CN113912537A

CN113912537A - 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compound and preparation method and application thereof

Info

Publication number: CN113912537A
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: 2022-01-11

Abstract

The invention provides a 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compound and a preparation method and application thereof. During preparation, substituted quinolinecarboxylic acid is used as a raw material, a chlorinating agent is added into a solvent, and the mixture reacts 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 overnight at room temperature, and removing the solvent by distillation to obtain a yellow solid product. The compound of the invention has high activity as herbicide for treating rice stem leaves and has special effect on barnyard grass, thereby effectively controlling the harm of the barnyard grass.

Description

2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone 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-diketone compound and a preparation method and application thereof.

Background

Barnyard grass, Latin school name: echinochloa crusgalli (L.) Beauv, an annual herbaceous plant, has a very similar appearance to barnyard grass and rice. Barnyard grass grows in rice fields, swamps, near ditches and in low-lying wastelands. The shape is similar to rice but the leaves are rough and astringent and the color is lighter. The barnyard grass and the rice absorb the nutrients in the rice field together, so the barnyard grass is a malignant weed in the rice field. It was reported that barnyard grass grown for one week per square meter reduced yield by 2%, about 10% for 5 weeks, about 19% for 10 weeks, and about 35% for 20 weeks. The barnyard grass in the existing paddy field weeds is still the biggest problem.

Although herbicides have been disclosed in the prior art, for example, CN102249996A discloses a compound represented by formula (3) wherein R1 and R2 are selected from methyl, halogen, nitro or methylsulfonyl. A compound represented by the following formula (4) is disclosed in EP0186118, a compound represented by the following formula (5) is disclosed in EP 1117639, and a compound represented by the following formula (6) is disclosed in JP 0625144.

Wherein the compound (4) and the compound (5) are corn field herbicides; although the compound (3) and the compound (6) are herbicides for paddy fields, the compound (3) is used in an amount of 50g or more per mu of land and has a narrow herbicidal spectrum, and the compound (6) has no good effect on barnyard grass. The development of herbicides capable of controlling barnyard grass is an urgent need in the agricultural field.

Disclosure of Invention

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

The purpose of the invention is realized by the following technical scheme:

2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones of the formula:

wherein R1 and R2 are any one of hydrogen base, 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 and 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, said R1, R2 are halogen; r3 is C1-C3 alkyl.

Preferably, the preparation method of the 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone 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 to obtain an esterification solution;

and S3, adding a translocating agent into the esterification solution obtained in the S2, continuously stirring at room temperature overnight, then adding water, and removing the solvent through distillation at normal pressure to obtain a yellow solid product.

The above reaction formula 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 S1 is one or a combination of more than one 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, triethylammonium, pyridine, and the like.

Preferably, the transfer 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-diones as herbicides to control barnyard grass growth.

Preferably, the herbicide contains 0.1-99 wt% of active ingredients, and the active ingredients are 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compounds.

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

The invention has the beneficial effects that: the compound of the invention has high activity as herbicide for treating rice stem leaves and has special effect on barnyard grass, thereby effectively controlling the harm of the barnyard grass.

Detailed Description

The following examples are provided to illustrate the present invention and disclose 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones of the formula:

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

table 1: R1-R3 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 preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones is described below with reference to the examples.

Example 1:

160g of 3, 7-dichloro-5-methanesulfonyl-8-quinolinecarboxylic acid, 400ml of dichloroethane, and 75g of thionyl chloride, were heated to 78 ℃ for reflux reaction for 2 hours to obtain an acid chloride solution. And then cooling to room temperature, adding 52g of cyclohexanedione, dropwise adding 60g of triethylamine at 20-25 ℃, and reacting for 1 hour after the addition is finished to obtain an esterification solution.

3g of acetone cyanohydrin was added and the stirring was continued overnight at room temperature to obtain the product. Then 400ml of water is added to the mixture and the mixture is distilled to about 100 ℃ under normal pressure to obtain 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 2:

160g of 3, 7-dichloro-5-methanesulfonyl-8-quinolinecarboxylic acid, 400ml of toluene and 75g of thionyl chloride are heated to 78 ℃ for reflux reaction for 2 hours to obtain an acyl chloride solution. And then cooling to room temperature, adding 52g of cyclohexanedione, dropwise adding 60g of triethylamine at 20-25 ℃, and reacting for 1 hour after the addition is finished to obtain an esterification solution.

3g of acetone cyanohydrin was added and the stirring was continued overnight at room temperature to obtain the product. Then 400ml of water is added, and the mixture is distilled to about 110 ℃ under normal pressure to obtain a yellow solid product.

Example 3:

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

Example 4:

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

3g of acetone cyanohydrin was added and the stirring was continued overnight at room temperature to obtain the product. Then 400ml of water is added to the mixture and the mixture is distilled to about 120 ℃ under normal pressure to obtain a yellow solid product.

The following examples are given to illustrate specific applications of the present 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones.

For the use of the compounds of the invention as herbicides, they are formulated by combining them with carriers, surfactants, dispersants or adjuvants of suitable type, for example wettable powders, emulsions, granules, suspensions and solvents. The compound is used as it is or after dilution with a suitable medium, as required. The furnish may be prepared from spray volumes of several hundred liters per acre to several thousand liters per acre. The formulations may optionally contain from about 0.1% to about 99% by weight of the active ingredient, with the addition of from 0.1% to about 20% surfactant or from 0% to about 99.9% solid or liquid diluent being suggested. The formulations will contain the corresponding active ingredients in the proportions shown in table 2.

Table 2: formulation composition

The specific ratio of active ingredients depends on the desired use. High ratios of surfactant to active ingredient are sometimes desirable and are achieved by incorporation into the formulation or mixing in a 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 formulations may contain small amounts of additives to prevent the formation, clumping, corrosion and growth of microorganisms.

According to conventional methods for preparing compositions, solutions can be mixed by merely pulverizing the ingredients and fine solids by blending and powdering with a hammer mill. Suspensions can be made by wet milling and granules can be made by spraying the active ingredient onto a particulate carrier.

The following description of typical ingredients is given in conjunction with specific preparation examples.

1, preparing materials: wettable powders

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

Active ingredient (Compound 1 in Table 1)	20% by weight
		Dodecyl phenol polyglycol ether	2% by weight
Lignosulfonic acid sodium salt	4% by weight
		Sodium aluminosilicate	6% by weight
Montmorillonite clay	68% by weight

And (3) preparing a material 2: wettable powders

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

Active ingredient (Compound 1 in Table 1)	80% by weight
		Sodium alkyl naphthalene sulfonate	2% by weight
Lignosulfonic acid sodium salt	2% by weight
		Synthetic amorphous silica	3% by weight
Kaolin clay	13% by weight

And (3) preparing materials: emulsion and method of making

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

Active ingredient (Compound 1 in Table 1)	30% by weight
		Cyclohexanone	20% by weight
Polyoxyethylene alkylaryl ethers	11% by weight
		Alkyl calcium benzene sulfonate	4% by weight
Methylnaphthalene	35% by weight

And (4) preparing materials: granules

The components were mixed well and 20 parts by weight of water were 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% by weight
		Ammonium lauryl sulfonate	2% by weight
Sodium lignosulfonate	5% by weight
		Carboxymethyl cellulose	2% by weight
Potassium sulfate	16% by weight
		Gypsum plaster	70% by weight

The formulations according to the invention are sprayed and diluted to a certain concentration.

The compound of the invention has high activity as herbicide for treating rice stem leaves and has special effect on barnyard grass, thereby effectively controlling the harm of the barnyard grass.

The dosage of the active ingredients can be 2 g/mu to 100 g/mu, preferably 5 g/mu to 45 g/mu. The amount of the compound of the present invention used depends on the age of the weeds. The herbicides of the present invention may be used alone or in combination with other herbicides, insecticides or fungicides. In particular, it is necessary to add one or more agents selected from the following: bentazone, quinclorac, propanil, simetryn, MCPA, fenpyr, flumetsulam, bentazon, prosulfocarb, bensulfuron-methyl, pyrazosulfuron-ethyl, metsulfuron-methyl, thifensulfuron-methyl, bentazone, penoxsulam, cyhalofop-butyl, metamifop and fluroxypyr.

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

Test example 1: stem and leaf treatment test

The method comprises the steps of placing seeds of rice, wheat and barnyard grass (seeds of the barnyard grass are collected from Lujiang Anhui, and are detected to generate drug resistance to penoxsulam, bispyribac and pyribenzoxim), digitaria sanguinalis, eleusine indica, setaria viridis and gynura bicolor in a plastic basin filled with soil, then covering the plastic basin with 0.5-2 cm of soil to enable the seeds to grow in a good greenhouse environment, treating test plants in a 4-5 leaf stage after sowing for 2-3 weeks, respectively dissolving a tested compound with DMF (dimethyl formamide) in the test solution, then adding Tween 80, diluting the solution with certain water into a solution with a certain concentration, and spraying the solution onto the plants by using 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 plants were evaluated for the degree of damage, expressed as% damage, relative to the untreated control sample.

In the tests, 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 have herbicidal activity as shown in Table 3.

Table 3: herbicidal activity of the compounds

These test results show that the compounds of the present invention have excellent selectivity for rice and excellent herbicidal activity against barnyard grass. Echinochloa crusgalli in paddy fields has become more and more resistant to drugs with the use of ALS inhibitor (penoxsulam, pyribenzoxim, bispyribac-sodium and the like) herbicides in the next year, and great challenges are created in China, southeast Asia and the like. Currently, the mainstream herbicides are ALS inhibitors, so that the search for medicaments with different mechanisms brings new choices, and has great social value and commercial value. Through long-term screening, we surprisingly found that the compound of the invention can have excellent control effect on barnyard grass which is resistant to ALS inhibitors and is from Anhui Lujiang county in China, and has good selectivity on rice.

There are, of course, many other specific embodiments of the invention and these are not to be considered as limiting. All technical solutions formed by adopting equivalent replacement or equivalent transformation are within the scope of the invention claimed by the invention.

Claims

A 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compound, characterized in that: the compound has the following structural formula:

wherein R1 and R2 are 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, and 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.
2. 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones according to claim 1, wherein: r1, R2 are halogen; r3 is C1-C3 alkyl.
3. A process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones 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 to obtain an esterification solution;

and S3, adding a translocating agent into the esterification solution obtained in the S2, continuously stirring at room temperature overnight, then adding water, and removing the solvent by distillation at normal pressure to obtain a yellow solid product.
4. A process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones according to claim 3, wherein: the solvent in the S1 is one or more of tetrahydrofuran, ethyl acetate, acetonitrile, toluene, xylene, hexane, dichloromethane, dichloroethane and carbon tetrachloride.
5. A process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones according to claim 3, wherein: and the chlorinating agent in the S1 is one or the combination of more than one of thionyl chloride, phosgene, diphosgene, triphosgene, oxalyl chloride, phosphorus trichloride, phosphorus oxychloride and phosphorus pentachloride.
6. A process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones according to claim 3, wherein: the S2 medium alkali is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, triethylamine, pyridine and the like.
7. A process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones according to claim 3, wherein: the transfer agent in the S3 is one or more of acetone cyanohydrin, butanone cyanohydrin, sodium cyanide, potassium cyanide and the like.
Use of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones as herbicides to control barnyard grass growth.
9. Use of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones as claimed in claim 8 as herbicides for controlling barnyard grass growth, characterized in that: the herbicide contains 0.1-99 wt% of active ingredients, and the active ingredients are 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compounds.
10. Use of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones as claimed in claim 9 as herbicides for controlling barnyard grass growth, characterized in that: the herbicide also comprises 0.1-20 wt% of a surfactant or 0-99.9 wt% of a solid or liquid diluent.