JPH0436271A - 2-alkoxycarbonyl-3-pyridinecarboxylic acid derivative, its production and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R<1> is H or lower alkyl; R<2> is lower alkyl; R<3> is OR<4> (R<4> is H or lower alkyl) or NHR<5> (R<5> is halogen or phenyl)] or a salt thereof. EXAMPLE:1-Butyl-2-ethoxycarbonyl-1,4-dihydro-6-methyl-4-oxy-3- pyridinecarboxylate ethyl ester. USE:A herbicide. PREPARATION:An oxaloacetic acid derivative shown by formula II (R<6> is lower alkyl) or formula II' is made to react with a 1,3-dioxin-4-one derivative shown by formula III (R<7> and R<8> are H, lower alkyl or phenyl) to give a compound shown by formula I wherein R<3> is alkoxy group. In using the compound shown by formula I as a herbicide, about 0.1-50g of the compound is used based on 1a.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel 2-alcoquinocarbonyl 3-birinonecarphonic acid derivative, a method for producing the same, and a herbicide containing the same as an active ingredient.

(Prior art) [74-Nohythro-4-oxo-3-pyrinonecarphonic acid derivatives are known in large numbers (for example, JP-A-62-2
No. 40664, etc.), and compounds having an alkoxysulfonyl group at the 2-position of the birinone ring, such as the compound of the present invention, have not been known so far.

(Structure of the Invention) This invention is based on the following formula (1) where R1 is a hydrogen atom, R7 is a lower alkyl group, R7 is a lower alkyl group, and R3'-OR'-XHR5 (
R' is a hydrogen atom or a lower alkyl group.R5 is a halogen atom, a lower alkyl group, or a lower alkokino group.
2-
Alcoquinocarnanyl-3-pyrinonecarphonic acid derivatives and salts thereof are provided.

In the definition of groups of compounds in this invention 'j:)R'.

The lower alkyl groups in R', R', R5, R', R', and RB may be the same or different, and mean straight-chain or branched alkyl groups having 1 to 6 carbon atoms. do. Specifically, lower alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, and hexyl groups. In addition, the lower alkoxy group in R5 means a linear or branched alkoxy group having 1 to 6 carbon atoms,
Examples include metquine, ethoxy, propoxy, isopropoxy, butoxy groups, and the like. Halogen atoms in the definition of compounds in this invention include chlorine, bromine, iodine or fluorine atoms.

Further, the compound of formula (I) of this invention can be prepared by a known method using an inorganic acid such as hydrochloric acid or phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, succinic acid,
Salts can be formed with organic acids such as oxalic acid and tartaric acid, and such salts are also within the scope of this invention.

Further, when R' in the compound of formula (1) is a hydrogen atom, it can take the structure of the following formula (■'') which is a tautomer.

Next, a method for producing the compound of this invention will be explained.

That is, first of all, as shown below, the oxaloacetic acid derivative represented by the formula (II) or (■') is combined with the formula (I[
Indicated by [)! , a 3-dioquinone-4one derivative to produce a compound represented by formula (I) (where R1 and R'' are the same as defined above; R3 is a lower alkoxy group).

(1) (鳳゛) (In both formulas, R11R1 is the same as the above definition: R3' is a lower alkoxy group: R6 is a lower alkyl group, R? and R are a hydrogen atom, a lower alkyl group, or a phenyl group) This reaction The compounds (II) and (■') used as raw materials are tautomers and can be obtained by reacting diester of oxaloacetic acid with ammonia or an amine. In the above reaction, the amount of the compound of formula (I) used is at least one equivalent, preferably 2 to 3 times the amount of the compound of formula (II) or (■'). The reaction temperature is 1
A range of 00 to 200°C is suitable. Also, the reaction time is 1
0 minutes to 2 hours is appropriate. As a solvent, toluene, kiln, mesitylene, chlorobenzene, etc. can be used.

Then, in the formula ([) obtained as shown below, R3
By hydrolyzing a compound in which R3 is a lower alkoxy group, a compound in formula (I) in which R3 is a hydroxy group can be obtained.

Appropriate. The amount of alkali used is preferably equivalent to the amount of the compound of formula (1). If the amount is too large, the ester group at the 2-position of the pyridine ring will be hydrolyzed. Moreover, the temperature of hydrolysis is preferably in the range of 0 to 100°C. Further, the reaction time is suitably 10 minutes to 10 hours, and water, alcohol, etc. are used as the solvent.

Next +: When a compound in which R3 is a hydroxy group in formula (I) is converted into an acid halide (V) with a halogenating agent such as thionyl chloride, and then treated with an aniline derivative (R') in the presence of a base. , in formula (1), R3 is -NH
A compound in which R' can be obtained.

(I) (However, P' is a lower alkoke group) (■) (However, R
3" is a hydroquine group) (R' and R" in both formulas are the same as defined above) The above hydrolysis is carried out with an acid such as hydrochloric acid or sulfuric acid or an alkali such as sodium hydroxide or potassium hydroxide, but the latter (1) (where P' is a hydroquine group) (1) (where R''- is a group -!IHR'') (in the formula a I
, R1 and R5 are the same as defined above; X is a halogen atom) Triethylamine, pyridine, etc. are suitable as the base used when reacting the above aniline derivative.

The reaction is carried out at 0-50°C for 1-12 hours.

Therefore, this invention relates to (summer) formula (II) or formula (II)
') : (In the formula, R7 and R11 are a hydrogen atom, a lower alkyl group or f2 is a phenyl group) By reacting a compound represented by the formula (1), , R3' is a lower alkoxy group), (2) If necessary, by hydrolyzing the compound of formula (1) obtained in step (1) above, formula (I) ( In the formula, R1 is a hydrogen atom or a lower alkyl group; R2 and R1 are a lower alkyl group). (3) If necessary, the compound of the above formula (1) obtained in step i2 (2) is reacted with a halogenating agent to convert it into an acid halide, and the obtained f-co The acid halide has the formula (if) R5N
A compound represented by H2 (in the formula, R5 is a phenyl group optionally substituted with 1 to 5 of a halogen atom, a lower alkyl group, or a lower alkokino group) is reacted in the presence of a base to form a compound of the formula (D [in the formula R1 and R1 are the same as defined above, R3-
formula (I) [in the formula R1 is a hydrogen atom or a lower alkyl group, R'' is a lower alkyl group, R3 is -OR' or -NHR' (R
' is a hydrogen atom or a lower alkyl group; R5 is a phenyl group that may be substituted with 1 to 5 of a halogen atom, a lower alkyl group, and a lower alkokino group)] 2-alcokynecarbonyl-3-pyrinonocarbonoic acid Derivative Mako provides a method for producing its salt.

The compound of this invention exhibits a remarkable growth-inhibiting effect on plants, and can be used as a herbicide in paddy fields, upland fields, orchards, non-agricultural lands, and the like.

Thus, the present invention provides a herbicide containing the compound of the above formula (]) or a salt thereof as an active ingredient.

When using the compound of this invention as the above herbicide,
They may be used as is, or they are generally mixed with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries to form formulations such as wettable powders, granules, and emulsions.

These formulations contain 10% of the compound of this invention in wettable powders.
~80%, 01-20% for granules, 10-50 for emulsions
% (all indicate weight %).

Solid carriers used in formulations include fine powders or granules such as kaolin, bentonite, clays, talc, diatomaceous earth, norcrite, zeolite, pyrophyllite, synthetic silicon dioxide, and carbonate; Carriers include aromatic hydrocarbons such as kiln, methylnaphthalene, alcohols such as ethanol, isopropanol, ethylene glycol, and methyl cellosolve, ketones such as acetopeisophorone and cyclohexanone, vegetable oils such as soybean oil and cottonseed oil, Examples include dimethylformamide, dimethyl sulfoxide, acetonitrile, and water.

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 Examples include nonionic surfactants such as propylene block polymers, anionic surfactants such as alkyl sulfate salts, alkyl sulfonate salts, alkylaryl sulfonate salts, and polyoxyethylene alkyl sulfate salts.

Formulation adjuvants include lignin sulfate, alginate, polyacrylates, polyvinyl alcohol, vegetable gums, carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), and the like.

The compounds of this invention can also be used as pond insecticides, if necessary.
It can also be used in combination with acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers or soil conditioners.

When the compound of this invention is used as a herbicide, the amount used varies depending on the location and method of use and the type of plant. However, the compounds of this invention are generally used in an amount of about 0.1 to 50 g per are.

(Examples) The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 Production of ethyl 1-butyl-2-ethoxycarbonyl-1,4-dihydro-6-methyl-4-oxo-3-pyridinecarboxylate Example 2 1-Butyl-2-ethoxycarbonyl-1,4 Preparation of dihydro-6-methyl-4-oxo-3-pyrinonecarboxylic acid A mixture of 4.14 g of diethyl oxaloacetate (i), 161 g of butylamine and 60 al of toluene was heated under reflux for 1.5 hours, during which time the water produced was distilled off using a Dean-Stark apparatus. While refluxing this reaction solution,
Diketene acetone adduct 7.81g toluene 10m
A solution of 1 was added dropwise over 7 minutes, and the mixture was further refluxed for 1 hour. After distilling off the solvent from the reaction mixture under reduced pressure, the residue was subjected to column chromatography to obtain the title compound (mountain) 1.
．． 84g was obtained.

'HNMR (CDC13) δ: 0.60-2.10
(a, 7B), 1.28 (t, 3H), 1.34
(t, 3H), 2.28 (s, 3h), 3.77
(t, 211) , 4.23 (q, 2H) , 4.3
0 (q, 2H), 6.26 (s, 11) Dissolve the compound (1 stone) 619+ag in Example 1 in ethanol 2a+1, add IN aqueous sodium hydroxide solution 21, and stir at room temperature for 4 hours. did. Ethanol was distilled off under reduced pressure. Next, an aqueous hydrochloric acid solution and methylene chloride were added for extraction, and the organic layer was washed with water, dried and concentrated to obtain 0.39 g of the title compound (iv).

'HNMR (CDCI,) δ: 0.70-2.20
(a+, 78), 1.39 (t, 3H), 2.46
(s, 3H), 3.88 (t, 2■), 4.47
(q, 2H), 6.55 (s, 1■), 16.
30 (br, IH) Example 3 1-Butyl-2-ethoxycarbonyl-N-(2,6-
(dinitylphenyl)-1,4-dihydro-6-methyl-
Production of 4-oxo-3-pyridineorboxamide (iv) 0.3 yg of the compound (ff) obtained in Example 2 was dissolved in 5 ml of methylene chloride, and 0.1 yg of thionyl chloride was added to the solution under cooling.
0.4ml of methylene chloride solution (2el) was added dropwise over 5 minutes. After further stirring for 4 hours and 40 minutes under cooling, 2.6-
Noethylaniline 235mg, ) ethylamine 2
A mixture of 92 ml and 5 ml of methylene chloride was cooled,
It was added dropwise over 10 minutes. The mixture was further stirred under cooling for 3 hours at room temperature overnight. The reaction mixture was washed with water and then with a saturated aqueous solution of sodium hydrogen carbonate, dried and concentrated, and the residue was subjected to column chromatography to obtain the title compound (v) 16.
Obtained 4mg.

IHNMR (CDC13) δ: 1.18 (t, 6H
), lJ6 (t.

3H), 2.43 (s, 31(), 2.63 (
q, 4H), 3.87 (t, 2Fl), 4.42 (
q, 2H), 6.50 (s, 18), 7.06
(s, 38), 11.93 (br, IH) Test example (plant physiological activity test) Talc (50 parts by weight), bentonite (25 parts by weight),
A carrier was prepared by mixing Trupol-9047 (Toho Chemical System, 2 parts by weight) and Sorbo-Rue 5039 (3 parts by weight, same as before). 50 parts by weight of each of the test compounds and 200 parts by weight of the carrier were mixed to prepare a 20% permanent agent. This hydrating powder was dispersed in pure water to obtain a hydrating powder dispersion having a predetermined concentration. Separately, prepare a petri dish containing germinated rice, wildflower, and 20-day radish seeds, add the above-mentioned hydrating agent dispersion, and grow the seedlings in a low-temperature room with lighting at 25°C for 7 days to check the growth level according to the following criteria. The results are shown in Table 1. No significant change in activity. Effect: 25% growth inhibition, 50% growth inhibition, 75% growth inhibition, complete withering. The following compounds are of interest:

Ethyl 2-ethquincarbonyl-1,4-dihydro 6-methyl-4-oxo-3-bilinonecarboxylate, 2-ethquincarbonyl-1,4-dihydro 1,6-nomethyl-4-oxo-3-bilinonecarboxylate Ethyl noncarboxylate, 2-ethoquinocarbonyl! , 4-nohytro6-methyl-4-year-old quino-3-bilinonecarphonic acid, 2-ethquincarbonyl-14-dihydro 1,6-dimethyl-4-oxo-3-bilinonocarbonoic acid, 2-ethquincarbonyl-N-( 2,6-noethylphenyl)-1,6-nomethyl-4-year-old xo-3-bilinone carboxamide and 2-methoquinosulfonyl-6-methyl-N-phenyl-
4-year-old xo-3-bilinone carboxamide.

Claims (1)

[Claims] 1. Formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 is a hydrogen atom or a lower alkyl group: R^2
is a lower alkyl group; R^3 is -OR^4 or -NHR
^5, (R^4 is a hydrogen atom or lower alkyl group; R^
5 is a phenyl group optionally substituted with 1 to 5 of a halogen atom, a lower alkyl group, and a lower alkoxy group)] or a salt thereof. 2. (1) Formula (II) or Formula (II'): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II') (R^1 in the formula is a hydrogen atom or a lower alkyl group; R^2
and R^6 is a lower alkyl group), the formula (
III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R^7 and R^8 are hydrogen atoms, lower alkyl groups, or phenyl groups) By reacting the compound represented by the formula ( I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 and R^2 are the same as the above definitions; R^3' is a lower alkoxy group) is produced, (2)
If necessary, by hydrolyzing the compound of formula (I) obtained in step (1) above, formula (I): ▲ Formula,
There are chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 and R^2 are the same as the above definition; R^3'' is a hydroxy group), and (3
) If necessary, the compound of formula (I) obtained in step (2) above is reacted with a halogenating agent to convert it into an acid halide, and the resulting acid halide is added with formula (IV) R^5NH
A compound represented by _2 (in the formula, R^5 is a phenyl group optionally substituted with 1 to 5 of a halogen atom, a lower alkyl group, or a lower alkoxy group) is reacted in the presence of a base to form the formula (I )▲There are mathematical formulas, chemical formulas, tables, etc.▼(
I) Produce a compound represented by [in the formula, R^1 and R^2 are the same as defined above; R^3'' is a group -NHR^5 (R^5 is the same as defined above)], and ( 4) Furthermore, if desired, there are ▲mathematical formulas, chemical formulas, tables, etc. for converting the compounds obtained in each of the above steps into salts▼(I) [In the formula, R^1 is a hydrogen atom or a lower alkyl group; R^2
is a lower alkyl group; R^3 is -OR^4 or -NHR
^5 (R^4 is a hydrogen atom or lower alkyl group; R^5
is a phenyl group optionally substituted with 1 to 5 of a halogen atom, a lower alkyl group, and a lower alkoxy group)] or a salt thereof. 3. Formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 is a hydrogen atom or a lower alkyl group; R^2
is a lower alkyl group; R^3 is -OR^4 or -NHR
^5, (R^4 is a hydrogen atom or lower alkyl group; R^
5 is a phenyl group optionally substituted with 1 to 5 of a halogen atom, a lower alkyl group, and a lower alkoxy group. A herbicide containing it as an active ingredient.