JPH08193011A - Herbicidal sulfonamide compound - Google Patents

Abstract

PURPOSE: To obtain a new sulfonamide compound useful as a strong herbicide, having excellent herbicidal activity free from phytotoxicity of rice plant. CONSTITUTION: This sulfonamide compound is shown by formula I [R<1> is H, a 2-10C alkanoyl or benzoyl (the benzoyl may be substituted with a halogen or methyl); R<2> to R<4> are each H or a halogen], or is a sulfonamide compound wherein R<1> is H, propionyl, butanoyl or benzoyl, R<2> and R<4> are each H or a halogen, R<3> is H in formula I or a sulfonamide compound wherein R<1> is H or propionyl, R<2> is H or a halogen, R<3> and R<4> are each H in formula I, for example, N-[4-(2-pyrimidinyloxy)phenyl]-trifluoromethanesulfonamide. The compound of formula I, for example, is obtained by subjecting a compound of formula II (Y is an eliminable group) and a compound of formula III to substitution reaction to give an ether of formula IV, then reducing the nitro group to give a compound of formula V and further reacting the resultant compound with a reactive derivative of trifluoromethanesulfonic acid.

Description

Detailed Description of the Invention

[0001]

[Object of the invention]

[0002]

TECHNICAL FIELD The present invention relates to a novel sulfoneanilide derivative having a strong herbicidal action and a herbicide containing the compound as an active ingredient.

[0003]

2. Description of the Related Art The fact that some sulfoneanilide derivatives have herbicidal activity has been reported in, for example, Japanese Patent Laid-Open No.
No. 149567 (however, a sulfonamide group and a pyrimidinyloxy or triazinyloxy group as a substituent of a benzene ring are only compounds limited to ortho substitution), and US Pat. No. 4,345,076. (However, the substituent corresponding to the pyrimidinyl group of the general formula (I) of the present application is a pyridazinyl group.). or,
JP-A-60-222461 also discloses certain sulfonanilide derivatives, but although they are shown to have insecticidal activity, they are not described to have herbicidal activity at all.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The compound described in Japanese Patent Publication No. 49567 does not have sufficient herbicidal activity at the time of applying a low dose, as shown in Test Examples described later.

The compounds described in the above-mentioned US Pat. No. 4,345,076 also have strong phytotoxicity to rice and cannot be safely used as herbicides, as shown in the test examples below.

The present inventors have conducted extensive studies for many years on the synthesis of a derivative having a sulfoneanilide structure and its pharmacological activity. As a result, a novel sulfoneanilide derivative having a structure completely different from that of a known compound was found. The present invention was completed by finding that it has an excellent herbicidal activity that is not harmful to rice.

[0007]

Configuration of the Invention

[0008]

The present invention has the general formula (I)

[0009]

[Chemical 4]

[Wherein R ¹ is a hydrogen atom, C 2 -C 10
An alkanoyl group or a benzoyl group (the benzoyl group may be substituted with one or two substituents selected from a halogen atom and a methyl group), R ² , R
³ and R ⁴ are the same or different and each represents a hydrogen atom or a halogen atom. ] A sulfonamide compound represented by
Suitably, [wherein R ¹ represents a hydrogen atom, a propionyl group, a butanoyl group or a benzoyl group (the benzoyl group may be substituted with 1 or 2 halogen atoms), R ² and R ⁴ is the same or different and represents a hydrogen atom or a halogen atom, and R ³ is a hydrogen atom. And more preferably [wherein R ¹ represents a hydrogen atom or a propionyl group, R ² represents a hydrogen atom or a halogen atom, and R ³ and R ⁴ represent a hydrogen atom] Indicates. ], Most preferably N- [4- (2-pyrimidinyloxy) phenyl] trifluoromethanesulfonamide and N- [2-chloro-4- (2-pyrimidinyloxy) phenyl] trifluoromethane. Sulfonamide,
And a herbicidal composition containing these sulfonamide compounds as active ingredients.

In the present application, the "C2-C10 alkanoyl group" means a total carbon such as acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, octanoyl, decanoyl, cyclopropanecarbonyl, cyclobutanecarbonyl, cyclopentanecarbonyl. A group in which a carbonyl group is bonded to a straight-chain, branched-chain or cyclic alkyl group of the number 1 to 9, and preferably
Propionyl, butyryl, cyclopropanecarbonyl,
Cyclobutanecarbonyl, more preferably propionyl.

In the present application, the "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom.

In the present application, the "benzoyl group optionally substituted by 1 or 2 substituents selected from halogen atom, methyl group and ethyl group" means, for example, benzoyl, 2-chlorobenzoyl, 3-chloro. Benzoyl, 4-
Chlorobenzoyl, 2,4-dichlorobenzoyl, 3,5-dichlorobenzoyl, 2,6-dichlorobenzoyl, 2-fluorobenzoyl, 3-fluorobenzoyl, 4-fluorobenzoyl, o-toluoyl, m-toluoyl, p-toluoyl , 2,
4-dimethylbenzoyl, 3,5-dimethylbenzoyl, 2,3-
A group such as dimethylbenzoyl and 2,6-dimethylbenzoyl, preferably benzoyl, 4-chlorobenzoyl, 2-fluorobenzoyl, p-toluoyl and 2,4-dimethylbenzoyl, and more preferably, Benzoyl and 2-fluorobenzoyl.

In the compound of the general formula (I) of the present application, R ¹
Is preferably a hydrogen atom or a propionyl group, and most preferably a hydrogen atom.

R ² is preferably a hydrogen atom or a chlorine atom.

R ³ is preferably a hydrogen atom.

R ⁴ is preferably a hydrogen atom.

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

In the table, "Ph" means a phenyl group and "cP"
"r" is a cyclopropyl group, "cBu" is a cyclobutyl group, "cPen" is a cyclopentyl group, and "cHex" is a cyclohexyl group.

[0020]

Embedded image

[0021]

[Table 1] ──────────────────────────────────── Compound number R ¹ R ² R ³ R ⁴ Physical properties / melting point (℃) ──────────────────────────────────── 1 H H H H 138-141 2 H H H Cl 176-177 3 H H H Br 178-179 4 H Cl H H 157-159 5 H H Cl H 180-183 6 H F H H 170-175 7 H H F H 166-169 8 H Cl Cl H 9 H H F Cl 119 10 H H H F 11 H Cl H Cl 158-162 12 H H Cl Cl 124-126 13 H F H Cl 133-136 14 COCH ₃ H H H 107-108 15 COCH ₂ CH ₃ H H H 86 16 CO (CH ₂ ) ₂ CH ₃ H H H 75 17 COCH (CH ₃ ) ₂ H H H 18 CO (CH ₂ ) ₃ CH ₃ H H H 81-84 19 COCH ₂ CH (CH ₃ ) ₂ H H H 84 20 COCH (CH ₃ ) CH ₂ CH ₃ H H H 21 COC (CH ₃ ) ₃ H H H 179-183 22 CO (CH ₂ ) ₄ CH ₃ H H H 23 CO (CH ₂ ) ₅ CH ₃ H H H 24 CO (CH ₂ ) ₈ CH ₃ H H H 66 25 CO (CH ₂ ) ₂ CH ₃ Cl H H 26 CO-cBu H Cl H 27 CO (CH ₂ ) ₂ CH ₃ F H H 28 CO-cPen H F H 29 CO-cBu Cl Cl H 30 CO-cPr H H H 80 31 CO-cBu H H H 103-105 32 CO-cPen H H H 33 CO-cHex H H H Oil 34 CO (CH ₂ ) ₂ CH ₃ H H Cl 35 COCH ₂ CH ₃ H H Cl 126-128 36 COCH ₂ CH ₃ Cl H H 116-120 37 CO (CH ₂ ) ₂ CH ₃ H H F 38 COCH ₂ CH ₃ Cl H Cl 95 39 COCH ₂ CH ₃ H Cl Cl 40 COCH ₂ CH ₃ F H Cl 41 CO-Ph H H H 126-128 42 CO- (2-Cl-Ph) H H H 43 CO- (3-Cl-Ph) H H H 44 CO- (4-Cl-Ph) H H H 112-115 45 CO- (2-F-Ph) H H H 134-136 46 CO- (2-CH ₃ -Ph) H H H 47 CO- (3 -CH ₃ -Ph) H H H 48 CO- (4-CH ₃ -Ph) H H H Oil 49 CO- (2,4-Cl ₂ -Ph) H H H 50 CO- (3,5-Cl ₂ -Ph) Cl H H 51 CO- ( 2,4- (CH 3) 2 -Ph) H H H 96-98 ───────────── ────────────────────── In Table 1, preferably, 1,2,4,5,6,
7, 9, 15, 16, 30, 31, 33, 35, 36,
Compound No. 38 can be mentioned, and more preferably,
1,4,5,6,7,15,16,36,41 compounds can be mentioned, and more preferably 1,4,4
Nos. 6,15 compounds can be mentioned, and most preferably, Nos. 1,4 compounds can be mentioned.

The compound numbers, compound names and nuclear magnetic resonance spectra of the compounds in Table 1 are shown below. In addition, [NMR (20
0MHz, CDCl ₃ ) δ (ppm)] is omitted.

Compound No. 1 N- [4- (2-pyrimidinyloxy) phenyl] tri
Fluoromethanesulfonamide 9.10 (br.s, 1H), 8.60 (d, 2H, J = 4.8Hz), 7.31 (d, 2H, J = 8.0
Hz), 7.15 (d, 2H, J = 8.0Hz), 7.12 (t, 1H, J = 4.8Hz). Compound No. 2 N- [4- (5-chloro-2-pyrimidinyloxy) phenyl
[Ethyl] trifluoromethanesulfonamide 8.48 (s, 2H), 7.33 (d, 2H, J = 9.0Hz), 7.17 (d, 2H, J = 9.0H)
z). Compound No. 3 N- [4- (5-bromo-2-pyrimidinyloxy ) phenyl
[Ethyl] trifluoromethanesulfonamide 8.57 (s, 2H), 7.33 (d, 2H, J = 9.0Hz), 7.18 (d, 2H, J = 9.0H)
z). Compound No. 4 N- [2-chloro-4- (2-pyrimidinyloxy) phenyl
[Ethyl] trifluoromethanesulfonamide 8.60 (d, 2H, J = 4.8Hz), 7.64 (d, 1H, J = 9.9Hz), 7.37 (d, 1H,
J = 2.6Hz), 7.20 (dd, 1H, J = 2.6,9.9Hz), 7.13 (t, 1H, J = 4.8
Hz). Compound No. 5 N- [3-chloro-4- (2-pyrimidinyloxy) phenyl
[Ethyl] trifluoromethanesulfonamide 8.50 (d, 2H, J = 3.2Hz), 7.38 (m, 1H), 7.29 (m, 2H), 7.06
(t, 1H, J = 3.2Hz). Compound No. 6 N- [2-fluoro-4- (2-pyrimidinyloxy)
Phenyl] trifluoromethanesulfonamide 8.60 (d, 2H, J = 4.8Hz), 8.01 (s, 1H), 7.55 (t, 1H, J = 8.7H
z), 7.03-7.22 (m, 3H). Compound No. 7 N- [3-fluoro-4- (2-pyrimidinyloxy)
Phenyl] trifluoromethanesulfonamide 8.52 (d, 2H, J = 4.8Hz), 7.03-7.23 (m, 4H). Compound No. 9 N- [3-Fluoro-4- (5-chloro-2-pyrimidi)
Nyloxy) phenyl] trifluoromethanesulfone
Mido 9.30 (br.s, 1H), 8.52 (s, 2H), 7.16-7.31 (m, 3H). Compound No. 11 N- [2-chloro-4- (5-chloro-2-pyrimidini )
Luoxy) phenyl] trifluoromethanesulfonami
De 8.52 (s, 2H), 7.67 (d, 1H, J = 9.0Hz), 7.36 (d, 1H, J = 2.7H
z), 7.18 (dd, 1H, J = 2.7,9.0Hz), 7.04 (br.s, 1H). Compound No. 12 N- [3-chloro-4- (5-chloro-2 -pyrimidini)
Luoxy) phenyl] trifluoromethanesulfonami
De 8.51 (s, 2H), 7.47 (br.s, 1
H), 7.45 (d, 1H, J = 2.0 Hz),
7.27 (m, 2H). Compound No. 13 N- [4- (5-chloro-2-pyrimidinyloxy)-
2-Fluorophenyl] trifluoromethanesulfone
Mid 8.47 (s, 2H), 7.45 (t, 1H, J =
9.0 Hz), 6.85-6.98 (m, 2H). Compound No. 14 N-acetyl-N- [4- (2-pyrimidinyloxy)
Phenyl] trifluoromethanesulfonamide 8.60 (d, 1H, J = 4.8Hz), 7.37 (s, 4H), 7.12 (t, 1H, J = 4.8H
z), 2.24 (s, 3H). Compound No. 15 N-propionyl-N- [4- (2-pyrimidinyloxy)
Si) Phenyl] trifluoromethanesulfonamide 8.59 (d, 2H, J = 4.8Hz), 7.36 (s, 4H), 7.12 (t, 1H, J = 4.8H
z), 2.35 (q, 2H, J = 7.2Hz), 1.11 (t, 3H, J = 7.2Hz). Compound No. 16 N-butyryl-N- [4- (2-pyrimidinyloxy)
Phenyl] trifluoromethanesulfonamide 8.58 (d, 2H, J = 4.9Hz), 7.35 (s, 4H), 7.11 (t, 1H, J = 4.9H
z), 2.30 (t, 2H, J = 7.2Hz), 1.64 (hexatet, 2H, J = 7.2Hz),
0.89 (t, 3H, J = 7.2Hz). Compound No. 18 N-pentanoyl-N- [4- (2-pyrimidinyloxy)
Si) Phenyl] trifluoromethanesulfonamide 8.58 (d, 2H, J = 4.8Hz), 7.35 (s, 4H), 7.11 (t, 1H, J = 4.8H
z), 2.32 (t, 2H, J = 7.2Hz), 1.60 (quintet, 2H, J = 7.2Hz),
1.28 (hexatet, 2H, J = 7.2Hz), 0.84 (t, 3H, J = 7.2Hz). Compound No. 19 N- (3-methylbutyryl) -N- [4- (2-pyrimy
Dinyloxy) phenyl] trifluoromethanesulfone
Amide 8.58 (d, 2H, J = 4.8Hz), 7.35 (s, 4H), 7.11 (t, 1H, J = 4.8H
z), 2.04-2.22 (m, 3H), 0.91 (d, 6H, J = 6.6Hz). Compound No. 21 N- (2,2-dimethylpropionyl) -N- [4-
(2-Pyrimidinyloxy) phenyl] trifluorome
Tan sulfonamide 8.58 (d, 2H, J = 4.8Hz), 7.43
(D, 2H, J = 8.9 Hz), 7.32 (d, 2
H, J = 8.9 Hz), 1.31 (s, 9H). Compound No. 24 N-decanoyl-N- [4- (2-pyrimidinyloxy
Si) Phenyl] trifluoromethanesulfonamide 8.58 (d, 2H, J = 4.8Hz), 7.35 (s, 4H), 7.11 (t, 1H, J = 4.8H
z), 2.31 (t, 2H, J = 7.2Hz), 1.61 (m, 2H), 1.22 (br.s, 12
H), 0.85 (t, 3H, J = 6.2Hz). Compound No. 30 N-cyclopropanecarbonyl-N- [4- (2 -pyri
Midinyloxy) phenyl] trifluoromethanesulfo
Amide 8.58 (d, 2H, J = 4.8Hz), 7.43 (d, 2H, J = 8.9Hz), 7.35 (d, 2H,
J = 8.9Hz), 7.12 (t, 1H, J = 4.8Hz), 1.55 (heptet, 1H, J = 4.3
Hz), 1.22 (m, 2H). Compound No. 31 N-cyclobutanecarbonyl-N- [4- (2-pyrimy
Dinyloxy) phenyl] trifluoromethanesulfone
Amide 8.58 (d, 2H, J = 4.8Hz), 7.31 (s, 4H), 7.11 (t, 1H, J = 4.8H
z), 3.05-3.20 (m, 1H), 2.21-2.45 (m, 2H), 1.72-1.98 (m,
4H). Compound No. 33 N-cyclohexanecarbonyl-N- [4- (2-pyri
Midinyloxy) phenyl] trifluoromethanesulfo
Amide 8.60 (d, 2H, J = 4.8Hz), 7.37 (s, 4H), 7.10 (t, 1H, J = 4.8H
z), 2.25-2.40 (m, 2H), 0.99-2.05 (m, 10H). Compound No. 35 N-propionyl-N- [4- (5-chloro-2-pyri
Midinyloxy) phenyl] trifluoromethanesulfo
Namide 8.52 (s, 2H), 7.35 (s, 4H),
2.38 (q, 2H, J = 7.3 Hz), 1.14
(T, 3H, J = 7.3 Hz). Compound No. 36 N-propionyl-N- [2-chloro-4- (2-pyri
Midinyloxy) phenyl] trifluoromethanesulfo
Amide 8.60 (d, 2H, J = 4.8 Hz), 7.50
(D, 1H, J = 2.6 Hz), 7.41 (d, 1
H, J = 8.8 Hz), 7.28 (dd, 1H, J =
4.8, 8.8 Hz), 7.15 (t, 1H, J =
4.8 Hz), 2.34 (q, 2H, J = 7.2H
z), 1.14 (t, 3H, J = 7.2 Hz). Compound No. 38 N-propionyl-N- [2-chloro-4- (5-chloro
(2-Pyrimidinyloxy) phenyl] trifluoro
Methanesulfonamide 8.52 (s, 2H), 7.48 (d, 1H, J = 2.5Hz), 7.42 (d, 1H, J = 8.7H
z), 7.26 (dd, 1H, J = 2.5,8.7Hz), 2.34 (q, 2H, J = 7.2Hz),
1.14 (t, 3H, J = 7.2Hz). Compound No. 41 N-benzoyl-N- [4- (2-pyrimidinyloxy)
Si) Phenyl] trifluoromethanesulfonamide 8.56 (d, 2H, J = 5.1Hz), 7.66 (d, 2H, J = 7.0Hz), 7.29-7.50
(m, 5H), 7.20 (d, 2H, J = 6.1Hz), 7.09 (t, 1H, J = 5.1Hz). Compound No. 44 N- (4-chlorobenzoyl) -N- [4- (2- Pili
Midinyloxy) phenyl] trifluoromethanesulfo
Amide 8.57 (d, 2H, J = 4.8Hz), 7.60 (d, 2H, J = 8.2Hz), 7.20-7.41
(m, 6H), 7.10 (t, 1H, J = 4.8Hz). Compound No. 45 N- (2-fluorobenzoyl) -N- [4- (2 -pi-
Limidinyloxy) phenyl] trifluoromethanesul
Hongamide 8.55 (d, 2H, J = 4.8Hz), 7.10-7.52 (m, 7H), 7.08 (t, 1H, J =
4.8Hz), 6.96 (t, 1H, J = 8.9Hz). Compound No. 48 N- (p-toluoyl) -N- [4- (2-pyrimidini
Luoxy) phenyl] trifluoromethanesulfonami
De 8.57 (d, 2H, J = 4.8Hz), 7.57 (d, 2H, J = 8.3Hz), 7.40 (d, 2H,
J = 9.1Hz), 7.21 (d, 2H, J = 9.1Hz), 7.13 (d, 2H, J = 8.3Hz),
7.09 (t, 1H, J = 4.8Hz). Compound No. 51 N- (2,4-dimethylbenzoyl) -N- [4- (2
-Pyrimidinyloxy) phenyl] trifluoromethane
Sulfonamide 8.55 (d, 2H, J = 4.8Hz), 7.30 (d, 2H, J = 8.9Hz), 7.05-7.22
(m, 4H), 6.96 (s, 1H), 6.86 (d, 1H, J = 7.7Hz), 2.44 (s, 3
H), 2.25 (s, 3H). The compound represented by the general formula (I) of the present invention is produced by the steps shown below.

[0024]

[Chemical 6]

In the formula, R ² , R ³ and R ⁴ have the same meanings as described above, Y represents a halogen atom or a methanesulfonyl group, and R ^1b represents a C2-C10 alkanoyl group or a benzoyl group (the benzoyl group). Is a halogen atom, a methyl group,
Which may be substituted with 1 or 2 substituents selected from an ethyl group).

Hereinafter, these general manufacturing methods will be described in more detail.

(Step A) In this step, compound (III)
And a compound (II) having a leaving group Y in the presence or absence of a solvent in a substitution reaction using a base to produce an ether represented by the general formula (IV).

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 undecene,
Alkali metal bases such as sodium hydride, calcium hydride, sodium, lithium, n-butyllithium, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium methoxide and potassium t-butoxide, sodium hydroxide, potassium hydroxide. ,
Inorganic bases such as sodium carbonate and potassium carbonate, preferably sodium hydride, lithium bis (trimethylsilyl) amide, and potassium carbonate.

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

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, 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,
It is 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.

(Step B) This step is a step for producing the compound (V) by reducing the nitro group of the compound (IV) to an amino group, and a method usually used for reducing the nitro group is used. You can

One example of such a case is catalytic reduction using a noble metal catalyst. Suitable catalysts used in the reaction include, for example, palladium-carbon, palladium-barium sulfate, platinum oxide and the like.

Suitable examples of the solvent used in the reaction include alcohols such as methanol and ethanol: tetrahydrofuran, ethers such as dioxane: or esters such as ethyl acetate.

The reaction temperature is preferably 10 ° C. to 80 ° C., and the reaction time is usually 10 minutes to 5 hours.

Another suitable reduction method is reduction with zinc dust or iron powder in an acetic acid solvent. The reaction temperature is preferably 0 ° C. to room temperature, and the reaction time is usually about 10 minutes to 2 hours.

Further, tin chloride (I
I) -Sodium borohydride can also be used.
Suitable examples of the solvent used in the reaction include alcohols such as methanol and ethanol. The reaction temperature is preferably 10 ° C to 80 ° C, and the reaction time is usually about 10 minutes to 5 hours. The amount of tin (II) chloride used is usually 4 to 20 equivalents, preferably 5 to 7 equivalents, and the amount of sodium borohydride is usually 0.2 to 1 equivalents, relative to compound (IV). It is preferably 0.5 equivalent.

(Step C) In this step, the ether represented by the general formula (V) is produced by subjecting compound (VI) and compound (II) to substitution reaction with a base in the presence or absence of a solvent. It is a process. This step can be performed in the same manner as in step A.

(Step D) In this step, the compound of the present invention is obtained by reacting the compound (V) as a raw material with a reactive derivative of trifluoromethanesulfonic acid in the presence of a solvent and a reaction aid. (Ia) and compound (VI
It is a process of manufacturing I).

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- Butyllithium, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, alkali metal bases such as potassium t-butoxy, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and preferably triethylamine And organic tertiary amines such as pyridine.

Suitable reactive derivatives of trifluoromethanesulfonic acid are, for example, acid halides and acid anhydrides, preferably acid chlorides, acid fluorides and acid anhydrides.

The amount of the reaction aid used is usually 1 to 20 times equivalent, preferably 1.5 to 5 times equivalent to the compound (V), and the amount of the reactive derivative of trifluoromethanesulfonic acid used is equal to that of the compound (V). It is usually 1 to 20 times equivalent, preferably 1.5 to 3 times equivalent to (V).

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 methylene chloride and 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.

In this step, compound (Ia) and compound (VII) are usually produced simultaneously. The ratio can vary greatly depending on the reaction conditions, particularly the reactivity of the compound (V) as the raw material and the amount and type of the reactive derivative of trifluoromethanesulfonic acid.

When the purpose is to obtain the compound (Ia), therefore, the reaction product of this step (usually, as described above,
The compound (Ia) and the mixture of (VII)) may be subjected to the below-mentioned hydrolysis reaction, Step E, without isolation or isolation to give Compound (Ia) in the whole amount. When the objective is to obtain the compound (VII), the reaction product of this step may be separated and purified by a usual purification method such as column chromatography.

(Step E) This step is a step of producing the compound (Ia) by isolating the reaction mixture of the above step D or subjecting it to the hydrolysis reaction of this step without isolation.

The hydrolysis reaction is carried out in a solvent in the presence of a base. Preferable examples of the base used include sodium acetate, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide and potassium hydroxide.

The solvent is not particularly limited as long as it does not participate in the reaction, and examples thereof include alcohols such as methanol, ethanol and propanol, diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, 2-
Ethers such as methoxyethyl ether, and water and mixtures of these solvents are used.

The reaction temperature and reaction time are not particularly limited,
Usually -10 ° C to 100 ° C, preferably 0 ° C to 50 ° C
And is 30 minutes to 15 hours, preferably 30 minutes to 8 hours.

(Step F) In this step, the compound of formula (Ia) is reacted with a carboxylic acid represented by the formula R ^1b OH or a reactive derivative thereof to form an amide bond,
A step of producing a compound of formula (Ib).

This step is an amidation reaction of the amino group of the sulfonamide of formula (Ia) with the carboxylic acid R ^1b OH and is therefore carried out by a known method known per se as an amidation reaction. .

Examples of the reactive derivative of carboxylic acid R ^1b OH include, for example, acid halides (acid chloride, acid bromide, etc.), acid anhydrides, mixed acid anhydrides, active esters (eg 2, 3, 4, 5-). Pentafluorophenyl ester), active amides and the like, which are usually used for amidation can be mentioned.

When using an acid halide of the carboxylic acid of formula R ^1b OH, the reaction is preferably carried out in the presence of a base. Suitable bases include, for example, triethylamine,
N, N-dimethylaniline, pyridine, 4-dimethylaminopyridine, 1,5-diazabicyclo [4.3.0]
Mention may be made of organic bases such as nonene-5 (DBN) or 1,8-diazabicyclo [5.4.0] undecene-7 (DBU).

The acid halide of the carboxylic acid R ^1b OH is usually 1 to 10 equivalents, preferably 1 to 3 equivalents, and the base is usually 1 to 10 equivalents, preferably 1.5 to the compound (Ia).
Used up to 10 equivalents.

The reaction is usually carried out in a solvent. The type of solvent is not particularly limited as long as it does not participate in the reaction, and examples thereof include hydrocarbons such as hexane, petroleum ether, benzene, toluene and xylene, halogenated compounds such as chloroform, methylene chloride and o-chlorobenzene. Examples thereof include hydrocarbons, ethers such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and esters such as ethyl acetate.

The reaction temperature is generally 0 ° C. to 100 ° C., preferably 20 ° C. to 60 ° C., and the reaction time is generally 30 minutes to 3 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 field and foliar treatment and soil treatment, 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, yellow grass, 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 action of suppressing the growth of a plant without dying it, it can prevent various lodgings such as prevention of lodging by shortening the paddy rice and reduction of the number of cuttings by suppressing the growth of lawn. Expected to be useful.

To prepare a herbicide and a plant growth regulator from the compound (I) of the present invention, the herbicide and the 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 1 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, upland fields, orchards, meadows, lawns, forests or non-agricultural fields.

The present invention will be described in more detail below with reference to formulation examples and examples, but the present invention is not limited to these.

[0069]

【Example】

[0070]

[Formulation Example 1] (Wettable powder) No. 1 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.

[0071]

[Formulation Example 2] (Emulsion) No. 4 compound 30%, emulsifier Solpol SM100
(Registered trademark) (Toho Chemical Co., Ltd. surfactant) 10%
And xylene 60% were mixed well to prepare an emulsion.

[0072]

[Formulation Example 3] (Granule) 5% of the compound No. 1, 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.

[0074]

Example 1 [Step A] 2- (4-Nitrophenoxy) pyrimidine 4-Nitrophenol (0.50 g, 3.6 mmol) in dimethylformamide (DMF) was added with 2-methanesulfonylpyrimidine (0.63 g, 4.0 mmol). Potassium carbonate (1.1 g, 7.
2 mmol) was added and the mixture was stirred at 90 ° C. for 1 hour. After the reaction,
The reaction solution was poured into water and extracted with ethyl acetate. The extract was dried over magnesium sulfate and concentrated. The residue was purified by column chromatography to give 0.60 g (77%) of the desired product.

Nuclear magnetic resonance spectrum (200 MHz) δ (CDCl ₃ ) p
pm: 8.61 (d, 2H, J = 4.8Hz), 8.32 (d, 2H, J = 9.2Hz), 7.38 (d, 2
H, J = 9.2Hz), 7.15 (t, 1H, J = 4.8Hz)

[0076]

Example 2 [Step B] 2- (4-Aminophenoxy) pyrimidine 2- (4-Nitrophenoxy) pyrimidine (0.23 g, 1.
After adding platinum dioxide (1.0 g) to an ethanol solution of (04 mmol), the mixture was stirred under a hydrogen stream for 1 hour. The reaction solution was filtered through Celite and the filtrate was concentrated to give 0.19 g (95%).
The desired product was obtained.

Nuclear magnetic resonance spectrum (200 MHz) δ (CDCl ₃ ) p
pm: 8.51 (d, 2H, J = 4.8Hz), 6.97 (t, 1H, J = 4.8Hz), 6.96 (d, 2
H, J = 8.9Hz), 6.68 (d, 2H, J = 8.9Hz)

[0078]

Example 3 [Step C] 2- (4-aminophenoxy) pyrimidine 4-aminophenol (0.50 g, 4.6 mmol) in DMF was treated with sodium hydride (0.27 g 6.8 mmo) under an argon atmosphere.
1; 60% purity) and stirred for 15 minutes. Then, 2
-Chloropyrimidine (0.52 g, 4.6 mmol) was added, and the temperature was 90 ° C.
It was stirred for 1 hour. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was dried over magnesium sulfate and concentrated, and the residue was purified by column chromatography to obtain 0.48 g (56%) of the desired product.

[0079]

Example 4 [Step D] 2- [4-N, N-bis (trifluoromethanesulfonyl chloride)
) Aminophenoxy] pyrimidine 2- (4-aminophenoxy) pyrimidine (0.23 g, 1.
23 mmol) in methylene chloride solution under ice-cooling with triethylamine (0.5 ml) and trifluoromethanesulfonic anhydride (0.4 ml).
(9 ml) were sequentially added, and the mixture was stirred for 1 hour. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated to give 0.56 g (100%) of a crude product of the title compound.

Nuclear magnetic resonance spectrum (200 MHz) δ (CDCl ₃ ) p
pm: 8.60 (d, 2H, J = 4.8Hz), 7.25-7.55 (m, 5H).

[0081]

Example 5 [Step E] N- [4- (2-pyrimidinyloxy)] phenyltri
Fluoromethanesulfonamide (Compound No. 1) 2- [4-N, N-bis (trifluoromethanesulfonyl) aminophenoxy] pyrimidine (0.72 g, 1.58 mmo
3N aqueous sodium hydroxide solution was added to the THF solution of l), and the mixture was stirred at room temperature for 1 hour. After the reaction was completed, the reaction solution was poured into water, adjusted to pH 7 with diluted hydrochloric acid, and then extracted with ethyl acetate. The extract was dried over magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 0.26 g (52%) of the desired product.

Nuclear magnetic resonance spectrum (200 MHz) δ (CDCl ₃ ) p
pm: 9.10 (br.s, 1H), 8.60 (d, 2H, J = 4.8Hz), 7.31 (d, 2H, J
= 8.0Hz), 7.15 (d, 2H, J = 8.0Hz), 7.12 (t, 1H, J = 4.8Hz). Mass spectrum (m / Z): 319 (M ⁺ ), 240,
200,187

[0083]

Example 6 [Step F] N-propionyl-N- [4- (2-pyrimidinyloxy)
Si) Phenyl] -trifluoromethanesulfonamide
(Compound No. 15) N- [4- (2-pyrimidinyloxy) phenyl] trifluoromethanesulfonamide (0.25 g, 0.78 mm
ol) in methylene chloride at 0 ° C.
(0.33 ml) and propionyl chloride (0.14 ml) were added, and the mixture was stirred for 1 hour. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with 1N hydrochloric acid and saturated saline and then dried over magnesium sulfate. After concentration, the residue was purified by silica gel column chromatography to give 0.26 g.
(88%) of the desired product was obtained.

Nuclear magnetic resonance spectrum (200 MHz) δ (CDCl ₃ ) p
pm: 8.59 (d, 2H, J = 4.8Hz), 7.36 (s, 4H), 7.12 (t, 1H, J = 4.
8Hz), 2.35 (q, 2H, J = 7.2Hz), 1.11 (t, 3H, J = 7.2Hz).

[0085]

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

[0086]

[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 Tainubie and firefly, which were awakened, were mixed in the A pot to the surface layer of 1 cm. Into the B pot, the tubers of the budded Cyperus esculentum and Kuguwai were planted, and in the C pot, seedlings of paddy rice at the 2-leaf stage were transplanted. Each pot was submerged and grown in a greenhouse, and after 3 days (before germination of weeds) or 10 days (1.5 leaf stage of the fly), a prescribed amount was obtained using a wettable powder prepared according to Formulation Example 1. Was treated with flooded soil, and 21 days after the treatment, an investigation was conducted according to the following criteria. The results of the 3-day post-treatment are shown in Table 2, and the results of the 10-day post-treatment are shown in Table 3.

Criteria for Evaluation 0 --- Growth Inhibition Rate 0-10% 1 --- Growth Inhibition Rate 11-30% 2--Growth Inhibition Rate 31-50% 3 --- Growth Inhibition Rate 51-70% --- Growth inhibition rate 71-90% 5--Growth inhibition rate 91-100% In addition, Comparative Compound 1 in Table 2, Table 3 and Table 4 is disclosed in Japanese Patent Laid-Open No. HEI-2.
The following compounds are included in Japanese Patent Publication No. 149567:

[0088]

[Chemical 7]

Comparative compound 2 in Tables 2 and 3 is the following compound described in US Pat. No. 4,345,076.

[0090]

Embedded image

In Tables 2 and 3, EO is Tainubie, SJ is Firefly, CS is Mizugaya, EK is Kurogwai, OS is paddy rice, EC is barnyard grass, and SH is SH.
Indicates Johnson Glass, DS indicates Meshishiba, IS indicates morning glory, SA indicates mustard, and AR indicates blue-green agate.

[0092]

[Table 2] (Before germination of weeds) ───────────────────────────── Compound No. Dosage (g / a) EO SJ CS EK OS ───────────────────────────── 1 5 5 5 5 5 5 4 5 5 5 5 5 5 0 5 5 5 5 5 5 5 0 6 5 5 5 5 5 5 5 0 7 5 5 5 5 4 5 0 12 5 4 5 5 5 5 1 13 13 5 5 5 5 5 5 1 14 5 5 5 5 5 4 0 15 5 5 5 5 5 5 5 0 16 5 5 5 0 18 5 5 5 5 5 5 0 19 5 5 5 5 5 5 0 21 21 5 5 5 5 5 5 0 24 5 5 5 5 5 4 0 30 30 5 5 5 5 5 5 0 31 5 5 5 5 5 5 0 33 5 5 5 5 5 36 5 5 5 5 5 5 0 41 5 5 5 5 5 5 0 44 4 5 5 5 5 5 5 0 45 5 5 5 5 5 4 0 48 5 5 5 5 5 5 5 51 5 5 5 5 5 5 5 0 Comparative compound 1 5 4 0 0 1 0 Comparative compound 2 5 5 5 5 5 4 ───────────────────────────────

[0093]

[Table 3] (Left 1.5 leaf stage) ───────────────────────────── Compound number Drug dose (g / a) EO SJ CS EK OS ───────────────────────────── 1 5 5 5 4 4 0 4 5 5 5 5 4 5 0 6 5 5 5 4 4 0 7 5 5 5 5 4 4 0 14 5 5 5 5 4 4 0 15 15 5 5 5 5 5 4 0 16 5 5 5 5 5 5 0 18 5 5 5 5 5 5 0 0 19 5 5 5 5 5 5 0 21 5 5 4 0 24 5 5 5 5 5 4 0 30 5 5 5 5 5 5 0 31 31 5 5 5 5 5 5 0 33 5 5 5 5 5 5 5 36 5 5 5 5 5 4 0 41 5 5 5 5 5 4 5 4 5 5 3 0 45 5 5 5 5 5 4 0 48 5 5 5 5 5 4 0 Comparative compound 1 5 0 0 0 1 0 Comparative compound 2 5 5 4 3 4 5 5 ──────────────── ──── ──────────

[0094]

[Test Example 2] Soil treatment before the emergence of upland weeds Upland soil was filled in a plastic pot with an area of 150 cm ² , and seeds of weeds such as barnyard grass, Johnson grass, crabgrass, morning glory, mustard and agatela were seeded, and then covered with a soil of 1 cm thick. And left it in the greenhouse.

Immediately after covering with soil, the wettable powder prepared according to Formulation Example 1 was used to treat the soil surface with a predetermined amount. On the 21st day after the treatment, the investigation was performed according to the criteria shown in Test Example 1. The results are shown in Table 4.

[0096]

[Table 4] ──────────────────────────────── Compound No. Dosage (kg / ha) EC SH DS IS IS SA AR ──────────────────────────────── 1 5 5 5 5 5 4 5 5 2 5 5 5 5 5 5 5 5 4 4 5 4 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 6 5 4 4 4 4 4 4 5 5 7 5 4 5 5 5 4 5 5 9 5 5 4 3 5 5 5 4 11 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 4 5 5 3 5 24 5 5 5 4 5 4 5 5 31 5 5 5 5 5 4 5 5 Comparative compound 1 5 1 1 3 4 3 3 3 ─────────────────── ─────────────

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiyoshi Oi 1041 Sansu Stock Association, Yasu-cho, Yasu-gun, Shiga Prefecture In-house (72) Inventor Junji Kadoya 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga Prefecture In-house

Claims (6)

[Claims] 1. A compound represented by the general formula (I): [In the formula, R ¹ represents a hydrogen atom, a C2-C10 alkanoyl group or a benzoyl group (the benzoyl group may be substituted with one or two substituents selected from a halogen atom and a methyl group). , R ² , R ³ and R ⁴ are
The same or different, a hydrogen atom or a halogen atom is shown. ] The sulfonamide compound represented by these. 2. A compound represented by the general formula (I): [Wherein R ¹ represents a hydrogen atom, a propionyl group, a butanoyl group or a benzoyl group (the benzoyl group is 1 or 2
May be substituted with one halogen atom), R ² and R ⁴ are the same or different and each represents a hydrogen atom or a halogen atom, and R ³ represents a hydrogen atom. ] The sulfonamide compound represented by these. 3. A compound represented by the general formula (I): [In the formula, R ¹ represents a hydrogen atom or a propionyl group,
R ² represents a hydrogen atom or a halogen atom, and R ³ and R
⁴ represents a hydrogen atom. ] The sulfonamide compound represented by these. 4. N- [4- (2-pyrimidinyloxy) phenyl] trifluoromethanesulfonamide. 5. N- [2-chloro-4- (2-pyrimidinyloxy) phenyl] trifluoromethanesulfonamide. 6. A herbicidal composition containing the sulfonamide compound according to claim 1 as an active ingredient.