KR930002276B1 - Novel quinoline derivatives - Google Patents

Abstract

Quinoline derivs. of formula (I) are new. In (I), X=H or halogen; Y=H, halogen or nitro. Also claimed is the prepn. of (I) which comprises reacting 3,7-dichloro-8- quinoline carboxylic acid of formula (II) with an oxime deriv. of formula (III) and thionyl chloride in an organic solvent in the presence of an acid-bonding agent selected from pyridine, triethylamine, triisopropylamine, 2- methyl-5-ethyl pyridine, sodium carbonate, potassium carbonate. The reaction temperature is pref. 0-140 deg.C; and the solvent is pref. toluene, xylene, benzene, tetrahydrofurane, CCl4, CHCl3 or C5-7 hydrocarbon.

Description

New quinoline derivatives

The present invention relates to a novel quinoline derivative represented by the following structural formula (I) having herbicidal activity.

Wherein X is hydrogen or a halogen atom, and Y is hydrogen or a halogen atom or represents a nitro group.

The use of compounds to control weeds has been around for a long time, but recently, studies on selective control based on the physicochemical properties of crops and weeds are in full swing.

Such selection of herbicides has greatly contributed to improving productivity and reducing labor in the agricultural economy. In particular, in recent years, high efficiency, low toxicity and high selection have been considered in consideration of environmental pollution and toxicity to human beings. The development of herbicides is urgently needed.

As a compound having herbicidal activity developed as part of this effort, the following compound of formula (II) described in US Pat. No. 4,497,651 is known to have very high herbicidal activity.

However, the compound of the formula (II) has a problem in that the weakness against young seedlings of rice is severe and the soil adsorption property is low due to the physicochemical properties, so that the loss of the compound is not expected. In other words, in the case of seedling transfer of crops, which is a recent trend, treatment of herbicides using the structural formula (II) as an active ingredient (3 leaf stages) causes weakness such as height inhibition, cleavage inhibition, reduction of biomass weight, and whole leaves. As a result, the herbicide treatment of seedling Yiangsi by economic farming is impossible.

In addition, the structural formula (II) compound has an organic acid in its chemical structure, so the solubility in water is relatively high and the adsorption property to the soil is poor, it is difficult to expect the residual effect, especially in the case of sandy soils having low adsorption power is temporarily absorbed by the root Not only is there a high possibility of causing weakness, but there is a problem that it is difficult to control the weeds generated after the treatment.

Therefore, the present invention solves the problems in the conventional gymnastic active compound as described above exhibits significantly lower weakness than the compound of the formula (II), exhibits effective selective herbicidal activity without regard to the treatment time and economically advantageous It is an object to provide novel preparation active compounds.

Hereinafter, the present invention will be described in detail.

The present invention relates to a novel quinoline derivative compound represented by the above formula (I), and includes a herbicide containing the compound of the above formula (I) as an active ingredient.

The compound of formula (I) according to the present invention consists of a structure in which an oxime group represented by formula (III) is introduced into the compound of formula (II), which is generally reported as a weakening agent of herbicide. Pesticide biochemistry and physiology 34,69-75 (1989). To date, no compound in which an oxime group is introduced into the compound of formula II is known.

Structural formula (I) according to the present invention reacts with quinoline carboxylic acid of quinoline carboxylic acid of formula (II) to form an acid chloride (formula (IV)) and then reacts with substituted phenyloxime of formula (III) in the presence of an acid binder. It is manufactured as shown below.

When the reaction is described in detail, the amount of thionyl chloride to prepare the acid chloride is 1.0 to 3.0 equivalents relative to the organic acid, and as the acid binder, pyridine, 2-methyl-5-ethylpyridine, triethylamine, triisopropylamine, Potassium carbonate, sodium carbonate and the like are preferred. The use amount is 1.3-3.0 equivalents with respect to thionyl chloride. Toluene, xylene, n-pentane, n-hexane, carbon tetrachloride, chloroform, and the like are used as the reaction solvent, and need not necessarily be anhydrous. Appropriate reaction temperature is 0-140 degreeC.

As described above, the present invention has a new structure in which an oxime group is introduced into the compound of formula (II), which can be treated with little damage even in the 3 to 4 leaf stages immediately after rice transplantation. It can be used. In addition, the structural characteristics due to the introduction of oxime ester groups not only lower the solubility in water, but also increase soil adsorption, thereby preventing the loss of active ingredients by relational water and the like, thereby increasing the residual efficiency, and The premise is possible so that the economic effect is also enhanced.

On the other hand, the herbicide formulation containing the compound of formula (I) as an active ingredient can be prepared by a general method. That is, it is possible to mix with solid extenders such as montmorillonite, clay, talc, bentonite, and liquid extenders such as alcohols, ethers, esters, ketones, chlorinated hydrocarbons and aromatic hydrocarbons. It can be mixed with an electrodeposition agent, a stabilizer, etc., and used to make a desired formulation such as an emulsion, a hydrate, a powder, a granule, or a liquid. The active ingredient content in such a formulation is usually preferably used in the range of 1.0 to 8.0% by weight based on the weight ratio, but the content is not limited.

The compounds of the formula (I) of the present invention as described above can be preferably used without harm to the human body in formulated fields as well as paddy fields, orchards and other areas with the necessity of weed removal, especially for rice. In the present invention, the herbicidal effect is found to be particularly selective for herbicidal effect, for example, blood, orchard glass, sesame, parrot, sesame, yeast, silkworm grass, buckthorn.

This herbicidal effect is suitable for the herbicide according to the present invention 10g per hectare based on the weight ratio of the active ingredient, but there are some differences depending on the application.

As described above, according to the present invention, the application time and application method of the herbicide are improved, and the herbicidally active compound and the herbicide as an active ingredient which are highly effective for sustaining the drug efficacy, improving the selectivity, increasing the economic efficiency, reducing the risk and the like can be provided. It becomes the number.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Example 1

Synthesis of Compound (I -a)

2.61 g (10 mM) of 3,7-dichloro-8-quinoline carboxylic acid (II) was added to 15 ml xylene, and then 2.53 g of thionyl chloride was slowly added at room temperature while stirring. After the addition, the reaction solution was refluxed for 30 minutes, and unreacted thionyl fluoride was removed under reduced pressure to obtain 3,7-dichloro-8-quinolinate (formula IV). 1.30 g (13 mM) of triethylamine was added to the reaction solution, and 1.70 g (10 mM) of 4'-chloroacetophenone oxime was dissolved in 5 ml of xylene, and then added at room temperature, followed by stirring for 12 hours.

The resulting triethylamine and hydrochloride solids were removed by filtration, and the filtrate was concentrated under reduced pressure to give crude crystals, which were then recrystallized from alcohol to give 3.14 g of 4'-chloroacetophenone-O- (3,7- Oxime ester of dichro-8-quinoline carbonyl) was obtained.

EXAMPLES 2-6

Synthesis of Compound (I -a)

In Example 1, after obtaining 3,7-dichloro-8-quinolinate (formula IV), the result of using another acid binder instead of triethylamine was as follows.

EXAMPLES 7-12

Synthesis of Compound (I-a)

The result obtained by using another solvent instead of xylene used as a reaction solvent in Example 1 is as follows.

Example 13

Synthesis of Compound (I-b)

In Example 1, 3,7-dichloro-8-quinolinate (formula IV) was obtained, and then reacted with 4'-fluoroacetophenone oxime 1.53 g (10 mM) in the same manner to obtain 4'-fluoro as a target compound. 2.85 g of acetophenone-O- (3,7-dichloro-8-quinolinecarbonyl) oxime ester was obtained.

[Examples 14 to 47]

In Example 1, the compound (I-c) to (I-f) were synthesized by obtaining 3,7-dichloro-8-quinolinate (formula IV) and reacting with an oxime derivative of formula (III) in the same manner.

TABLE 1

Example 18

1.5% of the compound of formula (I), 50% of bentonite, and 48.5% of talc are mixed in a weight ratio, and then a small amount of water or a lower alcohol is added to the mixture, followed by stirring.

Example 19

8.0% of the compound of formula (I), 90% of clay, Triton X-100 2% by weight and then mixed to prepare a homogeneous hydrating agent. When the herbicidal activity of the granules of Example 7 and the hydrating agent of Example 8 was compared at the same concentration, there was no difference.

Example 20

After sowing seed and seed on 1 / 1,100 ar paddy soil, the hydration of the compound of the above formula (I) was treated by each concentration the next day after sowing as shown in Table 2, and then irradiated after 2 weeks. Where X and Y are as defined above.

TABLE 2

* X and Y are substituents of the above formula (I).

Example 21

Next, as shown in Table 3, two- and four-leaf rices were transferred to the 1 / 1,000 ar paddy soil, respectively, and then three- and five-leafed rice were treated at two weeks after treatment with the drug.

TABLE 3a

TABLE 3b

Example 22

As shown in the following Table 4, one week after seeding the seed soil in 1 / 1,000 ar soil was treated with the drug, and two weeks later, we tested the herbicidal effect on each weed by the crown tube.

TABLE 4

Example 23

As shown in Table 5, after weeding the seeds in 1 / 1,000 field soil, the herbicide effect on each of the weeds was tested by the crown tube 2 weeks after the treatment with the drug when the target seedlings were about 3 to 4 leaves.

TABLE 5

Claims (5)

A novel quinoline derivative having herbicidal activity represented by the following structural formula (I). Wherein X represents hydrogen or a halogen atom, and Y represents hydrogen or a halogen atom or a nitro group. A herbicide containing a quinoline derivative compound represented by the following structural formula (I) as an active ingredient. Wherein X represents hydrogen or a halogen atom, and Y represents hydrogen or a halogen atom or a nitro group. The quinoline oxime of formula (I) according to claim 1, wherein the 3,7-dichloro-8-quinoline carboxylic acid of formula (II) is reacted with thionyl chloride and the oxime of formula (III) in an organic solvent. How to prepare an ester. (X, Y are as described above) According to claim 3, wherein the reaction temperature is 0 to 140 DEG C when preparing the compound represented by the structural formula (I), the amount of thionyl chloride is 1 to 3 equivalents to the organic acid (II), pyridine and trie as an acid binder A method according to claim 1, wherein the amount is selected from chilamine, triisopropylamine, 2-methyl-5-ethylpyridine, sodium carbonate and potassium carbonate and the amount thereof is used in an amount of 1.3 to 3.0 equivalents based on the amount of thionyl chloride. 4. The process according to claim 3, wherein toluene, xylene, benzene, tetrahydrofuran, carbon tetrachloride, chloroform and C _{5 to} C ₇ hydrocarbons are used as a solvent when preparing the compound represented by formula (I).