CN109336882B - Fluorine-containing pyridine acyl piperazine compound and application thereof - Google Patents
Fluorine-containing pyridine acyl piperazine compound and application thereof Download PDFInfo
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- CN109336882B CN109336882B CN201811319890.7A CN201811319890A CN109336882B CN 109336882 B CN109336882 B CN 109336882B CN 201811319890 A CN201811319890 A CN 201811319890A CN 109336882 B CN109336882 B CN 109336882B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
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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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
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- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
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- Plural Heterocyclic Compounds (AREA)
Abstract
The invention provides a fluorine-containing pyridine acyl piperazine compound, which has a structure shown as a general formula I:
wherein R is:
Description
The invention belongs to the field of pesticides in pesticides, and particularly relates to a fluorine-containing pyridine acyl piperazine compound and application thereof.
Background agricultural pests harm the growth of crops, resulting in reduced yield and reduced quality. At present, the prevention and the treatment of pests mainly depend on chemical pesticides, and along with the wide use of pesticides, the resistance problem of pests is increasingly serious, so that a series of problems of larger and larger dosage, lower and lower prevention effect, shortened lasting period, increased pesticide residue and the like are caused. Therefore, the development and application of new pesticides with different action mechanisms are effective means for solving pest resistance. 2, 3-dichloro-5- (trifluoromethyl) pyridine is a fluorine-containing organic intermediate with high activity and low toxicity, and is also a key intermediate of a plurality of high-efficiency insecticides, namely pyridalyl, bactericides fluazinam and fluopyram. Piperazine and its derivatives not only have wide application in medicine, but also are good active intermediates in pesticides, and piperazine itself has good insecticidal and anthelmintic activities. The commercialized chlorantraniliprole has pyridine ring and pyrazole ring structures, has the excellent characteristics of broad spectrum, long lasting period, low toxicity to fish, bees, aquatic organisms and mammals, environmental friendliness and the like, and is an effective pesticide for preventing and treating lepidoptera pests. Patent CN 101921228A discloses a bioactive Compound (CK) which has a completely new chemical structure, gives it a new mechanism of action and outstanding product performance, and shows higher bioactivity to diamondback moth. According to the invention, an active group trifluoromethyl-pyridine-piperazine and a heterocyclic compound are connected through acyl by an active group splicing technology to obtain a compound (general formula I) with a new chemical structure. The compounds of the general formula I shown in the invention and the application thereof as agricultural and forestry insecticides in the prior art are not disclosed.
The invention aims to provide a fluorine-containing pyridine acyl piperazine compound with a novel structure, which can be used as an agricultural pesticide.
The technical scheme of the invention is as follows:
a fluorine-containing pyridine acyl piperazine compound has a structure shown as a general formula I:
the compounds of formula I can be prepared by the following reaction:
reacting a compound IV with piperazine to generate a compound III, and reacting the compound III with IIa or IIb in ethyl acetate, dichloromethane or acetonitrile by taking triethylamine as an acid-binding agent to obtain a compound shown in a formula Ia or Ib; the compound III reacts with chloroacetyl chloride to produce a compound IIc, which then reacts with 2-cyanoimino-1, 3-thiazolidine to produce the compound of formula Ic. Specific preparations of intermediates III, IIa-c and compounds of formula I are described in the synthetic examples herein.
Table 1 shows the structures and physical properties of the compounds of formula I.
TABLE 1 Structure and physical Properties of Compounds of formula I
The compound of the general formula I has good insecticidal effect on diamond back moths through insecticidal tests, so the invention also comprises the application of the compound of the general formula I in the prevention and treatment of agricultural and forestry insect pests.
The invention has the advantages and positive effects that:
with the continuous enhancement of the resistance of pests to the traditional pesticide, the pesticide effect of the existing pesticide is less and less obvious, and the invention takes piperazine as a bridge chain and combines fluorine-containing pyridine with other heterocyclic active components to design a pesticide with a new structure. The compound (general formula I) as the pesticide has the advantages of novel structure, safety, high efficiency, simple and convenient preparation method and the like. Compared with the existing commercial pesticides, the compound (general formula I) has different structures and insecticidal mechanisms, is particularly suitable for controlling the currently ubiquitous drug-resistant pests, and has good development and application prospects when being used as a new variety of created pesticides.
When the compound is used for preventing and controlling pests, the compound can be used alone or combined with other active substances according to actual needs to provide comprehensive performance of products.
The invention also comprises an insecticidal composition taking the compound in the general formula I as an active component, wherein the weight percentage of the active composition in the insecticidal composition is between 1 and 99 percent. The pesticide composition also comprises a forestry and agricultural acceptable carrier.
The composition of the invention can be used in the form of a preparation, and the compound of the general formula I as an active component is dissolved or dispersed in a carrier or a solvent, and is added with a proper amount of a surfactant to prepare missible oil, a suspending agent, a microemulsion and the like.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
Detailed Description
The following synthetic examples and results of the biological tests are provided to further illustrate the invention and are not meant to limit the invention.
Synthesis examples
Example 1 preparation of Compound Ia
(1) Synthesis of intermediate III
Adding 17.2g (0.2mol) of anhydrous piperazine into a 250mL reaction bottle, adding 50g of methanol, stirring for dissolving, heating to 40 ℃, diluting 21.6g (0.1mol) of 2, 3-dichloro-5- (trifluoromethyl) pyridine with 40g of methanol, slowly dripping, reacting at constant temperature of 40 ℃ for 6 hours after dripping, tracking by TLC until the raw materials are completely reacted, cooling to room temperature, performing suction filtration, performing rotary evaporation on filtrate to remove the methanol, separating out a white solid, adding water, stirring for dissolving the residual anhydrous piperazine, performing suction filtration, and washing a filter cake for 2 times to obtain 22.6g of the white solid, wherein the melting point is 65.8-67.3 ℃, and the yield is 85%.
Of intermediate III1H NMR(500MHz,DMSO-d6)δ(ppm)：8.53(s,1H),8.15(s,1H),3.37–3.35(t,4H),2.82–2.80(t,4H)，2.10(s,1H)。
(2) Preparation of intermediate IIa
0.02mol (6.06g) of 1- (3-chloropyridin-2-yl) -3- (2, 2-difluoroethoxy) -1H-pyrazole-5-carboxylic acid was added to a 250mL single-necked flask, toluene was used as a solvent, 0.03mol (3.57g) of thionyl chloride was added, the reaction was carried out at 80 ℃ for 5 hours, TLC was used to follow the completion of the reaction, and toluene and excess thionyl chloride were removed by rotary evaporation to obtain 6.44g of an oily product IIa, which was used in the next reaction.
(3) Preparation of Compounds Ia
Adding 5.3g (0.02mol) of the intermediate III into a 250mL three-mouth reaction bottle, then adding 30g of ethyl acetate, adding 2.22g of triethylamine, dropwise adding a mixed solution of 10g of ethyl acetate and 6.40g (0.02mol) of IIa under stirring, reacting at room temperature for 50min after dropwise adding, tracking by TLC that the intermediate III completely reacts, adding 100g of water, stirring, separating, drying an organic phase by using anhydrous sodium sulfate, removing the ethyl acetate by rotary evaporation, cooling to obtain 10.34g of white solid, wherein the melting point is 145.7-147.1 ℃, and the yield is 94%.
Example 2 preparation of Compound ic
(1) Synthesis of intermediate IIc
21.24g (0.08mol) of the intermediate III, 50g of ethyl acetate and 10g of triethylamine are respectively added into a 250mL single-neck bottle, magnetic stirring is carried out, 9.04g (0.08mol) of chloroacetyl chloride is dropwise added, reaction is carried out for 1h at normal temperature, TLC tracking reaction is complete, water is added for extraction and liquid separation, anhydrous sodium sulfate is used for drying, ethyl acetate is removed by rotary evaporation, and cooling is carried out to obtain 26.53g of white solid IIc.
(2) Preparation of Compounds ic
Adding 3.42g (0.01mol) of the intermediate IIc into a 250mL reaction bottle, then adding 30g of acetonitrile, adding 1.2g of triethylamine, dropwise adding a mixed solution of 10g of acetonitrile and 1.27g (0.01mol) of 2-cyanoimino-1, 3-thiazolidine under stirring, heating and refluxing for 2 hours after dropwise adding, tracking the intermediate IIc by TLC to completely react, adding 150g of water, stirring to precipitate a solid, performing suction filtration, and drying to obtain 4.14g of a light yellow solid, wherein the yield is 96%.
For the synthesis of compound ib reference is made to example 1.
The nuclear magnetic data of the compounds of formula I are as follows:
a compound Ia:1H NMR(500MHz,DMSO-d6)δ(ppm)：8.59(s,1H),8.45(dd,1H),8.25(s,1H),8.18(dd,1H),7.52(dd,1H),6.49(s,1H),6.55–6.28(m,1H),4.49(q,2H),3.79–3.63(m,4H),3.57–3.40(m,4H)。
a compound Ib:1H NMR(500MHz,Chloroform-d)δ(ppm)：8.45(s,1H),7.81(s,1H),3.94(t,2H),3.57(t,2H),3.53–3.45(m,4H),2.78(s,3H)。
a compound ic:1H NMR(500MHz,DMSO-d6)δ(ppm)：8.58(s,1H),8.23(s,1H),4.44(s,2H),3.94(t,2H),3.62–3.54(m,4H),3.54–3.48(m,4H),3.47–3.43(m,2H)。
biological activity assay
Example 3 insecticidal Activity assay
The method for testing the activity of killing the plutella xylostella comprises the following steps: the compound of the invention adopts a leaf dipping method proposed by the International Resistance Action Committee (IRAC) for measuring the activity of the plutella xylostella. Soaking cabbage leaves with the prepared liquid medicine to be detected by using straight-head ophthalmological forceps for 3-5 seconds, throwing off residual liquid, 1 piece each time, wherein 3 pieces of each sample are put on the processing paper in sequence according to the sample marking sequence. After the liquid medicine is dried, the liquid medicine is put into a straight pipe with the length of 10cm and provided with a mark, 30 heads of 3-year-old plutella xylostella larvae are inoculated, and the pipe orifice is covered by gauze. The test treatment is placed in a standard treatment chamber, the result is checked for 48h, the insect body is touched by pulling the needle, and the insect is dead. The mortality was calculated. (test was repeated 3 times, average value was obtained)
Table 2 plutella xylostella killing activity test results of the series of compounds
According to the test results, the killing effect of the compound on the plutella xylostella is obviously superior to that of a KC compound.
Claims (3)
1. A fluorine-containing pyridine acyl piperazine compound has a structure shown in a formula I:
2. the use of a fluoropyridine acyl piperazine compound as claimed in claim 1, wherein the compound of formula I is used as an agricultural or forestry pesticide.
3. A pesticidal composition comprising a compound of formula I as defined in claim 1 as an active ingredient and an agriculturally acceptable carrier.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130769A (en) * | 2013-01-25 | 2013-06-05 | 青岛科技大学 | 3-difluoro ethoxy-pyrazole amides compounds and application thereof |
| CN104418800A (en) * | 2013-09-06 | 2015-03-18 | 中国中化股份有限公司 | Aryl pyridine/pyrimidine compound and application thereof |
| CN108341808A (en) * | 2018-03-28 | 2018-07-31 | 青岛科技大学 | Yi Zhong oxadiazoles connect pyrazole compound and application thereof |
| CN108440519A (en) * | 2018-04-03 | 2018-08-24 | 青岛科技大学 | Oxadiazole neighbour's benzene ethoxy base class compound and purposes |
| CN108640871A (en) * | 2018-06-06 | 2018-10-12 | 青岛科技大学 | A kind of fluorine-containing pyridine piperazine carbamide compounds and its application |
-
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- 2018-11-07 CN CN201811319890.7A patent/CN109336882B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130769A (en) * | 2013-01-25 | 2013-06-05 | 青岛科技大学 | 3-difluoro ethoxy-pyrazole amides compounds and application thereof |
| CN104418800A (en) * | 2013-09-06 | 2015-03-18 | 中国中化股份有限公司 | Aryl pyridine/pyrimidine compound and application thereof |
| CN108341808A (en) * | 2018-03-28 | 2018-07-31 | 青岛科技大学 | Yi Zhong oxadiazoles connect pyrazole compound and application thereof |
| CN108440519A (en) * | 2018-04-03 | 2018-08-24 | 青岛科技大学 | Oxadiazole neighbour's benzene ethoxy base class compound and purposes |
| CN108640871A (en) * | 2018-06-06 | 2018-10-12 | 青岛科技大学 | A kind of fluorine-containing pyridine piperazine carbamide compounds and its application |
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