JPS63277675A - Novel benzoxazines - 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 of formula I. USE:Useful as a synthetic intermediate for herbicidal 2-[4-cyanomethyl-7-fluoro-2 H-1,4-benzoxazin-3(4H)on-6-yl]-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione. The compound of formula I itself can be used as a herbicide. PREPARATION:The compound of formula I can be produced by reacting 4- carbamoylmethyl-7-fluoro-6-amino-2H-1,4-benzoxazin-3(4H)--one of formula II with tetrahydrophthalic anhydride. The starting compound of formula II is produced by reducing a compound of formula IV which can be produced by reacting a compound of formula III with concentrated nitric acid in sulfuric acid.

Description

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

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

2-[Hiro-carnogmoylmethyl-7-fluoro-2H-/, Hiro-benzoxazine-3 (≠H) represented by
On-ot-il〕-≠J, Desk 7-Chitrahydro λH-
Isoindole-to-3-dione.

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

Production method a) Formula: ≠-carbamoylmethyl-7-fluoro-
Otsu-amino-,2H-/,! A method for producing benzoxazines of formula (I), which comprises reacting benzoxazin-3C H)-one with tetrahydrophthalic anhydride.

The benzoxazines of the formula (1) of the present invention have a herbicidal property represented by the following formula, as shown in the reference examples below!
-[Hiro-cyanmethyl-7-fluoro-j)f-/, ≠
-benzoxazine-3IH)on-ot-yl]-≠,
It is useful as a new intermediate for the production of j,A,7-tetrahydro-2H-inindole-to-3-dione, and the benzoxazines of formula (I) themselves are new useful compounds that exhibit herbicidal activity. .

(If) In the manufacturing method (Hatake), the compound of formula (If) is as shown in the Examples below, and the manufacturing method b); -/, 4'-benzoxazine-3C
Obtained by reducing IAH>-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 (III) in production method b) is a new compound, as shown in the examples below, and production method C); -Fluoror2H-/,≠-benzoxazin-3(≠H)-one is reacted with concentrated nitric acid in the presence of sulfuric acid, or production method d
); Formula: ≠-cal is oxymethyl-7-fluoro-6
-nitro 2H-/, IA-benzoxazine-j (F
It is obtained by reacting H)-one with thionyl chloride and then reacting the product with ammonia.

Manufacturing method C) is described in Syn, Org, Ch@n, (Synthetic Organic Chemistry), pages 7≠7-71, or European Patent Publication No. 770. The reaction can be carried out according to the nitration reaction described in the specification of No. 1.

Production method d) can be carried out according to the production method g) and production method e) described below.

The compound of formula (IV) in production method C) is a new compound, for example, production method 6): ≠-chlorocarbonylmethyl-7-fluoro-,2H-/, Hiro-benzo represented by the formula: CH2COCl Oxazine-31-H)-
or production method f); Formula: % Formula % Hiro-ethoxycarbonylmethyl-7-fluoro 2H-/, tA-benzoxanone-3 (≠H)
It can be obtained by reacting -one with ammonia.

The compound of the above formula 1) in production method e) is a new compound, as shown in the examples below.
It is obtained by reacting H-/,4'-henzoxazin-3(≠H)-one with thionyl chloride.

When synthesizing the compound of formula (IV) in the above production method e)K, when carrying out the above production method g) and then the production method e), the compound of formula (■) is separated as shown in the examples below. It can be easily obtained by reacting the compound of formula (■) with thionyl chloride without separating them, and then reacting with ammonia.

Manufacturing method f) is 5ynthstie Organic C
hemistry (synthetic organic chemistry), j! ~j1! ;ri page, RoBe Wagner
*r, H, D, Zook, JohnWil@y
& 5ons Inc., /5'33.

The compound of formula (■) in production method g) is a new compound, and as shown in the examples below, production method h); Hiro-benzoxazine-3 (l/LH
)-one by hydrolysis.

The compound of formula (■) in production method f) and production method h) is, as shown in the examples below, production method l); 7-[≠-(ethoxycarbonylmethyl) represented by the formula:
-2H-/,! -benzoxazine-3(≠H)one]
Diazonium tetrafluoro? Rate, Organi
Schiema described in c Reactions, Volume 5, pages 57-20.
It is obtained by thermal decomposition according to the nn (Ziemann) reaction.

Production method i) The compound of the above formula in K (the compound of DO is as shown in the examples below, Production method j): Formula: 7-amino-≠-ethoxycarbonylmethyl-2H-/, ≠ expressed as % formula % -Benzoxazine-3C41H)-
It is obtained by reacting K with sodium nitrite and tetrafluoroboric acid.

As shown in the reference examples below, the compound (X) in production method j) is produced by production method k); formula: Hiro-ethoxycarbonylmethyl-7-nitro, 2H-/, 4 '-Benzoxazine-3 (≠H)
It can be easily obtained by reducing -one.

The compound of the above formula (XI) is produced by manufacturing method 1); as shown in the reference examples below; 7-nitro-2H-≠-benzoxazin-3(≠H)-one and Reacting with ethyl ester of hernoacetic acid, preferably ethyl bromoacetate, or preparation method m); represented by the formula:! -Amino; easily obtained by reacting trophenol with ethyl bromoacetate.

The above manufacturing method l) is described in Pharmaceutical Journal, Vol. 6 (Mu 3), 207-.
This can be done by following the method described on page 2/3.

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

The compound of formula (kari) in production method l) is 5ynthes
is (synthesis), /rif, 2 years,! ；'♂Otsu~91
It is obtained from 2-amino-5-ditrophenol as described on page 7.

The compound of formula (V) in the above production method d) is a new compound, and as shown in the examples below, the compound of formula (V) is produced by production method n); -7,≠-Benzoxacin-
3(IAH)-one is hydrolyzed or production method O)
; to ≠-benzoxazin-3(≠H)-one of the formula (■);
It can be obtained by reacting with concentrated nitric acid in the presence of sulfuric acid.

The compound of formula (XIV) in production method n) is a new compound, and the compound of formula (XIV) in production method p); Nylmethyl-7-fluoro-2H-i, tt -benzoxazine-3 (≠
It is obtained by reacting H)-one with concentrated nitric acid in the presence of sulfuric acid.

Furthermore, on the other hand, ≠-lupamoylmethyl-7-fluoro-6-nitro-2H-/, lA-benzoxazin-3(≠H)-one of the formula (III), and the formula %, 2H-/ , ≠-benzoxazin-3(H)-one are also intermediates in other processes 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 following reference example: O-amino-≠-cyanmethyl-7-fluoro-,2H-/ , lAL-benzoxazin-3(H)-one and tetrahydrophthalic anhydride.

The compound of the above formula (XV) is a new compound as of the filing date of the present application, and as shown in the Examples below, it is manufactured by the production method q); -Benzoxazine-3 (≠H)-
It can be obtained by reducing the on.

Manufacturing method q) is from Beriehte, volume 77,
3t/L By the reduction method using iron and acetic acid described on page 3,
can be done.

The compound of the above formula (X■) in the production method q) is a new compound, and as shown in the examples below, the compound of the formula (I) in the production method r); ≠-carbamoylmethyl-7-fluoro- -Nidrow 2H-7,4t-benzoxazine-3
(≠H)-one and thionyl chloride in a catalytic amount of N,
Reaction in the presence of N-dimethylformamide or production method S); Formula: ≠-cyanomethyl-7-fluoro2H-
/, ≠-benzoxazine-3 <4LH)-one,
It is obtained by reacting concentrated nitric acid and acetic anhydride in the presence of a catalytic amount of sulfuric acid.

The compound of formula (XMi) in production method S) is a new compound, and as shown in the examples below, production method 1); , ≠-benzoxazin-3(H)-one and thionyl chloride are reacted in the presence of a catalytic amount of N,N-dimethylformamide.

The method for converting the amide compound into a nitrile (cyanide compound) by dehydration in the above production method r) and production method t) is described in The Che
mistry of IMIDOYL HALIDgS
(The Chemistry Iotsimi Doil Halize), jJ″
~page 10j, by H. Ulrieh, Plenum Pr
ess, N@W York/76 according to which description,
can be done.

When carrying out the above production method -), 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.

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

In carrying out production method a), for example, by reacting 1 mol of the compound of formula (It) with about 1 mol to about 41 mol of tetrahydrophthalic anhydride in the presence of the above-mentioned diluent, the desired formula can be obtained. Compound (1) can be obtained.

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, tetrachloride longitudinal cord, ethylene chloride, chlorobenzene, etc., ether M examples,
T Ha,? x thyl ether, methyl ethyl ether,
Di-1sO-glopylether, dibutyl ether, dioxane, tetrahydro-7rane; alcohols e.g.
Methanol, ethanol, 1so-7' lono mother alcohol;
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 /jO°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 from about -20 to about 30°C, preferably from about θ to It can be carried out at a temperature of about 20°C.

When carrying out the abovementioned production processes d) and .) 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, penzecy, toluene, xylene. , methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, chlorobenzene; others, 8 ethers, t
-/ethyl ether, methyl ethyl ether, di-lsO-deropyl ether, dibutyl ether, dioxane, tetrahydro-7rane; ketones such as acetone,
Methyl ethyl ketone, methyl-1so-7'ropylketone, methyl-1so-butylketone; Nitriles such as acetonitrile, propionitrile, acrylonitrile; Alcohols such as methanol; Esters such as ethyl acetate, amyl acetate; Acid amides such as dimethyl Formamide, dimethylacetamide; sulfone,
Mention may be made of sulfoxides such as dimethyl sulfoxide, sulfolane; and bases such as pyridine.

Processes d), .) 1g) can be carried out within a substantially wide temperature range. Generally, about -20 to about i
It can be carried out at 0.degree. C., preferably between about .theta. and about 100.degree. In addition, it is desirable that the reaction be carried out under normal pressure,
It is also possible to operate under elevated or reduced pressure.

When carrying out the above manufacturing 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; other ethers such as diethyl ether, methyl ethyl ether, 1so-7' propyl ether, dibutyl ether, dioxane, tetrahydro7rane; ketones such as acetone, methyl ethyl ketone, methyl-1so-propyl ketone, methyl -Igo-
Butyl ketone; Alcohols such as methanol, ethanol, 1so-7' lobanol, butanol, ethylene glycol, etc. can be mentioned.

Process f) can be carried out within a substantially wide temperature range. Generally, it can be carried out at a temperature of about jθ to about 200°C, preferably between about go to about /even θ°C. Further, although the reaction can be carried out under normal pressure, operation under increased pressure is preferred.

When carrying out the abovementioned preparation 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 hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene. , methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, chlorobenzene: others, ether a example, t
For example, diethyl ether, methyl ethyl ether,
10-propyl ether, dibutyl ether, dioxane, tetrahydro7ran; ketones such as acetone, methyl ethyl ketone, methyl-1so-propyl ketone,
Methyl-1so-butylketone; Nitriles such as acetonitrile, propionitrile, acrylonitrile;
Alcohols such as methanol, ethanol, 1so
-7'rono! Examples include alcohol, butanol, ethylene glycol; acid amides such as dimethylformamide, dimethylacetamide; sulfones, sulfoxides such as dimethylsulfoxide, sulfolane; and bases such as pyridine.

Processes h), n) can be carried out within a substantially wide temperature range. Generally about -20 to about isoC
, preferably about -70 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.

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 730° C.) of the formula (DO).

Examples of such diluents include aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated)
For example, petroleum ether, xylene, chlorobenzene, etc.
-I can give.

Process i) can be carried out within a substantially wide temperature range. Generally, about /23 to about /! It can be carried out at rθ°C, preferably between about 730 and about /≠Q°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 3θ°C, preferably between about -20°C and about 20°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 q), as a suitable diluent,
Water; alcohols such as methanol, ethanol, 1
so-pro/J? Mention may be made of: alcohol, 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, it can be carried out at a temperature of about 0 to about /20°C, preferably about 30 to 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 t), all inert organic solvents may be mentioned as suitable diluents.

Examples of such diluents include aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated)
For example, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, chlorobenzene; and other ethers such as diis.

-propyl ether, dibutyl ether, dioxane;
Nitriles such as acetonitrile, propionitrile; Esters such as ethyl acetate, amyl acetate; Acid amides such as dimethylformamide, dimethylacetamide; Sulfones, sulfoxides such as dimethylsulfoxide, sulfolane; and bases such as pyridine. be able to.

Process r)It) can be carried out within a substantially wide temperature range. Generally, about 6θ to about 200°C
, preferably about 0 to about i! It can be carried out between ro°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 S), 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; other ethers such as diethyl ether, methyl ethyl ether, di-1go-7'lopyl ether, Butyl ether, dioxane, tetrahydro7
Ran: and organic acids such as acetic acid, propionic acid, etc. can be used.

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

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

In addition, using 7-nitro 2H-/'A-benzoxazin-3(H)-one of the above formula as a starting material, it is added to the compound of Renbu (XI), which is generally known as an alkylating agent. ing.

Formula: Z -CH-R' (XVI) where,
2 represents halogen or -0802-R", where R
"represents alkyl or aryl optionally having a substituent, R represents a hydrogen atom or methyl, R' represents an aromatic heterocyclic group such as alkyl, alkylthioalkyl, cycloalkyl, or pyridyl, The compound represented by the formula: In the formula, R and R ′ is the same as above, a nitro compound represented by is prepared, and further renbu (X
It is also possible to obtain an amino compound represented by the following formula: where R and R' are the same as above, by subjecting the compound (IX) to a conventional reduction reaction, for example.

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 / ≠-Carbamoylmethyl-7-fluoro-6-nitro 2H-1, Hiro-penzoxazin-J(FH)-one C
1,711), N,N-dimethylformamide C301
Ll), / 0 '11 /4 radium-carbon (α39
) is catalytically reduced at normal pressure. After absorption of hydrogen gas is completed, it is filtered, and then the solvent is distilled off under reduced pressure, and acetic acid <301d> and tetrahydrophthalic anhydride (7 g) are added to the residue.
and heated under reflux for 3 hours. After the reaction is completed, the solvent is distilled off under reduced pressure, tetrahydrofuran (10θd) is added to the residue, it is filtered while hot, and the solution is then distilled under reduced pressure to obtain a solid residue. Wash this with toluene and ethanol <130
Add m1) and activated carbon CO, jli), heat for 7 minutes and filter. Concentrate the p liquid, cool it to room temperature, take it to the door, and
- 2-[Hiro-carpamoylmethyl-7-fluorojH-/, Hiro-penzoxazine-3 for washing with hexane]
(HiroH)-on-ot-yl]-HiroJa6.7-titrahydro, 2H-isoindole-/, 3-)on<o,
si> is obtained.

ml, 2g3-2gOtsu℃ Example λ CH2CONH2 Kurehiro-carpamoylmethyl-7-fluoro I: l-, 2H-
/,≠-benzoxazin-3CIAH)-one (lA
Cool to ♂p>to-j°C, add to concentrated sulfuric acid, and stir thoroughly. To this, add 0-j nitrate (/,≠jJ)
Drop at t:. After stirring for 7 hours, the solid 'tF obtained by pouring into ice water was collected, washed with water, and dried.
Carpamoylmethyl-7-fluoro-nidrow 2H
-/Kishi-benzoxazine-3C4tH)-oneC'A
Og) is obtained.

rnp,, 220-226°C Example 3 CH2CONH2 ■ ≠-carboxymethyl-7-fluoro-2H-/, Hiro-
Penzoxazin-3(≠H)-one (Mupi9), chloroform (/♂y) and thionyl chloride (3, Otsug
) Add 3 drops of pyridine to the mixture and heat under reflux for 5 hours. After concentrating the solvent, toluene C! After distilling off the solvent, the residue is dissolved in toluene (Qrrtl) and ammonia gas is introduced at 10-20°C. After saturation with ammonia, the solid was stirred at room temperature for 7 hours, washed in order of toluene, sodium bicarbonate aqueous solution, and water, and dried. Benzoxadi/-J(4'H)-
On<2. /11) is obtained.

mp, 2/, 2~. 2/4t°C Example ≠ CHC0NH ≠-ethoxycardenylmethyl-7-fluoro-2H-
to≠-benzoxazin-3(H)-one C1,27
ethanol (201rLl) and 2♂thiammonia water C1011') were refluxed at room temperature for 2 hours and further for 3 hours. After concentrating the solvent, it is mixed with water, washed several times with water and ethanol, and reconstituted from methyl isobutyl ketone to obtain the desired H-carpamoylmethyl-7-fluoro-2H-7,4t-benzoxazine- J(l/LH
)-on (0, ≠, so 1 is obtained.

mp, 2/ Otsu, j ~, 2/ Ta °C Example j CHC0OH ≠-ethoxycargonylmethyl-7-fluoro-2H-
Hehiro-benzoxazin-J(lILH)-one (3,
Sodium hydroxide C0,71) and water C10d) are added to a mixture of C71/) and ethanol C20111>, and the mixture is heated under reflux for 5 hours. After the reaction, the solvent was concentrated and water (j (7 m
/), washed with methyl isobutyl ketone, acidified the aqueous layer with hydrochloric acid, extracted with methyl isobutyl ketone, and dried over anhydrous sodium sulfate. After distilling off the solvent, mix with a mixed solvent of toluene-hexane (/:
- When washed with hexane, the desired ≠ -roxymethyl-7
-fluoro-2H-/, 4'-benzoxazine-3(
≠H)-one C3,27i) is obtained.

mp, /END3～/END≠℃ Example B≠-ethoxycarbonylmethyl-7-fluoro-OT-nitro 2H-/, 4t-benzoxanone-3 (4tI
()-on (yorioty) and to≠-nooxane (!Om
l>, add sodium hydroxide (0,71) and water (
2011) and stirred at room temperature for 7 days.

After distilling off the solvent, it is mixed with water (C100rttl) and filtered. The mixture was then acidified with hydrochloric acid and extracted with methyl isobutyl ketone (Cl3011). After washing with water, drying with anhydrous sodium sulfate and distilling off the solvent, the desired ≠-carboxymethyl-7-fluoro-6-nitro-2H-
Benzoxazin-J(11tH)-one (44gg)
is obtained.

mp, / 77-7 g 3°C Example 7 CH2COOC2H5 ≠-Ethoxylic? Nylmethyl-7-fluorocoH-
/, 4t-benzoxazin-J(4LH)-one C2
01) is added to concentrated sulfuric acid at 0-j°C. After thorough stirring (about 70 minutes), 70% dinitric acid (y≠1) was added dropwise.

After stirring for 3 hours at 0-j°C, pour into ice water and drain the resulting solid. The desired ≠-
Ethoxycarmeni/l/) f Roux 7-Fluoro-O-nito0-,? H-/,≠-benzoxazine-3
(≠H)-one (,2/l) is obtained.

mp, 77~end/℃ Example g CH2COOC2H5 7-(≠-ethoxycardenylmethyl-, 2H- to Koichi penzoxazin-J(lAH)-one)diazoniumtetrafluorolate (j, 4t 11') k/30
Heat to ~/3j°C for approximately 5 minutes until gas evolution ceases. The reaction is mixed with toluene (601111) and evaporated to dryness under reduced pressure. Convert the residue into ethanol (ClOILI)
and treated with activated carbon. After filtration, the filtrate is distilled under reduced pressure, and the resulting residue (2.7 g) is reconsolidated from ethanol-hexane to obtain the desired ≠-ethoxycarboxylate. Nylmethyl-7-fluoro-! ■-8≠benzoxazine-j
lH)-one (0, OtsuI) is obtained.

mp, 20~! ; l/, 5°C Example CH2C00C2H5 3 Add hydrochloric acid (l!≠g) to water<200rrtl), cool to 10°C, and prepare 7-amino-≠-ethoxycarbonylmethyl, :zH-/ , 4t-benzoxazine-
3(lAH)-one C,20,29') and stir. To this, sodium nitrite dissolved in water (30rlLl) was added dropwise at 0~j°C, and after 30 minutes,
4tles tetrafluoroboric acid (,2j,f) was added dropwise, and after stirring at 0 to 1°C for 7 hours, the target material was taken out and poured with cold water.
Wash twice with Qal and air dry to obtain the desired 7-[≠-ethoxycarbonylmethyl-,2H-/,≠-penzoxazine-3(≠H)-oncosiazoniumtetrafluorobole) C227j). Reru.

mp, /27~/30℃ (decomposition) Reference example/CH2C00C2H5 ≠-ethoxycarbonylmethyl-7-nitro,,zH
-htt-benzoxazin-3(≠H)-one C30
fi ), / 01 mother radium-carbon (3I) and ethanol CI! A mixture of 9/cyn2 (D hydrogen injection hill,
One catalytic reduction is carried out under conditions of 0 to 70°C, tetrahydrofuran is added, filtered, the ν liquid is distilled under reduced pressure, and the obtained solid is reconsolidated from ethanol to obtain the desired 7-amino-≠
-ethoxycargenylmethyl-2H-/, tA-benzoxazin-J(lJtH)-one<201/) is obtained.

mp, /3A to 37°C Reference Example 2 CH2COOC2H5 7-nitro-2H-≠-benzoxaX)/-3(4
LH)-one (/Z≠II), potassium carbonate (/Yokol
) and acetonitrile (ioory).
At ≠θ°C, ethyl bromoacetate C/f, 4All) was added dropwise, and the mixture was heated under reflux for 3 hours. After the reaction is completed, it is filtered, and the filtrate is distilled and reconstituted from the resulting solid toluene-hexane to obtain the desired Hiro-ethoxycargenylmethyl-7-nitro-2H-7,≠-benzoxazine-3. (≠H)-one C,201 is obtained.

mp, /20. j ~ / j /, j °C Reference example 3 CH2C00C2H5 2-amino-j-ditrophenol (3f, j, 9
), potassium carbonate (10, ≠, !i'), N, N-
To the mixture of dimethylformamide C100d>,! 0~
Ethyl bromoacetate (72 g) was added dropwise at 0°C.

After continued stirring at 100~/10°C for 6 hours, it was cooled and poured into ice water (!00j!). Toluene (300ml)
The extracts are combined, washed successively with water, a 3% aqueous potassium hydroxide solution, and water, dried over anhydrous sodium sulfate, and then the solvent is distilled off. The residue was reconstituted from toluene-hexane to give the desired ≠-ethoxycarzanylmethyl-7-nitro2H-/, 1. t-benzoxazine-3(≠H)-
On<301! 'I get it. Distillation of the mother liquor and recondensation from ethanol yields an additional 7.3 g of target material.

mp-/20, j~/ko/, , 5'℃ Reference Example 3 above
In this case, the amount of washing liquid with potassium hydroxide water bath solution 1'
is acidified with hydrochloric acid, the solvent is distilled off, the solid is separated, washed with water, and then reconsolidated from ethanol to obtain the formula (
]) 7-nitro, 2H-/, 4'-benzoxazin-3(≠H)-one (≠/, 9) is obtained.

Example 10 Hiroki Lupamoylmethyl-7-Fluoro6-2tro-
2H-to≠-benzoxazin-3('AH)-one (
/, ≠II), thionyl chloride (/, 2II),
Two drops of N,N-dimethylformamide are added to the mixture of toluene (C2011) and stirred at 100~/10°C for 6 hours. After cooling, methyl isobutyl ketone C300d) is added, and the mixture is washed with water, a saturated aqueous sodium bicarbonate solution, water, and saturated brine in this order, and dried over anhydrous sodium sulfate. After distilling off the solvent, toluene (<3001 Ll) and activated carbon (0.6 g) are added to the residue, heated for 7 minutes, and filtered while hot. After standing overnight at room temperature, the resulting crystals are separated and dried to form the desired ≠-xyanmethylfluoro-
6 ditro 2H-/,'I--benzoxazine-3 (
≠I()-on(0, OtlA, p) is obtained. The residue obtained by distilling the mother liquor is recondensed from a minimum amount of toluene,
An additional amount (0,,3/i) is obtained.

mp, 15;'6~. TLC method using a 200°C silica dull plate [Developing solvent: tetrahydrofuran (/01fLl), toluene (30g)
and acetic acid (/1111)], it is confirmed that the substance is the same as the substance obtained from Example below.

Example//HCN Acetic anhydride C//, 3rrtl) at 0°C, 7g% nitric acid C
0.7/11) Add k drops. Next, a few drops of concentrated sulfuric acid are added as a catalyst, and stirring is continued for a while at 0°C.

This I/C1,4-cyanomethyl-7-fluoro-2H
-/, 41. -benzoxanone-3(≠H)-one (
2. Add θty) little by little and continue stirring at 0°C for 30 minutes. A solution consisting of sodium hydroxide <ioi> and water Cl#d>, which has been cooled in advance to 0°C, is added dropwise to this at 0°C to neutralize the reaction liquid. After extraction with methyl isobutyl ketone, the extract was washed with water and brine, dried over anhydrous sodium sulfate, and the solvent was distilled off to give the desired Hiro-cyanomethyl-7-fluoro-ot-nitro-2H-. Oxazin-3(H)-one (237II) is obtained.

mp, 20 Hiroshi - 20 Otsu C. Example/2 H2CN ≠-Lupamoylmethyl-7-fluoro2H-/Jun-
Benzoxazine-3(≠14)-y! (7(2,24
! -1), toluene (20d), thionyl chloride (
2,≠g) and N,N-trimethylformamide (3 drops)
The mixture is stirred at 70-100°C for 2 hours. The solvent was distilled off, methyl isobutylkaton (1001 fLl) was added, and the resulting mixed solution was filtered. The lachrymal fluid was washed with water, an aqueous sodium bicarbonate solution, and then water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. When removed, the desired ≠-cyanmethyl-7-fluoro2H-7, Hiro-benzoxazine-
j'(1)-one (7,7≠l) is obtained.

mp, iii~//3℃ Example/3 Ethanol (13ml), acetic acid (7g), water (2J-1
11/) and iron (3 g).

Stir at °C. To this, ≠-cyanomethyl-7-fluoro-nidrow, 2H-/, ≠-benzoxazine-j
Add (!H)-one (!l-/, 9) little by little and continue stirring until gas evolution stops. The reaction solution was filtered, and the F solution was extracted with ethyl acetate. Meanwhile, the residue was extracted several times with ethyl acetate. The ethyl acetate extracts were combined, washed with food, brine, and aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain the desired O-amino-≠-cyanmethyl-7-fluoro2H-/,≠- Benzoxazin-3(jH)-one C1,77&> is obtained.

mp, 763-767°C Reference example≠ [Production example of herbicidal compound formula (E) above] 2-
C11-monolupamoylmethyl-7-fluoro-jH-
to≠-benzoxazine-3(4LH)-one-ot-yl]-≠, j, l), 7-titrahydro, 2H-isoindo-room 3-dione <0.2f! >, toluene (
N,N-trimethylformamide (3 drops) is added to a mixture consisting of 30R1) and thionyl chloride (O,,2N) and heated under reflux for 3 hours. After concentrating the solvent, toluene (
30d), mix well, distill off the toluene, and reconsolidate the resulting solid from ethanol to obtain the desired low
-cyanomethyl-7-fluoro2H-/, Hiro-penzoxazin-3(jH)-one-6-yl]-≠I +
tlO,7-chitrahi)'0-,2H-1twindol-/,3-dione CO,/3;11) is obtained.

mp, 223-227°C As developing solvent: 3 pairs of toluene-tetrahydrofuran/
(V/V) by silica dull 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] υ Otsu-amino-Hiro-cyanmethyl-7-fluoro-2H-
/Kishi-penzoxazine-3(jH)-one <o, si
), tetrahydrophthalic anhydride <0.3ffi) and acetic acid (10 mj) are mixed and heated under reflux for 3 hours.

After cooling, it is added to water (≠Qml) and the precipitated crystals are extracted with dichloromethane C3011). Next, the mixture is washed with a saturated aqueous sodium bicarbonate solution and water, dried over anhydrous sodium sulfate, and then concentrated.

The precipitated crystals were washed with a small amount of ether to give the desired 2-[Hiro-cyanomethyl-7-fluoro-2H-Hiro-benzoxacin-JIH)-one-6-yl]-≠,! , B,
7-titrahydro-2H-isoindole-to-3-dione (0,j-I) is obtained.

mp, 227-227°C Next, using the above formula (IX) as a starting material, the following is an example of obtaining the compound of the above formula (IV) through production methods i), h), g) and e). Shown below.

Example/≠ (■) (■) CH2C00H I (■) Diazonium salt of formula (■) (A, l') toxylene C/
A mixture of 1.0 ml) is heated under reflux for 30 minutes.

After removing the solvent several times, sodium hydroxide (30 ml) dissolved in ethanol (700111) and water (30 rrtl) was added to the residue.
, j, 9) is added and heated under reflux for 3 hours.

The reaction mixture was concentrated to dryness under reduced pressure, the resulting residue was dissolved in water, and methyl isobutyl ketone <30 tul) was mixed therein.
Collect the entire aqueous layer and acidify it with hydrochloric acid.

The acidic reaction mixture of hydrochloric acid was mixed with methyl isobutyl ketone (Otsu0
Extract twice with m1) and dry the extract with anhydrous sodium sulfate. The solvent was completely distilled off, and the resulting residue <3.11> was mixed with chloroform <sip> and thionyl chloride (Otsu, /l).
) and pyridine (6 drops) and reflux at 5o-to C for 5 hours. After concentrating the solvent, toluene (C30111) is mixed, filtered, and distilled under reduced pressure to remove remaining thionyl chloride and hydrochloric acid. Then toluene (70m
) and mix 70~. Ammonia gas was introduced at 20 DEG C., the apparatus was kept under saturated conditions at room temperature overnight, and the solids were removed.

This is washed with water, then hydrogen carbonate) and then with water, dried, and converted to the desired formula (IV) of ≠-rubamoylmethyl-7-fluoro, 2H-≠-benzoxanone-
j<≠H)-one (14tN) is obtained.

mp, 2/6 to 2/litre C. Weeding test example Pre-emergence soil treatment test compound for upland weeds: Preparation: Carrier Nia Seven Tonta Parts by weight Emulsifier: Penzyloxypolyglycol ether/Parts by weight The preparation of active compound is as follows: An emulsion is obtained by mixing 7 parts by weight of the active compound with the above-mentioned amounts of carrier and emulsifier. A predetermined dose of the preparation is prepared by diluting it with water.

Test method: In a greenhouse, soybean seeds were sown in J001M2 pots filled with field soil, and on top of the soybean seeds were
Each seed of pigweed was seeded to the depth of the soil rough soil mixed with it.

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.

When comparing the effectiveness with the untreated area, j: Weed killing rate over the untreated area J-1. or more (dead) 4t: Weed killing rate over the untreated area ♂ 0 chi or more! Less than 3:
3; 0% or more and less than go% 2:
Over 30 inches! Less than 0chi/:
10 or more and less than 30% 0:
Evaluation of chemical damage to crops less than 10 inches (no effect) when compared to untreated plots! :Rate of chemical damage compared to untreated area Tθchi or more (fatal damage) 'A: 30chi or more 70
Less than 3 = 30 inches or more SO%
Less than 2: 10% or more and 30%
Less than/: Over 0 and less than 10 O:
It was set as 0% (no chemical damage).

-The results are shown below.

Margin below

Claims (1)

[Claims] 2-[4-carbamoylmethyl-7-fluoro-2H-1,4-benzoxazin-3(4H)one-6-] represented by the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ yl]-4,5,6,7-tetrahydro-2H
-isoindole-1,3-dione.