CN113845473B - Fluopicolide derivative as well as preparation method and application thereof - Google Patents
Fluopicolide derivative as well as preparation method and application thereof Download PDFInfo
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- CN113845473B CN113845473B CN202111125862.3A CN202111125862A CN113845473B CN 113845473 B CN113845473 B CN 113845473B CN 202111125862 A CN202111125862 A CN 202111125862A CN 113845473 B CN113845473 B CN 113845473B
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- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The present invention belongs to agricultureThe field of pharmaceutical chemistry, and relates to a fluopicolide derivative, a preparation method and application thereof, wherein the structural formula of the fluopicolide derivative is as follows
Description
Technical Field
The invention belongs to the field of pesticide chemical industry, and relates to a fluopicolide derivative, a preparation method and application thereof.
Background
Fluazifop-butyl (Picolinafen), a picolinamide structural compound, is an herbicide developed by BASFSE (basf corporation) at the earliest time, and is marketed in 2002 and is mainly used for preventing and killing various annual grassy weeds and broadleaf weeds in corn, soybean and wheat fields. The strain is a selective contact and residual herbicide and has a mode of action of inhibiting biosynthesis of carotenoid through inhibition of phytoene dehydrogenase. Compared with other pyridine amide herbicides, the flupirfenidone has the characteristics of high herbicidal activity, long duration, difficult decomposition and safety to crops. The related derivatives of the inhibitors have been reported by Pasteur and Bayer companies in the 90 th century, and the development of novel fluopicolide derivatives still has wide application value. The novel flupirfenidone derivative (A) provided by the invention is not reported at present.
Disclosure of Invention
The invention aims to further improve the weeding effect, and provides a fluopicolide derivative, a preparation method and application thereof.
In order to achieve the purpose of the invention, the technical scheme adopted is as follows:
a flupirfenidone derivative having the structural formula:
wherein R is any one of H, methyl, ethyl, n-propyl or isopropyl.
The preparation method of the fluopicolide derivative comprises the following reaction processes:
(1) 2-chloro-6-carboxyl pyridine (compound 2) is prepared from 2-chloro-6-trichloromethyl pyridine (compound 1) under the action of concentrated sulfuric acid;
(2) 2-chloro-6-carboxypyridine (compound 2) is prepared into 2-chloro-6-acyl chloropyridine (compound 3) under the action of phosphorus trichloride, phosphorus pentachloride or thionyl chloride;
(3) 2-chloro-6-acyl-chloropyridine (compound 3) and p-fluoroaniline are prepared by amidation reaction(intermediate 4);
(4) N-substituted m-trifluoromethylaniline (structural formula is) Substitution ofThe chlorine substituent in (2) to obtain the fluopicolide derivative.
Further, the specific method of the step (1) is as follows: heating 2-chloro-6-trichloromethyl pyridine (compound 1) and concentrated sulfuric acid to 100+/-20 ℃ for reaction, cooling to 60+/-20 ℃ after the reaction is finished, adding ammonia water to neutralize residual acid (generally using 27% ammonia water by mass concentration), stirring and cooling to room temperature, precipitating, and carrying out vacuum filtration to obtain 2-chloro-6-carboxypyridine (intermediate 2).
Further, the specific preparation method of the intermediate 4 comprises the following steps: 2-chloro-6-carboxypyridine and chlorous acidAdding toluene into sulfone for reflux reaction, cooling to room temperature after reaction, adding p-fluoroaniline and triethylamine, reacting at room temperature, washing with water to neutrality after reaction, evaporating toluene under reduced pressure, and recrystallizing the residue with ethanol to obtain(intermediate 4).
Further, the specific method of the step (4) is as follows: adding intermediate 4, N-substituted m-trifluoromethylaniline, anhydrous sodium carbonate and cuprous chloride into DMF (N, N-dimethylformamide), heating to 120+/-20 ℃ under stirring, filtering after the reaction is finished, evaporating DMF under reduced pressure, adding toluene into the reactant, washing with 10% potassium carbonate and saturated saline solution in sequence, evaporating toluene under reduced pressure, and recrystallizing with ethanol to obtain the fluopicolide derivative (a compound shown in a general formula A).
The flupirfenidone derivative is used for preparing herbicides.
Compared with the prior art, the invention has the following beneficial effects:
the flupirfenidone derivative (A) has good herbicidal activity and can be used for preparing herbicides.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described in detail below in connection with the examples:
in an embodiment, the preparation of the flupirfenidone derivative specifically comprises the following structure:
the reaction process is as follows:
example one preparation of Compound a
1, preparation of intermediate 2
To a round bottom flask was added 2-chloro-6-trichloromethyl pyridine (230.9 g,1.0 mol) and 98% concentrated sulfuric acid (120 g,1.2 mol) in this order, followed by stirring at 120℃for 6h. After the reaction, the temperature was lowered to 60℃and 172.8ml of 27% aqueous ammonia (1.2 mol) was slowly added dropwise. Cooled to room temperature, filtered under reduced pressure to give 146.8g of white solid (intermediate 2) in 93.5% yield.
2, preparation of intermediate 4
To a round bottom flask was added 2-chloro-6-carboxypyridine (157.0 g,1.0 mol), thionyl chloride (142.8 g,1.2 mol), 300ml toluene and the mixture was refluxed for 5 hours. After cooling to room temperature, p-fluoroaniline (111.1 g,1.0 mol) was added, and triethylamine (121.5 g,1.2 mol) was added dropwise. The reaction was carried out at room temperature for 5 hours. Washing with water to neutrality, and evaporating toluene. Recrystallization from ethanol gave 205.5g of a white crystalline solid (intermediate 4) in 82.2% yield.
Preparation of Compound a
To a round bottom flask was added in order intermediate 4 (250.0 g,1.0 mol), m-trifluoromethylaniline (193.3 g,1.2 mol), potassium tert-butoxide (134.7 g,1.2 mol), 1200ml DMF. Stirring and heating to 120 ℃ for reaction for 3h. Filtration and distillation under reduced pressure remove DMF. Cooling to room temperature, adding 500ml toluene to dissolve the reactant, 500ml 10% potassium carbonate to dissolveThe solution was washed, and toluene was distilled off under reduced pressure. Recrystallization from ethanol, drying gave 310.6g of a white solid (compound a) in 82.8% yield. ESI MS 376.3[ M+H ]] +1 ,1H-NMR(400MHz,DMSO)δ9.87(s,1H),9.25(s,1H),8.03(d,1H,J＝7.6Hz),7.91(d,1H,J＝7.6Hz),7.62-7.41(m,3H),7.39(m,2H),7.23(s,1H),7.18(m,1H),7.03(m,2H)。
Example two preparation of Compound b
The synthesis was carried out in the same manner as the synthesis method of the compound a except that N-methyl m-trifluoromethylaniline was used instead of m-trifluoromethylaniline, and the total yield was 50.6%. The structural formula is as follows:
ESI MS:390.2[M+H] +1 , 1 H-NMR(400MHz,DMSO)δ9.22(s,1H),8.02(d,1H,J＝7.5Hz),7.88(d,1H,J＝7.5Hz),7.69-7.51(m,3H),7.33(m,2H),7.27(s,1H),7.13(m,2H),6.93(m,1H),2.13(s,3H)。
example III preparation of Compound c
The synthesis was carried out in the same manner as the synthesis method of the compound a except that N-ethyl m-trifluoromethylaniline was used instead of m-trifluoromethylaniline, and the total yield was 51.2%. The structural formula is as follows:
ESI MS:404.6[M+H] +1 , 1 H-NMR(400MHz,DMSO)δ9.17(s,1H),8.11(d,1H,J＝7.5Hz),7.93(d,1H,J＝7.5Hz),7.62-7.43(m,3H),7.35(m,2H),7.27(s,1H),7.16(m,2H),6.97(m,1H),2.27(m,2H),1.35(m,3H)。
example IV preparation of Compound d
The synthesis was carried out in the same manner as the synthesis method of the compound a except that N-propyl m-trifluoromethylaniline was used instead of m-trifluoromethylaniline, and the total yield was 48.7%. The structural formula is as follows:
ESI MS:418.1[M+H] +1 , 1 H-NMR(400MHz,DMSO)δ9.08(s,1H),8.03(d,1H,J＝7.6Hz),7.88(d,1H,J＝7.6Hz),7.61-7.47(m,3H),7.31(m,2H),7.22(s,1H),7.17(m,2H),6.82(m,1H),2.23(m,2H),1.36(m,2H),1.22(m,3H)。
example five preparation of Compound e
The synthesis was carried out in the same manner as the synthesis method of the compound a except that N-propyl m-trifluoromethylaniline was used instead of m-trifluoromethylaniline, and the total yield was 52.9%. The structural formula is as follows:
ESI MS:418.3[M+H] +1 , 1 H-NMR(400MHz,DMSO)δ9.31(s,1H),8.12(d,1H,J＝7.6Hz),7.93(d,1H,J＝7.6Hz),7.69-7.42(m,3H),7.33(m,2H),7.26(s,1H),7.12(m,2H),6.93(m,1H),2.31(m,1H),1.27(m,6H)。
the products obtained in examples 1 to 5 were tested for herbicidal activity
Test methods refer to the patent "preparation method and application of a flupyraclostrobin derivative (CN 109761896A)". The dosage of the flupirfenidone derivative (A) is 150ga.i/hm 2 . Selecting Amaranthus retroflexus, herba Eleusines Indicae, rumex Acetosa, herba Capsellae and herba Achillea Wilsonianae seeds, germinating, and sowing into plastic flowerpot (diameter 10cm, depth 12 cm), sowing 5 seeds in each pot, and covering with soil 0.5cm. The sown flowerpots are soaked from the bottom, cultured in a laboratory until the 3-6 leaf period, and sprayed with an emulsion of the compound to be tested. After spraying, the flowerpot is moved back to a laboratory, cultured at room temperature and watered according to the requirement. Experiments were repeated 3 times to apply an emulsion containing equal amounts of dichloromethane and tween-80 as a control. The fresh weight of the aerial parts was weighed on day 40 after the administration, and the fresh weight inhibition ratio was calculated. The results are shown in the following table:
herbicidal activity test results of the compounds of Table 1
N.D. no inhibitory activity was detected
The activity test shows that under the same condition, the flupirfenidone derivative (A) has better inhibition rate on several weeds after stem and leaf treatment, and has better effect on the weeds than flupirfenidone. Wherein, the inhibition rate of the compound a to the stem and leaf treatment of the amaranthus retroflexus and the lycopodium clavatum reaches more than 60 percent; the inhibition rate of the compound b on the stem and leaf treatment of amaranthus retroflexus and shepherd's purse reaches more than 50%; the inhibition rate of the compound c on stem and leaf treatment of the sorrel and the shepherd's purse reaches more than 70%; the stem and leaf treatment inhibition rate of the compound d to the red and green grass reaches more than 70 percent; the inhibition rate of the compound c on the stem and leaf treatment of the eleusine indica and the shepherd's purse reaches more than 60%. Therefore, the compounds have better control effect on dicotyledonous weeds, and can be used as candidate compounds of herbicides.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and it is verified that the reaction temperature in the above examples can be up and down shifted by 20 ℃, and any person skilled in the art should be able to apply equivalent substitutions or modifications according to the technical solution and the concept of the present invention within the scope of the present invention.
Claims (6)
1. A flupirfenidone derivative which is characterized in that: has the following structural formula:
wherein R is any one of H, methyl, ethyl, n-propyl or isopropyl.
2. A process for the preparation of flupirfenidone derivatives as claimed in claim 1 wherein: the method comprises the following steps:
(1) 2-chloro-6-carboxyl pyridine is prepared from 2-chloro-6-trichloromethyl pyridine under the action of concentrated sulfuric acid;
(2) 2-chloro-6-carboxypyridine is prepared into 2-chloro-6 acyl chloride pyridine under the action of phosphorus trichloride, phosphorus pentachloride or thionyl chloride;
(3) The 2-chloro-6 acyl chloride pyridine and p-fluoroaniline are prepared through amidation reaction
(4) N-substituted m-trifluoromethylanilinesSubstitution->The chlorine substituent in (2) to obtain the fluopicolide derivative.
3. The method for producing a flupirfenidone derivative according to claim 2, characterized in that: the specific method of the step (1) is as follows: heating 2-chloro-6-trichloromethyl pyridine and concentrated sulfuric acid to 100+/-20 ℃ for reaction, cooling to 60+/-20 ℃ after the reaction is finished, adding ammonia water to neutralize residual acid, stirring and cooling to room temperature, separating out precipitate, and carrying out vacuum suction filtration to obtain 2-chloro-6-carboxypyridine.
4. The method for producing a flupirfenidone derivative according to claim 2, characterized in that: the specific method of the step (3) is as follows: adding toluene to reflux 2-chloro-6-carboxypyridine and thionyl chloride for reaction, cooling to room temperature after the reaction is finished, adding p-fluoroaniline and triethylamine for reaction at room temperature, washing with water to be neutral after the reaction is finished, evaporating toluene under reduced pressure, and recrystallizing the remainder with ethanol to obtain
5. The method for producing a flupirfenidone derivative according to claim 2, characterized in that: the specific method of the step (4) is as follows: will beAdding N-substituted m-trifluoromethyl aniline, anhydrous sodium carbonate and cuprous chloride into DMF, heating to 120+/-20 ℃ under stirring, filtering after the reaction is finished, evaporating DMF under reduced pressure, adding toluene into the reactant, washing with 10% potassium carbonate and saturated saline water in sequence, evaporating toluene under reduced pressure, and recrystallizing with ethanol to obtain the fluopicolide derivative.
6. Use of a flupirfenidone derivative according to claim 1 wherein: the flupirfenidone derivative is used for preparing herbicides.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530351A (en) * | 2018-07-19 | 2018-09-14 | 陈磊 | A kind of preparation method of fluorine pyrrole acyl grass amine |
| CN109761896A (en) * | 2019-03-12 | 2019-05-17 | 合肥玖知和科技信息咨询有限公司 | A kind of preparation method and application of fluorine pyrrole acyl grass amine derivative |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530351A (en) * | 2018-07-19 | 2018-09-14 | 陈磊 | A kind of preparation method of fluorine pyrrole acyl grass amine |
| CN109761896A (en) * | 2019-03-12 | 2019-05-17 | 合肥玖知和科技信息咨询有限公司 | A kind of preparation method and application of fluorine pyrrole acyl grass amine derivative |
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