CN105439979B - Benzoyl hydazone derivative containing 1,2,3 thiadiazoles and preparation method and application - Google Patents
Benzoyl hydazone derivative containing 1,2,3 thiadiazoles and preparation method and application Download PDFInfo
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- CN105439979B CN105439979B CN201510765295.6A CN201510765295A CN105439979B CN 105439979 B CN105439979 B CN 105439979B CN 201510765295 A CN201510765295 A CN 201510765295A CN 105439979 B CN105439979 B CN 105439979B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/06—1,2,3-Thiadiazoles; Hydrogenated 1,2,3-thiadiazoles
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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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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
The invention belongs to organic compound to synthesize field, and in particular to benzoyl hydazone derivative containing 1,2,3 thiadiazoles and preparation method and application.Shown in formula I, in the present invention, the synthetic method of compound of formula I is simple to operate, raw material is easy to get, does not produce harmful side product, and yield is higher for such compound structure.Found through biological activity test, compound shown in formula I shows excellent bactericidal activity, it can be used for preventing and treating canker of apple fruit, rice sheath blight disease, melon and fruit corruption mildew, graw mold of tomato, early blight of tomato and bakanae disease of rice in agricultural production, there is preferable application and development value.
Description
Technical field
The invention belongs to organic chemical synthesis field, and in particular to benzoyl hydazone derivative containing 1,2,3- thiadiazoles and its
Preparation method, and application of such compound in sterilization.
Background technology
Heterocyclic compound has become the main flow field of novel pesticide research and development, and nitrogen heterocyclic ring is the emphasis wherein studied, according to
Count ultra high efficiency agricultural chemicals in there are about 70% for nitrogen heterocyclic ring (Chen, Q.et.al.Eur.J.Med.Chem.2008,43,
595.).Wherein, 1,2,3- thiadiazoles unique structures, there is good Environmental compatibility and extensive bioactivity, increasingly by
Researcher favors, and the report on its bioactivity is growing day by day.1,2,3- thiadiazoles derivatives have sterilization, weeding, desinsection,
Anticancer, disease-resistant isoreactivity (Zuo, X.et.al.J.Agric.Food.Chem.2010,58,2755.；Tripathy,
R.et.al.Bioorg.Med.Chem.Lett.2007,17,1793.；Fan,Z-J.et.al.J.Agric.Food
Chem.2009,57,4279.), many researcher's faces this carry out deeper into research.
The bioactivity of salicylic acid and its derivative has had many reports, and Miyazawa, which is reported, acts on tomato
It can induce the resistance to droop；Nasser Yalpani report resistance of the energy evoking tobacco to TMV；Katsumichi is reported
There is preferable bacteriostasis (Nasser to rice blast, downy mildew of garpe, tomato and the late blight of potato, rust etc.
Yalpani,et.al.The Plant Cell.2001.；Miyazawa.Physiol Mol Plant P.1988.；Aoki,
Katsumichi.UK Pat.Appl.1979.)。
Acylhydrazone is as a kind of special Shiff alkali, containing a good active group (CONHN=CH),
Excellent bioactivity and strong coordination ability (Syarmal, A.et.al.Chem.Rev.1989,9 (2) with unique:
183-185), it is always that (Wang Jianping etc., organises the widely studied object of people in agricultural chemicals, medicine and analytical reagent etc.
Learn, 2007,27 (4):524-529；Li Qinghan etc., chemical research and application, 2008,20 (8):988-991.).Acylhydrazone class chemical combination
Thing O in treatment tuberculosis, removing organism2-Free radical and antibacterial aspect have been widely used (NAM, N H.et
al.J.Chem.Soc.1953,(3):1358-1364.).But on the research text of the acylhydrazone containing Thiadiazole
Offer actually rare.
In order to obtain the new drug molecule with excellent bioactivity, spliced according to the active substructure of medicine and designed
Principle, by 1,2,3- thiadiazoles molecule and salicyclic acid derivatives by acylhydrazone key connection to together, design has been synthesized containing 1,2,3-
The benzoyl hydazone derivative of thiadiazoles, and sterilization bioactivity screening has been carried out, to provide candidate compound for New pesticides discovery
Thing.
The content of the invention
It is an object of the invention to provide benzoyl hydazone derivative of the thiadiazoles containing 1,2,3- and preparation method thereof with preventing and treating
Application on agricultural disease.Concrete technical scheme is as follows：
Benzoyl hydazone derivative containing 1,2,3- thiadiazoles, the formula of the derivative is Formulas I：
Wherein R1For H, C1~C10Alkyl, haloalkyl, phenyl, benzyl, halogen, nitro, thiazole or pyridine；R2For phenyl ring
On monosubstituted group or disubstituted group, the group include H, alkyl, halogen, alkoxy, epoxy radicals, naphthyl, nitro or
Trifluoromethyl.
Further, the R1For bromine, chlorine, fluorine, methyl, ethyl, propyl group or normal-butyl；R2Taken for monosubstituted group or two
For group, the group includes fluorine, chlorine, bromine or trifluoromethyl.
The preparation method of benzoyl hydazone derivative as described above containing 1,2,3- thiadiazoles, comprises the following steps：
Compound shown in Formula II is added to organic solvent A stirring, acidic materials is then added and is activated, then by formula
Compound is dissolved in organic solvent A shown in III, is slowly added to reaction system；After completion of the reaction, through recrystallizing or filtering, Formulas I is obtained
Shown compound；
Reaction equation a:
The organic solvent A includes aliphatic, alicyclic or aromatic hydrocarbon or its halogenated product：Benzene, toluene, diformazan
Benzene, chlorobenzene, dichloro-benzenes, petroleum ether, hexane, hexamethylene, dichloromethane, chloroform or carbon tetrachloride；Ethers：Ether, diisopropyl ether,
Tetrahydrofuran, glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, glycol dimethyl ether
Or ethylene glycol diethyl ether；Ketone：Acetone, butanone or methylisobutylketone；Nitrile：Acetonitrile, propionitrile or butyronitrile；Amide-type：Such as N, N-
Dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl-formailide, 1-METHYLPYRROLIDONE or HMPA；
Esters：Such as methyl acetate or ethyl acetate；Sulfoxide type：Dimethyl sulfoxide (DMSO)；Alcohols：In methanol, ethanol, normal propyl alcohol or isopropanol
One or more any combination.
The organic solvent be preferably one kind in dichloromethane, acetonitrile, petroleum ether, methanol, ethanol and tetrahydrofuran or
More than one any combination.
The acid compound be selected from hydrochloric acid, sulfuric acid, acetic acid, p-methyl benzenesulfonic acid, iron chloride, stannous chloride, butter of tin,
At least one in alchlor, zinc chloride, copper sulphate, ferric sulfate, ammonium ferric sulfate, ceric sulfate, zirconium chloride and niter cake
Kind, preferably at least one of formic acid and acetic acid, more preferably acetic acid.
The reaction temperature is -20~100 DEG C, and preferably 20~80 DEG C, the reaction time is 1~20h, preferably 3~8h.
The mass ratio of compound shown in compound shown in Formula II and formula III is 1:(0.8~1.6), preferably 1:0.8~
1.0；The dosage of the organic solvent is 15-60 times, preferably 25-30 times of compound amount shown in Formula II.
Wherein, 4-R shown in Formula II1- 1,2,3- thiadiazoles -5- formaldehyde, are prepared by the method shown in reaction equation b：
Reaction equation b:
Take a certain amount of 4-R1- 1,2,3- thiadiazoles -5- Ethyl formates (formula IV) are dissolved in ethanol, are slowly added to appropriate
NaBH4, aqueous slkali quenching reaction after completion of the reaction, organic solvent extraction, depressurize and steam solvent, obtain 4-R1- 1,2,3- thiophenes two
Azoles -5- methanol (compound shown in Formula V).
Compound shown in Formula V is dissolved in q. s. methylene chloride, then adds PCC, after reacting a period of time, is filtered, filter
The rotated evaporation of solvent of liquid, obtains compound shown in Formula II.
Wherein 4-R1- 1,2,3- thiadiazoles -5- Ethyl formates (formula IV) obtain (Wang Shouxin, having by reference to literature method
Chemical machine, 2013,33,2367-2375.).
Substituted benzoyl hydrazides shown in formula (III), is prepared by the following method：Substituted ethyl benzoate is pressed with hydrazine hydrate
According to material amount than 1:1~1.5 input reaction, in ethanol back flow reaction 3-12 hours, reaction stand a night after terminating, taken out
Filter, filtration cakes torrefaction, obtains substituted benzoyl hydrazides.
By various substituted benzoic acids, esterification obtains the substituted ethyl benzoate in ethanol.
Medicine using the benzoyl hydazone derivative of the thiadiazoles containing 1,2,3- as described above as active component.
Application of the benzoyl hydazone derivative of the thiadiazoles containing 1,2,3- on crops as bactericide as described above.
The germ that bactericide is prevented and treated is Valsa mali, Rhizoctonia solani Kuhn, Pythium aphanidermatum, graw mold of tomato
Bacterium, tomato early blight bacterium or fusarium moniliforme.
When needing, acceptable carrier in one or more pesticidal preparations can also be added in the medicine,
The carrier includes diluent conventional in pesticidal preparations, excipient, filler, adhesive, wetting agent, sorbefacient, table
Face activating agent, lubricant, stabilizer, defoamer, diatomite etc..The formulation of manufactured medicine is also various, can be pulvis,
Emulsion, aqua, granule, corrosion inhibiter, effervescent tablet etc..
Beneficial effects of the present invention are：
(1) preparation method of the present invention is simple and easy to do, and product purification is easy, and cost is relatively low, and yield is higher.
(2) present invention contains the benzoyl hydazone derivative of 1,2,3- thiadiazoles, through testing to Valsa mali, rice banded sclerotial blight
Germ, Pythium aphanidermatum, botrytis cinerea, tomato early blight bacterium and fusarium moniliforme have higher inhibitory activity, can
Agriculturally to be applied as bactericide.
Embodiment
The substantial feature of the present invention can emerge from from following embodiments, but it is not construed as making the present invention
Any restrictions.Method in following embodiments, it is conventional method unless otherwise instructed.The material, unless otherwise instructed,
It can be obtained from open commercial sources.
Embodiment 1：The preparation of 4- butyl -1,2,3- thiadiazoles -5- methanol (V-05) and Structural Identification
8.56g (0.04mol) 4- butyl -1,2 is weighed, 3- thiadiazoles -5- Ethyl formates add in 100ml there-necked flasks
30mL ethanol dissolves, and is subsequently placed under ice salt bath and is cooled to less than 0 DEG C, is slowly added to 2.28g (0.06mol) sodium borohydride, removes
Deicing salt bath is warming up to 25 DEG C, is reacted 5 hours under normal temperature, to reaction system plus watery hydrochloric acid to the aobvious acidity of solution, uses dichloromethane
Extraction, organic phase are washed with saturated sodium bicarbonate solution and saturated nacl aqueous solution respectively, organic phase anhydrous sodium sulfate drying,
Filter, filtrate is concentrated to give yellow liquid 6.31g, as the intermediate V-05 of the present invention, yield 91.7%.
According to the identical methods of prepare compound V-05, successfully prepare V-01~V-04, its physicochemical data and
Structural Identification data are shown in Table 1, and from the related data of table 1, above-mentioned product V-01~V-05 structure is correct, is Formula V structure
Compound shown in formula.
Embodiment 2：The preparation of intermediate 4- butyl -1,2,3- thiadiazoles -5- formaldehyde (II-05) and Structural Identification
10.63g (0.05mol) PCC are weighed in 100ml there-necked flasks, add 40ml dichloromethane stirring and dissolvings, Ran Houhuan
Slow to add 6.02g (0.035mol) 4- butyl -1,2, the dichloromethane solution of 3- thiadiazoles -5- methanol, TLC is monitored to having reacted
Finish.Stop reaction, filter, filtrate washed with saturated sodium bicarbonate solution and saturated nacl aqueous solution respectively, and organic phase is with anhydrous
Sodium sulphate is dried, and is filtered, and filtrate is concentrated to give yellow liquid 5.39g, as intermediate II -05 of the present invention, yield 90.6%.
According to the identical methods of prepare compound II-05, successfully prepare II-01~II-04, its physicochemical data
1 is shown in Table with Structural Identification data, from the related data of table 1, above-mentioned product II-01~II-05 structure is correct, is Formula II
Compound shown in general structure.
Table 1 intermediate V and II physicochemical data and Structural Identification data
Embodiment 3：4- methyl isophthalic acids, the preparation of the bromo- benzoyl hydrazones (numbering I-01) of 2,3- thiadiazoles -5- formaldehyde -2- and knot
Structure is identified
Add compound 4- methyl isophthalic acids shown in 20mL methanol and 0.32g (2.5mmol) Formula II into 50mL three-necked flasks, 2,
3- thiadiazoles -5- formaldehyde, stirring, disposably add 0.6mg (0.01mmol) acetic acid and activated, then by 0.43g (2mmol) formula
Compound (R shown in III2For the bromines of 2 substitutions) the bromo- benzoyl hydrazines of 2- are dissolved in methanol, and it is slowly added in above-mentioned three-necked flask, adds
Heat stopped reaction to 78 DEG C of back flow reactions 6 hours.Rotary evaporation removes solvent and obtains crude product, ethyl alcohol recrystallization, obtains white solid
0.56g, yield 87%.The outward appearance and fusing point of the white solid product are shown in Table 2, its1H H NMR spectroscopy data are shown in Table 3.As shown in Table 3,
The product structure is correct, is compound shown in Formulas I, numbering I-01.
According to the identical methods of prepare compound I-01, successfully prepare I-02~I-25, its physicochemical data is shown in
Table 2, its Structural Identification data are shown in Table 3, and from the related data of table 3, above-mentioned product I-01~I-25 structure is correct, is formula
Compound shown in I general structures, wherein, R group is listed in Table 2 below.
Embodiment 4：The system of 4- propyl group -1,2,3- thiadiazoles -5- formaldehyde -3- Trifluoromethyl-phenacyl hydrazones (numbering I-31)
Standby and Structural Identification
Compound 4- propyl group -1,2,3- shown in 20mL ethanol and 0.47g (3mmol) Formula II is added into 50mL three-necked flasks
Thiadiazoles -5- formaldehyde, stirring, disposably add 0.6mg (0.01mmol) acetic acid and activated, then by 0.62g (3mmol) formula
Compound (R shown in III2For the trifluoromethyls of 3 substitutions) 3- Trifluoromethyl-phenacyl hydrazines are dissolved in ethanol, it are slowly added to above-mentioned
In three-necked flask, under normal temperature after condensation reaction 4 hours, stop reaction.Reaction solution is placed into refrigerator overnight, filtered, filtration cakes torrefaction
Obtain yellow solid 0.81g, yield 79%.The outward appearance and fusing point of the white solid product are shown in Table 2, its1H H NMR spectroscopy data are shown in Table 3.
As shown in Table 3, the product structure is correct, is compound shown in Formulas I, numbering I-31.
According to the identical methods of prepare compound I-31, successfully prepare I-26~I-51, its physicochemical data is shown in
Table 2, its Structural Identification data are shown in Table 3, and from the related data of table 3, above-mentioned product I-26~I-51 structure is correct, is formula
Compound shown in I general structures, wherein, R group is listed in Table 2 below.
The physicochemical data of the target compound of table 2 (Formulas I)
[1] I-03 and I-06 replace R with structural formula.
The nuclear magnetic data of the target compound of table 3 (Formulas I)
Embodiment 5：Part of compounds bactericidal activity of the present invention
Bactericidal activity measure is carried out using mycelial growth rate method to target compound.
It it is Valsa mali, Rhizoctonia solani Kuhn, Pythium aphanidermatum, botrytis cinerea, tomato morning for examination strain
Epidemic disease bacterium and fusarium moniliforme etc..
Weigh 50mg target compounds respectively, sample be then dissolved in dimethyl sulfoxide, respectively constant volume into concentration be 5000mg/
L decoction is standby.
The decoction that 2mL concentration is 5000mg/L and potato dextrose agar (PDA) culture medium that 98mL melts is taken to mix,
It is the toxic culture medium 100mL of 50mg/L to be prepared into concentration.Toxic culture medium is divided into 4 parts, pour into respectively 4 it is a diameter of
In 9cm culture dish, toxic PDA plate is made.After toxic culture medium condensation in ware, it is respectively connected to cultured a diameter of
0.5cm pathogen bacteria cake.It is placed in 25 DEG C of incubators and cultivates.Using the Difenoconazole of same concentrations as comparison medicament, diformazan
Sulfoxide is solvent control, while sets sterilized water as blank control, each 4 repetitions of sample, and above operation is sterile working.Treat
After bacterium colony in blank control fully grows, the colony diameter of each processing is measured with crossing method, takes its average value.
Calculated with the bacterium colony average diameter of the blank control after correction and processing
Inhibiting rate=(control colony diameter-processing colony diameter)/control colony diameter * 100
Bactericidal activity test result is shown in Table 4.
The compound of formula I bactericidal activity of table 4
The result of table 4 shows that compound of the invention has the change of obvious bactericidal activity, especially halogen substituent group
Compound such as I-18, I-26, I-27, I-35, I-37, I-42, I-47 bactericidal activity becomes apparent, particularly to canker of apple fruit
Jun ﹑ botrytis cinereas have more prominent inhibitory activity, if I-35, I-37, I-42, I-47 are to the activity of Valsa mali
(being 100%) and comparison medicament Difenoconazole (100%) quite, and are better than comparison medicament tiadinil (95%)；I-35、
I-37, I-42, I-47 are better than comparison medicament thiophene acyl to the activity (being respectively 85%, 85%, 85%, 83%) of botrytis cinerea
Bacterium amine (81%), there is the value further studied as bactericide.
Claims (11)
1. the benzoyl hydazone derivative containing 1,2,3- thiadiazoles, it is characterised in that the formula of the derivative is Formulas I：
Wherein R1For H, C1~C10Alkyl, haloalkyl, phenyl, benzyl, halogen, nitro, thiazole or pyridine；R2For on phenyl ring
Monosubstituted group or disubstituted group, the group include H, alkyl, halogen, alkoxy, epoxy radicals, naphthyl, nitro or trifluoro
Methyl.
2. the benzoyl hydazone derivative according to claim 1 for containing 1,2,3- thiadiazoles, it is characterised in that the R1For bromine,
Chlorine, fluorine, methyl, ethyl, propyl group or normal-butyl；R2For monosubstituted group or disubstituted group, the group includes fluorine, chlorine, bromine
Or trifluoromethyl.
3. the preparation method of the benzoyl hydazone derivative according to claim 1 or 2 for containing 1,2,3- thiadiazoles, its feature exist
In comprising the following steps：
Compound shown in Formula II is added in organic solvent A and stirred, acidic materials is then added and is activated, then by formula III
Shown compound is dissolved in organic solvent A, is slowly added to reaction system；After completion of the reaction, through recrystallizing or filtering, Formulas I institute is obtained
Show compound；
Reaction equation is:
4. preparation method according to claim 3, it is characterised in that the organic solvent A is aliphatic or aromatic
One or more in hydrocarbon or its halogenated product, ethers, ketone, nitrile, amide-type, esters, sulfoxide type and alcohols.
5. preparation method according to claim 4, it is characterised in that the aliphatic or aromatic hydrocarbon or its halides
For benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, petroleum ether, hexane, hexamethylene, dichloromethane, chloroform or carbon tetrachloride；
The ethers is ether, diisopropyl ether, tetrahydrofuran, glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol list first
Ether, diethylene glycol monoethyl ether, glycol dimethyl ether or ethylene glycol diethyl ether；
The ketone is acetone, butanone or methylisobutylketone；
The nitrile is acetonitrile, propionitrile or butyronitrile；
The amide-type is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl-formailide, N- methylpyrroles
Alkanone or HMPA；
The esters are methyl acetate or ethyl acetate；
The sulfoxide type is dimethyl sulfoxide (DMSO)；
The alcohols is the one or more in methanol, ethanol, normal propyl alcohol or isopropanol.
6. according to the method for claim 3, it is characterised in that the acid compound is selected from hydrochloric acid, sulfuric acid, acetic acid, right
Toluenesulfonic acid, iron chloride, stannous chloride, butter of tin, alchlor, zinc chloride, copper sulphate, ferric sulfate, ammonium ferric sulfate, sulfuric acid
At least one of high cerium, zirconium chloride and niter cake.
7. preparation method according to claim 3, it is characterised in that the reaction temperature is -20~100 DEG C, during reaction
Between be 1~20h.
8. preparation method according to claim 3, it is characterised in that compound shown in compound shown in Formula II and formula III
Mass ratio be 1:(0.8~1.6), the dosage of the organic solvent are 15-60 times of compound amount shown in Formula II.
9. using the benzoyl hydazone derivative of the thiadiazoles containing 1,2,3- described in claim 1 as the medicine of active component.
10. the benzoyl hydazone derivative of the thiadiazoles containing 1,2,3- described in claim 1 answering as bactericide on crops
With.
11. application according to claim 10, it is characterised in that the germ that bactericide is prevented and treated be Valsa mali,
Rhizoctonia solani Kuhn, Pythium aphanidermatum, botrytis cinerea, tomato early blight bacterium or fusarium moniliforme.
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| 含噻二唑环苯甲酰脲化合物的合成及杀虫活性;李兴海 等;《化学通报》;20030531(第5期);第333-336页 * |
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