CN107474022B - Thiazolyl neonicotine compound and preparation method and application thereof - Google Patents

Thiazolyl neonicotine compound and preparation method and application thereof Download PDF

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CN107474022B
CN107474022B CN201710800233.3A CN201710800233A CN107474022B CN 107474022 B CN107474022 B CN 107474022B CN 201710800233 A CN201710800233 A CN 201710800233A CN 107474022 B CN107474022 B CN 107474022B
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chloro
thiazolyl
compound
methyl
neonicotinoid
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CN107474022A (en
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武海林
董军杰
戴占勇
龚建
李大铁
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Lianyungang Liben Crop Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • 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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Abstract

The invention discloses a thiazolyl neonicotine compound and a preparation method and application thereof. The structural formula of the thiazolyl neonicotinoid compound is shown as a formula I
Figure DDA0001401353830000011
R1Is hydrogen, methyl or ethyl, R2Is hydrogen, methyl, 2-chloro-5-thiazolylmethyl or 6-chloro-3-picolyl, 2-chloro-5-chloromethylthiazole is firstly reacted with ethylamine to generate 2-chloro-5-ethylamino methylthiazole, and then 1, 1-dichloronitroethylene or 1,1, 1-trichloronitroethane and 2-chloro-5-ethylamino methylthiazole and a compound R1NH2R2In the presence of a base. The thiazolyl neonicotinoid compound can be independently prepared into an insecticide, and can also be mixed with other pesticides to prepare the insecticide. The thiazolyl neonicotinoid compound has the advantages of high insecticidal activity, low toxicity, wide insecticidal spectrum and the like, and has obvious insecticidal effect on plant hoppers, aphids and the like.

Description

Thiazolyl neonicotine compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and relates to a thiazolyl neonicotine compound and a preparation method and application thereof.
Background
The first generation of neonicotinoid insecticides, represented by imidacloprid, have been used for nearly 20 years, but have no insecticidal activity against borers, aphids and the like, and are limited in use. Nitenpyram, acetamiprid, thiamethoxam, clothianidin, dinotefuran and the like have insecticidal activity on stem borers, aphids and the like, but can generate resistance after long-term use. At present, organophosphorus high-toxicity insecticides such as chlorpyrifos, triazophos, profenofos and the like are mainly used for preventing and treating aphids and borers, and have certain harmfulness to the environment and people.
CN102633740A discloses a neonicotinoid compound, a preparation method and application thereof, which mainly introduces the synthesis and insecticidal activity of (E) -N- (2-chloro-5-thiazolylmethyl) -N-ethyl-N' -methoxy-2-nitroethylene diamine, has obvious insecticidal effect on plant hoppers, stem borers and aphids, and has the advantages of high insecticidal activity, low toxicity, wide insecticidal spectrum and the like.
Disclosure of Invention
The invention aims to provide a thiazolyl neonicotinoid compound which has higher insecticidal activity and lower toxicity and particularly has better control effect on plant hoppers, aphids and stem borers.
The technical scheme for realizing the purpose of the invention is as follows:
the thiazolyl neonicotinoid compound has a structural formula shown as a formula I:
Figure BDA0001401353820000011
R1is hydrogen, methyl or ethyl; r2Is hydrogen, methyl, 2-chloro-5-thiazolylmethyl or 6-chloro-3-pyridylmethyl.
The invention also provides a preparation method of the thiazolyl neonicotinoid compound, which comprises the steps of firstly reacting 2-chloro-5-chloromethyl thiazole with ethylamine to generate 2-chloro-5-ethylamino methylthiazole shown in a formula II,
Figure BDA0001401353820000021
then 1, 1-dichloronitroethylene or 1,1, 1-trichloronitroethane and 2-chloro-5-ethylamino methylthiazole and compound R1NH2R2In the presence of a base, to give the compound R1NHR2In, R1Selected from hydrogen, methyl or ethyl, R2Selected from hydrogen, methyl, 2-chloro-5-thiazolylmethyl or 6-chloro-3-pyridylmethyl, the specific steps are as follows:
step 1, mixing 2-chloro-5-chloromethylthiazole with dichloroethane, dropwise adding an ethylamine aqueous solution while stirring, uniformly mixing, heating to 20-60 ℃ for reaction, cooling to room temperature when gas chromatography detects that the 2-chloro-5-chloromethylthiazole is completely converted, adding water, standing to separate an oil phase, extracting the water phase with the dichloroethane, mixing with the oil phase, and removing a solvent to obtain 2-chloro-5-ethylamino methylthiazole;
step 2, mixing 1, 1-dichloronitroethylene or 1,1, 1-trichloronitroethane with dichloromethane, stirring and cooling to 0-10 ℃, dropwise adding 2-chloro-5-ethylamino methylthiazole, dropwise adding an alkali solution, carrying out heat preservation reaction, and dropwise adding a compound R at 5-10 ℃ when the conversion rate of N- (2-chloro-5-thiazole) methyl-N-ethylamine reaches more than 98% by HPLC analysis1NHR2And (2) stirring the aqueous solution, heating to 20-25 ℃, carrying out heat preservation reaction, standing to separate an oil phase, extracting the water phase by using dichloromethane, mixing the water phase with the oil phase, removing the solvent, adding ethyl acetate, fully stirring, cooling to 0-5 ℃, filtering and drying to obtain the thiazolyl neonicotinoid compound.
In the step 1, the reaction temperature is 45-50 ℃.
In the step 1, the molar ratio of the 2-chloro-5-chloromethylthiazole to the ethylamine is 1: 1-1: 5, preferably 1: 3.
In the step 2, the reaction temperature is-10 ℃ to 30 ℃, and more preferably-5 ℃ to 25 ℃.
In step 2, the 1, 1-dichloronitroethylene or 1,1, 1-trichloronitroethane and a compound R1NHR2And the molar ratio of the 2-chloro-5-ethylamino methylthiazole is (1.1-1.3): (1-4): 1, more preferably 1.1: 2.5: 1.
in the step 2, the alkali is potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, triethylamine, N-dimethylaniline or pyridine, preferably potassium carbonate, sodium carbonate or triethylamine.
Furthermore, the invention also provides application of the thiazolyl neonicotinyl compound in preparing pesticides.
The thiazolyl neonicotinoid compound can be used for preparing an insecticide independently, or can be mixed with pyrethroid pesticides, carbamate pesticides, pyridine pesticides, triazone pesticides, amide pesticides, organophosphorus pesticides or abamectin pesticides to prepare an insecticide, and when the thiazolyl neonicotinoid compound is mixed to prepare the insecticide, the weight percentage of the thiazolyl neonicotinoid compound is 1% -99%.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the thiazolyl neonicotinoid compound has the advantages of high insecticidal activity, low toxicity, wide insecticidal spectrum and the like;
(2) the thiazolyl neonicotinoid compound has obvious insecticidal effect on plant hoppers, aphids and the like.
Detailed Description
The present invention will be described in more detail with reference to specific examples.
Example 1
The thiazolyl neonicotinoid compound of this example is (E) -N- (2-chloro-5-thiazolylmethyl) -N-ethyl-N' -methyl-2-nitroethenediamine, and its structural formula is as follows:
Figure BDA0001401353820000031
the thiazolyl neonicotinoid compound is prepared by the following steps:
① A500 mL four-necked flask was charged with 34.3g (98%) of 2-chloro-5-chloromethylthiazole (0.2mol) and 100mL of dichloroethane, stirred at room temperature for about half an hour, dropped with 38.6g of 70% aqueous ethylamine (0.6mol), stirred at 45-50 ℃ to react for 4-5 h, sampled by gas chromatography until 2-chloro-5-chloromethylthiazole was completely converted, cooled to 20 ℃, added with 100mL of water and stirred for half an hour, allowed to stand to separate an oil layer, the water layer was extracted 3 times with dichloroethane, the oil layer was combined and desolventized to obtain 35.51g of 2-chloro-5-ethylamino methylthiazole, with 98.5% of content and 98.5% of yield.
② A500 mL four-necked flask was charged with 35.1g (89%) of 1, 1-dichloronitroethylene (0.22mol) and 150mL of dichloromethane, stirred and cooled to 0-10 deg.C, then dropped with 36.2g (98%) of 2-chloro-5-ethylamino methylthiazole (0.2mol), then dropped with 52g (40%) of potassium carbonate aqueous solution at this temperature, kept warm for 2 hours, sampled and analyzed by HPLC for N- (2-chloro-5-thiazole) methyl-N-ethylamine conversion rate to be 98% or more, then dropped with 38.8g (40%) of methylamine aqueous solution (0.5mol) at 5-10 deg.C, stirred for 1 hour after completion, warmed to 20-25 deg.C and kept warm for 2 hours, left to separate an oil layer, extracted with dichloromethane for 3 times, combined oil layers and desolventized, added with 70g of ethyl acetate, stirred thoroughly, cooled to 0-5 deg.C, filtered and dried to obtain 50g of (E) -N- (2-chloro-5-thiazolylmethyl) -N-ethyl-N' -methyl-2-ethylenediamine-2-nitrosodiamine with 98.6% yield.
Example 2
This example is substantially the same as example 1 except that 10% sodium carbonate was used in place of potassium carbonate in step ②, whereby 49.6g of (E) -N- (2-chloro-5-thiazolylmethyl) -N-ethyl-N' -methyl-2-nitroethenylenediamine was obtained in a content of 98.2% and a yield of 88.1%.
Example 3
This example is substantially the same as example 1 except that 2-fold molar amount of triethylamine was used in place of potassium carbonate in step ②, whereby 49.7g of (E) -N- (2-chloro-5-thiazolylmethyl) -N-ethyl-N' -methyl-2-nitroethylenediamine was obtained in a content of 98.1% and a yield of 88.2%.
Example 4
This example is substantially the same as example 1 except that in step ②, 44.6g (88%) of 1,1, 1-trichloronitroethane (0.22mol) was used in place of 1, 1-dichloronitroethylene, and a 0.12mol aqueous solution of potassium carbonate (40%) was added dropwise at 0 to 10 ℃ with the addition of methylene chloride, whereby 49.5g of (E) -N- (2-chloro-5-thiazolylmethyl) -N-ethyl-N' -methyl-2-nitromethylenediamine was obtained in a content of 98.2% and a yield of 88.0%.
Example 5
This example is substantially the same as example 1 except that 40% dimethylamine was used instead of 40% monomethylamine in step ②, whereby 52.3g of (E) -N- (2-chloro-5-thiazolylmethyl) -N-ethyl-N' -dimethyl-2-nitroethylenediamine was obtained in a content of 98.2% and a yield of 88.4%.
Example 6
This example is essentially the same as example 1 except that 170g (15%) of sodium carbonate was used in place of 52g (40%) of aqueous potassium carbonate solution and 41.8g (98%) of 2-chloro-5-ethylaminomethylpyridine was used in place of 40% of methylamine in step ②, and as a result, 70.5g of (E) -N- (2-chloro-5-thiazolylmethyl) -N-ethyl-N '- (6-chloro-3-pyridylmethyl) -N' -ethyl-2-nitroethenylidenediamine was obtained in a 98.1% yield of 83.1%.
Example 7
Adding 31.9g (89%) of 1, 1-dichloronitroethylene (0.2mol) and 150mL of dichloromethane into a 500mL four-neck flask, stirring and cooling to 0-10 ℃, dropwise adding 75.6g (98%) of 2-chloro-5-ethylamino methylthiazole (0.42mol), dropwise adding 76g (40%) of potassium carbonate aqueous solution at the temperature after the addition, keeping the temperature for 2 hours, heating to 20-25 ℃, keeping the temperature for 2 hours, standing to separate an oil layer, extracting a water layer for 3 times by using dichloromethane, merging the oil layers, desolventizing, adding 70g of ethyl acetate into residual liquid, fully stirring, cooling to 0-5 ℃, filtering and drying to obtain 69g of 1, wherein the content of 1-bis [ N- (2-chloro-5-thiazolylmethyl) -N-ethyl ] -2-nitrovinylidene diamine is 98%, and the yield is 80.1%.
Application example 1
Thiazolyl neonicotinoid compounds prepared in examples 1, 5, 6 and 7 are used as pesticides, indoor bioactivity tests are carried out, and the results are as follows:
(1) the indoor measurement results of brown planthopper and sogatella furcifera show that: when the concentration of the thiazolyl neonicotinoid compounds is 0.5mg/L, the insecticidal rate is 100% in 7 days, and the knockdown rate of the compound in example 1 within 1 hour reaches 85%.
(2) The results of indoor aphid measurement show that: when the concentration of the thiazolyl neonicotinoid compounds is 125mg/L, the insecticidal rate is 100% in 7 days, and the knockdown rate of the compound in example 1 within 1 hour reaches 83%.
Comparative application example 1
Imidacloprid was used as the insecticide and indoor bioactivity assays were performed with the following results:
(1) the indoor measurement results of brown planthopper and sogatella furcifera show that: when the concentration of the imidacloprid is as high as 10mg/L, the insecticidal rate is 80% in 7 days, and no obvious knock-down effect is produced.
(2) The results of indoor aphid measurement show that: when the concentration of imidacloprid is as high as 125mg/L, the 7-day insecticidal rate is 100%, and no obvious knock-down effect is produced.
Application example 2
The thiazolyl neonicotinoid compounds prepared in example 1 are processed into 50% dispersible granules, and are subjected to a rice field test at a dosage of 10 g/mu, and the results are as follows:
(1) for brown planthopper (25%), sogatella furcifera (75%): the insecticidal rate in 20 minutes is 60%, and the insecticidal rate in 12 hours is 100%.
Comparative application example 2
The 50% nitenpyram dispersible granules are used as the insecticide for carrying out the rice field test, and the result is as follows at the dosage of 10 g/mu:
(1) for brown planthopper (25%), sogatella furcifera (75%): the 6-hour insecticidal rate is 60%, and the 24-hour insecticidal rate is 100%.
Application example 3
The thiazolyl neonicotinoid compound 20% prepared in example 1 + pymetrozine 60% are processed into 80% dispersible granules, and a rice field test is carried out, wherein the dosage is 12 g/mu, and the results are as follows:
(1) for brown planthopper (25%), sogatella furcifera (75%): the insecticidal rate in 20 minutes is 50%, and the insecticidal rate in 12 hours is 100%.
Comparative application example 3
The nitenpyram 20% + pymetrozine 60% is processed into 80% nitenpyram, pymetrozine dispersible granules which are used as pesticides for rice field tests at the dosage of 12 g/mu, and the results are as follows:
(1) for brown planthopper (25%), sogatella furcifera (75%): the 6-hour insecticidal rate is 47%, and the 24-hour insecticidal rate is 100%.

Claims (1)

1. The compound pesticide is characterized by being prepared by mixing a thiazolyl neonicotinoid compound with a pyrethroid pesticide, a carbamate pesticide, a pyridine pesticide, a triazone pesticide, an amide pesticide, an organophosphorus pesticide or an abamectin pesticide, wherein the thiazolyl neonicotinoid compound accounts for 1-99 wt%, and the structural formula of the thiazolyl neonicotinoid compound is shown as a formula I:
Figure FDA0002371218940000011
R1is hydrogen, methyl or ethyl; r2Is hydrogen, methyl, 2-chloro-5-thiazolylmethyl or 6-chloro-3-pyridylmethyl.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5364989A (en) * 1989-01-31 1994-11-15 Takeda Chemical Industries, Ltd. 1,1,1-trichloro-2-nitroethane production
CN1203593A (en) * 1995-12-01 1998-12-30 诺瓦蒂斯公司 Process for preparing 2-chlorothiazole compounds
EP0966961A1 (en) * 1998-06-08 1999-12-29 Sumitomo Chemical Company, Limited Method for controlling ectoparasites
CN102633740A (en) * 2012-02-29 2012-08-15 江苏省农用激素工程技术研究中心有限公司 Anabasine compound, preparation method and application of nabasine compound

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5364989A (en) * 1989-01-31 1994-11-15 Takeda Chemical Industries, Ltd. 1,1,1-trichloro-2-nitroethane production
CN1203593A (en) * 1995-12-01 1998-12-30 诺瓦蒂斯公司 Process for preparing 2-chlorothiazole compounds
EP0966961A1 (en) * 1998-06-08 1999-12-29 Sumitomo Chemical Company, Limited Method for controlling ectoparasites
CN102633740A (en) * 2012-02-29 2012-08-15 江苏省农用激素工程技术研究中心有限公司 Anabasine compound, preparation method and application of nabasine compound

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Isao MINAMIDA et al..Synthesis and Insecticidal Activity of Acyclic Nitroethene Compounds Containing a Heteroarylmethylamino Group.《J. Pesticide Sci.》》.1993,第18卷第41-48页. *
Synthesis and Insecticidal Activity of Acyclic Nitroethene Compounds Containing a Heteroarylmethylamino Group;Isao MINAMIDA et al.;《J. Pesticide Sci.》》;19931231;第18卷;第41-48页 *
含2-氯-5-噻唑甲氧基氯虫苯甲酰胺类化合物合成及生物活性;张画轻 等;《农药》;20160331;第55卷(第3期);第170-173 *

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