CN103450170A - Pyridine-containing 1,3,4-oxadiazole derivative, and preparation method and application thereof - Google Patents
Pyridine-containing 1,3,4-oxadiazole derivative, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a pyridine-containing 1,3,4-oxadiazole derivative, and a preparation method and application thereof. The preparation method of the pyridine-containing 1,3,4-oxadiazole derivative particularly comprises the following two steps of esterification reaction of triethyl phosphite and Wittig-Horner reaction. The pyridine-containing 1,3,4-oxadiazole derivative disclosed by the invention has obvious insecticidal activity on prodenia litura lepidoptera insects and has an important application value in developing an environment-friendly, high-efficiency and novel insecticide.
Description
Technical field
The invention belongs to pesticide technology and fine chemistry field, be specifically related to 1,3 of pyridine, 4-oxadiazole derivative and preparation method thereof and its application as sterilization or sterilant.
Background technology
Prodenia litura is the important rural economy insect of China, distributed more widely in China, and the diversified economy farm crop such as cotton and vegetables are brought about great losses, and because its fecundity is strong, through the China that is everlasting, causes explosive disaster.
1,3,4-oxadiazole derivative has multiple biological activity: as desinsection, sterilization, anticancer, anti-inflammatory etc.Why this analog derivative has so numerous biological activity, depends primarily on the basic framework that tool in molecule has oxadiazole rings.2,5-bis-replace 1,3,4-oxadiazole analog derivatives along with its 2, the difference of 5 bit substituents and show the biological activity widely such as desinsection, weeding, sterilization, a large amount of results of study shows, some is 2 years old, 5-bis-replaces 1,3,4-oxadiazole derivative and has insect growth inhibition activity.Offshore company has developed agricultural chemicals containing 1,3,4-oxadiazole structure in succession as weedicide humulone (oxadiazon), sterilant worm ketone (metoxadiazone) etc.This compounds has unique biological activity, has caused many broad interests, and they are conducted in-depth research.
Nitrogen-containing heterocycle compound has become the focus of current novel pesticide exploitation, novel agrochemical type containing pyridine ring is various, biological activity is also varied, at aspects such as weeding, sterilization and desinsections, extremely successful example is all arranged, sterilant chlorantraniliprole (Rynaxypyr as the sterilant fluopicolide (fluopicolide) by Beyer Co., Ltd's research and development, E.I.Du Pont Company's research and development, Altacor), the outstanding pesticide new varieties such as weedicide fluorine pyridine second sulphur grand (flucetosulfuron) of Korea S chemical research institute research and development.
[agriculture new millennium, 2008] such as Song Yanli etc. [Institutes Of Chifeng's journal, 2012] and Li Zhifen are all to containing 1 of pyridine, 3, the 4-oxadiazole derivative is studied, but at present containing 1,3, the compou nd synthesis process complexity of 4-oxadiazole and pyridine groups, productive rate is generally 40%-65%, will carry out in sub-zero temperature long reaction time and use a large amount of alkali in production process, the synthesis condition harshness, to environment.
The present invention is intended to utilize the active group principle of hybridization that pyridine groups is introduced in 1,3,4-oxadiazole analog derivative and obtained target compound, and has measured its insecticidal activity.
Summary of the invention
The object of the present invention is to provide containing 1,3 of pyridine, the 4-oxadiazole derivative, the concrete structure formula is as follows:
Another object of the present invention is to provide containing 1,3 of pyridine, the preparation method of 4-oxadiazole derivative, its synthetic route is as follows:
The preparation method of said derivative specifically comprises the following steps:
(1) esterification
By mol ratio, be 1:(1.1～1.5) 2-naphthyl-5-(4-(brooethyl) phenyl)-1,3, after 4-oxadiazole and oily liquids triethyl-phosphite mixed dissolution, in temperature, be stirring and refluxing 3～5h under 125～130 ℃ of conditions, after removing triethyl-phosphite excessive in reaction system, stir and add normal hexane to separate out solid product while hot, then obtain product B with tetrahydrofuran (THF) and normal hexane mixed solution recrystallization.
(2) Wittig-Horner reaction
Respectively equimolar product B and 2-pyridine aldehydes or 4-pyridine aldehydes are dissolved in DMF obtaining to lysate; Ethanol solution to adding the potassium tert.-butoxide that mass percent is 15～30% in described lysate, carry out the Wittig-Horner reaction, and reaction is cooling and filter the gained reaction solution after finishing; The gained filter cake is (2～3) by volume ratio: 1 dimethyl sulfoxide (DMSO) and alcohol mixeding liquid recrystallization make containing 1,3 of pyridine the 4-oxadiazole derivative.
In step (2), DMF is 10～15ml/g with the volume mass ratio of product B.
In step (2), the condition of Wittig-Horner reaction is: 60～70 ℃ of stirring reaction 5h.
Described in step (1), the volume ratio of tetrahydrofuran (THF) and normal hexane is 1:(1～4).
While removing in reaction system triethyl-phosphite in step (1), under reduced pressure, carry out.
The ethanol solution of potassium tert.-butoxide described in step (2) is 3～4ml/g with the volume mass ratio of product B.
The purpose of this invention is to provide containing 1,3 of pyridine, the 4-oxadiazole derivative has good optical activity.
The purpose of this invention is to provide the 2-naphthyl shown in chemical structural formula I and II-5-(4-(2-(4-pyridyl) vinyl) phenyl)-1,3,4-oxadiazole and 2-naphthyl-5-(4-(2-(2-pyridyl) vinyl) phenyl)-1,3, the application of 4-oxadiazole in preparing sterilant.
The present invention compared with prior art has following advantage:
(1) of the present invention containing 1,3 of pyridine, the preparation condition of 4-oxadiazole derivative is gentle, synthetic operation is easy;
(2) the present invention is containing 1,3 of pyridine, and the 4-oxadiazole derivative contains pyridine and 1,3,4-oxadiazole nitrogen heterocyclic ring structure simultaneously, and prodenia litura is had to significant insecticidal activity, can be used for preparing novel pesticide.
The accompanying drawing explanation
Fig. 1 is the uv-visible absorption spectra figure of derivative of the present invention (I) in different solvents.
Fig. 2 is the fluorescence emission spectrogram of derivative of the present invention (I) in different solvents.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the scope of protection of present invention is not limited to this.
The fusing point of the prepared final product of embodiment and nuclear magnetic resonance data are recorded by RY-1 melting point apparatus (Tianjin analytical instrument factory) and BrukerAVANCE-400NMR nuclear magnetic resonance analyser (Brooker,Switzerland company) respectively.The raw materials used 2-naphthyl of the present invention-5-(4-(brooethyl) phenyl)-1,3, the 4-oxadiazole is published on Soft Matter magazine by people such as Parul Rungta, according to people such as Li Xinwei, is published in the synthetic method preparation on Dys and Pigments magazine.
Embodiment 1
2-naphthyl-5-(4-(2-(4-pyridyl) vinyl) phenyl)-1,3,4-oxadiazole (I) synthetic
(1) by 0.0088mol2-naphthyl-5-(4-(brooethyl) phenyl)-1,3, the 4-oxadiazole is dissolved in the 0.0132mol triethyl-phosphite, is heated to 130 ℃, stirring and refluxing reaction 5h, after boiling off triethyl-phosphite excessive in reaction system, stir and add the 5ml normal hexane to separate out solid product while hot, then obtain 3.32g4-(5-naphthyl-1,3 with tetrahydrofuran (THF) and the normal hexane mixed solution recrystallization of 1:1,4-oxadiazole-2-yl) phenmethyl phosphonic acid ester, productive rate: 89.4%.Fusing point: 139-140 ℃.Proton nmr spectra structural characterization data:
1hNMR (400MHz, CDCl
3) δ 9.30 (d, J=8.6Hz, 1H, naphthalene-H), 8.29 (d, J=7.2Hz, 1H, naphthalene-H), 8.18 (d, J=7.9Hz, 2H, C
6h
4, 2,6-H), 8.07 (d, J=8.2Hz, 1H, naphthalene-H), 7.97 (d, J=8.1Hz, 1H, naphthalene-H), 7.73 (t, J=7.7Hz, 1H, naphthalene-H), 7.63 (t, J=7.6Hz, 2H, naphthalene-H), 7.53 (d, J=7.9Hz, 2H, C
6h
4, 3,5-H), 4.08 (q, J=7.2Hz, 4H, CH
2), 3.27 (d, J=22.1Hz, 2H, CH
2), 1.30 (t, J=7.0Hz, 6H, CH
3).
(2) by 0.002mol4-(5-naphthyl-1,3,4-oxadiazole-2-yl) phenmethyl phosphonic acid ester and 0.002mol4-pyridine aldehydes are dissolved in 15ml N, in dinethylformamide, then to dripping the ethanol solution 3ml of the potassium tert.-butoxide that mass ratio is 25% in solution, at 70 ℃ of lower stirring reaction 5h, obtain reaction solution, cooling and filter, the dimethyl sulfoxide (DMSO) that the gained solid is 3:1 by volume ratio and alcohol mixeding liquid recrystallization obtain 0.70g, productive rate: 93.3%.Fusing point: 204-206 ℃.Proton nmr spectra structural characterization data:
1h NMR (400MHz, CDCl
3) δ 9.30 (d, J=8.5Hz, 1H, naphthalen-H), 8.64 – 8.59 (m, 2H, C
5h
4n, 3,5-H), 8.29 (dd, J=7.3,0.9Hz, 1H, naphthalen-H), 8.22 (d, J=8.4Hz, 2H, C
6h
4, 2,6-H), 8.07 (d, J=8.2Hz, 1H, naphthalene-H), 7.96 (d, J=8.1Hz, 1H, naphthalene-H), 7.75 – 7.69 (m, 3H, naphthalene-H, C
6h
4, 3,5-H), 7.62 (t, J=7.8Hz, 2H, naphthalene-H), 7.41 (d, J=6.0Hz, 2H, C
6h
4, 2,6-H), 7.35 (d, J=16.4Hz, 1H, CH=CH), 7.15 (d, J=16.4Hz, 1H, CH=CH).
Embodiment 2
2-naphthyl-5-(4-(2-(2-pyridyl) vinyl) phenyl)-1,3,4-oxadiazole (II) synthetic
(1) by 0.0088mol2-naphthyl-5-(4-(brooethyl) phenyl)-1,3, the 4-oxadiazole is dissolved in the 0.0097mol triethyl-phosphite, is heated to 125 ℃, stirring and refluxing reaction 3h, in the pressure reducing and steaming reaction system after excessive triethyl-phosphite, stir and add the 5ml normal hexane to separate out solid product while hot, then obtain 2.98g4-(5-naphthyl-1,3 with tetrahydrofuran (THF) and the normal hexane mixed solution recrystallization of 1:4,4-oxadiazole-2-yl) phenmethyl phosphonic acid ester, productive rate: 80.2%.
(2) by 0.0020mol4-(5-naphthyl-1,3,4-oxadiazole-2-yl) phenmethyl phosphonic acid ester and 0.0020mol2-pyridine aldehydes are dissolved in 10ml N, in dinethylformamide, then to dripping the ethanol solution 4ml of the potassium tert.-butoxide that mass ratio is 15% in solution, at 60 ℃ of lower stirring reaction 5h, obtain reaction solution, cooling and filter, the dimethyl sulfoxide (DMSO) that the gained solid is 2:1 by volume ratio and alcohol mixeding liquid recrystallization obtain 0.60g, productive rate: 79.9%.Fusing point: 187-188 ℃.Proton nmr spectra structural characterization data:
1h NMR (400MHz, CDCl
3) δ 9.30 (d, J=8.6Hz, 1H, naphthalen-H), 8.64 (d, J=4.2Hz, 1H, C
5h
4n, 3-H), 8.29 (d, J=7.2Hz, 1H, naphthalen-H), 8.20 (d, J=8.2Hz, 2H, C
6h
4, 2,6-H), 8.06 (d, J=8.2Hz, 1H, naphthalene-H), 7.95 (d, J=8.1Hz, 1H, naphthalene-H), 7.73 (dd, J=19.1,7.3Hz, 5H, CH=CH, naphthalene-H, C
6h
4, 3,5-H, C
5h
4n, 6-H), 7.62 (dd, J=10.7,4.8Hz, 2H, naphthalene-H), 7.44 (d, J=7.8Hz, 1H, C
5h
4n, 5-H), 7.30 (d, J=16.1Hz, 1H, CH=CH), 7.23 – 7.17 (m, 1H, C
5h
4n, 4-H).
Embodiment 3
2-naphthyl-5-(4-(2-(4-pyridyl) vinyl) phenyl)-1,3, the optically active mensuration of 4-oxadiazole (I)
(1) solution (DMSO, THF, the CHCl with opposed polarity by compound (I)
3) be made into same concentrations 1 * 10
-5the solution of mol/L, getting range of wavelengths on ultraviolet-visible spectrophotometer is that 200-500nm measures uv-absorbing, obtains its uv-visible absorption spectra (Fig. 1).
(2) solution (DMSO, THF, the CHCl with opposed polarity by compound (I)
3) be made into same concentrations 1 * 10
-5the solution of mol/L, measure its fluorescence with fluorescence analyser, obtains fluorescence fluorescence emission spectrum (Fig. 2).
(3) can find out that from Fig. 1 and Fig. 2 compound (I) has good optical activity.
Embodiment 4
2-naphthyl-5-(4-(2-(4-pyridyl) vinyl) phenyl)-1,3,4-oxadiazole (I) and 2-naphthyl-5-(4-(2-(2-pyridyl) vinyl) phenyl)-1,3, the insecticidal activity assay of 4-oxadiazole (II).
1. test objective
In indoor test new compound virulence to the prodenia litura insect under confession examination concentration, estimate its insecticidal activity.
2. test conditions
2.1 for the examination target
Prodenia litura 2 instar larvaes.
2.2 culture condition
In 25 ± 1 ℃, RH75%, the incubator under the L:D=14:10 condition is brought up.
2.3 medicament preparation
Take (I) and (II) aequum with analytical balance; Molten Ji: DMF, 0.2%; Emulsifying agent: Tween80,0.1%; Add clear water to be diluted to desired concn; With existing sterilant Resitox for contrasting.
3. test method
Leaf dipping method: with reference to IRAC(1990) No. 7 methods, (I), (II) and Resitox are made into to 5 series concentration, with clear water and solvent in contrast, fresh blade is pressed to clear water successively, solvent, lower concentration to the order of high density are flooded 5s in the medicament prepared, after taking-up, dry, put into again culture plate, then access 2 age Spodoptera litura larvae, 1 of every plate, each concentration repeats 3 times, be placed in 25 ± 1 ℃, RH75%, the incubator under the L:D=14:10 condition is brought up, and after processing, 48h observes the record death toll.Data processing SPSS software.
4. test result
The relatively responsive virulence baseline of table one Spodoptera litura larvae in 2 age to target product
* RTI relative virus force coefficient be take Resitox as 1 calculating.
As can be seen from Table I, 2-naphthyl-5-(4-(2-(4-pyridyl) vinyl) phenyl)-1, 3, 4-oxadiazole (I) and 2-naphthyl-5-(4-(2-(2-pyridyl) vinyl) phenyl)-1, 3, 4-oxadiazole (II) has good insecticidal activity to prodenia litura, be better than the sterilant Resitox, and 2-naphthyl-5-(4-(2-(4-pyridyl) vinyl) phenyl)-1, 3, the insecticidal activity of 4-oxadiazole (I) is than 2-naphthyl-5-(4-(2-(2-pyridyl) vinyl) phenyl)-1, 3, 4-oxadiazole (II) is strong, therefore synthetic compound can be used as the application for preparing sterilant.
Claims (8)
1. containing 1,3 of pyridine, the 4-oxadiazole derivative, is characterized in that, the structure of this derivative is as follows:
Wherein R is 4-pyridine or 2-pyridine.
2. the preparation method of the described derivative of claim 1, is characterized in that, comprises the following steps:
(1) by mol ratio, be 1:(1.1～1.5) 2-naphthyl-5-(4-(brooethyl) phenyl)-1,3, after 4-oxadiazole and oily liquids triethyl-phosphite mixed dissolution, in temperature, be stirring and refluxing 3～5h under 125～130 ℃ of conditions, after removing triethyl-phosphite excessive in reaction system, stir and add normal hexane to separate out solid product while hot, then use the mixed solution recrystallization of tetrahydrofuran (THF) and normal hexane, make product B;
(2) respectively equimolar product B and 2-pyridine aldehydes or 4-pyridine aldehydes are dissolved in DMF obtaining to lysate; Ethanol solution to adding the potassium tert.-butoxide that mass percent is 15～30% in described lysate, carry out the Wittig-Horner reaction, and reaction is cooling and filter the gained reaction solution after finishing; The gained filter cake is (2～3) by volume ratio: 1 dimethyl sulfoxide (DMSO) and alcohol mixeding liquid recrystallization make containing 1,3 of pyridine the 4-oxadiazole derivative.
3. preparation method according to claim 2, is characterized in that, in step (2), DMF is 10～15ml/g with the volume mass ratio of product B.
4. preparation method according to claim 2, is characterized in that, in step (2), the condition of Wittig-Horner reaction is: 60～70 ℃ of stirring reaction 5h.
5. according to claim 2 or 3 or 4 described preparation methods, it is characterized in that, described in step (1), the volume ratio of tetrahydrofuran (THF) and normal hexane is 1:(1～4).
6. according to claim 2 or 3 or 4 described preparation methods, it is characterized in that, carry out under reduced pressure while removing in reaction system triethyl-phosphite in step (1).
7. according to claim 2 or 3 or 4 described preparation methods, it is characterized in that, the ethanol solution of potassium tert.-butoxide described in step (2) is 3～4ml/g with the volume mass ratio of product B.
8. the application of derivative according to claim 1 in preparing sterilant.
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| CN102161646A (en) * | 2011-03-11 | 2011-08-24 | 华南理工大学 | Stilbene derivative with 1,3,4-oxadiazole and preparation method and application thereof |
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2013
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102161646A (en) * | 2011-03-11 | 2011-08-24 | 华南理工大学 | Stilbene derivative with 1,3,4-oxadiazole and preparation method and application thereof |
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| CN104430546B (en) * | 2014-12-09 | 2017-04-19 | 陈干忠 | High-yield disease-resistant and mothproof composite preparation for rubber trees as well as preparation method and application thereof |
| CN108164515A (en) * | 2018-02-08 | 2018-06-15 | 华南理工大学 | A kind of double target spot disinfectant use in agriculture containing diphenylethyllene and preparation method and application |
| CN108164515B (en) * | 2018-02-08 | 2021-09-21 | 华南理工大学 | Double-target-point agricultural bactericide containing distyryl and preparation method and application thereof |
| CN108314679A (en) * | 2018-03-30 | 2018-07-24 | 华南理工大学 | One kind talan amide fungicide of oxadiazole rings containing 1,3,4- and its preparation method and application |
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| CN108558850A (en) * | 2018-03-30 | 2018-09-21 | 华南理工大学 | One kind amide fungicide of talan containing thiphene ring and its preparation method and application |
| CN108314679B (en) * | 2018-03-30 | 2021-06-08 | 华南理工大学 | Bactericide containing 1,3, 4-oxadiazole ring stilbene amide and preparation method and application thereof |
| CN108558850B (en) * | 2018-03-30 | 2021-06-08 | 华南理工大学 | Bactericide containing thiophene ring and stilbene amide, and preparation method and application thereof |
| CN108456201B (en) * | 2018-03-30 | 2021-06-08 | 华南理工大学 | Stilbene-containing succinate dehydrogenase inhibitor and preparation method and application thereof |
| CN110987847A (en) * | 2019-12-11 | 2020-04-10 | 吉林大学 | Application of 1,3, 4-oxadiazole derivative in acid detection and data encryption and storage |
| CN110987847B (en) * | 2019-12-11 | 2021-02-19 | 苏州今蓝纳米科技有限公司 | Application of 1,3, 4-oxadiazole derivative in acid detection and data encryption and storage |
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