CN108727258B - Phenylpyridine derivative, application thereof and herbicide - Google Patents
Phenylpyridine derivative, application thereof and herbicide Download PDFInfo
- Publication number
- CN108727258B CN108727258B CN201710273955.8A CN201710273955A CN108727258B CN 108727258 B CN108727258 B CN 108727258B CN 201710273955 A CN201710273955 A CN 201710273955A CN 108727258 B CN108727258 B CN 108727258B
- Authority
- CN
- China
- Prior art keywords
- compound
- herbicide
- formula
- cooch
- phenylpyridine
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention relates to the field of pesticides, and discloses a phenylpyridine derivative, application thereof and a herbicide, wherein the phenylpyridine derivative has a structure shown in a formula (1), and R in the formula (1)1Is selected from C1‑6Alkyl groups of (a); r2And R3Each independently selected from H, halogen, C1‑4Alkyl of (a), -COOR1and-COR4At least one of, and R4Is selected from C1‑4Alkyl groups of (a); x is H or halogen. The phenylpyridine derivative provided by the invention has obvious excellent safety for field crops on the premise of ensuring excellent control effect on weeds in the field crops. Particularly, the phenylpyridine derivative provided by the invention has obviously better safety for vegetable crops such as eggplant, hot pepper and the like than the medicament provided by the prior art.
Description
Technical Field
The invention relates to the field of pesticides, in particular to a phenylpyridine derivative, application thereof in preventing and controlling field crop weeds, and a herbicide.
Background
A number of picolinic acids and their herbicidal properties have been described in the art. For example, 4-amino-3, 4, 5-trichloropicolinic acid derivatives and their use as plant growth regulators and herbicides are disclosed in US 3285925. US3325272 discloses 4-amino-3, 5-dichloropicolinic acid derivatives and their use as plant growth regulators and herbicides.
And there is also a wealth of prior art disclosing that certain 6-aryl or heteroaryl-4-amino-picolinic acids and their derivatives are effective herbicides with broad spectrum weed control and excellent crop selectivity against woody, grassy and sedge species and broad-leaved trees.
However, the prior art provides 6-aryl or heteroaryl-4-amino-picolinic acid and derivatives thereof which have the disadvantage of being not high in safety when used for controlling field crops, in particular vegetable crops such as eggplants, hot peppers and the like.
Therefore, there is a need for a novel herbicide which has an excellent weed control effect and is highly safe when used for controlling field crops, particularly vegetable crops such as eggplant, pepper and the like.
Disclosure of Invention
The invention aims to overcome the defect of low safety of phenylpyridine derivatives provided by the prior art when the phenylpyridine derivatives are used for preventing and controlling field crops, particularly vegetable crops such as eggplants, hot peppers and the like, and provide a novel phenylpyridine derivative with excellent safety for the field crops on the premise of ensuring better weed prevention and control effects.
In order to achieve the above object, the present invention provides, in a first aspect, a phenylpyridine derivative having a structure represented by formula (1),
wherein, in the formula (1), R1Is selected from C1-6Alkyl groups of (a);
R2and R3Each independently selected from H, halogen, C1-4Alkyl of (a), -COOR1and-COR4At least one of, and R4Is selected from C1-4Alkyl groups of (a);
x is H or halogen.
In a second aspect, the present invention provides a process for preparing a phenylpyridine derivative, the process being selected from any one of the following modes;
mode 1:
the derivative has a structure shown in a formula (1), wherein in the formula (1), R1Is selected from C1-6Alkyl groups of (a); r2And R3Is H; x is H or halogen;
the method comprises the following steps: reacting a compound represented by the formula (2) with CH in the presence of lithium bis (trimethylsilyl) amide (LiHMDS) and a protective gas3(CH2)nCOOR1Carrying out a first contact reaction, wherein N is 0 or an integer more than or equal to 1, and optionally reacting a product obtained after the first contact reaction with N-chlorosuccinimide or N-bromosuccinimide;
mode 2:
the derivative has a structure shown in a formula (1), wherein in the formula (1), R1Is selected from C1-6Alkyl groups of (a); r2And R3The same and all are halogen; x is H or halogen; the method comprises the following steps:
(1) preparing a compound represented by formula (1-1) by the method described in mode 1;
(2) carrying out a second contact reaction on the compound shown in the formula (1-1) obtained in the step (1) and carbon tetrachloride in the presence of N-chlorosuccinimide or N-bromosuccinimide;
mode 3:
the derivative has a structure shown in a formula (1), wherein in the formula (1), R1Is selected from C1-6Alkyl groups of (a); r2is-COOR1；R3Is H; x is H or halogen; the method comprises the following steps:
(1) carrying out a third contact reaction on the compound shown in the formula (2) and dibenzothiazyl disulfide in the presence of triethylamine and triethyl phosphite to obtain a compound shown in a formula (3);
(2) in the presence of sodium hydride, carrying out fourth contact reaction on the compound shown in the formula (3) obtained in the step (1) and dialkyl malonate, wherein alkyl in the dialkyl malonate is C1-6Alkyl group of (1).
In a third aspect, the present invention provides the use of the phenylpyridine derivative of the first aspect and/or the phenylpyridine derivative produced by the method of the second aspect for controlling weeds in crops in the field.
In a fourth aspect, the present invention provides a herbicide, which comprises an active ingredient and an adjuvant, wherein the active ingredient comprises at least one of the phenylpyridine derivatives described in the first aspect of the present invention and the phenylpyridine derivatives prepared by the method described in the second aspect of the present invention.
The phenylpyridine derivative provided by the invention has obvious excellent safety for field crops on the premise of ensuring excellent control effect on weeds in the field crops.
Particularly, the phenylpyridine derivative provided by the invention has obviously better safety for vegetable crops such as eggplant, hot pepper and the like than the medicament provided by the prior art.
The method for preparing the phenylpyridine derivative is simple and low in cost.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a phenylpyridine derivative having a structure represented by formula (1),
wherein, in the formula (1), R1Is selected from C1-6Alkyl groups of (a);
R2and R3Each independently selected from H, halogen, C1-4Alkyl of (a), -COOR1and-COR4At least one of, and R4Is selected from C1-4Alkyl groups of (a);
x is H or halogen.
Said "R" is1Is selected from C1-6Alkyl of (2) represents R1Has a total number of carbon atoms of 1 to 6, and the alkyl group may be a straight or branched alkyl or cycloalkyl group, C1-6The alkyl group of (b) may be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, an isopentyl group, a cyclopentyl group, a n-hexyl group or a cyclohexyl group.
The "halogen" includes fluorine, chlorine, bromine or iodine.
Said "C1-4Alkyl of (2) represents R2And R3Each independently of the other is 1 to 4, and the alkyl group may be a straight or branched alkyl group or a cycloalkyl group, C1-4The alkyl group of (a) may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
said-COOR1"means: r2And R3Each independently may be-COOR1", and R1Is selected from C1-6Alkyl group of (1).
According to a preferred embodiment, in formula (1),
R1is selected from C1-4Alkyl groups of (a);
R2and R3Each independently selected from H, chloro, bromo, methyl, ethyl, isopropyl, -COOR1and-COR4At least one of, and R4Selected from methyl, ethyl and isopropyl;
x is H or F.
According to another preferred embodiment, the phenylpyridine derivative of the present invention is at least one of the following compounds:
compound 1A: r1is-CH3；R2is-COOCH3；R3is-H; x is H;
compound 2A: r1is-CH2CH3；R2is-H; r3is-H; x is H;
compound 3A: r1is-CH2CH3；R2is-CH3；R3is-H; x is H;
compound 4A: r1is-CH3；R2is-CH3；R3is-H; x is H;
compound 5A: r1is-CH3；R2is-Br; r3is-H; x is H;
compound 6A: r1is-CH2CH3；R2is-CH3；R3is-CH3(ii) a X is H;
compound 7A: r1is-CH3；R2is-Cl; r3is-Cl; x is H;
compound 8A: r1is-CH3；R2is-H; r3is-H; x is H;
compound 9A: r1is-CH2CH3；R2is-CH2CH3；R3is-H; x is H;
compound 10A: r1is-CH2CH3；R2is-COOCH2CH3；R3is-H; x is H;
compound 11A: r1is-CH2CH2CH2CH3；R2is-COOCH2CH2CH2CH3；R3is-H; x is H;
compound 12A: r1is-CH (CH)3)2；R2is-COOCH (CH)3)2；R3is-H; x is H;
compound 1B: r1is-CH3；R2is-COOCH3；R3is-H; x is F.
In a second aspect, the present invention provides a process for the preparation of a phenylpyridine derivative selected from any one of the following embodiments;
detailed description of the preferred embodiment 1：
A process for producing a phenylpyridine derivative having a structure represented by formula (1), wherein R in formula (1)1Is selected from C1-6Alkyl groups of (a); r2And R3Is H; x is H or halogen;
the method comprises the following steps: reacting a compound represented by the formula (2) with CH in the presence of lithium bis (trimethylsilyl) amide (LiHMDS) and a protective gas3(CH2)nCOOR1Carrying out a first contact reaction, wherein N is 0 or an integer more than or equal to 1, and optionally reacting the product obtained after the first contact reaction with N-chlorosuccinimide or N-bromosuccinimide.
Preferably, the first contact reaction is carried out in the presence of at least one solvent selected from the group consisting of tetrahydrofuran, acetonitrile and isopropyl ether.
Preferably, the conditions of the first contact reaction include: the temperature is 60 ℃ below zero to 4 ℃ below zero, and the time is 5-120 min.
In embodiment 1, the method may further comprise post-treating the product obtained after the first contact reaction, for example, adding water and ethyl acetate to extract, and drying and concentrating the organic phase.
Detailed description of the preferred embodiment 2：
A process for producing a phenylpyridine derivative having a structure represented by formula (1), wherein R in formula (1)1Is selected from C1-6Alkyl groups of (a); r2And R3The same and all are halogen; x is H or halogen; the method comprises the following steps:
(1) preparing formula (1-1) using the procedure described in embodiment 1;
(2) and (2) carrying out a second contact reaction on the compound shown in the formula (1-1) obtained in the step (1) and carbon tetrachloride in the presence of N-chlorosuccinimide (NCS) or N-bromosuccinimide (NBS).
Preferably, the conditions of the second contact reaction include: and reacting for 2-24 h under the reflux condition.
In embodiment 2, the method may further comprise post-treating the product obtained after the second contact reaction, for example, adding water and carbon tetrachloride for extraction, and drying the organic phase.
Detailed description of preferred embodiments 3：
A process for producing a phenylpyridine derivative having a structure represented by formula (1), wherein R in formula (1)1Is selected from C1-6Alkyl groups of (a); r2is-COOR1；R3Is H; x is H or halogen; the method comprises the following steps:
(1) carrying out a third contact reaction on the compound shown in the formula (2) and dibenzothiazyl disulfide in the presence of triethylamine and triethyl phosphite to obtain a compound shown in a formula (3);
(2) in the presence of sodium hydride, carrying out fourth contact reaction on the compound shown in the formula (3) obtained in the step (1) and dialkyl malonate, wherein alkyl in the dialkyl malonate is C1-6Alkyl group of (1).
Preferably, the third contact reaction is carried out in the presence of at least one solvent selected from acetonitrile and isopropyl ether.
Preferably, the conditions of the third contact reaction include: the temperature is 5-45 ℃ and the time is 0.5-8 h.
Preferably, the fourth contact reaction is carried out in the presence of at least one solvent selected from the group consisting of tetrahydrofuran, acetonitrile and isopropyl ether.
Preferably, the conditions of the fourth contact reaction include: the temperature is 5-45 ℃ and the time is 0.2-5 h.
In embodiment 3, the method may further include post-treating the product obtained after the fourth contact reaction, for example, adding water and ethyl acetate to perform extraction, and drying the organic phase.
The protective gas in the present invention may be, for example, an inert gas such as nitrogen or argon.
In the foregoing embodiments 1 to 3 of the present invention, there is no particular requirement on the ratio of the amounts of the substances, and those skilled in the art can determine the appropriate ratio of the amounts of the substances according to the structure of the target compound and the conventional technical means in the field, and the examples of the present invention exemplify the specific synthetic methods of some compounds, and those skilled in the art should not be construed as limiting the scope of the present invention.
Other phenylpyridine derivatives not specifically listed in the present invention can be prepared by one skilled in the art by changing the starting materials according to the specific embodiments provided above, and the present invention is not described herein again.
In a third aspect, the invention provides the application of the phenylpyridine derivative in the first aspect and/or the phenylpyridine derivative prepared by the method in the second aspect in controlling weeds in field crops.
In the aforementioned application of the present invention, the field crop is at least one of corn, wheat, rice, eggplant and pepper.
In the aforementioned use of the present invention, the weeds include at least one of abutilon, amaranthus retroflexus, echinochloa crusgalli, chenopodium album and setaria viridis.
The inventor of the present invention found in research that the phenylpyridine derivative provided by the present invention has the advantage of having herbicidal activity comparable to or even better than that of the prior art agents when used for controlling weeds such as piemarker, amaranthus retroflexus, cockspur grass, quinoa and green bristlegrass in field crops such as corn, wheat, rice, eggplant and hot pepper, and particularly, the phenylpyridine derivative provided by the present invention has safety on field crops such as corn, wheat, rice, eggplant and hot pepper generally significantly higher than that of the prior art agents.
In a fourth aspect, the present invention provides a herbicide, which comprises an active ingredient and an adjuvant, wherein the active ingredient comprises at least one of the phenylpyridine derivatives described in the first aspect of the present invention and the phenylpyridine derivatives prepared by the method described in the second aspect of the present invention.
Preferably, the content of the active ingredient is 10-100 wt%; more preferably 15 to 98 wt%; particularly preferably 20 to 95% by weight.
Preferably, the adjuvant includes at least one additive selected from the group consisting of an emulsifier, a dispersant, a wetting agent, a spreader, a stabilizer, a defoamer, a synergist, a penetrant, a binder, a preservative, an antifreeze, a disintegrant, a safener, a solvent, a cosolvent, a carrier, and a filler.
The dosage form of the herbicide can be various dosage forms which are conventional in the field, and preferably, the dosage form of the herbicide is at least one selected from wettable powder, suspending agent, aqueous emulsion, water dispersible granule, dispersible oil suspending agent and missible oil.
The present invention will be described in detail below by way of examples.
In the following examples, various raw materials used are commercially available without specific description.
Preparation example 1: preparation of Compound 1A
(1) A three-necked flask was charged with 0.01mol of chlorofluoropyridine ester, 0.01mol of triethylamine, 0.012mol of triethyl phosphite, and 20mL of acetonitrile, and reacted at 25 ℃ for 3 hours. The reaction was completed by TLC detection, and the reaction solution became turbid. Filtering, spin-drying the filtrate to obtain 4.0 g of intermediate, and carrying out the next reaction directly after impurity.
(2) A three-necked flask was taken, and 20mL of acetonitrile, 0.01mol of sodium hydride and 0.006mol of dimethyl malonate were added, and then 0.005mol of the intermediate obtained in step (1) was dissolved in 20mL of tetrahydrofuran and added to the reaction solution. After all addition, stir for 1h at 25 ℃. After the completion of the TLC detection reaction, 50mL of water was added to the reaction solution, and the mixture was extracted with ethyl acetate. Drying, filtering and spin-drying the organic phase to obtain a crude product, and performing column chromatography to obtain the product, wherein the yield is 73.2 percent, and the purity is 94 percent.
The resulting product was characterized as follows:1H NMR(400MHz,DMSO)7.63–7.54(m,1H),7.42(dd,1H),7.24(d,1H),,3.91(d,,6H).4.02(d,1H)4.13(s,4H).
preparation example 2: preparation of Compound 2A
Taking a three-neck flask, adding 0.01mol of fluorochloropyridine ester, 0.06mol of ethyl acetate and 50mL of tetrahydrofuran under the protection of nitrogen, controlling the temperature to be 50 ℃ below zero after all the fluorochloropyridine ester, then adding 30mL of lithium bis (trimethylsilyl) amide into the three-neck flask, raising the temperature in the flask to 20 ℃ below zero, reacting for 30min, and finishing the TLC detection reaction. 50mL of water was added, followed by 50X 3 extraction with ethyl acetate. The organic phase is dried, filtered and spin-dried to obtain the product, the yield is 81 percent, and the purity is 97 percent.
The resulting product was characterized as follows:1H NMR(400MHz,DMSO)7.68(q,1H),7.45(dt,1H),7.36(d,1H),6.92(s,2H),4.16–3.99(m,4H),3.94(s,3H),1.09(t,3H).
preparation example 3: preparation of Compound 3A
Taking a three-neck flask, adding 0.01mol of fluorochloropyridine ester, 0.06mol of ethyl propionate and 50mL of isopropyl ether under the protection of nitrogen, controlling the temperature to be 50 ℃ below zero after all the materials are added, then adding 30mL of lithium bis (trimethylsilyl) amide into the three-neck flask, raising the temperature in the flask to 20 ℃ below zero, reacting for 30min, and finishing the TLC detection reaction. 50mL of water was added, followed by 50X 3 extraction with ethyl acetate. The organic phase is dried, filtered and spin-dried to obtain the product, the yield is 81 percent, and the purity is 97 percent.
The resulting product was characterized as follows:1H NMR(400MHz,DMSO)7.68(q,1H),7.45(dt,,1H),7.36(d,1H),4.16–3.99(m,3H),3.94(s,3H),1.09(t,2H)3.58(S，1H).
preparation example 4: preparation of Compound 4A
Taking a three-neck flask, adding 0.01mol of fluorochloropyridine ester, 0.06mol of methyl propionate and 50mL of tetrahydrofuran under the protection of nitrogen, controlling the temperature to be 50 ℃ below zero after all the materials are added, then adding 30mL of lithium bis (trimethylsilyl) amide into the three-neck flask, raising the temperature in the flask to 20 ℃ below zero, reacting for 30min, and finishing the TLC detection reaction. 50mL of water was added, followed by 50X 3 extraction with ethyl acetate. The organic phase is dried, filtered and spin-dried to obtain the product, the yield is 81 percent, and the purity is 97 percent.
The resulting product was characterized as follows:1H NMR(400MHz,DMSO)7.68(q,1H),7.45(dt,,1H),7.36(d,1H),,4.16–3.99(m,3H),3.94(s,3H),3.58(S，1H).
preparation example 5: preparation of Compound 5A
(1) Taking a three-neck flask, adding 0.01mol of fluorochloropyridine ester, 0.06mol of methyl acetate and 50mL of tetrahydrofuran under the protection of nitrogen, controlling the temperature to be 50 ℃ below zero after all the fluorochloropyridine ester, then adding 30mL of lithium bis (trimethylsilyl) amide into the three-neck flask, raising the temperature in the flask to 20 ℃ below zero, reacting for 30min, and finishing the TLC detection reaction. 50mL of water was added, followed by 50X 3 extraction with ethyl acetate. Drying, filtering and spin-drying the organic phase to obtain an intermediate.
(2) Taking a three-neck flask, adding 0.01mol of intermediate and 10mL of carbon tetrachloride, adding 0.015mol of NBS at room temperature, and stirring at room temperature overnight. After completion of the TLC detection reaction, 50mL of water was added, followed by 50 × 3 extraction with ethyl acetate. The organic phase is dried, filtered and spin-dried to obtain the product, the yield is 81 percent, and the purity is 97 percent.
The resulting product was characterized as follows:1H NMR(400MHz,DMSO)7.68(q,1H),7.45(dt,,1H),7.36(d,1H),6.92(s,1H),1.09(t,3H).
preparation example 6: preparation of Compound 6A
Taking a three-neck flask, adding 0.01mol of fluorochloropyridyl ester, 0.06mol of methyl isobutyrate and 50mL of acetonitrile under the protection of nitrogen, controlling the temperature to be 50 ℃ below zero after all the materials are added, then adding 30mL of lithium bis (trimethylsilyl) amide into the three-neck flask, raising the temperature in the flask to 20 ℃ below zero, reacting for 30min, and detecting the reaction by TLC to end. 50mL of water was added, followed by 50X 3 extraction with ethyl acetate. The organic phase is dried, filtered and spin-dried to obtain the product, the yield is 81 percent, and the purity is 97 percent.
The resulting product was characterized as follows:1H NMR(400MHz,DMSO)7.68(q,1H),7.45(dt,,1H),7.36(d,1H),6.92(s,2H),4.16–3.99(m,6H),3.94(s,3H),1.09(t,2H).
preparation example 7: preparation of Compound 7A and Compound 8A
(1) Taking a three-neck flask, adding 0.01mol of raw material of fluorochloropyridine ester, 0.06mol of methyl acetate and 50mL of tetrahydrofuran under the protection of nitrogen, controlling the temperature to be 50 ℃ below zero after all the raw materials are added, then adding 30mL of lithium bis (trimethylsilyl) amide into the three-neck flask, raising the temperature in the flask to 20 ℃ below zero, reacting for 30min, and finishing the TLC detection reaction. 50mL of water was added, followed by 50X 3 extraction with ethyl acetate. The organic phase was dried, filtered and spin-dried to give compound 8A in 75% yield and 98% purity.
The resulting product (compound 8A) was characterized as follows:1H NMR(400MHz,DMSO)7.63–7.54(m,1H),7.42(dd,1H),7.24(d,J＝1.7Hz,1H),6.91(s,2H),3.91(d,3H).
(2) taking 0.007mol of the product in the step (1) and 50mL of carbon tetrachloride, adding 0.016mol of NCS0.016 at 25 ℃, refluxing overnight, and detecting by TLC to finish the reaction. Then 50mL of water and carbon tetrachloride are added into the mixture for extraction, the organic phase is dried by spinning to obtain a crude product, and the crude product is subjected to column chromatography to obtain a compound 7A, wherein the yield is 66% and the purity is 95%.
The resulting product (compound 7A) was characterized as follows:1H NMR(400MHz,DMSO)7.63–7.54(m,1H),7.42(dd,1H),7.24(d,1H),3.91(d,3H).
preparation example 8: preparation of Compound 9A
Taking a three-neck flask, adding 0.01mol of fluorochloropyridine ester, 0.06mol of methyl n-butyrate and 50mL of tetrahydrofuran under the protection of nitrogen, controlling the temperature to be 50 ℃ below zero after all the fluorochloropyridine ester, then adding 30mL of lithium bis (trimethylsilyl) amide into the three-neck flask, then raising the temperature in the flask to 20 ℃ below zero, reacting for 30min, and finishing the TLC detection reaction. 50mL of water was added, followed by 50X 3 extraction with ethyl acetate. The organic phase is dried, filtered and spin-dried to obtain the product, the yield is 81 percent, and the purity is 97 percent.
The resulting product was characterized as follows:1H NMR(400MHz,DMSO)7.68(q,1H),7.45(dt,,1H),7.36(d,1H),6.92(s,2H),6.78(S,2H),3.94(s,3H),3.89(S,3H)1.09(t,1H).
preparation example 9: preparation of Compound 10A
(1) A three-necked flask was charged with 0.01mol of chlorofluoropyridine ester, 0.01mol of triethylamine, 0.012mol of triethyl phosphite, and 20mL of acetonitrile, and reacted at 25 ℃ for 3 hours. The reaction was completed by TLC detection, and the reaction solution became turbid. Filtering, spin-drying the filtrate to obtain 4.0 g of intermediate, and carrying out the next reaction directly after impurity.
(2) A three-neck flask was taken, and 20mL of tetrahydrofuran, 0.01mol of sodium hydride and 0.006mol of diethyl malonate were added. Then, 0.005mol of the intermediate obtained in step (1) was dissolved in 20mL of tetrahydrofuran and added to the reaction solution. After the addition was completed, the mixture was stirred at 25 ℃ for 1 hour, TLC checked for completion of the reaction, and 50nmL of water was added to the reaction solution and extracted with ethyl acetate. Drying, filtering and spin-drying the organic phase to obtain a crude product, and carrying out column chromatography to obtain the product, wherein the yield is 82.6%, and the purity is 96%.
The obtained product listCharacterized by the following:1H NMR(400MHz,DMSO)7.63–7.54(m,1H),7.42(dd,1H),7.24(d,1H),,3.91(d,,6H).4.02(d,1H)4.13(s,4H),1.29(s,6H).
preparation example 10: preparation of Compound 11A
(1) An intermediate was prepared in the same manner as in the step (1) of preparation example 1;
(2) a three-necked flask was taken, and 20mL of tetrahydrofuran, 0.01mol of sodium hydride and 0.006mol of dibutyl malonate were added, and then 0.005mol of the intermediate obtained in step (1) was dissolved in 20mL of tetrahydrofuran and added to the reaction solution. After all addition, stir for 1h at 25 ℃. After the completion of the TLC detection reaction, 50mL of water was added to the reaction solution, and the mixture was extracted with ethyl acetate. Drying, filtering and spin-drying the organic phase to obtain a crude product, and performing column chromatography to obtain the product, wherein the yield is 79.2 percent, and the purity is 96 percent.
The resulting product was characterized as follows:1H NMR(400MHz,DMSO)7.63–7.54(m,1H),7.42(dd,1H),7.24(d,1H),,3.45(d,,18H).4.02(d,1H).
preparation example 11: preparation of Compound 12A
(1) An intermediate was prepared in the same manner as in the step (1) of preparation example 1;
(2) a three-necked flask was taken, and 20mL of tetrahydrofuran, 0.01mol of sodium hydride and 0.006mol of diisopropyl malonate were added, and then 0.005mol of the intermediate obtained in step (1) was dissolved in 20mL of tetrahydrofuran and added to the reaction solution. After all addition, stir for 1h at 25 ℃. The reaction was terminated by TLC detection, and 50mL of water was added to the reaction solution and extracted with ethyl acetate. Drying, filtering and spin-drying the organic phase to obtain a crude product, and performing column chromatography to obtain the product, wherein the yield is 76%, and the purity is 95%.
The resulting product was characterized as follows:1H NMR(400MHz,DMSO)7.63–7.54(m,1H),7.42(dd,1H),7.24(d,1H),,3.91(d,,12H).4.02(d,1H)4.13(s,2H).
preparation example 12: preparation of Compound 1B
Compound 1B was prepared in a similar manner to that of preparation 7, except that the starting material was changed to give Compound 1B in 82.6% yield and 96% purity.
The resulting product was characterized as follows:1H NMR(400MHz,DMSO)7.63–7.54(m,1H),7.42(dd,1H),3.91(d,,6H).4.02(d,1H)4.13(s,4H).
test example
Preparing a medicament:
weighing a certain mass of original drug, dissolving the original drug with DMF containing 1 weight percent of Tween-80 emulsifier to prepare 1.0 weight percent of mother liquor, and then diluting the mother liquor with distilled water for later use.
The test method comprises the following steps:
preliminary screening test (potting method): the test targets are Abutilon, Amaranthus retroflexus, Echinochloa crusgalli, Chenopodium album and Setaria viridis, paper cups with the inner diameter of 6cm are taken, compound soil (garden soil: seedling culture medium, 1: 2, v/v) is filled to 3/4 of the positions, the five weed targets are directly sown (the germination rate is more than or equal to 85 percent), soil is covered for 0.2cm, and the weeds are reserved when the weeds grow to about 3-leaf stage. After the compounds in the table 1 are applied in an automatic spraying tower according to the dosage of 0.5, 1 and 5ga.i./ha, the weed foliage liquid medicine is aired and then is transferred into a greenhouse for culture, and the results are investigated by an eye measurement method after 15 days. The control agent was fluorochloropyridine ester.
The investigation method comprises the following steps: after 30 days of test treatment, the target damage symptoms and growth inhibition condition are visually observed, the fresh weight of the overground part is weighed, and the fresh weight inhibition rate (%) is calculated.
Fresh weight inhibition (%) - (control fresh weight-treated fresh weight)/control fresh weight × 100
The results are shown in Table 1.
Crop safety (potting method): the test targets are corn, wheat, rice, eggplant and pepper, a paper cup with the inner diameter of 6cm is taken, composite soil (garden soil: seedling culture medium, 1: 2, v/v) is filled to 3/4 of the positions, crop seeds are directly sown (the bud rate is more than or equal to 85 percent), soil is covered for 0.2cm, and the plants are kept for standby when the plants grow to 4-5 leaves. After the compounds in the table 2 are applied in an automatic spray tower according to the dosage of 0.5, 1 and 5g.a.i./mu, the crop leaf liquid medicine is aired and then transferred into a greenhouse for culture, and the results are visually inspected 7 days later. The control agent was fluorochloropyridine ester. The results are shown in Table 2.
The safety test results were carried out by the evaluation methods shown in table 3:
TABLE 1
TABLE 2
TABLE 3
| Growth inhibition rate/%) | Evaluation (inhibition, abnormality, whitening, etc.) |
| 0 | Has no influence on the growth of crops and is safe. |
| 0-10 | Slightly influences the growth of crops and has no obvious phytotoxicity. |
| 10-30 | Has influence on the growth of crops and slight phytotoxicity. |
| 30-50 | Has large influence on the growth of crops and moderate phytotoxicity. |
| 50-100 | Has great influence on the growth of crops and serious phytotoxicity. |
| 100 | The crop dies completely. |
As can be seen from the results in the above table, the phenylpyridine derivative provided by the present invention has significantly excellent safety for field crops while ensuring excellent control effect for weeds in field crops. Particularly, the safety of the pesticide for vegetable crops such as eggplants, hot peppers and the like is obviously better than that of the pesticide provided by the prior art.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. A phenylpyridine derivative having a structure represented by formula (1),
wherein, in the formula (1), R1Is selected from C1-6Alkyl groups of (a);
R2and R3Each independently selected from H, halogen, C1-4Alkyl of (a), -COOR1and-COR4At least one of, and R4Is selected from C1-4Alkyl groups of (a);
x is H or halogen.
2. The derivative according to claim 1, wherein, in formula (1),
R1is selected from C1-4Alkyl groups of (a);
R2and R3Each independently selected from H, chloro, bromo, methyl, ethyl, isopropyl, -COOR1and-COR4At least one of, and R4Selected from methyl, ethyl and isopropyl;
x is H or F.
3. The derivative according to claim 2, wherein the derivative is at least one of the following compounds:
compound 1A: r1is-CH3；R2is-COOCH3；R3is-H; x is-H;
compound 2A: r1is-CH2CH3；R2is-H; r3is-H; x is-H;
compound 3A: r1is-CH2CH3；R2is-CH3；R3is-H; x is-H;
compound 4A: r1is-CH3；R2is-CH3；R3is-H; x is-H;
compound 5A: r1is-CH3；R2is-Br; r3is-H; x is-H;
compound 6A: r1is-CH2CH3；R2is-CH3；R3is-CH3(ii) a X is-H;
compound 7A: r1is-CH3；R2is-Cl; r3is-Cl; x is-H;
compound 8A: r1is-CH3；R2is-H; r3is-H; x is-H;
compound 9A: r1is-CH2CH3；R2is-CH2CH3；R3is-H; x is-H;
compound 10A: r1is-CH2CH3；R2is-COOCH2CH3；R3is-H; x is-H;
compound 11A: r1is-CH2CH2CH2CH3；R2is-COOCH2CH2CH2CH3；R3is-H; x is-H;
compound 12A: r1is-CH (CH)3)2；R2is-COOCH (CH)3)2；R3is-H; x is-H;
compound 1B: r1is-CH3；R2is-COOCH3；R3is-H; x is-F.
4. Use of a phenylpyridine derivative according to any one of claims 1 to 3 for controlling weeds in crops of field crops.
5. The use of claim 4, wherein the field crop is at least one of corn, wheat, rice, eggplant and pepper.
6. The use of claim 4, wherein the weeds comprise at least one of abutilon, amaranthus retroflexus, echinochloa crusgalli, chenopodium album and setaria viridis.
7. A herbicide consisting of an active ingredient and adjuvants, characterized in that the active ingredient comprises at least one of the phenylpyridine derivatives of any one of claims 1 to 3.
8. A herbicide as claimed in claim 7, wherein the active component is present in an amount of 10 to 100% by weight.
9. A herbicide as claimed in claim 7, wherein the content of the active ingredient is 15-98% by weight.
10. A herbicide as claimed in claim 7, wherein the content of the active ingredient is 20-95% by weight.
11. A herbicide as claimed in any one of claims 7 to 10, wherein the adjuvants include at least one additive selected from emulsifiers, dispersants, wetting agents, spreaders, stabilizers, defoamers, builders, penetrants, stickers, preservatives, antifreeze agents, disintegrants, safeners, solvents, co-solvents, carriers and fillers.
12. The herbicide according to any one of claims 7 to 10, wherein the formulation of the herbicide is at least one selected from the group consisting of wettable powders, suspensions, aqueous emulsions, water dispersible granules, dispersible oil suspensions and emulsifiable concentrates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710273955.8A CN108727258B (en) | 2017-04-25 | 2017-04-25 | Phenylpyridine derivative, application thereof and herbicide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710273955.8A CN108727258B (en) | 2017-04-25 | 2017-04-25 | Phenylpyridine derivative, application thereof and herbicide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108727258A CN108727258A (en) | 2018-11-02 |
| CN108727258B true CN108727258B (en) | 2020-11-24 |
Family
ID=63934705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710273955.8A Active CN108727258B (en) | 2017-04-25 | 2017-04-25 | Phenylpyridine derivative, application thereof and herbicide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108727258B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6110871A (en) * | 1996-12-12 | 2000-08-29 | American Cyanamid Company | Herbicidal cyanopyridines |
| WO2006006569A1 (en) * | 2004-07-12 | 2006-01-19 | Nihon Nohyaku Co., Ltd. | Phenylpyridine derivative or salt thereof, herbicide containing the same as active ingredient, and method of use thereof |
| CN103380116A (en) * | 2010-12-16 | 2013-10-30 | 拜耳知识产权有限责任公司 | 6-(2-aminophenyl)picolinates and their use as herbicides |
| EP2421832B1 (en) * | 2009-02-27 | 2013-12-18 | Dow AgroSciences LLC | N-alkoxyamides of 6-(substituted phenyl)-4-aminopicolinates and 2-(substituted phenyl)-6-amino-4-pyrimidinecarboxylates and their use as selective herbicides for crops |
| CN105208864A (en) * | 2013-03-12 | 2015-12-30 | 美国陶氏益农公司 | Herbicidal compositions comprising 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl) pyridine-2-carboxylic acid |
-
2017
- 2017-04-25 CN CN201710273955.8A patent/CN108727258B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6110871A (en) * | 1996-12-12 | 2000-08-29 | American Cyanamid Company | Herbicidal cyanopyridines |
| WO2006006569A1 (en) * | 2004-07-12 | 2006-01-19 | Nihon Nohyaku Co., Ltd. | Phenylpyridine derivative or salt thereof, herbicide containing the same as active ingredient, and method of use thereof |
| EP2421832B1 (en) * | 2009-02-27 | 2013-12-18 | Dow AgroSciences LLC | N-alkoxyamides of 6-(substituted phenyl)-4-aminopicolinates and 2-(substituted phenyl)-6-amino-4-pyrimidinecarboxylates and their use as selective herbicides for crops |
| CN103380116A (en) * | 2010-12-16 | 2013-10-30 | 拜耳知识产权有限责任公司 | 6-(2-aminophenyl)picolinates and their use as herbicides |
| CN105208864A (en) * | 2013-03-12 | 2015-12-30 | 美国陶氏益农公司 | Herbicidal compositions comprising 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl) pyridine-2-carboxylic acid |
Non-Patent Citations (2)
| Title |
|---|
| （2,6-二氯-5-氟-吡啶-3-羰基）-乙酸乙酯的合成;陈磊等;《精细化工中间体》;20051231;第35卷(第6期);29-31 * |
| Efficient one-pot selective reduction of esters in b-ketoesters using LiHMDS and lithium aluminium hydride;K. Sivagurunathan et al.;《Tetrahedron Letters》;20110114;第52卷(第11期);1205-1207 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108727258A (en) | 2018-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2017224992A1 (en) | Crystal of flumioxazin | |
| CN111410630B (en) | Preparation and application of cyanoacrylate derivative containing trifluoromethyl pyridyloxy aryl unit | |
| JPS62255469A (en) | Acrylic acid derivative, manufacture and fungicide, insecticide or plant growth regulator composition containingsame | |
| KR20200131841A (en) | Plant growth regulator compounds | |
| JP7065835B2 (en) | Plant growth regulator | |
| US4447256A (en) | N-(Unsubstituted or substituted pyridyl)aminomethylene-diphosphonic acids, herbicidal compositions containing same, their use for herbicides, and process for preparing same | |
| CN108727258B (en) | Phenylpyridine derivative, application thereof and herbicide | |
| CN115160238B (en) | Quinoxaline phenoxyacetic acid ester compound, and preparation method and application thereof | |
| CN107602494B (en) | Preparation and application of cyanoacrylate derivative containing tetrazole group | |
| HU177122B (en) | Herbicide composition containing antidotum,and process for producing the antidotum | |
| KR20170115053A (en) | 2-oxo-3,4-dihydroquinoline compound as a plant growth regulator | |
| AU2017254862A1 (en) | Crystal of flumioxazin | |
| CN114591230A (en) | Cyclohexenone compound, application thereof and pesticide herbicide | |
| CN110818649B (en) | Preparation and application of 2-cyanoacrylate derivative containing 1, 2, 4-triazole benzylamine unit | |
| US4072499A (en) | Use of pyridyl phthalimides as plant growth regulants | |
| JPS62145052A (en) | Substituted benzamide derivative, manufacture and bactericide or plant growth regulant composition | |
| EP0017994A2 (en) | Cyclobutanedicarboximides, process for their preparation and their use as fungicides; intermediate products | |
| AU2018217789B2 (en) | Germination promoters | |
| DE2943019C2 (en) | ||
| HU195080B (en) | Fungicide compositions containing 2-cyano-imidazo/4,5-b/-pyridine derivatives and process for producing the active components | |
| CN112125912B (en) | Sulfonamide derivative containing 3-aryl oxadiazole structure and preparation method and application thereof | |
| CN112028894B (en) | Preparation and application of sulfonamide compound containing trifluoromethyl pyridine biaryloxy unit | |
| NL7906888A (en) | SUBSTITUTED THIOSEMICARBAZIDES, METHOD FOR PREPARING IT AND PREPARATION AND METHOD FOR CONTROLLING PLANT GROWTH. | |
| CN110183434B (en) | Oxadiazole compound and preparation method and application thereof | |
| US4396414A (en) | Method of increasing the yield of legumes utilizing chloroacetylamino-1,3-dioxanes |
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 |