CN106167472B - A kind of 2,5- substituent groups -1,3,4- oxadiazole double thioethers analog derivative, preparation method and application - Google Patents
A kind of 2,5- substituent groups -1,3,4- oxadiazole double thioethers analog derivative, preparation method and application Download PDFInfo
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- CN106167472B CN106167472B CN201610189517.9A CN201610189517A CN106167472B CN 106167472 B CN106167472 B CN 106167472B CN 201610189517 A CN201610189517 A CN 201610189517A CN 106167472 B CN106167472 B CN 106167472B
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- 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
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
- C07D271/113—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
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Abstract
The invention discloses a kind of chalcone derivative, preparation method and uses containing 1,1 dichloropropylene, have following logical formula (I)：R1Selected from substituent groups such as 4 chlorphenyls, 4 fluorophenyls, benzyl and 4 chlorobenzyls；R2Selected from substituent groups such as methyl, ethyl, benzyl, 4 chlorobenzyls and ethyl acetate.The configuration of the present invention is simple, preparation process is simple, and production cost is low, has preferably activity to bacterial blight of rice, bacterial leaf streak of rice pathogen and Caenorhabditis elegans.
Description
Technical field
The present invention relates to chemical industry and technical field of pesticide, the technology of relating in particular to is one kind 2,5- substituent groups -1,3,4-
Oxadiazole double thioether analog derivative also relates to 2, the 5- substituent groups -1,3, the preparation of 4- oxadiazole double thioether analog derivatives
Method, and the application in prevention rop bacterium venereal disease evil, nematodiasis etc..
Background technology
The status of pesticide is of crucial importance in ensureing agricultural production, in recent years crop bacterium and nematodiasis in agricultural production
Evil show frequency height, serious extent, occurrence scope extensively, the features such as prevention and control difficulty is big, in addition conventional dose preventive effect it is undesirable,
Disease drug resistance enhancing, agricultural product remain the factors such as exceeded, and huge economic loss is caused to agricultural production.For current agriculture
Industry significant crop is bacillary and nematodiasis problem, development of new low toxicity, low-residual, safety green chemical pesticide be novel pesticide
The vital task faced in initiative basic research.
The rop bacterium venereal disease evil caused by pathogenetic bacteria is a kind of Major Diseases of crop, wherein bacterial blight of rice and
The rop bacterium venereal disease evils such as bacterial leaf streak of rice are all worldwide important diseases.Bacterial blight of rice is also known as white leaf pest, thatch
Careless pest, burn, each rice region has generation, larger to yield effect, once morbidity the underproduction up to 20%~30%, it is serious
Can the underproduction 50%~60%, or even No kernels or seeds are gathered, as in a year of scarcity；Bacterial leaf streak of rice is also known as slice disease, cecospora spot, in recent years, disease by
Year expands, and harm is on the rise.Currently, lacking effective chemical prevention medicament for bacterial diseases of plants, cause crop thin
Fungal disease once is difficult to be effectively controlled in a short time on a large scale.
Nematode is widely distributed in the whole world, and host range is extensive, and hazard of plant is serious；Perennial plant and in same piece of land
On the crop planted year after year, when be subjected to the serious harm of nematode.Root knot nematode disease is with pathogenic nematode parasitism and host plant
Root formed root nodule be characterized.Root nodule starts such as syringe needle size, and white is later swollen successively with root skin cell to yellow-white
Greatly, hyperplasia, it is in nodule shape or chicken feet shape that multiple root nodules, which are connected, yellowish-brown, rough surface, easily corruption, lateral root or fibrous root shorten and
Few, fibrous root such as sends out plexi and is also failed therewith by parasitic root functionality after root system deformity is abnormal, moisture, nutrient conveying channel resistance
It is stagnant, or even be seriously obstructed, often cause the branch of its aerial part, leaf performance yellow thin, for root like fertilizer deficiency shape, growth potential is weak, yield
Fall sharply, low quality；When aggrieved serious, blade is withered to fall off, and branch is withered so that complete stool is dead.
1,3,4- oxadiazole derivatives have the biologies such as antimycotic, antibacterium, weeding, desinsection, antiviral in terms of pesticide
Activity has developed a variety of pesticides for containing 1,3,4- oxadiazole structures in succession, such as except the annual unifacial leaf in paddy field and double
Cotyledon weeds Evil humulones have stomach toxicity, action of contace poison to insect, are mainly used as hygienic insecticide prevention housefly, cockroach.To aphid,
The specific Sha Chong Ji Evil worms ketone of the agricultural pests such as plant hopper, leafhopper also contains 1,3,4- oxadiazole structures.Meanwhile thioether class derives
Object has broad-spectrum biological activity, has the bioactivity such as desinsection, antimycotic, antibacterium, weeding, antiviral in terms of pesticide.Sulphur
Ether compound is by more concern in terms of agricultural bactericidal, and people have carried out this kind of compound deep in recent decades
Research, develops the pesticides such as S-Ethyl ethylthio sulfonate, thioether phosphorus and pyrithiobac-sodium in succession.Due to its excellent physiological activity, thus to its molecule
Design, synthesis and bioactivity research are still a hot spot of current environment friendly agricultural initiative.
Xu Wei in 2013 bright equal (Xu, W.M.；Li,S.Z.；He,M.；Yang,S.；Li,X.Y.；Li.P.Synthesis
and bioactivities of novel thioether/sulfone derivatives containing 1,2,3-
thiadiazole and 1,3,4-oxadiazole/thiadiazole
Moiety.Bioorg.Med.Chem.Lett.2013,23,5821-5824.) report a series of Evil containing 1,3,4- (thiophene) diazole
Thioether analog derivative, biological activity determination the result shows that, part of compounds all has Fusarium oxysporum and tobacco mosaic virus (TMV)
Preferable inhibitory activity.(Chen, the X.H. such as Chen Xuehai in 2014；Yin,J.；Li,P.；He,M.；Jin,L.H.；Wu,J.；
Yang,S.；Hu,D.Y.Synthesis and antibacterial activity of bisthioether
derivatives containing a 1,3,4-thiadiazoles moiety.Phosphorus Sulfur
Relat.Elem.2014,189,134-142.) a series of double thioether analog derivatives for containing 1,3,4- thiadiazoles are reported, biology
Determination of activity the result shows that, part of compounds has preferable inhibit under the conditions of a concentration of 200 μ g/mL to tobacco ralstonia solanacearum
Activity.
Invention content
The purpose of the present invention is to provide a kind of to bacterial blight of rice, bacterial leaf streak of rice pathogen and beautiful hidden
Rhabditida has preferable active 2,5- substituent groups -1,3,4- oxadiazole double thioether analog derivatives.
Another object of the present invention is to provide the preparations of the 2,5- substituent group -1,3,4- oxadiazole double thioether analog derivatives
Method.
It is still another object of the present invention to provide the 2,5- substituent group -1,3,4- oxadiazole double thioether analog derivatives to prevent
Application in terms of bacterial blight of rice, bacterial leaf streak of rice pathogen and Caenorhabditis elegans.
One kind 2,5- substituent groups -1,3 of the present invention, 4- oxadiazole double thioether analog derivatives have following general formula：
In formula (I)：R1Selected from 4- chlorphenyls, 4- fluorophenyls, benzyl and 4- chlorobenzyls；R2Selected from methyl, ethyl, benzyl, 4-
Chlorobenzyl and ethyl acetate.
Preferred compound is：
Compound 1:2- ((4- fluorophenylthios) methyl) -5- methyl mercapto -1,3,4- oxadiazoles；
Compound 2:2- ((4- fluorophenylthios) methyl) -5- ethylmercapto group -1,3,4- oxadiazoles；
Compound 3:2- ((4- fluorophenylthios) methyl) -5- benzyl sulfenyl -1,3,4- oxadiazoles；
Compound 4:2- ((4- fluorophenylthios) methyl) -5- (4- chlorobenzyls sulfenyl) -1,3,4- oxadiazoles；
Compound 5:(2- ((4- fluorophenylthios) methyl) -1,3,4- oxadiazole -5- bases) ethyl thioacetate；
Compound 6:2- ((4- chlorophenylthios) methyl) -5- methyl mercapto -1,3,4- oxadiazoles；
Compound 7:2- ((4- chlorophenylthios) methyl) -5- ethylmercapto group -1,3,4- oxadiazoles；
Compound 8:2- ((4- chlorophenylthios) methyl) -5- benzyl sulfenyl -1,3,4- oxadiazoles；
Compound 9:2- ((4- chlorophenylthios) methyl) -5- (4- chlorobenzyls sulfenyl) -1,3,4- oxadiazoles；
Compound 10:(2- ((4- chlorophenylthios) methyl) -1,3,4- oxadiazole -5- bases) ethyl thioacetate；
Compound 11:2- (benzyl sulphomethyl) -5- methyl mercapto -1,3,4- oxadiazoles；
Compound 12:2- (benzyl sulphomethyl) -5- ethylmercapto group -1,3,4- oxadiazoles；
Compound 13:2- (benzyl sulphomethyl) -5- benzyl sulfenyl -1,3,4- oxadiazoles；
Compound 14:2- (benzyl sulphomethyl) -5- (4- chlorobenzyls sulfenyl) -1,3,4- oxadiazoles；
Compound 15:(2- (benzyl sulphomethyl) -1,3,4- oxadiazole -5- bases) ethyl thioacetate；
Compound 16:2- ((4- chloro benzyl sulfur generations) methyl) -5- methyl mercapto -1,3,4- oxadiazoles；
Compound 17:2- ((4- chloro benzyl sulfur generations) methyl) -5- ethylmercapto group -1,3,4- oxadiazoles；
Compound 18:2- ((4- chloro benzyl sulfur generations) methyl) -5- benzyl sulfenyl -1,3,4- oxadiazoles；
Compound 19:2- ((4- chloro benzyl sulfur generations) methyl) -5- (4- chlorobenzyls sulfenyl) -1,3,4- oxadiazoles；
Compound 20:(2- ((4- chloro benzyl sulfur generations) methyl) -1,3,4- oxadiazole -5- bases) ethyl thioacetate.
One kind 2,5- substituent groups -1,3 of the present invention, the preparation method of 4- oxadiazole double thioether analog derivatives, including it is following
Step：
(1) synthesis of substituent group thioacetyl hydrazine
(2) 2- sulfydryls -5- (substituent group is thio) methyl-1, the synthesis of 3,4- oxadiazoles
(3) synthesis of target compound 2- (substituent group is thio) methyl -5- substituted Thio -1,3,4- oxadiazoles
In formula (I)：R1Selected from 4- chlorphenyls, 4- fluorophenyls, benzyl and 4- chlorobenzyls；R2Selected from methyl, ethyl, benzyl, 4-
Chlorobenzyl and ethyl acetate.
2,5- substituent group -1,3,4- oxadiazole double thioether the analog derivatives of prevention rop bacterium venereal disease evil of the present invention
Application, the compound is to concentration EC in the inhibition of bacterial blight of rice pathogen50The range of value is 4.82~148.54 μ g/
The activity of mL, part of compounds are better than existing commercial References medicament Yekuzuo (92.61 μ g/mL) and Thiodiazole-copper (121.82 μ g/
mL)；To the EC of bacterial leaf streak of rice pathogen50The range of value is 11.15~109.56 μ g/mL, is superior to existing quotient
Product comparison medicament Yekuzuo (151.66 μ g/mL) and Thiodiazole-copper (269.80 μ g/mL).
2,5- substituent group -1,3,4- oxadiazole double thioether the analog derivatives of prevention crop nematodiasis of the present invention
Using half lethal concentration (LC of the compound to Caenorhabditis elegans50) range of value is：2.89~56.54 μ g/mL, portion
The activity of compound is divided to be better than commercial References medicament phonamiphos (23.20 μ g/mL) and thiazoline (72.52 μ g/mL).
2,5- substituent group -1,3,4- oxadiazole double thioether the analog derivatives of prevention rop bacterium venereal disease evil of the present invention
Application, wherein compound 2- ((4- chlorophenylthios) methyl) -5- methyl mercaptos -1,3,4- oxadiazoles to bacterial blight of rice disease
The EC of opportunistic pathogen and bacterial leaf streak of rice pathogen50Value is respectively 4.82 and 11.15 μ g/mL, to bacterial blight of rice live body
The treatment of pot experiment and protecting effect are respectively 51.29% and 56.65%, and control effect is best.
2,5- substituent group -1,3,4- oxadiazole double thioether the analog derivatives of prevention crop nematodiasis of the present invention
Using wherein compound 2- ((4- chlorophenylthios) methyl) -5- methyl mercaptos -1,3,4- oxadiazoles are to Caenorhabditis elegans
LC50Value is 2.89 μ g/mL, and control effect is best.
Invention effect：It is using substituted benzenethiol and benzyl mercaptan as raw material, design has synthesized a series of substituent group -1 2,5-,
3,4- oxadiazole double thioether analog derivatives have been filtered out to bacterial blight of rice, bacterial leaf streak of rice pathogen and beautiful
Hidden rhabditida has preferable active compound.
The present invention mainly based on the work of seminar's early period, using substituted benzenethiol and benzyl mercaptan as raw material, designs
A series of 2,5- substituent groups -1,3,4- oxadiazole double thioether analog derivatives have been synthesized, and turbidity is used to the compound of synthesis
Method carries out in vitro bioactivity screening to bacterial blight of rice and bacterial leaf streak of rice pathogen, the experimental results showed that：Portion
Point compound all has preferable inhibitory activity to bacterial blight of rice and bacterial leaf streak of rice pathogen；Using the method for tagging
In vitro bioactivity screening is carried out to Caenorhabditis elegans, the experimental results showed that：Part of compounds has Caenorhabditis elegans
Preferable inhibitory activity；Meanwhile live body pot experiment of the high-activity compound to bacterial blight of rice is determined using leaf-cutting method,
Test result shows：High-activity compound has preferable preventive effect to bacterial blight of rice.
1. 2,5- substituent groups -1,3,4- oxadiazole double thioether analog derivatives are applied to prevention rop bacterium venereal disease evil, effect
It is good.
2. 2,5- substituent groups -1,3,4- oxadiazole double thioether analog derivatives are applied to prevention rop bacterium venereal disease evil, specifically
The rop bacterium venereal disease evils such as bacterial blight of rice and bacterial leaf streak of rice can be prevented.
3. 2,5- substituent groups -1,3,4- oxadiazole double thioether analog derivatives are applied to prevention crop nematodiasis, effect
It is good.
4. 2,5- substituent groups -1,3,4- oxadiazole double thioether analog derivatives are applied to prevention crop nematodiasis, specifically may be used
To prevent the crops nematodiasis such as Caenorhabditis elegans.
5. 2,5- substituent group -1,3,4- oxadiazole double thioether analog derivatives are applied to prevention rop bacterium venereal disease evil and line
Parasitosis is done harm to, and simple in structure, preparation process is simple, and production cost is low, has a extensive future.
Specific implementation mode
Embodiment 1：2- (4- chlorophenylthios) methyl -5- methyl mercaptos -1,3, the preparation method of 4- oxadiazoles, including it is following
Step：
(1) synthesis of 4- chlorophenylthios acethydrazide
4- chlorothio-phenols (0.01mol) and absolute ethyl alcohol (20mL) are thrown in 25mL there-necked flasks, are slowly added dropwise at room temperature
Ethyl chloroacetate (0.012mol), reacts at room temperature 6h, and hydrazine hydrate is slowly added dropwise to the end of reaction in TLC tracking reactions
(0.012mol) is then refluxed for reaction 8h, TLC tracking reaction, extra ethyl alcohol is removed under reduced pressure, intermediate is obtained with ethyl alcohol recrystallization
4- chlorophenylthio acethydrazides.
(2) 2- sulfydryls -5- (4- chlorophenylthios) methyl-1, the synthesis of 3,4- oxadiazoles
By the 4- chlorophenylthios acethydrazide (0.01mol) and potassium hydroxide (0.012mol), absolute ethyl alcohol of preparation
(10mL), water (5mL) are added separately in 25mL there-necked flasks, are stirred at room temperature, are waited for that solid is completely dissolved, two sulphur are then slowly added dropwise
It is warming up to back flow reaction 7h after changing carbon (0.015mol), TLC, which is tracked, to react, and to the end of reaction, ethyl alcohol is then removed under reduced pressure, uses
3% dilute hydrochloric acid tune pH=1 or so obtains white solid, filters, drying, then recrystallizes to obtain intermediate 2- mercaptos with absolute ethyl alcohol
Base -5- (4- chlorophenylthios) methyl-1,3,4- oxadiazoles.
(3) synthesis of target compound 2- (4- chlorophenylthios) methyl -5- methyl mercapto -1,3,4- oxadiazoles
By 2- sulfydryls -5- (4- chlorophenylthios) methyl-1 of preparation, 3,4- oxadiazoles (0.01mol), water (15mL),
NaOH (0.012mol) is added separately in 25mL there-necked flasks, and 10min is stirred at room temperature, and after solid all dissolving, sulfuric acid is added
Dimethyl ester (0.012mol), is stirred to react 2h at room temperature, and TLC tracking reactions purify to obtain target compound to the end of reaction.
Embodiment 2：2- ((4- fluorophenylthios) methyl) -5- ethylmercapto groups -1,3, the preparation method of 4- oxadiazoles, including with
Lower step：
Step (1)~(2) are the same as embodiment 1；
Step (3) and 1 step of embodiment (3) difference lies in：Dithyl sulfate is added and replaces dimethyl suflfate.
Embodiment 3：2- ((4- fluorophenylthios) methyl) -5- benzyl sulfenyls -1,3, the preparation method of 4- oxadiazoles, including
Following steps：
Step (1)~(2) are the same as embodiment 1；
Step (3) and 1 step of embodiment (3) difference lies in：Benzyl chloride is added and replaces dimethyl suflfate.
Embodiment 4：The preparation side of 2- ((4- fluorophenylthios) methyl) -5- (4- chlorobenzyls sulfenyl) -1,3,4- oxadiazoles
Method includes the following steps：
Step (1)~(2) are the same as embodiment 1；
Step (3) and 1 step of embodiment (3) difference lies in：4- benzyl chloride chloros are added and replace dimethyl suflfate.
Embodiment 5：The preparation of (2- ((4- fluorophenylthios) methyl) -1,3,4- oxadiazole -5- bases) ethyl thioacetate
Method includes the following steps：
Step (1)~(2) are the same as embodiment 1；
Step (3) and 1 step of embodiment (3) difference lies in：Ethyl chloroacetate is added and replaces dimethyl suflfate.
Embodiment 6：2- ((4- chlorophenylthios) methyl) -5- methyl mercaptos -1,3, the preparation method of 4- oxadiazoles, including with
Lower step：
Step (1) and 1 step of embodiment (1) difference lies in：4- chlorothio-phenols are added and replace 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：4- chlorophenylthio acethydrazides are added and replace 4- fluorophenyls
Thioacetyl hydrazine；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryls -5- (4- chlorophenylthios) methyl-1 is added,
3,4- oxadiazoles replace 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles.
Embodiment 7：2- ((4- chlorophenylthios) methyl) -5- ethylmercapto groups -1,3, the preparation method of 4- oxadiazoles, including with
Lower step：
Step (1) and 1 step of embodiment (1) difference lies in：4- chlorothio-phenols are added and replace 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：4- chlorophenylthio acethydrazides are added and replace 4- fluorophenyls
Thioacetyl hydrazine；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryls -5- (4- chlorophenylthios) methyl-1 is added,
3,4- oxadiazoles replace 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles that dithyl sulfate is added and replaces sulfuric acid
Dimethyl ester.
Embodiment 8：2- ((4- chlorophenylthios) methyl) -5- benzyl sulfenyls -1,3, the preparation method of 4- oxadiazoles, including
Following steps：
Step (1) and 1 step of embodiment (1) difference lies in：4- chlorothio-phenols are added and replace 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：4- chlorophenylthio acethydrazides are added and replace 4- fluorophenyls
Thioacetyl hydrazine；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryls -5- (4- chlorophenylthios) methyl-1 is added,
3,4- oxadiazoles replace 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles that benzyl chloride is added and replaces dimethyl sulfate
Ester.
Embodiment 9：The preparation side of 2- ((4- chlorophenylthios) methyl) -5- (4- chlorobenzyls sulfenyl) -1,3,4- oxadiazoles
Method includes the following steps：
Step (1) and 1 step of embodiment (1) difference lies in：4- chlorothio-phenols are added and replace 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：4- chlorophenylthio acethydrazides are added and replace 4- fluorophenyls
Thioacetyl hydrazine；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryls -5- (4- chlorophenylthios) methyl-1 is added,
3,4- oxadiazoles replace 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles that 4- benzyl chloride chloros are added and replace sulfuric acid two
Methyl esters.
Embodiment 10：The preparation of (2- ((4- chlorophenylthios) methyl) -1,3,4- oxadiazole -5- bases) ethyl thioacetate
Method includes the following steps：
Step (1) and 1 step of embodiment (1) difference lies in：4- chlorothio-phenols are added and replace 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：4- chlorophenylthio acethydrazides are added and replace 4- fluorophenyls
Thioacetyl hydrazine；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryls -5- (4- chlorophenylthios) methyl-1 is added,
3,4- oxadiazoles replace 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles that ethyl chloroacetate is added and replaces sulfuric acid
Dimethyl ester.
Embodiment 11：2- (benzyl sulphomethyl) -5- methyl mercaptos -1,3, the preparation method of 4- oxadiazoles, including following step
Suddenly：
Step (1) and 1 step of embodiment (1) difference lies in：Benzyl mercaptan is added and replaces 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：Dibenzylsulfide is added and replaces 4- fluorophenylthios for acethydrazide
Acethydrazide；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryl -5- dibenzylsulfides are added for methyl-1,3,4- Evil
Diazole replaces 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles.
Embodiment 12：2- (benzyl sulphomethyl) -5- ethylmercapto groups -1,3, the preparation method of 4- oxadiazoles, including following step
Suddenly：
Step (1) and 1 step of embodiment (1) difference lies in：Benzyl mercaptan is added and replaces 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：Dibenzylsulfide is added and replaces 4- fluorophenylthios for acethydrazide
Acethydrazide；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryl -5- dibenzylsulfides are added for methyl-1,3,4- Evil
Diazole replaces 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles that dithyl sulfate is added and replaces dimethyl sulfate
Ester.
Embodiment 13：2- (benzyl sulphomethyl) -5- benzyl sulfenyls -1,3, the preparation method of 4- oxadiazoles, including it is following
Step：
Step (1) and 1 step of embodiment (1) difference lies in：Benzyl mercaptan is added and replaces 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：Dibenzylsulfide is added and replaces 4- fluorophenylthios for acethydrazide
Acethydrazide；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryl -5- dibenzylsulfides are added for methyl-1,3,4- Evil
Diazole replaces 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles that benzyl chloride is added and replaces dimethyl suflfate.
Embodiment 14：2- (benzyl sulphomethyl) -5- (4- chlorobenzyls sulfenyl) -1, the preparation method of 3,4- oxadiazoles, packet
Include following steps：
Step (1) and 1 step of embodiment (1) difference lies in：Benzyl mercaptan is added and replaces 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：Dibenzylsulfide is added and replaces 4- fluorophenylthios for acethydrazide
Acethydrazide；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryl -5- dibenzylsulfides are added for methyl-1,3,4- Evil
Diazole replaces 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles that 4- benzyl chloride chloros are added and replace dimethyl suflfate.
Embodiment 15：The preparation method of (- 1,3,4- oxadiazole -5- bases of 2- (benzyl sulphomethyl)) ethyl thioacetate,
Include the following steps：
Step (1) and 1 step of embodiment (1) difference lies in：Benzyl mercaptan is added and replaces 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：Dibenzylsulfide is added and replaces 4- fluorophenylthios for acethydrazide
Acethydrazide；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryl -5- dibenzylsulfides are added for methyl-1,3,4- Evil
Diazole replaces 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles that ethyl chloroacetate is added and replaces dimethyl sulfate
Ester.
Embodiment 16：2- ((4- chloro benzyl sulfur generations) methyl) -5- methyl mercaptos -1,3, the preparation method of 4- oxadiazoles, including
Following steps：
Step (1) and 1 step of embodiment (1) difference lies in：4- chloro benzyl mercaptans are added and replace 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：4- chloro benzyl sulfurs are added and replace 4- fluorophenyls for acethydrazide
Thioacetyl hydrazine；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryls -5- (4- chloro benzyl sulfur generations) methyl-1 is added,
3,4- oxadiazoles replace 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles.
Embodiment 17：2- ((4- chloro benzyl sulfur generations) methyl) -5- ethylmercapto groups -1,3, the preparation method of 4- oxadiazoles, including
Following steps：
Step (1) and 1 step of embodiment (1) difference lies in：4- chloro benzyl mercaptans are added and replace 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：4- chloro benzyl sulfurs are added and replace 4- fluorophenyls for acethydrazide
Thioacetyl hydrazine；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryls -5- (4- chloro benzyl sulfur generations) methyl-1 is added,
3,4- oxadiazoles replace 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles that dithyl sulfate is added and replaces sulfuric acid
Dimethyl ester.
Embodiment 18：2- ((4- chloro benzyl sulfur generations) methyl) -5- benzyl sulfenyls -1,3, the preparation method of 4- oxadiazoles, packet
Include following steps：
Step (1) and 1 step of embodiment (1) difference lies in：4- chloro benzyl mercaptans are added and replace 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：4- chloro benzyl sulfurs are added and replace 4- fluorophenyls for acethydrazide
Thioacetyl hydrazine；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryls -5- (4- chloro benzyl sulfur generations) methyl-1 is added,
3,4- oxadiazoles replace 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles that benzyl chloride is added and replaces dimethyl sulfate
Ester.
Embodiment 19：The preparation side of 2- ((4- chloro benzyl sulfur generations) methyl) -5- (4- benzyls sulfenyl) -1,3,4- oxadiazoles
Method includes the following steps：
Step (1) and 1 step of embodiment (1) difference lies in：4- chloro benzyl mercaptans are added and replace 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：4- chloro benzyl sulfurs are added and replace 4- fluorophenyls for acethydrazide
Thioacetyl hydrazine；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryls -5- (4- chloro benzyl sulfur generations) methyl-1 is added,
3,4- oxadiazoles replace 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles that 4- benzyl chloride chloros are added and replace sulfuric acid two
Methyl esters.
Embodiment 20：The preparation of (2- ((4- chloro benzyl sulfur generations) methyl) -1,3,4- oxadiazole -5- bases) ethyl thioacetate
Method includes the following steps：
Step (1) and 1 step of embodiment (1) difference lies in：4- chloro benzyl mercaptans are added and replace 4- fluoro thiophenols；
Step (2) and 2 step of embodiment (1) difference lies in：4- chloro benzyl sulfurs are added and replace 4- fluorophenyls for acethydrazide
Thioacetyl hydrazine；
Step (3) and 1 step of embodiment (3) difference lies in：2- sulfydryls -5- (4- chloro benzyl sulfur generations) methyl-1 is added,
3,4- oxadiazoles replace 2- sulfydryls -5- (4- fluorophenylthios) methyl-1,3,4- oxadiazoles that ethyl chloroacetate is added and replaces sulfuric acid
Dimethyl ester.
Synthetic method more than utilization, it is raw material to choose different substituted benzenethiols or benzyl mercaptan, passes through substitution, hydrazine
The reaction designings such as solution, closed loop and thioetherification have synthesized a series of 2,5- substituent groups -1,3,4- oxadiazole thioether analog derivatives.Target
The structural formula and molecular formula of compound are as shown in table 1, and physicochemical property and spectrogram information are as shown in table 2.
The structural formula and molecular formula of 1 target compound 1-20 of table
The physicochemical property and spectrogram information of 2 target compound of table
Test example 1：Bacterial blight of rice and bacterial leaf streak of rice pathogen activity is inhibited to survey in target compound room
It is fixed
By bacterial blight of rice and bacterial leaf streak of rice pathogen in NB (beef extracts：3g, peptone：5g, yeast carry
Take object：1g, glucose：10g, agar：20g, secondary water：1L；With 5mol/L NaOH solution tune pH=7 or so, 121 DEG C of sterilizings
It 20min) crosses above solid medium, culture is until growing single bacterium colony at 30 DEG C.Water on picking NB solid mediums
The bacterial blight of rice and bacterial leaf streak of rice pathogen single bacterium drop down onto NB fluid nutrient medium (beef extracts：3g, peptone：5g, ferment
Female extract：1g, glucose：10g, secondary water：1L；With 5mol/L NaOH solution tune pH=7 or so, 121 DEG C of sterilizing 20min)
In, it is spare to growth logarithmic phase in 28 DEG C, 180rpm constant-temperature tables shaken cultivation.
Synthesized compound and commercial References medicament are configured to the drug containing NB liquid of a concentration of 200 and 100 μ g/mL respectively
Being trained containing the NB liquid of bacterial blight of rice and bacterial leaf streak of rice pathogen for the 40 above-mentioned preparations of μ L is added in body culture medium
It supports base and the bacterium solution of each concentration is measured into OD values in microplate reader in 30 DEG C, 180rpm constant-temperature table 24~48h of shaken cultivation
(OD595).And the NB fluid nutrient medium OD values that other measured concentration is 200 and 100 μ g/mL medicaments and comparison medicament, to medicament
OD values caused by itself are corrected.The calculation formula for correcting OD values and inhibiting rate is as follows：
Correct the OD values=values of OD containing bacterium culture medium-aseptic culture medium OD values；
It is compareed after inhibiting rate (%)=(control medium bacterium solution OD values-toxic culture medium OD values of correction after correction)/correction
Value × 100 culture medium bacterium solution OD；
The inhibitory activity and EC of target compound are measured according to above method50Value, the results are shown in Table 3~table 6.
Inhibitory activity of 3 target compound of table to bacterial blight of rice pathogen
Inhibitory activity of 4 target compound of table to bacterial leaf streak of rice pathogen
It can be seen that by table 3 and table 4：At the concentration tested, target compound is to bacterial blight of rice and paddy bacterial
Cecospora spot pathogen all has certain inhibitory activity.Under 200 and 100 μ g/mL concentration, target compound 1,2,6 and 7 pairs of water
The inhibiting rate of bacterial blight of rice opportunistic pathogen is 100%, the inhibiting rate of 1,6 and 7 pair of bacterial leaf streak of rice pathogen of compound
It is 100%, is superior to commercial References medicament Yekuzuo and Thiodiazole-copper.
EC of 5 target compound of table to bacterial blight of rice pathogen50Value
EC of 6 target compound of table to bacterial leaf streak of rice pathogen50Value
As can be seen from Table 5：The EC of 1~20 pair of bacterial blight of rice pathogen of target compound50Value is range 4.82
~148.54 μ g/mL, part of compounds are better than commercially available medicine comparison medicament Yekuzuo (92.61 μ g/mL) and Thiodiazole-copper (121.82 μ
g/mL).As can be seen from Table 6：The EC of 1~20 pair of bacterial leaf streak of rice pathogen of target compound50Value is ranging from
11.15~109.56 μ g/mL are superior to commercially available medicine comparison medicament Yekuzuo (151.66 μ g/mL) and Thiodiazole-copper (269.80 μ g/
ML), and compound 6 is best to the inhibitory activity of bacterial blight of rice and bacterial leaf streak of rice pathogen.Due to the present invention
In 2,5- substituent groups -1,3,4- oxadiazole double thioether analog derivative structures are closely similar, it is anticipated that other compounds also have
There is the effect of the bacterial diseases pathogens such as certain inhibition bacterial blight of rice and bacterial leaf streak of rice.
Test example 2：Inhibit Caenorhabditis elegans determination of activity in target compound room
Aseptically, the NGM culture (agar that a fritter is in the hermaphroditic nematode in egg-laying season (L3 phases) is cut
17g, peptone 2.9g, NaCl 3g, cholesterol 1mL, 1mol/L CaCl21mL, 1mol/L MgSO41mL, 1mol/L
K2HPO4-KHPO4Buffer solution 25mL, secondary water 980mL) it is placed in one and is coated with Escherichia coli (E.coli) OP50's
It is cultivated on new NGM culture plates, new NGM culture plates is placed in 20 DEG C of sterile biochemical cultivation cases and cultivate 72h.With appropriate
M9 (1mol/L K2HPO4-KHPO4Buffer solution) nematode in NGM tablets is washed down, it is fitted into the centrifuge tube of 15mL, allows nematode
(L3 phases) natural sedimentation, discards supernatant liquid, then uses M9 constant volumes to 10mL, reprecipitation 3 times repeatedly, will be in solution
E.coli OP50 fully dilute, and isometric lysate is added, and (5mol/L NaOH 0.3mL, M9 2.7mL, sodium hypochlorite are molten
Liquid 2.0mL), shake 6min with vortex concussion instrument, until the thorough fragmentation of nematode polypide, centrifuge tube filled it up with M9 solution, 3000rpm from
The heart 4~5 times, makes lysate adequately be diluted, discards supernatant liquid, pour into the culture dish containing M9.The worm that cracking is obtained
Ovum is cultivated in M9 obtains first-instar young for 24 hours, then by nematode centrifugal concentrating, pours into and be covered in the NGM culture plates of E.coli OP50
Culture obtains second instar larvae for 24 hours, is used for screening active ingredients.
Target compound is configured to the liquid of a concentration of 100 and 50 μ g/mL with the aqueous solution containing 1%Tween-20, so
It takes the liquid that 200 μ L are prepared to be added in 48 hole biochemical culture plates afterwards, then the nematode of 10 μ L (about 30~100 nematodes) is taken to suspend
Liquid adds into the liquid.48 hole biochemical culture plates are put in after cultivating 48h in 20 DEG C of insulating boxs and count the death rate, with 1% containing DMF
Tween-20 solution each handles three repetitions, and calculate LC of the target compound to Caenorhabditis elegans as blank control50
Value, the results are shown in Table 7 and table 8.
Bioactivity of 7 target compound of table to Caenorhabditis elegans
LC of 8 target compound of table to Caenorhabditis elegans50Value
As can be seen from Table 7：Under the conditions of a concentration of 100 and 50 μ g/mL, compound 1,2,6 and 7 pairs of Caenorhabditis elegans
Preferable activity is all had, the death rate is 100%, is better than commercial References medicament phonamiphos and thiazoline.Meanwhile by table 8
It can be seen that：Target compound 1,2,5,6,7,8,9,10 and 16 pairs of Caenorhabditis elegans all have preferable activity, LC50Value
The μ g/mL of respectively 5.69,8.19,17.82,2.89,6.90,16.23,15.31,16.97 and 16.09, are superior to commercial References
Medicament phonamiphos (23.20 μ g/mL) and thiazoline (72.52 μ g/mL), wherein compound 6 to Caenorhabditis elegans activity most
It is good, LC50Value is 2.89 μ g/mL.Due to the 2,5- substituent group -1,3,4- oxadiazole double thioether analog derivative structures in the present invention
It is closely similar, it is anticipated that other compounds also have the effect of certain inhibition Caenorhabditis elegans.
Test example 3：High-activity compound bacterial blight of rice live body pot experiment
1, bacterial blight of rice live body pot experiment protecting effect
The preferable compound 6 of bacterial blight of rice pathogen activity and comparison medicament Yekuzuo and Thiodiazole-copper will be used respectively
0.1% Tween solution be made into a concentration of 200 μ g/mL contain drug solns, the blade surface in rice is sprayed, until there is drop
Until dripping.After Yu Yizhou, use the scissors for speckling with rice bacterial leaf spot bacterium solution leaf at 1~2cm of blade tip in rice leaf
Point is cut off, and wound is impregnated 10s or so in bacterium solution, while setting clear water control and the bacterium solution control of not adding medicine.Each place
20 plants of rice seedlings are managed, dispenser checks incidence in 14 days, records the scab length of rice leaf, and calculates its disease index and prevent
Effect, the results are shown in Table 9.
2, bacterial blight of rice live body pot experiment therapeutic effect
Blade tip is cut off with the scissors for speckling with bacterial blight of rice pathogen at 1~2cm of blade tip in rice leaf, and
Wound is impregnated 10s or so in bacterium solution.It, will be to the preferable compound of bacterial blight of rice pathogen activity 6 after Yu Yizhou
It is made into the drug solns that contain of a concentration of 200 μ g/mL with 0.1% Tween solution respectively with comparison medicament Yekuzuo and Thiodiazole-copper, and
The blade surface in rice is sprayed, until thering is drop to drip.Clear water control and the bacterium solution control of not adding medicine are set simultaneously.Often
20 plants of rice seedlings of a processing, dispenser check incidence in 14 days, record the scab length of rice leaf, and calculate its disease index
And preventive effect, it the results are shown in Table 10.
Preventive effect (%)=(control group scab length-processing group scab length)/control group scab length × 100
9 bacterial blight of rice live body pot experiment protecting effect of table
As can be seen from Table 9：Under the conditions of a concentration of 200 μ g/mL, compound 6 has bacterial blight of rice preferable
Protecting effect, preventive effect 56.65% are better than commercial References medicament Yekuzuo (44.86%) and Thiodiazole-copper (49.77%).
10 bacterial blight of rice live body pot experiment therapeutic effect of table
As can be seen from Table 10：Under the conditions of a concentration of 200 μ g/mL, compound 6 has bacterial blight of rice preferable
Therapeutic effect, preventive effect 51.29% are better than commercial References medicament Yekuzuo (42.26%) and Thiodiazole-copper (46.77%).
Claims (3)
1. one kind 2,5- substituent groups -1,3,4- oxadiazole thioether analog derivatives have following general formula：
In formula (I)：R1 is selected from 4- chlorphenyls, 4- fluorophenyls, benzyl and 4- chlorobenzyls；R2 is selected from methyl, ethyl, benzyl, 4- chlorine
Benzyl and ethyl acetate base.
2. one kind 2,5- substituent groups -1,3 as described in claim 1,4- oxadiazole thioether analog derivatives, wherein particular compound
For：
Compound 1:2- ((4- fluorophenylthios) methyl) -5- methyl mercapto -1,3,4- oxadiazoles；
Compound 2:2- ((4- fluorophenylthios) methyl) -5- ethylmercapto group -1,3,4- oxadiazoles；
Compound 3:2- ((4- fluorophenylthios) methyl) -5- benzyl sulfenyl -1,3,4- oxadiazoles；
Compound 4:2- ((4- fluorophenylthios) methyl) -5- (4- chlorobenzyls sulfenyl) -1,3,4- oxadiazoles；
Compound 5:(2- ((4- fluorophenylthios) methyl) -1,3,4- oxadiazole -5- bases) ethyl thioacetate；
Compound 6:2- ((4- chlorophenylthios) methyl) -5- methyl mercapto -1,3,4- oxadiazoles；
Compound 7:2- ((4- chlorophenylthios) methyl) -5- ethylmercapto group -1,3,4- oxadiazoles；
Compound 8:2- ((4- chlorophenylthios) methyl) -5- benzyl sulfenyl -1,3,4- oxadiazoles；
Compound 9:2- ((4- chlorophenylthios) methyl) -5- (4- chlorobenzyls sulfenyl) -1,3,4- oxadiazoles；
Compound 10:(2- ((4- chlorophenylthios) methyl) -1,3,4- oxadiazole -5- bases) ethyl thioacetate；
Compound 11:2- (benzyl sulphomethyl) -5- methyl mercapto -1,3,4- oxadiazoles；
Compound 12:2- (benzyl sulphomethyl) -5- ethylmercapto group -1,3,4- oxadiazoles；
Compound 13:2- (benzyl sulphomethyl) -5- benzyl sulfenyl -1,3,4- oxadiazoles；
Compound 14:2- (benzyl sulphomethyl) -5- (4- chlorobenzyls sulfenyl) -1,3,4- oxadiazoles；
Compound 15:(2- (benzyl sulphomethyl) -1,3,4- oxadiazole -5- bases) ethyl thioacetate；
Compound 16:2- ((4- chloro benzyl sulfur generations) methyl) -5- methyl mercapto -1,3,4- oxadiazoles；
Compound 17:2- ((4- chloro benzyl sulfur generations) methyl) -5- ethylmercapto group -1,3,4- oxadiazoles；
Compound 18:2- ((4- chloro benzyl sulfur generations) methyl) -5- benzyl sulfenyl -1,3,4- oxadiazoles；
Compound 19:2- ((4- chloro benzyl sulfur generations) methyl) -5- (4- chlorobenzyls sulfenyl) -1,3,4- oxadiazoles；
Compound 20:(2- ((4- chloro benzyl sulfur generations) methyl) -1,3,4- oxadiazole -5- bases) ethyl thioacetate.
3. one kind 2,5- substituent groups -1,3 as claimed in claim 1 or 2, the preparation method of 4- oxadiazole thioether analog derivatives,
Include the following steps：
(1) synthesis of substituent group thioacetyl hydrazine
(2) 2- sulfydryls -5- (substituent group is thio) methyl-1, the synthesis of 3,4- oxadiazoles
(3) synthesis of target compound 2- (substituent group is thio) methyl -5- substituted Thio -1,3,4- oxadiazoles
In formula (I)：R1 is selected from 4- chlorphenyls, 4- fluorophenyls, benzyl and 4- chlorobenzyls；R2 is selected from methyl, ethyl, benzyl, 4- chlorine
Benzyl and ethyl acetate base.
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