JPS632978A - Nicotinic acid derivative, production thereof and plant growth regulator - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R<1> is alkyl, lower alkenyl, cycloalkyl, (substituted)aryl, 5- or 6-heterocyclic group, etc.; R<2>-R<4> are H, halogen, cyano, nitro amino, lower alkyl, OH, etc.; R<5> and R<6> are lower alkyl, halogenated lower alkyl, cycloalkyl, (substituted)aryl, etc.; group shown by formula II is carboxy group or esterified carboxyl group] or an l-oxide or a salt thereof. EXAMPLE:4-Butyl-5-( 2,6-diethylphenylcarbamoyl )-2,6-dimethyl-3-pyridinecarboxy lic acid methyl ester. USE:A plant growth regulator. PREPARATION:A 1,4-dihydropyridine derivative shown by formula III (group shown by formula IV is esterified carboxyl group) is oxidized with an oxidizing agent such as nitrous acid, sulful, etc., to give a compound shown by formula I when a group shown by formula II is group shown by formula IV.

Description

Detailed Description of the Invention (Industrial Application Field) This invention relates to a novel compound belonging to 2,4,6-trisubstituted nicotinic acid anilide and 2,4,6-trisubstituted nicotinic acid anilide 1-oxide, and a method for producing the same. and a plant growth inhibitor.

(Prior art) Compounds belonging to nicotinic acid anilide in which the substituents at the 2-, 4-, and 6-positions of the pyridine ring all have carbon-carbon bonds with the carbon forming the pyridine ring are God,
5ofij, tlniv, nihim, Fak.

, Volume Date 1977.72. Pt, 1
．． 37-44 (see Chemical Abstracts Vol. 96, 162501y) is known. However, these compounds differ from the compounds of this invention in that a phenylcarbamoyl group is bonded to the 5-position of the pyridine ring. -Tri-substituted nicotinic acid anilide derivatives have not been known at all.

(Purpose and Structure) The present invention provides a compound represented by the following formula (I) and its 1-oxide or addition salt thereof.

[In the formula, R1 is an alkyl group, a lower alkenyl group, a lower alkynyl group, a halogenated lower alkyl group, a lower alkoxy lower alkyl group, a lower alkylthio lower alkyl group,
Cycloalkyl group, optionally substituted aryl group, optionally substituted aralkyl group, or 5- or 6-membered heterocyclic group; R2, R3, and R4 are the same or different, hydrogen atom, halogen atom, cyanide group, nitro group, amine group,
Lower alkyl group, halogenated lower alkyl group, hydroxy group, lower alkoxy group, aryloxy group, carboxy group, or lower alkoxycarbonyl group: R5 and R6
are the same or different, a lower alkyl group, a halogenated lower alkyl group, a lower alkoxy lower alkyl group, a cycloalkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group; the group Re 0CO- is carbon acid group or esterified carboxyl group].

The present invention also provides a plant growth inhibitor containing at least one of the above compounds as an active ingredient. Furthermore, the present invention provides a method for producing the above-mentioned compounds.

In the above compound of formula (I), the alkyl group means a straight chain or branched hydrocarbon group having 1 to 12 carbon atoms, including methyl, ethyl, propyl, isopropyl, butyl,
Isobutyl, secondary butyl, pentyl, isopentyl,
Includes 1-methylbutyl, 1-ethylpropyl, hexyl, octyl, and the like. Also included are alkyl groups having a cycloalkyl group such as a cyclohexylmethyl group and a cyclopropylmethyl group.

The term "lower" used in this invention means a carbon number of 1 to 6. For example, lower alkyl, lower alkenyl, and lower alkynyl groups include methyl,
ethyl, propyl.

Includes isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, allyl, 2-methyl-2-propenyl, 2-butenyl, 2-pentenyl, 2-propynyl, and the like.

For lower alkoxy lower alkyl groups and lower alkylthio lower alkyl groups, methoxymethyl, ethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl, methoxypropyl.

Includes ethoxypropyl, methylthioethyl, ethylthioethyl, etc.

Lower alkoxy groups include methoxy and ethoxy.

This includes propoxy.

For the lower alkoxycarbonyl group, methoxycarbonyl Includes carbonyl.

The halogenated lower alkyl group includes trifluoromethyl,
Difluoromethyl, fluoromethyl.

Includes chloromethyl, 2-chloroethyl, 3-chloropropyl, 2-bromoethyl, 4-chlorobutyl, and the like.

Cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

Halogen atoms include chlorine, bromine, fluorine and iodine.

Aryl groups include phenyl or naphthyl groups.

Aralkyl groups include benzyl, 2-phenylethyl, 3
-Phenylpropyl, 4-phenylbutyl, etc.

Aryloxy groups include phenyloxy, naphthyloxy groups, and the like.

In addition, the benzene ring of the aryl group or aralkyl group is 1-
3i11i1 halogen atom, cyano group, nitro group, amine group, lower alkyl group, halogenated lower alkyl group,
Hydroxy group, lower alkoxy group, aryloxy group,
It may be substituted with a carboxy group or a lower alkoxycarbonyl group.

A nitrogen atom in a 5- or 6-membered heterocyclic group.

! 12 elementary atoms, 1 beta atom selected from sulfur atoms
5- or 6-membered heterocyclic groups containing ~3 are included.

For example, furyl, tetrahydrofuryl, thienyl, thiazolyl, isothiazolyl.

5 such as oxasilyl, isoxasilyl, pyrazolyl, etc.
Member ring group; pyridyl, pyrimidinyl.

Examples include 6-membered ring groups such as pyrazinyl and pyridazinyl. These groups may be substituted with alkyl groups such as methyl or ethyl, halogen atoms or phenyl groups. When substituted with a phenyl group, it may be bonded to two carbon atoms within the ring to form a fused ring. Examples of fused rings include benzothiazolyl and benzofuryl.

Examples include quinazolinyl and quinoxalinyl groups.

In addition, the group Re 0CO- in formula (I) means a carboxylic acid group or an esterified carboxyl group, and an esterified carboxyl group can be easily removed by hydrolysis, thermal decomposition, or reductive decomposition. It means a carboxyl group having an ester group. Specific examples include lower alkoxycarbonyl group, phenoxycarbonyl group, hensyloxycarbonyl group, tetrahydropyranyloxycarbonyl group, and benzhydryloxycarbonyl group.

Further, the compound of formula (I>) or its 1-oxide compound of the present invention can form an addition salt with an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, etc. When R6 is a carboxylic acid group, it can form a metal salt (for example, a lithium, sodium, or potassium salt) or can be converted into a mixed salt thereof.Therefore, compounds in the form of such salts are also included in the present invention. Included in the range.

The compound of formula (I>) of this invention can be prepared by the method shown below.

That is, the 1,4-dihydropyridine derivative (IV) is obtained by any of the methods of reaction formulas (a) to (e), and by oxidizing it, and optionally removing the ester group, the formula The compound (I) can be obtained [see reaction formulas (g) and (h)].

Reaction formula (c)〉 (■) GI[)〈Reaction formula (d)〉 T(2 (V) (VID)〈Reaction formula (e)〉 al) (■〕(■) Reaction formula (f)〉 Hole 2 (Vl) (Vl) (IX)〈Reaction formula (g)〉 (IV) α)〈Reaction formula (
h)> α) (■) [(II>, (IVY, (V) among the above formulas).

The group R70CO in (■) and (X) means an esterified carboxyl group. Other symbols are the formula (I
) has the same meaning as the symbol. ) Formula (II) used as a raw material in each reaction of reaction formulas (a) to (f),
(I[I), (V) (Vl)l■) and (■)
The compounds are known or can be prepared by known methods. Each reaction of reaction formulas (a) to (e) is carried out in water or an inert organic solvent at 20 to 150'C. Preferred solvents include alcohols such as ethanol, methanol or isopropanol; ethers such as dioxane, diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether; acetic acid, dimethylformamide.

Examples include dimethyl sulfoxide, acetonitrile, and pyridine.

The reaction of reaction formula (g) can be carried out using known oxidation methods, especially Chemical Reviews, 1972, Vol. 72, No. 1, 31.
The method described on page can be applied.

For example, by reacting the compound of formula (IV) with an oxidizing agent such as nitrous acid, nitric acid, chromic acid, iodine or sulfur, or by heating in the presence of a dehydrogenation catalyst such as palladium.

The reaction of reaction formula (H) is carried out by hydrolyzing, thermally decomposing or reductively decomposing the compound of formula (X). These three decomposition methods can be selected depending on the type of R7 in the formula. When R7 is a methyl group, ethyl group, isopropyl group, isopropenyl group, tertiary butyl group, tetrahydropyranyl group, P-methoxybenzyl group, benzhydryl group, etc., acid, alkali or other hydrolysis methods are used. . For hydrolysis with acid or alkali, generally known methods are used. Other hydrolysis methods include a method in which lithium iodide, lithium bromide, sodium cyanide, or sodium acetate is reacted with lutidine, collidine, dimethylformamide, etc. as a solvent under heating, and then treated with an acid. Can be done.
The latter method is particularly preferred when R7 in formula (X) is a methyl group.

When R7 is a tertiary butyl group, isopropyl group, etc.,
By thermally treating the compound of formula (X), (
XI) can be obtained. This process is carried out at temperatures above 150°C.

When R7 is a benzyl group, benzhydryl group, etc., (XI) can be obtained by a known reductive decomposition method such as catalytic reduction using palladium or the like as a catalyst.

The 1-oxide of the compound of formula (1) of this invention can be produced by the method shown below.

<Reaction formula (S)> In addition, each symbol in each of the above formulas has the same meaning as the symbol in formula (I). This method comprises preparing a compound of formula (I) in a suitable solvent with hydrogen peroxide, a hydroperoxide such as t-butyl hydroperoxide, or peracetic acid, perbenzoic acid,
This is done by treatment with an oxidizing agent such as an organic peracid such as m-chloroperbenzoic acid. In addition, the above formula (I-)
When the group Re 0CO- in is an esterified carboxyl group, the ester group may be further decomposed and converted into a carboxylic acid group as described above.

In the plant growth inhibitor of the present invention, the compound represented by the formula (I), its 1-oxide, or a salt thereof may be used as an active ingredient as it is, but - generally, a solid carrier,
It is mixed with liquid carriers, surfactants, and other formulation auxiliaries to formulate wettable powders, granules, emulsions, etc. These preparations contain 10 to 80% active ingredients in wettable powders, 2 to 20% in granules, and 10 to 50% in emulsions (all by weight).
It is preferable to contain a) showing the following.

Kaolin is used as a solid carrier for formulations.

Bentonite, clays, talc, diatomaceous earth, gicrite, zeolite, pyrophyllite.

There are fine powders or granules such as synthetic silicon oxide and calcium carbonate, and the liquid carrier is xylene.

Aromatic hydrocarbons such as methylnaphthalene, ethanol,
Alcohols such as isopropanol, ethylene glycol, and methyl cellosolve; ketones such as acetone, isophorone, and cyclohexanone; vegetable oils such as soybean oil and cottonseed oil;
Examples include dimethylformamide, dimethyl sulfoxide, acetonyl, water, and the like. Surfactants used for dispersion, emulsification, etc. include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester.

Nonionic surfactants such as polyoxyethylene polyoxypropylene block polymers, alkyl sulfate salts, and alkyl sulfonate salts.

Examples include anionic surfactants such as alkylaryl sulfonates and polyoxyethylene alkyl Ij [ester salts].

Lignosulfonate is used as a formulation adjuvant.

Alginates, polyacrylates, polyvinyl alcohol, vegetable gums, carboxymethylcellulose (CM
C), hydroxyethyl cellulose ()-IEc), and the like.

The wettable powders and emulsions prepared as described above are usually diluted with water, and the granules can be used as they are by spraying on the soil or on grass and soil.

The plant growth inhibitor of this invention may include other plant growth regulators, insecticides, and fungicides, if necessary.

It can also be used in combination with fertilizer or soil conditioner.

Hereinafter, this invention will be explained by reference examples (manufacture of formula (IV)) and examples. Table 1-3 shows the physical property values of the compounds listed in the Reference Examples and Examples and the compounds obtained by the reaction processes shown in the Reference Examples and Examples or the reaction processes conducted in accordance with these. Table 4 also shows the growth inhibiting effect of the compounds of this invention on plants.

In addition to the compounds shown in Examples, the following are specific names of interesting compounds included in the present invention.

Ethyl 4-butyl-6-edyru-5-(2,6-dinitylphenylcarbamoyl)-2-methyl-3-pyridinecarboxylate 4-Butyl-5-(4-chloro-2,6-dinitylphenyl) Tertiary butyl carbamoyl-3-pyridinecarboxylate 5-(3-chloro-2-methylphenylcarbamoyl)-2,6-dimethyl-4-pentyl-3-pyridinecarboxylate phenyl 5-(4-bromo-2,6 -Methyl dinitylphenylcarbamoyl 2-methyl-3-pyridinecarboxylate 4-butyl-2-ethyl-5- (2.6-Methyl dinitylphenylcarbamoyl-3-pyridinecarboxylate 2-methyl-4-( 2-methoxyethyl)-5-(3-
Benzyl 2,6-cymethyl-4-(3-nitrophenylcarbamoyl)-6=phenyl-3-pyridinecarboxylate
-Nitrophenyl>-5-phenylcarbamoyl-3-
Methyl pyridinecarboxylate 4-(3-chloropropyl)-5-(4-cyanophenylcarbamoyl)-2.6-dimethyl-3-pyridinecarboxylate 5-(2-methoxycarbonylphenylcarbamoylropenyl)-3-pyridine Methyl carboxylate 5-(2-
Methoxyphenylcarbamoyl-2-methyl-4-(2
-methylthioethyl)-6-phenylmethyl-3-pyridinecarboxylate, 4-butyl-5-(3-trifluoromethylphenylcarbamoyl-2-methyl-3-pyridinecarboxylate, ethyl 4-butyl-5-(2. 6-dinitylphenylcarbamoyl)-
Methyl 6-trifluoromethyl-2-methyl-3-pyridinecarboxylate 5-(4-bromo-2,6-dinitylphenylcarbamoyl>-4-butyl-6-1-lifluoromethyl-2-
Methyl-3-pyridinecarboxylate 5-(4-bromo-2,6-dinitylphenylcarbamoyl)-4-butyl-2-trifluoromethyl-6-methyl-monoate Methyl 5-(4-bromo- Lithium 4-butyl-5-(2,6-dinitylphenylcarbamoyl)-4-butyl-2,6-pisdrifluoromethyl-3-pyridinecarboxylate 4-Butyl-5-(2,6-dinitylphenylcarbamoyllysinecarboxylic acid sodium 4-butyl-5-(2,6-dinitylphenylcarbamoyllysinecarboxylic acid potassium) Reference example 1 4-butyl-5-( 2. Methyl 6-dinitylphenylcarbamoyl-dimethyl-3-pyridinecarboxylate (compound N
06) N-(2.6-dinitylphenyl)-3-oxobutyric acid amide 9.33 g (40 mmol), pentanal 4.
48g (52mmol), piperidine 0,04Inf!
A mixture of 40 d of methylene chloride and 40 d of methylene chloride was stirred for 5.5 hours while cooling with water. After removing the generated water with anhydrous sodium sulfate, the solvent was removed by drying using a vacuum bottom-tally evaporator. 4. Methyl 3-aminocrotonate was added to the obtained residue. 6 1 'j (40 mmol) and 40 mmol of ethanol were added, and the mixture was refluxed for 3 hours. The reaction mixture was allowed to cool, and the precipitated crystals were filtered and dried to give 4-butyl-5-(2,6-dinitylphenylcarbamoyl)-1.
, 10.349 methyl 4-dihydro-2,6-dimethyl-3-pyridinecarboxylate (yield 65%) was obtained.

Melting point: 221-225°C IR (KBr disk): 1608.1640°167
5o++-” NMR (CDCl2) δ value: , 050-1.70
(m, 9H).

1.17 (t, 6 old, 2.20 (s, 3H), 2.25
(s, 3 old.

2.59 (q, 4H), 3.69 (s, 3H),
3.6o-4,03(m, IH), 5.78(S
, 1 old, 6.90 (S, IH), 6.95-7.25 (
From the corresponding β-ketoamide derivatives and aldehydes, the compounds Nα1 and Nα1,
2, 3, 4.5. 7. 's, 9,10゜11
．． 12, 13, 14, 17.18.19゜20.21,
Compounds 22, 23, and 25 were obtained.

The structure and physical properties of each compound are shown in Table 1.

Reference example 2 5-(2,6-dinitylphurnylcarbamoyl)-1
,7! I-dihydro-2,6-dimethyl-4-[2-(
5-methylfuryl)]-]3-pyridinecarboxylic acid methyl compound No. 16)N-(2,6-dinitylphenyl)-3-oxobutyric acid amide 9.33 g (40 mmo
l), 5-methylfurfural 4.409 (40mm
O+).

Piperidine 0.2oj! , a mixture of 11?0.5 m of vinegar and 40 m of benzene was heated, and while removing the by-product water,
Refluxed for an hour. The reaction mixture was washed successively with IN hydrochloric acid, water, and saturated aqueous sodium bicarbonate, and then the solvent was removed under reduced pressure. To the obtained residue, 4.16 g of methyl 3-amic D-tonate (4
0 mmol) and 40 d of ethanol were added, and the mixture was heated under reflux for 5 hours. After removing the solvent from the reaction mixture under reduced pressure,
Crystallization from ether gives 5-(2,6-dinitylphenylcarbamoyl)-1,4-dihydro-2,6
-Simethyl-4-[2-(5-methylfuryl) was obtained in an amount of 12.3 g (yield: 73%).

Melting point: 150-153℃ IR (KBr disk): 1610, 1623.

1688rrI NMR (CDCl2 > δ value: 1.12 (t, 6 old.

2, 17(s, 3H), 2. 22(s, 6N
), 2. 51 (q, 4 old.

3, 67 (s, 3 old, 4.99 (S, 1 old, 5.
70-6. OO (m, 2 old, 6.33 (S, 1 old, 6.90-7.20 (m, 3H), 7.34 (S, 1 old)
From the corresponding β-ketoamide derivatives and aldehydes, Compound No. .

15, 24.26 compounds were obtained. The structure and physical properties of each compound are shown in Table 1.

Example 1 4-Butyl-5-(2.6-dinitylphenylcarbamoylridinecarboxylate methyl (compound Nα31) 4-butyl-5-(2.6-dinitylphenylcarbamoyl)-'
Methyl l,4-dihydro-2,6-dimethyl-3-pyridinecarboxylate 7.

Add 2.07 g of sodium nitrite to a mixture of 97 g (20 mmol) and 30 d of acetic acid using a water bath, controlling the temperature of the reaction mixture so that it does not exceed 25°C.
(30 mmol) was added little by little. After stirring at about 20-25°C for 2 hours, the reaction mixture was poured onto ice and neutralized with Fuchi aqueous ammonia.

This was transferred to a separatory funnel and extracted with methylene chloride. After washing the organic layer with saturated brine, it was dried and concentrated using a conventional method, and the resulting crystalline residue was recrystallized from ethyl acetate.
7.22 g (yield 91%) of methyl 4-butyl-5-(2,6-dinitylphenylcarbamoyl 2,6-dimethyl-3-pyridinecarboxylate) was obtained.

Melting point: 149-1 50℃ IR (KBr disk): 163B.

1728cx-” NMR (CDCl2 > δ value: 0.60-2.00(
m, 7H).

1, 23 (t,, 6H), 2.30-3.10 (m, 2
Old, 2. 47(s, 3H).

2, 65 (S, 3N), 2. 71 (Q,
4H), 3. 88 (S, 3H), 6. 87-
Compound No. 7, 30 (m, 4) was prepared from the corresponding 1,4-dihydro-3-bilysine caffleboic acid methyl derivatives by similar operations.
30,34.35.37,39,42゜43.44.4
5,46.48 compounds were obtained.

The structure and physical properties of each compound are shown in Table-2.

Example 2 Methyl 4-cyclohexyl-5-(2,6-dinitylphenylcarbamoyl)-2,6-dimethyl-3-pyridinecarboxylate (Compound Nα36) 4-Cyclohexyl-5-(2,6-dinithylphenylcarbamoyl)-2,6-dimethyl-3-pyridinecarboxylate Methyl tylphenylcarbamoyl-2,6-dimethyl-3-pyridinecarboxylate 6
, 379 (15 mmol) and 0 sulfur.

489 (15 mmol) of a mixture of about 225-23
Processed at 0°C for 45 minutes. The reaction mixture was crystallized from ether to obtain 4.489 methyl 4-cyclohexyl-5-(2,6-dinitylphenylcarbamoyl-2,6-dimethyl-3-pyridinecarboxylate (71% yield)). Ta.

Melting point: 177-181℃ IR (KBr disk): 1650.

1733σ-1 NMR (CDC I3) δ value: 0. 80-2.
15 (m, 10 old 1, 23 (t,, 6 old, 2.
38 (s, 3 old, 2.50-3.30 (m, 18).

2, 59 (S, 3 old, 2. 71 (0.4H),
3. 86 (S, 3H), 6. 70-7. 5
0(m,4H) From the corresponding methyl 1,4-dihydro-3-pyridinecarboxylic acid derivatives, compound N
o. 28.32, 33.38.

40, 41.47 compounds were obtained. The structure and physical properties of each compound are shown in Table-2.

Example 3 4-Butyl-5-(2,6-dinitylphenylcarbamoyl)-2,6-dimethyl-3-pyridinecarboxylic acid (compound Nα53). 4-Butyl-5-(2,6-dinitylphenylcarbamoyl)-2,6-cymethyl-3-
Methyl pyridinecarboxylate 3.97g (10mmol)
, lithium iodide 1.61 g (12 mmol> and 2,
The mixture of 6-lutidine 35d was heated to reflux for 7 hours.

The solvent was removed from the reaction mixture using a vacuum bottom-tally evaporator. The obtained residue was transferred to a separatory funnel together with water and ethyl acetate and mixed well. IN to water layer
1 salt! The precipitated crystals were filtered and dried to yield 4-butyl-5-(2,6-diethylephenylcarbamoyl)-2,6-dimethyl-3-pyridinecarboxylic acid (3.839%). 100%) was obtained.

Melting point: 305-306℃ (decomposition) IR (KBr disk): 1645.

1713α-1 Compounds Nα50 and 51.52 were obtained from the corresponding methyl 3-pyridinecarboxylate derivatives by similar operations.
．． 54.55.56.57.

5B, 59.60.61.62.63.64.

Compounds 65, 66 and 67 were obtained. The structure and physical properties of each compound are shown in Table 3.

Example 4 Methyl 4-butyl-5-(2,6-dinitylphenylcarbamoylridinecarboxylic acid 1-oxide (compound Nα49
) 4-Butyl-5-(2.6-dinitylphenylcarbamoyl: methyl lysinecarboxylate 79 3rpy (2mm
ol).

A mixture of 0.86 g of commercially available m-chloroperbenzoic acid and 20 d of chloroform was stirred at room temperature for 3 hours. The reaction mixture was transferred to a separatory funnel and washed successively with 10% aqueous sodium bisulfite solution, saturated aqueous sodium bicarbonate, and saturated brine. The organic layer was dried and concentrated using a conventional method. The residue was dissolved in a mixture of hexane and ether. The title mixture is crystallized from 74
3my<yield 90%) was obtained.

Melting point: 154-157℃ (decomposition) IR (KBr disc l'1650.

1735c "I NMR (CDCl2) δ value: 0.60-2.OQ(
m, 7H).

1, 30 (t, , 6H), 2.34 (s, 3
H), 2.50-3.10(m, 2 old, 2.60(
S, 3 old, 2.70 (Q, 4 old, 3.93 (s, 3
Old.

7, 05-7.35 (m, 3 old, 9, oa(s, i
Old Example 5 Talc (50'Ji 1 part), bentonite (25 parts by weight), Tsurupol-5039 (manufactured by Toho Chemical, 2 parts by weight),
A carrier was prepared by mixing Trupol-5039 (same as before, 3 parts by weight). A 20% wettable powder was prepared by mixing 50 parts by weight of the test compound and 200 parts by weight of the carrier. This hydrating powder was dispersed in pure water to obtain a hydrating powder dispersion having a predetermined concentration. Separately, petri dishes in which seeds of rice, Japanese millet, and Japanese radish were germinated were prepared, the above-mentioned hydrating agent dispersion was added, and the seedlings were grown for 7 days in a constant temperature warehouse with lighting at 25° C., and the degree of growth was observed. How to display the results: 1=no effect, 2=25
% growth inhibition, 3 = 50% growth inhibition, 4 = 75% growth inhibition, 5 = complete death.

The results are summarized in Table 4.

Claims (11)

[Claims] (1) Formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 is an alkyl group, lower alkenyl group, lower alkynyl group, halogenated lower alkyl group, lower alkoxy lower alkyl group , lower alkylthio lower alkyl group,
Cycloalkyl group, optionally substituted aryl group, optionally substituted aralkyl group, or 5- or 6-membered heterocyclic group; R^2, R^3, and R^4 are the same or different and are hydrogen atoms , halogen atom, cyano group, nitro group, amino group, lower alkyl group, halogenated lower alkyl group, hydroxy group, lower alkoxy group, aryloxy group, carboxy group or lower alkoxycarbonyl group; R^5
and R^6 are the same or different, lower alkyl group, halogenated lower alkyl group, lower alkoxy lower alkyl group, cycloalkyl group, optionally substituted aryl group, or optionally substituted aralkyl group; group R ^8OCO-
is a carboxylic acid group or an esterified carboxyl group], or its 1-oxide, or a nicotinic acid derivative consisting of a salt thereof. (2) There are ▲mathematical formulas, chemical formulas, tables, etc. for formula (I)▼
is 2,3-dimethylphenyl, 2,6-diethylphenyl, 4-bromo-2,6-diethylphenyl, or 4
The compound according to claim 1, which is a -chloro-2,6-diethylphenyl group. (3) The compound according to claim 1 or 2, wherein R^1 in formula (I) is an alkyl group having 2 to 6 carbon atoms. (4) The compound according to claim 1 or 2, wherein R^1 in formula (I) is an optionally substituted phenyl group. (5) The compound according to any one of claims 1 to 4, wherein R^5 in formula (I) is an alkyl group having 1 to 5 carbon atoms. (6) The compound according to any one of claims 1 to 5, wherein R^6 in formula (I) is an alkyl group having 1 to 5 carbon atoms. (7) The compound according to any one of claims 1 to 6, wherein R^8 in formula (I) is an alkyl group having 1 to 5 carbon atoms, an anikenyl group, or a phenyl group. (8) Formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R^1 is an alkyl group, lower alkenyl group, lower alkynyl group, halogenated lower alkyl group, lower alkoxy lower alkyl group , lower alkylthio lower alkyl group,
cycloalkyl group, optionally substituted aryl group, optionally substituted aralkyl group, or 5- or 6-membered heterocyclic group; R^2, R^3, R^4 are the same or different, hydrogen Atom, halogen atom, cyano group, nitro group, amino group, lower alkyl group, halogenated lower alkyl group, hydroxy group, lower alkoxy group, aryloxy group, carboxy group or lower alkoxycarbonyl group; R^5
and R^6 are the same or different, lower alkyl group, halogenated lower alkyl group, lower alkoxy lower alkyl group, cycloalkyl group, optionally substituted aryl group, or optionally substituted aralkyl group; group R ^7OCO-
is an esterified carboxyl group)
-The dihydropyridine derivative is oxidized and if necessary hydrolyzed to form the formula (I): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R^1 to R^6 are each formula (IV) 1. A method for producing a nicotinic acid derivative, which is characterized by obtaining a compound represented by the following definition, wherein the group R^8OCO- represents a carboxylic acid group or an esterified carboxyl group. (9) The method according to claim 8, wherein the oxidation is carried out by the action of nitrous acid or sulfur. (10) The method according to claim 8, wherein the hydrolysis is carried out by applying lithium iodide or lithium bromide and then treating with an acid. (11) Formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 is an alkyl group, lower alkenyl group, lower alkynyl group, halogenated lower alkyl group, lower alkoxy lower alkyl group , lower alkylthio lower alkyl group,
Cycloalkyl group, optionally substituted aryl group, optionally substituted aralkyl group, or 5- or 6-membered heterocyclic group: R^2, R^3, R^4 are the same or different and are hydrogen atoms , halogen atom, cyano group, nitro group, amino group, lower alkyl group, halogenated lower alkyl group, hydroxy group, lower alkoxy group, aryloxy group, carboxy group or lower alkoxycarbonyl group; R^5
and R^6 are the same or different, lower alkyl group, halogenated lower alkyl group, lower alkoxy lower alkyl group, cycloalkyl group, optionally substituted aryl group, or optionally substituted aralkyl group; group R ^6OCO-
is a carboxylic acid group or an esterified carboxyl group], its 1-oxide, or a salt thereof as an active ingredient.