CN104370899A - Formanilide compounds having 1,2,4-oxadiazole structure as well as preparation method and application of formanilide compounds - Google Patents
Formanilide compounds having 1,2,4-oxadiazole structure as well as preparation method and application of formanilide compounds Download PDFInfo
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- CN104370899A CN104370899A CN201410587095.1A CN201410587095A CN104370899A CN 104370899 A CN104370899 A CN 104370899A CN 201410587095 A CN201410587095 A CN 201410587095A CN 104370899 A CN104370899 A CN 104370899A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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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
- A01N43/82—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 three ring hetero atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
The invention discloses formanilide compounds having a 1,2,4-oxadiazole structure as well as a preparation method and an application of the formanilide compounds. According to the formanilide compounds and the preparation method disclosed by the invention, 2-substituted-6-chloro/bromo-8-methyl-4H-3,1-benzoxazine-4-acetone is taken as a raw material to have a dehydration condensation reaction with substituting amidine so as to obtain the a series of formanilide compound having the 1,2,4-oxadiazole structure through ring closure reaction. The compounds have an excellent effect of preventing harmful insects, can be used for preventing diseases and insect pests of various crops and has the advantages of high efficiency, low toxin and environmental friendliness.
Description
Technical field
The invention belongs to agricultural chemical insecticide field, a kind of carboxanilides compounds containing 1,2,4-oxadiazole structure and preparation method thereof and application.
Technical background
Along with the widespread use of sterilant, the understanding of people to sterilant is more and more deep.The continuous progress of society and development, impel the concept of sterilant to there occurs deep change.Traditions of the past agricultural chemicals can not meet the growth requirement of society, and finds efficient, and low toxicity, low residue, the New-type wide-spectrum insecticide of environmentally friendly type is then be placed on problem urgently to be resolved hurrily in face of researcher.
Carboxanilides compounds is the effective sterilant for lepidopteran class pest developed in recent years.Du pont company in a class of exploitation in 2000 novel take ryanodine receptor as the compound of action target.The features such as this compounds has efficiently, low toxicity, wide spectrum, safety, environmental friendliness.Its representation compound Rynaxypyr (common name: Chlorantraniliprole, trade(brand)name: Aliaco, Coragen, Rynaxypyr) has good insecticidal activity to various agricultural and gardening lepidoptera pest.
Carboxanilides compounds, as agricultural chemicals, has caused the common concern of initiative field scientific research personnel, one of up-to-date focus becoming rapidly new pesticides innovative research.Carboxanilides compounds, according to its constitutional features, can be divided into three parts that are shown below: phenyl ring part (A), aromatic amine moiety (B) and fatty amine moieties (C).
In the structure of modification of phenyl ring part (A), the most successfully be represented as cyanogen insect amide (WO2004067528), it is E.I.Du Pont Company's s-generation ryanodine receptor inhibitor insecticides that success is developed after chlorantraniliprole, cyanogen insect amide is formed by the various polar groups changed on phenyl ring, have more efficient, applicable crops is more extensive, can effectively prevent and treat lepidopteran, Hemiptera and coleopteran pest.E.I.Du Pont Company is (Bioorg Med Chem Lett also in the literature, 2007,17 (22): 6274-6279.) report with structural transformations such as phenyl ring, substituted benzene ring, naphthalene nucleus, heterocycle, fused heterocycles, wherein with phenyl ring and 3, the phenyl ring research that 5-position replaces is more, and insecticidal activity is better than other aromatic nucleus.In addition, CN 102924433 A reports and phenyl ring is replaced to methyl, and synthesize a series of containing pyridine pyrazoles diformylamino radical derivative, this compounds has agricultural insecticidal effect.
In the structure of modification of aromatic amine moiety (B), be mainly divided into the derivative of amido linkage and R
2change.Amide group derivative in, US 20040186141 reports the position changing pyridine in chlorantraniliprole and connect pyrazoles, is connected directly between by pyridine ring in the atom N of acid amides, shows certain insecticidal activity; US2004192731 reports and is replaced with sulfoamido by amide group, the activation analysis of these compounds less but from Preliminary activation test can find out that the activity of these compounds is all not as good as chlorantraniliprole; WO 2007043677 reports and changes amide group into sulfonyl amido, shows certain insecticidal activity; WO 2012163095A1 reports and acid amides is modified to carbonyl thiocarbamide, and part of compounds can reach 100% to the control of small cabbage moth Pyrausta nubilalis (Hubern)., small cabbage moth, beet armyworm under low concentration; At R
2change in, du pont company WO 0170671 A2 first reported R in calendar year 2001
2substituting group, on the impact of such compound activity, points out R in patent
2group is to be significantly improved for activity during substituting group containing N, S heterocycle (as pyridine, pyrazoles, oxazole, triazole, thiazole), and during with heterocycle-phenyl ring or heterocycle-heterocycle for substituting group, activity also significantly improves, wherein, and R
2substituting group is active the highest connects pyrazole group for pyridine.The people such as Lahm in 2007 to R
2for compound when pyridine connects pyrazoles substituting group has carried out structure activity study, when result shows pyrazoles 3 for different substituents, its active magnitude relationship is: OCH
3< OCHF
2< OCH
2cF
3, Cl < Br ≈ CF
3(Bioorg Med Chem, 2009,174:127-4133.).Li Zhengming academician seminar in 2010 Australia of pyrazoles 3 is replaced with azido-methyl under show certain activity (J.Agric.Food Chem.2010,58 (23), 12327-12336.).Pyridine group is replaced with the phenyl that nitro replaces by CN 103467380 A, at low concentrations, all shows very excellent insecticidal effect to small cabbage moth and mythimna separata.
In the structure of modification of fatty amine moieties (C), be mainly divided into the derivative of amido linkage and R
3change.Amido linkage derivative in, US 2004192731 reports that to change acid amides be sulphonamide, and it is sulphamide that WO 2007043677 changes acid amides, and WO 2007024833 reports and inserts at amido linkage the structure that a carbonyl obtains being similar to carbonyl amide group.Above-mentioned transformation compound all shows certain insecticidal activity; At R
3change in CN 102093335 A report acid amides be modified to hydrazone, and good activity is shown to small cabbage moth; WO 2006040113 A2 reports amido modified upper fatty alkyl, alkylamine etc., has all showed good activity to small cabbage moth and mythimna separata.
The present invention is from the developing direction of novel pesticide, paraphenylene terephthalamide compounds does further structure of modification, fatty amide is hidden in 1,2, in 4-oxadiazole, obtain series have no bibliographical information containing 1,2, the carboxanilides compounds of 4-oxadiazole structure, this compounds has larger change to primer chlorantraniliprole.By carrying out biological activity test to this compounds, find that this compounds has good insecticidal activity.
Summary of the invention
The object of the invention is to have synthesized a class brand new containing 1,2,4-oxadiazole carboxanilides compounds, it can be used for the sterilant preparing control agricultural insect pest.
According to bioisosterism, fatty amide is hidden in 1,2, in 4-oxadiazole, structural modification is carried out to primer, synthesized a series of carboxanilides compounds represented by general formula (I) having no bibliographical information and cross, these compounds are excellent agricultural and gardens sterilant, this completes the present invention.
The present invention relates to the formylaniline derivative represented by general formula (I):
Wherein X is H, Cl or Br; R
1for 3-Australia-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-base; 1-methyl ethylene; Adjacent, to containing one or more substituent phenyl, substituting group is hydrogen, halogen, cyano group, nitro, hydroxyl, sulfydryl, amino, C
1-C
3alkoxyl group, C
1-C
3alkylthio, C
1-C
3halogenated alkoxy, C
1-C
3halogenated alkylthio; R
2for containing one or more substituting group pyrazinyl, substituting group is hydrogen, halogen, cyano group, nitro, hydroxyl, sulfydryl, amino, C
1-C
3alkoxyl group, C
1-C
3alkylthio, C
1-C
3halogenated alkoxy, C
1-C
3halogenated alkylthio; Containing one or more substituent pyridine base, substituting group is hydrogen, halogen, cyano group, nitro, hydroxyl, sulfydryl, amino, C
1-C
3alkoxyl group, C
1-C
3alkylthio, C
1-C
3halogenated alkoxy, C
1-C
3halogenated alkylthio; Containing one or more substituent thienyl, substituting group is hydrogen, halogen, cyano group, nitro, hydroxyl, sulfydryl, amino, C
1-C
3alkoxyl group, C
1-C
3alkylthio, C
1-C
3halogenated alkoxy, C
1-C
3halogenated alkylthio; Containing one or more substituting group phenyl, substituting group is hydrogen, halogen, cyano group, nitro, hydroxyl, sulfydryl, amino, C
1-C
3alkoxyl group, C
1-C
3alkylthio, C
1-C
3halogenated alkoxy, C
1-C
3halogenated alkylthio; Halogen in wherein said halogeno-group is selected from as one or more in fluorine, chlorine, bromine, iodine.Containing above-claimed cpd as the agricultural of activeconstituents and horticultural insecticides, and their using method.
Be suitable for preventing and treating lepidopteran class pest as the agricultural of activeconstituents and horticultural insecticides containing above-claimed cpd, as agricultural and gardening lepidoptera pest, the cereal lepidoptera pest of storage, the lepidoptera pest etc. of health field.These insects are harmful to paddy rice, fruit tree, other crops of vegetables, flowers, ornamental plant etc.
Preparation in accordance with the present invention is as follows, but it is never that method limits the scope of the invention in any form.
Synthetic route is as follows:
Wherein X, R
1and R
2as defined above.
In inert solvent, under the condition having alkali, formylaniline derivative (III) obtains through dehydrating condensation the formylaniline derivative (I) containing 1,2,4-oxadiazole with heterocycle amidine derivative (II).
Compound II per is obtained by currently known methods, can refer to document European Joumal ofMedicinal Chemistry, 2008,43,513-539. and Bioorganic & Medicinal Chemistry Letters, 2008,18,3661-3666. etc.
Compound III is obtained by currently known methods, can refer to document Organic & Biomolecular Chemistry, 2013,11,3979-3988. and Tetrahedron Letter, 2012,53,388-391. etc.
Compound III synthetic compound I:
For this reaction inert solvent such as: DMF, N,N-dimethylacetamide, acetone, acetonitrile, tetrahydrofuran (THF), chloroform, methylene dichloride, ether, methyl tertiary butyl ether, benzene, chlorobenzene, toluene, Isosorbide-5-Nitrae-dioxy six alkane etc.
Can be used for the alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, the saleratus etc. that react.
After having reacted, required compound is separated from containing the system of required compound by ordinary method, if necessary, through the purifying such as recrystallization, column chromatography, can required compound be prepared thus.
List in table 1 as the typical compound of formylaniline derivative (I) of the present invention, but it limits the scope of the invention never by any way.
General formula (I)
Table 1
Representative instance of the present invention is described below, but they are not because being regarded as limitation of the present invention.
Embodiment
Following specific embodiment is used for further illustrating the present invention
Synthesis example
The preparation of the bromo-1-of example 1:3-(3-chloropyridine-2-base)-N-(2-methyl-6-(3-methyl isophthalic acid, 2,4-oxadiazole-5-base) phenyl)-1H-pyrazoles-5-methane amide
In 100mL single port bottle, by intermediate 2-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-yl)-8-methyl-4H-3, 1-benzoxazine-4-ketone (1.00g, 2.39mmol) with ethanamidine (0.21g, 2.87mmol) be dissolved in N, in dinethylformamide (DMF), stirring at normal temperature 15min, then sodium hydroxide (0.04g is added, 1.00mmol) continue to stir, reaction 8h, TLC point plate is followed the tracks of, after raw material point disappears, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, dry, column chromatography is purified.
The preparation of the bromo-N-of example 2:3-(4-chloro-2-methyl-6-(3-(pyridine-2-base)-1,2,4-oxadiazole-5-base) phenyl)-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-methane amide
In 100mL single port bottle, by intermediate 2-(3-Australia-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-base) the chloro-8-methyl of-6--4H-3, 1-benzoxazine-4-ketone (1.00g, 2.21mmol) with 2-pyridine amidine (0.36g, 2.65mmol) be dissolved in N, in dinethylformamide (DMF), stirring at normal temperature 15min, then sodium hydroxide (0.04g is added, 1.00mmol) continue to stir, reaction 8h, TLC point plate is followed the tracks of, after raw material point disappears, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, dry, column chromatography is purified.
The preparation of the bromo-N-of example 3:3-(4-chloro-2-methyl-6-(3-(pyridin-3-yl)-1,2,4-oxadiazole-5-base) phenyl)-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-methane amide
In 100mL single port bottle, by intermediate 2-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base) the chloro-8-methyl of-6--4H-3, 1-benzoxazine-4-ketone (1.00g, 2.21mmol) with 3-pyridine amidine (0.36g, 2.65mmol) be dissolved in N, in dinethylformamide (DMF), stirring at normal temperature 15min, then sodium hydroxide (0.04g is added, 1.00mmol) continue to stir, reaction 8h, TLC point plate is followed the tracks of, after raw material point disappears, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, dry, column chromatography is purified.
The preparation of example 4:3-Australia-N-(4-chloro-2-methyl-6-(3-(pyridin-4-yl)-1,2,4-oxadiazole-5-base) phenyl)-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-methane amide
In 100mL single port bottle, by intermediate 2-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base) the chloro-8-methyl of-6--4H-3, 1-benzoxazine-4-ketone (1.00g, 2.21mmol) with 4-pyridine amidine (0.36g, 2.65mmol) be dissolved in N, in dinethylformamide (DMF), stirring at normal temperature 15min, then sodium hydroxide (0.04g is added, 1.00mmol) continue to stir, reaction 8h, TLC point plate is followed the tracks of, after raw material point disappears, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, dry, column chromatography is purified.
The preparation of the bromo-N-of example 5:3-(the bromo-2-methyl of 4--6-(3-(pyridine-2-base)-1,2,4-oxadiazole-5-base) phenyl)-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-methane amide
In 100mL single port bottle, by bromo-for intermediate 6-2-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base)-8-methyl-4H-3, 1-benzoxazine-4-ketone (1.00g, 2.01mmol) with 2-pyridine amidine (0.18g, 2.42mmol) be dissolved in N, in dinethylformamide (DMF), stirring at normal temperature 15min, then sodium hydroxide (0.04g is added, 1.00mmol) continue to stir, reaction 8h, TLC point plate is followed the tracks of, after raw material point disappears, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, dry, column chromatography is purified.
The preparation of example 6:3-Australia-N-(4-Australia-2-methyl-6-(3-(pyridin-3-yl)-1,2,4-oxadiazole-5-base) phenyl)-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-methane amide
In 100mL single port bottle, by intermediate 6-Australia-2-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base)-8-methyl-4H-3, 1-benzoxazine-4-ketone (1.00g, 2.01mmol) with 3-pyridine amidine (0.18g, 2.42mmol) be dissolved in N, in dinethylformamide (DMF), stirring at normal temperature 15min, then sodium hydroxide (0.04g is added, 1.00mmol) continue to stir, reaction 8h, TLC point plate is followed the tracks of, after raw material point disappears, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, dry, column chromatography is purified.
The preparation of example 7:3-Australia-N-(the bromo-2-methyl of 4--6-(3-(pyridin-4-yl)-1,2,4-oxadiazole-5-base) phenyl)-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-methane amide
In 100mL single port bottle, by bromo-for intermediate 6-2-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base)-8-methyl-4H-3, 1-benzoxazine-4-ketone (1.00g, 2.01mmol) with 4-pyridine amidine (0.18g, 2.42mmol) be dissolved in N, in dinethylformamide (DMF), stirring at normal temperature 15min, then sodium hydroxide (0.04g is added, 1.00mmol) continue to stir, reaction 8h, TLC point plate is followed the tracks of, after raw material point disappears, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, dry, column chromatography is purified.
The preparation of the bromo-N-of example 8:3-(4-chloro-2-methyl-6-(3-(pyrazine-2-base)-1,2,4-oxadiazole-5-base) phenyl)-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-methane amide
In 100mL single port bottle, by intermediate 2-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base) the chloro-8-methyl of-6--4H-3, 1-benzoxazine-4-ketone (1.00g, 2.01mmol) with 2-pyrazine amidine (0.33g, 2.42mmol) be dissolved in N, in dinethylformamide (DMF), stirring at normal temperature 15min, then sodium hydroxide (0.04g is added, 1.00mmol) continue to stir, reaction 8h, TLC point plate is followed the tracks of, after raw material point disappears, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, dry, column chromatography is purified.
The preparation of the bromo-N-of example 9:3-(the bromo-2-methyl of 4--6-(3-(pyrazine-2-base)-1,2,4-oxadiazole-5-base) phenyl)-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-methane amide
In 100mL single port bottle, by bromo-for intermediate 6-2-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base)-8-methyl-4H-3, 1-benzoxazine-4-ketone (1.00g, 2.01mmol) with 2-pyrazine amidine (0.33g, 2.42mmol) be dissolved in N, in dinethylformamide (DMF), stirring at normal temperature 15min, then sodium hydroxide (0.04g is added, 1.00mmol) continue to stir, reaction 8h, TLC point plate is followed the tracks of, after raw material point disappears, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, dry, column chromatography is purified.
The preparation of example 10:N-(2-methyl-6-(3-methyl isophthalic acid, 2,4-oxadiazole-5-base) phenyl) benzamide
In 100mL single port bottle, by intermediate 8-methyl-2-phenyl-4H-3,1-benzoxazine-4-ketone (1.00g, 4.21mmol) with ethanamidine (0.37g, 5.06mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
The preparation of example 11:N-(2-methyl-6-(3-(pyridin-3-yl)-1,2,4-oxadiazole-5-base) phenyl) benzamide
In 100mL single port bottle, by intermediate 8-methyl-2-phenyl-4H-3,1-benzoxazine-4-ketone (1.00g, 4.21mmol) with 3-pyridine amidine (0.69g, 5.06mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
The preparation of example 12:N-(4-chloro-2-methyl-6-(3-(pyridin-3-yl)-1,2,4-oxadiazole-5-base) phenyl) benzamide
In 100mL single port bottle, by chloro-for intermediate 6-8-methyl-2-phenyl-4H-3,1-benzoxazine-4-ketone (1.00g, 3.68mmol) with 3-pyridine amidine (0.61g, 4.42mmol) be dissolved in 50mLN, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
The preparation of example 13:N-(4-chloro-2-methyl-6-(3-(pyridin-4-yl)-1,2,4-oxadiazole-5-base) phenyl) benzamide
In 100mL single port bottle, by chloro-for intermediate 6-8-methyl-2-phenyl-4H-3,1-benzoxazine-4-ketone (1.00g, 3.68mmol) with 4-pyridine amidine (0.61g, 4.42mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
The preparation of example 14:N-(4-Australia-2-methyl-6-(3-(pyridin-3-yl)-1,2,4-oxadiazole-5-base) phenyl) benzamide
In 100mL single port bottle, by intermediate 6-Australia-8-methyl-2-phenyl-4H-3,1-benzoxazine-4-ketone (1.00g, 3.68mmol) with 3-pyridine amidine (0.61g, 4.42mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
The preparation of example 15:N-(4-chloro-2-methyl-6-(3-(pyridin-3-yl)-1,2,4-oxadiazole-5-base) phenyl) propionic acid amide
In 100mL single port bottle, by chloro-for intermediate 6-2-ethyl-8-methyl-4H-3,1-benzoxazine-4-ketone (1.00g, 3.73mmol) with 3-pyridine amidine (0.61g, 4.48mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
The preparation of example 16:N-(4-chloro-2-methyl-6-(3-(pyridin-3-yl)-1,2,4-oxadiazole-5-base) phenyl) propionic acid amide
In 100mL single port bottle, by chloro-for intermediate 6-2-ethyl-8-methyl-4H-3,1-benzoxazine-4-ketone (1.00g, 3.73mmol) with 4-pyridine amidine (0.61g, 4.48mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
The preparation of example 17:N-(the bromo-2-methyl of 4--6-(3-(pyridin-3-yl)-1,2,4-oxadiazole-5-base) phenyl) propionic acid amide
In 100mL single port bottle, by bromo-for intermediate 6-2-ethyl-8-methyl-4H-3,1-benzoxazine-4-ketone (1.00g, 3.73mmol) with 3-pyridine amidine (0.61g, 4.48mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
The preparation of example 18:N-(4-chloro-2-methyl-6-(3-(pyridine-2-base)-1,2,4-oxadiazole-5-base) phenyl) but-2-enamides
In 100mL single port bottle, by chloro-for intermediate 6-8-methyl-2-(the third-1-alkene-1-base)-4H-3,1-benzoxazine-4-ketone (1.00g, 4.24mmol) with 2-pyridine amidine (0.70g, 5.09mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5 h, by solid filtering, drying, column chromatography is purified.
The preparation of example 19:N-(4-chloro-2-methyl-6-(3-(pyridin-3-yl)-1,2,4-oxadiazole-5-base) phenyl) but-2-enamides
In 100mL single port bottle, by chloro-for intermediate 6-8-methyl-2-(the third-1-alkene-1-base)-4H-3,1-benzoxazine-4-ketone (1.00g, 4.24mmol) with 3-pyridine amidine (0.70g, 5.09mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
The preparation of example 20:N-(4-chloro-2-methyl-6-(3-(pyridin-4-yl)-1,2,4-oxadiazole-5-base) phenyl) but-2-enamides
In 100mL single port bottle, by chloro-for intermediate 6-8-methyl-2-(the third-1-alkene-1-base)-4H-3,1-benzoxazine-4-ketone (1.00g, 4.24mmol) with 4-pyridine amidine (0.70g, 5.09mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
The preparation of example 21:N-(the bromo-2-methyl of 4--6-(3-(pyridine-2-base)-1,2,4-oxadiazole-5-base) phenyl) but-2-enamides
In 100mL single port bottle, by bromo-for intermediate 6-8-methyl-2-(the third-1-alkene-1-base)-4H-3,1-benzoxazine-4-ketone (1.00g, 4.24mmol) with 2-pyridine amidine (0.70g, 5.09mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
The preparation of example 22:N-(the bromo-2-methyl of 4--6-(3-(pyridin-3-yl)-1,2,4-oxadiazole-5-base) phenyl) but-2-enamides
In 100mL single port bottle, by intermediate 6-Australia-8-methyl-2-(the third-1-alkene-1-base)-4H-3,1-benzoxazine-4-ketone (1.00g, 4.24mmol) with 3-pyridine amidine (0.70g, 5.09mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
The preparation of example 23:N-(the bromo-2-methyl of 4--6-(3-(pyridin-4-yl)-1,2,4-oxadiazole-5-base) phenyl) but-2-enamides
In 100 mL single port bottles, by bromo-for intermediate 6-8-methyl-2-(the third-1-alkene-1-base)-4H-3,1-benzoxazine-4-ketone (1.00g, 4.24mmol) with 4-pyridine amidine (0.70g, 5.09mmol) be dissolved in 50mL N, in dinethylformamide (DMF), stirring at normal temperature 15min, then adds sodium hydroxide (0.04g, 1.00mmol) and continues to stir, react after 8h hour, reaction solution is poured in 500mL saturated sodium bicarbonate solution, stir 0.5h, by solid filtering, drying, column chromatography is purified.
Biological activity test
Example 24: to the insecticidal effect of small cabbage moth
Select 3 instar larvaes, adopt leaching leaf dish feeding method to carry out insecticidal activity test.Take the former medicinal acetone solution of 20mg, tween water is mixed with the mother liquor of 2000ppm.Namely the mother liquor tween water dilution of 0.05% obtains desired concn liquid.Each process 3 repeats, if blank.Ready-made fresh luxuriant dish leaf dish is flooded 10 seconds in liquid, takes out nature and dry.Put 3 leaf dish in each culture dish, access 7 third-instar larvaes simultaneously, sealing.Investigation 1d, 2d, 3d check borer population anyway, and carry out statistical study.
Corrected mortality (%)=insect death toll ÷ insect sum × 100%
: result is shown in table 2 below
Table 2
Any those skilled in the art, without departing from the spirit and scope of the present invention, should make various amendment and change.Therefore protection scope of the present invention should be considered as appending claims limited range.
Claims (4)
1. the carboxanilides compounds (I) containing 2,4-oxadiazole structure, its general structure is:
Wherein X is H, Cl or Br;
R1 is the bromo-1-of 3-(3-chloro-2-pyridyl)-1H-pyrazoles-5-base; 1-methyl ethylene; Adjacent, to containing one or more substituent phenyl, substituting group is hydrogen, halogen, cyano group, nitro, hydroxyl, sulfydryl, amino, C
1-C
3alkoxyl group, C
1-C
3alkylthio, C
1-C
3halogenated alkoxy, C
1-C
3halogenated alkylthio;
R2 is for containing one or more substituent pyrazinyl, and substituting group is hydrogen, halogen, cyano group, nitro, hydroxyl, sulfydryl, amino, C
1-C
3alkoxyl group, C
1-C
3alkylthio, C
1-C
3halogenated alkoxy, C
1-C
3halogenated alkylthio; Containing one or more substituent pyridyl, substituting group is hydrogen, halogen, cyano group, nitro, hydroxyl, sulfydryl, amino, C
1-C
3alkoxyl group, C
1-C
3alkylthio, C
1-C
3halogenated alkoxy, C
1-C
3halogenated alkylthio; Containing one or more substituent thienyl, substituting group is hydrogen, halogen, cyano group, nitro, hydroxyl, sulfydryl, amino, C
1-C
3alkoxyl group, C
1-C
3alkylthio, C
1-C
3halogenated alkoxy, C
1-C
3halogenated alkylthio; Containing one or more substituent phenyl, substituting group is hydrogen, halogen, cyano group, nitro, hydroxyl, sulfydryl, amino, C
1-C
3alkoxyl group, C
1-C
3alkylthio, C
1-C
3halogenated alkoxy, C
1-C
3halogenated alkylthio; Halogen in wherein said halogeno-group is selected from as one or more in fluorine, chlorine, bromine, iodine.
2., as a synthetic method for Compound I as described in any one in claim 1, it is characterized in that: in the basic conditions, in inert solvent, by the compound III of 1 times amount, amount of substance is unit, lower same, is obtained by reacting Compound I with the Compound II per of 1-2 times amount;
3. a synthetic method as claimed in claim 2, is characterized in that: the alkali described in reaction is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, salt of wormwood, one of sodium bicarbonate or saleratus; React described inert solvent and be selected from DMF, N,N-dimethylacetamide, acetone, acetonitrile, tetrahydrofuran (THF), chloroform, methylene dichloride, ether, methyl tertiary butyl ether, benzene, chlorobenzene, one of toluene or Isosorbide-5-Nitrae-dioxy six alkane.
4. agricultural and a horticultural insecticides, be characterised in that containing claim 1 containing the carboxanilides compounds of 1,2,4-oxadiazole structure as activeconstituents.
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