JPH0789941A - Phenylguanidine derivative and herbicide - Google Patents

Abstract

PURPOSE:To obtain a novel phenylguanidine derivative capable of safely using for main crops and useful as a herbicide exhibiting high herbicidal action on many weeds at a low dose. CONSTITUTION:A compound of formula I (R<1> is 1-4C a haloalkyl, 2-4C alkyl or halogen; R<2> is H or methyl; A<1> is halogen or methyl; A<2> is halogen, 1-4C alkyl or CF3; A<3> is H or halogen), e.g. 2-(2,4-difluoro-3-methylphenyl)amino-3,5- dimethyl-6-trifluoromethyl-4 (3H)-pyrimidinone. The compound of formula I wherein R<2> is H is obtained by reacting a 2-mercaptopyrimidine derivative of formula II [(r) is 0-2] with formanilide of formula III. This compound can be used in either treating method of soil treatment and foliage treatment as a herbicide for upland, paddy field and uncultivated land.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel phenylguanidine derivative and a selective herbicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art It is clear that the productivity of important crops affects the food economy of each country as the population of the world increases in recent years. With these changes, it is inevitable that the traditional agricultural form will change toward the 21st century. Actually, it is more and more necessary for agricultural workers to develop a herbicide capable of economically and efficiently killing or controlling weeds which are obstacles during crop cultivation.

As such a herbicide, there is a strong demand for the development of a drug having the following conditions. Those that have a high herbicidal effect at low doses (especially it is necessary to kill weeds by spraying as low a dose as possible from the viewpoint of environmental protection), those that have an appropriate residual effect (remaining soil residue in recent years). It has been a problem that long-term drugs damage the succeeding crops, and it is important that they show appropriate residual effects after spraying.) Those that kill weeds immediately after spraying (chemical treatment) After that, the next crop can be sown and transplanted in a short period of time.), The number of times of chemical treatment is small (it is important for farmers to reduce the number of complicated weed control work as much as possible), Weed control is wide-ranging (for broad-leaved weeds, gramineous weeds, perennial weeds, and other weed species with different properties, it is desirable to use a single agent to control them). Combines soil treatment and foliage treatment effects By having it, a stronger weeding effect can be obtained.), Which does not show harmful chemical damage to crops (which can selectively kill only weeds in arable land where crops and weeds are mixed) Is preferable). However, existing herbicides do not meet all of these requirements.

[0004]

In view of such a situation, the present inventors show selectivity for important crops and have excellent herbicidal effect against many weeds with a low dose. As a result of continued research to develop a herbicide having both soil treatment and foliar treatment, the formula (1)

[0005]

[Chemical 2]

[Wherein R ¹ represents a C _{1 to} C ₄ haloalkyl group, a C _{2 to} C ₄ alkyl group or a halogen atom,
R ² represents a hydrogen atom or a methyl group, A ¹ represents a halogen atom or a methyl group, A ² represents a halogen atom, C ₁
~ Represents a C ₄ alkyl group or a trifluoromethyl group,
A ³ represents a hydrogen atom or a halogen atom. ] The phenylguanidine derivative represented by the formula (hereinafter referred to as the compound of the present invention) was found.

The structural feature of the compound of the present invention is 4 (3H).
A methyl group at the 3- and 5-positions of the pyrimidinone ring, a haloalkyl group, an alkyl group or a halogen atom at the 6-position, 2
It has a substituted phenylamino group at the − position and has a unique combination of A ¹ , A ² and A ³ as a substituent on the benzene ring of the phenylamino group. Next, the substituents will be specifically described.

R ¹ is a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro n-propyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, difluoromethyl group, chlorodifluoromethyl group, fluorine atom, chlorine atom, bromine atom And iodine atoms.

Examples of R ² include a hydrogen atom and a methyl group. Examples of A ¹ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a methyl group. A ² is a fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-
Examples thereof include a butyl group, an i-butyl group, an s-butyl group, a t-butyl group and a trifluoromethyl group.

Examples of A ³ include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The compound of the present invention can be used as a weeding agent for upland fields, paddy fields, and non-cultivated land in any treatment method of soil treatment and foliage treatment. The target weeds as a herbicide of the compound of the present invention include wild sorghum, giant millet, Johnsongrass, barnyardgrass, barnyard grass, oats, Ohishiba, Enochologsa, Poaceae and other grass family weeds, Cyperaceae weeds such as Hayamage, Hiraomodaka, Omodaka, and Omodaka. , Tamagayatsuri, Mizugayatsuri, Firefly, Kurogui, Azena,
Examples include eels, hirsutus white, yellow sedge, and squirrel.

The compounds of the present invention include compounds which can be safely used for important crops such as wheat, corn, barley, soybean, rice, cotton, beet, sorghum and the like. The compound of the present invention is also useful as a defoliant.
The present invention compound represented by the formula (1), when R ² is a hydrogen atom, may take the tautomers as shown below, the compounds of the present invention, R ² is a hydrogen atom In this case, all of these forms are included.

[0012]

[Chemical 3]

The compounds of the present invention can be synthesized, for example, by the methods shown in the following schemes 1 to 4.
(R ¹ , R ² , A ¹ , A ² and A ^{3 in} Schemes 1 to 4
Represents the same meaning as described above, G ¹ represents a C ₁ -C ₄ alkyl group or a benzyl group, Hal represents a halogen atom, and r represents 0, 1 or 2. )

[0014]

[Chemical 4]

(1) Scheme 1 represents a method for producing a phenylguanidine derivative b ¹ by reacting a 2-mercaptopyrimidine derivative a with a formanilide f . Normal
f 0.5 to 2.0 equivalents relative to a, preferably 0.8 to
Use 1.2 equivalents. The reaction usually requires a solvent, and as the solvent, aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, halogenated carbonization such as chloroform and methylene chloride. Hydrogens, ethers such as diethyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and isobutyronitrile, pyridine, tertiary amines such as N, N-diethylaniline, N , N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone and other acid amides,
Examples thereof include sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, and preferably the above-mentioned aliphatic hydrocarbons, aromatic hydrocarbons, acid amides, sulfur-containing compounds and mixtures thereof.

Usually 0.5 to 3.0 equivalents of a base with respect to a ,
Preferably 0.8 to 1.5 equivalents are used. Pyridine, triethylamine, N, N-dimethylalinine, N, N-diethylaniline, 4- (N, N-dimethylamino) pyridine, 1,4-diazabicyclo [2.
2.2] Nitrogen-containing organic base such as octane, inorganic base such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, n-
Examples thereof include organic metal bases such as butyl lithium and phenyl lithium, and preferable examples include inorganic bases such as sodium hydride, sodium hydroxide and potassium hydroxide.

The reaction temperature is generally -10 to 200 ° C, preferably room temperature to the reflux temperature of the reaction mixture. The reaction time is usually 10 minutes to 96 hours, preferably 30 minutes to 4 hours.
It takes 8 hours.

[0018]

[Chemical 5]

(2) Scheme 2 represents a method for producing a phenylguanidine derivative b ² by reacting a 2-mercaptopyrimidine derivative a with an aniline derivative g . G 0.8 a large excess of equivalents to normal a, preferably 1.0 to 1
Use 0 equivalents. The reaction usually proceeds without a solvent, but the solvent and base mentioned in Scheme 1 can also be used.

The reaction temperature is -10 to 250 ° C, preferably room temperature to the reflux temperature of the reaction mixture. The reaction time is usually 5 minutes to 72 hours, preferably 10 minutes to 48 hours.
It takes time.

[0021]

[Chemical 6]

(3) Scheme 3 shows a method in which the phenylguanidine derivative b ¹ is reacted with a methylating agent to substitute the methyl group for the nitrogen atom of the phenylamino group. Usually 0.5 to 10 equivalents of methylating agent relative to b ¹ , preferably 0.8 to
Use 5 equivalents. Examples of the methylating agent include dimethyl sulfate, methyl chloride, methyl bromide, methyl iodide, diazomethane and the like.

In the reaction, a solvent and a base are usually used, and the solvent and the base described in Scheme 1 can be used. The reaction temperature is generally -10 ° C to 200 ° C, preferably 0 ° C to the reflux temperature of the reaction mixture. The reaction time is usually 5 minutes to 95 hours, preferably 10 minutes to 48 hours.

[0024]

[Chemical 7]

(4) Scheme 4 represents a method for producing b ³ by reacting a phenylguanidine derivative h with an organic alkali metal and subsequently reacting it with a methylating agent. Usually, 0.5 to 10 equivalents, preferably 0.8 to 3.0 equivalents of an organic alkali metal, and 0.5 to 10 equivalents, preferably 0.8 to 5 equivalents of a methylating agent, relative to h . use. Examples of the organic alkali metal include n-butyllithium, t-butyllithium and phenyllithium, and examples of the methylating agent include methyl halides such as methyl chloride, methyl bromide and methyl iodide, and dimethylsulfate. And so on.

The reaction usually requires a solvent, and n is used as the solvent.
-Hexane, cyclohexane, n-heptane and other aliphatic hydrocarbons, diethyl ether, tetrahydrofuran,
Examples thereof include ethers such as dioxane, aromatic hydrocarbons such as benzene, toluene and xylene, and preferably the above-mentioned aliphatic hydrocarbons and ethers. The reaction temperature is generally −100 ° C. to 200 ° C., preferably −78.
C to the reflux temperature of the reaction mixture.

The reaction time is 1 minute to 3 hours, preferably 5 minutes to 2 hours when the organic alkali metal is allowed to act, and 1 minute to 24 in the subsequent reaction with the alkylating agent.
It takes time, preferably 10 minutes to 6 hours. The synthetic intermediates a and h as starting materials can be produced, for example, according to the following reaction formulas a, b and c. Reaction formula a

[0028]

[Chemical 8]

(In the reaction formula, R ¹ , G ¹ and r have the same meanings as described above, G ² represents a C ₁ -C ₄ alkyl group or a phenyl group, and Hal represents a halogen atom. Except when ¹ is a halogen atom.) Reaction formula b

[0030]

[Chemical 9]

(In the reaction formula, R ¹ , G ¹ , r, G ² and Hal have the same meanings as described above, provided that R ¹ is C ₁ to C ₁ .
Excluding the case of a C ₄ haloalkyl group or a C ₂ -C ₄ alkyl group. ) Reaction formula c

[0032]

[Chemical 10]

(In the reaction formula, R ¹ , A ¹ , A ² , A ³ and Hal have the same meanings as described above.) When it is necessary to purify the compound of the present invention, recrystallization and column chromatography are carried out. It can be separated and purified by any purification method such as. The synthesis examples of the compound of the present invention will be specifically described below as Reference Examples and Examples, but the present invention is not limited thereto.

[0034]

【Example】

[Reference Example 1] 3,5-dimethyl-2-methylthio-6
-Synthesis of trifluoromethyl-4 (3H) -pyrimidinone.

[0035]

[Chemical 11]

2-methyl-4,4,4-trifluoro-
Ethyl 3-aminocrotonate 1.9 g (9.6 mmo
l) was dissolved in 10 ml of N, N-dimethylformamide, and 0.42 g of 60% sodium hydride was added. 0 ° C
In the following, in the solution, methylthioisocyanate 0.
After dropping 74 g (10 mmol), the mixture was reacted at room temperature for 3 hours. Then, 2.7 g (19 mmol) of methyl iodide was added dropwise to the solution at 5 ° C. or lower, and the mixture was reacted overnight at room temperature. After completion of the reaction, cold diluted hydrochloric acid was added and the mixture was extracted with ethyl acetate. The extract was washed with water and saturated brine, dried over anhydrous sodium sulfate, and ethyl acetate was removed under reduced pressure to give 2.2 g of the desired compound (yield 96
%) As yellow crystals.

Reference Example 2 2- [N- (3-chloro-
2,4-Difluorophenyl) -N-methyl] amino-
5-Bromo-3-methyl-6-trifluoromethyl-4
Synthesis of (3H) -pyrimidinone.

[0038]

[Chemical 12]

2- [N- (3-chloro-2,4-difluorophenyl) -N-methyl] amino-6-trifluoromethyl-3-methyl-4 (3H) -pyrimidine 3.9
g (11.0 mmol) was dissolved in 20 ml of acetic acid, and 2.2 g (13.8 mmol) of bromine was added dropwise at room temperature with stirring. After completion of the reaction, acetic acid and excess bromine were distilled off, water,
It was diluted with ethyl acetate and made basic with aqueous sodium hydrogen carbonate. After extraction with ethyl acetate, the extract was washed with water and dried over sodium sulfate. By removing ethyl acetate under reduced pressure, 4.8 g of the desired product was obtained.
(Quantitative) was obtained as white crystals.

¹ H-NMR (ppm) [CDCl ₃ ]:
3.07 (3H, s), 3.37 (3H, s), 6.8
0 to 7.35 (2H, m) [Example 1] 2- (2,4-difluoro-3-methylphenyl) amino-3,5-dimethyl-6-triflomethyl-4 (3
H) -Synthesis of pyrimidinone (No. 1)

[0041]

[Chemical 13]

0.21 g of 60% sodium hydride was added to a solution of 0.69 g (4.8 mmol) of 2,4-difluoro-3-methylaniline and 7 ml of N, N-dimethylformamide, and the mixture was stirred at room temperature for 30 minutes. After doing 3,5
-Dimethyl-2-methylthio-6-trifluoromethyl-4 (3H) -pyrimidinone 1.15 g (4.8 mmo
1) was added and the mixture was reacted at 60 ° C. for 2 hours and 30 minutes. After the reaction was completed, ice water was added and the mixture was extracted with ethyl acetate. The extract was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and ethyl acetate was removed under reduced pressure to give a crude product. This crude product was subjected to preparative thin layer chromatography (developing solvent n-hexane: ethyl acetate = 2:
0.72 g of the target compound by purification in 1)
(Yield 45%) was obtained as crystals.

Example 2 2- [N- (2,4-difluoro-3-methylphenyl) -N-methyl] amino-3,5-dimethyl-6-trifluoromethyl-4 (3H) -pyrimidinone Synthesis of (Compound 2)

[0044]

[Chemical 14]

0.72 g (2.2 mmol) of 2- (2,4-difluoro-3-methylphenyl) amino-3,5-dimethyl-6-trifluoromethyl-4 (3H) -pyrimidinone synthesized in Example 1 ) To 7 ml of acetonitrile
Dissolved in 0.9 g of potassium carbonate (6.5 mmol)
Was added. 0.61 ml of dimethylsulfate in the solution
After adding (6.5 mmol) dropwise, the mixture was reacted at room temperature for 1 day. After the reaction was completed, ice water was added and the mixture was extracted with ethyl acetate.
The extract was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and ethyl acetate was removed under reduced pressure to give a crude product. The crude product was purified by preparative thin layer chromatography (developing solvent n-hexane: ethyl acetate = 5: 1) to give the target compound (0.1%).
63 g (84% yield) were obtained.

Example 3 2- [N- (3-chloro-2,4-difluorophenyl) -N-methyl] amino-3,5-dimethyl-6-trifluoromethyl-4 (3H) -pyrimidinone Synthesis of (Compound 3)

[0047]

[Chemical 15]

2- [N- (3-chloro-2,4-difluorophenyl) -N-methyl] amino-5-bromo-6-trifluoromethyl-3-methyl-4 (3H) synthesized in Reference Example 2 ) -Pyrimidinone 0.6 g (1.4 mmo
l) was dissolved in 20 ml of dry tetrahydrofuran and then -7
At 8 ° C., 1 ml of n-butyllithium (1.60 mol, hexane solution) was added. After stirring for 40 minutes, 0.3 g (2.1 mmol) of methyl iodide was added, and the mixture was stirred at the same temperature for 1 hour, heated to 0 ° C., and further stirred for 15 minutes. After the reaction, aqueous ammonium chloride was added, and the mixture was extracted with ethyl acetate. The extract was washed with water, dehydrated and dried over sodium sulfate, filtered, and the solvent was distilled off. The obtained residue was purified by preparative liquid chromatography to give 64 mg of the desired compound (yield 1
2.6%) was obtained as white crystals.

The structural formulas of the compounds of the present invention synthesized according to the above schemes or examples, including the compounds synthesized in the above examples, are shown in Table 1 and the physical properties are shown in Table 2. [Table 1]

[0050]

[Chemical 16]

[0051]

[Table 1] ────────────────────────────── Compound No. R ¹ R ² Q ────────────────────────────── 1 CF ₃ H 2,4-F ₂ -3-Me- _{Ph 2 CF 3 Me 2,4-F} 2 -3-Me-Ph 3 CF 3 Me 2,4-F 2 -3-Cl-Ph 4 CF 3 H 2,4-F 2 -3-Cl-Ph 5 CF ₃ H 2-Me-3-Br-Ph 6 CF ₃ H 2-Me-3-I-Ph ────────────────────────── ─────

However, Me is a methyl group, Et is an ethyl group,
Ph represents a phenyl group.

[0053]

[Table 2] [Table 2] ─────────────────────────────────── Compound No. ¹ H-NMR δ (ppm) [solvent] Physical properties ─────────────────────────────────── 1 2 .00~2.34 (6H, m), 3.55 (3H, s), 6.58~7.02 (2H, m), 7.21~8.19 (1H, m) [CDCl _3] Melting point 84 to 85 ° C ─────────────────────────────────── 2 2.08 to 2.32 (6H , M), 3.01 (3H, s), 3.31 (3H, s), 6.63 to 6.95 (2H, m) [CDCl ₃ ] melting point 98 to 100 ° C ──────── ──────────────────────────── 3 2.00-2.30 (3H, m), 3.03 (3H, s) , 3.30 (3H, s), 6.75 to 7.35 (2H, m) [CDC l ₃ ] ─────────────────────────────────── 4 1.93 to 2.20 (3H, m ), 3.62 (3H, s), 6.84 to 7.23 (2H, m), 8.62 (1H, br s) [CDCl ₃ + d ₆ -DMSO] melting point 151 to 152 ° C. ─────────────────────────────── 5 1.98 to 2.18 (3H, m), 2.25 (3H , S), 3.56 (3H, s), 6.84 to 7.10 (3H, m), 8.66 (1H, br s) [CDCl ₃ + d ₆ -DMSO] melting point 219 to 220 ° C. ──────────────────────────────────

[0054]

[Table 3] [Continued Table 2] ─────────────────────────────────── Compound No. ¹ H-NMR δ (ppm) [solvent] Physical properties ─────────────────────────────────── 6 1 .93 to 2.16 (3H, m), 2.31 (3H, s), 3.54 (3H, s), 6.73 to 7.07 (1H, m), 7.17 to 7.41 (1H, m), 7.62 to 7.84 (1H, m), 8.74 (1H, br s) [CDCl ₃ + d ₆ -DMSO] Melting point 210 to 211 ° C ────────── ──────────────────────────

Examples of the compound of the present invention synthesized according to the above scheme or Examples 1 to 3 are shown in Table 3 including the above compounds 1 to 6, but the present invention is not limited thereto. The abbreviations in Table 3 have the following meanings. Me: methyl group, Et: ethyl group, Pr
o: normal propyl group, i-Pro: isopropyl group, Bu: normal butyl, i-Bu: isobutyl group,
s-Bu: Secondary butyl group, t-Bu: Tertiary butyl group, Ph: Phenyl group.

[Table 3]

[0057]

[Chemical 17]

[0058]

[Chemical 18]

[0059]

[Table 4] ───────────────────────────── R ² Q ─────────────── ─────────────── Me 2-Me-3-F-Ph Me 2-Me-3-Cl-Ph Me 2-Me-3-Br-Ph Me 2-Me- 3-I-Ph Me 2- Me-3-CF 3 -Ph Me 2-F-3-Br-Ph Me 2-F-3-I-Ph Me 2-F-3-CF 3 -Ph Me 2- Cl-3-Br-Ph Me 2-Cl-3-I-Ph Me 2-Cl-3-CF 3 -Ph Me 2,4-F 2 -3-Me-Ph Me 2,4-F 2 -3 _{-Et-Ph Me 2,4-F 2} -3-i-Pro-Ph Me 2,4-F 2 -3-t-Bu-Ph Me 2,4-F 2 -3-CF 3 -Ph Me 2 _{, 4-F 2 -3-Cl} -Ph Me 2 _{4-F 2 -3-Br-} Ph Me 2,4-F 2 -3-I-Ph Me 2,4-Cl 2 -3-Br-Ph Me 2,4-Cl 2 -3-I-Ph Me _{2,4-Cl 2 -3-CF 3} -Ph H 2-Me-3-F-Ph ─────────────────────────── ──

[0060]

[Table 5] [Continued Table 3] ───────────────────────────── R ² Q ───────── ───────────────────── H2-Me-3-Cl-PhH2-Me-3-Br-PhH2-Me-3-I- _{Ph H 2-Me-3-} CF 3 -Ph H 2-F-3-Br-Ph H 2-F-3-I-Ph H 2-F-3-CF 3 -Ph H 2-Cl-3- br-Ph H 2-Cl- 3-I-Ph H 2-Cl-3-CF 3 -Ph H 2,4-F 2 -3-Me-Ph H 2,4-F 2 -3-Et-Ph _{H 2,4-F 2 -3-i} -Pro-Ph H 2,4-F 2 -3-t-Bu-Ph H 2,4-F 2 -3-CF 3 -Ph H 2,4-F _{2 -3-Cl-Ph H 2,4} -F 2 -3-Br-Ph H 2,4-F 2 -3- _{I-Ph H 2,4-Cl 2} -3-Br-Ph H 2,4-Cl 2 -3-I-Ph H 2,4-Cl 2 -3-CF 3 -Ph ─────── ──────────────────────

In applying the compound of the present invention as a herbicide, generally, a suitable carrier, for example, a solid carrier such as clay, talc, bentonite, diatomaceous earth and white carbon, or water, alcohols (isopropanol, butanol, benzyl alcohol, fluroalcohol) is used. Furyl alcohol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), ethers (anisole), ketones (cyclohexanone, isophorone), esters (butyl acetate, etc.), acid amides (N-methylpyrrolidone, etc.) ) Or halogenated hydrocarbons (chlorobenzene etc.) and other liquid carriers can be mixed and applied, and if desired, surfactants, emulsifiers, dispersants, penetrants, spreading agents, thickeners, antifreeze. Agents, anti-caking agents, stabilizers, disintegrants, etc.
It can be put into practical use in any dosage form such as wettable powder, dry flowable agent, flowable agent, powder agent, granule agent, gel agent and the like.

If desired, the compound of the present invention may be mixed with other herbicides, various insecticides, fungicides, plant growth regulators, synergists and the like at the time of formulation or spraying. In particular,
By applying it in combination with other herbicides, it is expected that the cost will be reduced by reducing the amount of the applied drug, the herbicidal spectrum will be expanded by the synergistic action of the mixed agents, and a higher herbicidal effect will be expected. At this time, it is possible to combine a plurality of known herbicides at the same time. Examples of the type of herbicide used in combination with the compound of the present invention include, for example, Farm Chemicals Handbook (F
arm Chemicals Handbook) 19
There are compounds described in the 1993 edition.

[0063] Examples of preferred drugs to be used in combination with the compound of the present invention include pyrazosulfuron-ethyl (py
Razosulfuron Ethyl / generic name), Bensulfuron methyl
hyl / generic name), cinosulfon
uron / generic name), imazosulfuron (imazos)
ulfuron / generic name), pretilachlor (pre
tilaclor / generic name, esprocarb (es)
Procarb / generic name, pyrazolate (pyraz)
Olate / generic name, pyrazoxifene (pyraz)
oxyfen / generic name), benzophenap (benz)
ofnap / generic name, dymron /
(General name), bromobutide (general name), naproanilide /
(Generic name), clomeprop (generic name), CNP (generic name), clomethoxynil (chlo)
methoxynil / generic name), bifenox (b
ifenox / generic name), oxadiazon (oxadi)
azon / generic name), mefenac
et / generic name), butachlor (butachlor /
(Generic name), butenachlor /
(General name), dithiopyr (general name), benfresate (benfuresate / generic name), pyributicarb (general name), benchiocarb (general name), dimepiperate (dimipeperate /
Common name), molinate (common name),
Butamiphos (general name), quinclorac (general name), cinmethyrin (cinnamelin / general name), propanil (propanil / general name), cimetrin (symmetry)
trin / generic name), SAP (bensulide / generic name), dimethamethrin
/ Generic name), MCPA, MCPB, 2 ', 3'-dichloro-ethoxymethoxybenzanilide (test name HW-5
2), 1- (2-chlorobenzyl) -3- (α, α-dimethylbenzyl) urea (test name JC-940), N-
[2 '-(3'-methoxy) thienylmethyl] -N-chloroacetyl-2,6-dimethylanilide (Test name NS
K-850), the compound (II) described in JP-A-5-25009, and the like.

The application amount of the compound of the present invention as a herbicide varies depending on the application scene, application time, application method, cultivated crop and the like, but in general, the amount of the active ingredient is ha (ha).
Per 0.0001 to 10 kg, preferably 0.0
About 01 to 5 kg is suitable. Next, specific examples of formulation of the preparation when the compound of the present invention is used are shown. However, the compounding examples of the present invention are not limited to these. In the following formulation examples, "part" means part by weight.

[Wettable powder] Compound of the present invention 5 to 80 parts Solid carrier 10 to 85 parts Surfactant 1 to 10 parts Others 0 to 5 parts Other examples include anticaking agents.

[Emulsion] Compound of the present invention 1 to 30 parts Liquid carrier 30 to 95 parts Surfactant 1 to 15 parts Others 0 to 10 parts Other examples include stabilizers and the like.

[Flowable agent] Compound of the present invention 5 to 70 parts Liquid carrier 15 to 65 parts Surfactant 0.1 to 12 parts Others 0.1 to 30 parts Others include, for example, antifreezing agents, thickeners and the like. To be

[Particulate wettable powder (dry flowable agent)] Compound of the present invention 20 to 90 parts Solid carrier 9 to 60 parts Surfactant 1 to 20 parts Others 0 to 40 parts Others include, for example, disintegrating agents and the like.

[Granule] Compound of the present invention 0.01 to 10 parts Solid carrier 90 to 99.99 parts Others 0 to 5 parts

[Formulation Example 1] Wettable powder Compound 1 of the present invention 1 50 parts DIKELITE PFP 43 parts (Kaolin clay: trade name of Sikhlite Industry Co., Ltd.) Sorpol 5050 2 parts (anionic surfactant: Toho Chemical Industry) Trade name: Lunox 1000C 3 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. product name) Carplex # 80 (anti-caking agent) 2 parts (White carbon: Shionogi Pharmaceutical Co., Ltd. product name ) The above is uniformly mixed and pulverized to obtain a wettable powder.

[Formulation Example 2] Emulsion Compound 2 of the present invention 3 parts Xylene 76 parts Isophorone 15 parts Sorpol 3005X 6 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) ) Mix the above uniformly to make an emulsion.

[Formulation Example 3] Flowable agent Compound of the present invention 6 35 parts Agrisol S-711 8 parts (Nonionic surfactant: Kao Corporation trade name) Lunox 1000C 0.5 part (Anionic surfactant: Toho Chemical Industry Co., Ltd. product name 1% Rhodopol water 20 parts (Thickener: Lone Poulean Company product name) Ethylene glycol (antifreeze) 8 parts Water 28.5 parts Flowable by evenly mixing the above Use as an agent.

[Formulation Example 4] Granular wettable powder (dry flowable agent) Inventive compound 5 75 parts Isoban No. 1 10 parts (anionic surfactant: Kuraray Isoprene Chemical Co., Ltd. trade name) Vanilex N 5 parts (anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd. trade name) Carplex # 80 10 parts (white carbon: Shiono Gyosei Co., Ltd. trade name) The above is uniformly mixed and pulverized to obtain a dry flowable agent.

[Formulation Example 5] Granules Compound of the present invention 3 0.1 parts Bentonite 55.0 parts Talc 44.9 parts The above materials are uniformly mixed and pulverized, and then a small amount of water is added to the mixture and the mixture is stirred and kneaded for extrusion. Granulate with a granulator and dry to make granules.

In use, the above-mentioned wettable powder, emulsion, flowable agent and granular wettable powder are diluted 50 to 1000 times with water to contain 1 to 10,000 ppm of active ingredient or 1 hectare (ha) of active ingredient. Per 0.0001-10
Disperse so that it becomes kg. Next, the usefulness of the compound of the present invention as a herbicide will be specifically described in the following test examples.

[Test Example 1] Herbicidal effect test by soil treatment Put sterilized diluvial soil in a plastic box having a length of 15 cm, a width of 22 cm, and a depth of 6 cm, and sow seeds of Novier, Mehibushiba, Enochologsa, corn, rice and soybean. After covering the soil with about 1.5 cm, a small spray was uniformly sprayed on the soil surface so that the amount of the active ingredient was a predetermined ratio. As the drug solution for spraying, a formulation appropriately prepared according to the above-mentioned formulation example or the like was diluted with water and used, and this was sprayed on the entire surface. Four weeks after spraying the chemical solution, the herbicidal effect on crops and various weeds was investigated according to the following criteria.

The results are shown in Table 4. Some of the compounds of this invention are selective for certain crops. Criteria 5: Complete death or 90% or more suppression 4: 70-90% suppression 3: 40-70% suppression 2: 20-40% suppression 1: 5-20% suppression 0: 5% or less The degree of inhibitory control was determined by visual observation.

[Test Example 2] Herbicidal effect test by pretreatment of weeds generation under flooded condition After alluvial soil was put into a 1/5000 are Wagner pot, water was added to mix to make a flooded condition with a water depth of 4 cm. . After sowing the seeds of Novier in the above pot, 2.5
Leaf stage rice seedlings were transplanted. The pot was placed in a greenhouse at 25 to 30 ° C. to grow a plant, and one day after seeding, the drug diluent was dropped on the water surface with a measuring pipette so that a predetermined amount was obtained. The herbicidal effect on rice and green millet was investigated 3 weeks after the dropping of the drug according to the criteria of Test Example 1. The results are shown in Table 5.

Test Example 3 Herbicidal Effect Test by Weeding Stage Treatment under Flooding Condition After alluvial soil was placed in a 1/5000 ares Wagner pot, water was added to mix to make a flooding condition at a water depth of 4 cm. . After sowing the seeds of Novier in the above pot, 2.5
Leaf stage rice seedlings were transplanted. The pot is placed in a greenhouse at 25 to 30 ° C. to grow the plant, and when the Nobye reaches the 2-leaf stage and the rice reaches the 4-leaf stage, the drug dilution solution is pipetted so that the prescribed amount of the drug is brought to the water surface. Was added dropwise. After drug treatment, 3
Test Example 1 for herbicidal effect against rice and novier at week
The investigation was conducted according to the criteria of. The results are shown in Table 6.

The symbols in each table have the following meanings. N
(Novier), M (Mexico), E (Ecologosa), T
(Corn), R (rice), S (soybean).

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[Table 6] [Table 4] ─────────────────────────────────── Compound No. kg / ha) N M E TR S ──────────────────────────────────── 1 2.5 5 5 5 0 0 0 2 2.5 5 5 5 5 0 0 0 0 3 2.5 5 5 5 5 0 0 0 4 4 2.5 5 5 5 5 0 0 0 5 5 2.5 5 5 5 5 0 0 0 6 2.5 5 5 5 0 0 ────────────────────────────────────

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[Table 7] [Table 5] ──────────────────────────── Compound No. Dosage (g / a) Novie transplant rice ──────────────────────────── 1 10 5 0 2 10 5 0 3 3 10 5 0 4 10 5 5 0 5 5 10 5 0 6 10 5 0 ─────────────────────────────

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[Table 8] [Table 6] ──────────────────────────── Compound No. Dosage (g / a) Novie Transplanted rice ──────────────────────────── 1 40 5 0 2 40 5 5 0 3 40 5 5 0 4 40 5 5 0 5 5 40 5 0 6 40 5 0 ─────────────────────────────

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Eiichi Oya Eiichi Oya 722 Tsuboi-cho, Funabashi-shi, Chiba 1 Central Research Laboratory, Nissan Chemical Industry Co., Ltd. (72) Kaoru Ito 722 Tsuboi-cho, Funabashi-shi, Chiba 1 Nissan Chemical Kogyo Co., Ltd. Central Research Laboratory (72) Inventor Hiroshi Kita No. 1 722, Tsuboi-cho, Funabashi, Chiba Prefecture Nissan Chemical Co., Ltd. Central Research Center (72) Inventor Naoshi Nakata 1 722, Tsuboi-cho, Funabashi, Chiba Nissan Chemical Kogyo Co., Ltd. Central Research Laboratories (72) Inventor Tsutomu Namaki 1470 Shiraoka, Shiraoka-cho, Minami Saitama-gun, Saitama Nissan Chemical Industry Co., Ltd. Bioscience Research Institute (72) Inventor Seiichi Fujii Shiraoka, Shirooka-cho, Minami-Saitama-gun, Saitama Prefecture 1470 Nissan Kagaku Kogyo Co., Ltd., Institute of Biological Sciences (72) Inventor Shigenomi Watanabe 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Prefecture Inside Institute of Biological Sciences (72) Inventor Kimihiro Ishikawa 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Nissan Chemical Industry Co., Ltd. Inside Institute for Biological Sciences (72) Yoichi Ito 1470 Shiraoka, Shirooka-cho, Minami-Saitama-gun, Saitama Gaku Kogyo Co., Ltd. Biological Science Laboratory

Claims (3)

[Claims] 1. Formula (1): [In the formula, R ¹ is a C _{1 to} C ₄ haloalkyl group, C _{2 to} C ₄
Represents an alkyl group or a halogen atom, R ² represents a hydrogen atom or a methyl group, A ¹ represents a halogen atom or a methyl group, A ² represents a halogen atom, a C ₁ -C ₄ alkyl group or a trifluoromethyl group , A ³ represents a hydrogen atom or a halogen atom. ] The phenyl guanidine derivative represented by these. 2. R ¹ represents trifluoromethyl, A ²
The phenylguanidine derivative according to claim _{1, wherein} is a halogen atom or a C ₁ -C ₄ alkyl group. 3. A herbicide containing the phenylguanidine derivative according to claim 1.