JPH01197481A - Novel benzoxazines and utilization thereof as herbicide - Google Patents

Abstract

NEW MATERIAL:2-[4-Carbamoylmethyl-7-fluoro-2H-1,4-benzoxazin-3(4H)on-6-yl] -4,5,6,7-tetrahydro-2H-isoindole-1,3-dione. USE:A herbicide. PREPARATION:4-Carbamoylmethyl-7-fluoro-6-amino-2H-1,4-benzoxazin-3(4H) -one expressed by formula II is reacted with tetrahydrophthalic anhydride expressed by formula III to afford the aimed compound expressed by formula I. The starting raw material compound expressed by formula II may be produced by reducing 4-carbamoylmethyl-7-fluoro-6-nitro-2H-1,4-benzoxazin-3(4H)-one expressed by formula IV. Furthermore, the compound expressed by formula IV is a novel substance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel benzoxazines, their preparation and their use as herbicides, and intermediates of the compounds.

The present inventors have now succeeded in synthesizing a benzoxazine represented by the following formula (1).

λ-[≠-carb7ylmethyl-7-fluoro-2H-/, ≠-benzoxazin-3(H)one-6-yl]-μ, j, Otsu, 7-titrahydro 2H, represented by
-isoindole-/3-dione.

The benzoxazines of formula (1) of the present invention can be synthesized, for example, by the following method.

Production method 1) Gucarbamoylmethyl-7-fluoro-
Otsu-amino-, 2H-/, Hiro-benzoxazine-3 (
4tH)-one and tetrahydrophthalic anhydride are reacted. A method for producing benzoxazines of formula (I).

The benzoxazines of formula (1) of the present invention have herbicidal activity, particularly as a herbicide for upland fields.

Furthermore, the benzoxazines of the formula (1) of the present invention are:
Special request Showa 1. /-210726, herbicidal no [≠-cyanomethyl-7-fluoro2] represented by the following formula:
H-/,≠-benzoxazine-3(lItH)on-6-yl]-μ,j,g,7-titrahydro2H-
It is useful as a new intermediate for the production of isoindole-/3-dione. (See reference side below) The specific reaction formula for the production method a) is shown below.

In production method a), the compound of formula (I) is as shown in the Examples below, production method b); ,≠-benzoxazine-J(l
Obtained by reducing ItH)-one.

In this reaction, catalytic reduction using a catalytic amount of palladium-carbon is convenient. Further, a general reduction method typified by the action of iron in the presence of an acid such as acetic acid can also be applied.

The compound of the above formula (II[) in production method b) is a new compound, as shown in the examples below, and production method c); Hiro-carpamoylmethyl-7-fluoro, 2H- /, 11-benzoxazin-3(gH)-one is reacted with M nitric acid in the presence of sulfuric acid, or production method d): Guccarboxymethyl-twofluoro-ot-nidro represented by the formula: jH-/, l1t-benzoxazine-3 (
By reacting H)-one with thionyl chloride and then reacting the product with ammonia,
can get.

Manufacturing method C) is SFneOrga Chenl, (Synthetic Organic Chemistry), 7≠7~741
? The nitration reaction can be carried out according to the nitration reaction described in Page or Miirotsuno Patent Publication No. I7O, IRI7.

Production method d) can be carried out in accordance with production method g) and production method .) described below.

The compound of the above formula (■) in the production method C) is a new compound, for example, the compound represented by the formula: ≠-chlorocarbonylmethyl-7-fluoro-,2H-/,4t-benzo Oxazine-J (lIA
H)-one and ammonia are reacted, or the preparation method f);
Reacting LH)-one with ammonia,
can get.

The compound of the above formula (vI) in production method e) is a new compound, as shown in the examples below, and production method g); Fluoro,
2H-/,! Obtained by reacting -benzoxazin-3(gH)-one with thionyl chloride.

When synthesizing the compound of the formula (rl/) in the above production method C), when carrying out the above production method g) and then the production method), the compound of the formula (■) as shown in the examples below may be used. K without separating the compound of formula (■) and thionyl chloride, and then reacting with ammonia.
Yes, it's easy to get.

Manufacturing method f) is 5ynthetic Organic C
h@m1stry (synthetic organic chemistry), sts~j Otori page, RIB, Wag
ner, H, D* Written by Zook, John Wile
As described in y & 5ons Ine, /ri 1953.

can be done.

Production method g) The compound of the above formula (2) in K is a new compound, as shown in the examples below, Production method h); ≠-ethoxycargonylmethyl-7 of the above formula (Vll)
-fluoro-2H-/,≠-benzoxazine-3(≠
It is obtained by hydrolyzing H)-one.

The compound of formula (■) in production method f) and production method h) is as shown in the Examples below, and production method l); 7-[≠-(ethoxycargenyl methyl )
-2H-≠-benzoxazin-3(4tH)one]
Ciazonium tetrafluoro? Rate, Organi
c R@actions, Volume 5, / Tata~201. 5chi@ma listed on page
It can be obtained by thermal decomposition according to the nn (Ziemann) reaction.

The compound of the above formula (■) in production method i) K is as shown in the examples below, production method j): 7-amino-hiro-ethoxycar represented by formula: %formula% is nylmethyl-2H-/, ≠-Benzoxazine-3 (IItH)
It is obtained by reacting -one with sodium nitrite and tetrafluoroboric acid.

The compound (X) above in production method j) K is as shown in the reference examples below, production method k); Formula: CH2COOC2H5 ■ It is easily obtained by reducing oxazin-3(H)-one.

The compound of the above formula (Xl) is as shown in the reference examples below, and the production method t); 7-nitro-,2H-/, l/l-benzoxazin-3(H)-one represented by the formula: and ethyl ester of α-haloacetic acid, preferably ethyl bromoacetate, or, alternatively, by reacting trophenol with ethyl bromoacetate, or by reacting trophenol and ethyl bromoacetate, It can be easily obtained by reaction.

The above manufacturing method t) is published in Pharmaceutical Journal, Volume 6 (A 3) 1.2
This can be done according to the method described on pages 05' to 2/3, /ri Ootoshi.

Process m) can be carried out by reacting 2 equivalents of ethyl bromoacetate with /equivalents of the compound of formula (X [[I)] in the presence of an excess amount of base, such as potassium carbonate. .

The compound of formula (to) in production method t) is 5ynth@5
is (synthesis), /ri♂λ year, ygt~ri♂ As described on page 7,! -Amino-yom; Obtained from trophenol.

The compound of formula (V) in the above production method d) is a new compound, as shown in the Examples below. 2H-/, 4L-benzoxacin-J(4tH)-one, or production method o): ≠-Caldexymethyl-7-fluoro 2H-/, goobenzo of the formula (Vl) It is obtained by reacting oxazin-3(riH)-one with concentrated nitric acid in the presence of sulfuric acid.

The compound of the above formula (X[V) in production method n) K is a new compound, production method p); ≠-ethoxycal of the above formula (■)? Nylmethyl-7-fluoro-2H-/, Hiro-penzoxazine-3CIIH
)-one and concentrated nitric acid in the presence of sulfuric acid.

Furthermore, on the other hand, Hiro-carpamoylmethyl-7-fluoro4-6-nitro-2H-/, ≠-benzoxazin-3(μH)-one of the formula (I[[), and the formula (IY)
≠-carbamoylmethyl-7-fluoro-,2H-/
, 4t-benzoxazin-3(4tH)-one are also intermediates in another process for producing the herbicidal compound of formula (E). That is, the herbicidal compound of the formula (E) can alternatively be used as a herbicidal compound represented by the formula: O-amino-≠-cyanomethyl-7-fluoro-,2H-/,4L-benzo Oxazine-J (1)
It is obtained by reacting -one with tetrahydrophthalic anhydride.

The compound of the above formula (XV) was prepared as of the filing date of the present application and is a new compound, as shown in the Examples below, and the production method q); , I/L-benzoxazine-3 (≠
It is obtained by reducing H)-one.

Manufacturing method q) is B@riehte (Perichte), volume 77,
This can be carried out by the reduction method using iron and acetic acid described on page 373.

The compound of the above formula (XA) in the production method q) is a new compound, as shown in the Examples below, and the compound of the formula (I[[) of ≠-carbamoylmethyl-7-fluoro- 6-nitro-2H-/, 4t-benzoxazine-3
(≠H)-one and thionyl chloride in a catalytic amount of N,
1 reaction in the presence of N-dimethylformamide, or production method 8): Guccianomethyl-7-fluoro-2H- represented by the formula:
/, 'l-benzoxazin-3(μH)-one,
It can be obtained by reacting concentrated nitric acid and acetic anhydride in the presence of a catalytic amount of sulfuric acid.

The compound of the above formula (expletive) in production method 1) is a new compound, as shown in the Examples below.Production method t); Hiro-carpamoylmethyl-7-fluoro 2 of the above formula (IV)
H-/, 4t-benzoxazine-j (l/LH)
-one and thionyl chloride in a catalytic amount of N,N-
It can be obtained by reaction in the presence of dimethylformamide.

The method for converting the amide form into a nitrile (cyanide form) by dehydration in the above production method r) and production method t) is as follows:
mistry of IMIDOYL HALIDES
(Dechemistry Iotsimidoil Harai) e), 5
Pages 5-705, by H0Ulrteh, Pl@num
One can do so as described by Pr@ms, New York/Re6jr.

When carrying out the above production method a), an organic acid such as acetic acid or propionic acid can be used as a diluent, and the process can be carried out between room temperature and the boiling point of the organic acid used.

Further, although it is desirable to carry out one reaction under normal pressure, it is also possible to operate under increased pressure or reduced pressure.

In carrying out production method a), for example, tetrahydrophthalic anhydride is added to 1 mol of the compound of formula (n).

The target compound of formula (1) can be obtained by reacting about 7 mol to about 42 mol in the presence of the above diluent.

When carrying out the above manufacturing method b), as a suitable diluent,
Mention may be made of all inert organic solvents.

Examples of such diluents include water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene. , xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, chlorobenzene: others, ether M Example t
C, diethyl ether, methyl ethyl ether, di 1s.

-Clopyl ether, dibutyl ether, dioxane,
Tetrahydrofuran; Alcohols such as methanol, ethanol, 1so-7'lonomol; Esters such as ethyl acetate, amyl acetate; Acid amides such as:
Dimethylformamide, dimethylacetamide; sulfones, sulfoxides such as dimethylsulfoxide, sulfolane; and organic acids such as acetic acid.

Process b) can be carried out within a substantially wide temperature range. Generally, it can be carried out between about θ and about /60°C, preferably between about 20 and about 100°C. The reaction is preferably carried out under normal pressure, but it can also be operated under elevated or reduced pressure.

When carrying out the above production methods c), o) and p), suitable diluents include sulfuric acid, acetic acid or acetic anhydride, and generally at about -20 to about 30°C,
Preferably, it can be carried out at a temperature between about 0 and about 20°C.

When carrying out the above processes d) and e) and g], all inert organic solvents may be mentioned as suitable diluents.

Examples of such diluents include water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene. , methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, chlorobenzene; other examples of ethers, t
C, C-Z thyl ether, methyl ethyl ether, di-
18O-globyl ether, dibutyl ether, dioxane, tetrahydro7rane; ketones such as acetone,
Methyl ethyl ketone, methyl-1io-propyl ketone, methyl-1so-butyl ketone; Nitriles e.g.
Acetonitrile! Ropionitrile, acrylonitrile; alcohols such as methanol; esters such as ethyl acetate, amyl acetate; acid amides such as dimethylformamide, dimethylacetamide; sulfones, sulfonates such as dimethylsulfoxide, sulfolane; and bases such as pyridine, etc. can be given.

Processes d), .) 1g) can be carried out within a substantially wide temperature range. Generally, about -20 to about /
J-0°C, preferably about 0 to about io.

Can be carried out between ℃. Further, although the reaction is preferably carried out under normal pressure, it can also be operated under increased pressure or reduced pressure.

In carrying out the above process f), as a suitable diluent,
Mention may be made of all inert organic solvents.

Examples of such diluents include water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene. , chlorobenzene; In addition, ethers such as diethyl ether, methyl ethyl ether, di-1ao-7" lobil ether, dibutyl ether, dioxane, tetrahedron 1:17; ketones such as acetone, methyl ethyl ketone, methyl-1io-propyl Ketone, methyl-1
so-butyl ketone; alcohol examples c, methanol, ethanol, 1so-7' lovanol, butanol,
Examples include ethylene glycol.

Process f) can be carried out within a substantially wide temperature range. Generally, it can be carried out at a temperature between about
Although the reaction can be carried out under normal pressure, operation under elevated pressure is preferred.

When carrying out the abovementioned processes h) and n), all inert organic solvents may be mentioned as suitable diluents.

Examples of such diluents include water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as hexanes, cyclohexane, petroleum ether, ligroin, benzene, toluene. , xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, chlorobenzene; other examples of ethers, t
C, C Z thyl ether, methyl ethyl ether, C 1s.

-Clopyl ether, dibutyl ether, dioxane,
Tetrahydro7ran; Ketones such as atentone, methyl ethyl ketone, methyl O-propyl ketone, methyl O-butyl ketone; Nidols such as acetonitrile, gropiotrile, acrylonitrile; Alcohols such as methanol, Ethanol, 1io-7
Examples include lovanol, butanol, ethylene glycol; acid amides such as dimethylformamide, dimethylacetamide; sulfones, sulfonamides such as dimethylsulfoxide, sulfolane; and bases such as pyridine.

Processes h), n) can be carried out within a substantially wide temperature range. Generally, it can be carried out at a temperature of about -20 to about 70°C, preferably about -10 to about 100°C. (9) Although the reaction is preferably carried out under normal pressure, it can also be operated under elevated or reduced pressure.

When carrying out the above production method 1), suitable diluents include all inert organic solvents having a boiling point higher than the thermal decomposition point (approximately /30° C.) of formula (D()).

Examples of such diluents include aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated).
Examples include petroleum ether, xylene, and chlorobenzene.

Process 1) can be carried out within a substantially wide temperature range. Generally, it can be carried out at a temperature of about /2t to about /0°C, preferably about 730 to about /≠θ°C. Further, although the reaction is preferably carried out under normal pressure, it can also be operated under reduced pressure.

When carrying out the above manufacturing method j), as a suitable diluent,
Examples include water, dilute hydrochloric acid, concentrated hydrochloric acid, dilute sulfuric acid, and fluoroboric acid.

Process j) can be carried out within a substantially wide temperature range. Generally, it can be carried out at a temperature of about -30°C to about 30°C, preferably between about -20°C and about 20°C. Yes,
The reaction is preferably carried out under normal pressure, but it can also be operated under elevated or reduced pressure.

When carrying out the above manufacturing method q), as a suitable diluent,
Water; alcohols such as methanol, ethanol, 1
Mention may be made of so-f lobanol, butanol, ethylene glycol; esters such as ethyl acetate, amyl acetate; and organic acids such as acetic acid.

Process q) can be carried out within a substantially wide temperature range. Generally, from about 0 to about 7. ! It can be carried out at 0°C, preferably between about 30 and about 0°C. Further, although the reaction is preferably carried out under normal pressure, it can also be operated under increased pressure or reduced pressure.

When carrying out the above processes r) and ri, all inert organic solvents may be mentioned as suitable diluents.

Examples of such diluents include aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated)
For example, hexanes, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, tetraroform, carbon tetrachloride, ethylene chloride, chlorobenzene; other examples of ethers, t t
f, sea 1 g.

-propyl ether, diptyle ether, dioxane;
Nitriles such as acetonitrile, probionitrile; esters such as ethyl acetate, amyl acetate; acid amides such as dimethylformamide, dimethylacetamide; sulfones, sulfoxides such as dimethylsulfoxide, sulfolane; and bases such as pyridine. Can be done.

Process r) + t) can be carried out within a substantially wide temperature range. Generally, about 60 to about 200
℃, preferably about rO to about /! It can be carried out between 0°C. Further, although the reaction is preferably carried out under normal pressure, it can also be operated under increased pressure or reduced pressure.

When carrying out the above manufacturing method 8), as a suitable diluent,
Mention may be made of all inert organic solvents.

Examples of such diluents include aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated)
For example, hexane, cyclohexane, petroleum ether, ligroin, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride! ', Chlorobenzene, nitrobenzene; Sono et al., Ethers such as diethyl ether, methyl ethyl ether, ? -1so-7'robyl ether, dibutyl ether, dioxane, tetrahydro7rane; and organic acids such as acetic acid, gropionic acid and the like.

Process S) can be carried out within a substantially wide temperature range. Generally, it can be carried out at a temperature of about -20°C to about 30°C, preferably between about -10°C and about 0°C. Further, although the reaction is preferably carried out under normal pressure, it can also be operated under increased pressure or reduced pressure.

When carrying out production method (-), hydrolysis of the cyano group occurs extremely quickly due to the action of the frequently used mixed acid.
Acetyl nitrate can be used to solve such problems.

In addition, 7-nitro 2H-/,≠-benzoxazin-j(41:H)-one of the formula (6) is used as a starting material.

The compounds of formula (-) are generally known as alkylating agents.

Formula % Formula % () In the formula, 2 represents halodane or -0802-R1, where RI represents alkyl or aryl which may optionally have a substituent, and R represents a hydrogen atom or methyl. g/
ij Reacting an aromatic heterocyclic compound such as alkyl, alkylthioalkyl, cycloalkyl or pyridyl, followed by the reduction of the above process k) and process j)
And through the same operation as 1), further manufacturing method C) or
Using the tl@) method, a nitro compound represented by the formula: where R and R' are the same as above was prepared, and further the compound of the formula (5
) are subjected to conventional reduction reactions 1, e.g. production method b) and
) by reducing according to the general procedure according to the formula: where R and R/ are the same as above.

It is also possible to obtain an aponoform compound represented by

The compounds of formula (1) of the present invention can be used as herbicides.

A weed is broadly defined as any plant that grows in an undesirable location.

The compounds of the invention act as non-selective or selective herbicides depending on the concentration used.

The active compounds according to the invention can be used, for example, with the following plants:

Genus of dicotyledonous weeds: Sinapig, L@pidium, Ga 11 um, St@llar
1m), Chenopodium
), Urticm, Senecro, Amaranthus, Portulacm, Xant
hium), morning glory (Ipomoaa), willow willow (Polygonum), butafusa (Ambroslm)
), Clrsium, Sonchua, Rorippm,
Lamlum, Veronicm, D.
atura), Viola, Galeopsls, Papav
er), Yaguru-tdfri (C@ntaur@a),
Gal 1nsoga, Rotalm, Azena (Llndarnim), etc.

Genus of dicotyledonous plants: Gosyplum, Glyalne, Chard/sugar beet (B@ta), Carrot (Dueus), 'fnr
Phaseolus, Japanese pea (PLsun), eggplant and potato (Solanum)
), Linum, sweet potato morning glory (Ipomoe), Viei
a), Tobacco (Nicotimna),) Mado (Ly)
cop@rsion), ten bean (Araahi
g) %Brassica, Chinese cabbage, Kapra cabbage (Br
assicm), LacLuaa
, Cucumber melon (Cucumis), Kagocha (
etc. 0 Genus of monocot weeds: Echinochloa, Echinochloa, Sstartm, Panl
eum), Digltarim, Phleum, Phleum, Phleum (Pea), FesLuca, FesLuca, Phleum x-
(Eleualne), Lolium, Bromus 7, Oat, Oat (Avena), Cyperus papyrus, Cyperus japonica, Cyp@rus
), Sorghum, A
gropyron), Monochorlm (Monochorlm)
), Tentsuki (Fimbristylis), Omodaka Kuwai (Sagtttarim), Harii Kurogwai (Eleoeharlm), Hotarui Ukyag 2
・Futoi (Sc 1rpus), Sparrowfly (Pas
palum), Platypus (Isehasmum), NukaN (Agrostim), and Sparrowfly (Al).
opscurus ), Gyōgishino (Cynodo)
n) etc.

Genus of monocotyledonous plants: rice (Oryza), corn/hopcorn (Zea), wheat (Triticu)
m), barley (Hordeum), oat (Avena), rye (Secale), sorghum (Sorghum), millet (Panlcum), sugarcane association Waseopana (Sa)
caharum), /4' Ananaa
, Asparagus, Leek-leek (
Allium), etc.

The use of the compounds of the present invention is not limited to the above-mentioned plants, but can be applied to other plants as well. Also,
Depending on the concentration used, the active compounds can control weeds non-selectively and can be used, for example, on industrial sites such as factories, railway tracks, roads and on plantations as well as non-plantation areas.

Furthermore, the active compounds can be used for weed control in perennial plant cultivation, for example in afforestation, ornamental plantations, orchards, button orchards, citrus orchards, nut orchards, banana plantations, coffee plantations, It can be applied to tea farms, rubber farms, Guinea oil palm farms, cocoa farms, small orchards and hop farms, and for selective weed control in annual plant cultivation.

The active compounds according to the invention can be put into customary pharmaceutical forms. and such forms include solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active compound infiltration - natural and synthetic, microcapsules, seed coatings, preparations with combustion devices. (e.g. combustion devices such as fumigation and fume cartridges, cans and coils);
d m1st), warm mist (warm m1s
t) ).

These formulations can be manufactured by known methods.

Such methods include, for example, combining the active compound with a vehicle, i.e. a liquid diluent; a liquefied gas diluent; a solid diluent or a carrier, optionally a surfactant, i.e. an emulsifier and/or a dispersant and/or a foam. This is done by using a forming agent and mixing.

When using water as a developing agent, organic solvents can also be used as co-solvents, for example.

Liquid diluents or carriers generally include aromatic hydrocarbons (e.g. xylene, toluene, alkylnaphthalenes, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (
Examples include chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons (e.g., cyclohexane, etc., paraffins (e.g., mineral oil fractions, etc.)), alcohols (e.g., butanol, glycols, and their , esters, etc.), ketones (eg acetone, methyl ethyl ketone, methyl isoptyl lactone or cyclohexanone, etc.), strongly polar solvents (eg dimethylformamide, dimethyl sulfoxide, etc.) and water.

The liquefied gas diluent or carrier is a gas at normal temperature and pressure, and examples thereof include butane, propane, nitrogen gas,
Mention may be made of aerosol propellants such as carbon dioxide and helodenated hydrocarbons.

Solid diluents include soil natural minerals (e.g. kaolin, clay, melk, chalk, quartz, attapulgite,
montmorillonite or diatomaceous earth, etc.), soil synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.).

Solid carriers for granules include crushed and fractionated rocks (e.g. calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules of inorganic and organic powders, and organic substances (e.g. sawdust, Examples include fine grains of coconut (cobs of coconut, cobs of corn, stalks of tobacco, etc.).

Emulsifiers and/or foaming agents include nonionic and anionic emulsifiers [e.g., polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (e.g., alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfones); salts, etc.)] and albumin hydrolysis products.

As the dispersion liquid, for example, lignin sulfide waste liquid,
and includes methylcellulose.

Fixing agents can also be used in formulations (powders, granules, emulsions), and such fixing agents include Cal? Oxymethylcellulose and natural and synthetic? Rimmer (side light, Arabic 0)
polyvinyl alcohol, polyvinyl acetate, etc.).

Coloring agents may also be used, including inorganic pigments such as iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and also iron, Mention may be made of trace elements such as manganese, boron, copper, cobalt, molybdenum, their salts of zinc. .

The formulation generally contains 0.0% of the active ingredient. / ~ 5% by weight, preferably O1! -O can be contained in excess of the weight.

The active compounds according to the invention can be used on their own or in their formulation form for weed control, and also as a mixture with known herbicides; such mixtures can be used in the final formulation form. Or tank mix is possible.

When using the active compounds of the invention, they can be used directly as such, or in the form of formulations such as spray preparations, emulsions, suspensions, powders, pastes and granules, or prepared in further dilutions. It can be used in the following manner.

The active compounds can be used by watering, spraying, powdering, etc.

The active compounds of the invention can be used both before and after germination of plants. They can also be incorporated into the soil before sowing.

The concentration of active compound can vary within a substantial range. It differs fundamentally depending on the nature of the desired effect. When used as a herbicide, the concentration used may be e.g.
Examples include oos to about th, preferably 0.00/ to about 3Kf.

Next, the content of the present invention will be specifically explained with reference to Examples and Reference Examples, but the present invention should not be limited thereto.

Synthesis Examples Examples/
A mixture of 70% palladium-carbon C0,3P) is catalytically reduced at normal pressure. After absorption of hydrogen gas is completed, it is filtered, the solvent is distilled off under reduced pressure, and acetic acid (J) is added to the residue.
olllj) and tetrahydrophthalic anhydride (/2) were added, and the mixture was heated under reflux for 3 hours. After the reaction is completed, the solvent is distilled off under reduced pressure, and tetrahydro7rane Cl00111) is added to the residue, which is filtered while hot, and then the filtrate is distilled under reduced pressure to obtain a solid residue. Wash this with toluene, add ethanol (/Od) and activated carbon (0,1'), heat for 7 minutes, and filter. After concentrating the furnace liquid and cooling it to room temperature,
~2-[Hiro-carpamoylmethyl-7-fluoro, 2H-/, 4-benzoxazine-] for washing with hexane
3(≠H)-one-6-yl]-μ,! , O, 7-titrahydro 2H-inoindole-/, 3-dione (O
6ta? ).

mp, 3-2 g in λ℃ Example λ CH2CONH2 ≠-carbamoylmethyl-7-fluoro-2H-/, ≠
-benzoxazine-J(4LH)-one (lA11t
Cool ♂i) to 0-3°C, add to concentrated sulfuric acid, and stir thoroughly. To this, 9% nitric acid (B≠2F) was added dropwise at O-t°C. After stirring for 7 hours, the solid obtained is poured into ice water, washed with water, and dried.
≠-benzoxazine-J(!H)-one (440P
) is obtained.

mp, 220-. 2.2A'C Example 3 ≠-carboxymethyl-7-fluoro-2H-/, 4t
-benzoxazin-3(4LH)-one (2,1-P
), chloroform (/15') and hytheonyl chloride (3, Otsu?). Add 3 drops of pyridine and heat to reflux in the evening. After concentrating the solvent, it is mixed with toluene (j0a/), and after distilling off the solvent, the residue is dissolved in toluay (AOrtl), and ammonia gas is introduced at 10 to 20°C. After saturation with ammonia, stir at room temperature for 7 hours, remove solids,
Wash in order of toluene, sodium bicarbonate aqueous solution, and water.
When dried, the desired ≠-carbamoylmethyl-7-fluoro-2H-/, lI-benzoxazine-3 (≠H)
-on (215') is obtained.

mp-, 2/, 2~. 2/4”C Example ≠ CH2CONH2 ≠-ethoxycarbonylmethyl-7-fluoro-,2H
-/+4'-pe/dioxazine-J(lAH)-one (
/, ,i! 7p), ethanol C20111)
and 2f% ammonia water (CHOP) were refluxed at room temperature for λ hours, and then for 3 hours. After concentrating the solvent, it is mixed with water, washed several times with water and ethanol, and recondensed from methyl imbutyl ketone to obtain the desired Hiro-carpamoyl methyl-7-
Fluoro 2H-/,'! -benzoxazine-3(t
AH)-one (0, hirozy-) is obtained.

mp, 2/1 pJ-2/litre °C Example l CH2CoOH ≠-Ethoxycarbonylmethyl-7-fluoro-2H-
/, lA-benzoxazin-3(H)-one (3,
Sodium hydroxide (0,7P) and water (/(717)) are added to a mixture of 71i') and ethanol C,20Lt) and heated under reflux for 5 hours. After the reaction, the solvent is concentrated and dissolved in water (jOd). , washed with methyl isobutyl,
The aqueous layer is acidified with hydrochloric acid, extracted with methyl isobutyl ketone, and dried over anhydrous sodium sulfate. After distilling off the solvent, it is mixed with a mixed solvent of toluene-hexane (/:j), washed several times with n-hexane, and the desired amount of carboxymethyl-7-fluoro-2H-/, goobenzoxazine is obtained. −
3(11tH)-one C3,2P) is obtained.

mp, /♂3-7r Hiro℃ Example 6 ≠-Ethoxycardenylmethyl-7-fluoro-6-nitro-2H-/, 4t-benzoxazine-3 (lAH
)-on (YoriotP) and 79 μm dioxane (jOm
), add sodium hydroxide (o, ri?) and water (,
20 IJ) and stirred at room temperature for 7 days.

After distilling off the solvent, it is mixed with water (Cl0011) and filtered.

Next, solution F is acidified with hydrochloric acid and extracted with methyl in butyl ketone (iroy). After washing with water, drying with anhydrous sodium sulfate and distilling off the common solvent, the desired H-carpoxymethyl-7-fluoro-nidrow, 2H-/, 4I-
Benzoxazin-3(≠H)-one (4', f?
) is obtained.

mp, /77~/d3℃ Example 7 CH2C00C2H5 ≠-Ethoxylic? Nylmethyl-7-fluoro-2H-
/,≠-benzoxazin-3(≠H)-one C209
-) is added to concentrated sulfuric acid ot'c. After thorough stirring (about 70 minutes), 7.5 nitric acid (yo≠5') was added dropwise. After stirring at 0-t°C for 2.3" hours, pour into ice water and collect the resulting solid. Wash thoroughly with water until the washings show no acidity, dry, and reconsolidate from ethanol to obtain the desired product. ≠-Ethoxycargenylmethyl-7-fluoro-
Nitro 2H-/, ≠-benzoxazine-3 (4tH
)-on C2/S') is obtained.

mp, 7ri~♂/℃ Example? 7-(≠-ethoxyl is nylmethyl-2H-/, ≠-
Benzoxazine-3(4tH)-o/]diazoniumtetrafluoro(J,41S4)t'/30~
Heat to /33°C for approximately 5 minutes until gas evolution ceases. The reaction product was mixed with toluene (sol) and evaporated to dryness under reduced pressure. The residue was mixed with ethanol (100 N) and treated with activated carbon. When reconsolidating Z/li') from ethanol-hexane, the desired Hiroshi-ethoxycarbunylmethyl-
Two fluoro-, 2H-/, 1IA-benzoxazin-3(11tH)-one (0,65') is obtained.

rnp, 90~9/, 3; °C Add 36% hydrochloric acid (241) to water C, 200M1),
Cooled to 10°C, 7-amino-≠-ethoxycargenylmethyl-2H-/,'l-benzoxazine-3 (4Z
Add H)-one (,20,,2P) and stir. To this, sodium nitrite (?) dissolved in water (jOd) was added dropwise at O-t℃, and after 30 minutes, ≠2% tetrafluoroboric acid (,2j5') was added dropwise to the solution. After stirring for 7 hours in 'c, pour out the target and add cold water! After washing with 0- twice and air drying, the desired 7-[≠-ethoxycargonylmethyl-2H-/,'A-benzoxacin-3(≠H)-onfudiazoniumtetrafluorobole) (,2, 2P
) is obtained.

mp, /2~/30°C (decomposition) Reference example/ ≠-Ethoxylgonylmethyl-7-nitro-2H-7
,≠-benzoxazin-3(lIlH)-one (30
5'), a mixture of 10% palladium-carbon (jl) and 10% palladium-carbon (/joy) was charged into an autoclave,
Kg/cm” hydrogen pressure and 10 to 70°C,
Catalytic reduction, addition of tetrahydrofuran, filtration, F
The liquid is distilled under reduced pressure, and the resulting solid is reconsolidated from ethanol to obtain the desired 7-amino-≠-ethoxycargenylmethyl-, 2H-/, 4t-benzoxazine-3 (4'H
)-on C, 20'! −) is obtained.

mp-136~737°C Reference Example I CH2COOC2H5 7-nitro-,2H-/, Hiro-penzoxadi/-3(
l,tH)-one (/ZIAP), potassium carbonate (/Yoko2) and acetonitrile (100I, 117L) at 30-' AO °C, ethyl bromoacetate (/F, ≠y
-) was added dropwise and heated under reflux for 3 hours. After the reaction is completed, it is filtered, the furnace liquid is distilled, and the obtained solid is mixed with toluene-hexane/
The desired ≠-ethoxyrudenylmethyl-7-nitro, 2H-/,4'-benzoxazine-
3(≠H)-on C, 20? ) is obtained.

mp, /20j~/,2/,! i°C Reference Example 3 2-amino-yo-nitrophenol (3o-jli'),
To a mixture of potassium carbonate (10A, 1A54), N,N-dimethylformamide (iooy>, 30-O
Ethyl bromoacetate (21) is added dropwise at °C.

After continuing stirring at 700~/10°C for 6 hours, it is cooled and poured into ice water (sooy). Extract twice with toluene (300g), combine the extracts, water,! After washing with an aqueous potassium pentahydroxide solution and water in order, and drying over anhydrous sodium sulfate, the solvent was distilled off. The residue was recrystallized from toluene-hexane to give the desired Hiro-ethoxycargenylmethyl-7-nitro, 2H
−/, ≠-benzoxatur 3(II-H)-one (
J□P) is obtained. Distill the mother liquor and reconstitute it from ethanol to obtain additional target material/,3? is obtained.

rflp, /, 2θ, i, zi, sc In the above reference example 3, the washing solution with 5% potassium hydroxide aqueous solution was acidified with concentrated hydrochloric acid, the solvent was distilled off, and the solid was collected in a furnace. After washing with water, reconsolidation from ethanol yields 7-nitro-,2H-/,1A-benzoxazin-3(4LH)-one (1A/P) of the formula (X[l).

Example 10 ≠-carbamoylmethyl-7-fluoro-6-nitro 2H-/, IA-benzoxanone-3(11,H)-
on (/,≠1), thionyl chloride C1,2F),
Add 2 drops of N,N-dimethylformamide to a mixture of toluene (20m) and stir at 100-/10°C for 6 hours. After cooling, methyl isobutyl ketone (3001Lt
), water, saturated hydrogen carbonate) IJum aqueous solution,
Wash with water and saturated saline in that order, and dry with anhydrous sodium sulfate. After distilling off the solvent, toluene (300!L/
) and activated carbon (o, jl), heat for 7 minutes, and filter while hot. After standing overnight at room temperature, the resulting crystals are separated and dried to yield the desired ≠-cyanomethyl-7-fluoro-nitro-2H-/, ≠-benzoxazin-3(≠H)-one (0,641). is obtained. The residue obtained by distilling the mother liquor is recondensed from a minimum amount of toluene,
An additional amount (O, JP) is obtained.

mp, /2~200°C By TLC method using a silica dull plate [developing solvent: mixed solvent consisting of tetrahydrofuran (10iu), toluene (J (7m) and acetic acid (/d)]), the following Examples// It is confirmed that the substance is the same as that obtained from.

Example // Acetic anhydride (/ /, 311) at 0 °C, hydrogen% nitric acid <
0.7 IP) was added dropwise. Next, a few drops of concentrated sulfuric acid are added as a catalyst, and stirring is continued for a while at 0°C.

This was followed by Hiro-cyanomethyl-7-fluoro-2H-/, Hiro-benzoxanone-J(II-H)-one (,2,O
Add y-) little by little and continue stirring at 0°C for 30 minutes. To this, sodium hydroxide (t
A solution consisting of '05') and water (f, rj!7) is added dropwise at 0°C to neutralize the reaction solution. Extracted with methyl isobutyl ketone, washed the extract with water and brine, dried over anhydrous sodium sulfate, and distilled off the solvent to obtain the desired ≠-cyanmethyl-7-fluoro-nitro, 2H-/,
4'-benzoxanone-3(≠H)-one <2.32
2) is obtained.

mp, 20≠~, 20℃ Example 7.2 ≠-carbamoylmethyl-7-fluoro-. 2H-/,
4L-Benzoxazin-3(≠H)-one (22≠y
-), toluene (,20t/), theonyl chloride (
,2,4'5') and N,N-dimethylformamide (
3 drops) is stirred at 0-700°C for 2 hours.

The solvent was distilled off, methyl isobutyl ketone <ioow) was added, the resulting mixed solution was filtered, the filtrate was washed with water and hydrogen carbonate in that order, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. When distilled off, the desired ≠-cyanomethyl-7-fluoro-,! H-/, ≠-benzoxazin-3(≠H)-one (7,7≠P) is obtained.

mp, ///~//3℃ Example/3 Ethanol (/JHl), acetic acid (/P), water C, 231
tt) and iron (31) is stirred at ♂0°C. This was added to ≠-kucyanomethyl-f-fluoro-6 ditro2H-/,4L-benzoxazine-J (4LI(
)-one (,2l-154) is added little by little and stirring is continued until gas evolution stops. The reaction solution was filtered, and the p solution was extracted with ethyl acetate. Meanwhile, the residue was extracted several times with ethyl acetate. The ethyl acetate extracts were combined, washed with brine and an aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain the desired monoamino≠-cyanmethyl-7-fluoro-2H-/, 4L. -benzoxazin-3(≠H)-one (/, 7754) is obtained.

mp, 763-767°C Reference example≠ [Production example of herbicidal compound formula (E)] υ λ- [≠-carbamoylmethyl-7-fluoro-2H-
/, Hiro-benzoxazin-3(4tH)-one-6-
yl]-≠l j l, 7-tetrahydro-2H-ynindole-/, 3-dioy ((7,j5'),)luene C30W and thionyl chloride (0,25')
Add N,N-dimethylformamide (3 drops) to the mixture and heat under reflux for 3 hours. After concentrating the solvent, toluene (jOd) was added, mixed well, and the toluene was distilled off.
When the obtained solid is reconsolidated from ethanol, the desired 2-
[≠-cyanmethyl-7-fluoro-, 2H-/, 4'
-Benzoxazin-3(41H)-one-6-yl]
-≠e j l B, 7-ketone hydro, 2H-isoindole-/, 3-dione CO,/! ;9-) is obtained.

mp, Mu2J-229℃ As developing solvent, toluene-tetrahydrofuran 3 pairs/
(V/V) by silica del thin layer chromatography using a mixed solvent. It is confirmed that the result is the same as that obtained by .

Reference example [Production example of herbicidal compound formula (E) above] B-
Amino≠-cyanmethyl-7-fluoro-,2H-/
, l/l-benzoxazin-3(riH)-one (0,
6'? ), tetrahydrophthalic anhydride (0,3♂?), and acetic acid (10d) were mixed and heated under reflux for 3 hours.

After cooling, add water (≠0d) and treat the precipitated crystals as ν.
Extract with dichloromethane (31117). Then, the mixture is washed with a saturated aqueous solution of hydrogen carbonate and then with water, dehydrated with anhydrous sodium sulfate, and then concentrated.

Wash the precipitated crystals with a small amount of ether and transfer to the desired coat [≠
-cyanmethyl-7-fluorojH-/,≠-penzoxazine-3(≠H)-one-6-yl]-4t,j
, B, 7-ketonehydro, 2H-isoindole-/
, 3-dione (O, Tata?) is obtained.

mpo, 2.27-222°C Next, using the above formula (IX) as a starting material, the compound of the above formula (IV) is obtained through production methods 1), h), g), and .) is shown below.

Examples/Hiroshi (■) (■) A mixture of the diazonium salt (6,4'li') of formula (IX) and xylene Cal, 0il) is heated under reflux for 30 minutes.

After concentrating the solvent, the residue contains sodium hydroxide (3,,5') dissolved in ethanol (Cl0011) and water (C30m)
? ) and heated under reflux for 3 hours.

The reaction mixture is concentrated to dryness under reduced pressure, and the resulting residue is dissolved in water, mixed with methyl in butyl ketone (J□su), and the separated aqueous layer is separated and acidified with hydrochloric acid.

The acidic reaction mixture of hydrochloric acid was diluted with methyl isobutyl ketone (
Extract twice in step d) and dry the extract over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue (3, do?) contained chloroform (j/i?) and thionyl chloride (otsu, /?).
) and pyridine (6 drops) and reflux at 50-60°C for j hours. After concentrating the solvent, toluene (!Ogo) is mixed and filtered, and the solution F is distilled under reduced pressure to remove remaining thionyl chloride and hydrochloric acid. Next, toluene (70m)! Combined, 10-. Ammonia gas was introduced at 20 DEG C., the apparatus was kept under saturated conditions at room temperature overnight, and the solids were removed. Wash this with water, then hydrogen carbonate solution, then water,
Dried, the desired Hiro-carbamoylmethyl- of formula (IV)
7-fluoro2H-/,≠-benzoxazine-J(
4LH)-one (,2,4Z?) is obtained.

mp-2/Otsu~2/Ri℃ Biological Test Example Test Compound Reference Compound υ [European Patent Publication Tube 170. Example/j Pre-emergence soil treatment test preparation for upland weeds: Carrier: 75 parts by weight of acetate Emulsifier: Penzyloxine polyglycol ether/heavy-weight active compound preparation contains 7 parts by weight of active compound The compound is mixed with the above-mentioned amounts of carrier and emulsifier to obtain an emulsion. A predetermined dose of the preparation is prepared by diluting it with water.

Test method: Soil packed with field soil in a greenhouse
Seeds of rice, soybeans, and corn were sown in pots, and on top of them, soil mixed with seeds of goldenrod and pigweed was added for 7 hours.
It was covered with soil to a depth of cm.

Seven days after sowing, a predetermined amount of the prepared chemical solution was uniformly sprayed on the soil surface layer of each test pot as described above.

After ≠ weeks of spraying, the herbicidal effect and the degree of chemical damage to crops were graded and evaluated according to the following criteria.

The effectiveness is evaluated when compared to the untreated area.
60% or more but less than 0% 2:
30% or more and less than 0%/:
10% or more but less than 30% 0:
Less than 10% (no effect) Evaluation of chemical damage to crops when compared to untreated area: j: Phytotoxicity rate compared to untreated area 70% or more (fatal damage) ≠: 50% or more but less than 70% 3 = 30% or more Less than 50%J
: 70% or more and less than 30%/2000 less than 70% 0:
It was set as 0% (no chemical damage).

The results are shown below.

Table 1: Example / Test of foliar treatment against field weeds In a greenhouse, rice, soybeans and corn were sown in "zoocsr" pots filled with field soil, and on top of them,
The soil was covered with soil mixed with seeds of goldenrod and pigweed to a depth of /α.

After sowing, the plants were grown for 4 days, and a predetermined amount of a chemical solution prepared in the same manner as in Example/J'' was uniformly sprayed on each test plant.

After ≠ weeks of spraying, the herbicidal effect and the degree of phytotoxicity on crops were investigated using the same criteria as in Example/j above. The results are shown in Table 2.

Table λ

Claims (2)

[Claims] (1) Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 2-[4-carbamoylmethyl-7-fluoro-2H-1,4-benzoxazin-3(4H)one-6-yl]- 4,5,6,7-tetrahydro-2H
-isoindole-1,3-dione. (2) Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 2-[4-carbamoylmethyl-7-fluoro-2H-1,4-benzoxazin-3(4H)one-6-yl]- 4,5,6,7-tetrahydro-2H
- A herbicide containing isoindole-1,3-dione as an active ingredient.