JPS63230665A - Novel phenoxy derivative and herbicide thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [X is substituted phenyl, substituted pyridyl or substituted quinoxalyl in which the substituent group is halogen or CF3; Y is H or -CH3; Z is azide, -O-N=CR<1>R<2> (R<1> and R<2> are H, 1-6C alkyl, 1-6C alkoxycarbonyl, etc.) or formula II (R<3> and R<4> are H, 1-6C alkyl or 1-6C alkoxycarbonyl)]. EXAMPLE:1-Azido-2-[4-(3,5-dichloro-pyridyl-2-oxy)phenoxy]propane. USE:A herbicide capable of exhibiting selectivity between not only broad-leaved plants and gramineous plants but also gramineous weeds and gramineous crop plants. PREPARATION:A compound expressed by formula III (R<5> is Cl, Br, I, -OSO2CH3, etc.) is reacted with a compound expressed by the formula MN3 (M is Li, K or Na) in a solvent, such as DMF, at 50-120 deg.C to afford the aimed compound expressed by formula I (Z is azide). Sodium azide, lithium azide, etc., are cited as the compound expressed by the formula MN3.

Description

[Detailed description of the invention]

The present invention provides a phenoxy derivative that exhibits excellent herbicidal activity and selectivity and is useful in the field of herbicides, and which has not been described in prior art publications, as well as a process for producing the compound, as well as the use of the compound as a herbicide. More specifically, the present invention uses known phenoxylic acids that exhibit strong herbicidal activity against plants of the Herbaceae family, but have almost no herbicidal activity against broad-leaved plants. Compared to derivative-based herbicidal active compounds, it has unique herbicidal activity properties in that it can show selectivity between 2I grass plants and crop plants of the family Herbaceae, and has not been described in any known literature in the US v')7 This invention relates to chemical/oxidant derivatives and herbicides thereof. In the present invention, the present invention relates to a substituted phenyl group, a substituted pyrinol group, or a substituted phenyl group having at least one substituent selected from the group consisting of a halogen atom and Represents a substituted quinoxalyl group, Y represents a hydrogen atom or -CHs, Z represents an at group, -0-N=CRIR2 group

[Here, R
' and R2 are each independently selected from a hydrogen atom, C, -C, alkyl, C1-C, alkoxycarbonyl and hydroxycarbonyl [wherein R'' and R4 are each independently a hydrogen atom,
The present invention also relates to a novel phenoxy derivative represented by C, -Ca alkyl and (/C, -C@alkoxycarbonyl), wherein at least one of the above formula (I) compounds The present invention also relates to a herbicide characterized by containing as an active ingredient. Several proposals have been made regarding polycyclic oxyphenoxy derivatives that exhibit herbicidal or growth-controlling effects on plants and their use as herbicides. For example, in Machikai No. 51-106735, the following formula (a), where XI and X2 are halogen atoms, Y is a hydrogen atom or an alkyl group of C6 or less, and Z is O or Sl. A herbicide has been disclosed which is characterized in that it contains as an active ingredient at least one compound in the group consisting of carboxylic acids, thiocarboxylic acids, and their salts, esters, 7-amides, or halides.However, Among the precepts (I) specified in the compound of formula (I) of the present invention, -
As is already clear from comparing the CH,.2 moiety and the -〇-Z-H moiety in the above formula (A) compound corresponding to this part number, this proposed formula (A) carboxylic acid or thiocarboxylic acid and their Salts, esters, amides or halides cannot include compounds of the formula (I) of the present invention, and therefore, naturally, this proposal also covers the herbicidal activity of the compounds of the formula (I) of the present invention. has not been covered at all. As another proposal, JP-A-52-54026 includes the following formula (b), where X is a 4-halogen-substituted phenoxy group, 4-F+7
A fluoromethylphenoxy group, a 5-halogen-substituted pyritrue-2-oxy group, or a 3,5-dihalogen-substituted birytrue-2-oxy group, and Y is a hydrogen atom, a lower alkylcarbonyl group, or substituted with one or more halogen atoms or methyl group. A herbicide characterized by containing as an active ingredient at least one kind of compound represented by the following formula, which is a phenylcarbonyl group which may be uncontained, has been proposed. However, as is already clear from comparing the 2 moieties in chain formula (I) specified in the compound of formula (I) of the present invention and the OY moiety in the compound of formula (b) above, which corresponds to this moiety, this proposal The compound of formula (B) in the formula cannot include the compound of formula (I) of the present invention. Therefore, it is a matter of course that "this proposal, the compound of formula (I) of the present invention, and its herbicidal activity" Total fever, not mentioned. As another proposal, the JP-A-54-24879 plug has the following formula (c), where '1' is O or Sl, X is C1, Br or CF, Y is HSBr or CF, and X At least one of the upstream Y is CF, Z bar COR1-CN R+ R2, R3, -CH
,0CR1 or -CSRs are disclosed and described as having herbicidal activity. However, when comparing the -CH2-2 moiety in the chain formula (I) specified in the compound of the formula (I) of the present invention and the corresponding Z moiety in the above formula (c) compound, it is found that Z in Z
In the case of 1002OR, R5 is H or C1 to C
4-furkyl group, and the formula (
c) Compounds also cannot include the compound of formula (I) of the present invention.Therefore, as a matter of course, this proposal also makes no mention of the compound of formula (I) of the present invention and its herbicidal activity. do not have. As mentioned above, a fairly wide range of general formula compounds have been proposed for heterocyclic oquinphenoxy derivatives having herbicidal activity. However, the compound of the formula (I) of the present invention and its herbicidal activity have been completely unknown until now.Furthermore, heterocyclic oxyphenoxy derivatives generally exhibit excellent herbicidal activity against plants of the Herbaceae family. It is known that there is a selectivity between broad-leaved plants and plants of the genus family, such that they have low activity against broad-leaved effects.
Proposal No. 1-106735 states that the method is suitable for selectively removing weeds of the Physaceae family in areas where broad-leaved crops are cultivated. However, conventionally, there has been a lack of selectivity among plants of the family Herbaceae, and that of plants that exhibit strong herbicidal activity against weeds of the family Herbaceae but not against plants of the family Herbaceae. - Although it is desired to develop a drug with high selectivity even in the dark between broad-leaved plants and plants in the Herbaceae family, the present situation is that it is difficult to provide it. , we have conducted research to develop phenoxy derivatives that can exhibit practical selectivity between weed plants of the family Herbaceae and crop plants of the family Herbaceae.As a result, we have found that the phenoxy derivatives represented by the above formula (I), which have not been previously described in known literature, We succeeded in synthesizing a phenoxy derivative, and further developed a chain formula ((
) The new compound not only shows selectivity between broad-leaved plants and plants of the Herbaceae family, but also shows selectivity between weedy plants of the Herbaceae family and crop plants of the Herbaceae family compared to known phenoxy derivative herbicidal compounds. The researchers discovered that this compound has unique properties of spore grass activity. According to the research conducted by the present inventors, the novel compound of formula (I) has good selectivity for broad-leaved crops such as soybean, cotton, sugar beet, rapeseed, and sunflower, as well as for legume crops such as rice, corn, and wheat. It has been found that this herbicidal activating compound has excellent properties unexpected from conventional technology, such as having a herbicidal activity against 2I grasses, which are a problem in the cultivation of these crops. Accordingly, it is an object of the present invention to provide novel compounds of formula ([)]. Another object of the present invention is to provide a herbicide characterized by containing the novel compound of formula (I) as an active ingredient. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The novel 7-eth/oxy derivatives of the present invention are represented by the following formula (I), where X is a halogen atom or -CF, a substituted phenyl group having at least one substituent selected from the group consisting of a substituted phenyl group, a substituted pyrinol or a substituted quinoxalyl group, Y represents a hydrogen atom or -CH, Z represents an and group, -0-N = CRI R2 group [where R' and R'' are each independently a hydrogen atom , C1~
Jl or -〇-N group representing a group selected from C6 alkyl, C1~C@alkoxy-carbonyl and hydroxycarbonyl [where R'
and R4 each independently represent a hydrogen atom, a group selected from C, -C, furkyl, and C1 to C6 alkoxycarbonyl. In the above formula (I), examples of the substituent halogen atom in group X include heptad, chlorine, and bromine. The number of substituents can be selected appropriately, and in the case of a substituted phenyl group, mono- to Venter substitution, in the case of a substituted bilinol group, mono- to tetra-substitution, and in the case of a substituted quinoxalyl group, mono- to tetra-substitution. - Can be a substitution. 11 substituents! In the case of M numbers, they may be the same or different. In the above formula (I), %R1 and (/C8 in R2)
Examples of Cs alkyl groups include methyl, ethyl, n-propyl,! go-propyl, n-butyl, n
-pentyl and n-hexyl, and further C
, -C, alkoxy- Examples of alkoxy in the carbonyl group include methoxy, ethoxy, n-propoxy,
Examples include 1so-propoxy, n-butoxy, n-bentoxy and n-hexyloxy. In addition, examples of C3 to Cm alkyl groups in R' and vR4 include the same alkyl groups as exemplified above for R1 and R2, and furthermore, C3 to Cm alkyl groups in R' and R4.
Examples of alkoxy in the 5-06 flukoxycarbonyl group include the same alkoxy groups as exemplified above for R1 and R2. The novel phenoxy derivative of formula (I) of the present invention can be easily produced, for example, by the method described below. In the novel phenoxy derivative of formula (I), Z is an azido group (N3
Compound (Im) is, for example, the following reaction formula I (n) (In) 1, where X and ICY have the same meanings as described above for formula (I), and Rli is C1, Br, I, -0802CHi ,
-oso*ctt-ti and 10802C@84
1 represents a group selected from CHs, and M represents Li1K or Nu.
It can be produced by reacting with. The reaction can be carried out, for example, by bringing the compound of formula (if) into contact with MN in an inert solvent such as trimethylformamide or trimethylsulfoxide. The compound of formula (II) and its production method are described, for example, in JP-A-52
-54026, European Patent No. 3877, etc., and can be used in the present invention. MN
Examples include sodium anodide, potassium heptanide, and thicum acylate.The amount used for the 0 reaction formula can be selected as appropriate, but for example, the amount used is about 1 to about 1.0% for the compound of formula (n). An example of the amount used is 5 equivalents of MN. The reaction temperature can also be selected as appropriate; for example, about 5
Mention may be made of reaction temperatures such as from 0° to about 120°C. In the novel phenoxy derivative of formula (I), Z is -0-N=CR
, R2 group), for example, in the following reaction formula 2 E formula, X, Y, R1 and (/R'' are synonymous with directly connected in formula (I), It can be produced according to the method represented by J, which has the same meaning as described in the reaction formula 1. The reaction to form the 7-talmidoxy derivative represented by formula (I) can be carried out using an inert organic solvent such as trimethylformamide or dimethyl sulfoxide. In this case, it is preferable to carry out the reaction in the presence of a base, and examples of such bases include triethylamine, pyridine, etc. Examples of organic or inorganic bases such as potassium carbonate, sodium hydroxide, sodium hydride, etc. can be selected based on the amount of base used; The amount of N-hydroxy 7-thalamide used can be selected as appropriate, but for example, the amount of N-hydroxy 7-thalamide used can be 1 to about 2 equivalents, based on the compound of formula (n). The amount used can be exemplified as follows.The reaction temperature and time can also be changed appropriately, for example, from about 0" to about 120".
C. and reaction times, such as from about 1 to about 24 hours. The talmidoxy conductor of formula (■) 7, which can be obtained as described above, can be converted to amide 7 of formula (fV) by contacting it with hydrated hydranone in a suitable inert organic solvent such as methanol or ethanol. Can be converted into Saikin derivatives. This reaction can be carried out under a temperature condition of, for example, about 0°C to about 80°C, and the amount of hydrazine hydrate to be used can be changed appropriately. An example of the amount used is about 1 to 2 equivalents based on the derivative. The aminooxy derivative of formula (IV) obtained in this way is reacted with a ketone or aldehyde represented by 2〇=CR'R2 to
), compounds of formula (Ib) in which Z is 10-N=CRIR2 can be obtained. This reaction follows the formula 0=CR' R
! The ketone or aldehyde represented by the formula (IV)
The aminooxy derivative is used in an amount of about 1 part to a large excess, and a suitable inert organic solvent, such as meta/-
This can be carried out by contacting in a solvent such as alcohol, ethanol, or under MtfJ medium conditions, and can be easily carried out using the formula (
lb) The reaction temperature and time at which the compound can be softened can be selected appropriately, for example, from about 10°C to reflux temperature and from about 1°C to about 2°C.
4Fi? ! Mention may be made of reaction conditions such as between. Further, among the novel phenoxy derivatives of formula (I), the compound (re) in which Z is R co-0-N can be, for example, the following reaction formula 3 [wherein X, Y, R'' and R4 are the same as described above for formula (I)]. and Hal represents a chlorine atom, a bromine atom, or an iodine atom.] In the embodiment of the above reaction formula 3, an aminooxy derivative represented by the formula (IV) Hah in an inert growth solvent such as hydrous or anhydrous noxane, dihydrofuran, etc.
A compound of formula (ld) can be formed by contacting with R'. At this time, it is preferable to carry out the reaction in the presence of a base, and examples of such bases include organic or Examples include inorganic bases. The amount of such a base to be used can be appropriately selected, and for example, it can be used in an amount of about 1 to about 2 equivalents relative to the compound of formula (IV). Furthermore, the amount of Hal-R' to be used can be selected as appropriate, but it is about 1 to
By illustrating the usage amount such as about 2 equivalents, 1! The reaction temperature and time can also be varied as appropriate, for example, from about 0 DEG to reflux temperature and from about 1 to about 24 hours. Additionally, compounds of formula (Id) can also be converted to compounds of formula (Ic) by reacting with Hal-R' using similar conditions. Takashi-jlJ! Synthesis examples of the novel phenoxy derivatives of the present invention are listed below, and the products in the synthesis examples were confirmed by ①R1 NMR, mass spectrometry, etc. Preparation Example 1 Synthesis of 11-at-2-[4-(3,5-fuchlorobilysyl-2-oto)phenoquine]-propane 4.10 g (I0,5 of) of 2-[4- (3,5
-ychloropyridyl-2-oxy)phenoxy1-1-
7 tank l lefonyloxypropane 0.75g (I1,
A solution of sodium azide (5-ol) and trimethylformamide (30-ol) was heated to 100°C for 2 hours with stirring. After cooling the reaction solution to 20°C, 100-1
of ethyl acetate and dilute the mixture with 100ml of water.
I washed it several times. After drying the faM with magnesium sulfate,
The oily crude product obtained by concentration under reduced pressure was subjected to silica del column chromatography to obtain n-hexane-ethyl acetate (
eluted with 3.3'7 g of 1-7 nodule 2-
(4-(3,5-cycloviridyl-2-oxy)7
E/xyJ-propane was obtained. IR(NaCI) NMR(CI)cl, solvent, δ); 7,95 (I H
, -d), 7.7 4 (I H, d), 6, 8
6-7, 2 3 (4H, m), 4.5 0 (I
H, Hitomi), 3.40 (2H, Theory), 1.35 (3I
・I, d) 'J1m Example 2 1-771'-2-[4-(3-rioo
-5-)17 Synthesis of fluoromethyl-pyridyl-2-oxy)phenoxy-1-propane 2.02g (4,76-01) of 2-(4-(3-chloro-5-tripleomethyl-pyridyl-2) -oxy)
Phenoquine J-1-7 tansulfonyloxypropane,
・0.34g (5,23e+nol) of sodium acetate (1-79 of 2.22H, similar to example I except that 720 so 1 of trimethylformamide was used)
F-2-14-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)phenoxy"-p! Got bread. l R (NaCl) N M R (CD CI3m medium, θ); 8.23 (I
H, d), 7.90 (IH%d), 7.00 (4H,
m), 4.50 (IR1), 3.40 (2H, Cao)
, 1.3 6(3Hld) Production Example 3 2-14-(
Synthesis of 2.36 g (6,03 mmol) of 2-[4-(3,5
-dichloro-pyridyl-2-oxy)phenoxyl-1
-7 tansulfonyloxypropane, 1.47 g (I9
, 02m5+ol) of N-hydroxy 7-talamide, 0.
95. A solution of (9,411 m5 iol) of F ethylamine and 15 ml of dimethylformamide was heated to 100° C. for 4 hours with stirring. After cooling the reaction solution to 20°C, 501 ethyl acetate was added, and the mixture was diluted with 50
) ml of water twice. The organic layer was dried over 9 ml of sulfuric acid magnesium, concentrated under reduced pressure, and the resulting crude product was subjected to silica sol column chromatography eluting with n-hexane-ethyl acetate (3:1) to obtain 1.1 ag of 2-14-
(3,5-fuchloropyridyl-2-oxy)phenoxy]-1-7 talmidoxypropane was obtained. NMR (CDC1, solvent, #); 7.97-7.78
(f3H, u+), 6.97 (4H, S), 5
．． 00-4.56 (IT4, -), 4.32 (2Hl
L), 1.47(3H,d)yJ, Example 4 2-t
Synthesis of 4-(3,5-fuchloropyridyl-2-oxy)7e/xy]-1-iso-propylideneaminooxypropane 0.86 g (I, 88 mmol) of 2-14-(3,5
-cyclolowbilitrue2-oxy)7e7xy]-1
-7 walmid oxibu a pan and 20+*I methanol +7) rf#m E 0.12 with stirring at room temperature
g (2.16 mmof) of 530% hydrazine hydrate was added and stirred at room temperature for 3 hours. The precipitated heptalic acid hydranide was separated, and the generated 1-7minoxy-2-[4-(
7 of 31 to this reaction solution without purifying the 3,5-cyclolopyric-2-oxy)phenoxy]propane.
7 tons were added, and the mixture was further stirred at room temperature for 1 hour. This mixture was concentrated under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography using n-hexane-ethyl acetate (
2-[4-(3,
5-7 Chlorobilino-2-oxy)7eth/xyl-
1-iso-propylideneaminooxypropane was obtained. NMR(C1,)C1, solvent, δ); 7,97(If(
, ugly), 7.7 3 (I H, m), 4, 85
~4.3 0 (I H, m), 4.25-4.15 (
2H, m), 1.85 (3H, s), 1.80 (3H
,s), 1.35 (3H1d) Production Example 5 Methyl N
-[2-[4-(3,5-dichloropyridyl-2-oxy)7e/xypropoxy]carbamate 0.57 g (I, 24 gmol) of 2-(4-(3,5
-dichloropyricyl-2-oxy)phenoquine J-17
0.08 g (I, 44 mm
of) 90% hydranone hydrate was added, and the mixture was stirred at room temperature for 3 hours. The precipitated heptalic acid hydranide was separated off, and the reaction solution was concentrated under reduced pressure. Generated 1-7mi7oxy2-14
-(3,5-dichloropyricyl-2-oxy)phenoxy]propane without purification, 5111 nooxane, 11 water and 0.16 g (I°90+s+ol)
of sodium bicarbonate was added. To this solution, 0.15 g (I, 59 mmol) of methyl chloroformate was added at room temperature while stirring for 2 hours. 20 ml of ethyl acetate was added to this reaction solution, and the mixture was washed twice with 10 ml of water. The organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and the resulting crude product was subjected to silica sol column chromatography eluting with n-hexane-ethyl acetate (4:1) to give 0.35 g of methyl N-12-[ 4-(3,5-dichloropyrite-2-oxy)7e/xypropoquine 1
I got a carbamate. NMR (CD Clz solvent, δ); 7,85 (IHld), 7.73 (I1-1,
d), 6.92 (4H, m), 4°77-4.30 (
I Hl -), 3.9 5 (2H, d), 3
゜70(31(,S), 1.30(3H,d)) An example of the compound of the present invention obtained by a method similar to the above example is represented by the general formula (
The compounds are listed in Table 1 according to the indication of I), but the present invention is not limited thereto. 1・T 1±°゛・i deception and instruction 20 = mouth jI
α cc a C:
口＝：I：l ７＝；＝ 工
=== Engineering −c+IC+) ω
υ Q ω 2++=e CJ
Ro Roco To oo's o -N
Zeng: The compound of formula (I) of the present invention exhibits excellent herbicidal activity and is useful for controlling various grasshoppers.
It exhibits field herbicidal activity against weeds of the grass family, and has good selectivity for broad-leaved crops as well as crops of the family grass family, and can be an agriculturally useful herbicide. Thus, according to the present invention, the following formula (I), where X
represents a substituted phenyl group, a substituted bilinol group, or a substituted quinoxalyl group having at least one substituent selected from the group consisting of a herodene atom and (/-CF), and Y represents a 1kX atom of water or a -CH , Z is an at group, -〇-N=CR'R'' group [where R' and R2 are each independently a hydrogen atom, 01~G, furkyl, C3~
C, 1 representing a group selected from flucoxycarbonyl, hydroxycarbonyl, or -〇-N group [where R3
and R4 each independently represent water 1 and 1 representing a group selected from C3-C, alkyl and C1-C6 alkoxycarbonyl. It is possible to provide a herbicide characterized by containing it as an ingredient. The compound of the formula (I) of the present invention can control weeds of the Physaceae family from before their emergence to during the growing season growing in paddy fields and fields. For example, common names such as dog millet, Japanese millet, and Japanese millet, common weeds of paddy fields such as Japanese millet, red bean millet, blackberry, blackweed, slime weed, and blackberry grass, and common weeds such as blackberry, blackberry, foxtail grass, seipang lokoshi, millet, and black grass, etc. It is possible to control grasses of the family Helicoptera in fields, such as Sparrow grass, Sparrow mullet, Sparrow grass, Oat oat, Shiba wheat, Chimney spp. Moreover, the compound of the present invention has high selectivity for cultivated crops, such as soybean, cotton,
Practical for wide-leaved crops such as sugar beets, rapeseed, and sunflowers, as well as other crops such as rice, corn, wheat, barley, turgid, sugarcane, etc.2 Does not cause problematic chemical damage 6 Particularly effective for rice among other crops It has high selectivity, and in the treatment of stems and leaves, it does not cause any phytotoxicity to rice, and it controls insects such as 11 < essential, ≠ / Bini, 7 Zeya, etc. ! 1 can be done. Historically, the compound of the present invention has been used not only in rice fields and upland fields, but also in fruit fields (
It can also be used in gardens, mulberry gardens, lawns, and non-agricultural lands). When the compound of the present invention is actually used as a herbicide,
It is mixed with carriers or diluents, additives, and 1111fl additives by known methods to form formulations commonly used as good medicines, such as powders, granules, hydrated powders, emulsions, aqueous solutions, etc.
1 prepared and used as a sol, etc., and other agricultural chemicals such as bactericides, insecticides, acaricides, demulcents, and plant raw YJ1
It can be used in combination with or mixed with 11 moderators, fertilizers, soil conditioners, etc. In particular, by using it in combination with other herbicides, it is possible to not only reduce the amount of chemicals used and save labor, but also to expand the herbicidal spectrum due to the synergistic action of the two herbicides, and to have even greater commercial effects due to the attracting action. As the carrier or diluent, commonly used solid or liquid carriers are used. Solid carriers include clays such as kaolinite group, montmorillonite group, or attapaltzite group, talc, phyllite, pumice, vermiculite, gypsum, calcicarbonate, dolomite, diatomaceous earth, magnesium coal, Apatite, zeophyte, anhydrous silicic acid, synthetic calcium silicate, etc. j! 1! Organic substances; Plant organic substances such as soybean powder, tobacco powder, walnut powder, wheat flour, wood flour, starch, crystalline cellulose; Coumarone resin, petroleum resin, alkyd resin,
Polyvinyl chloride, polyalkylene glycol, ketone resin, esthetics) V, Iyllum, copalgam, dammaru
Synthetic or natural polymer compounds such as carnauba wax,
Examples include waxes such as beeswax, urea, etc. Suitable liquid carriers include paraffinic or trivalent hydrocarbons such as chemicin, mineral oil, spindle oil, and white oil; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and methylnaphthalene; and tetrachloride. Carbon, chloroform, trichlorethylene, monochlorobenzene, 0-altoluene, and other salt-cured hydrocarbons; dioxane, tetrahydrochloride, and other ethers; acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone, and other ketones. Class; ethyl acetate, amyl acetate, ethylene glycol 7 acetate, diethylene glycol acetate,
Esters such as dibutyl maleate and noethyl succinate; Alcohols such as methanol, n-hexyl, ethylene glycol, diethylene glycol, cyclohexyl and benol; ethylene glycol ethyl ether, diethylene glycol ethyl ether, Examples include ether alcohols such as ethylene glycol butyl ether; polar solvents such as dimethylformamide and trimethylsulfoxide; and water. In addition, emulsification, dispersion, wetting, spreading of the compound of the present invention,
Surfactants and other auxiliary agents may also be used for the purposes of binding, disintegrability, stabilization of active ingredients, fluidity improvement, rust prevention, etc. Examples of surfactants used include nonionic, anionic, cationic and zwitterionic surfactants, but typically nonionic and/or anionic surfactants can be used. Sexual things are used. Suitable nonionic surfactants include, for example, those obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol; and those obtained by polymerizing ethylene oxide to alkylphenols such as isooctyl 7-ethyl and /nylphenols. Additions: Polymerization and addition of ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; Polymerization and addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, and oleic acid; Stearyl phosphoric acid, dilauryl phosphoric acid Products obtained by polymerizing and adding ethylene oxide to mono- or difurkyl phosphoric acid such as acids; products obtained by polymerizing and adding ethylene oxide to amines such as dodecylamine and stearic acid 7mide; higher fatty acid esters of polyhydric alcohols such as sorbitan, and ethylene oxide added to them. Polymerization and addition; Examples include polymerization and addition of ethylene oxide and propylene oxide. Suitable anionic surfactants include, for example, alkyl sulfate ester salts such as sodium lauryl mpH and oleyl alcohol sulfate amine salt; furkylsulfonate salts such as sodium sulfosuccinate dioctyl ester and sodium 2-ethylhexene sulfonate. ; Sodium inpropylnaphthalene sulfonate,
Examples include 79-lsulfonic acid salts such as sodium methylene bisna-7talenesulfonate, sodium ligninsulfonate, and sodium dodecylbenzenesulfonate. Furthermore, the compounds of the present invention include casein, gelatin, albumin,
Glue, sodium alginate, carboxymethyl cell a-
s, methylcellulose, hydroxyethylcellulose,
Polymer compounds such as polyvinyl alcohol and other auxiliary agents can also be used in combination. The above-mentioned carriers and various adjuvants may be used depending on the dosage form of the preparation, the place of application.
Each of them may be used alone or in combination as appropriate depending on the purpose, taking into account N, etc. The content of the active ingredient of the compound of the present invention in the various formulations thus obtained varies depending on the formulation, but is 0.1 to 99% by weight, preferably 1 to 80% by weight. Powders, for example, usually contain 1 to 25% of the active ingredient compound.
The crosspiece is a solid carrier. Irrigation agents, for example, usually contain 25 to 90% of the active ingredient compound, with the remainder being a solid carrier and a number wetting agent, with protective colloid agents, thixotrope agents, antifoaming agents, etc. being added as necessary. . Granules, for example, usually contain 1 to 351% by weight of the active ingredient compound, with the remainder being mostly solid carriers. Is the active ingredient compound homogeneously mixed with the solid carrier?
Alternatively, it is fixed or adsorbed uniformly on the surface of a solid carrier, and the particle size is about 0.2 to 1°5+sm. Emulsions, for example, usually contain 1 to 30% by weight of the active ingredient compound.
This includes about 5 to 20% by weight of an emulsifier, the remainder being a liquid carrier, and a rust inhibitor added if necessary. The 72/xy compound herbicide of the present invention obtained as described above can be applied as the compound of general formula (I) or in the form of any II4 formulation as described in 1-1. The herbicide of the present invention can be applied to Atf grown in paddy fields and fields.
It can be applied to all kinds of plants from to ff stage, but it is especially preferable to apply it to genus gs'# in stage f1, and the amount of application is determined according to the purpose! The selection can be changed as appropriate depending on the type of grass, growth stage, application location, application period, weather, etc. In general, the amount of the compound (active ingredient amount) removed by the -shell formula (I) is approximately 0.01 to 10 kg per Iha, preferably approximately 0.01 to 2 kg. Next 111 Next, several embodiments of formulation examples using the compound of the present invention are shown.
In the following formulation examples, "parts" are based on weight.6Compound numbers are according to Table 1. Formulation example 1 (granules) Compound No. 1 5 parts bentonite 50 parts talc
40 parts Sog dodecylbenzenesulfonate 2 parts Sodium ligninsulfonate
After sufficiently mixing 2 parts and 1 part or more of polyoxyethylene alkylaryl ether, an appropriate amount of water was added, kneaded, and granulated using a granulator to obtain 100 n of granules. Formulation example 2 (hydrating powder) Compound No. 1 20 parts diatomaceous powder ± 60 parts white carbon 15 g sodium lignin sulfonate 3 parts 'dodecylbenzenesulfone rying soda Mix 2 or more parts and homogeneously mix and crush with a Nigu to make an irrigation agent. Got 100 copies. Formulation Example 3 (Emulsion) Compound No. 1 30 parts xylene 55 parts cyclohexanone 10WS calcium dodecylbenzenesulfonate 3W1 polyoxyethylene furkyl 7-lyl ether w6 The following were uniformly mixed and dissolved to obtain 100 parts of an emulsion. Drugs containing the compounds of the present invention were prepared according to the above-mentioned formulation examples. Test Example 1 (Stem and leaf treatment) Fill a square box (30 x 30 x 9 cm) with field soil,
Seeds of various crops and various weeds shown in Table 2 were sown in fixed amounts and allowed to grow in a greenhouse until each plant reached the 1.5-3 leaf stage (18 days after sowing). The compounds of the present invention shown in Table 2 were prepared using acetone:water; 1:1 (
Table 1
The solution was evenly sprayed on the leaves and foliage to achieve the amount of active ingredient shown in . 21 days after the chemical spraying, the herbicidal effect on each weed and the degree of chemical damage to each crop were determined according to the following criteria.
The results are shown in Table 1. Test Example 2 Leaf treatment test (selectivity between grass crops and grass weeds) Square plastic pot (20 cm2, height 9 am)
Filled with paddy soil, rice (variety: Nipponbare), corn (variety: Pioneer), and seeds of seven grass weeds such as millet, azalea, mehishiba, aki, maize, and japonica were sown in a certain amount, and the seeds were grown in a greenhouse. accomplished. Chemical treatment was carried out at the 2.5 to 3.5 leaf stage of each plant.
77 tons of the compound of the present invention:water=1:lH'l'we
En 20 Jo (containing 2%) was dissolved in a predetermined amount in a solution, and the entire stem and leaves were uniformly sprayed at an amount of water equivalent to 500β/ha. On the 21st day after chemical treatment, the degree of chemical damage to rice and corn and the herbicidal effect on grass weeds were investigated according to Test Example 1, and the results are shown in Table 3. Test Example 3 Leaf treatment test (selectivity among Poaceae weeds) Square plastic pot (20Oc theory 2, height 9c-)
The soil was filled with paddy soil, and certain amounts of seeds of rice (variety Nipponbare) and the grass weeds Novie and Azea were sown and grown in a greenhouse. The chemical treatment was carried out by administering the compound No. 1 of the present invention at the 3.5-leaf stage for rice and the 2.5-leaf stage for wildflowers and azaleas:
Water = 1:1 ("Tween 20 Jo, 2%
5004! The entire stem and leaves were sprayed uniformly with an amount of water equivalent to /ha. The investigation was carried out on the degree of chemical damage to rice and the herbicidal effect on No. japonica and zebra zebra on the 21st day after chemical treatment according to Test Example 1, and the results are shown in Table 4.

Claims (1)

[Claims] 1. The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) However, in the formula, X is a halogen atom and a small group selected from the group consisting of -CF_3. Both represent a substituted phenyl group, a substituted biridyl group, or a substituted quinoxalyl group having one substituent, Y represents a hydrogen atom or -CH_3, and Z represents an azide group, -O-N=CR^1R^2 group [Here, R^1 and R^2 are each independently a hydrogen atom, C_
Indicates a group selected from 1 to C_6 alkyl, C_1 to C_6 alkoxy-carbonyl and hydroxycarbonyl], or ▲Mathematical formula, chemical formula, table, etc.▼
A novel phenoxy derivative represented by: [wherein R^3 and R^4 each independently represent a hydrogen atom, a group selected from C_1 to C_6 alkyl and C_1 to C_6 alkoxy-carbonyl]. 2. The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) However, in the formula, X is a halogen atom and at least one substituent selected from the group consisting of -CF_3 represents a substituted phenyl group, a substituted biridyl group, or a substituted quinoxalyl group having 1 and R^2 are each independently a hydrogen atom, C_
Indicates a group selected from 1 to C_6 alkyl, C_1 to C_6 alkoxy-carbonyl and hydroxycarbonyl], or ▲Mathematical formula, chemical formula, table, etc.▼
a group [wherein R^3 and R^4 each independently represent a group selected from a hydrogen atom, C_1 to C_6 alkyl, and C_1 to C_6 alkoxy-carbonyl]; A herbicide characterized by containing one type of herbicide as an active ingredient.