JPH078859B2 - Pyridine-3-carboxamide compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel compound belonging to 1,4-dihydro-4-oxo-3-pyridinecarboxamide. The compound of the present invention shows a growth inhibitory action on plants and also has an anti-inflammatory action.

(Prior Art) Certain compounds belonging to 1,4-dihydro-4-oxo-3-pyridinecarboxamide are known.

For example, Sankowskaya Sinska.W (Zankowska−J
asinska.W.) et al. N- (4-chlorophenyl) -1,4-
Dihydro-4-oxo-1,2,6-triphenyl-3-pyridinecarboxamide, 1- (4-chlorophenyl)-
1,4-dihydro-4-oxo-N, 2,6-triphenyl-3
-Pyridinecarboxamide reported [Bull.Acad.Pol.
Sci., Ser. Sci. Chem. 23 (11), 901 (1975)], and the like, 1,4-dihydro-4-oxo-N, 2,6-triphenyl-3-pyridinecarboxamide, 1 , 4-dihydro-
4-oxo-N, 1,2,6-tetraphenyl-3-pyridinecarboxamide, 1,4-dihydro-2,6-dimethyl-4-
Oxo-N, 1-diphenyl-3-pyridinecarboxamide is reported. (Zesz.Nauk.Uniw.Jagiellon., Pr.C
him. 21 , 141 (1976)].

Kato Tetsuzo et al. Are N- (4-chlorophenyl) -1,4-dihydro-2,6-dimethyl-4-oxo-3-pyridinecarboxamide, 1,4-dihydro-2,6-dimethyl-4-oxo. -N-phenyl-1- (phenylmethyl) -3-pyridinecarboxamide, 1,4-dihydro-N- (4-methoxyphenyl) -2,6-dimethyl-4-oxo-1-
(Phenylmethyl) -3-pyridinecarboxamide and N- (4-chlorophenyl) -1,4-dihydro-2,6-
Dimethyl-4-oxo-1- (phenylmethyl) -3-
Although four compounds of pyridinecarboxamide have been reported [see Pharmaceutical Journal, Vol. 101, page 40 (1981)], this reference relates to the reactivity of ketene derivatives, and these compounds are used in any field. There is no mention of Ruka. Canadian Patent No. 1,115,278 [and J.
B. Pierce et al., J. Med. Chem. 25, 131 (1982)],
A description about a 4-pyridone compound having an anti-inflammatory action is found, and 1,4-dihydro-2,6-dimethyl-4-oxo-N, 1-diphenyl-3-pyridinecarboxamides,
N, 1-dibutyl-1,4-dihydro-2,6-dimethyl-4-
Oxo-3-pyridinecarboxamide, N, 1-didodecyl-1,4-dihydro-2,6-dimethyl-4-oxo-3-
Pyridinecarboxamide and N- (4-chlorophenyl) -1-ethyl-1,4-dihydro-2,6, -dimethyl-
4-oxo-3-pyridinecarboxamide and the like are disclosed.

Further, JP-A-54-24,892, JP-A-51-43,783 and JP-A-51-48,686 disclose that 1,4-dihydro-4-oxo-3-pyridinecarboxamide is used as a medicine. Disclosed are cephalosporins having a partial structure.

On the other hand, as a compound showing activity as a plant growth regulator, particularly a chemical mating agent, 1,4-dihydro-4-oxo-3-
Although derivatives of pyridinecarboxylic acid are known,
52-144,676, JP-A-57-114,573), 1,4-dihydro-4-oxo-3-, such as compound (I).
A plant growth inhibitor containing a pyridinecarboxamide compound as an active ingredient has not been known. The present invention provides a group of novel compounds belonging to 1,4-dihydro-4-oxo-3-pyridinecarboxamide compounds and a plant growth inhibitor containing at least one of these compounds as an active ingredient. .

(Object and Structure) The present invention provides a compound represented by the following formula (I) and an addition salt thereof.

Formula (I): [In the formula, R is a hydrogen atom or-(CH ₂ ) n-R ₁ (n is 1 to
3 is an integer, R ₁ is a hydrogen atom, a C _{3 to} C ₁₁ alkyl group, a heterocyclic group on page 5 or 6, or a phenyl group which may be substituted with 1 to 2 halogen atoms and lower alkyl groups) ; R ₂
And R ′ ₁ are the same, and a C _{2 to} C ₁₁ alkyl group; R ₃ , R ₄ and R ₅ are the same or different and each is a hydrogen atom or a lower alkyl group; R ₆ is a hydrogen atom, respectively. means. Further, according to the present invention, there is provided a plant growth inhibitor containing, as an active ingredient, at least one of the compound represented by the above formula (I) and its addition salt.

In the present invention, the term “lower” used for a lower alkyl group means a group containing a C _{1 to} C ₅ carbon atom. Specific examples include lower alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl and isopentyl.

The halogen atom includes chlorine, bromine, iodine or fluorine atom.

The 5- or 6-membered heterocyclic group includes a nitrogen atom, an oxygen atom,
Included are 5 or 6 membered heterocyclic groups containing 1 to 3 heteroatoms selected from sulfur atoms. Examples thereof include 5-membered ring groups such as furyl, tetrahydrofuryl, thiconyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl and pyrazolyl: 6-membered ring groups such as pyridyl, pyrimidinyl, pyrazinyl and pyridazinyl.
These groups are alkyl groups such as methyl or utilyl,
It may be substituted with a halogen atom or a phenyl group. When substituted with a phenyl group, it may combine with two carbon atoms in the ring to form a fused ring. Examples of the case where a condensed ring is formed include benzothiazolyl, benzofuryl, quinazolinyl, quinoxalinyl groups and the like.

When the compound of formula (I) of the present invention shows basicity, it is an addition salt with an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, paratoluenesulfonic acid, trifluoroacetic acid, or a carboxyl group in the molecule. May form an addition salt with an inorganic base. Such addition salts are also included in the scope of the present invention.

The compound of formula (I) of the present invention can be prepared, for example, by the following method.

[In the formulas (II) and (III), R, R ₂ , R ′ ₂ , R ₃ , R ₄ , R ₅ and R ₆ are the same as the definition of the formula (I)] 4-pyrone compound (I
I), that is, 4-oxo-N-phenyl-4H-pyran-3-carboxad derivative and ammonia or amine represented by the formula (III) or a salt thereof, in a suitable solvent (for example, ethanol, water, toluene, ethyl ether, Methylene chloride, chloroform, etc.) at room temperature to 60 ° C. The amount of ammonia or amine used is equimolar or more to the 4-pyrone compound, and if necessary, a large excess amount is used. In addition, a base such as sodium carbonate or sodium hydroxide may be added to accelerate this reaction.

In the plant growth inhibitor of the present invention, the active ingredient compound represented by the above formula (I) or its addition salt may be used as it is, but generally, it is a solid carrier, liquid carrier or surfactant depending on the purpose of use. , Mixed with other pharmaceutical auxiliaries,
Formulated in wettable powders, granules, emulsions, etc.

These formulations contain 10-80% wettable powder as the active ingredient.
%, 1 to 10% for granules, and 10 to 50% for emulsions (all represent% by weight).

Solid carriers used in the formulation include kaolin, bentonite, clays, talc, diatomite, sieglite, zeolite, pyrophyllite, synthetic hydrous silicon oxide, fine powder or granules of calcium carbonate, etc. The aromatic hydrocarbons such as xylene and methylnaphthalene, ethanol, isopropanol, ethylene glycol, alcohols such as methyl cellosolve, acetone, isophorone, ketones such as cyclohexanone, soybean oil, vegetable oil such as cottonseed oil, dimethylformamide, There are dimethyl sulfoxide, acetonitrile, water and the like.

Surfactants used for emulsification, dispersion, wet extension, etc. include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxy There are nonionic surfactants such as ethylene polyoxypropylene block polymer, anionic surfactants such as alkyl sulfate ester salts, alkyl sulfonates, alkylaryl sulfonates, polyoxyethylene alkyl sulfate ester salts and the like.

Pharmaceutical auxiliary agents include lignin sulfonate, alginate, polyacrylates, polyvinyl alcohol, plant gums, carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC) and the like.

The wettable powder and emulsion prepared as described above can usually be diluted with water, and the granules can be sprayed on the soil or foliage and applied.

The plant growth inhibitor of the present invention is a nematicide, a fungicide,
It can also be used as a mixture with fertilizers or soil conditioners.

When the plant growth inhibitor of the present invention is used in either soil treatment or foliage treatment, the application rate can be varied within a wide range, but usually 1 g to 200 g of the active ingredient per are.
It is preferably 5 g to 100 g, and the application concentration is 1% to 80% for wettable powders and water diluents for emulsions. The application amount and application concentration can be increased or decreased depending on the type of preparation, application place, method, time, crop, degree of weed damage, weather conditions, etc. without regard to the above range.

The present invention will be described below with reference to examples. In addition, the inhibitory effect of the compounds of this invention on plant growth is shown in Reference Examples.
In addition to the compounds shown in the examples, the following compounds may be mentioned as specific names of the compounds of interest included in the present invention.

2,6-Diethyl-1,4-dihydro-4-oxo-N-phenyl-1- (2-pyridylmethyl) -3-pyridinecarboxamide, 2,6-diethyl-1,4-dihydro-4-oxo- N-phenyl-1- (3-pyridylmethyl) -3-pyridinecarboxamide, 2,6-diethyl-1,4-dihydro-4-oxo-N-phenyl-1- (4-pyridylmethyl) -3-pyridine Carboxamide, 2,6-diethyl-1- (2-furylmethyl) -1,4-dihydro-4-oxo-N-phenyl-3-pyridinecarboxamide, 1-cyclohexylmethyl-2,6-diethyl-1,4 -Dihydro-4-oxo-N-phenyl-3-pyridinecarboxamide, 2,6-diethyl-1,4-dihydro-N- (2-methylphenyl) -4-oxo-1-phenylmethyl-3-pyridinecarboxamide , -(2-chlorophenyl) -2,6-diethyl-1,4-dihydro-4-oxo-1-phenylmethyl-3-pyridinecarboxamide, 2,6-diethyl-N- (2-ethylphenyl) -1 , 4-Dihydro-4-oxo-1- (3-phenylpropyl)-
3-pyridinecarboxamide, 2,6-diethyl-1,4-dihydro-N- (2,3-dimethylphenyl) -4-oxo-1- (2-phenylethyl)
-3-Pyridinecarboxamide, 2,6-diethyl-1-hexyl-1,4-dihydro-N-
(2,6-Dimethylphenyl) -4-oxo-3-pyridinecarboxamide, 1-butyl-2,6-diethyl-N- (2,6-diethylphenyl) -1,4-dihydro-4-oxo-3 -Pyridinecarboxamide, 2,6-diethyl-N- (2-ethyl-6-methylphenyl) -1,4-dihydro-4-oxo-1-pentyl-3
-Pyridinecarboxamide, 1,4-dihydro-4-oxo-N-phenyl-2,6-dipropyl-1- (3-pyridylmethyl) -3-pyridinecarboxamide, 1,4-dihydro-4-oxo-N- Phenyl-2,6-dipropyl-1- (4-pyridylmethyl) -3-pyridinecarboxamide, 1- (2-furylmethyl) -1,4-dihydro-4-oxo-N-phenyl-2,6-dipropyl -3-Pyridinecarboxamide, 1,4-dihydro-N- (2-methylphenyl) -4-oxo-1-phenylmethyl-2,6-dipropyl-3-pyridinecarboxamide, 1- (4-chlorophenylmethyl) -1,4-dihydro-
N- (2-methylphenyl) -4-oxo-2,6-dipropyl-3-pyridinecarboxamide, 5-bromo-1-butyl-2,6-diethyl-N- (2,6-
Diethylphenyl) -1,4-dihydro-4-oxo-3
-Pyridinecarboxamide, 2,6-diethyl-N- (2,6-diethylphenyl) -1,4
-Dihydro-5-methyl-4-oxo-1- (2-phenylethyl) -3-pyridinecarboxamide, 2,6-dibutyl-1,4-dihydro-4-oxo-N-phenyl-1-phenylmethyl- 3-pyridinecarboxamide, 2,6-dibutyl-1,4-dihydro-1- (4-methylphenylmethyl) -4-oxo-N-phenyl-3-pyridinecarboxamide, 2,6-dibutyl-1- (4 -Chlorophenylmethyl)-
1,4-dihydro-N- (2-methylphenyl) -4-oxo-3-pyridinecarboxamide, and 1,4-dihydro-4-oxo-2,6-dipentyl-
N-phenyl-1-phenylmethyl-3-pyridinecarboxamide.

(Example) Production Example 1-Butyl-1,4-dihydro-4-oxo-N-phenyl-2,6-dipropyl-3-pyridinecarboxamide 4-oxo-N-phenyl-2,6-dipropyl-4H- To a mixture of 1 g (3.34 mmol) of pyran-3-carboxamide, 0.37 g (5.01 mmol) of butylamine and 5 ml of toluene was added 1 ml of 1N sodium hydroxide methanol solution, and the mixture was stirred at room temperature for one day. About 10 ml of water and about 10 ml of ethyl acetate in the reaction mixture
In addition, it was shaken well in the separating funnel. The organic layer was washed with saturated brine, dried and concentrated by a conventional method, and crystallized from toluene-cyclohexane to give the title compound (737 mg).
Got Melting point 133.5-136.5 ° C Tables 1 and 2 listed below summarize the physical properties and the like of the compounds according to the present invention.

The "performance evaluation" in Table 2 was performed under the following conditions.

Talc (50 parts by weight), Bentonite (25 parts by weight) Solpol-9047 (2 parts by Toho Chemical), Solpol-50
39 (the same as above, 3 parts by weight) were mixed to prepare a carrier.
50 parts by weight of the test compound and 200 parts by weight of the carrier were mixed to prepare a 20% wettable powder. This wettable powder was dispersed in pure water to obtain a wettable powder dispersion having a predetermined concentration.

Separately, prepare a Petri dish that germinates rice, rice, and radish seeds for 20 days.
Seedlings were cultivated for 7 days in a constant temperature cabinet with illumination to observe the degree of growth.

The method of displaying the results is as follows: 1 = no effect, 2 = 25% growth suppression, 3 =
50% growth inhibition, 4 = 75% growth inhibition, 5 = complete death.

Claims (7)

[Claims] 1. Formula (I): [In the formula, R is a hydrogen atom or-(CH ₂ ) n-R ₁ (n is 1 to
An integer of 3, R ₁ is a hydrogen atom, a C ₃ -C ₁₁ alkyl group, a 5- or 6-membered heterocyclic group, or a phenyl group which may be substituted with 1 to 2 halogen atoms and lower alkyl groups; R ₂ and R ′ ₂ are both the same and are a C _{2 to} C ₁₁ alkyl group;
R ₃ , R ₄ and R ₅ are the same or different and each is a hydrogen atom or a lower alkyl group; R ₆ is a hydrogen atom. ] The pyridine-3-carboxamide compound represented by these or its addition salt. 2. A compound of formula (I) Is phenyl, 2-methylphenyl, 2-ethylphenyl, 2,3-dimethylphenyl, 2,6-dimethylphenyl,
The compound according to claim 1, which is a 2,6-dimethylphenyl or 2-ethyl-6-methylphenyl group. 3. The compound according to claim 1, wherein R ₂ and R ′ _{2 in the} formula (I) are C ₂ -C ₅ alkyl groups. 4. The compound according to any one of claims 1 to 3, wherein R _{6 in} formula (I) is a hydrogen atom. 5. R in formula (I) is C ₄ -C ₆ alkyl, phenylmethyl, substituted phenylmethyl, 2-phenylethyl,
The compound according to any one of claims 1 to 4, which is a substituted 2-phenylethyl or 3-phenylpropyl group. 6. The compound according to any one of claims 1 to 4, wherein R in the formula (I) is a 2-, 3- or 4-pyridylmethyl or 2-furylmethyl group. 7. Formula (I): [In the formula, R is a hydrogen atom or-(CH ₂ ) n-R ₁ (n is 1 to
An integer of 3, R ₁ is a hydrogen atom, a C _{3 to} C ₁₁ alkyl group, a 5 or 6-membered heterocyclic group, or a phenyl group which may be substituted with 1 to 2 halogen atoms and lower alkyl groups) ; R ₂
And R ′ ₂ are the same, and C _{2 to} C ₁₁ alkyl groups: R ₃ , R ₄ and R ₅ are the same or different and each is a hydrogen atom or a lower alkyl group; R ₆ is a hydrogen atom, respectively. means. ] The plant growth inhibitor which contains at least 1 sort (s) of the pyridine-3-carboxamide compound or its addition salt represented by these as an active ingredient.