also be produced by the following method.

[F]

[0031]

[Chemical formula 11]

(In the formula, R2, R3, X1, X2, Y1,
Y22 and Z are as described above, R5 is an alkoxy group, and M is a sodium atom, potassium atom, or lithium atom)

The reaction [F] is usually carried out in the presence of a solvent and, if desired, a catalyst. Examples of the catalyst include a complex of cuprous bromide and dimethyl sulfide, copper catalysts such as cuprous chloride, cuprous iodide, and copper, and alkali metal halide catalysts such as potassium iodide. Examples of the solvent include the same solvents as those listed in reaction [A] above.

[0034] The reaction temperature of the above reaction [F] is usually 0 to 30
0℃, preferably 100-200℃, reaction time is usually 0℃
．． The time is 1 to 100 hours, preferably 0.1 to 48 hours. In the general formula (I), when R1 is -PO(OR4)2 group, it can also be produced by the following method.

[G]

[0036]

[Chemical formula 12]

(wherein R2, R3, R4, X1, X2,
Y1, Y2 and Z are as described above)

The above reaction [G] is carried out in the presence of a solvent, if desired. Examples of the solvent include the same solvents as those listed in reaction [A] above. The reaction temperature of the reaction [G] is usually 0 to 300°C, preferably 100 to 200°C, and the reaction time is usually 0.1 to 100 hours, preferably 0.1 to 200°C.
It is 48 hours. The compound represented by the general formula [II] in the above reaction [A] can be produced by the following method.

[H] When R1 is a halogen atom:

[
0040

[Chemical formula 13]

(wherein R2, R3, X1, X2 and Ha
l is as described above) The reaction [H] is the reaction [H]
B].

[I] When R1 is a -CH2R1' group (R1' is as described above): i)

[0043]

[Chemical formula 14]

(wherein R2, R3, X1, X2 and R1
′ is as described above)

ii)

[0046]

[Chemical formula 15]

(In the formula, R1' and W are as described above.) i) of the above reaction [I] is carried out according to the above reaction [D], and ii) is carried out according to the above reaction [E]. It will be done.

[J] When R1 is an alkoxy group:

[
0049

[Chemical formula 16]

(wherein R2, R3, X1, X2 and R5
is as described above) The reaction [J] is the reaction [F
].

[K] When R1 is -PO(OR4) 2 groups:

[0052]

[Chemical formula 17]

(wherein R2, R3, R4, X1 and X2
is as described above)

The above reaction (K) is carried out according to the above reaction [G].The above reactions [H] to [K] are carried out by protecting the -OH group, if desired.As the protecting group, the reaction Any group may be used as long as it does not inhibit the reaction, and examples thereof include a benzyl group, a methoxymethyl group, a tetrahydropyranyl group, a trimethylsilyl group, and a tertiary butyl group.

The compounds represented by the general formulas (IV) and (VI) are, for example,

[0056]

[Chemical formula 18]

Reimer-Tiemman (R1 is as described above)
ann) reaction to introduce an aldehyde group to form the general formula

0
058]

[Chemical formula 19]

[0059] A compound represented by (R1 is as described above) is prepared, and then the above reaction [A], JP-A-63-
It can be manufactured according to the method described in Japanese Patent No. 115870.

[Examples] Examples of the present invention will be described below, but the present invention is not limited thereto.

(Synthesis Example) Synthesis Example 1 2-bromo-6-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzaldehyde
Synthesis of ethylene acetal (compound No. 1) 1)
6-bromosalicylaldehyde 5.1g (2.54×1
0-2 mol), ethylene glycol 4.71 g (7.
61 x 10-2 mol) and p-toluenesulfonic acid 1
A small amount of the hydrate was dissolved in 70 ml of toluene, and azeotropic dehydration reaction was carried out overnight. After that, since there were unreacted raw materials, 4.71 g of ethylene glycol was added, and an additional 5.7 g of ethylene glycol was added.
A time azeotropic dehydration reaction was carried out. After the reaction was completed, the mixture was cooled to room temperature, sodium hydrogen carbonate was added, and the mixture was stirred for a while. Thereafter, the solvent was distilled off from the obtained filtrate, and the residue was purified by silica gel column chromatography (developing solvent: toluene:methylene chloride = 8:2) to obtain 2-bromo-6- as a pale yellow oil. hydroxybenzaldehyde
5.25 g of ethylene acetal (Intermediate No. 1) was obtained.

2) 550 mg (2.24 mmol) of 2-bromo-6-hydroxybenzaldehyde ethylene acetal obtained in step 1), 2-chloro-4,
6-dimethoxypyrimidine 430 mg (2.46 mmo
l) and potassium carbonate 340 mg (2.46 mmol)
was dissolved in about 10 ml of dry dimethyl sulfoxide, and reacted at 90 to 100° C. for 1 hour with stirring. After the reaction was completed, the mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. After washing with brine three times and drying over anhydrous sodium sulfate, the solvent was distilled off. After that, it was purified by silica gel column chromatography (developing solvent: toluene:methylene chloride = 1:9), and the melting point was 115.5-117.0.
℃ target compound (compound No. 1) (white crystal) 700 mg
I got it.

Synthesis Example 2 Synthesis of 2-(diethylphosphoryl)-6-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzaldehyde ethylene acetal (Compound No. 6) Obtained in Synthesis Example 1 above 2-Bromo-6-[(4,6-
Dimethoxypyrimidin-2-yl)oxy]benzaldehyde ethylene acetal (compound No. 1) 60
3 mg and 5 ml of triethyl phosphite, 140
The reaction was allowed to proceed at ~150° C. for 13 hours with stirring. After the reaction was completed, the mixture was cooled to room temperature and excess triethyl phosphite was distilled off under reduced pressure. After that, it was purified by silica gel column chromatography (developing solvent: methylene chloride) to obtain the target compound (compound No. 6) with a melting point of 104.0 to 106.0°C.
(White crystals) 670 mg was obtained.

Next, representative examples of the intermediate compound represented by the general formula (II) produced according to the above synthesis example are shown in Table 1, and representative examples of the compound represented by the general formula (I) are shown in Table 2. Each is listed in the table.

[0064]

[Table 1]

[0065]

[Table 2]

As shown in the test examples below, the azine compounds of the present invention include those that exhibit excellent herbicidal effects when used as active ingredients of herbicides, and at the same time exhibit safety against rice and soybeans. The scope of application of the herbicide of the present invention is agricultural land such as fields, orchards, mulberry orchards, mountains, forests, farm roads, grounds, etc.
It can be applied to a wide variety of non-agricultural lands such as factory sites, and the application method can be selected from soil treatment and foliage treatment as appropriate. When the herbicide of the present invention is applied, it is usually mixed with a carrier and, if necessary, various auxiliary agents such as diluents, solvents, emulsifiers, spreading agents, antifreeze agents, surfactants, etc. Japanese additives, hydrating agents, emulsions,
It is used in formulations such as liquids and suspensions. The appropriate blending weight ratio of the active ingredient compound and the pesticide adjuvant is generally 1:9.
The ratio is 9 to 90:10, preferably 5:95 to 80:20. The appropriate amount of the active ingredient compound to be used depends on weather conditions, soil conditions,
Although it cannot be definitively defined due to differences in the formulation form of the drug, the type of target weed, the time of application, etc., the amount of active ingredient applied per are is generally 0.005g to 50g, preferably 0.01g to 30g, and more preferably. is 0.05g~1
It is 0g.

[0067] The herbicide of the present invention can be used in combination with other agricultural chemicals, agricultural chemical auxiliaries,
It can be mixed or used in combination with a drug-toxicity reducer, and in this case it may show even better effects and action. When mixed or used in combination with other herbicides, examples of the active ingredients of the herbicides to be mixed include the following. In that case, a synergistic effect may be obtained.

・(±)-2-[4-[(6-chloro-2
-quinoxalinyl)oxy]phenoxy]ethyl propionate (common name: quizalofopethyl) 3-(1-methylethyl)-(1H)-2,1,3-benzothiadiazin-4(3H)-one -2,2-dioxide (generic name: bentazone) ・5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-sodium nitrobenzoate (generic name: acifluorfen) ・2-[[ [(4-chloro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]
Ethyl benzoate (generic name: chlorimuronethyl: chl)
orimuron-ethyl) ・(±)-5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid 2-ethoxy-
1-Methyl-2-oxoethyl (common name; lactofen) ・4-(2,4-dichlorophenoxy)butyric acid (common name;
2,4-DB: 2,4-DB)

・2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide (generic name: metolachlor) ・(±)
-2-[4-[(6-chloro-2, benzoxazolyl)
Ethyl oxy]phenoxy]propionate (common name: fenoxaprop ethyl) ・(±)-2-[4-[[[5-(trifluoromethyl)]
-2-pyridinyl]oxy]phenoxy]butyl propionate (common name: fluazifop) ・2-chloro-N-(2,6-diethylphenyl)-N
-(methoxymethyl)acetamide (generic name: alachlor) ・3-(3,4-dichlorophenyl)-1-methoxy-
1-Methylurea (generic name: linuron)/4-amino-
6-(1,1-dimethylethyl)-3-(methylthio)
-1,2,4-triazin-5(4H)-one (common name; metribuzin) ・2-[1-(ethoxyimino)butyl]-5-[2-
(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one (generic name: setoxydim)

00
70]・(±)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5-ethyl-3-pyridinecarvone Acid (generic name: imazethapyr)・5-[2-chloro-
4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenzamide (common name: fomesafen) ・2-[4,5-dihydro-4-methyl-4-(1-methylethyl)- 5-oxo-1H-imidazole-2-
yl]-3-quinolinecarboxylic acid (generic name: imazaquin) ・2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)aniline (generic name: trifluralin)
・3-[(methoxycarbonyl)amino]phenyl
(3-methylphenyl)carbamate (generic name; phenmedipham) ・Ethyl[3-[[(phenylamino)carbonyl]oxy]phenyl]carbamate (generic name; desmedipham) ・7-oxabicyclo[2.2 .1] Heptane-2,3
-Ethyl dicarboxylic acid (common name: endothal)
Diisopropylthiocarbamate (generic name; EPTC)

・Methyl 2-[4-[[3-chloro-5-(trifluoromethyl)-2-pyridinyl]oxy]phenoxy]propionate (common name: haloxyfop)・
(±)-Methanesulfonic acid 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl (common name: ethofumesate) ・5-amino-4-chloro-2-phenyl-3 (2H)
-Pyridazinone (generic name; chloridazone)・2,4-dichlorophenoxyacetic acid (generic name; 2,4-D:2,
4-D) ・4-chloro-2-methylphenoxyacetic acid (generic name; MCP: MCP) ・3',4'-dichloropropionanilide (generic name;
DCPA)

Next, test examples of the herbicide of the present invention will be described. Test Example 1 Upland soil was filled in a 1/1500 are pot, and seeds of various plants were sown. After that, the plant grows to a certain leaf age (rice 1
．． 3 to 2.0 leaf stage, soybean primary leaf to 0.2 leaf stage, corn 2.5 to 3.0 leaf stage, wheat 2.5 to 2.8 leaf stage, Japanese fir tree 2.0 leaf stage, morning glory 0. 4-1.0 leaf stage,
Golden Deer 0.2-1.0 leaf stage, Aobu 0.
3-1.0 leaf stage, Japanese barnyard grass 1.6-2.0 leaf stage, Japanese barnyard grass 1
．． 5 to 2.0 leaf stage), a predetermined amount of the wetting agent of the herbicide of the present invention was weighed out and diluted with 5 liters of water per area. Furthermore, 0.0% of an agricultural spreading agent was added to the aqueous solution.
2% and treated the leaves with a small spray. 21 to 31 days after the treatment, the growth status of various plants was visually observed and the degree of growth suppression was evaluated on a 10-point scale (1: same as untreated area to 10: completely suppressed), and Table 3 shows the results. I got the result.

[0073]

[Table 3]

Next, formulation examples of the herbicide of the present invention will be described. Formulation example 1 (1) Newlight (trade name; manufactured by Japan Refractories Materials Co., Ltd.)
97 parts by weight (2) Dixsol W-92 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
2 parts by weight (3) Compound No. 1
A powder is obtained by mixing and pulverizing 1 part by weight or more of each component.

Formulation Example 2 (1) Compound No. 2
80 parts by weight (2) Demol EP powder (Product name: Kao Corporation)
8.5 parts by weight (3) NaCl

10 parts by weight (4) Dextrin
0.5 parts by weight (5) TP-89121 (Product name: Takemoto Yushi Co., Ltd.)
1 part by weight or more of each component is placed in a high-speed mixer and granulator, 20% water is added thereto, granulated, and dried to obtain a granular wettable powder.

Formulation Example 3 (1) Kaolin
78 parts by weight (2) Labelin S (Product name: Daiichi Kogyo Seiyaku Co., Ltd.)
2 parts by weight (3) Solpol 5039 (Product name: manufactured by Toho Chemical Industry Co., Ltd.)
5 parts by weight (4) Carplex (Product name: Shionogi & Co., Ltd.)
A mixture of 15 parts by weight or more of components (1) to (4) and compound No. 5 in a weight ratio of 9:1 to obtain a wettable powder.

Formulation Example 4 (1) Diatomaceous earth
63 parts by weight (2) Dixsol W-66 (Product name: Daiichi Kogyo Seiyaku Co., Ltd.)
5 parts by weight (3) Dixsol W-0913 (Product name: Same as above)
2 parts by weight (4) Compound No.
．． 3
A wettable powder is obtained by mixing 30 parts by weight or more of each component.

Formulation Example 5 (1) Kaolin
33 parts by weight (2) Solpol 5050 (Product name: manufactured by Toho Chemical Industry Co., Ltd.)
3 parts by weight (3) Solpol 5073 (trade name: same as above) 4 parts by weight (4) Compound No. 1
60
A wettable powder is obtained by mixing parts by weight or more of each component.

Formulation Example 6 (1) Compound No. 1
40 parts by weight (2) Solpol 729
0P 4 parts by weight (Product name: Toho Chemical Industry Co., Ltd.) (3) Veegum
1.5 parts by weight (Product name: Vanderhilt) (4) Propylene glycol
10 parts by weight (5) water

44.5 parts by weight or more of each component are uniformly mixed and wet-pulverized to obtain an aqueous suspension.

Formulation Example 7 (1) Compound No. 5
50 parts by weight (2) xylene

40 parts by weight (3) Solpol 7660
10 parts by weight (Product name:
Toho Chemical Industry Co., Ltd.) by mixing and dissolving each of the above components,
An emulsion is obtained.

Claims (5)

[Claims] Claim 1: General formula (I);
) 2 groups, R2 and R3 are each independently a hydrogen atom or an alkyl group, R4 is an alkyl group, X1 and X2 are each independently an oxygen atom or a sulfur atom, and Y
1 and Y2 are each independently a methyl group or a methoxy group, and Z is a =CH- group or a nitrogen atom). Claim 2: General formula (II);
)2 groups, R2 and R3 are each independently a hydrogen atom or an alkyl group, R4 is an alkyl group, and X1 and X2 are each independently an oxygen atom or a sulfur atom) , general formula (III); [Formula 3] (wherein, Q is a halogen atom, an alkylsulfonyl group, a benzylsulfonyl group, or a substituted benzylsulfonyl group, and Y1 and Y2 are each independently a methyl group or a methoxy group; , Z is a =CH- group or a nitrogen atom).
I); A method for producing an azine compound represented by the following formula: (wherein R1, R2, R3, X1, X2, Y1, Y2 and Z are as described above). [Claim 3] General formula (I-2); is an oxygen atom or a sulfur atom, and Y1
and Y2 are each independently a methyl group or a methoxy group, and Z is a =CH- group or a nitrogen atom), and a compound represented by the general formula P(OR4)3 (wherein, R4 is an alkyl group) ); wherein R2, R3, R4, X1, X2, Y1, Y2 and Z are as described above; A method for producing an azine compound represented by [Claim 4] General formula (I);
) 2 groups, R2 and R3 are each independently a hydrogen atom or an alkyl group, R4 is an alkyl group, X1 and X2 are each independently an oxygen atom or a sulfur atom, and Y
1 and Y2 are each independently a methyl group or a methoxy group, and Z is a =CH- group or a nitrogen atom. [Claim 5] General formula (II);
)2 groups, R2 and R3 are each independently a hydrogen atom or an alkyl group, R4 is an alkyl group, and X1 and X2 are each independently an oxygen atom or a sulfur atom).