CN108822082A - A kind of fluorine-containing pyridine piperazine acidamide compound and its application - Google Patents

A kind of fluorine-containing pyridine piperazine acidamide compound and its application Download PDF

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CN108822082A
CN108822082A CN201810587086.0A CN201810587086A CN108822082A CN 108822082 A CN108822082 A CN 108822082A CN 201810587086 A CN201810587086 A CN 201810587086A CN 108822082 A CN108822082 A CN 108822082A
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compound
fluorine
formula
containing pyridine
mite
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CN108822082B (en
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王明慧
彭壮
崔焕奇
崔建强
许良忠
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Qingdao University of Science and Technology
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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
    • C07D401/02—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 two hetero rings
    • C07D401/12—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 two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • 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
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention provides a kind of fluorine-containing pyridine piperazine acidamide compounds, and structure is as shown in general formula I：

Description

A kind of fluorine-containing pyridine piperazine acidamide compound and its application
Technical field
The invention belongs to acaricide fields in pesticide, and in particular to a kind of fluorine-containing pyridine piperazine acidamide compound and its answer With.
Background technique
Acarid destroys the normal physiological function of plant, leads to crop production reduction and normal growth, prevents the acaricide of mite evil There are many, such as fenisobromolate, avermectin, Envidor, fenpyroximate.Envidor to acarid have good fragmentation effect, but with A large amount of uses of pesticide so that acarid enhances the resistance of medicine.2,3- bis- chloro- 5- (trifluoromethyl) pyridine is a kind of fluorinated High activity, less toxic organic intermediate and many efficient pesticides, acaricide, bactericide agricultural chemicals key intermediate.Such as pyridine worm Grand, fluazinam and fluopyram etc..Piperazine inherently has excellent bioactivity, is widely used in pesticide.? In the prior art, as representative of the present invention it compound of Formula I and its is had not been reported as agriculture and forestry acaricide.
Summary of the invention
The purpose of the present invention is to provide a kind of fluorine-containing pyridine piperazine acidamide compounds of structure novel, as a kind of high The acaricide of effect safety is for preventing and treating agriculture and forestry mite evil.
Technical scheme is as follows：
The present invention provides a kind of fluorine-containing pyridine piperazine compounds, as shown in general formula I：
R is in formula：C1~C5 alkyl, C1~C4 alkoxy, substituted-phenyl, heterocyclic aryl.
Compound of formula I can be made by following reaction：
Each group definition is the same in formula.
Compound III and II reacts obtained type I compound by acid binding agent of triethylamine in ethyl acetate or methylene chloride. Present example is shown in the specific preparation of intermediate III and type I compound.
Table 1 lists the structure and physical property of I compound of partial Formula.
The structure and physical property of 1 part compound of formula I of table
The compounds of this invention all shows higher activity to mite ovum, therefore the invention also includes type I compounds for preventing Control the purposes of agriculture and forestry mite evil.
Advantages of the present invention and good effect：
As acarid constantly enhances the acaricidal resistance of tradition, existing acaricidal drug effect is more and more unobvious, this Invention is combined into amide using piperazine as bridging, by fluorine-containing pyridine and acyl chlorides or carboxyl acid component, has devised a kind of novel acaricide. The compound of the present invention avoids acarid high drug-resistance problem, has unexpected excellent acaricidal activity (see biology of the invention Determination of activity example), have the characteristics that dosage is few, toxicity is low, drug effect is high.The biological degradability of the compounds of this invention is good, uses peace Entirely, environmental pollution is small.In addition, I synthesis technology of the compounds of this invention formula is simple, production cost is low, has and kills as initiative property The prospect of mite agent new varieties industrialization.
The compounds of this invention can both can be used alone according to actual needs when preventing and treating acarid, can also be with other active matters Matter is applied in combination, to provide the comprehensive performance of product.
Miticide composition the invention also includes compound of formula I as active component, active component in the miticide composition Weight percentage between 1-99%.It further include forestry, agriculturally acceptable carrier in the miticide composition.
Composition of the invention can be used in the form of preparation：Compound of formula I is dissolved or dispersed in as active component In carrier or solvent, adds suitable surfactant and missible oil, suspending agent, microemulsion etc. is made.
It should be appreciated that various transformation and change can be carried out in the range of the restriction of claim of the invention.
Specific embodiment
Following synthetic example and raw test result can be used to further illustrate the present invention, but be not intended to limit this hair It is bright.
Synthesize example：
The preparation of example 1, intermediate III
17.2g (0.2mol) Piperazine anhydrous is added in 250mL reaction flask and 60mL methanol, stirring and dissolving are simultaneously warming up to 40 DEG C, chloro- 5- (trifluoromethyl) pyridine of 50mL methanol dilution 21.6g (0.1mol) 2,3- bis- then to be used, is slowly added dropwise, drop finishes, and 40 DEG C isothermal reaction 6h, TLC track to raw material fully reacting, are down to room temperature, filter, and filter vacuum revolving removes methanol, are precipitated white Color solid adds water and stirs the remaining Piperazine anhydrous of dissolution, filters, washes filter cake, obtains white solid 22.6g, and fusing point 65.8~ 67.3 DEG C, yield 85%.
1H 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).
Example 2, compound I1Preparation
5.3g (0.02mol) intermediate III is taken to be added in 250mL reaction flask, then addition 35mL ethyl acetate, then plus 2.22g triethylamine stirs lower dropwise addition 10mL ethyl acetate and 3.45g (0.02mol) 3- ethyl -1- methyl-1 H- pyrazoles -5- first The mixed liquor of acyl chlorides drips and reacts at room temperature 30min after finishing, and TLC tracks III fully reacting of intermediate, divides after the stirring of 100mL water is added Liquid, organic phase is dry with anhydrous sodium sulfate, and revolving removes ethyl acetate, cooling white solid 7.3g, and fusing point 103.0~ 105.1 DEG C, yield 91%.
1H NMR(500MHz,DMSO-d6)δ(ppm)8.56(s,1H),8.23(s,1H),6.38(s,1H),3.97(s, 2H),3.82(s,3H),3.58–3.44(m,6H),2.57–2.51(m,2H),1.24–1.21(t,3H).
According to I in example 21Synthetic method synthesize other compounds I2-I13Compound, their hydrogen spectrum nuclear magnetic data is such as Under：
I2Compound：1H NMR(500MHz,DMSO-d6)δ(ppm)8.56(s,1H),8.23(s,1H),3.79(s,2H), 3.74(s,3H),3.56–3.46(m,6H),2.56–2.50(m,2H),1.17–1.14(t,3H).
I3Compound：1H NMR(500MHz,DMSO-d6)δ(ppm)8.59(s,1H),8.25(s,1H),6.26(s,1H), 4.12–4.08(m,2H),3.78–3.66(d,4H),3.52–3.48(d,4H),2.18(d,3H),1.31–1.28(m,3H).
I4Compound：1H NMR(500MHz,DMSO-d6)δ(ppm)8.59(s,1H),8.26(s,1H),4.06(s,2H), 3.85–3.79(d,2H),3.51–3.42(d,6H),2.16(s,3H),1.31–1.29(t,3H).
I5Compound：1H NMR(500MHz,DMSO-d6)δ(ppm)8.58(s,1H),8.23(s,1H),7.73–7.72 (t,1H),7.54(d,2H),3.77(s,2H),3.60–3.42(m,6H).
I6Compound：1H NMR(500MHz,DMSO-d6)δ(ppm)8.57(s,1H),8.22(s,1H),7.47(d,Hz, 2H),7.39(d,Hz,2H),3.76–3.60(m,8H),1.30(s,9H).
I7Compound：1H NMR(500MHz,DMSO-d6)δ(ppm)8.59(s,1H),8.25(s,1H),3.87–3.82 (m,2H),3.56–3.52(m,4H),3.46–3.40(m,2H).
I8Compound：1H NMR(500MHz,DMSO-d6)δ(ppm)8.58(s,1H),8.24(s,1H),7.84–7.83 (d,1H),7.79–7.76(t,1H),7.69–7.66(t,1H),7.56–7.55(d,1H),3.87–3.73(m,2H),3.63– 3.39(m,4H),3.30–3.19(m,2H).
I9Compound：1H NMR(500MHz,DMSO-d6)δ(ppm)8.56(s,1H),8.21(s,1H),3.58–3.56 (dd,4H),3.47–3.45(t,2H),3.40–3.38(t,2H),2.02(s,3H).
I10Compound：1H NMR(500MHz,DMSO-d6)δ(ppm)8.56(s,1H),8.21(s,1H),3.71–3.69 (dd,3.4Hz,4H),3.45–3.43(dd,3.5Hz,4H),1.63–1.59(m,2H),1.17(s,6H),0.82–0.79(t, 3H).
I11Compound：1H NMR(500MHz,DMSO-d6)δ(ppm)8.54(s,1H),8.20(s,1H),3.97–3.94 (t,2H),3.52–3.50(dd,4H),3.42–3.40(dd,4H),1.61–1.57(m,2H),0.89–0.86(t,3H).
I12Compound：1H NMR(500MHz,DMSO-d6)δ(ppm)8.55(s,1H),8.20(s,1H),4.01(t, 2H),3.51(t,4H),3.45–3.40(m,4H),1.59–1.50(m,2H),1.37–1.30(m,2H),0.88(t,3H).
I13Compound：1H NMR(500MHz,DMSO-d6)δ(ppm)8.56(s,1H),8.22(s,1H),7.81–7.70 (m,1H),7.47–7.46(d,1H),7.14–7.12(dd,1H),3.81–3.79(t,4H),3.54–3.52(dd,4H).
Biological activity determination
Example 3, acaricidal activity measurement
Acaricidal ovum activity is measured using infusion process and the method for statistical correction Mortality of insect.Detailed process is：It will be for examination Medicament is diluted to required concentration by effective component respectively, is aseptically respectively drawn in 50mL medical fluid injection culture dish, then divide Jin Ru there be the blade of cinnabar mite ovum (group that mite ovum is normally raised by indoor standardized method), to add 50mL aqua sterilisa Plate does blank control.Culture dish is placed in 24 ± 1 DEG C of constant incubators.The investigation statistics death rate after 48h.
The acaricidal activity test result of 1 series compound of table
According to test result it is found that the compounds of this invention has excellent acaricidal activity, under same dose, chemical combination of the present invention Object I1~I13In acaricidal activity be generally higher than Envidor, especially I1、I2、I4、I6、I7、I12In 1ppm, mite killing ovum mite ovum is killed Rate of going out is significantly higher than comparison medicament Envidor 90% or more.Wherein compound I12Active highest, the mite killing ovum mite in 1ppm Ovum killing rate is still up to 96%.
It should be noted that only several embodiments mentioned in the present invention, the present invention is not limited to implement reality above Example, similar invention belongs to the protection scope of the patent therewith for other.

Claims (3)

1. a kind of fluorine-containing pyridine piperazine acidamide compound, structure is as shown in general formula I：
R is in formula：C1~C5 alkyl, C1~C4 alkoxy, substituted-phenyl, heterocyclic aryl.
2. a kind of purposes of fluorine-containing pyridine piperazine acidamide compound according to claim 1, it is characterised in that general formula I is changed It closes object and is used as acaricide, prevention and treatment agricultural or forestry harmful mites.
3. a kind of miticide composition contains compound of Formula I described in claim 1 and is subjected to as active component and agriculturally Carrier.
CN201810587086.0A 2018-06-06 2018-06-06 Fluorine-containing pyridine piperazine amide compound and application thereof Active CN108822082B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011072174A1 (en) * 2009-12-09 2011-06-16 Agios Pharmaceuticals, Inc. Therapeutically active compounds for use in the treatment of cancer characterized as having an idh mutation
US20130072497A1 (en) * 2005-06-30 2013-03-21 Dow Agrosciences Llc N- substituted piperazines
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130072497A1 (en) * 2005-06-30 2013-03-21 Dow Agrosciences Llc N- substituted piperazines
WO2011072174A1 (en) * 2009-12-09 2011-06-16 Agios Pharmaceuticals, Inc. Therapeutically active compounds for use in the treatment of cancer characterized as having an idh mutation
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

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