CN109384713B - Dichloropropylene ether compound containing azido pyridine, preparation method and application thereof, and pesticide - Google Patents

Dichloropropylene ether compound containing azido pyridine, preparation method and application thereof, and pesticide Download PDF

Info

Publication number
CN109384713B
CN109384713B CN201810925025.0A CN201810925025A CN109384713B CN 109384713 B CN109384713 B CN 109384713B CN 201810925025 A CN201810925025 A CN 201810925025A CN 109384713 B CN109384713 B CN 109384713B
Authority
CN
China
Prior art keywords
compound
formula
group
remaining
alkyl
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
Application number
CN201810925025.0A
Other languages
Chinese (zh)
Other versions
CN109384713A (en
Inventor
杨光富
吴琼友
潘金环
王震宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central China Normal University
Original Assignee
Central China Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Central China Normal University filed Critical Central China Normal University
Publication of CN109384713A publication Critical patent/CN109384713A/en
Application granted granted Critical
Publication of CN109384713B publication Critical patent/CN109384713B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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

Landscapes

  • 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)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to the field of pesticides, and discloses a dichloropropylene ether compound containing azido pyridine, a preparation method and application thereof, and a pesticide, wherein the compound has a structure shown in formula (1), R1、R2、R3And R4Any one of which is an azido group and the remaining three are the same or different and are each independently selected from H, C1‑6Alkyl, halogen, NO2、CN、COR4、CO2R4C substituted by 1-3 halogens1‑6Alkyl groups of (a); and R is4Is H or C1‑6Alkyl group of (1). The dichloropropylene ether compound containing azido pyridine provided by the invention has excellent pest control effect, and has the advantages of higher activity and better broad spectrum compared with the prior art.

Description

Dichloropropylene ether compound containing azido pyridine, preparation method and application thereof, and pesticide
Technical Field
The invention relates to the field of pesticides, in particular to a dichloropropylene ether compound containing azido pyridine, a method for preparing the dichloropropylene ether compound containing azido pyridine, a dichloropropylene ether compound containing azido pyridine prepared by the method, application of the dichloropropylene ether compound containing azido pyridine in preventing and treating lepidoptera and thysanoptera pests and a pesticide.
Background
With the enhancement of human civilization degree and the continuous improvement of environmental awareness, the negative effects caused by the use of a large amount of high-toxicity pesticides are widely concerned by people.
Traditional organophosphorus insecticides have been gradually banned and eliminated due to toxicity and environmental problems, and on the other hand, pest resistance problems have become more and more serious due to the long-term repeated use of single-action-mechanism insecticides for pest control.
Therefore, development of a green pesticide having high activity, low toxicity and high safety, and particularly having a new action mechanism, has been a goal pursued by pesticide researchers in recent years. Among them, dichloropropene compounds are a class of insecticidal activity having a novel mechanism of action.
Many prior arts disclose dihalopropene-containing ether compounds having insecticidal activity, for example, CN101921228A, CN1137265A, CN1318535A, CN1681771A and the like.
However, all of the dihalopropenyl ether compounds disclosed in the above prior art have a good control effect on a very small number of pests, and have a certain limitation in broad spectrum.
Disclosure of Invention
The invention aims to overcome the defect of poor broad spectrum of pest control of dihalopropene ether compounds disclosed in the prior art, and provides a dichloropropene ether compound containing azido pyridine with good pest control effect and good broad spectrum.
In order to achieve the above object, a first aspect of the present invention provides a dichloropropylene ether-based compound containing azidopyridine, which has a structure represented by formula (1),
Figure BDA0001765149900000021
wherein the content of the first and second substances,
q is selected from unsubstituted or substituted C1-3Alkyl-substituted C of1-12Alkylene of (C)3-12Cycloalkylene radical of (2)2-6And at least two carbon atoms forming the cycloalkylene group are on the main chain structure represented by formula (1);
R1、R2、R3and R4Any one of which is an azido group and the remaining three are the same or different and are each independently selected from H, C1-6Alkyl of (C)6-12Aryl, halogen, NO2、CN、COR4、CO2R4C substituted by 1-3 halogens1-6Alkyl groups of (a); and R is4Is H or C1-6Alkyl group of (1).
The second aspect of the present invention provides a method for producing a dichloropropylene ether compound containing azido pyridine, the dichloropropylene ether compound having a structure represented by formula (1), the method comprising:
(1) carrying out a first reaction on a compound shown as a formula (11) and iron powder in the presence of ammonium chloride to obtain an intermediate shown as a formula (12);
(2) carrying out a second reaction on the intermediate shown in the formula (12) and sodium azide under an acidic condition in the presence of nitrite;
Figure BDA0001765149900000022
Figure BDA0001765149900000031
q, R in formula (1), formula (11), and formula (12)1、R2、R3And R4The definition of (a) is the same as the aforementioned definition of the present invention;
r in the formula (11)11、R12、R13And R14Any one of which is nitro, the remaining three being as defined for R in the invention1、R2、R3And R4The remaining three groups in (1) except for the azido group correspond toThe same is carried out;
r in the formula (12)21、R22、R23And R24Any one of which is amino and the remaining three are as defined for R in the invention1、R2、R3And R4The remaining three groups in (a) other than the azide group are correspondingly the same.
In a third aspect of the present invention, there is provided a dichloropropylene ether-based compound containing an azido pyridine, which is produced by the process according to the second aspect.
In a fourth aspect, the invention provides an application of the dichloropropylene ether compound containing azido pyridine in controlling lepidoptera and thysanoptera pests.
In a fifth aspect, the present invention provides a pesticide, which is composed of an active ingredient and an auxiliary material, wherein the active ingredient includes at least one of the dichloropropylene ether compounds containing azido pyridine of the present invention.
The dichloropropylene ether compound containing azido pyridine provided by the invention has excellent pest control effect and has the advantage of good broad spectrum compared with the prior art.
Particularly, the dichloropropylene ether compound containing azido pyridine provided by the invention has more remarkable effect in preventing and controlling lepidoptera and thysanoptera pests compared with the medicament provided by the prior art.
Specifically, it can be seen from the data listed in the examples section of the present invention that the compounds provided by the present invention have excellent effects on controlling pests such as diamondback moth, cotton bollworm, prodenia litura, beet armyworm, chilo suppressalis, and thrips. Moreover, the compound provided by the invention has more obvious effect on preventing and controlling diamondback moth pests compared with the medicament provided by the prior art.
Detailed Description
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.
As described above, according to a first aspect of the present invention, there is provided a dichloropropylene ether-based compound containing azidopyridine, which has a structure represented by the formula (1),
Figure BDA0001765149900000041
wherein the content of the first and second substances,
q is selected from unsubstituted or substituted C1-3Alkyl-substituted C of1-12Alkylene of (C)3-12Cycloalkylene radical of (2)2-6And at least two carbon atoms forming the cycloalkylene group are on the main chain structure represented by formula (1);
R1、R2、R3and R4Any one of which is an azido group and the remaining three are the same or different and are each independently selected from H, C1-6Alkyl of (C)6-12Aryl, halogen, NO2、CN、COR4、CO2R4C substituted by 1-3 halogens1-6Alkyl groups of (a); and R is4Is H or C1-6Alkyl group of (1).
“C1-3The "alkyl group" of (1) represents an alkyl group having 1 to 3 carbon atoms, and includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group.
“C1-12The "alkylene group" of (a) represents an alkylene group having 1 to 12 carbon atoms, and may be, for example, -CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-。
Is composed of1-3Alkyl-substituted C of1-12The alkylene group of (1) represents a group having a total number of carbon atoms of 1 to 12, including carbon atoms contained in the substituent, and may be, for example, -CH (CH)3)-、-CH(CH3)CH2-、-CH(CH3)CH2CH2-、-C(CH3)2-、-CH(CH3)CH(CH3)-、-CH2C(CH3)2CH2-、-CH2C(CH3)2CH2CH2CH2-、-CH2CH2CH(CH3)CH2CH2-and the like.
“C3-12The "cycloalkylene group" of (a) represents a cyclic alkylene group having 3 to 12 carbon atoms, which may include a saturated ring or an unsaturated ring; that is, at least 3 carbon atoms together form a ring, e.g. may comprise
Figure BDA0001765149900000051
Figure BDA0001765149900000052
And the like.
“C2-6By saturated or unsaturated cycloalkylene group containing a heteroatom selected from S or O "is meant a cyclic alkylene group containing 2 to 6 carbon atoms and containing a heteroatom selected from S or OThe saturated or unsaturated cyclic alkylene group containing hetero atoms of O, i.e. at least two carbon atoms forming together a ring and containing at least one hetero atom chosen from S or O, may, for example, comprise
Figure BDA0001765149900000053
And the like.
“C1-6The "alkyl group" in (1) represents an alkyl group having 1 to 6 carbon atoms, and 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 tert-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a cyclopropyl group, a methylcyclopropyl group, an ethylcyclopropyl group, a cyclopentyl group, a methylcyclopentyl group, or a cyclohexyl group.
"C substituted by 1-3 halogens1-6The "alkyl group of (1)" represents an alkyl group having 1 to 4 carbon atoms, and 1 to 3H's on the alkyl group are substituted with a halogen.
“C6-12The "aryl group" of (a) represents an aromatic group having 6 to 12 carbon atoms, for example, a phenyl group substituted with an alkyl group having 1 to 6 carbon atoms, or the like.
Preferably, Q is selected from unsubstituted or substituted C1-3Alkyl-substituted C of1-8Alkylene of (C)3-9Cycloalkylene radical of (2)2-6And at least two carbon atoms forming the cycloalkylene group are on the main chain structure represented by formula (1); preferably, Q is selected from unsubstituted or substituted C1-3Alkyl-substituted C of1-6Alkylene of (C)3-6Cycloalkylene radical of (2)2-6And at least two carbon atoms forming the cycloalkylene group are on the main chain structure represented by formula (1); preferably, Q is selected from the group consisting of-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH(CH3)-、-CH(CH3)CH2-、-CH(CH3)CH2CH2-、-C(CH3)2-、-CH(CH3)CH(CH3)-、-CH2C(CH3)2CH2-、
Figure BDA0001765149900000061
Figure BDA0001765149900000062
A group of the group consisting of.
Preferably, R1、R2、R3And R4Any one of which is azido and the remaining three are the same or different and are each independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, methylcyclopropyl, ethylcyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, phenyl, F, Cl, Br, NO2、CN、COR4、CO2R4C substituted by 1-3 halogens selected from F or Cl1-6Alkyl groups of (a); and R is4Is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, methylcyclopropyl, ethylcyclopropyl, cyclopentyl, methylcyclopentyl or cyclohexyl; more preferably, R1、R2、R3And R4Any one of them is azido, the remaining three are the same or different, and are each independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, F, Cl, NO2、Br、CN、COR4、CO2R4C substituted by 1-3 halogens selected from F or Cl1-6Alkyl groups of (a); and R is4Is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, cyclopentyl or cyclohexyl; more preferably, R1、R2、R3And R4Any one of them is azido, the remaining three are the same or different and are each independently selected from H, methyl, ethyl, n-propyl, isopropyl, cyclopropylN-butyl, isobutyl, tert-butyl, methylcyclopropyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl, F, Cl, Br, NO2、CN、COR4、CO2R4C substituted by 1-3 elements selected from F1-3Alkyl groups of (a); and R is4Is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
According to a first preferred embodiment, in formula (1),
q is selected from unsubstituted or substituted C1-3Alkyl-substituted C of1-8Alkylene of (C)3-6Cycloalkylene radical of (2)2-6And at least two carbon atoms forming the cycloalkylene group are on the main chain structure represented by formula (1);
R1、R2、R3and R4Any one of which is an azido group and the remaining three are the same or different and are each independently selected from H, C1-6Alkyl, phenyl, F, Cl, Br, NO2、CN、COR4、CO2R4C substituted by 1-3 halogens selected from F or Cl1-6Alkyl groups of (a); and R is4Is H or C1-6Alkyl group of (1).
According to a second preferred embodiment, in formula (1),
q is selected from-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH(CH3)-、-CH(CH3)CH2-、-CH(CH3)CH2CH2-、-C(CH3)2-、-CH(CH3)CH(CH3)-、-CH2C(CH3)2CH2-、
Figure BDA0001765149900000071
Figure BDA0001765149900000072
A group of the group consisting of;
R1、R2、R3and R4Any one of them is azido, the remaining three are the same or different and are each independently selected from H, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, methylcyclopropyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl, F, Cl, Br, NO2、CN、COR4、CO2R4C substituted by 1-3 elements selected from F1-3Alkyl groups of (a); and R is4Is H or C1-4Alkyl group of (1).
According to a particularly preferred embodiment, the dichloropropylene ether-based compound containing azidopyridine of the invention is selected from at least one of the specific compounds described in claim 4.
As described above, the second aspect of the present invention provides a method for producing a dichloropropylene ether-based compound containing azidopyridine, the compound having a structure represented by formula (1), the method comprising:
(1) carrying out a first reaction on a compound shown as a formula (11) and iron powder in the presence of ammonium chloride to obtain an intermediate shown as a formula (12);
(2) carrying out a second reaction on the intermediate shown in the formula (12) and sodium azide under an acidic condition in the presence of nitrite;
Figure BDA0001765149900000081
q, R in formula (1), formula (11), and formula (12)1、R2、R3And R4The definition of (a) is the same as the aforementioned definition of the present invention;
r in the formula (11)11、R12、R13And R14Any one of which is nitro, the remaining three being as defined for R in the invention1、R2、R3And R4The remaining three groups in (a) other than the azide group are correspondingly the same;
r in the formula (12)21、R22、R23And R24Any one of which is amino and the remaining three are as defined for R in the invention1、R2、R3And R4The remaining three groups in (a) other than the azide group are correspondingly the same.
In the second aspect and the following aspects of the present invention, the substituents of the dichloropropene ether compounds containing azido pyridine with the structure represented by formula (1) are the same as those of the dichloropropene ether compounds containing azido pyridine in the first aspect of the present invention, so in order to avoid repetition, detailed descriptions of specific types of the dichloropropene ether compounds containing azido pyridine are not provided herein, and those skilled in the art should not be construed as limiting the present invention.
Preferably, the conditions of the first reaction include: the temperature is 50-300 ℃, and the time is 0.5-48 h.
Preferably, the conditions of the second reaction include: the temperature is from minus 20 ℃ to minus 30 ℃, and the time is 0.5 to 48 hours.
Preferably, in step (2), the acidic condition is formed by at least one acidic substance selected from hydrochloric acid and sulfuric acid.
Preferably, the step (1) is performed in the presence of at least one solvent selected from the group consisting of methanol, ethanol, tetrahydrofuran, DMF, and water.
The method of the present invention is not particularly limited with respect to the source of the compound represented by the formula (11) and the compound represented by the formula (12), and the compounds may be commercially available, or may be synthesized by selecting a synthetic method conventionally used in the art according to the difference in substituents.
The compound represented by the formula (11) of the present invention may be carried out by a method comprising the steps of:
a third reaction of the compound represented by the formula (13) with a nitropyridine compound represented by the formula (14) in the presence of sodium hydride,
Figure BDA0001765149900000091
wherein the substituents in formula (13) and formula (14) are as defined for the substituents in formula (1) and formula (11).
Preferably, the third reaction is carried out in the presence of at least one organic solvent such as tetrahydrofuran, DMF, ethanol, and the like.
Various post-treatment steps conventionally used in the art may be further included between the steps of the aforementioned preparation method of the present invention, and the present invention is not particularly limited thereto.
The preparation method of the present invention is not particularly limited to the ratio of the raw materials, and those skilled in the art can determine the ratio of the raw materials to be added according to the structural formula provided by the present invention and the reaction relationship between the raw materials. Several amounts of substances are provided as examples in the preparation of the present invention and the person skilled in the art should not be understood as limiting the invention.
As described above, the third aspect of the present invention provides the dichloropropylene ether-based compound containing azido pyridine prepared by the method of the second aspect.
As described above, the fourth aspect of the present invention provides the use of the dichloropropylene ether compound containing azidopyridine of the first and third aspects for controlling lepidoptera and thysanoptera pests.
Preferably, in the application, the lepidoptera pests comprise at least one of cnaphalocrocis medinalis, armyworms, cotton bollworms, chilo suppressalis, corn borers, tryporyza incertulas, oriental tobacco budworms, tobacco aphid moths, diamond back moths, beet armyworms, prodenia litura, prodenia lituras, bagworms, cabbage worms, bean worms and hornworms.
Preferably, in said use, said thysanoptera pest comprises at least one of thrips tabaci, thrips oryzae, thrips floribunda and thrips greenhouse.
Particularly, the dichloropropylene ether compound containing azido pyridine provided by the invention has excellent effect on controlling pests such as diamondback moth, cotton bollworm, prodenia litura, beet armyworm, striped rice borer, thrips and the like.
As described above, according to a fifth aspect of the present invention, there is provided a pesticide comprising an active ingredient and an adjuvant, wherein the active ingredient comprises at least one of the dichloropropylene ether-based compounds containing azido-pyridine according to the first and third aspects of the present invention.
Preferably, the active ingredient is present in an amount of 1 to 99.9 wt%, preferably 5 to 98 wt%, 8 to 95 wt%, 10 to 92 wt%, 12 to 90 wt%, 15 to 87 wt%, 18 to 85 wt%, 20 to 82 wt%, 22 to 80 wt%, 25 to 78 wt%, 28 to 75 wt%, 30 to 72 wt%, 32 to 70 wt%, 35 to 68 wt%, 38 to 65 wt%, 40 to 62 wt%, 42 to 60 wt%, 45 wt%, 47 wt%, 48 wt%, 50 wt%, 52 wt%, 55 wt%, 58 wt%.
Preferably, the formulation of the pesticide is at least one selected from the group consisting of an emulsion, a wettable powder, a suspension, an emulsion in water, a granule and a water dispersible granule.
In the pesticide of the present invention, the kind of the adjuvant is not particularly limited, and those skilled in the art can select the corresponding kind of adjuvant according to the kind of the formulation. The adjuvants may include, for example, surfactants, solvents, and the like.
The present invention will be described in detail below by way of examples.
In the following examples, the various starting materials used are commercially available in chemical purity, unless otherwise specified.
Preparation example 1: preparing a compound represented by the formula (11) wherein Q is-CH2CH2CH2CH2-，R12Is NO2，R14Is Cl, R11And R13Are all H.
2.2mmol of the compound represented by the formula (13) was placed in a 50mL round-bottom flask, dissolved with 20mL of anhydrous THF, and stirred at 25 ℃ followed by addition of 0.18g of 60% by weight NaH (4.4mmol), addition of 2mmol of the nitropyridine compound represented by the formula (14) after no more bubbles were generated, and heating to reflux. TLC monitoring, the reaction is basically complete after 12 h. And (3) adding ice water to quench the reaction after the system is cooled, extracting an organic phase by using ethyl acetate, washing by using saturated salt solution, drying by using anhydrous sodium sulfate, finally removing the solvent, and carrying out silica gel column chromatography to obtain the compound shown in the formula (11).
The compound represented by the formula (11) was characterized as follows:1H NMR(600MHz,CDCl3)8.65(s,1H),8.49(s,1H),6.85(s,2H),6.12(t,J＝6.0Hz,1H),4.69(t,J＝6.0Hz,2H),4.59(d,J＝6.0Hz,2H),4.04(t,J＝6.0Hz,2H),2.21–2.11(m,2H),2.05–2.02(m,2H).
preparation example 2: preparing a compound represented by the formula (12) wherein Q is-CH2CH2CH2CH2-，R12Is NH2，R14Is Cl, R11And R13Are all H.
Adding 1.8mmol of the compound shown in the formula (11) and ammonium chloride (1.8mmol) into a 50mL round-bottom flask, adding 30mL ethanol and 5mL water, heating to reflux, adding reduced iron powder (5.4mmol), stopping the reaction after TLC monitors that the raw materials react, filtering the iron powder by using kieselguhr, concentrating the filtrate under reduced pressure, removing most of the solvent by spinning, adding ethyl acetate to extract an organic phase, washing with saturated saline water, adding anhydrous sodium sulfate for drying, and spinning out the solvent to obtain the compound shown in the formula (12), wherein the yield is over 90%. The obtained product is directly put into the next reaction.
Preparation example 3: preparing a compound represented by the formula (1) wherein Q is-CH2CH2CH2CH2-，R12Is N3，R14Is Cl, R11And R13Are all H.
A50 mL round-bottom flask was charged with 1.5mmol of the compound represented by formula (12), dissolved in 10mL glacial acetic acid, and then 0.5mL concentrated hydrochloric acid was added, and then the mixture was placed in a low-temperature reactor to keep the temperature at about 0 deg.C, and NaNO was added dropwise2Solution (1.6mmol of NaNO)2Dissolved in 0.5mL of water), the reaction is continued for 0.5h after the dropwise addition is finished, and 3.75mmol of NaN is added3TLC detection allowed the reaction to complete. After the reaction is finished, adding a large amount of water into the system, washing out solids, performing suction filtration to obtain a crude product, and finally performing silica gel column chromatography on the crude product to obtain a pure target compound.
Yield of the target compound (compound 1) was 65%, white solid, m.p.: 56-57 ℃;1H NMR(600MHz,CDCl3)7.84(s,1H),7.26(s,1H),7.17(s,1H),6.84(s,2H),6.11(t,J＝6.0Hz,1H),4.58(d,J＝6.0Hz,2H),4.47(t,J＝6.0Hz,2H),4.02(t,J＝6.0Hz,2H),2.16–2.05(m,2H),2.04–1.95(m,2H)；13C NMR(151MHz,CDCl3)155.21,153.87,145.93,140.19,129.74,127.91,124.92,124.53,124.49,123.94,115.19,73.01,66.94,65.47,26.73, 25.39; HRMS (MALDI) calculation C18H15Cl5N4O3[M+H]+510.9587. Found 510.9587.
The remaining specific compounds in Table 1 were prepared in the same manner as in the above-mentioned preparation examples 1 to 3, and the characterization data are respectively as follows.
TABLE 1
Figure BDA0001765149900000131
Figure BDA0001765149900000141
Compound 2:
Figure BDA0001765149900000151
the yield is 55%; a white solid; m.p. 73-74 ℃;1H NMR(600MHz,CDCl3)8.18(s,1H),7.38(s,1H),6.85(s,2H),6.12(t,J＝6.0Hz,1H),4.84(t,J＝4.2Hz,2H),4.59(d,J＝6.0Hz,2H),4.39(t,J＝4.2Hz,2H)；13C NMR(151MHz,CDCl3)158.12,154.09,145.48,139.41,129.61,125.96,124.96,124.51,124.40,124.16,122.36,121.32,121.10,120.88,115.15,70.96,66.33, 65.41; HRMS (MALDI) calculation C17H11Cl4F3N4O3[M+H]+516.9537. Found 516.9537.
Compound (I) was synthesized in a similar manner as described above, all of which were confirmed by nuclear magnetic and high-resolution mass spectrometry, and structural information and characterization data of some of the compounds are as follows.
Compound 3:
Figure BDA0001765149900000152
the yield is 60 percent; a white solid; m.p. 70-71 ℃;1HNMR(400MHz,CDCl3)7.80(d,J＝2.4Hz,1H),7.16(d,J＝2.4Hz,1H),6.81(s,2H),6.09(t,J＝6.0Hz,1H),4.73(t,J＝4.8Hz,2H),4.56(d,J＝6.0Hz,2H),4.34(t,J＝4.8Hz,2H)；13C NMR(101MHz,CDCl3)166.90,154.38,153.83,145.37,139.82,129.50,127.88,124.30,124.20,115.04,71.14,65.94, 65.47; HRMS (MALDI) calculation C16H11Cl5F3N4O3[M+H]+482.9274. Found 482.9273.
Compound 4:
Figure BDA0001765149900000161
the yield is 56 percent; a grey solid; m.p. 67-69 ℃;1HNMR(600MHz,CDCl3)8.21(s,1H),7.36(s,1H),6.85(s,2H),6.13(t,J＝6.0Hz,1H),4.78(t,J＝6.0Hz,2H),4.60(d,J＝6.6Hz,2H),4.18(t,J＝6.0Hz,2H),2.44–2.31(m,2H)；13C NMR(151MHz,CDCl3)158.63,153.98,145.63,139.71,139.68,129.68,124.91,124.47,124.23,124.13,122.43,121.03,120.81,120.59,120.36,115.16,114.71,69.79,65.43,64.42, 29.32; HRMS (MALDI) calculation C18H13Cl4F3N4O3[M+H]+530.9766. Found 530.9764.
Compound 5:
Figure BDA0001765149900000162
the yield is 61%; a white solid; m.p.:66-67℃；1H NMR(600MHz,CDCl3)7.85(d,J＝1.8Hz,1H),7.17(d,J＝1.8Hz,1H),6.83(s,2H),6.11(t,J＝6.0Hz,1H),4.66(t,J＝6.0Hz,2H),4.58(d,J＝6.0Hz,2H),4.15(t,J＝6.0Hz,2H),2.39–2.28(m,2H)；13C NMR(151MHz,CDCl3)155.11,153.90,145.64,140.22,129.67,127.93,124.86,124.47,124.31,123.97,115.10,69.90,65.39,63.84, 29.37; HRMS (MALDI) calculation C17H13Cl5F3N4O3[M+H]+496.9503. Found 496.9501.
Compound 6:
Figure BDA0001765149900000163
the yield is 56 percent; a yellow solid; m.p. 54-55 ℃;1H NMR(600MHz,CDCl3)7.91(d,J＝2.4Hz,1H),7.28(dd,J＝8.4,3.0Hz,1H),6.83(s,2H),6.76(d,J＝8.4Hz,1H),6.11(t,J＝6.0Hz,1H),4.13(t,J＝6.0Hz,2H),2.38–2.24(m,2H)；13C NMR(151MHz,CDCl3)161.21,153.85,145.80,137.33,130.03,129.70,129.53,124.85,124.53,124.46,115.08,111.69,70.20,65.40,62.86, 29.64; HRMS (MALDI) calculation C17H14Cl4N4O3[M+H]+462.9892. Found 462.9890.
Compound 7:
Figure BDA0001765149900000171
the yield thereof was found to be 61%; a white solid; m.p. 53-54 ℃;1H NMR(600MHz,CDCl3)8.17(s,1H),7.35(s,1H),6.84(s,2H),6.12(t,J＝6.0Hz,1H),4.58(t,J＝6.0Hz,4H),4.03(t,J＝6.0Hz,2H),2.19–2.07(m,2H),2.07–1.93(m,2H)；13C NMR(101MHz,CDCl3)158.14,153.36,145.39,139.16,139.12,129.25,124.41,124.37,124.06,123.81,121.57,120.38,120.05,119.71,115.09,114.79,72.62,67.18,65.20,26.53, 25.20; HRMS (MALDI) calculation C19H15F3Cl4N4O3[M+H]+544.9850. Found 544.9851.
Compound 8:
Figure BDA0001765149900000172
the yield is 65%; a white solid; m.p. 56-57 ℃;1H NMR(600MHz,CDCl3)7.84(s,1H),7.26(s,1H),7.17(s,1H),6.84(s,2H),6.11(t,J＝6.0Hz,1H),4.58(d,J＝6.0Hz,2H),4.47(t,J＝6.0Hz,2H),4.02(t,J＝6.0Hz,2H),2.16–2.05(m,2H),2.04–1.95(m,2H)；13C NMR(151MHz,CDCl3)155.21,153.87,145.93,140.19,129.74,127.91,124.92,124.53,124.49,123.94,115.19,73.01,66.94,65.47,26.73, 25.39; HRMS (MALDI) calculation C18H15Cl5N4O3[M+H]+510.9587. Found 510.9587.
Compound 9:
Figure BDA0001765149900000181
the yield is 67%;1H NMR(600MHz,cdcl3)7.93(d,J＝2.1Hz,1H),7.29(d,J＝2.1Hz,1H),6.84(s,2H),6.12(t,J＝6.2Hz,1H),4.58(d,J＝6.3Hz,2H),4.47(t,J＝6.4Hz,2H),4.02(t,J＝6.1Hz,2H),2.09(dd,J＝14.7,6.5Hz,2H),2.00(dd,J＝14.7,6.2Hz,2H).
13C NMR(600MHz,CDCl3)157.55,155.83,147.88,144.46,132.36,131.70,126.83,126.49,117.15,113.18,78.60,74.96,68.87,67.43,28.69,27.34.
compound 10:
Figure BDA0001765149900000182
the yield is 69%;1H NMR(600MHz,cdcl3)8.01–7.95(m,2H),7.44(t,J＝7.6Hz,2H),7.38(t,J＝7.3Hz,1H),7.32(d,J＝7.9Hz,1H),7.24(d,J＝8.0Hz,1H),6.84(s,2H),6.12(t,J＝6.2Hz,1H),4.64(dd,J＝7.6,5.0Hz,2H),4.58(d,J＝6.2Hz,2H),4.05(t,J＝6.2Hz,2H),2.19–2.12(m,2H),2.06(dd,J＝14.6,6.2Hz,2H).
13C NMR(151MHz,cdcl3)157.86,155.75,154.97,152.07,147.94,140.11,131.67,130.61,130.55,128.24,126.84,126.49,124.12,117.11,115.10,75.13,68.15,67.38,28.81,27.41.
compound 11:
Figure BDA0001765149900000191
the yield is 68 percent;1H NMR(600MHz,cdcl3)7.71(s,1H),7.26(s,1H),6.84(s,2H),6.12(t,J＝6.2Hz,1H),4.58(d,J＝6.2Hz,2H),4.46(t,J＝6.3Hz,2H),4.02(t,J＝6.1Hz,2H),2.23(s,3H),2.08(dd,J＝14.2,6.5Hz,2H),2.05–1.98(m,2H).
13C NMR(151MHz,cdcl3)156.79,155.79,147.94,143.64,131.72,130.96,128.50,126.83,126.52,125.01,117.13,75.11,68.20,67.42,28.75,27.45,19.21.
compound 12:
Figure BDA0001765149900000192
the yield is 66%;1H NMR(400MHz,CDCl3)7.75(d,J＝2.7Hz,1H),6.98(dd,J＝8.2,2.7Hz,1H),6.84(s,2H),6.11(t,J＝6.2Hz,1H),4.58(d,J＝6.2Hz,2H),4.46(t,J＝6.2Hz,2H),4.02(t,J＝6.0Hz,2H),2.14–2.05(m,2H),2.00(dt,J＝12.9,6.3Hz,2H).
compound 13:
Figure BDA0001765149900000201
the yield is 65%;1H NMR(400MHz,CDCl3)7.75(d,J＝2.7Hz,1H),6.98(dd,J＝8.2,2.7Hz,1H),6.84(s,2H),6.11(t,J＝6.2Hz,1H),4.58(d,J＝6.2Hz,2H),4.46(t,J＝6.2Hz,2H),4.02(t,J＝6.0Hz,2H),2.14–2.05(m,2H),2.00(dt,J＝12.9,6.3Hz,2H).
compound 14:
Figure BDA0001765149900000202
the yield is 66%;1H NMR(400MHz,CDCl3)7.75(d,J＝2.7Hz,1H),6.98(dd,J＝8.2,2.7Hz,1H),6.84(s,2H),6.11(t,J＝6.2Hz,1H),4.58(d,J＝6.2Hz,2H),4.46(t,J＝6.2Hz,2H),4.02(t,J＝6.0Hz,2H),2.14–2.05(m,2H),2.00(dt,J＝12.9,6.3Hz,2H).
test example 1: insecticidal Activity test
The test method comprises the following steps: referring to the method of 'pesticide bioassay SOP', the adult leaf soaking method is adopted in the experiment, and the stomach toxicity activity of the compound to the target can be detected, which is as follows:
fresh cabbage is beaten into a leaf disk of 5cm, soaked in a technical solution with the concentration matched in an experiment for 15s, taken out, naturally dried, then placed in a culture dish, inoculated with about 10 diamondback moth larvae of 2 years old, the treatment is repeated for 5 times, the death rate of the diamondback moth is recorded at 24h, 48h and 96h respectively, and the results are listed in Table 2.
Pyridalyl (Pyridalyl) and kangda were purchased from carbofuran as control agents, and CK was used as a blank control.
Table 2: insecticidal activity test result of compound on diamondback moth
Figure BDA0001765149900000211
From the results in the table, the compound provided by the invention has a good control effect on plutella xylostella, and particularly, at a concentration of 100ppm for 96 hours, the compound 4, the compound 5, the compound 6, the compound 7 and the compound 8 have a control effect of 100% on the plutella xylostella.
Furthermore, at a dose of 10ppm, compound 4 and compound 7 showed higher lethality, 72% and 100%, respectively.
Test example 2: insecticidal activity compound sieve
Selecting compound 7 for screening insecticidal spectrum and LD50And (4) measuring the value. The test methods and results are as follows:
the indoor toxicity of cotton bollworm, prodenia litura, beet armyworm and diamond back moth is measured by soaking leaf method. Preparing stock solution with high concentration from raw medicine to be tested with DMSO, diluting with 1 ‰ triton to desired concentration during test, soaking fresh cabbage leaf disc with diameter of 5cm in the prepared medicinal solution for 10s, taking out, air drying, placing in culture dish, inoculating insect, and inspecting result after 6 days. When in inspection, the body of the larva is touched lightly with a writing brush, and the condition that the larva can not move coordinately is taken as the death standard.
Data processing:
using POLOplusAnalysis software calculates regression formula of toxicity, LD50Value and 95% confidence limit thereof, in terms of Compound LD50Whether 95% confidence limits of the values overlap serves as a criterion for distinguishing significant differences in virulence.
The results are shown in Table 3.
Table 3: LD of Compound 7 against various target insects50Results of value measurement
Figure BDA0001765149900000221
The above results show that:
1. and (3) diamondback moth: LD of indoor toxicity of compound 7 to diamondback moth50The value is 0.831ppm, which is reduced by 2.5 times compared with pyridalyl (LD of pyridalyl)50The value is 2.021ppm), therefore, the control effect is obviously better than that of pyridalyl;
2. cotton bollworm: LD of indoor toxicity of Compound 7 to Heliothis armigera50The value is 4.011ppm, which is higher than that of pyridalyl (LD) which is a control medicament50A value of 2.933ppm), but the two 95% confidence intervals overlap significantly, with no significant difference between the two;
3. beet armyworm: LD of indoor toxicity of compound 7 to beet armyworm50The value was 2.721ppm, which is lower than that of the control pyridalyl (LD)50Value of 2.997ppm), but both with a 95% confidence intervalLarge overlap, the difference between the two is not significant;
4. prodenia litura: LD of indoor toxicity of compound 7 to prodenia litura50The value is 1.212ppm, and the activity is slightly higher than that of reference medicament pyridalyl (LD)50The value was 1.901ppm), but the two 95% confidence intervals had a large overlap, with no significant difference between the two.
Test example 3: insecticidal activity compound sieve
Compound 7 was carried out for mythimna separata, chilo suppressalis, corn borer, and frankliniella occidentalis of lepidoptera in a similar manner to test example 2, and the test methods, age of the insects used, observation time, and test results are shown in table 4.
Table 4: results of measurement of Compound 7 on Each target insect
Figure BDA0001765149900000231
From the results in Table 4, it can be seen that Compound 7 still has a high control effect against lepidopteran insects at a concentration of 10ppm, and is superior to the control agent; at the concentration of 100ppm, the control effect on the frankliniella occidentalis nymphs of the thysanoptera is 87 percent, and is slightly better than that of a control medicament pyridalyl.
In combination with the above results, compound 7 showed a certain control effect on the western flower thrips nymphs of the order thysanoptera in the indoor activity test, while showing a higher insecticidal activity on various lepidoptera insects. It is worth mentioning that the compound 7 has particularly outstanding control effect on diamond back moths, and indoor toxicity test LD thereof50Compared with pyridalyl, the value is reduced by nearly 2.5 times, and is obviously superior to that of the reference pyridalyl.
Test example 4: insecticidal activity of compound 7 and compound 8 against resistant plutella xylostella
The control of resistant plutella xylostella (collected from southern vegetable fields, Guangzhou) was tested with compound 7 and compound 8 in a similar manner to test example 2, and the test results are shown in Table 5.
Table 5: results of measurement of Compound 7 and Compound 8 for each target insect
Figure BDA0001765149900000241
L3: third instar larva
From the results in table 5, it is clear that compound 7 had a control effect of 71.6% and compound 8 had a control effect of 63.7% against plutella xylostella of the resistant line at a concentration of 10ppm, whereas the commercial control chemical pyridalyl was completely ineffective at the same concentration. That is, the compound of the invention has far better control effect on the diamondback moth of a resistant strain than a commercial control medicament.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (11)

1. A dichloropropylene ether compound containing azido pyridine, which has a structure shown in a formula (1),
Figure FDA0002722358850000011
wherein the content of the first and second substances,
q is selected from-CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH(CH3)-、-CH(CH3)CH2-、-CH(CH3)CH2CH2-、-C(CH3)2-、-CH(CH3)CH(CH3) -and-CH2C(CH3)2CH2-a constituent group;
R1、R2、R3and R4Any one of them isThe remaining three are the same or different and are each independently selected from H, C1-6Alkyl, cyclopropyl, methylcyclopropyl, ethylcyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, halogen, NO2CN, C substituted by 1-3 halogens1-6Alkyl group of (1).
2. The compound according to claim 1, wherein, in formula (1),
R1、R2、R3and R4Any one of which is an azido group and the remaining three are the same or different and are each independently selected from H, C1-6Alkyl, cyclopropyl, methylcyclopropyl, ethylcyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, F, Cl, Br, NO2CN, C substituted by 1-3 halogens selected from F or Cl1-6Alkyl group of (1).
3. The compound according to claim 2, wherein, in formula (1),
R1、R2、R3and R4Any one of them is azido, the remaining three are the same or different and are each independently selected from H, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, methylcyclopropyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, F, Cl, Br, NO2CN, C substituted by 1-3 elements selected from F1-3Alkyl group of (1).
4. The compound according to claim 1, wherein the compound is selected from at least one of the following specific compounds:
compound 1: q is-CH2CH2CH2CH2-；R1And R3Is H, R2Is N3，R4Is Cl;
compound 4: q is-CH2CH2CH2-；R1And R3Is H, R2Is CF3，R4Is N3；
Compound 5:q is-CH2CH2CH2-；R1And R3Is H, R2Is Cl, R4Is N3；
Compound 6: q is-CH2CH2CH2-；R1、R3And R4Is H, R2Is N3；
Compound 7: q is-CH2CH2CH2CH2-；R1And R3Is H, R2Is CF3，R4Is N3；
Compound 8: q is-CH2CH2CH2CH2-；R1And R3Is H, R2Is Cl, R4Is N3；
Compound 9: q is-CH2CH2CH2CH2-；R1And R3Is H, R2Is Br, R4Is N3；
Compound 11: q is-CH2CH2CH2CH2-；R1And R3Is H, R2Is CH3，R4Is N3；
Compound 12: q is-CH2CH2CH2CH2-；R1And R3Is H, R2Is F, R4Is N3；
Compound 13: q is-CH2CH2CH2CH2-；R1And R3Is H, R2Is N3，R4Is H;
compound 14: q is-CH2CH2CH2-；R1And R3Is H, R2Is Br, R4Is N3；
Compound 15: q is-CH2-；R1、R2And R3Is H, R4Is N3；
Compound 16: q is-CH2-；R1And R3Is H, R2Is F, R4Is N3；
Compound 17: q is-CH (CH)3)-；R1And R3Is H, R2Is Cl, R4Is N3；
Compound 18: q is-CH (CH)3)-；R1And R3Is H, R2Is Br, R4Is N3；
Compound 19: q is-C (CH)3)2-；R1And R3Is H, R2Is CF3，R4Is N3；
Compound 20: q is-C (CH)3)2-；R1And R3Is H, R2Is CN, R4Is N3；
Compound 21: q is-CH2C(CH3)2CH2-；R1And R3Is H, R2Is CH3，R4Is N3；
Compound 22: q is-CH2C(CH3)2CH2-；R1And R3Is H, R2Is NO2，R4Is N3；
Compound 23: q is-CH2CH2CH2-；R1And R2Is H, R3Is Cl, R4Is N3；
Compound 24: q is-CH (CH)3)CH2CH2-；R1Is Cl, R2And R3Is H, R4Is N3；
Compound 25: q is-CH2C(CH3)2CH2-；R1And R2Is H, R3Is CF3，R4Is N3；
Compound 51: q is-CH2C(CH3)2CH2-；R1And R2Is H, R3Is CHF2，R4Is N3；
Compound 52: q is-CH2C(CH3)2CH2-；R1And R3Is H, R2Is CHCl2，R4Is N3。
5. A method for preparing dichloropropylene ether compound containing azido pyridine, wherein the compound has a structure shown as a formula (1), and the method comprises the following steps:
(1) carrying out a first reaction on a compound shown as a formula (11) and iron powder in the presence of ammonium chloride to obtain an intermediate shown as a formula (12);
(2) carrying out a second reaction on the intermediate shown in the formula (12) and sodium azide under an acidic condition in the presence of nitrite;
Figure FDA0002722358850000031
Figure FDA0002722358850000032
Figure FDA0002722358850000033
q, R in formula (1), formula (11), and formula (12)1、R2、R3And R4Is as defined in any one of claims 1 to 4;
r in the formula (11)11、R12、R13And R14Any one of which is nitro and the remaining three of which are as defined for R in claims 1 to 41、R2、R3And R4The remaining three groups in (a) other than the azide group are correspondingly the same;
r in the formula (12)21、R22、R23And R24Any one of which is amino and the remaining three are as defined for R in claims 1-41、R2、R3And R4The remaining three groups other than the azide group in (1) correspond toThe same is true.
6. The method of claim 5, wherein the conditions of the first reaction comprise: the temperature is 50-300 ℃, and the time is 0.5-48 h;
the conditions of the second reaction include: the temperature is from minus 20 ℃ to minus 30 ℃, and the time is 0.5 to 48 hours.
7. The method according to claim 5 or 6, wherein, in step (2), the acidic condition is formed by at least one acidic substance selected from hydrochloric acid and sulfuric acid.
8. Use of dichloropropylene ether compounds containing azido pyridine according to any one of claims 1 to 4 for controlling lepidopteran and thysanopteran pests.
9. An insecticide comprising an active ingredient and an adjuvant, wherein the active ingredient comprises at least one of the dichloropropylene ether compounds containing azido pyridine according to any one of claims 1 to 4.
10. The insecticide of claim 9, wherein the active ingredient is present in an amount of 1 to 99.9 wt%.
11. The insecticide according to claim 9 or 10, wherein the insecticide is in a dosage form selected from at least one of wettable powder, suspending agent, aqueous emulsion and water dispersible granule.
CN201810925025.0A 2017-08-14 2018-08-14 Dichloropropylene ether compound containing azido pyridine, preparation method and application thereof, and pesticide Active CN109384713B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2017106931161 2017-08-14
CN201710693116 2017-08-14

Publications (2)

Publication Number Publication Date
CN109384713A CN109384713A (en) 2019-02-26
CN109384713B true CN109384713B (en) 2021-01-01

Family

ID=65418457

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810925025.0A Active CN109384713B (en) 2017-08-14 2018-08-14 Dichloropropylene ether compound containing azido pyridine, preparation method and application thereof, and pesticide

Country Status (1)

Country Link
CN (1) CN109384713B (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW307746B (en) * 1994-10-14 1997-06-11 Sumitomo Chemical Co
CN101921228A (en) * 2009-06-15 2010-12-22 中国中化股份有限公司 Piperazine-contained propylene ether dihalide compound and applications thereof
CN104974083B (en) * 2014-04-04 2017-12-15 华中师范大学 Dichloro allyl ether series compound, insecticide and its application
CN105254558A (en) * 2014-07-14 2016-01-20 湖南化工研究院有限公司 Dichloroallyl ether compound, preparation method and applications thereof

Also Published As

Publication number Publication date
CN109384713A (en) 2019-02-26

Similar Documents

Publication Publication Date Title
KR102445236B1 (en) m-diamide-based compound and its preparation and application
CN105636444B (en) The method for preparing Pesticidal compound
WO2010060231A1 (en) Condensed amino nitroguanidine compounds, synthesis and use as botanical insecticides thereof
CN107445947B (en) One kind containing the pyrazoles oxime ether compound and its preparation method and application of 1,2,3- triazole biphenyl structures
CN112661665B (en) Amide compound and preparation method and application thereof
CN113735769B (en) Quinolinone alkaloid derivative containing acylhydrazone structure at 3-position and preparation method and application thereof
CN102503851B (en) Ferulic acid phenethyl alcohol amine derivative and application thereof
CN109422745B (en) Matrine acylhydrazone derivative, preparation method thereof and application of matrine acylhydrazone derivative in prevention and treatment of plant diseases and insect pests
CN106432081B (en) Preparation method and application of pyrazole oxime ether compound containing 4-chloro-3-ethyl-1-methylpyrazole structure
WO2014172924A1 (en) Quinoline derivative and application thereof
CN109384713B (en) Dichloropropylene ether compound containing azido pyridine, preparation method and application thereof, and pesticide
CN106866649B (en) The preparation method and application of the pyrazol acid amide compounds of -1,3,4- oxadiazoles structure of aryl containing 5-
CN109232550B (en) 3-chloro-5-trifluoromethylpyridyl-1, 3, 4-oxadiazole-2-ketone compound and application thereof
CN109320505B (en) Preparation and application of halogenated butenolide compound with insecticidal activity
CN115872904B (en) N-hydroxy-N-phenyl aromatic amide derivative and application thereof
WO2010075760A1 (en) Heterocyclic nitrogenous compounds with insecticidal activity, their preparation methods and uses thereof
CN109384722B (en) N-substituted amide compound, preparation method and application thereof, and bactericide
CN106749288B (en) N- (substituted-phenyl) Bi Zuo Bing fraxinellones analog derivative, preparation method and application
CN109897031B (en) Benzothiazole derivative containing coumarin group and preparation method and application thereof
CN113461630A (en) Nootkatone thioether derivative containing 1,3, 4-oxadiazole ring, and preparation method and application thereof
CN113024379A (en) Carbonyl-containing compound and preparation method and application thereof
CN110357820A (en) A kind of pyrazoles oxime ether compound of -3- of methyl containing 1- substituted phenyl pyrazole structure and its preparation method and application
CN111057024A (en) Sydneone and sydneone imine compound and preparation method and application thereof
CN109988150B (en) N-alkyl-N-cyanoalkyl benzamide compounds and application thereof
CN109336879A (en) A kind of 3- pyridyl group -1,2,4- furodiazole compound and its application

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