JPH0616664A - Herbicidal oxazoline compound - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a herbicide. CONSTITUTION:The compound of formula I {X is H or Cl; Y is Cl or F; R is H or lower alkyl; A-B is N(R<1>)-(C=O) [R<1> is H, (substituted) lower alkyl, benzyl, etc.] or CH(-W<1>)-CH2 (W<1> is t-butyldimethylsilyloxy or OH) or C(=W<2>)-CH2 (W<2> is O or N-OCH3)} such as 5-t-butyl-3-(2H-7-fluoro-4- methoxymethyl-3,4-dihydro-1,4-benzoxazin-3-one-6-yl)-4-oxazolin-2-one. The compound of formula I is obtained by condensing a carbamate compound of formula II {Aa-B is N(R<1a>)-(C=O) [R<1a> is (substituted) lower alkyl, benzyl, etc.],etc.} with alpha-bromopinacolin optionally in the presence of a solvent by using a base.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel oxazoline derivative having a strong herbicidal action, specifically a 4-oxazoline-2-one derivative and a herbicide containing the compound as an active ingredient.

[0002]

2. Description of the Prior Art As a 4-oxazoline-2-one derivative, a general formula has been disclosed in Japanese Patent Laid-Open Publication No. 62-42976.

[0003]

[Chemical 2]

[0004] A compound having ## STR1 ## is also described, and the above publication describes a method for producing a 4-oxazoline-2-one derivative.

[0005]

However, in the above publication,
The substituent R ^{2 at the} 5-position of the oxazoline ring is a methyl group,
Examples of ethyl group, n-propyl group, i-propyl group, and chloromethyl group are shown, and a phenyl group which may have a substituent is shown for the substituent R ^{3 at the} 3-position. Furthermore, although it is described that the herbicidal activity is effective, the activity is not sufficient when a low dose is applied, as shown in the test examples below.

The present inventors have conducted extensive research on the synthesis of oxazoline derivatives and their herbicidal activity for many years, and as a result, found that a novel oxazoline derivative having a structure different from that of a known one has excellent herbicidal activity. Found and completed the present invention.

[0007]

[Constitution of the invention]

[0008]

The present invention has the general formula (I)

[0009]

[Chemical 3]

[Wherein, X represents a hydrogen atom or a chlorine atom, Y represents a chlorine atom or a fluorine atom, R represents a hydrogen atom or a lower alkyl group, and AB represents N (R ¹ ). −
(C = O) group, CH (-W ¹⁾ -CH ₂ group or C (= W
² ) —CH ₂ group (wherein R ¹ represents a hydrogen atom, a lower alkoxy group or a lower alkyl group which may be substituted with a lower alkoxy lower alkoxy group, a lower alkynyl group, a benzyl group or a p-methoxybenzyl group) , W ¹ represents a t-butyldimethylsilyloxy group or a hydroxyl group, and W ² represents
An oxygen atom or N-OCH ₃ groups. ) Is shown. ] And a herbicide containing the compound as an active ingredient.

In the above, "lower alkyl group" in the definition of R and R ¹ is, for example, methyl, ethyl, n-
It is a linear or branched alkyl group having 1 to 4 carbon atoms such as propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, preferably a methyl group or an ethyl group.

In the above, the "lower alkynyl group" in the definition of R ¹ is ethynyl, 2-propynyl, 1-
It is a linear or branched alkynyl group having 2 to 4 carbon atoms such as methyl-2-propynyl, 2-butynyl and 3-butynyl.

In the above, the "lower alkoxy group" in the definition of R ¹ is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy,
A straight-chain or branched-chain alkoxy group having 1 to 4 carbon atoms in which the above-mentioned "lower alkyl group" is bonded to an oxygen atom, such as s-butoxy, and preferably a straight-chain alkoxy group having 1 to 2 carbon atoms. Is.

In the above, the "lower alkoxy lower alkoxy group" in the definition of R ¹ is, for example, methoxymethoxy, ethoxymethoxy, (2-methoxy) ethoxy, n-propoxymethoxy, isopropoxymethoxy, (2-ethoxy). Ethoxy, (3-methoxy) propoxy, (2-methoxy-1-methyl) ethoxy, (2
A lower alkoxy lower alkoxy group having a total of 2 to 4 carbon atoms, such as -methoxy) propoxy.

A lower alkyl group or a lower alkynyl group which may be substituted with a group, more preferably a methyl group, an ethyl group, a methoxymethyl group or a 2-propynyl group,
Most preferably, it is a 2-propynyl group.

When an oxime bond is present in the molecule of the compound of the present invention, isomers having different relative configurations with respect to the oxime bond may exist. In general, the physicochemical properties of these compounds may differ, and in Table 1 below, when such a compound is mentioned, it is described as "isomer A" or "isomer B".

Hereinafter, the compounds of the present invention are shown in Table 1 together with the compound numbers, but the present invention is not limited to these compounds.

In Table 1, Prg represents a 2-propynyl group, MEM represents a (2-methoxy) ethoxymethyl group, and MOM.
Represents a methoxymethoxy group, TBDMS represents a t-butyldimethylsilyl group, Bz represents a benzyl group, and PMB represents a p-methoxybenzyl group.

[0019]

[Table 1]

[0020]

[Chemical 4]

──────────────────────────────────── Compound No. XYR AB Melting point (℃) ─── ───────────────────────────────── 1 Cl FH NH-C (= O) Oil 2 Cl FHN (CH ₃ ) -C (= O) 90 to 95 3 Cl FHN (C ₂ H ₅ ) -C (= O) 185 to 190 4 Cl FHN (C ₃ H ₇ ) -C (= O) 5 Cl FHN (iC ₃ H ₇ ) -C (= O) 142 ~ 145 6 HFHN (Prg) -C (= O) 7 Cl FHN (Prg) -C (= O) Oil 8 Cl Cl HN (Prg) -C (= O) 9 Cl FHN (MEM) -C (= O) 90 ~ 93 10 HFHN (MOM) -C (= O) Oil 11 Cl Cl HN (MOM) -C (= O) 12 Cl FHN (MOM) -C (= O) 120 to 122 13 Cl F CH ₃ N (MOM) -C (= O) 14 Cl F CH ₃ N (Prg) -C (= O) 15 Cl FC ₂ H ₅ N (Prg) -C (= O) 16 Cl Cl CH ₃ N (Prg) -C (= O) 17 Cl F CH ₃ N (C ₂ H ₅ ) -C (= O) 170 to 175 18 Cl FHN (Bz) -C (= O) 19 Cl FHN (PMB) -C (= O) Oil 20 HFH CH (OTBDMS) -CH ₂ 117 to 119 21 Cl FH CH (OTBDMS) -CH ₂ Oil 22 Cl FH CH (OH) -CH ₂ Oil 23 Cl FHC (= O ) -CH ₂ 150 to 156 24 Cl FHC (= N-OCH ₃ ) -CH ₂ 99 to 106 (isomer A) 25 Cl FH C (= N-OCH ₃ ) -CH ₂ 33 to 35 (isomer B) ──────────────────────────────── —————————————————————————————————————————————————————— In In In Table 1 below, the NMR spectra and mass spectra (MS) of compounds whose melting point or “oil” are indicated in the physical properties column are shown below.

Compound No. 1 ¹ H-NMR (CDCl ₃ , 200 MHz) δ; 9.49 (1H, brs), 6.88 (1H, d, J = 7.
0Hz), 6.85 (1H, d, J = 9.8Hz), 4.63 (2H, s), 1.36 (9H, s) MS (m / z); 340 (M ⁺ ), 325 (M ⁺ -Me), 149 , 83 (base), 55 Compound No. 2 ¹ H-NMR (CDCl ₃ , 200MHz) δ; 6.94 (1H, d, J = 3.1Hz), 6.90 (1H,
d, J = 5.9Hz), 4.69 (2H, s), 3.38 (3H, s), 1.37 (9H, s) MS (m / z); 354 (M ⁺ ), 339 (base, M ⁺ -Me) , 295,57 Compound No. 3 ¹ H-NMR (CDCl ₃ , 200MHz) δ; 6.93 (1H, d, J = 4.6Hz), 6.89 (1H,
d, J = 7.4Hz), 4.65 (2H, s), 3.97 (2H, dq, J = 7.2,2.6Hz), 1.37
(9H, s), 1.28 (3H, t, J = 7.2Hz) MS (m / z); 368 (M ⁺ ), 353 (base, M ⁺ -Me), 309,57 Compound No. 5 ¹ H-NMR (CDCl ₃ , 200MHz) δ; 7.08 (1H, d, J = 7.0Hz), 6.91 (1H,
d, J = 9.6Hz), 4.68 (1H, heptet, J = 7.0Hz), 4.55 (2H, s), 1.54
(6H, d, J = 7.0Hz), 1.37 (9H, s) MS (m / z); 382 (M ⁺ ), 367 (base, M ⁺ -Me), 325,57 Compound No. 7 ¹ H-NMR (CDCl ₃ , 200MHz) δ; 7.15 (1H, d, J = 6.9Hz), 6.93 (1H,
d, J = 9.6Hz), 4.83 (1H, dd, J = 18.0,2.3Hz), 4.71 (2H, s), 4.5
6 (1H, dd, J = 18.0,2.3Hz), 2.32 (1H, t, J = 2.3Hz), 1.37 (9H,
s) MS (m / z); 378 (M ⁺ ), 363 (base, M ⁺ -Me), 319,55 Compound No. 9 ¹ H-NMR (CDCl ₃ , 200 MHz) δ; 7.37 (1H, d, J = 7.2Hz), 6.90 (1H,
d, J = 9.6Hz), 5.40 (2H, brs), 4.69 (2H, s), 3.73 ~ 3.78 (2H,
m), 3.51 ~ 3.56 (2H, m), 3.56 (3H, s), 1.38 (9H, s) MS (m / z)
δ; 428 (M ⁺ ), 413 (M ⁺ -Me), 69, 57 (base) Compound number 10 ¹ H-NMR (CDCl ₃ , 200 MHz) δ; 7.50 (1 H, d, J = 7.5 Hz), 6.86 (1H,
d, J = 10.6Hz), 6.34 (1H, d, J = 2.3Hz), 5.28 (2H, s), 4.64 (2
H, s), 3.38 (3H, t, J = 2.8Hz), 1.23 (9H, s) Compound No. 12 ¹ H-NMR (CDCl ₃ , 200MHz) δ; 7.28 (1H, d, J = 6.7Hz), 6.90 (1H,
d, J = 9.7Hz), 5.29 (2H, s), 4.69 (2H, s), 3.41 (3H, s), 1.36 (9
H, s) MS (m / z); 384 (M ⁺ ), 369 (base, M ⁺ -Me), 325,55 Compound No. 17 ¹ H-NMR (CDCl ₃ , 200 MHz) δ; 6.93 (1H, d , J = 1.3Hz), 6.88 (1H,
d, J = 4.2Hz), 4.68 (1H, m), 3.96 (2H, brq, J = 7.2Hz), 1.55〜
1.62 (3H, m), 1.37 (9H, s), 1.27 (3H, t, J = 7.2Hz) MS (m / z); 382 (M ⁺ ), 367 (base, M ⁺ -Me), 57 compounds No. 19 ¹ H-NMR (CDCl ₃ , 200 MHz) δ; 7.19 (2H, d, J = 8.8Hz), 6.84 to 6.
92 (4H, m), 5.27 (1H, d, J = 16.9Hz), 4.90 (1H, d, J = 16.9Hz),
4.76 (2H, s), 3.78 (3H, s), 1.34 (9H, s) MS (m / z); 460 (M ⁺ ), 445 (M ⁺ -Me), 122 (base) Compound No. 20 ¹ H -NMR (CDCl ₃ , 200MHz) δ; 7.40 (1H, d, J = 8.6Hz), 6.63 (1H,
d, J = 11.9Hz), 6.30 (1H, d, J = 2.5Hz), 4.77 (1H, t, J = 4.4Hz),
4.19 ~ 4.42 (2H, m), 1.88 ~ 2.12 (2H, m), 1.23 (9H, s), 0.90
(9H, s), 0.16 (3H, s), 0.15 (3H, s) MS (m / z); 421 (M ⁺ ), 364 (base), 336 Compound No. 21 ¹ H-NMR (CDCl ₃ , 200MHz ) δ; 7.14 (1H, d, J = 8.0Hz), 6.67 (1H,
d, J = 10.9Hz), 4.76 (1H, t, J = 4.2Hz), 4.20 ~ 4.45 (2H, m),
1.91 ~ 2.12 (2H, m), 1.36 (9H, s), 0.89 (9H, s), 0.16 (3H,
s), 0.13 (3H, s) MS (m / z); 491 (M ⁺ ), 476,456,434,406 Compound No. 22 ¹ H-NMR (200MHz, CDCl ₃ ) δ; 7.31 (1H, d, J = 8.3Hz), 6.66 (1H,
d, J = 11.0Hz), 4.72 (1H, brs), 4.27 (2H, brs), 3.16 (1H, br
s), 2.04 (2H, brs), 1.34 (9H, s) MS (m / z); 341 (M ⁺ ), 326 (base, M ⁺ -Me), 142 Compound No. 23 ¹ H-NMR (200MHz, CDCl ₃ ) δ; 7.94 (1H, d, J = 8.5Hz), 6.86 (1H,
d, J = 10.3Hz), 4.62 (2H, t, J = 6.4Hz), 2.85 (2H, t, J = 6.4Hz),
1.36 (9H, s) MS (m / z); 339 (M ⁺ ), 324 (base, M ⁺ -Me), 280,162,57 Compound No. 24 ¹ H-NMR (200MHz, CDCl ₃ ) δ; 7.92 (1H , d, J = 8.5Hz), 6.76 (1H,
d, J = 10.4Hz), 4.26 (2H, t, J = 6.0Hz), 3.96 (3H, s), 2.90 (2H,
t, J = 6.0Hz), 1.36 (9H, s) MS (m / z); 368 (M ⁺ ), 353 (base, M ⁺ -Me), 250,57 Compound No. 25 ¹ H-NMR (200MHz, CDCl ₃ ) δ; 8.61 (1H, d, J = 8.8Hz), 6.77 (1H,
d, J = 10.7Hz), 4.41 (2H, t, J = 5.8Hz), 4.00 (3H, s), 2.73 (2H,
t, J = 5.8Hz), 1.37 (9H, s) MS (m / z); 368 (M ⁺ ), 353 (base, M ⁺ -Me), 250,57 Compounds of general formula (I) of the present invention Is manufactured by each of steps A to H shown below.

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[In the above formula, X, Y and R have the same meanings as described above, and A _a -B is N (R ^1a )-(C = O) or CH.
(OTBDMS) -CH ₂ (wherein R ^1a represents a lower alkyl group which may be substituted with a lower alkoxy group or a lower alkoxy lower alkoxy group, a lower alkynyl group, a benzyl group or a p-methoxybenzyl group, and TBDMS
Represents a t-butyldimethylsilyl group. ) Is shown. ] The general manufacturing method will be described in more detail below.

(Step A) In this step, the carbamate compound (IIa) and α-bromopinacholine are condensed with a base in the presence or absence of a solvent to give a compound of formula (Ia) It is a step of producing an oxazolin-2-one derivative.

Examples of the base used in this step include triethylamine, tributylamine, diethylisopropylamine, pyridine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0]. ] Organic tertiary amines such as -7-undecene, sodium hydride, calcium hydrogen, sodium, lithium, n-butyllithium, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium methoxide, t-butoxy potassium and the like. Alkali metal base, sodium hydroxide, potassium hydroxide,
An inorganic base such as sodium carbonate, potassium carbonate,
Preferred are alkali metal bases such as sodium hydride and lithium bis (trimethylsilyl) amide.

The amount of the base used is usually 2 to 20 times equivalent, preferably 2 to 10 times equivalent to the compound (IIa).

The reaction is preferably carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but preferably hexane is used. , Hydrocarbons such as petroleum ether, benzene and toluene, halogenated hydrocarbons such as chloroform and methylene chloride, ethers such as ethyl ether and tetrahydrofuran, amides such as N, N-dimethylformamide, dimethyl Sulfoxides such as sulfoxide, nitriles such as acetonitrile, and a mixture of these solvents, and the like, preferably N,
It is N-dimethylformamide.

The reaction temperature is usually -70 to 90 ° C, preferably 20 to 60 ° C. The reaction time varies depending mainly on the reaction temperature, the raw material compound, the reaction reagent or the type of solvent used, but is usually 15 minutes to one day and night, and preferably 15 minutes to 4 hours.

Of the starting materials (IIa) used in this step, A _a
A compound in which -B is N (R ^1a )-(C═O) is a compound obtained by specially treating a 6-aminobenzoxazinone derivative and ethyl chlorocarbonate prepared according to the method described in JP-A-61-30586. It is produced by reacting according to the method described in Kaihei 2-42057.

Also in the compound (IIa), the compound in which A _a -B is CH (OTBDMS) -CH ₂ has the same properties as the aminobenzoxazine derivative, that is, 6-aminochroman derivative and ethyl chlorocarbonate. Kaihei 2-4205
It is produced by reacting according to the method described in Japanese Patent Publication No. 7. Further, a 6-aminochroman derivative, that is, a 6-amino-4-t-butyldimethylsilyloxychroman derivative is a compound of 6-nitrochroman-4-one derivative described in JP-A-3-24076. After reduction with sodium borohydride in methanol, which is a conventional method, the obtained 4-alcohol compound was converted to 4-silyl ether using t-butyldimethylsilyl chloride and imidazole in dimethylformamide, The 6-position nitro group can be easily produced by the reduction method using iron powder in acetic acid described in JP-A-3-20274.

(Step B) This step is an intermediate of the compound of the present invention by reacting the compound represented by the general formula (Ia) with a chlorinating agent such as chlorine gas in the presence of a solvent. Dichlorooxazolidine-a raw material of step C described later
It is a step of producing a 2-one derivative (IIIa).

In this step, the reaction is usually carried out by blowing chlorine gas into the solution of compound (Ia).

The amount of chlorine gas used is usually 1 to 20 times equivalent, preferably 2 to 10 times equivalent to the compound (Ia).

The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting materials to some extent, but preferably, a halogenated hydrocarbon such as carbon tetrachloride, chloroform or methylene chloride. It is a kind.

The reaction temperature is usually 0 to 100 ° C., preferably about room temperature. The reaction time varies depending mainly on the reaction temperature, the raw material compound, the reaction reagent, the rate at which chlorine gas is blown, or the type of solvent used, but is usually 1 minute to 3 hours, and preferably 3 minutes to 30 minutes. .

(Step C) In this step, the dichloro compound (IIIa) produced in step B is mixed with a dehydrochlorinating agent in the presence or absence of a solvent to give a compound of the present invention 4- It is a step of producing a chloro-4-oxazolin-2-one derivative (Ib).

The dehydrochlorinating agent used is, for example, triethylamine, tributylamine, diethylisopropylamine, pyridine, 4-dimethylaminopyridine, 1,8.
-Organic amines such as bis (dimethylamino) naphthalene, 1,4-diazabicyclo [5,4,0] octane, 1,8-diazabicyclo [5,4,0] -7-undecene, sodium hydride, hydrogen Alkali metal bases such as calcium oxide, metallic sodium, metallic lithium, n-butyllithium, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium methoxide, potassium t-butoxide, sodium hydroxide, potassium hydroxide, carbonic acid. Inorganic bases such as sodium and potassium carbonate, etc., preferably 1,8-diazabicyclo [5,4,0] -7-undecene, lithium bis (trimethylsilyl) amide, and more preferably 1, 8-
It is diazabicyclo [5,4,0] -7-undecene.

The amount of the dehydrochlorination agent used is the same as that of the compound (IIIa).
It is usually 1 to 20 times equivalent, preferably 2 to 10 times equivalent.

The reaction is preferably carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting materials to some extent.
Preferred are hydrocarbons such as hexane, petroleum ether, benzene and toluene, halogenated hydrocarbons such as chloroform and methylene chloride, ethers such as ethyl ether and tetrahydrofuran, N, N-dimethylformamide and the like. Amides, sulfoxides such as dimethylsulfoxide, nitriles such as acetonitrile, and mixtures of these solvents, more preferably N, N-dimethylformamide and dimethylsulfoxide, and even more preferably dimethylsulfoxide. Is.

The reaction temperature is usually -70 to 90 ° C, preferably 0 to 50 ° C. The reaction time varies depending mainly on the reaction temperature, the starting compound, the reaction reagent or the type of solvent used, but is usually 15 minutes to 24 hours, and preferably 30 minutes to 6 hours. (Step D) In this step, the compound (Ia ^′ ) or (Ib ^′ )
By reacting the amide group protected with a methoxymethyl group with a deprotecting agent in the presence or absence of a solvent,
This is a step of producing an amide compound (Ic) which is a compound of the present invention.

The deprotecting agent used is usually an acidic one, and examples thereof include inorganic acids such as hydrochloric acid and sulfuric acid, titanium tetrachloride, boron trifluoride ether complex, Lewis acids such as dichlorozinc and trifluoromethane. Organic acids such as acetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and the like, and preferably organic acids such as trifluoroacetic acid.

The amount of the deprotecting agent used is usually 1 to 20 times equivalent to the amount of the compound (Ia ^' ) or (Ib ^' ), preferably 2 times.
It is equivalent to 10 times.

The solvent used when the reaction is carried out in the presence of a solvent is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but is preferably hexane, petroleum ether or benzene. , Hydrocarbons such as toluene, chloroform, methylene chloride, halogenated hydrocarbons such as 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, ethers such as ethyl ether and tetrahydrofuran, N , Amides such as N-dimethylformamide, sulfoxides such as dimethylsulfoxide, nitriles such as acetonitrile, and a mixture of these solvents, and the like.
1,2-dichloroethane and 1,1,2,2-tetrachloroethane.

The reaction temperature is usually 0 to 150 ° C, preferably 60 to 120 ° C. The reaction time varies depending mainly on the reaction temperature, the starting compound, the reaction reagent or the type of solvent used, but is usually 15 minutes to one day and night,
It is preferably 2 to 6 hours.

(Step E) In this step, the above compound (Ic) is used.
In the presence of a solvent and a reaction aid,
In this step, compound (Id) is produced by reacting with a reactive derivative of group R ^1a .

The reaction aid used in this step usually has a good basicity, for example, triethylamine, tributylamine, diethylisopropylamine, pyridine, 1,4-
Organic tertiary amines such as diazabicyclo [2,2,2] octane and 1,8-diazabicyclo [5,4,0] -7-undecene, sodium hydride, calcium hydride, sodium, lithium, n- Butyl lithium, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, alkali metal bases such as potassium t-butoxy, inorganic bases such as sodium hydroxide, potassium hydride, sodium carbonate, potassium carbonate, and preferably sodium hydroxide. , Alkali metal bases such as potassium hydride, lithium bis (trimethylsilyl) amide.

[0049] In this case, suitable are the reactive derivatives, for example, a halide or sulfonic acid esters of group R ^1a, preferably chloro of radicals R ^1a is bromine body, mesyloxy body, tosyloxy and the like And more preferably a chloro body, a mesyloxy body, and a tosyloxy body.

The amount of the reaction aid used is usually 1 to 20 times equivalent, preferably 2 to 10 times equivalent to compound (Ic).

The reaction is preferably carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent.
Preferred are hydrocarbons such as hexane, petroleum ether, benzene and toluene, halogenated hydrocarbons such as chloroform and methylene chloride, ethers such as ethyl ether and tetrahydrofuran, N, N-dimethylformamide and the like. Amides, sulfoxides such as dimethyl sulfoxide, nitriles such as acetonitrile, and mixtures of these solvents, more preferably N, N-dimethylformamide.

The reaction temperature is usually -70 to 150 ° C, preferably room temperature to 120 ° C. The reaction time varies depending mainly on the reaction temperature, the raw material compound, the reaction reagent or the type of solvent used, but is usually 15 minutes to 24 hours, and preferably 30 minutes to 4 hours.

(Step F) In this step, the compound (Ia '') (Ia '') or (Ia) having a protected alcohol is used.
b ″) is a step of producing an alcohol derivative (Ie) by reacting b ″) with a deprotecting agent.

The deprotecting agent used may be either acidic or basic, as long as it is usually used as a deprotecting agent for silyl groups. Examples of acidic ones include trifluoroacetic acid and methanesulfonic acid. Preferred are organic acids such as trifluoromethanesulfonic acid and p-toluenesulfonic acid, and hydrofluoric acid. Further, as the basic one, a fluorinated base such as tetrabutylammonium fluoride or potassium fluoride is preferable.

The amount of the deprotecting agent used is the compound (Ia ″)
Or, it is usually 1 to 20 times equivalent, preferably 2 to 10 times equivalent to (Ib ″).

Usually, this step is carried out in the presence of a solvent,
The solvent used is not particularly limited as long as it does not interfere with the reaction, but is, for example, hydrocarbons such as hexane, petroleum ether, benzene and toluene, chloroform, methylene chloride, 1,2-dichloroethane and the like. Halogenated hydrocarbons, ethyl ether, tetrahydrofuran,
Ethers such as 1,4-dioxane, a mixture of these solvents, and the like, and ethers such as tetrahydrofuran and 1,4-dioxane are preferable.

The reaction temperature is usually from -20 to 100 ° C, preferably from 0 ° C to room temperature. The reaction time varies depending on the deprotecting agent used, but is usually 15 minutes to 24 hours, and preferably 1 to 6 hours.

(Step G) In this step, the alcohol compound (I
In this step, e) is reacted with an oxidizing agent to produce a ketone (If). The oxidizing agent used is not particularly limited as long as it usually oxidizes an alcohol to a ketone, and for example, manganese dioxide, oxalyl chloride-dimethyl sulfoxide, acetic anhydride-dimethyl sulfoxide, pyridinium chlorochromate, pyridinium dichromate and the like. It is suitable.

The amount of the oxidizing agent used is usually 2 to 30 equivalents with respect to the compound (Ie), but can be largely changed depending on the kind of the oxidizing agent used.

This step is usually carried out in the presence of a solvent,
The solvent used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include hydrocarbons such as hexane, petroleum ether, benzene and toluene, chloroform, methylene chloride, 1,2-dichloroethane and the like. Halogenated hydrocarbons, ethyl ether, tetrahydrofuran,
These include ethers such as 1,4-dioxane, amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide and nitriles such as acetonitrile, and a mixture of these solvents. Preferred are halogenated hydrocarbons such as chloroform and methylene chloride.

The reaction temperature is usually -20 to 100 ° C, preferably 0 ° C to around room temperature. The reaction time varies depending on the type of oxidizing agent used, but is usually 15 minutes to
One day and one night, preferably 1 to 6 hours.

(Step H) In this step, the ketone (If) is added to
This is a step of producing a compound (Ig) by reacting with O-methylhydroxylamine or a salt thereof (for example, a salt with a mineral acid such as hydrochloric acid, nitric acid or sulfuric acid) to oxime a ketone.

The reaction is usually carried out in an inert solvent,
Examples of such a solvent include alcohols such as methanol and ethanol, ethers such as diethyl ether and tetrahydrofuran, fatty acids such as acetic acid or water, and a mixture of these solvents. Is a mixture of alcohols such as methanol and ethanol and water.

The reaction temperature is preferably 30 to 90 ° C., and the reaction time is usually 1 hour to 24 hours, preferably 2 to 6 hours.

After completion of the reaction in each of the above steps, the reaction target product is collected from the reaction mixture by a conventional method. For example, it can be obtained by adding an organic solvent immiscible with water to the reaction mixture, washing with water, and distilling off the solvent. The obtained target compound is
If necessary, it is further purified by a conventional method such as recrystallization, reprecipitation, and chromatography.

The compound (I) of the present invention is used for various weeds which are problematic in the foliar treatment and soil treatment of upland fields, for example,
Buckwheat, purslane, chickweed, white-faced, blue-toothed, white horned squirrel, Ebisugusa, Noragarashi, nazuna, ichweed, stag deer, field pansy, yamegura, bindweed, black-billed dragonfly, red-billed dragonfly, red-billed dragonfly, red-billed dragonfly, red-billed dragonfly, red-billed dragonfly Broad-leaved weeds such as gold; millet, barnyard grass, green locust, crabgrass, crabgrass, grasshopper,
Herbicidal activity against various weeds such as blackgrass, cranaceae, oats, sorghum, sorghum, cedar, weeds such as Erythronium serrata, and communis weeds such as Commelina communis; , And it does not cause any harmful phytotoxicity to major crops such as corn, wheat and soybean.

The compound (I) of the present invention is a variety of weeds that are problematic in paddy fields, for example, weeds such as gramineous grass; broad-leaved weeds such as konagi, azena, sedgegrass, and zochabe; It exhibits herbicidal activity against cyperaceae weeds such as pine and cypress, and does not show a problematic phytotoxicity to rice.

Further, it can be used not only in upland fields and paddy fields but also in orchards, mulberry fields and non-agricultural fields.

Since the compound of the present invention also has an effect of suppressing the growth of plants without dying them, it can prevent various lodgings such as prevention of lodging by shortening of paddy rice and reduction of lawn growth to reduce the number of cuttings. Expected to be useful.

To prepare a herbicide and a plant growth regulator from the compound (I) of the present invention, a herbicide and a plant growth regulator are diluted with a carrier such as a solid carrier or a liquid carrier, and if necessary, another carrier such as a surfactant is used. It is possible to prepare powders, coarse powders, granules, fine granules, emulsions, suspensions, wettable powders, flowables, aqueous solutions, liquids and the like by adding a formulation auxiliary agent. Of course, the crude product can be used as an active ingredient by stopping the purification at any stage of the purification.

The carrier means a synthetic or natural inorganic substance which is mixed with a herbicide and a plant growth regulator to assist the accessibility of the active ingredient to the plant or to facilitate the storage, transportation or handling of the active ingredient. Means organic material.

When it is used as a herbicide or a plant growth regulator, other fungicides, insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc. It can also be mixed with, the scope of application can be expanded, and labor can be saved.

As a treatment method, a formulation is usually prepared and soil treatment, foliage treatment or flooding treatment is carried out before or within about one month after emergence of the weeds. Soil treatment includes soil surface treatment, soil admixture treatment, etc., and foliage treatment includes treatment from above the plant body and local treatment such as treatment of only weeds so as not to adhere to crops. The treatment includes spraying granules and irrigating the water surface.

The compound of the present invention can be used as a herbicide for paddy fields, uplands, orchards, pastures, lawns, forests or non-agricultural lands.

Hereinafter, the present invention will be described in more detail by showing formulation examples and examples, but the present invention is not limited to these.

[0076]

【Example】

[0077]

[Formulation Example 1] (Wettable powder) No. 7 compound 10%, Emulgen 810 (registered trademark) (Kao Corporation surfactant) 0.5%, Demol N (registered trademark) (Kao Corporation surfactant) 0.5
%, 20% of Kunilite 201 (diatomaceous earth manufactured by Kunimine Industry Co., Ltd.), and 69% of Siglite CA (clay manufactured by Siglite Mining Co., Ltd.) were uniformly mixed and pulverized to obtain a wettable powder.

[0078]

[Formulation Example 2] (Emulsion) No. 7 compound 30%, emulsifier Solpol SM100
(Registered trademark) (Toho Chemical Co., Ltd. surfactant) 10%
And xylene 60% were mixed well to prepare an emulsion.

[0079]

[Formulation Example 3] (Granule) 5% of No. 12 compound, 2% of sodium salt of lauryl alcohol sulfate, 5% of sodium ligninsulfonate, 2% of sodium salt of carboxymethylcellulose and 86% of clay are uniformly mixed and ground. To do. 20 parts by weight of water was added to 100 parts by weight of this mixture, and the mixture was kneaded, processed into granules of 14 to 32 mesh using an extrusion granulator, and then dried to obtain granules.

Next, the present invention will be described more specifically with reference to examples.

[0081]

Example 1 (Step A) 5-t-Butyl-3- (2H-7-fluoro-4-methoxymethyl-3,4-dihydro-1,4-benzoxazin-3-one-6-yl) -4-oxazoline-2-
On (Compound No. 10)

[0082]

[Chemical 7]

Ethyl N- (2H-7-fluoro-4-
Methoxymethyl-3,4-dihydro-1,4-benzoxazin-3-one-6-yl) carbamate 1.0 g
(3.3 mmol) and 0.72 g of α-bromopinacholine
To a solution of (4.0 mmol) in dimethylformamide (DMF),
7.35 ml of lithium bis (trimethylsilyl) amide
(1 molar tetrahydrofuran solution) was slowly added dropwise at room temperature. After stirring for 1 hour, the mixture was poured into water and extracted with ethyl acetate. The extract was dried (MgSO ₄ ), concentrated and the residue was purified by silica gel column chromatography to give 1.3 g (43
%) Of the title compound was obtained.

[0084]

Example 2 (Step B and Step C) 5-t-butyl-4-chloro-3- (2H-7-fluoro-4-methoxymethyl-3,4-dihydro-1,4-
Benzoxazin-3-one-6-yl) -4-oxazolin-2-one (Compound No. 12)

[0085]

[Chemical 8]

Chlorine gas was blown into the carbon tetrachloride solution of 1.3 g (3.7 mmol) of the compound of Compound No. 10 produced in Example 1 at room temperature for 4 minutes. The reaction solution was stirred for 5 minutes, poured into saturated sodium bicarbonate water, and extracted with dichloromethane. The extract was dried (MgSO _4), concentrated, 5-t-butyl-4,5-dichloro-3-(2H-7- fluoro-4-
Methoxymethyl-3,4-dihydro-1,4-benzoxazin-3-one-6-yl) oxazolidin-2-
1.4 g of a crude on product were obtained.

1.4 g of the above crude product was dissolved in dimethyl sulfoxide, and 1,8-diazabicyclo [5.4.
4 ml of 0] -7-undecene was slowly added dropwise. Thirty
After stirring for 1 minute, the reaction solution was poured into water and extracted with ethyl acetate. The extract was dried (MgSO ₄ ), concentrated and the residue was purified by silica gel chromatography to give 0.51 g (total yield 36%) of the desired product.

[0088]

Example 3 (Step D) 5-t-butyl-4-chloro-3- (2H-7-fluoro-3,4-dihydro-1,4-benzoxazine-3
-On-6-yl) -4-oxazolin-2-one (Compound No. 1)

[0089]

[Chemical 9]

5-t-butyl-4-chloro-3- (2H-7-fluoro-4-methoxymethyl-3,4-dihydro-1,4-benzoxazine-3-, prepared by the method of Example 2. On-6-yl) -4-oxazolin-2-one 0.10 g (0.26 mmol) of a 1,1,2,2-tetrachloroethane solution (2 ml) was added with trifluoroacetic acid (0.1 ml).
60 ml (7.8 mmol) was added and the mixture was stirred at 110 ° C. for 6.5 hours. The reaction solution was poured into saturated sodium bicarbonate water and extracted with ethyl acetate. The extract was dried (MgSO ₄ ), concentrated, and then the residue was purified by silica gel chromatography to recover 32 mg of the raw material (recovery rate 32%) to obtain 32 mg (36%) of the desired product.

[0091]

Example 4 (Step E) 5-t-butyl-4-chloro-3- [2H-7-fluoro-4- (2-propynyl) -3,4-dihydro-1,
4-benzoxazin-3-one-6-yl] -4-oxazolin-2-one (Compound No. 7)

[0092]

[Chemical 10]

5-t-butyl-4-chloro-3- (2H-7-fluoro-3,4-dihydro-1,4-benzoxazin-3-one-6-yl prepared by the method of Example 3 ) -4-Oxazolin-2-one 32 mg (0.092 mmol)
Of dimethylformamide solution of 0 ° C under argon gas
5.1 mg of sodium hydride (60% oil dispersion reagent)
Was added to the dimethylformamide suspension. After stirring for 10 minutes, 12 μl of propargyl bromide was added. 3 at room temperature
After stirring for an hour, the mixture was poured into water and extracted with ethyl acetate. The extract was dried (MgSO _4), concentrated, and purified by silica gel chromatography to give the desired product 15mg (43%).

[0094]

Example 5 (Step F) 5-t-butyl-4-chloro-3- (7-fluoro-4)
-Hydroxychroman-6-yl) -4-oxazolin-2-one (Compound No. 22)

[0095]

[Chemical 11]

5-t-prepared according to the method of Example 2
Butyl-4-chloro-3- (7-fluoro-4-t-butyldimethylsilyloxychroman-6-yl) -4-
To a tetrahydrofuran solution containing 0.10 g (0.22 mmol) of oxazolin-2-one, 0.23 ml of tetrabutylammonium fluoride (1M tetrahydrofuran solution)
Was added and stirred at room temperature for 30 minutes. Pour the reaction solution into water,
It was extracted with ethyl acetate. The extract was washed with saturated brine, dried (MgSO ₄ ) and concentrated, and the residue was purified by silica gel column chromatography to give 0.075 g (100
%) Was obtained.

[0097]

Example 6 (Step G) 5-t-butyl-4-chloro-3- (7-fluorochroman-4-on-6-yl) -4-oxazoline-2-
On (Compound No. 23)

[0098]

[Chemical 12]

5-t-butyl-4-chloro-3- (7-fluoro-4-hydroxychroman-6-yl) -4-oxazolin-2-one prepared by the method of Example 5
0.94 g of manganese dioxide was added to a dichloromethane solution of 081 g (0.24 mmol), and the mixture was stirred at room temperature for 1 hour. The reaction solution was filtered and the filtrate was concentrated to 45 mg (55
%) Of the title compound was obtained.

[0100]

Example 7 (Step H) 5-t-butyl-4-chloro-3- (7-fluoro-4)
-Methoxyiminochroman-6-yl) -4-oxazolin-2-one (Compound Nos. 24 and 25)

[0101]

[Chemical 13]

5-t-butyl-4-chloro-3- (7-fluorochroman-4-one-6-yl) -4-oxazolin-2-one prepared by the method of Example 6 0.070
g (0.21 mmol) of water and ethanol mixed solution (water: 0.
To 1 ml of ethanol and 2.9 ml of ethanol, add 0.028 g of O-methylhydroxylamine hydrochloride and 0.35 g of baking soda,
The mixture was stirred at 80 ° C for 2.5 hours. The reaction solution was poured into water and extracted with ethyl acetate. Wash the extract with saturated saline and dry (M
gSO ₄ ), concentrated, and the residue was purified by silica gel column chromatography to give 41 mg (53%) of the title compound as the less polar isomer and 17 mg (22%) of the more polar isomer as the title compound. (Compound No. 25) was obtained.

[0103]

[Effects of the Invention] Next, the effects will be specifically shown with reference to biological test examples.

[0104]

[Test Example 1] Paddy field weeding Submerged soil treatment 100 cm ² polypropylene pot 3 pots (A,
(B and C) were filled with paddy soil, and seeds of broad-leaved weeds, such as denuded algae, fireflies, eels, azaleas, and yellow cypresses, were mixed in the A pot to the surface layer 1 cm. Germination was carried out in pot B, and tubers of Mizugaya-tsuguri, Kurowai, Urikawa and pineapple were planted, and seedlings of paddy rice at the two-leaf stage were transplanted in pot C. Each pot was submerged, grown in a greenhouse, and after 3 days, the wettable powder prepared in Formulation Example 1 was used to treat the submerged soil with a predetermined amount, and 21 days later, an investigation was conducted according to the following criteria. I did. The results are shown in Table 2.

Judgment Criteria 0 --- Growth inhibition rate 0-10% 1 --- Growth inhibition rate 11-30% 2--Growth inhibition rate 31-50% 3--Growth inhibition rate 51-70% 4 --- Growth inhibition rate 71-90% 5 --- Growth inhibition rate 91-100% In addition, all the comparative compounds of Table 2, Table 3 and Table 4 are the following compounds described in JP-A-62-42976. It is a compound.

[0106]

[Chemical 14]

In Tables 2, 3, and 4, EO is Taenia muscaria, BL is broadleaf weeds, SJ is firefly, and EA.
Is Matsubayashi, CS is Mizugaya, EK is Kurogwai, OS is paddy rice, SP is Urikawa, EC is barnyard grass, SV is Enocologsa, and DS is Mejishiba, AR
Stands for hiyu, AT stands for hibiscus, SN stands for physalis, Z
M indicates corn, TA indicates wheat, and GM indicates soybean.

[0108]

[Table 2]   ──────────────────────────────────   Compound   Dosage   number   (g / a)   EO   BL   SJ   EA   SP   CS   EK   OS   ──────────────────────────────────   Two   10   5   5   5   Three   5   Three   5   Three   Two   5   5   5   5   −   −   −   −   1   Three   10   5   5   5   Four   5   5   Four   Two   Three   5   5   5   5   5   −   −   −   1   5   10   5   5   5   Three   5   Two   5   1   5   5   5   5   5   5   −   −   −   0   7   10   5   5   5   Three   5   5   5   Three   7   5   5   5   5   −   −   −   −   0   9   10   5   5   5   5   5   1   5   1   9   5   5   5   5   −   −   −   −   0   12   10   5   5   5   5   5   5   5   Two   12   5   5   5   5   −   −   −   −   1     17   10   5   5   5   Two   5   1   5   0   17   5   5   5   Four   −   −   −   −   0   19   10   5   5   5   Two   5   1   Four   0   19   5   5   5   Four   −   −   −   −   0   24   10   5   5   Four   1   Two   Two   5   0   24   5   5   5   Three   −   −   −   −   0   25   10   5   5   Four   Two   Two   Three   5   0   25   5   5   5   Four   −   −   −   −   0   ──────────────────────────────────   Comparison   10   Two   Four   Two   Three   0   Two   Three   0   Compound   Comparison   5   0   Three   0   0   0   0   1   0   Compound   ──────────────────────────────────  

[0109]

[Test Example 2] Soil treatment before outbreak of field weeds Field soil was filled in a plastic pot with an area of 150 cm ² , and after sowing seeds of weeds, Echinochlox globosa, Mehibushus, millet, velvetleaf, physalis and corn, wheat and soybean were sown. , Cover with a thickness of 1 cm,
It was placed in a greenhouse. Immediately after covering with soil, the wettable powder prepared in Formulation Example 1 was used to treat the soil surface with a predetermined amount. On the 21st day after the treatment, the investigation was conducted according to the criteria shown in Test Example 1. The results are shown in Table 3.

[0110]

[Table 3] ──────────────────────────────────── Compound dose No. kg / ha ES SV DS AR AT SN ZM TA GM ──────────────────────────────────── 2 1 5 5 5 5 5 4 − 3 0 0 2 0.5 5 5 5 5 5 3-0 0 0 0 3 1 5 5 5 5 5 3 -1 1 1 1 3 0.5 5 5 4 5 5 3-0 0 0 0 7 1 5 5 5 5 5 5-2 1 1 0 7 0.5 5 5 5 5 5-1 0 0 9 1 5 4 4 5 5 3-0 0 0 9 9 0.5 4 2 3 5 3-0 0 0 0 12 1 5 5 5 5 5 5 5 2 2 0 12 12 0.5 5 5 5 5 5 5 5 5 1 10 ──────────────────────────────────── Comparison 1 2 3 3 3 3 4 0 0 0 compounds Comparative 0.5 0 1 1 1 1 1 2 0 0 0 Compounds ─────── ─────────────────────────────

[0111]

[Test Example 3] Field weed foliage treatment Stem and foliage Field soil is filled in a plastic pot with an area of 150 cm ² and seeds of weed seeds of barnyardgrass, green locusts, crabgrass, millet, velvetleaf, physalis, and corn, wheat, soybean are sown. After that, the soil was covered with a thickness of 1 cm. After that, it was grown in a greenhouse, and after 2 weeks, Formulation Example 1
A prescribed amount of the drug was prepared using the wettable powder prepared in (1) and sprayed on the foliage of the plant. On the 14th day after the treatment, the investigation was conducted according to the criteria shown in Test Example 1. The results are shown in Table 4.

[0112]

[Table 4] ──────────────────────────────────── Compound concentration number (ppm) ES SV DS AR AT SN ZM TA GM ──────────────────────────────────── 2 125 4 4 4 5 5-0 0 2 3 125 4 4 4 5 5 − 0 0 1 5 125 1 1 1 1 5 5 − 0 0 1 1 7 125 3 2 3 5 5 − 0 0 2 9 125 3 3 3 3 5 5 − 0 0 3 12 12 125 5 5 5 5 5 5 2 0 3 17 17 125 0 0 0 5 5-5-0 0 0 0 25 125 2 2 2 4 5-0 0 0 0 ────────────────────── ─────────────── Comparison 125 1 2 1 3 4 4 0 0 0 Compounds ──────────────────────── ─────────────

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeshi Endo 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga In-house (72) Inventor Masahiro Shindo 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga In-house

Claims (2)

[Claims] 1. A compound represented by the general formula (I): [In the formula, X represents a hydrogen atom or a chlorine atom, Y represents a chlorine atom or a fluorine atom, R represents a hydrogen atom or a lower alkyl group, and AB represents N (R ¹ )-(C = O) group,
CH (-W ¹ ) -CH ₂ group or C (= W ² ) -CH ₂ group (in the formula, R ¹ is a hydrogen atom, a lower alkoxy group or a lower alkyl group which may be substituted with a lower alkoxy lower alkoxy group) , A lower alkynyl group, a benzyl group or a p-methoxybenzyl group, W ¹ represents a t-butyldimethylsilyloxy group, a hydroxyl group, W ² represents an oxygen atom or N
It shows a —OCH ₃ group. ) Is shown. ] The compound represented by. 2. A herbicide containing the compound according to claim 1 as an active ingredient.