JPH0730026B2 - Pyridine-3-carboxylic acid phenyl ester derivative and plant growth inhibitor - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel compound belonging to 1,4-dihydro-4-oxo-3-pyricincarboxylic acid phenyl ester and a plant growth inhibitor containing the same. Is.

PRIOR ART So far 1,4-dihydro-4-oxo-3-pyridinecarboxylic acid esters can be found in the literature. For example, a 1,4-dihydro-4-oxo-3-pyridinecarboxylic acid derivative is known as a compound having activity as a plant growth regulator, particularly as a chemical mating agent (Japanese Patent Laid-Open No. 52-1446).
76 and 57-114573). For pharmaceutical use, JP-A-60-89472 and JP-A-56-79668 describe 1,4-dihydro-4-oxo-3-pyridinecarboxylic acid derivatives having an antibacterial action. Other 1,4-dihydro-4
A compound having an -oxo-3-pyridinecarbonyl group as a partial structure of an antibiotic such as cephalosporin is known, and 1,4-dihydro-4-oxo-
3-Pyridinecarboxylic acid derivatives are described. For example, JP-A-54-24892 and JP-A-54-30197 may be mentioned. However, the 1,4-dihydro-4-oxo-3-pyridinecarboxylic acid phenyl ester compound represented by the compound (I) has not been known at all.

The present invention provides a group of novel compounds belonging to a 1,4-dihydro-4-oxo-3-pyridinecarboxylic acid phenyl ester compound and a plant growth inhibitor containing at least one of these compounds as an active ingredient. .

(Object and Structure) According to the present invention, a compound represented by the following formula (I) and an addition salt thereof are provided.

Wherein, R represents a hydrogen atom; an optionally substituted phenyl group which may be substituted or _{- (CH 2) n-R} 1 (n is an integer of 1 to 3, R ₁ is a hydrogen atom, a hydroxy group, a lower alkoxy group, a mercapto Group, lower alkylthio group, amino group, di-lower alkylamino group; C _{3 to} C ₁₁ alkyl group, lower alkenyl group, lower alkynyl group, cycloalkyl group, 5- or 6-membered heterocyclic group, or halogen atom, An aryl group which may be substituted with 1 to 2 lower alkyl and lower alkoxy groups); R ₂ and R ₉ are the same or different and are a C _{1 to} C ₁₁ alkyl group, a lower alkenyl group, a lower alkynyl group, cycloalkyl A group, a lower alkoxyalkyl group, a lower alkylthioalkyl group, a phenyl group which may be optionally substituted, and a nucleus which may be substituted with 1 to 2 halogen atoms, lower alkyl and lower alkoxy groups. Good aralkyl group, halogenated alkyl group or 5- or 6-membered heterocyclic group; R ₃ , R ₄ , R ₅ ,
R ₆ and R ₇ are the same or different and each is a hydrogen atom, a halogen atom,
Lower alkyl group, hydroxy group, halogenated lower alkyl group, lower alkoxy group, aryloxy group, carboxy group, lower alkoxycarbonyl group, cyano group or nitro group; R ₈ means hydrogen atom, halogen atom, or lower alkyl group To do.

The term “lower” used in the present invention for a lower alkyl group, a lower alkoxy group and the like means a group containing a C _{1 to} C ₅ carbon atom. Specifically, methyl, ethyl, propyl,
Lower alkyl groups such as isopropyl, butyl, isobutyl, pentyl, isopentyl; methoxy, ethoxy,
Lower alkoxy groups such as propoxy, isopropoxy, butoxy; lower alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl; lower alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, pentylthio. Etc.

Further, the lower alkenyl group and the lower alkynyl group include
Vinyl, allyl, isopropenyl, 2-butenyl, 1,3
-Butadienyl, 2-pentenyl, 1,4-pentadienyl, 1,6-heptadienyl, 1-hexenyl, ethynyl, 2-propynyl and the like.

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

Halogenated alkyl groups include trifluoromethyl, chloromethyl groups and the like.

Lower alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl groups and the like.

Lower alkylthioalkyl groups include methylthiomethyl,
It includes ethylthiomethyl, propylthiomethyl, butylthiomethyl groups and the like.

Halogen atoms include chlorine, bromine, iodine or fluorine atoms.

Aralkyl groups include benzyl, 3-phenylpropyl,
A 4-phenylbutyl group and the like are included.

The aryloxy group includes a phenyloxy group and a naphthyloxy group.

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. Frills, for example
5-membered ring groups such as tetrahydrofuryl, thienyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, and pyrazolyl; and 6-membered ring groups such as pyridyl, pyrimidinyl, 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 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.

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

The plant growth inhibitory action of the compound of the present invention is useful as a herbicide for paddy fields, uplands, orchards, meadows, lawns, forests or non-agricultural lands. Therefore, the present invention also provides a plant growth inhibitor containing, as an active ingredient, at least one of the compound of formula (I) and its addition salt.

When the compound of the present invention is used as the above herbicide,
Although it may be used as it is, it is generally mixed with a solid carrier, a fluid carrier, a surfactant, and other auxiliary agents for formulation to prepare a wettable powder, granules, emulsion and the like.

In these formulations, the compound of the present invention is used as a wettable powder at 10 to
It is desirable to contain 80%, 2 to 20% in granules, and 10 to 50% in emulsions (all represent weight percent).

Solid carriers used in the formulation include kaolin, bentonite, clays, talc, diatomaceous earth, zealite, zeolite, pyrophyllite, synthetic silicon oxides, calcium carbonate, and other fine powders or granules. Is
Aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as ethanol, isopropanol, ethylene glycol and methyl cellosolve, ketones such as acetone, isophorone and cyclohexanone, vegetable oils such as soybean oil and cottonseed oil, dimethylformamide, dimethylsulfoxide and acetonitrile. , Water, etc.

Surfactants used for dispersion, emulsification, etc. include polyoxyethylene alkyl ether, polyoxyethylne alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene polyether. Examples include nonionic surfactants such as oxypropylene block polymers, anionic surfactants such as alkyl sulfate ester salts, alkyl sulfonates, alkylaryl sulfonates, and polyoxyethylene alkyl sulfate ester salts.

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

In addition, the compound of the present invention, if necessary, other insecticide,
It can also be used as a mixture with acaricide, nematicide, fungicide, herbicide, plant growth regulator, fertilizer or soil conditioner.

The compounds of formula (I) of this invention can be made by the following methods.

(Method A) [Wherein R, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ in the formula (II) are the same as the definition of the formula (I)] Acid phenyl ester derivative (II) and 4H-1,3-dioxin-4-one derivative (X) without solvent or in a suitable solvent (eg toluene, xylene, mesitylene, etc.) under heating (eg 100-). 170 ° C.). In carrying out this method, the 3-aminoacrylic acid phenyl ester derivative (II) does not need to use an isolated substance, and the formula (III): RNH ₂ formula (III) and formula (IV): [In the formulas (III) and (IV), R, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are the same as those defined in the formula (I)] Good. In fact,
It is more convenient to use this reaction mixture.

(Method B) [In the formulas (V) and (III), R, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are the same as the definition of the formula (I)] 4-pyrone compound (V) corresponding to formula (I), that is, 4-oxo-N-phenyl-4H-pyran-3-carboxylic acid phenyl ester derivative and formula (III)
Reaction with ammonia or amine represented by or in a suitable solvent (eg, ethanol, water, etc.), if necessary, in the presence of a base such as sodium hydroxide, sodium carbonate, etc., at room temperature to 60 ° C. It is what makes me. 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. When the amine is obtained as a salt, it is necessary to provide the amine in a free form with a neutralizing amount or more of an organic or inorganic base.

(Method C) [R, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ in formulas (VI) and (VII) are the same as the definition of formula (I)] Carboxylic acids corresponding to (I), ie 1,4
-A dihydro-4-oxo-3-pyridinecarboxylic acid derivative (VI) and a phenol derivative (VII) are reacted in the presence of a dehydration condensation agent. When this method is actually carried out, for example, 1-substitution-described in JP-A-52-57102 is used.
A method of using a 2-halopyridinium salt and a tertiary amine as a dehydration condensation agent can be advantageously used.

(Method C ') [In the formulas (VIII) and (VII), R, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are the same as those in the formula (I), and X is a halogen atom. This method involves reacting (VI) with an acid halide (VIII) easily obtained from a halogenating agent such as thionyl chloride and a phenol derivative (VII) in the presence of a base.

(Method D) A 1,4-dihydro-formula represented by the formula (IX) [wherein R, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₉ are the same as the definition of the formula (I)] 4-
The oxo-3-pyridinecarboxylic acid phenyl ester derivative can be reacted with a halogenating agent to produce a compound of the formula (I) (wherein R ₈ in the formula (I) is a halogen atom). Particularly convenient is to use a halogenating agent such as N-chlorosuccinimide or N-bromosuccinimide in a solvent such as chlorinated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethane, The reaction is carried out in the presence or absence of a radical initiator. In addition, the compound represented by the formula (IX) is dissolved in the above-mentioned chlorinated hydrocarbon, and chlorine or bromine is blown into the reaction mixture by a suitable method in a gaseous state or in a liquid state to carry out the reaction. You can also

As for the method of halogenating the compound of the formula (IX) as described above, it is recognized that a halogen atom is additionally introduced into the phenyl group of the ester.

(Method E) In this method, a compound represented by the formula (I) [wherein R ₈ in the formula (I) is a halogen atom] is treated with an alkali metal halide to form a compound represented by the formula (I). _The halogen atom represented by ₈ is exchanged. This method is useful for the synthesis of compounds in which R ₈ in formula (I) is fluorine, which is difficult to directly introduce.

The present invention will be described below with reference to examples. In addition to the compounds shown in the examples, the following are specific names of the compounds of interest included in the present invention.

2,6-Dimethylphenyl 2-butyl-1,4 dihydro-1,6
-Dimethyl-4-oxo-3-pyridinecarboxylate 2,6-dimethylphenyl 5-bromo-2-butyl-1,4-
Dihydro-1,6-dimethyl-4-oxo-3-pyridinecarboxylate 2,6-dimethylphenyl 5-bromo-1-butyl-1,4 dihydro-1,6-dimethyl-4-oxo-3-pyridinecarboxy Rate 2,6-dimethylphenyl 2-butyl-1,4 dihydro-1,5,
6-Trimethyl-4-oxo-3-pyridinecarboxylate Phenyl 2-butyl-1,4 dihydro-6-methyl-4-
Oxo-1-phenylmethyl-3-pyridinecarboxylate Phenyl 1,4 dihydro-2,6-dimethyl-1- (4-methylphenylmethyl) -4-oxo-3-pyridinecarboxylate 2,6-dimethylphenyl 1 , 4 dihydro-1,6-dimethyl-
4-oxo-2-propyl-3-pyridinecarboxylate 2,6-dimethylphenyl 1,4-dihydro-1,5,6-trimethyl-4-oxo-2-propyl-3-pyridinecarboxylate 2,6- Dimethylphenyl 5-bromo-1,4-dihydro-1,
6-Dimethyl-4-oxo-2-propyl-3-pyridinecarboxylate 4-Bromo-2,6-dimethylphenyl 2-butyl-1,4-
Dihydro-1,6-dimethyl-4-oxo-3-pyridinecarboxylate 4-bromo-2,6-dimethylphenyl 5-bromo-2-
Butyl-1,4-dihydro-1,6-dimethyl-4-oxo-
3-Pyridinecarboxylate 4-bromo-2,6-dimethylphenyl 5-bromo-1-
Butyl-1,4-dihydro-2,6-dimethyl-4-oxo-
3-Pyridinecarboxylate 4-Bromo-2,6-dimethylphenyl 2-butyl-1,4-
Dihydro-1,5,6-trimethyl-4-oxo-3-pyridinecarboxylate 4-bromo-2,6-dimethylphenyl 1,4-dihydro-
1,6-Dimethyl-4-oxo-2-propyl-3-pyridinecarboxylate 4-bromo-2,6-dimethylphenyl 1,4-dihydro-
1,5,6-trimethyl-4-oxo-2-propyl-3-
Pyridinecarboxylate 4-bromo-2,6-dimethylphenyl 5-bromo-1,4-
Dihydro-1,6-dimethyl-4-oxo-2-propyl-3-pyridinecarboxylate 2,6-diethylphenyl 2-butyl-1,4-dihydro-1,
6-Dimethyl-4-oxo-3-pyridinecarboxylate 2,6-diethylphenyl 5-bromo-2-butim-1,4-
Dihydro-1,6-dimethyl-4-oxo-3-pyridinecarboxylate 2,6-diethylphenyl 5-bromo-1-butyl-1,4-
Dihydro-2,6-dimethyl-4-oxo-3-pyridinecarboxylate 2,6-diethylphenyl 2-butyl-1,4-dihydro-1,
5,6-Trimethyl-4-oxo-3-pyridinecarboxylate 2,6-diethylphenyl 1,4-dihydro-1,6-dimethyl-4-oxo-2-propyl-3-pyridinecarboxylate 2,6- Diethylphenyl 1,4-dihydro-1,5,6-trimethyl-4-oxo-2-propyl-3-pyridinecarboxylate 2,6-diethylphenyl 5-bromo-1,4-dihydro-1,
6-dimethyl-4-oxo-2-propyl-3-pyridinecarboxylate 4-bromo-2,6-diethylphenyl 2-butyl-1,4-
Dihydro-1,6-dimethyl-4-oxo-3-pyridinecarboxylate 4-bromo-2,6-diethylphenyl 5-bromo-2-
Butyl-1,4-dihydro-1,6-dimethyl-4-oxo-
3-Pyridinecarboxylate 4-bromo-2,6-diethylphenyl 5-bromo-1-
Butyl-1,4-dihydro-2,6-dimethyl-4-oxo-
3-Pyridinecarboxylate 4-bromo-2,6-diethylphenyl 2-butyl-1,4-
Dihydro-1,5,6-trimethyl-4-oxo-3-pyridinecarboxylate 4-bromo-2,6-diethylphenyl 1,4-dihydro-
1,6-Dimethyl-4-oxo-2-propyl-3-pyridinecarboxylate 4-bromo-2,6-diethylphenyl 1,4-dihydro-
1,5,6-trimethyl-4-oxo-2-propyl-3-
Pyridinecarboxylate 4-bromo-2,6-diethylphenyl 5-bromo-1,4-
Dihydro-1,6-dimethyl-4-oxo-2-propyl-3-pyridinecarboxylate Example 1 Phenyl 1,4-dihydro-2,6-dimethyl-4-oxo-1-phenyl-3-pyridinecarboxylate 1,4-Dihydro-2,6-dimethyl-4-oxo-1-phenyl-3-pyridinecarboxylic acid (1,44 g, 5.9 mmol) was dissolved in methylene chloride (10 ml), and thionyl chloride (0.1 ml) was added to the solution.
43 ml was added, and the mixture was stirred at room temperature for 5 hours. 60% in advance in this solution
A mixed solution of 10 ml of a tetrahydrofuran solution of sodium phenoxide prepared from 0.24 g (5.9 mmol) of NaH and 0.56 g (5.9 mmol) of phenol and 0.83 ml of triethylamine was added dropwise, and the mixture was further stirred at room temperature for 5 hours. The reaction mixture was concentrated under reduced pressure, the obtained residue was transferred to a separating funnel together with ethyl acetate and water, the organic layer was washed with aqueous sodium hydrogen carbonate and then with water, and the organic layer was dried over magnesium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was separated and purified by column chromatography to give the title compound (0.24 g).

Examples 2 to 10 Each compound was obtained according to the method shown in the column of “Production method” in Table 1.

Tables 1 to 3 summarize the physical properties, performance evaluations and the like of each compound produced by the above examples. The performance evaluation in Table 3 is as follows.

Talc (50 parts by weight), Bentonite (25 parts by weight) Solpol-9047 (Toho Chemical, 2 parts by weight), Solpol-5039
(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 liquid having a predetermined concentration. Separately, prepare a petri dish in which rice, novier, and Japanese radish seeds have been germinated, add the above-mentioned wettable powder dispersion, and raise the seedlings for 7 days in a constant temperature cabinet at 25 ° C to evaluate the degree of growth according to the following criteria. did.

Judgment Activity intensity 1 No effect 2 25% growth suppression 3 50% growth suppression 4 75% growth suppression 5 Complete death

Claims (9)

[Claims] 1. General formula (I): [In the formula, R is a hydrogen atom; an optionally substituted phenyl group or-(CH ₂ ) n-R ₁ (n is an integer of 1 to 3, R ₁ is a hydrogen atom, a hydroxy group, a lower alkoxy group, a mercapto group, a lower alkylthio group, an amino group, a di-lower alkylamino group; an alkyl group of C ₃ -C _11, a lower alkenyl group, lower alkynyl group, a cycloalkyl group, a 5- or 6-membered heterocyclic group or a halogen atom, , An aryl group which may be substituted with 1 to 2 lower alkyl and lower alkoxy groups); R ₂ and R ₉ are the same or different and are a C _{1 to} C ₁₁ alkyl group, a lower alkenyl group, a lower alkynyl group, cyclo An alkyl group, a lower alkoxyalkyl group, a lower alkylthioalkyl group, an optionally substituted phenyl group, and a nucleus substituted with 1 to 2 halogen atoms, lower alkyl and lower alkoxy groups Aralkyl group, halogenated alkyl group or 5- or 6-membered heterocyclic group; R ₃ , R ₄ , R ₅ ,
R ₆ and R ₇ are the same or different and each is a hydrogen atom, a halogen atom,
Lower alkyl group, hydroxy group, halogenated lower alkyl group, lower alkoxy group, aryloxy group, carboxy group, lower alkoxycarbonyl group, cyano group or nitro group; R ₈ is hydrogen atom, halogen atom, or lower alkyl group] The compound or addition salt represented. 2. The compound according to claim 1, wherein R in the formula (I) is a C ₁ -C ₄ alkyl group. 3. The compound according to claim 1, wherein R in the formula (I) is a phenylmethyl or 4-methylphenylmethyl group. 4. The compound according to any one of claims 1 to 3, wherein R ₂ and R _{9 in} the formula (I) are C _{1 to} C ₄ alkyl groups. 5. A compound according to any one of claims 1 to 4, wherein R _{8 in} formula (I) is a halogen atom. 6. A compound according to any one of claims 1 to 4, wherein R _{8 in} formula (I) is a methyl or ethyl group. 7. A compound of formula (I) Is phenyl, 2,6-dimethylphenyl, 4-bromo-2,6
-Dimethylphenyl, 2,6-diethylphenyl, 4-bromo-2,6-diethylphenyl, 2-chlorophenyl,
A compound according to claims 1 to 6 which is 2-methylphenyl. 8. Phenyl 1,4-dihydro-2,6-dimethyl-4-oxo-1-phenylmethyl-3-pyridinecarboxylate, 2,6-dimethylphenyl 1-butyl-1,4
-Dihydro-2,6-dimethyl-4-oxo-3-pyridinecarboxylate, 2,6-dimethylphenyl 1,4-dihydro-2,6-dimethyl-4-oxo-1-phenylmethyl-3-pyridinecarboxy The compound according to claim 1, which is a rate or an addition salt thereof. 9. General formula (I): [In the formula, R is a hydrogen atom; an optionally substituted phenyl group or-(CH ₂ ) n-R ₁ (n is an integer of 1 to 3, R ₁ is a hydrogen atom, a hydroxy group, a lower alkoxy group, a mercapto group, a lower alkylthio group, an amino group, a di-lower alkylamino group; an alkyl group of C ₃ -C _11, a lower alkenyl group, lower alkynyl group, a cycloalkyl group, a 5- or 6-membered heterocyclic group or a halogen atom, , An aryl group which may be substituted with 1 to 2 lower alkyl and lower alkoxy groups); R ₂ and R ₉ are the same or different and are a C _{1 to} C ₁₁ alkyl group, a lower alkenyl group, a lower alkynyl group, cyclo An alkyl group, a lower alkoxyalkyl group, a lower alkylthioalkyl group, an optionally substituted phenyl group, and a nucleus substituted with 1 to 2 halogen atoms, lower alkyl and lower alkoxy groups Aralkyl group, halogenated alkyl group or 5- or 6-membered heterocyclic group; R ₃ , R ₄ , R ₅ ,
R ₆ and R ₇ are the same or different and each is a hydrogen atom, a halogen atom,
Lower alkyl group, hydroxy group, halogenated lower alkyl group, lower alkoxy group, aryloxy group, carboxy group, lower alkoxycarbonyl group, cyano group or nitro group; R ₈ is hydrogen atom, halogen atom, or lower alkyl group] At least one of the represented compounds or addition salts
A plant growth inhibitor comprising seeds as an active ingredient.