WO1990002113A1

WO1990002113A1 - Oxime derivatives and herbicides containing same as active ingredients

Info

Publication number: WO1990002113A1
Application number: PCT/JP1988/000837
Authority: WO
Inventors: Shizuo Azuma; Toshiyuki Hiramatsu; Koji Nakagawa; Yataro Ichikawa
Original assignee: Teijin Limited
Priority date: 1988-08-24
Filing date: 1988-08-24
Publication date: 1990-03-08

Abstract

Compounds of specific oxime derivatives or salts thereof and herbicidal compounds containing said compounds as herbicidal ingredients are disclosed. The oxime derivatives show an excellent weed-killing effect against both of broadleaf and narrowleaf weeds, and their effect is rapid even when used only in small amounts.

Description

Description Name of Invention

FIELD OF THE INVENTION Field of the Invention

TECHNICAL FIELD The present invention relates to a novel oxime derivative and a herbicide containing the same as an active ingredient. More specifically, the present invention exhibits excellent herbicidal activity against broadleaf weeds and fineleaf weeds, and, depending on the method of use, the method of treatment, and the amount of treatment, does not substantially impair the growth of the crop. It relates to a herbicide having a property. Description of the prior art

Heretofore, herbicides that selectively kill broadleaf weeds, such as 2,4-dichlorophenoxyacetic acid, are known as selective herbicidally active compounds. The selective herbicidal activity of 2,4 diclomouth phenoxyacetic acid is a selective herbicidal activity between fine plants including crop plants and weeds and broadleaf plants also including crop plants and weeds . 2,4-Dichlorophenoxyacetic acid is known to have extremely low or no activity on narrow-leaved plants (see, for example, Mature, 155, 498 (1945)). On the other hand, based on these compounds, aromatic groups are Introduced compounds such as chloro- or trifluryl-substituted methyloxy groups or chlor- or trifluryl-methyl-substituted pyridyl oxy groups, etc., have the activity of selectively killing fine plants. It is also known

(U.S. Pat.Nos. 4,270,948, 309,562, 4,314,069, 4,332,961 and 3,954,442, JP-A-52-125626, JP-A-52- No. 15825 and British Patent 1,579, 201. However, these compounds also kill useful crops such as rice or corn.

Herbicides containing certain N-phosphonomethylglycine derivatives as main active ingredients are known and commercially available. This N-phosphonomethylglycine derivative is basically a non-selective herbicide, but at a low dose, it can be used for herbicides against perennial weeds, such as lycopodium, and broadleaf weeds, such as akaza and asaibu. Activity is reduced. Especially on convolvulaceous weeds such as Malva morning glory, they show almost no herbicidal effect even after 2 weeks of treatment. In addition, N-phosphonomethylglycine derivatives are slow-acting and are not suitable for quickly removing weeds on agricultural or non-agricultural lands and performing the following operations. For example, in arable land, all weeds must be killed before crops are sown.However, in the case of slow-acting crops, effects such as delayed seeding of crops or harm to crop seeds may occur. Conceivable. In addition, building or railway construction or non-farmland N-phosphonomethylglycine derivatives are not sufficient as low-dose, fast-acting, non-selective herbicides due to delays in road weeding. Object and Summary of the Invention

An object of the present invention is to provide a novel oxime derivative.

Another object of the present invention is to provide a herbicide having excellent herbicidal activity against broadleaf weeds and fineleaf weeds.

Yet another object of the present invention is to provide substantially no harm to useful crops, especially soybeans and corn, depending on the method of use, the method of treatment and the amount of treatment, and thus to substantially inhibit their growth. It is an object of the present invention to provide a selective compound for destroying broadleaf weeds and fineleaf weeds and a herbicide containing the same.

Still another object of the present invention is to act on plants to kill or suppress the growth of many broad-leaf and fine-leaf grasses, and to reduce the growth of narrow-leaf crops such as sorghum and broad-leaf crops such as soybean. A compound that does not cause substantial phytotoxicity on the other hand, and thus can form a state in which the useful crop can easily grow beyond the harmful weeds in an area where useful crops and harmful weeds coexist, for example, as described above. And to provide a selective herbicide containing the same.

Still another object of the present invention is to provide weeds for weeding purposes. On the other hand, by spraying on the foliage, not only killing or growth can be suppressed, but also by applying to soil before germination, the germination and growth of useful crops are not substantially inhibited by germination and growth of useful crops. An object of the present invention is to provide a selective herbicide that can control growth and kill a growing body, that is, a herbicide that can be applied to both foliage application and soil treatment.

Still another object of the present invention is to provide a herbicide having low animal and fish toxicity and low soil persistence.

Still another object of the present invention is to use the above novel oxime derivative of the present invention together with an N-phosphonomethylglycine derivative known per se to take advantage of these herbicidal properties to make comparisons. An object of the present invention is to provide a herbicidal composition and a method capable of killing both narrow-leaf and broad-leaf weeds at an extremely low application rate.

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

According to the study of the present inventor, it has been found that these objects and advantages can be achieved by the following oxime derivatives. That is, according to the present invention, the following formula (e)

Y

0 ^ C ^-O-R ² (I)

OR ³ Here, X and Y are the same or different and are each a hydrogen atom, a halogen atom, one CF3 or an alkyl group having 1 to 5 carbon atoms.

Ζ is —CH— or = Ν—.

R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ² is a hydrogen atom; a halogen atom, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms or 1 COR ⁴ (where R ⁴ is a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms or

R ⁵

— N: (where R ⁵ and R ⁶ are hydrogen atoms or carbon atoms Ί R ⁶

~ 5 alkyl groups. 〉. } Saturated or unsaturated aliphatic carbon hydrocarbon group having to carbon atoms, which may have I～ 10 substituted; halogen atom, a hydroxyl group, one _{C F3 - N0 2, - C} Ν, alkyl Ί~5 carbons Group, carbon number ^! 5 to 5 alkoxy, 1 GOR ⁴ , a phenyl group optionally substituted with a halogen atom or 110 F 3, or a phenoxy group optionally substituted with a halogen atom or 1 CF 3. An aromatic hydrocarbon group having 6 to 20 carbon atoms; or a halogen atom,

-CF ₃ , an aromatic heterocyclic group having 3 to 20 carbon atoms and containing at least one nitrogen atom, which may be substituted with an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. R ³ is a hydrogen atom or a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having an alkoxy group or ten OR ⁴ carbon atoms but it may also be substituted with I～10.

Here, when R ² is a hydrogen atom and R ³ is a hydrogen atom, an alkyl group, a cycloalkyl group or an aralkyl group, both X and Y are not hydrogen atoms.

Or a salt thereof when ^ is a hydroxyl group.

The inventive oxime derivative of the present invention has a wide range of herbicidal spectrum showing excellent herbicidal activity against broadleaf weeds and fine-leafed weeds. Furthermore, depending on the method of use, treatment method, amount of treatment, etc., useful crops, especially soybeans and sorghum, do not substantially damage the phytotoxicity, and thus do not substantially inhibit the growth of these crops, and can be used for broadleaf weeds and narrowleaf weeds. It is a herbicide that can be destroyed. In addition, the oxime derivative of the present invention has a herbicidal effect even in a small amount, and has a fast-acting herbicidal activity. DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

Hereinafter, the present invention will be described in detail.

In the above general formula (e), X and Y are the same or different and are each a hydrogen atom, a halogen atom, a 10 F ₃ or an alkyl group having 1 to 5 carbon atoms.

A halogen atom is, for example, fluorine, chlorine, bromine, etc. is there. The alkyl group having from 5 to 5 carbon atoms may be linear or branched, such as methyl, ethyl, n-propyl, iso-propyl, π-butyl, sec-butyl, iso. —Butyl, 1: -butyl, n-pentyl, etc. In the above formula (E), at least one halogen atom of X and Y, is preferably a ten F3 or alkyl Le group with carbon number I～ 5, an X gar CF _3, Y is a halogen atom Is particularly preferred.

In the above formula (e), Z is = CH— or = N—, and is preferably = 〇H—.

In the above formula (I), R ¹ is a hydrogen atom or an alkyl group having 炭素 to 5 carbon atoms, wherein the alkyl group having Ί to 5 carbon atoms is the same as the specific examples described above for X and Υ. Examples of the alkyl group include 5. R ¹ is preferably a hydrogen atom.

In the above formula (I), R ² is a hydrogen atom; a halogen atom, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms or —COR ⁴ (here, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms).

R ⁵

Coxy group or —N: (where R ⁵ and R ⁶ are hydrogen atoms or

R ⁶

Is an alkyl group having from 5 to 5 carbon atoms. ). }, A saturated or unsaturated aliphatic hydrocarbon group having from Ί to 10 carbon atoms which may be replaced by; a halogen atom, a hydroxyl group, -C Fa, -NOz, -CN, an alkyl group having Ί5 carbon atoms, an alkoxy group having Ί5 carbon atoms, —〇OR ⁴ , a halogen atom or a phenyl group optionally substituted by 1 C F3, or A halogen atom or a phenoxy group which may be substituted with CF ₃ , an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with cfc, or a halogen atom,

CF ₃ , an alkyl group having 1 to 5 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms and containing at least 2 nitrogen atoms, which may be substituted with an alkoxy group having 1 to 5 carbon atoms; is there.

Here, the aliphatic hydrocarbon group includes a linear or branched hydrocarbon group and an alicyclic hydrocarbon group. The aromatic hydrocarbon group may be a single benzene nucleus or a naphthalene nucleus, or a combination thereof. The aromatic heterocyclic group has a structure in which, for example, Ί or more carbon atoms in a benzene nucleus or a naphthalene nucleus are substituted with an oxygen atom, a nitrogen atom, a nitrogen atom, or the like.

The alkoxy group having 1 to 5 carbon atoms may be linear or branched, for example, methoxy, ethoxy, η-propoxy, iso-propoxy, n-butoxy. sec—butoxy, 1: butoxy, π-pentyl. Examples of the halogen atom and the alkyl group having 1 to 5 carbon atoms include the same halogen atom and the same alkyl group having 1 to 5 carbon atoms as those described above for X and Y. The main skeleton of R ² includes vinyl, probenyl, butenyl, pentenyl, ethynyl, propenyl and the like.

2-7 unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups having 6-15 carbon atoms such as phenyl and naphthyl, pyridyl, piperazine, quinolyl, quinoxalyl, quinazolyl, pyridazinyl, pyrimidyl, triliazinyl, etc. Is preferably an aromatic heterocyclic group having 3 to 1 carbon atoms containing a nitrogen atom. As the substituent, an unsaturated aliphatic hydrocarbon group has no substituent, and an aromatic hydrocarbon group and an aromatic heterocyclic group have no substituent or a halogen atom, —〇F3, -NOz, -CN, methyl group, or It is preferably substituted with a methoxy group.

Further, R ² is a propenyl group as an unsaturated aliphatic hydrocarbon group, is unsubstituted as an aromatic hydrocarbon group, or is substituted with a halogen atom CF3, -NOz, -CN, methyl or methoxy. Examples of the phenyl group and the aromatic heterocyclic group include a pyridyl group which may be unsubstituted or substituted with a hydrogen atom, a halogen atom, 1 N〇, —〇N, methyl or methoxy. Particularly preferred is a piperazyl group, a quinolyl group or a pyridazinyl group.

The aliphatic hydrocarbon for R ^{3 in the} above formula (I) is a linear or branched chain hydrocarbon group, an alicyclic group, or a chain hydrocarbon group substituted with an aromatic hydrocarbon group. Ha port Gen atom, an alkoxy group, - COR ⁴ is the same halogen atom as specific examples given above for R ^2, an alkoxy group, - COR ⁴ Can be mentioned.

R ³ is a linear aliphatic hydrocarbon having 5 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, etc.

Group, preferably one CHz— COR ⁴ , — CH—

And particularly preferably 1 CH—COR (where R is a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group or a propyl group.).

Further, when R ² is a hydrogen atom and R ³ is a hydrogen atom, an alkyl group, a cycloalkyl group, or an aralkyl group, both X and Y are not hydrogen atoms. When ^ is a hydroxyl group, salts thereof may be used.

Among the compounds of the above formula (I), compounds exhibiting particularly excellent herbicidal activity are each particularly preferably selected from the following. X CF ₃

Y

z = C H-

R ¹ H, CH ₃

R ⁷ R ⁷

R ² :-CH ₂ -CH = CH ₂ , ~ i— N:

7

R

(Where R ⁷ is hydrogen atom, halogen, one CN

-Oz, one CH3 or one O Chb.

R ³ : One CH— COR

(Here, R ⁴ 'is a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group.)

Examples of the oxime derivative of the above formula (I) include the following compounds.

(1) 2-ethoxy-1 4- (2-chloro-4-trimethyl phenoxy) benzaldehyde

(2) 2- (2-methoxycarbonylethoxy) 14- (2-chloro-1-trifluoromethyl-E-oxy) benzaldehyde

(3) 2— (Petroxycarbonyl) 1 41 (2—Chloro 4—Triflurylmethylphenoxy) Benzaldehyde

(4) 0-Methyl 2-ethoxy 4- (2-chloro-1-4-methylphosphonyl) benzaldehyde

(5) 0-Methyl 2- (Ί-Methoxycarbonylethoxy) 1-41 (2-Chloro-4-trimethylfuroxy) Benzaldehyde oxime

(6) 0-Ethyl 2— (Ί-Methoxycarbonylethoxy) 1-41 (2-Chloro-1-4-trimethyl ro-methylphenoxy) Benzaldehyde

(7) 0—n—propyl 2— (Ί-methoxycarbonylethoxy) 1-4— (2-chloro-1-4-triflorime rome tylphenoxy) benzaldehyde

(δ) 0—Isopropyl 2— (Ί—Methoxycarbonylethoxy) Chilphenoxy) Benzaldehyde

(9) 0-Cyclohexyl 2- (Ί-Methoxy carbonyl 2-methoxy) — 4 -— (2-Chloro-4-tri-methyl phenoxy) Benzaldehyde

(10) 0—Ethoxycarbonylmethyl 2——Methoxycarborethoxy> 1—4— (2—Chloro—4— Trimethylfuromethylphenoxy) Benzaldehyde

(11) 0— 2—Propenyl 2— (Ί—Methoxy carbonyl 2-methoxy) — 4— (2-Chloro 4- 4-Methyl phenoxy) Benzaldehyde

(12) 0—2—Pthenyl 2— (Ί—Methoxycarbonylethoxy) 1—4— (2-Chloro—4—Trifur-l-ome Tylphenoxy) Benzaldehyde

(13) 0—3—Pthenyl 2— (1—Methoxycarbonylethoxy) 1—4— (2—Chloro—4—Trifur-l-ometylphenoxy) Benzaldehyde-l-xime

(14) 0— 2—Propenyl 2— (Ί—Ethoxycarbone luteoxy) 1-41 (2—Chloro-1- 4-trimethylfuromethylphenoxy) Benzaldehyde

(15) 0— 2—Propenyl 2— (1—Methoxy carbonyl) 4- (2-Chloro 4- 4-Methylphenoxy) Methylphenoxy) Benzaldehyde

(16) 2-(Ί—Methoxy carbonyl) (2-Chloro-1-trimethyl-l-methyl-oxy) Acetofenone-kissim

(17) 0—Methyl 2— (1—Methoxy carbonyl) 14 1 (2-Chloro 4- 4-methyltrimethoxy) Acetofenone Oxime

(18) 0—Benzyl 2— (Pyroxy methoxycarbonyl) 1 4— (2—Chloro 4—Trifuryl romethylphenoxy) Benzaldehyde

(19) 0-phenyl 2-ethoxy-1 41- (2-chloro-1

4— Trifle, Romethylf I-Noxi) Benzaldehyde, Kissim

(20) 0—Phenyl 2— (Ί—Methoxy carbonyl) 14— (2—Chloro 4—41 Trimethyl romethylphenoxy> Benzaldehyde

(21) 0-(4-furofilo-phenyl) 2--one-methoxy-carbone-l-oxy-> 1-4-1

(22) 0-(2-full-year rophenyl) 2--1-methoxycarbone-l-methoxy> 1-41- (2-chloro-1-4-methylfuroxy-methylphenoxy) benzaldehyde

(23) 0- (3-full-year rophenyl) 2-(1 methoxycarbonyl) 1 4-(2-chloro 4-1 lt Rifuru-shi methyl fu I-noxy) benzaldehyde

(24) 0- (4-chlorophenyl) 2-— (Ί—methoxycarbonyl- methoxy) 4- (2-chloro-1-4-trimethyloxymethyl) I-benzaldehyde

(25) 0- (4-Cyanophenyl) 2— (Ί—Methoxy carbonyl) 4- (2-Chloro-1- 4-tri-methyl phenoxy) Benzaldehyde

(26) 0- (4-122 phenyl) 2— (Ί—Methoxy carbonyl) 1 4-— (2-Chloro 4- 4-trimethyl romethylphenoxy) Benzaldehyde Sai Shim

(27) 0- (3-2-nitro carbonyl) 2- 2-methoxy carbonyl 2-ethoxy 4- (2-chloro 1-4 trifluoromethylphenoxy) benzaldehyde

(28) 0- (3-Triphenyl phenyl) 2-(Ί-Methoxycarbonyl 2-1-4-(2-Chloro 1-4-Trimethyl romethylphenoxy) Benzaldehyde

(29) 0- (3-Methoxy phenyl) 2 -—— Methoxy carbonyl Rifuru-shi methyl fu I-noxy) benzaldehyde

(30) 0- (4-Methylphenyl) 2— (Ί—Methoxy carbonyl ethoxy) 1-41 (2-Chloro-4-4-trimethyl ro-methylphenoxy) Benzaldehyde

(31) 0- (4-phenylphenyl) 2-— (Ί—methoxycarbonyl) 4-4-1 (2-chloro-1-4-methylphenylmethyl) benzaldehyde

(32) 0— [4- (4-trimethyl rophenoxy) phenyl] 2— (Ί-Methoxy carbonyl ethoxy) 1-4— (2-Chloro 4- 4-trimethyl romethylphenoxy) Benzaldehyde

(33) 0- (3,4—Dichlorofurinyl) 2— (P-Methoxy carbonyl) 4-4-1 (2-Chloro-1-41-Trifluoromethylinoxy) Benzaldehyde

(34) 0— (2,4—Dimethyl mouth phenyl) 2— (P-Methoxy carbonyl) 4-1-1 (2-Chloro-1-4-methyltriphenyl) Benzaldehyde Kissim

(35) 0-(2-Chloro 4-Trimethylfuromethylphenyl) 2-(Ί-Methoxycarbonyl) 1-4 One (2-chloro-1-4-methyl phenoxy) benzaldehyde

(36) 0-(3,5 —Dimethoxy phenyl) 2— (1 —Methoxycarbonyl) 4- 1 (2-Chloro 1 — Trimethyl romethylphenoxy) Benzaldehyde

(37) 0— (3,5-Dimethylphenyl) 2— (1-Methoxyxycarbonyl) — 4 -— (2-Chloro-4-trimethylfurinoxy) Benzaldehyde

(38) 0—Phenyl 2— (Ί—Methoxycarbonyl) 1 4— (2,4—Dichlorophenoxy) Benzaldehyde

(39) 0-(4 -Fluorophyl: πnil) 2-(Ί-methoxycarbonyl) 1 4-(2,4-dichlorophenoxy) benzaldehyde

(40) 0— (4—Nitrophenyl) 2— (1—Methoxycarbenyloxy) 1-4— (2, Dichlorophenoxy) Benzaldehyde

(41) 0-(3-methoxyphenyl) 2-(1-methoxycarbonyl) 1 4-(2, dichlorophenoxy) benzaldehyde

(42) 0-(3-trimethylfurinomethylphenyl) 2-

(1 —Methoxycarbonyl) Dichlorphenoxy> benzaldehyde

(43) 0-(4-Methylphenyl) 2— (Ί—Methoxy carbonyl ethoxy) 1-4— (2,4—Dichlorophenoxy) Benzaldehyde

(44) 0-(4-Cyanophenyl) 2— (1-Methoxycarbonyl) 4-14-1 (2, Dichlorophenoxy) Benzaldehyde

(45) 0-(2-Chloro 4- 4-trimethyl phenyl) 2-(Ί-Methoxy carbonyl ethoxy) 1-4 1 (2,4-Dichlorophenoxy) Benzaldehyde

(46) 0—Phenyl 2— (Ί—Methoxycarbenyloxy) 1 4— (4-Trifluoromethylphenoxy) Benzaldehyde

(47) 0-(4 -Fluorinyl) 2-(1-Methoxycarbonyl) 1-4 (4-Triflume lome tylphenoxy) Benzaldehyde loxime

(48) 0- (4-chlorof;!: Nil) 2— (Ί-Methoxy carbonyl carbonyl) 1 4-1 (4-trifluoro-methyl-l-oxyl) I-benzaldehyde

9) 0— (3—Trifluoromethylphenyl) 2— (Ί—Methoxycarbonylcarbonyl) 1-41 (4—Trifluoromethylphenyl) Benzaldehyde (50) 0- (2-pyridyl) 2— (1-methoxycarboxyl-methoxy) 1-41 (2-chloro-1-4-trimethyl-l-methylphenoxy) benzaldehyde

(51) 0- (6-Methoxy-2-pyridyl) 2— (Ί1-Methoxycarbonyl-ethoxy) 1-4- (2-Chloro-4- 4-trimethylfuromethylphenoxy) Benzaldehyde Kissim

(52) 0-(3-Chloro-2-pyridyl) 2— (1—Methoxycarbone methoxy) — 4- (2-Chloro-4-trimethylfuromethylphenoxy) Benzaldehyde

(53) 0- (2-Vilazyl) 2- ((—Methoxycarbo-2-rethoxy) 1-41- (2-Chloro-1-4-trimethyl-l-methylphenoxy) Benzaldehyde-loxime

(54) 0-(3,6-I-dimethyl-2-virazil) 2— (P-Methoxy carbonyl 2-methoxy) 1-41 (2-Chloro-1-4-trimethyl-l-methyloxy) Benzaldehyde Hydoxi-x

(55) 0- (2-quinolyl) 2— (1—Methoxycarbo-2-lethoxy) 1-41 (2-chloro-1-4-trimethylfuromethylphenoxy) Benzaldehyde

(56) 0-(6-Chloro-3-pyridazino) 2- (1-Methoxycarbonyl) 4- (2-Chloro-4- 4-trimethyl romethylphenoxy) Benzardeh De Sai Kissim

(57) 0— (6-Chloro-2-pyridyl) 2— (1—Methoxyloxycarbonyl) 1-41 (2, Dichlorophenoxy) benzaldehyde

(58) 0- (3,6-Dimethyl-2-virazil) 2- (1 -Methoxycarborenyloxy) 1-41 (2,4 Dichlorophenoxy) Benzaldehyde

(59) 0- (6-Chloro-2-pyridyl) 2— (Ί—Methoxycarborenyloxy) 1-41 (4-Trimethyl romethylphenoxy) Benzaldehyde Axime

(60) 0— (6-Methoxy-1-2-pyridyl) 2 -— (1-Methoxycarbonylcarbonylethoxy) 1-4— (4-Trimethyl-l-methylphenoxy) Benzaldehyde

(61) 0-(3-Chloro-2-pyridyl) 2- (Ί-Methoxycarbonyldiethoxy) 1-41- (2,4—Dichlorophenoxy) Benzaldehyde Axime

(62) 0-Phenyl 2- (Ί—Methoxy carbonyl) 14-Chlorophenoxybenzaldehyde

(63) 0-Phenyl 2— (カルボキシ —Carboxyethoxy) 1- (2-Chloro-1--4-trimethyl-l-methyl) I-Benzaldehyde

(64) 0-Phenyl 2-hydroxy-4- (2-Chloro-1-trimethyl romethylphenoxy) Benzarde Hide

(65) 0-F: t-nil 2— (Ί—methoxycarbonyl-2-oxy) 1-41 (3-chloro-5—trifluromethyl-1-2—pyridyl) benzylaldehyde

(66) 0-2-Propenyl 2-Methoxycarbinoxy 4- (2-Chloro-4-trimethyl-4-methyloxy) benzaldehyde

(67) 0-2-Propenyl 2-methoxycarboxyl 4- (2-chloro-1- 4-methyl-methyl) benzaldehyde

(68) 0-phenyl 2-methoxycarbonyl 4- (2-chloro-4-methyltrimethyl) benzaldehyde

(69) 0-Phenyl 2-ethoxycarbonyl-methoxy- (2-chloro-1-4-methylphenyl) Benzardaldehyde

(70) 0-2-Propenyl 2-(Ί-n-butoxycarbonyl methoxy)-4- (2- chloro-4- 4-trimethyl r-methylphenoxy) Benzaldehyde Deximix

(71) 0—Phenyl 2— (Ί—ethoxycarbonyl) 4- 1- (2-chloro-1-4-methylbenzoyl) Benzaldehyde Dexoxime

(72) 0-Phenyl 2— (Ί n-propoxycarboryl methoxy) 1-41 (2-chloro-1 -4-trifur τί mouth Methyl (nonoxy) benzaldehyde

(73) 0-Furnyl 2- (1-ISO SO-Propoxycarboryl-2-oxy) 1-4- (2-Chloro-4-4-Trifluoromethyl-I-oxy) Benzaldehyde Axime

(74) 0-F: L-nil 2- (（-n-butoxycarbonylethoxy) 1-4- (2-chloro-1-4-trimethyl-l-methyl-phenoxy) Benzaldehyde-l-xime

(75) 0-Phenyl 2- (Ί 力力力力力 4 4 4 4 4 4 4)

(76) 0—Finyl 2— (Ί—iso—Propylcarbomoylethoxy) 1-41 (2-Chloro-4-trifluoromethylphenoxy) Benzaldehyde

(Π) 0—Phenyl 2— (Ί—Dimethylcarbamoyl ethoxy) 1-41 (2-Chloro 4-trifluorotrifluoromethyl 1 oxy) Benzaldehyde

(78) 0—Phenyl 2— (Ί—Jetylcarbamoylethoxy) 14— (2-Chloro-4- 4-trimethyl phenoxy) Benzaldehyde

The compound of the above formula (e) can be produced, for example, by the following reaction method. 〇 Hz N-0-R ²

()

1

YR ¹

0 C = N-0-R ²

X OR ³ ik) and (B) X in the reaction represented by 'represents CFI, Br, and I, X, Y, Z, R 1', R 2 and R ³ are the same as defined in the preceding .

The above-mentioned oxime derivatives of the formula (I) of the present invention affect the metabolism of plants, for example, suppress the growth of certain plants, regulate the growth of certain plants, and dwarf certain plants. Or has the property of killing certain plants.

The compound of the above formula (I) of the present invention can be applied to plant seeds, and can also be applied to plants at various stages of growth via foliage or roots. The plant that is trying to inhibit growth, either as such or in the form of a composition, is a plant that seeks to regulate metabolism, the seeds of such a plant, the place where such a plant is growing, or such a plant. Applied in places where growth is expected, with sufficient cloudiness to regulate plant metabolism.

The compounds according to the invention can regulate the metabolism of plants, for example in an amount of 0.001 to 20 kg / ha, more preferably in an amount of 0.005 to 10 kg / ha, particularly preferably in an amount of 0.01 to 5 kg / ha. it can.

The compound of the present invention can be used as a preparation in a usual form such as a solution, an emulsion, a suspension, a powder, a paste or a granule.

Such preparations include, for example, talc, bentonite, flaky kaolin, diatomaceous earth, white carbon, vermikinifi Solid carriers such as ethanol, slaked lime, ammonium sulfate, and urea; water, alcohol, dioxane, acetate, xylene, cyclohexane, methyl naphthalene, dimethylformamide, N-methylvinylidone, dimethylsulfoxide, Liquid carriers such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone; alkyl sulfates, alkyl sulfonates, lignin sulfonates, polyxylene ethylene glycol alcohol, polyxylene ethylene glycol Use one or more of surfactants, emulsifiers or dispersants, such as mono-ter, poly-xylethylene sorbitan monoalkylate, and dinaphthylmethane disulfonate; various adjuvants, such as carboxymethyl cellulose and arabia rubber Prepared.

Such a preparation can be prepared, for example, by mixing the compound with the above-mentioned carrier and a carrier or emulsifier.

The compounds of the invention can be present in the formulations usually in a proportion of from 0.01 to 99% by weight, preferably from 0.1 to% by weight.

The compounds of the invention may be applied to the plants as such, or in a mixture with other active compounds, or in the form of a formulation as described above, for example by conventional means such as spraying, spraying, dusting or dusting. Can be.

When the compound of the present invention is used for the purpose of inhibiting the growth or extermination of harmful plants, the compound of the present invention may be used as it is. Or in the form of a composition, where the beneficial plants or their seeds and the harmful plants or their seeds coexist or are likely to coexist, in order to suppress the growth of plants that are harmful to these plants or seeds directly or to the upper lands. It can be applied in an amount sufficient to destroy it.

Harmful plants are generally human-created environments, for example, plants that enter and propagate from the surrounding natural world in fields, or that are perceived by humans to be useless or harmful in that environment. Such harmful plants are generally referred to as weeds. As weeds, for example, the following various species are targeted.

Hyu (maranthaceae);

Amaranthus retrof lexas,

Ainubu (Amaranthus 1 i idus),

Convol vu laceae;

Ma </ Lesbian Asaga (Ipotnoea purpurea),

Cuttlefish (Cuscuta joponica),

Polygonaceae (Poiygonaceae);

Buckwheat (Polygonum convolvulus),

Polygonum ydropi er,

Polygonum lapat ifolium,

Chenopod iaceae;

Shiroza (Chenopdium album),

Akaza (Chenopod ium album var. Centrorubrum), Core kaza (Chenopod i urn f icifol ium),

Svetlana ¹ Li fuse Department (Portu lacaceae);

Sleek Hy (Portu lac a oleracea),

Legumes (Oegumi nosae);

Jizuzogi (Desmod ium tortuosum),

Malvaceae;

Aichi (Abut i I on theophrast i),

American sika deer (Sida spinosa),

Solanaceae (Solanaceae);

Inuho-suzuki (Solarium nigrum),

White-headed Asaga (Datula stramonium), Asteraceae (Compositae);

Hymezion (Erigeron annuus),

Ragweed (Ambrosia artemisiaefolia var. El ator),

7} Namomi (Xanthi um strumarium),

Cirsiuni arvense var. Etosum Grami neae;

Sorghum halepense

Oats (Avena f atua)

Crabgrass (Dig i taria adscendens)

Aquino nokorogosa (Setaria faberi)

Barley (gropyron repens)

Tequili spanicam (pan i cum texanum)

Barnyard (Echi nochloa crus-gal I i) Enokolog (Setaria vi rid is)

Poa annua

Hoshiba (Eleu sine i nd i ca)

Carpet glass (AxonoDus af finis)

American Acne (Bachiaria platyphy I la)

ゥ Manochiyahiki (Bromus tectorum)

Giant z3 cypress (Cynodon dactylon)

Year old τί wedge mill (Panicum d ichotomi f lorum)

Red-necked squirrel (Paspalum d i latatum)

Echinochloa colona

Gnoccus, Panicum capi I lare

Kinenokoro (Setaria faberi)

Sparrow Note (Alopecurus acqual is var.

amurensi s)

Cyperaceae;

Red sedge (Cyperus rotundus)

Callarigusa (Cyperus microi ria)

Mizukayari ¹ (Cyperus serotinus)

Hota Rei (Sc Ί rpus otaru i)

Pine bye (E I eochari s ac icu lari s var. Longiseta)

ゥ¹ Lika ヮ (Sagittaria pygmaea)

A family (Pontederiaceae);

Eel (Monochoria vaginal is) Further, the compound of the above formula (I) substantially does not cause harm to useful crops, especially soybeans and maize sorghum, depending on the method of use, treatment method and treatment, and therefore substantially inhibits their growth. It can also be used as a selective herbicide to destroy broadleaf weeds and narrowleaf weeds.

For example, the compound of the present invention, or a composition containing the compound of the present invention, can not only suppress the death or growth by spraying on the foliage of a weed to be removed, but also germinate it. By applying it to soil beforehand, it can be used as a selective herbicide that does not substantially inhibit the germination and growth of useful crops and can suppress the germination and growth of weeds.

The compounds of the general formula (I) according to the invention can be used together with various herbicide compounds known per se. At this time, the compound of the formula (I) of the present invention is used together with another compound having an excellent herbicidal activity against, for example, narrow leaf weeds so as to sufficiently exert herbicidal activity against broad-leaved weeds and narrow leaf weeds. It can be used to provide an effective herbicide composition for both broadleaf weeds and fineleaf weeds.

Therefore, according to the present invention, a compound of the general formula (I) and a compound of the following formula (E)

0

R ²¹ -P-C Hz-NHC Hz-COR ²³ … （Π〉

R ²² Here, R21 and R22 are the same or different and is an 0H or a OR ²⁴ respectively, R ^£ ^ - 0H, there Hide -OR 2 ⁴ or a NR ²⁵ R ^2. Here, R ²⁴ is an alkyl group having 5 to 5 carbon atoms, a cyclohexyl group, a haloalkyl group having 1 to 5 carbon atoms, an alkenyl group or an alkoxyalkyl group having 2 to 5 carbon atoms, a haloalkoxyalkyl group, or an alkoxyalkoxy group. Alkyl groups (where each alkoxy, haloalkoxy and alkyl has 1 to 5 carbon atoms) and phenoxy groups. R ²⁵ and R ²⁶ are the same or different each represents a hydrogen atom, an alkyl group of Ί~5 carbon atoms, a hydroxyalkyl group Ί~5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, also, R ²⁵ and R ²⁶ Can form morpholino, piperidino or pyrrolidino groups together with the nitrogen atom to which they are attached.

A herbicidal composition containing a ホスホ -phosphonomethyldaricin derivative represented by the formula (I) or an acid addition salt or a salt thereof with a base as a herbicidal component, and also containing a carrier and a surfactant or a surfactant is also provided. Is done.

In the above formula (Ε), R ²¹ and R 22 are the same or different, each being 10 ° or 100 R ²⁴ , and R ²⁰ is — 0Η, 10 R ²⁴ or 1 NR ²⁵ R ²⁶ Here, R ²⁴ is an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group, a haloalkyl group having 1 to 5 carbon atoms, and a C 2 to 5 carbon atom. These are alkenyl groups, alkoxyalkyl groups, haloalkoxyalkyl groups, or alkoxyalkoxyalkyl groups (where each alkoxy, haloalkoxy and alkyl has from 1 to 5 carbon atoms) and phenoxy groups. R ²⁵ and R ²⁶ are the same or different and are respectively a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, and an alkynyl group having 2 to 5 carbon atoms. ⁵ and R ⁶ can form a morpholino, piperidino or pyrrolidino group together with the nitrogen atom to which they are attached.

Examples of the alkyl group for R ²⁴ , R ⁵ and are the same as those described above for X and Y in the formula (I).

In R ⁴ , examples of the haloalkyl group having 1 to 5 carbon atoms include halomethyl, haloethyl, dihaloethyl, and!口 Mouth propyl, halobutyl and halopentyl can be mentioned. Examples of the halogen atom include fluorine, chlorine, and bromine.

Examples of the alkenyl group having 2 to 5 carbon atoms for R ²⁴ , R ²⁵ and R ²⁶ include vinyl, propenyl, butenyl and pentenyl.

As the alkoxyalkyl group for R ²⁴ , for example, methoxethyl, ethoxyxyl and the like can be mentioned as preferred. Preferred haloalkoxyalkyl groups for R 24 include, for example, chloroethoxyl and chloromethoxyl.

Preferred examples of the alkoxyalkoxyalkyl group for R ²⁴ include methoxyxethyl and ethoxyxethyl.

And a hydroxy § alkyl group having 1 to 5 carbon atoms for R ^26, such as hydroxymethyl, hydroxy Shechiru can ani gel as preferred hydroxy pentyl.

The compound represented by the above formula (E) is disclosed in JP-B-56-6401 (US Pat. No. 7,123,057) and is known per se.

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

As an acid for forming an acid addition salt, for example, a strong acid having a pKa of 2.5 or less is preferable. Examples of such an acid include hydrochloric acid, sulfuric acid, phosphoric acid, trifluroacetic acid, and trichloroacetic acid.

When at least one of R ²¹ , R ²² and R ^{23 in} the above formula (Π) represents 100, for example, a salt thereof with an alkali metal, alkaline earth metal, copper , Zinc, ammonium or organic ammonium Formed as a salt with the cation.

Alkali metal refers to, for example, lithium, sodium or potassium, and alkaline earth metal refers to, for example, magnesium or calcium.

Organic ammonium salts are prepared from low molecular weight organic amines, for example, those having a molecular weight of about 300 or less. Examples of such organic amines are, for example, alkylamines, alkylenepolyamines and alkanolamines, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isoptyramine, secondary-butylamine, n-amylamine. , Iso-amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pendecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, octadecylamine, octadecylamine Methyl isopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyl octadecylamine, Leptylamine, ethylheptylamine, ethylethyl octylamine, hexylheptylamine, hexyloctylamine, dimethylamine, getylamine, di-n-propylamine, diisopropylamine, di-π-amylamine, diisoamylamine , Dihexylamine, jeeptyla Min, di-octylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-secondary butyramine, tri-n-amylamine, ethanolamine Min, n-Propanolamine, Isopropanolamine, Diethanolamine, N, N-Getylethanolamine, N-Ethylpropanolamine, N-Butylethanolamine, Arylamine, n— Ptenyl 2-amine, n-pentenyl 2-amine, 2,3-dimethylpentenyl 2-amine, jeptenyl-2-amine, n-hexenyl-2-amine and propylene diamine, primary arylamine, for example, aniline , Methoxyxaniline, ethoxyxaniline, 0, m, p-triluidine Phenylenediamine, 2, 4, 6—Tripromore diline, benzidine, naphthylamine, 0, m, p-chloroaniline, etc .; Heterocyclic amines such as pyridine, morpholine, piperidine, pyrrolidine, indoline, azepine And the like.

In the above formula (E>, Ί one or two one 〇_H out of R ^21, R ²² and R ^23, - OH a salt or single OR 2 ⁴ of and the remaining one of R ^21, R ²² and R ² Compounds in which the compound is 10 H or a salt thereof are preferred.

Also, in the above formula (E), one or two of R ²¹ , R ²² and R ²³ are salts of 10H, and R ²¹ , Compounds in which the remaining one of R22 and R23 is 100H can be mentioned. Examples of the salt of 1 OH include ammonium or organic ammonium (where the organic ammonium group is a monoalkyl ammonium, a dialkyl ammonium, a trialkyl ammonium, a monoalkenyl ammonium, a dialmium). Nil ammonium, trialkyl ammonium, monoalkynyl ammonium, dialkynylammonium, trialkynyl ammonium, monoalkanol ammonium, dialkanol ammonium, trialkanol ammonium, heterocyclic ammonium Selected from the group consisting of luammonium, and such organic ammonium groups have 〜 to 18 carbon atoms).

The salt of the compound of the above formula (Π) with the acid or base as described above is produced from the compound of the above formula (Π) and the acid or base according to a method known per se.

Examples of the compound of the above formula (II), the acid addition salt or the salt thereof with a base which are preferably used in the present invention are as follows.

(101) Ν —phosphonomethyldaricin

(102) Ν —phosphonomethyldaricin sodium salt

(103) Ν—Phosphonomethylglycine ammonium salt

(104) Ν-Phosphonomethylglycine calcium ♦ 1 Water salt

(105) Ν —phosphonomethyldaricin magnesium salt (106) N-phosphonomethylglycine potassium salt

(107) N-phosphonomethylglycine dimethylamine salt

(108) Bis (N-phosphonomethylglycine) copper salt

(109) N-(phosphonomethyl) glycine ♦ zinc salt

N-phosphonomethylglycinamide

Methyl-N- (phosphonomethyl) glycinate

(112) Ethyl N- (phosphonomethyl) glycinate

(113) n-Propyl-N- (phosphonomethyl) glycine

(114) n-Butyl-N- (phosphonomethyl) glycinate

(115) Cyclohexyl-N- (phosphonomethyl) glycinate

Chloroethyl N- (phosphonomethyl) glycine

N-phosphonomethylglycine isopropylamine

N-phosphonomethylglycine methylamine salt

(119) N-phosphonomethyldaricin diisopropylamine salt

(120) N-phosphonomethyldaricin pyridine salt

(121) N-phosphonomethylglycineaniline salt

The composition of the present invention comprising the compound of the above formula (e) and the compound of the formula (E) comprises a compound of the above formula (I) and a compound of the formula (I) It is preferable that the compound is contained in a ratio by weight of the former (e) to the latter (Π) of Ί: 5 to 50:。, and the ratio is more preferably 1: 20 to 20: 1, particularly preferably 1:10 to 10: Ί.

Also, the amount of the composition to be actually applied depends on a number of factors, such as the type of the particular target plant to be inhibited from growing, but is generally from 0.1 to 10 kg / ha, preferably from 0 to 10 kg / ha. An amount of 5 to 5 KgZ ha is appropriate. Particularly suitable proportions also without a large number of experiments by conventional tests Bok which is standardized by those skilled in the art, _u amount used can be readily determined by

The composition of the present invention can be applied in the form of a composition in which the active ingredient is mixed with a carrier comprising a solid or liquid diluent. Further, the composition may further contain an additive such as a surfactant. As such a diluent, carrier and surfactant, the same ones as described above can be used.

By containing the composition of the present invention together with a carrier and Z or a surfactant, it can be used as a normal form preparation such as a solution, emulsion, suspension, powder or paste.

The composition of the present invention can be prepared by combining the compound (I) and the compound (H) and then mixing the compound (I) with a carrier or the like to prepare a preparation. Alternatively, the composition of the compound (I) and the compound (E) These compositions are separately prepared, and if necessary, carriers and the like are added. It can be prepared by, for example, a method of mixing the products together to form a preparation.

According to the present invention, there is further provided a weed comprising applying the compound (I) and the compound () simultaneously or in an arbitrary order to a place where the weed is growing in an amount effective for killing the weed. It is a method of killing.

In the above method, the compound (I> and the compound (n) may be referred to as the above composition containing these compounds (I> and (E)) or separately prepared as a composition of the compound (I) and the compound (I). By applying together the composition of I), it can be applied simultaneously to the place where weeds are growing.

Further, the composition of compound (I) and the composition of compound (I) separately prepared can be applied to a place where weeds grow over time.

In that case, the application order of the composition of the compound (I) and the composition of the compound (I>) may be any order.

In addition, the time from the application of one of the compositions to the application of the other composition may be, for example, after the application of one of the compositions, the active compound (I) or the active compound (I) in the composition.

It is preferred to apply the other composition while (I) remains on the surface of the weed. Although it depends on the target plant, climatic conditions, etc., it is usually preferable to apply the other within a few words immediately after applying one.

According to the present invention, as described above, for example, the compound (e) By applying the compound (E>) before the crop emerges, the crops that grow there will die before the crop emerges, and the crop will grow smoothly.

When carrying out these methods, the application rates of the compounds (I). And (E) are appropriately determined based on the application rates described for the composition.

According to the above method of the present invention, it is possible to kill both broadleaf weeds and fine-leaf weeds advantageously with a relatively low application rate.

The following examples illustrate the invention in detail.

In the examples, parts means parts by weight. The herbicidal activity was evaluated on a six-point scale unless otherwise specified. That is, after the active compound is applied, the healthy state, which is almost the same as before the application, is set to 0, and the whole plant is wilted and withered by the application of the active compound is set to 5, during which 4 steps according to the strength of the plant (Ί, 2, 3, and 4> were provided for evaluation.

Synthesis of C F G-O -f ^-C H = N-0 H

0 CH ₂ C H3 2-Ethoxy 4 — (2-Chloro-1-trimethylfuromethylphenoxy) Benzaldehyde 3. A solution of 45 parts in 20 parts of tetrahydrofuran, 0.7 parts of hydroxylamine hydrochloride and 5 parts of water Then, 0.7 δ parts of potassium carbonate was added at room temperature with stirring, and the mixture was further stirred at room temperature for 1 hour, and tetrahydrofuran was distilled off under reduced pressure, and 20 parts of water was added. The resulting mixture was extracted with ether, the ether layer was dried over anhydrous sodium sulfate, the ether was removed, and the residue was separated by silica gel column chromatography to obtain 3.2 parts of the desired product. And nuclear magnetic resonance spectrum are shown in Table 18. Example 2

02

No

CF s Γ V 0-< ⁷ c Η = Ν-0 合成

0 C i hi C 0 0 C Hs

(2) CH ₃

In Example II, 2-ethoxy-14-1 (2-chlor-4-methylphosphonyl) benzaldehyde 3. 2-45 instead of 45 parts 2- (methoxycarbonylcarbonyl) 1-4 — (2-Chloro-41-trimethyl romethylf: L-noxy) Using benzaldehyde (4.03 parts), the reaction was followed in exactly the same manner to obtain 3.85 parts of the desired product. Table 8 shows the infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound. Example 3

Synthesis of CF

In Example II, 2-ethoxy 4- (2-chloro-1-4-trimethyl-l-methylphenyloxy) benzaldehyde 3. Instead of 45 parts, 2- (1-ethoxycarbonylethoxy) 1-4-1 2-Chloro-1--4-trifluoromethylphenoxy> 4.16 parts of benzaldehyde were used, and the reaction and work-up were carried out in exactly the same manner to obtain 3.90 parts of the desired product. The spectrum and the nuclear magnetic resonance spectrum are shown in Table 18. Example 4

CF ₃ , — V-· 0-0 Synthesis of CH ₃

( Four ) In Example I, instead of 0.7 parts of hydroxylamine hydrochloride, 0.84 parts of 0-methylhydroxylamine hydrochloride was used, and the reaction and post-treatment were carried out in exactly the same manner to obtain 3.80 parts of the target compound. Table 18 shows the infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound. Example 5

Synthesis of CF ₃ N-O CH3

00 C Hs

In Example 2, instead of 0.7 parts of hydroxylamine hydrochloride, 0.84 parts of 0-methylhydroxylamine hydrochloride was used, and the reaction and post-treatment were carried out in exactly the same manner to obtain 3.85 parts of the desired product. Table 8 shows the infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound. Example 6 to Ί3

Synthesis of compounds (6) to (13)

2- (2-methoxycarbonyl-2-ethoxy) 1-41 (2-chloro-4-trifluoromethylphenoxy) A solution prepared by dissolving 4.03 parts of benzaldehyde in 20 parts of tetrahydrofuran is shown in Table 1 below. Of the 0-substituted hydroxylamine shown in An aqueous solution containing an equimolar amount was added at room temperature, and the mixture was further stirred at room temperature for another 4 hours. Thereafter, tetrahydrofuran was distilled off under reduced pressure, 20 parts of water was added, and the mixture was extracted with ether. The ether layer was dried over anhydrous sodium sulfate, and the ether was removed. The residue was subjected to silica gel column chromatography to obtain the desired product in the weight shown in Table 1 below. Table 18 shows the infrared absorption spectrum and nuclear magnetic resonance spectrum of each product. Table 1

Example 0-Substituted hydroxyylamine Yield Produced No. (part) Compound No.

6 Hz N-0 C Hz C Hs O C 3.66 (6)

9

7 Hz N-0 C Hz C Hz C Ha 3.7 32 (7)

CH ₃

Hz N-0-CH 4.05 (8)

10 HZN-O- CHZCOOCZHB 3.78

11 Hz N ~ 0 C Hz C H = C Hz 3.89

12 Hz-O CHz C H ^ C H-CHs

3.75 (12)

(13) Example Ί 4

CF3 -O CH ₂ CH = CH2

Synthesis of 0 CH COOCzHs

CHs Example In Example Ί 2 （2- (Ί-methoxycarbonyloxy) 1-41 (2-chloro-4-trimethylfuromethylphenoxy) Benzaldehyde Instead of 4.03 parts, 2— (1-ethoxycarbonyl) Toxy> 1.41 (2-chloro 4-trifluoromethylphenoxy) 4.16 parts of benzaldehyde was used, and the reaction and post-treatment were carried out in exactly the same manner to obtain 3.90 parts of the desired product. The infrared absorption spectrum and the nuclear magnetic resonance spectrum of the compound are shown in Table 18. Example 5

CF ₃ ^ίΓ -0-^ ζ C Η = Ν-0 C Hz CCH

Synthesis of 0 CHC 00 C Ha (15) CH _{3 In} Example 6 as 0-substituted hydroxylamine Using 0-2-propylhydroxylamine, the reaction and post-treatment were carried out in the same manner as described above to obtain 3.0 parts of the desired product. Table 18 shows the infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound. Example 16

Synthesis of Hs

(16) CH _{3 In} Example 1, 2-ethoxy-4- (2-chloro-4-trimethylphenoxy) benzaldehyde 3.45 parts instead of 2.45 parts 2- (Ί-methoxycarbonyl) Xish> 14- (2-chloro-1-4-trimethylfuromethylphenoxy) 4.17 parts of acetophenone were used, and the reaction and after-treatment were carried out in the same manner to obtain 3.0 parts of the target compound. Table 18 shows the infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound. Example 17

Synthesis of

In Example 6, 0.8 part of 0-methylhydroxylamine hydrochloride was used in place of 0.7 part of hydroxylamine hydrochloride, and the reaction and post-treatment were carried out in the same manner to obtain 3.1 parts of the desired product. Table 18 shows the infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound. Example Ί 8-Ο ΟΗΖΗΠ

Synthesis of OO CHs

CHs

2- (2-methoxycarbonylethoxy) 1-4- (2-chloro-4-trimethyl romethylphenoxy) Benzaldehyde 4.03 parts dissolved in a solution of 20 parts tetrahydrofuran 0-benzylhydroxyl Add 1.23 parts After stirring at room temperature for 2 hours, tetrahydrofuran was removed under reduced pressure, and the obtained residue was separated by silica gel column chromatography to obtain 4.67 parts of the desired product. The infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound are shown in Table 18

Synthesis of

(19) In Example No. 8, 2— (Ί—Methoxycarbonylethoxy) 1-4— (2—Chloro-4-l / fluoromethylphenoxy) benzaldehyde 4.0 2- (ethoxy) instead of 03 parts 1. 4- (2-chloro-4-trimethyl rophenoxy) 3.45 parts of benzaldehyde, and 1.1 parts of 0-phenylhydroxylamine instead of 1.23 parts of 0-benzylhydroxylamine, Thereafter, the reaction and post-treatment were carried out in exactly the same manner to obtain 3.70 parts of the desired product.Table 18 shows the infrared absorption spectrum and nuclear magnetic mirror spectrum of the compound. Show.

New paper Examples 20 to 37

Synthesis of compounds (20) to (37)

Two

2-o (P-Methoxy carbonyl diethoxy) 14-1 (2-Chloro-4-trifluoromethyl phenoxy) A solution prepared by dissolving 4.03 parts of benzaldehyde in 20 parts of tetrahydrofuran is shown in Table 1 below. An equimolar amount of the 0-substituted hydroxylamine shown in 2 was added, and the mixture was stirred at room temperature for 2 to 5 hours. Thereafter, tetrahydrofuran was removed under reduced pressure, and the obtained residue was separated by silica gel column chromatography to obtain each having the weight shown in Table 12 below. Table 18 shows the infrared absorption spectrum and nuclear magnetic resonance spectrum of each product. Table 1 9

Example 0- Exchanged Hydroxamine Yield Produced N0. (Parts) Compound No,

Hz one 0 -f 4.4 (20)

F

22 Hz-0 -TS 4.2 (22) CCC Co Ϊ 3

CO Oo to C 4 ^ C

n

^

3 n> ~ Oo c, C

Ό

C C CO ro C Co r ro h ro

Oo Cn 4 = »o

w 2 -ao ' 2 (continued)

36 3 〔

37

Examples 38 to 45

Synthesis of compounds (38) to 5)

In Example 20, 2- (Ί-methoxycarbonylethoxy) 1-41 (2-chloro-4-trifluryl-methylphenoxy) Instead of 4.03 parts of benzaldehyde, 2- (Ίmethoxyethoxycarbonyl) Xi> 1-41 (2, Fluorofoxy) Use benzaldehyde (3.70 parts) and 0-substituted hydroxylamine as shown in Table 13 below. As a result, each product was obtained in the weight shown in Table 13. The infrared absorption spectrum and nuclear magnetic resonance spectrum of each product are shown in Table 18. Table 1 3

o-Substituted hydroxyylamine yield

NO, Compound No,

38 Hz 1 0 -ί 4.1 (38)

40 Hz N-0-< ⁷ V Oz 4.5 (40)

0 CH

/

41 Hz N-0 A> 4.4 (41)

r "

Shu

Come

42 HzN-0 4.5 (42)

43 Hz-0-~ C Hs 4.0 (43)

45 Hz N -O- ^ CP ₃ 5.0 (45)

C. Examples 46-49

Synthesis of compounds (4 &) to (49)

Example 20 In Example 20, 2— (Ί—Methoxycarbonyl 1-4-1 (2-Chloro-4-trimethyl ro-methylphenoxy) Benzaldehyde Instead of 4.03 parts 2- (1-methoxycarbonyldimethoxy) 1-4-1 (4-Trifluoromethyl roxinoxy) ) Using 3.68 parts of benzaldehyde and 0-substituted hydroxylamine as shown in Table 14 below, the reaction and post-treatment were carried out in exactly the same manner to obtain the respective weights shown in Table 14 below. Table 18 shows the infrared absorption spectrum and nuclear magnetic resonance spectrum of each product.

Example 0-Substituted Hydroxylamine Yield Produced No. (Part) Compound No.

47 HzN-0 F 4.0 (47)

r "

J Square 3

49 Hz-0 JI \ 4.5 (49) Examples 50-56

Synthesis of Compounds (59) to (5δ) In Example 20, the same reaction and post-treatment were carried out in exactly the same manner as in Example 20 except that the 0-substituted hydroxyylamine shown in Table 15 below was used. The target product was obtained with the weight shown in Table 1-5. Table 18 shows the infrared absorption spectrum and nuclear magnetic resonance spectrum of each product.

Table `` One ⁵

Example 0-Substituted Hydroxylamine Yield Production

No. (Part) Compound Wo.

Five

Two

O CHs

Then k

52 Hz N-0-^ H j 3.7

53 Hz N-0-C .4 (53) 5 (continued)

56 Hz 1 0 C5 3.7 (56)

Example 5 7, 58, 6

Synthesis of compounds (57), (58), (δ1)

In Example 38, the 0-substituted hydroxylamine shown in Table 16 below was used, and the reaction and post-treatment were carried out in exactly the same manner to obtain the desired product in the weight shown in Table 16 below. I got Table 18 shows the infrared absorption spectrum and nuclear magnetic resonance spectrum of each product. 6

Example 0-Substituted hydroxyylamine Yield Produced No. (part) Compound No.

Examples 59, 60

Synthesis of compounds (59) and (60)

Example 2 In Example 2 2-(Ί-methoxycarbonyloxy) 14-(2-chloro-1-4-trifluoromethylphenoxy) Benzaldehyde Instead of 4.03 parts of 2-(4.0-methoxycarbonyl) Ethoxy> 4- (4-trimethylaminophenoxy) Using 3.68 parts of benzaldehyde, the 0-substituted hydroxyylamine shown in Table 17 below was used, and the rest was exactly the same. The desired product was obtained by the reaction and post-treatment, each having the weight shown in Table 17. The infrared absorption spectrum and nuclear magnetic resonance spectrum of each product were obtained. The vectors are shown in Table 8 Table 1 7

Example 0-Substituted Hydroxylamine Yield Produced No. (Parts) Compound No.

Example 62

Synthesis of OCHCOOCHs

(o2) U Π3 In Example 20, 2- (2-methoxycarbonylethoxy) 1-4- (2-chloro-4-trimethylaminomethylphenoxy) Benzaldehyde Instead of 4.03 parts, 2- (1-methyl) Xicarborethoxy) 3.4 parts of 4- (4-chlorophenoxy) benzaldehyde were used, and the reaction and work-up were carried out in exactly the same manner to obtain 3.8 parts of the desired product. Infrared absorption spectrum and nuclear magnetic resonance of the compound The sounding spectrum is shown in Table 18 Example 6 3

C5

c h

Synthesis of

2— (Ί—Carboxyethoxy) 1-41 (2—Black mouth—4-trimethyl ro-methylphenoxy) Dissolve 0.41 part of benzaldehyde in 30 parts by volume of tetrahydrofuran and add 0 to the solution. —H: A mixture of 0.23 part of L-dihydroxylamine hydrochloride, 0.2 part of sodium carbonate and 2 parts by volume of water was added, and the mixture was stirred at room temperature for about 3 hours. The organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.The crude product was separated by silica gel column chromatography. 0.3 parts of the desired compound (63) were obtained, and the spectrum data of the compound are shown in Table 18. Example 64

Synthesis of OH

(64)

In Example 20, 2- (Ί-methoxycarbonylethoxy) 1-41 (2-chloro-1-4-trimethylfuromethylphenoxy) benzaldehyde 2-hydroxy-1-41 instead of 4.03 parts of benzaldehyde 2-Chloro-1-tetrafluoromethylphenoxy) Using 3.17 parts of benzaldehyde, the reaction and post-treatment were carried out in the same manner as described above to obtain 2.90 parts of the desired product. The nuclear magnetic resonance spectrum is shown in Table 18. Example 65

CF _3- <, '-0-, one "V f C Η

Ν Synthesis of O CH COO CH3

(65) Γΐ3 In Example 20, 2- (2-methoxycarbonylethoxy) 1-41 (2-chloro-1-4-methyltrimethoxyphenoxy) benzaldehyde 4. Instead of 03 parts, 2— (Ί-methoxy) Xicarbonyl ethoxy> 1-41 (3-chloro-5-trimethyl-methyl-2-pyridyl-hydroxy) Benzaldehyde 4.03 parts are used, and the reaction and post-treatment are performed in exactly the same way. 3.90 parts of the compound were obtained, and the infrared absorption spectrum and nuclear magnetic resonance spectrum of the compound are shown in Table 18.

εϊΙΝ 一 / IDlossdftgso /-

Table 1 8 (continued)

Compound Infrared absorption Nuclear magnetic resonance spectroscopy

Spectrum

NO. (Cm-i) (in CDCLs) δ (ppm)

(16) 3250 1.60 (3H) 7.20-7.67 (4H)

1750 2.27 (3H)

1595 3.87 (3H)

1320 4.70 (1H)

1130 6.37-6.57 (2H)

δ.97 (1Η)

(17) 1755 1.60 (3H) 6.97 (1H)

1595 2.27 (3H) 7.23-7.73 (3H)! 1320 3.70 (3H) j 1130 3.97 (3H)

4.73 (1H)

6.40-6.63 (2H)

(18) 1750 1.60 (3H) 7.27-7.60 (6H)

1595 3.70 (3H) 7.77-7.97 (2H) 1320 4.73 (1H) 8.63 (1H)

1125 5.23 (2H)

6.40-6.70 (2H)

7.03 (1H)

(19) 1590 1.40 (3H)

1320 3.95 (2H)

1125 6.27-6.63 (2H) | 1080 6.77-7.47 (7H)

7.63-7.98 (2H)

8.68 (1H)

(20) 1750 1.67 (3H) 8.03 (1H)

1590 3.73 (3H) 8.90 (1H)

1320 4.78 (1H)

1125 δ.47-6.73 (2Η) | 1080 7.03-7.63 (7H);

7.82 (1H);

Preparation example 1

1 part of the active compound of the present invention in a mixed solution of acetone and water

A solution was prepared by adding 2.6 parts of a nonionic surfactant (trade name: Solpol 2680) in addition to 5,000 parts (volume ratio 1: Ί). Preparation example 2

One part of the compound of the present invention, 8.7 parts of an equivalent mixture of talc and bentonite, and 0.3 part of an equivalent mixture of S0 LP0R 5060 (trade name) and S0 LP0R 800A (trade name) were pulverized and mixed well. This was used as the base of wettable powder. Test example Ί

The active compounds according to the invention were prepared according to Preparation Example 1 above. Plants were sown on soil and cultivated for 2-3 weeks after germination.

To this plant, a preparation containing the active compound of the present invention was applied so that the total amount of each active compound became a predetermined amount. Thereafter, cultivation was continued for 3 weeks without applying the preparation. Table 9 shows the results. Test example 2

Seeds of the plants to be evaluated are sown on the soil, treated on the second day after sowing as follows, and observed for 3 weeks for plant growth. Was. ,

In the chemical treatment method, a mixture containing the active compound of the present invention prepared according to Preparation Example 2 is suspended in water, and the active compound is uniformly applied to the soil surface after sowing so that the total amount of each active compound becomes a predetermined amount. After that, the cultivation was continued without applying the preparation. The results are shown in Table 110.

The alphabets shown in the plants column in Table 9 and Table 0 are the following plants.

a Me Hishiba

b Enokorogosa

c Severn sorghum

d akaza

e Hu

ΐ Vetch

g ichibi

h

i-year-old naomi

j soybean

k ゥ sorghum

837

76

Table 1 10

Θ

Compound Treated star 1

No. (Kg / ha) a b c e T Q n i 1——

J k rr

(2) L. Hi 4 3 2 5 cr

0 4 A

0 4 u u n r A

H.b 3 1 2 0 4 ά o cr

0 1 u U n r: r- c:

(11) 2, 0 D 0 0 0 0 0 0 0 u U υ. J 4 3 3 5 J ά 1

J 1 n u

(20) 2, 0 5 5 5 4 5 5 5 5 0 0

0.5 4 3 3 5 5 4 5 2 0 0

(21) 2.0 5 5 5 5 5 5 5 5 0 0

0.5 5 5 5 5 5 5 5 4 0 0

(26) 2.0 5 5 5 5 5 5 5 5 0 0

0.5 5 5 5 5 5 5 5 4 0 0

Test Examples 3 to 6 and Comparative Examples Ί to 2

A mixed solvent of water and acetone (volume ratio 1: 1, non-ionized) was prepared so that each of the oxime derivative and the Ν-phosphonomethylglycine derivative shown in Table 1Ί at a predetermined mixing ratio and in a predetermined treatment amount. Surfactant; trade name contained 0.05%> was dissolved in 16 parts by volume to prepare a spraying solution.

Plants were cultivated in a Darin house for 2-3 weeks after germination by sowing or rhizome transplantation in a plastic pot (diameter 10 cm) containing soil.

The herbicidal activity was examined by applying the above-mentioned preparation solution to this plant so that the total applied volume was 4 (00 cm ² ).

Table 11 shows the results.

The alphabets shown in the "Plant" column in Table 1 are the following plants. -ϋ Morning glory

m Ebisugusa

n American sika deer

0 Putaksa

p White-winged morning glory

q oats

r shibamugi

s dinubier

t texas honeycomb 1 1

Comparing the results of Test Examples 3 to 6 and Comparative Examples Ί to 2, the herbicidal composition of the present invention has a faster and faster onset of herbicidal activity as compared to the case where the N-phosphonomethyldaricin derivative is used alone. Excellent in nature.

When the N-phosphonomethyldaricin derivative is used alone, the herbicidal activity of broadleaf grasses such as morning glory and American stag is reduced, especially at low doses, and the activity is reduced even U days after the treatment. Either rarely indicated or insufficient.

On the other hand, the composition of the present invention, for example, the composition of Test Example 5 can kill all the weeds described in Table II in about one week. As in this example, the composition of the present invention is surprisingly improved in synergistic effects by applying a combination of the oxime derivative and the N-phosphonomethyldaricin derivative as a synergistic effect. We found that the expansion of the herbicidal skull became remarkable.

Claims

Sought

1. Below §Self-expression, 丄)

Y

XN-0-R ² (I)

main

Here, X and Y are the same or different and are each a hydrogen atom, a halogen atom, one C F3 or an alkyl group having 1 to 5 carbon atoms.

Ζ is —CH— or = Ν—.

R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ² is a hydrogen atom; a halogen atom, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms or 1 COR ⁴ (here, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms or

R ⁵

-; (Where R ⁵ and R ^S are a hydrogen atom or carbon number Ί

R ⁶

To 5 alkyl groups. 〉. } Aliphatic carbon hydrocarbon radical, saturated or unsaturated which may one carbon atoms which may have ~ 10 substituted; halogen atom, a hydroxyl group, one _{C F3 - 0 2, - CN} , an alkyl group having 1 to 5 carbon atoms , an alkoxy group Ί~5 carbon atoms, one C0R ^4, a halogen atom if Or a phenyl group optionally substituted by 1 C F3, or a halogen atom or a phenoxy group optionally substituted by 1 F 3, and the number of carbon atoms optionally substituted by

An aromatic hydrocarbon group having 6 to 20 atoms; or a halogen atom, -CF ₃ , an alkyl group having 1 to 5 carbon atoms, and optionally substituted with an alkoxy group having 1 to 5 carbon atoms, at least one nitrogen atom An aromatic heterocyclic group having 3 to 20 carbon atoms containing an atom;

R ³ is a hydrogen atom or a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having an alkoxy group or single C OR ⁴ carbon atoms but it may also be substituted with I～10.

A compound which is a oxime derivative represented by or a salt thereof when is a hydroxyl group.

2. A herbicidal composition comprising a compound of the formula (I) as a herbicidal component and a carrier and / or a surfactant.

3. The compound of formula (I) and the following formula (E)

0

R 21 P- CH2- N H CH2-COR 23 (I)

R 22 (Wherein, R21 and R22 are the same or different and is a ²⁴ one 0 H or a OR ^{respectively, R 2 3- OH, -OR 2} 4 or -. Is NR ^2a R ²⁶ wherein R ²⁴ is Ί carbon atoms Alkyl group, cyclohexyl group, haloalkyl group having 1 to 5 carbon atoms, alkenyl group or alkoxyalkyl group having 2 to 5 carbon atoms, haloalkoxyalkyl group, or alkoxyalkoxyalkyl group (wherein Alkoxy, haloalkoxy and alkyl have one to five carbon atoms.) And a phenoxy group, R ^2} and R ²⁶ are the same or different and are each a hydrogen atom, an alkyl group having 5 to 5 carbon atoms, and a carbon atom of And R ²⁶ are a morpholino group, a piperidino group or a alkenyl group having 2 to 5 carbon atoms, and R ²⁶ together with the nitrogen atom to which they are bonded. Can form a pyrrolidino group.

A herbicidal composition containing a ホスホ -phosphonomethylglycine derivative represented by the formula (I) or an acid addition salt or a salt thereof with a base as a herbicidal component, and further comprising a carrier and a surfactant or a surfactant.