JPH06239819A - Amide derivative and herbicide comprising the same as active ingredient - Google Patents

Abstract

(57) [Summary] [Objective] A novel compound having excellent herbicidal activity against paddy field weeds, capable of efficiently removing paddy field weeds at a low dose, and capable of suppressing extremely low phytotoxicity to paddy rice. provide. According to claim 1, which has a phenyl skeleton, the phenyl skeleton is substituted with a halogen-substituted alkenyl group or an epoxidized alkenyl group, and further an amide group is bonded to the phenyl skeleton via a carbon atom. Amide derivative.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel amide derivative and a herbicide containing the same as an active ingredient.

[0002]

2. Description of the Related Art Herbicides are extremely important agents for labor saving of weed control work and improvement of productivity of agricultural and horticultural crops. Therefore, research and development of herbicides have been actively conducted for many years, and a wide variety of agents are currently available. Has been put to practical use. But,
Even today, there is a demand for the development of a new drug having more excellent herbicidal properties, in particular, a drug capable of controlling only the target weeds at a low dose without causing phytotoxicity on cultivated crops.

Along with paddy rice, various weeds in paddy fields, such as annual grass weeds such as Nobie, annual cyperaceous weeds such as tabular clam, annual broad-leaved weeds such as eel, yellow cypress, urinary cucumber, hirshiro, hiramemodaka, firefly, matsubai, mizugaya, are available. It is known that perennial weeds such as kurogwai, Japanese sardines, and celery grow, and it is extremely important for rice cultivation that these weeds do not cause chemical damage to paddy rice, and that they are effectively weeded with a small amount of spraying because of environmental pollution. is important. In particular, since Nobie is a grass weed, a drug having herbicidal activity against Nobie is likely to cause phytotoxicity to paddy rice. Therefore, it has high herbicidal activity against Nobie and has an intergeneric selection between paddy and Nobie. The development of highly effective drugs has become an important issue.

As the similar compound having herbicidal activity, for example, a compound described in JP-B-53-37409 can be used.

[Chemical 7] Compound represented by [generic name: tridifane (trid
iphane)] and the formulas described in JP-A-1-508736.

[Chemical 8] The compound represented by (Compound No. 1 in the publication) is known.

[0005]

However, the compound represented by the formula (I) described in JP-B-53-37409 has already been put to practical use as a herbicide for controlling weeds of grass family in the corn field. However, when it is used as a herbicide for paddy rice, its selectivity is poor, and it may cause phytotoxicity to paddy rice.

Further, the compound represented by the formula (II) described in JP-A-1-508736 has an excellent herbicidal effect on paddy field weeds such as Nobie, Tamagami-tsutsui, Mizuhaya-tsui, and annual broad-leaved weeds. Requires a relatively high dose and is not always satisfactory for practical use.

Therefore, an object of the present invention is to provide a novel compound having excellent herbicidal activity against paddy field weeds, capable of efficiently removing the paddy field weeds at a low dose, and capable of suppressing the phytotoxicity against paddy rice to an extremely low level. And to provide a herbicide containing the same as an active ingredient.

[0008]

[Means for Solving the Problems] The present inventors focused on the fact that the above-mentioned known compounds have herbicidal activity against grasses, and against other paddy weeds such as annual grass weeds such as Nobie. Also conducted extensive research on derivatives having excellent herbicidal activity and selectivity.

As a result, a novel derivative having a phenyl skeleton and having an amide group bonded to the phenyl skeleton via a carbon atom has an excellent herbicidal effect on paddy weeds such as Nobie, Tamagaya, Mizugaya, and annual broad-leaved weeds. In addition to having a high selectivity, especially excellent intergeneric selectivity of rice and Nobie, it is possible to efficiently remove paddy weeds at a low dosage, and to find that there is almost no phytotoxicity to rice, The present invention has been completed based on this finding.

That is, the present invention has the general formula

[Chemical 9] (In the formula, A is

[Chemical 10] And B is

[Chemical 11] X in the formula A represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms, R ¹ in the formula B represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² represents hydrogen. An atom, an alkyl group having 1 to 4 carbon atoms, an acyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, R ³
Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 4 carbon atoms
Haloalkyl group or -CH ₂ -OR ⁴ (R ⁴ is a is acyl group having 1 to 4 carbon alkyl group or a C 1 to 4 carbon atoms) indicates, m is an integer of from 2 to 6, n represents 0 or 1 Indicates an integer. ) And an herbicide containing the amide derivative as an active ingredient.

The amide derivative represented by the above general formula (III) is a novel compound and is represented by the formulas A, B, X, R ¹ and R.
^The details of ² , R ³ and R ⁴ , and m and n are as follows.

A is

[Chemical 12] Is.

X in the formula A is a halogen atom or a haloalkyl group having 1 to 4 carbon atoms. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the haloalkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group having one or more of the above halogen atoms.

B is

[Chemical 13] Is.

R ¹ of B in the formula is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group.

In the formula, R ² of B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms.
4 is an alkoxy group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group. As the acyl group having 1 to 4 carbon atoms,
Formyl group, acetyl group, propionyl group and butyryl group can be mentioned. As the alkoxy group having 1 to 4 carbon atoms,
Examples thereof include a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

In the formula, R ³ of B is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or --C.
It is a H ₂ -OR ^4. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. The alkyl group having 3 or more carbon atoms may be a cycloalkyl group. . . Examples of the haloalkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group having one or more of the above halogen atoms. R ⁴ in —CH ₂ —OR ^4, which is one embodiment of B in the formula, is an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms. Here, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the acyl group having 1 to 4 carbon atoms include a formyl group, an acetyl group, a propionyl group, and a butyryl group. Is mentioned.

In the formula, m of B is an integer of 2 to 6, and n is an integer of 0 or 1.

In the following, the methyl group is Me and the ethyl group is E
t, n-propyl group is n-Pr, i-propyl group is i-
The Pr, n-butyl group may be abbreviated as n-Bu.
Representative examples of the amide derivative of the present invention represented by the general formula (III) include those listed in Tables 1 to 6.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

[0023]

[Table 4]

[0024]

[Table 5]

[0025]

[Table 6]

Further, the amide derivative of the present invention has an enantiomer based on the quaternary carbon of the benzyl moiety and the oxirane moiety and is usually obtained as a racemate, but each enantiomer is obtained by a known method such as asymmetric synthesis. It is also possible to get a body. The compound of the present invention may be a racemate or each enantiomer alone, and each can be used as a herbicide.

When the amide derivative of the present invention has two asymmetric carbons, diastereomers exist, and each diastereomer can be obtained by a known method such as column chromatography. The compound of the present invention may be a mixture of diastereomers or individual diastereomers, each of which can be used as a herbicide.

Of the amide derivatives (III) of the present invention, polyhaloalkene derivatives (IV) (compounds (IV
a) and the compound (IVb) in Table 3 can be produced using the propene derivative (VI) as a raw material, as shown in FIG.

That is, in the presence of a catalyst such as cuprous chloride and amines such as piperidine and cyclohexylamine, a propene derivative (VI) and a polyhaloalkane (CCl) are used.
_The desired polyhaloalkene derivative (IV) or polyhaloalkane derivative (VII) can be obtained by reacting ₂ XX ') with a temperature of 0 ° C to the boiling point of the polyhaloalkane for about 1 to 20 hours. In this case, the polyhaloalkene derivative (IV) may be directly led or the polyhaloalkane derivative (VII) may be led by appropriately selecting the reaction conditions. Polyhaloalkane derivative (VII)
When this is obtained, heating this to a suitable temperature in the presence of a catalyst such as cuprous chloride or ferric chloride in a solvent such as o-dichlorobenzene or 1,2-dichloroethane. Can lead to the desired polyhaloalkene derivative (IV).

Among the amide derivatives (III) of the present invention, the oxirane derivative (V) (compounds of Table 4 and Table 5 (V
a) and the compound (Vb) in Table 6 can be produced by epoxidizing the polyhaloalkene derivative (IV) with a peroxide as shown in FIG.

The peroxide used in this reaction is not particularly limited, and those usually used for the epoxidation of ethylenic double bonds such as cumene hydroperoxide, t-butyl-hydroperoxide and cyclohexyl hydroperoxide. And peracetic acid, α-hydroperoxyisobutyric acid, perbenzoic acid, m-chloroperbenzoic acid and other perorganic carboxylic acids, and hydrogen peroxide, oxone and the like can be used. Acids are preferred, especially peracetic acid and m-chloroperbenzoic acid. The reaction is usually carried out in an inert solvent, preferably at a temperature in the range 0-80 ° C. Examples of the inert solvent include methylene chloride, chloroform,
Halogenated hydrocarbons such as carbon tetrachloride, dichloroethane, 1,1,1-trichloroethane and o-dichlorobenzene are preferably used. Further, if desired, the reaction may be carried out by adding a buffering agent such as sodium acetate, sodium benzoate, disodium hydrogen phosphate, lithium carbonate or the like to this reaction system. Regarding the use ratio of the alkene derivative (IV) and the peroxide, it is desirable to use the peroxide in a ratio of 1 to 4 times the equivalent of the alkene derivative (IV). The reaction time varies depending on the reaction temperature and the type of peroxide used, and cannot be uniquely determined, but it is usually about 1 to 50 hours.

The propene derivative (V) used as a raw material in the production of the amide derivative (III) of the present invention.
I) can be produced by a usual method using easily available raw materials. Typical examples thereof are shown in FIGS. 3 and 4.

The amide derivative of the present invention has excellent herbicidal activity against annual weeds such as grasshoppers such as Nobie, which is a paddy field weed; It also has herbicidal activity against perennial weeds. It also has high selectivity, eg 5 per 10 ares.
A dose of about 0 g can effectively control these weeds, and the dose does not cause any phytotoxicity to paddy rice.

The herbicide of the present invention is the above-mentioned amide derivative,
That is, it contains a novel amide derivative of the present invention represented by the general formula (III) as an active ingredient, these compounds are mixed with a liquid carrier such as a solvent or a solid carrier such as a fine mineral powder, It can be used by formulating it in the form of a hydrating agent, emulsion, powder, granule, and the like. A surfactant may be added in order to impart emulsifying property, dispersibility, spreadability and the like during formulation.

When the herbicide of the present invention is used in the form of a wettable powder, it is usually used in a proportion of 10 to 55% by weight of the amide derivative of the present invention, 40 to 88% by weight of a solid carrier and 2 to 5% by weight of a surfactant. The composition may be blended to prepare a composition, and this may be used.
When used in the form of an emulsion, it is usually prepared by mixing 20 to 50% by weight of the amide derivative of the present invention, 35 to 75% by weight of solvent and 5 to 15% by weight of surfactant.

On the other hand, when used in the form of a powder, the amide derivative of the present invention is usually contained in an amount of 0.5 to 16% by weight and a solid carrier
˜97.5 wt% and a surfactant in an amount of 2 to 5 wt%. When used in the form of granules, the amide derivative of the present invention may be added in an amount of 0.5 to 16% by weight, a solid carrier of 80 to 97.5% by weight, and a surfactant of 2 to 5% by weight. Good. Here, a fine powder of a mineral substance is used as a solid carrier, and examples of the fine powder of a mineral substance include diatomaceous earth, oxides such as slaked lime, phosphates such as apatite, sulfates such as gypsum, talc and pyro. Examples thereof include silicates such as ferrite, clay, kaolin, bentonite, acid clay, white carbon, quartz powder, and silica powder.

An organic solvent is used as the solvent,
Specifically, aromatic hydrocarbons such as benzene, toluene and xylene, chlorinated hydrocarbons such as o-chlorotoluene, trichloromethane and trichloroethylene, alcohols such as cyclohexanol, amyl alcohol and ethylene glycol, isophorone, cyclohexanone and cyclohexenyl. There may be mentioned ketones such as cyclohexanone, ethers such as butyl cellosolve, dimethyl ether and methyl ethyl ether, esters such as isopropyl acetate, benzyl acetate and methyl phthalate, amides such as dimethylformamide and mixtures thereof.

Further, as the surfactant, any of anionic type, nonionic type, cationic type and zwitterionic type (amino acid, betaine, etc.) can be used.

The herbicide of the present invention may contain other herbicidal active ingredients, if necessary, together with the amide derivative represented by the general formula (III) as an active ingredient. As such other herbicidal active ingredients, conventionally known herbicides,
For example, phenoxy-based, diphenyl ether-based, triazine-based, urea-based, carbamate-based, thiocarbamate-based, acid anilide-based, pyrazole-based, phosphoric acid-based, sulfonylurea-based, oxadiazone-based and the like, among these herbicides It can be appropriately selected and used. Furthermore, the herbicide of the present invention can be mixed with insecticides, fungicides, plant growth regulators, fertilizers and the like, if necessary.

[0040]

EXAMPLES Next, the present invention will be described in more detail with reference to production examples and test examples, but the present invention is not limited to these examples. (Compounds (IVa) in Tables 1 and 2 and Compounds (IVb) in Table 3)
Production Example 1) Production Example 1 N- [3- (1,1,1-trichloro-3-butene-3
-Yl) Benzyl] acetamide (Compound No. 2) Preparation of N- (3-isopropenylbenzyl) acetamide 1.
0 g (5.3 mmol) of bromotrichloromethane 20
Dissolve in 0.01 ml of cuprous chloride 0.01 g, piperidine 0.
6 ml (6.1 mmol) was added sequentially and then heated at 70 ° C. for 30 minutes. Next, 5% by weight hydrochloric acid was added, and the mixture was extracted with chloroform and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 3), and N- [3- (1,
0.80 g (yield 51%) of 1,1-trichlorobuten-3-yl) benzyl] acetamide was obtained. Table 7 shows the analytical values of this product.

Production Example 2 Production of N- [3- (2,2-dichloro-1,1,1-trifluoro-4-penten-4-yl) benzyl] acetamide (Compound No. 17) N- ( 3-isopropenylbenzyl) acetamide
60 g (3.2 mmol) of 1,1,1-trichloro-
It was dissolved in 40 ml of 2,2,2-trifluoroethane, 0.03 g of cuprous chloride and 0.5 ml (5.0 mmol) of piperidine were added successively, and the mixture was heated under reflux for 1 hour. Next, 5% by weight hydrochloric acid was added, and the mixture was extracted with chloroform and dried over anhydrous sodium sulfate. Chloroform was distilled off under reduced pressure to give the intermediate N- [3- (2,2,4-trichloro-1,1,1
-Trifluoropentan-4-yl) benzyl] acetamide was obtained. This intermediate was converted to 1,2-dichloroethane 2
It was dissolved in 0 ml, 0.24 g (1.5 mmol) of anhydrous ferric chloride was added, and then heated at 70 ° C. for 30 minutes.

Next, 5% by weight hydrochloric acid was added and the mixture was extracted with chloroform and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 3, N- [3- (2,2-dichloro-1,1,1-trifluoro-4-penten-4-yl). ) Benzyl] acetamide 0.61 g (yield 58%)
Got Table 11 shows the analytical values of this product.

Similarly, the other compounds shown in Table 1, Table 2 and Table 3 were produced according to the method described in Production Example 1 or Production Example 2. The analytical values of these are shown in Tables 7-14.

[0044]

[Table 7]

[0045]

[Table 8]

[0046]

[Table 9]

[0047]

[Table 10]

[0048]

[Table 11]

[0049]

[Table 12]

[0050]

[Table 13]

[0051]

[Table 14]

(Production Example of Compounds (Va) in Tables 4 and 5 and Compound (Vb) in Table 6) Production Example 3 N- [3- (1,1,1-trichloro-3,4-epoxybutane] Production of -3-yl) benzyl] acetamide (Compound No. 31) N- [3- (1,1,1-trichloro-3-buten-3-yl) benzyl] acetamide 0 obtained in Production Example 1 0.80 g (2.7 mmol) of methylene chloride 30 m
1 g, disodium hydrogen phosphate 0.01 g, 70
% M-Chloroperbenzoic acid 0.92 g (3.8 mmol)
Were sequentially added, and the mixture was stirred at room temperature for 24 hours. Next, the methylene chloride layer was washed with a saturated sodium carbonate aqueous solution and dried over anhydrous sodium sulfate. Column chromatography of the crude product (silica gel, ethyl acetate: hexane = 1: 3)
Purified with N- [3- (1,1,1-trichloro-3,
0.62 g (yield 74%) of 4-epoxybutan-3-yl) benzyl] acetamide was obtained. Table 15 shows the analytical values of this product.

Similarly, other compounds shown in Table 4, Table 5 and Table 6 were produced according to the method described in Production Example 3. The analytical values of these are shown in Tables 15-22.

[0054]

[Table 15]

[0055]

[Table 16]

[0056]

[Table 17]

[0057]

[Table 18]

[0058]

[Table 19]

[0059]

[Table 20]

[0060]

[Table 21]

[0061]

[Table 22]

Production Example 4 Production of 3-isopropenylbenzonitrile (Compound VIII) (Step (a) in FIG. 3) Methyltriphenylphosphonium bromide 26.0 g
(72.8 mmol) of tetrahydrofuran 100 ml
And hexane solution of normal butyllithium in hexane (1.60 mol / l) at room temperature under nitrogen flow (46.0 ml (7)
(3.6 mmol) was added dropwise and stirred for 5 minutes. Next 3-
Cyanoacetophenone 10.0 g (68.9 mmol)
What was melt | dissolved in 100 ml of tetrahydrofuran was dripped, and it stirred for 12 hours. Next, a saturated ammonium chloride aqueous solution and water were added, the mixture was extracted with ether, the organic layer was washed with saturated saline and then dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 30) to give 3-isopropenylbenzonitrile (Compound VIII) 8.92 g (yield 90
%) Was obtained. Table 23 shows the analytical values of this product.

Production Example 5 3-Isopropenylbenzylamine (Compound XI, R ¹ =
Production of H) (step (b) in FIG. 3) 0.96 g (25.3 mmol) of lithium aluminum hydride and 1.1 g (8.2 mmol) of aluminum chloride were sequentially added to 50 ml of tetrahydrofuran at room temperature under a nitrogen stream. After stirring for 10 minutes, a solution of 3-isopropenylbenzonitrile (3.0 g, 21.0 mmol) in tetrahydrofuran (25 ml) was added dropwise. After stirring at room temperature for 1 hour, 25 ml of water and 20 ml of 10% aqueous sodium hydroxide solution were sequentially added dropwise at 0 ° C. Then, the reaction solution was filtered through Celite, extracted with ether, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and 2.78 g of 3-isopropenylbenzylamine (compound XI, R ¹ = H) (yield 90
%) Was obtained. Table 23 shows the analytical values of this product.

Preparation Example 6 Preparation of α-methyl-3-isopropenylbenzylamine (Compound XI, R ¹ = Me) Step 1 (step (c) in FIG. 3) 1.4 g (9 of 3-isopropenylbenzonitrile) 0.8 mmol) was dissolved in 30 ml of benzene, 5 ml of an ether solution of methylmagnesium bromide (3 mol / 1) was added at 0 ° C., the mixture was returned to room temperature, and then heated under reflux for 5 hours. Then 0 ℃
Then, 20 ml of a saturated ammonium chloride solution was added, and the mixture was returned to room temperature and stirred for 30 minutes. The reaction solution was extracted with ether, and the organic layer was washed successively with 5% by weight hydrochloric acid and saturated saline,
It was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and 3
-Isopropenylacetophenone (compound IX, R ¹ = M
e) 1.5 g (yield 96%) was obtained.

Step 2 (step (d) in FIG. 3) 1.5 g (9.4 mmol) of 3-isopropenylacetophenone and 0.8 g (11.5) of hydroxylamine hydrochloride.
Mmol), pyridine 1.5 ml (18.5 mmol)
Was dissolved in 30 ml of ethanol and heated under reflux for 2 hours.
Next, after returning to room temperature, water and 5 wt% hydrochloric acid were added, the reaction solution was extracted with ether, the organic layer was washed successively with 5 wt% hydrochloric acid and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.46 g (yield 89%) of 3-isopropenylacetophenone oxime.

The obtained 3-isopropenylacetophenone oxime was treated with lithium aluminum hydride and aluminum chloride in the same manner as in Production Example 5 above to obtain α
-Methyl-3-isopropenylbenzylamine (compound
XI, to obtain a ^{R 1 = Me) 1.27g (94} % yield). Table 23 shows the analytical values of this product.

Production Example 7 Production of N- (3-isopropenylbenzyl) acetamide (raw material for compounds No. 2, 17, 21) (step (e) in FIG. 4 using R ² COCl) 3-isopropenylbenzyl Amines (compounds XI, R ³ =
H) 2.0 g (13.9 mmol), pyridine 2.5 m
1 (30.9 mmol) and 0.1 g of N, N-dimethylaminopyridine were dissolved in 70 ml of methylene chloride, and 1.9 ml (26.7 mmol) of acetyl chloride was added at 0 ° C.
Then, the mixture was stirred for 2 hours. Next, water and 5% by weight hydrochloric acid were sequentially added, and the mixture was extracted with methylene chloride. The organic layer was washed with saturated aqueous sodium carbonate solution and then dried over anhydrous sodium sulfate.
The solvent was evaporated under reduced pressure to give N- (3-isopropenylbenzyl) acetamide (compound VIa, R ¹ = R ² = H, R ³
= Me) (2.6 g, yield 98%) was obtained. Table 23 shows the analytical values of this product.

Similarly, the compound Nos. Shown in Tables 1 and 2 were used. 3-
The raw materials 10, 16, 18, 20, 22, and 59 were produced according to the method described in Production Example 7. The production of these was confirmed by NMR.

Production Example 8 Production of N-methyl-N- (3-isopropenylbenzyl) acetamide (raw material for compound No. 12) (Step (e) in FIG. 4 using R ² I and NaH) Production Example N- (3-isopropenylbenzyl) acetamide obtained in 7 (Compound VIa, R ¹ = R ² = H, R
³ = Me) 0.6 g (3.1 mmol) and methyl iodide 1.0 ml (16.1 mmol) were dissolved in a mixed solvent of tetrahydrofuran 20 ml and N, N-dimethylformamide 2 ml, and 60% sodium hydride 0 .20 g
(5.0 mmol) was added and the mixture was heated under reflux for 3 hours. Next, water and a saturated sodium carbonate aqueous solution were sequentially added dropwise at 0 ° C., followed by extraction with ether. The organic layer was washed successively with a saturated sodium carbonate aqueous solution and a saturated saline solution, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and N-methyl-N- (3-
Isopropenylbenzyl) acetamide (compound VIa,
R ¹ = H, R ² = R ³ = Me) 0.6 g (yield 95%)
Got Table 23 shows the analytical values of this product.

Similarly, the compound No. shown in Table 2 was used. 13-1
The raw materials 5 and 19 were produced according to the method described in Production Example 8. The production of these was confirmed by NMR.

Production Example 9 3-Isopropenylbenzyl alcohol (Compound XII,
Production of R ¹ = H) Step 1 (Step (f) in FIG. 3) 2.0 g of 3-isopropenylbenzonitrile (14.0)
(Mmol) was dissolved in 30 ml of ethanol, 15 ml of 20% aqueous potassium hydroxide solution was added, and the mixture was heated under reflux for 8 hours. Next, 20 wt% hydrochloric acid was added dropwise at 0 ° C. to adjust the pH to 1, then extracted with chloroform, and dried with anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 2.01 g (yield 89%) of 3-isopropenylbenzoic acid (Compound X).

Step 2 (step (g) in FIG. 3) Production was carried out except that 3-isopropenylbenzoic acid (Compound X) was used in place of 3-isopropenylbenzonitrile (Compound VIII) in Production Example 5. The same operation as in Example 5 was carried out to obtain 1.81 g (yield 98%) of 3-isopropenylbenzyl alcohol (Compound XII). Table 23 shows the analytical values of this product.

Production Example 10 3-Isopropenylbenzyl chloride (Compound XIII)
(Step (h) in FIG. 4) 3-isopropenylbenzyl alcohol (Compound XII)
2.6 g (17.6 mmol), triethylamine 4.
9 ml (35.2 mmol) was dissolved in 25 ml of methylene chloride and 2.7 ml of methanesulfonyl chloride was added at 0 ° C.
(35.2 mmol) was added dropwise, the mixture was stirred at room temperature for 30 hours, water was added, the mixture was extracted with methylene chloride, the organic layer was washed with saturated sodium hydrogen carbonate and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and 2.5 g of 3-isopropenylbenzyl chloride (Compound XIII) was added.
(Yield 85%) was obtained. The analytical values of this product are shown in Table 23.

Production Example 11 Production of N- (3-isopropenylbenzyl) caprolactam (raw material for compound Nos. 27 and 29) (step (i) in FIG. 3) 3-isopropenylbenzyl chloride (compound XIII)
0.80 g (4.8 mmol), .epsilon.-caplactam.
82 g (7.2 mmol) of tetrahydrofuran 20 m
It was dissolved in a mixed solvent of 1 and 2 ml of N, N-dimethylformamide, 0.29 g (7.2 mmol) of 60% sodium hydroxide was added, and the mixture was heated under reflux for 7 hours. Then water at 0 ° C,
Saturated aqueous sodium carbonate solution was added dropwise successively, followed by extraction with ether. The organic layer was washed successively with saturated aqueous sodium carbonate solution and saturated saline, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to give N- (3-isopropenylbenzyl).
Caplactam (compound VIb, R ¹ = H, m = 5, n =
0) 1.1 g (yield 98%) was obtained. Table 23 shows the analytical values of this product.

Similarly, the compound Nos. Shown in Table 1, Table 2 and Table 3 were used. The raw materials 1, 11, 23 to 26, 28 were produced according to the method described in Production Example 11. The structures of these were confirmed by NMR.

Production Example 12 Production of α-methyl-3-isopropenylbenzyl alcohol (Compound XII, R ¹ = Me) (Step (j) in FIG. 3) 1.5 g (9.4 mmol) of 3-isopropenylacetophenone ) Was dissolved in 30 ml of ethanol, 0.40 g (10.3 mmol) of sodium borohydride was added at 0 ° C., and the mixture was stirred for 1 hour. Next, water and 5 wt% hydrochloric acid were sequentially added, and the mixture was extracted with chloroform and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.51 g (yield 99%) of α-methyl-3-isopropenylbenzyl alcohol. The analytical values of this product are shown in Table 23.

Production Example 13 (Step (k) in FIG. 4) N- (3-isopropenylbenzyl) -O-methylhydroxylamine (Compound XIV, R ¹ = H, R ² = OM
Preparation of e) 3-isopropenylbenzyl chloride (Compound XIII)
0.50 g (3.0 mmol) of ethanol 6.0 ml
Dissolved in O-methylhydroxylamine hydrochloride 0.4
0 g (4.8 mmol), potassium carbonate 0.98 g
(7.1 mmol) was added, and the mixture was stirred at room temperature for 5 hours. Then, water was added, the mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and N- (3-
0.42 g (yield 63%) of isopropenylbenzyl) -O-methylhydroxylamine was obtained. The analytical values of this product are shown in Table 23.

[0078]

[Table 23]

Test Examples 1 to 64 (1) Preparation of herbicide: 97 parts by weight of talc (trade name: Zyklite) as a carrier, an alkylaryl sulfonate as a surfactant (trade name: Neoperex, Kao Atlas (stock) ))
1.5 parts by weight and nonionic and anionic surfactants (trade name: Solball 800A, Toho Chemical Industry Co., Ltd.)
1.5 parts by weight were uniformly pulverized and mixed to obtain a wettable powder carrier. 90 parts by weight of this carrier for wettable powder and Tables 1 to 6 above
10 parts by weight of the amide derivative of 1 was uniformly pulverized and mixed to obtain a herbicide.

(2) Biological test (flooded soil treatment test) Paddy soil was filled in a porcelain pot of 1/15500 are,
The seeds of Nobie and Tamagawai are evenly sown on the surface,
Two-leaf stage paddy rice was transplanted. After that, when the weeds germinated, a predetermined amount of the diluted solution of the herbicide obtained in the above (1) was uniformly dropped on the surface of the water for treatment, and then the pot was left at room temperature and sprinkled appropriately.

Tables 24 to 28 show the results of investigations on the herbicidal effect and damage to rice crops 20 days after the treatment with the chemical solution. The dose is shown as the amount of active ingredient per 10 ares. Further, the herbicidal effect and the damage to paddy rice were measured by air-dry weight and displayed as follows. (Standard) Degree of herbicidal effect Herbicidal effect (compared to untreated area) 0 100% 1 61 to 99% 2 21 to 60% 3 11 to 20% 4 1 to 10% 50% Degree of chemical damage Treatment area ratio) 0 100% 195-99% 290-94% 380-89% 460-79% 550-59%

Test Comparative Example 1 In Test Example 1, compound No. Instead of 1, the structural formula

[Chemical 14] Represented 2- (3,5-dichlorophenyl) -2-
(2,2,2-Trichloroethyl) oxirane [A]
(General name: Toridifan, Japanese Examined Patent Publication No. 53-3749), the same operation as in Test Example 1 was performed. The results are shown in Table 28.

[0083]

[Table 24]

[0084]

[Table 25]

[0085]

[Table 26]

[0086]

[Table 27]

[0087]

[Table 28]

Test Examples 65 to 71 Biological test (tube test) Novie was decompressed in water for 30 minutes and incubated at 30 ° C for 24 hours. After that, when the seeds have germinated to a state of 1 mm, the diluted solution of the herbicide obtained in (1) above is dispensed into a sample tube bottle (volume 50 ml), and 10 germinated seeds are put in each, and an artificial weather device is used. Incubation was carried out (at a temperature of 25 ° C. and light and dark every 12 hours). Further, as a control, a sample containing only ion-exchanged water was also incubated. After one week, the length of the Novier foliage part (first leaf) was measured to determine the elongation disorder rate [(1-average value of each drug / average value of control) x 100]. The result is 5
It is shown in Table 29 at 0% elongation inhibitory concentration.

Test Comparative Example 2 In Test Example 65, compound No. Instead of twelve,
Structural formula

[Chemical 15] [3- (5-tolufluoromethyl-2-pyridyloxy) phenyl] -2- (2,2,2-trichloroethyl) oxirane [B] represented by the formula (JP-A-1-508736).
Gazette, compound No. The same operation as in Test Example 65 was performed except that 1) was used. The results are shown in Table 29 at 50% elongation inhibition concentration.

[0090]

[Table 29]

As is clear from Tables 24 to 28 and Table 29 described above, the compound of the present invention is superior to the comparative compound in intergeneric selectivity between paddy rice and Nobie, and exerts an excellent inhibitory effect on Nobie growth at a remarkably low leaf amount. .

Further, the compounds used in Test Examples 1 to 64 show a herbicidal effect on annual broadleaf weeds. When the above was evaluated in the same manner, Test Examples 3, 9, 10, 12, 17, 1
8, 31, 32, 33, 37-39, 41-47, 4
The degree of herbicidal effect of the compounds used in 9, 51, 54, 56 to 58, 62 to 64 was 5.

[0093]

INDUSTRIAL APPLICABILITY The novel amide derivative of the present invention has excellent herbicidal activity against paddy field weeds and is excellent in selectivity, particularly intergeneric selectivity between paddy rice and Nobie. Moreover, weeds can be effectively weeded with a low dosage, and the dosage does not cause any phytotoxicity to paddy rice. Therefore, the amide derivative of the present invention is extremely useful as a herbicide for paddy rice.

[Brief description of drawings]

FIG. 1 is a production process diagram of compound (IV) of the present invention

FIG. 2 is a production process diagram of the compound (V) of the present invention

[FIG. 3] The first half of the manufacturing process diagram of raw material compound (VI)

FIG. 4 is the latter half of the manufacturing process diagram of raw material compound (VI)

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 28, 1994

[Procedure Amendment 1]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 1

[Correction method] Change

[Correction content]

[Figure 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location A01N 43/36 C 9159-4H 43/40 101 Q 9159-4H 43/46 C07C 235/16 7106- 4H C07D 207/404 8217-4C 211/88 9165-4C 223/10 227/087 227/093 303/36 405/10 227 7602-4C (72) Inventor Hiroshi Yamamoto 1280 Kamizumi, Sodegaura, Chiba Idemitsu Kosan Stock company

Claims (2)

[Claims] 1. A general formula: (In the formula, A is , And B is And X in the formula A represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms, R ¹ in the formula B represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² represents hydrogen. An atom, an alkyl group having 1 to 4 carbon atoms, an acyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, R ³
Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 4 carbon atoms
Haloalkyl group or -CH ₂ -OR ⁴ (R ⁴ is a is acyl group having 1 to 4 carbon alkyl group or a C 1 to 4 carbon atoms) indicates, m is an integer of from 2 to 6, n represents 0 or 1 Indicates an integer. ) An amide derivative represented by. 2. A general formula: (In the formula, A is And B is And X in the formula A represents a halogen atom or a haloalkyl group having 1 to 4 carbon atoms, R ¹ in the formula B represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² represents hydrogen. An atom, an alkyl group having 1 to 4 carbon atoms, an acyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, R ³
Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 4 carbon atoms
Haloalkyl group or -CH ₂ -OR ⁴ (R ⁴ is a is acyl group having 1 to 4 carbon alkyl group or a C 1 to 4 carbon atoms) indicates, m is an integer of from 2 to 6, n represents 0 or 1 Indicates an integer. ) The herbicide which contains the amide derivative represented by these as an active ingredient.