JPH1160562A - Sulfonanilide derivative and herbicide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound, having a wide range of application time for weeds such as barnyardgrass emerging in paddy fields, capable of suppressing the emergence and growth of the weeds for a long period, controlling the weeds with a low dose and useful as a herbicide having high safety for rice plants. SOLUTION: This sulfonanilide derivative is represented by formula I [R<1> is a (substituted)alkyl or the like; R<2> is H or the like; R<3> is H or the like; Q is a group CH(NR<4> R<5> ) or the like; R<4> and R<5> are each H or the like; (m) is 1-4] and its salt, e.g. 2'-[1-(4,6-dimethoxypyrimidin-2-yl)-1-(4-morpholino) methyl]-1,1-difluoromethanesulfonanilide. The compound represented by formula I is obtained by reacting, e.g. an aniline derivative represented by formula II [A is a group C(C=O) or the like] with a sulfonyl halide or an anhydride of a sulfonic acid derivative in a molar amount of 1-2 times based on 1 mol aniline derivative in or without 0.5-5 L solvent such as chloroform in the presence of a base such as pyridine in a molar amount of 1-2 times based on 1 mol aniline derivative at -20 deg.C to ambient temperature for 5 min to 1 week.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel sulfonanilide derivative and a herbicide containing the same as an active ingredient.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open No. Hei 7-501053 and WO 96/41799 disclose 2 ′ of anilide.
It is described that a sulfonanilide compound substituted with a pyrimidin-2-yl group at the 2-position has herbicidal activity.

However, in the specification of this publication, in the substitution of the pyrimidin-2-yl group at the 2'-position of the anilide, the bond between the 2-position of the pyrimidine and the 2'-position of the anilide is a methylene group or a halogen-substituted methylene group. , A carbonyl group, a hydroxyl group, an oxomethylene group, an alkoxy group, a thioxomethylene group or an alkylthio group and derivatives thereof are described. However, as in the sulfonanilide derivative of the present invention, the pyrimidine 2 position and the anilide No compound having an aminomethylene group or an iminomethylene group in the bond to the 2′-position of the compound is known. That is, specific herbicidal effects and production methods of the sulfonanilide derivative of the present invention and a herbicide containing the same as an active ingredient have not been known so far. Furthermore, the compounds described in JP-T-7-501053 and WO96 / 41799 are not satisfactory because of insufficient herbicidal activity and poor selectivity between crops and weeds. hard.

[0004]

At present, various difficult-to-control weeds such as cyperaceae are becoming a problem in paddy fields. The occurrence of these weeds is irregular, and they occur over a long period of time during the cultivation period of paddy rice. Therefore, there is a demand for the development of a drug having a wide suitable treatment period that can control them. In addition, it is extremely difficult to use herbicides safely with current rice herbicides even for small-leaf rice and rice with a short transplanting depth. In particular, the emergence of herbicides having high safety for paddy rice enables simultaneous treatment of herbicides at the time of transplantation, and there is a great demand for streamlining and increasing the size of rice cultivation.

[0005]

The present inventors have made various studies in view of such circumstances, and as a result, have devised a novel sulfonanilide derivative and a method for producing the same. The present inventors have found that the present invention has a herbicidal action, and have completed the present invention.

That is, the present invention relates to (1) a compound represented by the general formula [I]:

[0007]

Embedded image {In the formula, R ¹ (this group may be substituted by a halogen atom or a cyano group.) Alkyl group indicates or an alkenyl group (which may be substituted with a halogen atom.), R ² are each Independently, a hydrogen atom, a halogen atom, an alkoxy group or an alkyl group (the group may be substituted with a halogen atom, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an alkylthio group, a mono- or dialkylamino group. R ³ represents a hydrogen atom, an alkyl group (the group may be substituted with a halogen atom, a hydroxyl group, an alkenyloxy group, an alkynyloxy group, a mono- or dialkylamino group, an alkoxy group or an alkylthio group), and benzyl group, an acyl group, an alkoxycarbonyl group, a substituted carbamoyl group, a thiocarbamoyl group or a group -SO ₂ substituted ¹ (wherein ^{R 1} is as defined above.) Indicates, Q is group ^{-CH (NR 4 R 5) -} [ wherein ^R 4, ^{R 5} are identical to or different or different, a hydrogen atom, an alkyl group (The group may be substituted with a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, an alkylthio group or a phenyl group.), An alkenyl group, an alkynyl group, a cycloalkyl group, a phenyl group (the group is a halogen atom, an alkyl group Or an alkoxy group), an acyl group, an alkoxycarbonyl group, a substituted carbamoyl group, a substituted thiocarbamoyl group, a group —SO ₂ R ¹ (where R
¹ has the same meaning as described above. ), A group —NR ⁷ R ⁸ [where R ⁷ and R ⁸ are the same or different and are each a hydrogen atom, an alkyl group (the group is substituted with a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, an alkylthio group or a phenyl group) An alkenyl group, an alkynyl group, a cycloalkyl group, a phenyl group (the group may be substituted with a halogen atom, an alkyl group or an alkoxy group), an acyl group, an alkoxycarbonyl group, a group -SO ₂ R ¹ (where R ¹ has the same meaning as described above), represents a substituted carbamoyl group or a substituted thiocarbamoyl group. ] Or group-
OR ⁹ [where R ⁹ is a hydrogen atom, an alkyl group (the group may be substituted with a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, an alkylthio group, a phenyl group), an alkenyl group, an alkynyl group, a cycloalkyl Group, phenyl group (the group may be substituted with a halogen atom, an alkyl group, or an alkoxy group), acyl group, alkoxycarbonyl group, alkylsulfonyl group (the group may be substituted with a halogen atom), It represents a substituted carbamoyl group or a substituted thiocarbamoyl group. Or, optionally, R ⁴ and R ⁵ may be combined with these bonded nitrogen atoms to form a nitrogen-containing heterocyclic group having one or more hetero atoms. ] Or a group -C (= N
R ⁶ )-[where R ⁶ is a hydrogen atom, an alkyl group (the group may be substituted with a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, an alkylthio group, a phenyl group), an alkenyl group, an alkynyl group, Cycloalkyl group, phenyl group (the group may be substituted with a halogen atom, an alkyl group, or an alkoxy group), an acyl group, an alkoxycarbonyl group, a substituted carbamoyl group, a substituted thiocarbamoyl group, a group -SO ₂ R ¹ (where R ¹ has the same meaning as described above), a group —NR ⁷ R ⁸ (where R ⁷ and R ⁸
Has the same meaning as described above. ) Or a group —OR ⁹ (where R
⁹ has the same meaning as described above. ). And m represents an integer of 1 to 4. And a salt thereof, and (2) a general formula [II] which is an intermediate for producing the compound represented by the general formula [I]

[0008]

Embedded image 中 In the formula, R ² and m have the same meaning as described above. The present invention provides a herbicide comprising a 4,6-dimethoxypyrimidin-2-yl derivative represented by｝ and (3) a sulfonanilide derivative represented by the general formula [I] or a salt thereof as an active ingredient.

[0009] The terms used in this specification are defined below.

[0010] The halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The alkyl group means a linear or branched alkyl group having 1 to 10 carbon atoms unless otherwise specified. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-alkyl group. Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isoamyl group, neopentyl group, n-hexyl group, isohexyl group, 3,3-dimethylbutyl group, n-heptyl group, n
-Octyl group, n-nonyl group, n-decyl group and the like.

The term "acyl group" means a formyl group, a benzoyl group or an alkyl moiety having the above-mentioned meaning (alkyl) -C.
It represents an O- group, and examples thereof include an acetyl group and a propionyl group.

The term "alkoxy" refers to a (alkyl) -O- group in which the alkyl moiety has the above-mentioned meaning, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy group, tert-butoxy group, n-hexyloxy group,
Examples thereof include an n-octyloxy group.

The term "alkoxycarbonyl group" means a (alkoxy) -CO- group in which the alkoxy moiety has the above-mentioned meaning, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.

The alkenyl group is a linear or branched alkenyl group having 2 to 6 carbon atoms, such as a vinyl group,
And a propenyl group.

The alkenyloxy group is a (alkenyl) -O- group in which the alkenyl moiety has the above-mentioned meaning, and examples thereof include an allyloxy group.

The term "alkynyl group" means a linear or branched alkynyl group having 2 to 6 carbon atoms, such as a propargyl group.

The alkynyloxy group means a (alkynyl) -O- group in which the alkynyl moiety has the above-mentioned meaning, and examples thereof include a propargyloxy group.

The cycloalkyl group is a cycloalkyl group having 3 to 7 carbon atoms, and examples thereof include a cyclopropyl group and a cyclopentyl group.

The alkylthio group and the alkylsulfonyl group mean that the alkyl moiety has the above meaning (alkyl)-
S- group, an (alkyl) -SO 2 _- can be given a group, such as methylthio, ethylthio group, methylsulfonyl group, ethylsulfonyl group.

A mono- or dialkylamino group is a (alkyl) -NH- group in which the alkyl portion has the above-mentioned meaning,
(Alkyl) ₂ N- group, for example, methylamino group,
A dimethylamino group and the like can be mentioned.

The substituted carbamoyl group is an N-monosubstituted or N, N-disubstituted carbamoyl group,
For example, an N, N-dimethylcarbamoyl group and the like can be mentioned.

The substituted thiocarbamoyl group is defined as N-
It represents a monosubstituted or N, N-disubstituted thiocarbamoyl group, such as an N-methylthiocarbamoyl group.

The term "acyloxy group" or "alkylsulfonyloxy group" means an (acyl) -O- group or an (alkylsulfonyl) -O- group in which the acyl or alkylsulfonyl moiety has the above-mentioned meaning, for example, an acetoxy group or a mesyloxy group. And the like.

The nitrogen-containing heterocyclic group means a 5- or 6-membered nitrogen-containing heterocyclic group, and examples thereof include a piperidino group, a morpholino group and an imidazolyl group.

The salt is a salt of a compound represented by the general formula [I] and an acid or a salt of a compound represented by the general formula [I] of a sulfonamide and a metal or an organic base, Examples thereof include hydrohalic acids such as hydrochloric acid and hydrobromic acid, and sulfonic acids such as sulfuric acid and methanesulfonic acid.
Alkali metals such as sodium and potassium as metals,
Examples include alkaline earth metals such as magnesium and calcium, and examples of the organic base include triethylamine and diisopropylamine.

In the above general formula [I], a preferable compound group includes R ¹ is a trifluoromethyl group or a difluoromethyl group, R ² is a hydrogen atom, and C ¹ to C 3.
Is an alkyl group and an alkoxy group having 1 to 3 carbon atoms, a halogen atom or a methoxymethyl group, R ³ is a hydrogen atom or a methoxymethyl group, and Q is a group —CH (NR ⁴ R
⁵ )-, wherein R ⁴ and R ⁵ are the same or different and are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a compound group in which m is 1 or 2.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Next, typical examples of the compounds of the present invention represented by the general formulas [I] and [II] are shown in Tables 1 to 3.
Although shown in 5, the compound of the present invention is not limited to these. The compound numbers will be referred to in the following description.

The following notations in the tables in the present specification represent the corresponding groups as follows.

Me: methyl group, Et: ethyl group, Pr: propyl group, Pr-i: isopropyl group, Bu: butyl group, Bu-i: isobutyl group, Bu-s: sec-butyl group, Bu-t: tert-butyl group, Pen: n-pentyl group, Bn: benzyl group, Pr-c: cyclopropyl group, Bu-c: cyclobutyl group, Pen-c: cyclopentyl group, Ph: phenyl group,

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

[Table 5]

[0036]

[Table 6]

[0037]

[Table 7]

[0038]

[Table 8]

[0039]

[Table 9]

[0040]

[Table 10]

[0041]

[Table 11]

[0042]

[Table 12]

[0043]

[Table 13]

[0044]

[Table 14]

[0045]

[Table 15]

[0046]

[Table 16]

[0047]

[Table 17]

[0048]

[Table 18]

[0049]

[Table 19]

[0050]

[Table 20]

[0051]

[Table 21]

[0052]

[Table 22]

[0053]

[Table 23]

[0054]

[Table 24]

[0055]

[Table 25]

[0056]

[Table 26]

[0057]

[Table 27]

[0058]

[Table 28]

[0059]

[Table 29]

[0060]

[Table 30]

[0061]

[Table 31]

[0062]

[Table 32]

[0063]

[Table 33]

[0064]

[Table 34]

[0065]

[Table 35]

Next, the compound of the present invention represented by the general formula [I] can be produced according to the following production methods, but is not limited to these methods.

<Production Method 1>

[0068]

Embedded image (Wherein, A represents a group —C (＝ O) —, a group —CH (OH) — or Q [wherein Q has the same meaning as described above];
Represents a halogen atom, and R ¹ , R ² , R ³ and m have the same meaning as described above. )

One to two moles of an anhydride of a sulfonyl halide derivative or a sulfonic acid derivative is added to 1 mole of the aniline derivative represented by the general formula [III] in the absence of a solvent or in 0.5 to 5 l of a suitable solvent. By reacting in the presence of up to 2 times the molar amount, the desired sulfonanilide derivative represented by the general formula [IV] can be obtained.

Examples of the solvent include hydrocarbons such as n-hexane; cyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene and xylene; ethers such as 1,4-dioxane and tetrahydrofuran (THF); , N-
Amides such as dimethylformamide (DMF), N, N
-Sulfur compounds such as dimethylsulfoxide (DMSO) and sulfolane; aromatic nitrogen-containing compounds such as quinoline and pyridine; aniline derivatives such as N, N-diethylaniline; organic acids such as acetic acid and trifluoroacetic acid; and esters such as ethyl acetate. Examples thereof include halogenated hydrocarbons such as chloroform, nitriles such as acetonitrile, aromatic nitro compounds such as nitrobenzene, alcohols such as methanol and ethanol, and water.

Examples of the base include metal hydrides such as sodium hydride, organic metal compounds such as n-butyllithium, organic bases such as pyridine and triethylamine, and alkali metals or alkalis such as sodium carbonate, potassium carbonate and calcium carbonate. Examples thereof include carbonates, hydroxides and bicarbonates of earth metals, and metal salts of alcohols such as sodium methoxide and potassium t-butoxide.

The reaction is carried out in a temperature range of -70 ° C to 250 ° C, preferably in a temperature range of -20 ° C to room temperature, and the reaction time is completed in 5 minutes to 1 week.

<Production Method 2>

[0074]

Embedded image (Wherein B represents a group —NHR ³ , a group —NR ³ (SO ₂ R ¹ )
Or m represents a nitro group, and m, R ¹ , R ² , R ³ , and R ⁶ have the same meaning as described above. )

The amine represented by R ⁶ NH _{2 is used} in an amount of 1 to 5 moles per mole of the carbonyl compound represented by the general formula [V] without solvent or in a suitable solvent (eg, aromatic hydrocarbons such as benzene, methanol). And the like.) By subjecting to dehydration condensation in 0.5 to 5 l, the desired imine compound represented by the general formula [VI] can be obtained. Here, if necessary, a suitable catalyst (for example, Lewis acids such as titanium tetrachloride, bases such as potassium acetate, etc.) may be added in an amount of 0.01 to 2 moles.

The reaction is carried out in a temperature range of -70 ° C to 250 ° C, preferably in a temperature range of -20 ° C to 150 ° C, and the reaction is completed in 5 minutes to 1 week.

<Production Method 3>

[0078]

Embedded image (In the formula, m, B, R ² , R ⁴ , R ⁵ , and X have the same meaning as described above.)

The hydroxyl group of 1 mol of the compound represented by the general formula [VII] can be prepared by adding a halogenating agent (thionyl chloride) in 0.5 to 5 l of a suitable solvent (same as described in the production method 1) without solvent or in an appropriate solvent. And the like.) 1 to 5
The compound represented by the general formula [VIII] is obtained by halogenation using twice the molar amount, and then in a solvent free or in an appropriate solvent (same as described in the production method 1) in 0.5 to 5 l, the general formula R ⁴
The target amine compound represented by the general formula [IX] can be obtained by reacting the amine represented by R ⁵ NH with 1 to 5 moles of the amine. Here, an appropriate base (a metal hydride such as sodium hydride, an organic metal compound such as n-butyllithium, an organic base such as pyridine or triethylamine), an alkali metal such as sodium carbonate, potassium carbonate, or calcium carbonate, or an alkali metal such as alkali Examples thereof include carbonates, hydroxides and bicarbonates of earth metals, and metal salts of alcohols such as sodium methoxide and potassium t-butoxide. good.

The reaction is carried out in a temperature range of -70 ° C to 250 ° C, preferably in a temperature range of -20 ° C to 100 ° C, and the reaction is completed in 5 minutes to 1 week.

<Production Method 4>

[0082]

Embedded image (In the formula, L ¹ represents a leaving group such as a halogen atom, an acyloxy group, an alkylsulfonyloxy group, a 1-imidazolyl group, and R ¹ , R ² , R ³ , and A have the same meanings as described above.)

An alkylating agent, an acylating agent or a sulfonylating agent (1-2 moles) represented by the general formula R ³ -L ¹ is added to the compound (1 mol) represented by the general formula [IVa] without solvent. Or a base (metal hydride such as sodium hydride, organometallic compound such as n-butyllithium, or the like) in 0.5 to 5 l of a suitable solvent (same as described in Production method 1).
Pyridine, organic bases such as triethylamine, sodium carbonate, potassium carbonate, carbonate compounds of alkali metals or alkaline earth metals such as calcium carbonate, the same hydroxide compounds, the same hydrogen carbonate compounds, further sodium methoxide,
Examples thereof include metal salts of alcohols such as potassium t-butoxide. ) By reacting in the presence of 1 to 2 moles, the desired sulfonanilide derivative represented by the general formula [IV] can be obtained.

The reaction is carried out in a temperature range of -70 ° C to 250 ° C, preferably in a temperature range of -20 ° C to 100 ° C, and the reaction is completed in 5 minutes to 1 week.

Incidentally, the general method for producing sulfoneanilides is described in the above-mentioned Japanese Patent Application Laid-Open No. 7-501053 and WO96 / 41799, and is also described in Journal of Agricultural Technology. Food Chemistry (J. Agr. Food Che)
m. ), Volume 22 (6), No. 1111 (1974)
And so on.

Next, the compound of the present invention represented by the general formula [II] and the general formula [III] described in the production methods 1 to 4,
Some of the intermediates represented by [V] and [VII] are as follows:
For example, it can be produced according to the scheme shown in Chemical formula 9, but is not limited to these methods.

[0087]

Embedded image (In the formula, L ² represents a leaving group such as a halogen atom or an alkylsulfonyl group, and m, R ² , R ³ and X have the same meanings as described above.)

<Production Method 5> Production method of intermediates represented by general formulas [XII] and [XIV].

One mole of the benzyl cyanide derivative represented by the general formula [Xa] or [XIII] is combined with the general formula [XIa]
And 1 to 2 moles of the pyrimidine derivative represented by the formula (1) in the absence of a solvent or an appropriate solvent (same as described in Production method 1).
By condensing in 5 to 5 l in the presence of 1 to 5 moles of a suitable base (same as described in Production method 1),
The desired compound represented by the general formula [XII] or [XIV] can be obtained.

Alternatively, 1 mol of the nitro compound represented by the general formula [Xb] and 1 to 2 mols of the pyrimidine derivative represented by the general formula [XIb] can be used without solvent or in a suitable solvent (as described in Production method 1). In 0.5 to 5 l,
The desired compound represented by the general formula [XII] can be obtained by condensing in the presence of an appropriate base (same as described in Production method 1) in an amount of 1 to 5 moles.

In each case, the reaction temperature was from -70 ° C to 2 ° C.
It is carried out in a temperature range of 50 ° C, preferably from -20 ° C to
The temperature range is 0 ° C., and the reaction is completed in 5 minutes to 1 week.

<Production Method 6> Production method of intermediates represented by general formulas [Va] and [Vc].

One mole of the cyanide compound represented by the general formula [XII] or [XIV] is mixed with 0.5 to 5 l of an oxidizing agent (m-chloroperoxide) in a suitable solvent (the same as described in Production Method 1). Organic peracids such as benzoic acid can be exemplified.) 1-2
After treating with a 1-fold molar amount, a suitable solvent (eg, an alkali metal such as sodium hydroxide, etc.) is treated with 1 to 10-fold molar amount in 0.5 to 5 l of an appropriate solvent (eg, water). To perform an oxidative decyanoation reaction,
The desired carbonyl compound represented by the general formula [Va] or [Vc] can be obtained.

The reaction is carried out in a temperature range from -70 ° C to the boiling point of the solvent, preferably in a temperature range from -20 ° C to 100 ° C, and the reaction is completed in 5 minutes to 1 week.

<Production Method 7> A method for producing a 4,6-dimethoxypyrimidine derivative represented by the general formula [II].

One mole of the carbonyl compound represented by the general formula [Vc] is mixed with an appropriate solvent (an amide such as N, N-dimethylformamide, N, N-dimethylsulfoxide (DM)
SO) and sulfolane. ) In 0.5 to 5 l, by treating with 1 to 5 moles of sodium azide or the like, the objective 4,6-dimethoxypyrimidine derivative represented by the general formula [II] can be obtained.

The reaction is carried out at a temperature ranging from -70 ° C to the boiling point of the solvent, preferably from -20 ° C to 150 ° C, and the reaction is completed in 5 minutes to 1 week.

<Production Method 8> Production method of intermediates represented by general formulas [Vb] and [VIIb].

The 4,6-dimethoxypyrimidine derivatives represented by the general formula [II] or the general formulas [Va] and [VI
1 mol of the nitro compound represented by Ia] is mixed with 0.5 to 5 l of an appropriate solvent (similar to that described in Production method 1) to obtain an appropriate reducing agent (for example, metals such as iron). ~ 5
By reducing the compound by a molar amount, the corresponding general formula [Vb]
And the desired amino compound represented by [VIIb]. In some cases, 0.01 to 1 mole of an acid (eg, organic acids such as acetic acid) may be added as a catalyst.

Alternatively, 4,6 represented by the general formula [II]
A dimethoxypyrimidine derivative or a compound of the general formula [V
a], 1 mol of the nitro compound represented by [VIIa]
Suitable solvent (same as described in Production method 1) 0.5 to
In 5 l, a suitable reducing agent (such as ammonium formate or hydrogen) is used in the presence of 0.01 to 1 mole of a catalyst (such as metals such as palladium) in 1 to 1 mole.
By reducing in a 5-fold molar amount, the corresponding general formula [V
b] and [VIIb] can be obtained.

In each case, the reaction is carried out in a temperature range from -70 ° C to the boiling point of the solvent, preferably in a temperature range from -20 ° C to 100 ° C, and the reaction is completed in 5 minutes to 1 week.

<Production method 9> [VIIa], [VIIb] or [VII]
c] A process for producing an intermediate represented by the formula:

The formula [Va], [Vb] or [V
d) in a suitable solvent (similar to that described in Production Method 1) in 0.5 to 5 l of an appropriate reducing agent (alkali metal hydride complex such as sodium borohydride) Can be exemplified by reduction in a 1- to 5-fold molar amount to obtain the corresponding general formula [VIIa],
The desired alcohol compound represented by [VIIb] or [VIIc] can be obtained.

The reaction is carried out at a temperature ranging from -70 ° C to the boiling point of the solvent, preferably from -20 ° C to 100 ° C, and the reaction is completed in 5 minutes to 1 week.

<Production Method 10> Production method of an intermediate represented by the general formula [Vd].

One mole of the compound represented by the general formula [Vc] is represented by the general formula R ³ NH ₂ without solvent or in an appropriate solvent (the same as described in the production method 1) in 0.5 to 5 l. The desired amine compound represented by the general formula [Vd] can be obtained by reacting the amine with 1 to 5 moles of the amine.

The reaction is carried out in a temperature range of -70 ° C to 250 ° C, preferably in a temperature range of -20 ° C to 150 ° C, and the reaction is completed in 5 minutes to 1 week.

The synthesis of the above-mentioned intermediate is described in Journal of Chemical Research (S) (J. Ch.
em. Research (S)) No. 186 Tribute (1977)
Years), Heterocycles
Volume 38 (1), 125th Tribute (1994) and WO9
A similar reaction example is described in, for example, JP-A-4 / 08975.

[0109]

EXAMPLES Next, the production method, formulation method and use of the compound of the present invention will be specifically described with reference to examples. In addition, the method for producing an intermediate for producing the compound of the present invention is also described.

Example 1 2 ′-[1- (4,6-Dimethoxypyrimidin-2-yl) -1- (4-morpholino) methyl] -1,1-difluoromethanesulfonanilide (Compound No. of the present invention) I-
296) Manufacturing

(1) Preparation of 2- [1- (4,6-dimethoxypyrimidin-2-yl) -1- (4-morpholino) methyl] aniline (compound III) Dimethoxypyrimidin-2-yl) -1-hydroxymethyl] aniline 2.0 g (7.
7 mmol) was dissolved in 30 ml of chloroform, and 1.0 g (8.4 mmol) of thionyl chloride was stirred at 0 ° C.
Was added dropwise. After stirring at 0 ° C. to room temperature for 30 minutes, 1.4 g (16 mmol) of morpholine was added dropwise at room temperature, and the mixture was stirred at room temperature for 30 minutes, and further stirred under heating and reflux for 30 minutes. The reaction solution was extracted with 5% aqueous hydrochloric acid, and the extract was neutralized with saturated aqueous sodium hydrogen carbonate and extracted with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent, ethyl acetate: n-hexane = 1: 3) to obtain a light brown viscous liquid, 2- [1- (4,6-dimethoxy). Pyrimidin-2-yl) -1- (4-morpholino)
0.5 g (yield 20%) of methyl] aniline was obtained.

(2) 2 '-[1- (4,6-Dimethoxypyrimidin-2-yl) -1- (4-morpholino) methyl] -1,1-difluoromethanesulfonanilide (Compound No. I- of the present invention) 296) Preparation of 2- [1- (4,6-dimethoxypyrimidin-2-yl) -1- (4-morpholino) methyl] aniline 0.5
g (1.5 mmol) and 0.3 g (3.8 mmol) of pyridine were dissolved in 15 ml of chloroform, and 0.6 g (4.0 mmol) of 1,1-difluoromethanesulfonic acid chloride was stirred at room temperature while stirring. It was dropped. After continuing stirring at room temperature for 3 hours, the reaction solution was poured into ice water and extracted with chloroform. The organic layer was washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent, ethyl acetate: n-hexane = 1: 3) to obtain 2 ′-[1- (1) -white powder (melting point: 143 to 144 ° C.). (4,6-
0.3 g (yield 45%) of dimethoxypyrimidin-2-yl) -1- (4-morpholino) methyl] -1,1-difluoromethanesulfonanilide was obtained.

Example 2 2 ′-[1- (4,6-Dimethoxypyrimidin-2-yl) -1- (methoxyimino) methyl] -1,1,1-
Production of trifluoromethanesulfonanilide (Compound No. II-55 of the present invention)

(1) Production of 2 '-(4,6-dimethoxypyrimidin-2-ylcarbonyl) -1,1,1-trifluoromethanesulfonanilide (compound V) 2- (4,6-dimethoxypyrimidine-2) -Ylcarbonyl) aniline (3.0 g, 11.6 mmol) and triethylamine (1.5 g, 14.8 mmol) were dissolved in dichloromethane (50 ml).
3.9 g of 1-trifluoromethanesulfonic anhydride (1
(3.8 mmol) was added dropwise over about 10 minutes, and stirring was continued for 1 hour. The reaction solution was poured into ice water and extracted twice with a 5% aqueous sodium hydroxide solution (20 ml), and the aqueous layer was collected.
After acidifying with 10% hydrochloric acid, the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the precipitated crude crystals were washed with diisopropyl ether to give an ocher powder (melting point: 10
2 '-(4,6-dimethoxypyrimidin-2-ylcarbonyl) -1,1,1-trifluoromethanesulfonanilide (2 to 104 ° C.) (3.0 g, yield 69%).

(2) 2 '-[1- (4,6-dimethoxypyrimidin-2-yl) -1- (methoxyimino) methyl] -1,1,1-trifluoromethanesulfonanilide (Compound No. II of the present invention) Preparation of 2 ′-(4,6-dimethoxypyrimidin-2-ylcarbonyl) -1,1,1-trifluoromethanesulfonanilide 3.0 g (7.7 mmol), potassium acetate
0 g (40.8 mmol) and 4.0 g (47.9 mmol) of methoxyamine hydrochloride in 50 ml of ethanol
And stirred under reflux with heating. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent, ethyl acetate: n-hexane = 1: 3) to obtain 2 ′-[1- (1) -white crystals (melting point: 89 to 91 ° C.).
(4,6-dimethoxypyrimidin-2-yl) -1-
(Methoxyimino) methyl] -1,1,1-trifluoromethanesulfonanilide 0.9 g (yield 28%) was obtained.

Example 3 2 '-[1- (4,6-Dimethoxypyrimidin-2-yl) -1- (ethylamino) methyl] -6'-methoxymethyl-1,1-difluoromethanesulfonanilide Production of (Invention Compound No. I-359)

(1) 2 '-[1- (4,6-dimethoxypyrimidin-2-yl) -1-hydroxymethyl]-
Preparation of 6'-methoxymethyl-1,1-difluoromethanesulfonanilide (compound VII) 2- [1- (4,6-dimethoxypyrimidin-2-yl) -1-hydroxymethyl] -6-methoxymethylaniline 4 2.0 g (13.1 mmol) and pyridine 2.
0 g (25.3 mmol) was dissolved in 30 ml of dichloromethane, and 3.6 g (23.9 mmol) of 1,1-difluoromethanesulfonic acid chloride was added dropwise with stirring at room temperature. After stirring at room temperature for 7 days, the reaction solution was poured into ice water and extracted with dichloromethane. The organic layer was washed with 5% aqueous hydrochloric acid and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue is subjected to silica gel column chromatography (elution solvent, ethyl acetate: n
-Hexane = 1: 3) to give colorless granular crystals (mp 7
6-77 ° C.) 2 ′-[1- (4,6-dimethoxypyrimidin-2-yl) -1-hydroxymethyl] -6′-
2.0 g (36% yield) of methoxymethyl-1,1-difluoromethanesulfonanilide was obtained.

(2) 2 '-[1-chloro-1- (4,6
-Dimethoxypyrimidin-2-yl) methyl] -6'-
Preparation of methoxymethyl-1,1-difluoromethanesulfonanilide (compound VIII) 2 ′-[1- (4,6-dimethoxypyrimidin-2-yl) -1-hydroxymethyl] -6′-methoxymethyl-1, 2.0 g of 1-difluoromethanesulfonanilide
(4.8 mmol) and 0.7 g of thionyl chloride (5.9).
(Mmol) was dissolved in 15 ml of chloroform and stirring was continued at room temperature for 2 hours. The solvent and excess thionyl chloride were distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent, ethyl acetate: n-hexane = 1: 3) to give pale yellow crystals (melting point: 88-89 ° C.). '-
[1-chloro-1- (4,6-dimethoxypyrimidine-
2-yl) methyl] -6'-methoxymethyl-1,1-
2.0 g of difluoromethanesulfonanilide (95 yield)
%).

(3) 2 '-[1- (4,6-dimethoxypyrimidin-2-yl) -1- (ethylamino) methyl] -6'-methoxymethyl-1,1-difluoromethanesulfonanilide (this compound) Preparation of Invention Compound No. I-359) 2 '-[1-Chloro-1- (4,6-dimethoxypyrimidin-2-yl) methyl] -6'-methoxymethyl-
1.0 g of 1,1-difluoromethanesulfonanilide
(2.3 mmol) was dissolved in 10 ml of tetrahydrofuran and 0.3 g of ethylamine was stirred at room temperature.
(6.7 mmol) was added dropwise. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (elution solvent, ethyl acetate: n-hexane = 1: 1) to give a pale red powder (melting point: 188-80).
189 ° C) 2 '-[1- (4,6-dimethoxypyrimidin-2-yl) -1- (ethylamino) methyl]-
0.9 g (yield 88%) of 6'-methoxymethyl-1,1-difluoromethanesulfonanilide was obtained.

Example 4 N-methoxymethyl-2 ′-[1- (4,6-dimethoxypyrimidin-2-yl) -1- (diethylamino) methyl] -1,1-difluoromethanesulfonanilide (this compound) Preparation of Invention Compound No. I-256) 0.8 g of 2 ′-[1- (4,6-dimethoxypyrimidin-2-yl) -1- (diethylamino) methyl] -1,1-difluoromethanesulfonanilide (1. 9 mmol) and 1.0 g (7.2 mmol) of potassium carbonate were suspended in 15 ml of N, N-dimethylformamide, and 0.5 ml of chloromethyl methyl ether was stirred at room temperature.
g (6.2 mmol) were added dropwise. After continuing stirring at room temperature for 3 hours, the reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (elution solvent, ethyl acetate: n-hexane = 1: 5) to give colorless crystals (melting point: 67 to 69 ° C.) of N-methoxymethyl-2 ′-[1-
(4,6-dimethoxypyrimidin-2-yl) -1-
(Diethylamino) methyl] -1,1-difluoromethanesulfonanilide 0.8 g (91% yield) was obtained.

Example 5 3- (4,6-dimethoxypyrimidin-2-yl) -4
Preparation of -Fluoro-2,1-benzoisoxazole (Compound No. III-2 of the present invention) 2- (2,6-difluorobenzoyl) -4,6-dimethoxypyrimidine 4.0 g (14.3 mmol) and azide 1.1 g (16.9 mmol) of sodium was dissolved in 30 ml of N, N-dimethylformamide,
Stirred at 20 ° C. for 3 hours. The reaction solution was returned to room temperature, poured into ice water, extracted with ethyl acetate, and the organic layer was washed with saturated saline and dried. The solvent was distilled off under reduced pressure, and the crystal residue was washed with diisopropyl ether to obtain a red powder (melting point: 145).
-147 ° C) 3- (4,6-dimethoxypyrimidine-
1.8 g (yield 46%) of 2-yl) -4-fluoro-2,1-benzoisoxazole was obtained.

(Production Example of Intermediate) Reference Example 1 (1) Production of 2- (2-nitrophenyl) -2- (4,6-dimethoxypyrimidin-2-yl) acetonitrile (Compound XII) (2-Nitrophenyl) acetonitrile 50 g
(0.31 mol) was dissolved in 500 ml of N, N-dimethylformamide, and 24.7 g of 60% sodium hydride was dissolved.
(0.62 mol) and stirred at room temperature for 2 hours.
Next, 67.7 g (0.31 mol) of 2-methylsulfonyl-4,6-dimethoxypyrimidine was added, and the mixture was stirred at 80 ° C for 1 hour. The reaction solution was poured into water, neutralized with 10% aqueous hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was crystallized from ethanol to give 2- (2-nitrophenyl)-as a white powder (melting point: 88-89 ° C.).
73.3 g (yield 79%) of 2- (4,6-dimethoxypyrimidin-2-yl) acetonitrile was obtained.

(2) Preparation of 2- (2,6-difluorophenyl) -2- (4,6-dimethoxypyrimidin-2-yl) acetonitrile (Compound XIV) 2- (2,6-difluorophenyl) acetonitrile 1
2 g (78 mmol) are dissolved in 100 ml of N, N-dimethylformamide and 60% sodium hydride 6.3.
g (0.16 mol) was added and the mixture was stirred at room temperature for 2 hours. Next, 17 g (78 mmol) of 2-methylsulfonyl-4,6-dimethoxypyrimidine was added, and the mixture was stirred at 80 ° C for 1 hour. The reaction solution was poured into water, neutralized with 10% aqueous hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (elution solvent, ethyl acetate: n-hexane = 1: 3) to give a colorless candy, 2- (2,6-difluorophenyl) -2- (4,6-dimethoxy). (Pyrimidin-2-yl) acetonitrile 19 g (83% yield) was obtained.

(3) 2- (4-fluoro-2-nitrophenyl) -2- (4,6-dimethoxypyrimidine-2-
Il) Production of acetonitrile (compound XII) 11.2 g (0.28 mol) of 60% sodium hydride was suspended in 100 ml of N, N-dimethylformamide, cooled to 10 ° C or lower in an ice water bath, and stirred. (4,6
-Dimethoxypyrimidin-2-yl) acetonitrile 2
A solution of 5 g (0.14 mol) of N, N-dimethylformamide in 100 ml was added dropwise. After the completion of the dropwise addition, the mixture was stirred at room temperature until no more hydrogen was generated. 10 ℃ again in ice water bath
While cooling and stirring below, a solution of 22 g (0.14 mol) of 2,5-difluoronitrobenzene in 100 ml of N, N-dimethylformamide was added dropwise. After stirring at room temperature for 12 hours, the reaction solution was poured into ice water, acidified with 10% aqueous hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The precipitated crude crystals were washed with a mixed solvent of ethanol / isopropyl ether to give colorless granular crystals (melting point: 111
To 112 ° C.) to obtain 42 g of 2- (4-fluoro-2-nitrophenyl) -2- (4,6-dimethoxypyrimidin-2-yl) acetonitrile (94% yield).

Similarly, the following compounds (compounds XII) were obtained by the methods (1) and (3). 2- (3-methyl-2-nitrophenyl) -2- (4,
6-dimethoxypyrimidin-2-yl) acetonitrile: pale red granular crystals (melting point 108-110 ° C) 2- (3-ethyl-2-nitrophenyl) -2- (4,
6-dimethoxypyrimidin-2-yl) acetonitrile: brown powder (melting point 113-114 ° C) 2- (3-methoxymethyl-2-nitrophenyl) -2
-(4,6-dimethoxypyrimidin-2-yl) acetonitrile: reddish brown powder (melting point 112-113 ° C)

Reference Example 2 (1) 5-Fluoro-2- (4,6-dimethoxypyrimidin-2-ylcarbonyl) nitrobenzene (compound V
Preparation of a) 2- (4-Fluoro-2-nitrophenyl) -2-
3.2 g (10 mmol) of (4,6-dimethoxypyrimidin-2-yl) acetonitrile and 6.0 g (17 mmol) of m-chloroperbenzoic acid (50%) were dissolved in 30 ml of chloroform and left at room temperature for 12 hours. Stirred. Then, 15 ml of a 10% aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 1 hour, and then extracted with 50 ml of chloroform. The organic layer was washed with 5% aqueous hydrochloric acid and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (elution solvent, ethyl acetate: n-hexane = 1: 5) to give 5-fluoro-2-white granular crystals (melting point: 187 to 189 ° C.).
2.7 g (88% yield) of (4,6-dimethoxypyrimidin-2-ylcarbonyl) nitrobenzene were obtained.

(2) Preparation of 2- (2,6-difluorobenzoyl) -4,6-dimethoxypyrimidine (compound Vc) 2- (2,6-difluorophenyl) -2- (4,6-
Dimethoxypyrimidin-2-yl) acetonitrile 19
g (65 mmol), m-chloroperbenzoic acid (50%)
30 g (87 mmol) was dissolved in 150 ml of chloroform, and the mixture was stirred for 6 hours while heating under reflux. Then, the temperature was returned to room temperature, 15 ml of a 10% aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 2 hours, and extracted with 50 ml of chloroform. The organic layer was washed with 5% aqueous hydrochloric acid and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (elution solvent, ethyl acetate: n-hexane = 1: 3) to give 2- (2,6-difluorobenzoyl) -4,6 as white crystals (melting point: 104 to 105 ° C.). -13 g of dimethoxypyrimidine
(Yield 71%) was obtained.

In the same manner, the compound shown below (compound V
a) was obtained. 2- (4,6-dimethoxypyrimidin-2-ylcarbonyl) nitrobenzene: light brown crystal (mp 164-16
5 ° C.) 6-fluoro-2- (4,6-dimethoxypyrimidine-
2-ylcarbonyl) nitrobenzene: light brown granular crystals (melting point: 181 to 183 ° C.) 6-methyl-2- (4,6-dimethoxypyrimidine-2)
-Ylcarbonyl) nitrobenzene: colorless granular crystals (melting point 166-171 ° C) 6-ethyl-2- (4,6-dimethoxypyrimidine-2)
-Ylcarbonyl) nitrobenzene: white powder (melting point 1
16-117 ° C) 6-methoxymethyl-2- (4,6-dimethoxypyrimidin-2-ylcarbonyl) nitrobenzene: white powder (melting point 111-113 ° C)

Reference Example 3 (1) Production of 5-fluoro-2- (4,6-dimethoxypyrimidin-2-ylcarbonyl) aniline (Compound Vb) 5-Fluoro-2- (4,6-dimethoxypyrimidine −
3.1 g (10 mmol) of 2-ylcarbonyl) nitrobenzene, 3 g (54 mmol) of iron powder, 20 ml of water,
A mixture of 150 ml of ethyl acetate and 1 ml of acetic acid was stirred for 5 hours while heating under reflux. Insolubles in the reaction solution were removed using a filter aid, and the organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the precipitated crude crystals were washed with diisopropyl ether to obtain 5-fluoro-2-powder of pale yellow granular crystals (melting point: 177 to 179 ° C).
2.4 g (yield 87%) of (4,6-dimethoxypyrimidin-2-ylcarbonyl) aniline was obtained.

(2) Preparation of 3-fluoro-2- (4,6-dimethoxypyrimidin-2-ylcarbonyl) aniline (compound Vb) 3- (4,6-dimethoxypyrimidin-2-yl) -4
-Fluoro-2,1-benzoisoxazole 1.2 g
(4.4 mmol), 0.1 g of palladium carbon and 0.8 g (12.7 mmol) of ammonium formate were suspended in 100 ml of methanol, and stirred under reflux with heating for 1 hour. The insolubles in the reaction solution were separated by filtration, and methanol was distilled off under reduced pressure.
0 ml of water was added, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the precipitated crude crystals were washed with diisopropyl ether, and yellow granular crystals (melting point: 129 to 130 ° C.) of 3-fluoro-2- (4,6-
1.1 g (yield 91%) of dimethoxypyrimidin-2-ylcarbonyl) aniline was obtained.

In the same manner, the following compound (compound Vb) was obtained by the method (1). 2- (4,6-dimethoxypyrimidin-2-ylcarbonyl) aniline: yellow crystal (melting point: 166 to 167 ° C) 6-fluoro-2- (4,6-dimethoxypyrimidine-
2-ylcarbonyl) aniline: yellow granular crystals (melting point 1
31-134 ° C) 6-methyl-2- (4,6-dimethoxypyrimidine-2
-Ylcarbonyl) aniline: yellow granular crystals (melting point 13
0-132 ° C) 6-ethyl-2- (4,6-dimethoxypyrimidine-2
-Ylcarbonyl) aniline: yellow powder (melting point 122 to
123 ° C) 6-methoxymethyl-2- (4,6-dimethoxypyrimidin-2-ylcarbonyl) aniline: fluorescent yellow crystal (melting point 100 to 101 ° C)

Reference Example 4 1- (2-amino-4-fluorophenyl) -1-
(4,6-dimethoxypyrimidin-2-yl) methano-
Preparation of Compound (VIIb) 5-Fluoro-2- (4,6-dimethoxypyrimidine-
1.1 g (4.0 mmol) of 2-ylcarbonyl) aniline was mixed with 50 parts of a mixed solvent of tetrahydrofuran: water = 1: 1.
Then, 0.3 g (7.9 mmol) of sodium borohydride was added while stirring at room temperature, and stirring was continued at room temperature for another 2 hours. 50 ml of ice water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the precipitated crude crystals were washed with diisopropyl ether to obtain 1- (2-amino-4-fluorophenyl) -1- (4,6-dimethoxy) as colorless granular crystals (melting point: 94 to 95 ° C.). Pyrimidine-
1.0 g (yield 90%) of 2-yl) methanol was obtained.

In the same manner, the compound shown below (compound V
IIb) was obtained. 1- (2-aminophenyl) -1- (4,6-dimethoxypyrimidin-2-yl) methanol: white powder (melting point: 78-80 ° C.) 1- (2-amino-3-fluorophenyl) -1 −
(4,6-dimethoxypyrimidin-2-yl) methano-
: Colorless granular crystals (melting point 92-94 ° C) 1- (2-amino-6-fluorophenyl) -1-
(4,6-dimethoxypyrimidin-2-yl) methano-
: White powder (melting point 109-110 ° C) 1- (2-amino-3-methylphenyl) -1- (4,
6-dimethoxypyrimidin-2-yl) methanol: colorless granular crystals (melting point 109-112 ° C) 1- (2-amino-3-ethylphenyl) -1- (4,
6-dimethoxypyrimidin-2-yl) methanol: white crystal (melting point 85-86 ° C) 1- (2-amino-3-methoxymethylphenyl) -1
-(4,6-dimethoxypyrimidin-2-yl) methanol: white crystal (melting point 40 to 42 ° C)

The herbicide of the present invention comprises a sulfonanilide derivative represented by the general formula [I] as an active ingredient.

In order to use the compound of the present invention as a herbicide, the compound of the present invention itself may be used. , Powders, wettable powders, emulsions, fine granules or granules and the like.

[0136] Carriers used in the formulation are as follows:
Examples include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, calcium carbonate, slaked lime, silica sand, ammonium sulfate, and urea, and liquid carriers such as isopropyl alcohol, xylene, cyclohexane, and methylnaphthalene.

Examples of the surfactant or dispersant include metal salts of alkyl benzene sulfonic acid, metal salts of dinaphthyl methane disulfonic acid, alkyl sulfates, alkyl aryl sulfonates, formalin condensates, lignin sulfonates, polyoxyethylene glycols. Ether, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan monoalkylate, and the like.

Examples of the auxiliary include carboxymethylcellulose, polyethylene glycol, gum arabic and the like.

For use, they are diluted to an appropriate concentration and sprayed or applied directly.

The herbicide of the present invention can be used by foliage application, soil application or water application. The compounding ratio of the active ingredient is appropriately selected as needed, but when it is used as a powder or granule, it is appropriately selected from the range of 0.01 to 10% (weight), preferably 0.05 to 5% (weight). Is good. In the case of using an emulsion and a wettable powder, it may be appropriately selected from the range of 1 to 50% (weight), preferably 5 to 30% (weight).

The application rate of the herbicide of the present invention varies depending on the type of the compound used, the target weed, the tendency to emerge, the environmental conditions, the dosage form used, and the like. The active ingredient may be appropriately selected from the range of 0.1 g to 5 kg, preferably 1 g to 1 kg per 10 ares. When used in the form of a liquid such as an emulsion or a wettable powder, it may be appropriately selected from the range of 0.1 to 50,000 ppm, preferably 10 to 10,000 ppm.

The compounds of the present invention may be mixed with insecticides, fungicides, other herbicides, plant growth regulators, fertilizers and the like, if necessary.

Next, the preparation method will be specifically described with reference to typical preparation examples. The types and compounding ratios of the compounds and additives are not limited to these and can be changed in a wide range. In the following description, “parts” means parts by weight.

<Formulation Example 1> Water-dispersible agent 10 parts of compound (I-253), 0.5 parts of polyoxyethylene octyl phenyl ether, 0.5 parts of sodium salt of β-naphthalenesulfonic acid formalin condensate, diatomaceous earth Are mixed and pulverized to obtain a wettable powder.

<Formulation Example 2> Water-dispersible agent 10 parts of compound (I-353), 0.5 parts of polyoxyethylene octylphenyl ether, 0.5 parts of sodium salt of β-naphthalenesulfonic acid formalin condensate, diatomaceous earth 20 parts, 5 parts of white carbon, 64 parts of clay
The mixture is pulverized to obtain a wettable powder.

Formulation Example 3 Wettable powder 0.5 parts of polyoxyethylene octylphenyl ether, 0.5 part of sodium salt of β-naphthalenesulfonic acid formalin condensate, 10 parts of compound (I-367), diatomaceous earth And 5 parts of white carbon and 64 parts of calcium carbonate are mixed and pulverized to obtain a wettable powder.

<Formulation Example 4> Emulsion 30 parts of compound (I-335), 60 parts of an equal mixture of xylene and isophorone, surfactant polyoxyethylene sorbitan alkylate, polyoxyethylene alkylaryl polymer and alkylaryl sulfonate An emulsion is obtained by adding 10 parts of the mixture and stirring them well.

Formulation Example 5 Granules 10 parts of compound (I-269), 80 parts of a bulking agent obtained by mixing talc and bentonite at a ratio of 1: 3, 5 parts of white carbon, surfactant polyoxyethylene 10 parts of water was added to 5 parts of a mixture of sorbitan alkylate, polyoxyethylene alkylaryl polymer and alkylarylsulfonate, and the mixture was kneaded well and extruded through a sieve having a diameter of 0.7 mm, dried and dried. Cut to a length of 5 to 1 mm to obtain granules.

Next, the effects of the compound of the present invention will be described with reference to Test Examples.

<Test Example 1> Herbicidal effect test by paddy field flooding treatment A 100 cm ² plastic pot was filled with paddy field soil, and after scraping, various seeds of Tainubie (Ec), Konagi (Mo) and Firefly (Sc) were removed. The seeds were sown and flooded at a depth of 3 cm. The next day, the wettable powder prepared according to Formulation Example 1 was diluted with water and dropped on the water surface. The application rate is 10 active ingredients.
100 g per are. After that, grow in the greenhouse,
Twenty-eight days after the treatment, the herbicidal effect was examined according to the criteria in Table 36. The results are shown in Tables 37 to 43.

[0151]

[Table 36]

[0152]

[Table 37]

[0153]

[Table 38]

[0154]

[Table 39]

[0155]

[Table 40]

[0156]

[Table 41]

[0157]

[Table 42]

[0158]

[Table 43]

<Test Example 2> Crop selectivity test by paddy field flooding treatment A 100 cm ² plastic pot was filled with paddy field soil, and after scraping, various seeds of Konagi (Mo) and firefly (Sc) were placed in a 0.5 cm-size plastic pot. Seed to a depth, and transplant two rice plants (Or) at the 2 leaf stage at a transplanting depth of 2 cm and a water depth of 3 cm
Flooded. On the next day, a predetermined amount of the active ingredient (ai, g / 10a) of the wettable powder prepared according to Formulation Example 1 was diluted with water and dropped on the water surface. Then, it is grown in a greenhouse, and after treatment 2
On the eighth day, the herbicidal effect and the degree of phytotoxicity were examined according to the criteria in Table 36. The results are shown in Tables 44 to 49.

[0160]

[Table 44]

[0161]

[Table 45]

[0162]

[Table 46]

[0163]

[Table 47]

[0164]

[Table 48]

[0165]

[Table 49]

[0166]

Industrial Applicability The compound of the present invention represented by the general formula [I] is a perennial weed that occurs in a paddy field, such as Tainubie, Tamagatsuri, Konagi and Azena, and a perennial perennial such as Hera Modaka, Hotarui, Urikawa, Omodaka, Mizugayatsuri and Krogwai. For a weed, the occurrence and growth of the weed can be suppressed for a long period of time before the emergence and over a wide range of the growing season, and it can be controlled at a low dose. On the other hand, it has high safety against rice at the same time.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 403/06 233 C07D 403/06 233 413/04 239 413/04 239 (72) Inventor Chiharu Suzuki Fukuda-cho, Iwata-gun, Shizuoka Prefecture 408-1 Shioda Shinoda, K.I. Research Institute Co., Ltd. (72) Inventor Masao Nakatani 408-1, Fukuda-cho, Fukuda-cho, Iwata-gun, Shizuoka Pref. 408, Shioda, Fukuda-cho, Iwata-gun, Japan Inside the KI Research Institute, Inc. (72) Inventor Tomasa Ono 2--13, Shizuoka-shi, Shizuoka Prefecture, Japan 10 (72) Inventor Tomohisa Ida, Kikugawa, Ogasa-gun, Shizuoka 3353 Kamo, Machimachi (72) The inventor, Katsutoshi Yanagisawa, 881, 3061 Haneda, Kikukawa-cho, Ogasa-gun, Shizuoka Prefecture (72) The inventor, Hideo Sadohara 2-3-9, Horinouchi, Niiza-shi, Niiza-shi, Saitama

Claims (3)

[Claims] 1. A compound of the general formula [I] {In the formula, R ¹ (this group may be substituted by a halogen atom or a cyano group.) Alkyl group indicates or an alkenyl group (which may be substituted with a halogen atom.), R ² are each Independently, a hydrogen atom, a halogen atom, an alkoxy group or an alkyl group (the group may be substituted with a halogen atom, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an alkylthio group, a mono- or dialkylamino group. R ³ represents a hydrogen atom, an alkyl group (the group may be substituted with a halogen atom, a hydroxyl group, an alkenyloxy group, an alkynyloxy group, a mono- or dialkylamino group, an alkoxy group or an alkylthio group), and benzyl group, an acyl group, an alkoxycarbonyl group, a substituted carbamoyl group, a thiocarbamoyl group or a group -SO ₂ substituted ¹ (wherein ^{R 1} is as defined above.) Indicates, Q is group ^{-CH (NR 4 R 5) -} [ wherein ^R 4, ^{R 5} are identical to or different or different, a hydrogen atom, an alkyl group (The group may be substituted with a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, an alkylthio group or a phenyl group.), An alkenyl group, an alkynyl group, a cycloalkyl group, a phenyl group (the group is a halogen atom, an alkyl group Or an alkoxy group), an acyl group, an alkoxycarbonyl group, a substituted carbamoyl group, a substituted thiocarbamoyl group, a group —SO ₂ R ¹ (where R
¹ has the same meaning as described above. ), A group —NR ⁷ R ⁸ [where R ⁷ and R ⁸ are the same or different and are each a hydrogen atom, an alkyl group (the group is substituted with a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, an alkylthio group or a phenyl group) An alkenyl group, an alkynyl group, a cycloalkyl group, a phenyl group (the group may be substituted with a halogen atom, an alkyl group or an alkoxy group), an acyl group, an alkoxycarbonyl group, a group -SO ₂ R ¹ (where R ¹ has the same meaning as described above), represents a substituted carbamoyl group or a substituted thiocarbamoyl group. ] Or group-
OR ⁹ [where R ⁹ is a hydrogen atom, an alkyl group (the group may be substituted with a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, an alkylthio group, a phenyl group), an alkenyl group, an alkynyl group, a cycloalkyl Group, phenyl group (the group may be substituted with a halogen atom, an alkyl group, or an alkoxy group), acyl group, alkoxycarbonyl group, alkylsulfonyl group (the group may be substituted with a halogen atom), It represents a substituted carbamoyl group or a substituted thiocarbamoyl group. Or, optionally, R ⁴ and R ⁵ may be combined with these bonded nitrogen atoms to form a nitrogen-containing heterocyclic group having one or more hetero atoms. ] Or a group -C (= N
R ⁶ )-[where R ⁶ is a hydrogen atom, an alkyl group (the group may be substituted with a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, an alkylthio group, a phenyl group), an alkenyl group, an alkynyl group, Cycloalkyl group, phenyl group (the group may be substituted with a halogen atom, an alkyl group, or an alkoxy group), an acyl group, an alkoxycarbonyl group, a substituted carbamoyl group, a substituted thiocarbamoyl group, a group -SO ₂ R ¹ (where R ¹ has the same meaning as described above), a group —NR ⁷ R ⁸ (where R ⁷ and R ⁸
Has the same meaning as described above. ) Or a group —OR ⁹ (where R
⁹ has the same meaning as described above. ). And m represents an integer of 1 to 4. And sulfonanilide derivatives and salts thereof. 2. A compound of the general formula [II] (Wherein, R ² and m have the same meanings as described in claim 1). 4,6-Dimethoxypyrimidin-2-yl derivative which is an intermediate for producing a sulfonanilide derivative according to claim 1 . 3. A herbicide comprising the sulfonanilide derivative according to claim 1 or a salt thereof as an active ingredient.