JPH04500074A - Oxime derivatives and herbicides containing them as active ingredients - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] name of invention Field of invention of oxime derivatives and herbicides containing them as active ingredients The present invention relates to oxime derivatives and herbicides containing them as active ingredients. It is something. More specifically, the present invention provides excellent control over broad-leaved weeds and narrow-leaved weeds. It exhibits grass activity and, depending on the method of use, treatment method, and amount of treatment, can almost impede crop growth. It relates to herbicides that have selective herbicidal activity without causing any harm.

Description of prior art Traditionally, 2,4-dichlorophenoxyacetic acid has been used to selectively kill broad-leaved weeds, as represented by 2,4-dichlorophenoxyacetic acid. Herbicides that kill herbicides are known as selective herbicidal compounds. 2.4- The selective herbicidal activity of dichlorophenoxyacetic acid has been shown to be effective against small-leafed plants, including crop plants and weeds. selective herbicidal activity between plants and broad-leaved plants, including crop plants and weeds as well. be. 2,4-dichlorophenoxyacetic acid has extremely low activity against narrow-leaved plants. or have no activity at all (e.g. Natur=, (See Vol. 155, p. 498 (1945)).

On the other hand, based on these compounds, aromatic groups such as chloro or trifluoro are added. Introduction of methyl-substituted phenoxy group, etc., chloro- or trifluoromethyl mono-substituted Compounds introduced with pyridyloxy groups have the activity of selectively killing narrow-leaved plants. It is also known that (U.S. Pat. No. 4.270.948, 4.30 9.562, 4.314.069, 4, 332.961 and 3.954 ．． 442, JP-A-52-125626, JP-A-52-15825 and English (See National Patent No. 1.579.201). However, these compounds e.g. It also kills useful crops such as rice or corn.

It also contains certain N-phosphonomethylglycine derivatives as the main active ingredient. Herbicides are known and commercially available. This N-phosphonomethylglycine derivative is basically a non-selective herbicide, but at low doses, it The herbicidal activity against perennial weeds such as Pigweed and broad-leaved weeds such as Pigweed and Pigweed is reduced. ing. Especially for weeds of the Convolvulaceae family, such as Maruba morning glory, two weeks after chemical treatment. It shows almost no herbicidal effect even after a period of time.

In addition, N-phosphonomethylglycine derivatives are slow-acting and can be used in agricultural or non-agricultural land. It is not suitable for quickly removing weeds on the ground and carrying out the following work.

For example, in agricultural land, all weeds must be killed before sowing crops. However, if it is slow-acting, it may delay crop sowing or damage crop seeds. is possible.

In addition, delays in construction of buildings or railways, weeding of roads, etc. in non-agricultural land may also occur. N-phosphonomethylglycine derivatives are considered to be a non-selective drug that is fast-acting at low doses. It is insufficient as a selective herbicide.

Furthermore, herbicides containing certain glufosinate compounds as their main active ingredient known and commercially available.

This glufosinate compound is also basically a non-selective herbicide, but at low doses it The disadvantage is that the herbicidal activity against broad-leaved weeds such as lilyweed and ichito is reduced. .

Purpose and outline of the invention An object of the present invention is to provide novel oxime derivatives.

Another object of the present invention is to control weeds that exhibit excellent herbicidal activity against broad-leaved weeds and narrow-leaved weeds. The aim is to provide agents for

Still another object of the present invention is to produce useful crops depending on the method of use, treatment method and amount of treatment. In particular, it does not cause any phytotoxicity to soybeans or corn, and therefore Selective compounds and compounds that eliminate broad-leaved and narrow-leaved weeds without inhibiting their growth. An object of the present invention is to provide a herbicide containing the same.

Still another object of the present invention is to kill many broad-leaved weeds and narrow-leaved weeds by acting on the plant body. Kill or suppress the growth of thin-leaved crops such as corn and broad-leaved crops such as soybeans. It does not cause substantial phytotoxic damage to plants, and therefore, for example, useful crops and noxious weeds such as those mentioned above. In areas where weeds coexist, the growth of useful crops tends to outpace the growth of noxious weeds. to provide compounds capable of forming conditions and selective herbicides containing the same. Is Rukoto.

Still another object of the present invention is to spray the foliage of weeds for the purpose of weeding. Not only can it kill or inhibit growth by applying germination, but it can also be applied to the soil before germination. By doing so, it does not substantially inhibit the germination and growth of useful crops and suppresses the germination of weeds. A selective herbicide that can kill and kill the growing body, in other words, the application method is foliar spraying. The object of the present invention is to provide a herbicide that can be used for both soil treatment and soil treatment.

Still another object of the present invention is to have low toxicity to animals and fish, and low persistence in soil. Our goal is to provide the best herbicides.

Yet another object of the present invention is to obtain the above novel oxime derivatives of the present invention which are known per se. with N-phosphonomethylglycine derivatives and/or glufosinate compounds. By using these herbicides together, you can take advantage of these herbicide properties and eliminate fine-leaved weeds at low application rates. Provides a herbicide composition and method capable of killing both grasses and broadleaf weeds It's about doing.

Yet another object of the present invention is the production of the above novel oxime derivatives of the present invention. , a novel intermediate that makes it possible to efficiently produce the oxime derivative with good yield. An object of the present invention is to provide a benzaldehyde derivative which is a metal compound.

Further objects and advantages of the present invention will become apparent from the following description.

According to the research of the present inventor, these purposes and advantages are achieved by the following oxime derivatives. I know that this can be achieved.

That is, according to the present invention, an oxime derivative represented by the following formula or its Compounds that are salts are provided.

The oxime derivatives of the present invention exhibit excellent herbicidal activity against broad-leaved and narrow-leaved weeds. It has a wide range of herbicidal spectrum. Furthermore, how to use, how to treat, Causes substantial phytotoxicity to useful crops, especially soybeans and corn, due to physical measurements, etc. Therefore, it eliminates broad-leaved weeds and narrow-leaved weeds without substantially inhibiting their growth. It is a possible herbicide. Further, the oxime derivative of the present invention is preferably used in small amounts. Description of aspects The present invention will be explained in detail below.

In the above general formula (1), X and Y are the same or different, and each is a hydrogen atom. child, halogen atom, -CF3.

Or it is an alkyl group having 1 to 5 carbon atoms.

Examples of the halogen atom include fluorine, chlorine, and bromine. Al having 1 to 5 carbon atoms Kill groups may be linear or branched, for example methyl, ethyl, n -propyl, 1so-propyl, n-butyl, 5ee-butyl.

1so-butyl, t-butyl, n-pentyl, etc. X and Y are the same or are different, and each is preferably chlorine or -CF3.

In the above formula (1), Z is =CH- or -N-.

In the above formula (1), R1 is a hydrogen atom or a hydroxyl group.

It is an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. charcoal here The alkyl group with a prime number of 1 to 5 has 1 to 5 carbon atoms as in the specific example above for X and Y. 5 alkyl groups can be mentioned. As the alkoxy group having 1 to 5 carbon atoms, It may be linear or branched, such as methoxy, ethoxy, n-propylene. Ropoxy,.

1so-propoxy, n-butoxy, 5ee-butoxy, so-butoxy, n- Bentaloxy group, etc. Preferably, R1 is a hydrogen atom.

In the above formula (1), R2 is a group selected from the groups shown in a) to g) above. .

Here, aliphatic hydrocarbon group refers to linear or branched chain hydrocarbon group, alicyclic hydrocarbon group, Examples include hydrogen groups. Halogen atom, alkyl group having 1 to 5 carbon atoms, 1 to 5 carbon atoms Examples of the alkoxy group include the same groups as mentioned above for X, Y and R1. I can do it. Alkenyloxy groups having 1 to 5 carbon atoms include ethenoxy and propenoxy. , butenoxy.

Such as pentenoxy group. Aromatic hydrocarbon groups include benzene and naphthalene nuclei. They can be used alone or in combinations thereof. An aromatic heterocyclic group is, for example, One or more carbon atoms in the benzene nucleus and naphthalene nucleus are oxygen atoms.

Refers to structures substituted with sulfur atoms, nitrogen atoms, etc.

In addition, when Q is a direct bond, R2 has e) 6 to 2 carbon atoms which may be substituted. at least one nitrogen atom optionally substituted with 0 aromatic hydrocarbon groups or is preferably an aromatic heterocyclic group having 3 to 20 carbon atoms, and Q is represented by the above formula (1 ), examples of aliphatic hydrocarbons include linear or branched chain hydrocarbon groups, aliphatic hydrocarbon groups, and A chain hydrocarbon group substituted with a cyclic group or an aromatic hydrocarbon group. halogen Atom, alkoxy group, -COR4 is the same halogen as in the above specific example for R2. Examples include atoms, alkoxy groups, and -COR4.

Further, R3 is a methyl group, an ethyl group, a propyl group, or a butyl group.

Chain aliphatic hydrocarbon groups having 1 to 5 carbon atoms, CH3C2 groups, etc. l -CH2-C0R4, -CH-COR', -CH-C0R4 and CH3 vinegar Especially preferred is -CH-C0R4'.

It is an oxygen group, an ethoxy group, a propoxy group or a butoxy group. ) is preferable. Delicious.

○　S In the above formula (1), Q is preferably a direct bond, -C-, or -C-. Here Q is a direct bond, R2 is C) an optionally substituted alkoxy group, d) a substituted has been replaced/R5 It is a phenoxy group or g)-N which may be do not have.

Among the compounds of formula (1) above, each compound exhibiting particularly excellent herbicidal activity is Particularly preferred are those selected from the table below.

Examples of the oxime derivative of the above formula <I> include the compounds shown in the table below. Can be done.

The compound of the above formula <I> can be produced, for example, by the following reaction method, It is not limited to these.

Method (i) Method (ii) Method (iii) Method (ivl The formylation reaction in the above method <il and (it) includes, for example, cyanide. Using hydrogen hydride or zinc cyanide together with hydrogen chloride, and in some cases AlCl5 Alternatively, the specified aldehyde induction (19 571; Ber, 3L 1149 (1898); Ber, 32. 284 (1g99); Ann, 35.313 (1907); J, A m, Chem, Soc, 45°2373 (1932); J, 1m, Chem, Soc, 46.1518 (1924), etc. dichloromethyl methyl ether, dichloromethyl ethyl ether, dichloromethyl butylene dichloromethyl alkyl ether such as TtCI4. AlCl3 etc. Dichloromethyl alkyl ether method [ Chem, Her, 93.88 (1960); Ann, 662.1 05 (1963): Chem, Ber, 96.308 (1963) etc.], in the presence of an alkali such as alkali hydroxide or alkali carbonate, chlorophonone Formylating agents such as chlorine, bromoform, trichloroacetic acid or chloral hydrate Reimer-Tiemann reaction [B=r,, 9.423 (1 876): J, Chem.

Soc,, 1929.469; Organic 5ynthesis, m , 463 (described in 19551 etc., AlCl3, ZnCh, Ti Orthoformic acid esters such as methyl orthoformate and ethyl orthoformate in the presence of Cl4 etc. A specific aldehyde can be produced by reacting the aldehyde and hydrolyzing the acetal produced. The ortho@acid ester method [Chem, Ber, 96.308 ( (1963) etc.], in the presence of glycerin-boric acid or acetic acid-formic acid, etc. Hexamethylenetetramine is applied and the generated 5chiff base is hydrolyzed with acid. Duff method [J, Chem, Soc,.

1941, 547: J, Chem, Soc, 1945.276; etc. described], the N-methylformanilide method [Ber , , 60. 119 (1927) etc., above B6. N-methylform Dimethylformamide is used to introduce formyl groups instead of anilide. Formamide method [J, Am, Chem, Soc, 75.989 ( 1953) etc.].

Here, the following formula <n> A compound which is a benzaldehyde derivative or a salt thereof represented by the above formula ( It is useful as an intermediate for the compound represented by I).

Examples of the benzaldehyde derivative of the above formula (n) include the compounds shown in the table below. can do.

The oxime derivatives of formula (1) of the present invention affect plant metabolism, such as Suppresses the growth of certain plants, regulates the growth of certain plants, and phosphoruses certain plants. It has the property of causing certain types of plants to wither or wither.

The compound of the above formula (I) of the present invention can be applied to plant seeds, and can be applied to various plants. It can also be applied via the foliage or roots to plants during the growing stage. i.e. book The compounds of the invention, either as such or in the form of compositions, are intended to inhibit growth. Plants, i.e. plants whose metabolism is to be regulated, seeds of such plants, such [Places where things grow or where such plants are expected to grow] and in amounts sufficient to regulate the plant's metabolism.

The compound of the present invention is, for example, 0.001 to 20 kg/ha, more preferably 0.00 kg/ha. Plant in an amount of 5 to 10 kg/ha, particularly preferably in an amount of 0.01 to 5 kg/ha. It can regulate the metabolism of things.

The compounds of the present invention can be prepared in the form of solutions, emulsions, clouds, powders, pastes or granules. It can be used as a conventional formulation.

Such formulations include, for example, talc, bentonite, clay.

Kaolin, diatomaceous earth, white carbon, vermikinilite, slaked lime, ammonium sulfate, urea Solid carriers such as water, alcohol.

Dioxane, acetone, xylene, cyclohexane, methylnaphthalene, dimethylene formamide, N-methylpyrrolidone, dimethyl sulfoxide, cyclohexane No.

Liquid carriers such as methyl ethyl lactone and methyl isobutyl getone; alkyl sulfate esters ter, alkyl sulfonates.

Lignosulfonates, polyoxyethylene glycol ethers, polyoxygen Cyethylene alkyl aryl ether, polyoxyethylene orkylaryl ether Surfactants such as luchelate and dinaphthylmethane disulfonate.

Emulsifier or dispersant; various auxiliaries such as carboxymethyl cellulose, gum arabic, etc. Prepared using one or more types of agents, etc. Such formulations can be prepared, for example, by mixing the compound with the carrier and/or emulsifier as described above. It can be prepared by

The compound of the present invention is usually 0.01 to 99% by weight, preferably 0.1 to 9% by weight in the preparation. It can be present in a proportion of 6% by weight.

The compounds of the invention may be used as such or in admixture with other active compounds or as above. In the form of preparations as described above, for example, spray, rJR mist, dusting or dust. It can be applied to plants in a conventional manner such as ng.

When the compound of the present invention is intended to suppress or exterminate the growth of harmful plants, The compounds of the present invention, either as such or in the form of a composition, are added to beneficial plants or their seeds. Planting harmful plants or their seeds in areas where they coexist or are likely to coexist. or directly on the seeds or in the soil sufficient to suppress or eliminate the growth of harmful plants. It can be applied in amounts.

Harmful plants refer to the environment created by humans, for example, the surrounding plants in a field. A species that enters from the natural world and reproduces, is of no use or harm in its environment. It can be said that it is a plant that is recognized by humans. Such harmful plants are generally It is called a weed. Examples of weeds include the following: becomes.

Malva morning glory Gunbai Nazuna Japanese radish American horned beetle American golden deer White-bellied Datura Plantain Himedion Dandelion texas panicum Merikennikkibi Tmanmanochahiki Western cabbage Euphorbius Scrophulariaceae Mizukatsuri Furthermore, the compound of formula (1) above can be used for useful crops, especially crops, depending on the method of use, treatment method, and amount of treatment. It has virtually no phytotoxic effects on soybeans and corn; Used as a selective herbicide that eliminates broad-leaved and narrow-leaved weeds without inhibiting growth. It can also be used.

For example, the compounds of the present invention or compositions containing the compounds of the present invention may be used for herbicidal purposes. Kills or inhibits the growth of target weeds by spraying them on the stems and leaves. Not only does it improve the germination and growth of useful crops, but it can also be applied to the soil before germination. Selective weed control that can inhibit weed germination and growth without substantially inhibiting weed growth. It can be used as a herbicide.

The uninvented compound of general formula (1) can be used together with various herbicide compounds known per se. can be used. In this case, the compound of formula (1) of the present invention can be applied to broad-leaved weeds and narrow-leaved weeds. In order to fully exhibit herbicidal activity against weeds, we have developed It is used together with other compounds that exhibit herbicidal activity, thus controlling broad-leaved and narrow-leaved weeds. An effective herbicide composition can be provided for both.

Therefore, according to the present invention, a compound of general formula (I> and the following formula <m> N-phosphonomethylglycine derivatives represented by and/or the following formula (r V) ○ R31 CHa　P(-CFz+2C-COR32-(IV)OHNR2 glufosinate compound represented by, or its acid addition salt or salt with a base; A herbicide containing as a herbicidal ingredient, a carrier and/or a surfactant Compositions are also provided.

In <I) above, R21 and R22 are the same or different, and each -OH or -Q)% 24, ■ 23 is 10H, -OR" or -N It is R”R”. Here, R24 is an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group , a haloalkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. xyalkyl group, haloalkoxyalkyl group, or alkoxyalkoxy alkyl group (where each alkoxy, haloalkoxy and alkyl is 1- It has 5 carbon atoms. ) and phenoxy group. If R25 and R26 are the same hydrogen atom, alkyl group having 1 to 5 carbon atoms, hydrogen having 1 to 5 carbon atoms, respectively. Roxyalkyl group, alkenyl group having 2 to 5 carbon atoms, and R25 and R26 together with the nitrogen atom to which they are bonded form a morpholino group, piperidino group or or a pyrrolidino group.

1424, R25 and R'', X or The same examples as those mentioned above for Y and Y can be exemplified.

In R24, examples of the haloalkyl group having 1 to 5 carbon atoms include halomethyl, List herroethyl, dihaloethyl, herobropyl, halobutyl, and halopentyl. be able to. Examples of halogen atoms include fluorine and chlorine.

Mention may be made of bromine.

)124. The alkenyl group having 2 to 5 carbon atoms for R25 and R'' is , for example vinyl, propenyl, butenyl, pentenyl.

Examples of the alkoxyalkyl group for R24 include methoxyethyl, ethyl Preferred examples include xyethyl.

As the haloalkoxyalkyl group for R'', for example, chloroethoxyethyl and chloromethoxyethyl are preferred.

As the alkoxyalkoxyalkyl group for R2', for example, methoxyeth For xyethyl, ethoxyethoxyR" and R", hydroxyl having 1 to 5 carbon atoms Examples of sialkyl groups include hydroxymethyl, hydroxyethyl, hydroxy Cypentyl may be mentioned as preferred.

The compound represented by the above formula <III) is disclosed in Japanese Patent Publication No. 56-6401 (USP 7,123,057> and is known per se.

The compound of formula (Iff) above can be used as an acid addition salt or as a base in the composition of the present invention. It can also be used as a salt.

As the acid for forming the acid addition salt, for example, a strong acid having a pKa of 2.5 or less is preferable. Yes. Such acids include, for example, hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, and trichloric acid. Examples include roloacetic acid.

A salt with a base is a salt of R21, R22 and R23 in the above formula (III). When either one of these represents -OH, for example, those alkali metals, potash earth metals.

copper, ammonium or organic ammonium or trimethylsulfonium, Triethylsulfonium, tripropylsulfonium, trimethylsulfoxoni Umm.

Triethyl sulfoxonium, tribrovir sulfoxo: Yum-like cations It is formed as a salt with.

Alkali metals are, for example, lithium, sodium or potassium; Potassium earth metals represent, for example, magnesium or calcium.

Organic ammonium salts include low molecular weight organic amines, such as those having a molecular weight of about 300 or less. manufactured from amines that Examples of such organic amines include, for example, alkylene amines. alkylene polyamines and alkanolamines, such as methyl amines ethylamine, n-propylamine, isopropylamine, n-butylamine amine, isobutylamine, secondary-butylamine, n-amylamine.

Iso-amylamine, hexylamine, heptylamine.

Octylamine, nonylamine, decylamine, undecylamine, dodecylamine amine, tridecylamine, tetradecylamine, pentadecylamine, hexade Cylamine, heptadecylamine, octadecylamine, methylethylamine, Methylisopropylamine, methylhexylamine, methylnonylamine, methyl Lupentadecylamine, Methyloctadecylamine, Ethylbutylamine, Ethylamine Hebutylamine, ethyl octylamine.

Hexylhebutylamine, hexyloctylamine, dimethylamine, diethyl Amine, di-n-propylamine, diisopropylamine, di-n-amylamine diisoamylamine, dihexylamine, diheptylamine, dioctyl Amine, trimethylamine, triethylamine, trilopropylamine, lyisopropylamine, tri-n-butylamine, tri-isobutylamine, tri-n-butylamine - Secondary butylamine, triloamylamine, ethanolamine, n-pro Paturamine, Isopropaturamine, Jetanolamine, N,N-die Tylethanolamine, N-ethylpropanolamine, N-butylethanol Amine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine hmm.

2.3-dimethylbutenyl-2-amine, di-butenyl-2-amine, n-hex Monyl-2-amines and pro- and diamines, primary arylamines, e.g. Aniline.

Methoxyaniline, ethoxyaniline, o, m, p-toluidine, phenylene di amine, 2,4.6-tribromoaniline, benzidine 1 naphthylamine, o, m, p-chloroaniline, etc.; heterocyclic amines such as pyridine, morpholine, pyridine, Peridine, pyrrolidine, indoline, azepine, etc. may be mentioned.

In the above formula (I[), one or two of R21, R22 and R23 are Salts of -○H, -OH or -0R24 and R21, R22 and R Compounds in which the remainder of 23 is -OH or a salt thereof are preferred.

Furthermore, in the above formula (I), one or two of R21, R22 and R23 one is the salt of 1〇H and the remainder of R21゜R22 and R23 Mention may be made of compounds in which is -OH. Here, the salts of −〇H are: For example, ammonium or organic ammonium (where the organic ammonium group is Monoalkyl ammonium.

Dialkyl ammonium, trialkylammonium.

Monoalknylammonium, dialgenylammonium, trialgenylammonium monium, monoalkynylammonium, dialkynylammonium, trial Quinylammonium, monoalkanol ammonium, dialkanol ammonium um, trialkanol ammonium.

removed from the group consisting of heterocyclic ammonium or arylammonium, and such organic ammonium groups have 1 to 18 carbon atoms). .

A salt of the compound of the above formula (III) with the above acid or base is a salt of the compound of the above formula (I). and M= or a base according to methods known per se.

The compound of the above formula (III) preferably used in the present invention, its acid addition salt or Examples of salts with bases are as follows.

+101) N-phosphonomethylglycine <102) N-phosphonomethylglycine Synsodium salt (103) N-phosphonomethylglycine ammonium salt (1 041N-phosphonomethylglycine calcium monohydrate (105) N-phosphonomethylglycine calcium monohydrate Nomethylglycine magnesium salt (106) N-phosphonomethylglycine potassium um salt (107) N-phosphonomethylglycine dimethylamine salt <1081 N-phosphonomethylglycine copper salt (109) N-phosphonomethylglycine zinc Salt (1101N-phosphonomethylglycinamide+111)methyl N-phospho Nomethylglycinate (112) Ethyl N-phosphonomethylglycinate (1 13) n-propyl N-phosphonomethylglycinate (114) n-buty N-phosphonomethylglycinate fl151 cyclohexyl N-phospho Nomethylglycinate (116) tetraloethyl N-phosphonomethylglycinate fl171 N-pho Sulfonomethylglycine isoprobylamine salt <118) N-phosphonomethylglycine methylamine salt (119) N-phosphonomethylglycine methylamine salt Honomethylglycine diisoprobylamine salt (120) N-phosphonomethylglycine pyridine salt f1211 N-phosphono Methylglycine aniline salt (122) N-phosphonomethylglycine trimethyl Sulfonium salt (1231N-phosphonomethylglycine trimethylsulfoxonium salt In the above formula <rV), R'' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Yes, R32 is -○H, -NR2゜N　HN　R2, N　HCs　R5 or It is an alkoxyl group having 1 to 12 carbon atoms which may be substituted with -oH.

As the alkyl group for R31, those mentioned above for X and Y in the above formula (1) can be used. Of these, an alkyl group having 1 to 4 carbon atoms can be mentioned.

The alkoxy group of R32 may be linear or branched, for example, Toxy, ethoxy, n-propoxy, 1so-propoxy, n-butoxy, 5ec-butoxy, 1so-butoxy, tert-butoxy, n-pentoxy Sh.

n-hexoxy, n-hebutoxy, n-octoxy, n-nonanoxy, n-deca Mention may be made of noxy, n-undecanoxy and n-dodecanoxy. child These alkoxy groups may be substituted with a hydroxyl group (-○H). For example, hydro Such as xyethoxy.

The compound represented by the above formula (rV) is disclosed in Japanese Patent Publication No. 57-26564 (TLS P. 4,168,963) and is believed to be known per se. Ru.

The compound represented by the above formula <IV) may be used as an acid addition salt or salt in the composition of the present invention. It can also be used as a salt with groups.

As the acid for forming such an acid addition salt, in the case of the acid addition salt of the formula <II[), The same acids as those exemplified above can be used. Acid addition salts are represented by formula (IV) It is believed to be formed in the primary amino group of.

Examples of the base that forms a salt with the base include the above formula (III). The same bases as those mentioned above can be exemplified.

In the above formula (rV), R" is preferably a hydrogen atom, and R32 is -○H, -NH 2, ~N　HN　R2, alkoxy having 1 to 4 carbon atoms, hydroxy having 2 to 4 carbon atoms Alkoxy is preferred.

Further, as the salt of the compound of the above formula (■), for example, Na.

K, Cu, Mg, Ca, Zn, Ni, Mn and Fe salts, ammonia mono-, di- or tri-alkyl salts, each alkyl group having 1 to 4 carbon atoms Salts with bases such as salts with amines or salts with aniline; or salts with hydrochloric acid, sulfuric acid, odor Hydrohydric acid.

Acid addition salts of acids such as chloric acid or oxalic acid may be mentioned as preferred. Wear.

A salt of the compound of the above formula (IV) with the above acid or base is a salt of the above formula (rV). and an acid or base according to a method known per se.

The metal compound of the above formula (rV) preferably used in the present invention, its acid addition salt or Examples of salts with bases are as follows.

(500) [(3-Amino-3-carboxy)-propyl-1]-methyl-pho Sphinic acid :501) [(3-aminol 3-carboxy)-propyl-1-comethyl-pho Suphine monosodium salt (502) [(3-amino-3-carboxy)- Propyl-1]-methyl-phosphinic acid monopotassium salt (5031[(3-amino) Nor-3-levoxy)-propyl-1-comethyl-phosphinic acid monoammonium salt (5041[(3-amino-3-levoxy)-propyl-1comethyl Rhuposphinate diammonium salt (505) [(3-amino-3-carboxylic acid C)-propyl-1-comethyl-phosphinate magnesium salt (506) [( 3-Amino-3-carboxy)-propyl-1]-methyl-phosphinic acid monopropylene Lopylammonium salt (5071[(3-amino-3-carboxy)-propyl-1]-methyl-phos Finic acid mono(diisopropylammonium) salt (508) [<3-Amino-3-levomethoxy)-propyl-1]-methy Ruphosphinic acid (509) [(3-amino-3-carbomethoxy)-propyl-1]-methylphos Sphinate sodium salt (510) [(3-amino-3-carbomethoxy)- Propyl-1-comethylphosphinate diisopropyl-ammonium salt (5111[<3diamino-3-carbamide)-propyl-11-methylphosph phosphoric acid (512) [(3-amino-3-carbamido)-propyl-1-comethylphos Funic acid sodium salt f513) [(3-amino-3-carbamide)-propylene Ru-1 comethylphosphinate ammonium salt (514) [(3-amino-3 -methifure-3-levoxy)-propyl-1-comethylphosphinic acid (5) 5) [(3-amino-3-methyl-3-levoxy)-propyl-1]-methyl Tyrphosphinic acid monosodium salt (516) [(3-Amino-3-methyl-3-carboxy)-propyl-1] -Methylphosphinic acid monoammonium salt As a similar compound of the above general formula <TV), bialaphos can also be used in combination. It is possible.

In addition to the compounds of the above formulas (■> and (rV)), triazine herbicides (simazine , atrazine, cyanazine, cymetrine, 10methrine, metribuzine, book It is also possible to use it in combination with a compound of the general formula <1) of the invention.

The composition containing the compound of the above formula (1) of the present invention and other herbicide compounds is the above-mentioned compound. The compound of formula (1) and other herbicide compounds are mixed in a ratio of the former (1) to the latter compound. It is preferably contained in a quantitative ratio of 1:500 to 500:1.

The ratio is more preferably 1:200 to 200:1, particularly preferably The ratio is 1:100 to 100:1.

The actual amount of the composition to be applied will also depend on a number of factors, such as the specificity to inhibit growth. Although it depends on the type of target plant, generally 0.01 to 10 kg/ha. , preferably from 0.05 to )kg/ha. Be a person skilled in the art Unless a particularly large number of experiments are carried out using standard standardized tests, If so, the amount used can be easily determined.

The above compositions of the invention include mixing the active ingredient with a carrier consisting of a solid or liquid diluent. It can also be applied in the form of a composition. In addition, the composition further contains a surfactant. It may also contain additives such as: with such diluents, carriers and surfactants. As such, the same ones as those already described above can be used.

The composition of the present invention can be prepared by containing a carrier and/or a surfactant together with a carrier and/or a surfactant. as a preparation in the usual forms such as solvents, emulsions, suspensions, powders or pastes. Can be used.

The composition of the present invention is prepared by combining compound (1) and other herbicide compounds, and then A method of preparing a preparation by mixing with a carrier etc., or a method of preparing a preparation by mixing with a carrier etc., or a method of preparing a preparation by mixing the composition of compound (1) with other Separately prepare herbal compound compositions, add a carrier etc. if necessary, and add these compositions. It can be prepared by mixing ingredients together to form a formulation.

According to the present invention, compound <I> and other herbicide compounds may also be present at the same time. or one application effective for killing weeds in any order in areas where weeds are growing. This is a method of killing weeds by doing so.

In the above method, compound (1) and other herbicide compounds are these compounds! P! I<Tech), as above compositions containing other herbicide compounds, or separately. Application of the prepared composition of compound (I) and other herbicide compound compositions together By doing so, it can be applied to areas where weeds are growing at the same time.

Additionally, a composition of compound (1) prepared separately and a composition of other herbicide compounds may be combined. can also be applied to areas where weeds are growing over time.

At that time, the order of application of the composition of compound (1) and the composition of other herbicide compounds is determined. The deviation may come first.

Also, the time from applying one of the compositions to applying the other composition. For example, after application of one composition, the active compound (I> or is applied while the other herbicide compound remains on the surface of the weeds. is preferred. It varies depending on the target plant, climate conditions, etc., but usually immediately after applying one or the other. It is preferable to apply the other within 2 to 3 days.

According to the present invention, as described above, for example, compound (1) and other herbicide compounds and in situ before crop emergence. It is possible to kill weeds that grow in certain places and allow crops to grow in their original condition.

Application rates of compounds and other herbicide compounds when implementing these methods The application rates listed above for the composition are suitable guidelines.

According to the above method of the invention, both broad-leaved weeds and narrow-leaved weeds are advantageously reduced. It can be killed by controlling the amount of application.

Furthermore, the compound of general formula (1) of the present invention can be used with various insecticide compounds known per se. can also be used together. Here, examples of the insecticide include barathion, fluorophore, etc. Organophosphorus insecticides such as enitrothion, diazinon, and fenthion; carba Carbamate insecticides such as Zyl, dioxacarb, and carbalt; permetri Allethrin, Fenvalerate, Cypermethrin, Bifensone, Flu Pyrethroid insecticides such as cisurinate, cyhalothrin, tefluthrin, DD T, methoxychlor, dicofol, chlorobenzylate, fluoromobroile diphenyl insecticides such as Insecticides such as chloride, chlordane, etc.

In addition to the aforementioned triazine herbicides glyphosate and glufosinate, e.g. For example, alloxydim, sethoxydim, chloroxydim, cycloxydim, etc. Lohexadione herbicides; fluazifop, diclofop.

Kinohop, Bovenate, Trihopsim, Herohop.

Chloradifop, Fenoxaprop, Fentiaprop, 2.4-D, MC Phenoxyacetic acid herbicides such as P; 2.3.6-TBA, dinoben, chlorambe N, daikanba.

Benzoic acid herbicides such as chlortal; chloropropham, phenmedipham, Carbamates such as Ashram, Molinate, Benthiocarb, and Ethiolate Herbicides: propanil, naptalam, eridochlor, metolachlor, arac Amide herbicides such as Roll, Butachlor; Bromophenoxidim, Ioxy Nitrile herbicides such as Nil, dichlobeninil; Deeuron, Linuron.

Urea herbicides such as fenuron and benzthiazuron; nitrofen and aciflu Diphenyl ether herbicides such as Orphen and Cromethoxynil: Other diphenyl ether herbicides t.

Herbicides include baraquat, trifluralin, and ginosep.

The invention is illustrated by the following examples.

In the examples, parts mean parts by weight. In addition, unless otherwise specified, herbicidal activity is Evaluation was made on a 6-level scale. i.e. after and before application of the active compound. 0 is a healthy state similar to The dead state is rated as 5, and in between, there are 4 stages <1.2.3 and 4 depending on the strength and weakness of the plant. 4) was established and evaluated.

Example IA 52 parts of 3-(2-chloro-4-trifluoromethylphenoxy)phenol was diluted with TiCl439.6 was dissolved in 900 parts by volume of chloromethane and the solution was cooled on ice. Add capacity.

Next, 34.1 parts of dichloromethyl methyl ether was added while keeping the reaction temperature at about 0°C. Drip. After stirring for 15 minutes after the dropwise addition, 113 parts by volume of 5% HCI was carefully added. Add more. The reaction solution was extracted with ether, the organic layer was washed with water, and extracted with anhydrous sodium sulfate. After drying with a vacuum cleaner, concentrate under reduced pressure. Purify the residue using silica gel column chromatography 42 parts of the desired compound (IA) were obtained. The melting point (m, p,) of the compound is 37~ The temperature was 40°C. We also provide infrared absorption spectrum and nuclear magnetic resonance spectrum data. Shown in Table IA.

Examples 2A-5A In Example IA, 3-(2-di-4-trifluoromethylphenoxy) In place of phenol, each of the phenol derivatives shown in Table 2A was substituted with 3-(2-chloro). As per the same number of moles as rho-4-trifluoromethylphenoxy)phenol The following reaction and post-treatment were carried out in the same manner as in Example IA. Yield of each product are shown in Table 2A, and infrared absorption spectrum and nuclear magnetic resonance spectrum data are shown in Table I. Shown in A.

Table 2A Example: Phenol derivative production Yield No. Hardware No. (parts) 2A3-<4-)Lifluoromethi<2A) 35ruphenoxy)phenol 3A3-<4-chlorophenoxy) (3Al 32phenol 4A3-(2,4-dichloropheno (4A) 40xy)phenol 5A3-(3-chloro-5-tri(5A) 30fluoromethyl-2-pyridi phenol Example 6A 2-ethoxy-4-(2-chloro-4-trifluoromethylphenoxy)benz Synthesis of aldehyde (8A) Compound synthesized in Example IA <IA) 2.0 parts, iodine 1.0 parts of ethyl chloride, 1.7 parts of anhydrous potassium carbonate, 30 parts by volume of methyl ethyl ketone The mixture is refluxed for about 5 hours. After filtering and washing the f solution with water, anhydrous sodium sulfate Dry and concentrate under reduced pressure. The crude product was purified by silica gel column chromatography. , 8 parts of the given compound <8A)' were obtained. Infrared absorption spectrum, nuclear magnetism of the compound Gas resonance spectral data are shown in Table IA.

Example 7A 2-methoxycarbonylmethoxy-4-(2-chloro-4-trifluoromethyl Synthesis of phenoxy)benzaldehyde (9A) Compound synthesized in Example IA <1. A) 1.5 parts, methyl α-bromoacetate 0.7 3 parts by volume of anhydrous potassium carbonate, 1.3 parts by volume of anhydrous potassium carbonate, and 2 parts by volume of methyl ethyl ketone. Reflux for 2 hours.

After filtering and washing the solution f with water, it is dried over anhydrous sodium sulfate and concentrated under reduced pressure. raw The product was purified by silica gel column chromatography, and the predetermined compound <9A) 1.6 I got the department.

The infrared absorption spectrum and nuclear magnetic resonance spectrum data of the compound are shown in Table IA. .

Example 8A 2-ethoxycarbonylmethoxy-4-(2-chloro-4-trifluoromethyl Synthesis of phenoxy)benzaldehyde (10A) In Example 7A, ethyl α-bromoacetate was substituted for methyl α-bromoacetate. ．． The reaction and post-treatment were carried out in exactly the same manner except that 79 parts were used. Compound <10A ) yield was 1.7 parts. Infrared absorption spectrum and nuclear magnetic resonance spectrum The data are shown in Table IA.

Example 9A 8.2 parts of the compound el(LA) synthesized in Example IA, methyl α-bromopropionate A mixture of 5.2 parts of potassium carbonate, 7.2 parts of anhydrous potassium carbonate, and 100 parts by volume of methyl ethyl ketone. The mixture was refluxed for approximately 3 hours. After filtration, liquid f was concentrated under reduced pressure, and the crude product was filtered onto silica gel. Purification was performed using ram chromatography to obtain 9.5 parts of the desired compound (IIA). °Applicable The melting point (m, p,) of the compound is 77-79°C, and the infrared absorption spectrum and and nuclear magnetic resonance spectral data are shown in Table IA.

Example 10A 2-(1-ethoxycarbonylethoxy)-4-(2-chloro-4-trifluoro Synthesis of lomethylphenoxy)benzaldehyde <12A> In Example 9A, α-bromopropylene was used instead of methyl α-bromopropionate. The reaction and post-treatment were carried out in exactly the same manner except that 5.6 parts of ethyl onate was used.

The yield of compound (12A> was 9.6 parts.The infrared absorption spectrum and and nuclear magnetic resonance spectral data are shown in Table IA.

Example 11A In Example 9A, α-bromopropionate was replaced with methyl α-bromopropionate. The reaction was carried out in exactly the same manner except that 6.5 parts of pion [ln-butyl] was used. I understood.

The yield of compound <13A) was 9.7 parts. Infrared absorption spectrum and and nuclear magnetic resonance spectral data are shown in Table IA.

Examples 12A-15A In Example 9A, 2-hydroxy-4-(2-chloro-4-trifluoromethane) tylphenoxy)benzaldehyde (IA) as shown in Table 3A, respectively. The amount of aldehyde derivatives (2A) to (5A) that gives the same number of moles as in the case of (IA) The reaction and post-treatment were carried out in exactly the same manner except that . each reacting generation The yields of the products are shown in Table 3A. Also, the infrared absorption spectrum of the product and the nuclear magnetic mirror surface. Spectral data are shown in Table IA.

Table 3A Example Aldehyde Product compound Yield No. Derivative N.0 (parts) 12A (2A) (14A) 8.813/, A) (15), J 7. 914 A (4, to) (16Al 8.515A (5Al (17A) 9 ．． 4 Example 16A 2-(1-carboxyethoxy)-4-<2-chloro-4-trifluoromethyl Synthesis of phenoxy)t＼zaldehyde<　19.4　) 0.5 parts of the compound <11A) synthesized in Example 9A was mixed with 6 parts by volume of methanol and 0.5 parts of water. Dissolved in 4 parts by volume of mixed solution, added 48 parts by volume of IN KO3 to the solution, and stirred overnight. Leave at room temperature. Remove methanol under reduced pressure and acidify with hydrochloric acid to liberate. The product is extracted with ether and washed with water.

The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the desired compound <19A>. Get 0.4 copies. Infrared absorption spectrum and nuclear magnetic resonance spectrum data of the compound The data are shown in Table IA.

Example 17A Synthesis of compound (5A) 2.16 parts of 2.3-dichloro-5-trifluoromethylpyridi, 2.4-dichloro-5-trifluoromethylpyridi Mixture of 1.41 parts of hydroxybenzaldehyde and 10 parts of dimethyl sulfoxide Add 0.42 parts of 60% sodium hydride to the solution, then heat and stir at 120°C for 5 hours. After stirring, the mixture was cooled to room temperature, added to ice water, and extracted with ethyl ether. remove organic layer After drying with sodium sulfate, the ether was removed under reduced pressure, and the residue was transferred to a silica gel column. By chromatographic separation, 2.5 parts of the target product (5,4) was obtained. Infrared of the compound Absorption spectra and nuclear magnetic resonance spectra data are shown in Table IA.

Examples 18A-20A Synthesis of compounds (20A) to (22A) In Example 9A, instead of methyl α-bromopropionate, the compounds listed in Table 4A below were used. The desired product was obtained by using a halogen compound. Infrared absorption spectrum of these compounds The spectral and nuclear magnetic resonance spectral data are shown in Table IA.

Table IA Table 1. A <Continued> Table IA (continued) Table IA (continued) Table IA <Continued) Table IA (continued) Example IB Synthesis of compound (IB) 2-ethoxy-4-(2-chloro-4-trifluoromethylphenoxy)benz Add heat to a solution of 3.45 parts of aldehyde (8A) dissolved in 20 parts of tetrahydrofuran. Add a solution of 0.7 parts of droxylamine hydrochloride dissolved in 5 parts of water, and add the solution while stirring. 0.76 parts of potassium carbonate was added at room temperature, and the mixture was further stirred at room temperature for 1 hour. after that , distill off tetrahydrofuran under reduced pressure, add 20 parts of water and extract with ether. After drying the ether layer over anhydrous sodium sulfate, the ether was removed. Silica gel residue 3.2 parts of the target product were obtained by column chromatography separation. Infrared absorption of the compound The spectra and nuclear magnetic resonance spectra are shown in Table IB.

Example 2B Synthesis of compound (2B) In Example IB, 2-nitoxy-4-(2-chloro-4-trifluoromethyl phenoxy)benzaldehyde <8. 2-(1-meth) instead of A>3.45 parts xycarbo:nilethoxy)-4-(2-chloro-4-trifluoromethylphene Using 4.03 parts of oxy)benzaldehyde <IIA), the rest was reacted in exactly the same manner. By post-treatment, 3.85 parts of the target product were obtained. Infrared absorption spectrum of the compound Table 1B shows a spectrum of both the nuclear magnetic field and the nuclear magnetic field.

Example 3B Synthesis of compound (3B) In Example IB, 2-ethoxy-4-(2-chloro-4-trifluoromethyl 2-(1-ethoxy) instead of 3.45 parts of phenoxy)benzaldehyde (8A) cyclo-4-(2-chloro-4-trifluoromethylphenol) Using 4.16 parts of xy>benzaldehyde<12A), the rest was reacted in exactly the same manner. By the treatment, 3.90 parts of the target product was obtained. Infrared absorption spectrum and and nuclear magnetic resonance spectra are shown in Table 1B.

Example 4B Synthesis of compound (4B) In Example IB, 0.7 part of hydroxylamine hydrochloride was replaced with O-methylhydrochloride. Using 0.84 part of droxylamine hydrochloride, react and post-process in exactly the same manner. As a result, 3.80 parts of the target product was obtained. Infrared absorption spectrum and nuclear magnetism of the compound The gas resonance spectra are shown in Table IB.

Example 5B Synthesis of compound (5B) In Example 2B, 0-methylhydrochloride was used instead of 0.7 parts of hydroxylamine hydrochloride. Using 0.84 part of droxylamine hydrochloride, react and post-process in exactly the same manner. As a result, 3.85 parts of the compound was obtained. Infrared absorption spectrum and nucleus of the compound The magnetic resonance spectra are shown in Table IB.

Examples 6B-13B Synthesis of compounds (6B) to (13B) 2-(1-methoxycarbonylethoxy>4(2-chloro-4-trifluoro (romethylphenoxy)benzaldehyde <11. A > 4.03 parts as tetrahydro A solution of 〇-substituted hydroxylamine shown in Table 2B below was dissolved in 20 parts of furan. An aqueous solution containing an equimolar amount was added at room temperature, and the mixture was further stirred at room temperature for 1 hour. Then under reduced pressure Tetrahydrofuran was distilled off, 20 parts of water was added, ether extracted, and the ether layer After drying over anhydrous sodium sulfate, the ether was removed.

By separating the residue by silica gel column chromatography, the desired products were obtained as shown in Table 2B below. It was obtained with the weight shown in . Infrared absorption spectrum and nuclear magnetic resonance spectrum of each product are shown in Table IB.

Table 2B Example 0-Substituted hydroxylamine yield Production No. f part) Hardware N.

6B H2N-0CH2CHa 3.66 (6B) 7B H2N-0CH2C H2CH33,72(7B)/CH3 8B H2N-〇-CH4,05+8B)\CH3 9B H2N-0-■ 4.00 +9B) 10B H2N-〇-CH2COO C2H5'3-78 (IOB) 11B H2N-〇CH2CH=CH23,8 9 (IIB112B H2N-〇CH2CH=CH-C ratio 3.75 (12B) 13B H2N-0+CH2+2CH=CH23,93, (13B) Example 14B Synthesis of compound (14B) In Example 11B, 2-(1-methoxycarbonylethoxy)-4-<2-k Rolo-4-trifluoromethylphenoxy)benzaldehyde <IIA> 4.0 2-(1-ethoxyl levonylethoxy)-4-(2-chloro -4-trifluoromethylphenoxy)benzaldehyde <12A> 4.16 parts 3.90 parts of the target product were obtained by performing the reaction and post-treatment in exactly the same manner. .

The infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound are shown in Table IB.

Example 15B Synthesis of compound (15B> In Example 6B, 0-2-propylhydro as 〇-substituted hydroxylamine Target product 3 is obtained by using xylamine and performing the reaction and post-treatment in exactly the same manner. ．． I got 0 copies. Display the infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound. Shown in IB.

Example 16B Synthesis of compound (16B) In Example IB 2-ethoxy-4-chloro-4-trifluoromethyl phenoxy) benzaldehyde (2-1-methoxy instead of 8A>3.45 parts) Cicarbomethylphenoxy〉Using 4.17 parts of acetophenone, the rest is exactly the same. By reaction and post-treatment, 3.0 parts of the target product was obtained. The infrared absorption spectrum of the compound The vector and nuclear magnetic resonance spectra are shown in Table IB.

Example 17B Synthesis of compound <17B> In Example 16B, O-methyl was used instead of 0.7 parts of hydroxylamine hydrochloride. Using 0.84 parts of hydroxylamine hydrochloride, the reaction and post-treatment were carried out in exactly the same manner. By doing so, 3.1 parts of the target product was obtained. Infrared absorption spectrum and nuclear magnetism of the compound The gas resonance spectra are shown in Table IB.

Example 18B Synthesis of compound (18B> 2-(1-methoxycarbonylethoxy)-4-<2-chloro-4-trifluoro 4.03 parts of methylphenoxy)benzaldehyde (IIA) was added to Add 1.23 parts of O-benzylhydroxylamine to a solution dissolved in 20 parts of oran. After stirring at room temperature for 2 hours, tetrahydrofuran was removed under reduced pressure and the resulting residue was Separation was performed using silica gel column chromatography to obtain the desired product 4.67. the compound The infrared absorption spectrum and nuclear magnetic resonance spectrum of is shown in Table IB.

Example 19B Synthesis of compound (19B> In Example 18B, 2-(1-methoxycarbonylethoxy)-4-(2-k Rolo-4-trifluoromethylphenoxy)benzaldehyde (IIA) 4.0 2-ethoxy-4-(2-chloro-4-trifluoromethylphene) in place of 3 parts. O-benzaldehyde (8A>3.45 parts) Using 1.10 parts of ○-phenylhydroxylamine instead of 1.23 parts of 3.70 parts of the desired product was obtained by performing the reaction and post-treatment in exactly the same manner. Applicable The infrared absorption spectra and nuclear magnetic resonance spectra of the compounds are shown in Table IB.

Examples 20B-37B A' Synthesis of binding (20B) to <37B) 2-(1-methoxycarbonyl ethoxy )-4-(2-chloro-4-trifluoromethylphenoxy)benzaldehye Table 3B below was added to a solution of 4.03 parts of de(IIA) dissolved in 20 parts of tetrahydrofuran. Add equimolar amount of 〇--substituted hydroxylamine shown in above and leave at room temperature for 2 to 5 hours. Stirred. Tetrahydrofuran was then removed under reduced pressure and the resulting residue was silicaed. By separating using Kagel column chromatography, the results are shown in Table 3B below. Good weight.

The infrared absorption spectra and nuclear magnetic resonance spectra of each product are shown in Table IB.

Table 3B Example 〇-substituted bitroxylamine yield Production No., part f) Hardware No. .

Table 3B (continued) C.I. 2N Table 3B (continued) Type 0 %formula% Combine! ! In Synthesis Example 2OB of 51J(38B) to (45B>, 2-(1- methoxycarbonylethoxy)-4-(2-chloro-4-trifluoromethyl fluoride) 2-(1-methoxy)benzaldehyde (IIA>4.03 parts) (cycarbonylethoxy)-4-(2,4-difluorophenoxy)benzaldehye Using 3.70 parts of de(16A), the following Table 4B was used as 〇-substituted hydroxylamine. By using the materials shown and performing the reaction and post-treatment in exactly the same manner, each The weights shown in Table 4B below were obtained. Infrared absorption spectra and nuclear magnetic resonance spectra of each product. The spectra are shown in Table IB.

C.I. Synthesis of compounds (46B) to (49B) In Example 20B, 2-<1-methoxycarbonylethoxy)-4-(2-k Rolo-4-trifluoromethylphenoxy)benzaldehyde (IIA) 4.0 2-(1-methoxycarbonylethoxy)-4-trifluor instead of 3 parts Using 3.68 parts of olomethylphenoxy)benzaldehyde<14A), Using the substituted hydroxylamine shown in Table 4B below, the rest was carried out in exactly the same manner. By reaction and post-treatment, the respective weights shown in Table 5B below were obtained. of each product The infrared absorption spectrum and nuclear magnetic resonance spectrum are shown in Table IB.

Table 3B Example: Yield of 0--converted hydroxylamine Production No. (parts) Hardware N.

Examples 50B to 56B Synthesis of compounds <50B) to <56B) In Example 20B, the 〇-substituted hydroxylamine shown in Table 6B below was used. By using the following reaction and post-treatment in exactly the same manner, the following Table 6B was obtained. The target product was obtained with the weight shown in . Infrared absorption spectra and nuclear magnetic resonance spectra of each product. The spectra are shown in Table IB.

Table 6B No. f part) Hardware N.

I H3 H3 N=N Examples 57B, 58B, 61B In Synthesis Example 38B of compound (57B), <58B), <61B) 〇-- Using the substituted hydroxylamine shown in Table 7B below, the rest was carried out in exactly the same manner. Through the reaction and post-treatment, the desired products were obtained with the weights shown in Table 7B below. each The infrared absorption spectrum and nuclear magnetic resonance spectrum of the product are shown in Table IB.

Example 〇--Converted hydroxylamine yield 1.1α (parts) to compound 10 I H3 H3 Examples 59B, 60B Synthesis of compounds <59B), <60B) In Example 20B, 2-(1-methoxycarbonylethoxy)-4-<2- Chloro-4-trifluoromethylphenoxy)benzaldehyde (IIA)4. 2-(1-methoxycarbonylethoxy)-4-(4-trif) instead of 03 parts. Using 3.68 parts of fluoromethylphenoxy)benzaldehyde (14A), The rest is exactly the same as the one shown in Table 8B below as the -converted hydroxylamine. By reacting and post-treating, each product was obtained with the weight shown in Table 8B below. each product The infrared absorption spectrum and nuclear magnetic resonance spectrum of is shown in Table IB.

Example 〇-Substituted human xylamine yield Production No. (part) Hardware No. I CH8 Example 62B Synthesis of compound (62B> In Example 20B, 2-(1-methoxycarbonylethoxy)-4-(2-k Rolo-4-trifluoromethylphenoxy)benzaldehyde <IIA> 4.0 2-<1'-methoxyl levonylethoxy>-4-(4-chloro) instead of 3 parts. Using 3.4 parts of lophenoxy)benzaldehyde (15A), the rest was carried out in exactly the same manner. By reaction and post-treatment, 3.8 parts of the target product were obtained. The infrared absorption spectrum of the compound The vector and nuclear magnetic resonance spectra are shown in Table IB.

Example 63B Synthesis of compound (63B’) 2-(1-carbonylethoxy)-4-(2-chloro-4-trifluoromethyl 0.41 part of phenoxy)benzaldehyde <19A) and tetrahydrofura>'3 0 parts by volume, and 0.23 parts of O-phenylhydroxylamine hydrochloride was added to the solution. , 0.14 parts of sodium carbonate, and 2 parts of water by volume were added, and the mixture was stirred at room temperature for about 3 hours. Stirred. After the reaction, tetrahydrofuran was removed under reduced pressure, diluted with water, and then HCI acid The mixture was dried and extracted with ether. The organic layer was washed with water and dried over anhydrous sodium sulfate. Then concentrate under reduced pressure. The crude product was separated into the desired compound by silica gel column chromatography. (obtained >0.3 parts of 63B. Spectral data for the compound are shown in Table IB.

Example 64B Synthesis of compound (64B>) In Example 20B, 2-(1-methoxycarbonylethoxy)-4-<2-k Rolo-4-trifluoromethylphenoxy)benzaldehyde (IIA) 4.0 2-hydroxy-4-(2-chloro-4-trifluoromethylfluoride) in place of 3 parts. Using 3.17 parts of benzaldehyde (1, 2°), the rest was carried out in exactly the same manner. By reaction and post-treatment, 2.90 parts of the target product was obtained. Infrared absorption spectrum of the compound The spectra and nuclear magnetic resonance spectra are shown in Table IB.

Example 65B Synthesis of compound <65B) In Example 20B, 2-(1-methoxycarbonylethoxy)-4-<2-k Rolo-4-trifluoromethylphenoxy)benzaldehyde (IIA>4.0 2-(1-methoxycarbonylethoxy)-4-(3-chloro- 5-trifluoromethyl-2-pyridyloxy)benzaldehyde (17A>4 ．． By using 03 parts and carrying out the reaction and post-treatment in exactly the same manner, the desired product 3.9 I got 0 copies. Table I shows the infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound. Shown in B.

Example 66B Shiaimono <26 B>, <34 B), <50 B) ~ (61 B), (84B), synthesis of <1'43B> 4.18 parts of compound (2B) obtained in Example 2B, 4-fluoronitro 1.55 parts of benzene was dissolved and stirred in 20 parts of N-methylpyrrolidone, and 60% hydrogen was added. 0.42 part of sodium chloride was added at room temperature. After that, after further stirring at room temperature for 5 hours The reaction mixture was added to ice water and extracted with ethyl ether. The organic layer is treated with anhydrous sulfuric acid. After drying with sodium, ethyl ether was removed under reduced pressure, and the residue was passed through a silica gel column. 4.2 parts of the target product (26B) were obtained by chromatographic separation. Interpolate and convert In place of compound (2B), aldehyde oxime listed in Table 9B below was used, and 4-fluorocarbon By reacting the halogen compounds listed in Table 9B below in place of lonitrobenzene. The desired compound was obtained. Infrared absorption spectra and nuclear magnetism of these compounds The gas resonance spectra are shown in Table IB.

Table 9B Generated aldehyde halogen compound Hardware No. Oxime (26B) (2B) 4-furumenitrobenzene (34Bl (2B) 2 ．． 4-dinitrochlorobenzene (50Bl (2B) 2-chloropyridine (5 1Bl (2B) 2-chloro-6-medoxyviridine (52B) (2B) 2.3-dichloropyridine (53B) (2B) 2-chloropyridine (54B ) (2B) 2-chloro-3,6-dimethylvirazine (55B) (2Bl 2-chloroquinoline (56B) (2B) 3,6-dichloropyridazine (57 B) (78B) 2,6-dichloropyridine (58Bl (78B) 2-k Rollo-3,6-dimethylvirazine (59Bl (2B) 2,6-dichloropyri gin (60B) (2B) 2-on-6-medoxyviridine (61B) ( 78B) 2,3-dichloropyridine<84B) (2B) 4-chloro-2- Methyltipak pyrimidine (143B) (2B) 2,6-dichloroquinoxaline Example 67B compounds (66B) to (70B>, (74B), (79B), (80B), (82 B), (83B), <85B) ~ Example 6B By reacting the aldehyde compound and 〇-substituted hydroxylamine, the following table 1 Obtain the object listed in 0B. Infrared absorption spectra and nuclear magnetic resonance of these compounds The sound spectra are shown in Table IB.

Generated aldehyde O-substituted hydroxylamine metal NO derivative (66B) (9A) 0-7 sole droxylamine (67B) (IOA ) 0-Arylhydroxydylamine! 68B+ +9A) 0-2 enyl hydride Roxylamine + 69B) (IOA) O-phenylhydroxylamine (7 0Bl (13 people) 0-arylhydroxylamine (74B) (13AI O-phenyl droxylamine (79B) (24A) 0-4-nitroff phenylhydroxylamine +80B) +22A) 0-4-nitrophenylamine Droxylamine +82B+ +IIA) 0-4-chloro-2-nitropheny hydroxylamine (83B) (IIA) 0-2-nitrophenylhydro Xylamine (85Bl (IIA) 0-4-nitropenzyl hydroxyl Mine (86B) (17Ai 0-4-nitrophenylhydroxylamine (8 7Bl f17A) 0-4-fluorophenyl droxylamine f89Bl (IIA) Chl-nito-2-naphthylhydroxylamine (91B) ( ! IA) 0-4-(1,1-dimethylethyl)phenyl droxylamine! 95Bl (IIA) 0-(4-methoxycarbonylmethyl)-2-nitroff phenylhydroxylamine (96Bl (11 people) 0-4-methoxycarbonylphenylhydroxylua <97B) (IIA) 0-4-trifluoromethylphenylhydroxy <98B+ (9A) 0-4-nitrophenylhydroxylamine ( 99B) (20Ai 0-4-nitrophenylhydroxylamine (100B) I (21A) 0-4-nitrophenylhydroxylamine (146B) ( IA) 0-4-nitrophenylhydroxylamine (150Bl (IIA, ) 0-i-cyano-2-propenylphenylhydroxylamine Example 68B Compounds (73B), <75B), (77B), <78B), <8.8B), (1 Synthesis of 45B) In Example 2B, <IIA) was replaced with an aldehyde listed in Table 11B below, The rest of the reaction was carried out in exactly the same manner to obtain the compounds shown in Table 11B below. these The infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound are shown in Table IB.

Table 11B Product compound No. Aldehyde derivative 173B) (21Al f75Bl f9A1 f77B) (20A) (78B) (16Al (88B) (17Al (145B) (24Al Example 69B Synthesis of compound <90B) Compound (146B>0.24 part, α-bromopropionic acid amide 0.09 part, no Add 0.15 parts of potassium hydroxide to 20 parts of methyl ethyl ketone and reflux for 5 hours. Ta. The reaction mixture was filtered, the r liquid was concentrated and subjected to silica gel column chromatography. Further purification yielded 0.05 part of the desired compound <90B>. the compound The JR, NMR spectrum data of is shown in Table IB.

Example 70B Synthesis of compounds (92B) to (94B) Dissolve the compound (154B>0.2 parts in 4 parts by volume of ether, add diazometha to the solution) Add the ethereal solution of water in small portions. After the reaction was completed, the ether was removed under reduced pressure and the silica Purified by gel chromatography to obtain the given compound 'F'lJ (93B) 0.1 I got 6 copies. The IR and NMR spectral data of the compound are shown in Table IB.

In the same manner, (155B>, (156B) is substituted for the compound <154B). By using each, predetermined compounds <94B> and <92B) were obtained. these IR and NMR spectral data of the compounds are shown in Table IB.

Example 71B Compound (10IB) ~ (Co09B>, <IIIB) ~ Obtained by Example 2B 4.18 parts of compound <2B) and 1.11 parts of triethylamine were added to tetrahydrofurane. The solution was dissolved in 40 parts of water and stirred in a water bath. Add 4-nitrobenzoic acid chloride to this solution. A solution of 1.94 parts of hydrogen dissolved in 5 parts of tetrahydrofuran was added dropwise, and the mixture was heated at room temperature for 1 hour. After stirring for a while, tetrahydrofuran was removed under reduced pressure. Then add 20 parts of water , extracted with ethyl ether. After drying the organic layer with anhydrous sodium sulfate, ethyl ethyl The target product ( 10IB) 4.3 parts were obtained. Similarly, instead of the compound '$A<2B), Table 12 below The aldehyde oxime described in B can also be used below instead of 4-nitrobenzoic acid chloride. The target compound was obtained by using the acid chloride listed in Table 12B. these The infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound are shown in Table IB6 Hardware No. Oxime (102Bl (2B) 3,5-dinitrobenzoic acid chloride (103B) ( 2B) 2,4-dihydrobenzoic acid chloride (104B) (2B) 4-fur Orobenzoic acid chloride (105B) (2Bi 4-methoxycarbonyl-2, 3,5゜6-tetrachlorobenzoic acid chloro de (106Bl (:)Bl 2-nitro-5-(2-chloro-4-trifluoro Methylphenoki C) Anshizoic acid chloride (107Bi (2Bl) Isonicotinic acid chloride (108B) (145Bl '4-Nitrobenzoic acid chloride (109B) (2Bl 4-(N, N-di Methylamino)benzoic acid chloride <111B+ +2B+ 4-) Lifluoromethylbenzoic acid chloride (112B) (2B) 4-cyanobenzoic acid chloride + 113B! (88B ) 4-nitrobenzoic acid chloride (114B) f73B) 4-nitrobenzoic acid chloride (114B) f73B) 4-nitrobenzoic acid chloride (114B) f73B) Acid chloride (115B) (77Bl 4-nitrobenzoic acid chloride m6B+ (75B+ 4-nitrobenzoic acid chloride (117B) +2Bl chloroformic acid Phenyl (124B) (2Bl 2+ 4-dichlorobenzoic acid chloride (125B) (2B) 2,4-dichlorophenoxyacetic acid chloride (126B) (2B+ 1-[4-<3-chloro-5-trifluoromethyl- 2-pyri Zyloxy) phenoxypropyl onic acid chloride (127B) <2B+ Acetyl chloride (128Bl (2B) 1-[4-< 5-)Lifluoromethyl-2-pyridyloxy) Phenoxypropionic acid chloro de <129B) (2B+ Ethyl chloroformate (130Bl (2B) n-cap Lyric acid chloride (131Bl (2B) 1,1-dichloropropionic acid chloride de (132Bl (8gB) Acetyl chloride (133B) (2B) Chloroformic acid 2,2,2-trichloromethyl ester (135B) (2B) 3-aminobenzoic acid chloride (136B) (2B) 3- <N, N-dimethylcarbamoylamino)benzoic acid chloro de fi37B) (2B) 4-ethoxycarbonylaminobenzoic acid chloride (138B) +2B) Benzoic acid chloride (139Bl (2B) 2,4. 6-) Limethylbenzoic acid chloride <140B+ +2B) 4-<1.1-dimethylethyl)benzoic acid chloride (141B) (2B) 4-chloroacetylaminobenzoic acid chloride f142Bl (2B) 4-<1.1-dimethylpropiogonylamino)an Zozoic acid chloride Example 72B Synthesis of compound <ll0B> Compound (109B>4.2 parts was dissolved in 50 parts of ethyl ether, and methane iodide was added to it. Add 4.3 parts of chilli and stir at room temperature for one week. After that, filter out the formed crystals. , 3.2 parts of the desired product was obtained by washing with 50 parts of ethyl ether.

The infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound are shown in Table IB.

Example 73B 3 to a combined solution (5 parts by volume) of compounds <118B) to (123B) and (134B) ．． 0.19 parts of 4-dichlorophenylisocyanate and 0.1 parts of triethylamine. 01 part was added and reacted at room temperature. After the reaction is complete, remove the ether under reduced pressure and remove the crude product. A given compound can be purified by silica gel column chromatography. (118B) 0.45 part was obtained. Display the IR and NMR spectral data of the compound. Shown in IB.

3. Each corresponding incyanate in place of 4-dichlorophenylisocyanate By using the above compound, compounds (119B) to (123B) can be prepared in the same manner. .

<134B). IR;, NMR spectral data of these compounds The data are shown in Table IB.

Example 74B Synthesis of ingredients <147B>, <149B), (151B) to (153B) A solution of 0.59 parts of 4-fluorobenzoylaminoacetonitrile in ethyl acetate (3 5 parts by volume) was cooled to 0°C, and 0.58 parts of bromine was added dropwise (a few drops of bromine was added). Now add a few drops of hydrogen bromide in acetic acid solution, then add the remaining bromine), dropwise After completion, the compound synthesized in Example 2B<2B) was cooled to -25°C and 15 parts of acetic acid was added. Ethyl solution (7 parts by volume) and 0.73 parts of triethylamine are simultaneously added dropwise. drop After stirring at O'C for 15 minutes, aspirate the reaction mixture. filtrate and concentrate P solution to obtain crude The product was purified by silica gel column chromatography, and the predetermined compound <149B > obtained. The IR and NMR spectra of the compound are shown in Table IB.

Instead of 4-fluorobenzoylaminoacetonitrile, each corresponding acetate By reacting in the same manner using a nitrile derivative, a predetermined compound <147 B).

<151B) to (153B) were obtained. JR, NMR spectra of these compounds The data are shown in Table 1B.

Example 75B Synthesis of compound (148B) 4.18 parts of compound <2B), 1-bromo-1-<4-nitrophenyl)-acetate 2.41 parts of 1-nitrile, 1.39 parts of anhydrous potassium carbonate, 40 parts of acetonitrile After heating and stirring the mixture at 100°C for 5 hours, acetonitrile was removed under reduced pressure, and water was added. was added and extracted with ethyl ether. The organic layer was dried with anhydrous sodium sulfate and then diluted with ethyl ethyl ethyl ether. By removing the ether and separating the residue by silica gel column chromatography, <14 8B) 3.2 parts were obtained. Infrared absorption spectrum and nuclear magnetic resonance spectrum It is shown in Table IB.

Example 76B Synthesis of compounds (154B) to (156B) Methyl 2-[2-carboxy-5- 2-chloro-4-trifluoromethylphenoxy)]phenoxypropionate Add 1.07 parts of thionyl chloride to 1.9 parts and heat at 60 to 70°C for 2 hours. reaction After completion, excess thionyl chloride was removed under reduced pressure, and the resulting crude product was dissolved in benzene solution <5 0.83 parts of 0-4-nitrophenylhydroxylamine dissolved in benzene (parts by volume) (10 parts by volume) is added at room temperature. After the reaction is complete, add water and separate the organic layer. After that, dry with anhydrous sodium sulfate. The solvent was removed under reduced pressure and the crude product was purified on silica gel. Purification by column chromatography yielded 2.5 parts of the desired compound <154B).

The IR and NMR spectra of this compound are shown in Table IB.

○-Ethoxycarbo in place of ○-4-nitrophenylhydroxylamine Nylmethylhydroxylamine, 0-2-propenyloxycarbonylmethylhydroxylamine By using droxylamine, the given compounds <155B), (156 B) was obtained. The IR, NMR spectra of these compounds are shown in Table IB.

Table IB Table IB <Continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB <Continued) Table IB (continued) Table IB <Continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB <Continued) Table IB (continued) Table IB (continued) Table IB <Continued) Ji and IB (continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB (continued) Table IB <Continued) Table IB (continued) Table IB (continued) Takumi's sudden rebellion Active compound of the present invention! Add 1 part of Fl to a mixed solution of acetone and water at a volume ratio of 1 to 1) 5,000 parts plus a nonionic surfactant (trade name: Solbol 2680) A solution was prepared by adding 2.6 parts.

Preparation example 2C 1 part of the compound of the invention, 8.7 parts of 1 mixture of talc and bentonite, 5OLP A mixture of OP, 5060 (product name) and 5OLPOR800A (product name), etc. 0.3 parts were thoroughly ground and mixed to obtain a raw material for a wettable powder.

Test example IC The active compounds of the invention were prepared according to Formulation Example IC above.

The plants used were seeds sown in soil and cultivated for 2 to 3 weeks after germination.

This plant is then treated with a preparation containing the active compounds of the invention, each containing a total of the active compounds. After that, cultivation was continued for 3 weeks without applying any preparations. I got it.

The results are shown in Table IC.

Test example 2C Seeds of plants to be evaluated are sown in soil, and treated as follows on the second day after sowing. Observe the growth of the plants for three weeks.

The drug processing method comprises a mixture containing an active compound of the invention prepared according to Preparation Example 2C above. Suspend the active compound in water and add it to the soil after sowing so that the total amount of each active compound is the specified amount. It was applied uniformly to the soil surface, and cultivation was continued thereafter without applying any preparation. The result The results are shown in Table 20.

The alphabets shown in the plant column in Tables IC and 2C are the following plants. .

C Saban Sorghum k corn Table IC Table IC (continued) Table IC (continued) Table IC (continued) Table IC <Continued) Table IC <Continued) Table IC <Continued) Table IC (continued) Table IC <Continued) Table 20 Test Examples 3C to 6C and Comparative Examples 10 to 2C The oxime derivatives shown in Table 3C and N- Each phosphonomethylglycine derivative was mixed at a predetermined mixing ratio and at a predetermined processing amount. A mixed solvent of water and acetone (volume ratio 11, nonionic surfactant; trade name Contains 0.05% SOP, POL-2680) 16 volumes! Dissolve the spray solution in Prepared.

Plants are sown or grown from rhizomes in plastic pots (10 cm in diameter) filled with soil. The seeds were transplanted and cultivated in a greenhouse for 2 to 3 weeks after germination.

The above prepared solution was applied to this plant at a total spray volume of 4 cc/100 cA. Check the herbicidal activity.

The results are shown in Table 3C.

The alphabets shown in the plant column of Table 3C are the following 'ItM products.

n America Kingoji Power 0 Butafusa p White-bellied morning glory t Texas Bunicum Table 30 Test Examples 7C to 14C and Comparative Examples 30 to 4C The oxime derivatives shown in Table 40 and N - each of the phosphonomethylglycine derivatives at a predetermined mixing ratio and a predetermined processing amount; A mixed solvent of water and acetone (volume ratio 1:1, nonionic surfactant; commercially available) Dissolve product name 5ORPOL-2680 in 16 parts by volume (containing 0.05%) and make a spray solution. was prepared.

Plants are grown by sowing or rhizomes in plastic pots (diameter 10 cm) placed in soil. The seeds were transplanted and cultivated in a greenhouse for 2 to 3 weeks after germination.

Spray the above solution onto this plant at a total spray volume of 4 cc/100 cxA. The herbicidal activity was investigated.

The results are shown in Table 40.

Comparing the results of Test Examples 7C to 14C and Comparative Examples 3C to 4C, the weed control of the present invention Compared to the case where the N-phosphonomethylglycine derivative is used alone, the agent composition has It exhibits herbicidal activity quickly and is highly effective.

In contrast, the composition of the present invention, for example, the composition of Test Example 13C, has all of the components listed in Table 4C. It can kill all kinds of weeds in about a week. As in this example, the present invention The composition combines an oxime derivative and an N-phosphonomethylglycine derivative. Surprisingly, the synergistic effect of the application is to improve fast-acting and lower dosage. It was found that the herbicidal spectrum was significantly expanded.

Table 40 Table 4C (continued) Test Examples 15C to 16C and Comparative Examples 50 to 6C with the oxime derivatives shown in Table 50. Atrazine was mixed with water and acetic acid at the specified mixing ratio and treatment amount. ton of mixed solvent (volume ratio 1:1. Nonionic surfactant; trade name SOP, POL- 2680 (containing 0.05%) was dissolved in 16 parts by volume to prepare a spraying solution.

Plants are sown or grown from rhizomes in plastic pots (10 cm in diameter) placed in soil. The seeds were transplanted and cultivated in a greenhouse for 2 to 3 weeks after germination.

The above prepared solution was sprayed onto this plant at a total spray volume of 4 cc/'100 cJ. The weight removal activity was investigated using locks. Table 50 shows the results 3A after treatment.

Table 50 Test Examples 17C to 18C and Comparative Examples 7C to 8C Compound <26B) and Compound (50 0) in a predetermined amount of a mixed solvent (volume ratio 1:1. Nonionic surfactant; trade name 5ORPOL-2680 (containing 0.05%) in 16 parts by volume to prepare a spraying solution. Manufactured.

Plants are grown by sowing or rhizomes in plastic pots (diameter 10 cm) placed in soil. The seeds were transplanted and cultivated in a greenhouse for 2 to 3 weeks after germination.

The above prepared solution was applied to this plant at a total spray volume of 4eC/100cJ. The herbicidal activity was investigated. The results are shown in Table 60.

Table 60 Comparing the results of Test Examples 3C to 14C and Comparative Examples IC to 4C, the weed control of the present invention Compared to the case where the N-phosphonomethylglycine derivative is used alone, the agent composition has It exhibits herbicidal activity quickly and is highly effective.

When N-phosphonomethylglycine derivatives are used alone, especially at low iff, Herbicidal activity against broad-leaved weeds such as sagao and golden deer decreases after treatment. Even after 14 days, little or no activity is shown.

In contrast, the composition of the present invention, for example, the composition of Test Example 13C, has all of the components listed in Table 40. It can kill all kinds of weeds in about a week. As in this example, the present invention The composition combines an oxime derivative and an N-phosphonomethylglycine derivative. Surprisingly, the synergistic effect of the application is to improve fast-acting and lower dosage. It was found that the herbicidal spectrum was significantly expanded.

When compound (500) is used alone, at low doses as shown in Table 60, Chenopodium The herbicidal activity against broad-leaved weeds such as , bluegrass, and ichito is reduced. On the other hand, this The herbicidal composition of the invention overcomes these drawbacks and exhibits sufficient herbicidal activity.

Copy and translation of amendment) Article 184-8 of the Patent Act submitted in February 1991 Day

Claims (6)

[Claims] (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼…(I) [Here, X and Y are the same or are different, and each contains a hydrogen atom, a halogen atom, -CF3, or an alkali of 1 to 5 carbon atoms. It is a kill group. Z is =CH- or =N-. R1 is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group having 1 to 5 carbon atoms; 5 is an alkoxy group. R2 is a group selected from the groups shown in a) to g) below. a) Hydrogen atom: b) Saturated or unsaturated fat having 1 to 10 carbon atoms that may be substituted with the following substituents: Aliphatic hydrocarbon group: substituent i) halogen atom; ii) hydroxyl group; iii) alkoxy group having 1 to 5 carbon atoms; iv) -COR4 [Here, R4 is a hydroxyl group, a carbon number 1 which may be substituted with a halogen atom ~5 alkyl group, phenyl group optionally substituted with halogen atom, carbon number 1 ~5 alkoxy group, C1-5 alkenyloxy group, or ▲ mathematical formula, chemical formula, There are tables, etc. ▼ (Here, R5 and R6 are hydrogen atoms or alkyl having 1 to 5 carbon atoms. It is the basis. ); v) phenyl group Here, the phenyl group is a halogen atom, a hydroxyl group, -CF3, -NO2, -C N, alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, -COR4 or may be replaced with ▲ which is a mathematical formula, chemical formula, table, etc.; vi) Phenoxy group Here, phenoxy group is phenyl group, phenoxy group or pyridyloxy group (here The phenyl group, phenoxy group, or pyridyloxy group is a halogen atom or a pyridyloxy group, respectively. or -CF3. ), in addition to those indicated in v) above. It may be substituted with a substituent. vii) ▲There are mathematical formulas, chemical formulas, tables, etc.▼Here, R7 is a hydrogen atom, and has 1 to 1 carbon atoms. 5 alkyl group or -COR4; viii)-CN; c) Alkoxy group substituent which may be substituted with the following substituents: i) halogen atom; ii) Phenyl group Here, the phenyl group may be substituted with a substituent shown in v) of b) above; d) Phenoxy group substituent which may be substituted with the following substituents: Same as the substituents shown in v) of b) above; e) Substituted with the following substituents an aromatic hydrocarbon group having 6 to 20 carbon atoms; substituent i) halogen atom; ii) hydroxyl group; iii)-CF3; iv)-NO2; v)-CN; vi) an alkyl group having 1 to 5 carbon atoms; vii) an alkoxy group having 1 to 5 carbon atoms; viii) -COR4; ix) ▲There are mathematical formulas, chemical formulas, tables, etc. ▼x) -N+R5R6R8 (Here, R8 is an alkyl group having 1 to 5 carbon atoms) xi) Phenyl group Here, the phenyl group may be substituted with a substituent shown in v) of b) above; xii) Phenoxy group Here, the phenoxy group may be substituted with a substituent shown in vi) of b) above. stomach; xiii)-CH2COR4 f) 3 carbon atoms containing at least one nitrogen atom which may be substituted with the following substituent: ~20 aromatic heterocyclic groups: substituents Same as the substituents shown in e) above; g) ▲Mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R9 is b), e) or f) above. ): R3 is a hydrogen atom: or a halogen atom, a hydroxyl group, an alkoxy group, -CO R4 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R10 or R11 are the same or different. It may be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group. . ) is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with There are tangential bonds, ▲ mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here, if Q is a direct bond, R2 is c), d) or g) above. do not have. ] A compound that is an oxime derivative or a salt thereof represented by: (2) The following formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼…(III) [Here, X, Y, Z, R1 and and R3 are the same as defined in formula (I) above. However, if Z is =CH- When R1 and R3 are at the same time R1 is an alkyl group having 1 to 5 carbon atoms, and R3 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with -COR4 do not have. ] A compound that is a benzaldehyde derivative or a salt thereof. (3) A herbicide-effective amount of the compound according to claim 1, additives, carriers, insecticides, etc. and at least one herbicide selected from other herbicides. (4) An effective amount as a herbicide of the compound according to claim 1 as an active ingredient and a carrier and and/or a surfactant. (5) The compound according to claim 1 is selected from additives, carriers, insecticides and other herbicides. A method for producing a herbicidal composition, the method comprising mixing at least one herbicide composition. (6) Compound of formula (I) and the following formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ...(III) [Here, R21 and R22 are the same or different, each -OH or -OR24, and R23 is -OH, -OR24 or -NR25R26 It is. Here, R24 is an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group, or a carbon number Haloalkyl group having 1 to 5 carbon atoms, alkenyl group having 2 to 5 carbon atoms, or alkoxyalkyl group having 2 to 5 carbon atoms Kyl group, haloalkoxyalkyl group, or alkoxyalkoxyalkyl group (where each alkoxy, haloalkoxy and alkyl have 1 to 5 carbon atoms) Has atoms. ) and phenoxy group. R25 and R26 are the same or different hydrogen atom, alkyl group having 1 to 5 carbon atoms, and hydroxyl group having 1 to 5 carbon atoms, respectively. alkyl group, alkenyl group having 2 to 5 carbon atoms, and R25 and R26 are Together with the bonded nitrogen atom, a morpholino group, a piperidino group, or a pyrrolytic group is formed. A dino group can be formed. ]N-phosphonomethylglycine derivative represented by conductor, and/or the following formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼…(IV) [Here, R31 is a hydrogen atom or is an alkyl group having 1 to 4 carbon atoms, and R32 is -OH, -NH2, -NHNH2 , - is an alkoxyl group having 1 to 12 carbon atoms. ] Glufosinate represented by compound, or its acid addition salt or salt with a base as a herbicidal ingredient, and A herbicidal composition containing a carrier and/or a surfactant.