JPH0749418B2 - 1,4-Dihydro-4-thioxo-3-pyridinecarboxamide compound and plant growth inhibitor - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel compound belonging to a 1,4-dihydro-4-thioxo-3-pyridinecarboxamide compound. The compound of this invention has a plant growth inhibitory action.

(Prior Art) Conventionally, compounds belonging to 4 (1H) -pyridinethione are known. Japanese Unexamined Patent Publication (Kokai) No. 51-51520 discloses 3-phenyl-4.
The (1H) pyridinethione derivative is described as a post-emergence treatment herbicide. These compounds do not describe a compound having an N-allylcarbamoyl group at the 3-position as represented by the general formula (I).

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

[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, Mercapto group, lower alkylthio group, amino group, di-lower alkylamino group, C ₃ -C ₁₁ alkyl group, lower alkenyl group, lower alkynyl group, cycloalkyl group, 5- or 6-membered heterocyclic group, or halogen atom , A phenyl group which may be substituted with 1 or 2 lower alkyl and lower alkoxy groups); R ₂ and R ₉ are the same or different and each is a hydrogen atom, a C ₁ -C ₁₁ alkyl group, a lower alkenyl group, a lower group. Alkynyl group, cycloalkyl group, lower alkoxyalkyl group, optionally substituted phenyl group, aralkyl group whose nucleus may be substituted with 1 to 2 halogen atoms, lower alkyl and lower alkoxy groups, halogen Or an alkyl group, a 5- or 6-membered heterocyclic group; R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are the same or different and are a hydrogen atom, a halogen atom, a cyano group, a nitro group or an amino group. , A lower alkyl group, a halogenated lower alkyl group,
Hydroxy group, lower alkoxy group, aryloxy group,
A carboxy group or a lower alkoxycarbonyl group; R ₈ represents a hydrogen atom, a halogen atom, a lower alkyl group, or an optionally substituted aralkyl group; or R ₈ and R ₉ together represent-
(CH ₂ ) _m- ( _m is 3 or 4) is meant. In the present invention, the term “lower” used in a lower alkyl group, a lower alkoxy group and the like means a group containing a C _{1 to} C ₅ carbon atom. Specifically, lower alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl; lower alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy; methoxycarbonyl, ethoxycarbonyl, Lower alkoxycarbonyl groups such as propoxycarbonyl, butoxycarbonyl; methylthio, ethylthio, propylthio, isopropylthio, butylthio,
Lower alkylthio groups such as pentylthio are mentioned.

Further, the lower alkenyl group and lower alkynyl group include vinyl, allyl, isopropenyl, 2-butenyl and 1,3-
It includes butadienyl, 2-pentenyl, 1,4-pentadienyl, 1,6-heptadienyl, 1-hexenyl, ethynyl, 2-provinyl 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, ethoxyethyl, propoxymethyl, butoxymethyl groups and the like.

The halogen atom includes chlorine, bromine, iodine or fluorine atom, and the aralkyl group includes benzyl, 3-phenylpropyl, 4-phenylbutyl group and the like.

The 5- or 6-membered heterocyclic group includes a nitrogen atom, an oxygen atom,
The heterocyclic group is contained in a 5- or 6-membered member containing 1 to 3 heteroatoms selected from sulfur atoms. For example,
Furyl, tetrahydrofuryl, thienyl, thiazolyl,
5-membered ring groups such as isothiazolyl, oxazolyl, isoxazolyl, and pyrazolyl; pyridyl, pyrimidinyl,
Examples thereof include 6-membered rings such as pyrazinyl and pyridazinyl.
These groups are alkyl groups such as methyl or ethyl,
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 is basic, hydrochloric acid,
It may form an addition salt with an acid such as sulfuric acid, phosphoric acid, methanesulfonic acid, paratoluenesulfonic acid, trifluoroacetic acid, or an inorganic base when a carboxyl group is present in the molecule. Such addition salts are also included in the scope of the present invention.

The plant growth-regulating action of the compound of the present invention includes paddy fields, upland fields,
It has useful properties as a herbicide for fruit gardens, meadows, lawns, forests or non-agricultural lands. When the compound of the present invention is used as the above herbicide, it may be used as it is,
Generally, it is mixed with a solid carrier, a liquid carrier, a surfactant, and other auxiliaries for formulation to prepare wettable powders, granules, emulsions and the like. In these formulations, the compound of the present invention is 10 to 10 in a wettable powder.
It is preferable to contain 80%, 2 to 20% in granules, and 10 to 50% in emulsions (all represent% by weight). Solid carriers used in the formulation include kaolin, bentonite, clays, talc, diatomaceous earth, zealite, zeolite, pyrophyllite, synthetic silicon oxide, calcium oxide, and other fine powders or granules. Aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as ethanol, isopropanol, ethylene glycol and methyl cellosolve, ketones such as acetone, ilophorone and cyclohexanone, vegetable oils such as soybean oil and cottonseed oil, dimethylformamide and dimethyl. Examples include sulfoxide, acetonitrile, 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, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene polyoxy. There are nonionic surfactants such as propylene block polymers, and 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.

Further, the compound of the present invention can be used in combination with other insecticide die agents, nematicides, fungicides, herbicides, plant growth regulators, fertilizers or soil conditioners, if necessary.

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

(R represented in the formula _{(II), 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)) The compound represented by the general formula (II) is treated with phosphorus pentasulfide, 2,4-bis [4-methoxyphenyl] -1,3 in an inert solvent. It can be obtained by reacting with a sulfiding agent such as -dityl-2,4-diphosphetane-2,4-disulfide.

(In the formulas (IV) and (III), R, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R
₇ , R ₈ and R ₉ are the same as defined in formula (I)) This method corresponds to formula (I), i.e. N-phenyl-4-thioxo-4H-pyran-3-carboxamide compound (V) Ammonia or amine represented by formula (III) or a salt thereof is reacted in a suitable solvent (eg, ethanol, water, etc.) at room temperature to about 60 ° C. The amount of ammonia or amine used is equimolar or more to the 4-virone compound, and a large excess amount is used if necessary. 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.

(R, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ in the formulas (V) and (VI),
R ₇ , R ₈ and R ₉ are the same as defined in formula (I)) This method is for the carboxylic acid corresponding to formula (I), namely 1,4
-Dihydro-4-thioxo-3-pyridinecarboxylic acid derivative (VI) and aniline 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.

(R, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R in formulas (VII) and (VI)
₇ , R ₈ and R ₉ have the same meaning as defined in formula (I), and X means a halogen atom. ) This method provides an acid halide (VII) which is easily obtained from formula (VI) and a halogenating agent such as thionyl chloride.
And aniline derivative (VI) are reacted in the presence of a base.

(In the formula (XI), R, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₉ are
1,4-dihydro-4 represented by the same definition as formula (I))
- oxo-3-pyridinecarboxamide derivatives, is reacted with a halogenating agent formula (I) (where R ₈ is a halogen atom) it is possible to produce a compound of. Particularly convenient is to use a halogenating agent such as N-chlorosuccinimide or N-bromosuccinimide in a solvent such as dichloromethane, chloroform, carbon tetraoxide, trichloroethylene, tetrachloromethane and the like chlorinated carbon hydrogen. 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 on the amidobromine.

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

Next, the present invention will be described 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.

5-Bromo-N- (2,6-diethylphenyl) -1,4-dihydro-1,6-dimethyl-2-propyl-4-thioxo-3-pyridinecarboxamide.

5-Bromo-1-butyl-N- (2,6-diethylphenyl) -1,4-dihydro-2,6-dimethyl-4-thioxo-
3-Pyridinecarboxamide.

1- (4-chlorophenylmethyl) -1,4-dihydro-
2,6-Dimethyl-N- (2-methylphenyl) -4-thioxo-3-pyridinecarboxamide.

1,4-dihydro-6-methyl-N-phenyl-1-phenylmethyl-6-propyl-4-thioxo-3-pyridinecarboxamide.

2,6-diethyl-1,4-dihydro. -N-phenyl-1-
Phenylmethyl-4-thioxo-3-pyridinecarboxamide.

2-Butyl-1,4-dihydro-6-methyl-N, 1-diphenyl-4-thioxo-3-pyridinecarboxamide.

5-chloro-N- (2,6-diethylphenyl) -1,4-dihydro-1,6-dimethyl-4-thioxo-3-pyridinecarboxamide.

5-Bromo-N- (4-bromo-2,6-diethylphenyl) -1,4-dihydro-1,6-dimethyl-4-thioxo-
3-Pyridinecarboxamide.

Example 1. Synthesis of 2-butyl-1,4-dihydro-6-methyl-N, 1-diphenyl-4-thioxo-3-pyridinecarboxamide.

2-butyl-1,4-dihydro-6-methyl- as a raw material
N-phenyl-1-phenylmethyl-4-oxo-3-
Pyridinecarboxamide, 1.1g (2.96mmol) is used and Lawesson reagent 0.6g (1.6mmol) toluene 20ml
The mixture was refluxed for 2 hours. Toluene was distilled off under reduced pressure, and the obtained crystalline residue was recrystallized from a mixed solution of ethanol and ethyl acetate to obtain 0.83 g of the title compound.

Melting point: 161-164 ° C Example 2. Synthesis of 1,4-dihydro-2,6-dimethyl-N-phenyl-1-phenylmethyl-4-thioxo-3-pyridinecarboxamide.

The title compound was prepared in the same manner as in Example 1 except that 0.5 g of 1,4-dihydro-2,6-dimethyl-N-phenyl-1-phenylmethyl-4-oxo-3-pyridinecarboxamide was used as a starting material.
0.38 g was obtained.

Example 3. N- (2,6-diethylphenyl) -1,4-dihydro-1,6
-Synthesis of dimethyl-2-propyl-4-thioxo-3-pyridinecarboxamide.

In Example 1, 0.57 g of N- (2,6-diethylphenyl) -1,4-dihydro-1,6-dimethyl-2-propyl-4-oxo-3-pyridinecarboxamide was used as a starting material. 0.19 g of compound was obtained.

Next, 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 is as follows.

Talc (50 parts by weight), bentonite (25 parts by weight), Solpol-9047 (2 parts by Toho Chemical), Solpol-
A carrier in which 5039 (same as above, 3 parts by weight) was mixed was prepared. 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, a petri dish in which rice, Taenia serrata, and Japanese radish seeds were germinated was prepared, the above-mentioned wettable powder dispersion was added, and seedlings were grown for 7 days in a constant temperature cabinet at 25 ° C 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 (2)

[Claims] 1. A 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, Mercapto group, lower alkylthio group, amino group, di-lower alkylamino group, C ₃ -C ₁₁ alkyl group, lower alkenyl group, lower alkynyl group, cycloalkyl group, 5- or 6-membered heterocyclic group, or halogen atom , A phenyl group which may be substituted with 1 or 2 lower alkyl and lower alkoxy groups); R ₂ and R ₉ are the same or different and each is a hydrogen atom, a C ₁ -C ₁₁ alkyl group, a lower alkenyl group, a lower group. Alkynyl group, cycloalkyl group, lower alkoxyalkyl group, optionally substituted phenyl group, aralkyl group whose nucleus may be substituted with 1 to 2 halogen atoms, lower alkyl and lower alkoxy groups, halogen Or an alkyl group, a 5- or 6-membered heterocyclic group; R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are the same or different and are a hydrogen atom, a halogen atom, a cyano group, a nitro group or an amino group. , A lower alkyl group, a halogenated lower alkyl group,
Hydroxy group, lower alkoxy group, aryloxy group,
A carboxy group or a lower alkoxycarbonyl group; R ₈ represents a hydrogen atom, a halogen atom, a lower alkyl group, or an optionally substituted aralkyl group; or R ₈ and R ₉ together represent-
(CH ₂ ) _m- ( _m is 3 or 4) is meant. ] 1,4-dihydro-4-thioxo-3-
A pyridinecarboxamide compound or an addition salt thereof. 2. 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, Mercapto group, lower alkylthio group, amino group, di-lower alkylamino group, C ₃ -C ₁₁ alkyl group, lower alkenyl group, lower alkynyl group, cycloalkyl group, 5- or 6-membered heterocyclic group, or halogen atom , A phenyl group which may be substituted with 1 or 2 lower alkyl and lower alkoxy groups); R ₂ and R ₉ are the same or different and each is a hydrogen atom, a C ₁ -C ₁₁ alkyl group, a lower alkenyl group, a lower group. Alkynyl group, cycloalkyl group, lower alkoxyalkyl group, optionally substituted phenyl group, aralkyl group whose nucleus may be substituted with 1 to 2 halogen atoms, lower alkyl and lower alkoxy groups, halogen Or an alkyl group, a 5- or 6-membered heterocyclic group; R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are the same or different and are a hydrogen atom, a halogen atom, a cyano group, a nitro group or an amino group. , A lower alkyl group, a halogenated lower alkyl group,
Hydroxy group, lower alkoxy group, aryloxy group,
A carboxy group or a lower alkoxycarbonyl group; R ₈ represents a hydrogen atom, a halogen atom, a lower alkyl group, or an optionally substituted aralkyl group; or R ₈ and R ₉ together represent-
(CH ₂ ) _m- ( _m is 3 or 4) is meant. ] 1,4-dihydro-4-thioxo-3-
A plant growth inhibitor containing at least one pyridinecarboxamide compound or an addition salt thereof.