CN113912537B

CN113912537B - 2- (Quinoline-8-yl) carbonyl-cyclohexane-1, 3-dione compound and preparation method and application thereof

Info

Publication number: CN113912537B
Application number: CN202110993556.5A
Authority: CN
Inventors: 宋春雨
Original assignee: Chongqing Chemical Industry Vocational College
Current assignee: Chongqing Chemical Industry Vocational College
Priority date: 2021-08-27
Filing date: 2021-08-27
Publication date: 2024-05-07
Anticipated expiration: 2041-08-27
Also published as: CN113912537A

Abstract

The invention provides a 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-dione compound, and a preparation method and application thereof. During preparation, substituted quinolinecarboxylic acid is taken as a raw material, and a chlorinating agent is added into a solvent to react at the temperature of 0-100 ℃ to obtain an acyl chloride solution; cooling to room temperature, adding 1, 3-cyclohexanedione, adding alkali at 0-100 ℃, reacting to obtain an esterification solution, adding a transposition agent into the esterification solution, continuously stirring at room temperature overnight, and removing the solvent by distillation to obtain a yellow solid product. The compound of the invention has high activity as a herbicide for rice stem and leaf treatment and special effect on barnyard grass, thus being capable of effectively controlling the harm of barnyard grass.

Description

2- (Quinoline-8-yl) carbonyl-cyclohexane-1, 3-dione compound and preparation method and application thereof

Technical Field

The invention belongs to the technical field of compound synthesis, and relates to a 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-dione compound, and a preparation method and application thereof.

Background

Barnyard grass, latin's name: echinochloa crusgalli (l.) Beauv, an annual herb, is very similar in shape to barnyard grass and rice. Barnyard grass grows in paddy fields, swamps, beside ditches and low-lying wastelands. The shape is similar to rice but the leaves Mao Se are lighter in color. Barnyard grass and rice together absorb nutrients in the paddy field, so barnyard grass is a malignant weed in the paddy field. Barnyard grass was reported to grow for one week per square meter, resulting in a 2% reduction in yield, about 10% reduction in 5 weeks of growth, about 19% reduction in 10 weeks of growth, and about 35% reduction in 20 weeks of growth. Barnyard grass remains the biggest problem in existing paddy weeds.

Although herbicides are disclosed in the prior art, a compound represented by formula (3) wherein R1, R2 are selected from methyl, halogen, nitro or methylsulfonyl is disclosed in CN 102249996A. The compound of the following formula (4) is disclosed in EP0186118, the compound of the following formula (5) is disclosed in EP 1117639, and the compound of the following formula (6) is disclosed in JP 0625144.

But wherein compound (4) and compound (5) are corn field herbicides; although the compound (3) and the compound (6) are herbicide for paddy fields, the dosage of the compound (3) is more than 50g per mu of land, the weeding spectrum is narrow, and the compound (6) has poor effect on barnyard grass. The development of herbicides that control barnyard grass is an urgent need in the agricultural arts.

Disclosure of Invention

Aiming at the problems existing in the prior art, the invention provides a 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-dione compound, and a synthesis method and application thereof.

The aim of the invention is achieved by the following technical scheme:

2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compounds having the structural formula:

Wherein R1, R2 is any one of hydrogen, benzyl, phenyl, trifluoromethyl, halogen, C1-C6 alkyl, C1-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C3 haloalkyl, C1-C3 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C3 alkoxycarbonyl, C1-C3 alkylcarbonyl;

R3 is any one of C1-C6 alkyl, benzyl, phenyl, trifluoromethyl, C1-C6 cycloalkyl, C1-C3 haloalkyl, C2-C4 alkoxyalkoxy, C2-C6 alkenyl and C2-C6 alkynyl.

Preferably, R1, R2 are halogen; r3 is C1-C3 alkyl.

Preferably, the preparation method of the 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-dione compound comprises the following steps:

S1, taking substituted quinolinecarboxylic acid as a raw material, adding a chlorinating agent into a solvent, and reacting at the temperature of 0-100 ℃ to obtain an acyl chloride solution;

S2, cooling to room temperature, adding 1, 3-cyclohexanedione, adding alkali at 0-100 ℃, and reacting after adding to obtain an esterification solution;

And S3, adding an indexing agent into the esterified solution obtained in the step S2, continuously stirring at room temperature overnight, then adding water, and removing the solvent by normal pressure distillation to obtain a yellow solid product.

The above equation is shown below:

preferably, the solvent in S1 is one or more of tetrahydrofuran, ethyl acetate, acetonitrile, toluene, xylene, hexane, dichloromethane, dichloroethane, and carbon tetrachloride.

Preferably, the chlorinating agent in the S1 is one or more of thionyl chloride, phosgene, diphosgene, triphosgene, oxalyl chloride, phosphorus trichloride, phosphorus oxychloride and phosphorus pentachloride.

Preferably, the base in S2 is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, triethylamine, pyridine, and the like.

Preferably, the translocation agent in S3 is one or more of acetone cyanohydrin, butanone cyanohydrin and sodium cyanide.

Preferably, the use of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compounds as herbicides for controlling barnyard grass growth.

Preferably, the herbicide contains 0.1-99% by weight of active ingredient, wherein the active ingredient is 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compound.

Preferably, the herbicide also comprises 0.1 to 20% by weight of surfactant or 0 to 99.9% by weight of solid or liquid diluent.

The beneficial effects of the invention are as follows: the compound of the invention has high activity as a herbicide for rice stem and leaf treatment and special effect on barnyard grass, thus being capable of effectively controlling the harm of barnyard grass.

Detailed Description

The following examples are presented to illustrate the technical scheme of the present invention, and the present invention discloses 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compounds having the structural formula shown below:

R1-R3 of the compound in the structural formula are shown in the table 1:

Table 1: and R1-R3 are selected from groups in the structural formula.

	R1	R2	R3
				1	Cl	Cl	SO₂CH₃
2	Br	Cl	SO₂CH₃
				3	F	Cl	SO₂CH₃
4	Br	Br	SO₂CH₃
				5	F	F	SO₂CH₃
6	CH₃	Cl	SO₂CH₃
				7	Cl	Cl	SO₂CH₂CH₃
8	Br	Cl	SO₂CH₂CH₃
				9	F	Cl	SO₂CH₂CH₃
10	Br	Br	SO₂CH₂CH₃
				11	F	F	SO₂CH₂CH₃
12	CH₃	Cl	SO₂CH₂CH₃

The following examples illustrate the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compounds.

Example 1:

160g of 3, 7-dichloro-5-methanesulfonyl-8-quinolinecarboxylic acid, 400ml of dichloroethane, 75g of thionyl chloride, and heating to 78℃and reflux reaction for 2 hours to obtain an acid chloride solution. Then 52g of cyclohexanedione is added at room temperature, 60g of triethylamine is added dropwise at 20-25 ℃, and the esterification solution is obtained after the reaction for 1 hour.

3G of acetone cyanohydrin was added thereto, and stirring was continued at room temperature overnight to give a product. Then 400ml of water is added for normal pressure distillation to about 100 ℃ to obtain yellow solid products.

¹³C NMR:δ20.0(1C,s),42.0(2C,s),44.3(1C,s),80.8(1C,s), 126.5(1C,s),126.8(1C,s),127.0(1C,s),128.0(1C,s),129.0(1C,s),132.7(1C,s),142.6(1C,s),146.9(1C,s),156.0(1C,s),197.7(1C,s), 211.6(2C,s).

Example 2:

160g of 3, 7-dichloro-5-methanesulfonyl-8-quinolinecarboxylic acid, 400ml of toluene, 75g of thionyl chloride, and heating to 78℃and reflux reaction were carried out for 2 hours to obtain an acid chloride solution. Then 52g of cyclohexanedione is added at room temperature, 60g of triethylamine is added dropwise at 20-25 ℃, and the esterification solution is obtained after the reaction for 1 hour.

3G of acetone cyanohydrin was added thereto, and stirring was continued at room temperature overnight to give a product. 400ml of water was then added and distilled at atmospheric pressure to about 110℃to give a yellow solid product.

¹³C NMR:δ20.0(1C,s),42.0(2C,s),44.3(1C,s),80.8(1C,s), 126.5(1C,s),126.8(1C,s),127.0(1C,s),128.0(1C,s),129.0(1C,s), 132.7(1C,s),142.6(1C,s),146.9(1C,s),156.0(1C,s),197.7(1C,s), 211.6(2C,s).

Example 3:

160g of 3, 7-dichloro-5-methanesulfonyl-8-quinolinecarboxylic acid, 400ml of dichloroethane, 75g of thionyl chloride, and heating to 70℃for reflux reaction for 4 hours to obtain an acid chloride solution. Then 52g of cyclohexanedione is added at room temperature, 60g of triethylamine is added dropwise at the temperature of 10-15 ℃ and the reaction is carried out for 1 hour after the addition, so as to obtain an esterification solution.

Example 4:

160g of 3, 7-dichloro-5-methanesulfonyl-8-quinolinecarboxylic acid, 400ml of xylene, 75g of thionyl chloride, and heating to 70℃for reflux reaction for 4 hours to obtain an acid chloride solution. Then 52g of cyclohexanedione is added at room temperature, 60g of triethylamine is added dropwise at the temperature of 10-15 ℃ and the reaction is carried out for 1 hour after the addition, so as to obtain an esterification solution.

3G of acetone cyanohydrin was added thereto, and stirring was continued at room temperature overnight to give a product. Then 400ml of water is added for normal pressure distillation to about 120 ℃ to obtain yellow solid products.

Specific applications of the present 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compounds are described below in connection with specific examples.

In order to use the compounds of the invention as herbicides, they are formulated in suitable types, such as wettable powders, emulsions, granules, suspensions and solvents, by combination with carriers, surfactants, dispersing agents or adjuvants. The compounds are used as such or after dilution with a suitable medium. The ingredients can be prepared from spray volumes of hundreds of liters per mu to thousands of liters per mu. The formulations may optionally contain from about 0.1% to 99% by weight of active ingredient, with the addition of 0.1% to 20% surfactant or 0% to 99.9% solid or liquid diluent being recommended. The formulations will contain the corresponding active ingredients in the proportions shown in Table 2.

Table 2: formulation composition

The specific active ingredient ratio depends on the intended use. A high ratio of surfactant to active ingredient is sometimes desirable, either by introduction into the ingredients or mixing in the tank.

Solid diluents with high adsorptivity are preferred for wettable powders. The liquid diluent and solvent are preferably stable to phase separation at 0 ℃. All ingredients may contain minor amounts of additives to prevent the formation, clumping, corrosion and growth of microorganisms.

According to the conventional method for preparing a composition, the solution may be mixed by merely pulverizing the respective components and the fine solid by blending with a hammer mill. The suspension may be prepared by wet milling and the particles may be prepared by spraying the active ingredient onto a particulate carrier.

The following description of typical formulations is made in connection with specific preparation examples.

And (2) material preparation 1: wettable powder

The components are thoroughly mixed, the liquid surfactant is sprayed onto the solid components and then mixed, and hammer milled until all solids are substantially less than 100 μm.

Active ingredient (Compound 1 in Table 1)	20 Wt%
		Dodecyl phenol polyethylene glycol ether	2 Wt%
Lignosulfonic acid sodium salt	4 Wt.%
		Sodium aluminosilicate	6 Wt%
Montmorillonite	68 Wt%

And (2) material mixing: wettable powder

The components were mixed, hammer milled until all solids were substantially less than 25 μm, and packaged.

Active ingredient (Compound 1 in Table 1)	80 Wt.%
		Sodium alkyl naphthalene sulfonate	2 Wt%
Lignosulfonic acid sodium salt	2 Wt%
		Synthesis of amorphous silica	3 Wt%
Kaolin clay	13 Wt.%

And (3) material mixing 3: emulsion

The components were mixed and uniformly dissolved to obtain an emulsion.

Active ingredient (Compound 1 in Table 1)	30% By weight
		Cyclohexanone	20 Wt%
Polyoxyethylene alkylaryl ethers	11% By weight
		Calcium alkyl benzene sulfonate	4 Wt.%
Methylnaphthalene	35 Wt.%

And (4) material preparation: particles

The components were thoroughly mixed and 20 parts by weight of water was added to 100 parts by weight of the component mixture.

The component mixture was granulated to a size of 14 to 32 mesh with an extrusion granulator and dried.

Active ingredient (Compound 1 in Table 1)	5 Wt.%
		Ammonium laurylsulfonate	2 Wt%
Sodium lignosulfonate	5 Wt.%
		Carboxymethyl cellulose	2 Wt%
Potassium sulfate	16 Wt%
		Gypsum plaster	70 Wt.%

The formulation according to the invention is sprayed and diluted to a certain concentration.

The compound of the invention has high activity as a herbicide for rice stem and leaf treatment and special effect on barnyard grass, thus being capable of effectively controlling the harm of barnyard grass.

The dosage of the active ingredients can be 2 g/mu-100 g/mu, preferably 5 g/mu-45 g/mu. The amount of the compound of the present invention used depends on the age of the weed. The herbicides of the present invention can be used alone or in combination with other herbicides, insecticides or fungicides. In particular, one or more agents selected from the following must be added: thioxazin, quinclorac, propanil, simetryn, MCPA, carfentrazone-ethyl, flucarbazone, bentazone, carbosulfuron, pyrazosulfuron-ethyl, metsulfuron-ethyl, thifensulfuron-methyl, bentazone, penoxsulam, cyhalofop-butyl, oxadiazon and fluroxypyr.

The herbicidal effect of the compounds of the present invention was examined and tested as follows.

Test example 1: stem and leaf treatment test

Rice, wheat, barnyard grass (barnyard grass seeds are picked from Anhui Lujiang, and are detected to generate drug resistance to penoxsulam, bispyribac-sodium and pyribenzoxim), crabgrass, goosegrass, golden green bristlegrass and hollow lotus seed grass are placed in a plastic basin filled with soil, then covered with soil for 0.5-2 cm, so that the seeds grow in a good greenhouse environment, after sowing for 2-3 weeks, test plants are treated in a 4-5 leaf period, the tested compounds of the invention are respectively dissolved by DMF, then Tween 80 is added, and the mixture is diluted into a solution with a certain concentration by a certain water, and is sprayed onto the plants by a spray tower. The concentration of the spray is chosen such that a specific amount of active compound is desired. After a further 14 days of treatment, the extent of damage of the plants, expressed as% damage, was assessed relative to the untreated control sample.

In the experiments, the active compounds according to the invention have excellent selectivity for plants and herbicidal activity against weeds. Among the compounds of the present invention, some of the compounds in Table 1 were shown in Table 3 for herbicidal activity.

Table 3: herbicidal activity of compounds

These test results show that the compound of the invention has excellent selectivity to rice and excellent herbicidal activity against barnyard grass. Barnyard grass in paddy fields has become increasingly resistant to drugs as ALS inhibitors (penoxsulam, pyribenzoxim, bispyribac-sodium, etc.) are used in successive years, creating a great challenge in china, southeast asia, etc. Currently, the main stream herbicides are ALS inhibitors, so searching for agents with different mechanisms brings new choices, and has great social value and commercial value. Through long-term screening, the compound disclosed by the invention can be surprisingly found to have an excellent preventing and killing effect on barnyard grass which is resistant to ALS inhibitors from Lujiang county of Anhui in China, and has good selectivity on rice.

There are, of course, many specific embodiments of the invention, not set forth herein. All technical solutions which are formed by equivalent substitutions or equivalent transformations fall within the scope of the invention as claimed.

Claims

2- (Quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compounds, characterized in that: the structural formula of the compound is shown as follows:

Wherein R1-R3 of the compound in the structural formula are specifically shown as follows:

R1＝R2＝Cl、R3＝CH₃；

R1＝R2＝F、R3＝CH₃；

R1＝R2＝Cl、R3＝CH₂CH₃；

The application of the 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-dione compound as herbicide for controlling barnyard grass growth.
2. The process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compounds according to claim 1, wherein: the method comprises the following steps:

s1, taking substituted quinolinecarboxylic acid as a raw material, adding a chlorinating agent into a solvent, and reacting at the temperature of 0-100 ℃ to obtain an acyl chloride solution;

S2, cooling to room temperature, adding 1, 3-cyclohexanedione, dropwise adding organic base at 0-100 ℃, and reacting after adding to obtain an esterification solution;

and S3, adding an indexing agent into the esterified solution obtained in the step S2, continuously stirring overnight at room temperature, then adding water, and distilling under normal pressure to remove the solvent to obtain a yellow solid product.
3. The process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compounds according to claim 2, wherein: the solvent in the S1 is one or more of tetrahydrofuran, ethyl acetate, acetonitrile, toluene, xylene, hexane, dichloromethane, dichloroethane and carbon tetrachloride.
4. The process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compounds according to claim 2, wherein: the chlorinating agent in the S1 is one or more of thionyl chloride, phosgene, diphosgene, triphosgene, oxalyl chloride, phosphorus trichloride, phosphorus oxychloride and phosphorus pentachloride.
5. The process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compounds according to claim 2, wherein: the alkali in the S2 is one or a combination of more than one of triethylamine and pyridine.
6. The process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compounds according to claim 2, wherein: the transposition agent in the step S3 is one or more of acetone cyanohydrin, butanone cyanohydrin, sodium cyanide and potassium cyanide.