CN103588768B - Replace-1,3,4-thiadiazole compound containing furan nucleus 2,5-bis-and prepare the application in phytophthora infestans fungistat - Google Patents
Replace-1,3,4-thiadiazole compound containing furan nucleus 2,5-bis-and prepare the application in phytophthora infestans fungistat Download PDFInfo
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- CN103588768B CN103588768B CN201310631983.4A CN201310631983A CN103588768B CN 103588768 B CN103588768 B CN 103588768B CN 201310631983 A CN201310631983 A CN 201310631983A CN 103588768 B CN103588768 B CN 103588768B
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- hydrogen
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- furan nucleus
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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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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- Pest Control & Pesticides (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract
The invention discloses and a kind of replace-1,3,4-thiadiazole compound containing furan nucleus 2,5-bis-and preparing the application in phytophthora infestans fungistat.Describedly replace-1,3,4-thiadiazole compound have such as formula structure shown in I containing furan nucleus 2,5-bis-, described R
1or R
2for the substituting group on corresponding phenyl ring, R
1be selected from alkyl or alkoxyl group that hydrogen, 4-halogen or 4-carbonatoms are 1 ~ 4; R
2be selected from hydrogen, 2-halogen, 4-halogen or 3-nitro, and R
1with R
2be asynchronously hydrogen.The experiment proved that, describedly replace-1,3,4-thiadiazole compound and have good biocidal property containing furan nucleus 2,5-bis-to phytophthora infestans, may be used for sterilant.
Description
Technical field
The invention belongs to heterogeneous ring compound Application Areas, particularly replace-1,3,4-thiadiazole compound containing furan nucleus 2,5-bis-and preparing the application in phytophthora infestans fungistat.
Background technology
In recent years, heterogeneous ring compound occupies very consequence in novel super-high effect pesticides discovery, when finding novel structure and having bioactive compound, designing and synthesizing various heterogeneous ring compound is one of very important approach, has already become quite active field.In heterogeneous ring compound; thiazole compound is more and more subject to the concern (Liu Changling of investigator; thiazole series compound. meticulous and specialty chemicals, 2007,15 (9); 36-37); 1,3,4-thiadiazole compound is wherein because having efficient, low toxicity, excellent biological activity and the various feature of structural changes; agricultural chemicals and medical in have a wide range of applications, be always organic chemistry research focus and emphasis ((a) Kempegowda; Senthil, K.G.P.; Prakash, D.; Tamiz, M.T.Thiadiazoles:progressreportonbiologicalactivities.Ph armaChem., 2011,3 (2), 330-341; (b) Gupta, J.K.; Yadav, R.K.; Dudhe, R.; Sharma, P.K.Recentadvancementsinthesynthesisandpharmacologicalev aluationofsubstituted1,3; 4-thiadiazolederivatives.Int.J.PharmTechRes.; 2010,2 (2), 1493-1507; (c) Siddiqui, N.; Ahuja, P.; Ahsan, W.; Pandeya, S.N.; Alam, M.S.Thiadiazoles:progressreportonbiologicalactivities.J. Chem.Pharm.Res., 2009,1 (1), 19-30.).1,3, the biological activity of 4-thiadiazoles derivative and its " nitrogen carbon sulphur " basic structure skeleton have close relationship, because " nitrogen carbon sulphur " structure can as some metal ion in the chelating organism of active centre, thus there is good histocyte permeability, thus drug effect can be played better, thus its widely biological activity more and more cause the interest of people.Furan nucleus has aromaticity, sp in its Sauerstoffatom
2there are a pair lone-pair electron in track, can participate in the formation of hydrogen bond in organism, increases the interaction between giving and accepting, and contributes to improving biological activity.
Phytophthora infestans is a kind of germ parasitized on Solanaceae Solanaceae, is common in potato, and phytophthora infestans can cause potato to have no harvest, and after the potato caught an illness is eaten by pregnant woman, can cause Fetal Defects; Therefore, hazardness is large, but existing sterilant is to its prevention effect Shortcomings, and the fungistat developing a kind of new sterilization effect higher has practical significance.
Summary of the invention
The object of the present invention is to provide and replace-1,3,4-thiadiazole compound containing furan nucleus 2,5-bis-and preparing the application in phytophthora infestans fungistat.Describedly replace the rejection of-1,3,4-thiadiazole compound to phytophthora infestans be better than existing fungistat containing furan nucleus 2,5-bis-, have a good application prospect.
Above-mentioned purpose of the present invention is achieved by following technical solution:
Replace-1,3,4-thiadiazole compound containing furan nucleus 2,5-bis-and preparing the application in phytophthora infestans fungistat, describedly replace-1,3,4-thiadiazole compound have such as formula structure shown in I containing furan nucleus 2,5-bis-:
Described R
1or R
2for the substituting group on corresponding phenyl ring, R
1be selected from alkyl or alkoxyl group that hydrogen, 4-halogen or 4-carbonatoms are 1 ~ 4; R
2be selected from hydrogen, 2-halogen, 4-halogen or 3-nitro, and R
1with R
2be asynchronously hydrogen.
As a kind of preferred version, R
1be selected from hydrogen, 4-chlorine or 4-methoxyl group; R
2be selected from hydrogen, 2-chlorine, 2-fluorine, 4-fluorine or 3-nitro, and R
1with R
2be asynchronously hydrogen.
As one most preferably scheme, R
1for 4-chlorine, R
2for hydrogen.There is the compound of this structure, best to the inhibition of phytophthora infestans.
Phytophthora infestans colonizes in tomato, Herba Solani Lyrati, and the plants of Solanaceae such as potato all have report, and as a kind of preferred version, described phytophthora infestans is the phytophthora infestans parasitized on potato.
A kind of described furan nucleus 2,5-bis-that contains replaces the phytophthora infestans fungistat that-1,3,4-thiadiazole compound is activeconstituents.
The described preparation method replacing-1,3,4-thiadiazole compound containing furan nucleus 2,5-bis-, comprises the steps:
In the existence, inert atmosphere of thinner, compound shown in formula II and sulfuration cyclization reagent are reacted and obtain at 40 ~ 160 DEG C;
Described R
1or R
2for the substituting group on corresponding phenyl ring, R
1be selected from alkyl or alkoxyl group that hydrogen, 4-halogen or 4-carbonatoms are 1 ~ 4; R
2be selected from hydrogen, 2-halogen, 4-halogen or 3-nitro, and R
1with R
2be asynchronously hydrogen.
Reaction equation is as follows:
The preparation method of described formula II compound, can carry out with reference to prior art, as ((a) Yang Xin tinkling of pieces of jade, Qian Jianhong, kingly way is complete, Chen Fuheng. there is the aryl hydrazide compound of activity of inhibiting growth of mosqito larva, Chinese invention patent ZL01104175.7, authorized announcement date: on February 4th, 2004; (b) Cui, Z.-N.; Zhang, L.; Huang, J.; Yang, X.-L.; Ling, Y.SynthesisandBioactivityofNovelN, N '-DiacylhydrazineDerivativesContainingFuran(III) .Chin.J.Chem., 2010,28 (7), 1257-1266; C () Cui Zining, Zhang Li, Huang Juan, reach the clouds, Yang Xinling. containing the synthesis of furan nucleus bishydrazide derivative, insecticidal activity and 3D-QSAR research. and organic chemistry, 2010,30 (10), 1482-1491).
As a kind of preferred version, described thinner is preferably inert organic solvents.
As one more preferably scheme, described thinner is more preferably benzene, toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin, ether, diisopropyl ether, dioxan, tetrahydrofuran (THF), glycol dimethyl ether, ethylene glycol diethyl ether, acetone, butanone, mibk, acetonitrile, propionitrile, butyronitrile, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-methyl-formylaniline, N-Methyl pyrrolidone, HMPA, methyl acetate, ethyl acetate, dimethyl sulfoxide (DMSO), methyl alcohol, ethanol, n-propyl alcohol, Virahol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether.
As one more preferably scheme, described thinner is selected from benzene, toluene or tetrahydrofuran (THF).
The effect of sulfuration cyclization reagent carries out sulfuration to two carbonyls in formula II compound, and as a kind of preferred version, described sulfuration cyclization reagent is preferably thiophosphoric anhydride or Lawson (Lawesson) reagent.
As one most preferably scheme, described sulfuration cyclization reagent most preferably is Lawson (Lawesson) reagent.
According to the selection of thinner, reaction can be carried out under wide temperature range, as a kind of preferred version, is preferably 90 ~ 110 DEG C.
According to the difference of substrate, the General reactions time is 3 ~ 9 hours.Be more preferably 6 hours.
As a kind of preferred version, shown in described formula II, the mol ratio of compound and sulfiding reagent is 1 ~ 1.5:1 ~ 1.5.
As one most preferably scheme, shown in described formula II, the mol ratio of compound and sulfiding reagent most preferably is 1:1.5.
As a kind of preferred version, the volume of thinner is preferably 5 ~ 50mL:1 ~ 5mmol with the ratio of the amount of substance of compound shown in formula II.
As one most preferably scheme, the volume of thinner most preferably is 10mL:2mmol with the ratio of the amount of substance of compound shown in formula II.
The described furan nucleus 2,5-bis-that contains replaces the application of-1,3,4-thiadiazole compound in sterilant.-1,3 are replaced containing furan nucleus 2,5-bis-, the substituting group of 4-thiadiazole compound on two phenyl ring is different, can have diverse biological activity, find through contriver's long-term experiment, compound shown in formula I, according to substituent difference, all has significant prevention effect to phytophthora infestans.
Compared with prior art, the present invention has following beneficial effect:
The present invention openly replaces-1,3,4-thiadiazole compound containing furan nucleus 2,5-bis-has significant prevention effect to phytophthora infestans.The described furan nucleus 2,5-bis-that contains replaces the preparation method of-1,3,4-thiadiazole compound simply simultaneously, and productive rate is high.
Embodiment
Below in conjunction with specific embodiment, the present invention is further explained, but embodiments of the present invention is not limited in any way.Unless stated otherwise, involved in embodiment reagent, method are the conventional reagent in this area and method.
Embodiment 1: replace-1,3,4-thiadiazole compound (R containing furan nucleus 2,5-bis-shown in preparation formula I
1for hydrogen, R
2for 4-fluorine):
In the 25mL there-necked flask of drying; add 2mmolN-benzoyl-N '-5-(4 '-fluorophenyl)-2-furoyl hydrazine and 3mmol lawesson reagent (LawessonReagent); 10mL dry toluene, nitrogen protection, stirs 6h under 110 DEG C of conditions.React complete, boil off most of toluene, residual solids acetic acid ethyl dissolution, then carry out silica gel column chromatography separation, eluent is sherwood oil+ethyl acetate (volume ratio 4: 1), obtains yellow solid, m.p.:178-179 DEG C, yield 68%.
According to the method for embodiment 1, only change the R in compound shown in formula II
1and R
2, obtain type I compound shown in table 1, numbering is followed successively by I 1 ~ I 5.The outward appearance of above-claimed cpd and productive rate are all listed in table 1, and nucleus magnetic hydrogen spectrum detected result is all listed in table 2.As from the foregoing, above-mentioned numbering is followed successively by the compound structure of I 1-I 5 correctly, is compound shown in formula I.
The physical constant of compound shown in table 1 formula I
Infrared and the hydrogen nuclear magnetic resonance modal data of compound shown in table 2 formula I
Replace the agricultural bactericidal activity of-1,3,4-thiadiazole compound containing furan nucleus 2,5-bis-shown in embodiment 2 formula I
For examination pathogen species: phytophthora infestans, potato disease can be caused.Sample test concentration: 50 μ g/mL.
Making with medicine substratum: to diameter be 10cm culture dish in inject 1ml liquid to be measured, then injecting 9ml(temperature 85 ~ 90 DEG C wherein) substratum, super clean bench shakes up, is paved into a uniform planar.
The compound that institute's call number is followed successively by I1-I5 prepared by embodiment 1, adopt growth rate method, for above-mentioned shaker test of carrying out agricultural in vitro fungicidal activity for examination pathogen species.This tests pathogenic bacteria used is sample from the site of pathological change of field crops, takes cause of disease from by sick position, inoculation and purifying on corresponding substratum.
In super clean bench, with the substratum fritter of object bacteria with inoculating needle picking one piece in the strain tube for examination bacterium, be put in the large culture dish containing PDA substratum, cover culture dish rapidly, be tamping with sealing compound, cultivate in constant incubator.After bacterium colony is evenly distributed in culture dish for examination bacterium, is the punching of 0.6cm sampler with the internal diameter after sterilizing, obtains the bacterium cake that diameter is 0.4-0.8cm.By the bacterium cake made, be placed on band medicine substratum, put into 1 bacterium cake in every culture dish, repeat twice.
Culture dish is put into incubator cultivate, after 24-48 hour, according to target bacterium colony expansion situation check result, and at the colony diameter that each bacterium cake of suitable timing is expanded.According to object bacteria expansion diameter with contrast diameter and calculate and try out the inhibiting rate of medicament.
The compounds of this invention prevents and treats the selection result in table 3 to confession examination pathogen species.
Compound shown in table 3 formula I composes the selection result (50 μ g/mL) to for the control of examination pathogenic bacteria
As can be seen from Table 3, shown in the application's formula I, compound has significant prevention effect to phytophthora infestans, substituent difference, prevention effect is variant, shown in same concentrations formula I, compound is generally better than existing sterilant, especially, I3 compound prevention effect can reach 99.99%, has better sterilization effect than any one phytophthora infestans sterilant existing.
Claims (6)
1. replacing-1,3,4-thiadiazole compound preparing the application in phytophthora infestans fungistat containing furan nucleus 2,5-bis-, it is characterized in that, describedly replace-1,3,4-thiadiazole compound containing furan nucleus 2,5-bis-and have such as formula structure shown in I:
Described R
1or R
2for the substituting group on corresponding phenyl ring, R
1being selected from hydrogen, 4-halogen or 4-carbonatoms is the alkoxyl group of 1 ~ 4; R
2be selected from hydrogen, 2-halogen, 4-halogen or 3-nitro, and R
1with R
2be asynchronously hydrogen.
2. application according to claim 1, is characterized in that, R
1be selected from hydrogen, 4-chlorine or 4-methoxyl group; R
2be selected from hydrogen, 2-chlorine, 2-fluorine, 4-fluorine or 3-nitro, and R
1with R
2be asynchronously hydrogen.
3. application according to claim 1, is characterized in that, R
1for 4-chlorine, R
2for hydrogen.
4. the application any one of claims 1 to 3 described in claim, is characterized in that, described phytophthora infestans is the phytophthora infestans parasitized on potato.
5. one kind replaces to contain furan nucleus 2,5-bis-described in claim any one of claims 1 to 3 the phytophthora infestans fungistat that-1,3,4-thiadiazole compound is activeconstituents.
6. there is the compound replacing-1,3,4-thiadiazole compound structure any one of claims 1 to 3 as described in claim containing furan nucleus 2,5-bis-.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102159079A (en) * | 2008-07-17 | 2011-08-17 | 拜尔农作物科学股份公司 | Heterocyclic compounds used as pesticides |
| CN102153602A (en) * | 2011-02-24 | 2011-08-17 | 中国农业大学 | Furanosyl modified 1,3,4-thiadiazole derivative and preparation method thereof as well as application of derivative as bactericide |
| CN102816158A (en) * | 2012-08-01 | 2012-12-12 | 南开大学 | 5-methyl-1,2,3-thiadiazole-1,3,4-oxadiazole derivatives, and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102159079A (en) * | 2008-07-17 | 2011-08-17 | 拜尔农作物科学股份公司 | Heterocyclic compounds used as pesticides |
| CN102153602A (en) * | 2011-02-24 | 2011-08-17 | 中国农业大学 | Furanosyl modified 1,3,4-thiadiazole derivative and preparation method thereof as well as application of derivative as bactericide |
| CN102816158A (en) * | 2012-08-01 | 2012-12-12 | 南开大学 | 5-methyl-1,2,3-thiadiazole-1,3,4-oxadiazole derivatives, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 2,5-二取代-1,3,4-噁二唑类化合物的合成及其昆虫生长调节活性的研究进展;崔紫宁等;《有机化学》;20061231;第26卷(第12期);第1647-1656页 * |
| Microwave-Assisted Synthesis and Biological Activity of 2,5-disubstituted-1,3,4-thiadiazole;YU YUYE;《Asian Journal of Chemistry》;20071231;第19卷(第4期);第3143页第一段以及TABLE-2 * |
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