CN109836393B - Cyclohexene carboxylate compound and application thereof - Google Patents
Cyclohexene carboxylate compound and application thereof Download PDFInfo
- Publication number
- CN109836393B CN109836393B CN201711221343.0A CN201711221343A CN109836393B CN 109836393 B CN109836393 B CN 109836393B CN 201711221343 A CN201711221343 A CN 201711221343A CN 109836393 B CN109836393 B CN 109836393B
- Authority
- CN
- China
- Prior art keywords
- compound
- compounds
- formula
- nmr
- ppm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a cyclohexene carboxylate compound, which is shown as a general formula I:
Description
Technical Field
The invention belongs to the field of herbicides, and particularly relates to an ammonium cyclohexene carboxylate compound and application thereof.
Background
Due to succession and transition of weed populations and generation and rapid development of chemical pesticide resistance, people continuously strengthen the awareness of ecological environment protection, and continuously increase the attention to chemical pesticide pollution, understanding of the influence of pesticides on non-target organisms and problems of lodging in the pesticide ecological environment. With the diminishing area of cultivated land in the world, the increasing population and the increasing demand for food, people are forced to rapidly develop agricultural production techniques, improve the complete cultivation system, and need to continuously invent novel and improved herbicidal compounds and compositions.
Ammonium cyclohexenecarboxylate compounds have good lipid solubility and water solubility, and some compounds have also been reported to have herbicidal activity. As reported in US4003926A, certain cyclohexenecarboxylate ammonium compounds are useful as herbicides, for example the compound KC:
in the prior art, the cyclohexene carboxylate compound with the structure shown as the general formula I is not reported.
Disclosure of Invention
The invention aims to provide an ammonium cyclohexene carboxylate compound with a novel structure and application of a weeding composition taking the compound as an active component.
In order to achieve the purpose, the technical scheme of the invention is as follows:
an ammonium cyclohexenocarboxylate compound represented by the general formula I:
in the formula:
a is selected from C 1 -C 6 Alkyl radical, C 3 -C 8 Cycloalkyl, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl radical, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Haloalkynyl or C 1 -C 6 Alkoxy C 1 -C 6 An alkyl group;
R 1 、R 2 can be the same or different and are respectively selected from hydrogen and C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 1 -C 6 Hydroxyalkyl radical, C 1 -C 6 Alkoxy C 1 -C 6 Alkyl, unsubstituted or substituted by 1-5 halogens, nitro, cyano, C 1 -C 6 Alkyl or C 1 -C 6 Haloalkyl-substituted phenyl;
R 3 、R 4 can be the same or different and are respectively selected from hydrogen and C 1 -C 18 Alkyl radical, C 1 -C 18 Haloalkyl, C 1 -C 18 Hydroxyalkyl radical, C 1 -C 18 Alkoxy C 1 -C 6 Alkyl, unsubstituted or substituted by 1-5 halogens, nitro, cyano, C 1 -C 6 Alkyl or C 1 -C 6 Haloalkyl-substituted phenyl;
R 1 、R 2 、R 3 、R 4 any two of which may also be taken together with the attached N to form:
the cyclohexene carboxylate compound shown in the general formula I also has a corresponding Z or E configuration.
Further, in formula I:
a is selected from C 2 -C 6 Alkyl radical, C 2 -C 6 Haloalkyl, C 3 -C 6 Alkenyl radical, C 3 -C 6 Halogenated alkenyl group, C 3 -C 6 Alkynyl, C 3 -C 6 Haloalkynyl or C 2 -C 6 Alkoxy C 1 -C 4 An alkyl group;
R 1 、R 2 can be the same or different and are respectively selected from hydrogen and C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 1 -C 4 Hydroxyalkyl radical, C 1 -C 4 Alkoxy C 2 -C 4 Alkyl, unsubstituted or substituted by 1-2C 1 -C 6 Alkyl-substituted phenyl;
R 3 、R 4 are respectively selected from hydrogen and C 1 -C 16 Alkyl radical, C 1 -C 4 Hydroxyalkyl radical, C 1 -C 4 Alkoxy C 2 -C 4 Alkyl, unsubstituted or substituted by 1-2C 1 -C 6 Alkyl-substituted phenyl;
R 3 、R 4 together with the linking N, may also form:
still further, in formula I:
a is selected from C 2 -C 4 Alkyl radical, C 2 -C 4 Haloalkyl, C 3 -C 6 Alkenyl radical, C 3 -C 6 Haloalkenyl, C 3 -C 6 Alkynyl or C 2 -C 4 Alkoxy C 1 -C 3 An alkyl group;
R 1 、R 2 can be the same or different and are respectively selected from hydrogen and C 1 -C 4 Alkyl radical, C 2 -C 4 Hydroxyalkyl radical, C 2 -C 4 An alkoxyethyl or benzyl group;
R 3 、R 4 can be the same or different and are respectively selected from hydrogen and C 1 -C 16 Alkyl radical, C 2 -C 4 Hydroxyalkyl radical, C 2 -C 4 An alkoxyethyl or benzyl group;
R 3 、R 4 together with the linking N, may also form:
application of cyclohexene carboxylate ammonium compounds represented by formula I in weed control is provided.
A herbicidal composition comprising as active ingredient a compound of formula I according to claim 1 and an agriculturally acceptable carrier, wherein the weight percentage of the active ingredient in the composition is between 1 and 99%.
A method for controlling weeds by applying a herbicidally effective amount of said herbicidal composition to the weeds or to a growth medium or locus of the weeds.
In the definitions given above for compounds of the general formula I, the terms used are generally defined as follows:
alkyl refers to straight or branched forms of alkane substituents such as methyl, ethyl, n-propyl, isopropyl, and the like. Cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopropylmethyl, methylcyclopropyl and the like. Haloalkyl refers to a group in which the alkyl group is substituted with one or more halogen atoms, such as chloroethyl, trifluoromethyl, and the like. Alkenyl refers to straight or branched chain forms of olefinic substituents containing carbon-carbon double bonds, such as vinyl, propenyl, allyl, 2-methylallyl, and the like. Haloalkenyl refers to a group in which an alkenyl group is substituted with one or more halogen atoms, such as 3-chloroallyl, 3-dichloroallyl, and the like. Alkynyl refers to straight or branched chain forms of alkyne substituents containing carbon-carbon triple bonds, such as ethynyl, propynyl, propargyl, 1-methylpropynyl, and the like. The alkoxy group means a group having an oxygen atom attached to the end of an alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, and the like. Halogen means fluorine, chlorine, bromine, iodine.
The compounds of the general formula I according to the invention can be prepared by the following processes, in which the radicals are as defined above.
When R is 1 、R 2 、R 3 、R 4 At least one of them is hydrogen (R is not set) 1 Hydrogen) is used:
general formula I a The compound can be prepared by reacting the compound of the general formula II with the compound of the general formula III in a suitable solvent at a temperature of between 10 ℃ below zero and the boiling point of the suitable solvent for 0.5 to 48 hours.
Suitable solvents are selected from dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, diethyl ether, tetrahydrofuran, dioxane, methanol, ethanol or isopropanol, etc.
The compounds of formula III are commercially available as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, and the like.
When R is 1 、R 2 、R 3 、R 4 When none of them is hydrogen:
in the formula: x represents a suitable leaving group such as chlorine, bromine, iodine or hydroxy, etc.
General formula I b The compound can be prepared by reacting the compound of the general formula II with the compound of the general formula IV in a proper solvent at the temperature of between 10 ℃ below zero and the boiling point of the proper solvent for 0.5 to 48 hours.
Suitable solvents are selected from dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, diethyl ether, tetrahydrofuran, dioxane, methanol, ethanol or isopropanol, etc.
The addition of suitable alkali substances is beneficial to the reaction. Suitable bases are selected from organic bases such as sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide, etc.; or an inorganic base such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate or sodium hydride, etc.
Compounds of formula IV are commercially available as tetramethyl ammonium bromide, tetrabutyl ammonium bromide, benzyltriethyl ammonium chloride or methyltris-butyl ammonium bromide.
The preparation of the compounds of formula II is as follows:
the compound of formula II can be prepared by reacting the compound of formula V with the compound VI in a suitable solvent at a temperature of-10 deg.C to the boiling point of the suitable solvent for 0.5-48 hours to obtain the product II.
Suitable solvents are selected from dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, formic acid, acetic acid, diethyl ether, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide, and the like.
Compound VI (3,4,5,6-tetrahydrophthalic anhydride, CAS No.: 2426-02-0) is commercially available.
The preparation of the compounds of formula V is as follows:
the compound of formula V can be prepared by reacting a compound of formula VII with a suitable reducing agent in a suitable solvent at a temperature of-78 deg.C to the boiling point of the suitable solvent for 0.5-96 hours.
The suitable solvent is one or a mixture of two or more of water, methanol, ethanol, isopropanol, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, diethyl ether, tetrahydrofuran, dioxane, formic acid, acetic acid, N-dimethylformamide or dimethyl sulfoxide.
Suitable reductant species are selected from reducing gases, such as hydrogen, and the like; or a metallic reducing agent such as metallic sodium, metallic potassium, reduced iron powder, reduced zinc powder, etc.; or metal organic complexes such as lithium aluminum hydride, sodium borohydride, sodium cyanoborohydride, and the like; or other reducing substances such as borane, hydrazine hydrate, sodium sulfide, ammonium polysulfide, stannous chloride, and the like.
The addition of suitable catalyst materials is beneficial to the reaction. Suitable catalysts are selected from platinum (Pt), palladium-carbon (Pd/C), raney nickel (Raney Ni), and the like.
The preparation of the compound of formula VII is as follows:
in the formula: l represents a suitable leaving group such as chloro, bromo, iodo, mesyloxy or p-toluenesulfonyloxy and the like.
The compound of formula VII may be prepared by reacting the compound VIII and the compound of formula IX in a suitable solvent at a temperature of from-10 ℃ to the boiling point of the suitable solvent for a period of from 0.5 to 48 hours.
The suitable solvent is one or a mixture of two or more of water, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide.
The addition of suitable alkaline substances favors the reaction. Suitable bases are selected from organic bases such as triethylamine, N-dimethylaniline, pyridine, sodium methoxide, sodium or potassium tert-butoxide, etc.; or an inorganic base such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate or sodium hydride, etc.
The addition of a suitable phase transfer catalyst material is advantageous for the reaction. Suitable phase transfer catalysts are selected from quaternary ammonium salts such as tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), benzyltrimethylammonium chloride (TMBAC), benzyltriethylammonium chloride (TEBAC), benzyltriethylammonium bromide (TEBAB), and the like; or crown ethers such as 18-crown-6, 15-crown-5, etc.
Compounds of formula IX are commercially available, e.g., methyl iodide, ethyl bromide, allyl bromide, propargyl bromide, 1, 3-trichloropropene, and the like.
For the specific preparation of compound VIII (CAS No.: 103361-67-7) reference is made to the procedures described in EP170191, J.Agri.food chem.,2009,57 (20): 9585-9592., J.Med.chem.,2015,58 (1): 222-236.
Some of the compounds of the present invention can be illustrated by, but are not limited to, the specific compounds listed in table 1, which lists the structure and physical properties of some of the compounds of formula I.
Table 1 structural and physical properties of some compounds of formula I
The compound of the general formula I has herbicidal activity and can be used for preventing and controlling various weeds in agriculture. Such as: can effectively control weeds when used after seedling. The cyclohexene carboxylate compound has excellent herbicidal activity. The technical solution of the invention therefore also includes the use of the compounds of the general formula I for controlling weeds.
The invention also comprises a weeding composition taking the compound shown in the general formula I as an active component. The weight percentage of the compound of the general formula I of the active component in the weeding composition is between 1 and 99 percent. The herbicidal composition also includes an agriculturally acceptable carrier.
The herbicidal compositions of the present invention may be applied in a variety of formulations. The compounds of the present invention are typically formulated to be more easily dispersed for use as herbicides by dissolving or dispersing the compounds in a carrier. For example: the chemical preparation can be prepared into wettable powder or missible oil and the like. Thus, in these compositions, at least one liquid or solid carrier is added, and it is generally necessary to add a suitable surfactant.
The present invention also provides an implementation method for controlling weeds, which comprises applying a herbicidally effective amount of the herbicidal composition of the present invention to the weeds or to the locus where the weeds grow or to the surface of a growth medium thereof. Preferably the effective dose is from 1 to 1000 grams per hectare, preferably the effective dose is from 10 to 500 grams per hectare. For certain applications, one or more additional herbicides may be added to the herbicidal compositions of the present invention, thereby providing additional advantages and benefits.
The compounds of the present invention may be used either alone or in combination with other known insecticides, fungicides, plant growth regulators or fertilizers, and the like, thereby providing additional advantages and effects.
It should be understood that various changes and modifications may be made within the scope of the invention as defined by the appended claims.
Detailed Description
The following synthetic examples, biological activity assay examples, are intended to further illustrate the invention, but are not intended to limit the invention.
Synthetic examples
Example 1 preparation of compound 85:
(1) Preparation of (E) -4- (3-chloroallyl) -7-fluoro-6-nitrobenzoxazin-3-one
To a 500 ml round bottom flask, 7-fluoro-6-nitrobenzoxazin-3-one (12.73 g, 0.060 mol) and potassium carbonate (9.95 g, 0.072 mol) were added and dissolved in 60 ml of N, N-dimethylformamide to form a suspension, which was heated to 80 ℃ and, after maintaining the reaction at this temperature for 30 minutes, (E) -1, 3-dichloropropene (8.00 g, 0.072 mol) was added dropwise thereto and the reaction was maintained at 80 ℃ for 4 hours. After stopping the reaction, it was naturally cooled to room temperature, poured into 200 ml of water, extracted with ethyl acetate (100 ml × 3), and the combined organic phases were washed with a saturated aqueous sodium chloride solution (50 ml × 3), dried over anhydrous magnesium sulfate, concentrated and column-chromatographed (eluent: ethyl acetate: petroleum ether = 1) to give 12.20 g of (E) -4- (3-chloroallyl) -7-fluoro-6-nitrobenzoxazin-3-one as a yellow solid with a yield of 71%.
(2) Preparation of (E) -6-amino-4- (3-chloroallyl) -7-fluorophenoxazin-3-one
To a 100 ml round-bottomed flask at room temperature were added (E) -4- (3-chloroallyl) -7-fluoro-6-nitrobenzoxazin-3-one (5.73 g, 0.020 mol), 50 ml of acetic acid and 10 ml of water, and to this was added reduced iron powder (3.35 g, 0.060 mol) in portions under ice-cooling, and the reaction was carried out at room temperature for 4 hours. After completion of the reaction, the reaction solution was poured into 200 ml of water, extracted with ethyl acetate (100 ml × 3), and the combined organic phases were washed with a saturated aqueous sodium chloride solution (50 ml × 3), dried over anhydrous magnesium sulfate, concentrated, and subjected to column chromatography (eluent: ethyl acetate: petroleum ether = 1) to obtain 4.95 g of (E) -6-amino-4- (3-chloroallyl) -7-fluorophenoxazin-3-one as a yellow solid in a yield of 96%.
(3) Preparation of (E) -2- ((4- (3-chloroallyl) -7-fluoro-3-oxo-3, 4-dihydrobenzoxazin-6-yl) carbamoyl) cyclohex-1-ene-1-carboxylic acid
A100 mL round-bottomed flask was charged with (E) -6-amino-4- (3-chloroallyl) -7-fluorophenoxazin-3-one (3.85 g, 0.015 mol) and 30 mL toluene at room temperature to form a solution, and 3,4,5, 6-tetrahydrophthalic anhydride (2.74 g, 0.018 mol) was allowed to react at room temperature for 4 hours, whereupon a large amount of yellow solid precipitated out of the system, which was filtered and air-dried to give 5.24 g of (E) -2- ((4- (3-chloroallyl) -7-fluoro-3-oxo-3, 4-dihydrobenzoxazin-6-yl) carbamoyl) cyclohex-1-ene-1-carboxylic acid as a yellow solid in 85% yield.
(4) Preparation of ammonium (E) -2- ((4- (3-chloroallyl) -7-fluoro-3-oxo-3, 4-dihydrobenzoxazin-6-yl) carbamoyl) cyclohex-1-ene-1-carboxylate (Compound 85)
A50 mL round-bottomed flask was charged with (E) -2- ((4- (3-chloroallyl) -7-fluoro-3-oxo-3, 4-dihydrobenzoxazin-6-yl) carbamoyl) cyclohex-1-ene-1-carboxylic acid (0.41 g, 1.0 mmol) and 10 mL ammonia at room temperature to form a suspension, which was allowed to react overnight at room temperature to become a clear solution. The reaction was stopped and the volatiles were evaporated under reduced pressure to give 0.40 g of compound 85 as a yellow solid in 93% yield.
Nuclear magnetic hydrogen spectroscopy data for compound 85 are as follows:
compound 85: 1 H NMR(600MHz,D 2 O)δ(ppm):7.48(d,1H),6.96(d,1H),6.40(d,1H),6.06(dt,1H),4.73(s,2H),4.58(d,2H),2.32(m,4H),1.69(m,4H)。
example 2 preparation of (E) -tetramethylammonium 2- ((4- (3-chloroallyl) -7-fluoro-3-oxo-3, 4-dihydrobenzoxazin-6-yl) carbamoyl) cyclohex-1-ene-1-carboxylate (Compound 104):
to a 50 ml round-bottom flask at room temperature were added (E) -2- ((4- (3-chloroallyl) -7-fluoro-3-oxo-3, 4-dihydrobenzoxazin-6-yl) carbamoyl) cyclohex-1-ene-1-carboxylic acid (0.41 g, 1.0 mmol) and 20 ml of methanol to form a solution, and at room temperature were added sodium hydroxide (0.04 g, 1.0 mmol) and tetramethylammonium bromide (0.15 g, 1.0 mmol) in this order, and the reaction was maintained at room temperature for 4 hours. Insoluble matter was removed by filtration, and the volatile matter in the filtrate was evaporated under reduced pressure to give 0.32 g of compound 104 as a brown solid in a yield of 63%.
Nuclear magnetic hydrogen spectroscopy data for compound 104 are as follows:
compound 104: 1 H NMR(600MHz,D 2 O)δ(ppm):7.49(d,1H),6.96(d,1H),6.40(d,1H),6.04-6.08(m,1H),4.73(s,2H),4.57(d,2H),3.20(s,12H),2.32(m,4H),1.69(m,4H)。
example 3 preparation of compound 111:
(1) Preparation of 4- (3, 3-dichloroallyl) -7-fluoro-6-nitrobenzoxazin-3-one
To a 500 ml round bottom flask, 7-fluoro-6-nitrobenzoxazin-3-one (12.73 g, 0.060 mol) and potassium carbonate (9.95 g, 0.072 mol) were added and dissolved in 60 ml of N, N-dimethylformamide to form a suspension, which was heated to 80 ℃ and, after maintaining the reaction at this temperature for 30 minutes, 1, 3-trichloropropene (10.47 g, 0.072 mol) was added dropwise thereto and the reaction was maintained at 80 ℃ for 4 hours. After the reaction was stopped, it was naturally cooled to room temperature, poured into 200 ml of water, extracted with ethyl acetate (100 ml × 3), and the combined organic phases were washed with a saturated aqueous sodium chloride solution (50 ml × 3), dried over anhydrous magnesium sulfate, concentrated, and subjected to column chromatography (eluent: ethyl acetate: petroleum ether = 1) to obtain 13.67 g of 4- (3, 3-dichloroallyl) -7-fluoro-6-nitrobenzoxazin-3-one as a yellow solid with a yield of 71%.
(2) Preparation of 6-amino-4- (3, 3-dichloroallyl) -7-fluorophenoxazin-3-one
To a 100 ml round-bottomed flask at room temperature were added 4- (3, 3-dichloroallyl) -7-fluoro-6-nitrobenzoxazin-3-one (6.42 g, 0.020 mol), 50 ml of acetic acid and 10 ml of water, and to this was added reduced iron powder (3.35 g, 0.060 mol) in portions under ice bath, and the reaction was carried out at room temperature for 4 hours. After completion of the reaction, the reaction solution was poured into 200 ml of water, extracted with ethyl acetate (100 ml × 3), and the combined organic phases were washed with a saturated aqueous sodium chloride solution (50 ml × 3), dried over anhydrous magnesium sulfate, concentrated, and subjected to column chromatography (eluent: ethyl acetate: petroleum ether = 1) to obtain 5.59 g of 6-amino-4- (3, 3-dichloroallyl) -7-fluorophenoxazin-3-one as a yellow solid in a yield of 96%.
(3) Preparation of 2- ((4- (3, 3-dichloroallyl) -7-fluoro-3-oxo-3, 4-dihydrobenzoxazin-6-yl) carbamoyl) cyclohex-1-ene-1-carboxylic acid
6-amino-4- (3, 3-dichloroallyl) -7-fluorophenoxazin-3-one (4.36 g, 0.015 mol) and 30 ml of toluene were added to a 100 ml round bottom flask at room temperature to form a solution, and 3,4,5, 6-tetrahydrophthalic anhydride (2.74 g, 0.018 mol) was further reacted at room temperature for 4 hours to precipitate a large amount of yellow solid in the system, which was then filtered and dried to obtain 5.65 g of 2- ((4- (3, 3-dichloroallyl) -7-fluoro-3-oxo-3, 4-dihydrobenzoxazin-6-yl) carbamoyl) cyclohex-1-ene-1-carboxylic acid as a pale yellow solid in 85% yield.
(4) Preparation of ammonium 2- ((4- (3, 3-dichloroallyl) -7-fluoro-3-oxo-3, 4-dihydrobenzoxazin-6-yl) carbamoyl) cyclohex-1-ene-1-carboxylate (Compound 111)
To a 50 ml round bottom flask at room temperature was added 2- ((4- (3, 3-dichloroallyl) -7-fluoro-3-oxo-3, 4-dihydrobenzoxazin-6-yl) carbamoyl) cyclohex-1-ene-1-carboxylic acid (0.44 g, 1.0 mmol) and 10 ml ammonia to form a suspension, which was allowed to react overnight at room temperature to become a clear solution. The reaction was stopped and the volatiles were evaporated under reduced pressure to give 0.43 g of compound 111 as a white solid in 93% yield.
1 H NMR(600MHz,D 2 O)δ(ppm):7.43(d,1H),6.98(d,1H),6.07(t,1H),4.73(s,2H),4.70(d,2H),2.33(m,4H),1.69(m,4H)。
Example 4 preparation of tetramethylammonium 2- ((4- (3, 3-dichloroallyl) -7-fluoro-3-oxo-3, 4-dihydrobenzoxazin-6-yl) carbamoyl) cyclohex-1-ene-1-carboxylate (compound 130):
to a 50 ml round-bottom flask at room temperature were added 2- ((4- (3, 3-dichloroallyl) -7-fluoro-3-oxo-3, 4-dihydrobenzoxazin-6-yl) carbamoyl) cyclohex-1-ene-1-carboxylic acid (0.44 g, 1.0 mmol) and 20 ml of methanol to form a solution, and at room temperature were added sodium hydroxide (0.04 g, 1.0 mmol) and tetramethylammonium bromide (0.15 g, 1.0 mmol) in this order, and the reaction was maintained at room temperature for 4 hours. Insoluble matter was removed by filtration, and the volatile matter in the filtrate was evaporated under reduced pressure to give 0.39 g of compound 130 as a yellow solid in a yield of 76%.
1 H NMR(600MHz,D 2 O)δ(ppm):7.43(d,1H),6.96(d,1H),6.05(t,1H),4.71(s,2H),4.68(d,2H),3.19(s,12H),2.32(m,4H),1.69(m,4H)。
The other compounds in table 1 can be synthesized by methods similar to the above examples, and the nuclear magnetic hydrogen spectrum data of some compounds are as follows:
the nuclear magnetic hydrogen spectrum data of part of the compounds are as follows:
compound 10: 1 H NMR(600MHz,D 2 O)δ(ppm):7.48(d,1H),6.95(d,1H),4.69(s,2H),3.95(q,2H),2.33(m,4H),1.69(m,4H),1.24(t,3H)。
compound 11: 1 H NMR(600MHz,D 2 O)δ(ppm):7.48(d,1H),6.95(d,1H),4.69(s,2H),3.95(q,2H),2.60(s,3H),2.33(m,4H),1.69(m,4H),1.25(t,3H)。
compound 18: 1 H NMR(300MHz,D 2 O)δ(ppm):7.45(d,1H),6.86(d,1H),4.61(s,2H),3.87(q,2H),3.42(hept.,2H),2.27(m,4H),1.63(m,4H),1.23(d,12H),1.18(t,3H)。
compound 23: 1 H NMR(600MHz,D 2 O)δ(ppm):7.54(d,1H),7.00(d,1H),4.74(s,2H),4.64(dt,2H),4.32(dt,2H),2.34(m,4H),1.70(m,4H)。
compound 25: 1 H NMR(600MHz,D 2 O)δ(ppm):7.53(d,1H),6.98(d,1H),4.74(s,2H),4.72(dt,2H),4.32(dt,2H),3.05(q,2H),2.33(m,4H),1.69(m,4H),1.28(t,3H)。
compound 42: 1 H NMR(600MHz,D 2 O)δ(ppm):7.53(d,1H),6.97(d,1H),4.76(dt,2H),4.72(s,2H),4.31(dt,2H),3.19(s,12H),2.32(m,4H),1.68(m,4H)。
compound 46: 1 H NMR(600MHz,D 2 O)δ(ppm):7.53(d,1H),6.98(d,1H),4.76(dt,2H),4.73(s,2H),4.31(dt,2H),3.26(q,8H),2.32(m,4H),1.69(m,4H),1.26(t,12H)。
compound 60: 1 H NMR(600MHz,D 2 O)δ(ppm):7.47(d,1H),6.96(d,1H),5.91-5.96(m,1H),5.27(d,1H),5.21(d,1H),4.76(s,2H),4.55(d,2H),2.60(s,3H),2.32(m,4H),1.68(m,4H)。
compound 61: 1 H NMR(600MHz,D 2 O)δ(ppm):7.48(d,1H),6.94(d,1H),5.90-5.95(m,1H),5.27(d,1H),5.21(d,1H),4.74(s,2H),4.53(d,2H),3.04(q,2H),2.31(m,4H),1.68(m,4H),1.27(t,3H)。
compound 76: 1 H NMR(600MHz,D 2 O)δ(ppm):7.48(d,1H),6.95(d,1H),5.95-5.90(m,1H),5.27(d,1H),5.20(d,1H),4.75(s,2H),4.54(d,2H),3.21(q,6H),2.31(m,2H),1.68(m,4H),1.29(t,9H)。
compound 80: 1 H NMR(600MHz,D 2 O)δ(ppm):7.48(d,1H),6.94(d,1H),5.89-5.95(m,1H),5.26(d,1H),5.20(d,1H),4.74(s,2H),4.52(s,2H),4.05(m,2H),3.51(m,2H),3.20(s,9H),2.31(m,4H),1.68(s,4H)。
compound 137: 1 H NMR(600MHz,D 2 O)δ(ppm):7.55(d,1H),6.88(d,1H),4.63(s,4H),2.61(t,1H),2.22(m,4H),1.59(m,4H)。
compound 138: 1 H NMR(300MHz,D 2 O)δ(ppm):7.57(d,1H),6.91(d,1H),4.66(s,4H),2.63(t,1H),2.52(s,3H),2.25(m,4H),1.62(m,4H)。
compound 139: 1 H NMR(600MHz,D 2 O)δ(ppm):7.66(d,1H),6.99(d,1H),4.74(s,4H),3.05(q,2H),2.33(m,4H),1.69(m,4H),1.27(t,3H)。
compound 140: 1 H NMR(600MHz,D 2 O)δ(ppm):7.66(d,1H),6.97(d,1H),4.72(s,4H),2.95(t,2H),2.32(m,4H),1.69(m,4H),1.66(m,2H),0.97(t,3H)。
compound 141: 1 H NMR(600MHz,D 2 O)δ(ppm):7.67(d,1H),6.96(d,1H),4.71(s,4H),3.49(hept.,1H),2.73(s,1H),2.33(m,4H),1.69(m,4H),1.29(d,6H)。
compound 142: 1 H NMR(300MHz,D 2 O)δ(ppm):7.52(d,1H),6.84(d,1H),4.61(s,4H),2.87(t,2H),2.58(s,1H),2.21(m,4H),1.57(m,6H),1.27(m,2H),0.81(t,3H)。
compound 143: 1 H NMR(600MHz,D 2 O)δ(ppm):7.66(d,1H),6.98(d,1H),4.73(s,4H),2.83(d,2H),2.32(m,4H),1.94(m,1H),1.69(m,4H),0.98(d,6H)。
compound 144: 1 H NMR(300MHz,D 2 O)δ(ppm):7.53(d,1H),6.85(d,1H),4.61(s,4H),3.17(m,1H),2.58(s,1H),2.21(m,4H),1.57(m,4H),1.50(m,2H),1.16(d,3H),0.85(t,3H)。
compound 145: 1 H NMR(600MHz,D 2 O)δ(ppm):7.67(d,1H),7.50(m,5H),7.00(d,1H),4.75(s,4H),4.19(s,2H),2.35(m,4H),1.71(m,4H)。
compound 147: 1 H NMR(600MHz,D 2 O)δ(ppm):7.68(d,1H),6.96(d,1H),4.72(s,4H),3.69(m,2H),3.41(s,3H),3.19(m,2H),2.33(m,4H),1.69(m,4H)。
compound 158: 1 H NMR(600MHz,D 2 O)δ(ppm):7.67(d,1H),6.98(d,1H),4.73(s,4H),3.20(s,12H),2.33(m,4H),1.69(m,4H)。
compound 161: 1 H NMR(600MHz,D 2 O)δ(ppm):7.68(d,1H),6.97(d,1H),4.72(s,4H),3.23(m,6H),2.98(s,3H),2.33(m,4H),1.68-1.72(m,10H),1.34-1.40(m,6H),0.95(t,9H)。
compound 170: 1 H NMR(600MHz,D 2 O)δ(ppm):7.60(d,1H),6.98(d,1H),5.35(d,2H),4.74(s,2H),3.68(q,2H),2.32(m,4H),1.68(m,4H),1.22(t,3H)。
compound 189: 1 H NMR(600MHz,D 2 O)δ(ppm):7.62(d,1H),6.98(d,1H),5.37(s,2H),4.73(s,2H),3.70(q,2H),3.20(s,12H),2.32(m,4H),1.69(m,4H),1.22(t,3H)。
examples of measurement of biological Activity
Example 3 determination of herbicidal Activity
The compound of the invention is preliminarily tested by adopting a stem and leaf treatment mode in a pot culture method sensitive to an action mechanism, and the test method comprises the following steps:
sowing seeds of broadleaf weeds (zinnia elegans and abutilon) or gramineae weeds (green bristlegrass and barnyard grass) in a paper cup with the diameter of 7cm and containing nutrient soil respectively, covering soil for 1cm after sowing, compacting, spraying water, culturing in a greenhouse according to a conventional method, and spraying stems and leaves after 2-3 leaf periods of the broadleaf weeds.
Dissolving the crude drug with acetoneAnd then, standing tap water by 1 per mill of Tween 80 according to test requirements to prepare the liquid to be tested with the required concentration. The spray treatment (spray pressure 1.95 kg/cm) was carried out on a crawler-type crop sprayer (Engineer Research Ltd. In England) at the experimental design dose 2 The amount of the liquid spray is 500L/hm 2 And the track speed is 1.48 km/h). The experiment was set to 2 replicates.
After being treated, the test material is placed in an operation hall, after the liquid medicine is naturally dried in the shade, the test material is placed in a greenhouse for management according to a conventional method, the reaction condition of weeds to the agent is observed and recorded, the control effect of the test agent to the weeds is regularly observed and visually, the control effect is represented by 0-100, and the '0' level represents no control effect and the '100' level represents 100% control effect.
Test results show that the compound of the general formula I has higher control effect on broad-leaved weeds generally. Some of the test results are as follows:
in some of the tested compounds, the following compounds were administered at a dose of 75g a.i./hm, according to the above test method 2 The prevention effect on the zinnia elegans is better (the prevention effect is more than or equal to 95 percent after seedling): 10. 11, 12, 13, 14, 15, 16, 18, 20, 23, 24, 25, 28, 42, 43, 44, 46, 48, 59, 60, 61, 62, 63, 64, 76, 78, 79, 80, 82, 84, 85, 90, 104, 112, 114, 116, 130, 134, 137, 138, 139, 140, 141, 142, 143, 144, 145, 147, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 170, 171, 173, 189, 190, 191, 193, 194, 195.
According to the test method, a part of the compounds of the invention and a known compound KC are selected to carry out parallel determination on the herbicidal activity of the zinnia (the control compounds are all self-made, and the structure is consistent with that described in the existing open literature after the hydrogen spectrum confirmation of nuclear magnetic resonance), and the test results are shown in Table 2.
Table 2: activity of some Compounds of formula I on zinnia (post-emergence)
Note: "-" indicates not measured.
In some of the compounds tested according to the above test method, the following compounds were administered at a dose of 75g a.i./hm 2 The prevention effect on abutilon is better (the prevention effect is more than or equal to 95 percent after seedling): 10. 11, 12, 13, 14, 15, 16, 18, 20, 23, 24, 25, 26, 28, 43, 46, 48, 59, 60, 61, 62, 63, 64, 76, 82, 84, 85, 112, 113, 116, 137, 138, 139, 140, 141, 142, 143, 144, 145, 147, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 170, 171, 172, 173, 175, 190, 193, 194.
According to the above test method, compounds 191, 192, 193 and 229 of the present invention were selected and used together with known compound KC to conduct parallel determination of herbicidal activity against abutilon (all the control compounds were made by oneself, and the structure was confirmed by nmr hydrogen spectrum to be consistent with that described in the prior publication), and the test results are shown in table 3.
Table 3: activity of some compounds of formula I against Abutilon (post-emergence)
Note: "-" indicates not measured.
The control effect on grassy weeds is as follows:
in some of the tested compounds, the following compounds were administered at a dose of 75g a.i./hm, according to the above test method 2 The effect of the composition on green bristlegrass is better (the effect is more than or equal to 80 percent after seedling): 10. 12, 141, 145, 147, 150, 154, 157, 194.
In some of the compounds tested according to the above test method, the following compounds were administered at a dose of 75g a.i./hm 2 The effect of preventing barnyard grass is better (the prevention effect is more than or equal to 80 percent after seedling): 139. 149 and 157.
Claims (4)
1. An ammonium cyclohexenocarboxylate compound, characterized by the following general formula I:
I
in the formula:
a is selected from CH 2 CH 2 F or CH 2 OCH 2 CH 3 ；
R 1 Selected from hydrogen or methyl;
R 2 selected from hydrogen or n-butyl;
R 3 selected from hydrogen, methyl, isopropyl or butyl;
R 4 selected from hydrogen, methyl, ethyl, isopropyl, butyl or CH 2 CH 2 OH。
2. Use of the ammonium cyclohexenecarboxylate compounds of formula I according to claim 1 for controlling weeds.
3. A herbicidal composition characterized by: a composition comprising as active ingredient a compound of formula I according to claim 1 and an agriculturally acceptable carrier, wherein the weight percentage of the active ingredient in the composition is between 1 and 99%.
4. A method of controlling weeds with the herbicidal composition according to claim 3, wherein: applying a herbicidally effective amount of said herbicidal composition to the weeds or to a growth medium or locus of the weeds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711221343.0A CN109836393B (en) | 2017-11-29 | 2017-11-29 | Cyclohexene carboxylate compound and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711221343.0A CN109836393B (en) | 2017-11-29 | 2017-11-29 | Cyclohexene carboxylate compound and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109836393A CN109836393A (en) | 2019-06-04 |
| CN109836393B true CN109836393B (en) | 2022-11-15 |
Family
ID=66881640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711221343.0A Active CN109836393B (en) | 2017-11-29 | 2017-11-29 | Cyclohexene carboxylate compound and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109836393B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4844425A (en) * | 1971-10-14 | 1973-06-26 | ||
| US4003926A (en) * | 1975-01-30 | 1977-01-18 | E. I. Du Pont De Nemours And Company | Herbicidal 2-arylaminocarbonyl-1-cyclohexene-1-carboxylic acids and salts thereof |
| US5468719A (en) * | 1992-02-26 | 1995-11-21 | Central Glass Company, Limited | N-acyl-n-phenyltetrahydrophthalamic acid derivatives, methods of producing same, and herbicides containing same as effective components |
| US5817603A (en) * | 1992-04-25 | 1998-10-06 | Basf Aktiengesellschaft | Substituted cyclohexene-1,2-dicarboxylic acid derivatives and intermediates for their preparation |
| CN105646328A (en) * | 2014-12-02 | 2016-06-08 | 沈阳中化农药化工研发有限公司 | Quaternary ammonium salt compound and application thereof |
-
2017
- 2017-11-29 CN CN201711221343.0A patent/CN109836393B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4844425A (en) * | 1971-10-14 | 1973-06-26 | ||
| US4003926A (en) * | 1975-01-30 | 1977-01-18 | E. I. Du Pont De Nemours And Company | Herbicidal 2-arylaminocarbonyl-1-cyclohexene-1-carboxylic acids and salts thereof |
| US5468719A (en) * | 1992-02-26 | 1995-11-21 | Central Glass Company, Limited | N-acyl-n-phenyltetrahydrophthalamic acid derivatives, methods of producing same, and herbicides containing same as effective components |
| US5817603A (en) * | 1992-04-25 | 1998-10-06 | Basf Aktiengesellschaft | Substituted cyclohexene-1,2-dicarboxylic acid derivatives and intermediates for their preparation |
| CN105646328A (en) * | 2014-12-02 | 2016-06-08 | 沈阳中化农药化工研发有限公司 | Quaternary ammonium salt compound and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109836393A (en) | 2019-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5089581B2 (en) | 1,2-Benzisothiazole derivatives and plant disease control agents for agriculture and horticulture | |
| CN101279950B (en) | 2-pyrimindinyloxy (pyrimindinylthio) benzoxy acetamide compound and application thereof | |
| JPS60155164A (en) | Herbicidal 3-isoxazolidinones | |
| MX2010014311A (en) | 5-heterocyclylalkyl-3-hydroxy-2-phenylcyclopent-2-enones as herbicides. | |
| JPWO2015020156A1 (en) | Substituted pyrazolylpyrazole derivatives and their use as herbicides | |
| JP2004508309A (en) | 5-benzyloxymethyl-1,2-isoxazoline derivatives having herbicidal activity | |
| WO2011160568A1 (en) | 3-methoxy pyrazole amide compounds and uses thereof | |
| CN109836393B (en) | Cyclohexene carboxylate compound and application thereof | |
| CN112390727B (en) | Oxime carboxylate compound and application thereof | |
| US20170001961A1 (en) | Oxime ether acetate compound, preparation method therefor and weeding application thereof | |
| CN109574956B (en) | Thiadiazole amide compound and application thereof | |
| AU4762593A (en) | Herbicidal quinolinyloxadiazoles | |
| JPH0645617B2 (en) | Chloroacetamide derivative | |
| CN101407490B (en) | 3-benzoxy acrylic ester compounds and uses thereof | |
| EP3719011B1 (en) | Pyrazole amide compound having pesticidal activity and use thereof | |
| CN112939953B (en) | Benzamide compound and application thereof as herbicide | |
| CN103833744B (en) | 1 ethyl pyrazolyl acrylonitrile compound and application thereof | |
| JPH11158131A (en) | Arylacetamide derivative and antimicrobial agent for agriculture and horticulture | |
| CN112741095B (en) | Application of pyridazinone isoxazole methyl sulfide compound as bactericide | |
| JP2993839B2 (en) | 3-pyrrolin-2-one derivative, and herbicide characterized by containing the same | |
| JPWO2006004215A1 (en) | Benzoxazole compounds | |
| CN108610283B (en) | Secondary amine compound and preparation and application thereof | |
| JP2561524B2 (en) | Pyrimidine derivatives and herbicides | |
| CN116120235A (en) | Phenoxyacetyl pyrazole compound and application thereof | |
| CN112939958A (en) | Condensed ring acyl compound and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |